KR20220153086A - Adhesive and its use - Google Patents

Abstract

A pressure-sensitive adhesive containing an acrylic polymer (F) containing a fluorine-containing acrylic monomer (M1) as a monomer unit is provided. The pressure-sensitive adhesive has a refractive index of 1.46 or less, and a storage elastic modulus G' at 25°C of 400 kPa or less.

Description

Adhesive and its use

The present invention relates to an adhesive, and more particularly, to an adhesive containing an acrylic polymer containing a fluorine-containing acrylic monomer as a monomer unit and its use.

This application relates to Japanese Patent Application No. 2020-052408 filed on March 24, 2020, Japanese Patent Application No. 2020-166428 filed on September 30, 2020, and filed on March 23, 2021. Priority based on Japanese Patent Application No. 2021-049062 is claimed, and the entire contents of those applications are incorporated herein by reference.

In general, pressure-sensitive adhesives (also referred to as pressure-sensitive adhesives; the same applies hereinafter) exhibit a flexible solid (viscoelastic material) state in a temperature range around room temperature, and have a property of being easily adhered to an adherend by pressure. Taking advantage of these properties, adhesives are widely used for purposes such as bonding, fixing, and protection in various industrial fields such as home appliances, automobiles, various machines, electrical devices, and electronic devices. As the technical literature related to the pressure-sensitive adhesive, Patent Documents 1 to 4 can be cited.

Japanese Patent No. 6014781 Japanese Patent Application Publication No. 2020-111740 Japanese Patent Application Publication No. 2019-210343 Japanese Patent Application Publication No. 2018-193553

Patent Literatures 1 to 4 propose pressure-sensitive adhesives comprising a (meth)acrylate copolymer containing structural units derived from a fluorine-containing acrylic monomer. All of these are adhesives focusing on sebum resistance and/or chemical resistance, and the refractive index is not considered.

An object of the present invention is to provide a pressure-sensitive adhesive having a low refractive index and being flexible. Another related object is to provide a laminated sheet including a pressure-sensitive adhesive layer composed of such a pressure-sensitive adhesive and a light emitting device including the laminated sheet.

According to this specification, a pressure-sensitive adhesive containing an acrylic polymer (F) containing a fluorine-containing acrylic monomer (M1) as a monomer unit is provided. The refractive index of the pressure-sensitive adhesive is 1.46 or less. The pressure-sensitive adhesive has a storage modulus G' at 25°C (hereinafter sometimes referred to as "storage modulus G' _V2 (25)") of 400 kPa or less (for example, 1.0 kPa or more and 400 kPa or less). it is desirable Such an adhesive may be preferably used for the purpose of controlling the behavior of light, for example, in the form of being laminated on a layer having a higher refractive index (which may be an adhesive layer). Since the adhesive has a storage modulus G′ _V2 (25) limited to a predetermined value or less, from the viewpoints of ease of sticking and adhesion to an adherend, conformability to the surface shape of an adherend, conformability to deformation of an adherend, etc. It is advantageous.

In the monomer component constituting the acrylic polymer (F), the content of the fluorine-containing acrylic monomer (M1) is preferably 25% by weight or more. A pressure-sensitive adhesive having a refractive index of 1.46 or less can be suitably realized by including the acrylic polymer (F) composed of monomer components having such a composition. The fluorine-containing acrylic monomer (M1) preferably contains a fluorine atom-containing (meth)acrylic acid alkyl ester from the viewpoint of the ease of polymerization and the effect of lowering the refractive index.

In some embodiments, the acrylic polymer (F) contains a hydroxyl group-containing monomer as a monomer unit. A monomer unit derived from a hydroxyl group-containing monomer can be useful in realizing a pressure-sensitive adhesive that achieves both desired flexibility and appropriate cohesiveness.

According to this specification, a laminated sheet comprising a low refractive index pressure-sensitive adhesive layer formed of any of the pressure-sensitive adhesives disclosed herein and a high refractive index pressure-sensitive adhesive layer laminated on the low-refractive pressure-sensitive adhesive layer is provided. According to the laminated sheet including the pressure-sensitive adhesive layers having different refractive indices in a laminated form, the behavior of light passing through the laminated sheet can be controlled by using the difference in refractive index between the high-refractive-index pressure-sensitive adhesive layer and the low-refractive-index pressure-sensitive adhesive layer. The ratio of the refractive index n ₁ of the high refractive index adhesive layer and the refractive index n ₂ of the low refractive index adhesive layer (n ₁ /n ₂ ) may be, for example, 1.02 or more.

In some embodiments, the refractive index n ₁ of the high refractive index adhesive layer may be greater than 1.570. The laminated sheet having such a high-refractive-index pressure-sensitive adhesive layer has a large refractive index difference with the low-refractive-index pressure-sensitive adhesive layer, so that the behavior of light passing through the laminated sheet can be better controlled.

In some aspects, the high refractive index pressure-sensitive adhesive layer has a storage modulus G' at 25°C (hereinafter sometimes referred to as "storage modulus G' _V1 (25)") of 700 kPa or less. Thus, the laminated sheet provided with the high refractive index pressure-sensitive adhesive layer in which the storage elastic modulus _G'V1 (25) is limited to a predetermined level or less is preferable from the viewpoint of ease of sticking and flexibility.

In some aspects, the laminated sheet has a total light transmittance of 86% or more and a haze value of 3.0% or less. Such a highly transparent laminated sheet can be suitably used for applications such as bonding optical members and controlling the behavior of light passing through the laminated sheet.

The laminated sheet disclosed herein is suitable as a component of a light emitting device, for example. Therefore, according to this specification, a light emitting device comprising any of the laminated sheets disclosed herein and a self-light emitting element is provided.

In addition, an appropriate combination of each element described in this specification may also be included in the scope of the invention requiring protection by a patent according to the present patent application.

1 is a cross-sectional view schematically showing the configuration of an adhesive sheet according to an embodiment.
Fig. 2 is a cross-sectional view schematically showing the structure of a laminated sheet according to an embodiment.
3 is a cross-sectional view schematically showing the configuration of a light emitting device according to an embodiment.

Preferred embodiments of the present invention will be described below. Matters other than matters specifically mentioned in this specification and necessary for the practice of the present invention can be understood by those skilled in the art based on the teachings for the practice of the invention described in this specification and common technical knowledge at the time of filing. The present invention can be implemented based on the content disclosed in this specification and common technical knowledge in the field.

Note that in the following drawings, the same reference numerals may be given to members and parts exhibiting the same action, and overlapping explanations may be omitted or simplified. In addition, the embodiments described in the drawings are modeled in order to clearly explain the present invention, and do not necessarily accurately represent the size or scale of products actually provided.

In this specification, a self-luminous element means a light-emitting element capable of controlling the luminance of light emitted by a value of current flowing therethrough. The self-luminous element may be composed of a single body or may be composed of an aggregate. Specific examples of self-luminous devices include, but are not limited to, light emitting diodes (LEDs) and organic ELs. The light-emitting device disclosed herein includes such a self-luminous element as a component. Examples of the light emitting device include, but are not limited to, a light source module device (eg, area light emitting module) used as illumination and a display device in which pixels are formed.

In the technology disclosed by this specification, a low refractive index pressure-sensitive adhesive and a pressure-sensitive adhesive composition used for its formation, a high refractive index pressure-sensitive adhesive layer and a pressure-sensitive adhesive composition used for its formation, a laminated sheet comprising a high refractive index pressure-sensitive adhesive layer and a low refractive index pressure-sensitive adhesive layer (adhesive sheet), a laminated sheet having a release liner in which an adhesive surface of the laminated sheet is protected by a release liner, a light emitting device including a high refractive index adhesive layer and a low refractive index adhesive layer, and the like may be included. The technology disclosed by this specification may also include an interlayer sheet including a high refractive index pressure sensitive adhesive layer and a low refractive index pressure sensitive adhesive layer and disposed between the layers of the optical laminate.

<Configuration example of adhesive sheet>

The pressure-sensitive adhesive disclosed herein can be used, for example, as a pressure-sensitive adhesive sheet containing a layer (pressure-sensitive adhesive layer) formed of the pressure-sensitive adhesive, and is preferably used in the form of a pressure-sensitive adhesive sheet having an adhesive surface formed by the pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet having a base material having a pressure-sensitive adhesive layer on one side or both sides of a non-peelable base material (supporting base material), or an inorganic pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is held by a release liner. (That is, an adhesive sheet having no non-peelable base material. Typically, an adhesive sheet composed of an adhesive layer) may be used. The concept of the pressure-sensitive adhesive sheet herein may include what is called an adhesive tape, an adhesive label, an adhesive film, and the like. The PSA sheet disclosed herein may be in the form of a roll or sheet. Alternatively, it may be a pressure-sensitive adhesive sheet processed into more diverse shapes.

1 shows an example of a configuration of a pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive disclosed herein. This PSA sheet 1 is laminated on the PSA layer 10, the first surface 10A of which serves as an adhesion surface (adhesive surface) to the adherend, and the second surface 10B of the PSA layer 10. It is constituted as a single-sided adhesive PSA sheet (single-sided PSA sheet) including a supporting substrate 20. The second surface 10B of the pressure-sensitive adhesive layer 10 is bonded to the first surface (non-peelable surface) 20A of the supporting substrate 20 . As the support substrate 20, a plastic film such as a polyester film may be used, for example. The supporting substrate 20 may be, for example, an optical film such as a polarizing plate. In the PSA sheet 1 before use (before sticking to an adherend), as shown in, for example, FIG. It may be in the form of an adhesive sheet 50 having a release liner, protected by the release liner 30 thereon. Alternatively, the second surface 20B of the supporting substrate 20 (a surface opposite to the first surface 20A, also referred to as a back surface) is a release surface, and an adhesive surface ( 10A) may be wound or laminated so that the adhesive surface 10A is protected.

The pressure-sensitive adhesive layer 10 may have a single-layer structure or may have a laminated structure in which two or more sub-pressure-sensitive adhesive layers having different compositions are laminated in direct contact (ie, not separated by a layer of non-adhesive material). The refractive index of the sub adhesive layer constituting the laminated structure may be the same or different. In the pressure-sensitive adhesive layer of the laminated structure including two or more sub-sensitive adhesive layers having different refractive indices, at least one sub-sensitive adhesive layer satisfies the refractive index of 1.46 or less (preferably, the storage modulus G'(25) of 400 kPa or less). Do) It is preferable that it is a low refractive index adhesive layer. The refractive index and storage elastic modulus G'(25) of the other sub-adhesive layer are not particularly limited, and for example, the refractive index may be 1.46 or less and may exceed 1.46, and the storage elastic modulus G'(25) may be 400 kPa. It may be less than or more than 400 kPa.

The PSA sheet disclosed herein may be in the form of an inorganic double-sided PSA sheet composed of a PSA layer. The pressure-sensitive adhesive layer constituting the inorganic double-sided pressure-sensitive adhesive sheet may have a single-layer structure, similarly to the pressure-sensitive adhesive layer 10 in the pressure-sensitive adhesive sheet 1 shown in FIG. may be a laminated structure. 2 shows a configuration example of an inorganic double-sided pressure-sensitive adhesive sheet 2 composed of a pressure-sensitive adhesive layer 10 having a laminated structure including a first pressure-sensitive adhesive layer 11 and a second pressure-sensitive adhesive layer 12 having different compositions. . The second pressure-sensitive adhesive layer 12 may be a low-refractive-index pressure-sensitive adhesive layer that satisfies a refractive index of 1.46 or less, and may also be a layer that satisfies a storage modulus G'(25) of 400 kPa or less. The first pressure sensitive adhesive layer 11 may be a pressure sensitive adhesive layer having a relatively higher refractive index (high refractive index pressure sensitive adhesive layer) in relation to the second pressure sensitive adhesive layer 12 . The pressure-sensitive adhesive sheet 2 having such a configuration can be understood as a laminated sheet having a laminated structure of a high-refractive-index pressure-sensitive adhesive layer/low-refractive-index pressure-sensitive adhesive layer.

As shown in FIG. 2 before use, the inorganic double-sided pressure-sensitive adhesive sheet 2 has a first surface (first adhesive surface) 10A and a second surface (second adhesive surface) of the pressure-sensitive adhesive layer 10. 10B may be of a form protected by release liners 31 and 32 in which at least the pressure-sensitive adhesive layer side is a release surface (release surface). Alternatively, the back surface of the release liner 31 (surface on the opposite side to the adhesive side) is a release surface, and the adhesive surface 10A is formed by winding or stacking so that the adhesive surface 10B is in contact with the back surface of the release liner 31. 10B) may be in a protected form. Such an inorganic double-sided pressure-sensitive adhesive sheet may be, for example, a base material (preferably a light-transmitting base material, for example, an optical member such as an optical film) on at least one of the first adhesive face and the second adhesive face. ) can be used in combination.

The low-refractive-index adhesive disclosed herein (a pressure-sensitive adhesive having a refractive index of 1.46 or less) can be used, for example, in a form embedded in a light emitting device. An example of the configuration of such a light emitting device is shown in FIG. 3 . The light-emitting device 100 shown in FIG. 3 is directly connected to the self-light emitting element 70, the low-refractive-index adhesive layer 12 disposed on the viewing side of the self-light-emitting element 70, and the low-refractive-index adhesive layer 12. It includes a high refractive index adhesive layer 11 laminated in contact with each other. The light emitting device 100 may further include a cover window member 80 disposed on the viewing side of the high refractive index adhesive layer 11 . In the light emitting device 100 shown in FIG. 3 , a laminated sheet 10 composed of a high refractive index adhesive layer 11 and a low refractive index adhesive layer 12 is provided between the self-luminous element 70 and the cover window member 80 is placed. Between the self-luminous element 70 and the low-refractive-index adhesive layer 12, between the high-refractive-index adhesive layer 12 and the cover window member 80, and on the more visible side of the cover window member 80, each independently, not shown One or two or more layers may or may not be interposed. In addition, contrary to FIG. 3, the high refractive index adhesive layer 11 may be arrange|positioned on the self-light-emitting element side, and the low refractive index adhesive layer 12 may be arrange|positioned on the cover window member side. Alternatively, the low refractive index adhesive disclosed herein is a light emitting device configured in which the high refractive index adhesive layer 11 in FIG. 3 is omitted or replaced with a high refractive index layer (hard resin layer or the like) having no adhesiveness. may be used.

The PSA sheet disclosed herein may be a component of an optical member comprising a PSA sheet in which an optical member is bonded to at least one surface of the PSA layer. For example, the pressure-sensitive adhesive sheet 1 shown in FIG. 1 may be a component of an optical member including a pressure-sensitive adhesive sheet in which an optical member is bonded to the first surface 10A of the pressure-sensitive adhesive layer 10 . The optical member may be, for example, a glass plate, a resin film, or a metal plate. In addition, in the PSA sheet 1 shown in FIG. 1 , when the supporting substrate 20 is an optical member such as an optical film, the PSA sheet 1 has a second surface 10B of the PSA layer 10 It can be understood as an optical member having an adhesive sheet to which an optical member is bonded.

Further, although not particularly shown, the PSA sheet disclosed herein includes a support substrate having a non-releasable first surface and a second surface, a first pressure-sensitive adhesive layer is fixedly laminated on the first surface, and the first surface is fixedly laminated. It may be in the form of a double-sided adhesive pressure-sensitive adhesive sheet having a base material in which the second pressure-sensitive adhesive layer is fixedly laminated on two surfaces (double-sided pressure-sensitive adhesive sheet having a base material). As an example of the configuration of a double-sided pressure-sensitive adhesive sheet having such a base material, in the single-sided pressure-sensitive adhesive sheet 1 shown in FIG. A second pressure-sensitive adhesive layer is provided on (20B), the second surface of the second pressure-sensitive adhesive layer is bonded to the second surface 20B of the supporting base material 20, and the first surface (first surface of the second pressure-sensitive adhesive layer) The surface on the opposite side to 2 surface) is a form in which it becomes the 2nd adhesive surface of the double-sided adhesive sheet provided with a base material is mentioned. The composition of the pressure-sensitive adhesive constituting the second pressure-sensitive adhesive layer may be the same as or different from the composition of the pressure-sensitive adhesive constituting the first pressure-sensitive adhesive layer. The double-sided pressure-sensitive adhesive sheet provided with the substrate before use may have a form in which the first adhesive surface and the second adhesive surface are protected by a release liner, similarly to the inorganic double-sided pressure-sensitive adhesive sheet described above.

In addition, in the following, for convenience of explanation, the adhesive having a refractive index of 1.46 or less (low refractive index adhesive) may be described in comparison with a layer having a higher refractive index, but the use mode of the low refractive index adhesive disclosed herein It is not intended to be limiting.

<Low refractive index adhesive>

According to this specification, a pressure-sensitive adhesive having a refractive index of 1.46 or less is provided. A pressure-sensitive adhesive having such a refractive index may be preferably used for the purpose of controlling the behavior of light, for example, in the form of being laminated on a layer having a higher refractive index (which may be a pressure-sensitive adhesive layer). In some embodiments, the refractive index n ₂ of the low-refractive-index pressure-sensitive adhesive layer is preferably 1.45 or less, from the viewpoint of increasing the refractive index difference with the refractive index n ₁ of the high refractive index layer to facilitate enhancing the frontal luminance improvement effect described later, It is preferably 1.44 or less, may be 1.43 or less, may be 1.41 or less, may be 1.40 or less, or may be less than 1.40 (eg less than 1.39, furthermore less than 1.38). Further, from the viewpoint of ease of availability of materials and ease of compatibility with adhesive properties, in some embodiments, the refractive index n ₂ of the low refractive index adhesive may be, for example, 1.35 or more, preferably 1.36 or more, and may be 1.38 or more. It may be 1.40 or more, or 1.42 or more may be sufficient. The technology disclosed herein can be preferably implemented in an aspect in which the refractive index n ₂ of the low refractive index adhesive is 1.35 or more and 1.46 or less (more preferably, 1.36 or more and 1.45 or less), for example.

In addition, in this specification, the refractive index of an adhesive means the refractive index of the surface (adhesive surface) of this adhesive. The refractive index of the pressure-sensitive adhesive can be measured using a commercially available refractive index measuring device (Abe refractometer) under conditions of a measurement wavelength of 589 nm and a measurement temperature of 25°C. As the Abbe refractometer, for example, a type "DR-M4" manufactured by ATAGO or an equivalent thereof is used. As a measurement sample, the adhesive layer which consists of the adhesive of evaluation object can be used. The refractive index of the pressure-sensitive adhesive can be specifically measured by the method described in Examples described later. The refractive index of the pressure-sensitive adhesive can be adjusted by, for example, the composition of the pressure-sensitive adhesive (eg, the composition of monomer components constituting the base polymer, additives that can be used as needed, etc.).

The storage elastic modulus _G'V2 (25) of the low-refractive-index pressure-sensitive adhesive disclosed herein is preferably 400 kPa or less from the viewpoint of ease of sticking to an adherend, adhesion, surface shape followability, deformation followability, and the like. In some embodiments, the storage modulus _G'V2 (25) is preferably 300 kPa or less, more preferably 200 kPa or less (eg 180 kPa or less or 150 kPa or less), and may be 120 kPa or less , may be 90 kPa or less, and may be 70 kPa or less. The low storage modulus G ' _V2 (25) is, for example, in the use mode of being laminated on the high refractive index layer, it is also advantageous from the viewpoint of enhancing the effect of imparting flexibility by the low refractive index pressure-sensitive adhesive layer or improving followability to deformation. have. The lower limit of the storage modulus G' _V2 (25) is not particularly limited, and may be, for example, 1.0 kPa or more. In some aspects, from the viewpoint of making it easy to impart appropriate cohesiveness to the low-refractive-index pressure-sensitive adhesive layer, the storage elastic modulus _G'V2 (25) is, for example, suitably 5.0 kPa or more, preferably 10 kPa or more, and 15 It may be kPa or more, 25 kPa or more, 35 kPa or more, 60 kPa or more, or 80 kPa or more. From the viewpoint of making it easier to realize higher cohesive force and adhesive properties, in some aspects, the storage elastic modulus _G'V2 (25) may be 95 kPa or more, 110 kPa or more, or 140 kPa or more.

In some preferred embodiments, the storage elastic modulus G' at 25°C of the low refractive index pressure sensitive adhesive layer (i.e., the storage elastic modulus G' _V2 (25)) is a high refractive index layer that can be disposed adjacent to the low refractive index pressure sensitive adhesive layer. It is preferable that it is lower than the storage elastic modulus G' at 25 ° C. (hereinafter sometimes described as "storage elastic modulus G' _V1 (25)"). That is, it is preferable that G' _V2 (25) <G' _V1 (25). According to this configuration, by laminating a low refractive index adhesive layer having a relatively low storage elastic modulus on a high refractive index layer (for example, a high refractive index adhesive layer) in which the storage elastic modulus G' tends to increase as an object of high refractive index, adhesion and By imparting flexibility, conformability to steps or conformability to curved surfaces is improved, and a laminated sheet (adhesive sheet) that can be suitably applied to various device design applications can be realized.

The low refractive index adhesive disclosed herein contains an acrylic polymer (F) containing a fluorine-containing acrylic monomer (M1) as a monomer unit. It is preferable that the low refractive index adhesive is an acrylic adhesive containing such an acrylic polymer (F) as a base polymer.

In addition, in this specification, the "base polymer" of an adhesive refers to the main component of the rubber-like polymer contained in the said adhesive, and is not interpreted restrictively at all other than this. The rubbery polymer refers to a polymer that exhibits rubber elasticity in a temperature range around room temperature. In addition, in this specification, a "main component" refers to a component contained in excess of 50% by weight, unless otherwise specified.

In addition, in this specification, "acrylic polymer" refers to a polymer containing a monomer unit derived from a monomer having at least one (meth)acryloyl group in one molecule as a monomer unit constituting the polymer. Hereinafter, a monomer having at least one (meth)acryloyl group in one molecule is also referred to as an "acrylic monomer". Therefore, the acrylic polymer in this specification is defined as a polymer containing a monomer unit derived from an acrylic monomer. As a typical example of the acrylic polymer, a polymer in which the proportion of the acrylic monomer out of the total monomers used in the synthesis of the acrylic polymer is more than 50% by weight (preferably more than 70% by weight, for example more than 90% by weight) is exemplified. .

In addition, in this specification, "(meth)acryloyl" is the meaning which points out acryloyl and methacryloyl comprehensively. Similarly, "(meth)acrylate" means acrylate and methacrylate, and "(meth)acryl" means acryl and methacryl respectively comprehensively. Therefore, the concept of the acrylic monomer here may include both a monomer having an acryloyl group (acrylic monomer) and a monomer having a methacryloyl group (methacrylic monomer).

(Acrylic Polymer (F))

The acrylic polymer (F) in the technique disclosed herein contains a fluorine-containing acrylic monomer (M1) as a monomer component constituting the polymer. That is, the acrylic polymer (F) contains the fluorine-containing acrylic monomer (M1) as a monomer unit. By appropriate use of the fluorine-containing acrylic monomer (M1), the refractive index of the acrylic polymer (F) can be reduced.

Here, in the present specification, the "monomer component constituting the acrylic polymer" refers to whether it is included in the pressure-sensitive adhesive composition in the form of a preformed polymer (which may be an oligomer) or an unpolymerized monomer, regardless of whether it is included in the pressure-sensitive adhesive composition. , In the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition, it means a monomer constituting a repeating unit of an acrylic polymer. That is, the monomer component constituting the acrylic polymer may be contained in the pressure-sensitive adhesive composition in any form of a polymer, unpolymer, or partially polymer. From the viewpoint of ease of preparation of the pressure-sensitive adhesive composition, in some embodiments, a pressure-sensitive adhesive composition containing substantially all of the monomer components (for example, 95% by weight or more, preferably 99% by weight or more) in the form of a polymer desirable. A pressure-sensitive adhesive composition containing substantially all of the monomer components in the form of a polymer is also preferable from the viewpoint of being easy to form a pressure-sensitive adhesive sheet with little deformation or warping.

The acrylic polymer (F) contains at least a fluorine-containing acrylic monomer (M1) (hereinafter sometimes abbreviated as "monomer (M1)") and another monomer copolymerizable with the monomer (M1) (copolymerizable). monomer) may be a polymer of a monomer raw material which may further contain. The monomer (M1) is not particularly limited as long as it is an acrylic monomer having at least one fluorine atom in its molecule. For example, fluorine-containing (meth)acrylic acid esters can be suitably used. Preferred examples of fluorine-containing (meth)acrylic acid esters include those having a fluorinated hydrocarbon group at the ester terminal. As a fluorinated hydrocarbon group, a fluorinated aliphatic hydrocarbon group, a fluorinated alicyclic hydrocarbon group, a fluorinated aromatic hydrocarbon group etc. are mentioned, for example. As the fluorinated hydrocarbon group, a fluorinated aliphatic hydrocarbon group is suitable. As a fluorinated aliphatic hydrocarbon group, a fluorinated alkyl group etc. are mentioned. In the fluorinated aliphatic hydrocarbon group, the aliphatic hydrocarbon moiety may be linear or branched. In addition, in the fluorinated aliphatic hydrocarbon group, the fluorine atom may be bonded to any carbon atom at the aliphatic hydrocarbon group site. The number of fluorine atoms bonded to one carbon atom may be singular or plural. The number of carbon atoms to which the fluorine atoms are bonded is not particularly limited.

In the fluorinated aliphatic hydrocarbon group (particularly, the fluorinated alkyl group), the number of carbon atoms at the hydrocarbon group site is not particularly limited. In some embodiments, a fluorinated aliphatic hydrocarbon group having, for example, 1 to 18 (preferably 1 to 12) carbon atoms is preferred in view of compatibility with other copolymerizable monomers. As a specific example of a fluorinated aliphatic hydrocarbon group, Fluorinated methyl groups, such as a trifluoromethyl group, a difluoromethyl group, and a monofluoromethyl group; Pentafluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,2,2,2-tetrafluoroethyl group, 1,1,2-trifluoroethyl group, 1,2,2-trifluoro Roethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 2,2-difluoroethyl group, 1-monofluoroethyl group, 2- fluorinated ethyl groups such as monofluoroethyl groups; etc. can be mentioned. Examples of the fluorinated alkyl group having 3 or more carbon atoms include various fluorinated alkyl groups in which one or more fluorine atoms are bonded to any one or more carbon atoms of the alkyl group site, similarly to the fluorinated methyl group and fluorinated ethyl group of the above examples. .

As a fluorinated alicyclic hydrocarbon group, a fluorinated cycloalkyl group etc. are mentioned. Similar to the above fluorinated aliphatic hydrocarbon group, in the fluorinated alicyclic hydrocarbon group, the fluorine atom may be bonded to any carbon atom of the alicyclic hydrocarbon group, and the fluorine atom bonded to one carbon atom may be singular or plural. do. Also, the number of carbon atoms to which fluorine atoms are bonded is not particularly limited. Examples of the fluorinated alicyclic hydrocarbon group include a cyclohexyl group having one fluorine atom such as a 2-fluorocyclohexyl group, a 3-fluorocyclohexyl group, and a 4-fluorocyclohexyl group; a cyclohexyl group having two fluorine atoms such as a 2,4-difluorocyclohexyl group and a 2,6-difluorocyclohexyl group; and cyclohexyl groups having three fluorine atoms, such as a 2,4,6-trifluorocyclohexyl group.

The fluorinated hydrocarbon group may or may not have a substituent. Such a substituent is not particularly limited, and examples thereof include a hydrocarbon group such as an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, an amino group, a nitro group, a cyano group, and a halogen atom. A substituent can be used individually by 1 type or in combination of 2 or more types.

Examples of fluorine atom-containing (meth)acrylic acid esters [fluorinated (meth)acrylates] include fluorine atom-containing (meth)acrylic acid alkyl esters [fluorinated alkyl (meth)acrylates], fluorine atom-containing (meth)acrylic acid cycloalkyl esters. [Fluorinated cycloalkyl (meth)acrylates], fluorine atom-containing (meth)acrylic acid aryl esters [fluorinated aryl (meth)acrylates] and the like are included.

As the fluorine atom-containing (meth)acrylic acid ester, fluorinated alkyl (meth)acrylates (particularly fluorinated alkyl acrylates) are suitable. As fluorinated alkyl (meth)acrylates, for example, 2,2,2-trifluoroethyl acrylate (trade name "Biscott 3F" manufactured by Osaka Yuki Chemical Industry Co., Ltd.), 2,2,3, 3-tetrafluoropropyl acrylate (trade name "Viscott 4F", etc., manufactured by Osaka Yuki Chemical Industry Co., Ltd.), 1H, 1H, 5H-octafluoropentyl acrylate (manufactured by Osaka Yuki Chemical Industry Co., Ltd.) (trade name "Biscott 8F", etc.), 1H,1H,5H-octafluoropentyl methacrylate (trade name "Biscott 8FM", etc., manufactured by Osaka Yuki Chemical Industry Co., Ltd.), 2-(heptadecafluoro Nonyl) ethyl acrylate (trade name "FA-108" manufactured by Kyoeisha Chemical Co., Ltd., etc.), 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate (manufactured by Osaka Yuki Chemical Industry Co., Ltd.) (trade name "Viscot 13F", etc.) of

The number of carbon atoms in the fluorinated alkyl group in the fluorinated alkyl (meth)acrylate is advantageously 3 or more, preferably 4 or more, more preferably 5 or more, more preferably 6 or more, from the viewpoint of the effect of reducing refractive index and flexibility. or more preferably 7 or more, particularly preferably 8 or more. The number of carbon atoms in the fluorinated alkyl group is advantageously 18 or less, preferably 14 or less, more preferably 12 or less, may be 10 or less, or may be 9 or less, from the viewpoint of adhesive performance and the like. In some embodiments, the number of carbon atoms in the fluorinated alkyl group may be 7 or less, or 5 or less. In some aspects, as the fluorine atom-containing (meth)acrylic acid ester, a fluorinated alkyl (meth)acrylate in which fluorine is not bonded to carbon at the 1st position of the alkyl group is preferable, for example, 1H, 1H, Fluorinated alkyl (meth)acrylates in which fluorine is not bonded to either of the 1-position carbon and 2-position carbon of the alkyl group, such as 2H,2H-tridecafluorooctyl acrylate, can be preferably employed.

The content of the monomer (M1) in the monomer raw material for preparing the acrylic polymer (F) may be, for example, 10% by weight or more, suitably 25% by weight or more, and may be 35% by weight or more. From the viewpoint of making it easier to realize a pressure-sensitive adhesive with a lower refractive index, the content of the monomer (M1) is preferably 40% by weight or more, more preferably 45% by weight or more, still more preferably 55% by weight or more, and 60% by weight It may be % or more, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. The upper limit of the content of the monomer (M1) in the monomer raw material is not particularly limited, and may be 100% by weight. In some embodiments, the content of the monomer (M1) is suitably 99.9% by weight or less, preferably 99.5% or less, may be 99% by weight or less, or may be 97% by weight or less, from the viewpoint of cohesiveness of the pressure-sensitive adhesive, etc. and may be 92% by weight or less. Monomer (M1) can be used individually by 1 type or in combination of 2 or more types.

The monomer raw material for preparing the acrylic polymer (F) may be a composition containing a copolymerizable monomer in addition to the monomer (M1). The copolymerizable monomer may be useful for introducing a crosslinking point into the acrylic polymer or increasing the cohesive force of the acrylic polymer. Examples of the copolymerizable monomer include a carboxy group-containing monomer, a hydroxyl group-containing monomer, an acid anhydride group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, and a monomer having a nitrogen atom-containing ring (eg, N-vinyl-2- N-vinyl cyclic amides such as pyrrolidone), functional group-containing monomers such as sulfonic acid group-containing monomers and phosphoric acid group-containing monomers can be used. Other examples of copolymerizable monomers include non-aromatic ring-containing (meth)acrylates such as alkyl (meth)acrylates, cycloalkyl (meth)acrylates and isobornyl (meth)acrylates, and vinyl esters such as vinyl acetate. A type monomer, aromatic vinyl compounds, such as styrene, and an alkoxy group-containing monomer, etc. are mentioned. Specific examples of the copolymerizable monomer include, but are not limited to, those similar to the monomers that can be used for preparation of the acrylic polymer (A) described later.

In some embodiments, from the viewpoint of improving cohesion, etc., as the copolymerizable monomer, one or two or more monomers selected from the group consisting of hydroxyl group-containing monomers and carboxyl group-containing monomers (hereinafter also referred to as "monomer (M2)" ) is preferably used as the acrylic polymer (F). Examples of the hydroxyl group-containing monomer include the same hydroxyl group-containing monomers exemplified for the monomer (m2) described later. Preferable examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate. From the viewpoint of flexibility, 4-hydroxybutyl acrylate is more preferred. Examples of the carboxy group-containing monomer include the same carboxy group-containing monomers exemplified for the monomer (m2) described later. Preferable examples of the carboxy group-containing monomer include acrylic acid and methacrylic acid.

The content of the monomer (M2) in the monomer raw material for preparing the acrylic polymer (F) is not particularly limited, and can be appropriately set so that a desired use effect is exhibited. The content of the monomer (M2) can be, for example, 0.01% by weight or more (preferably 0.1% by weight or more, more preferably 0.5% by weight or more). In some aspects, the content of the monomer (M2) may be 0.7% by weight or more, 0.9% by weight or more, or 1.5% by weight or more of the monomer raw material. The upper limit of the content of the monomer (M2) is not particularly limited, and can be appropriately set so that the total content of the other monomers does not exceed 100% by weight. From the viewpoint of facilitating lowering the refractive index by relatively increasing the content of the monomer (M1), the content of the monomer (M2) is suitably, for example, 15% by weight or less or 10% by weight or less, and 10% by weight It is preferably less than 5% by weight, more preferably less than 5% by weight, may be less than 3% by weight, may be less than 2.5% by weight, or may be less than 1.5% by weight. It is not necessary to use the monomer (M2).

In some preferable aspects, the monomer raw material for preparing the acrylic polymer (F) may be a composition containing a hydroxyl group-containing monomer as the monomer (M2). A hydroxyl group-containing monomer can be useful for improving cohesive force or introducing a crosslinking point. Preferable examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate. From the viewpoint of improving the flexibility in the room temperature region, 4-hydroxybutyl acrylate can be used more preferably. The content of the hydroxyl group-containing monomer in the monomer raw material is not particularly limited, and may be, for example, 0.01% by weight or more (preferably 0.1% by weight or more, more preferably 0.5% by weight or more). In some aspect, content of the said hydroxyl-containing monomer may be 0.7 weight% or more, 0.9 weight% or more, or 1.5 weight% or more of the said monomer raw material. The upper limit of the content of the hydroxyl group-containing monomer is not particularly limited, and may be, for example, 15% by weight or less or 10% by weight or less. In some embodiments, from the viewpoint of lowering the refractive index, the content of the hydroxyl group-containing monomer in the monomer raw material is preferably less than 10% by weight, preferably less than 5% by weight, and even less than 3% by weight. It may be less than 2.5% by weight or less than 1.5% by weight.

In some aspects, the monomer raw material for preparing the acrylic polymer (F) may contain a copolymerizable monomer other than the monomer (M2) (ie, a copolymerizable monomer having no hydroxyl group or carboxyl group-containing monomer). Hereinafter, such a copolymerizable monomer may be referred to as "monomer (M3)". As the monomer (M3), among the various copolymerizable monomers described above, those not corresponding to the monomer (M2) may be used.

The content of the monomer (M3) in the monomer raw material for preparing the acrylic polymer (F) is not particularly limited, and can be appropriately set so that a desired use effect is exhibited. The content of the monomer (M3) can be, for example, 0.1% by weight or more (preferably 1% by weight or more, more preferably 5% by weight or more). In some aspects, the content of the monomer (M2) may be 7% by weight or more, 10% by weight or more, or 15% by weight or more of the monomer raw material. From the viewpoint of improving flexibility, etc., in some embodiments, the content of the monomer (M2) may be 10% by weight or more, 25% by weight or more, 35% by weight or more, or 45% by weight or more. , It may be more than 55% by weight or more than 60% by weight. The upper limit of the content of the monomer (M3) is not particularly limited, and can be appropriately set so that the total amount of the content of the other monomers does not exceed 100% by weight. The content of the monomer (M3) may be, for example, 90% by weight or less, or 85% by weight or less. From the viewpoint of facilitating lowering the refractive index by relatively increasing the content of the monomer (M1), the content of the monomer (M3) is preferably 80% by weight or less, and more preferably 70% by weight or less. In some aspects, from the viewpoint of lowering the refractive index, the content of the monomer (M3) in the monomer raw material is suitably less than 60% by weight, preferably less than 50% by weight, even if it is less than 45% by weight , may be less than 35% by weight, may be less than 20% by weight, may be less than 10% by weight, may be less than 5% by weight. It is not necessary to use the monomer (M3).

Preferable examples of the monomer that can be used as the monomer (M3) include alkyl (meth)acrylates and monomers having a nitrogen atom-containing ring (for example, N-vinyl cyclic amides such as N-vinyl-2-pyrrolidone). , non-aromatic ring-containing (meth)acrylates such as cycloalkyl (meth)acrylates and isobornyl (meth)acrylates. Monomer (M3) may be used individually by 1 type, and may be used in combination of 2 or more types. For example, an aspect in which one type of alkyl (meth)acrylate is used alone, an aspect in which two or more types of alkyl (meth)acrylates are used in combination, and an alkyl (meth)acrylate and N-vinyl cyclic amide are used in combination. An aspect of using it by using it, an aspect of using an alkyl (meth)acrylate and a non-aromatic ring-containing (meth)acrylate in combination, and the like can be preferably employed.

As an alkyl (meth)acrylate, the compound represented by following formula (1) can be used suitably, for example.

CH ₂ =C(R ¹ )COOR ² (1)

Here, R ¹ in the formula (1) is a hydrogen atom or a methyl group. In addition, R ² is a chain-like alkyl group having ₁ to 20 carbon atoms (hereinafter, such a range of carbon atoms may be expressed as “C _1-20 ”). From the viewpoint of the storage modulus of the pressure _- sensitive adhesive, etc., an alkyl (meth)acrylate in which R ² is a C _1-12 (eg C _2-10 , typically C _4-8 ) chain alkyl group is preferable. The alkyl (meth)acrylates in which R ² is a C _1-20 chain alkyl group can be used alone or in combination of two or more. Preferred alkyl (meth)acrylates include n-butyl acrylate and 2-ethylhexyl acrylate.

In some aspects, the monomer raw material for preparing the acrylic polymer (F) preferably has a limited content of the carboxy group-containing monomer from the viewpoint of suppressing coloring or discoloration (for example, yellowing) of the pressure-sensitive adhesive. The content of the carboxyl group-containing monomer in the monomer raw material may be, for example, less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.3% by weight, and less than 0.1% by weight (for example, 0.05% by weight). less than %) is more preferable. The reason why the content of the carboxyl group-containing monomer is limited in this way is because of corrosion of a metal material (eg, metal wiring or metal film that may be present on an adherend) that may be placed in contact with or in proximity to the pressure-sensitive adhesive disclosed herein. It is also advantageous from the point of view of suppressing The technology disclosed herein can be preferably implemented in an aspect in which the monomer raw material does not contain a carboxy group-containing monomer.

For the same reasons, in some aspects, the monomer raw material for preparing the acrylic polymer (F) has a limited content of monomers having an acidic functional group (including a sulfonic acid group, a phosphoric acid group, etc. in addition to a carboxy group) desirable. As the content of the acidic functional group-containing monomer in the monomer raw material of this aspect, the above-described preferable content of the carboxy group-containing monomer can be applied. The technique disclosed herein can be preferably carried out in an aspect in which the monomer raw material does not contain an acidic group-containing monomer (that is, an aspect in which the acrylic polymer (F) is acid-free).

Like the acrylic polymer (A) described later, the acrylic polymer (F) can be prepared by appropriately employing a known polymerization method. The weight average molecular weight (Mw) of the acrylic polymer (F) is not particularly limited, and may be, for example, in the range of approximately 10×10 ⁴ to 500×10 ⁴ , or approximately 20×10 ⁴ to 200×10 ⁴ . may be In some embodiments, from the viewpoint of adhesion to an adherend or an adjacent layer (which may be a high refractive index layer such as a high refractive index adhesive layer), the acrylic polymer (F) Mw is preferably 150 × 10 ⁴ or less. 120 × 10 ⁴ or less (for example, 95 × 10 ⁴ or less) is preferable, 75 × 10 ⁴ or less may be sufficient, 68 × 10 ⁴ or less may be sufficient, or 60 × 10 ⁴ or less may be sufficient. In some embodiments, from the viewpoint of cohesiveness of the pressure-sensitive adhesive, etc., the Mw of the acrylic polymer (F) may be, for example, 30×10 ⁴ or more, 40×10 ⁴ or more, or 50×10 ⁴ or more. may be continued In order to prepare Mw, a conventionally well-known chain transfer agent can be used as needed.

Although not particularly limited, from the viewpoint of adhesiveness, it is advantageous that the acrylic polymer (F) has a Tg of approximately 0°C or lower, preferably approximately -5°C or lower (eg approximately -15°C or lower, or -25°C). below). From the viewpoint of the cohesive force of the pressure-sensitive adhesive layer, the Tg of the acrylic polymer (F) is approximately -75°C or higher, preferably approximately -70°C or higher (eg -50°C or higher, further -30°C or higher). . The Tg of the acrylic polymer (F) can be adjusted by appropriately changing the monomer composition (that is, the type and usage ratio of the monomers used in the synthesis of the polymer).

When using an alkyl (meth)acrylate as the monomer (M3), from the viewpoint of making it easier to lower the Tg of the acrylic polymer (F), in some embodiments, based on the amount of the alkyl (meth)acrylate alone Thus, the Tg calculated by Fox's formula is advantageously less than -50°C, preferably less than -55°C, and may be less than -60°C or less than -65°C.

(Preparation method of acrylic polymer (F))

In the technology disclosed herein, the method for obtaining the acrylic polymer (F) composed of the above-described monomer components is not particularly limited, and solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization Well-known polymerization methods, such as a method, can be employ|adopted suitably. In some aspects, a solution polymerization method can be preferably employed. The polymerization temperature when performing solution polymerization can be appropriately selected according to the types of monomers and solvents used, the type of polymerization initiator, etc., and is, for example, about 20°C to 170°C (typically about 40°C to 140°C). can do.

The solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents. For example, aromatic compounds (typically aromatic hydrocarbons) such as toluene; Acetate esters, such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; halogenated alkanes such as 1,2-dichloroethane; lower alcohols such as isopropyl alcohol (for example, monohydric alcohols having 1 to 4 carbon atoms); ethers such as tert-butyl methyl ether; ketones such as methyl ethyl ketone; Any one type of solvent selected from the like or a mixed solvent of two or more types can be used.

The initiator used for polymerization can be appropriately selected from conventionally known polymerization initiators depending on the type of polymerization method. For example, one or two or more azo polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) can be preferably used. Other examples of the polymerization initiator include persulfates such as potassium persulfate; peroxide-based initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds; etc. can be mentioned. Another example of the polymerization initiator is a redox system initiator obtained by a combination of a peroxide and a reducing agent. A polymerization initiator can be used individually by 1 type or in combination of 2 or more types. The usage amount of the polymerization initiator may be a normal usage amount, and for example, it can be selected from the range of about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight) with respect to 100 parts by weight of the monomer component.

For the above polymerization, conventionally known various chain transfer agents can be used as needed. For example, mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan, thioglycolic acid, and α-thioglycerol can be used. Alternatively, a chain transfer agent (non-sulfur chain transfer agent) that does not contain a sulfur atom may be used. Examples of non-sulfur chain transfer agents include anilines such as N,N-dimethylaniline and N,N-diethylaniline; terpenoids such as α-pinene and terpinolene; styrenes such as α-methylstyrene and α-methylstyrene dimer; etc. can be mentioned. A chain transfer agent can be used individually by 1 type or in combination of 2 or more types. The usage amount in the case of using a chain transfer agent can be, for example, about 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer raw material.

The weight average molecular weight (Mw) of the base polymer is not particularly limited, and may be, for example, approximately in the range of 10×10 ⁴ to 500×10 ⁴ . In terms of adhesive performance, the Mw of the base polymer is approximately 20×10 ⁴ to 400×10 ⁴ (more preferably approximately 30×10 ⁴ to 150×10 ⁴ , for example approximately 50×10 ⁴ to 130×10 ⁴ ) is preferred.

Here, the Mw of the polymer can be calculated in terms of polystyrene by gel permeation chromatography (GPC). Specifically, it can be obtained by measuring under the following conditions using a trade name "HLC-8220GPC" (manufactured by Tosoh Corporation) as a GPC measuring device.

[Measurement conditions of GPC]

Sample concentration: 0.2% by weight (tetrahydrofuran solution)

Sample injection volume: 10 μL

Eluent: tetrahydrofuran (THF)

Flow rate (flow rate): 0.6 mL/min

Column temperature (measurement temperature): 40°C

column:

Sample column: 1 brand name "TSKguardcolumn SuperHZ-H" + 2 brand names "TSKgel SuperHZM-H" (manufactured by Tosoh Corporation)

Reference column: 1 product name “TSKgel SuperH-RC” (manufactured by Tosoh Corporation)

Detector: Differential Refractometer (RI)

Standard Sample: Polystyrene

(crosslinking agent)

In the technique disclosed herein, the pressure-sensitive adhesive composition used for forming the low-refractive-index pressure-sensitive adhesive layer may contain a crosslinking agent as necessary for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive. As the crosslinking agent, crosslinking agents known in the field of pressure-sensitive adhesives such as isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, melamine resins, and metal chelate crosslinking agents can be used. Among them, an isocyanate-based crosslinking agent can be preferably employed. Other examples of the crosslinking agent include monomers having two or more ethylenically unsaturated groups in one molecule, that is, polyfunctional monomers. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types. Regarding the specific examples and amount of the crosslinking agent, the description of the crosslinking agent that can be used in the pressure-sensitive adhesive composition for forming the high refractive index pressure-sensitive adhesive layer described later can also be applied to the pressure-sensitive adhesive composition for forming the low-refractive index pressure-sensitive adhesive layer.

In the aspect in which the pressure-sensitive adhesive composition used for formation of the low-refractive-index pressure-sensitive adhesive layer contains a crosslinking agent, as the crosslinking agent, for example, an isocyanate-based crosslinking agent can be preferably employed. In some embodiments, the amount of the isocyanate-based crosslinking agent used per 100 parts by weight of the acrylic polymer (F) may be, for example, less than 0.5 parts by weight, or 0.3 parts by weight, from the viewpoint of adhesion to an adherend or an adjacent layer. It may be less than part, less than 0.2 part by weight, or less than 0.15 part by weight. From the viewpoint of appropriately exhibiting the effect of using the crosslinking agent, in some embodiments, the amount of the isocyanate crosslinking agent relative to 100 parts by weight of the acrylic polymer (F) may be, for example, 0.005 parts by weight or more, or 0.01 parts by weight. Part or more may be sufficient, 0.05 part by weight or more may be sufficient, or 0.08 part by weight or more may be sufficient.

(other additives)

A plasticizing material, a leveling agent, a tackifier, an inorganic particle, other additives, etc. can be contained in the low refractive index adhesive as an arbitrary component. These optional components can be suitably selected from the same ones that can be used for the high refractive index adhesive layer, and can be used in an appropriate amount.

<High refractive index adhesive>

The pressure-sensitive adhesive (low-refractive-index pressure-sensitive adhesive) disclosed herein may be used in a laminated form with a pressure-sensitive adhesive having a relatively higher refractive index (high-refractive index pressure-sensitive adhesive) in relation to the pressure-sensitive adhesive. In such a usage form, the ratio (n ₁ /n ₂ ) of the refractive index n ₁ of the high refractive index pressure sensitive adhesive and the refractive index n ₂ of the low refractive index pressure sensitive adhesive layer may be, for example, greater than 1.00, may be approximately 1.01 or greater, or may be approximately 1.02 or greater. It is suitable and may be about 1.03 or more. In some embodiments, the ratio (n ₁ /n ₂ ) is advantageously approximately 1.05 or higher, preferably approximately 1.07 or higher, more preferably approximately 1.10 or higher, and may be approximately 1.11 or higher. The upper limit of the ratio (n ₁ /n ₂ ) is not particularly limited. In some embodiments, the adhesive properties of the adhesive face formed by the high refractive index adhesive and/or the adhesive face formed by the low refractive index adhesive, the transparency of each adhesive layer, and the laminate containing the high refractive index adhesive and the low refractive index adhesive From the viewpoint of sheet transparency and the like, the ratio (n ₁ /n ₂ ) may be, for example, approximately 1.20 or less, approximately 1.18 or less, approximately 1.16 or less, approximately 1.14 or less, or approximately 1.12 or less. .

In some aspects, the difference between the refractive index n ₁ of the high refractive index adhesive and the refractive index n ₂ of the low refractive index adhesive, that is, the refractive index difference (n ₁ -n ₂ ) may be greater than 0.00, may be 0.01 or more, It is preferably 0.02 or more, may be 0.03 or more, may be 0.05 or more, may be 0.10 or more, may be 0.15 or more, may be 0.20 or more, may be 0.25 or more. The upper limit of the refractive index difference (n ₁ -n ₂ ) is not particularly limited. In some embodiments, the adhesive properties of the adhesive face formed by the high refractive index adhesive and/or the adhesive face formed by the low refractive index adhesive, the transparency of each adhesive layer, and the laminate containing the high refractive index adhesive and the low refractive index adhesive From the viewpoint of sheet transparency and the like, the refractive index difference (n ₁ -n ₂ ) may be, for example, 0.30 or less, 0.26 or less, 0.21 or less, 0.18 or less, or 0.16 or less.

The preferable lower limit of the refractive index of the high refractive index pressure sensitive adhesive is not limited to a specific range since it may vary in relation to the refractive index of the low refractive index pressure sensitive adhesive. For example, the refractive index of the high refractive index adhesive may be 1.45 or more, 1.47 or more, 1.50 or more, 1.53 or more, 1.55 or more, or 1.56 or more. Using a high refractive index adhesive having a higher refractive index is preferable from the viewpoint of increasing the refractive index difference with the low refractive index adhesive, and is also advantageous from the viewpoint of increasing the design freedom of the low refractive index adhesive.

In some embodiments, the refractive index of the high refractive index pressure sensitive adhesive may be, for example, 1.570 or more, advantageously more than 1.570, preferably 1.580 or more, more preferably 1.585 or more, still more preferably 1.590 or more. (eg 1.595 or higher). According to the high refractive index adhesive layer having such a refractive index, the behavior of light passing through the low refractive index adhesive layer and/or the high refractive index adhesive layer is determined by using the relationship between the relative refractive index of the high refractive index adhesive layer and the low refractive index adhesive layer as described above. can be effectively controlled. In some aspects of the technology disclosed herein, the refractive index of the high refractive index pressure sensitive adhesive may be, for example, greater than or equal to 1.600 or greater than 1.600, greater than or equal to 1.605 or greater than 1.605, or greater than or equal to 1.610 or greater than 1.610. The preferred upper limit of the refractive index of the high refractive index pressure sensitive adhesive is not limited to a specific range since it may vary depending on the refractive index of adjacent layers and the like. In some aspects, the refractive index of the high refractive index adhesive may be, for example, 1.700 or less, 1.670 or less, or 1.650 or less, in consideration of the balance with adhesive properties and transparency.

(Storage modulus G')

In the technology disclosed herein, the storage elastic modulus G' (hereinafter also referred to as "storage elastic modulus G' _V1 (25)") of the high refractive index pressure sensitive adhesive at 25 ° C. is appropriately set according to the purpose of use or usage mode, etc. , but not limited to a specific range. The storage modulus G′ _V1 (25) may be, for example, approximately 700 kPa or less. In some aspects, from the viewpoint of ease of sticking to the adherend, etc., the storage elastic modulus G' _V1 (25) is advantageously approximately 600 kPa or less, preferably 500 kPa or less, and 400 kPa or less (for example, 350 kPa or less) is more preferable. In some aspects, from the viewpoint of enhancing the flexibility of the high refractive index adhesive in the room temperature region (eg 25°C) and making it easy to adhere to the adherend, the storage modulus G' _V1 (25) is approximately 330 kPa or less. It is advantageous, and it is preferable that it is 300 kPa or less. In some embodiments in which adhesion and flexibility in the room temperature region are more important, the storage modulus G ' _V1 (25) may be, for example, less than 270 kPa or less than 250 kPa, and less than 200 kPa is advantageous, and 180 It is preferably less than kPa, and more preferably less than 160 kPa (for example, less than 140 kPa). In some aspects, the storage elastic modulus G' _V1 (25) may be less than 100 kPa or less than 90 kPa. The lower limit of the storage modulus G′ _V1 (25) is not particularly limited, but may be, for example, 30 kPa or more, 50 kPa or more, or 70 kPa or more from the viewpoints of workability and handleability. In some aspects, considering the high refractive index, the storage modulus G' _V1 (25) may be 100 kPa or more, 150 kPa or more, 200 kPa or more, 250 kPa or more, or 300 kPa or more. It can be more than that.

In the technology disclosed herein, the storage modulus G' (hereinafter also referred to as "storage modulus G' _V1 (50)") of the high refractive index adhesive at 50°C is not particularly limited, and is, for example, 100 kPa. may be less than In some embodiments, the storage modulus G′ _V1 (50) is suitably less than 60 kPa, preferably less than 40 kPa, and more preferably less than 38 kPa (for example, less than 36 kPa). Thus, the high refractive index adhesive with limited storage elastic modulus _G'V1 (50) can easily increase the adhesiveness to an adherend by performing appropriate heating as necessary, thereby improving the adhesiveness to the adherend. . The lower limit of the storage modulus G' _V1 (50) is not particularly limited. In some aspects, from the viewpoint of heat resistance, etc., the storage elastic modulus G ' _V1 (50) may be, for example, 10 kPa or more, 15 kPa or more, 20 kPa or more, or 23 kPa or more. .

In some aspects of the technology disclosed herein, the high refractive index pressure-sensitive adhesive layer is under the following conditions:

(a) those whose storage modulus _G'V1 (25) is 350 kPa or less (preferably less than 200 kPa, for example, 180 kPa or less); and

(b) those with a storage modulus G′ _V1 (50) of less than 60 kPa (preferably less than 50 kPa, more preferably less than 40 kPa, for example less than 38 kPa);

It is desirable to satisfy at least one of them. A high refractive index pressure-sensitive adhesive layer that satisfies at least the above condition (a) is preferable from the viewpoint of adhesion to an adherend in a room temperature region (eg 25°C) or flexibility. A high refractive index pressure-sensitive adhesive layer that satisfies at least the above condition (b) is preferable because the adhesiveness (adhesiveness) to an adherend can be easily improved by heating at a temperature slightly higher than room temperature. The pressure-sensitive adhesive sheet having a high refractive index pressure-sensitive adhesive layer that does not satisfy the above condition (a) and satisfies the above (b) has good reworkability (re-adhesion property) in the initial stage of sticking in the room temperature region, and is slightly higher than room temperature. It can be used as a heat-activated type of pressure-sensitive adhesive sheet capable of effectively increasing the peel strength from an adherend by heating to a temperature of about a degree. The thermal activation may be performed by heating the pressure-sensitive adhesive sheet to a temperature slightly higher than room temperature during application to an adherend. The temperature slightly higher than room temperature is, for example, about 60°C or less, and preferably about 55°C or less (eg, about 50°C or less).

In some aspects of the technology disclosed herein, the ratio of the storage modulus G' _V1 (50) [kPa] to the storage modulus G' _V1 (25) [kPa], i.e., the storage modulus ratio G' _V1 (50) /G' _V1 (25) is, for example, 70% or less, may be 40% or less, may be 30% or less, or may be 20% or less. A pressure-sensitive adhesive sheet having a high refractive index pressure-sensitive adhesive layer having a small _G'V1 (50)/ _G'V1 (25) is suitable for use as the heat-activated type pressure-sensitive adhesive sheet. The lower limit of G' _V1 (50)/G' _V1 (25) is not particularly limited. _G'V1 (50)/ _G'V1 (25) is, for example, 5% or more, preferably 10% or more, may be 12% or more, or 15% or more from the viewpoint of heat resistance.

The storage modulus _G'V1 (25) and _G'V1 (50) can be determined by dynamic viscoelasticity measurement, and _G'V1 (50)/ _G'V1 (25) can be calculated from the results. The dynamic viscoelasticity measurement can be performed by a conventional method using a commercially available dynamic viscoelasticity measuring device, for example, using ARES manufactured by TA Instruments or an equivalent product thereof, and can be performed under the following measurement conditions. As a sample for measurement, what was prepared to about 1.5 mm in thickness by laminating|stacking the adhesive layer of evaluation target as needed is used.

[Measuring conditions]

Deformation Mode: Torsion

Measurement frequency: 1Hz

Heating rate: 5°C/min

Shape: Parallel plate 7.9mmφ

The storage modulus G' _V1 (25), G' _V1 (50) and the storage modulus ratio (G' _V1 (50) / G' _V1 (25)) are the selection of the composition of the monomer component constituting the base polymer of the pressure-sensitive adhesive ( For example, selection of the type and content of the monomer (m1) described later), selection of the use of a crosslinking agent, type and amount of use, selection of the use of a refractive index improver or plasticizing material described later, type and amount of use, etc. Can be adjusted. have. For example, as the monomer (m1), in addition to the first monomer, which is the main component of the monomer (m1), a second monomer having a chemical structure different from that of the first monomer is used in combination with the first monomer in a relatively small amount. , In addition to the case of using the first monomer alone as the monomer (m1), _G'V1 (50) can be made small, and _G'V1 (50)/ _G'V1 (25) can be reduced.

The kind of adhesive constituting the high refractive index adhesive layer is not particularly limited. The pressure-sensitive adhesive includes acrylic polymers, rubber-based polymers (natural rubber, synthetic rubber, mixtures thereof, etc.), polyester-based polymers, urethane-based polymers, polyether-based polymers, silicone-based polymers, and polyamide-based polymers that can be used in the field of pressure-sensitive adhesives. , one or two or more of various rubbery polymers such as fluorine-based polymers may be included as an adhesive polymer (hereinafter also referred to as "base polymer" in the sense of a structural polymer forming an adhesive). From the standpoint of adhesive performance, cost, etc., an adhesive containing an acrylic polymer or a rubber polymer as a base polymer can be preferably employed. Among them, an adhesive having an acrylic polymer as a base polymer (acrylic adhesive) is preferable. The technique disclosed herein is preferably implemented in an aspect using an acrylic pressure-sensitive adhesive.

Hereinafter, the high refractive index pressure-sensitive adhesive layer composed of the acrylic pressure-sensitive adhesive is mainly described, but the high refractive index pressure-sensitive adhesive layer in the technique disclosed herein is not intended to be limited to the acrylic pressure-sensitive adhesive layer.

(Acrylic Polymer (A))

The high refractive index pressure-sensitive adhesive layer disclosed herein may be an acrylic pressure-sensitive adhesive layer. As the acrylic polymer that is the base polymer of the acrylic pressure-sensitive adhesive layer, it is preferable to include an aromatic ring-containing monomer (m1) as a monomer component constituting the acrylic polymer. That is, an acrylic polymer containing an aromatic ring-containing monomer (m1) as a monomer unit is preferable. Hereinafter, such an acrylic polymer is also referred to as "acrylic polymer (A)".

(monomer (m1))

As the monomer (m1), a compound containing at least one aromatic ring and at least one ethylenically unsaturated group in one molecule is used. As a monomer (m1), 1 type of these compounds can be used individually or in combination of 2 or more types.

As an example of the said ethylenically unsaturated group, a (meth)acryloyl group, a vinyl group, a (meth)allyl group, etc. are mentioned. A (meth)acryloyl group is preferable from the viewpoint of polymerization reactivity, and an acryloyl group is more preferable from the viewpoint of flexibility or adhesiveness. From the viewpoint of suppressing the decrease in flexibility of the pressure-sensitive adhesive, as the monomer (m1), a compound in which the number of ethylenically unsaturated groups contained in one molecule is 1 (ie, a monofunctional monomer) is preferably used.

The number of aromatic rings contained in one molecule of the compound used as the monomer (m1) may be one or two or more. The upper limit of the number of aromatic rings contained in the monomer (m1) is not particularly limited, and may be 16 or less, for example. In some aspects, from the viewpoint of the ease of preparation of the acrylic polymer (A) and the transparency of the pressure-sensitive adhesive, the number of aromatic rings may be, for example, 12 or less, preferably 8 or less, more preferably 6 or less, It may be 5 or less, 4 or less, 3 or less, or 2 or less.

The aromatic ring of the compound used as the monomer (m1) is, for example, a benzene ring (which may be a benzene ring constituting a part of a biphenyl structure or a fluorene structure); condensed rings of naphthalene rings, indene rings, azulene rings, anthracene rings, and phenanthrene rings; etc. may be a carbocyclic ring, for example, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, thiophene ring; etc., may be a heterocyclic ring. In the heterocycle, heteroatoms included as ring-constituting atoms may be, for example, one or two or more selected from the group consisting of nitrogen, sulfur, and oxygen. In some aspects, the heteroatom constituting the heterocycle may be one or both of nitrogen and sulfur. The monomer (m1) may have a structure in which one or two or more carbocycles and one or two or more heterocycles are condensed, such as a dinaphthothiophene structure.

The aromatic ring (preferably carbocyclic ring) may have one or two or more substituents on the ring-constituting atoms, or may have no substituents. When it has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxyalkyl group, a hydroxyalkyloxy group, a glycidyloxy group, and the like. Although exemplified, it is not limited thereto. In the substituent containing carbon atoms, the number of carbon atoms included in the substituent is preferably 1 to 4, more preferably 1 to 3, and may be, for example, 1 or 2. In some embodiments, the aromatic ring is an aromatic ring having no substituents on ring atoms or having one or two or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and a halogen atom (for example, a bromine atom). can In addition, that the aromatic ring of the monomer (m1) has a substituent on the ring-constituting atom means that the aromatic ring has a substituent other than the substituent having an ethylenically unsaturated group.

The aromatic ring and the ethylenically unsaturated group may be bonded directly or through a linking group. The linking group is, for example, an alkylene group, an oxyalkylene group, a poly(oxyalkylene) group, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, a group having a structure in which one or two or more hydrogen atoms are substituted with hydroxyl groups in these groups (eg , hydroxyalkylene group), an oxy group (-O- group), a thiooxy group (-S- group), and the like. In some embodiments, an aromatic ring having a structure in which an aromatic ring and an ethylenically unsaturated group are bonded directly or through a linking group selected from the group consisting of an alkylene group, an oxyalkylene group, and a poly(oxyalkylene) group. A monomer can be preferably employed. The number of carbon atoms in the alkylene group and the oxyalkylene group is preferably 1 to 4, more preferably 1 to 3, and may be 1 or 2, for example. The number of repetitions of oxyalkylene units in the poly(oxyalkylene) group may be, for example, 2 to 3.

Examples of compounds that can be preferably employed as the monomer (m1) include aromatic ring-containing (meth)acrylates and aromatic ring-containing vinyl compounds. An aromatic ring-containing (meth)acrylate and an aromatic ring-containing vinyl compound can be used individually by 1 type or in combination of 2 or more types, respectively. You may use combining 1 type, or 2 or more types of aromatic ring-containing (meth)acrylate, and 1 type, or 2 or more types of aromatic ring-containing vinyl compounds.

The content of the monomer (m1) in the monomer component constituting the acrylic polymer (A) is not particularly limited, and the desired refractive index and adhesive properties (eg peel strength, flexibility, etc.) and/or optical properties (eg, For example, total light transmittance, haze value, etc.) can be set so as to realize an adhesive layer that achieves both. In some embodiments, the content of the monomer (m1) in the monomer component may be, for example, 30% by weight or more, preferably 50% by weight or more, 60% by weight or more, or 70% by weight. It can be more than that. From the viewpoint of making it easier to obtain a higher refractive index, in some preferred embodiments, the content of the monomer (m1) may be, for example, more than 70% by weight, 75% by weight or more, or 80% by weight or more. , 85% by weight or more may be sufficient, 90% by weight or more may be sufficient, or 95% by weight or more may be sufficient. The upper limit of the content of the monomer (m1) in the monomer component is 100% by weight. From the viewpoint of achieving both a high refractive index and adhesive characteristics and/or optical characteristics in a well-balanced manner, the content of the monomer (m1) is advantageously less than 100% by weight, for example, preferably approximately 99% by weight or less, and 98 It is more preferably less than or equal to weight%, may be less than or equal to 97% by weight, or less than or equal to 96% by weight. In some embodiments, the content of the monomer (m1) may be 93% by weight or less, 90% by weight or less, 80% by weight or less, or 75% by weight or less. In some embodiments in which adhesive properties and/or optical properties are more important, the content of the monomer (m1) in the monomer component may be 70% by weight or less, 60% by weight or less, or 45% by weight may be below.

In some aspects of the technology disclosed herein, as the monomer (m1), a monomer having two or more aromatic rings (preferably carbocyclic rings) in one molecule is selected from the viewpoint of easily obtaining a high refractive index effect. can be preferably employed. As an example of a monomer having two or more aromatic rings in one molecule (hereinafter also referred to as "a monomer containing multiple aromatic rings"), a monomer having a structure in which two or more non-condensed aromatic rings are bonded via a linking group, and two or more non-condensed aromatic rings are directly ( That is, a monomer having a chemically bonded structure without passing through another atom), a monomer having a condensed aromatic ring structure, a monomer having a fluorene structure, a monomer having a dinaphthothiophene structure, a monomer having a dibenzothiophene structure, and the like. can A monomer containing multiple aromatic rings can be used individually by 1 type or in combination of 2 or more types.

The linking group, for example, an oxy group (-O-), a thiooxy group (-S-), an oxyalkylene group (eg -O-(CH ₂ ) _n - group, where n is 1 to 3, preferably 1), a thiooxyalkylene group (eg -S-(CH ₂ ) _n -group, where n is 1 to 3, preferably 1), a straight-chain alkylene group (ie -(CH ₂ ) _n -group, where n is 1 to 6, preferably 1 to 3), the alkylene groups in the oxyalkylene group, the thiooxyalkylene group and the straight-chain alkylene group may be partially halogenated or fully halogenated groups, etc. . From the standpoint of the flexibility of the pressure-sensitive adhesive, etc., suitable examples of the linking group include an oxy group, a thiooxy group, an oxyalkylene group and a straight-chain alkylene group. As a specific example of a monomer having a structure in which two or more non-condensed aromatic rings are bonded via a linking group, phenoxybenzyl (meth)acrylate (eg, m-phenoxybenzyl (meth)acrylate), thiophenoxybenzyl ( meth)acrylate, benzylbenzyl (meth)acrylate, etc. are mentioned.

The monomer having a structure in which two or more non-condensed aromatic rings are directly chemically bonded may be, for example, biphenyl structure-containing (meth)acrylate, triphenyl structure-containing (meth)acrylate, or vinyl group-containing biphenyl. As a specific example, o-phenylphenol (meth)acrylate, biphenylmethyl (meth)acrylate, etc. are mentioned.

Examples of the monomer having the condensed aromatic ring structure include (meth)acrylate containing a naphthalene ring, (meth)acrylate containing an anthracene ring, naphthalene containing a vinyl group, and anthracene containing a vinyl group. As specific examples, 1-naphthylmethyl (meth)acrylate (alias: 1-naphthalenemethyl (meth)acrylate), hydroxyethylated β-naphthol acrylate, 2-naphthoethyl (meth)acrylate, 2- Naphthoxyethyl acrylate, 2-(4-methoxy-1-naphthoxy)ethyl (meth)acrylate, etc. are mentioned.

As a specific example of the monomer which has the said fluorene structure, 9,9-bis (4-hydroxyphenyl) fluorene (meth) acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] flu Orene (meth)acrylate etc. are mentioned. In addition, since a monomer having a fluorene structure includes a structural portion in which two benzene rings are directly chemically bonded, it is included in the concept of a monomer having a structure in which two or more non-condensed aromatic rings are directly chemically bonded.

Examples of the monomer having the dinaphthothiophene structure include (meth)acryloyl group-containing dinaphthothiophene, vinyl group-containing dinaphthothiophene, and (meth)allyl group-containing dinaphthothiophene. Specific examples include (meth)acryloyloxymethyldinaphthothiophene (for example, a compound having a structure in which CH ₂ CH(R ¹ )C(O)OCH ₂ - is bonded to the 5-position or 6-position of the dinaphthothiophene ring). Here, R ¹ is a hydrogen atom or a methyl group), (meth) acryloyloxyethyl dinaphthothiophene (for example, at the 5-position or 6-position of the dinaphthothiophene ring, CH ₂ CH (R ¹ ) C (O) OCH(CH ₃ )- or CH ₂ CH(R ¹ )C(O)OCH ₂ CH ₂ - compound having a bonded structure, wherein R ¹ is a hydrogen atom or a methyl group), vinyldinaphthothiophene ( For example, a compound having a structure in which a vinyl group is bonded to the 5th or 6th position of the naphthothiophene ring), (meth)allyloxydinaphthothiophene, and the like. In addition, a monomer having a dinaphthothiophene structure is included in the concept of a monomer having the above-mentioned condensed aromatic ring structure by including a naphthalene structure and also by having a structure obtained by condensing a thiophene ring and two naphthalene structures.

Examples of the monomer having the dibenzothiophene structure include (meth)acryloyl group-containing dibenzothiophene and vinyl group-containing dibenzothiophene. In addition, since a monomer having a dibenzothiophene structure has a structure in which a thiophene ring and two benzene rings are condensed, it is included in the concept of a monomer having a condensed aromatic ring structure.

In addition, both a dinaphthothiophene structure and a dibenzothiophene structure do not correspond to the structure which two or more non-condensed aromatic rings chemically bonded directly.

As the monomer (m1) in the technique disclosed herein, a monomer having one aromatic ring (preferably a carbocyclic ring) in one molecule may be used. A monomer having one aromatic ring per molecule can be useful, for example, for improving the flexibility of the pressure-sensitive adhesive, adjusting the adhesive properties, and improving the transparency. In some embodiments, a monomer having one aromatic ring per molecule is preferably used in combination with a monomer containing a plurality of aromatic rings from the viewpoint of improving the refractive index of the pressure-sensitive adhesive.

Examples of monomers having one aromatic ring per molecule include benzyl (meth)acrylate, methoxybenzyl (meth)acrylate, phenyl (meth)acrylate, ethoxylated phenol (meth)acrylate, and phenoxypropyl (meth)acrylate. ) Carbon aromatic rings such as acrylate, phenoxybutyl (meth)acrylate, cresyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and chlorobenzyl (meth)acrylate containing (meth)acrylate; 2-(4,6-dibromo-2-s-butylphenoxy)ethyl(meth)acrylate, 2-(4,6-dibromo-2-isopropylphenoxy)ethyl(meth)acrylate , 6-(4,6-dibromo-2-s-butylphenoxy)hexyl(meth)acrylate, 6-(4,6-dibromo-2-isopropylphenoxy)hexyl(meth)acrylate bromine-substituted aromatic ring-containing (meth)acrylates such as late, 2,6-dibromo-4-nonylphenyl acrylate, and 2,6-dibromo-4-dodecylphenyl acrylate; carbon aromatic ring-containing vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and tert-butylstyrene; compounds having a vinyl substituent on the heteroaromatic ring, such as N-vinylpyridine, N-vinylpyrimidine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, and N-vinyloxazole; etc. can be mentioned.

As the monomer (m1), you may use a monomer having a structure in which an oxyethylene chain is interposed between the ethylenically unsaturated group in the various aromatic ring-containing monomers described above and the aromatic ring. In this way, a monomer having an oxyethylene chain interposed between an ethylenically unsaturated group and an aromatic ring can be regarded as an ethoxide product of the original monomer. The repeating number of oxyethylene units (-CH ₂ CH ₂ O-) in the oxyethylene chain is typically 1 to 4, preferably 1 to 3, more preferably 1 to 2, for example is 1 Specific examples of the ethoxylated aromatic ring-containing monomer include ethoxylated o-phenylphenol (meth)acrylate, ethoxylated nonylphenol (meth)acrylate, ethoxylated cresol (meth)acrylate, and phenoxyethyl (meth)acrylate. , phenoxydiethylene glycol di(meth)acrylate, etc. are mentioned.

The content of the monomer containing multiple aromatic rings in the monomer (m1) is not particularly limited, and may be, for example, 5% by weight or more, 25% by weight or more, or 40% by weight or more. In some embodiments, from the viewpoint of facilitating realization of a pressure-sensitive adhesive having a higher refractive index, the content of the monomer containing a plurality of aromatic rings in the monomer (m1) may be, for example, 50% by weight or more, and 70% by weight. It is preferably above, 85% by weight or more may be sufficient, 90% by weight or more may be sufficient, and 95% by weight or more may be sufficient. Substantially 100% by weight of the monomer (m1) may be a monomer containing multiple aromatic rings. That is, as the monomer (m1), only one or two or more aromatic ring-containing monomers may be used. In some aspects, for example, considering the balance between the high refractive index and the adhesive properties and/or optical properties, the content of the monomer containing a plurality of aromatic rings in the monomer (m1) is less than 100% by weight. 98% by weight or less, 90% by weight or less, 80% by weight or less, or 65% by weight or less. In some embodiments, in consideration of adhesive properties and/or optical properties, the content of the monomer containing multiple aromatic rings in the monomer (m1) may be 70% by weight or less, may be 50% by weight or less, or 25% by weight It may be % or less, and may be 10% by weight or less. The technique disclosed herein can also be implemented in an aspect in which the content of the monomer containing multiple aromatic rings in the monomer (m1) is less than 5% by weight. It is not necessary to use a monomer containing multiple aromatic rings.

The content of the monomer component containing a plurality of aromatic rings in the monomer component constituting the acrylic polymer is not particularly limited, and the desired refractive index and adhesive properties (eg peel strength, flexibility, etc.) and/or optical properties (eg total light ray permeability, haze value, etc.) The content of the monomer containing a plurality of aromatic rings in the monomer component may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In some embodiments, from the viewpoint of facilitating realization of a pressure-sensitive adhesive having a higher refractive index, the content of the aromatic ring-containing monomer in the monomer component may be, for example, greater than 35% by weight, or greater than 50% by weight It is preferably more than 70% by weight, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. The content of the aromatic ring-containing monomer in the monomer component may be 100% by weight, but from the viewpoint of achieving a well-balanced high refractive index and adhesive properties and / or optical properties, it is advantageous to set it to less than 100% by weight, It is preferably approximately 99% by weight or less, more preferably 98% by weight or less, may be 96% by weight or less, may be 93% by weight or less, may be 90% by weight or less, may be 85% by weight or less, It may be 80% by weight or less, and may be 75% by weight or less. In some embodiments, the content of the aromatic ring-containing monomer in the monomer component may be 70% by weight or less, 50% by weight or less, or 25% by weight in consideration of adhesive properties and / or optical properties. It may be less than, 15 weight% or less may be sufficient, and 5 weight% or less may be sufficient. The technique disclosed herein can also be implemented in an aspect in which the content of the monomer containing multiple aromatic rings in the monomer component is less than 3% by weight.

In some aspects of the technology disclosed herein, as at least a part of the monomer (m1), a high refractive index monomer can be preferably employed. Here, "high refractive index monomer" refers to a monomer whose refractive index is, for example, approximately 1.510 or higher, preferably approximately 1.530 or higher, and more preferably approximately 1.550 or higher. The upper limit of the refractive index of the high refractive index monomer is not particularly limited, but is, for example, 3.000 or less, may be 2.500 or less, or may be 2.000 or less, from the viewpoint of the ease of preparation of the pressure-sensitive adhesive composition and the ease of compatibility with the flexibility suitable as the pressure-sensitive adhesive. It may be 1.900 or less, 1.800 or less, or 1.700 or less. A high refractive index monomer can be used individually by 1 type or in combination of 2 or more types.

In addition, the refractive index of a monomer is measured on conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 degreeC using the Abbe refractometer. As an Abbe refractometer, model "DR-M4" by ATAGO or its equivalent can be used. When a nominal value of the refractive index at 25°C is provided by a manufacturer or the like, the nominal value can be employed.

As the high refractive index monomer, those having a corresponding refractive index can be appropriately employed from among the compounds (for example, the compounds and compound groups exemplified above) included in the concept of the aromatic ring-containing monomer (m1) disclosed herein. have. Specific examples include m-phenoxybenzyl acrylate (refractive index: 1.566, homopolymer Tg: -35°C), 1-naphthylmethyl acrylate (refractive index: 1.595, homopolymer Tg: 31°C), ethoxylated o- Phenylphenol acrylate (repeating number of oxyethylene units: 1, refractive index: 1.578), benzyl acrylate (refractive index (nD20): 1.519, Tg of homopolymer: 6 ° C), phenoxyethyl acrylate (refractive index (nD20): 1.517, homopolymer Tg: 2 ℃), phenoxydiethylene glycol acrylate (refractive index: 1.510, homopolymer Tg: -35 ℃), 6-acryloyloxymethyldinaphthothiophene (6MDNTA, refractive index: 1.75) , 6-methacryloyloxymethyldinaphthothiophene (6MDNTMA, refractive index: 1.726), 5-acryloyloxyethyldinaphthothiophene (5EDNTA, refractive index: 1.786), 6-acryloyloxyethyldinaphthothiophene Opene (6EDNTA, refractive index: 1.722), 6-vinyldinaphthothiophene (6VDNT, refractive index: 1.802), 5-vinyldinaphthothiophene (abbreviation: 5VDNT, refractive index: 1.793) and the like, but are not limited thereto. does not

The content of the high refractive index monomer (ie, an aromatic ring-containing monomer having a refractive index of about 1.510 or more, preferably about 1.530 or more, more preferably about 1.550 or more) in the monomer (m1) is not particularly limited, and examples include For example, it may be 5% by weight or more, 25% by weight or more, 35% by weight or more, or 40% by weight or more. In some aspects, from the viewpoint of making it easier to obtain a higher refractive index, the content of the high refractive index monomer in the monomer (m1) may be, for example, 50% by weight or more, preferably 70% by weight or more, and 85 It may be 90% by weight or more, or 95% by weight or more. Substantially 100% by weight of the monomer (m1) may be a high refractive index monomer. In some aspects, for example, from the viewpoint of achieving a well-balanced balance between high refractive index and adhesive properties and/or optical properties, the content of the high refractive index monomer in the monomer (m1) may be less than 100% by weight. , 98 wt% or less may be sufficient, 90 wt% or less may be sufficient, 80 wt% or less may be sufficient, and 65 wt% or less may be sufficient. In some embodiments, considering the adhesive properties and / or optical properties, the content of the high refractive index monomer in the monomer (m1) may be 70% by weight or less, 50% by weight or less, or 25% by weight or less may be present, may be 15% by weight or less, or may be 10% by weight or less. The technique disclosed herein can also be implemented in an aspect in which the content of the high refractive index monomer in the monomer component (m1) is less than 5% by weight. It is not necessary to use a high refractive index monomer.

The content of the high refractive index monomer in the monomer component constituting the acrylic polymer is not particularly limited, and the desired refractive index and adhesive properties (eg peel strength, flexibility, etc.) and/or optical properties (eg total light transmittance, haze value, etc.) can be set so as to be able to realize an adhesive layer that achieves both. The content of the high refractive index monomer in the monomer component may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In some aspects, from the viewpoint of making it easier to realize an adhesive having a higher refractive index, the content of the high refractive index monomer in the monomer component may be, for example, more than 35% by weight, and more than 50% by weight It is preferably more than 70% by weight, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. Although the content of the high refractive index monomer in the monomer component may be 100% by weight, it is advantageous to set it to less than 100% by weight from the viewpoint of achieving a well-balanced high refractive index and adhesive properties and/or optical properties, and 99% by weight It is preferably 98% by weight or less, more preferably 98% by weight or less, 96% by weight or less, 93% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less It may be less than or equal to 75% by weight or less. In some embodiments, considering adhesive properties and/or optical properties, the content of the high refractive index monomer in the monomer component may be 70% by weight or less, 50% by weight or less, or 25% by weight or less. It may be 15% by weight or less, and may be 5% by weight or less. The technique disclosed herein can also be implemented in an aspect in which the content of the high refractive index monomer in the monomer component is less than 3% by weight.

In some preferred embodiments of the technology disclosed herein, as at least a part of the monomer (m1), the homopolymer has a Tg of 10 ° C or less (preferably 5 ° C or less or 0 ° C or less, more preferably -10 ° C or less) , more preferably -20°C or less, for example -25°C or less) of an aromatic ring-containing monomer (hereinafter sometimes referred to as "monomer L") is employed. When the content of the aromatic ring-containing monomer (m1) in the monomer component (particularly, the aromatic ring-containing monomer (m1) corresponding to one or both of the above-mentioned monomer containing a plurality of aromatic rings and the high refractive index monomer) is increased, the pressure-sensitive adhesive is stored. Since the elastic modulus G' generally tends to increase, the increase in the storage elastic modulus G' can be suppressed by adopting the monomer L as part or all of the monomer (m1). Thereby, the refractive index can be improved while maintaining the flexibility suitable as an adhesive. The lower limit of the Tg of the monomer L is not particularly limited. Considering the balance with the refractive index improving effect, in some embodiments, the Tg of the monomer L may be, for example, -70°C or higher, -55°C or higher, or -45°C or higher. Monomer L can be used individually by 1 type or in combination of 2 or more types.

As the monomer L, among the compounds included in the concept of the aromatic ring-containing monomer (m1) disclosed herein (for example, the compounds and compound groups exemplified above), those having a corresponding Tg can be appropriately employed. One preferred example of the aromatic ring-containing monomer that can be used as the monomer L is m-phenoxybenzyl acrylate (Tg of homopolymer: -35°C). Another preferred example is phenoxydiethylene glycol acrylate (Tg of homopolymer: -35°C).

The content of the monomer L in the monomer (m1) is not particularly limited, and may be, for example, 5% by weight or more, 25% by weight or more, or 40% by weight or more. In some aspects, from the viewpoint of making it easier to obtain an adhesive that achieves both a high refractive index and flexibility at a higher level, the content of the monomer L in the monomer (m1) may be, for example, 50% by weight or more, and 60% by weight It may be % or more, may be 70% by weight or more, may be 75% by weight or more, may be 85% by weight or more, may be 90% by weight or more, may be 95% by weight or more. Substantially 100% by weight of the monomer (A1) may be the monomer L. Further, in some aspects, from the viewpoint of, for example, balancing the flexibility and high refractive index suitable as an adhesive, the content of the monomer L in the monomer (m1) may be less than 100% by weight, or 98% by weight. It may be less than, 90% by weight or less, 80% by weight or less, 70% by weight or less, 50% by weight or less, 25% by weight or less, or 10% by weight or less. The technique disclosed herein can be implemented also in an aspect in which the content of the monomer L in the monomer (m1) is less than 5% by weight. It is not necessary to use monomer L.

The content of the monomer L in the monomer component constituting the acrylic polymer may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In some aspects, from the viewpoint of making it easier to obtain an adhesive that achieves both a high refractive index and flexibility at a higher level, the content of the monomer L in the monomer component may be, for example, greater than 35% by weight, or greater than 50% by weight It is preferably more than 70% by weight, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. The content of the monomer L in the monomer component may be 100% by weight, but considering the balance between the high refractive index and adhesive properties and/or optical properties, it is advantageous to set it to less than 100% by weight, and about 99% by weight It is preferably less than or equal to, preferably 98% by weight or less, more preferably 96% by weight or less, 95% by weight or less, 93% by weight or less, 90% by weight or less, 85% by weight or less, 80 It may be less than 75% by weight or less than 75% by weight. In some embodiments, the content of the monomer L in the monomer component may be 70% by weight or less, 50% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight may be below. The technique disclosed herein can also be implemented in an aspect in which the content of the monomer L in the monomer component is less than 3% by weight.

In some embodiments, the glass transition temperature Tg _m1 based on the composition of the monomer (m1) is advantageously approximately 20 ° C. or less, and preferably 10 ° C. or less (eg 5 ° C. or less), more preferably 0°C or less, still more preferably -10°C or less, -20°C or less, or -25°C or less. The lower limit of the glass transition temperature Tg _m1 is not particularly limited. Considering the balance with the refractive index improving effect, in some embodiments, the glass transition temperature Tg _m1 may be, for example, -70°C or higher, -55°C or higher, or -45°C or higher. The technology disclosed herein may be suitably implemented in an aspect in which the glass transition temperature Tg _m1 is, for example, -40°C or higher, -35°C or higher, -33°C or higher, -30°C or higher, or -25°C or higher. .

Here, the glass transition temperature Tg _m1 based on the composition of the monomer (m1) refers to Tg obtained by Fox's formula described later based on the composition of only the monomer (m1) among the monomer components constituting the acrylic polymer. The glass transition temperature Tg _m1 is the glass transition of the homopolymer of each aromatic ring-containing monomer used as the monomer (m1) by applying Fox's formula to be described later to only the monomer (m1) among the monomer components constituting the acrylic polymer. It can be calculated from the temperature and the weight fraction of each aromatic ring-containing monomer to the total amount of monomers (m1). In an aspect in which only one type of monomer is used as the monomer (m1), the Tg of the homopolymer of the monomer and the glass transition temperature Tg _m1 are the same.

In some embodiments, as the aromatic ring-containing monomer (m1), monomer L (that is, the Tg of the homopolymer is 10 ° C. or less, preferably 5 ° C. or less or 0 ° C. or less, more preferably -10 ° C. or less, More preferably -20°C or lower, for example, -25°C or lower aromatic ring-containing monomer) and monomer H having a Tg higher than 10°C can be used in combination. The Tg of the monomer H may be, for example, greater than 10°C, greater than 15°C, or greater than 20°C. By using the monomer L and the monomer H in combination, for example, in a configuration in which the content of the aromatic ring-containing monomer (m1) in the monomer component is relatively high, the high refractive index and flexibility of the pressure-sensitive adhesive can be achieved at a higher level. The usage ratio of the monomer L and the monomer H can be set so as to suitably express these effects, and is not particularly limited. For example, it is preferable to set the usage ratio of the monomer L and the monomer H so as to satisfy the glass transition temperature Tg _m1 of any of the above.

In some aspects, the aromatic ring-containing monomer (m1) can be preferably selected from compounds that do not contain a structure in which two or more non-condensed aromatic rings are directly chemically bonded (for example, a biphenyl structure). For example, the content of a compound containing a structure in which two or more non-fused aromatic rings are directly chemically bonded is less than 5% by weight (more preferably less than 3% by weight, and may be 0% by weight) composed of monomer components of a composition. Acrylic polymers are preferred. In this way, limiting the amount of a compound containing a structure in which two or more non-condensed aromatic rings are directly chemically bonded can be advantageous from the viewpoint of realizing a pressure-sensitive adhesive having a well-balanced balance between flexibility and adhesiveness and high refractive index.

(monomer (m2))

In some aspects of the technique disclosed herein, the monomer component constituting the acrylic polymer may further contain a monomer (m2) in addition to the above monomer (m1). The monomer (m2) is a monomer corresponding to at least one of a monomer having a hydroxyl group (hydroxyl group-containing monomer) and a monomer having a carboxy group (carboxy group-containing monomer). The hydroxyl group-containing monomer is a compound having at least one hydroxyl group and at least one ethylenically unsaturated group in one molecule. The carboxy group-containing monomer is a compound containing at least one carboxy group and at least one ethylenically unsaturated group in one molecule. The monomer (m2) can be useful for introducing a crosslinking point into the acrylic polymer or imparting appropriate cohesiveness to the pressure-sensitive adhesive. Monomer (m2) can be used individually by 1 type or in combination of 2 or more types. The monomer (m2) is typically a monomer that does not contain an aromatic ring.

As an example of the ethylenically unsaturated group which the monomer (m2) has, a (meth)acryloyl group, a vinyl group, a (meth)allyl group, etc. are mentioned. A (meth)acryloyl group is preferable from the viewpoint of polymerization reactivity, and an acryloyl group is more preferable from the viewpoint of flexibility or adhesiveness. From the viewpoint of suppressing the decrease in flexibility of the pressure-sensitive adhesive, as the monomer (m2), a compound in which the number of ethylenically unsaturated groups contained in one molecule is 1 (ie, a monofunctional monomer) is preferably used.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and (meth)acrylic acid. Hydroxy (meth)acrylates such as 8-hydroxyoctyl, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate alkyl, but is not limited thereto. Examples of the hydroxyl group-containing monomer that can be preferably used include 4-hydroxybutyl acrylate (Tg: -40°C) and 2-hydroxyethyl acrylate (Tg: -15°C). From the viewpoint of improving the flexibility in the room temperature region, 4-hydroxybutyl acrylate having a lower Tg is more preferred. In a preferred aspect, 50% by weight or more (eg, greater than 50% by weight, greater than 70% by weight or greater than 85% by weight) of the monomer (m2) may be 4-hydroxybutyl acrylate. A hydroxyl group-containing monomer can be used individually by 1 type or in combination of 2 or more types.

In some embodiments using a hydroxyl group-containing monomer as the monomer (m2), the hydroxyl group-containing monomer may be one or two or more selected from compounds having no methacryloyl group. Preferable examples of the hydroxyl group-containing monomer having no methacryloyl group include the various hydroxyalkyl acrylates described above. For example, it is preferable that more than 50 weight%, more than 70 weight%, or more than 85 weight% of the hydroxyl-containing monomer used as a monomer (m2) is hydroxyalkyl acrylate. By using hydroxyalkyl acrylate, it is possible to introduce a hydroxyl group that is helpful in providing a crosslinking point and imparting appropriate cohesiveness to the acrylic polymer, and also, compared to the case where only the corresponding hydroxyalkyl methacrylate is used, the room temperature range It is easy to obtain a pressure-sensitive adhesive having good flexibility and adhesiveness.

Examples of the carboxyl group-containing monomer include acrylic monomers such as (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate, as well as itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, etc. It is not limited to these. Examples of the carboxy group-containing monomer that can be preferably used include acrylic acid and methacrylic acid. Carboxy group-containing monomers can be used individually by 1 type or in combination of 2 or more types. A hydroxyl group-containing monomer and a carboxyl group-containing monomer may be used together.

The content of the monomer (m2) in the monomer component constituting the acrylic polymer is not particularly limited and can be set according to the purpose. In some embodiments, the content of the monomer (m2) may be, for example, 0.01% by weight or more, 0.1% by weight or more, or 0.5% by weight or more. From the viewpoint of obtaining a higher use effect, in some embodiments, the content of the monomer (A2) is preferably 1% by weight or more, may be 2% by weight or more, or may be 4% by weight or more. . The upper limit of the content of the monomer (m2) in the monomer component is set such that the sum of the content of the other monomers does not exceed 100% by weight. In some embodiments, the content of the monomer (m2) is suitably, for example, 30% by weight or less or 25% by weight or less, and the content of the monomer (m1) is relatively increased to facilitate high refractive index. From the viewpoint of making it possible, it is preferably 20% by weight or less, more preferably 15% by weight or less, and may be less than 12% by weight, less than 10% by weight, or less than 7% by weight.

In the aspect in which a hydroxyl group-containing monomer is used as the monomer (m2), the content of the hydroxyl group-containing monomer in the monomer component is not particularly limited, and is, for example, 0.01% by weight or more (preferably 0.1% by weight or more, more preferably 0.5% by weight or more). In some aspects, the content of the hydroxyl group-containing monomer is preferably 1% by weight or more, 2% by weight or more, or 4% by weight or more of the monomer component. The upper limit of the content of the hydroxyl group-containing monomer in the monomer component is set so that the total content of the other monomers does not exceed 100% by weight, for example, 30% by weight or less or 25% by weight or less. From the viewpoint of relatively increasing the content of the monomer (m1) and facilitating high refractive index, it is preferably 20% by weight or less, more preferably 15% by weight or less, may be less than 12% by weight, or 10% by weight It may be less than % or less than 7% by weight.

In the aspect using a carboxyl group-containing monomer as the monomer (m2), the content of the carboxy group-containing monomer in the monomer component is not particularly limited, and is, for example, 0.01% by weight or more (preferably 0.1% by weight or more, more preferably 0.1% by weight or more). preferably 0.3% by weight or more). In some embodiments, the content of the carboxy group-containing monomer may be 1% by weight or more, 2% by weight or more, or 4% by weight or more. The upper limit of the content of the carboxyl group-containing monomer in the monomer component is set so that the total amount of the other monomers used does not exceed 100% by weight, for example, 30% by weight or less or 25% by weight or less. From the viewpoint of relatively increasing the content of the monomer (m1) to facilitate high refractive index, it is preferably 20% by weight or less, more preferably 15% by weight or less, may be less than 12% by weight, or 10% by weight It may be less than % by weight. In some aspects, from the viewpoint of improving the flexibility of the pressure-sensitive adhesive, the content of the carboxy group-containing monomer is advantageously less than 7% by weight, preferably less than 5% by weight, and may be less than 3% by weight , It is good also as less than 1 weight%, and good also as less than 0.5 weight%. The technique disclosed herein can be preferably carried out in an aspect using, for example, only a hydroxyl group-containing monomer as the monomer (m2), ie, no carboxyl group-containing monomer.

The total content of the monomer (m1) and the monomer (m2) in the monomer components constituting the acrylic polymer may be, for example, 31% by weight or more, preferably 51% by weight or more, and may be 61% by weight or more, 71% by weight or more may be sufficient. In some embodiments, the total content of the monomer (m1) and the monomer (m2) in the monomer component constituting the acrylic polymer is, for example, 76 weight It may be % or more, preferably 81% by weight or more, may be 86% by weight or more, may be 91% by weight or more, may be 96% by weight or more, may be 99% by weight or more, or may be substantially 100% by weight.

(monomer m3)

The monomer component constituting the acrylic polymer may contain monomers other than the above-mentioned monomer (m1) and the above-mentioned monomer (m2) as needed. An example of such an optional component is an alkyl (meth)acrylate (hereinafter also referred to as "monomer (m3)"). The monomer (m3) can be useful for adjusting the flexibility of the pressure-sensitive adhesive and improving compatibility within the pressure-sensitive adhesive.

As the monomer (m3), an alkyl (meth)acrylate having a C 1 to C 20 (ie, C _1-20 ) linear or branched chain alkyl group at the ester end can be preferably used. Specific examples of the C _{1-20 alkyl} (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. Isobutyl acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate , (meth)acrylate 2-ethylhexyl, (meth)acrylate isooctyl, (meth)acrylate nonyl, (meth)acrylate isononyl, (meth)acrylate decyl, (meth)acrylate isodecyl, (meth)acrylate undecyl , (meth)acrylate dodecyl, (meth)acrylate tridecyl, (meth)acrylate tetradecyl, (meth)acrylate pentadecyl, (meth)acrylate hexadecyl, (meth)acrylate heptadecyl, (meth)acrylate stearyl, Although isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. are mentioned, it is not limited to these.

In some embodiments, as at least a part of the monomer (m3), an alkyl (meth)acrylate having a homopolymer Tg of -20 ° C or lower (more preferably -40 ° C or lower, for example -50 ° C or lower) can be preferably employed. Such low Tg alkyl (meth)acrylates can be useful for improving the flexibility of the pressure-sensitive adhesive. The lower limit of the Tg of the alkyl (meth)acrylate is not particularly limited, and may be, for example, -85°C or higher, -75°C or higher, -65°C or higher, or -60°C or higher. Specific examples of the low-Tg alkyl (meth)acrylate include n-butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and isononyl acrylate (iNA).

In some aspects using the monomer (m3), it is preferable that at least a part of the monomer (m3) is an alkyl acrylate from the viewpoints of flexibility, adhesiveness and the like. For example, it is preferable that 50% by weight or more (more preferably 75% by weight or more, still more preferably 90% by weight or more) of the monomer (m3) is an alkyl acrylate. As a monomer (m3), the aspect which uses only 1 type, or 2 or more types of alkyl acrylate and does not use an alkyl methacrylate may be sufficient.

In the aspect in which the monomer component contains an alkyl (meth)acrylate, the content of the alkyl (meth)acrylate in the monomer component can be set so that the effect of use thereof is exhibited appropriately. In some embodiments, the content of the alkyl (meth)acrylate may be, for example, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more. In some aspects, the content of the alkyl (meth)acrylate may be 15% by weight or more, 30% by weight or more, or 45% by weight or more. The upper limit of the content of the monomer (m3) in the monomer component is set such that the sum of the content of the other monomers does not exceed 100% by weight, and may be, for example, less than 50% by weight. In some embodiments, the content of the monomer (m3) may be less than 35% by weight, for example. In general, since the refractive index of alkyl (meth)acrylate is relatively low, it is advantageous to limit the content of the monomer (m3) in the monomer component and increase the content of the monomer (m1) relatively in order to increase the refractive index. . From this point of view, the content of the monomer (m3) is advantageously 24% by weight or less, preferably less than 23% by weight, more preferably less than 20% by weight, may be less than 17% by weight, or 12% by weight of the monomer component. It may be less than 7% by weight, may be less than 3% by weight, or may be less than 1% by weight. It is not necessary to substantially use the monomer (m3).

(other monomers)

The monomer component constituting the acrylic polymer may contain monomers other than the above-mentioned monomers (m1), (m2), and (m3) (hereinafter referred to as "other monomers") as needed. The above other monomers can be used for purposes such as adjusting the Tg of the acrylic polymer, adjusting the adhesive performance, and improving the compatibility in the pressure-sensitive adhesive layer. Said other monomer can be used individually by 1 type or in combination of 2 or more types.

As an example of the said other monomer, the monomer (functional group containing monomer) which has functional groups other than a hydroxyl group and a carboxy group is mentioned. For example, other monomers capable of improving the cohesive force and heat resistance of the pressure-sensitive adhesive include a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, and a cyano group-containing monomer. Further, as a monomer capable of introducing a functional group capable of serving as a starting point for crosslinking into an acrylic polymer or contributing to improvement of peel strength and improvement of compatibility in the pressure-sensitive adhesive layer, an amide group-containing monomer (for example, (meth) ) acrylamide, N-methylol (meth) acrylamide, etc.), amino group-containing monomers (eg, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, etc.), nitrogen atom-containing A monomer having a ring (eg, N-vinyl-2-pyrrolidone, N-(meth)acryloylmorpholine, etc.), an imide group-containing monomer, an epoxy group-containing monomer, a keto group-containing monomer, an isocyanate group-containing monomer , an alkoxysilyl group-containing monomer, and the like. In addition, among the monomers having a nitrogen atom-containing ring, there are also those corresponding to amide group-containing monomers, such as N-vinyl-2-pyrrolidone. The same applies to the relationship between the monomer having a nitrogen atom-containing ring and the amino group-containing monomer.

Examples of other monomers that can be used other than the functional group-containing monomer include vinyl ester monomers such as vinyl acetate; non-aromatic ring-containing (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; olefinic monomers such as ethylene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride; alkoxy group-containing monomers such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and ethoxyethoxyethyl (meth)acrylate; vinyl ether monomers such as methyl vinyl ether; etc. can be mentioned. As a suitable example of another monomer that can be used for the purpose of improving the flexibility of the pressure-sensitive adhesive, etc., ethoxyethoxyethyl acrylate (alias: ethyl carbitol acrylate, homopolymer Tg: -67°C) can be mentioned.

In the case of using the above other monomers, the amount used is not particularly limited, and the total amount of the monomer components can be appropriately set within a range not exceeding 100% by weight. In some embodiments, from the viewpoint of facilitating the use of the monomer (m1) to exhibit the effect of improving the refractive index, the content of the other monomers in the monomer component can be, for example, approximately 35% by weight or less. It is appropriate to be about 25% by weight or less (for example, 0 to 25% by weight), about 20% by weight or less (eg 0 to 20% by weight), or about 10% by weight or less. It may be 5% by weight or less, for example, approximately 1% by weight or less. The technology disclosed herein can be preferably implemented in an aspect in which the monomer component does not substantially contain the other monomers.

In some aspects, the monomer component constituting the acrylic polymer may be a composition in which the amount of the methacryloyl group-containing monomer used is suppressed to a predetermined level or less. The amount of the methacryloyl group-containing monomer used in the monomer component may be, for example, less than 5% by weight, less than 3% by weight, less than 1% by weight, or less than 0.5% by weight. Limiting the amount of the methacryloyl group-containing monomer used in this way can be advantageous from the viewpoint of realizing a pressure-sensitive adhesive in which flexibility, adhesiveness, and high refractive index are well-balanced. The monomer component constituting the acrylic polymer may be a composition that does not contain a methacryloyl group-containing monomer (for example, a composition consisting only of an acryloyl group-containing monomer).

In some embodiments, the monomer component constituting the base polymer (eg, acrylic polymer) of the high refractive index pressure-sensitive adhesive layer contains a carboxyl group from the viewpoint of suppressing coloring or discoloration (eg, yellowing) of the pressure-sensitive adhesive layer It is preferable that the amount of monomer used is limited. The amount of the carboxyl group-containing monomer used in the monomer component may be, for example, less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.3% by weight, less than 0.1% by weight, or less than 0.05% by weight. may be continued The reason why the amount of the carboxyl group-containing monomer is limited is to prevent corrosion of metal materials (eg, metal wires or metal films that may be present on an adherend) that may be placed in contact with or in proximity to the high refractive index adhesive layer. It is also advantageous from the point of view of suppression. The technology disclosed herein can be preferably implemented in an aspect in which the monomer component does not contain a carboxy group-containing monomer.

For the same reasons, in some embodiments, the monomer component constituting the base polymer of the high refractive index pressure-sensitive adhesive layer has an acidic functional group (including a sulfonic acid group, a phosphoric acid group, etc. in addition to a carboxyl group). it is desirable As the usage amount of the acidic functional group-containing monomer in the monomer component of this aspect, the preferred usage amount of the carboxyl group-containing monomer described above can be applied. The technology disclosed herein can be preferably implemented in an aspect in which the monomer component does not contain an acidic group-containing monomer (ie, an aspect in which the base polymer of the high refractive index pressure-sensitive adhesive layer is acid-free).

(Glass transition temperature Tg _T of the base polymer)

In some aspects, it is appropriate that the base polymer (eg, acrylic polymer) of the pressure-sensitive adhesive layer has a glass transition temperature Tg _T based on the composition of monomer components constituting the polymer of about 20°C or less, and about It is preferably 10°C or lower, more preferably 0°C or lower, and may be -10°C or lower, -20°C or lower, -25°C or lower, -28°C or lower, or -30°C or lower. A low glass transition temperature Tg _T can be advantageous from the viewpoint of improving the flexibility of the pressure-sensitive adhesive. Further, the glass transition temperature Tg _T may be, for example, -60°C or higher, and from the viewpoint of facilitating high refractive index of the pressure-sensitive adhesive, it is preferably -50°C or higher, more preferably -45°C or higher, It may be more than -40°C, may be more than -35°C, may be more than -25°C, may be more than -15°C, may be more than -5°C.

Here, the glass transition temperature Tg _T of a polymer means the glass transition temperature calculated|required by Fox's formula based on the composition of the monomer component which comprises this polymer, unless otherwise specified. As described below, Fox's formula is a relational expression between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer obtained by homopolymerization of each of the monomers constituting the copolymer.

1/Tg = Σ (Wi/Tgi)

In the above formula of Fox, Tg is the glass transition temperature of the copolymer (unit: K), Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio by weight), and Tgi is the homopolymer of the monomer i Shows the glass transition temperature (unit: K).

As the glass transition temperature of the homopolymer used for calculation of Tg, a value described in known materials such as "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) shall be used. For a monomer for which a plurality of types of values are described in the above Polymer Handbook, the highest value is adopted. When the Tg of the homopolymer is not described in publicly known materials, the value obtained by the measurement method described in Japanese Patent Application Laid-Open No. 2007-51271 shall be used.

(Preparation method of base polymer)

In the technique disclosed herein, the method of obtaining the base polymer (eg, the acrylic polymer (A) composed of the above-mentioned monomer components) of the high refractive index pressure-sensitive adhesive layer is not particularly limited. For example, the above description of the method for preparing the acrylic polymer (F) can also be applied to the method for preparing the base polymer of the high refractive index adhesive layer.

(refractive index improver)

In some aspects of the technique disclosed herein, in addition to the base polymer, a refractive index improver may be incorporated in the high refractive index adhesive layer (eg, acrylic adhesive layer) as needed. Here, the refractive index improver in this specification refers to a material that can increase the refractive index of the pressure-sensitive adhesive layer by using the agent. As the refractive index improver, a material having a higher refractive index than the refractive index of the pressure-sensitive adhesive layer containing the refractive index improver can be preferably used. As the refractive index improver, a material having a higher refractive index than the base polymer (eg, the acrylic polymer (A)) of the pressure-sensitive adhesive layer containing the refractive index improver can be preferably used. By appropriate use of the refractive index improver, a higher refractive index and practical adhesive performance can be suitably compatible. In some embodiments, it is preferred that the refractive index enhancer is an organic material. The organic material used as the refractive index improver may be a polymer or a non-polymer. In addition, it may or may not have a polymerizable functional group. A refractive index improver can be used individually by 1 type or in combination of 2 or more types.

Since the refractive index of the refractive index improver (eg, an additive (H _RO ) described later) can be set within an appropriate range in relation to the refractive index of the base polymer, it is not limited to a specific range. The refractive index of the refractive index improver is, for example, greater than 1.55, greater than 1.56, or greater than 1.57, and can be selected from a range higher than the refractive index of the base polymer. From the viewpoint of increasing the refractive index of the pressure-sensitive adhesive, in some embodiments, the refractive index of the refractive index improver is advantageously 1.58 or higher, preferably 1.60 or higher, more preferably 1.63 or higher, may be 1.65 or higher, or may be 1.70 or higher. , may be 1.75 or more. According to the refractive index improver having a higher refractive index, the target refractive index can be achieved even by using a smaller amount of the refractive index improver. This is preferable from the viewpoint of suppressing deterioration of adhesive properties and optical properties. The upper limit of the refractive index of the refractive index improver is not particularly limited, but is, for example, 3.000 or less, may be 2.500 or less, or 2.000 It may be less than, 1.950 or less, 1.900 or less, or 1.850 or less may be sufficient.

In some embodiments, the difference between the refractive index n _b of the refractive index improver (eg, an additive ( _HRO ) described later) and the refractive index n _a of the base polymer, that is, n _b -n _a (hereinafter also referred to as "Δn _A " ) is set to be greater than 0. In some aspects, Δn _A may be, for example, 0.02 or more, 0.05 or more, 0.07 or more, 0.10 or more, 0.15 or more, 0.20 or more, or 0.25 or more. By selecting the base polymer and the refractive index improver so that Δn _A becomes larger, the refractive index improving effect by use of the refractive index improver tends to increase. Further, from the viewpoints of compatibility in the pressure-sensitive adhesive layer, transparency of the pressure-sensitive adhesive layer, etc., in some embodiments, Δn _A may be, for example, 0.70 or less, 0.60 or less, 0.50 or less, or 0.40 It may be less than or 0.35 or less.

In some embodiments, the difference between the refractive index n _b of the refractive index improver (eg, an additive (H _RO ) described later) and the refractive index n _T of the pressure-sensitive adhesive layer containing the refractive index improver, that is, n _b -n _T ( Hereinafter, also referred to as “Δn _B ”) is set to be greater than 0. In some aspects, Δn _B may be, for example, 0.02 or more, 0.05 or more, 0.07 or more, 0.10 or more, 0.15 or more, 0.20 or more, or 0.25 or more. By selecting the composition of the pressure-sensitive adhesive layer and the refractive index improver so that Δn _B becomes larger, the effect of improving the refractive index by use of the refractive index improver tends to increase. Further, from the viewpoints of compatibility in the pressure-sensitive adhesive layer, transparency of the pressure-sensitive adhesive layer, etc., in some embodiments, Δn _B may be, for example, 0.70 or less, 0.60 or less, 0.50 or less, or 0.40 It may be less than or 0.35 or less.

The amount of the refractive index improver used (in the case of using a plurality of refractive index improvers, the total amount thereof) relative to 100 parts by weight of the base polymer is not particularly limited and can be set according to the purpose. From the viewpoint of increasing the refractive index of the pressure-sensitive adhesive, the amount of the refractive index improver relative to 100 parts by weight of the base polymer can be, for example, 1 part by weight or more, preferably 3 parts by weight or more, and 5 parts by weight or more. It is preferably 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more. In some embodiments, the amount of the refractive index improver relative to 100 parts by weight of the base polymer can be, for example, 80 parts by weight or less, and the high refractive index of the pressure-sensitive adhesive and suppression of deterioration in adhesive properties and optical properties are balanced. From the viewpoint of good compatibility, it is advantageous to set it as 60 parts by weight or less, and it is preferable to set it as 45 parts by weight or less. In some embodiments in which adhesive properties and optical properties are more important, the amount of the refractive index improver relative to 100 parts by weight of the base polymer may be, for example, 30 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less. may be, may be 10 parts by weight or less, may be 5 parts by weight or less, may be 3 parts by weight or less. The technique disclosed herein can also be preferably carried out in an aspect where the amount of the refractive index improver is less than 1 part by weight based on 100 parts by weight of the base polymer in the pressure-sensitive adhesive layer, or the refractive index improver is not substantially used. Here, not using substantially means not using at least intentionally.

(Additive (H _RO ))

In some aspects, as the refractive index improver, an organic material having a higher refractive index than that of the base polymer can be preferably used. Hereinafter, such an organic material may be described as "additive (H _RO )". Here, "H _RO " indicates that it is an organic material with a high refractive index. By using a base polymer (eg acrylic polymer, preferably acrylic polymer (A)) and an additive (H _RO ) in combination, refractive index and adhesive properties (peel strength, flexibility, etc.) and/or optical properties (total light transmittance, Haze value, etc.) can be realized. The organic material used as the additive (H _RO ) may be a polymer or a non-polymer. In addition, it may or may not have a polymerizable functional group. The additive (H _RO ) can be used individually by 1 type or in combination of 2 or more types.

The refractive index of the additive (H _RO ) is measured using an Abbe refractometer under conditions of a measurement wavelength of 589 nm and a measurement temperature of 25°C, similarly to the refractive index of the monomer. When a nominal value of the refractive index at 25°C is provided by a manufacturer or the like, the nominal value can be employed.

The molecular weight of the organic material used as the additive (H _RO ) is not particularly limited and can be selected according to the purpose. The molecular weight of the additive (H _RO ) can be selected from the range of 30000 or less, for example. Further, the additive (H _RO ) is preferably a polymer or non-polymer having a lower molecular weight than the base polymer. From the viewpoint of balancing the effect of high refractive index with other properties (for example, optical properties such as flexibility and haze suitable for pressure-sensitive adhesives) in a well-balanced manner, in some embodiments, the molecular weight of the additive (H _RO ) is approximately 10000 It is suitably less than 5000, preferably less than 3000 (for example, less than 1000), more preferably less than 800, less than 600, less than 500, or less than 400. The fact that the molecular weight of the additive (H _RO ) is not too large can be advantageous from the viewpoint of improving the compatibility in the pressure-sensitive adhesive layer. In addition, the molecular weight of the additive (H _RO ) may be, for example, 130 or more, or 150 or more. In some embodiments, the molecular weight of the additive (H _RO ) is preferably 170 or more, more preferably 200 or more, may be 230 or more, or 250 or more, from the viewpoint of increasing the refractive index of the additive (H _RO ) It may be 270 or more, 500 or more, 1000 or more, or 2000 or more may be sufficient. In some aspects, a polymer having a molecular weight of about 1000 to about 10000 (for example, 1000 or more and less than 5000) can be used as the additive (H _RO ).

As the molecular weight of the additive (H _RO ), the molecular weight calculated based on the chemical structure can be used for non-polymers or polymers with a low degree of polymerization (for example, about 2 to 5 polymers). When the additive (H _RO ) is a polymer having a higher polymerization degree, a weight average molecular weight (Mw) based on GPC performed under appropriate conditions can be used. When a nominal value of molecular weight is provided by a manufacturer or the like, the nominal value can be employed.

Examples of organic materials that can be selected as the additive (H _RO ) include organic compounds having an aromatic ring, organic compounds having a heterocyclic ring (which may be an aromatic ring or non-aromatic heterocycle), and the like. is not limited to

The aromatic ring of the organic compound having an aromatic ring (hereinafter also referred to as "aromatic ring-containing compound") used as the additive (H _RO ) may be selected from the same aromatic rings as those of the compound used as the monomer (m1). can

The aromatic ring may have one or two or more substituents on ring-constituting atoms, and may have no substituents. When it has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxyalkyl group, a hydroxyalkyloxy group, a glycidyloxy group, and the like. Although exemplified, it is not limited thereto. In the substituent containing carbon atoms, the number of carbon atoms contained in the substituent is, for example, 1 to 10, advantageously 1 to 6, preferably 1 to 4, more preferably 1 to 10. 3, and may be, for example, 1 or 2. In some embodiments, the aromatic ring is an aromatic ring having no substituents on ring atoms or having one or two or more substituents selected from the group consisting of an alkyl group, an alkoxy group, and a halogen atom (for example, a bromine atom). can

Examples of aromatic ring-containing compounds that can be used as the additive (H _RO ) include, for example: compounds that can be used as the monomer (m1); an oligomer containing as a monomer unit a compound that can be used as the monomer (m1); From the compound that can be used as the monomer (m1), a hydrogen atom or an ethylenically unsaturated group, except for a group having an ethylenically unsaturated group (which may be a substituent bonded to a ring constituent atom) or a portion constituting an ethylenically unsaturated group in the group Compounds with structures substituted with groups not having (eg, hydroxyl group, amino group, halogen atom, alkyl group, alkoxy group, hydroxyalkyl group, hydroxyalkyloxy group, glycidyloxy group, etc.); Although the etc. are mentioned, it is not limited to these. Non-limiting examples of aromatic ring-containing compounds that can be used as additives (H _RO ) include benzyl acrylate, m-phenoxybenzyl acrylate, 2-(o-phenylphenoxy)ethyl acrylate, and phenoxyethyl acrylate. rate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, a monomer having the above-mentioned fluorene structure, a monomer having a dinaphthothiophene structure, dibenzothio aromatic ring-containing monomers such as monomers having an opene structure; 3-phenoxybenzyl alcohol, dinaphthothiophene and derivatives thereof (for example, the dinaphthothiophene ring has one or two or more substituents selected from a hydroxyl group, a methanol group, a diethanol group, a glycidyl group, etc. aromatic ring-containing compounds having no ethylenically unsaturated group, such as compounds having a structure in which 1 or 2 or more are bonded together); etc. may be included. Further, the aromatic ring-containing compound is an oligomer containing such an aromatic ring-containing monomer as a monomer unit (preferably an oligomer having a molecular weight of about 5000 or less, more preferably about 1000 or less. For example, about 2 to 5 monomers low polymers). The oligomer may be, for example: a homopolymer of an aromatic ring-containing monomer; copolymers of one or two or more aromatic ring-containing monomers; copolymers of one or two or more aromatic ring-containing monomers with other monomers; etc. As said other monomer, 1 type(s) or 2 or more types of monomers which do not have an aromatic ring can be used.

In some aspects, as an additive (H _RO ), an organic compound having two or more aromatic rings in one molecule (hereinafter also referred to as “a compound containing multiple aromatic rings”) from the viewpoint that a high refractive index-raising effect is easily obtained ) can be preferably employed. The compound containing multiple aromatic rings may or may not have a polymerizable functional group such as an ethylenically unsaturated group. In addition, the compound containing multiple aromatic rings may be a polymer or a non-polymer. In addition, the above-mentioned polymer is an oligomer (preferably an oligomer having a molecular weight of about 5000 or less, more preferably about 1000 or less. For example, a low polymer of about 2 to 5 monomers) containing a monomer containing a plurality of aromatic rings as a monomer unit. can be The oligomer may be, for example: a homopolymer of a monomer containing a plurality of aromatic rings; copolymers of one or two or more aromatic ring-containing monomers; copolymers of one or two or more aromatic ring-containing monomers and other monomers; etc. The other monomer may be an aromatic ring-containing monomer that does not correspond to the monomer containing multiple aromatic rings, a monomer without an aromatic ring, or a combination thereof.

Non-limiting examples of compounds containing multiple aromatic rings include compounds having a structure in which two or more non-condensed aromatic rings are bonded via a linking group, compounds having a structure in which two or more non-condensed aromatic rings are directly (ie, not through other atoms) chemically bonded, A compound having a condensed aromatic ring structure, a compound having a fluorene structure, a compound having a dinaphthothiophene structure, a compound having a dibenzothiophene structure, and the like are exemplified. A compound containing multiple aromatic rings can be used individually by 1 type or in combination of 2 or more types.

As a specific example of the compound having the fluorene structure, 9,9-bis (4-hydroxyphenyl) fluorene (refractive index: 1.68, in addition to the monomer having the above-mentioned fluorene structure and oligomers that are homopolymers or copolymers of these monomers) ), 9,9-bis (4-aminophenyl) fluorene (refractive index: 1.73), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (refractive index: 1.68), 9,9-bis [ 9,9-bisphenylfluorene and derivatives thereof, such as 4-(2-hydroxyethoxy)phenyl]fluorene (refractive index: 1.65).

As a specific example of the compound which has the said dinaphthothiophene structure, Dinaphthothiophene (refractive index: 1.808) other than the monomer which has the above-mentioned dinaphthothiophene structure, the oligomer which is a homopolymer or a copolymer of this monomer; hydroxyalkyl dinaphthothiophenes such as 6-hydroxymethyldinaphthothiophene (refractive index: 1.766); dihydroxydinaphthothiophenes such as 2,12-dihydroxydinaphthothiophene (refractive index: 1.750); dihydroxyalkyloxydinaphthothiophenes such as 2,12-dihydroxyethyloxydinaphthothiophene (refractive index: 1.677); diglycidyloxydinaphthothiophenes such as 2,12-diglycidyloxydinaphthothiophene (refractive index: 1.723); dinaphthothiophenes having two or more ethylenically unsaturated groups such as 2,12-diallyloxydinaphthothiophene (abbreviation: 2,12-DAODNT, refractive index: 1.729); and the like, dinaphthothiophene and derivatives thereof.

As specific examples of the compound having the dibenzothiophene structure, dibenzothiophene (refractive index: 1.607), 4-dimethyldi, in addition to monomers having the above-mentioned dibenzothiophene structure and oligomers that are homopolymers or copolymers of these monomers. Benzothiophene (refractive index: 1.617), 4,6-dimethyldibenzothiophene (refractive index: 1.617), and the like.

Examples of the organic compound having a heterocycle (hereinafter, also referred to as a heterocycle-containing organic compound) that can be used as an additive (H _RO ) include a thioepoxy compound and a compound having a triazine ring. Examples of the thioepoxy compound include bis(2,3-epithiopropyl) disulfide described in Japanese Patent No. 3712653 and a polymer thereof (refractive index: 1.74). Examples of the compound having a triazine ring include compounds having at least one (for example, 3 to 40, preferably 5 to 20) triazine rings in one molecule. In addition, since the triazine ring has aromaticity, the compound having a triazine ring is also included in the concept of the compound containing an aromatic ring, and the compound having a plurality of triazine rings is also included in the concept of the compound containing a plurality of aromatic rings.

In some aspects, as the additive (H _RO ), a compound having no ethylenically unsaturated group can be preferably employed. Thereby, deterioration (advance of gelation or decrease in leveling property due to increase in viscosity) of the pressure-sensitive adhesive composition due to heat or light can be suppressed, and storage stability can be improved. Adoption of an additive (H _RO ) having no ethylenically unsaturated group means that the pressure-sensitive adhesive layer containing the additive (H _RO ) or the laminate (eg, laminated sheet) containing the pressure-sensitive adhesive layer has ethylenically unsaturated It is also preferable from the viewpoint of suppressing dimensional change or deformation (bending, waviness, etc.), occurrence of optical distortion, etc. due to the reaction of the group.

In the aspect using an oligomer as the additive (H _RO ), the oligomer can be obtained by polymerizing a corresponding monomer component by a known method. When the oligomer is produced by radical polymerization, polymerization can be performed by appropriately adding a polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization to the monomer component. The polymerization initiator, chain transfer agent, emulsifier, etc. used in the radical polymerization are not particularly limited, and can be appropriately selected and used. In addition, the weight average molecular weight of an oligomer is controllable by the usage-amount of a polymerization initiator and chain transfer agent, and reaction conditions, and the usage-amount is adjusted suitably according to these types.

As said chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, α-thioglycerol, thioglycolic acid, 2-ethylhexyl thioglycolic acid, 2,3-dimer Capto-1-propanol etc. are mentioned. A chain transfer agent may be used individually by 1 type, and may mix and use 2 or more types. The amount of chain transfer agent used can be set so as to obtain an oligomer having a desired weight average molecular weight, depending on the composition of the monomer component used in the synthesis of the oligomer, the type of chain transfer agent, and the like. In some embodiments, the amount of chain transfer agent used for 100 parts by weight of the total amount of monomers used in the synthesis of oligomers is suitably about 15 parts by weight or less, may be 10 parts by weight or less, or about 5 parts by weight or less. may be The lower limit of the amount of the chain transfer agent used per 100 parts by weight of the total amount of monomers used in the synthesis of the oligomer is not particularly limited, but may be, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, or 0.5 parts by weight or more. , 1 part by weight or more may be sufficient.

In the aspect of using the additive (H _RO ) as the refractive index improver, the amount of the additive (H _RO ) relative to 100 parts by weight of the base polymer (when using a plurality of compounds, their total amount) is not particularly limited. , can be set according to the purpose. From the viewpoint of increasing the refractive index of the pressure-sensitive adhesive, the amount of the additive (H _RO ) relative to 100 parts by weight of the base polymer can be, for example, 1 part by weight or more, advantageously 3 parts by weight or more, and 5 parts by weight It is preferable to set it as above, and may be 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more. In some embodiments, the amount of the additive (H _RO ) relative to 100 parts by weight of the base polymer can be, for example, 80 parts by weight or less, to increase the refractive index of the pressure-sensitive adhesive and suppress the decrease in adhesive properties and optical properties. It is advantageous to set it as 60 parts by weight or less, and it is preferable to set it as 45 parts by weight or less from the viewpoint of achieving well-balanced compatibility. In some embodiments in which adhesive properties and optical properties are more important, the amount of the additive (H _RO ) relative to 100 parts by weight of the base polymer may be, for example, 30 parts by weight or less, 20 parts by weight or less, or 15 parts by weight. It may be less than the weight and may be less than 10 parts by weight.

(plasticized material)

In some aspects, the high-refractive-index pressure-sensitive adhesive layer may contain a plasticizing material having a lower molecular weight than the base polymer of the pressure-sensitive adhesive layer. By using a plasticizing material, the flexibility of the high-refractive-index pressure-sensitive adhesive layer can be enhanced, and adhesion to an adherend, flexibility as a whole, conformability to deformation, and the like can be improved. As the plasticizing material, an organic material can be preferably employed from the viewpoint of compatibility and transparency in the pressure-sensitive adhesive layer. The plasticizing material may be a material that can be used also as the above-described refractive index improver (eg, the additive (H _RO )).

The molecular weight of the plasticizing material should just be lower than that of the base polymer, and is not particularly limited. In some embodiments, the molecular weight of the plasticizing material may be 30000 or less, 25000 or less, or less than 10000, preferably less than 5000, preferably less than 3000 (eg, For example, less than 1000) is more preferable, and may be less than 800, less than 600, less than 500, or less than 400. If the molecular weight of the plasticizing material is not too large, it may be advantageous from the viewpoint of improving the compatibility in the pressure-sensitive adhesive layer. Further, in some embodiments, the molecular weight of the plasticizing material is preferably 130 or more, preferably 150 or more, may be 170 or more, or may be 200 or more, from the viewpoint of making it easy to exhibit a sufficient plasticizing effect. 250 or more may be sufficient, and 300 or more may be sufficient. In some aspects, the molecular weight of the plasticizing material may be 500 or more, 1000 or more, or 2000 or more. It is preferable also from the viewpoint of the heat resistance performance of the pressure-sensitive adhesive layer and the stain suppression of the adherend that the molecular weight of the plasticizing material is not too low.

Non-limiting examples of compounds that can be selected as plasticizing materials include compounds that can be used as the monomer (m1) (eg, (meth)acrylates having an aromatic ring such as a benzyl group, a phenoxy group, or a naphthyl group). , a monomer having a fluorene structure, a monomer having a dinaphthothiophene structure, a monomer having a dibenzothiophene structure, etc.); an oligomer containing as a monomer unit a compound that can be used as the monomer (m1); Compounds having a structure substituted with hydrogen atoms or groups having no ethylenically unsaturated groups, excluding portions having ethylenically unsaturated groups, from compounds that can be used as the monomer (m1) (eg, 3-phenoxybenzyl alcohol); etc. are included. From the viewpoint of improving flexibility, a low Tg monomer such as n-butyl acrylate or 2-ethylhexyl acrylate may be copolymerized in the oligomer containing the compound that can be used as the monomer (m1) as a monomer unit, for example. As the plasticizer, one or two or more of known plasticizers (for example, phthalic acid esters, terephthalic acid esters, adipic acid esters, adipic acid polyesters, benzoic acid glycol esters, etc.) may be used.

In some aspects, as the plasticizing material, an organic material having a refractive index of approximately 1.50 or more (more preferably 1.53 or more) can be preferably used. Specific examples of compounds that can be selected as plasticizing materials include diethylene glycol dibenzoate (refractive index 1.55), dipropylene glycol dibenzoate (refractive index 1.54), 3-phenoxytoluene (refractive index 1.57), 3-ethyl Biphenyl (refractive index 1.59), 3-methoxybiphenyl (refractive index 1.61), 4-methoxybiphenyl (refractive index 1.57), polyethylene glycol dibenzoate, 3-phenoxybenzyl alcohol (refractive index 1.59), triphenyl phosphate (refractive index 1.56 ), benzyl benzoate (refractive index 1.57), 4-(tert-butyl)phenyldiphenylphosphate (refractive index 1.56), trimethylphenylphosphate (refractive index 1.55), butylbenzylphthalate (refractive index 1.54), rosin methyl ester (refractive index 1.53), alkyl Benzyl phthalate (refractive index 1.53), butyl (phenylsulfonyl)amine (refractive index 1.53), trimethyl trimellitate (refractive index 1.52), benzyl phthalate (refractive index 1.52), 2-ethylhexyldiphenyl phosphate (refractive index 1.51), trisphosphite ( 2,4-di-tert-butylphenyl) and the like, but are not limited thereto. From the viewpoint of refractive index and compatibility, for example, diethylene glycol dibenzoate can be preferably employed. The upper limit of the refractive index of the plasticizing material is not particularly limited, and may be, for example, 3.00 or less. In some aspects, from the viewpoints of ease of preparation of the pressure-sensitive adhesive composition and compatibility within the pressure-sensitive adhesive, the refractive index of the plasticized material is suitably 2.50 or less, preferably 2.00 or less, may be 1.90 or less, or 1.80 It may be less than or equal to 1.70.

In addition, the refractive index of a plasticized material is measured using the Abbe refractometer similarly to the refractive index of a monomer on condition of a measurement wavelength of 589 nm and a measurement temperature of 25 degreeC. When a nominal value of the refractive index at 25°C is provided by a manufacturer or the like, the nominal value can be employed.

In the aspect of using the plasticizing material, the amount of the plasticizing material used per 100 parts by weight of the base polymer is not particularly limited and can be set according to the purpose. From the viewpoint of enhancing the plasticizing effect, the amount of plasticizing material used per 100 parts by weight of the base polymer may be, for example, 0.1 parts by weight or more, or 0.5 parts by weight or more, and from the viewpoint of obtaining a higher plasticizing effect, 1 part by weight It is preferably 3 parts by weight or more, more preferably 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more. It can be more than that. In addition, from the viewpoint of balancing the high refractive index of the pressure-sensitive adhesive with the transparency and plasticizing effect in a well-balanced manner, the amount of the plasticizing material relative to 100 parts by weight of the base polymer is suitably approximately 100 parts by weight or less, and 80 parts by weight or less It is preferably set to 60 parts by weight or less, more preferably 45 parts by weight or less, 35 parts by weight or less, or 25 parts by weight or less. In some embodiments in which adhesive properties and optical properties are more important, the amount of plasticizing material used per 100 parts by weight of the base polymer may be 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. .

(leveling agent)

In some embodiments, the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer has the purpose of improving the appearance of the pressure-sensitive adhesive layer formed of the composition (for example, improving the uniformity of thickness) or improving the coatability of the pressure-sensitive adhesive composition. Thus, a leveling agent may be incorporated as needed. Non-limiting examples of the leveling agent include acrylic leveling agents, fluorine-based leveling agents, silicone-based leveling agents, and the like. An appropriate leveling agent can be selected from commercially available leveling agents and used according to a conventional method, for example.

In some aspects, as the leveling agent, a monomer having a polyorganosiloxane skeleton (hereinafter also referred to as "monomer S1") and a monomer raw material containing an acrylic monomer (hereinafter also referred to as "monomer raw material B") of A polymer that is a polymer (hereinafter, also referred to as "polymer (B)") can be preferably used. Polymer (B) can be said to be a copolymer of monomer S1 and an acrylic monomer. Polymer (B) can be used individually by 1 type or in combination of 2 or more types.

It does not specifically limit as monomer S1, Any monomer containing a polyorganosiloxane skeleton can be used. As monomer S1, one of a structure having a polymerizable reactive group at one end can be preferably used. Among them, monomer S1 having a structure that has a polymerizable reactive group at one end and does not have a functional group that causes a crosslinking reaction with the base polymer (eg acrylic polymer) of the pressure-sensitive adhesive composition to which the leveling agent is blended at the other end is preferable. can be employed Examples of commercially available products include single-end reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (for example, product numbers such as X-22-174ASX, X-22-2426, X-22-2475, and KF-2012). have. Monomer S1 can be used individually by 1 type or in combination of 2 or more types.

The functional group equivalent of monomer S1 may be about 100 g/mol to 30000 g/mol, for example. In some preferred aspects, the functional group equivalent weight may be, for example, 500 g/mol or more, 800 g/mol or more, 1500 g/mol or more, or 2000 g/mol or more. In addition, the functional group equivalent may be, for example, 20000 g/mol or less, less than 10000 g/mol, 7000 g/mol or less, or 5500 g/mol or less. When the functional group equivalent of monomer S1 is within the above range, a favorable leveling effect is likely to be exhibited.

In the case of using two or more types of monomers having different functional group equivalents as the monomer S1, the functional group equivalent of the monomer S1 can be the sum of the products of the functional group equivalents of each type of monomer and the weight fraction of the monomer.

Here, "functional group equivalent" means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group. Regarding the notational unit g/mol, it is converted to 1 mol of the functional group. The functional group equivalent of monomer S1 can be calculated, for example, from the spectral intensity of ¹ H-NMR (proton NMR) based on nuclear magnetic resonance (NMR). Calculation of the functional group equivalent (g/mol) of monomer S1 based on the spectrum intensity of ¹ H-NMR is based on a general structural analysis method related to ¹ H-NMR spectrum analysis, and, if necessary, is described in Japanese Patent No. 5951153. can be done with reference to In the functional group equivalent of monomer S1, the functional group means a polymerizable functional group (for example, an ethylenically unsaturated group such as a (meth)acryloyl group, a vinyl group, or an allyl group).

The content of the monomer S1 in the monomer raw material B can be an appropriate value within a range in which a desired effect is exhibited using the monomer S1, and is not limited to a specific range. In some aspects, the content of the monomer S1 in the monomer raw material B may be, for example, 5 to 60% by weight, 10 to 50% by weight, or 15 to 40% by weight.

The monomer raw material B contains, in addition to monomer S1, an acrylic monomer copolymerizable with monomer S1. Thereby, the compatibility of the polymer (B) in the pressure-sensitive adhesive layer can be improved. Examples of the acrylic monomer that can be used for the monomer raw material B include acrylic acid alkyl esters. "Alkyl" here refers to a chain (including straight-chain and branched-chain) alkyl (group), and does not contain an alicyclic hydrocarbon group described later. In some embodiments, the monomer raw material B is (meth)acrylic acid C _4-12 alkyl ester (preferably (meth)acrylic acid C _4-10 alkyl ester, for example (meth)acrylic acid C _6-10 alkyl ester ) may contain at least one of them. In some other aspects, the monomer raw material B is methacrylic acid C _1-18 alkyl ester (preferably methacrylic acid C _1-14 alkyl ester, for example methacrylic acid C _1-10 alkyl ester) It may contain at least 1 type. The monomer raw material B is an acrylic monomer, for example, one or two or more selected from methyl methacrylate (MMA), n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (2EHMA). can include

Other examples of the acrylic monomer include (meth)acrylic acid esters having an alicyclic hydrocarbon group. For example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, etc. can be used It is not necessary to use a (meth)acrylic acid ester having an alicyclic hydrocarbon group.

The content of the alkyl (meth)acrylic acid ester and the (meth)acrylic acid ester having an alicyclic hydrocarbon group in the monomer raw material B may be, for example, 10% by weight or more and 95% by weight or less, and 20% by weight or more and 95% by weight. It may be below, 30 weight% or more and 90 weight% or less may be sufficient, 40 weight% or more and 90 weight% or less may be sufficient, and 50 weight% or more and 85 weight% or less may be sufficient.

As other examples of monomers that can be included in the monomer raw material B together with monomer S1, as monomers that can be used for acrylic polymers, the carboxy group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, and cyano group-containing monomers exemplified above Monomer, isocyanate group-containing monomer, amide group-containing monomer, monomer having a nitrogen atom-containing ring, (meth)acrylic acid aminoalkyls, vinyl esters, vinyl ethers, olefins, (meth)acrylic acid esters having an aromatic hydrocarbon group, halogen An atom-containing (meth)acrylate etc. are mentioned.

The Mw of the polymer (B) may be, for example, 5,000 or more, preferably 10,000 or more, and may be 15,000 or more. Further, the Mw of the polymer (B) may be, for example, 200,000 or less, preferably 100,000 or less, 50,000 or less, or 30,000 or less. By setting the Mw of the polymer (B) in an appropriate range, suitable compatibility and leveling properties can be exhibited.

Polymer (B) can be produced, for example, by polymerizing the above-mentioned monomers by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or photopolymerization.

In order to adjust the molecular weight of polymer (B), a chain transfer agent can be used as needed. Examples of the chain transfer agent to be used include compounds having a mercapto group such as t-dodecylmercaptan, mercaptoethanol, and α-thioglycerol; thioglycolic acid esters such as thioglycolic acid and methyl thioglycolate; α-methylstyrene dimer; etc. can be mentioned. The amount of the chain transfer agent used is not particularly limited and can be appropriately set so as to obtain a polymer (B) having a desired molecular weight. In some embodiments, the amount of chain transfer agent used per 100 parts by weight of monomers may be, for example, 0.1 to 5 parts by weight, 0.2 to 3 parts by weight, or 0.5 to 2 parts by weight.

The amount of polymer (B) used per 100 parts by weight of the base polymer (eg, acrylic polymer) can be, for example, 0.001 part by weight or more, and may be 0.01 part by weight or more from the viewpoint of obtaining a higher use effect. , It is good also as 0.03 part by weight or more. In addition, the amount of the polymer (B) used may be, for example, 3 parts by weight or less, and from the viewpoint of reducing the effect on the refractive index, it is appropriate to be 1 part by weight or less, 0.5 parts by weight or less, or 0.1 parts by weight. may be below.

(inorganic particles)

The technique disclosed herein can be preferably carried out in an aspect that does not substantially use inorganic particles as a refractive index improver. However, in some aspects, the use of inorganic particles as the refractive index improver may be permitted as long as the application effect of the technique disclosed herein is not significantly impaired. Examples of inorganic particles that can be used as the refractive index improver include titania (titanium oxide, TiO ₂ ), zirconia (zirconium oxide, ZrO ₂ ), aluminum oxide, zinc oxide, tin oxide, copper oxide, barium titanate, niobium oxide (Nb ₂ O ₅ etc.) or the like), and inorganic particles composed of inorganic oxides (specifically, metal oxides). The average particle diameter of the inorganic particles (referring to a 50% volume average particle diameter based on the laser scattering/diffraction method) can be selected from, for example, a range of about 10 nm to 100 nm. In addition, the refractive index of the inorganic particles was measured using a commercially available spectroscopic ellipsometer for a monolayer film (with a film thickness capable of measuring the refractive index) of the material constituting the inorganic particles, measured at a wavelength of 589 nm and a measurement temperature of 23 It is measured under conditions of ℃. As a spectroscopic ellipsometer, a product name "EC-400" (made by JA. Woolam) or its equivalent is used, for example. In the case of using inorganic particles as the refractive index improver, the amount used is preferably less than 5 parts by weight, more preferably less than 1 part by weight, based on 100 parts by weight of the base polymer. In the aspect using the additive (H _RO ), the amount of the inorganic particles used is preferably 2 times or less, and is 1 time or less or 0.5 times or less, based on weight, of the amount of the additive (H _RO ) used. more preferable

(crosslinking agent)

In the technique disclosed herein, the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer may contain a crosslinking agent as necessary for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive. As the crosslinking agent, crosslinking agents known in the field of pressure-sensitive adhesives such as isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, melamine resins, and metal chelate crosslinking agents can be used. Among them, an isocyanate-based crosslinking agent can be preferably employed. Other examples of the crosslinking agent include monomers having two or more ethylenically unsaturated groups in one molecule, that is, polyfunctional monomers. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

As the isocyanate-based crosslinking agent, a bifunctional or higher functional isocyanate compound can be used, and examples thereof include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), and 1,3-bis(isocyanatomethyl)cyclohexane; aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate (XDI); modified polyisocyanate obtained by modifying the isocyanate compound with an allophanate bond, a biuret bond, an isocyanurate bond, a uretdione bond, a urea bond, a carbodiimide bond, a uretonimine bond, an oxadiazinetrione bond, or the like; etc. can be mentioned. As an example of a commercial item, the trade name Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, Takeda Yakuhin Kogyo Co., Ltd.), Smidur T80, Smidur L, Desmodur N3400 (above, Sumika Bayer Urethane Co., Ltd.), Milionate MR, Milionate MT, Coronate L, Coronate HL, Coronate HX (above, manufactured by Tosoh Corporation), etc. are mentioned. An isocyanate compound can be used individually by 1 type or in combination of 2 or more types. A bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound may be used together.

As an epoxy crosslinking agent, for example, bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6 -hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N', N'-tetraglycidyl-m-xylylenediamine and 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di( meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexane Dioldi(meth)acrylate, 1,12-dodecanedioldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate, allyl(meth)acrylate, vinyl (meth)acrylate, divinylbenzene, bisphenoxyethanol fluorenedi(meth)acrylate, bisphenol A di(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, butyldiol (meth)acrylate, ) acrylate, hexyldioldi(meth)acrylate, etc. are mentioned. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

The amount used in the case of using a crosslinking agent (which may be a polyfunctional monomer) is not particularly limited, and can be, for example, in the range of about 0.001 part by weight to about 5.0 parts by weight with respect to 100 parts by weight of the base polymer. . From the viewpoint of improving the flexibility of the pressure-sensitive adhesive, in some embodiments, the amount of the crosslinking agent relative to 100 parts by weight of the base polymer is preferably 3.0 parts by weight or less, more preferably 2.0 parts by weight or less, even if it is 1.0 parts by weight or less. It may be 0.5 parts by weight or less, or 0.2 parts by weight or less. Further, from the viewpoint of appropriately exhibiting the effect of using the crosslinking agent, in some embodiments, the amount of the crosslinking agent relative to 100 parts by weight of the base polymer may be, for example, 0.005 parts by weight or more, or 0.01 parts by weight or more, 0.05 part by weight or more may be sufficient, and 0.08 part by weight or more may be sufficient.

In order to advance a crosslinking reaction more effectively, you may use a crosslinking catalyst. Examples of the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, butyl tin oxide, and dioctyl tin dilaurate. Among them, tin-based crosslinking catalysts such as dioctyltin dilaurate are preferred. The amount of the crosslinking catalyst used is not particularly limited. The amount of the crosslinking catalyst relative to 100 parts by weight of the base polymer may be, for example, approximately 0.0001 part by weight or more and 1 part by weight or less, in consideration of the balance between the speed of the crosslinking reaction rate and the length of the pot life of the pressure-sensitive adhesive composition. , It is preferable to set it as the range of 0.001 weight part or more and 0.5 weight part or less.

The pressure-sensitive adhesive composition may contain a compound that generates keto-enol tautomerism as a crosslinking retardant. Thereby, the effect of extending the pot life of the pressure-sensitive adhesive composition can be realized. For example, in the pressure-sensitive adhesive composition containing an isocyanate-based crosslinking agent, a compound that generates keto-enol tautomerism can be preferably used. As the compound generating keto-enol tautomerism, various β-dicarbonyl compounds can be used. For example, β-diketones (acetylacetone, 2,4-hexanedione, etc.) and acetoacetate esters (methyl acetoacetate, ethyl acetoacetate, etc.) can be preferably employed. Compounds that generate keto-enol tautomerism can be used alone or in combination of two or more. The amount of the compound that generates keto-enol tautomerism can be, for example, 0.1 part by weight or more and 20 parts by weight or less, or 0.5 part by weight or more and 10 parts by weight or less, based on 100 parts by weight of the base polymer. It is good also considering it as 5 parts weight or less by weight part or more.

(tackifier)

The pressure-sensitive adhesive layer in the technique disclosed herein may contain a tackifier. As the tackifier, rosin-based tackifying resin, terpene-based tackifying resin, phenol-based tackifying resin, hydrocarbon-based tackifying resin, ketone-based tackifying resin, polyamide-based tackifying resin, epoxy-based tackifying resin, elastomer-based Well-known tackifying resins, such as tackifying resin, can be used. These can be used individually by 1 type or in combination of 2 or more types. The amount of the tackifying resin used is not particularly limited, and can be set so that appropriate adhesion performance is exhibited depending on the purpose or use. In some embodiments, from the viewpoint of refractive index and transparency, the amount of the tackifier used is preferably 30 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the base polymer of the pressure-sensitive adhesive layer. , It is more preferable to set it as 5 parts by weight or less. The technique disclosed herein can be preferably carried out in an aspect without using a tackifier.

(other additives)

In the technique disclosed herein, the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer may contain a plasticizer, a softener, a colorant, an antistatic agent, an antiaging agent, an ultraviolet absorber, an antioxidant, Known additives that can be used in the pressure-sensitive adhesive composition, such as light stabilizers and preservatives, may be included as necessary. Regarding these various additives, conventionally known ones can be used by conventional methods, and since they do not particularly characterize the present invention, detailed descriptions are omitted.

<Preparation of pressure-sensitive adhesive layer>

In the technology disclosed herein, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer (which may be a high refractive index pressure-sensitive adhesive layer and/or a low-refractive index pressure-sensitive adhesive layer. The same applies hereinafter) is a solvent type, an active energy ray curing type, a water dispersion type, a hot melt type, etc. It may be a pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition in the form of drying, crosslinking, polymerization, cooling, or the like, that is, a cured product of the pressure-sensitive adhesive composition. As for the curing means (for example, drying, crosslinking, polymerization, cooling, etc.) of the pressure-sensitive adhesive composition, only one type may be applied, or two or more types may be applied simultaneously or in multiple steps. In the solvent-type pressure-sensitive adhesive composition, the pressure-sensitive adhesive can be formed by drying (preferably, further crosslinking) the composition typically. In an active energy ray-curable pressure-sensitive adhesive composition, a pressure-sensitive adhesive is typically formed by irradiating an active energy ray to advance a polymerization reaction and/or a crosslinking reaction. What is necessary is just to irradiate an active energy ray after drying, when it is necessary to dry with an active energy ray-curable adhesive composition.

The pressure-sensitive adhesive layer in the technique disclosed herein can be formed by applying (for example, applying) an pressure-sensitive adhesive composition to an appropriate surface and then curing the composition. Application of the pressure-sensitive adhesive composition can be performed using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater, for example.

The pressure-sensitive adhesive layer in the technique disclosed herein may be a pressure-sensitive adhesive layer having post-curing properties or may be a pressure-sensitive adhesive layer having no post-curing properties. Here, the pressure-sensitive adhesive layer having post-curing properties refers to a pressure-sensitive adhesive layer that can be further cured by irradiation with heat or active energy rays (for example, ultraviolet rays). Examples of the pressure-sensitive adhesive layer having post-curing properties include a pressure-sensitive adhesive layer having an unreacted ethylenically unsaturated group in the side chain of the base polymer and a pressure-sensitive adhesive layer containing an unreacted polyfunctional monomer. In some aspects, it is preferable that the pressure-sensitive adhesive layer does not have post-curing properties. Since the pressure-sensitive adhesive layer without post-curing property does not cause dimensional change accompanying the post-curing reaction (that is, has good dimensional stability), it is easy to suppress warpage of the pressure-sensitive adhesive layer or the adherend to which the pressure-sensitive adhesive layer is attached. The fact that dimensional change (for example, curing shrinkage) due to post-curing does not occur can be advantageous also from the viewpoint of suppressing optical distortion of the pressure-sensitive adhesive layer.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, and can be, for example, 3 μm or more, and is preferably 5 μm or more. According to the adhesive layer with a thickness of 5 micrometers or more, favorable adhesive properties are easy to be obtained. In addition, a pressure-sensitive adhesive layer having such a thickness absorbs unevenness that may exist on the surface of an adherend and is easily bonded to the adherend with good adhesion. The thickness of the pressure-sensitive adhesive layer (for example, the thickness of the high-refractive-index pressure-sensitive adhesive layer) of 5 μm or more is preferable also from the viewpoint of preventing coloration and color unevenness due to light interference. In some aspects, the thickness of the pressure-sensitive adhesive layer may be 10 μm or more, 20 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, or 85 μm or more. In some embodiments, the pressure-sensitive adhesive layer may have a thickness of, for example, 300 μm or less, 250 μm or less, 200 μm or less, 150 μm or less, or 120 μm or less. A thickness of the pressure-sensitive adhesive layer that is not too large can be advantageous from the viewpoint of reducing the thickness of the laminated sheet or light-emitting device including the pressure-sensitive adhesive layer. The technology disclosed herein can be preferably implemented in an aspect in which the thickness of the pressure-sensitive adhesive layer is in the range of, for example, 3 μm to 200 μm (more preferably 5 μm to 100 μm).

In some aspects, the thickness of the pressure-sensitive adhesive layer described above can be applied to at least the thickness T ₁ of the high-refractive-index pressure-sensitive adhesive layer. The thickness T ₂ of the low refractive index pressure sensitive adhesive layer can also be selected from the same range. The thickness T ₁ of the high refractive index adhesive layer and the thickness T ₂ of the low refractive index adhesive layer may be about the same or different. The ratio of the thickness T ₁ of the high refractive index adhesive layer to the thickness T ₂ of the low refractive index adhesive layer (T ₁ /T ₂ ) may be, for example, 0.1 or more, 0.3 or more, 0.5 or more, or 0.8 or more. , 1.2 or more may be sufficient, and 1.5 or more may be sufficient. In addition, the ratio (T ₁ /T ₂ ) may be, for example, 20 or less, 10 or less, 5 or less, or 3 or less. In some aspects, the ratio (T ₁ /T ₂ ) may be less than 2, less than 1.5, or less than 1.

As a method for obtaining a structure (laminated sheet) in which a low refractive index adhesive layer and a high refractive index layer (typically, a high refractive index adhesive layer) are laminated, on a release surface (for example, a release surface of a release liner) A method of forming a high refractive index adhesive layer and a low refractive index adhesive layer, respectively, and bonding them, a method of bonding a low refractive index adhesive layer formed on a peelable surface to a non-adhesive high refractive index layer, and a low refractive index adhesive layer A method of applying a pressure-sensitive adhesive composition for formation on a high refractive index layer and curing it, conversely, a method of applying a composition for forming a high refractive index layer on a low-refractive index pressure-sensitive adhesive layer and curing it, etc. can be employed, but are not limited thereto. don't When bonding a high-refractive-index layer and a low-refractive-index adhesive layer, if necessary, you may perform the process of promoting adhesion of these layers. For example, although autoclave treatment, roll press treatment, etc. can be performed, it is not limited to these.

(peel strength)

In some embodiments, the peel strength of the pressure-sensitive adhesive layer disclosed herein to the glass plate is suitably approximately 1.0 N/25 mm or more (for example, 1.5 N/25 mm or more), preferably 2 N/25 mm or more, more preferably 3 N/25 mm or more, may be 4 N/25 mm or more, may be 6 N/25 mm or more, may be 8 N/25 mm or more, may be 10 N/25 mm or more, may be 12 N/25 mm or more It can be more than that. The upper limit of the peel strength is not particularly limited, and may be, for example, 30 N/25 mm or less, 25 N/25 mm or less, or 20 N/25 mm or less.

Here, the peel strength is measured by bonding to an alkali glass plate as an adherend, leaving it for 30 minutes in an environment of 23°C and 50% RH, and then putting it into a pressure defoaming device (autoclave) under conditions of a temperature of 50°C and a pressure of 0.5 MPa. After performing an autoclave treatment for 30 minutes and leaving it to stand for 24 hours in an atmosphere of 23 ° C. and 50% RH, it is understood by measuring the 180 ° peel adhesive force under the conditions of a peel angle of 180 degrees and a tensile speed of 300 mm / min. In the measurement, if necessary, it can be reinforced by attaching an appropriate wiring material (for example, a polyethylene terephthalate (PET) film having a thickness of about 25 µm to about 50 µm) to the measurement target. Peel strength can be measured more specifically according to the method described in the Example mentioned later.

When the low-refractive-index pressure-sensitive adhesive layer disclosed herein is laminated with the high-refractive-index pressure-sensitive adhesive layer to form a laminated sheet in the form of a double-sided pressure-sensitive adhesive sheet having a first adhesive surface and a second adhesive surface, in some embodiments, The peel strength described above is preferably applied to at least the second adhesive face (adhesive face composed of the low refractive index adhesive layer), more preferably applied to both the first adhesive face and the second adhesive face. The peel strength of the first adhesive surface to the glass plate and the peel strength of the second adhesive surface to the glass may be the same or different.

<Support Substrate>

The low-refractive-index pressure-sensitive adhesive disclosed herein can be used in the form of a pressure-sensitive adhesive sheet comprising a base material including a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive and a supporting base material.

The material of the supporting base material is not particularly limited and can be appropriately selected according to the purpose of use or the mode of use. As a non-limiting example of the base material that can be used, a polyolefin film mainly composed of polyolefin such as polypropylene (PP) or ethylene-propylene copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene plastic films such as a polyester film containing polyester such as phthalate (PEN) as a main component and a polyvinyl chloride film containing polyvinyl chloride as a main component; foam sheets made of foams such as polyurethane foam, polyethylene (PE) foam, and polychloroprene foam; woven fabrics and non-woven fabrics of various fibrous materials (natural fibers such as hemp and cotton, synthetic fibers such as polyester and vinylon, and semi-synthetic fibers such as acetate) alone or blended; Paper, such as washi paper, fine paper, kraft paper, and crepe paper; metal foils such as aluminum foil and copper foil; etc. can be mentioned. A base material having a structure in which these are compounded may be used. Examples of such a composite substrate include, for example, a substrate having a structure in which metal foil and the aforementioned plastic film are laminated, and a plastic substrate reinforced with inorganic fibers such as glass cloth.

In some embodiments, various film substrates can be preferably used. The film substrate may be a porous substrate, such as a foam film or a non-woven fabric sheet, or a non-porous substrate, or a substrate having a structure in which a porous layer and a non-porous layer are laminated. In some aspects, as the film base material, one containing an independently shape-retainable (self-supporting or independent) resin film as a base film can be preferably used. Here, the "resin film" has a non-porous structure and typically means a resin film substantially free of air bubbles (voidless). Therefore, the resin film is a concept different from a foam film or a nonwoven fabric. As the resin film, one capable of independently maintaining its shape (self-supporting or independent) can be preferably used. The resin film may have a single-layer structure or a multilayer structure of two or more layers (for example, a three-layer structure).

As a material constituting the resin film, for example, a polyester-based resin containing polyester as a main component, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyethylene (PE) , polyolefin resins mainly composed of polyolefins such as polypropylene (PP), ethylene-propylene copolymers, and ethylene-butene copolymers, cellulose resins such as triacetyl cellulose, acetate-based resins, polysulfone-based resins, and polyethersulfone-based resins. Resin, polycarbonate-based resin, polyamide (PA)-based resin such as nylon 6, nylon 66, partially aromatic polyamide, polyimide (PI)-based resin, transparent polyimide resin, polyamideimide (PAI), polyimide Ether ether ketone (PEEK), polyether sulfone (PES), cyclic polyolefin resins such as norbornene resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, polyarylate resin, polyphenylene sulfide (PPS) resin, polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), and fluorine-based resins such as polytetrafluoroethylene (PTFE) and fluorinated polyimide.

The resin film may be formed using a resin material containing one type of such resin alone, or may be formed using a resin material in which two or more types are blended. The resin film may be unstretched or stretched (for example, uniaxial stretching or biaxial stretching). For example, PET film, PBT film, PEN film, unstretched polypropylene (CPP) film, biaxially oriented polypropylene (OPP) film, low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, PP/ A PE blend film or the like can be preferably used. Examples of preferable resin films from the viewpoint of strength and dimensional stability include PET film, PEN film, PPS film and PEEK film. From the standpoint of availability, etc., a PET film and a PPS film are particularly preferred, and among these, a PET film is preferred.

In the resin film, known additives such as light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, slip agents, and antiblocking agents are necessary to the extent that the effects of the present invention are not significantly impaired. can be combined according to The blending amount of the additive is not particularly limited and can be appropriately set according to the use of the pressure-sensitive adhesive sheet.

The manufacturing method of a resin film is not specifically limited. For example, conventionally known general resin film forming methods such as extrusion molding, inflation molding, T-die cast molding, and calender roll molding can be appropriately employed.

The substrate may be substantially constituted of such a base film. Alternatively, the substrate may include an auxiliary layer in addition to the base film. Examples of the auxiliary layer include an optical property adjustment layer (e.g., a coloring layer, an antireflection layer), a printed layer for imparting a desired appearance to the base material, a laminate layer, an antistatic layer, an undercoat layer, and a surface treatment layer such as a release layer. can be heard

In some aspects, as the support substrate, a substrate having light transmission properties (hereinafter, also referred to as a light transmission substrate) can be preferably employed. This makes it possible to construct a pressure-sensitive adhesive sheet comprising a base material having light transmission properties. The total light transmittance of the light transmissive substrate may be, for example, greater than 50% or greater than 70%. In some preferred aspects, the total light transmittance of the supporting substrate is 80% or more, more preferably 90% or more, and may be 95% or more (for example, 95 to 100%). The total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136:2000. As the transmittance meter, a trade name "HAZEMETER HM-150" manufactured by Murakami Shikisai Kijutsu Genkyujo Co., Ltd. or an equivalent thereof is used. A preferable example of the light-transmitting substrate is a resin film having light-transmitting properties. An optical film may be sufficient as the said light transmissive base material.

The thickness of the substrate is not particularly limited, and can be selected according to the purpose of use or the mode of use. The thickness of the substrate may be, for example, 500 μm or less, preferably 300 μm or less from the viewpoint of handleability and workability, 150 μm or less, 100 μm or less, 50 μm or less, or 25 μm or less. , and may be 10 μm or less. When the thickness of the substrate is reduced, the followability to the surface shape of the adherend tends to be improved. Further, from the viewpoint of handleability, processability, etc., the thickness of the substrate may be, for example, 2 μm or more, 10 μm or more, or 25 μm or more.

Conventionally, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, formation of an undercoating layer by application of an undercoating agent (primer), etc. A known surface treatment may be performed. Such surface treatment may be a treatment for improving anchoring properties of the pressure-sensitive adhesive layer to the base material. The composition of the primer used for formation of the undercoat layer is not particularly limited, and can be appropriately selected from known ones. The thickness of the undercoating layer is not particularly limited, but is usually about 0.01 μm to 1 μm, and preferably about 0.1 μm to 1 μm. Other treatments that can be applied to the base material as needed include antistatic layer formation treatment, colored layer formation treatment, printing treatment, and the like. These treatments can be applied alone or in combination.

In the technology disclosed herein, when the low-refractive-index pressure-sensitive adhesive layer constitutes a pressure-sensitive adhesive sheet including a base material, the thickness of the pressure-sensitive adhesive sheet may be, for example, 1000 μm or less, 350 μm or less, or 200 μm or less. , may be 120 μm or less, may be 75 μm or less, or may be 50 μm or less. Further, the thickness of the pressure-sensitive adhesive sheet may be, for example, 10 μm or more, 25 μm or more, 80 μm or more, or 130 μm or more from the viewpoint of handleability or the like.

In addition, the thickness of an adhesive sheet means the thickness of the part affixed to the adherend. For example, in the non-material double-sided pressure-sensitive adhesive sheet 2 having the configuration shown in Fig. 2, the pressure-sensitive adhesive layer covers from the first surface (first adhesive surface) 10A to the second surface (second adhesive surface) 10B. The thickness is indicated, and the thickness of the release liners 31 and 32 is not included.

<Adhesive Sheet>

The low-refractive-index pressure-sensitive adhesive disclosed herein includes a pressure-sensitive adhesive layer (low-refractive-index pressure-sensitive adhesive layer) formed of the pressure-sensitive adhesive, and may further include other layers (high-refractive-index pressure-sensitive adhesive layer, support substrate, etc.) It can be used in the form of a pressure-sensitive adhesive sheet. have.

(total light transmittance)

In the technique disclosed herein, the total light transmittance of the low-refractive-index pressure-sensitive adhesive layer is suitably 86% or higher, preferably 88% or higher, more preferably 90% or higher (for example, greater than 90.0%), and 90.5 % or more may be sufficient, 93% or more may be sufficient, or 95% or more may be sufficient. The upper limit of the total light transmittance is, theoretically, a value obtained by subtracting light loss (Fresnel loss) due to reflection occurring at the air interface from 100%, and may be approximately 98% or less or approximately 96% or less in practical use. , may be approximately 95% or less. In some aspects, considering the refractive index and adhesive properties, the total light transmittance of the low-refractive-index pressure-sensitive adhesive layer may be approximately 94% or less, approximately 93% or less, or approximately 92% or less. The total light transmittance is measured using a commercially available transmittance meter based on JIS K 7136:2000. As the transmittance meter, a trade name "HAZEMETER HM-150" manufactured by Murakami Shikisai Kijutsu Genkyujo Co., Ltd. or an equivalent thereof is used. More specifically, for example, the total light transmittance of the low-refractive-index pressure-sensitive adhesive layer can be measured according to Examples described later. The total light transmittance of the low-refractive-index pressure-sensitive adhesive layer can be adjusted by, for example, selection of the composition or thickness of the low-refractive-index pressure-sensitive adhesive layer.

The above description regarding the total light transmittance of the low refractive index pressure sensitive adhesive layer is the total light transmittance of the pressure sensitive adhesive sheet including the low refractive index pressure sensitive adhesive layer and the supporting base material, the total light transmittance of the high refractive index layer, the low refractive index pressure sensitive adhesive layer and the high refractive index layer (typically high refractive index layer). It can also be applied to the total light transmittance of a laminated sheet (pressure-sensitive adhesive sheet) including a refractive index pressure-sensitive adhesive layer).

(Haze value)

The haze value of the low refractive index adhesive layer is suitably 3.0% or less, preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.9% or less. The reason why the haze value of the low refractive index adhesive layer is low is for applications requiring high light transmittance (for example, optical applications) or for applications requiring good visibility of an adherend through the low refractive index adhesive layer. It is advantageous. In some aspects, the haze value of the low refractive index adhesive layer may be 0.8% or less, 0.5% or less, or 0.3% or less. The lower limit of the haze value of the low-refractive-index pressure-sensitive adhesive layer is not particularly limited, and from the viewpoint of improving transparency, the lower the haze value, the better. On the other hand, in some aspects, in consideration of the refractive index and adhesive properties, the haze value of the low refractive index adhesive layer may be, for example, 0.05% or more, 0.1% or more, 0.2% or more, or 0.3% or more. and may be 0.4% or more.

The above description of the haze value of the low refractive index pressure sensitive adhesive layer is the haze value of the pressure sensitive adhesive sheet comprising the low refractive index pressure sensitive adhesive layer and the supporting base material, the haze value of the high refractive index layer, the low refractive index pressure sensitive adhesive layer and the high refractive index layer (typically high refractive index layer). It can also be applied to the haze value of the laminated sheet (pressure-sensitive adhesive sheet) including the refractive index pressure-sensitive adhesive layer).

Here, "haze value" refers to the ratio of diffused transmitted light to total transmitted light when visible light is irradiated to a measurement object. Also called cloudiness. A haze value can be represented by the following formula.

Th(%)=Td/Tt×100

In the above formula, Th is haze value (%), Td is scattered light transmittance, and Tt is total light transmittance. The haze value can be measured according to the method described in Examples described later. The haze value of the pressure-sensitive adhesive layer can be adjusted by selection of the composition, thickness, or the like of the pressure-sensitive adhesive layer, for example.

(Surface smoothness of adhesive surface)

In some aspects, it is preferable that the surface (adhesive surface) of the pressure-sensitive adhesive layer has high surface smoothness.

For example, it is preferable that the arithmetic mean roughness Ra of the adhesive surface is limited to a predetermined value or less. A structure provided with an adhesive surface designed so that the arithmetic mean roughness Ra is low is preferable from the viewpoint of optical homogeneity. By restricting the arithmetic mean illuminance Ra, for example, in a usage mode in which light is extracted through the adhesive surface (a pressure-sensitive adhesive sheet disposed on the viewpoint side of a self-light emitting device in a light emitting device, etc.), it is due to the surface state of the pressure-sensitive adhesive layer It is possible to exert an effect of suppressing the occurrence of luminance non-uniformity. A low arithmetic average roughness Ra of the adhesive surface is advantageous for suppression of optical distortion, and suppression of optical distortion also contributes to improvement in optical homogeneity. When the PSA sheet disclosed herein is in the form of a double-sided PSA sheet having a first adhesive surface and a second adhesive surface (for example, a laminated sheet including a high refractive index PSA layer and a low refractive index PSA layer), at least It is preferable that the arithmetic average roughness Ra of the first adhesive surface is limited to a predetermined value or less, and it is more preferable that both the arithmetic average roughness Ra of both adhesive surfaces are limited to a predetermined value or less. When each adhesive face of the double-sided pressure-sensitive adhesive sheet has high surface smoothness, adhesion excellent in optical homogeneity can be preferably realized.

In some embodiments, the arithmetic average roughness Ra of the adhesive surface is preferably approximately 70 nm or less, more preferably approximately 65 nm or less, still more preferably approximately 55 nm or less, and may be less than 50 nm. , may be less than 45 nm or less than 40 nm. From the viewpoint of production efficiency and the like, in some embodiments, the arithmetic average roughness Ra of the adhesive surface may be, for example, approximately 10 nm or more, approximately 20 nm or more, or approximately 30 nm or more (for example, approximately 40 nm or more). nm or more). In the aspect in which the PSA sheet has the first adhesive surface and the second adhesive surface, the arithmetic average roughness Ra of the first adhesive surface and the arithmetic average roughness Ra of the second adhesive surface may be the same or different.

Further, for example, it is preferable that the maximum height Rz of the adhesive face is limited to a predetermined value or less. A configuration having an adhesive surface designed to have a low maximum height Rz is preferable from the viewpoint of optical homogeneity. By restricting the maximum height Rz, for example, in a usage mode in which light is taken out through the adhesive surface as described above, an effect of suppressing occurrence of luminance nonuniformity due to the surface state of the adhesive layer can be exhibited. The low maximum height Rz of the adhesive surface is also advantageous for suppression of optical distortion. When the PSA sheet disclosed herein is in the form of a double-sided PSA sheet having a first adhesive surface and a second adhesive surface, it is preferable that at least the maximum height Rz of the first adhesive surface is limited to a predetermined value or less, and both sides are adhered to each other. It is more preferable that all of the maximum heights Rz of the surfaces are limited to a predetermined value or less. When each adhesive face of the double-sided pressure-sensitive adhesive sheet has high surface smoothness, adhesion excellent in optical homogeneity can be preferably realized.

In some embodiments, the maximum height Rz of the adhesive surface is preferably about 600 nm or less, more preferably about 500 nm or less, even more preferably about 450 nm or less, and particularly preferably about 400 nm or less. It may be less than 350 nm, less than 300 nm, or less than 250 nm. From the viewpoint of production efficiency and the like, in some embodiments, the maximum height Rz of the adhesive surface may be, for example, approximately 10 nm or more, approximately 50 nm or more, approximately 100 nm or more, or approximately 200 nm or more may be continued In the aspect having the first adhesive face and the second adhesive face, the maximum height Rz of the first adhesive face and the maximum height Rz of the second adhesive face may be the same or different.

The arithmetic average roughness Ra and the maximum height Rz of the adhesive surface are measured using a non-contact type surface roughness measuring device. As a non-contact type surface roughness measuring device, a surface roughness measuring device of an optical interference method is used, and for example, a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO) or its equivalent can be used. Specifically, for example, the arithmetic mean roughness Ra and the maximum height Rz can be measured by the following measuring method or by setting measurement operation and measurement conditions so that equivalent or corresponding results are obtained with the measuring method. can

That is, in an environment of 23°C and 50% RH, the surface shape of the measurement sample is measured under the following conditions using a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO). Arithmetic surface roughness Ra is calculated from the measured data according to JIS B 0601-2001. The maximum height Rz is obtained as the sum of the height Rp of the highest peak upward from the average line of the roughness curve and the depth Rv of the deepest valley downward from the average line with respect to the data (roughness curve) obtained by the measurement. Measurements were made 5 times (i.e. N=5), and their average value was used.

The sample for measurement can be prepared, for example, by cutting the pressure-sensitive adhesive layer to be measured or the pressure-sensitive adhesive sheet containing the pressure-sensitive adhesive layer to a size of about 150 mm in length and 50 mm in width. When the adhesive face is protected by a peeling liner, the peeling liner is gently peeled off (for example, under conditions of a pulling speed of 300 mm/min and a peeling angle of 180°) to expose the adhesive face. It is preferable to measure after leaving still for about 30 minutes after exposing the adhesive surface.

[Measuring conditions]

Measuring area: 5.62 mm × 4.22 mm

(Objective lens: 2.5x, inner lens: 0.5x)

Interpretation mode:

Remove: Cylinder

Data Fill: ON (Max: 25)

Remove Spikes: ON (xRMS: 1)

Filter: OFF

The arithmetic average roughness Ra and maximum height Rz of the adhesive surface are determined by the composition and properties (viscosity, leveling properties, etc.) of the adhesive composition used for forming the adhesive layer, the properties of the surface (release surface) of the release liner that protects the adhesive surface, etc. can be regulated by

(absorption rate)

In some aspects in which the low refractive index pressure sensitive adhesive disclosed herein is used together with a high refractive index pressure sensitive adhesive layer, it is preferable that the high refractive index pressure sensitive adhesive layer has a water absorption limited to a predetermined value or less. By limiting the water absorption of the high refractive index pressure sensitive adhesive layer, the dimensional change of the high refractive index pressure sensitive adhesive layer due to fluctuations in the amount of moisture in the high refractive index pressure sensitive adhesive layer (for example, absorption and release of moisture such as moisture in the environment) tends to be suppressed. . In this way, the high refractive index pressure sensitive adhesive layer or the high refractive index pressure sensitive adhesive layer due to mismatch in dimensional change between the high refractive index pressure sensitive adhesive layer and the layer adjacent to the pressure sensitive adhesive layer (which may be a low refractive index pressure sensitive adhesive layer, a supporting substrate, a release liner, an adherend, etc.) It is possible to suppress the warpage of the optical laminated body to do. It is preferable also from the viewpoint of keeping the flatness, transparency, refractive index, etc. of a high refractive index adhesive layer constant that the fluctuation|variation of the water content in a high refractive index adhesive layer can be suppressed. In addition, since the high refractive index pressure-sensitive adhesive layer with low water absorption is difficult to absorb moisture, it is suitable as a component of a product or a member containing an element vulnerable to moisture, such as an organic EL element, for example.

In some embodiments, the water absorption of the high refractive index pressure-sensitive adhesive layer is suitably approximately 1.0% or less, preferably 0.7% or less, more preferably 0.5% or less (eg less than 0.5%), and 0.4% or less. may be present, may be 0.3% or less, or may be 0.2% or less. The lower limit of the water absorption of the high refractive index pressure-sensitive adhesive layer is not particularly limited, but from the viewpoint of practicality such as coexistence with adhesive properties, for example, it may be 0.01% or more, 0.05% or more, 0.1% or more, or 0.15%. It may be greater than or equal to 0.25%. The water absorption of the low refractive index adhesive layer may be about the same as or different from the water absorption of the high refractive index adhesive layer. From the viewpoint of obtaining a higher effect, it is more preferable that the water absorption of both the high refractive index pressure sensitive adhesive layer and the low refractive index pressure sensitive adhesive layer is limited to a predetermined value or less.

In addition, the water absorption (also referred to as water content) of the high refractive index pressure-sensitive adhesive layer is measured by the following method. The water absorption of the low refractive index pressure sensitive adhesive layer is also measured by the same method.

[Measurement of moisture content]

The pressure-sensitive adhesive layer to be evaluated was cut out to a size of 4 cm × 5 cm (area: 20 cm 2 ) together with two release liners disposed on one side and the other side, and the release liner on one side was cut out. is removed and bonded to a pre-weighed aluminum foil. Next, the peeling liner on the other side of the pressure-sensitive adhesive layer is removed, put into a constant temperature and humidity chamber at a temperature of 60°C and a relative humidity of 90%, and taken out after 72 hours. After weighing the test piece in which the adhesive layer and the aluminum foil are laminated, using a moisture meter (Mitsubishi Chemical Analytec CA-200 type) equipped with a heat vaporization device (Mitsubishi Chemical Analytec CA-200 type), Karl Fischer coulometric titration method By this, the moisture content is measured under the following conditions.

Anolyte: Aquamicron AKX (manufactured by Mitsubishi Chemical)

Catholyte: Aquamicron CXU (manufactured by Mitsubishi Chemical)

Heat vaporization temperature: 150°C

(gel fraction)

The gel fraction of the pressure-sensitive adhesive layer disclosed herein is appropriately set according to the purpose of use, the mode of use, and the like, and is not limited to a specific range. The gel fraction is, for example, about 99% or less, and about 97% or less is appropriate. From the viewpoint of making it easy to suitably achieve both low refractive index and adhesive properties, in some preferred embodiments, the gel fraction is approximately 95% or less, more preferably approximately 92% or less (for example, approximately 90% or less). can If the gel fraction is not too high, it properly follows irregularities that may exist on the surface of the adherend (for example, a concave-convex structure provided for the purpose of improving light extraction efficiency in a light emitting device) and adheres well. It is also desirable from the point of view. In some embodiments, the gel fraction may be approximately 88% or less, approximately 75% or less, or approximately 65% or less. The gel fraction is, for example, about 10% or more, preferably about 20% or more, and may be about 30% or more, from the viewpoint of imparting appropriate cohesiveness to the adhesive and appropriately expressing adhesive properties. . From the viewpoint of resistance to deformation of the pressure-sensitive adhesive layer (prevention of bubbles due to protrusion due to pressure or inclusion of foreign matter, etc.), the gel fraction is preferably about 30% or more, more preferably about 40% or more, It may be about 45% or more, about 50% or more, about 65% or more, or about 75% or more. The gel fraction of the pressure-sensitive adhesive sheet containing the high refractive index pressure-sensitive adhesive layer and the low-refractive-index pressure-sensitive adhesive layer (for example, a laminated sheet in the form of an inorganic double-sided pressure-sensitive adhesive sheet composed of a high refractive index pressure-sensitive adhesive layer and a low-refractive index pressure-sensitive adhesive layer) is also within the range exemplified above. It is preferable to The gel fraction can be adjusted by the molecular weight, molecular structure, concentration, degree of crosslinking, etc. of the base polymer. Gel fraction is measured by the following method.

[Measurement of Gel Fraction]

A predetermined amount of the pressure-sensitive adhesive sample (weight Wg ₁ ) was wrapped in a drawstring bag with a porous polytetrafluoroethylene film (weight Wg ₂ ) having an average pore diameter of 0.2 μm, and the inlet was tied with a twine (weight Wg ₃ ). As the porous polytetrafluoroethylene (PTFE) membrane, a trade name "Nitoflon (registered trademark) NTF1122" available from Nitto Denko (average pore diameter: 0.2 µm, porosity: 75%, thickness: 85 µm) or an equivalent thereof is used. do.

The wrapped material is immersed in a sufficient amount of ethyl acetate, maintained at room temperature (typically 23° C.) for 7 days to elute only the sol content in the adhesive to the outside of the film, and then the wrapped material is taken out and the ethyl acetate adhering to the outer surface is obtained. is wiped off, and the wrapped thing is dried at 130°C for 2 hours, and the weight (Wg ₄ ) of the wrapped thing is measured. The gel fraction of the pressure-sensitive adhesive layer is obtained by substituting each value into the following formula.

Gel fraction (%)=[(Wg ₄ -Wg ₂ -Wg ₃ )/Wg ₁ ]×100

The gel fraction of the high refractive index adhesive layer and the gel fraction of the low refractive index adhesive layer may be about the same or different. In some aspects, the gel fraction of the low refractive index adhesive layer can be made lower than the gel fraction of the high refractive index adhesive layer. According to this structure, the softness as a whole is easy to be improved by the contribution of the low-refractive-index pressure-sensitive adhesive layer having a relatively low gel fraction. This makes it possible to achieve both high refractive index and flexibility in a well-balanced manner.

In some aspects of the technology disclosed herein, the tan δ peak temperature of the pressure-sensitive adhesive constituting the high refractive index pressure-sensitive adhesive layer is preferably approximately -50°C or higher, and is preferably approximately 50°C or lower. Here, the tan δ (loss tangent) of the pressure-sensitive adhesive refers to the ratio of the loss modulus G" to the storage modulus G' of the pressure-sensitive adhesive. That is, tan δ = G"/G'. The tanδ of the pressure-sensitive adhesive was measured by inserting a disk-shaped pressure-sensitive adhesive sample having a thickness of about 2 mm and a diameter of 7.9 mm between parallel plates, and applying shear strain at a frequency of 1 Hz using a viscoelasticity tester in a measurement temperature range of -60°C to 60°C. , under the conditions of a temperature increase rate of 5 ° C./min, the temperature dispersion test of the pressure-sensitive adhesive was conducted in shear mode, and from the storage modulus G' (Pa) and loss modulus G" (Pa) at that time, the following formula: tanδ = G" / It is obtained by G';. From the transition of tan δ in the above temperature range, the peak temperature of tan δ of the pressure-sensitive adhesive (hereinafter sometimes referred to as Tpeak) is obtained. As the viscoelasticity tester, ARES manufactured by TA Instruments or an equivalent product thereof can be used.

In some embodiments, the Tpeak of the high refractive index pressure-sensitive adhesive layer is advantageously 45 ° C. or less or 35 ° C. or less, preferably 30 ° C. or less (eg 25 ° C. or less), may be 20 ° C. or less, 15 ° C. may be below. A pressure-sensitive adhesive having a lower Tpeak tends to be easier to obtain good initial adhesion and adhesion in the room temperature region. On the other hand, a pressure-sensitive adhesive having a Tpeak that is not too low is preferable from the viewpoint of imparting appropriate cohesiveness to the pressure-sensitive adhesive, and tends to be compatible with high refractive index. From this point of view, in some embodiments, the Tpeak of the pressure-sensitive adhesive may be, for example, -40°C or higher, -30°C or higher, -20°C or higher, -5°C or higher, or 5°C or higher. It may be, it may be 15 ° C. or higher, and further 25 ° C. or higher may be sufficient. A pressure-sensitive adhesive having a relatively high Tpeak can be preferably used in an aspect in which one or both of the pressure-sensitive adhesive and the adherend are heated to a temperature slightly higher than room temperature, as needed, when the pressure-sensitive adhesive has a relatively high Tpeak. The Tpeak of the pressure-sensitive adhesive can be adjusted by selecting the composition of the pressure-sensitive adhesive (for example, selecting the composition of monomer components constituting the base polymer, whether or not a refractive index improver or plasticizing material is used, the type and amount used), and the like.

Tpeak of the above-mentioned adhesive is preferably applied to at least the high refractive index adhesive layer, and more preferably applied to both the high refractive index adhesive layer and the low adhesive refractive index layer. The Tpeak of the high refractive index adhesive layer and the Tpeak of the low adhesive refractive index layer may be the same or different.

<Laminate sheet provided with release liner>

The high-refractive-index pressure-sensitive adhesive layer and the low-refractive-index pressure-sensitive adhesive layer disclosed herein have a form in which the pressure-sensitive adhesive surface of a laminated sheet containing the high-refractive-index pressure-sensitive adhesive layer and the low-refractive index pressure-sensitive adhesive layer is brought into contact with the peelable surface of a release liner before being incorporated into a light emitting device. can take the form of an adhesive product (laminated sheet with a release liner) of Therefore, according to this specification, a laminated sheet having a release liner (adhesive product) comprising a laminated sheet of a high refractive index adhesive layer and a low refractive index adhesive layer, and a release liner having a release surface abutting the adhesive surface of the laminated sheet. is provided.

The release liner is not particularly limited, and examples thereof include a release liner having a release treatment layer on a release liner substrate such as a resin film or paper (which may be paper laminated with a resin such as polyethylene), a fluorine-based polymer ( A release liner made of a resin film formed of a low-adhesive material such as polytetrafluoroethylene or the like) or a polyolefin-based resin (polyethylene, polypropylene, or the like) can be used. The release treatment layer may be formed by surface treatment of a release liner substrate with a release treatment agent. The release treatment agent may be a known release treatment agent such as a silicone-based release treatment agent, a long-chain alkyl-based release treatment agent, a fluorine-based release treatment agent, or molybdenum (IV) sulfide. In some aspects, a release liner having a release treatment layer of a silicone-based release treatment agent can be preferably employed. The thickness and formation method of the release treatment layer are not particularly limited, and can be set so that appropriate release properties are exhibited on the surface on the adhesive side of the release liner.

In some aspects, from the viewpoint of the smoothness of the adhesive surface, etc., a release liner (hereinafter also referred to as a release film) having a release treatment layer on a resin film as a release liner substrate (hereinafter also referred to as a release film substrate) can be preferably employed. As the release film substrate, various plastic films can be used. In this specification, a plastic film is typically a non-porous sheet, and is a concept different from, for example, a non-woven fabric (ie, does not include a non-woven fabric).

Examples of the material of the plastic film include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), Polyolefin-based resins such as ethylene-propylene copolymers and ethylene-butene copolymers, cellulose resins such as triacetyl cellulose, acetate-based resins, polysulfone-based resins, polyethersulfone-based resins, polycarbonate-based resins, and polyamide-based resins Resins, polyimide resins, cyclic polyolefin resins such as norbornene resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, ethylene-vinyl acetate Copolymer resin, ethylene-vinyl alcohol copolymer resin, polyarylate type resin, polyphenylene sulfide type resin, etc. are mentioned. A release film base material formed of any one type or a mixture of two or more types of these resins can be used. Among them, as a preferred peeling film base material, a polyester-based resin film (for example, PET film) formed of a polyester-based resin is exemplified.

Any of a non-stretched film, a uniaxially stretched film, and a biaxially stretched film may be sufficient as the plastic film used as the above-mentioned peeling film base material. Further, the plastic film may have a single layer structure or a multilayer structure including two or more sublayers. Antioxidants, anti-aging agents, heat-resistant stabilizers, light stabilizers, ultraviolet absorbers, colorants such as pigments and dyes, lubricants, fillers, antistatic agents, nucleating agents, etc. Additives may be blended. In the plastic film having a multilayer structure, each additive may be incorporated in all sublayers or only in some sublayers.

In some preferred embodiments, as the release film substrate (typically a plastic film), the content of particles such as inorganic particles (eg, pigments, lubricants, fillers, etc.) in the layer on the side of the release surface is limited It can be preferably used, or one that does not substantially contain such particles. Substantially not included herein means that the amount of particles (eg inorganic particles) in the layer is less than 1% by weight, preferably less than 0.1% by weight (eg 0 to 0.01% by weight). . A peeling film provided with such a peeling film base material tends to be low in arithmetic mean roughness Ra and maximum height Rz of the peeling surface. When the release film substrate (typically a plastic film) has a multilayer structure, the particle content in the layer on the release surface side is 1/10 or less (for example, 1/10) of the particle content in layers other than the layer on the release surface side. /50 or less).

A laminated sheet comprising a release liner having a release liner on a first adhesive surface and a second adhesive surface, respectively, comprising: a release liner (hereinafter referred to as one release liner) disposed on one adhesive surface; The release liner disposed on the other adhesive surface (hereinafter, also referred to as the other release liner) may have the same material and structure, or may have a different material and structure.

The thickness of the release liner (preferably the release film) is not particularly limited, and may be, for example, about 10 µm to 500 µm. From the viewpoint of strength and dimensional stability of the release liner, the thickness of the release liner is suitably 20 μm or more, preferably 30 μm or more, may be 35 μm or more, may be 40 μm or more, or may be 45 μm or more. Further, from the standpoint of handling of the release liner (e.g. ease of winding), the thickness of the release liner is suitably 300 μm or less, preferably 250 μm or less, may be 200 μm or less, or may be 150 μm or less. and may be 130 μm or less. In some preferred embodiments, the thickness of the release liner is less than or equal to about 125 μm, less than or equal to about 115 μm, less than or equal to about 105 μm, less than or equal to about 90 μm, or less than or equal to about 70 μm. By setting the thickness of the release liner to a predetermined value or less, it is difficult to form winding marks when it is formed into a roll shape, removal from the adhesive sheet is smooth, and high surface smoothness is easily obtained on the adhesive surface after removal of the release liner.

In the laminated sheet provided with the release liner of the aspect including one release liner and the other release liner, the thicknesses of the release liners may be the same or different. In some aspects, from the viewpoint of peeling workability, etc., it is preferable that one release liner and the other release liner have different thicknesses. It is preferably approximately 1.1 times or more (for example, approximately 1.25 times or more. The upper limit is not particularly limited, but is, for example, 5 times or less) the thickness of the release liner.

(Arithmetic average roughness Ra of the surface on the adhesive surface side)

In some aspects, the release liner (preferably the release film) has an arithmetic mean roughness Ra of the surface on the adhesive surface side limited to a predetermined value or less (for example, approximately 100 nm or less, furthermore less than 50 nm), It is preferable from the viewpoint of realizing an adhesive surface having high surface smoothness. In some embodiments, the arithmetic mean roughness Ra of the surface on the adhesive side of the release liner is, for example, preferably about 30 nm or less, more preferably about 25 nm or less, may be about 20 nm or less, or about 18 nm or less. may be Further, from the viewpoint of ease of manufacture and handling of the release liner, in some embodiments, the arithmetic average roughness Ra may be, for example, approximately 5 nm or more, approximately 10 nm or more, or approximately 15 nm or more. may be continued In a laminated sheet provided with a release liner in which a release liner is disposed on the first adhesive face and the second adhesive face, respectively, it is preferable that the surfaces of both release liners on the adhesive face side satisfy the arithmetic average roughness Ra of any of the above. do. The arithmetic mean roughness Ra of the surface on the side of the adhesive side of both release liners may be the same or different.

(maximum height Rz of the surface on the adhesive surface side)

In some aspects, the release liner (preferably the release film) preferably has a maximum height Rz of 700 nm or less on the surface on the side of the adhesive surface from the viewpoint of realizing an adhesive surface having high surface smoothness. In some aspects, the maximum height Rz of the surface on the adhesive face side of the release liner is preferably approximately 600 nm or less, approximately 500 nm or less, approximately 400 nm or less, or approximately 300 nm or less. Further, from the viewpoint of ease of manufacture and handling of the release liner, in some embodiments, the maximum height Rz may be, for example, approximately 50 nm or more, approximately 80 nm or more, or approximately 100 nm or more. It may be about 200 nm or more, or about 300 nm or more. In a laminated sheet having a release liner in which release liners are disposed on the first adhesive face and the second adhesive face, respectively, it is preferable that the adhesive side surfaces of both release liners satisfy the maximum height Rz of any of the above. . The maximum height Rz of the surface on the side of the adhesive face of both release liners may be the same or different.

(Surface appearance of the back side)

The arithmetic mean roughness Ra or the maximum height Rz of the back surface (reverse surface to the pressure-sensitive adhesive layer side) of the release liner (preferably the release film) is not particularly limited. The arithmetic mean roughness Ra of the back surface of the release liner may be, for example, greater than 30 nm (for example, greater than 35 nm, further approximately 50 nm or more) from the viewpoint of productivity and the like. The maximum height Rz of the back surface of the release liner may be, for example, greater than 400 nm (eg, approximately 500 nm or more) or greater than 800 nm (eg, 1000 nm or more) from the viewpoint of productivity and the like.

The arithmetic mean roughness Ra and the maximum height Rz of the surface of the release film can be adjusted by selection of the film material, forming method, surface treatment such as release treatment, and the like. For example, adjustment of the smoothness of the layers constituting the release surface (anti-blocking layer, hard coat layer, oligomer prevention layer, etc.), reduction or non-use of filler particles in the surface layer or release film substrate (particle-free), In addition, adjustment of stretching conditions, etc. are mentioned.

The arithmetic average roughness Ra and the maximum height Rz of the surface of the release liner (preferably the release film) are measured using a non-contact type surface roughness measuring device. As a non-contact type surface roughness measuring device, a surface roughness measuring device of an optical interference method is used, and for example, a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO) or its equivalent can be used. For example, a glass plate (a soda-lime glass plate manufactured by MATSUNAMI, 1.3 mm in thickness) is bonded and fixed to the surface of the release liner on the opposite side to the measurement surface with an adhesive, and in an environment of 23°C and 50% RH, three-dimensional The surface shape can be measured using an optical profiler (trade name "NewView7300", manufactured by ZYGO).

<Use>

The pressure-sensitive adhesive disclosed herein (for example, low-refractive-index pressure-sensitive adhesive) can be bonded to various adherends and used. The constituent material of the adherend (adherent material) is not particularly limited, and examples thereof include copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, indium, zinc, etc., or among these Metal materials such as alloys containing two or more types, for example, polyimide-based resins, acrylic resins, polyethernitrile-based resins, polyethersulfone-based resins, polyester-based resins (PET-based resins, polyethylene naphthalate-based resins) etc.), polyvinyl chloride-based resins, polyphenylene sulfide-based resins, polyether ether ketone-based resins, polyamide-based resins (so-called aramid resins, etc.), polyarylate-based resins, fluorine-based resins, polycarbonate-based resins, Cellulose polymers such as acetyl cellulose and triacetyl cellulose, vinyl butyral polymers, liquid crystal polymers, various resin materials (typically plastic materials) such as carbon materials such as graphene, alumina, zirconia, titania, SiO ₂ , ITO ( metal oxides and mixtures thereof, such as indium tin oxide) and ATO (antimony-doped tin oxide), nitrides and composites thereof, such as aluminum nitride, silicon nitride, titanium nitride, gallium nitride, and indium nitride, alkali glass, alkali-free glass, quartz glass, Inorganic materials, such as borosilicate glass and sapphire glass carbon, etc. are mentioned. The pressure-sensitive adhesive disclosed herein can be used by sticking it to a member (for example, an optical member) having at least a surface composed of the above material.

The pressure-sensitive adhesive disclosed herein can be used in an adhesive mode that does not require heating at a temperature higher than a temperature range of about room temperature (for example, 20° C. to 35° C.) after being bonded to an adherend. In the case where it is permitted depending on the type of adherend, etc., the heat treatment may be performed at least at any timing of after bonding to the adherend, at the time of bonding, and before bonding. The heat treatment can be performed for the purpose of improving the adhesion of the pressure-sensitive adhesive to the adherend or promoting adhesion. The heat treatment temperature can be appropriately set so as to obtain a desired effect, taking into consideration the surface state of the adherend, etc. within an allowable range depending on the material of the adhesive sheet and the type of adherend, and is, for example, about 100°C or higher. It may be less than or equal to 80°C, may be less than or equal to 60°C, or may be less than or equal to 50°C.

The member or material to which the pressure-sensitive adhesive is applied may have light transmission properties. In such an adherend, the advantage that the pressure-sensitive adhesive disclosed herein can be highly transparent is easily obtained. The total light transmittance of the adherend may be, for example, greater than 50% or greater than 70%. In some preferred embodiments, the adherend has a total light transmittance of 80% or more, more preferably 90% or more, still more preferably 95% or more (for example, 95 to 100%). The pressure-sensitive adhesive disclosed herein can be preferably used in an aspect of sticking to an adherend having a total light transmittance of a predetermined value or higher (for example, an optical member). The total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136:2000. As the transmittance meter, a trade name "HAZEMETER HM-150" manufactured by Murakami Shikisai Kijutsu Genkyujo Co., Ltd. or an equivalent thereof is used.

The refractive index of the adherend and the refractive index of the pressure-sensitive adhesive layer (typically a low-refractive-index pressure-sensitive adhesive layer, which may be a high-refractive-index pressure-sensitive adhesive layer in the form of having a high refractive index pressure-sensitive adhesive layer) disposed in contact with the adherend may be the same level, It can be different. For example, by making the refractive index of the pressure-sensitive adhesive layer relatively high compared to the refractive index of the adherend, light incident from the adherend side to the pressure-sensitive adhesive layer at an angle of less than a critical angle is refracted toward the front side, and the front luminance can be increased. In this case, the refractive index of the adherend may be, for example, 1.55 or less, 1.50 or less, 1.48 or less, 1.45 or less, or less than 1.45, and may be, for example, 1.10 or more, 1.20 or more, 1.30 or more, or 1.35 or more. Moreover, according to the adherend having a relatively high refractive index compared to the pressure-sensitive adhesive layer, light incident on the adherend from the pressure-sensitive adhesive layer side is refracted toward the front side, so that the front luminance can be increased. In this case, the refractive index of the adherend may be, for example, 1.60 or more, 1.65 or more, or 1.70 or more, and may be, for example, 3.00 or less, 2.50 or less, or 2.00 or less. On the other hand, light reflection at the interface can be suppressed by reducing the refractive index difference between the pressure-sensitive adhesive layer and the adherend. In this case, the refractive index of the adherend may be about 1.55 to 1.80, about 1.55 to 1.75, or about 1.60 to 1.70. The refractive index of the adherend can be measured in the same way as the refractive index of the pressure-sensitive adhesive.

In some preferred aspects, the adherend may have any of the refractive indexes described above and may have a total light transmittance of any of the above. In an optical product (e.g., a light emitting device) in which a high refractive index adhesive layer and/or a low refractive index adhesive layer are attached or stacked on such an adherend, the effect of the technique disclosed herein is particularly preferably exhibited. .

The low-refractive-index pressure-sensitive adhesive layer and the high-refractive-index pressure-sensitive adhesive layer disclosed herein can be used by attaching them to various adherends as described above in the form of a laminated sheet containing them. An example of a preferred application is an optical application. More specifically, the laminated sheet disclosed herein is a pressure-sensitive adhesive sheet for optics used, for example, for bonding optical members (for bonding optical members) or for manufacturing products (optical products) using the optical member. can be preferably used. The laminated sheet used in this aspect can also be conceived as an interlayer sheet disposed between the layers of an optical laminate.

The optical member refers to a member having optical properties (eg, polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, rotation, visibility, etc.). The optical member is not particularly limited as long as it has optical properties, but examples include members constituting devices (optical devices) such as display devices (image display devices) and input devices, or members used in these devices. It may be, for example, a polarizer, a wave plate, a retardation plate, an optical compensation film, a luminance enhancement film, a light guide plate, a reflective film, an anti-reflection film, a hard coat (HC) film, an impact absorbing film, an antifouling film, a photochromic film, Light control film, transparent conductive film (ITO film), design film, decorative film, surface protection plate, prism, lens, color filter, transparent substrate, and further members laminated thereon (these are collectively referred to as “functional film” in some cases) ) and the like. In addition, the said "plate" and "film" shall include forms, such as a plate shape, a film shape, and a sheet shape, respectively, For example, a "polarizing film" includes a "polarizing plate", a "polarizing sheet", etc. , "light guide plate" includes "light guide film" or "light guide sheet". In addition, the said "polarizing plate" shall contain a circular polarizing plate.

Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a micro LED (μLED), a mini LED (miniLED), a PDP (plasma display panel), and electronic paper. Moreover, as said input device, a touchscreen etc. are mentioned.

Examples of the optical member include, but are not particularly limited to, members made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, metal thin film, etc. (for example, sheet-like, film-like, or plate-like members) can be heard In addition, the "optical member" in this specification includes members (decorative film, decorative film, surface protection film, etc.) that play a role of decoration or protection while maintaining the visibility of the display device or input device.

The low refractive index pressure-sensitive adhesive layer disclosed herein (which may be in the form of a laminated sheet with a high refractive index layer) is, for example, a film having one or more functions such as light transmission, reflection, diffusion, waveguide, condensation, diffraction, etc. It can be used in an aspect disposed between an optical film such as a fluorescent film and another optical member (which may be another optical film), and can be preferably used to bond the optical film and the other optical member. Among them, in bonding an optical film having at least one function of light guide, condensing, and diffraction, it is preferable that the entire bulk of the bonding layer has a high refractive index, and the technique disclosed herein is used as a high refractive index layer (typically a high refractive index layer). A refractive index pressure-sensitive adhesive layer) can be a preferable application target in the case of carrying out in an aspect containing it.

The pressure-sensitive adhesive layer disclosed herein can be suitably used for bonding optical films such as a light guide film, a diffusion film, a fluorescent film, a color toning film, a prism sheet, a lenticular film, and a microlens array film. In these applications, from the viewpoints of miniaturization and high performance of optical members, reduction in thickness and improvement in light extraction efficiency are required. As a pressure-sensitive adhesive layer that can meet such a request, the pressure-sensitive adhesive layer disclosed herein can be preferably used. In more detail, for example, in bonding of a light guide film or a diffusion film, it is possible to contribute to thickness reduction by adjusting the refractive index of the pressure-sensitive adhesive layer as a bonding layer (for example, increasing the refractive index). In the bonding of the fluorescent film, the light extraction efficiency (which can also be understood as luminous efficiency) can be improved by appropriately adjusting the difference in refractive index between the fluorescent light emitting body and the pressure-sensitive adhesive. In the bonding of the toning film, scattering components can be reduced by appropriately adjusting the refractive index of the pressure-sensitive adhesive so that the refractive index difference with the coloring pigment is reduced, thereby contributing to improvement in light transmittance. In bonding such as a prism sheet, a lenticular film, a microlens array film, etc., diffraction of light can be controlled by appropriately adjusting the refractive index of the pressure-sensitive adhesive, thereby contributing to improvement in luminance and/or viewing angle.

The high-refractive-index pressure-sensitive adhesive layer disclosed herein is preferably used in the form of a laminated sheet with a low-refractive-index pressure-sensitive adhesive layer, affixed to a high refractive index adherend (which may be a high refractive index layer or member, etc.) , It is possible to suppress the interfacial reflection with the adherend. As described above, the high refractive index pressure-sensitive adhesive layer used in this aspect preferably has a small difference in refractive index with the adherend having a high refractive index and high adhesion at the interface with the adherend. Further, from the viewpoint of enhancing the homogeneity of appearance, it is preferable that the pressure-sensitive adhesive layer has high uniformity in thickness, and for example, it is preferable that the surface smoothness of the adhesive surface is high. When the thickness of the high refractive index adherend is relatively small (for example, 5 μm or less, 4 μm or less, or 2 μm or less), reflection at the interface is prevented from the viewpoint of suppressing coloration and color unevenness due to interference of reflected light. suppression is particularly meaningful. As an example of such a usage aspect, in a polarizing plate having a polarizer, a first retardation layer, and a retardation layer including a second retardation layer in this order, bonding of the polarizer and the first retardation layer and / or the first retardation An aspect used for bonding the layer and the second retardation layer may be mentioned.

In addition, the high-refractive-index pressure-sensitive adhesive layer disclosed herein can be preferably used in an aspect in which it is attached to a light-emitting layer (for example, a high-refractive light-emitting layer mainly composed of inorganic materials) such as an optical semiconductor. By reducing the difference in refractive index between the light-emitting layer and the high-refractive-index pressure-sensitive adhesive layer, reflection at their interface can be suppressed and light extraction efficiency can be improved. In addition, from the viewpoint of preventing deterioration of the self-luminous element due to moisture, the high refractive index pressure-sensitive adhesive layer preferably has a low water absorption rate. It is preferable that the high refractive index adhesive layer has low coloration from a viewpoint of brightness improvement. This can also be advantageous from the viewpoint of suppressing unintentional coloring caused by the high refractive index pressure-sensitive adhesive layer.

The high refractive index pressure-sensitive adhesive layer disclosed herein is a microlens or other lens member used as a constituent member of a camera or light emitting device (for example, a microlens constituting a microlens array film or a lens such as a microlens for a camera). member), a coating layer covering the lens surface, a bonding layer with a member facing the lens surface (eg, a member having a surface shape corresponding to the lens surface), and a filling layer filled between the lens surface and the member. etc. can be preferably used. Even if the high refractive index pressure-sensitive adhesive layer disclosed herein is placed in contact with a high refractive index lens (for example, a lens made of a high refractive index resin or a lens having a surface layer made of a high refractive index resin), the refractive index difference with the lens is reduced. can be reduced This is advantageous from the viewpoint of reducing the thickness of the lens and the product provided with the lens, and can also contribute to suppression of aberration and improvement of Abbe's number. In the technique disclosed herein, the pressure-sensitive adhesive (viscoelastic material) constituting the high-refractive-index pressure-sensitive adhesive layer may be used as a lens resin by itself, for example, in the form of filling the recesses or voids of an appropriate transparent member.

The aspect of bonding the optical member using the pressure-sensitive adhesive layer disclosed herein (which is a high refractive index pressure-sensitive adhesive layer and/or a low-refractive-index pressure-sensitive adhesive layer, preferably a low-refractive-index pressure-sensitive adhesive layer that may be laminated on the high refractive index layer) is not particularly limited. Although, for example, (1) an aspect of bonding optical members to each other via a pressure-sensitive adhesive layer disclosed herein, or (2) an aspect of bonding an optical member to a member other than an optical member via an adhesive layer disclosed herein (3) The pressure-sensitive adhesive layer disclosed herein may be in the form of a pressure-sensitive adhesive sheet containing an optical member, and the pressure-sensitive adhesive sheet may be bonded to an optical member or a member other than the optical member. In the aspect (3) above, the pressure-sensitive adhesive sheet having an optical member may be, for example, a pressure-sensitive adhesive sheet in which the support is an optical member (eg, an optical film). Such a pressure-sensitive adhesive sheet including an optical member as a support may also be regarded as a pressure-sensitive adhesive optical member (eg, a pressure-sensitive adhesive optical film). In the case where the pressure-sensitive adhesive layer disclosed herein constitutes a pressure-sensitive adhesive sheet having a support and the functional film is used as the support, the pressure-sensitive adhesive sheet is formed on at least one side of the functional film, and the pressure-sensitive adhesive layer disclosed herein is used. It can also be understood as an "adhesive functional film" having.

From the above, according to the technique disclosed herein, an optical laminate comprising the pressure-sensitive adhesive layer disclosed herein and a member to which the pressure-sensitive adhesive sheet is attached (for example, a resin film such as an optical film) is provided. The member to which the pressure-sensitive adhesive layer is affixed may have the above-described refractive index of the adherend material. In addition, the difference between the refractive index of the pressure-sensitive adhesive layer and the refractive index of the member (difference in refractive index) may be the above-described difference in refractive index between the adherend and the pressure-sensitive adhesive layer. Since the members constituting the laminate are as described above as the members, materials, and adherends, overlapping descriptions will not be repeated.

As understood from the above description and the following examples, the matters disclosed by this specification include the following.

[101] A pressure-sensitive adhesive containing an acrylic polymer (F) containing a fluorine-containing acrylic monomer (M1) as a monomer unit,

The refractive index is 1.46 or less, and

The adhesive whose storage modulus G' at 25 degreeC is 1.0 kPa or more and 400 kPa or less.

[102] The pressure-sensitive adhesive according to [101], wherein, in the monomer components constituting the acrylic polymer (F), the content of the fluorine-containing acrylic monomer (M1) is 25% by weight or more.

[103] The pressure-sensitive adhesive according to [101] or [102], wherein the fluorine-containing acrylic monomer (M1) contains a fluorine atom-containing (meth)acrylic acid alkyl ester.

[104] The pressure-sensitive adhesive according to any one of [101] to [103], wherein the acrylic polymer (F) contains a hydroxyl group-containing monomer as a monomer unit.

[105] A low refractive index pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive according to any one of [101] to [104],

A high refractive index pressure sensitive adhesive layer laminated on the low refractive pressure sensitive adhesive layer

Including, laminated sheet.

[106] The laminated sheet according to [105], wherein _the ratio (n ₁ /n ₂ ) of the refractive index n 1 of the high refractive index pressure sensitive adhesive layer to the refractive index n ₂ of the low refractive index pressure sensitive adhesive layer is 1.02 or more.

[107] The laminated sheet according to [105] or [106], wherein the high refractive index pressure-sensitive adhesive layer has a refractive index n ₁ of greater than 1.570.

[108] The laminated sheet according to any one of [105] to [107] above, wherein the high refractive index pressure-sensitive adhesive layer has a storage elastic modulus G' at 25°C of 700 kPa or less.

[109] The laminated sheet according to any one of [105] to [108], wherein the laminated sheet has a total light transmittance of 86% or more and a haze value of 3.0% or less.

[110] a self-luminous element;

The laminated sheet according to any one of [105] to [109] above

The light emitting device includes a light emitting device, wherein the laminated sheet is disposed on a viewing side of the self light emitting element.

[1] A pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer,

It has an adhesive surface constituted by the pressure-sensitive adhesive layer,

The pressure-sensitive adhesive layer has a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.

[2] The pressure-sensitive adhesive sheet according to [1], wherein the pressure-sensitive adhesive layer has a thickness of 5 µm or more.

[3] The adhesive sheet according to [1] or [2], wherein the peel strength (adhesive force) to the glass plate is 3 N/25 mm or more.

[4] The adhesive sheet according to any one of [1] to [3], wherein the adhesive surface has an arithmetic mean roughness Ra of 100 nm or less.

[5] The pressure-sensitive adhesive sheet according to any one of [1] to [4], wherein the pressure-sensitive adhesive layer has a water absorption of 1.0% or less.

[6] The pressure-sensitive adhesive sheet according to any one of [1] to [5], configured as a laminate comprising the pressure-sensitive adhesive layer and a light-transmitting substrate.

[7] The adhesive sheet according to [6], wherein the light-transmitting substrate is a resin film.

[8] The pressure-sensitive adhesive sheet according to any one of [1] to [5], which is a double-sided adhesive pressure-sensitive adhesive sheet composed of the pressure-sensitive adhesive layer.

[9] The pressure-sensitive adhesive sheet according to any one of [1] to [8] above;

A release liner disposed on the adhesive side of the adhesive sheet

A pressure-sensitive adhesive sheet comprising a release liner.

[10] A pressure-sensitive adhesive composition used to form a pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to any one of [1] to [8].

[11] an acrylic polymer (A) containing an aromatic ring-containing monomer (m1) as a monomer unit;

Additive (H _RO ) which is an organic material having a higher refractive index than the acrylic polymer (A)

Containing, the pressure-sensitive adhesive composition.

[12] The adhesive composition according to [11], wherein the additive (H _RO ) has a refractive index of 1.60 or more.

[13] The adhesive composition according to [11] or [12], wherein the content of the additive (H _RO ) with respect to 100 parts by weight of the acrylic polymer (A) is greater than 0 parts by weight and not greater than 60 parts by weight.

[14] The adhesive composition according to any one of [11] to [13], wherein the additive (H _RO ) contains at least one compound selected from the group consisting of an aromatic ring-containing compound and a heterocycle-containing compound.

[15] The adhesive composition according to any one of [11] to [14], wherein the additive (H _RO ) contains a compound having two or more aromatic rings in one molecule.

[16] The additive (H _RO ) is a compound having two or more aromatic rings in one molecule,

(i) containing a structure in which two non-condensed aromatic rings are directly chemically bonded, and

(ii) containing a structure in which two aromatic rings are condensed

The pressure-sensitive adhesive composition according to [15] above, comprising a compound satisfying at least one of the above.

[17] The pressure-sensitive adhesive composition according to any one of [11] to [16], wherein, in the monomer components constituting the acrylic polymer (A), the content of the aromatic ring-containing monomer (m1) is 50% by weight or more.

[18] In the monomer component constituting the acrylic polymer (A), the content of the aromatic ring-containing monomer (m1) is greater than 70% by weight and less than 100% by weight,

The adhesive composition according to any one of [11] to [17] above, wherein 50% by weight or more of the aromatic ring-containing monomer (m1) is a monomer having a homopolymer glass transition temperature of 10°C or less.

[19] The adhesive composition according to any one of [11] to [18], wherein the monomer component constituting the acrylic polymer (A) further contains a monomer (m2) having at least one of a hydroxyl group and a carboxy group.

[20] The pressure-sensitive adhesive composition according to any one of [11] to [18], which is used for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to any one of [1] to [8].

[21] A pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition according to any one of [11] to [20], and having a refractive index higher than 1.570.

[22] A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition according to any one of [11] to [20].

[23] The pressure-sensitive adhesive sheet according to [22], wherein the pressure-sensitive adhesive layer has a haze value of 1.0% or less.

[24] An interlayer sheet used by placing it between the layers of a laminate in optical applications,

a viscoelastic layer V ₁ having a refractive index n ₁ of 1.570 or more; and

Those with a total light transmittance of 86% or more;

Haze value is 1.0 % or less; and,

Those whose storage elastic modulus G' at 25°C is 30 kPa to 700 kPa;

to meet the interlayer sheet.

[25] The interlayer sheet according to [24] above, having a thickness of 5 μm or more.

[26] The interlayer sheet according to [24] or [25], wherein the viscoelastic layer V ₁ includes a main polymer and a plasticizing material having a molecular weight lower than that of the main polymer.

[27] The interlayer sheet according to [26], wherein the plasticizing material has a weight average molecular weight of 30000 or less.

[28] Further comprising a viscoelastic layer V ₂ laminated on the viscoelastic layer V ₁ ,

The storage modulus G′ _V2 of the viscoelastic layer V ₂ at 25° C. is lower than the storage modulus G′ _V1 of the viscoelastic layer V ₁ at 25° C. between layers according to any one of [24] to [27]. Sheet.

[29] The interlayer sheet according to [28], wherein the refractive index n ₂ of the viscoelastic layer V ₂ is lower than the refractive index n ₁ of the viscoelastic layer V ₁ .

[30] The interlayer sheet according to any one of [24] to [29], wherein the viscoelastic layer V ₁ is a layer formed of the pressure-sensitive adhesive composition according to any one of [11] to [18].

[31] The interlayer sheet according to any one of [24] to [29], wherein the viscoelastic layer V ₁ is a pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet according to any one of [1] to [5].

[32] The interlayer sheet according to any one of [24] to [31] above;

A resin film laminated on the interlayer sheet

Including, the optical laminate.

[33] The interlayer sheet according to any one of [24] to [31],

A release liner covering at least one surface of the interlayer sheet.

An interlayer sheet having a release liner comprising a.

[34] a self-luminous element,

a low refractive index layer disposed on the viewing side of the self-luminous element;

A high refractive index adhesive layer laminated in direct contact with the low refractive index layer

including,

The high-refractive-index pressure-sensitive adhesive layer has a refractive index n ₁ of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.

[35] The light emitting device according to [34], wherein a ratio (n ₁ /n ₂ ) of the refractive index n ₁ of the high refractive index adhesive layer to the refractive index n ₂ of the low refractive index layer is 1.05 or more.

[36] The light emitting device according to [35] or [36], wherein the high refractive index pressure-sensitive adhesive layer has an arithmetic mean roughness Ra of a surface of 100 nm or less.

[37] The light emitting device according to any one of [34] to [36], wherein _a ratio (T ₁ /T ₂ ) of the thickness T 1 of the high refractive index adhesive layer to the thickness T ₂ of the low refractive index layer is 0.5 to 5 .

[38] The light emitting device according to any one of [34] to [37], wherein the high refractive index pressure-sensitive adhesive layer has a thickness T ₁ of 5 µm or more.

[39] The light emitting device according to any one of [34] to [38] above, wherein the laminated sheet comprising the high refractive index pressure-sensitive adhesive layer and the low refractive index layer has a total light transmittance of 86% or more and a haze value of 3.0% or less.

[40] The light-emitting device according to any one of [34] to [39], wherein the high refractive index pressure-sensitive adhesive layer is a layer formed of the pressure-sensitive adhesive composition according to any one of [11] to [18].

[41] The light emitting device according to any one of [34] to [40] above, wherein the high refractive index pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet according to any one of [1] to [5] above.

[42] The light emitting device according to any one of [34] to [41], wherein the low refractive index layer is a layer made of the pressure-sensitive adhesive according to any one of [101] to [104].

[43] The interlayer sheet according to any one of [24] to [31], wherein the viscoelastic layer V ₂ is a layer made of the pressure-sensitive adhesive according to any one of [101] to [104].

Example

Hereinafter, some experimental properties related to the present invention will be described. In addition, in the following description, "part" and "%" which show usage amount or content are based on weight unless otherwise indicated.

<Preparation of pressure-sensitive adhesive composition C1>

1H,1H,2H,2H-tridecafluorooctyl acrylate (manufactured by Osaka Yuki Chemical Industry Co., Ltd., trade name " 99.0 parts of "Viscot 13F"), 1.0 parts of 4-hydroxybutyl acrylate (4HBA), 0.2 parts of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator, and ethyl acetate as a polymerization solvent 200 parts were introduced, nitrogen gas was introduced with gentle stirring, and a polymerization reaction was carried out for 9 hours while maintaining the liquid temperature in the flask at around 60°C to prepare a solution (33%) of acrylic polymer P1. The polymerization average molecular weight (Mw) of this acrylic polymer P1 was 800,000.

A solution (33%) of the acrylic polymer P1 was diluted to 30% with ethyl acetate, and an isocyanurate of hexamethylene diisocyanate as a crosslinking agent with respect to 100 parts of non-volatile content (solid content) (manufactured by Tosoh Corporation, trade name “Coronate”). 10 parts (0.1 part of non-volatile matter) of a 1% ethyl acetate solution of "HX", a trifunctional isocyanate compound) was added and mixed with stirring to prepare an adhesive composition C1.

<Preparation of pressure-sensitive adhesive composition C2 to C10>

Solutions of acrylic polymers P2 to P10 were prepared in the same manner as in the preparation of the solution of acrylic polymer P1, except that the composition of the monomer components was changed as shown in Table 1.

The adhesive compositions C2 to C10 were prepared in the same manner as in the preparation of the PSA composition C1, except that the solutions of the acrylic polymers P2 to P10 were respectively used instead of the solution of the acrylic polymer P1.

In addition, in the composition of the monomer components shown in Table 1, "V13F" is 1H,1H,2H,2H-tridecafluorooctyl acrylate (manufactured by Osaka Yuki Chemical Industry Co., Ltd., trade name "Viscot 13F" ), "V8F" represents 1H,1H,5H-octafluoropentyl acrylate (manufactured by Osaka Yuki Chemical Industry Co., Ltd., trade name "Viscote 8F"), and "V3F" represents 2,2 , 2-trifluoroethyl acrylate (trade name "Biscott 3F" manufactured by Osaka Yuki Chemical Industry Co., Ltd.) is shown. In addition, 2EHA represents 2-ethylhexyl acrylate, NVP represents N-vinyl-2-pyrrolidone, IBXA represents isobornyl acrylate, and CHA represents cyclohexyl acrylate.

<Production of adhesive sheet (1)>

(Example 1)

The pressure-sensitive adhesive composition C1 prepared above was applied to the silicone-treated surface of polyethylene terephthalate (PET) film R1 (thickness: 50 μm), which was subjected to silicone treatment on one side, and heated at 130 ° C. for 2 minutes to form a 25 μm-thick pressure-sensitive adhesive layer. was formed. To the surface of the pressure-sensitive adhesive layer, the silicone-treated side of PET film R2 (thickness: 38 μm), which was silicone-treated on one side, was bonded. In this way, a pressure-sensitive adhesive layer (inorganic double-sided pressure-sensitive adhesive sheet) having both surfaces protected by PET films (release liner) R1 and R2 was obtained. Moreover, peeling liner R2 is relatively light peeling compared with peeling liner R1.

(Examples 2 to 10)

PSA layers (inorganic double-sided pressure-sensitive adhesive sheets) according to Examples 2 to 10 were prepared in the same manner as in Example 1 except that PSA compositions C2 to C10 were used instead of PSA composition C1, respectively.

The obtained PSA sheet was sufficiently adapted to an environment of 23° C. and 50% RH, and then used for the following measurements and evaluations.

<Measurement and Evaluation (1)>

(refractive index)

About each adhesive layer, the refractive index was measured using the Abbe refractometer (made by ATAGO, model "DR-M4") on conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 degreeC. The results are shown in Table 1.

(Storage modulus G')

Each pressure-sensitive adhesive layer was laminated to have a thickness of about 1.5 mm and was used as a sample for measurement. Dynamic viscoelasticity was measured under the following conditions using ARES manufactured by TA Instruments. From the measurement results, the storage elastic modulus G' at 25°C was read. The results are shown in Table 1.

[Measuring conditions]

Deformation Mode: Torsion

Measurement frequency: 1Hz

Heating rate: 5°C/min

Shape: Parallel plate 7.9mmφ

(Total light transmittance and haze value)

A test piece in which the adhesive sheet according to each example was bonded to non-alkali glass (thickness: 0.8 to 1.0 mm, total light transmittance: 92%, haze: 0.4%) was used, and in a measurement environment of 23°C, a haze meter (Murakami Shikisai Gijutsu The total light transmittance and haze of the said test piece were measured using Genkyujo Co., Ltd. product name "HAZEMETER HM-150"). A value obtained by subtracting the total light transmittance and haze of the alkali-free glass from the measured value was used as the total light transmittance and haze value of the pressure-sensitive adhesive sheet. The results are shown in Table 1.

(to glass plate peel strength)

In a measurement environment of 23°C and 50% RH, the release liner was peeled off from one side of the pressure-sensitive adhesive sheet according to each example, and a PET film having a thickness of 50 µm was bonded and backed, and then a 25 mm wide and 100 mm long PET film was bonded. What was cut to size was used as a test piece. The release liner on the other side was peeled off from the test piece, and the surface of an alkali glass plate (manufactured by Matsunami Glass Industrial Co., Ltd., thickness 1.35 mm, polished blue plate) as an adherend was pressed by pressing a 2 kg roller once. This was left for 30 minutes in the same environment, then put into a pressurized defoaming device (autoclave), and autoclave treatment was performed for 30 minutes under the conditions of a temperature of 50 ° C. and a pressure of 0.5 MPa, and further in an atmosphere of 23 ° C. and 50% RH. After leaving it to stand for 24 hours, the peel strength (adhesive force) [N/25 mm] was measured using a universal tensile compression tester in accordance with JIS Z 0237: 2000 under conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees. . As a universal tension and compression tester, "Tension and compression tester, TG-1kN" manufactured by Minebea Co., Ltd. was used.

As shown in Table 1, the PSA sheets of Examples 1 to 9 had a refractive index of 1.46 or less, and a storage modulus G' (25) of 400 kPa. These pressure-sensitive adhesive sheets exhibited high transparency and practical peel strength suitable for bonding optical members.

<Preparation of pressure-sensitive adhesive composition C11>

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet pipe, and a condenser, 65 parts of 2EHA as a monomer component, 1H,1H,5H-octafluoropentyl acrylate (manufactured by Osaka Yuki Chemical Industry Co., Ltd., Trade name: Biscott 8F) 30 parts, N-vinyl-2-pyrrolidone (NVP, manufactured by Nippon Shokubai) 3 parts and 4HBA 2 parts, AIBN as a polymerization initiator 0.2 parts, and ethyl acetate 200 parts as a polymerization solvent were added Then, while stirring gently, nitrogen gas was introduced, and the liquid temperature in the flask was maintained at around 60°C to carry out a polymerization reaction for 9 hours to prepare a solution (33%) of acrylic polymer P11. The polymerization average molecular weight (Mw) of the acrylic polymer P11 was 550,000.

A solution (33%) of the acrylic polymer P11 was diluted to 30% with ethyl acetate, and an isocyanurate of hexamethylene diisocyanate as a crosslinking agent (trade name “Coronate, manufactured by Tosoh Corporation) with respect to 100 parts of non-volatile matter (solid content) 10 parts (0.1 part of non-volatile matter) of a 1% ethyl acetate solution of "HX", a trifunctional isocyanate compound) was added, stirred and mixed, and adhesive composition C11 was prepared.

<Preparation of pressure-sensitive adhesive composition C12>

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet pipe, and a condenser, m-phenoxybenzyl acrylate (manufactured by Kyoesha Chemical Co., Ltd., trade name "Light Acrylate POB-A" as a monomer component, Refractive index: 1.566, Tg of homopolymer: -35 ° C. (hereinafter abbreviated as "POB-A") 95 parts, 4HBA 5 parts, AIBN 0.2 part as a polymerization initiator, and toluene 100 parts as a polymerization solvent , Nitrogen gas was introduced while stirring gently, and the liquid temperature in the flask was maintained at around 60°C to carry out a polymerization reaction for 6 hours to prepare a solution (50%) of acrylic polymer P12. The polymerization average molecular weight (Mw) of this acrylic polymer P12 was 500,000. The acrylic polymer P12 has a Tg based on the composition of the monomer component (ie, Tg _T ) of -35°C, and a Tg based on the composition of the aromatic ring-containing monomer (ie, Tg _m1 ) of -35°C.

A solution (50%) of the acrylic polymer P12 was diluted to 30% with ethyl acetate, and an isocyanurate of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name " Coronate HX", trifunctional isocyanate compound) 10 parts (0.1 part non-volatile content) of 1% ethyl acetate solution, 2 parts of acetylacetone as a crosslinking retardant, 1% ethyl acetate solution of ferric nasem as a crosslinking catalyst 1 part (0.01 part of non-volatile content) was added, stirred and mixed, and adhesive composition C12 was prepared.

<Preparation of pressure-sensitive adhesive composition C13>

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet pipe, and a condenser, 72 parts of POB-A as a monomer component, 1-naphthylmethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light") Acrylate NMT-A", refractive index: 1.595, homopolymer Tg: 31°C. Hereinafter abbreviated as "NMT-A") 23 parts and 4HBA 5 parts, AIBN as a polymerization initiator 0.2 part, and polymerization solvent 100 parts of toluene was introduced as the mixture, nitrogen gas was introduced with gentle stirring, and a polymerization reaction was carried out for 6 hours while maintaining the liquid temperature in the flask at around 60°C to prepare a solution (50%) of acrylic polymer P13. The polymerization average molecular weight (Mw) of this acrylic polymer P13 was 500,000.

In a separable flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet pipe, 20 parts of POB-A and 80 parts of NMT-A as monomer components, 0.2 part of AIBN as a polymerization initiator, and α- as a chain transfer agent After throwing in 3.5 parts of thioglycerol and 67 parts of methyl ethyl ketone, nitrogen substitution was performed for about 1 hour, flowing nitrogen gas and stirring. Then, the flask was heated at 70°C and reacted for 12 hours to obtain an acrylic oligomer (oligomer B) having a weight average molecular weight (Mw) of 4000 and a refractive index of 1.63.

A solution (50%) of the above acrylic polymer C13 was diluted to 30% with ethyl acetate, and to 334 parts of this solution (100 parts of non-volatile content), 20 parts of the oligomer B prepared above, as a crosslinking agent, isocyanate of hexamethylene diisocyanate 10 parts (0.1 part of non-volatile content) of 1% ethyl acetate solution of an anurate (manufactured by Tosoh Corporation, trade name "Coronate HX", trifunctional isocyanate compound), 2 parts of acetylacetone as a crosslinking retardant, and a nasem agent as a crosslinking catalyst 1 part (0.01 part of non-volatile content) of 1% ferric ethyl acetate solution was added and stirred and mixed, and adhesive composition C13 was prepared.

<Production of adhesive sheet (2)>

(Example 11)

The pressure-sensitive adhesive composition C11 prepared above was applied to the silicone-treated surface of release liner R1 (thickness: 50 μm) and heated at 130° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 μm. The siliconized surface of release liner R2 (thickness: 38 μm) was bonded to the surface of the pressure-sensitive adhesive layer. In this way, a pressure-sensitive adhesive layer (inorganic double-sided pressure-sensitive adhesive sheet) formed of pressure-sensitive adhesive composition C11 in a form protected by PET films (release liner) R1 and R2 was obtained.

(Example 12)

The pressure-sensitive adhesive composition C12 prepared above was applied to the silicone-treated surface of the release liner R1 and heated at 130°C for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 25 µm. The siliconized surface of release liner R2 was bonded to the surface of the pressure-sensitive adhesive layer. In this way, a pressure-sensitive adhesive layer (inorganic double-sided pressure-sensitive adhesive sheet) formed of pressure-sensitive adhesive composition C12 in a form protected by PET films (release liner) R1 and R2 was obtained.

The release liner R2 was peeled from each of the obtained pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer produced in Example 11, the pressure-sensitive adhesive surfaces were bonded together, and pressure bonding was performed with a hand roller. About this laminated body, after performing an autoclave process for 30 minutes on conditions of 50 degreeC and 0.60 Mpa, it aged for 48 hours in a 50 degreeC environment. In this way, a laminated sheet (inorganic double-sided pressure-sensitive adhesive sheet) having a two-layer structure of a pressure-sensitive adhesive layer (high refractive index pressure-sensitive adhesive layer) formed of pressure-sensitive adhesive composition C12 / pressure-sensitive adhesive layer formed from pressure-sensitive adhesive composition C11 (low refractive index pressure-sensitive adhesive layer) was obtained. The surface of this pressure-sensitive adhesive sheet is protected by two pieces of release liner R1.

(Example 13)

Except for changing the type of the pressure-sensitive adhesive composition used for forming each pressure-sensitive adhesive layer and the thickness of each pressure-sensitive adhesive layer as shown in Table 2, in the same manner as Example 12, consisting of a two-layer structure of high refractive index pressure sensitive adhesive layer / low refractive index pressure sensitive adhesive layer A laminated sheet (inorganic double-sided pressure-sensitive adhesive sheet) was obtained.

(Ex 14, 15)

In the same manner as in Example 13, a pressure-sensitive adhesive layer having a single-layer structure composed of each of PSA compositions C12 and C13 and having a thickness shown in Table 2 was prepared to obtain PSA sheets according to Examples 14 and 15.

<Measurement and evaluation (2)>

After sufficiently adapting the PSA sheets obtained in Examples 11 to 15 to an environment of 23° C. and 50% RH, each item was measured and evaluated in the same manner as in “Measurement and Evaluation (1)” described above. In the inorganic double-sided pressure-sensitive adhesive sheet having a two-layer structure of high refractive index pressure sensitive adhesive layer/low refractive index pressure sensitive adhesive layer, the peel strength on the high refractive index pressure sensitive adhesive layer side was measured. The results are shown in Table 2.

As shown in Table 2, the PSA sheets of Examples 11 to 13 contained a PSA layer having a refractive index of 1.46 or less, and exhibited high transparency. These pressure-sensitive adhesive sheets exhibited practical peel strength suitable for bonding optical members.

<Evaluation of front luminance enhancement effect>

After sticking the adhesive sheet according to each example of Examples 11 to 15 on a white LED light emitting light source, turning on the light source for 30 minutes or more in a dark room environment to stabilize it, a spectroradiometer SR-UL1R (manufactured by Topcon Techno House Co., Ltd.) ) was used to measure the front luminance at the portion to which the pressure-sensitive adhesive sheet was attached. Using the average value of the luminance measured three times, those having a luminance improvement effect of 10% or more with respect to the luminance of the light source without the adhesive sheet were evaluated as G (Good), and those with a luminance improvement of less than 10% were evaluated as P (Poor). . The results are shown in Table 3.

As shown in Table 3, the pressure-sensitive adhesive sheet of Examples 12 and 13 having a pressure-sensitive adhesive layer having a laminated structure in which a pressure-sensitive adhesive layer having a low refractive index formed of the pressure-sensitive adhesive composition C11 and a pressure-sensitive adhesive layer having a high refractive index formed of the pressure-sensitive adhesive composition C12 or C13 are combined ( laminated sheet) showed an effect of improving the front luminance by 10% or more compared to the case where the pressure-sensitive adhesive sheet was not used. In the PSA sheets of Examples 11, 14, and 15 in which the PSA layer had a single-layer structure, the front luminance improvement effect by the PSA sheet alone was not observed.

<Preparation of pressure-sensitive adhesive composition C14>

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet pipe, and a condenser, 79 parts of POB-A as monomer components, 20 parts of n-butyl acrylate, 1 part of 4HBA, 0.2 part of AIBN as a polymerization initiator, Then, 100 parts of toluene was introduced as a polymerization solvent, nitrogen gas was introduced with gentle stirring, and polymerization was carried out for 6 hours while maintaining the liquid temperature in the flask at around 60°C to prepare a solution (50%) of acrylic polymer P14. Mw of this acrylic polymer P14 was 520,000.

A solution (50%) of the acrylic polymer P14 was diluted to 30% with ethyl acetate, and to 334 parts of this solution (100 parts of non-volatile matter), 10 parts of a 1% ethyl acetate solution of Coronate HX (0.1 part of non-volatile matter) was added as a crosslinking agent. part), 2 parts of acetylacetone as a crosslinking retardant and 1 part (0.01 part of non-volatile content) of a 1% ethyl acetate solution of ferric nasem as a crosslinking catalyst were added and stirred and mixed to prepare pressure-sensitive adhesive composition C14.

<Preparation of pressure-sensitive adhesive composition C15>

Except for changing the composition (weight ratio) of the monomer components to POB-A/ethyl carbitol acrylate (CBA)/4HBA=79/20/1, in the same manner as in the preparation of the solution of acrylic polymer P14, acrylic polymer P15 A solution (50%) was prepared. Mw of this acrylic polymer P15 was 460,000. Except having used the solution of acrylic polymer P15 instead of the solution of acrylic polymer P14, it carried out similarly to preparation of adhesive composition C14, and prepared adhesive composition C15.

<Preparation of pressure-sensitive adhesive composition C16>

A solution (50%) of acrylic polymer P16 was prepared in the same manner as in the preparation of the solution of acrylic polymer P14, except that the composition (weight ratio) of the monomer components was changed to P2H-A/4HBA=99/1. "P2H-A" in the composition of the monomer component is phenoxydiethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light Acrylate P2H-A", refractive index: 1.510, homopolymer Tg : -35°C). Mw of this acrylic polymer P16 was 1,000,000.

A solution (50%) of acrylic polymer _P16 was diluted to 30% with ethyl acetate, and 6-ethylacrylate-dinaphtho[2,1- 20 parts of b:1',2'-d]thiophene (Sugai Chemical Industry Co., Ltd. 6-acryloyloxyethyldinaphthothiophene, abbreviation: 6EDNTA, refractive index: 1.722), coronate as a crosslinking agent Add 10 parts of 1% ethyl acetate solution of HX (0.1 part of non-volatile content), 2 parts of acetylacetone as a crosslinking retardant, and 1 part of 1% ethyl acetate solution of ferric ferric nasem (0.01 part of non-volatile content) as a crosslinking catalyst and stirred and mixed to prepare PSA composition C16.

<Preparation of adhesive sheet>

(Examples 16 to 18)

Except that the type of the pressure-sensitive adhesive composition used for forming each pressure-sensitive adhesive layer and the thickness of each pressure-sensitive adhesive layer were set as shown in Table 4, in the same manner as in Example 12, a high refractive index pressure sensitive adhesive layer / low refractive index pressure sensitive adhesive layer Laminated sheet consisting of a two-layer structure (Inorganic material double-sided adhesive sheet) was obtained. In addition, Mw of acrylic polymer P4 which is the base polymer of PSA composition C4 is 550,000.

<Measurement and Evaluation (3)>

After sufficiently adapting the PSA sheets obtained in Examples 16 to 18 to an environment of 23° C. and 50% RH, each item was measured and evaluated in the same manner as in “Measurement and Evaluation (2)” described above. The results are shown in Table 4.

As shown in Table 4, Example 16 having a configuration in which a pressure-sensitive adhesive layer having a low refractive index formed of the pressure-sensitive adhesive composition C4 and a pressure-sensitive adhesive layer having a refractive index higher than that of the low-refractive-index pressure-sensitive adhesive layer by 0.01 or more (more specifically, 0.10 or more) are laminated. All of the laminated sheets of Nos. 1 to 18 exhibited high transparency. These pressure-sensitive adhesive sheets exhibited practical peel strength suitable for bonding optical members.

As mentioned above, although the specific example of this invention was demonstrated in detail, these are only examples and do not limit the claim. The technology described in the claims includes various modifications and changes of the specific examples exemplified above.

1: adhesive sheet
2: adhesive sheet (laminated sheet)
10: adhesive layer
10A: first surface (first adhesive surface)
10B: second surface (second adhesive surface)
11: 1st adhesive layer (high refractive index adhesive layer)
12: second adhesive layer (low refractive index adhesive layer)
70: self-luminous element
80: cover window member
100: light emitting device

Claims (10)

A pressure-sensitive adhesive containing an acrylic polymer (F) containing a fluorine-containing acrylic monomer (M1) as a monomer unit,
The refractive index is 1.46 or less, and
The adhesive whose storage modulus G' at 25 degreeC is 1.0 kPa or more and 400 kPa or less. According to claim 1,
In the monomer component constituting the acrylic polymer (F), the content of the fluorine-containing acrylic monomer (M1) is 25% by weight or more, the pressure-sensitive adhesive. According to claim 1 or 2,
The pressure-sensitive adhesive in which the fluorine-containing acrylic monomer (M1) contains a fluorine atom-containing (meth)acrylic acid alkyl ester. According to any one of claims 1 to 3,
The acrylic polymer (F) contains a hydroxyl group-containing monomer as a monomer unit. A low refractive index pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive according to any one of claims 1 to 4;
A high refractive index pressure sensitive adhesive layer laminated on the low refractive pressure sensitive adhesive layer
Including, laminated sheet. According to claim 5,
The laminate sheet, wherein the ratio (n ₁ /n ₂ ) of the refractive index n ₁ of the high refractive index pressure sensitive adhesive layer and the refractive index n ₂ of the low refractive index pressure sensitive adhesive layer is 1.02 or more. According to claim 5 or 6,
The laminated sheet in which the refractive index n ₁ of the high refractive index pressure-sensitive adhesive layer is greater than 1.570. According to any one of claims 5 to 7,
The laminated sheet in which the high refractive index pressure-sensitive adhesive layer has a storage elastic modulus G' at 25°C of 700 kPa or less. According to any one of claims 5 to 8,
A laminated sheet having a total light transmittance of 86% or more and a haze value of 3.0% or less. a self-luminous element;
The laminated sheet according to any one of claims 5 to 9
The light emitting device includes a light emitting device, wherein the laminated sheet is disposed on a viewing side of the self light emitting element.

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