WO2017086249A1

WO2017086249A1 - Pressure-sensitive-adhesive-coated resin film and optical laminate including same

Info

Publication number: WO2017086249A1
Application number: PCT/JP2016/083525
Authority: WO
Inventors: 光敬佐瀬; 公平森岡; 宰旭鄭
Original assignee: 住友化学株式会社
Priority date: 2015-11-17
Filing date: 2016-11-11
Publication date: 2017-05-26
Also published as: KR102653728B1; TW201730303A; CN108350325A; JP2022125327A; JP7158126B2; JP2017095700A; TWI816637B; KR20180082482A; CN108350325B

Abstract

[Problem] To provide a pressure-sensitive-adhesive-coated resin film in which the resin film serving as an adherend for the pressure-sensitive adhesive has high ion permeability and which is capable of retaining stable antistatic properties over a long period, and to provide an optical laminate obtained by applying the pressure-sensitive-adhesive-coated resin film to a glass substrate. [Solution] A pressure-sensitive-adhesive-coated resin film which comprises a resin film and a pressure-sensitive adhesive layer disposed on at least one surface of the resin film, wherein the pressure-sensitive adhesive layer is constituted of a pressure-sensitive adhesive comprising a resin and an ionic compound that has a solubility in 60ºC water of 0.4 g/100 g or less and, when the resin film is subjected to a treatment in which the resin film is immersed in 50 mass% aqueous potassium iodide solution for 4.5 hours in the air at 23ºC and 55% RH, rinsed with water for 15 seconds, and dried in the dark for 15 hours, then the maximum change in absorbance for light with a wavelength of 355-365 nm through the treatment is 5% or greater.

Description

Resin film with adhesive and optical laminate comprising the same

The present invention relates to a resin film on which an adhesive layer is formed, that is, a resin film with an adhesive. The present invention also relates to an optical laminate for liquid crystal display using a resin film having the pressure-sensitive adhesive layer formed thereon.

∙ Liquid crystal display devices may have problems with their display functions when static electricity is charged. Therefore, members such as a polarizing plate constituting the liquid crystal display device are desired to have an antistatic function. For example, a protective film, which is a kind of resin film, is laminated on one or both sides of a polarizing film to form a polarizing plate, but may impart an antistatic function to the pressure-sensitive adhesive layer. In addition, generally the polarizing plate is distribute | circulating in the state in which the adhesive layer concerning at least one surface of this protective film was formed, and the peeling film was stuck on the adhesive layer.

As a method for imparting antistatic properties to an adhesive, a method of blending an antistatic agent into the adhesive is known. In Patent Document 1, a specific ionic compound that becomes a solid at room temperature (25 ° C.) is contained in the pressure-sensitive adhesive so that the polarizing plate coated with the pressure-sensitive adhesive does not change over time even when left for a long time. Further, it is described that a resin film with an adhesive having excellent antistatic properties and durability can be obtained.

However, some resin films, which are adherends of adhesives, have a high ion permeability and a property of easily transmitting and transferring an ionic compound. For such an adherend, even when the ionic compound described in the above patent document is added to the pressure-sensitive adhesive, the desired antistatic property may not be maintained for a long time.

JP 2009-79205 A

An object of the present invention is to provide a resin film with an adhesive capable of maintaining stable antistatic properties over a long period of time in a resin film with an adhesive using a resin film having high ion permeability as an adherend of the adhesive, Is to provide an optical laminate in which the adhesive-attached resin film is bonded to a glass substrate having a liquid crystal cell as a representative example.

As a result of earnest research to solve such a problem, the inventors of the present invention have developed a specific ionic compound for a polarizing plate using a resin film having high ion permeability for a transparent protective film that is an adherend of an adhesive. It was found that a resin film with an adhesive capable of maintaining antistatic properties stably for a long period of time can be obtained by containing in the adhesive as an antistatic agent.
Furthermore, when the resin film with an adhesive obtained by this invention was bonded to glass and the optical laminated body was obtained, it also discovered having the outstanding durability and rework property.

The present invention provides the following preferred embodiments [1] to [6].
[1] A resin film with an adhesive having a resin film and an adhesive layer provided on at least one side of the resin film,
The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive containing a resin and an ionic compound having a solubility in water of 60 ° C. of 0.4 g / 100 g or less,
The resin film was immersed in a 50% by mass aqueous potassium iodide solution for 4.5 hours in an air atmosphere at 23 ° C. and 55% RH, washed for 15 seconds, and dried in the dark for 15 hours. A resin film with an adhesive, wherein the maximum amount of change in the light absorption amount of light having a wavelength of 355 to 365 nm with respect to that before the treatment is 5% or more.
[2] A resin film with an adhesive having a resin film and an adhesive layer provided on at least one side of the resin film,
The pressure-sensitive adhesive layer comprises a resin and the following formula (I):

[Wherein, R ₁ is H or a linear alkyl group having 1 to 3 carbon atoms, and R ₂ is a linear alkyl group having 5 to 14 carbon atoms or an aralkyl group having 7 to 13 carbon atoms. ]
Composed of a pressure-sensitive adhesive containing a pyridinium salt represented by
The resin film was immersed in a 50% by mass aqueous potassium iodide solution for 4.5 hours in an air atmosphere at 23 ° C. and 55% RH, washed for 15 seconds, and dried in the dark for 15 hours. A resin film with an adhesive, wherein the maximum amount of change in the light absorption amount of light having a wavelength of 355 to 365 nm with respect to that before the treatment is 5% or more.
[3] The resin film with an adhesive according to [1] or [2], wherein the adhesive contains 0.05 to 8 parts by mass of the ionic compound with respect to 100 parts by mass of the resin.
[4] The resin film with an adhesive according to any one of [1] to [3], wherein the resin is a (meth) acrylic resin.
[5] The resin film with an adhesive according to any one of [1] to [4], wherein the resin film has a thickness of 10 to 200 μm.
[6] An optical laminate comprising the adhesive-attached resin film according to any one of [1] to [5] and a glass substrate laminated on the adhesive layer side.

The resin film with a pressure-sensitive adhesive of the present invention can exhibit stable antistatic properties over a long period of time even when a resin film having high ion permeability is used as an adherend of a pressure-sensitive adhesive. Furthermore, the resin film with the pressure-sensitive adhesive of the present invention can be bonded to glass, and the optical laminate can exhibit excellent durability.

It is a cross-sectional schematic diagram which shows the example of the layer structure of the optical laminated body which is one embodiment of this invention. It is a cross-sectional schematic diagram which shows the example of the layer structure of the optical laminated body which is one embodiment of this invention. It is a cross-sectional schematic diagram which shows the example of the layer structure of the optical laminated body which is one embodiment of this invention. It is a cross-sectional schematic diagram which shows the example of the layer structure of the optical laminated body which is one embodiment of this invention.

The resin film with an adhesive of the present invention contains a resin film and an adhesive layer on at least one side of the resin film, and the adhesive layer contains a resin and a specific ionic compound. It is composed of an adhesive.

<Adhesive layer>
In this invention, an adhesive layer is provided in the at least one side of a resin film, and is comprised from an adhesive. The pressure-sensitive adhesive contains a resin and the ionic compound. Hereinafter, each component which comprises the adhesive in this invention is demonstrated.

[resin]
In the present invention, the type of resin contained in the pressure-sensitive adhesive is not particularly limited, and examples thereof include (meth) acrylic resin, silicone resin, urethane resin, and rubber. The said resin can be used individually or in combination. Among these, it is preferable to employ the (meth) acrylic resin (A) as the resin in that the functionality can be easily imparted to the pressure-sensitive adhesive by selecting the type of monomer to be introduced into the resin. . The structural unit constituting the (meth) acrylic resin (A) is not limited. As the (meth) acrylic resin (A), for example, a structural unit derived from a (meth) acrylic acid ester represented by the following formula (II) (hereinafter also referred to as “monomer (II)”) is a main component. A polymer is mentioned. In the present invention, the “polymer having a structural unit derived from the monomer (II) as a main component” means that the structural unit derived from the monomer (II) is the entire structural unit constituting the polymer. On the other hand, it means preferably 40% by mass or more, more preferably 60% by mass or more, for example 80% by mass or more. In this case, the structural unit derived from the monomer (II) is usually contained in an amount of 100% by mass or less, preferably 90% by mass or less, based on all the structural units constituting the polymer.

In the formula (II), R ₃ is a hydrogen atom or a methyl group, and R ₄ is usually an alkyl group or an aralkyl group having 14 or less carbon atoms, preferably 10 or less.

In one embodiment of the present invention, the (meth) acrylic resin (A) is derived from, in addition to the structural unit derived from the (meth) acrylic ester, another structural unit, particularly a monomer having a polar functional group. May contain a structural unit derived from a (meth) acrylic acid compound having a polar functional group. Examples of polar functional groups include carboxyl groups, hydroxyl groups, amino groups, and heterocyclic groups including epoxy rings. Examples of the (meth) acrylic acid compound having a polar functional group include (meth) acrylic acid, 2- (dimethylamino) ethyl acrylate, 2-hydroxyethyl (meth) acrylate, and glycidyl acrylate. . Furthermore, the (meth) acrylic resin (A) may include a structural unit derived from a monomer other than the monomer (II) having no polar functional group. As a structural unit (monomer) that can be suitably used, a structural unit derived from a monomer having one olefinic double bond and at least one aromatic ring in the molecule, preferably an aromatic ring ( Mention may be made of structural units derived from (meth) acrylic acid compounds. In the present specification, (meth) acrylic acid means that either acrylic acid or methacrylic acid may be used, and “(meth)” in the case of (meth) acrylate or the like has the same meaning. .

More specifically, among monomers (II), R ₄ is an alkyl group, and more specifically, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, and acrylic Linear alkyl acrylate esters such as lauryl acid; branched alkyl alkyl esters such as isobutyl acrylate, 2-ethylhexyl acrylate, and isooctyl acrylate; methyl methacrylate, ethyl methacrylate, methacrylic acid Linear alkyl methacrylates such as propyl, n-butyl methacrylate, n-octyl methacrylate, and lauryl methacrylate; and fractions such as isobutyl methacrylate, 2-ethylhexyl methacrylate, and isooctyl methacrylate. Branched Al methacrylate Examples include kill esters.

Among these, n-butyl acrylate is preferable. Specifically, among all structural units (monomers) constituting the (meth) acrylic resin (A), n-butyl acrylate is 50% by mass or more. And it is preferable to satisfy the above-mentioned provisions regarding the monomer (II).

Specific examples of monomers (II) in which R ₄ is an aralkyl group include benzyl acrylate and benzyl methacrylate.

These monomers (II) can be used alone or in combination.

In the formula (II), the alkyl group or aralkyl group constituting R ₄ may have a hydrogen atom substituted with a group —O— (C ₂ H ₄ O) _n —R ₅ .

When the hydrogen atom of the alkyl group or aralkyl group constituting R ₄ in the formula (II) is substituted with the group —O— (C ₂ H ₄ O) _n —R ₅ , n is 0 or 1 to 4 An integer is preferable, and 0, 1 or 2 is more preferable. R ₅ is an alkyl group or aryl group having 12 or less carbon atoms, and may be linear or branched as long as the alkyl group has 3 or more carbon atoms. Examples of the aryl group constituting R ₅ include phenyl and naphthyl, as well as nuclear alkyl-substituted phenyl including tolyl, xylyl, ethylphenyl, and biphenylyl (or phenylphenyl). R ₅ is particularly preferably these aryl groups.

R ₄ in formula (II) is an alkyl group or an aralkyl group, and the hydrogen atom of the alkyl group or aralkyl group of R ₄ is substituted with a group —O— (C ₂ H ₄ O) _n —R ₅ ( Specific examples of (meth) acrylic acid esters include 2-methoxyethyl acrylate, ethoxymethyl acrylate, 2-phenoxyethyl acrylate, 2- (2-phenoxyethoxy) ethyl acrylate, and 2- (o -Alkoxyalkyl-, aryloxyalkyl- or aryloxyethoxyalkyl-esters of acrylic acid, such as -phenylphenoxy) ethyl; 2-methoxyethyl methacrylate, ethoxymethyl methacrylate, 2-phenoxyethyl methacrylate, 2-methacrylic acid 2- (2-phenoxyethoxy) ethyl and 2- (o-methacrylic acid) Enirufenokishi) ethyl, such as, alkoxyalkyl methacrylate -, aryloxyalkyl - or aryloxy ethoxyalkyl - such esters are exemplified.

The (meth) acrylic resin (A) in the present invention may contain a structural unit derived from a monomer other than the monomer (II) having no polar functional group. As monomers other than the monomer (II) having no polar functional group, (meth) acrylic acid ester monomers, styrene monomers, vinyl monomers having an alicyclic structure in the molecule , (Meth) acrylamide derivatives, and monomers having a plurality of (meth) acryloyl groups in the molecule.

The (meth) acrylic acid ester monomer having an alicyclic structure in the molecule will be described. The alicyclic structure is a cycloparaffin structure having usually 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. Specific examples of acrylate monomers having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methyl cyclohexyl acrylate, trimethyl cyclohexyl acrylate, acrylic Examples thereof include tert-butylcyclohexyl acid, cyclohexyl α-ethoxyacrylate, cyclohexylphenyl acrylate, and the like. Specific examples of the methacrylic acid ester monomer having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, cyclododecyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate. Tert-butyl cyclohexyl methacrylate, cyclohexyl phenyl methacrylate, and the like.

Examples of styrenic monomers include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene. Alkyl styrenes; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; and nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene, and the like.

Examples of vinyl monomers include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl fatty acid esters such as vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; Vinylidene halides such as vinylidene chloride; nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene, and chloroprene; and acrylonitrile, methacrylonitrile, etc. .

Examples of (meth) acrylamide derivatives include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (4- Hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N- (methoxymethyl) (meth) acrylamide, N- (ethoxymethyl) ) (Meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (butoxymethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- Isopropyl (meth) acrylamide, N- (3- Methylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N- [2- (2-oxo-1-imidazolidinyl) ethyl] (meth) acrylamide, 2- And acryloylamino-2-methyl-1-propanesulfonic acid.

Examples of monomers having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonane. Two diols in the molecule, such as diol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate Monomers having a meth) acryloyl group; monomers having three (meth) acryloyl groups in the molecule, such as trimethylolpropane tri (meth) acrylate.

The monomer constituting the (meth) acrylic resin (A) has a (meth) acrylic acid ester represented by the formula (II) described above and / or a monomer having a polar functional group and a polar functional group. Two or more types of monomers other than the monomer (II) not to be used may be mixed.

The weight average molecular weight Mw in terms of standard polystyrene by the gel permeation chromatography (GPC) of the resin contained in the pressure-sensitive adhesive is not particularly limited, but the Mw is in the range of 500,000 to 2,000,000. Those in the range of 500,000 to 1,800,000 are more preferable. When the weight average molecular weight in terms of standard polystyrene is 500,000 or more, the adhesiveness under high temperature and high humidity is improved, and the possibility of occurrence of floating or peeling between the glass substrate and the pressure-sensitive adhesive layer tends to decrease. In addition, it is preferable because reworkability tends to be improved. In addition, when the weight average molecular weight is 2 million or less, even if the dimension of the resin film to be bonded to the pressure-sensitive adhesive layer changes, the pressure-sensitive adhesive layer changes following the change in the dimension, so that the liquid crystal cell This is preferable because there is no difference between the brightness of the peripheral edge and the brightness of the central portion, and white spots and color unevenness tend to be suppressed. The molecular weight distribution represented by the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is not particularly limited, but is preferably in the range of about 3 to 15, for example.

The resin contained in the pressure-sensitive adhesive can be produced by various known methods such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method. In the production of the resin, a polymerization initiator may be used, and the addition amount is about 0.001 to 5 parts by mass with respect to a total of 100 parts by mass of all monomers used in the production of the resin.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. Examples of thermal polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2′-azobis (2-methylpropio) And azo compounds such as 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroper Oxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, te Organic peroxides such as t-butyl peroxyneodecanoate, tert-butyl peroxypivalate, and (3,5,5-trimethylhexanoyl) peroxide; potassium persulfate, ammonium persulfate, and hydrogen peroxide Inorganic peroxides such as A redox initiator using a peroxide and a reducing agent in combination can also be used as the polymerization initiator.

As a method for producing the (meth) acrylic resin (A), the solution polymerization method is preferable among the methods shown above. A specific example of the solution polymerization method will be described. A desired monomer and an organic solvent are mixed, and a thermal polymerization initiator is added in a nitrogen atmosphere to about 40 to 90 ° C., preferably 50 to 80 ° C. A method of stirring at about 0 ° C. for about 3 to 15 hours can be mentioned. Moreover, in order to control reaction, you may add a monomer and a thermal-polymerization initiator continuously or intermittently during superposition | polymerization, or may be added in the state melt | dissolved in the organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; acetone, methyl ethyl ketone, and methyl isobutyl. Ketones such as ketones can be used.

[Ionic compounds]
The adhesive which comprises the resin film with an adhesive in this invention contains the ionic compound which is an antistatic agent for providing antistatic property to an adhesive layer. Such an ionic compound has a solubility in water at 60 ° C. of 0.4 g / 100 g or less, preferably 0.35 g / 100 g or less, more preferably 0.32 g / 100 g or less, and usually 0.001 g / 100 g or more. is there. When the solubility of the ionic compound contained in the pressure-sensitive adhesive layer in water at 60 ° C. is not more than the above upper limit, the antistatic function of the pressure-sensitive adhesive can be enhanced. Examples of such ionic compounds include pyridinium salts represented by the formula (I). In the present invention, the solubility means the solubility (g) of an ionic compound in 100 g of water at 60 ° C. In another embodiment of the present invention, a resin film with an adhesive having a resin film and an adhesive layer provided on at least one side of the resin film, wherein the adhesive layer is a resin And a pressure-sensitive adhesive containing a pyridinium salt represented by the following formula (I), wherein the resin film has a specific maximum amount of change.

The pyridinium salt represented by the formula (I) is a chemically stable salt. From the viewpoint of obtaining high antistatic properties, the pyridinium salt preferably has a melting point of 30 ° C. or higher. On the other hand, from the viewpoint of good compatibility with the resin, the pyridinium salt preferably has a melting point of 90 ° C. or lower, more preferably 70 ° C. or lower, more preferably 50 ° C. or lower, and even more preferably less than 50 ° C. .

In addition, the pyridinium cation, which is a cation component of the pyridinium salt represented by the formula (I), is formed from the viewpoint of durability when bonded to glass through the pressure-sensitive adhesive layer and compatibility in the pressure-sensitive adhesive. R _{2 in} I) is a linear alkyl group having 5 to 14 carbon atoms or an aralkyl group having 7 to 13 carbon atoms, such as a linear alkyl group having 7 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms Is used. Specific examples of the cationic component include those listed below.

N-pentylpyridinium ion N-hexylpyridinium ion N-heptylpyridinium ion N-octylpyridinium ion N-nonylpyridinium ion N-decylpyridinium ion N-dodecylpyridinium ion N-tridecylpyridinium ion N-tetradecylpyridinium ion N-octyl -2-methylpyridinium ion N-octyl-3-methylpyridinium ion N-octyl-4-methylpyridinium ion N-nonyl-4-methylpyridinium ion N-decyl-4-methylpyridinium ion N-dodecyl-4-methylpyridinium Ion N-tridecyl-4-methylpyridinium ion N-tetradecyl-4-methylpyridinium ion N-benzylpyridinium ion N-phenethyl Lysine ions N- benzyl-2-methylpyridinium ions N- benzyl-2-methylpyridinium ions N- benzyl-3-methyl pyridinium ion N- benzyl-4-methylpyridinium ions

When the carbon number of R ₂ of the pyridinium salt represented by the formula (I) is 4 or less, pyridinium to a resin film having high ion permeability (for example, a triacetyl cellulose base material) used as an adherend of an adhesive Salt migration occurs, making it difficult to maintain stable antistatic properties over a long period of time. Further, the carbon number of R ₂ is 15 or more, crystallinity of the pyridinium salt is increased, the compatibility of the pyridinium salt in the pressure-sensitive adhesive is lowered.

The pyridinium salt represented by the formula (I) can be appropriately selected from a combination of the cation component and the bis (fluorosulfonyl) imide ion which is an anion component. Specific examples of the combination include the following.

N-pentylpyridinium bis (fluorosulfonyl) imide N-hexylpyridinium bis (fluorosulfonyl) imide N-heptylpyridinium bis (fluorosulfonyl) imide N-octylpyridinium bis (fluorosulfonyl) imide N-nonylpyridinium bis (fluorosulfonyl) imide N-decylpyridinium bis (fluorosulfonyl) imide N-dodecylpyridinium bis (fluorosulfonyl) imide N-tetradecylpyridinium bis (fluorosulfonyl) imide N-dodecyl-4-methylpyridinium bis (fluorosulfonyl) imide N-tetradecyl-4 -Methylpyridinium bis (fluorosulfonyl) imide N-benzylpyridinium bis (fluorosulfonyl) imide N-ben Zir-2-methylpyridinium bis (fluorosulfonyl) imide N-benzyl-4-methylpyridinium bis (fluorosulfonyl) imide

The pyridinium salt represented by the formula (I) can be obtained by a known production method. For example, an alkylpyridinium bromide represented by the following formula (III) (wherein R ₁ and R ₂ are as defined above for formula (I)) and a lithium salt Li (FSO ₂ ) ₂ N The pyridinium salt represented by the formula (I) can be produced by a method of transferring the produced lithium bromide to the aqueous phase and recovering the organic phase by ion exchange reaction and then washing with water. The pyridinium salts represented by the formula (I) can be used alone or in combination of two or more. Of course, examples of the pyridinium salts are not limited to the compounds listed above.

In the present invention, the pressure-sensitive adhesive is preferably 0.05 to 8 parts by mass of an ionic compound (for example, a pyridinium salt represented by the formula (I)) with respect to 100 parts by mass of the resin contained in the pressure-sensitive adhesive. The content is preferably 0.1 to 7 parts by mass, more preferably 0.3 to 6 parts by mass. In this invention, antistatic property can further be improved as content of the said ionic compound in an adhesive is more than the said lower limit. When the content of the ionic compound in the pressure-sensitive adhesive is not more than the above upper limit value, it is easy to maintain the durability, and an antistatic function according to the content can be obtained, which is economically advantageous. Further, it is possible to suppress a decrease in the optical performance of the optical film due to the presence of an excess of the ionic compound.

[Additive]
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer in the resin film with a pressure-sensitive adhesive in the present invention contains other additives in addition to the resin and the ionic compound, for example, the pyridinium salt represented by the formula (1). Also good. Examples of other additives include cross-linking agents, silane compounds, cross-linking catalysts, weathering stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, organic acids, and organic acid metal salts. It is done.

Furthermore, it is also useful to blend an ultraviolet curable compound with this pressure-sensitive adhesive and to cure it by irradiating with ultraviolet light after forming the pressure-sensitive adhesive layer to form a harder pressure-sensitive adhesive layer.

(Crosslinking agent)
The crosslinking agent that can be included in the pressure-sensitive adhesive is a compound having at least two functional groups in the molecule that can crosslink the resin included in the pressure-sensitive adhesive. Specific examples include isocyanate compounds, epoxy compounds, metal chelate compounds, and aziridine compounds.

Isocyanate compounds are compounds having at least two isocyanato groups (—NCO) in the molecule, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, Examples thereof include hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. In addition, adducts obtained by reacting these isocyanate compounds with polyols such as glycerol and trimethylolpropane, and those obtained by converting isocyanate compounds to dimers and trimers are also crosslinking agents used in adhesives. sell. Two or more isocyanate compounds can be mixed and used.

The epoxy compound is a compound having at least two epoxy groups in the molecule, for example, bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether. 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine and the like. Two or more types of epoxy compounds can be mixed and used.

Examples of metal chelate compounds include compounds in which acetylacetone or ethyl acetoacetate is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. Is mentioned.

An aziridine-based compound is a compound having at least two 3-membered ring skeletons composed of one nitrogen atom and two carbon atoms, also called ethyleneimine, for example, diphenylmethane-4,4′-bis ( 1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1- (2-methylaziridine), tris-1-aziridinylphosphine oxide, hexamethylene 1,6-bis (1-aziridinecarboxamide), trimethylolpropane, tris-β-aziridinylpropionate, tetramethylolmethane, tris-β-aziridinylpropionate, and the like.

Among these crosslinking agents, isocyanate compounds, especially adducts obtained by reacting tolylene diisocyanate with polyols, dimers of tolylene diisocyanate, trimers of tolylene diisocyanate, and hexamethylene diisocyanate reacted with polyols. Adduct, hexamethylene diisocyanate dimer, hexamethylene diisocyanate trimer, xylene diisocyanate reacted with polyol adduct, hydrogenated xylylene diisocyanate reacted with polyol, isophorone diisocyanate, and / or An adduct obtained by reacting isophorone diisocyanate with a polyol, a mixture of these isocyanate compounds, and the like are preferably used.

The content of the crosslinking agent in the pressure-sensitive adhesive is usually about 0.01 to 5 parts by weight, preferably 0.03 to 2 parts by weight, and more preferably 0 to 100 parts by weight of the resin contained in the pressure-sensitive adhesive. 0.1 to 1.5 parts by mass.

(Silane compounds)
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive resin film of the present invention improves the adhesion to the glass substrate when the resin film with pressure-sensitive adhesive or the polarizing plate with pressure-sensitive adhesive is formed and then bonded to the glass substrate. From the viewpoint, it is preferable to contain a silane compound. In particular, it is preferable to contain a silane compound in the resin before blending the crosslinking agent.

Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxy Examples include propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane. Two or more silane compounds may be used.

The silane compound may be a silicone oligomer type. When the silicone oligomer is shown in the form of (monomer)-(monomer) copolymer, for example, the following can be mentioned.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxy A copolymer containing a mercaptopropyl group, such as a silane copolymer;

Mercaptomethyl groups, such as mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, and mercaptomethyltriethoxysilane-tetraethoxysilane copolymer Containing copolymers;

3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane -Tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-methacryloyloxypropylmethyldiethoxysilane-teto Such as silane copolymer, methacryloyloxypropyl group containing copolymers;

3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane -Tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane Such polymers, acryloyloxy propyl group-containing copolymer;

Vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, Vinyl group-containing copolymers such as vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, and vinylmethyldiethoxysilane-tetraethoxysilane copolymer.

These silane compounds are often liquids. The content of the silane compound in the pressure-sensitive adhesive is usually about 0.01 to 10 parts by weight, preferably 0.03 to 2 parts by weight, and more preferably 0 to 100 parts by weight of the resin contained in the pressure-sensitive adhesive. 0.03 to 1 part by mass.

<Resin film>
In the resin film with an adhesive, the adhesive layer and the resin film are in direct contact. That is, the adhesive layer and the resin film are laminated.

The resin film constituting the resin film with the pressure-sensitive adhesive of the present invention is not particularly limited, but is a polyolefin resin such as polyethylene, polypropylene, polymethylpentene; polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene. Fluorinated polyolefin resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyester resins such as polyethylene terephthalate / isophthalate copolymer; polyamides such as nylon 6,

nylon

6,6; polyvinyl chloride, Vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinyl polymers such as vinylon; triacetyl cellulose, diacetyl Cellulose resins such as roulose and cellophane; (meth) acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; others, polystyrene, polycarbonate, polyarylate, polyimide, etc. The resin film comprised from these is mentioned.

In the present invention, the resin film may contain various additives. Examples of the additive include an ultraviolet absorber, an antioxidant, a surfactant, a plasticizer, a lubricant, and an antiblocking agent. Examples of the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, cyanoacrylate compounds, nickel complex compounds, and the like. The resin film can be produced by film formation and stretching by a known method.

In the present invention, the thickness of the resin film is preferably 10 μm or more, more preferably 12 μm or more, further preferably 15 μm or more, preferably 200 μm or less, more preferably 180 μm or less, and even more preferably 150 μm or less. When the thickness of the resin film is equal to or more than the above lower limit value, the total amount of the ionic compound absorbed or adsorbed in the substrate increases, so that the effect of selecting an ionic compound, for example, a pyridinium salt in the present invention is increased. When the thickness of the resin film is equal to or less than the above upper limit value, when the polarizer is combined with the surface of the resin film opposite to the surface in contact with the pressure-sensitive adhesive layer, the ionic compound is transferred to the resin film. Since the total amount reaching the polarizer via the ionic compound increases, the polarizer is easily deteriorated by the ionic compound, and the effect of suppressing the migration of the ionic compound according to the present invention is increased.

In the present invention, the resin film is immersed in a 50% by mass aqueous potassium iodide solution for 4.5 hours in an air atmosphere at 23 ° C. and 55% RH, washed with water for 15 seconds, and placed in a dark place at 23 ° C. and 55% RH. The maximum amount of change D of the light absorption amount of light having a wavelength of 355 to 365 nm after the treatment for 15 hours in the air atmosphere with respect to that before the treatment is 5% or more, preferably 8% or more. When the maximum change amount D is not less than the above lower limit value, the ion permeability of the resin film is increased, and various ionic compounds are easily transmitted. However, the ion permeability of the ionic compound, particularly pyridinium salt in the present invention. Is very low, the antistatic function can be maintained, and the optical performance (for example, polarization performance) of the optical film is hardly adversely affected. The maximum change amount D is defined by equation (3) described later, and is usually 50% or less, for example, 25% or less. D can also be calculated from the absorbance.

Such a resin film has a high ability to permeate potassium iodide, which is a general ionic compound, into the base material. Similarly, the ionic compound in the present invention, such as a pyridinium salt, easily penetrates into the base material. Let

Examples of resin films having high ion permeability defined by the above method include trade names “ZRD40” and “ZRE34” manufactured by FUJIFILM Corporation. Examples of resin films with low ion permeability include the product names “Fujitac TD”, “Z-TAC” and “KC4ZDW” manufactured by Fuji Film Co., Ltd. and the product names “Konica Minolta Opto Co., Ltd.”. TAC film KC "and" Zero tack ".

As a resin film to be used in the present invention, for example, an optical film including a polarizing film, a protective film and / or a retardation film, and a surface opposite to the pressure-sensitive adhesive layer of this optical film are bonded and used. A surface protective film for protecting the surface can be mentioned.
When the resin film is a surface protective film, the resin film with the pressure-sensitive adhesive of the present invention can be bonded to the surface of the optical film to protect the surface until use. In this case, it exhibits an excellent antistatic function, and occurs, for example, when an optical film is bonded to a liquid crystal cell via an adhesive layer opposite to the surface protective film and then the surface protective film is peeled off. Can reduce static electricity.

<Preparation of pressure-sensitive adhesive and formation of pressure-sensitive adhesive layer>
The above components constituting the pressure-sensitive adhesive are mixed in a state dissolved in a solvent to form a solution, and then applied onto a suitable substrate and dried to obtain a pressure-sensitive adhesive layer sheet. The substrate used here is generally a plastic film, and a typical example thereof is a release film that has been subjected to a release treatment. The release film is, for example, a film on which a pressure-sensitive adhesive layer sheet of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate is formed and subjected to a release treatment such as silicone treatment. Can be. Moreover, an adhesive layer can also be formed by apply | coating an adhesive directly on a resin film, and making it dry.

<Resin film with adhesive and polarizing plate with adhesive>
The resin film with an adhesive of the present invention is obtained by providing an adhesive layer sheet composed of the above adhesive on at least one side of the resin film. Thus, a resin film with an adhesive in which the adhesive layer sheet is bonded to the resin film is formed. The resin film with an adhesive of the present invention is composed of a resin film and an adhesive layer provided on at least one side of the resin film. Moreover, when the resin film used as a to-be-adhered body is laminated | stacked with the polarizing film, the polarizing plate with an adhesive is formed. The pressure-sensitive adhesive layer sheet may be simply referred to as “pressure-sensitive adhesive layer” in the present specification.

The polarizing film used for a polarizing plate with an adhesive refers to a film in which a transparent protective film (transparent resin film) is laminated on one or both sides of a polarizer. Specific examples of the polarizing film include those in which a dichroic dye such as iodine or a dichroic dye is adsorbed and oriented on a uniaxially stretched polyvinyl alcohol resin film. The thickness of the polarizing film is not particularly limited, but a polarizing film having a thickness of 0.5 to 35 μm is usually used. In addition, the resin film used here may be a zero retardation film or a retardation film. It should be noted that the zero phase difference film, retardation R _th for the front retardation R _e and the thickness direction, both small as -15 ~ 15 nm, refers to the isotropic film optically, suitably used in a liquid crystal display device of IPS mode It is done. The retardation film refers to a film having a retardation value of −15 to 15 nm in at least one of the front retardation R _e and the retardation R _{th in} the thickness direction.

The front retardation R _e and the thickness direction retardation R _th are defined by the following expressions (1) and (2).
R _th = [(n _x + _ny ) / 2−n _z ] × d (1)
R _e = (n _x −n _y ) × d (2)

Wherein, n _x is a refractive index in a slow axis direction (x-axis direction) in the film plane, n _y is the fast axis direction in the film plane of the (y-axis direction orthogonal to the x-axis in a plane) The refractive index is _nz , the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface), and d is the film thickness.

Here, the retardation value may be a value at an arbitrary wavelength in the range of about 500 to 650 nm near the center of visible light, but in this specification, the retardation value at a wavelength of 590 nm is used as a standard. The retardation R _{th in the} thickness direction and the in-plane retardation R _e can be measured using various commercially available phase difference meters.

In the present invention, the pressure-sensitive adhesive can be directly applied onto a polarizing plate that is a laminate of a polarizing film and a resin film, and dried to provide a polarizing plate with a pressure-sensitive adhesive.

In another embodiment of the present invention, there is provided a resin film with an adhesive having the resin film and the adhesive layer provided on at least one side of the resin film, wherein the adhesive layer is , The resin, and a pressure-sensitive adhesive containing the pyridinium salt represented by the formula (1), and the resin film is added to a 50% by mass potassium iodide aqueous solution in an air atmosphere at 23 ° C. and 55% RH. The maximum change in the light absorption amount of light having a wavelength of 355 to 365 nm after the treatment of immersing for 5 hours, washing with water for 15 seconds, and drying in the dark for 15 hours is 5% or more, A resin film with an adhesive is also provided.

<Optical laminate>
In the present invention, an optical laminate (hereinafter also referred to as “optical laminate of the present invention”) is formed by laminating the pressure-sensitive adhesive layer side of the resin film with pressure-sensitive adhesive or the polarizing plate with pressure-sensitive adhesive on a glass substrate. can do. That is, the optical layered body of the present invention comprises the above resin film with an adhesive and the glass substrate laminated on the adhesive layer side. In order to laminate a resin film with an adhesive or a polarizing plate with an adhesive on a glass substrate to form an optical laminate, for example, the release film is peeled off from the resin film with an adhesive obtained as described above, and the exposed adhesive The layer surface may be bonded to the surface of the glass substrate. As a glass substrate, the glass substrate of a liquid crystal cell, the glass for glare-proof, the glass for sunglasses etc. can be mentioned, for example. Among them, a polarizing plate with an adhesive (upper polarizing plate) is laminated on the glass substrate on the front side (viewing side) of the liquid crystal cell, and another polarizing plate with an adhesive (lower polarizing plate) on the glass substrate on the back side of the liquid crystal cell. ) Is preferable because it can be used as a panel (liquid crystal panel) for a liquid crystal display device. Examples of the material of the glass substrate include soda lime glass, low alkali glass, non-alkali glass, and the like, and non-alkali glass is suitably used for the liquid crystal cell.

The optical laminate of the present invention absorbs and relieves stress caused by dimensional changes of the optical film and the glass substrate under wet heat conditions, so that local stress concentration is reduced, and the adhesive layer on the glass substrate Can be prevented from floating and peeling. Further, since optical defects due to non-uniform stress distribution are prevented, white spots can be suppressed. Furthermore, when the resin film with the pressure-sensitive adhesive of the present invention is once laminated on the glass substrate and then peeled again in order to eliminate the problem, even if the resin film is peeled off from the glass substrate together with the pressure-sensitive adhesive, There is little occurrence of glue residue or cloudiness on the surface, and it can be used again as a glass substrate, which is excellent in reworkability.

Examples of suitable layer structures for the optical laminate of the present invention are shown in schematic cross-sectional views in FIGS. In the example shown in FIG. 1, the adhesive layer 20 is formed on one surface of the resin film 3, and the resin film 5 with an adhesive is comprised. And the surface on the opposite side to the resin film 3 of the adhesive layer 20 is bonded to the liquid crystal cell 30 which is a glass substrate, and the optical laminated body 40 is comprised.

In the example shown in FIG. 2, the first resin film 4 having the surface treatment layer 2 is attached to one surface of the polarizer 1 on the surface opposite to the surface treatment layer 2. On the surface, the second resin film 3 is stuck to form a polarizing plate 10. An adhesive layer 20 is provided on the outside of the second resin film 3 constituting the polarizing plate 10 to form an adhesive-attached polarizing plate 15. And the surface on the opposite side to the polarizing plate 10 of the adhesive layer 20 is bonded to the liquid crystal cell 30 which is a glass substrate, and the optical laminated body 40 is comprised.

In the example shown in FIG. 3, the resin film 4 having the surface treatment layer 2 is attached to one surface of the polarizer 1 on the surface opposite to the surface treatment layer 2, and the resin film 4 of the polarizer 1 and On the opposite surface, a resin film 7 is stuck via an interlayer adhesive 6 to constitute a polarizing plate 10. A pressure-sensitive adhesive layer 20 is provided outside the resin film 7 constituting the polarizing plate 10 to form a polarizing plate 15 with a pressure-sensitive adhesive. And the surface on the opposite side to the resin film 7 of the adhesive layer 20 is bonded to the liquid crystal cell 30 which is a glass substrate, and the optical laminated body 40 is comprised.

In the example shown in FIG. 4, the first resin film 4 having the surface treatment layer 2 is attached to one surface of the polarizer 1 on the surface opposite to the surface treatment layer 2. A second resin film 3 is attached to the other surface, and a resin film 7 is attached to the outside of the second resin film 3 via an interlayer adhesive 6 to form a polarizing plate 10. ing. A pressure-sensitive adhesive layer 20 is provided outside the resin film 7 constituting the polarizing plate 10 to form a polarizing plate 15 with a pressure-sensitive adhesive. And the surface on the opposite side to the resin film 7 of the adhesive layer 20 is bonded to the liquid crystal cell 30 which is a glass substrate, and the optical laminated body 40 is comprised.

In these examples, the first resin film 4 and the second resin film 3 are generally composed of a triacetyl cellulose film, but may also be composed of the various transparent resin films described above. it can. The surface treatment layer formed on the surface of the first resin film 4 can be a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, or the like.
Of these, a plurality of layers may be provided.

When the resin film 7 is laminated in the polarizing plate 10 as in the example shown in FIGS. 3 and 4, a quarter wavelength plate is used as a suitable example of the resin film 7 as long as it is a medium-sized liquid crystal display device. Can be mentioned. In this case, the polarizer 1 is generally arranged so that the absorption axis of the polarizer 1 and the slow axis of the resin film 7 that is a quarter-wave plate intersect at about 45 degrees. Depending on the angle, the angle may be shifted from 45 degrees to some extent. On the other hand, in the case of a large liquid crystal display device such as a television, a retardation film having various retardation values in accordance with the characteristics of the liquid crystal cell 30 is used for the purpose of phase difference compensation and viewing angle compensation of the liquid crystal cell 30. . In this case, the polarizer 1 is generally arranged so that the absorption axis of the polarizer 1 and the slow axis of the resin film 7 are substantially orthogonal or substantially parallel. When the resin film 7 is composed of a quarter wavelength plate, a uniaxial or biaxial stretched film is preferably used. In addition, when the resin film 7 is provided for the purpose of phase difference compensation and viewing angle compensation of the liquid crystal cell 30, in addition to the uniaxial or biaxially stretched film, the film is oriented in the thickness direction in addition to the uniaxial or biaxially stretched film. In addition, what is called an optical compensation film, such as a film obtained by applying a phase difference material such as liquid crystal on a support film and fixing the orientation, can also be used as the resin film 7.

3 and 4, when the resin film 7 is bonded via the interlayer adhesive 6 in the configuration of the polarizing plate 10, the interlayer adhesive 6 includes a general acrylic adhesive. Although it is usual to use an agent, it is of course possible to use the pressure-sensitive adhesive layer sheet defined in the present invention. In the case where the polarizer 1 is arranged so that the absorption axis of the polarizer 1 and the slow axis of the resin film 7 are substantially orthogonal or substantially parallel as in the large liquid crystal display device described above, the polarizer is produced when the polarizing plate 10 is manufactured. When bonding 1 and the resin film 7 through the interlayer adhesive 6, it can roll-to-roll-bond. In applications where re-peelability between the two is not required, it is possible to use an adhesive that can be firmly bonded once bonded and cannot be peeled instead of the interlayer adhesive 6 shown in FIGS. . Examples of such an adhesive include an aqueous adhesive that is composed of an aqueous solution or an aqueous dispersion, and develops an adhesive force by evaporating water as a solvent, an ultraviolet curing that cures by ultraviolet irradiation and develops an adhesive force. Examples thereof include a mold adhesive.

3 and 4, the resin film 7 with the adhesive layer 20 formed on itself can be circulated by itself, and can be a resin film with an adhesive as referred to in the present invention. The adhesive-coated resin film with the pressure-sensitive adhesive layer formed on the retardation film can be bonded to a liquid crystal cell that is a glass substrate to form an optical laminate, and a polarizing plate is provided on the retardation film side. It can also bond and can be set as another resin film with an adhesive.

1 to 4 show an example in which the resin film 5 with an adhesive or the polarizing plate 15 with an adhesive is arranged on the viewing side of the liquid crystal cell 30, the resin film with an adhesive according to the present invention is a liquid crystal cell. It can also be arranged on the back side, that is, on the backlight side. When the resin film with pressure-sensitive adhesive of the present invention is arranged on the back side of the liquid crystal cell, a resin film having no surface treatment layer is employed instead of the resin film 4 having the surface treatment layer 2 shown in FIGS. However, the rest can be configured in the same manner as in FIGS. 1 to 4, and can be bonded to the liquid crystal cell 30 via the pressure-sensitive adhesive layer 20. In this case, it is also possible to provide various optical films known to be disposed on the back side of the liquid crystal cell, such as a brightness enhancement film, a light collecting film, and a diffusion film, on the outside of the resin film constituting the polarizing plate. is there.

As described above, the resin film with an adhesive and the optical laminate of the present invention can be suitably used for an organic EL display device and a liquid crystal display device. The liquid crystal display device formed from the adhesive-attached resin film and the optical laminate of the present invention includes, for example, a notebook type, a desktop type, a personal digital liquid crystal display including a PDA (Personal Digital Assistant), a television, and an in-vehicle display. It can be used for electronic dictionaries, digital cameras, digital video cameras, electronic desk calculators, watches, etc.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% indicating the amount used or content are based on mass unless otherwise specified.

In the following examples, the weight average molecular weight was calculated by adding four “TSKgel XL” manufactured by Tosoh Corporation and one “Shodex GPC KF-802” manufactured by Showa Denko Co., Ltd. as columns in the GPC apparatus. It is a value measured in terms of standard polystyrene using 5 pieces connected in series and using tetrahydrofuran as an eluent under the conditions of sample concentration 5 mg / mL, sample introduction amount 100 μL, temperature 40 ° C., flow rate 1 mL / min. .

“Solubility” is the solubility (g) of an ionic compound in 100 g of water at 60 ° C. The solubility was determined according to the following procedure. First, 300 mg of a precisely weighed ionic compound and 2 mL of pure water were mixed and then stored for 24 hours at a temperature of 60 ° C. with stirring. When the obtained ionic compound contained a solvent, the solvent was removed by distillation under reduced pressure to obtain a dry ionic compound, which was precisely weighed. Next, a part of the aqueous layer (precisely weighed) was sampled, and this was appropriately diluted with acetonitrile, and then the mass concentration of the ionic compound dissolved in the obtained measurement sample was determined by liquid chromatography mass spectrometry (LC / MS) was quantified by the absolute calibration curve method. The measurement conditions of LC / MS are as follows. Based on the quantitative results, the solubility of the ionic compound was determined. In addition, each fixed_quantity | quantitative_assay was implemented twice and the average value was made into solubility of this ionic compound.

Analytical apparatus: Agilent Technologies LC / MS apparatus 1260 type / 6130 type Separation column: Kinexex 2.6u C18 100A (3.0 × 100 mm, 2.7 μm)
Mobile phase: gradient method of 0.05 / TFA-added water / acetonitrile mixed solvent Mobile phase flow rate: 0.5 mL / min.
Sample injection volume: 2.5 μL
Oven temperature: 40 ° C
UV detection wavelength: 254 nm
MS detection conditions: Electrospray ionization (ESI) method Positive

[Preparation of adhesive]
A pressure-sensitive adhesive was prepared using the following components. Each component will be described.

<Acrylic resin>
[Polymerization Example 1]
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 81.8 parts of ethyl acetate as a solvent, 69.4 parts of butyl acrylate, 20.0 parts of methyl acrylate, 2- (acrylic acid 2- ( 2-phenoxyethoxy) ethyl 8.0 parts, 2-hydroxyethyl acrylate 1.0 parts, and 0.6 parts of acrylic acid mixed solution were charged, and the air in the apparatus was replaced with nitrogen gas to expel oxygen. The internal temperature was raised to 55 ° C. Thereafter, a total amount of a solution obtained by dissolving 0.15 part of azobisisobutyronitrile as a polymerization initiator in 10 parts of ethyl acetate was added. One hour after the addition of the initiator, while adding ethyl acetate continuously into the reaction vessel at an addition rate of 17.3 parts / hr so that the concentration of the resulting acrylic resin is 30%, the internal temperature is 54 to 56 ° C. Keep warm for hours.
Finally, ethyl acetate was added to the reaction vessel so that the concentration of the acrylic resin was 20%. The obtained acrylic resin had a polystyrene equivalent weight average molecular weight Mw of 1.35 million and Mw / Mn of 5.5 by GPC. This acrylic resin is referred to as “acrylic resin A” below.

<Ionic compounds>
Ionic compound 1: N-benzylpyridinium bis (trifluoromethanesulfonyl) imide (powder at 30 ° C.)

Ionic compound 2: N-decylpyridinium bis (trifluoromethanesulfonyl) imide (powder at 30 ° C.)

Ionic compound 3: N-nonyl-4-methylpyridinium hexafluorophosphate (powder at 30 ° C)

Ionic compound 4: N-methylpyridinium bis (trifluoromethanesulfonyl) imide (powder at 30 ° C.)

Ionic compound 5: N-propylpyridinium bis (trifluoromethanesulfonyl) imide (liquid at 25 ° C.)

<Crosslinking agent>
Coronate L: Ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate (resin concentration 75%), manufactured by Tosoh Corporation.

<Silane compounds>
KBM-403: Glycidoxypropyltrimethoxysilane (liquid), manufactured by Shin-Etsu Chemical Co., Ltd.

To 100 parts of the acrylic resin A produced in Polymerization Example 1, 0.5 part of the crosslinking agent and 1.5 parts of the silane compound are mixed, and the ionic compounds shown in Table 1 are mixed in the amounts shown in Table 1, respectively. Then, ethyl acetate was added so that the resin concentration was 14% to obtain adhesives.

[Examples 1 and 2 and Comparative Examples 1, 2, 4, and 5]
Each adhesive listed in Table 1 is subjected to release treatment on a release treatment surface of a release-treated polyethylene terephthalate film (trade name “PET 3811”, manufactured by Lintec Corporation, referred to as a separator) using an applicator. Was applied to a thickness of 20 μm and dried at 100 ° C. for 1 minute to form a sheet-like pressure-sensitive adhesive layer. Next, an acrylic resin film [trade name “Technoloy S001”, manufactured by Sumitomo Chemical Co., Ltd.] having a thickness of 80 μm containing an ultraviolet absorber is placed on the other side of the polyvinyl alcohol polarizing film on which iodine is adsorbed and oriented. A triacetyl cellulose film of a polarizing plate (P1) having a three-layer structure in which a triacetyl cellulose transparent resin film (trade name “ZRE34”, manufactured by Fuji Film Co., Ltd.) having a thickness of 32 μm is bonded as a transparent resin film. The surface of the sheet-like pressure-sensitive adhesive layer obtained above was bonded to the surface opposite to the separator (pressure-sensitive adhesive layer surface) with a laminator to obtain a polarizing plate with pressure-sensitive adhesive.

[Example 3 and Comparative Example 3]
A film made of an acrylic resin having a thickness of 80 μm containing an ultraviolet absorber on one side of a polyvinyl alcohol polarizing film in which iodine is adsorbed and oriented, instead of the above-mentioned pressure-sensitive adhesives. Trade name “Technoloy S001” (manufactured by Sumitomo Chemical Co., Ltd.) and a transparent resin film with a 42 μm-thick triacetylcellulose-based transparent resin film (manufactured by Fuji Film Co., Ltd., trade name “ZRD40”) on the other side A polarizing plate with an adhesive was obtained by the same method as in Example 1, except that the polarizing plate (P2) having a three-layer structure bonded and used as was replaced with the polarizing plate (P1).

[Reference Examples 1 and 2]
A film made of an acrylic resin having a thickness of 80 μm containing an ultraviolet absorber on one side of a polyvinyl alcohol polarizing film in which iodine is adsorbed and oriented, instead of the above-mentioned pressure-sensitive adhesives. Trade name “Technoloy S001” (manufactured by Sumitomo Chemical Co., Ltd.) and transparent resin film on the other side with a 41 μm thick triacetylcellulose-based transparent resin film (Konica Minolta Co., Ltd., trade name “KC4CR”) A polarizing plate with an adhesive was obtained by the same method as in Example 1, except that the polarizing plate (P3) having a three-layer structure bonded and used as was replaced with the polarizing plate (P1).

[Reference Example 3]
A film made of an acrylic resin having a thickness of 80 μm containing an ultraviolet absorber on one side of a polyvinyl alcohol polarizing film in which iodine is adsorbed and oriented, instead of the above-mentioned pressure-sensitive adhesives. The product name “Technoloy S001” (manufactured by Sumitomo Chemical Co., Ltd.) is used as the transparent resin film and the other side has a 53 μm thick cycloolefin-based transparent resin film (manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR”). A polarizing plate with an adhesive was obtained by the same method as in Example 1, except that the polarizing plate (P4) having a three-layer structure bonded and used was used instead of the polarizing plate (P1).

[Ion permeability evaluation of transparent resin film]
The ion permeability of each transparent resin film, which is an adhesive adherend used for the production of the above polarizing plate with an adhesive, was evaluated by the following procedure.

The transparent resin film was cut into a 4 cm × 4 cm square shape, and transmittance measurement was performed using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-2450). At this time, the minimum transmittance at wavelengths of 355 to 365 nm was defined as A ₀ [%]. The transparent resin film piece after the measurement was immersed in a 50% by mass aqueous potassium iodide solution for 4.5 hours in an air atmosphere at 23 ° C. and 55% RH, taken out, washed with running water for 15 seconds, and then air-dried in a dark room for 15 hours. And measured using an ultraviolet-visible spectrophotometer. At this time, the minimum value of transmittance at wavelengths of 355 to 365 nm was set to A _4.5 [%].

As an index indicating the ion permeability of the transparent resin film, the maximum amount of change (D) in the amount of light absorption before and after the film was immersed in an aqueous potassium iodide solution was defined as the following formula (3).
Maximum amount of change in absorbance D [%] = A ₀ -A _4.5 (3)
ZRE34 used in this study had D = 22% and ZRD40 had D = 15%. In contrast, KC4CR and ZEONOR had D <5%.

[Evaluation of antistatic property of polarizing plate with adhesive]
The separators of the polarizing plates with adhesives obtained in each of the examples, comparative examples and reference examples were peeled off, and the surface resistance value of the adhesive was measured using a surface resistivity measuring device [“Hirest-up MCP manufactured by Mitsubishi Chemical Corporation]. -HT450 "(trade name)] to evaluate the antistatic property.
Evaluation was carried out after 1 day and 14 days after curing under the conditions of a temperature of 23 ° C. and a relative humidity of 65% after the production of a polarizing plate with an adhesive. In order to maintain good antistatic properties over a long period of time, it is preferable that the difference between the surface resistance value (Rs ₁ ) after 1 day of curing and the surface resistance value (Rs ₁₄ ) after 14 days of curing is small. Specifically, the ratio of the surface resistance value after one day of curing to the surface resistance value after 14 days of curing is defined as the surface resistance value change rate (E) as an index of long-term stability of antistatic properties as defined by the following formula (4). did.
Surface resistance value change rate E [%] = Rs ₁₄ / Rs ₁ × 100 (4)
The results are summarized in Table 2.

[Production of optical laminate and heat resistance durability test]
After peeling the separator from the produced polarizing plate with the pressure-sensitive adhesive, the pressure-sensitive adhesive layer side is attached to one side of a glass substrate for liquid crystal cells [“Eagle XG” (trade name) manufactured by Corning Co., Ltd.]. Each body was made. The optical laminate was subjected to a heat durability test for 500 hours under dry conditions at a temperature of 80 ° C., and the optical laminate after the test was visually observed. The degree of floating and peeling of the optical laminate from the glass substrate after the test, that is, the distance from the end of the optical laminate to the position where the optical laminate was peeled was measured using a loupe.

As a result, in the optical laminates produced using the pressure-sensitive adhesive polarizing plates obtained in Examples 1 to 3, Comparative Examples 1 to 5 and Reference Examples 1 to 2, changes in appearance such as floating, peeling and foaming were observed. Was not. On the other hand, in Reference Example 3, changes in appearance such as floating, peeling and foaming were slightly noticeable.

As is clear from the above, in Examples 1 and 2 using the pressure-sensitive adhesive containing the ionic compounds (ionic compounds 1 and 2) defined in the present invention, the solubility of the ionic compounds in water at 60 ° C. is the present invention. Compared to Comparative Examples 1, 2, 4, and 5 in which ionic compounds 3 to 5 that are outside the range specified in the above were mixed, a triacetyl cellulose base material having a D ion of 5% or more and high ion permeability was used as an adherend. In some cases, the value of E is small, and stable antistatic properties can be expressed over a long period of time.

Further, from the comparison between Example 3 and Comparative Example 3, even in ZRD40 where D is smaller than ZRE34, it is possible to keep the E value low when the pressure-sensitive adhesive containing the ionic compound defined in the present invention is used. In addition, it was confirmed that the antistatic property can be maintained for a long time even when a resin film having higher ion permeability is used as the adherend.

The resin film with pressure-sensitive adhesive of the present invention is imparted with stable antistatic properties over a long period of time even when a resin film having high ion permeability is used as an adherend. Furthermore, it has excellent durability even when bonded to glass via an adhesive layer. This resin film with an adhesive and a polarizing plate with an adhesive are suitably used for a liquid crystal display device by sticking to a glass substrate.

DESCRIPTION OF SYMBOLS 1 Polarizer 2 Surface treatment layer 3 (Second) resin film 4 First resin film 5 Resin film with adhesive 6 Interlayer adhesive 7 Resin film 10 Polarizing plate 15 Polarizing plate with adhesive 20 Adhesive layer 30 Liquid crystal cell (Glass substrate)
40 Optical laminate

Claims

A resin film with an adhesive having a resin film and an adhesive layer provided on at least one side of the resin film,
The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive containing a resin and an ionic compound having a solubility in water of 60 ° C. of 0.4 g / 100 g or less,
The resin film was immersed in a 50% by mass aqueous potassium iodide solution for 4.5 hours in an air atmosphere at 23 ° C. and 55% RH, washed for 15 seconds, and dried in the dark for 15 hours. A resin film with an adhesive, wherein the maximum amount of change in the light absorption amount of light having a wavelength of 355 to 365 nm with respect to that before the treatment is 5% or more.
A resin film with an adhesive having a resin film and an adhesive layer provided on at least one side of the resin film,
The pressure-sensitive adhesive layer comprises a resin and the following formula (I):

[Wherein, R 1 is H or a linear alkyl group having 1 to 3 carbon atoms, and R 2 is a linear alkyl group having 5 to 14 carbon atoms or an aralkyl group having 7 to 13 carbon atoms. ]
Composed of a pressure-sensitive adhesive containing a pyridinium salt represented by
The resin film was immersed in a 50% by mass aqueous potassium iodide solution for 4.5 hours in an air atmosphere at 23 ° C. and 55% RH, washed for 15 seconds, and dried in the dark for 15 hours. A resin film with an adhesive, wherein the maximum amount of change in the light absorption amount of light having a wavelength of 355 to 365 nm with respect to that before the treatment is 5% or more.
The resin film with pressure-sensitive adhesive according to claim 1 or 2, wherein the pressure-sensitive adhesive contains 0.05 to 8 parts by mass of the ionic compound with respect to 100 parts by mass of the resin.
The resin film with an adhesive according to any one of claims 1 to 3, wherein the resin is a (meth) acrylic resin.
5. The resin film with an adhesive according to claim 1, wherein the resin film has a thickness of 10 to 200 μm.
An optical laminate comprising the resin film with an adhesive according to any one of claims 1 to 5 and a glass substrate laminated on the adhesive layer side.