KR102159516B1 - Method for producing molded body and molded body - Google Patents

Abstract

It has a process of bending while at least one surface of the resin plate is tightly constrained by a constrained object, and the product of the bending elastic modulus (MPa) of the constrained material and the thickness (m) of the constrained material is 3.0×10 ^-2 MPa·m or more, Water has at least one constraining layer D, and the storage modulus of the constraining layer D is 1.0×10 ² Pa or more and 1.0×10 ⁷ Pa or less at the glass transition temperature of the resin plate. , A method for producing a molded article obtained by bending by thermoforming such as press forming, vacuum forming, pressure forming, etc. while having excellent surface characteristics and appearance, and a molded article obtained by the manufacturing method are provided.

Description

Method for producing a molded body and a molded body TECHNICAL FIELD [Method for producing molded body and molded body]

In the present invention, the surface on the side to be suppressed from stretching and contracting occurring during bending processing, or the surface on the side where it is difficult to stretch and contract, is tightly constrained by a restraint, while compressive deformation, stretch deformation, and Or it relates to a manufacturing method for obtaining a molded article by shearing deformation, and a molded article obtained by the manufacturing method. For example, it is suitable as a method of bending a resin plate having a functional layer on at least one side, and is a manufacturing method capable of obtaining a molded article without impairing the function or appearance of the functional layer. The molded article obtained by the said manufacturing method is suitable, for example, as a surface protection panel disposed on the front side (viewer side) of an image display device and used, particularly as a front cover material for a mobile phone or a liquid crystal pen tablet having a touch panel function.

BACKGROUND ART Conventionally, in the field of an electronic device display cover material, glass has been widely used from the viewpoint of hardness, heat resistance, transparency, and gas barrier properties.

However, since glass is easily broken by impact and the weight of the glass itself is heavy, replacement of plastic is being considered.

In addition, in recent years, various electronic devices and devices have been diversified in design along with miniaturization, weight reduction, and high performance, and in making plastics such as a display cover material, along with surface properties such as excellent optical function, hardness, and design, Secondary workability such as moldability that can cope with various designs is required.

Several proposals have been made regarding a molded article having various surface characteristics and a method for obtaining the molded article. For example, in Patent Document 1, a transparent resin sheet having a protective sheet affixed on the surface thereof is heated and softened to perform vacuum molding, and then a light reflective layer made of a metal vapor deposition layer is formed on the back surface, and the protective sheet is finally removed. A manufacturing method for obtaining a resin molded article has been proposed.

In addition, in Patent Document 2, a laminated hard coating film for molding in which a protective film is provided on the surface of the uncured hard coating layer opposite to the side facing the resin-made base film is proposed. In addition, after preheating the laminated hard coat film and forming a resin molded body by forming a resin molded body by molding and simultaneously molding the laminated hard coat film, post-exposure with active energy rays is performed on the uncured hard coat layer of the laminated hard coat film, A manufacturing method for obtaining a resin molded article with a cured hard coating layer is also proposed.

In addition, Patent Document 3 proposes a molded plate capable of thermal processing excellent in scratch resistance in which a hard coat layer is formed on at least one side of a thermoplastic resin substrate through a primer layer.

In addition, in Patent Document 4, a sheet-like resin molded article having a hard coating layer, which can be thermoformed and has excellent scratch resistance, is proposed.

Japanese Patent Laid-Open No. 2003-205266 Japanese Patent Laid-Open No. 2012-210755 Japanese Patent Laid-Open No. 2005-178035 Japanese Patent Application Laid-Open No. Hei 10-36540

In the manufacturing method for obtaining a molded article such as a mirror-finished resin molded article disclosed in Patent Document 1, since the metal evaporation layer is formed after thermoforming by vacuum molding or the like, the evaporation layer is formed on a plane such as a sheet. In contrast, since irregularities exist, there is a concern that the thickness and performance of the deposited layer may become uneven. In addition, while a sheet can continuously form a vapor-deposited layer by roll-to-roll, in a molded article, since formation of a vapor-deposited layer is limited to batch operation, it is negative in terms of production efficiency. In addition, depending on the evaporation pot, there is a concern that the size and shape of the applicable molded body may be limited.

In the same manner as in the manufacturing method for obtaining the laminated hard coating film for molding and the resin molded article proposed in Patent Document 2, since the hard coat layer is cured and formed after setting it as a resin molded article, irradiation of active energy rays is required due to irregularities in the shape of the molded article. It does not spread evenly, and the surface properties such as hardness of the hard coating layer may become uneven.

Therefore, in Patent Document 3, a molded plate capable of thermal processing in which a hard coating layer is formed on at least one side of a thermoplastic resin substrate through a primer layer is proposed, and non-uniformity of surface properties due to the shape of the molded body concerned in Patent Documents 1 and 2 However, it is expected that the problem of production efficiency of the molded article will be solved. However, in the case of this molded plate, a primer layer is provided that absorbs the stress generated in the hard coating layer when performing heat processing such as thermal bending, but the flexibility of this primer layer is negative for the surface hardness of the hard coating layer formed thereon. There is a risk of acting as. In other words, there is a fear that the surface characteristics that must be provided may be canceled out.

In addition, in the sheet-shaped resin molded article disclosed in Patent Document 4, cracks are generated on the surface during thermoforming and the appearance is damaged, or the surface hardness of the hard coating layer is insufficient, and further improvement is sometimes required.

Accordingly, it is an object of the present invention to provide a method for producing a molded article obtained by bending by thermoforming such as press forming, vacuum forming, pressure forming, and a molded article obtained by the manufacturing method while having excellent surface properties and appearance. have. The molded article obtained by the production method has excellent surface characteristics and appearance, and can also be adapted to a complex shape having various curvatures ((curvature radius R); hereinafter, simply referred to as (R)).

The inventors of the present invention, by bending at least one side surface of the resin plate with a constrained object tightly constrained, without impairing its surface characteristics and appearance, and also to a complex shape having a curvature (R) of various curved portions. It has been discovered that it is possible to produce molded articles that are applicable.

The method for producing a molded article proposed by the present invention can be molded into a complex shape having a curvature R of various curved portions without impairing excellent surface properties and appearance by bending. In addition, since the obtained molded article maintains excellent surface characteristics and appearance, surface protection panels are used by placing them on the front side (viewing side) of an image display device, especially a front surface of a mobile phone or liquid crystal pen tablet having a touch panel function. It can be suitably used as a cover material.

Moreover, according to the manufacturing method of a molded article of the present invention, since the functional layer can be formed in a flat plate (resin plate) such as a film or sheet, thermoforming can be performed, so that a method for manufacturing a molded article having high productivity can be provided. .

1 shows a configuration of an embodiment of a resin plate for molding according to the present invention.
Fig. 2 shows a configuration of an embodiment of a molded article according to the present invention.
3 shows a configuration of an embodiment of a mold for shaping a molded article according to the present invention.

Hereinafter, as an example of the embodiment of the present invention, a method for manufacturing a molded article (referred to as "the main manufacturing method") and a molded article obtained by the present manufacturing method (referred to as a "main molded article") are described. However, the present invention is not limited to the present manufacturing method and the present molded article.

A method for producing a molded article according to the present invention is a method for producing a molded article, characterized in that bending is performed while at least one surface of a resin plate is tightly constrained by a restraint.

In addition, it is characterized in that the curved portion of the molded body is compressively deformed, and by bending with at least one surface of the resin plate tightly constrained by a constraining object, stretching deformation in the curved portion of the constrained surface is suppressed. And the constrained side and the symmetrical side of the curved portion in the plane direction to obtain a molded article.

Alternatively, the curved portion of the molded body is characterized in that the curved portion is elongated and deformed, and in the same manner, by bending with at least one side surface of the resin plate tightly constrained by a constrained object, the elastic deformation in the curved portion of the constrained surface is suppressed. On the other hand, it is a manufacturing method characterized in that a molded article is obtained by elongating and deforming a curved portion on the symmetric side of the restrained side in the plane direction.

In addition, the method for manufacturing a molded article according to the present invention is a method for manufacturing a molded article, characterized in that after bending, both surfaces of the resin plate forming the convex side and the concave side are subjected to a bending process while tightly constrained.

This is characterized in that the curved portion of the molded body is sheared and deformed, and by bending both surfaces of the resin plate forming the convex side and the concave side after the bending process, the constrained surfaces are It is a manufacturing method characterized in that, while suppressing elastic deformation in a curved portion, a portion sandwiched between both surfaces is sheared and deformed to obtain a molded article.

From the above, in the manufacturing method, while restraining the surface on the side where it is intended to be suppressed or difficult to stretch and contract, compressive deformation, stretch deformation, or shearing other parts It is a manufacturing method characterized by obtaining a molded article by deformation.

Therefore, for example, a resin plate having a thin film-like functional layer formed on at least one side surface by a coating method, a transfer method, a physical vapor deposition method, a chemical vapor deposition method, a pneumatic method, a printing method, or a lamination method, etc. In performing bending by molding, it is suitable as a manufacturing method for obtaining a molded article while maintaining its appearance and function by suppressing the stretch and contraction of the thin film layer in bending.

The curvature R of the curved portion in the present molded article is preferably in the range of 2 mm or more and 200 mm or less. The lower limit of the curvature (R) of the curved portion of the present molded body is preferably 2 mm or more, more preferably 4 mm or more, and particularly preferably 8 mm or more. If the curvature (R) of the curved portion is 2 mm or more, as a functional layer capable of responding to the bending process, among those formed by a coating method, a transfer method, a physical vapor deposition layer, a chemical vapor deposition method, a pneumatic method, a printing method, and a lamination method, It is preferable because you can select from a wide range. For example, when the functional layer is a high-hardness layer formed by coating a curable resin composition, it becomes possible to select and use a material from a wide range, such as an organic-based or organic-inorganic hybrid-based hard coating agent, and has excellent surface hardness for the body. It is preferable because it can impart. On the other hand, the upper limit value is preferably 200 mm or less, more preferably 100 mm or less, and particularly preferably 50 mm or less. If the curvature R of the curved portion is 200 mm or less, for example, it is preferable because it can cope with various designs of various electronic devices and devices.

The elongation (ΔL) of the curved portion of the molded article represented by the following equation (1) in the molded article in which the curved portion is compression-deformed within the range where the curvature (R) of the curved portion is 2 mm or more and 200 mm or less is -40% or more and 4% It is preferably less than.

ΔL (%) = (the thickness of the resin plate before molding-the thickness of the curved portion of the molded body) / the thickness of the resin plate before molding × 100. (One)

Here, the elongation rate (ΔL) of the curved portion of the molded article is a value representing the degree of elongation in the plane direction of the resin plate, where a positive value is the degree of elongation in the plane direction, and a negative value is the degree of compression in the plane direction. Indicates the degree.

In the case of the present molded body in which the curved portion is compression-deformed, the lower limit of ΔL is preferably -40% or more, more preferably -30% or more, and more preferably -15% or more. When ΔL is -40% or more, excessive compression in the plane direction with respect to the resin plate is suppressed, and there is no crack or the like, and a molded article having good appearance and surface characteristics can be obtained, which is preferable. On the other hand, it is preferable that the upper limit of ΔL is less than 4%. When ΔL is less than 4%, elongation in the surface direction is suppressed in the resin plate, and cracks and the like do not occur, so it is preferable. From this point of view, ΔL is more preferably less than 0%, particularly preferably less than -2%. It is preferable in the sense that the resin plate does not extend in the plane direction but is compressed in the plane direction that ΔL is less than 0%, that is, shows a negative value.

On the other hand, in the case of the main molded body in which the bent portion is elongated and deformed, the elongation rate (ΔL) of the bent portion represented by the equation (1) is 0% in the range where the curvature (R) of the bent portion of the molded article is 2 mm or more and 200 mm or less. It is preferably more than or equal to 40%. The lower limit of ΔL is preferably 0% or more, more preferably 1% or more, and particularly preferably 3% or more. When ΔL is 0% or more, compression in the plane direction with respect to the resin plate is suppressed, there are no cracks, cloudiness, etc., and a molded article having good appearance and surface characteristics can be obtained, which is preferable. On the other hand, it is preferable that the upper limit value of ΔL is less than 40%. When ΔL is less than 40%, excessive elongation in the surface direction is suppressed in the resin plate, and cracks and the like do not occur, so it is preferable. From this point of view, ΔL is more preferably less than 20%, more preferably less than 10%.

Further, in the case of the main molded body in which the bent portion is sheared deformed, the elongation (ΔL) of the bent portion represented by the equation (1) is -7 in the range where the curvature (R) of the bent portion of the molded article is 2 mm or more and 200 mm or less. It is preferable that it is more than% and less than 7%. The lower limit of ΔL is preferably -7% or more, more preferably -5% or more, and particularly preferably -3% or more. When ΔL is -7% or more, in the resin plate forming the molded article, compression in the surface direction is suppressed, there is no crack or the like, and a molded article having good surface characteristics and appearance can be obtained, which is preferable. On the other hand, the upper limit of ΔL is preferably less than 7%. When ΔL is less than 7%, elongation in the surface direction is suppressed in the resin plate, and cracks and the like do not occur, so it is preferable. From this point of view, ΔL is more preferably less than 5%, and particularly preferably less than 3%.

In the present manufacturing method, at least one surface of the resin plate, or both surfaces of the resin plate forming the convex side and the concave side after bending, are subjected to bending with a restraint tightly constrained, the It is characterized in that the product of the bending elastic modulus (MPa) of the restraint material and the thickness (m) of the restraint material is 3.0×10 ^-2 MPa·m or more.

Further, in the present manufacturing method, in that at least one surface of the resin plate, or both surfaces of the resin plate forming the convex side and the concave side after bending, are tightly constrained by a restraint object, It has at least one layer of restraint layer D, and the storage modulus of restraint layer D is preferably 1.0×10 ² Pa or more and 1.0×10 ⁷ Pa or less at the glass transition temperature of the resin plate. The lower limit of the storage modulus of the constraining layer D is preferably 1.0×10 ² Pa or more, more preferably 5.0×10 ² Pa or more, and particularly preferably 1.0×10 ³ Pa or more. When the storage elastic modulus is 1.0×10 ² Pa or more, it is preferable because cohesive failure of the constraining layer D does not occur during bending, and the bending deformation of the constraining material can be transmitted to the resin plate and/or the functional layer. On the other hand, the upper limit of the preferred range is preferably 1.0×10 ⁷ Pa or less, more preferably 1.0×10 ⁶ Pa or less, and particularly preferably 1.0×10 ⁵ Pa or less. When the storage elastic modulus is 1.0 × 10 ⁷ Pa or less, the constraining layer D is not too hard, and no slipping occurs at the interface with the resin plate and/or the functional layer. / Or it is preferable because it can be transmitted to the functional layer.

Moreover, in the said restraint object, when the restraint object itself has the said storage elasticity modulus, it is not necessary to specifically include a restraint layer D. However, in that case, it is limited to a restraint having a relationship between the above-described flexural modulus and thickness.

In the present manufacturing method, the resin plate may have a single-layer configuration consisting of only a resin substrate or only the functional layer, and having at least a functional layer on one side surface, a two-layer configuration of a functional layer/resin substrate or a functional layer/resin substrate /It does not matter if it is a lamination structure composed of a three-layer structure of functional layers. As an example of a lamination structure, a thin film formed on at least one side of a flat resin substrate such as a film or sheet formed of a resin composition, for example, by a coating method, a transfer method, a physical vapor deposition method, a chemical vapor deposition method, a pneumatic method, a printing method, or a lamination method. A resin plate having a functional layer is mentioned. For example, a high hardness layer formed by a coating method or a thin glass layer laminated by a lamination method may cause cracks when stretched and deformed by bending, and a gas barrier layer formed by a physical vapor deposition method or various optical functions When the layer is stretched and deformed by bending, the thickness of each functional layer increases or decreases, and there is a fear that the required characteristics may become uneven or disappear.

In the present manufacturing method, when the resin plate has a single-layer structure, bending is performed with one side surface tightly constrained by a constrained object, without deforming the constraining side surface, e.g., while maintaining the smoothness of the constraining side surface. can do. In this case, in the case where the tightly constrained side is a convex surface, a molded article can be obtained by compressing and deforming the curved portion on the side symmetrical to the constrained side in the plane direction. On the other hand, in the case where the tightly constrained side is a concave surface, a molded article can be obtained by elongating and deforming the curved portion on the side symmetrical to the restrained side in the plane direction.

In addition, when the resin plate has a laminated structure consisting of a two-layer structure of a functional layer/resin substrate, a bending process is performed while the one side surface having at least a functional layer of the resin plate is tightly constrained by a restraint, and the curved portion of the functional layer While suppressing the expansion and contraction of the resin substrate by compression deformation at the curved portion, it is possible to obtain a molded article having the functional layer on the convex surface and no cracks or the like in the functional layer. In addition, in the case of the two-layer configuration, when bending is performed with at least one side surface having a functional layer tightly constrained by a constraining object, the resin substrate is stretched and deformed at the curved portion, thereby having the functional layer on the concave surface. A molded body can be obtained.

In addition, when the resin plate has a laminated structure consisting of a three-layer structure of a functional layer/resin substrate/functional layer, both surfaces forming the convex side and the concave side of the resin plate are tightly constrained by a restraint after bending. The functional layers are formed on the convex side and the concave side by shearing the resin substrate while suppressing the expansion and contraction of the curved portions of the functional layers on both surfaces by bending while being processed, and cracks in the functional layer. It is possible to obtain a molded article in which the back does not occur.

Hereinafter, a resin plate, a resin base material and a functional layer constituting the resin plate, and a restraint will be sequentially described.

(Resin plate)

In the present invention, the resin plate may be a single-layered structure comprising only a resin substrate or only the functional layer. In addition, it is also possible to have a laminated structure consisting of a two-layer structure of a functional layer/resin substrate having at least a functional layer on one side surface, or a three-layer structure of a functional layer/resin substrate/functional layer.

(Resin description)

When the resin substrate is laminated with the functional layer, it plays a role in receiving compression deformation, elongation deformation or shear deformation by itself when performing bending in the present manufacturing method, thereby suppressing the elastic deformation of the curved portion of the functional layer. Plays a role. From this point of view, the resin substrate is preferably formed of a thermoplastic resin composition exhibiting plasticity by heating.

Moreover, although mentioned later, the resin base material may be a lamination structure in which at least two layers of resin layers formed of different thermoplastic resin compositions are laminated. For example, a resin substrate composed of a two-layer structure of a resin layer A/resin layer C in which a resin layer C formed of a thermoplastic resin composition c is laminated on a resin layer A formed of a thermoplastic resin composition a may be mentioned.

On the other hand, the glass transition temperature of the resin plate in the present invention is the glass transition temperature of the resin substrate when the resin plate has a resin substrate formed of the thermoplastic resin. In addition, when the resin substrate has at least two resin layers formed of different thermoplastic resin compositions, the glass transition temperature of the resin layer having the higher glass transition temperature among the resin layers is the glass transition temperature of the resin plate. do.

(Resin layer A)

As described above, the resin substrate is preferably formed of a thermoplastic resin composition, and has a resin layer A formed of a thermoplastic resin composition a.

(Thermoplastic resin composition a)

The thermoplastic resin that can be used for the thermoplastic resin composition a is not particularly limited as long as it is a thermoplastic resin capable of forming a film, sheet, or plate by melt extrusion, but preferred examples include polyethylene terephthalate, polyethylene naphthalate, and polypropylene terephthalate. , Polybutylene terephthalate, aromatic polyester such as poly-1,4-cyclohexylenedimethylene terephthalate, and aliphatic polyesters such as polylactic acid polymers, polyethylene, polypropylene, cyclo Polyolefin resin such as olefin resin, polycarbonate resin, acrylic resin, polystyrene resin, polyamide resin, polyether resin, polyurethane resin, polyphenylene sulfide resin, polyesteramide resin, Polyether ester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyallylate resin, Polysulfone resins, polyetherimide resins, polyamideimide resins, polyimide resins, and copolymers containing these as main components, or mixtures of these resins.

For example, consider that the molded article obtained by the present manufacturing method is used as a surface protection panel disposed on the front side (viewer side) of an image display device, particularly as a front cover material for a mobile phone or a liquid crystal pen tablet having a touch panel function. On the lower surface, polyester resins, polycarbonate resins, and acrylic resins with little absorption in the visible light region are preferred. Among them, for example, in terms of expressing excellent surface hardness, it is particularly preferably an acrylic resin.

On the other hand, when the thermoplastic resin composition a constituting the resin layer A is a mixture of two or more resins selected from the above, and they are incompatible with each other, the glass transition temperature of the thermoplastic resin having the highest volume fraction is determined by the resin layer. Let it be the glass transition degree of A.

(Acrylic resin)

As a monomer constituting the acrylic resin that can be used in the present invention, for example, methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylic Rate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate )Acrylate, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylic Rate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylic Rate, acrylic (meth)acrylate, 2-hydroxyethyl (meth)acrylate, succinic acid 2-(meth)acryloyloxyethyl, maleic acid 2-(meth)acryloyloxyethyl, phthalic acid 2-( Meth)acryloyloxyethyl, hexahydrophthalic acid 2-(meth)acryloyloxyethyl, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth) )Acrylate, diethylaminoethyl (meth)acrylate, etc. are mentioned.

These may be used singly by polymerization, or two or more types may be polymerized and used.

The monomer which can be copolymerized with the monomer constituting the acrylic resin may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, or a polyfunctional monomer, that is, a polymerizable carbon-carbon double bond in the molecule. A compound having at least two may be used.

Here, examples of the monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methyl styrene, and vinyltoluene; Alkenyl cyan compounds such as acrylonitrile and methacrylonitrile; Acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide; And the like. Further, examples of the polyfunctional monomer include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, and trimethylolpropane triacrylate; Alkenyl esters of unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, and allyl cinnamic acid; Polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate; Aromatic polyalkenyl compounds such as divinylbenzene; And the like. Two or more of them may be used as the monomer copolymerizable with alkyl methacrylate or alkyl acrylate, if necessary.

As a copolymer resin with a monomer constituting the acrylic resin, a methyl methacrylate-styrene copolymer can be preferably used, for example, from the viewpoint of improving the environmental resistance (warpage due to moisture absorption) of the acrylic resin. As the methyl methacrylate-styrene copolymer resin, one having 30 to 95% by weight of methyl methacrylate units and 5 to 70% by weight of styrene units is usually used based on the total monomer units, and preferably Those having 40 to 95% by weight of methyl methacrylate units and 5 to 60% by weight of styrene units are used, more preferably 50 to 90% by weight of methyl methacrylate units and 10 to 50% by weight of styrene units % Have is used. When the ratio of the methyl methacrylate unit decreases, the breaking strength of the surface layer itself decreases, the entire film is liable to crack, and the surface hardness also decreases. Moreover, when the ratio of the methyl methacrylate unit increases, environmental resistance decreases.

The acrylic resin usable in the present invention can be prepared by polymerizing the above-described monomer component by a known method such as suspension polymerization, emulsion polymerization, and bulk polymerization. In that case, it is preferable to use a chain transfer agent during polymerization in order to adjust the desired glass transition degree or to obtain a viscosity exhibiting suitable moldability when producing a laminate. The amount of the chain transfer agent may be appropriately determined depending on the type of the monomer component or its composition.

In addition, in the acrylic resin used for the resin plate, an acrylic resin having heat resistance (hereinafter, referred to as a heat-resistant acrylic resin) can also be preferably used as the thermoplastic resin composition a.

When the resin layer A is formed using a heat-resistant acrylic resin as the main component of the thermoplastic resin composition a, it is preferable because in some cases it becomes easy to impart not only heat resistance but also excellent thermoformability in the resin plate.

In addition, as described later, as a means for suppressing the warpage of the resin plate and the molded body, the resin substrate is a two-layered lamination structure composed of a resin layer A/resin layer C, and the difference in the glass transition temperature between the resin layer A and the resin layer C. It is mentioned that the absolute value of is within 30°C. To this end, if the main component of the thermoplastic resin composition c forming the resin layer C has a high glass transition temperature, it is preferable that the acrylic resin also has a high glass transition temperature, and from this viewpoint, a heat-resistant acrylic resin is used. Can be used as an advantage.

(Heat-resistant acrylic resin a1)

Examples of the heat-resistant acrylic resin a1 include those characterized by being a copolymer resin comprising a (meth)acrylic acid ester structural unit represented by the following formula (1) and an aliphatic vinyl structural unit represented by the following formula (2).

In formula (1), R1 is hydrogen or a methyl group, and R2 is an alkyl group having 1 to 16 carbon atoms.

In the formula (2), R3 is hydrogen or a methyl group, and R4 is a cyclohexyl group which may have an alkyl substituent having 1 to 4 carbon atoms.

R2 of the (meth)acrylic acid ester constituent unit represented by the formula (1) is an alkyl group having 1 to 16 carbon atoms, and includes a methyl group, ethyl group, butyl group, lauryl group, stearyl group, cyclohexyl group, isobornyl group, etc. I can. These can be used alone or in combination of two or more. Preferred among these are (meth)acrylic acid ester structural units in which R2 is a methyl group and/or ethyl group, and more preferable are methacrylic acid ester structural units in which R1 is a methyl group and R2 is a methyl group.

Examples of the aliphatic vinyl structural unit represented by the general formula (2) include those in which R3 is hydrogen or a methyl group, and R4 is a cyclohexyl group or a cyclohexyl group having an alkyl group having 1 to 4 carbon atoms. These can be used alone or in combination of two or more. Preferred among these are aliphatic vinyl structural units in which R3 is hydrogen and R4 is a cyclohexyl group.

The molar composition ratio of the (meth)acrylic acid ester constituent unit represented by the formula (1) and the aliphatic vinyl constituent unit represented by the formula (2) is in the range of 15:85 to 85:15, and is in the range of 25:75 to 75:25. It is preferable that it is a range, and it is more preferable that it is a range of 30:70-70:30.

If the molar composition ratio of the (meth)acrylic acid ester constituent unit to the total of the (meth)acrylic acid ester constituent unit and the aliphatic vinyl constituent unit is less than 15%, the mechanical strength is too low to become brittle, which is not practical. Moreover, when it exceeds 85%, heat resistance may become inadequate.

The heat-resistant acrylic resin a1 is not particularly limited as long as it is mainly composed of a (meth)acrylic acid ester constituent unit represented by formula (1) and an aliphatic vinyl constituent unit represented by formula (2), but the (meth)acrylic acid ester monomer and After copolymerizing an aromatic vinyl monomer, it is suitably obtained by hydrogenating an aromatic ring. On the other hand, (meth)acrylic acid represents methacrylic acid and/or acrylic acid. Specific examples of the aromatic vinyl monomer used at this time include styrene, α-methyl styrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and the like, and derivatives thereof. Among these, styrene is preferable.

In addition, as the (meth)acrylic acid ester monomer, specifically, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclo(meth)acrylate Alkyl (meth)acrylates, such as hexyl and isobornyl (meth)acrylate, etc. can be mentioned, but it is preferable to use alkyl methacrylate alone or in combination of alkyl methacrylate and alkyl acrylate from the balance of physical properties. desirable. Of the alkyl methacrylates, particularly preferred are methyl methacrylate or ethyl methacrylate.

In the heat-resistant acrylic resin a1 mainly composed of the (meth)acrylic acid ester constituent unit represented by the formula (1) and the aliphatic vinyl constituent unit represented by the formula (2), 70% or more of the aromatic ring of the aromatic vinyl monomer is obtained by hydrogenation. It is preferable that it is. That is, the proportion of the aromatic vinyl structural unit in the heat-resistant acrylic resin a1 is preferably 30% or less in the heat-resistant acrylic resin a1. If it exceeds 30%, the transparency of heat-resistant acrylic resin a1 may fall. More preferably, it is a range of 20% or less, and still more preferably, it is a range of 10% or less.

A known method can be used for the polymerization of the (meth)acrylic acid ester monomer and the aromatic vinyl monomer, but can be produced by, for example, a bulk polymerization method or a solution polymerization method. In the solution polymerization method, a monomer composition containing a monomer, a chain transfer agent, and a polymerization initiator is continuously supplied to a complete mixing tank, followed by continuous polymerization at 100 to 180°C.

The method of hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out in a batch type or continuous flow type at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250°C. When the temperature is set at 60°C or higher, the reaction time does not take too much, and when the temperature is set at 250°C or lower, the molecular chains are not cleaved or the ester moiety is hydrogenated.

Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or oxides or salts or complex compounds of these metals, such as carbon, alumina, silica, silica-alumina, and diatomaceous earth. And a solid catalyst supported on a porous carrier.

The glass transition temperature of the heat-resistant acrylic resin a1 is preferably 110°C or higher. When the glass transition temperature is 110°C or higher, the heat resistance of the laminate is not insufficient.

(Heat-resistant acrylic resin a2)

As the heat-resistant acrylic resin a2, based on the total monomer units constituting the acrylic resin, 60 to 95% by weight of methyl methacrylate units and methacrylic acid units, acrylic acid units, maleic anhydride units, N-substituted or unsubstituted malei A polymer having 5 to 40% by weight of a unit selected from a mid unit, a glutaric anhydride structural unit, and a glutarimide structural unit, and having a glass transition temperature of 110°C or higher can be mentioned.

Here, the methyl methacrylate unit is a unit [-CH ₂ -C(CH ₃ ) (CO ₂ CH ₃ )-] formed by polymerization of methyl methacrylate, and the methacrylic acid unit is methacrylic acid It is a unit formed by polymerization of [-CH ₂ -C(CH ₃ )(CO ₂ H)-], and the acrylic acid unit is a unit formed by polymerization of acrylic acid [-CH ₂ -CH(CO ₂ H)- 〕to be. In addition, the maleic anhydride unit is a unit formed by polymerization of maleic anhydride represented by formula (3), and the N-substituted or unsubstituted maleimide unit is N-substituted or non-substituted represented by formula (4). It is a unit formed by polymerization of ring maleimide.

In formula (4), R ¹ represents a hydrogen atom or a substituent, and examples of this substituent include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group. And the carbon number is usually about 1 to 20.

In addition, the glutaric anhydride structural unit is a unit having a glutaric anhydride structure, and the glutarimide structural unit is a unit having a glutarimide structure, and typically, the following formulas (5) and (6) ).

In formula (5), R ² represents a hydrogen atom or a methyl group, and R ³ represents a hydrogen atom or a methyl group. In formula (6), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a substituent, and examples of this substituent include an alkyl group such as a methyl group or an ethyl group, or a cyclohexyl group. A cycloalkyl group such as an actual group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group, and the number of carbon atoms is usually about 1 to 20.

Methyl methacrylate unit, methacrylic acid unit, acrylic acid unit, maleic anhydride unit, and N-substituted or unsubstituted maleimide unit, respectively, as polymerization raw materials, methyl methacrylate, methacrylic acid, acrylic acid, maleic anhydride It can be introduced by using, and N-substituted or unsubstituted maleimide.

The glutaric anhydride structural unit is a homopolymer of methyl methacrylate, or a copolymer of methyl methacrylate and methacrylic acid and/or acrylic acid, in the presence of an alkaline compound such as sodium hydroxide, potassium hydroxide, and sodium methylate. , In general, it can be introduced by heat treatment at 150 to 350°C, preferably 220 to 320°C to denature.

In addition, the glutarimide structural unit is a homopolymer of methyl methacrylate, or a copolymer of methyl methacrylate and methacrylic acid and/or acrylic acid, in the presence of ammonia or primary amine, usually 150 to 350°C, Preferably, it can be introduced by heat treatment in the range of 220 to 320°C to denature.

As the heat-resistant acrylic resin a2, the monomer unit composition of the acrylic resin is a methyl methacrylate unit is preferably 65 to 95% by weight, more preferably 70 to 92% by weight, a methacrylic acid unit, an acrylic acid unit, male The unit selected from an acid anhydride unit, an N-substituted or unsubstituted maleimide unit, a glutaric anhydride structural unit, and a glutarimide structural unit is preferably 5 to 35% by weight, more preferably 8 to 30% by weight. %to be. Moreover, the glass transition temperature of the acrylic polymer is preferably 115°C or higher, and usually 150°C or lower.

(Heat-resistant acrylic resin a3)

Examples of the heat-resistant acrylic resin a3 include those having a lactone ring structure formed by cyclization condensation reaction of a polymer (?) having a hydroxyl group and an ester group in a molecular chain. The polymer (α) is a copolymer obtained by polymerizing a monomer component containing at least a (meth)acrylate-based monomer (α1) and a 2-(hydroxyalkyl)acrylate-based monomer, and the lactone ring structure has the following formula It is a structure represented by (7).

In formula (7), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. On the other hand, an oxygen atom may be included in the organic residue.

In order to form the lactone ring structure represented by the formula (7), a polymer (α) having a hydroxyl group and an ester group in the molecular chain is represented by, for example, a (meth)acrylate monomer (α1) and the following formula (8). A polymer obtained by polymerizing a monomer component containing a vinyl monomer (?2) having a structural unit to be formed is preferably mentioned.

In formula (8), R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.

If the (meth)acrylate-based monomer (α1) is a so-called (meth)acrylate alkyl ester monomer other than a vinyl monomer having, for example, a 2-(hydroxymethyl)acrylic acid ester structural unit represented by the above formula (8), It is not particularly limited. For example, an aliphatic (meth)acrylate having an alkyl group or the like may be used, an alicyclic (meth)acrylate having a cyclohexyl group or the like may be used, or an aromatic (meth)acrylate having a benzyl group or the like may be used. Moreover, a desired substituent or functional group may be introduced into these groups.

Specific examples of the (meth)acrylate-based monomer (α1) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (Meth)acrylic acid esters, such as isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and benzyl (meth)acrylate, etc. are mentioned. These may be used alone or in combination of two or more. Among these, methyl methacrylate or methyl acrylate is preferable from the viewpoint of weather resistance, surface gloss, and transparency of the acrylic resin obtained, and methyl methacrylate is more preferable from the viewpoint of the surface hardness of the obtained acrylic resin. Further, the (meth)acrylate having a cyclohexyl group imparts hydrophobicity to the acrylic resin, and as a result, the water absorption rate of the acrylic resin can be reduced, and weather resistance can be imparted to the acrylic resin. Moreover, the (meth)acrylate having an aromatic group is preferable from the viewpoint of further improving the heat resistance of the acrylic resin obtained by an aromatic ring.

Among the monomer components, the proportion of the (meth)acrylate-based monomer (?1) is not particularly limited, but is preferably 95 to 10% by weight, and more preferably 90 to 10% by weight. In addition, in order to maintain good transparency and weather resistance, it is preferably 90 to 40% by weight, more preferably 90 to 60% by weight, still more preferably 90 to 70% by weight of all monomer components.

In the heat-resistant acrylic resin a3 used in the present invention, an unsaturated monocarboxylic acid (α1') may be used in combination as the (meth)acrylate-based monomer (α1). By using an unsaturated monocarboxylic acid (?1') together, an acrylic resin in which a glutaric anhydride ring structure is introduced together with a lactone ring structure can be obtained, and heat resistance and mechanical strength can be further improved, which is preferable. As the unsaturated monocarboxylic acid (α1'), for example, (meth)acrylic acid, crotonic acid, or an α-substituted acrylic acid monomer as a derivative thereof can be exemplified, but it is not particularly limited. Preferably, it is (meth)acrylic acid, and further, methacrylic acid is preferable from a heat resistance point. Further, the ester group derived from the (meth)acrylate-based monomer (α1) in the polymer (α) may have a structure equivalent to that of the unsaturated carboxylic acid (α1') under conditions such as heating. Further, the carboxyl group of the unsaturated carboxylic acid (?1') may have a structure of, for example, a salt such as a metal salt such as a sodium salt, as long as it does not interfere with the cyclization condensation reaction described later. On the other hand, in the monomer component, the ratio of the unsaturated monocarboxylic acid (?1') is not particularly limited, and may be appropriately set within a range that does not impair the effects of the present invention.

Examples of the vinyl monomer (?2) having the structural unit represented by the above formula (8) include derivatives of 2-(hydroxyalkyl)acrylic acid. Specifically, a 2-(hydroxymethyl)acrylic acid ester-based monomer is preferably mentioned. More specifically, for example, 2-(hydroxymethyl) methyl acrylate, 2-(hydroxymethyl) ethyl acrylate, 2-(hydroxymethyl) isopropyl acrylate, 2-(hydroxymethyl) normal butyl acrylate, 2 -(Hydroxymethyl)acrylic acid-t-butyl, etc. are mentioned. Among these, methyl 2-(hydroxymethyl)acrylate and ethyl 2-(hydroxymethyl)acrylate are especially preferable. Further, methyl 2-(hydroxymethyl)acrylate is most preferred because it has a high effect of improving surface hardness, hot water resistance, or solvent resistance. On the other hand, these may use only 1 type or may use 2 or more types together.

Among the monomer components, the proportion of the vinyl monomer (?2) having a structural unit represented by the above formula (8) is not particularly limited, but is preferably 5 to 50% by weight. It is more preferably 10 to 40% by weight, and more preferably 15 to 35% by weight. When the ratio of the vinyl monomer (?2) is less than the above range, the amount of the cyclic structure decreases, and thus the surface hardness of the laminate may be lowered, or the hot water resistance and solvent resistance may also decrease. In addition, the heat resistance of the laminate may be lowered. On the other hand, when it is more than the above range, when forming a lactone ring structure, a crosslinking reaction occurs, which tends to be gelled, the fluidity decreases, and melt molding may become difficult. In addition, since unreacted hydroxyl groups are liable to remain, when molding the obtained acrylic resin, the condensation reaction proceeds further to generate volatile substances, and bubbles or silver streaks in the laminate (silver streaks on the surface, etc.) May become easier to enter.

As the monomer component when obtaining the polymer (α), a polymerizable monomer other than the above (α1) and (α2) can also be used as long as the effect of the present invention is not impaired. For example, styrene, vinyltoluene, α-methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate, and the like may be mentioned. On the other hand, these may use only 1 type or may use 2 or more types together. When using the polymerizable monomer together as the monomer component when obtaining the polymer (α), the content of these monomers is preferably 0 to 30% by weight or less, and more preferably 0 to 20% by weight or less in the monomer component. , More preferably 0 to 10% by weight or less. In terms of physical properties, if a predetermined amount or more is used, physical properties such as weather resistance, surface gloss, or transparency, which are good physical properties derived from (meth)acrylate-based monomers, may be impaired.

Heat-resistant acrylic resin a3 is obtained by subjecting the polymer (?) to a cyclization condensation reaction to form a ring structure. The cyclization condensation reaction is a reaction in which a lactone ring structure is generated by cyclization condensation of a hydroxyl group and an ester group (or further carboxyl group) present in the molecular chain of the polymer (α) by heating. Alcohol and water are produced by it. Thus, when the ring structure is formed in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted, and high surface hardness, hot water resistance, and solvent resistance are imparted.

As a method of cyclization condensation of the polymer (α) to obtain an acrylic resin having a lactone ring structure, for example, 1) a method of cyclization condensation reaction by heating the polymer (α) in an extruder under reduced pressure (Polym. Prepr., 8) , 1, 576 (1967), 2) a method of carrying out the cyclization condensation reaction of the polymer (α) in the presence of a solvent and simultaneously devolatilization during the cyclization condensation reaction, 3) using a specific organophosphorus compound as a catalyst And a method of cyclization condensation of the polymer (α) (European Patent No. 1008606). Of course, it is not limited to these, and a plurality of methods may be employed among the methods 1) to 3). In particular, the reaction rate of the cyclization condensation reaction is high, it is possible to suppress the entry of bubbles or silver streaks into the laminate, and in that it is possible to suppress a decrease in mechanical strength due to a decrease in molecular weight during devolatilization, 2) and 3). The method used is preferred.

It is preferable that the heat-resistant acrylic resin a3 used in the present invention has a weight average molecular weight of 1,000 to 1,000,000, more preferably 5,000 to 500,000, and most preferably 50,000 to 300,000. If the weight average molecular weight is lower than the above range, not only the surface hardness, hot water resistance, or solvent resistance decrease, but also the mechanical strength is lowered and there is a problem that it is easy to be brittle. On the other hand, if it is higher than the above range, the fluidity is lowered and it is difficult to form. Therefore, it is not desirable.

The glass transition temperature (Tg) of the heat-resistant acrylic resin a3 is preferably 115°C or higher, more preferably 125°C or higher, and most preferably 130°C or higher.

As described above, when the resin layer A is formed from the thermoplastic resin composition a containing any of the above heat-resistant acrylic resins as a main component, it is preferable because the curvature of the resin plate and the molded article may be easily suppressed. For example, if a polycarbonate-based resin is used as the main component of the thermoplastic resin composition c forming the resin layer C, even if any of the above heat-resistant acrylic resins are used as the main component of the thermoplastic resin composition a forming the resin layer A, the resin layer In many cases, the absolute value of the difference between the glass transition temperature of A and the resin layer C can be made within 30°C, which is preferable. That is, by making the absolute value of the difference between the glass transition temperature of the resin layer A and the resin layer C within 30°C, it is preferable to suppress the curvature of the resin plate and the molded article.

(Heat-resistant acrylic resin a4)

As the heat-resistant acrylic resin a4, one having not only heat resistance but also excellent hardness, and containing a hard dispersed phase in a matrix of an acrylic resin can also be used. More specifically, in the acrylic resin, a material obtained by containing and dispersing a hard dispersed material superior in heat resistance or scratch resistance than acrylic resin can be used. The pencil hardness on the surface of the resin layer A can be made 5H or more by using an acrylic resin containing a hard dispersed phase in the matrix.

Examples of the material for forming the hard dispersion phase include thermosetting resins, specifically, polycondensation or addition of phenol resins, amino resins, epoxy resins, silicone resins, thermosetting polyimide resins, thermosetting polyurethane resins, etc. In addition to the condensed resin, an addition polymerization resin obtained by radical polymerization of an unsaturated monomer such as a thermosetting acrylic resin, a vinyl ester resin, an unsaturated polyester resin, and a diallyl phthalate resin may be mentioned.

Among these, if the unsaturated monomer is polyfunctional, it is preferable because the properties of a hard material (insoluble, high glass transition temperature) can be obtained by polymerization and crosslinking. Examples of the unsaturated monomer include polyols and polyesters of acrylic acid and/or methacrylic acid, and crosslinkable monomers such as polyallyl and polyvinyl ether of these polyols. However, it is not limited to these.

As an unsaturated monomer, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethoxylate (di-, tri-)acrylate, trimethylolpropane Diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpro Paine triacrylate or ethoxylated pentaerythritol tetraacrylate, and mixtures thereof. Among them, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA) can be suitably used in consideration of affinity with acrylic resins. However, it is not limited to these.

Thermosetting resins may be used alone or in combination of two or more. Moreover, you may use in combination of these thermosetting resins and a thermoplastic resin having a crosslinkable unsaturated bond.

The shape of the hard dispersed phase may be a particle shape, a spherical shape, a linear shape, a fibrous shape, or the like, and a spherical shape is preferable from the viewpoint of being easily dispersed evenly in an acrylic resin which is a thermoplastic matrix resin. However, it is not limited to this.

The particle diameter of the hard dispersion phase is appropriately set depending on the purpose of use, the use of the molded article, and the like, but is preferably 0.1 to 1000 μm. The blending amount of the hard dispersion phase in the acrylic resin phase is appropriately set depending on the purpose of use of the molded article, the application, etc., but is preferably 0.1 to 60% by weight.

Although it does not specifically limit as a method of including a hard dispersion phase in an acrylic resin phase, For example, the following method is mentioned.

a) A thermosetting resin material constituting the hard dispersion phase is added to the acrylic resin material.

b) Next, after melt-kneading and molding into a predetermined shape, a hard dispersed phase can be formed by causing phase separation and crosslinking. Further, the thermosetting resin may be previously molded into particles or the like, added to the acrylic resin, and kneaded and molded at a temperature at which the thermosetting resin does not melt.

(Other ingredients)

In addition to the resin component, the thermoplastic resin composition a forming the resin layer A includes various additives such as plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, flame retardants such as silicone compounds, fillers, glass fibers, and impact modifiers. You may contain in the range which does not impair the effect of this invention.

Further, the thermoplastic resin composition a forming the resin layer A may also contain acrylic rubber particles having an elastomer portion within a range not impairing the effects of the present invention. Such acrylic rubber particles have a layer made of an elastomer (elastomeric layer) mainly composed of an acrylic acid ester, and may be a single-layered particle made of only an elastomer, or a layer made of an elastomer layer and a hard polymer (hard polymer layer). Although it may be a particle|grains of a multilayer structure comprised by this, considering the surface hardness of the resin layer A arrange|positioned on the surface of a laminated body, it is preferable that they are multilayered structure particles. On the other hand, the number of acrylic rubber particles may be only one, and may be two or more.

Since the resin layer A is disposed on the back side (裏側) of the functional layer, it may serve as an assist when expressing excellent surface characteristics to the functional layer. For example, when expressing excellent surface hardness in the functional layer, it is preferable to use the resin layer A formed of the resin composition a containing an acrylic resin as a main component as described above, and the thickness of the resin layer A in that case is 40 μm or more. It is preferable, and it is more preferable that it is 60 micrometers or more. When the thickness of the resin layer A is 40 μm or more, even if the thickness of the functional layer having high hardness is made thin, it is preferable because excellent surface hardness is expressed on its surface. On the other hand, the thickness of the resin layer A is preferably 500 μm or less, more preferably 300 μm or less, and particularly preferably 100 μm or less. When the thickness of the resin layer A is 500 μm or less, the resin layer A has brittleness, and when the secondary processability such as thermoformability or punching is insufficient, lamination of the resin layer C makes it easy to compensate, so it is preferable. .

Similarly, when expressing excellent surface hardness to the functional layer, the hardness of the surface of the resin layer A is preferably 3H or more, and more preferably 5H or more in terms of pencil hardness. When the pencil hardness of the surface of the resin layer A is 3H or more, even if the thickness of the functional layer laminated thereon is made thin, excellent hardness is maintained on the surface, that is, excellent surface hardness can be imparted, which is preferable.

Moreover, if the thickness of the functional layer can be made thin, it is preferable because the thermoformability of the resin plate is improved.

(Resin layer C)

In the resin substrate, the resin layer C can be provided on the surface of the resin layer A opposite to the side on which the functional layer is laminated. In particular, when the resin layer A is formed of a thermoplastic resin composition a containing an acrylic resin as a main component, the resin layer C plays a role of imparting excellent impact resistance to the molded body or secondary processability such as punchability.

(Thermoplastic resin composition c)

The resin layer C is formed from the thermoplastic resin composition c. The thermoplastic resin that can be used for the thermoplastic resin composition c is not particularly limited as long as it is a thermoplastic resin capable of forming a film, sheet, or plate by melt extrusion, but preferred examples include polyethylene terephthalate, polyethylene naphthalate, and polypropylene tere. Polyester resins represented by aliphatic polyesters such as aromatic polyesters such as phthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and polylactic acid polymers, polyethylene, polypropylene, Polyolefin resin such as cycloolefin resin, polycarbonate resin, acrylic resin, polystyrene resin, polyamide resin, polyether resin, polyurethane resin, polyphenylene sulfide resin, polyester amide resin , Polyether ester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyallylate resin , Polysulfone resins, polyetherimide resins, polyamideimide resins, polyimide resins, copolymers containing these as a main component, or mixtures of these resins.

In particular, in the present invention, polyester resins, polycarbonate resins, or acrylic resins are preferable from the viewpoint of almost no absorption in the visible light region as described above.

Among them, polycarbonate-based resins are particularly preferred in terms of providing excellent impact resistance or secondary processability such as punchability to the molded article.

On the other hand, when the thermoplastic resin composition c constituting the resin layer C is a mixture of two or more resins selected from the above, and they are incompatible with each other, the glass transition temperature of the thermoplastic resin having the highest volume fraction Let the glass transition degree of C.

(Polycarbonate resin)

The polycarbonate resin that can be used in the present invention is not particularly limited as long as it can form a film, sheet, or plate by melt extrusion, and is selected from the group of aromatic polycarbonate, aliphatic polycarbonate, and alicyclic polycarbonate. At least one type can be used.

(Aromatic polycarbonate)

As an aromatic polycarbonate, for example, i) one obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method, ii) one obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method, etc. iii) What is obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method, etc. are mentioned. Among these, i) obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method, a melt transesterification method, or the like is preferable from the viewpoint of productivity.

Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, and bis{(4-hydroxy-3,5-di Methyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl) ) Propane (common name bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-dimethyl)phenyl }Propane, 2,2-bis{(4-hydroxy-3,5-dibromo)phenyl}propane, 2,2-bis{(3-isopropyl-4-hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3 -Methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2- Bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1- Bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4- Hydroxyphenyl)fluorene, 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α ,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydro Roxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide , 4,4'-dihydroxydiphenylketone, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenylester, etc., and two or more of them as necessary You can also use

As the dihydric phenol, among the above, bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydro Roxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and α,α'-bis(4-hydroxyphenyl)-m -It is preferable to use alone or two or more dihydric phenols selected from the group consisting of diisopropylbenzene, and in particular, the use of bisphenol A alone or 1,1-bis(4-hydroxyphenyl)-3, 3,5-trimethylcyclohexane and bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane and α,α'-bis(4-hydroxyphenyl)-m- Combination of at least one dihydric phenol selected from the group consisting of diisopropylbenzene is preferred.

Examples of the carbonylating agent include carbonyl halide such as phosgene, carbonate ester such as diphenyl carbonate, haloformate such as dihaloformate of dihydric phenol, and the like. You can also use the above.

(Other polycarbonate resins)

Examples of polycarbonate resins other than the aromatic polycarbonate include aliphatic polycarbonate and alicyclic polycarbonate. It is preferable to include at least a structural unit derived from a dihydroxy compound having a moiety represented by the following formula (9) in part of the structure.

(However, except for the case where the moiety represented by formula (9) is a part of -CH ₂ -OH.)

The dihydroxy compound is not particularly limited as long as a part of its molecular structure is represented by the formula (9), but specifically, 9,9-bis(4-(2-hydroxyethoxy)phenyl)flu Orene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)flu Orene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl Phenyl) fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3- Phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)- 3-tert-butyl-6-methylphenyl)fluorene, 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene, etc., having an aromatic group in the side chain, and in the main chain And compounds having an ether group bonded to an aromatic group.

In addition, from the viewpoint of heat resistance, a compound having a cyclic ether structure such as spiroglycol can also be preferably used. Specifically, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro (5.5)undecaine (common name: spiroglycol), 3 ,9-bis(1,1-diethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecaine, 3,9-bis(1,1-dipropyl-) 2-hydroxyethyl)-2,4,8,10-tetraoxaspiro (5.5) undecaine, and the like.

Other polycarbonate resins may contain structural units derived from dihydroxy compounds other than the dihydroxy compounds (hereinafter sometimes referred to as "other dihydroxy compounds"), and other dies. As the hydroxy compound, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butane Aliphatic dihydroxy compounds such as diol, 1,5-heptanediol, and 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 2,6-decalynedimethanol, 1,5-decalynedimethanol, 2,3-decalynedimethanol, 2,3 -Alicyclic dihydroxy compounds, such as noborne dimethanol, 2,5-norborne dimethanol, and 1,3-adamantane dimethanol, 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2- Bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4- Hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1, 1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl) )Sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3 '-Dichlorodiphenyl ether, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9 And aromatic bisphenols such as 9-bis(4-hydroxy-2-methylphenyl)fluorene.

In a resin substrate formed by laminating a resin layer C formed of a thermoplastic resin composition c and a resin layer A formed of a thermoplastic resin composition a, the absolute value of the difference between the glass transition temperature of the resin layer A and the resin layer C is within 30°C. Accordingly, even when the resin plate and the molded body are exposed to an environment of high temperature or high temperature and high humidity, such warpage can be suppressed, which is preferable. From this point of view, the absolute value of the difference between the glass transition temperature of the resin layer A and the resin layer C is more preferably 25°C or less, and still more preferably 20°C or less.

As a method of making the absolute value of the difference between the glass transition temperature of the resin layer A and the resin layer C within 30°C, for example, the following method may be mentioned.

(1) In the thermoplastic resin composition a and/or the thermoplastic resin composition c, by blending thermoplastic resins having different glass transition temperatures to obtain a mixture of at least two or more thermoplastic resins, the glass of the resin layer A and the resin layer C How to adjust the difference in transition temperature within 30℃. Here, as two or more types of thermoplastic resins having different glass transition temperatures, as long as they have different glass transition temperatures, the same or different types of thermoplastic resins may be used. Moreover, the thermoplastic resin blended here has compatibility with the thermoplastic resin composition a or the thermoplastic resin composition c.

(2) In the thermoplastic resin composition a and/or the thermoplastic resin composition c, a method of adjusting the difference between the glass transition temperature of the resin layer A and the resin layer C to within 30°C by using a copolymer with other components.

(3) In the thermoplastic resin composition a and/or the thermoplastic resin composition c, by mixing an additive such as a plasticizer, the difference between the glass transition temperature of the resin layer A and the resin layer C is adjusted to within 30°C.

In addition, for example, as another method of suppressing the warpage of the resin plate and the molded body by a method other than making the absolute value of the difference between the glass transition temperature of the resin layer A and the resin layer C within 30°C, thermoplastic resin composition a and/or thermoplastic In the resin composition c, a method of forming a mixture containing at least two or more thermoplastic resins incompatible with each other is exemplified.

In the method of making the absolute value of the difference between the glass transition temperature of the resin layer A and the resin layer C within 30°C, for the example of (1), the thermoplastic resin a is made of an acrylic resin as a main component, and the thermoplastic resin composition c is polycarbonate. The case of a mixture of a resin and other thermoplastic resins will be described in detail.

The thermoplastic resin composition c in the present invention may be a mixture composed of two or more thermoplastic resins as described above. For example, when the thermoplastic resin composition a is composed of an acrylic resin as a main component, and the thermoplastic resin composition c is composed of a polycarbonate-based resin as a main component, in order to make the absolute value of the difference between the two glass transition temperatures within 30°C, the latter polycarbonate A method of lowering the glass transition temperature of the polycarbonate resin by mixing another thermoplastic resin with the resin is mentioned. That is, a method of lowering the glass transition temperature of the polycarbonate-based resin by melt blending (mixing and heating-melting) a polycarbonate-based resin and another thermoplastic resin to form a polymer alloy.

In general, the glass transition temperature of polycarbonate-based resin is around 150°C, and it is close to 50°C higher than 100°C of the general glass transition temperature of acrylic resin. Therefore, polycarbonate-based resin is mixed with other thermoplastic resins to It lowers the glass transition temperature of the resin. From this point of view, examples of other thermoplastic resins include aromatic polyester, polyester resin having a cyclic acetal skeleton, and the like.

(Aromatic polyester d1)

Examples of the aromatic polyester d1 that can be used as other thermoplastic resins include resins obtained by polycondensation reaction of an aromatic dicarboxylic acid component and a diol component.

Here, representative examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. Further, a part of terephthalic acid may be substituted with another dicarboxylic acid component. Examples of other dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentylic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, p-oxybenzoic acid, etc. have. These may be 1 type or a mixture of 2 or more types may be sufficient, and the amount of another substituted dicarboxylic acid can also be selected suitably.

On the other hand, representative examples of the diol component include ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, and the like. A part of ethylene glycol may be substituted with another diol component. As other diol components, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, Trimethylol, methoxy polyalkylene glycol, and the like. These may be 1 type or a mixture of 2 or more types may be sufficient, and the amount of other diols substituted can also be selected suitably.

Specific examples of the aromatic polyester include polyethylene terephthalate obtained by polycondensation reaction of terephthalic acid and ethylene glycol, polybutylene terephthalate obtained by polycondensation reaction of terephthalic acid or dimethyl terephthalic acid and 1,4-butanediol. . Moreover, a copolymer polyester containing a dicarboxylic acid component other than terephthalic acid and/or a diol component other than ethylene glycol is also mentioned as a preferable aromatic polyester.

Among them, as a preferred example, in a copolymer polyester having a structure obtained by substituting part of ethylene glycol in polyethylene terephthalate, preferably 55 to 75 mol% with cyclohexanedimethanol, or polybutylene terephthalate And a copolymer polyester having a structure obtained by substituting a part of terephthalic acid of, preferably 10 to 30 mol% with isophthalic acid, or a mixture of these copolymerized polyesters.

Among the aromatic polyesters described above, it is preferable to select one that is polymer alloyed by melt blending with a polycarbonate-based resin and can sufficiently lower the glass transition temperature of the polycarbonate-based resin.

From this point of view, a copolymer polyester having a structure obtained by substituting 50 to 75 mol% of ethylene glycol, a diol component of polyethylene terephthalate, with 1,4-cyclohexanedimethanol (1,4-CHDM) (so-called `` PCTG"), or a copolymer polyester having a structure obtained by substituting a part of terephthalic acid of polybutylene terephthalate, preferably 10 to 30 mol% with isophthalic acid, or a mixture thereof is the most preferred example. It is known that these copolymerized polyesters are completely compatible and polymer alloyed by melt blending with a polycarbonate-based resin, and further, the glass transition temperature can be effectively lowered.

(Polyester resin d2 having a cyclic acetal skeleton)

Polyester resin d2 having a cyclic acetal skeleton that can be used as another thermoplastic resin is a polyester in which 1 to 60 mol% of the diol units, including dicarboxylic acid units and diol units, are diol units having a cyclic acetal skeleton. It's Suzy. The diol unit having a cyclic acetal skeleton is preferably a unit derived from a compound represented by the following formula (10) or (11).

R ¹ , R ² , and R ³ are each independently selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. It represents a hydrocarbon group.

As the compound of formulas (10) and (11), 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro [5.5] undecane, or Particularly preferred is 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane.

In addition, in the polyester resin d2 having a cyclic acetal skeleton, the diol units other than the diol unit having a cyclic acetal skeleton are not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol, and neopentyl glycol; Polyetherdiols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenedimethanol, 1,3-decahydronaphthalenedimethanol, 1,4-decahydronaphthalenedimethanol, 1,5-decahydronaphthalenedimethanol, 1,6-decahydronaphthalenedimethanol, 2,7-decahydronaphthalenedimethanol, tetralinylimethanol, nobornedimethanol, tricyclodecanedimethanol, pentacyclodode Alicyclic diols such as kanedimethanol; 4,4'-(1-methylethylidene)bisphenol, methylenebisphenol (bisphenol F), 4,4'-cyclohexylidenebisphenol (bisphenol Z), 4,4'-sulfonylbisphenol (bisphenol S), etc. Bisphenols; Alkylene oxide adducts of the bisphenols; Aromatic dihydroxy compounds such as hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenylbenzophenone; And an alkylene oxide adduct of the aromatic dihydroxy compound. Ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable in terms of mechanical performance, economy, etc. of the polyester resin of the present invention. Glycol is preferred. The illustrated diol unit may be used alone or in combination of two or more.

In addition, the dicarboxylic acid unit of the polyester resin d2 having a cyclic acetal skeleton used in the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, three Aliphatic dicarboxylic acids such as baic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid, nobornedicarboxylic acid, tricyclodecanedicarboxylic acid, and pentacyclododecanedicarboxylic acid; Terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, TE Aromatic dicarboxylic acids, such as tralindaicarboxylic acid, can be illustrated. In terms of mechanical performance and heat resistance of the film of the present invention, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid and The same aromatic dicarboxylic acid is preferable, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are particularly preferable. Among them, terephthalic acid is most preferred from the viewpoint of economy. The illustrated dicarboxylic acid may be used alone or in combination.

On the other hand, whether the melt-blended mixed resin composition is a polymer alloy, in other words, is fully compatible, is determined by whether the glass transition temperature measured at a heating rate of 10°C/min is single, for example by differential scanning calorimetry. I can judge. Here, the single glass transition temperature of the mixed resin composition means that the glass transition temperature of the mixed resin composition is measured using a differential scanning calorimeter at a heating rate of 10°C/min according to JIS K-7121. It means that only one peak indicating

In addition, when the mixed resin composition was measured by dynamic viscoelasticity measurement (measurement of dynamic viscoelasticity by JIS K-7198A method) at a strain of 0.1% and a frequency of 10 Hz, it is also determined whether or not there is one maximum value of the loss tangent (tanδ). I can judge.

When the mixed resin composition is completely compatible (polymer alloyed), the blended components become compatible with each other in nanometer order (molecular level).

On the other hand, as a means for polymerizing the polymer, a compatibilizing agent may be used, secondary block polymerization or graft polymerization, or a means of dispersing one polymer in a cluster may also be employed.

The mixing ratio of the polycarbonate resin and the polyester d1 or d2 described above is not limited as long as the absolute value of the difference between the glass transition temperature of the polycarbonate resin composition and the acrylic resin obtained by mixing is within 30°C, but transparency From the viewpoint of fat and oil, the mass ratio is preferably polycarbonate resin: polyester d1 or d2 = 20:80 to 90:10, and in particular, polycarbonate resin: polyester d1 or d2 = 30:70 to 80:20 In particular, polycarbonate resin: polyester d1 or d2 = 40:60 to 75:25 is preferred.

Next, in the method of making the absolute value of the difference between the glass transition temperature of the resin layer A and the resin layer C within 30°C, the thermoplastic resin composition a is composed of an acrylic resin as a main component, and the thermoplastic resin composition c The case where is a mixture of a polycarbonate resin and a plasticizer will be described in detail.

As described above, in general, the glass transition temperature of the polycarbonate-based resin is around 150°C, which is higher than 100°C of the general glass transition temperature of the acrylic resin, so the absolute value of the difference between the quantum glass transition temperature is 30°C. To be within the range, a method of lowering the glass transition temperature of the polycarbonate-based resin by mixing a plasticizer with the latter polycarbonate-based resin is exemplified.

Plasticizers that can be used for polycarbonate resins include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylene phosphate, cresyl Phosphoric acid ester compounds such as diphenyl phosphate and 2-ethylhexyl diphenyl phosphate; Phthalic acid ester compounds such as dimethylphthalate, diethylphthalate, dibutylphthalate, bis(2-ethylhexylphthalate), diisodecylphthalate, butylbenzylphthalate, diisononylphthalate, and ethylphthalylethylglycolate; Trimellitic acid ester compounds such as tris(2-ethylhexyl)trimelitate; Dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisodecyl adipate, bis(butyl diglycol) Aliphatic dibasic acid ester compounds such as adipate, bis(2-ethylhexyl) azelate, dimethyl sebacate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, and diethylsuccinate; Ricinoleic acid ester compounds such as methyl acetyl ricinolate; Acetic acid ester compounds such as triacetin and octyl acetate; Sulfonamide compounds such as N-butylbenzenesulfonamide; And the like. In particular, when the resin component is a polycarbonate resin, among the plasticizers described above, since compatibility with the polycarbonate resin is good and the transparency of the resin after compatibility is good, a phosphate ester-based compound is preferable. In particular, crezyldiphenyl Phosphate or tricresyl phosphate is more preferred.

When the thermoplastic resin composition c is a mixture of a polycarbonate-based resin and a plasticizer, the ratio of both is preferably a mass ratio, polycarbonate-based resin: plasticizer = 70:30 to 99:1, and polycarbonate-based resin: It is more preferable that it is a plasticizer=90:10-98:2. If the amount of the plasticizer is less than the above-described ratio, the effect of lowering the glass transition temperature due to plasticization becomes insufficient, and the absolute value of the difference between the glass transition temperature of the resin layer A and the resin layer C is not within 30°C. As a result, there is a fear that it becomes difficult to suppress the warpage of the obtained resin plate and the molded body. On the other hand, if the amount of the plasticizer is greater than the above-described ratio, the fluidity of the thermoplastic resin composition c containing the polycarbonate resin is remarkably increased.For example, when a laminated substrate is formed by coextrusion molding with the thermoplastic resin composition a, its appearance is impaired There is a risk of becoming.

(Other ingredients)

In addition to the resin component, the thermoplastic resin composition c forming the resin layer C includes various additives such as an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant such as a silicone compound, a filler, a glass fiber, and an impact modifier. They can be contained within a range that does not impair the effects of the invention.

As described above, the resin layer C plays a role of imparting secondary workability such as excellent impact resistance or punchability to the resin plate and the molded article by laminating it with the resin layer A and the functional layer. From this point of view, it is important that the thickness of the resin layer C is set based on the ratio of the total thickness of the resin layer A and the functional layer, and the corresponding thickness ratio is the resin layer C thickness/(resin layer A thickness + functional layer thickness). When represented by, it is preferably 2 or more, and more preferably 4 or more. When the thickness ratio is 2 or more, excellent impact resistance or secondary processability such as punching properties can be imparted to the resin plate and the molded article, and thus is preferable.

(Functional layer)

The functional layer in the present invention is a layer that serves to impart excellent surface properties to a resin plate and a molded article. In the present invention, the functional layer is not particularly limited, and examples thereof include a thin film formed by a coating method, a transfer method, a physical vapor deposition method, a chemical vapor deposition method, a pneumatic method, a printing method, or a lamination method. Although there is no particular limitation on the properties and functions of the functional layer, for example, high hardness, anti-fingerprint, water repellency, chemical resistance, photocatalytic activity, antistatic properties, conductivity, or physical properties of metals or inorganic oxides imparted by coating or transfer. Gas barrier properties, high reflectivity, antireflection properties, increased reflection properties, diffusivity, light condensing properties, polarization properties, and design properties given by precise printing, and ultra-high hardness given by lamination of thin glass And the like. On the other hand, in the functional layer in the present invention, at least two functional layers having the characteristics and functions selected from the above are stacked on at least one side of the resin substrate, or different characteristics and functions are provided for each side of the resin substrate. The functional layers described above may be laminated, or functional layers having the same characteristics and functions may be laminated on both surfaces of the resin substrate. Moreover, a resin plate may be constituted only by a functional layer.

For example, the functional layer having gas barrier properties can be formed by a physical vapor deposition layer of an inorganic oxide such as alumina. In addition, the functional layer having the increased reflection function is formed by laminating a physical vapor deposition layer made of an inorganic oxide having a low refractive index such as silica and a physical vapor deposition layer made of an inorganic oxide having a high refractive index such as titanium dioxide at a predetermined thickness ratio. Can be formed.

When a resin plate such as a film or sheet provided with these functional layers is subjected to bending to obtain a molded article, when the functional layer is stretched and deformed to increase or decrease its thickness, for example, gas barrier properties and increased reflection function are Depending on the location, when the function becomes uneven or undergoes excessive expansion and contraction deformation, the functional layer may be broken and the appearance may be damaged as well as the function. There is a similar concern about the precision printing layer.

Among them, the high-hardness layer is formed by curing and forming a curable resin composition by irradiation with ultraviolet rays or electron beams, or by heating, and it is difficult to elongate and deform, and even if it undergoes stretching and contracting during bending, the high-hardness layer absorbs it or Since it cannot be followed, there is a fear of causing appearance defects such as cracks.

In the present invention, the resin plate may have a single-layer configuration consisting of only a resin substrate or only the functional layer, but in order to solve the above concerns, a functional layer/resin substrate having a functional layer on at least one surface of the resin substrate It is preferable to apply the present manufacturing method to a resin plate having a two-layer structure or a three-layer structure of a functional layer/resin substrate/functional layer.

In the present manufacturing method, when the resin plate is a laminated structure consisting of a two-layer structure of a functional layer/resin substrate, a bending process is performed while the one surface of the resin plate having at least a functional layer is tightly constrained by a restraint, and the above It is preferable because a molded article having the functional layer on the convex surface can be obtained by compressively deforming the resin substrate at the curved portion while suppressing the stretching deformation of the curved portion of the functional layer. On the contrary, by bending the surface of the resin plate having at least a functional layer in close contact with a constraining object, while suppressing the elastic deformation of the curved portion of the functional layer, while stretching the resin substrate at the curved portion, It is preferable because it is possible to obtain a molded article having the functional layer on the concave surface.

In addition, when the resin plate is composed of a three-layer structure of a functional layer/resin substrate/functional layer, bending processing is performed with both surfaces of the resin plate forming the convex side and the concave side tightly constrained by a restraint. , It is preferable because a molded article having the functional layers on the convex side and the concave side can be obtained by shearing the resin substrate while suppressing the stretching deformation of the curved portions of the functional layers on both surfaces.

A case where the functional layer in the present invention is a high-hardness layer composed of a resin layer B will be described as an example.

(Resin layer B)

As resin layer B, what is formed from curable resin composition b is mentioned. In addition, the resin layer B can be laminated on at least one surface of the resin substrate or on both surfaces of the resin substrate. That is, by using the resin layer B-1 formed of the curable resin composition b-1 and the resin layer B-2 formed of the curable resin composition b-2, the resin layer B-1/two-layer structure of the resin substrate, the resin layer B -1/resin base material/resin layer B-2 or resin layer B-1/resin base material/resin layer B-1.

(Curable resin composition b-1)

The resin layer B-1 in the present invention is a layer that imparts excellent surface hardness to a resin plate and a molded article. The high-hardness layer is formed of a curable resin composition, and the curable resin composition b-1 usable in the present invention is cured by irradiating energy rays such as electron beams, radiation, and ultraviolet rays, or by heating. As long as it becomes, there is no restriction|limiting in particular, From the viewpoint of molding time and productivity, it is preferable to consist of an ultraviolet curable resin.

Preferred examples of the curable resin constituting the curable resin composition b-1 include an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a carboxyl group-modified epoxy acrylate compound, a polyester acrylate compound, a copolymerized acrylate, and an alicyclic Formula epoxy resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetane compounds, and the like may be mentioned, and these curable resins may be used individually or may be used in combination of a plurality of compounds. Among them, examples of curable resins that give excellent surface hardness include radical polymerization-based curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, and polyfunctional epoxy acrylate compounds, and alkoxysilanes and alkyls. Thermal polymerization system curable compounds, such as an alkoxysilane, are mentioned. Further, the curable resin composition b-1 of the present invention can also be used as an organic/inorganic composite curable resin composition obtained by making the curable resin contain an inorganic component.

As the curable resin composition b-1 which imparts particularly excellent surface hardness to the resin layer B-1, an organic/inorganic hybrid curable resin composition can be mentioned. Examples of the organic-inorganic hybrid-based curable resin composition include those composed of a curable resin composition containing an inorganic component having a reactive functional group in the curable resin.

By using an inorganic component having such a reactive functional group, for example, by copolymerizing and crosslinking the inorganic component with a radically polymerizable monomer, it is cured compared to an organic/inorganic composite curable resin composition in which an inorganic component is simply contained in an organic binder. It is preferable because shrinkage is less likely to occur and high surface hardness can be expressed. In addition, from the viewpoint of reducing cure shrinkage, a more preferable example is an organic/inorganic hybrid curable resin composition containing ultraviolet-reactive colloidal silica as an inorganic component having a reactive functional group.

As described above, the resin layer B-1 in the present invention is a layer that imparts excellent surface hardness to the resin plate and the molded body. As a means of imparting particularly excellent surface hardness to the resin layer B-1, a method of adjusting the concentration of the inorganic component and/or the inorganic component having a reactive functional group contained in the resin layer B-1 is exemplified. The preferred concentration range of the inorganic component and/or the inorganic component having a reactive functional group contained in the resin layer B-1 is 10% by mass or more and 65% by mass or less. The lower limit of the preferred concentration is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more. When the concentration is 10% by mass or more, it is preferable because the effect of imparting excellent surface hardness to the resin layer B-1 can be obtained. On the other hand, the upper limit of the preferred concentration is preferably 65% by mass or less, more preferably 60% by mass or less, and particularly preferably 55% by mass or less. When the concentration is 65% by mass or less, it is possible to closely fill the inorganic component and/or the inorganic component having a reactive functional group in the resin layer B-1, and excellent surface hardness can be effectively imparted, which is preferable.

As a method of laminating the resin layer B-1 on a resin substrate, for example, by dissolving or dispersing the curable resin composition b-1 in an organic solvent and applying the coating on the surface of the resin substrate as a cured film, the resin Although there is a method of forming and laminating on the surface of the substrate, it is not limited to this method.

As a lamination method with a resin substrate, a known method is used. For example, a lamination method using a cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, gravure And coating methods. In addition, for example, a method of laminating the resin layer B-1 on a resin substrate using a transfer sheet formed by forming a resin layer B-1 on a release layer may be employed.

The curable resin composition b-1 forming the resin layer B-1 is preferably made of an ultraviolet curable resin, that is, cured by irradiation with ultraviolet rays from the viewpoint of molding time and productivity. Here, as the light source emitting ultraviolet rays, an electrodeless high-pressure mercury lamp, an electrodeless high-pressure mercury lamp, an electrodeless metal halide lamp, an electrodeless metal halide lamp, a xenon lamp, an ultra-high pressure mercury lamp, or a mercury xenon lamp can be used. Among them, an electrodeless high-pressure mercury lamp is preferable because it is easy to obtain ultraviolet rays of high illuminance and is advantageous for curing an ultraviolet curable resin.

In addition, in the ultraviolet curable resin, the photopolymerization initiator to be added absorbs ultraviolet rays, excites and activates, thereby causing a polymerization reaction, and a curing reaction of the ultraviolet curable resin occurs. Therefore, selecting a light source corresponding to the photopolymerization initiator added to the ultraviolet curable resin, that is, corresponding to the excitation wavelength of the photopolymerization initiator, is advantageous for curing the ultraviolet curable resin, and is preferable.

(Photopolymerization initiator)

When the curable resin composition b-1 is made of an ultraviolet curable resin and is cured by irradiation with ultraviolet rays, a photopolymerization initiator is used as the curing agent. As a photoinitiator, for example, benzyl, benzophenone or derivatives thereof, thioxanthones, benzyldimethyl ketals, α-hydroxyalkylphenones, α-hydroxyacetophenones, hydroxyketones, aminoalkylphenones, acyl And phosphine oxides. Among them, α-hydroxyalkylphenones are preferable because they are less likely to cause yellowing during curing, and a transparent cured product can be obtained. Further, aminoalkylphenones are preferred because they have very high reactivity and a cured product of excellent hardness can be obtained. On the other hand, the addition amount of the photopolymerization initiator is generally in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the curable resin.

These photoinitiators can be used not only individually, but can also be used in combination of two or more. Moreover, since these various photoinitiators are commercially available, such a commercial item can be used. As commercially available photopolymerization initiators, for example, "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1000", "IRGACURE 2959", "DAROCUR 1173", "IRGACURE 127", "IRGACURE 907", "IRGACURE 369" , "IRGACURE 379", "IRGACURE 1700", "IRGACURE 1800", "IRGACURE 819", "IRGACURE 784" (the above IRGACURE series and DAROCUR series are sold by BASF Japan) , "KAYACURE ITX", "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACURE BMS", "KAYACURE 2-EAQ" (The above KAYACURE series sold by Nippon Explosives), etc. I can. Among these, examples of those belonging to the α-hydroxyalkylphenones include "IRGACURE 184", while those belonging to the aminoalkylphenones include, for example, "IRGACURE 907", "IRGACURE 369", and "IRGACURE 379. "It can be mentioned.

(Surface adjustment component)

The curable resin composition b-1 that forms the resin layer B-1 can contain a leveling agent as a surface adjustment component. Examples of the leveling agent include silicone leveling agents, acrylic leveling agents, and the like, particularly preferably having a reactive functional group at the terminal, and more preferably having a reactive functional group having two or more functions.

Specifically, polyether-modified polydimethylsiloxane having a double bond at both ends and having an acrylic group (e.g., ``BYK-UV 3500'', ``BYK-UV 3530'' manufactured by BIC Chemie Japan) or , Polyester-modified polydimethylsiloxane having an acrylic group ("BYK-UV 3570", manufactured by Bicchemi Japan Co., Ltd.) and the like, each having two double bonds at the terminal, and four in total.

Among these, polyester-modified polydimethylsiloxane having an acrylic group, which has a stable haze value and contributes to an improvement in scratch resistance, is particularly preferred.

(Other ingredients)

In addition to the curable resin component, the curable resin composition b-1 forming the resin layer B-1, for example, a lubricant such as a silicon-based compound, a fluorine-based compound, or a mixture thereof, an antioxidant, an ultraviolet absorber, an antistatic agent, a silicone-based Various additives such as flame retardants such as compounds, fillers, glass fibers, and impact modifiers can be contained within a range that does not impair the effects of the present invention.

When the curable resin composition b-1 is made of an ultraviolet curable resin and is cured by irradiation with ultraviolet rays, since the transparency to ultraviolet rays is high, the internal curing of the resin composition proceeds quickly, whereas the curing inhibiting action by oxygen ( For this reason, curing may be delayed on the surface of the resin composition. Regarding this oxygen disturbance, if the surroundings of the resin composition are placed in a nitrogen gas atmosphere by supply of nitrogen gas and then irradiated with ultraviolet rays, it is preferable because curing of the surface can be rapidly advanced together with the inside of the resin composition.

It is preferable that it is 5H or more, and, as for the pencil hardness of the surface of the resin layer B-1, it is more preferable that it is 7H or more. When the pencil hardness is 5H or more, a resin plate and a molded article having excellent surface hardness can be obtained.

Moreover, it is preferable that the surface hardness of the resin layer B-1 is 200 MPa or more and 900 MPa or less in universal hardness. The lower limit of the universal hardness of the resin layer B-1 is preferably 200 MPa or more, more preferably 400 MPa or more, and particularly preferably 600 MPa or more. When the universal hardness is 200 MPa or more, a resin plate and a molded article having excellent hardness can be provided. On the other hand, the upper limit of the universal hardness of the resin layer B-1 is preferably 900 MPa or less, more preferably 800 MPa or less, and particularly preferably 700 MPa or less. When the universal hardness is 900 MPa or less, it is preferable because cracks do not occur in the resin layer B-1 during bending molding.

The thickness of the resin layer B-1 is preferably 5 μm or more and 40 μm or less, more preferably 7 μm or more and 30 μm or less, and particularly preferably 7 μm or more and 20 μm or less. When the thickness is 5 μm or more, sufficient hardness can be imparted to the surface of the resin layer B-1, which is preferable. On the other hand, when the thickness is 40 μm or less, it is preferable because a molded article can be obtained without causing whitening or cracking in the resin layer B-1 when thermoforming the resin plate.

(Resin layer B-2)

The resin layer B-2 in the present invention is formed on the surface of the resin substrate opposite to the side on which the resin layer B-1 is laminated, and is a scratch prevention layer for preventing frictional scratches on the resin plate in the process. It is a layer that mainly plays a role as

(Curable resin composition b-2)

The resin layer B-2 of the present resin plate is formed of the curable resin composition b-2, and the curable resin composition b-2 usable in the present invention may be the same as the curable resin composition b-1 described above. .

In the case of compressive deformation or elongation deformation of the resin plate, the storage modulus of the resin layer B-2 at the glass transition temperature of the resin plate is preferably 50 MPa or more and 1000 MPa or less. When the storage modulus is 50 MPa or more, the resin layer B-2 can be given a role as an anti-scratch layer, which is preferable. From this point of view, the lower limit of the preferred storage modulus of the resin layer B-2 is more preferably 80 MPa or more, and particularly preferably 100 MPa or more. On the other hand, if the storage elastic modulus is 1000 MPa or less, the resin layer B-2 can absorb and respond to the stretching deformation occurring in the bending process of the present manufacturing method, so that the functional layer made of the resin layer B-2 is not tightly constrained by a restraint. It can be molded without impairing its surface properties or appearance. From this point of view, the upper limit of the preferred storage modulus is more preferably 800 MPa or less, and particularly preferably 500 MPa or less.

The thickness of the resin layer B-2 is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 40 μm or less, and particularly preferably 15 μm or more and 30 μm or less. When the thickness is 5 μm or more, it is preferable because sufficient hardness can be ensured to serve as a scratch prevention layer. On the other hand, if the thickness is 50 μm or less, it is preferable because the secondary workability of the resin plate and the molded article can be secured.

The formation method, photoinitiator, surface adjustment component, and other components applicable to the resin layer B-2 are the same as those of the case of the resin layer B-1.

(Restraint)

In the present manufacturing method, a bending process is performed while at least one surface of the resin plate and further a functional layer laminated on at least one surface of the resin plate are tightly constrained by a restraint. The constrained material serves to suppress the occurrence of elastic deformation of the surface layer which is closely constrained in bending.

In addition, the restraint material in the present manufacturing method is to suppress expansion and contraction deformation in the curved portion of the restrained surface of the resin plate and/or the functional layer in bending, and restrain the resin plate and/or the functional layer. It is necessary to have a reinforcing action that suppresses stretching and contraction in the curved portion of the surface, and a balanced mechanical property that can follow the bending deformation. In the present manufacturing method, the range of desirable mechanical properties required for the constrained article can be determined by the product of the bending modulus (MPa) of the constrained article and the thickness (m) of the constrained article.

The preferable range of the product of the bending elastic modulus of the restraint object and the thickness is preferably 3.0 × 10 ^-2 MPa m or more, more preferably 4.0 × 10 ^-2 MPa m or more, and 5.0 × 10 ^-2 MPa m or more. It is particularly preferred. If the product of the bending elastic modulus of the constrained object and the thickness is 3.0×10 ^-2 MPa·m or more, it is preferable because it acts as a reinforcing action to suppress the elastic deformation at the curved portion of the constrained surface of the resin plate and/or the functional layer in bending. . On the other hand, the upper limit of the preferred range is not particularly limited when the restraint is made of either a molded type having a restraining layer D described later or a metal belt having a restraining layer D. When the restraint is made of any of a protective film, a metal foil tape, or a glass cloth tape, it is preferably 50 MPa·m or less, more preferably 10 MPa·m or less, and particularly preferably 5.0 MPa·m or less. When the restraint object is made of any of a protective film, a metal foil tape, or a glass cloth tape, it is preferable that the restraint object itself can follow the bending deformation as long as the product of the bending elastic modulus and the thickness of the restraint object is 50 MPa·m or less. .

The flexural modulus of the restraint is not particularly limited when the product of the flexural modulus of the restraint and the thickness of the restraint is within the above range, but the preferred range is 1.5×10 ³ MPa or more and 3.0×10 ⁵ MPa or less. When the bending elastic modulus of the constrained object is 1.5×10 ³ MPa or more, it is preferable to obtain a reinforcing action for suppressing the elastic deformation at the curved portion of the constrained surface of the resin plate and/or the functional layer in bending. From this viewpoint, it is more preferable that it is 2.0×10 ³ MPa or more, and it is particularly preferable that it is 3.0×10 ³ MPa or more. On the other hand, when the bending elastic modulus of the restraint object is 3.0×10 ⁵ MPa or less, it is preferable that the restraint object itself easily follows the bending deformation. From this viewpoint, it is more preferable that it is 1.0×10 ⁵ MPa or less, and it is particularly preferable that it is 1.0×10 ⁴ MPa or less.

The thickness of the restraint material is not particularly limited when the restraint material is formed of a molded type having a restraint layer D or a metal belt having a restraint layer D. When the restraint is made of either a protective film, a metal foil tape, or a glass cloth tape, as described above, the product of the bending elastic modulus (MPa) of the restraint and the thickness (m) of the restraint is 3.0×10 ^-2 MPa· If it is m or more, it is not particularly limited, but the preferred lower limit of the thickness is preferably 10 μm or more, more preferably 20 μm or more, and particularly preferably 25 μm or more. When the thickness of the constrained object is 10 μm or more, it is preferable to obtain a reinforcing action for suppressing the elastic deformation in the curved portion of the resin plate and/or the constrained surface of the functional layer in bending. On the other hand, the upper limit of the preferred range is preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 150 μm or less. When the thickness of the constrained object is 300 μm or less, it is preferable as an operation for tightly constraining the resin plate, since handling properties for performing the bonding operation with the resin plate can be ensured.

Further, it is preferable that the restraint material has at least one restraint layer D. Among the restraints, the resin plate and/or the side to be in close contact with the functional layer is required to have an action of transmitting the bending deformation of the restraints without causing deviation or slipping at the interface. That is, it is preferable that the restraint material has at least one restraint layer D, and the restraint layer D has a cohesive force capable of transmitting the bending deformation of the restraint material to the resin plate and/or the functional layer. The cohesive force can be expressed, for example, by the storage modulus of the constraining layer D.

(Constrained Layer D)

The constrained object has a reinforcing action of suppressing the expansion and contraction of the curved portion of the constrained surface of the resin plate and/or the functional layer in bending, and has a balanced mechanical property capable of following the bending deformation, At the interface between the constrained object and the resin plate and/or the functional layer, two points are required, one having a cohesive force suitable for conveying the deformation without causing any deviation or slipping, and from this point of view, the constrained object is at least one layer of confinement. May have layer D.

A preferable range of the storage modulus of the constraining layer D is 1.0×10 ² Pa or more and 1.0×10 ⁷ Pa or less at the glass transition temperature of the resin plate. When the storage elastic modulus is 1.0×10 ² Pa or more, cohesive failure of the constraining layer D does not occur, and bending deformation of the constrained material can be transmitted to the resin plate and/or the functional layer, which is preferable. From this point of view, it is more preferably 5.0×10 ² Pa or more, and particularly preferably 1.0×10 ³ Pa or more. On the other hand, if the storage modulus is 1.0 × 10 ⁷ Pa or less, the restraining side is not too hard, and there is no slipping at the interface with the resin plate and/or the functional layer. And/or it is preferable because it can be transmitted to the functional layer. From this viewpoint, it is more preferable that it is 1.0×10 ⁶ Pa or less, and it is particularly preferable that it is 1.0×10 ⁵ Pa or less.

Preferred examples of the restraint having at least one restraint layer D include a protective film, a metal foil tape such as aluminum foil, a glass cloth tape, a mold with restraint layer D on the surface, and a metal belt with restraint layer D on the surface Although it can be mentioned, especially since a protective film can be applied to molded articles of various shapes, it is preferable.

(Protective film)

Hereinafter, a case where the restraint is a protective film will be described as an example.

In this manufacturing method, the protective film is provided with at least a base material layer and a restraint layer D, and in this case, the restraint layer D means an adhesive layer. As described above, the base layer serves as a constraining material and is capable of following bending deformation as well as a reinforcing action of suppressing stretching deformation at a curved portion of the constrained surface of the resin plate and/or the functional layer in bending.

(Substrate layer)

As the material for forming the base layer, any suitable material can be used depending on the application. For example, plastic, paper, non-woven fabric, etc. are mentioned, Preferably, it is plastic. The base material layer may be formed of one type of material, or may be formed of two or more types of materials. For example, it may be formed of two or more types of plastics.

The plastic is not particularly limited as long as the product of the bending modulus of the constrained material and the thickness is within the above range, but for example, vinyl chloride resin, vinylidene chloride resin, polyester resin, polyamide resin, polyolefin Resins, cycloolefin resins, polycarbonate resins, acrylic resins, and polyimide resins.

The base layer needs to have a reinforcing action sufficient to suppress stretching and contraction at the curved portion of the constrained surface of the resin plate and/or the functional layer at the thermoforming temperature, for example, the storage modulus at the glass transition temperature of the resin plate, It is preferably 100 MPa or more and 5000 MPa or less. From this point of view, polyamide resins, polyester resins, and polyimide resins are preferred, and among them, polyester resins are preferred because of their good balance between performance and cost.

The lower limit of the storage modulus of the substrate layer is preferably 100 MPa or more, more preferably 200 MPa or more, and particularly preferably 500 MPa or more at the glass transition temperature of the resin plate. When the storage modulus is 100 MPa or more, it is preferable since it is possible to suppress the elastic deformation at the curved portion of the constrained surface of the resin plate and/or the functional layer during thermoforming.

On the other hand, the upper limit of the storage modulus of the base layer at the glass transition temperature of the resin plate is preferably 5000 MPa or less, more preferably 3000 MPa or less, and particularly preferably 1000 MPa or less. When the storage modulus of the base layer is 5000 MPa or less, it is preferable because the base layer follows the bending deformation and does not obstruct shaping the molded article into a desired shape.

Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polylactic acid, and polyallylate.

The base material layer may contain any suitable additive as needed. Examples of additives that may be contained in the base layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, plasticizers, fillers, pigments, and the like. The type, number, and amount of additives that may be contained in the substrate layer may be appropriately set according to the purpose. In particular, when the material forming the base layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration or the like. From the viewpoint of improving weather resistance and the like, particularly preferably, antioxidants, ultraviolet absorbers, light stabilizers, and fillers are mentioned as additives.

The thickness of the substrate layer is not particularly limited when the product of the bending elastic modulus of the constraining object and the thickness is within the above range, and may be employed depending on the application, but is preferably 10 to 200 μm, more preferably 20 to 150 μm, more preferably 25 to 100 μm.

When the thickness of the base layer is 10 μm or more, it is preferable because it is possible to suppress stretching and contracting in the curved portion of the constrained surface of the resin plate and/or the functional layer during thermoforming. On the other hand, when the thickness of the base layer is 200 μm or less, the handling property of the protective film is ensured, and the bonding workability with the resin plate is improved, which is preferable. Among them, when the thickness of the base layer is 25 μm or more and 100 μm or less, it is preferable to prevent gas from being bitten when the protective film is laminated on the surface of the resin plate and/or the functional layer, so that smoothness can be secured when a molded article is formed. Do.

The base layer may be a single layer or a laminate of two or more layers. Moreover, the base material layer may be stretched.

(Adhesive layer)

As described above, the pressure-sensitive adhesive layer is a layer that serves to transmit the deformation of the substrate layer without causing deviation or slipping at the interface with the resin plate and/or the functional layer as the constraining layer D as described above, and has a cohesive force suitable for its role. Branches are layers. The pressure-sensitive adhesive layer is composed of an adhesive. Only 1 type may be sufficient as an adhesive agent, and 2 or more types may be sufficient as it.

The range of the storage elastic modulus preferable as the cohesive force of the pressure-sensitive adhesive layer is the same as that of the restraining layer D.

The pressure-sensitive adhesive preferably has a high molecular compound as a main component. Here, the polymeric compound may be a crosslinked polymeric compound. Further, an uncrosslinked polymeric compound, such as a polymeric compound cured by irradiation with energy rays such as electron beams, radiation, and ultraviolet rays, may be used. In the latter case, immediately before peeling the protective film from the molded article of the present invention, if it is cured by irradiation with energy rays such as electron beams, radiation, and ultraviolet rays, it is protected immediately without leaving an adhesive on the surface of the resin plate and/or the functional layer. You can peel off the film.

The content ratio of the polymeric compound in the pressure-sensitive adhesive is preferably 50% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more.

As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, any suitable pressure-sensitive adhesive can be used. Examples of such pressure-sensitive adhesives include olefin-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives. In the present invention, the pressure-sensitive adhesive is not particularly limited, but can withstand thermoforming processing, and an acrylic pressure-sensitive adhesive or a silicone pressure-sensitive adhesive can be preferably used.

In the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, any suitable additive can be contained. Examples of such additives include softeners, tackifiers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, heat stabilizers, polymerization inhibitors, silane coupling agents, lubricants, inorganic or organic fillers. , Metal powders, pigments, and solvents. However, in the present invention, in the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, preferably, a plasticizer is not included. When a pressure-sensitive adhesive layer to which a plasticizer is added is used, the wettability is improved, but there is a concern that the adherend is contaminated by the plasticizer.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer can be produced by any suitable method. The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is, for example, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, polymerization by ultraviolet (UV), etc., while using a polymerization method commonly used as a method for synthesizing a polymer, and any suitable It can be manufactured by employing a crosslinking method and using any suitable additives as necessary.

It is preferable that the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer has a small content ratio of the low molecular weight component in the colloidal solution component. When the content ratio of the low molecular weight component is small, it can be assumed that there is little contamination to the adherend and stable rework property can be obtained.

The thickness of the pressure-sensitive adhesive layer in the protective film is preferably 0.5 to 100 μm, more preferably 3 to 50 μm, and still more preferably 5 to 30 μm. If the thickness of the pressure-sensitive adhesive layer is 0.5 μm or more, it is easy to uniformly adjust the thickness of the pressure-sensitive adhesive layer, and stable adhesive strength can be secured, which is preferable. In addition, when the thickness of the pressure-sensitive adhesive layer is 100 μm or less, the adhesive strength does not increase excessively, and since it can be smoothly peeled after thermoforming, it is preferable.

The protective film used in this manufacturing method is a method of laminating a material that will be a melt-kneaded pressure-sensitive adhesive layer on one side of a previously formed substrate layer, or by coextrusion molding such as a T-die method or an inflation method to form the substrate layer and the pressure-sensitive adhesive layer. It can be obtained by a method of laminating at the same time or the like.

On the other hand, the method of laminating the protective film and the resin plate is not particularly limited, for example, a method of laminating by matching the pressure-sensitive adhesive layer surface of the protective film with the surface of the resin plate, or a hot press, a hot metal roll, a hot rubber roll, etc. And a method of thermal compression bonding using.

(Lamination structure of restraints and resin plates)

As a configuration for restraining the resin plate with a restraint material in the present manufacturing method, a restraint material/resin plate or a structure of a restraint material/resin plate/restraint may be mentioned. As a more specific configuration of the former, for example, constrained material/functional layer, constrained material/resin substrate, constrained material/functional layer/resin substrate, constrained material/functional layer 1/functional layer 2/resin substrate, and constrained material/functional layer /Resin base material/functional layer configuration is mentioned. In addition, as a more specific configuration of the latter, for example, restraints/functional layers/restraints, restraints/functional layers/resin substrates/functional layers/restraints, restraints/functional layers 1/functional layers 2/resin substrates/functions Layer 3/constraints.

As described above, the resin substrate may be a single-layered structure comprising a single resin layer or a laminated structure in which at least two different resin layers are laminated.

(thickness)

The thickness of the resin plate is not particularly limited, and is preferably 0.1 mm to 1.5 mm, for example, and particularly preferably about 0.2 mm to 1.0 mm or less in consideration of handling properties in practical use.

For example, as a surface protection panel disposed on the front side of an image display device and used, the thickness is preferably 0.2 mm to 1.2 mm, and as a front cover material such as a mobile phone or a liquid crystal pen tablet having a touch panel function, the thickness is It is preferably 0.3mm to 1.0mm.

(Method of manufacturing molded body)

In the present invention, the surface of the resin plate on the side to which the elastic deformation is to be suppressed during the bending process, or the surface of the side where it is difficult to stretch and contract, is tightly constrained by a constraining object, while compressive deformation, It is a manufacturing method for obtaining a molded article by elongation deformation or shear deformation.

The degree of elongation or compression of the resin plate in the surface direction in the present manufacturing method can be expressed as the elongation (ΔL) of the curved portion of the molded body as described above. In addition, when the resin plate has a two-layer structure of a functional layer/resin substrate having at least a functional layer on one surface, or a three-layer structure of a functional layer/resin substrate/functional layer, the resin substrate itself is compressed and deformed. It is also a feature of the present manufacturing method that it plays a role in receiving elongation deformation or shear deformation, thereby suppressing the elastic deformation of the curved portion of the functional layer. In this case, the degree to which the resin substrate receives each deformation in the plane direction can be expressed by the elongation rate (ΔLx), as described later. The preferable range is sequentially described along with each production method for the case of compression deformation, extension deformation, or shear deformation.

(Compressed deformation)

In the case of bending the resin plate by compressive deformation of the molded body, it is desirable to sufficiently plasticize the portion of the resin plate that undergoes compression deformation, that is, a portion disposed on the side symmetrical to the side closely constrained by the constrained object. Do. Therefore, in the present manufacturing method, heating the resin plate at a temperature equal to or higher than the glass transition temperature of -20°C and equal to or lower than the glass transition temperature +50°C is preferable because it can be sufficiently plasticized to compress and deform the resin plate. As described above, when the resin plate has at least two resin layers formed of different thermoplastic resin compositions, the glass transition temperature of the resin layer having the highest glass transition temperature is -20°C or higher and the glass transition temperature +50°C or lower. When heated, since any resin layer can be sufficiently plasticized to compressively deform, it is preferable.

In this case, the degree to which the resin substrate undergoes compressive deformation in the plane direction can be expressed by the elongation rate (ΔLx) obtained by the following equation (2). A positive value means the degree of elongation deformation in the plane direction, and a negative value means the degree of compression deformation in the plane direction.

ΔLx (%) = (thickness of the resin substrate before molding-the thickness of the resin substrate in the curved portion of the molded body) / thickness of the resin substrate before molding × 100. (2)

However, in the case where the resin base material is formed by laminating at least two different resin layers, the thickness of the resin layer disposed on the outermost layer on the side symmetrical to the functional layer on the side to be constrained by the constrained object in the above formula (2) The thickness of the resin substrate. That is, when the configuration of the resin plate is the functional layer/resin layer A/resin layer C, the elongation rate (ΔLx) is determined by using the thickness of the resin layer C as the thickness of the resin substrate.

The elongation rate (ΔLx), that is, the degree to which the resin substrate undergoes compression deformation in the plane direction, is preferably -50% or more and less than 0% in the range of the curvature (R) of the bent portion in the molded body is 2 mm or more and 200 mm or less. .

When ΔLx is -50% or more, deformation occurring in the resin substrate does not interfere with bending to a desired shape, and thus is preferable. From this viewpoint, it is more preferable that it is -30% or more, and it is more preferable that it is -20% or more. On the other hand, when ΔLx is less than 0%, stretching in the surface direction in the functional layer during bending is suppressed, and cracks or deterioration in performance do not occur in the functional layer, so it is preferable. From this viewpoint, it is more preferable that the upper limit of ΔLx is less than -3%.

As described above, in the case of bending by compressing and deforming a portion other than the portion tightly constrained by the constrained object, at least the side that becomes the convex surface of the molded object is tightly constrained by the constrained object to adjust ΔLx to the above range. I can. In addition, when the resin plate has a laminated structure consisting of a two-layer structure of a functional layer/resin substrate, a bending process is performed while the one side surface having at least a functional layer of the resin plate is tightly constrained by a restraint, and the curved portion of the functional layer It is preferable because, while suppressing the expansion and contraction deformation of, compressively deforming the resin substrate at the curved portion, it is possible to obtain a molded article having the functional layer on the convex surface.

(Height deformation)

In the present molded body, when bending is performed by stretching the resin plate, as in the case of the compression deformation, the portion of the resin plate that is subjected to the stretching deformation, that is, the side that is closely constrained by the constrained object, is disposed on the symmetric side. It is desirable to plasticize the part sufficiently. Therefore, in the present manufacturing method, heating the resin plate at a temperature equal to or higher than the glass transition temperature of -20°C and equal to or lower than the glass transition temperature of +50°C is preferable because it can be sufficiently plasticized to elongate and deform the resin plate. As described above, when the resin plate has at least two resin layers formed of different thermoplastic resin compositions, the glass transition temperature of the resin layer having the highest glass transition temperature is -20°C or higher, and the glass transition temperature is +50°C or lower. When heated, since any resin layer can be sufficiently plasticized to elongate and deform, it is preferable.

In this case, the degree to which the resin substrate undergoes elongation deformation in the plane direction can be expressed by the elongation rate (ΔLx) obtained by the following equation (2). A positive value means the degree of elongation deformation in the plane direction, and a negative value means the degree of compression deformation in the plane direction.

ΔLx (%) = (thickness of the resin substrate before molding-the thickness of the resin substrate in the curved portion of the molded body) / thickness of the resin substrate before molding × 100. (2)

However, in the case where the resin substrate is formed by laminating at least two different resin layers, the thickness of the resin layer disposed inside the outermost layer on the symmetric side from the functional layer on the side to be constrained by the constrained object is calculated as the above formula (2). It is set as the thickness of the resin substrate in. That is, when the configuration of the resin plate is the functional layer/resin layer A/resin layer C, the elongation rate (ΔLx) is determined by using the thickness of the resin layer A as the thickness of the resin substrate.

The elongation (ΔLx), that is, the extent to which the resin substrate is stretched and deformed in the plane direction, is preferably 1% or more and less than 45% in the range where the curvature R of the curved portion in the molded body is 2 mm or more and 200 mm or less.

When ΔLx is 1% or more, deformation occurring in the resin substrate does not interfere with bending to a desired shape, so it is preferable. From this viewpoint, it is more preferable that it is 3% or more, and it is especially preferable that it is 5% or more. On the other hand, when the elongation rate is less than 45%, stretching in the plane direction in the functional layer during bending is suppressed, and cracks or performance degradation do not occur in the functional layer, so it is preferable. From this point of view, the upper limit of ΔLx is more preferably less than 25%, and still more preferably less than 15%.

As described above, in the case of bending by elongating and deforming a portion other than the portion tightly constrained by the constrained object, at least the side which becomes the concave surface of the molded object is tightly constrained by the constrained object to adjust ΔLx to the above range. I can. In addition, when the resin plate has a laminated structure consisting of a two-layer structure of a functional layer/resin substrate, a bending process is performed while the one side surface having at least a functional layer of the resin plate is tightly constrained by a restraint, and the curved portion of the functional layer It is preferable because, while suppressing the stretching deformation of the resin substrate, a molded article having the functional layer in the concave surface can be obtained by stretching the resin substrate at the curved portion.

(Shear deformation)

In the case of bending the resin plate by shearing deformation of the molded body, heating the resin plate tightly constrained by the constrained object on both sides at a temperature of at least -20°C and not more than +50°C. It is preferable because it can plasticize sufficiently to shear-deform the resin plate. As described above, when the resin plate has at least two resin layers formed of different thermoplastic resin compositions, the glass transition temperature of the resin layer having the highest glass transition temperature is -20°C or higher, and the glass transition temperature is +50°C or lower. When heated, it is preferable because any resin layer can be sufficiently plasticized to shear deformation.

When shear deformation occurs, the extent to which the resin substrate expands and contracts in the plane direction can be expressed by the elongation rate (ΔLx) obtained by the following formula (2). A positive value means the degree of elongation deformation in the plane direction, and a negative value means the degree of compression deformation in the plane direction.

ΔLx (%) = (thickness of the resin substrate before molding-the thickness of the resin substrate in the curved portion of the molded body) / thickness of the resin substrate before molding × 100. (2)

Here, when the resin substrate is formed by laminating at least two different resin layers, the sum of the thicknesses is taken as the thickness of the resin substrate. That is, when the configuration of the resin plate is a functional layer/resin layer A/resin layer C/functional layer, the sum of the thicknesses of the resin layer A and the resin layer C is used as the thickness of the resin substrate to determine the elongation rate (ΔLx).

The elongation (ΔLx) of the resin substrate, that is, the extent to which the resin substrate is stretched and deformed in the plane direction, is preferably -10% or more and less than 10% in the range where the curvature (R) of the curved portion in the molded body is 2 mm or more and 200 mm or less. to be.

When ΔLx is -10% or more, deformation occurring in the resin substrate does not interfere with bending to a desired shape, so it is preferable. From this point of view, it is more preferably -7% or more, and particularly preferably -5% or more. On the other hand, when the elongation rate is less than 10%, stretching in the surface direction in the functional layer during bending is suppressed, and cracks or deterioration in performance do not occur in the functional layer, which is preferable. From this viewpoint, it is more preferable that it is less than 7%, and it is especially preferable that it is less than 5%.

As described above, in the case of bending by shearing the resin plate, the both surfaces, which are the convex side and the concave side of the molded body, are subjected to bending while tightly constrained by a constraining object, so that only the resin plate is sheared and deformed in the plane direction. Thereby, ΔLx can be adjusted within the above range. In addition, when the resin plate has a laminated structure consisting of a three-layer structure of a functional layer/resin substrate/functional layer, both surfaces to be convex side and concave side are tightly constrained by restraints while shearing the resin substrate from the curved portion. By deforming, a molded article having the functional layer on both the convex surface and the concave surface can be obtained, which is preferable.

In any of the above-described compression deformation, elongation deformation, and shear deformation, as a molding method, a method of molding using a molding apparatus such as a press molding machine may be mentioned as a preferred example. Since the molding method using a press molding machine enables shaping without holding the end of the resin plate, for example, when the resin plate has at least two resin layers formed of different thermoplastic resin compositions, the highest glass When the resin plate is heated at a temperature of -20°C or more and +50°C or less of the glass transition temperature of the resin layer having a transition temperature, any resin layer can be plasticized and molded. That is, according to the above method, since the end of the functional layer is not held, the plasticized resin base material or the resin layer is bent while suppressing the expansion and contraction of the functional layer that is not desired to be stretched or stretched. It is possible to shape and, as a result, it is preferable because a molded article having a function maintained can be obtained without causing cracks in the functional layer.

In addition, when bending is performed by clamping a resin plate between a male mold and a male mold using a molding apparatus such as a press molding machine, the height of the male mold is set to be larger than the height of the molded body. The use of a mold is mentioned as a preferable condition. When the height of the male mold is set larger than the height of the molded body, the end of the resin plate is not fixed, and it is possible to suppress the extension of the functional layer in the plane direction, which is preferable. Here, the material of the mold is not particularly limited as long as the effect of the present invention is not impaired, and for example, a metal mold can be used.

The method of removing the protective film after molding is not particularly limited as long as no adhesive remains on the surface of the functional layer. For example, as described above, when the pressure-sensitive adhesive mainly contains a polymeric compound that is cured by irradiating energy rays such as electron beams, radiation, and ultraviolet rays, immediately before removing the protective film from the molded body, electron beams, radiation, ultraviolet rays, etc. The protective film can be peeled off immediately and without leaving an adhesive on the surface of the functional layer by irradiating and curing the energy ray of.

FIG. 1 shows the configuration of an embodiment of a resin plate for molding made of a resin plate and a restraint, and in FIG. 1A, the resin layer A 13 and the resin layer B-1 14 are The resin plate 11 for molding in which the surface on the side of the resin layer B-1 (14) of the two-layer resin plate is closely constrained by a restraint 15 is illustrated.

In Fig. 1(b), the surface on the side of the resin layer B-1 (14) of the resin plate composed of three layers of the resin layer C (12), the resin layer A (13), and the resin layer B-1 (14) is The resin plate 16 for molding which is closely constrained by the restraint 15 is illustrated.

In Fig. 1(c), a resin layer of a resin plate comprising four layers of a resin layer B-2 (18), a resin layer C (12), a resin layer A (13), and a resin layer B-1 (14). The resin plate 17 for molding in which the surface on the B-1(14) side is closely and restrained by the restraint 15 is illustrated.

In Fig. 1(d), both surfaces of a resin plate composed of four layers of a resin layer B-2 (18), a resin layer C (12), a resin layer A (13), and a resin layer B-1 (14) are shown. The resin plate 19 for molding tightly restrained by the restraint 15 is illustrated.

Fig. 2(a) shows a molded article (front view) having a functional layer on the convex side by bending into a tunnel shape, which is an embodiment of the molded article, as a functional layer 21 and a resin substrate 22 The flat portion 23 of the formed tunnel-shaped body, the curvature (R) 24 of the curved portion of the formed body, and the central portion 25 of the curved portion of the formed body are illustrated.

Fig. 2(b) shows a molded article (front view) having a functional layer on the concave side by bending into a tunnel shape, which is an embodiment of the molded article, as a functional layer 21 and a resin substrate 22 The formed tunnel-shaped molded article is illustrated.

Fig. 3 shows the configuration of an embodiment with respect to a molding mold for shaping a molded article according to the present invention, and in Fig. 3A, the male mold 32 and the shape ( With respect to 33), the clearance 34 of the flat portion and the clearance 35 of the curved portion that are generated during clamping are illustrated, respectively.

Moreover, in FIG. 3(b), in the molded body 37 that is shaped by clamping a resin plate using the above-described molding mold 31, the height 36 of the male mold of the molding mold 31 A is illustrated about a configuration set larger than the height 38 of the molded body.

Thereby, the end of the resin plate is not fixed, and it is possible to suppress the stretching of the surface of the resin substrate or the functional layer provided on the resin substrate in the plane direction.

<Explanation of terms>

In general, ``film'' refers to a thin, flat product with extremely small thickness compared to the length and width, and the maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K-6900). Thus, the term "sheet" refers to a product that is thin by definition in JIS, and generally has a small and flat thickness compared to the length and width. However, since the boundary between the sheet and the film is not clear, and there is no need to distinguish both by word of mouth in the present invention, in the present invention, even when referred to as a "film", the "sheet" is included, and the "sheet Even when called "", "film" shall be included.

In the present invention, when expressed as ``X to Y'' (X and Y are arbitrary numbers), unless otherwise noted, together with the meaning of ``X or more and Y or less'', ``preferably greater than X'' and `` It includes the meaning of "preferably smaller than Y".

In addition, in the present invention, when expressed as ``X or more'' (X is an arbitrary number), the meaning of ``preferably greater than X'' is included, and ``Y or less'' (Y is arbitrary When expressed as a number), the meaning of ``preferably less than Y'' is included unless otherwise noted.

Example

The present invention will be described in more detail by showing examples below, but the present invention is not limited thereto, and various applications are possible without departing from the technical idea of the present invention.

<Measurement and evaluation method>

A method of measuring and evaluating various physical properties of the resin layer, resin plate, and molded article obtained in Examples and Comparative Examples will be described.

(Glass transition temperature (Tg) of resin layer, storage modulus)

For the resin layers obtained in Examples and Comparative Examples, dynamic viscoelasticity was measured according to JIS K-7198A using the following apparatus. For the resin layer A and the resin layer C, the peak temperature of the loss tangent (tan?) was read, and it was set as the glass transition temperature (Tg) of each resin layer. In addition, about the resin layer B-2, the storage modulus at the glass transition temperature of the resin layer having the higher glass transition temperature of the resin layer A and the resin layer C was read.

Device: Dynamic viscoelasticity measurement device DVA-200 (manufactured by Haiti Measurement & Control Co., Ltd.)

Chuck distance: 25mm

Strain: 0.1%

Temperature range: -50℃~250℃

Heating rate: 3℃/min

Frequency: 10Hz

On the other hand, for the resin layer A and the resin layer C, the resin composition a or c is supplied to an extruder equipped with a single-layer T die, respectively, and melt-kneaded at 240°C and 260°C in each extruder, and then having a thickness of 200 μm. A sheet-like sample having a single-layer structure was prepared and used as a sample for measurement.

In addition, about the resin layer B-2, a sample in which a 30 μm-thick resin layer B-2 was formed on a 12 μm polyethylene terephthalate film was prepared, and this was used as a measurement sample. On the other hand, drying conditions and curing conditions when forming the resin layer B-2 were the same as in the respective Examples and Comparative Examples.

(Pencil hardness of resin layer)

For the resin layers obtained in Examples and Comparative Examples, the measurement of the pencil hardness of the surface was performed in accordance with JIS K-5600-5-4. The load load during the test was 750 gf.

(Universal hardness of the resin layer B-1 surface)

With respect to the surface of the resin layer B-1 obtained in Examples and Comparative Examples, the indentation depth was measured by the following apparatus and conditions, and the universal hardness was calculated by substituting for the following formula (3).

Apparatus: Dynamic Ultra-Small Hardness Meter ``DUH-W201'' (manufactured by Shimadzu Corporation)

Indenter: 115 degrees between triangular weight indenter ridges

Test force: 20mN

Load speed: 0.142mN/s

Hold time: 5 seconds

Universal hardness (MPa) = 37.838 × test force (mN) / (press fit depth (μm)) ² … (3)

(Storage modulus of restraint layer D)

For the restraint layer D (in this case, the pressure-sensitive adhesive layer) of the protective film of Examples and Comparative Examples, dynamic viscoelasticity was measured using the following apparatus and measurement conditions, and which one of the resin layer A and the resin layer C is higher. The storage modulus of the pressure-sensitive adhesive at the glass transition temperature of the resin layer having the glass transition temperature was read. On the other hand, the pressure-sensitive adhesive of each protective film was laminated so as to have a thickness of 1 to 2 mm, and then punched into a circular shape having a diameter of 20 mm, and then inserted into an adhesive jig was used for measurement.

Device: Rheometer MARS (manufactured by Eiko Seiki)

Adhesive jig: φ20 parallel plate

Strain: 0.5%

Temperature range: -50℃~200℃

Heating rate: 3℃/min

Frequency: 1Hz

(Appearance of molded body)

The resin plate to which the restraints obtained in Examples and Comparative Examples were bonded was placed in a male mold with the resin layer B-1 side up, and heating was performed in a heating oven for each male mold. Thereafter, a shape heated under the same conditions is placed on a resin plate and set in the following molding apparatus to perform press molding and cooling, and to remove the constrained object, whereby the resin layer B-1 is disposed on the convex side of the tunnel. This shaped body was obtained. The following apparatus and molding mold were used for the molding mold. In addition, the set temperature and time at the time of heating and the press plate temperature, pressure and time at the time of press molding are shown in Table 1.

Molding equipment: Press equipment KVHC (manufactured by Katagawa Seiki)

Molding mold: tunnel shape

Male size; Flat part length 120mm × Flat part width 50mm × Height 8mm

Curvature R of shaped bend: 4, 6, 8 or 20mm

Clearance of bend: 0.340mm

Clearance of flat part: 0.340mm

Mold height: 5mm

Here, the clearance refers to the gap between the male shape and the shape when the molding die is molded.

About the obtained molded object, the external appearance was checked visually, and the molded object appearance was evaluated based on the following evaluation criteria.

○: There is no crack or breakage in the molded article

×: There is a crack or breakage in the molded article

(Elongation of the curved part of the molded body (ΔL))

In the molded articles obtained in Examples and Comparative Examples, cross-sectional observation was performed using the following apparatus, the thickness of the molded article at the center portion of the curved portion of the molded article was read, and the thickness of the curved portion of the molded article was obtained. Moreover, cross-sectional observation was also performed about the resin plate used for molding, the thickness was read, and it was set as the thickness of the resin plate before molding. The obtained numerical value was substituted into the following formula (1), and the elongation rate (ΔL) of the curved portion of the molded body was obtained.

Sectional observation device: Microscope VHX-600 type (made by Keyence Corporation)

Observation magnification: 250 times

ΔL (%) = (thickness of resin plate before molding-thickness of curved portion of molded body) / thickness of resin plate before molding x 100... (One)

(Elongation of the resin substrate in the curved portion of the molded body (ΔLx))

In the molded articles obtained in Examples and Comparative Examples, cross-sectional observation was performed in the same manner as described above, and the thickness of the resin substrate at the central portion of the curved portion of the molded article was read, and the thickness of the resin substrate in the curved portion of the molded article was determined. Moreover, cross-sectional observation of the resin plate used for molding was performed, the thickness of the resin base material was read, and it was set as the thickness of the resin base material before molding. The obtained numerical value was substituted into the following formula (2), and the elongation rate (ΔLx) of the resin substrate in the curved portion of the molded body was obtained.

ΔLx (%) = (thickness of the resin substrate before molding-the thickness of the resin substrate in the curved portion of the molded body) / thickness of the resin substrate before molding × 100... (2)

Here, in response to the types of processing performed in Examples and Comparative Examples, that is, compression deformation, elongation deformation, and shear deformation, the thickness of the target resin layer is measured, and the elongation rate (ΔLx) is obtained as the thickness of the resin substrate.

<Example 1>

(Preparation of resin composition a)

A pellet of acrylic resin A (manufactured by Mitsubishi Rayon, brand name "Acrifet VH001") was used as resin composition a as it is.

(Production of resin base material)

The resin composition a was supplied to an extruder A, melt-kneaded in an extruder at 240°C, and then extruded into a single-layered sheet of resin layer A using a single-layer T-die heated to 250°C, cooled and solidified. , A resin substrate having a thickness of 310 μm was obtained. The pencil hardness was evaluated about the obtained resin substrate, that is, the surface of the resin layer A. The results are shown in Table 2.

(Production of resin plate)

Organic-inorganic hybrid ultraviolet-curable resin composition b-1 (manufactured by MOMENTIVE, brand name "UVHC7800G", content of inorganic silica having a reactive functional group: 30 to 40% by mass) on one surface of the obtained resin substrate was applied using a bar coater And, after drying at 90 degreeC for 1 minute, it exposed with the exposure amount of 500 mJ/cm ² , and obtained the resin plate provided with the resin layer B-1 of 10 micrometers in thickness. The pencil hardness and universal hardness were evaluated about the surface of the resin layer B-1 of the obtained resin plate. The results are shown in Table 2.

(Adhesion operation of confined objects and resin plate)

On the surface of the resin layer B-1 of the resin plate, a protective film d-1 (substrate layer; polyethylene terephthalate resin; thickness 50 μm, flexural modulus 3050 MPa, pressure sensitive adhesive layer; acrylic pressure sensitive adhesive; thickness 5 μm) as a restraint material After matching, it was placed on a polycarbonate resin plate having a thickness of 8 mm, passed through a laminating apparatus as it is, and laminated to obtain a resin plate for molding. Below, the lamination conditions are shown.

Roll configuration: metal rolls for both top and bottom

Clearance between rolls: 8mm

Laminate pressure: 0.3MPa

Notification speed: 1.0m/min

(Manufacturing of molded body)

Using the obtained resin plate for molding, thermoforming was performed under molding condition 1 to obtain a tunnel-shaped protective film part molded body in which the resin layer B-1 is disposed on the convex surface side. About the molded object obtained by removing the protective film from the said protective film part molded object, the molded object appearance, the elongation rate of the curved part of a molded object, and the elongation rate of the curved part of a resin base material were evaluated. The results are shown in Table 2.

<Example 2>

In preparation of the molded article of Example 1, a molded article was obtained in the same manner as in Example 1 except that thermoforming was performed under the molding condition 2. On the other hand, a protective film d-2 (substrate layer; polyethylene terephthalate resin; thickness 25 μm, flexural modulus 3030 MPa, pressure-sensitive adhesive layer; acrylic pressure-sensitive adhesive; thickness 3 μm) was used as a restraint on the surface of the resin layer B-1 of the resin plate. . About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2.

<Example 3>

(Preparation of resin composition a)

A pellet of acrylic resin A (manufactured by Arkema, brand name "Altuglas HT121", containing a hard dispersed phase) was used as resin composition a as it is.

(Preparation of resin composition c)

Pellets of polycarbonate resin (manufactured by Sumica Styron; brand name "CALIBRE301-4") and pellets of polycarbonate resin (manufactured by Sumica Styron; brand name "SD Polya SP3030") and polyester resin (manufactured by SK Chemicals; After mixing the pellets of the brand name "SKYGREEN J2003") at a mass ratio of 55:25:20, they were pelletized using a twin screw extruder heated to 260°C to prepare a resin composition c.

(Production of resin base material)

The resin compositions a and c were supplied to extruders A and B, respectively, and melt-kneaded at 240°C and 260°C in each extruder, and then joined to a T die for two types and two layers heated to 250°C, and resin layer A /The resin layer C was extruded in a sheet form so as to have a two-layer structure, cooled and solidified, and a resin substrate having a thickness of 600 μm (resin layer A: 80 μm, resin layer C: 520 μm) was obtained. The pencil hardness was evaluated about the surface of the resin layer A of the obtained resin substrate. The results are shown in Table 2.

(Production of resin plate)

Organic-inorganic hybrid ultraviolet-curable resin composition b-1 (manufactured by MOMENTIVE, brand name ``UVHC7800G'', content of inorganic silica having a reactive functional group: 30 to 40% by mass) on the surface of the resin layer A side of the obtained resin substrate, a bar coater It applied using and, after drying at 90 degreeC for 1 minute, it exposed by the exposure amount of 500 mJ/cm ² , and obtained the resin plate provided with the resin layer B-1 of 9 micrometers in thickness. The pencil hardness and universal hardness were evaluated about the surface of the resin layer B-1 of the obtained resin plate. The results are shown in Table 2.

(Adhesion operation of confined objects and resin plate)

In the same manner as in Example 1, a resin plate for molding was produced in which a restraint was bonded to the surface of the resin layer B-1 of the resin plate. On the other hand, protective film d-3 (substrate layer; polyethylene terephthalate resin; thickness 50 μm, flexural modulus 3050 MPa, pressure-sensitive adhesive layer; acrylic pressure-sensitive adhesive; thickness 3 μm) was used as the restraint.

(Manufacturing of molded body)

In the production of the molded article of Example 1, a molded article was obtained in the same manner as in Example 1, except that the clearances of the mold curved portion and the flat portion were respectively 0.660 mm and thermoforming was performed under molding condition 3. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2.

<Example 4>

In Example 3, a molded article was obtained in the same manner as in Example 3, except that a molded article was obtained by performing thermoforming under the molding condition 4. On the other hand, a protective film d-4 (substrate layer; polyethylene terephthalate resin; thickness 25 μm, flexural modulus 3030 MPa, pressure-sensitive adhesive layer; acrylic pressure-sensitive adhesive; thickness 5 μm) was used as a restraint on the surface of the resin layer B-1 of the resin plate. . About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2.

<Example 5>

In Example 4, a molded article was obtained in the same manner as in Example 4, except that a molded article was obtained by performing thermoforming under the molding condition 5. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2.

<Example 6>

In Example 3, the same as in Example 3, except that a resin plate was produced with the thickness of the resin layer B-1 being 25 μm, and thermoforming was performed under molding condition 6 in the production of the molded body. Thus, a molded article was obtained. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2.

<Example 7>

In the production of the molded article of Example 3, with the resin layer B-1 side down and placed in a male mold, each male mold was heated in a heating oven, and thereafter, a mold heated under the same conditions was used as a resin plate. In the same manner as in Example 3, except for the above point and the point of thermoforming under the molding condition 6, a tunnel-shaped molded body in which the resin layer B-1 was disposed on the concave side was obtained. On the other hand, the protective film d-4 was used as a restraint. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2.

<Example 8>

In Example 3, the urethane acrylate-based ultraviolet curable resin composition b-2 (manufactured by Daisei Fine Chemical, brand name ``8BR-500'') on the surface of the resin layer C opposite to the side on which the resin layer A is laminated. ”) was applied using a bar coater, dried at 90° C. for 1 minute, exposed at an exposure amount of 500 mJ/cm ² , and a resin plate provided with a resin layer B-2 having a thickness of 8 μm was prepared and molding conditions A molded article was obtained in the same manner as in Example 3, except that the molded article was obtained by thermoforming in accordance with 6. On the other hand, only the resin layer B-1 side used the protective film d-4 as a restraint object. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2.

<Example 9>

(Production of resin plate)

In Example 3, on the surface of the resin layer C, on the side opposite to the side on which the resin layer A is laminated, the urethane acrylate ultraviolet-curable resin composition b-2 (manufactured by Asia Industries, brand name ``RUA-071'') Was applied using a bar coater, dried at 90° C. for 1 minute, exposed at an exposure amount of 500 mJ/cm ² , and a resin plate provided with a resin layer B-2 having a thickness of 8 μm was obtained.

(Adhesion operation of confined objects and resin plate)

In Example 3, a restraint was also bonded to the surface of the resin layer B-2 of the resin plate to obtain a molding resin plate. On the other hand, the protective film d-4 was used as the restraint of the resin layer B-1 and the resin layer B-2.

(Manufacturing of molded body)

Thermoforming was performed under molding condition 6 to obtain a molded article. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2.

<Comparative Example 1>

In Example 3, except that the protective film was not closely adhered to the surface of the resin layer B-1, it was attempted to obtain a molded article in the same manner as in Example 3, but in particular, cracks occurred in the curved portion of the resin layer B-1. , A molded article having a good appearance could not be obtained. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2. However, since cracks and fractures occurred in the resin layer B-1, it was difficult to measure the elongation ΔL.

<Comparative Example 2>

In Example 9, except that the protective film was not closely adhered to the surface of the resin layer B-2, it was attempted to obtain a molded article in the same manner as in Example 9, but in particular, cracks occurred in the curved portion of the resin layer B-2. , A molded article having a good appearance could not be obtained. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2. However, since cracks and fractures occurred in the resin layer B-2, it was difficult to measure the elongation ΔL.

<Comparative Example 3>

In the tight bonding operation of the restraint material and the resin plate of Example 3, on the surface of the resin layer B-1 of the resin plate, as a restraint material, a PET film (substrate layer; polyethylene terephthalate-based resin; thickness 50 μm, flexural modulus 3000 MPa, A molded body was attempted to be obtained in the same manner as in Example 3, except that the pressure-sensitive adhesive layer; nothing) was matched to form a resin plate for molding, but cracks extending to the resin layer B-1 and part of the resin layer C Formed, and a molded article having a good appearance could not be obtained. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2. However, since cracks and fractures occurred in the resin layer B-1 and the resin layer C, it was difficult to measure the elongation ΔL and ΔLx.

<Comparative Example 4>

In Example 7, except that the protective film was not closely adhered to the surface of the resin layer B-1, it was attempted to obtain a molded article in the same manner as in Example 7, but in particular, cracks occurred in the curved portion of the resin layer B-1. , A molded article having a good appearance could not be obtained. About the obtained molded body, it evaluated by the method similar to Example 1. The results are shown in Table 2. However, since cracks and fractures occurred in the resin layer B-1, it was difficult to measure the elongation ΔL.

As is clear from Table 2, the molded articles of the present invention of Examples 1 to 9 have excellent hardness with a hardness of 5H or more on the surface of the resin layer B-1, and the appearance thereof is whitening, cracking, and foaming during thermoforming. It was found that a good molded article could be obtained without causing the back. On the other hand, the laminates of Comparative Examples 1 to 4 have a pencil hardness of 5H or more on the surface of the resin layer B-1 and have excellent hardness, but at the time of thermoforming, the resin layer B-1, the resin layer C, or the resin layer B-2 Cracks and fractures occurred, and thus a molded article having an excellent appearance could not be obtained.

The method for producing a molded article proposed by the present invention can be molded into a complex shape having a curvature R of various curved portions without impairing excellent surface properties and appearance by bending. Therefore, the molded article obtained by this manufacturing method is suitably used for a surface protection panel used by placing it on the front side (viewer side) of an image display device, particularly a front cover material such as a mobile phone or a liquid crystal pen tablet having a touch panel function. do.

11, 16, 17, 19: resin plate for molding
12: resin layer C
13: resin layer A
14: resin layer B-1
15: Binding
18: resin layer B-2
21: functional layer
22: resin substrate
23: flat part
24: Curvature (R) of the curved portion of the molded article
25: central portion of the curved portion of the molded body
31: molding mold
32: male
33: shape
34: clearance of the flat part
35: clearance of bend
36: male height
37: molded body
38: molded body height

Claims (18)

A method for producing a molded article, comprising bending the functional layer surface of a resin plate comprising a resin substrate and a functional layer laminated on at least one side surface of the resin substrate while tightly constrained by a protective film,
The functional layer is a high hardness layer composed of resin layer B,
The protective film has at least a base layer and a restraint layer D,
The restraint layer D is an adhesive layer,
The resin layer B is formed of a curable resin composition,
The resin substrate is formed of a thermoplastic resin composition,
The surface hardness of the high hardness layer is 200 MPa or more in universal hardness,
Method for producing a molded article. The method of claim 1,
A method for producing a molded article, comprising bending the functional layer surfaces laminated on both surfaces of the resin substrate, which form the convex side and the concave side of the molded article after the bending process, while closely constraining it. The method of claim 1,
A method for manufacturing a molded article, characterized in that the curved portion of the molded article is compression-deformed. The method of claim 1,
A method for producing a molded article, characterized in that the curved portion of the molded article is elongated and deformed. The method of claim 2,
A method for producing a molded article, wherein the curved portion of the molded article is sheared and deformed. The method of claim 3,
In the molded article, the curvature (R) of the bent portion is 2 mm or more and 200 mm or less, and the elongation (ΔL) of the bent portion represented by the following formula (1) is -40% or more and less than 4%.
ΔL (%) = (the thickness of the resin plate before molding-the thickness of the curved portion of the molded body) / the thickness of the resin plate before molding × 100. (One) The method of claim 4,
In the above-described molded article, the curvature (R) of the bent portion is 2 mm or more and 200 mm or less, and the elongation (ΔL) of the curved portion represented by the following formula (1) is 0% or more and less than 40%.
ΔL (%) = (the thickness of the resin plate before molding-the thickness of the curved portion of the molded body) / the thickness of the resin plate before molding × 100. (One) The method of claim 5,
In the above-described molded article, the curvature (R) of the curved portion is 2 mm or more and 200 mm or less, and the elongation (ΔL) of the curved portion represented by the following formula (1) is -7% or more and less than 7%.
ΔL (%) = (the thickness of the resin plate before molding-the thickness of the curved portion of the molded body) / the thickness of the resin plate before molding × 100. (One) The method of claim 1,
In the protective film, the product of the bending elastic modulus (MPa) of the protective film and the thickness (m) of the protective film is 3.0 × 10 ^-2 MPa·m or more. The method of claim 1,
The method for producing a molded article, characterized in that the pencil hardness on the surface of the resin layer B is 5H or more. The method of claim 1,
The method for producing a molded article, wherein the curable resin composition is an organic/inorganic hybrid curable resin composition. The method of claim 1,
The method of manufacturing a molded article, wherein the resin substrate has at least two resin layers formed of different thermoplastic resin compositions. The method of claim 1,
A method for producing a molded article, wherein the pencil hardness of the side surface of the resin substrate on which the resin layer B is laminated is 3H or more and 5H or less. The method of claim 1,
The method for producing a molded article, wherein the base layer is made of any of a polyamide resin, a polyester resin, and a polyimide resin. The method of claim 1,
The storage modulus of the pressure-sensitive adhesive layer is 1.0×10 ² Pa or more and 1.0×10 ⁷ Pa or less at the glass transition temperature of the resin plate. A molded article obtained by the production method according to any one of claims 1 to 15. A display front cover material comprising the molded article according to claim 16. An image display device comprising the front cover material according to claim 17.

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