TW201431683A - Molding resin laminate and molded article - Google Patents

Abstract

The invention provides a molding resin laminate having excellent surface hardness and thermoformability, and a molded article obtained by thermally molding the molding resin laminate. The molding resin laminate is formed by laminating at least two layers including a resin layer A formed of a thermoplastic resin composition a and a resin layer B formed of a curable resin composition b, wherein the pencil hardness of the surface of the resin layer B is 5H or above, and the storage elastic modulus of the resin layer A and the resin layer B at the temperature of the glass transition temperature of the resin layer A -20 DEG C satisfies the relation of -2.0 (GPa) ≤ the storage elastic modulus of the resin layer B - the storage elastic modulus of the resin layer A ≤ 2.5 (GPa), or the extensibility of the molding resin laminate at the temperature of the glass transition temperature of the resin layer A -30 DEG C is 6% or more and 50% or less.

Description

Forming resin laminate and molded body

The present invention relates to a surface protection panel that is disposed on a front side (viewing side) of an image display device, and is particularly applicable to a mobile phone or a liquid crystal tablet having a touch panel function, a vehicle display, a guide, or a display panel. A molding resin laminate for a cover material before. In addition, the molded resin laminated body obtained by hot forming by vacuum forming or pressure forming is used.

In the field of a cover material for a display of an electronic device, glass can be widely used from the viewpoint of hardness, heat resistance, and transparency.

However, the glass is easily broken by the impact, and the weight of the glass itself is also heavier, so the replacement of the plastic is reviewed.

On the other hand, various electronic machines. The device is becoming smaller, lighter, higher-performance, and diversified in design. When the display is made of a plastic material such as a cover material, the requirements are becoming more stringent, and excellent surface hardness is expected, and thermoformability or rushing is provided. A hole-forming resin laminate and a molded body.

For such applications, an acrylic resin can be widely used from the viewpoint of high transparency and excellent surface hardness.

However, since acrylic resins are very brittle, their processing methods are carried out by cutting, but in general, they are by no means highly productive.

In the case where the brittleness and the scratch resistance of the disadvantage of the acrylic resin are lowered, for example, Patent Document 1 proposes laminating a single layer of a polycarbonate resin sheet by co-extruding an acrylic resin having a thickness of 50 to 120 μm. The laminate having a total thickness of 0.5 to 1.2 mm further imparts a composition of the hard coat layer.

Further, Patent Document 2 proposes to form a layer containing an acrylic resin by co-extrusion on the surface of a substrate containing a polycarbonate resin, and then subject the surface of the layer containing the acrylic resin to a hard coat treatment to obtain a surface. The hardness, especially the pencil hardness and the impact resistance are balanced, and it is suitable for the laminated body of the liquid crystal display cover.

Patent Document 3 proposes a film for decoration which is provided with a hard coat layer by applying a film having an ultraviolet curable hard coat layer and then curing it by UV irradiation.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-103169

[Patent Document 2] International Publication No. WO2008/047940

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-51247

In the resin laminate disclosed in the above Patent Documents 1 and 2, since the acrylic resin is generally difficult to extend under the polycarbonate resin, the polycarbonate resin layer and the acrylic resin are used in the thermoforming. Peeling, whitening or cracking, foaming, etc. occur at the interface between the layers. Also, hard coating agents are generally difficult to extend and are therefore not considered to be suitable for thermoforming applications.

Further, the resin laminated system disclosed in Patent Document 3 is subjected to UV hardening treatment after the decorative molding, and thus there is unevenness unlike the flat plate, and in particular, the side surface of the molded body cannot sufficiently cause hardening due to UV irradiation. It is assumed that the remaining portion of the hard coat layer is not hardened. As a result, there is a case where sufficient surface hardness cannot be obtained. Moreover, for the same reason, there is a concern that it cannot be applied to the formation of a complicated molded body.

Therefore, an object of the present invention is to provide a molding resin laminate having high surface hardness and various moldings obtained by thermoforming the resin laminate without causing problems such as whitening, cracking, and foaming during hot forming. body.

The inventors of the present invention have found that the resin laminated body formed by laminating at least two layers of the resin layer A formed of the thermoplastic resin composition a and the resin layer B formed of the curable resin composition b is a resin. The pencil hardness of the surface of the layer B is 5H or more, and the storage elastic modulus of the resin layer A and the resin layer B at a predetermined temperature (I) is adjusted to satisfy the lower According to the relationship, a novel molding resin laminate having excellent surface hardness and thermoformability can be provided.

-2.0 (GPa) storage elastic modulus of the resin layer B - storage elastic modulus of the resin layer A ≦ 2.5 (GPa)

Here, the predetermined temperature (I) means a temperature at which the glass transition temperature of the resin layer A is -20 °C.

Further, it has been found that at least three layers of the resin layer C formed of the thermoplastic resin composition c, the resin layer A formed of the thermoplastic resin composition a, and the resin layer B formed of the curable resin composition b are laminated in this order. In the formed resin laminated body, the pencil hardness of the surface of the resin layer B is 5H or more, and the storage elastic modulus of the resin layer A, the resin layer B, and the resin layer C at a predetermined temperature (I) is obtained. By adjusting the following relationship, it is possible to provide a novel molding resin laminate having excellent surface hardness and thermoformability.

-2.0 (GPa) storage elastic modulus of the resin layer B - storage elastic modulus of the resin layer A ≦ 2.5 (GPa)

-1.0 (GPa) storage elastic modulus of the resin layer A - storage elastic modulus of the resin layer C ≦ 1.0 (GPa)

Here, the predetermined temperature (I) means a temperature at which the glass transition temperature of the resin layer A is -20 °C.

In addition, the inventors of the present invention have found that the resin layer A formed of the thermoplastic resin composition a and the resin layer B formed of the curable resin composition b are at least two layers laminated. The pencil hardness of the surface of the resin layer B is 5H or more, and the elongation of the molding resin laminate under a predetermined temperature (II) is adjusted to be in a range of 6% or more and 50% or less. New surface hardness and thermoformability Resin laminate for molding.

Here, the predetermined temperature (II) means a temperature at which the glass transition temperature of the resin layer A is -30 °C.

Further, it has been found that at least three layers of the resin layer C formed of the thermoplastic resin composition c, the resin layer A formed of the thermoplastic resin composition a, and the resin layer B formed of the curable resin composition b are laminated in this order. In the formed resin laminate, the pencil hardness of the surface of the resin layer B is 5H or more, and the elongation of the molding resin laminate at a predetermined temperature (II) is adjusted to 6% or more and 50%. In the following range, a novel molding resin laminate having excellent surface hardness and thermoformability can be provided.

Here, the predetermined temperature (II) means a temperature at which the glass transition temperature of the resin layer A is -30 °C.

The molding resin laminate according to the present invention has excellent surface hardness and thermoformability, and thus can be suitably used as a surface protection panel which is disposed on the front side (viewing side) of the image display device, and particularly has a touch. The front cover of the control panel function mobile phone or LCD tablet, car display, guide or display panel.

11, 15, 16‧‧‧ This layer

12‧‧‧Resin layer C

13‧‧‧Resin layer A

14‧‧‧Resin layer B

1(a) to 1(c) are configuration diagrams of an embodiment of the present invention.

Hereinafter, a molding resin laminate (referred to as "this laminate") according to an embodiment of the present invention will be described. However, the invention is not limited to the present laminate.

The laminated body structure of the first aspect of the invention is a resin laminated body formed by laminating at least two layers of a resin layer A formed of a thermoplastic resin composition a and a resin layer B formed of a curable resin composition b; The pencil hardness of the surface of the resin layer B is 5H or more, and the storage elastic modulus of the resin layer A and the resin layer B at a predetermined temperature (I) satisfies the following relationship:

-2.0 (GPa) storage elastic modulus of the resin layer B - storage elastic modulus of the resin layer A ≦ 2.5 (GPa)

Here, the predetermined temperature (I) means a temperature at which the glass transition temperature of the resin layer A is -20 °C.

The lower limit of the storage elastic modulus difference between the resin layer B and the resin layer A at a predetermined temperature (I) is preferably -2.0 (GPa) or more, more preferably -1.5 (GPa) or more, and particularly excellent -1.0. (GPa) above. If the storage modulus difference is -2.0 (GPa) or more, the surface hardness of the laminate can be maintained, which is preferable.

On the other hand, the important upper limit of the storage modulus of the modulus of elasticity is below 2.5 (GPa). By the storage elastic modulus difference of 2.5 (GPa) or less, when the laminated body is subjected to thermoforming, the resin layer B can be easily deformed by tracking the deformation of the resin layer A. For this reason, the storage elastic modulus difference is preferably 2.0 (GPa) or less, and particularly preferably 1.5 (GPa) or less.

The laminated body structure of the second aspect of the invention is a resin laminated body formed by laminating at least two layers of a resin layer A formed of a thermoplastic resin composition a and a resin layer B formed of a curable resin composition b; The pencil hardness of the surface of the resin layer B is 5H or more, and the elongation of the molding resin laminate under a predetermined temperature (II) is adjusted to 6%. Above and below 50%.

Here, the predetermined temperature (II) means a temperature at which the glass transition temperature of the resin layer A is -30 °C.

It is important that the lower limit of the elongation of the laminate under the predetermined temperature (II) is 6% or more. When the elongation is 6% or more, when the laminate is subjected to hot forming, cracking or cracking does not occur on the surface of the molded body, and good thermoformability can be obtained. For example, it can be formed by bending by stamping. Font shape.

Further, when the elongation is 15% or more, for example, a vacuum three-dimensional shape such as a box type can be formed by a vacuum pressure forming method, and hot forming can be performed in a wider temperature range, which is preferable.

On the other hand, the upper limit of the elongation of the laminate is preferably 50% or less, more preferably 30% or less. If the elongation is 50% or less, the laminate can maintain a sufficient surface hardness, which is preferable.

The laminated structure of the third aspect of the invention is at least a resin layer C formed of the thermoplastic resin composition c, a resin layer A formed of the thermoplastic resin composition a, and at least a resin layer B formed of the curable resin composition b. a laminated body formed by sequentially laminating three layers; wherein the pencil hardness of the surface of the resin layer B is 5H or more, and the storage elastic modulus of the resin layer A, the resin layer B, and the resin layer C at a predetermined temperature (I) The following relationship is satisfied: -2.0 (GPa) storage elastic modulus of the resin layer B - storage elastic modulus of the resin layer A ≦ 2.5 (GPa)

-1.0 (GPa) storage elastic modulus of the resin layer A - storage elastic modulus of the resin layer C ≦ 1.0 (GPa)

Here, the predetermined temperature (I) means a temperature at which the glass transition temperature of the resin layer A is -20 °C.

The preferred range of the difference in the storage elastic modulus between the resin layer B and the resin layer A at a predetermined temperature (I) is as described in the first invention.

The lower limit of the storage elastic modulus difference between the resin layer A and the resin layer C at a predetermined temperature (I) is preferably -1.0 (GPa) or more, more preferably -0.5 (GPa) or more, and particularly preferably -0.1. (GPa) above. If the lower limit of the storage modulus difference is -1.0 (GPa) or more, the surface hardness of the laminate can be maintained, which is preferable. On the other hand, the upper limit of the storage elastic modulus difference is 1.0 (GPa) or less, more preferably 0.7 (GPa) or less, and particularly preferably 0.5 (GPa) or less. If the storage modulus difference is less than 1.0 (GPa), when the laminate is thermoformed, the resin layer C can be easily deformed by tracking the deformation of the resin layer A, that is, the thermoformability is improved, so that it is preferable and more preferable. It is preferable to maintain the rigidity of the laminate and to improve the workability. Here, the resin layer A and the resin layer C are composed of different thermoplastic resin compositions.

The laminate structure of the fourth aspect of the invention includes a resin layer C formed of the thermoplastic resin composition c, a resin layer A formed of the thermoplastic resin composition a, and a resin layer B formed of the curable resin composition b. a molding resin laminate formed by laminating at least three layers; wherein the resin layer B has a pencil hardness of 5H or more, and the molding resin laminate elongation at a predetermined temperature (II) is adjusted to 6%. Above and below 50%.

Here, the predetermined temperature (II) means a temperature at which the glass transition temperature of the resin layer A is -30 °C.

The lower limit of the elongation of the laminate under the predetermined temperature (II) is the second issue as described above. Bright.

In the configuration of the laminate, the pencil hardness of the surface of the resin layer B is preferably 5H or more, more preferably 7H or more. If the pencil hardness is 5H or more, a laminate having excellent surface hardness can be provided.

Further, when the surface of the resin layer B is wiped with a weight of 500 g of #0000 steel wool, the number of reciprocations until the occurrence of scratches is preferably 50 or more. When the above-mentioned steel wool is used for wiping, the number of reciprocations until the surface is scratched is 50 or more, and a laminated body having excellent scratch resistance and being easily scratched can be provided. From this point of view, the number of reciprocations until the surface is scratched is preferably 50 times or more, more preferably 100 times or more, and particularly preferably 500 times or more.

Hereinafter, the resin layer A, the resin layer B, and the resin layer C constituting the laminate will be described in order.

(resin layer A)

In the laminated system, at least two layers of the resin layer A formed of the thermoplastic resin composition a and the resin layer B formed of the curable resin composition b are laminated, or a resin formed of the thermoplastic resin composition c At least three layers of the layer C, the resin layer A formed of the thermoplastic resin composition a, and the resin layer B formed of the curable resin composition b are sequentially laminated. In either case, the resin layer A is disposed on the back side of the resin layer B, and the resin layer B exhibits an excellent surface hardness.

Wherein, if the resin layer A of high hardness is disposed on the back side of the resin layer B, because the resin layer A, such as the behavior of the hard underlayer, for example, when the pencil hardness is measured, the resin layer A itself has a function of repelling and preventing the needle-like object having a high hardness such as a pencil lead from entering the resin layer B, thereby preventing the pencil lead When the needle-like object causes the resin layer B to be scratched or cut, the resin layer B can exhibit excellent surface hardness, which is preferable. On the other hand, when the soft resin layer A is disposed on the back side of the resin layer B, for example, a needle-like object having a high hardness such as a pencil lead is eaten into the resin layer B, the resin layer A itself is recessed and cannot be absorbed. Preventing this from happening, the resin layer B is liable to be scratched or cut due to the intrusion of a needle-like object such as a pencil lead.

For this reason, the hardness of the surface of the resin layer A is preferably a pencil hardness of 3H or more, more preferably 5H or more. When the pencil hardness of the surface of the resin layer A is 3H or more, even if the thickness of the resin layer B laminated thereon is thinned, the surface of the resin layer B can maintain excellent hardness, which is preferable. When the resin layer A having a pencil hardness of 3H or more on the surface is disposed on the back side of the resin layer B, as described above, the behavior of the resin layer A such as the hard substrate layer, for example, when the pencil hardness is measured, the resin layer A itself has an inverse The needle-like object of high hardness such as a pencil core is prevented from being eaten by the resin layer B, so that even if the thickness of the resin layer B is thinned, the needle-like object such as a pencil lead can be prevented from being scratched or the resin layer B can be scratched or In the case of cutting, that is, the surface of the resin layer B can maintain excellent hardness, it is preferable. On the other hand, when the pencil hardness of the surface of the resin layer A disposed on the back side of the resin layer B is 2H or less, the resin layer A itself is prevented from being in the resin layer B by preventing the needle-like object having a high hardness such as a pencil lead from being eaten into the resin layer B. The surface hardness is not sufficient, and it is necessary to make it difficult to dent by increasing the thickness of the resin layer B, and to prevent the needle-like body such as a pencil lead from being eaten, resulting in scratching or cutting of the resin layer B.

Furthermore, if the thickness of the resin layer B is thinned, when the laminate is thermoformed, the resin The layer B can be easily formed by tracking the deformation of the resin layer A, which is preferable.

(The thermoplastic resin composition a)

The resin layer A of the laminate is formed of the thermoplastic resin composition a. The thermoplastic resin which can be used for the thermoplastic resin composition a is provided before the thermoplastic resin which can be formed into a film, a sheet or a sheet by melt extrusion, and the rest is not particularly limited, and preferred examples thereof are exemplified. : polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexyl dimethylene pair An aromatic polyester such as a phthalic acid ester or a polyester resin represented by an aliphatic polyester such as a polylactic acid polymer; a polyolefin resin such as polyethylene, polypropylene or a cycloolefin resin; a polycarbonate resin; Acrylic resin, polystyrene resin, polyamine resin, polyether resin, polyurethane resin, polyphenylene sulfide resin, polyester amide resin, polyether ester resin, chlorine Ethylene resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polydiphenyl ether resin, polyarylate resin, polyfluorene resin, polyether sulfoxide Resin, polyamidoximine resin, polyamidene resin, and Of copolymer such as a main component, or a mixture of such resins.

In the present invention, a polyester resin, a polycarbonate resin, and an acrylic resin are particularly preferable from the viewpoint of almost no absorption in the visible light region. In the above, the acrylic resin is particularly preferable from the viewpoint of exhibiting excellent surface hardness of the resin layer B and having a desired difference in storage elastic modulus from the resin layer B.

Further, when the thermoplastic resin composition a constituting the resin layer A is a mixture of two or more kinds of resins selected from the above, and the ones are incompatible with each other, the glass of the thermoplastic resin having the highest volume fraction can be transferred. The temperature is set to the glass transition temperature of the resin layer A.

(acrylic resin)

Examples of the monomer constituting the acrylic resin which can be used in the present invention include methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth)acrylate, n-butyl (meth)acrylate, and (methyl). ) isobutyl acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, (a) Base) octadecyl acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyl (meth) acrylate Ethyl ethyl ester, cyclohexyl (meth)acrylate, (meth)acrylic acid Ester, (meth)acrylic acid Ester, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (methyl) Acrylic acrylate, 2-hydroxyethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl succinate, maleic acid-2-(methyl) propylene methoxy ethoxylate Ester, 2-(methyl)propenyloxyethyl phthalate, 2-(methyl)propenyloxyethyl hexahydrophthalate, pentamethylpiperidine (meth)acrylate, (A) Base) tetramethyl piperidinyl acrylate, dimethylaminoethyl (meth)acrylate, diethylamine ethyl (meth)acrylate, and the like.

These may be used alone or in combination of two or more.

The monomer copolymerizable 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 compound having at least two polymerizable carbon-carbon double bonds in the molecule.

Here, examples of the monofunctional monomer include an aromatic alkenyl compound such as styrene, α-methylstyrene, and vinyltoluene; an alkenyl cyanide compound such as acrylonitrile or methacrylonitrile; and acrylic acid; , methacrylic acid, maleic anhydride, N-substituted maleimide, and the like. Further, examples of the polyfunctional monomer include polyunsaturated polyols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, and trimethylolpropane triacrylate. a carboxylic acid ester; an alkenyl ester of an unsaturated carboxylic acid such as allyl acrylate, allyl methacrylate or allyl cinnamate; for example, diallyl phthalate, diallyl maleate, A polyalkenyl ester of a polybasic acid of triallyl cyanurate or a triallyl cyanurate; an aromatic polyalkenyl compound such as divinylbenzene. A monomer which can be copolymerized with an alkyl methacrylate or an alkyl acrylate may be used in combination of two or more kinds as needed.

As a copolymerization resin produced by the monomer constituting the above acrylic resin, for example, from the viewpoint of improving the environmental resistance of the acrylic resin (warpage due to moisture absorption), it is preferred to use methacrylic acid. Ester-styrene copolymer. The methyl methacrylate-styrene copolymer resin is generally used in an amount of 30 to 95% by weight of the methyl methacrylate unit and 5 to 70% by weight of the styrene unit, based on the all monomer unit. 40 to 95% by weight of the methyl methacrylate unit and 5 to 60% by weight of the styrene unit may be used, and more preferably 50 to 90% by weight of the methyl methacrylate unit may be used, and the styrene unit may be used. 50% by weight. If the proportion of the methyl methacrylate unit becomes small, the destruction strength of the surface layer itself is lowered, and the entire film is easily broken, and the surface hardness is also lowered.

Moreover, when the ratio of the methyl methacrylate unit becomes large, environmental resistance will fall.

The acrylic resin which can be used in the present invention can be prepared by polymerizing the above-mentioned monomer component by a known method such as suspension polymerization, emulsion polymerization or bulk polymerization. At this time, in order to adjust to a desired glass transition temperature, or to obtain a viscosity which exhibits appropriate formability in the production of a laminate, it is preferred to use a chain transfer agent during polymerization. The amount of the chain transfer agent may be appropriately determined by blending the type of the monomer component or its composition.

Further, in the acrylic resin used in the laminate, heat resistant acrylic acid A resin (hereinafter referred to as "heat resistant acrylic resin") can also be preferably used as the thermoplastic resin composition a.

When the resin layer A is formed of a heat-resistant acrylic resin in the main component of the thermoplastic resin composition a, the laminated body is preferable because it has not only heat resistance but also excellent thermoformability.

In the case where the structure of the laminate is formed by sequentially laminating at least three layers of the resin layer C, the resin layer A, and the resin layer B, the resin at a predetermined temperature (I) is used. The means for setting the difference in the storage elastic modulus of the layer A and the resin layer C within a desired range, or as a means for setting the elongation of the laminated body at a predetermined temperature (II) within a desired range, The absolute value of the glass transition temperature difference between the layer A and the resin layer C is set to be within 30 °C. Therefore, in the case where the main component of the thermoplastic resin composition c forming the resin layer C is assumed to have a high glass transition temperature, the acrylic resin preferably has a high glass transition temperature as well. A heat resistant acrylic resin can be preferably used.

(heat-resistant acrylic resin a1)

The heat-resistant acrylic resin a1 is characterized by containing a copolymer of a (meth) acrylate structural unit represented by the following general formula (1) and an aliphatic vinyl structural unit represented by the following general formula (2). Resin.

[Chemical 1]

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

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

The R 2 -based alkyl group having 1 to 16 carbon atoms of the (meth) acrylate structural unit represented by the general formula (1) may, for example, be a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group or a cyclohexyl group. ,different Base. These may be used alone or in combination of two or more. Among these, R2 is preferably a (meth) acrylate structural unit of a methyl group and/or an ethyl group, and more preferably a methacrylate structural unit in which R1 is a methyl group and R2 is a methyl group.

The aliphatic vinyl structural unit represented by the general formula (2) may, for example, be a cyclohexyl group in which R 3 is hydrogen or a methyl group, and R 4 is a cyclohexyl group and an alkyl group having 1 to 4 carbon atoms. These lines can be separate It is used in one type or in combination of two or more types. Among these, an aliphatic vinyl structural unit in which R3 is hydrogen and R4 is a cyclohexyl group is preferred.

The ratio of the (meth) acrylate constituent unit represented by the general formula (1) to the molar composition of the aliphatic vinyl constituent unit represented by the general formula (2) is in the range of 15:85 to 85:15. Preferably, it is in the range of 25:75 to 75:25, and more preferably in the range of 30:70 to 70:30.

When the molar composition ratio of the (meth) acrylate constituent unit and the aliphatic vinyl constituting unit is less than 15%, the mechanical strength is excessively lowered to cause brittleness. No practicality. Moreover, if it exceeds 85%, heat resistance may be insufficient.

The heat-resistant acrylic resin a1 is mainly composed of a (meth) acrylate structural unit represented by the general formula (1) and an aliphatic vinyl constituting unit represented by the general formula (2), and the rest is It is not particularly limited, and it is preferably obtained by subjecting a (meth) acrylate monomer and an aromatic vinyl monomer to copolymerization, and then hydrogenating the aromatic ring. Further, the (meth)acrylic acid means methacrylic acid and/or acrylic acid. Specific examples of the aromatic vinyl monomer to be used in this case include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and the like, and derivatives thereof. Among these, styrene is preferred.

Further, specific examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and lauryl (meth) acrylate. Octadecylmethyl methacrylate, cyclohexyl (meth) acrylate, (meth) acrylate From the viewpoint of a balance of physical properties, such as an alkyl (meth)acrylate such as an ester, it is preferred to use an alkyl methacrylate alone or a combination of an alkyl methacrylate and an alkyl acrylate. Among the alkyl methacrylates, methyl methacrylate or ethyl methacrylate is particularly preferred.

The heat-resistant acrylic resin a1 mainly composed of a (meth) acrylate structural unit represented by the general formula (1) and an aliphatic vinyl constituting unit represented by the general formula (2) is preferably the above-mentioned aromatic The aromatic ring of the group vinyl monomer is obtained by hydrogenation of 70% or more. In other words, the ratio of the aromatic vinyl structural unit in the heat-resistant acrylic resin a1 is preferably 30% or less of the heat-resistant acrylic resin a1. When the range exceeds 30%, the transparency of the heat-resistant acrylic resin a1 may be lowered. More preferably, it is a range of 20% or less, and a range of 10% or less.

The polymerization of the (meth) acrylate monomer and the aromatic vinyl monomer can be carried out by a known method, for example, by 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, and is continuously polymerized 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 batch or continuous flow at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 °C. By setting the temperature to 60 ° C or higher, the reaction time is not excessively consumed, and by setting it at 250 ° C or lower, molecular chain cleavage or hydrogenation of the ester moiety is not caused.

Examples of the catalyst used in the hydrogenation reaction include a metal such as nickel, palladium, platinum, cobalt, rhodium or ruthenium, or an oxide or a salt or a wrong compound of the metal, which is supported on carbon, alumina, or cerium oxide. Ceria. A solid catalyst on a porous support such as alumina or diatomaceous earth.

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 more, the heat resistance of the laminate is not insufficient.

(heat resistant acrylic resin a2)

The heat-resistant acrylic resin a2 is a methacrylic acid unit, an acrylic acid unit, and a maleic anhydride unit, based on the all monomer unit constituting the acrylic resin, and has a methyl methacrylate unit of 60 to 95% by weight. , the N-substituted or unsubstituted maleimide unit, the glutaric anhydride structural unit, and the selected unit of the pentaneimine structural unit are 5 to 40% by weight, and the glass transition temperature is above 110 ° C. Polymer.

Here, the methyl methacrylate unit is a unit formed by polymerization of methyl methacrylate [-CH ₂ -C(CH ₃ )(CO ₂ CH ₃ )-]; the methacrylic unit is composed of methacrylic acid The unit formed by the polymerization [-CH ₂ -C(CH ₃ )(CO ₂ H)-]; the acrylic unit is a unit [-CH ₂ -CH(CO ₂ H)-] formed by polymerization of acrylic acid. Further, the maleic anhydride unit is a unit formed by polymerization of maleic anhydride represented by the general formula (3); the N-substituted or unsubstituted maleimide unit is derived from a general formula. (4) A unit formed by polymerization of an N-substituted or unsubstituted maleimide.

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

Further, the glutaric anhydride structural unit has a unit of glutaric anhydride structure; the pentane quinone imine structural unit has a unit of pentaneimine structure, and the typical systems are generally shown below (5) and (6) Said.

In the general formula (5), R ² represents a hydrogen atom or a methyl group; and R ³ represents a hydrogen atom or a methyl group. In the general formula (6), R ⁴ represents a hydrogen atom or a methyl group; R ⁵ represents a hydrogen atom or a methyl group; and R ⁶ represents a hydrogen atom or a substituent, and examples of the substituent include, for example, methyl group and ethyl group. The alkyl group, or a cycloalkyl group such as a cyclohexyl group, or an aryl group such as a phenyl group, or a benzyl aralkyl group, has a carbon number of usually about 1 to 20.

a methyl methacrylate unit, a methacrylic acid unit, an acrylic acid unit, a maleic anhydride unit, and an N-substituted or unsubstituted maleimide unit, by using methyl methacrylate, respectively Acrylic acid, acrylic acid, maleic anhydride, and N-substituted or The unsubstituted maleimide is used as a polymerization raw material and can be introduced.

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

Further, the pentamethylene imine structural unit is obtained by using a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid and/or acrylic acid in the presence of ammonia or a primary amine. It is usually modified by heat treatment in the range of 150 to 350 ° C, preferably 220 to 320 ° C, and can be introduced.

As the heat-resistant acrylic resin a2, the monomer unit composition of the acrylic resin is preferably 65 to 95% by weight, more preferably 70 to 92% by weight, based on the methacrylic acid unit, the acrylic acid unit, or the cis-butyl group. The unit selected from the enedic anhydride unit, the N-substituted or unsubstituted maleimide unit, the glutaric anhydride structural unit, and the pentaneimine structural unit is preferably 5 to 35% by weight, more preferably It is 8 to 30% by weight. Further, 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)

The heat-resistant acrylic resin a3 is a structure having a lactone ring formed by a cyclization condensation reaction of a polymer (α) having a hydroxyl group and an ester group in a molecular chain. The polymer (α) is a copolymer obtained by polymerizing at least a monomer component of a (meth) acrylate monomer (α 1) and a 2-(hydroxyalkyl) acrylate monomer, and the lactone ring Structure is as follows The configuration shown in the general formula (7).

In the general 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. Further, the organic residue may also contain an oxygen atom.

In order to form a lactone ring structure represented by the general formula (7), a polymer (α) having a hydroxyl group and an ester group in the molecular chain is preferably, for example, a (meth)acrylate monomer (α). 1) and a polymer obtained by polymerizing a monomer component of a vinyl monomer (α 2) having a structural unit represented by the following general formula (8).

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

The (meth) acrylate monomer (α 1) is a so-called vinyl monomer having a 2-(hydroxymethyl) acrylate structural unit as shown in the general formula (8), and The (meth)acrylic acid alkyl ester monomer is not particularly limited. For example, it may be an aliphatic (meth) acrylate having an alkyl group or the like, an alicyclic (meth) acrylate having a cyclohexyl group or the like, or an aromatic (meth) acrylate having a benzyl group or the like. ester. Further, the desired substituent or functional group may be introduced into the groups.

Specific examples of the (meth) acrylate monomer (α 1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (methyl). Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid-2 - (meth) acrylate such as hydroxyethyl ester or benzyl (meth) acrylate. These may be used alone or in combination of two or more. Among these, from the viewpoints of weather resistance, surface gloss, and transparency of the obtained acrylic resin, methyl methacrylate or methyl acrylate is preferred, and the surface hardness of the obtained acrylic resin is preferably In view of view, methyl methacrylate is more preferred. Further, the (meth) acrylate having a cyclohexyl group can impart hydrophobicity to the acrylic resin, and as a result, the water absorption of the acrylic resin can be lowered, and the weather resistance can be imparted to the acrylic resin. good. Further, the (meth) acrylate having an aromatic group is preferably an aromatic ring and can further improve the heat resistance of the obtained acrylic resin.

In the monomer component, the ratio of the (meth) acrylate monomer (α 1) is not particularly limited, but is preferably 95 to 10% by weight, more preferably 90 to 10% by weight. Further, in order to maintain good transparency and weather resistance, it is preferably 90 to 40% by weight, more preferably 90 to 60% in the total monomer component. % by weight, particularly preferably 90 to 70% by weight.

In the heat-resistant acrylic resin a3 used in the present invention, the (meth)acrylate monomer (α 1) may be used in combination with an unsaturated monocarboxylic acid (α 1 '). By using an unsaturated monocarboxylic acid (α 1 ') in combination, an acrylic resin having a structure in which a lactone ring structure and a glutaric anhydride ring are introduced together can be obtained, and heat resistance and mechanical strength can be further improved, which is preferable. The unsaturated monocarboxylic acid (α 1 ') may, for example, be (meth)acrylic acid, crotonic acid, or an α-substituted acrylic monomer belonging to the derivatives, but is not particularly limited. The (meth)acrylic acid is preferably a methacrylic acid from the viewpoint of heat resistance. Further, the ester group derived from the (meth) acrylate monomer (α 1) in the polymer (α) may have a structure equivalent to that of the unsaturated carboxylic acid (α 1 ') depending on conditions such as heating. Further, the carboxyl group having an unsaturated carboxylic acid (α 1 ') may be removed before the cyclization condensation reaction described later, and a salt structure such as a metal salt such as a sodium salt may be formed. In addition, the ratio of the unsaturated monocarboxylic acid (α 1 ') in the monomer component is not particularly limited, and may be appropriately set within a range that does not impair the effects of the present invention.

The vinyl monomer (α 2) having a structural unit represented by the above general formula (8) is, for example, a derivative of 2-(hydroxyalkyl)acrylic acid. Specifically, a 2-(hydroxymethyl) acrylate monomer is preferred. More specifically, for example, methyl 2-(hydroxymethyl)acrylate, ethyl 2-(hydroxymethyl)acrylate, isopropyl 2-(hydroxymethyl)acrylate, 2-(hydroxymethyl) N-butyl acrylate, tert-butyl 2-(hydroxymethyl) acrylate, etc., among which methyl 2-(hydroxymethyl)acrylate and ethyl 2-(hydroxymethyl)acrylate are particularly preferred. From the viewpoint of a high effect of improving surface hardness, hot water resistance or solvent resistance, methyl 2-(hydroxymethyl)acrylate is preferred. In addition, these types may be used alone or in combination of two or more.

The ratio of the vinyl monomer (α 2 ) having the structural unit represented by the above general formula (8) in the monomer component is not particularly limited, but is preferably 5 to 50% by weight. More preferably, it is 10 to 40% by weight, and particularly preferably 15 to 35% by weight. When the ratio of the vinyl monomer (α 2 ) is less than the above range, the amount of the ring structure is small, and the surface hardness of the laminate may be lowered, and the hot water resistance or solvent resistance may be lowered. Further, there is a case where the heat resistance of the laminate is lowered. On the other hand, when it is more than the above range, when a lactone ring structure is formed, a crosslinking reaction may be initiated to cause gelation, and fluidity may be lowered, and melt molding may not be easily performed. Further, since the unreacted hydroxyl group is likely to remain, when the obtained acrylic resin is molded, further condensation reaction occurs to generate a volatile substance, and bubbles or silver streaks are easily formed in the laminated body (silver surface) The case of a strip pattern, etc.).

The monomer component in the case where the polymer (α) is obtained can be removed without impairing the effects of the present invention, and a polymerizable monomer other than the above (α 1) and (α 2) can also be used. For example, styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl ketene, ethylene, propylene, vinyl acetate, etc. are mentioned. In addition, these types may be used alone or in combination of two or more. When the monomer component in the case where the polymer (α) is obtained is used in combination with the above polymerizable monomer, the content of the monomers is preferably 0 to 30% by weight or less, more preferably 0 to 20% by weight based on the monomer component. % or less, particularly preferably 0 to 10% by weight or less. From the viewpoint of the physical properties and the like, when the amount is more than or equal to the above, the physical properties such as weather resistance, surface gloss, and transparency which are derived from the good physical properties of the (meth)acrylate monomer may be impaired.

The heat-resistant acrylic resin a3 can be obtained by subjecting the polymer (α) to a cyclization condensation reaction to form a ring structure. The above-mentioned cyclization condensation reaction means that the hydroxyl group and the ester group (or further, the carboxyl group) present in the molecular chain of the polymer (α) are heated by heating. The cyclization condensation is carried out to form a reaction of the lactone ring structure, and the by-product alcohol and water are formed by the cyclization condensation. By forming a ring structure in the polymer molecular chain (in the main skeleton of the polymer), high heat resistance can be imparted, and high surface hardness, hot water resistance, and solvent resistance can be imparted.

A method of obtaining a acryl resin having a lactone ring structure by subjecting the polymer (α) to cyclization and condensation, for example, 1) the polymer (α) is heated by an extruder under reduced pressure to carry out a ring Method for the condensation reaction (Polym. Prepr., 8, 1, 576 (1967); 2) The cyclization condensation reaction of the above polymer (α) is carried out in the presence of a solvent, and the cyclization condensation reaction is simultaneously carried out. Method for volatilization; 3) A method in which a specific organophosphorus compound is used as a catalyst to cyclize and condense the above polymer (α) (European Patent No. 1008606) and the like. Of course, it is not limited to these, and the plural method in the above methods 1) to 3) can also be employed. The use of 2) and 3) is particularly advantageous in terms of a high reaction rate of the cyclization condensation reaction, suppression of foaming or silver streaks in the laminate, and suppression of a decrease in mechanical strength due to a decrease in molecular weight in devolatilization. method.

The heat-resistant acrylic resin a3 used in the present invention preferably 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. When the weight average molecular weight is less than the above range, not only surface hardness, hot water resistance or solvent resistance may be lowered, but also mechanical strength may be lowered and brittleness may occur; on the other hand, if it is higher than the above range, fluidity will be It is not good to reduce it and it is not easy to form.

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, heat using any of the above heat-resistant acrylic resins as a main component can be used. When the plastic resin composition a forms the resin layer A, it is preferable to impart excellent thermoformability to the laminated body. In other words, when the laminate system is formed by sequentially laminating at least three layers of the resin layer C, the resin layer A, and the resin layer B, for example, the main component of the thermoplastic resin composition c forming the resin layer C is polycarbonate. In the case of the resin, even if the main component of the thermoplastic resin composition a forming the resin layer A is directly used as the heat-resistant acrylic resin, the glass transition temperature difference between the resin layer A and the resin layer C can be absolutely absolute. The value is set within 30 ° C, so it is preferred. That is, by setting the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C to within 30 ° C, when the laminated body is subjected to hot forming, the molded body can be prevented from whitening, cracking, or even foaming. Therefore, it is better.

(heat resistant acrylic resin a4)

The heat-resistant acrylic resin a4 is not only heat-resistant, but also has a hard dispersed phase in the acrylic resin matrix from the viewpoint of having excellent hardness. More specifically, it can be used in acrylic resins, including. It is composed of a hard dispersed phase material which is more excellent in heat resistance and scratch resistance than an acrylic resin. By using an acrylic resin containing a hard disperse phase in the above-mentioned matrix, the pencil hardness of the surface of the resin layer A can be made 5H or more.

Examples of the material for forming the hard dispersed phase include thermosetting resins, and specific examples thereof include a phenol resin, an amine resin, an epoxy resin, a polyoxyxylene resin, a thermosetting polyimide resin, and a thermosetting polymer. A polycondensation or addition condensation resin such as a urethane resin, and examples thereof include a thermosetting acrylic resin, a vinyl ester resin, an unsaturated polyester resin, a diallyl citrate resin, and the like. An addition polymerization resin obtained by radical polymerization of an unsaturated monomer.

Among these, if the unsaturated single system is polyfunctional, the properties of the harder material (insoluble, high glass transition temperature) can be obtained by polymerization crosslinking, which is preferable. Examples of the unsaturated monomer include polyesters of polyhydric alcohols and acrylic acid and/or methacrylic acid, and crosslinkable monomers such as polyaryl groups of such polyols and polyvinyl ethers. However, it is not limited to these.

Specific examples of the unsaturated monomer include: trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane (di-, tri) acrylate, trimethylol Propane diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, bis(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate Ester, ethoxylated trimethylolpropane 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 an acrylic resin. However, it is not limited to these.

The thermosetting resin may be used singly or in combination of two or more. Further, a thermoplastic resin having an unsaturated bond crosslinkable with the thermosetting resin may be used in combination.

The shape of the hard dispersed phase is, for example, a particulate form, a spherical shape, a linear form, or a fibrous form, and is preferably spherical in view of being easily dispersed uniformly in the acrylic resin which is a thermoplastic matrix resin. However, it is not limited to these.

The particle size of the hard dispersed phase is appropriately set in accordance with the purpose of use, use, and the like of the laminate, and is preferably 0.1 to 1000 μm. The amount of the hard dispersed phase in the acrylic resin phase, It is suitably set according to the purpose of use, use, etc. of this laminated body, and is preferably 0.1 to 60% by weight.

The method of containing the hard dispersed phase in the acrylic resin phase is not particularly limited, and examples thereof include the following methods.

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

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

(other ingredients)

The thermoplastic resin composition a forming the resin layer A may contain, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a slip agent, etc., in addition to the resin component, within the range not impairing the effects of the present invention. Various additives such as a flame retardant such as a polyoxygen compound, a filler, a glass fiber, and an impact modifier.

Further, the thermoplastic resin composition a forming the resin layer A may contain acrylic rubber particles having an elastic polymer portion insofar as the effects of the present invention are not impaired. The acrylic rubber particles have a layer (elastic polymer layer) composed of an elastic polymer mainly composed of an acrylate, and may be a single layer of particles composed only of an elastic polymer, or may be polymerized by an elastic polymer layer and a hard polymer. When considering the surface hardness of the resin layer A disposed on the surface of the laminate, the multilayer structure particles formed by the layer (hard polymer layer) of the bulk structure Good multi-layered particles. Further, the acrylic rubber particles may be used alone or in combination of two or more.

As described above, the resin layer A is disposed on the back side of the resin layer B, so that the resin layer B exhibits an excellent surface hardness. For this reason, the thickness of the resin layer A is preferably 40 μm or more, and more preferably 60 μm or more. When the thickness of the resin layer A is 40 μm or more, even if the thickness of the resin layer B is reduced, the surface of the resin layer B can exhibit excellent surface hardness, which is preferable. 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 brittleness of the resin layer A which is hindered when performing hot forming or punching processing is easily compensated by the resin layer C, which is preferable.

(resin layer B)

The resin layer B of the present invention is a layer which imparts excellent surface hardness to the laminated body, and sets a storage elastic modulus difference between the resin layers A at a predetermined temperature (I) within a predetermined range or a predetermined temperature. The elongation of the laminate under (II) is set to a desired range, and the laminate can have excellent thermoformability.

Further, the resin layer B has a layer excellent in scratch resistance, and when the steel wool of #0000 is wiped at a load of 500 g, the number of reciprocations until the occurrence of scratches is preferably 50 or more, and more preferably 100. More than 500 times, and more than 500 times.

(curable resin composition b)

The resin layer B of the laminate is formed of a curable resin composition b, and the present invention can The curable resin composition b to be used is hardened by irradiation with an energy ray such as an electron beam, radiation, or ultraviolet rays, or hardened by heating, and the rest is not particularly limited, and the molding time and productivity are formed. From the viewpoint of the above, it is preferably composed of an ultraviolet curable resin.

Further, preferred examples of the curable resin constituting the curable resin composition b include an acrylate compound, an urethane acrylate compound, an epoxy acrylate compound, and a carboxy-modified epoxy acrylate compound. a polyester acrylate compound, a copolymerized acrylate, an alicyclic epoxy resin, a epoxidized propyl ether epoxy resin, a vinyl ether compound, an oxetane compound, etc., and these curable resins can be used alone. It can also be combined with a plurality of compounds. In addition, examples of the curable resin which imparts excellent surface hardness include a radical polymerizable curable compound such as a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, and a polyfunctional epoxy acrylate compound. Or a thermopolymerizable curable compound such as an alkoxydecane or an alkyl alkoxysilane. Further, the curable resin composition b of the present invention may be an organic material composed of the curable resin containing an inorganic component. Inorganic composite curable resin composition.

The curable resin composition b which can impart a particularly excellent surface hardness to the laminate can be exemplified. Inorganic composite curable resin composition. organic. The inorganic composite curable resin composition is composed of a curable resin composition in which the curable resin contains an inorganic component having a reactive functional group.

By using such an inorganic component having a reactive functional group, for example, by copolymerizing and crosslinking the inorganic component with a radical polymerizable monomer, it is organic compared to simply using an organic binder with an inorganic component. It is preferable that the inorganic composite-based curable resin composition is less likely to undergo hardening shrinkage and exhibits a high surface hardness. Again, lower From the viewpoint of hardening shrinkage, the inorganic component having a reactive functional group is more preferably an organic compound containing ultraviolet reactive colloidal ceria. Inorganic composite curable resin composition.

The resin layer B of the present invention is a layer which imparts excellent surface hardness to the laminate as described above. Further, in each of the configurations of the first invention and the third aspect, the storage elastic modulus of the resin layer A and the resin layer B at a predetermined temperature (I) can be adjusted to satisfy the following relationship, thereby providing excellent surface hardness. With thermoformability.

-2.0 (GPa) storage elastic modulus of the resin layer B - storage elastic modulus of the resin layer A ≦ 2.5 (GPa)

Here, the "predetermined temperature (I)" means the temperature at which the glass transition temperature of the resin layer A is -20 °C.

In addition, the means for adjusting the difference in the storage elastic modulus of the resin layer B and the resin layer A at a predetermined temperature (I) to a range of -2.0 (GPa) or more and 2.5 (GPa) or less is, for example, a resin. A method of adjusting the concentration of the inorganic component and/or the inorganic component having a reactive functional group contained in the layer B. In other words, the preferred concentration range of the inorganic component and/or the inorganic component having a reactive functional group contained in the resin layer B is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 40%. Below mass%. When the content of the inorganic component is 0% by mass or more and 50% by mass or less, the difference in storage elastic modulus between the resin layer B and the resin layer A at a predetermined temperature (I) can be adjusted to 2.0 (GPa) or more. And 2.5 (GPa) or less is preferred.

Further, the resin layer B of the present invention is as described above, and the laminate of the second invention and the fourth invention Any of the laminates of the present invention can have excellent surface hardness and thermoformability by adjusting the elongation of the laminate under a predetermined temperature (II) to a range of 6% or more and 30% or less. . Here, the "predetermined temperature (II)" means the temperature at which the glass transition temperature of the resin layer A is -30 °C.

In the meantime, the means for adjusting the elongation of the laminate under the predetermined temperature (II) to a range of 6% or more and 50% or less is, for example, an inorganic component contained in the resin layer B and/or a reaction. A method of adjusting the concentration of an inorganic component of a functional group. That is, the preferred concentration range of the inorganic component and/or the inorganic component having a reactive functional group contained in the resin layer B is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more. 40% by mass or less. When the concentration is in the range of 0% by mass or more and 50% by mass or less, the resin layer B can maintain excellent surface hardness, and on the other hand, the elongation of the laminated body at a predetermined temperature (II) can be maintained at 6% or more. Therefore, it is better.

The method of forming the resin layer B is formed by, for example, applying a coating material of the curable resin composition b onto the surface of the resin layer A, and forming a cured film. The method of laminating on the surface of the resin layer A is not limited to this method.

A well-known method can be used for the lamination method with the resin layer A. For example, a lamination method using a cover film, a dip coating method, a natural coating method, a reverse coating method, a batch roll coating method, a roll coating method, a spin coating method, a coating bar method, and an extrusion method may be mentioned. , curtain coating method, spray coating method, gravure coating method, and the like. For the other, a method of laminating the resin layer B on the resin layer A by using a transfer sheet formed by forming the resin layer B on the release layer may be employed.

(surface adjustment component)

The curable resin composition b forming the resin layer B may contain a leveling agent as a surface conditioning component. Examples of the leveling agent include a polyfluorene-based leveling agent and an acrylic leveling agent. Particularly preferred are those having a reactive functional group at the terminal end, and more preferably a reactive functional group having a bifunctional group or more.

Specifically, a polyether-modified polydimethyl siloxane having a double bond at both ends and having a propylene group (for example, "BYK-UV 3500" manufactured by BYK-Chemie. Japan Co., Ltd., "BYK-UV" 3530"); or polyester modified polydimethyl fluorene (four BYK-Chemie. Japan Co., Ltd. "BYK-UV 3570") having four double bonds and having a propylene group at the end .

Among these, a propylene-based polyester-modified polydimethyl siloxane having a stable haze value and contributing to scratch resistance improvement is particularly preferred.

A photopolymerization initiator is used when the curable resin is cured by ultraviolet rays. The photopolymerization initiator may, for example, be a benzyl group, a diphenyl ketone or a derivative thereof, or an oxygen sulphur A ketone, a benzyl dimethyl ketal, an α-hydroxy phenyl ketone, a hydroxy ketone, an amino phenyl ketone, a phosphine phosphine or the like. The amount of the photopolymerization initiator to be added is generally in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the curable resin.

These photopolymerization initiators may be used singly or in combination of two or more kinds in many cases. Further, these various photopolymerization initiators are commercially available, and thus such commercially available products can be used. Commercially available photopolymerization initiators include, for example, "IRGACURE651", "IRGACURE184", "IRGACURE500", "IRGACURE1000", "IRGACURE2959", "DAROCUR1173", "IRGACURE907", "IRGACURE369", "IRGACURE1700", " IRGACURE1800", "IRGACURE 819", "IRGACURE 784" [The above IRGACURE series and DAROCUR series are sold by Ciba Fine Chemicals Co., Ltd.]; "KAYACUREITX", "KAYACUREDETX-S", "KAYACUREBP-100", "KAYACUREBMS", "KAYACURE2-EAQ" "[The above KAYACURE series is sold by Nippon Kayaku Co., Ltd.] and the like.

(other ingredients)

In addition to the curable resin component, the curable resin composition b which forms the resin layer B may contain, for example, an anthraquinone compound, a fluorine compound, or a mixed compound, etc., insofar as the effect of the present invention is not impaired. A lubricant; an anti-oxidant such as an antioxidant, an ultraviolet absorber, an antistatic agent, or a polyfluorene-based compound; a filler, a glass fiber, an impact modifier, and the like.

The thickness of the resin layer B is preferably in the range of 5 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, which is preferable. On the other hand, when the thickness is 20 μm or less, it is preferable to impart excellent thermoformability to the laminate, and further, there is no hardening of the resin layer B. It is also preferable from the viewpoint of shrinkage and the possibility of warping, wave curling, peeling, and the like.

(resin layer C)

In the laminate, at least three layers of the resin layer C formed of the thermoplastic resin composition c, the resin layer A formed of the thermoplastic resin composition a, and the resin layer B formed of the curable resin composition b are In the layered product in which the layers are laminated, the resin layer C has a function of imparting excellent impact resistance or punching property to the laminate.

(The thermoplastic resin composition c)

The resin layer C of the laminate is formed of a thermoplastic resin composition c. The thermoplastic resin which can be used for the thermoplastic resin composition c is removed before the thermoplastic resin which can form a film, a sheet or a sheet by melt extrusion, and the rest is not particularly limited, and preferred examples thereof are exemplified. : polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexyl dimethylene pair An aromatic polyester such as a phthalic acid ester or a polyester resin represented by an aliphatic polyester such as a polylactic acid polymer; a polyolefin resin such as polyethylene, polypropylene or a cycloolefin resin; a polycarbonate resin; Acrylic resin, polystyrene resin, polyamine resin, polyether resin, polyurethane resin, polyphenylene sulfide resin, polyester amide resin, polyether ester resin, chlorine Ethylene resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polydiphenyl ether resin, polyarylate resin, polyfluorene resin, polyether sulfoxide Resin, polyamidoximine resin, polyamidene resin, and Of copolymer such as a main component, or a mixture of such resins. In the present invention, a polyester resin, a polycarbonate resin, or an acrylic resin is particularly preferable from the viewpoint of almost no absorption in the visible light region.

Among them, a polycarbonate-based resin is particularly preferable from the viewpoint of imparting excellent impact resistance and secondary workability such as punching property to the laminate.

Further, in the thermoplastic resin composition c constituting the resin layer C, a mixture of two or more kinds of resins is selected from the above, and when these are mutually incompatible, the thermoplastic resin having the highest volume fraction is used. The glass transition temperature is set to the glass transition temperature of the resin layer C.

(Polycarbonate resin)

The polycarbonate-based resin which can be used in the present invention is removed before it can be formed into a film, a sheet, or a sheet by melt extrusion, and the rest is not particularly limited, and it can be obtained from an aromatic polycarbonate or an aliphatic polycarbonate. At least one of the group of alicyclic polycarbonates is selected for use.

(aromatic polycarbonate)

Examples of the aromatic polycarbonates include i) obtaining a reaction between a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method; and ii) using a solid phase transesterification method for the carbonate prepolymer. And the like obtained by carrying out polymerization, etc.; iii) obtained by polymerization of a cyclic carbonate compound by a ring-opening polymerization method. Among these, from the viewpoint of productivity, it is preferred to obtain i) a reaction between a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method.

Examples of the above dihydric phenols include hydroquinone, resorcin, 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-dual (4 -Hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4hydroxy-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 Alkane, 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)-ortho Diisopropylbenzene, α, Α'-bis(4-hydroxyphenyl)-m-isopropylbenzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxybenzene) -5,7-dimethyl adamantane, 4,4'-dihydroxydiphenylfluorene, 4,4'-dihydroxydiphenylarsin, 4,4'-dihydroxydiphenyl sulfide, 4, 4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, etc., or two or more types may be used as needed.

Among the above, the above dihydric phenol is preferably used alone or in combination of two or more kinds from bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-double. (4-Hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethyl Butane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and α, Α'-bis(4-hydroxyphenyl)-m-isopropylbenzene is a dihydric phenol selected from the group; particularly preferred is bisphenol A alone or 1,1-bis(4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and from bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, and α,α'-double ( One or more kinds of dihydric phenols are selected from the group consisting of 4-hydroxyphenyl)-m-isopropylbenzene.

Examples of the above carbonylating agent include a carbonyl halide such as phosgene, a carbonate such as diphenyl carbonate, a halogenated formate such as a dihalogenated formic acid ester of a dihydric phenol, and the like, which may be used as needed. 2 or more types.

(Other polycarbonate resin)

Examples of the polycarbonate resin other than the above aromatic polycarbonate include an aliphatic polycarbonate and an alicyclic polycarbonate. One of the preferred structures has at least a structural unit derived from a dihydroxy compound having a moiety represented by the following general formula (9).

[Chemistry 7]

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

The above dihydroxy compound is mentioned before a part of the molecular structure is represented by the above general formula (9), and the rest is not particularly limited, and specific examples thereof include: 9,9-bis(4-(2-hydroxyl) Oxy)phenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy) 3-isopropylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)anthracene, 9,9-bis(4-(2-hydroxyl) Ethoxy)-3-t-butylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)anthracene, 9,9-bis(4- (2-hydroxyethoxy)-3-phenylphenyl)indole, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)anthracene, 9,9 - bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)indole, 9,9-bis(4-(3-hydroxy-2,2-dimethyl) A compound in which a side chain such as a propoxy)phenyl)anthracene has an aromatic group and the main chain has an ether group bonded to an aromatic group.

Further, from the viewpoint of heat resistance, a compound having a cyclic ether structure such as a spiro diol is preferably used. Specifically, it can be exemplified by 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane (common name: snail Glycol), 3,9-bis(1,1-diethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis ( 1,1-dipropyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, and the like.

Other polycarbonate-based resins may contain a structural unit derived from a dihydroxy compound other than the above-described dihydroxy compound (hereinafter also referred to as "other dihydroxy compound"), and examples of other dihydroxy compounds include ethylene glycol. , 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexyl An aliphatic dihydroxy compound such as a diol; 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclic fifteen Alkanediethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-nor Alkanediethanol, 2,5-lower An alicyclic dihydroxy compound such as alkane dimethanol or 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-nitrated phenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-dual ( 4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)anthracene, 2,4'-dihydroxydiphenylhydrazine, bis(4- Hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-(2-hydroxyethyl) Aromatic bisphenols such as oxy-2-methyl)phenyl)anthracene, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-2-methylphenyl)anthracene class.

(other ingredients)

The thermoplastic resin composition c which forms the resin layer C may contain, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, and a slip, in addition to the resin component, within the range not impairing the effects of the present invention. Various additives such as a flame retardant such as a polysiloxane compound, a filler, a glass fiber, and an impact modifier.

As described above, in the laminated body, at least three of the resin layer C formed of the thermoplastic resin composition c, the resin layer A formed of the thermoplastic resin composition a, and the resin layer B formed of the curable resin composition b a layered layer in which the layers are stacked in this order, by The storage elastic modulus of the resin layer A, the resin layer B, and the resin layer C at the temperature (I) is adjusted so as to satisfy the following relationship, and the laminated body can have excellent surface hardness and thermoformability.

-2.0 (GPa) storage elastic modulus of the resin layer B - storage elastic modulus of the resin layer A ≦ 2.5 (GPa)

-1.0 (GPa) storage elastic modulus of the resin layer A - storage elastic modulus of the resin layer C ≦ 1.0 (GPa)

Here, the "predetermined temperature (I)" means the temperature at which the glass transition temperature of the resin layer A is -20 °C.

Here, the means for forming the resin layer A formed of the thermoplastic resin composition a is a means for setting the difference in the storage elastic modulus between the resin layer A and the resin layer C at a predetermined temperature (I) within a desired range. The absolute value of the glass transition temperature difference of the resin layer C formed of the thermoplastic resin composition c is set to be within 30 °C. When the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is set to 30 ° C or less, the storage elastic modulus difference of the two layers satisfies a temperature range of -1.0 (GPa) or more and 1.0 (GPa) or less. It is preferred that the temperature range which is suitable for thermoforming is widened.

Further, as described above, in the laminated body, the resin layer C formed of the thermoplastic resin composition c, the resin layer A formed of the thermoplastic resin composition a, and the resin layer B formed of the curable resin composition b The molding resin laminated body formed by laminating at least three layers in this order is adjusted to have an elongation ratio of the molding resin laminated body at a predetermined temperature (II) in a range of 6% or more and 50% or less. This laminate can have excellent surface hardness and thermoformability.

Here, the "established temperature (II)" means the glass transition temperature of the resin layer A - 30 °C temperature.

Here, the means for adjusting the elongation of the laminate under a predetermined temperature (II) to a desired range includes a resin layer A formed of the thermoplastic resin composition a and a resin formed of the thermoplastic resin composition c. The absolute value of the glass transition temperature difference of layer C was set to be within 30 °C. When the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is set to be within 30 ° C, the elongation behaviors of the resin layer A and the resin layer C are close to each other, and the deformation is easily deformed to form a shape. good. Further, the temperature range in which the laminate exhibits a desired elongation becomes wider, that is, the temperature range suitable for thermoforming becomes wider, which is preferable.

According to this, when the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is set to 30 ° C or less, even when the laminate is subjected to hot forming, even if deep drawing is further performed, The molded body can be prevented from being whitened or cracked, and foamed. From this point of view, the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is more preferably set to be within 25 ° C, and particularly preferably set to be within 20 ° C.

The method of setting the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C to 30 ° C is, for example, the following method.

(1) In the thermoplastic resin composition a and/or the thermoplastic resin composition c, a thermoplastic resin having a different glass transition temperature is blended to form a mixture of at least two thermoplastic resins. The glass transition temperature difference between the resin layer A and the resin layer C is adjusted to within 30 °C. Among them, two or more types of thermoplastic resins having different glass transition temperatures may be used in the same or different types of thermoplastic resins depending on the glass transition temperature. Further, the thermoplastic resin blended therein is compatible with the thermoplastic resin composition a or the thermoplastic resin composition c.

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

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

In addition, for example, another method of imparting thermoformability to the laminated body by using a method in which the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is set to 30 ° C or less is exemplified by a thermoplastic resin composition. In the material a and/or the thermoplastic resin composition c, the storage elastic modulus difference between the resin layer A and the resin layer C is adjusted by containing at least two kinds of thermoplastic resins which are incompatible with each other. The method within the desired range, or the method in which the elongation behavior of the resin layer A and the resin layer C are close to each other.

In the method of setting the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C to be within 30 ° C, in the case of the above (1), the thermoplastic resin a is made of an acrylic resin as a main component, and the thermoplasticity is obtained. The case where the resin composition c is composed of a mixture of a polycarbonate resin and another thermoplastic resin will be described in detail.

The thermoplastic resin composition c of the present invention can be formed into a mixture of two or more thermoplastic resins as described above. For example, when the thermoplastic resin composition a is mainly composed of an acrylic resin and the thermoplastic resin composition c is mainly composed of a polycarbonate resin, the absolute temperature difference between the two glass transitions is When the value is set within 30 ° C, the other thermoplastic resin is mixed into the latter polycarbonate resin to make polycarbon. A method for lowering the glass transition temperature of an acid ester resin. In other words, a method in which a polycarbonate resin is melt-blended with a thermoplastic resin and mixed with another thermoplastic resin to form a polymer blend, thereby lowering the glass transition temperature of the polycarbonate resin.

In general, the glass transition temperature of the polycarbonate resin is around 150 ° C, which is nearly 50 ° C higher than the general glass transition temperature of the acrylic resin by 100 ° C. Therefore, other thermoplasticity is mixed in the polycarbonate resin. The resin and niobium lower the glass transition temperature of the polycarbonate resin. In view of this, a preferred example of the other thermoplastic resin may be an aromatic polyester or a polyester resin having a cyclic acetal skeleton.

(aromatic polyester d1)

The aromatic polyester d1 which is another thermoplastic resin can be used, for example, a resin obtained by condensation polymerization of an aromatic dicarboxylic acid component and a diol component.

In addition, typical examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. Further, one part of the terephthalic acid may be substituted with other dicarboxylic acid components. Examples of other dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, pivalic acid, isophthalic acid, naphthalene dicarboxylic acid, and diphenyl ether dicarboxylic acid. Hydroxybenzoic acid, etc. These may be used singly or in combination of two or more kinds, and the amount of other dicarboxylic acid to be substituted may be appropriately selected.

On the other hand, typical examples of the above diol component include ethylene glycol, diethylene glycol, triethylene glycol, and cyclohexane dimethanol. One part of the ethylene glycol may also be substituted by other diol components. Other diol components are propylene glycol, trimethylene glycol, butylene glycol, and six Methylene glycol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, trimethylol, methoxy polyalkylene Alcohol, etc. These may be used singly or in combination of two or more kinds, and the amount of other diols to be substituted may be appropriately selected.

Specific examples of the aromatic polyester include polyethylene terephthalate which condenses and polymerizes terephthalic acid with ethylene glycol, and terephthalic acid or dimethyl terephthalate with 1,4 - Butylene glycol is subjected to condensation polymerization of polybutylene terephthalate or the like. Further, a copolymerized polyester containing a dicarboxylic acid component other than terephthalic acid and/or a glycol component other than ethylene glycol is also a preferred aromatic polyester.

Preferred examples thereof include: a part of ethylene glycol in polyethylene terephthalate, preferably a copolymerized polyester having a structure of 55 to 75 mol% substituted by cyclohexanedimethanol; Or a portion of terephthalic acid in polybutylene terephthalate, preferably a copolymerized polyester having a structure of 10 to 30 mole % substituted with isophthalic acid; or a mixture of such copolymerized polyesters .

In the aromatic polyester described above, it is preferred to blend the polymer with the polycarbonate resin to melt the polymer, and to sufficiently lower the glass transition temperature of the polycarbonate resin.

From this point of view, the best example is a glycol component of polyethylene terephthalate having a glycol content of 50 to 75 mol%, which is 1,4-cyclohexanedimethanol (1,4-CHDM). a copolymerized polyester of the replaced structure (so-called "PCTG"); or a terephthalate of polybutylene terephthalate A portion of formic acid, preferably a copolymerized polyester having a structure of 10 to 30 mole % substituted with isophthalic acid; or a mixture of such. It is known that these copolymerized polyesters are melt-blended with a polycarbonate-based resin, are completely compatible, and are blended with a polymer, and can also effectively lower the glass transition temperature.

(polyester resin d2 having a cyclic acetal skeleton)

A polyester resin d2 having a cyclic acetal skeleton as another thermoplastic resin may be used, which contains a dicarboxylic acid unit and a diol unit, and 1 to 60 mol% of the diol unit has a cyclic acetal skeleton. A polyester resin of a glycol unit. The diol unit having a cyclic acetal skeleton is preferably derived from a unit of the compound represented by the following general formula (10) or (11).

R ¹ , R ² and R ³ are each independently represented by a 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. Selected hydrocarbyl groups.

General compounds of formula (10) and (11), particularly preferred are 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5 Undecane or 5-hydroxymethyl-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-di alkyl.

Further, in the polyester resin d2 having a cyclic acetal skeleton, the diol unit other than the diol unit having a cyclic acetal skeleton is not particularly limited, and examples thereof include ethylene glycol and trimethylene glycol. An aliphatic diol such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol or neopentyl glycol; polyethylene glycol, polypropylene glycol, Polyether glycols such as polybutylene glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decalin dimethanol, 1,3-decahydronaphthalene dimethanol , 1,4-decahydronaphthalene dimethanol, 1,5-decalin dimethanol, 1,6-decalin dimethanol, 2,7-decalin dimethanol, tetrahydronaphthalene dimethanol, lower An alicyclic diol such as alkane dimethanol, tricyclodecane dimethanol or pentacyclododecane dimethanol; 4,4'-(1-methylethylidene)bisphenol, methylene bisphenol (double Bisphenols such as phenol F), 4,4'-cyclohexylene bisphenol (bisphenol Z), 4,4'-sulfonyl bisphenol (bisphenol S); alkylene oxide addition of the above bisphenols Aromatic dihydroxyl such as hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether or 4,4'-dihydroxydiphenyldiphenyl ketone a compound; and an alkylene oxide adduct of the above aromatic dihydroxy compound. In terms of mechanical properties, economy, and the like of the polyester resin of the present invention, ethylene glycol, diethylene glycol, dimethylene glycol, 1,4-butanediol, and 1,4-ring are preferred. Hexane dimethanol, especially ethylene glycol. The exemplified diol units may be used singly or in combination.

Further, the dicarboxylic acid unit of the polyester resin d2 having a cyclic acetal skeleton used in the present invention is not particularly limited, and examples thereof include succinic acid, glutaric acid, adipic acid, pimelic acid, and bisphenol. Acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, stilbene dicarboxylic acid, lower An aliphatic dicarboxylic acid such as an alkanedicarboxylic acid, a tricyclodecanedicarboxylic acid or a pentacyclododecanedicarboxylic acid; terephthalic acid, isophthalic acid, citric acid, 2-methylterephthalic acid, 1, Aromatic two of naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, tetralin naphthalic acid, etc. carboxylic acid. For the mechanical properties and heat resistance of the film of the present invention, it is preferably terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6- Naphthalene dicarboxylic acid and aromatic dicarboxylic acid of 2,7-naphthalene dicarboxylic acid, particularly terephthalic acid, 2,6-naphthalene dicarboxylic acid, and isophthalic acid. Among them, on the economic level, the best is terephthalic acid. The exemplified dicarboxylic acid type may be used singly or in combination.

Further, whether or not the melt-blended mixed resin composition is a polymer blend, in other words, is it completely compatible, for example, by differential scanning calorimetry, whether the glass transition temperature measured at a heating rate of 10 ° C / min is Make judgments for a single thing. Here, the "glass transition temperature of the mixed resin composition is single" means that the mixed resin composition indicates the glass transition temperature when the glass transition temperature is measured by a differential scanning calorimeter according to JIS K-7121 at a heating rate of 10 ° C /min. There is only one spike.

In addition, when the mixed resin composition is measured by dynamic viscoelasticity measurement (dynamic viscoelasticity measurement by JIS K-7198A method) at a strain of 0.1% and a frequency of 10 Hz, the maximum value of the loss tangent (tan δ) may be There is one thing to judge.

If the mixed resin composition is completely compatible (polymer blending), the blended components exhibit a state of being compatible with each other at a relative inetane level (molecular level).

Further, the means for polymer blending may be carried out by using a compatibilizing agent, or by subjecting a secondary block polymerization or graft polymerization, or dispersing one of the polymers in a cluster form.

The mixing ratio of the polycarbonate resin to the polyester d1 or d2 is obtained by mixing to obtain an absolute value of the glass transition temperature difference between the polycarbonate resin composition and the acrylic resin, and can be a ratio of 30 ° C or less. In addition, the rest is not limited. From the viewpoint of transparency maintenance, a polycarbonate resin is preferable in terms of a mass ratio: polyester d1 or d2 = 20: 80 to 90: 10, more preferably polycarbonate. Ester resin: polyester d1 or d2 = 30: 70 to 80: 20, and particularly preferred polycarbonate resin: polyester d1 or d2 = 40: 60 to 75: 25.

Next, in the method of setting the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C to 30 ° C or less, in the case of the above (3), the thermoplastic resin composition a is mainly composed of an acrylic resin. The case where the thermoplastic resin composition c 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 resin is in the vicinity of 150 ° C, which is nearly 50 ° C higher than the glass transition temperature of the acrylic resin of 100 ° C. Therefore, the glass transition temperature difference between the two is high. The absolute value is set to be within 30 ° C, and a method in which a plasticizer is mixed in the latter polycarbonate resin and the glass transition temperature of the polycarbonate resin is lowered is exemplified.

Examples of the plasticizer which can be used in the present laminate include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate. a phosphate compound of tris(xylylene)phosphate, toluene diphenyl phosphate or 2-ethylhexyl diphenyl phosphate; such as dimethyl phthalate, diethyl phthalate, ortho Dibutyl phthalate, bis(2-ethylhexyl phthalate), diisononyl phthalate, a phthalate compound of butyl benzyl phthalate, diisononyl phthalate, ethyl ethyl phthalate, or ethyl phthalate; for example, tris(2-ethylhexyl) trimellitate a trimellitic acid ester compound; such as dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisoindole adipic acid Ester, diisononyl adipate, bis(butyl diglycol) adipate, bis(2-ethylhexyl) sebacate, dimethyl sebacate, dibutyl sebacate, An aliphatic dibasic acid ester compound of bis(2-ethylhexyl) sebacate or diethyl succinate; a ricinoleate compound such as methyl acetyl ricinolate; An acetate compound of triacetin or octyl acetate; a sulfonamide compound such as N-butylbenzenesulfonamide. In particular, when the resin component is a polycarbonate resin, the above-mentioned plasticizer is preferably a phosphate ester compound from the viewpoint of good compatibility with a polycarbonate resin and good transparency of the resin after compatibility. More preferably, it is a toluene diphenyl phosphate or a tricresyl phosphate.

When the thermoplastic resin composition c is a mixture of a polycarbonate resin and a plasticizer, the ratio of the two is preferably a polycarbonate resin: a plasticizer = 70:30 to 99: by mass ratio. 1. More preferred polycarbonate resin: plasticizer = 90:10~98:2. If the amount of the plasticizer is less than the above ratio, the effect of lowering the glass transition temperature by the plasticization is insufficient, and the absolute value of the glass transition temperature difference between the resin layer A and the thermal resin layer C cannot be within 30 ° C. As a result, it is difficult to increase the thermoformability of the obtained laminate. On the other hand, if the amount of the plasticizer is more than the above ratio, the fluidity of the thermoplastic resin composition c containing the polycarbonate resin is remarkably large, for example, when coextrusion is carried out together with the thermoplastic resin composition a. When the method of forming forms a laminate, the possibility of its appearance may be impaired.

(other ingredients)

The thermoplastic resin composition c forming the resin layer C may contain, for example, an antioxidant, an ultraviolet absorber, an antistatic agent, a slip agent, or a polyoxyl oxide, in addition to the resin component, within a range that does not impair the effects of the present invention. A flame retardant such as a compound; various additives such as a filler, a glass fiber, and an impact modifier.

As described above, the resin layer C is laminated with the resin layer A and the resin layer B, and has the function of imparting excellent workability such as impact resistance and punching property to the laminate. From this point of view, it is important that the thickness of the resin layer C is set based on the total thickness ratio of the resin layer A and the resin layer B, and if the thickness ratio is thicker than the resin layer C / (the resin layer A is thick) The thickness of the resin layer B is preferably 2 or more, more preferably 4 or more. When the thickness ratio is 2 or more, it is preferable to impart excellent workability such as impact resistance and punching property to the laminated body.

(Composition of this laminate)

The laminated system is formed by laminating at least two layers of the resin layer A and the resin layer B, and more specifically, the resin layer A/resin layer B, the resin layer B/resin layer A/resin layer B, and the like are exemplified. . Further, it may be composed of three or more layers including a layer other than the resin layer A and the resin layer B. For example, the resin layer D is laminated on the back side of the surface of the resin layer B on the surface of the resin layer B, and more specifically, the resin layer D/resin layer A/resin layer B may be used.

In addition, the laminated layer system is formed by laminating at least three layers of the resin layer C, the resin layer A, and the resin layer B in this order, but may have a multilayer structure of four or more layers other than the above layers. For example, in the surface of the resin layer C, on the back side of the surface which is laminated with the resin layer A, the layer is laminated. The structure in which the resin layer D is formed is more specifically a resin layer D/resin layer C/resin layer A/resin layer B.

(thickness)

The thickness of the laminate is not particularly limited, but is preferably, for example, 0.1 mm to 1.5 mm. When considering the operability of the practical surface, it is preferably about 0.2 mm to 1.0 mm.

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

Fig. 1 is a view showing a configuration of an embodiment of the present laminate, and Fig. 1(a) shows a molding resin laminate (11) formed by laminating a resin layer A (13) and a resin layer B (14) in this order. .

In addition, (b) of FIG. 1 exemplifies a molding resin laminate (15) formed by laminating three layers in the order of the resin layer C (12), the resin layer A (13), and the resin layer B (14).

In addition, (c) of FIG. 1 is exemplified by the formation of the resin layer B (14) on both sides of the laminate including the resin layer C (12) and the resin layer A (13). Resin laminate (16). According to this configuration, since the resin layer C (12) is also covered by the resin layer B (14), there is an advantage that it is possible to suppress the occurrence of scratches and the like on the surface of the resin layer C (12). Further, the resin layer B (14) on the resin layer C (12) side may be formed of a curable resin different from the resin layer B (14) on the resin layer A (13) side.

<word description>

Generally speaking, "thin film" refers to a thin flat product having a very small thickness and a maximum thickness which is arbitrarily defined in comparison with the length and the width, and is usually supplied in the form of a roll (Japanese industry) The specification "JISK-6900", and generally "slice" refers to a flat product whose thickness is much smaller than the length and width in terms of JIS. However, the boundary between the sheet and the film is not determined. In the present invention, since it is not necessary to distinguish between the two in the text, in the present invention, the case of "film" also covers "sheet", and the case of "sheet" is called Also covers "film".

In the present invention, when it is described as "X~Y" (X, Y is an arbitrary number), the meaning of "X or more and Y or less" and "better than X" are included unless otherwise stated. And the meaning of "preferably less than Y".

In addition, in the present invention, when it is described as "X or more" (X-type arbitrary number), unless otherwise stated, the meaning of "better than X" is included, and it is described as "Y or less" ( When Y is an arbitrary number, the meaning of "preferably less than Y" is covered unless otherwise stated.

[Examples]

The following exemplified embodiments are described in detail with reference to the present invention, but the present invention is not limited thereto, and various applications can be made without departing from the technical idea of the present invention.

<Measurement and evaluation method>

For the embodiment. The measurement method and evaluation method of various physical property values of the resin layer and the laminated body obtained by the comparative example are demonstrated.

(glass transition temperature (Tg) of resin layer, storage elastic modulus)

For the resin layers obtained in the examples and the comparative examples, the following apparatus was used in accordance with JIS. The K-7198A method performs a dynamic viscoelasticity measurement, and reads the peak temperature of the loss tangent (tan δ) to determine the glass transition temperature (Tg) of the resin layer. Further, the storage elastic modulus of the resin layer A at a glass transition temperature of -20 ° C was read, and the storage elastic modulus of the resin layer was determined.

Device: Dynamic viscoelasticity measuring device DVA-200 (manufactured by IT Measurement and Control Co., Ltd.)

Distance between fixtures: 25mm

Strain: 0.1%

Temperature range: -50 ° C ~ 250 ° C

Heating rate: 3 ° C / min

Frequency: 10Hz

(pencil hardness of resin layer)

The resin layers obtained in the examples and the comparative examples were subjected to pencil hardness measurement of the surface in accordance with JIS K-5600-5-4. The load load at the time of the test was set to 750 g.

(Scratch resistance of the surface of the resin layer B)

With respect to the surface of the resin layer B of the molding resin laminate obtained in the examples and the comparative examples, the number of reciprocations until the occurrence of scratches was investigated in accordance with the following apparatus and conditions. The scratch resistance evaluation was performed based on the following evaluation criteria with respect to the obtained measurement value. However, the symbol "△" is also above the practical level.

Device: Friction fastness test machine type (Dajei Scientific Seiki Co., Ltd.)

Steel wool number: #0000

Test load: 500gf

Test speed: 30 reciprocating / minute

Test stroke: 120mm

◎: The number of reciprocations until scratches occur ≧500 times

○: 50 times, the number of reciprocations until scratches occurred <500 times

△: the number of reciprocations until scratches occur <50 times

(extension of laminate)

The molding resin laminate obtained in the examples and the comparative examples was subjected to a tensile test according to JIS K-7161 using the following apparatus, and the distance between the jigs at the time of occurrence of cracks and cracks in the laminate was read, and substituting Formula, to obtain the elongation of the laminate.

Device: INTECCO200X universal tensile compression testing machine INTESCO200X

Distance between fixtures: 40mm

Test temperature: 114 ° C (glass transition temperature of resin layer A - 30 ° C)

Stretching speed: 10mm/min

Test piece shape: width 40mm. 100mm long slats

Laminated body elongation = (crack. Distance between clamps at the time of rupture - distance between initial clamps) / distance between initial clamps × 100 (%)

(The thermoformability of the laminate)

The molding resin laminate obtained in the examples and the comparative examples was subjected to hot forming by any of the following molding methods.

(forming method A)

Forming device: press forming machine

Preheating condition of laminate: 150 ° C, 2 minutes

Mold temperature: 130 ° C

Stamping pressure: 0.2MPa

Stamping time: 10 seconds

Forming die: longitudinal 180mm × horizontal 100mm × height 10mm tunnel shape

Corner R=20mm

(forming method B)

Forming device: vacuum pressure forming machine

Preheating temperature of laminate: 120 °C

Mold temperature: 100 ° C

Pressure air pressure: 0.2MPa

Vacuum pressure: -0.1MPa

Hold time: 10 seconds

Forming die: vertical 140mm × horizontal 70mm × height 5mm three-dimensional box shape

Corner R=8mm, 20mm

The appearance of the obtained molded body was visually confirmed, and the evaluation of the thermoformability was performed in accordance with the following evaluation criteria.

○: The molded body did not crack or crack

×: The molded body has cracks or cracks.

<Example 1> (Production of Resin Composition a-1)

The acryl-based resin A (available from Arkema Co., Ltd., trade name "Altuglas HT121", containing a hard dispersion phase) was directly used as the resin composition a-1.

(Production of Resin Composition c-1)

Polycarbonate resin (manufactured by Syron Co., Ltd., trade name "CALIBRE301-4") Granules of granules, polycarbonate resin (product name "SD POLYCA SP3030" manufactured by Syron Co., Ltd.), and particles of polyester resin (product name "SKYGREEN J2003", manufactured by SK Chemical Co., Ltd.), 55: After mixing at a mass ratio of 25:20, granulation was carried out using a twin-screw extruder heated to 260 ° C to obtain a resin composition c-1.

(Production of a single layer film constituting each resin layer)

For the single-layer sheet for evaluation, the resin composition a-1 or c-1 is supplied to the extruder in which the single-layer T-die is attached to each of the A-1 layer and the C-1 layer, and each of the extruders is used. The extruder was subjected to melt-kneading at 240 ° C and 260 ° C to obtain a flaky sample having a thickness of 200 μm.

The glass transition temperature and the storage elastic modulus were evaluated for the flaky samples of the obtained resin layers. The results are also shown in Table 1.

Further, a sample of a resin layer B-1 having a thickness of 30 μm was formed on a film of 12 μm polyethylene terephthalate for the layer B, and the storage elastic modulus of the resin layer B-1 was evaluated using the sample. The results are shown in Table 1.

(production of laminate 1)

The resin compositions a-1 and c-1 were supplied to extruders A and B, respectively, and melt-kneaded at 240 ° C and 260 ° C in each extruder, and then merged into two types of double heated to 250 ° C. The layer was extruded into a sheet shape by a two-layer structure of the resin layer A-1/resin layer C-1, and solidified by cooling to obtain a thickness of 600 μm (resin layer A-1: 80 μm, resin layer C). -1: 520 μm) of the laminated body 1. The surface of the resin layer A-1 of the obtained laminated body 1 was subjected to pencil hardness evaluation. The results are shown in Table 1.

(Production of molding resin laminate 1)

On the surface of the laminated body 1 on the resin layer A-1 side, the organic coating is applied using a bar coater. Inorganic composite ultraviolet curable resin composition b-1 (manufactured by MOMENTIVE Co., Ltd., trade name "UVHC7800FS") was dried at 90 ° C for 1 minute, and then exposed to an exposure amount of 500 mJ/cm ² to obtain a hardened layer having a thickness of 10 μm. The resin laminate 1 for molding of the resin layer B-1. The concentration of cerium oxide containing a reactive functional group in the resin layer B-1 was 46% by mass. In the obtained resin laminated body 1 for molding, the surface of the curable resin layer B-1 was evaluated for pencil hardness and scratch resistance. The results are shown in Table 1.

(Production of formed body 1)

The molded product 1 is obtained by performing hot forming by the molding method A using the obtained resin laminate 1 for molding. The molded body 1 obtained was subjected to thermoformability evaluation. The results are shown in Table 1.

<Example 2> (Production of molding resin laminate 2)

On the surface of the layered product 1 obtained in the first embodiment, the urethane acrylate-based ultraviolet curable resin composition b-2 was coated on the surface of the resin layer A-1 (manufactured by Daisei FINE CHEMICAL Co., Ltd.). (product name "8BR-500"), dried at 90 ° C for 1 minute, and then exposed to an exposure amount of 500 mJ/cm ² to obtain a molding resin laminate 2 having a thickness of 10 μm of the curable resin layer B-2. The same results as in Example 1 were carried out for the obtained molding resin laminate 2 and resin layer B-2. The results are shown in Table 1.

(Production of formed body 2)

The molded product 2 is obtained by performing hot forming by the molding method A using the obtained resin laminate 2 for molding. The same evaluation as in Example 1 was carried out on the obtained molded body 2. The results are shown in Table 1.

<Example 3> (Production of molding resin laminate 3)

The surface of the layered body 1 obtained in the first embodiment was coated with the ultraviolet curable resin composition b-3 on the surface of the resin layer A-1 (manufactured by DIC Corporation, "UVT CLEAR") After drying at 90 ° C for 1 minute, exposure was carried out at an exposure amount of 500 mJ/cm ² to obtain a molding resin laminate 3 having a curable resin layer B-3 having a thickness of 10 μm. The same evaluation as in Example 1 was carried out on the obtained molding resin laminate 3 and resin layer B-3. The results are shown in Table 1.

(Production of formed body 3)

The molded product 3 is obtained by performing the hot forming by the molding method A using the obtained resin laminate 3 for molding. The same evaluation as in Example 1 was carried out on the obtained molded body 3. The results are shown in Table 1.

<Example 4> (Production of molding resin laminate 4)

Will be organic. Inorganic composite ultraviolet curable resin composition b-1 (manufactured by MOMENTIVE Co., Ltd., trade name "UVHC7800FS"), and urethane acrylate-based ultraviolet curable resin composition b-2 (manufactured by Daisei FINE CHEMICAL Co., Ltd., The name "8BR-500")) was mixed at a mass ratio of 60:40, and was set as a curable resin composition b-4. The resin composition b-4 was applied onto the surface of the layered body 1 obtained in Example 1 on the resin layer A-1 side by a bar coater, dried at 90 ° C for 1 minute, and further dried at 500 mJ/cm. ² Exposure The exposure was carried out to obtain a molding resin laminate 4 having a curable resin layer B-4 having a thickness of 10 μm. The concentration of cerium oxide containing a reactive functional group in the resin layer B-4 was 31% by mass. The same evaluation as in Example 1 was carried out on the obtained molding resin laminate 4 and resin layer B-4. The results are shown in Table 1.

(Production of formed body 4)

The molded product 4 is obtained by performing hot forming by the molding method B using the obtained resin laminated body 4 for molding. The same evaluation as in Example 1 was carried out on the obtained molded body 4. The results are shown in Table 1.

<Comparative Example 1> (Production of molding resin laminate 5)

On the surface of the layered body 1 obtained in Example 1 on the resin layer A-1 side, the organic coating was applied using a bar coater. Inorganic composite ultraviolet curable resin composition b-5 (manufactured by MOMENTIVE Co., Ltd., trade name "UVHC7800G") was dried at 90 ° C for 1 minute, and then exposed to an exposure amount of 500 mJ/cm ² to obtain a hardened layer having a thickness of 10 μm. The resin laminated body 5 for forming the resin layer B-5. The concentration of cerium oxide containing a reactive functional group in the resin layer B-5 was 54% by mass. The same evaluation as in Example 1 was carried out on the obtained molding resin laminate 5 and resin layer B-5. The results are shown in Table 1.

(Production of the molded body 5)

The molding resin laminate 5 obtained is subjected to hot forming by the molding method A. The formed body 5 is obtained. The same evaluation as in Example 1 was carried out on the obtained molded body 5. The results are shown in Table 1.

As is apparent from Table 1, the resin layering system for molding of the present invention of Examples 1 to 4 has the hardness of the surface of the resin layer B of 5H or more, and the resin layer A and the resin layer B at a predetermined temperature (I). The storage elastic modulus of the resin layer C satisfies the following relationship, and therefore it is judged that it has excellent thermoformability.

-2.0 (GPa) storage elastic modulus of the resin layer B - storage elastic modulus of the resin layer A ≦ 2.5 (GPa)

-1.0 (GPa) storage elastic modulus of the resin layer A - storage elastic modulus of the resin layer C ≦ 1.0 (GPa)

On the other hand, the molding resin laminate of Comparative Example 1 has an excellent hardness of 5H or more on the surface of the resin layer B, but the storage elastic modulus of the resin layer B and the resin layer A at a predetermined temperature (I) is poor. If 3.1 (GPa) is too large, it is judged that the thermoformability is poor.

<Example 5> (Production of Resin Composition a-2)

A pellet of an acrylic resin (trade name "Altuglas HT121", which contains a hard disperse phase) was used as the resin composition a-2.

(Production of Resin Composition c-2)

Granules of polycarbonate resin (product name "CALIBRE301-4" manufactured by Syron Co., Ltd.) and particles of polycarbonate resin (product name "SD POLYCA SP3030" manufactured by Syron Co., Ltd.) and poly The particles of the ester resin (trade name "SKYGREEN J2003", manufactured by SK Chemical Co., Ltd.) are mixed at a mass ratio of 55:25:20. The granulation was carried out using a twin-screw extruder heated to 260 ° C to obtain a resin composition c-2.

(Production of a single layer film constituting each resin layer)

For the single-layer sheet for evaluation, the resin composition a-2 or c-2 is supplied to the extruder in which the single-layer T-die is attached to each of the A-2 layer and the C-2 layer, and each of the extruders is used. The extruder was subjected to melt-kneading at 240 ° C and 260 ° C to obtain a flaky sample having a thickness of 200 μm.

The evaluation of the glass transition temperature was performed on the flaky samples of the obtained resin layers. The results are shown in Table 2.

(production of laminate 2)

The resin compositions a-2 and c-2 were supplied to extruders A and B, respectively, and melt-kneaded at 240 ° C and 260 ° C in each extruder, and then combined into two types of double heated to 250 ° C. The layer was extruded into a sheet shape by a two-layer structure of the resin layer A-2/resin layer C-2, and was solidified by cooling to obtain a thickness of 600 μm (resin layer A-2: 80 μm, resin layer C). -2: 520 μm) of the layered body 2. The surface of the resin layer A-2 of the obtained laminated body 2 was subjected to pencil hardness evaluation. The results are shown in Table 2.

(Production of molding resin laminate 6)

On the surface of the laminate 2 on the resin layer A-2 side, the organic coating was applied using a bar coater. The inorganic composite ultraviolet curable resin composition b-6 (manufactured by MOMENTIVE Co., Ltd., trade name "UVHC7800FS") was dried at 90 ° C for 1 minute, and then exposed to an exposure amount of 500 mJ/cm ² to obtain a hardened layer having a thickness of 10 μm. The resin laminated body 6 for forming the resin layer B-6. The concentration of cerium oxide containing a reactive functional group in the resin layer B-6 was 46% by mass. With respect to the obtained molding resin laminate 6 , the laminate elongation and the surface of the resin layer B-6 were evaluated for pencil hardness and scratch resistance. The results are shown in Table 2.

(Production of formed body 6)

The molded body 6 is obtained by performing the hot forming by the molding method A using the obtained resin laminated body 6 for molding. The molded body 6 obtained was subjected to thermoformability evaluation. The results are shown in Table 2.

<Example 6> (Production of molding resin laminate 7)

Will be organic. Inorganic composite ultraviolet curable resin composition b-6 (manufactured by MOMENTIVE Co., Ltd., trade name "UVHC7800FS"), and urethane acrylate-based ultraviolet curable resin composition b-7 [manufactured by Daisei FINE CHEMICAL Co., Ltd. The name "8BR-500")] was mixed at a mass ratio of 85:15, and was set as a curable resin composition b-8. The resin composition b-8 was applied onto the surface of the layered body 2 obtained in Example 5 on the resin layer A-2 side by a bar coater, dried at 90 ° C for 1 minute, and further dried at 500 mJ/cm. ² Exposure The exposure was carried out to obtain a molding resin laminate 7 having a curable resin layer B-7 having a thickness of 10 μm. The concentration of cerium oxide containing a reactive functional group in the resin layer B-7 was 41% by mass. The same evaluation as in Example 5 was carried out on the surfaces of the obtained resin laminated body 7 and the resin layer B-7. The results are shown in Table 2.

(Production of the molded body 7)

The molded body 7 is obtained by performing the hot forming by the molding method A using the obtained resin laminated body 7 for molding. The same evaluation as in Example 5 was carried out on the obtained molded body 7. its The results are shown in Table 2.

<Example 7> (Production of molding resin laminate 8)

Will be organic. Inorganic composite ultraviolet curable resin composition b-6 (manufactured by MOMENTIVE Co., Ltd., trade name "UVHC7800FS"), and urethane acrylate-based ultraviolet curable resin composition b-7 [manufactured by Daisei FINE CHEMICAL Co., Ltd. The name "8BR-500")] was mixed at a ratio of 60:40 by mass, and it was set as the curable resin composition b-9. On the surface of the layered body 2 obtained in Example 5 on the side of the resin layer A-2, the resin composition b-9 was applied by a bar coater, dried at 90 ° C for 1 minute, and further dried at 500 mJ/cm. ² Exposure The exposure was carried out to obtain a molding resin laminate 8 having a thickness of 10 μm of the curable resin layer B-7. The concentration of cerium oxide containing a reactive functional group in the resin layer B-7 was 31% by mass. The same evaluation as in Example 5 was carried out on the surfaces of the obtained resin laminated body 8 and the resin layer B-7. The results are shown in Table 2.

(Production of formed body 8)

The molded product 8 is obtained by performing hot forming by the molding method A using the obtained resin laminate 8 for molding. The same evaluation as in Example 5 was carried out on the obtained molded body 8. The results are shown in Table 2.

<Example 8> (Production of formed body 9)

Using the molding resin laminate 8 obtained in Example 7, the molded body 9 was obtained by hot forming by the molding method B. The obtained molded body 9 was applied in the same manner as in the fifth embodiment. evaluation of. The results are also shown in Table 2.

<Comparative Example 2> (Production of molding resin laminate 10)

On the surface of the layered body 2 obtained in Example 5 on the resin layer A-2 side, the organic coating was applied using a bar coater. Inorganic composite ultraviolet curable resin composition b-10 (manufactured by MOMENTIVE Co., Ltd., trade name "UVHC7800G") was dried at 90 ° C for 1 minute, and then exposed to an exposure amount of 500 mJ/cm ² to obtain a hardened layer having a thickness of 10 μm. The resin laminated body 10 for forming the resin layer B-8. The same evaluation as in Example 5 was carried out on the surfaces of the obtained resin laminated body 10 and the resin layer B-8. The results are shown in Table 2.

(Production of the molded body 10)

The molded product 10 is obtained by performing hot forming by the molding method A using the obtained resin laminate 10 for molding. The same evaluation as in Example 5 was carried out on the obtained molded body 10. The results are shown in Table 2.

As is apparent from Table 2, the resin laminated body of the present invention of Examples 5 to 8 has an excellent surface hardness of 5H or more in the surface of the resin layer B, and the elongation of the laminated body at a predetermined temperature (II) is adjusted. Since it is in the range of 6% or more and 50% or less, it is judged that it has excellent thermoformability. In addition, the molding resin laminates of Example 7 and Example 8 in which the elongation of the laminate is 15% or more are not only applicable by the press forming method. The bending process of the shape of the shape can also be carried out by a vacuum pressure forming method to form a box-shaped complex three-dimensional shape.

On the other hand, the molding resin laminate of Comparative Example 2 has an excellent surface hardness of 5H or more in the surface of the resin layer B, but the elongation of the laminate under the predetermined temperature (II) is less than 6%. Therefore, it is judged that the hot formability is poor.

As described above, the resin-cladding system for molding of the present invention of Examples 1 to 8 has excellent surface hardness and thermoformability.

Further, by using the resin laminated body of the present invention of Examples 1 to 8 to perform thermoforming, a molded article having good transparency can be obtained.

The molding resin laminate according to the present invention has excellent surface hardness and thermoformability, and thus can be suitably used as a surface protection panel which is disposed on the front side (viewing side) of the image display device, and particularly has a touch. The front cover of the control panel function mobile phone or LCD tablet, car display, guide or display panel.

11, 15, 16‧‧‧ This layer

12‧‧‧Resin layer C

13‧‧‧Resin layer A

14‧‧‧Resin layer B

Claims (13)

A resin laminated body for molding, which is a resin laminated body formed by laminating at least two layers of a resin layer A formed of a thermoplastic resin composition a and a resin layer B formed of a curable resin composition b. The pencil hardness of the surface of the resin layer B is 5H or more; and the storage elastic modulus of the resin layer A and the resin layer B at a predetermined temperature (I) satisfies the following relationship: -2.0 (GPa) ≦ resin layer B Storage Elastic Modulus - Storage Elastic Modulus of Resin Layer A ≦ 2.5 (GPa) Here, the "predetermined temperature (I)" means the temperature at which the glass transition temperature of the resin layer A is -20 °C. A resin laminated body for molding, which is a resin laminated body formed by laminating at least two layers of a resin layer A formed of a thermoplastic resin composition a and a resin layer B formed of a curable resin composition b. The pencil hardness of the surface of the resin layer B is 5H or more; and the elongation of the molding resin laminate at a predetermined temperature (II) is 6% or more and 50% or less; wherein, the predetermined temperature (II) "The temperature at which the glass transition temperature of the resin layer A is -30 ° C. A resin laminated body for molding is at least three of a resin layer C formed of a thermoplastic resin composition c, a resin layer A formed of a thermoplastic resin composition a, and a resin layer B formed of a curable resin composition b. a molding resin laminate formed by laminating layers in this order, characterized in that the pencil hardness of the surface of the resin layer B is 5H or more; The storage elastic modulus of the resin layer A, the resin layer B, and the resin layer C at a predetermined temperature (I) satisfies the following relationship: -2.0 (GPa) storage elastic modulus of the resin layer B - storage of the resin layer A Elastic modulus ≦ 2.5 (GPa) - 1.0 (GPa) Storage elastic modulus of the resin layer A - Storage elastic modulus of the resin layer C ≦ 1.0 (GPa) wherein "the predetermined temperature (I)" means a resin layer The glass transition temperature of A is -20 °C. A resin laminated body for molding is at least three of a resin layer C formed of a thermoplastic resin composition c, a resin layer A formed of a thermoplastic resin composition a, and a resin layer B formed of a curable resin composition b. The molding resin laminate formed by laminating the layers in this order is characterized in that the pencil hardness of the surface of the resin layer B is 5H or more; and the elongation of the molding resin laminate at a predetermined temperature (II) is 6%. The above and 50% or less: "The predetermined temperature (II)" means the temperature at which the glass transition temperature of the resin layer A is -30 °C. The molding resin laminate according to the third or fourth aspect of the invention, wherein the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is within 30 °C. The molding resin laminate according to any one of the first to fifth aspects of the invention, wherein the resin layer A has a pencil hardness of 3H or more. The molding resin laminate according to any one of the first to sixth aspects of the invention, wherein the thermoplastic resin composition a is mainly composed of an acrylic resin. The molding resin laminate according to claim 7, wherein the acrylic system is The glass transition temperature of the resin is 110 ° C or higher. The resin laminated body for molding according to the seventh or eighth aspect of the invention, wherein the acrylic resin contains or disperses a hard dispersed phase material. The molding resin laminate according to any one of claims 3 to 9, wherein the thermoplastic resin composition c is a polycarbonate resin as a main component. The resin laminate for molding according to any one of claims 1 to 10, wherein the thickness of the resin layer B is 5 μm or more and 20 μm or less. The resin laminated body for molding according to any one of the first to eleventh aspect, wherein the curable resin composition b is a curable resin which is cured by an energy ray selected from an electron beam, a radiation, or an ultraviolet ray. The composition is the main component. A molded article obtained by thermoforming a molding resin laminate according to any one of claims 1 to 12.