JP2014180807A - Protective film-fitted resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate endowed with excellent surface hardness and dimensional stability and accompanied by scarce warpage even in a high-temperature, high-humidity environment.SOLUTION: The provided protective film-fitted resin laminate is a protective film-fitted resin laminate obtained by laminating, in proper order, at least four layers consisting of a resin layer C formed from a thermoplastic resin composition c, a resin layer A formed from a thermoplastic resin composition a, a resin layer B formed from a curable resin composition b, and a protective film D wherein the pencil hardness of the resin layer B surface is at least 5H and wherein the water vapor permeability of the protective film D is 3 g/(m-24 h) or above and 40 g/(m-24 h) or below.

Description

  The present invention is a surface protection panel used by being arranged on the front side (viewing side) of an image display device, in particular, a protective film that can be suitably used as a front cover material for a mobile phone or a liquid crystal pen tablet having a touch panel function. It is related with a resin laminated body.

Conventionally, glass has been widely used from the viewpoint of hardness, heat resistance, and transparency in the fields of display covers for electronic devices.
However, since glass is easily broken by impact and the weight of the glass itself is heavy, an alternative to plastic is being studied.

For these uses, acrylic resins are widely used because of their high transparency and excellent surface hardness.
However, since acrylic resins are very brittle, the processing method is generally performed by cutting, and it cannot be said that the productivity is high.
Further, when an acrylic resin is used, for example, when it comes into contact with a hard material such as steel wool, there is a problem that the matrix resin portion has a low scratch resistance and is easily damaged.

  Therefore, for example, in Patent Document 1, an acrylic resin layer mainly composed of an acrylic resin having a thickness of 10 to 40 μm is laminated on both surfaces or one surface of a resin sheet made of a resin material mainly composed of a polycarbonate resin, A polycarbonate resin laminated sheet for punching has been proposed in which a total thickness is 0.2 to 2.0 mm by laminating a hard coat layer on an acrylic resin layer. Such a resin laminated sheet has the properties of high productivity and excellent scratch resistance by having excellent punching processability.

  In Patent Document 2, a layer containing an acrylic resin is formed on the surface of a base material containing a polycarbonate resin by coextrusion, and the surface of the layer containing an acrylic resin is hard-coated, and surface hardness, particularly pencil hardness, A laminate suitable for a liquid crystal display cover with a good balance of impact has been proposed.

  Thus, in order to improve the scratch resistance of the surface of a resin molded body using an acrylic resin, a method of laminating a hard coat layer composed of an ultraviolet curable resin or the like with a predetermined thickness is generally used. . According to this resin laminate, surface hardness such as scratch resistance and abrasion resistance is improved by the laminated scratch-resistant resin layer.

  Furthermore, in Patent Document 3, the scratch resistance resin layer having a thickness of 1 to 5 μm is laminated on a substrate composed of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase. Resin laminates have been proposed. This scratch-resistant resin laminate has the property that even if the base material composed of an acrylic resin is different from the resin material, warping, waviness, peeling, etc. do not occur with the curing and shrinkage of the resin. .

JP 2008-049623 A International Publication Pamphlet WO2008 / 047940 JP 2007-296711 A

  In the resin laminate disclosed in Patent Documents 1 and 2, when the hard coat layer is laminated on a base material made of an acrylic resin or the like, warping and undulation are accompanied with the curing and shrinkage of the resin. There was a problem that peeling occurred.

In addition, the scratch-resistant resin disclosed in Patent Document 3 has a configuration in which a thermoplastic resin, which is a matrix resin, includes a hard resin obtained by radical polymerization as a dispersed phase.
This disperse phase improves the scratch resistance of the resin molded body, but there is still room for improvement from the viewpoint of surface hardness such as pencil hardness.

  Furthermore, in these resin laminates, the resin layers constituting the same may cause hygroscopic expansion during storage and the like, which may cause appearance troubles such as warpage and undulation.

  Therefore, the object of the present invention is to suppress the hygroscopic expansion of each resin layer constituting the resin laminate by laminating the protective film, so that the problem of warpage and undulation is eliminated, and the dimensional stability is good. It is providing the resin laminated body with a protective film which has the outstanding surface hardness.

The present inventors have a resin layer C formed from the thermoplastic resin composition c, a resin layer A formed from the thermoplastic resin composition a, a resin layer B formed from the curable resin composition b, and protection. In the resin laminate with a protective film formed by laminating at least four layers of the film D in this order,
Dimensional stability is achieved when the pencil hardness of the surface of the resin layer B is 5H or more and the water vapor permeability of the protective film D is 3 g / (m ² · 24 h) or more and 40 g / (m ² · 24 h) or less. It has been found that a resin laminate with a protective film having good surface hardness and excellent surface hardness can be provided.

  Since the resin laminate with a protective film proposed by the present invention has excellent surface hardness and dimensional stability, it is a surface protective panel, particularly a touch panel, used by being arranged on the front side (viewing side) of the image display device. It can be suitably used as a front cover material for mobile phones and liquid crystal pen tablets having functions.

The structure of one Embodiment is illustrated about the resin laminated body with a protective film concerning this invention.

  Hereinafter, a resin laminate with a protective film (referred to as “present resin laminate”) as an example of an embodiment of the present invention will be described. However, the present invention is not limited to this resin laminate.

The structure of the resin laminate according to the present invention includes a resin layer C formed from the thermoplastic resin composition c, a resin layer A formed from the thermoplastic resin composition a, and a resin formed from the curable resin composition b. The layer B and at least four layers of the protective film D are laminated in this order, the pencil hardness of the surface of the resin layer B is 5H or more, and the water vapor permeability of the protective film D is 3 g / (m ² · 24 h) to 40 g / (m ² · 24 h).
If the water vapor permeability of the protective film D is 3 g / (m ² · 24 h) or more, the resin layer A, the resin layer B, and the resin layer C constituting the present resin laminate are slightly moisture. Even when the resin laminate is subjected to a vacuum drying process or a vacuum forming process, it becomes possible to remove moisture contained in each resin layer even when the protective film D is laminated. In the case of forming a molded body using a body, it is preferable because foaming due to water content can be prevented. On the other hand, the upper limit of the water vapor permeability of the protective film D is preferably 40 g / (m ² · 24 h) or less, more preferably 30 g / (m ² · 24 h) or less, and 20 g / (m ² -It is especially preferable that it is 24h or less. If the water vapor permeability of the protective film D is 40 g / (m ² · 24 h) or less, moisture absorption of each resin layer constituting the resin laminate during storage or the like is suppressed, and warpage or This is preferable because appearance troubles such as swell can be prevented.

  The pencil hardness of the surface of the resin layer B constituting the resin laminate is preferably 5H or more, and 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 rubbed with a load of 500 g using # 0000 steel wool, it is preferable that the number of reciprocations until the scratch occurs is 50 times or more. When the number of reciprocations until the surface is scratched when rubbed with the steel wool is 50 times or more, it is possible to provide a laminate having excellent scratch resistance and being hardly scratched. 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.

The resin laminate includes a resin layer C formed from the thermoplastic resin composition c, a resin layer A formed from the thermoplastic resin composition a, a resin layer B formed from the curable resin composition b, And at least four layers of the protective film D are laminated in this order. As a result of the protective film D suppressing moisture absorption of the resin layer A, the resin layer B, and the resin layer C, warping and undulation as a resin laminate. This problem is solved and the dimensional stability is improved. The dimensional stability of the present resin laminate can be evaluated by, for example, the difference in warpage (referred to as environmental warpage) of the present resin laminate after an environmental test under a predetermined condition and before the environmental test. Can be determined by the method described below.
The lower limit of the environmental warp is preferably −2.0 (mm) or more, more preferably −1.5 (mm) or more, and particularly preferably −1.0 (mm) or more. If the lower limit value of the environmental warpage is −2.0 (mm) or more, the protective film D of the present resin laminate is peeled off and assembled as a surface protection panel arranged on the front side (viewing side) of the image display device. In such a case, it is preferable because an excessive pressure is not applied to the member under the protective panel and the member can be prevented from being distorted. On the other hand, the upper limit of environmental warpage is preferably 2.0 (mm) or less, more preferably 1.5 (mm) or less, and particularly preferably 1.0 (mm) or less.
When the upper limit of environmental warpage is 2.0 (mm) or less, the protective film D of the resin laminate is peeled off and assembled as a surface protection panel arranged on the front side (viewing side) of the image display device In addition, the protective panel is preferable because it does not protrude from the surrounding frame (referred to as a bezel) and the protective panel is less likely to be damaged. Here, when the environmental warp is a positive value, it indicates that the resin layer B is on the convex surface side. Conversely, when the environmental warp is a negative value, it indicates that the resin layer C is on the convex surface side. Shall.
As a suitable condition for adjusting the environmental warpage to the above range, the resin laminate is formed of the protective film D, the resin layer C formed from the thermoplastic resin composition c, and the resin formed from the thermoplastic resin composition a. It can be mentioned that at least five layers of the layer A, the resin layer B formed from the curable resin composition b, and the protective film D are laminated in this order. In this case, the protective film D may be different from each other as long as its water vapor permeability falls within a predetermined preferable range.

  Below, the resin layer A, the resin layer B, the resin layer C, and the protective film D which comprise this resin laminated body are demonstrated in order.

(Resin layer A)
In the present resin laminate, the resin layer A is disposed on the back side of the resin layer B, thereby playing a role of causing the resin layer B to exhibit excellent surface hardness.

For this reason, the hardness of the surface of the resin layer A is preferably a pencil hardness of 3H or more, and more preferably 5H or more. If the pencil hardness on the surface of the resin layer A is 3H or higher, even if the thickness of the resin layer B laminated thereon is reduced, excellent hardness is maintained on the surface of the resin layer B, that is, excellent surface hardness can be imparted. preferable.
Moreover, it is preferable if the thickness of the resin layer B can be reduced because warpage and undulation of the resin laminate can be suppressed.

(Thermoplastic resin composition a)
The resin layer A in the present resin laminate is formed from the thermoplastic resin composition a. The thermoplastic resin that can be used for the thermoplastic resin composition a is not particularly limited as long as it is a thermoplastic resin that can form a film, a sheet, or a plate by melt extrusion. Preferred examples include polyethylene terephthalate, Polyester resins represented by aromatic polyesters such as polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and aliphatic polyesters such as polylactic acid polymers, polyethylene, polypropylene , Polyolefin resins such as cycloolefin resins, polycarbonate resins, acrylic resins, polystyrene resins, polyamide resins, polyether resins, polyurethane resins, polyphenylenes Rufide resin, polyesteramide resin, polyether ester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyarylate resin, polysulfone resin , Polyetherimide resins, polyamideimide resins, polyimide resins, copolymers containing these as main components, or mixtures of these resins.
In particular, in the present invention, polyester resins, polycarbonate resins, and acrylic resins are preferable from the viewpoint that there is almost no absorption in the visible light region. Among these, an acrylic resin is particularly preferable in that the resin layer B exhibits excellent surface hardness as described above.

(Acrylic resin)
Examples of the monomer constituting the acrylic resin that can be used in the present invention include methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) succinic acid ) Acroyloxyethyl, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) Examples include acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate.
These may be used by polymerizing 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. The polyfunctional monomer may be a compound having at least two polymerizable carbon-carbon double bonds in the molecule.
Here, examples of the monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; alkenyl cyan compounds such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimides; and the like. Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate; allyl acrylate, allyl methacrylate, cinnamon Alkenyl esters of unsaturated carboxylic acids such as allyl acid; polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate; aromatic polyalkenyl compounds such as divinylbenzene; etc. Is mentioned. Two or more types of monomers that can be copolymerized with alkyl methacrylate or alkyl acrylate may be used as necessary.

  As a copolymer resin with a monomer constituting the acrylic resin, for example, a methyl methacrylate-styrene copolymer is preferably used from the viewpoint of improving environmental resistance (warpage due to moisture absorption) of the acrylic resin. I can do it. As the methyl methacrylate-styrene copolymer resin, those having 30 to 95% by weight of methyl methacrylate units and 5 to 70% by weight of styrene units are usually used based on all monomer units, preferably methyl methacrylate. Those having 40 to 95% by weight of units and 5 to 60% by weight of styrene units are used, more preferably those having 50 to 90% by weight of methyl methacrylate units and 10 to 50% by weight of styrene units. When the ratio of the methyl methacrylate unit is reduced, the breaking strength of the surface layer itself is lowered, the whole film is easily broken, and the surface hardness is also lowered. Moreover, when the ratio of a methylmethacrylate unit becomes large, environmental resistance will fall.

  The acrylic resin that can be used in the present invention can be prepared by polymerizing the above-described monomer components by a known method such as suspension polymerization, emulsion polymerization, or bulk polymerization. At that time, a chain transfer agent is preferably used at the time of polymerization in order to adjust the glass transition temperature to a desired value or to obtain a viscosity exhibiting suitable moldability when producing a laminate. The amount of the chain transfer agent may be appropriately determined according to the type of monomer component and the composition thereof.

Moreover, in the acrylic resin used for this resin laminated body, the acrylic resin which has heat resistance (henceforth a heat resistant acrylic resin) can also be preferably used as the thermoplastic resin composition a.
If the resin layer A is formed using a heat-resistant acrylic resin as the main component of the thermoplastic resin composition a, it may be easy to impart not only heat resistance but also excellent thermoformability in the resin laminate. preferable.
Moreover, although mentioned later, as a means for suppressing the curvature of this resin laminated body, making absolute value of the difference of the glass transition temperature of the resin layer A and the resin layer C into 30 degrees C or less is mentioned. For this reason, when the main component of the thermoplastic resin composition c forming the resin layer C has a high glass transition temperature, the acrylic resin preferably has a high glass transition temperature as well. From the viewpoint, a heat-resistant acrylic resin can be used advantageously.

(Heat resistant acrylic resin a1)
The heat resistant acrylic resin a1 is a copolymer resin containing a (meth) acrylic acid ester structural unit represented by the following general formula (1) and an aliphatic vinyl structural unit represented by the following general formula (2). The thing characterized by this is mentioned.

  In formula (1), R1 is hydrogen or a methyl group, and R2 is a C1-C16 alkyl group.

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

  R2 of the (meth) acrylic acid ester structural unit represented by the general formula (1) is an alkyl group having 1 to 16 carbon atoms, such as methyl group, ethyl group, butyl group, lauryl group, stearyl group, cyclohexyl group, isobornyl. Examples include groups. These can be used alone or in combination of two or more. Of these, a (meth) acrylic acid ester structural unit in which R2 is a methyl group and / or an ethyl group is preferable, and a methacrylic acid ester structural unit in which R1 is a methyl group and R2 is a methyl group is more preferable.

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

The molar composition ratio between the (meth) acrylic acid ester structural unit represented by the general formula (1) and the aliphatic vinyl structural unit represented by the general formula (2) is in the range of 15:85 to 85:15. Yes, preferably in the range of 25:75 to 75:25, more preferably in the range of 30:70 to 70:30.
If the molar composition ratio of the (meth) acrylic ester structural unit to the total of the (meth) acrylic ester structural unit and the aliphatic vinyl structural unit is less than 15%, the mechanical strength becomes too low and becomes brittle. Absent. If it exceeds 85%, the heat resistance may be insufficient.

  The heat-resistant acrylic resin a1 is mainly composed of a (meth) acrylic acid ester structural unit represented by the general formula (1) and an aliphatic vinyl structural unit represented by the general formula (2). Although not particularly limited, those obtained by copolymerizing a (meth) acrylate monomer and an aromatic vinyl monomer and then hydrogenating the aromatic ring are preferred. In addition, (meth) acrylic acid shows methacrylic acid and / or acrylic acid. Specific examples of the aromatic vinyl monomer used in this case include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.

  Specific examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. , (Meth) acrylic acid cyclohexyl, (meth) acrylic acid alkyl (meth) acrylates such as isobornyl, etc., but from the balance of physical properties, alkyl methacrylate is used alone, or alkyl methacrylate and It is preferable to use alkyl acrylate together. Of the alkyl methacrylates, methyl methacrylate and ethyl methacrylate are particularly preferable.

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

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

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

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

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

(Heat resistant acrylic resin a2)
As heat-resistant acrylic resin a2, on the basis of all monomer units constituting the acrylic resin, methyl methacrylate units 60 to 95% by weight, methacrylic acid units, acrylic acid units, maleic anhydride units, N- Examples thereof include a polymer having 5 to 40% by weight of a unit selected from a substituted or unsubstituted myremide unit, a glutaric anhydride structural unit, and a glutarimide structural unit, and having a glass transition temperature of 110 ° C. or higher.

Here, the methyl methacrylate unit is a unit [—CH ₂ —C (CH ₃ ) (CO ₂ CH ₃ ) —] formed by polymerization of methyl methacrylate, and the methacrylic acid unit is obtained by polymerization of methacrylic acid. Unit [—CH ₂ —C (CH ₃ ) (CO ₂ H) —] formed, and the acrylic acid unit is a unit [—CH ₂ —CH (CO ₂ H) — formed by polymerization of acrylic acid. ]. The maleic anhydride unit is a unit formed by polymerization of maleic anhydride represented by the general formula (3), and the N-substituted or unsubstituted maleimide unit is represented by the general formula (4). Units formed by polymerization of N-substituted or unsubstituted maleimide.

  In the formula (4), R1 represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, and an aryl such as a phenyl group. Group, an aralkyl group such as benzyl group, and the carbon number is usually about 1 to 20.

  Further, the glutaric anhydride structural unit is a unit having a glutaric anhydride structure, and the glutarimide structural unit is a unit having a glutarimide structure. Typically, each of the following general formula (5) and It is shown by (6).

  In formula (5), R2 represents a hydrogen atom or a methyl group, and R3 represents a hydrogen atom or a methyl group. In the formula (6), R4 represents a hydrogen atom or a methyl group, R5 represents a hydrogen atom or a methyl group, R6 represents a hydrogen atom or a substituent, and examples of the substituent include a methyl group and an ethyl group. Examples thereof include an alkyl group such as this, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group, and the carbon number thereof is 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 are used as polymerization raw materials, respectively, methyl methacrylate, methacrylic acid, acrylic acid, maleic anhydride. , And N-substituted or unsubstituted maleimides.

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

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

  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 of methyl methacrylate units, and methacrylic acid units and acrylic acid units. A unit selected from maleic anhydride units, N-substituted or unsubstituted maleimide units, glutaric anhydride structural units, and glutarimide structural units, preferably 5 to 35% by weight, more preferably 8 to 30% by weight. It is. The glass transition temperature of the acrylic polymer is preferably 115 ° C. or higher, and usually 150 ° C. or lower.

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

In formula (7), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.

  In order to form the lactone ring structure represented by the general formula (7), as the polymer (α) having a hydroxyl group and an ester group in the molecular chain, for example, a (meth) acrylate monomer (α1) A polymer obtained by polymerizing a monomer component containing a vinyl monomer (α2) having a structural unit represented by the following general formula (8) is preferred.

  In formula (8), R4 and R5 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.

  The (meth) acrylate monomer (α1) is a so-called (meth) other than a vinyl monomer having a 2- (hydroxymethyl) acrylate structural unit represented by the general formula (8), for example. If it is an acrylic acid alkylester monomer, it will not specifically limit. For example, 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 may be used. In addition, a desired substituent or functional group may be introduced into these groups.

  Specific examples of the (meth) acrylate monomer (α1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic acid ester and the like. These may be used alone or in combination of two or more. Among these, in terms of the weather resistance, surface gloss, and transparency of the resulting acrylic resin, methyl methacrylate and methyl acrylate are preferable, and in terms of the surface hardness of the resulting acrylic resin, methyl methacrylate is more preferable. Good. Further, (meth) acrylate having a cyclohexyl group is preferable in that it imparts hydrophobicity to the acrylic resin and, as a result, can reduce the water absorption rate of the acrylic resin and can impart weather resistance to the acrylic resin. In addition, (meth) acrylate having an aromatic group is preferable in that the aromatic ring can further improve the heat resistance of the resulting acrylic resin.

  The ratio of the (meth) acrylate monomer (α1) in the monomer component is not particularly limited, but is preferably 95 to 10% by weight, more preferably 90 to 10% by weight. Furthermore, in order to maintain good transparency and weather resistance, it is preferably 90 to 40% by weight, more preferably 90 to 60% by weight, and still more preferably 90 to 70% by weight in the total monomer components. % Should be good.

  In the heat-resistant acrylic resin a3 used in the present invention, an unsaturated monocarboxylic acid (α1 ′) may be used in combination as the (meth) acrylate monomer (α1). By using an unsaturated monocarboxylic acid (α1 ′) in combination, an acrylic resin into which a glutaric anhydride ring structure is introduced together with a lactone ring structure can be obtained, and heat resistance and mechanical strength can be further improved. It is preferable because it is possible. Examples of the unsaturated monocarboxylic acid (α1 ′) include (meth) acrylic acid, crotonic acid, and α-substituted acrylic acid monomers which are derivatives thereof, but are not particularly limited. (Meth) acrylic acid is preferred, and methacrylic acid is preferred from the viewpoint of heat resistance. In addition, the ester group derived from the (meth) acrylate monomer (α1) in the polymer (α) may have a structure equivalent to that of the unsaturated carboxylic acid (α1 ′) depending on conditions such as heating. Further, the carboxyl group possessed by the unsaturated carboxylic acid (α1 ′) may have a structure of a salt such as a metal salt such as a sodium salt, as long as it does not interfere with the cyclization condensation reaction described later. In the monomer component, the ratio of the unsaturated monocarboxylic acid (α1 ′) is not particularly limited, and may be appropriately set within a range not impairing the effects of the present invention.

  Examples of the vinyl monomer (α2) having the structural unit represented by the general formula (8) include 2- (hydroxyalkyl) acrylic acid derivatives. Specifically, 2- (hydroxymethyl) acrylic acid ester monomers are preferred. More specifically, for example, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, normal butyl 2- (hydroxymethyl) acrylate, 2 -(Hydroxymethyl) acrylic acid-t-butyl and the like can be mentioned, among which methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are particularly preferable. Furthermore, 2- (hydroxymethyl) methyl acrylate is most preferred because it has a high effect of improving surface hardness, hot water resistance or solvent resistance. In addition, these may use only 1 type or may use 2 or more types together.

  In the monomer component, the ratio of the vinyl monomer (α2) having the structural unit represented by the general formula (8) is not particularly limited, but is preferably 5 to 50% by weight. . More preferably, it is 10 to 40 weight%, More preferably, it is 15 to 35 weight%. When the proportion of the vinyl monomer (α2) is less than the above range, the amount of the ring structure is reduced, so that the surface hardness of the laminate may be lowered, and the hot water resistance and solvent resistance may be lowered. Moreover, the heat resistance of the laminate may be lowered. On the other hand, when the amount is more than the above range, when a lactone ring structure is formed, a crosslinking reaction occurs and gelation tends to occur, the fluidity is lowered, and melt molding may be difficult. In addition, since unreacted hydroxyl groups are likely to remain, when the resulting acrylic resin is molded, a condensation reaction further proceeds to generate a volatile substance, and bubbles or silver streaks (silver strips on the surface) are generated in the laminate. Pattern or the like) may be easy to enter.

  As the monomer component for obtaining the polymer (α), a polymerizable monomer other than the above (α1) and (α2) can be used as long as the effects of the present invention are not impaired. . Examples thereof include styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate and the like. In addition, these may use only 1 type or may use 2 or more types together. When the polymerizable monomer is used in combination as a monomer component for obtaining the polymer (α), the content of these monomers is 0 to 30% by weight or less in the monomer component. Preferably, it is 0 to 20% by weight or less, more preferably 0 to 10% by weight or less. When a predetermined amount or more is used in terms of physical properties, physical properties such as weather resistance, surface gloss or transparency, which are good physical properties derived from a (meth) acrylate monomer, may be impaired.

The heat resistant acrylic resin a3 is obtained by forming a ring structure by subjecting the polymer (α) to a cyclization condensation reaction. The cyclocondensation reaction is a reaction in which a hydroxyl group and an ester group (or more carboxyl group) present in the molecular chain of the polymer (α) are cyclized and condensed to form a lactone ring structure by heating, Alcohol and water are by-produced by cyclocondensation. Thus, by forming the ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted and high surface hardness, hot water resistance, and solvent resistance are imparted.
Examples of a method for obtaining an acrylic resin having a lactone ring structure by cyclization condensation of the polymer (α) include 1) cyclization condensation by heating the polymer (α) under reduced pressure in an extruder. Method of reaction (Polym. Prepr., 8, 1,576 (1967), 2) The cyclization condensation reaction of the polymer (α) is carried out in the presence of a solvent, and depolymerization is performed simultaneously with the cyclization condensation reaction. There are a method of volatilization, 3) a method of cyclocondensing the polymer (α) using a specific organophosphorus compound as a catalyst (European Patent No. 1008606), and the like. Of course, it is not limited to these, A plurality of methods may be adopted among the methods 1) to 3). In particular, the reaction rate of the cyclization condensation reaction is high, it is possible to suppress the foam and silver streak from entering the laminate, and the reduction in mechanical strength due to the decrease in molecular weight during devolatilization can be suppressed 2) And 3) are preferred.

  The heat-resistant acrylic resin a3 used in the present invention has a weight average molecular weight of 1,000 to 1,000,000, more preferably 5,000 to 500,000, and most preferably 50,000 to 300,000. Is preferred. When the weight average molecular weight is lower than the above range, not only the surface hardness, hot water resistance or solvent resistance is lowered, but also there is a problem that the mechanical strength is lowered and it is likely to become brittle. This is not preferable because the properties are lowered and the molding becomes difficult.

  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, it is preferable to form the resin layer A from the thermoplastic resin composition a mainly composed of any one of the above heat-resistant acrylic resins because warpage of the laminate may be easily suppressed. For example, if a polycarbonate resin is used as the main component of the thermoplastic resin composition c forming the resin layer C, any one of the above heat resistant acrylic resins may be used as the main component of the thermoplastic resin composition a forming the resin layer A. Even if it is used as it is, it is often preferable that the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C can be within 30 ° C. That is, it is preferable to set the absolute value of the difference between the glass transition temperatures of the resin layer A and the resin layer C within 30 ° C., since warpage of the laminate can be suppressed.

(Heat resistant acrylic resin a4)
As the heat-resistant acrylic resin a4, not only heat resistance but also excellent hardness can be used in which a hard dispersed phase is contained in an acrylic resin matrix. More specifically, an acrylic resin containing and dispersing a hard dispersed phase material that has better heat resistance or scratch resistance than the acrylic resin can be used. By using an acrylic resin containing a hard dispersed phase in the matrix, the pencil hardness of the surface of the resin layer A can be 5H or more.

  Examples of the material that forms the hard dispersed phase include thermosetting resins. Specifically, phenol resins, amino resins, epoxy resins, silicone resins, thermosetting polyimide resins, thermosetting polyurethane resins, etc. In addition to these polycondensation or addition condensation resins, addition polymerization resins obtained by radical polymerization of unsaturated monomers such as thermosetting acrylic resins, vinyl ester resins, unsaturated polyester resins, diallyl phthalate resins, etc. It is done.

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

  Specific examples of the unsaturated monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethoxylate (di-, tri-) acrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, penta Examples include erythritol tetraallyl ether, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate or ethoxylated pentaerythritol tetraacrylate, and mixtures thereof. Among these, considering the affinity with acrylic resins, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA) can be preferably used. However, it is not limited to these.

  You may use a thermosetting resin individually or in combination of 2 or more types. Moreover, you may use combining these thermosetting resins and the thermoplastic resin which has the unsaturated bond which can be bridge | crosslinked.

Examples of the shape of the hard dispersed phase include particles, spheres, lines, fibers, and the like. From the viewpoint of being easily dispersed evenly in the acrylic resin that is a thermoplastic matrix resin, a sphere is preferable. However, it is not limited to this.
The particle size of the hard dispersed phase is appropriately set depending on the purpose of use, application, etc. of the resin laminate, but is preferably 0.1 to 1000 μm. Although the compounding quantity of the hard dispersion phase in an acrylic resin phase is suitably set according to the intended purpose, use, etc. of this resin laminated body, Preferably it is 0.1-60 weight%.

Although it does not specifically limit as a method of including a hard dispersion phase in an acrylic resin phase, For example, the following method is mentioned.
a) A thermosetting resin material constituting a hard dispersed phase is added to the acrylic resin material.
b) Next, after melt-kneading and forming into a predetermined shape, a hard dispersed phase can be formed by causing phase separation and crosslinking. Alternatively, the thermosetting resin may be molded into a particulate form in advance, added to the acrylic resin, and kneaded and molded at a temperature at which the thermosetting resin does not dissolve.

(Other ingredients)
In addition to the resin component, the thermoplastic resin composition a that forms the resin layer A includes, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant such as a silicone compound, a filler, Various additives such as glass fiber and impact modifier may be contained within a range not impairing the effects of the present invention.

  Further, the thermoplastic resin composition a forming the resin layer A can also contain acrylic rubber particles having an elastic polymer portion as long as the effects of the present invention are not impaired. Such acrylic rubber particles have a layer (elastic polymer layer) made of an elastic polymer mainly composed of an acrylate ester, and may be single-layer particles made only of an elastic polymer or elastic. Particles having a multilayer structure composed of a polymer layer and a layer made of a hard polymer (hard polymer layer) may be used, but considering the surface hardness of the resin layer A disposed on the surface of the laminate, A particle having a multilayer structure is preferable. In addition, only 1 type may be sufficient as acrylic rubber particle, and 2 or more types may be sufficient as it.

  As described above, the resin layer A is arranged on the back side of the resin layer B, thereby playing a role of making the resin layer B exhibit 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. If the thickness of the resin layer A is 40 μm or more, it is preferable because even if the thickness of the resin layer B is reduced, excellent surface hardness is expressed on the surface of the resin layer B. 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. A thickness of the resin layer A of 500 μm or less is preferable because the resin layer C can easily compensate for the brittleness of the resin layer A that hinders thermoforming or punching.

(Resin layer B)
The resin layer B in the present invention is a layer that imparts excellent surface hardness to the laminate. It is also a layer having excellent scratch resistance, and when it is rubbed with a load of 500 g using # 0000 steel wool, it is preferable that the number of reciprocations until scratching is 50 times or more, and 100 times or more. More preferably, it is more preferably 500 times or more.

(Curable resin composition b)
Among the resin laminates, the resin layer B is formed from the curable resin composition b, and the curable resin composition b that can be used in the present invention includes, for example, electron beams, radiation, ultraviolet rays, and the like. Although it will not specifically limit if it hardens | cures by irradiating an energy ray, or it hardens | cures by heating, It is preferable to consist of a ultraviolet curable resin from a viewpoint of shaping | molding time and productivity.
Preferred examples of the curable resin constituting the curable resin composition b include acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, copolymer acrylates, and alicyclic epoxies. Examples thereof include resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetane compounds and the like. These curable resins may be used alone or in combination with a plurality of compounds. Among them, examples of the curable resin imparting excellent surface hardness include radical polymerization curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, polyfunctional epoxy acrylate compounds, alkoxysilanes, and alkylalkoxys. Examples thereof include curable compounds of thermal polymerization type such as silane. Furthermore, the curable resin composition b of the present invention can be an organic / inorganic composite curable resin composition obtained by adding an inorganic component to the curable resin.

Examples of the curable resin composition b that imparts a particularly excellent surface hardness to the resin layer B include organic / inorganic hybrid curable resin compositions. Examples of the organic / inorganic hybrid curable resin composition include those composed of a curable resin composition containing an inorganic component having a reactive functional group in the curable resin.
Utilizing such an inorganic component having a reactive functional group, for example, this inorganic component is copolymerized and cross-linked with a radical polymerizable monomer, so that the organic / inorganic is simply made to contain an inorganic component in an organic binder. Compared to the composite curable resin composition, curing shrinkage is unlikely to occur and high surface hardness can be expressed, which is preferable. Furthermore, from the viewpoint of reducing curing shrinkage, an organic / inorganic hybrid curable resin composition containing ultraviolet-reactive colloidal silica as an inorganic component having a reactive functional group can be mentioned as a more preferable example.

  As described above, the resin layer B in the present invention is a layer that imparts excellent surface hardness to the laminate.

As a forming method of the resin layer B, for example, there is a method of forming and laminating on the surface of the resin layer A by coating the surface of the resin layer A as a paint of the curable resin composition b and forming a cured film Although there is, it is not limited to this method.
As a lamination method with the resin layer A, a known method is used. For example, laminating method using cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, The gravure coat method etc. are mentioned. In addition, for example, a method of laminating the resin layer B on the resin layer A using a transfer sheet in which the resin layer B is formed on the release layer may be employed.

(Surface conditioning component)
The curable resin composition b forming the resin layer B can contain a leveling agent as a surface adjustment component. Examples of the leveling agent include silicone leveling agents and acrylic leveling agents. In particular, those having a reactive functional group at the terminal are preferable, and those having a reactive functional group having two or more functionalities are more preferable. preferable.
Specifically, a polyether-modified polydimethylsiloxane having an acrylic group having a double bond at both ends (for example, “BYK-UV 3500”, “BYK-UV 3530” manufactured by Big Chemie Japan Co., Ltd.), Polyester-modified polydimethylsiloxane having an acrylic group having a total of four double bonds at the end (“BYK-UV 3570” manufactured by Big Chemie Japan Co., Ltd.).
Among these, polyester-modified polydimethylsiloxane having an acrylic group that has a stable haze value and contributes to improvement of scratch resistance is particularly preferable.

  When the curable resin is cured with ultraviolet rays, a photopolymerization initiator is used. Examples of the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyl dimethyl ketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones, and acylphosphine oxides. The addition amount of the photopolymerization initiator is generally in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable resin.

  These photopolymerization initiators can be used alone, or many can be used in combination of two or more. Moreover, since these various photoinitiators are marketed, such a commercial item can be used. Examples of commercially available photopolymerization initiators include “IRGACURE 651”, “IRGACURE 184”, “IRGACURE 500”, “IRGACURE 1000”, “IRGACURE 2959”, “DAROCUR 1173”, “IRGACURE 907”, “IRGACURE 369”, “IRGACURE 1”, “IRGACURE 1”, “IRGACURE1” "IRGACURE819", "IRGACURE784" [The above IRGACURE (Irgacure) series and DAROCUR series are sold by Ciba Specialty Chemicals Co., Ltd.], "KAYACUREITTX", "KAYACUREDETX-S", "KAYACUREB-" “KAYACUREBMS”, “KAYACURE2-EAQ [More KAYACURE (Kayacure) series, sold by Nippon Kayaku Co., Ltd.], and the like.

(Other ingredients)
In addition to the curable resin component, the curable resin composition b that forms the resin layer B includes, for example, a lubricant such as a silicon compound, a fluorine compound, or a mixed compound thereof, an antioxidant, an ultraviolet absorber, Various additives such as antistatic agents, flame retardants such as silicone compounds, fillers, glass fibers, impact modifiers and the like can be contained within a range not impairing the effects of the present invention.

  The thickness of the resin layer B is preferably in the range of 5 μm to 20 μm. If thickness is 5 micrometers or more, since sufficient hardness can be provided to the resin layer B surface, it is preferable. On the other hand, if the thickness is 20 μm or less, it is preferable in that there is no possibility of warping, waviness, peeling, etc. accompanying the curing / shrinking of the resin layer B in the laminate.

(Resin layer C)
In the present resin laminate, the resin layer C plays a role of imparting secondary workability such as excellent impact resistance or punchability to the laminate.

(Thermoplastic resin composition c)
The resin layer C in the present resin laminate is formed from the thermoplastic resin composition c. The thermoplastic resin that can be used for the thermoplastic resin composition c is not particularly limited as long as it is a thermoplastic resin that can form a film, sheet, or plate by melt extrusion. Preferred examples include polyethylene terephthalate, Polyester resins represented by aromatic polyesters such as polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and aliphatic polyesters such as polylactic acid polymers, polyethylene, polypropylene , Polyolefin resins such as cycloolefin resins, polycarbonate resins, acrylic resins, polystyrene resins, polyamide resins, polyether resins, polyurethane resins, polyphenylenes Rufide resin, polyesteramide resin, polyether ester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyarylate resin, polysulfone resin , Polyetherimide resins, polyamideimide resins, polyimide resins, copolymers containing these as main components, or mixtures of these resins. In particular, in the present invention, a polyester resin, a polycarbonate resin, or an acrylic resin is preferable from the viewpoint that there is almost no absorption in the visible light region.
Among these, polycarbonate resins are particularly preferable because they can impart secondary workability such as excellent impact resistance or punchability to the laminate.

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

(Aromatic polycarbonate)
Examples of the aromatic polycarbonate include i) those obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method, and ii) a solid phase transesterification method of a carbonate prepolymer. And iii) those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. Among these, i) a product obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method is preferable in terms of productivity.

  Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1 -Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5- Dibromo) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis { 4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxy) Phenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydro Cis-3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α ′ -Bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ester, and the like. It can also be used.

Among the above-mentioned dihydric phenols, among those described above, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, , 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, alone or in combination with a dihydric phenol selected from the group consisting of It is preferable to use two or more kinds. In particular, bisphenol A alone or 1,1-bis (4-hydroxyphenyl) -3,3, -Selected from the group consisting of trimethylcyclohexane, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene Use in combination with one or more dihydric phenols is preferred.
Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, haloformates such as dihaloformates of dihydric phenols, and two or more of them can be used as necessary.

(Other polycarbonate resins)
Examples of the polycarbonate resin other than the aromatic polycarbonate include aliphatic polycarbonate and alicyclic polycarbonate. What contains at least the structural unit derived from the dihydroxy compound which has a site | part represented by following General formula (9) in a part of structure is preferable.

(Unless moiety represented by the formula (9) is part of _-CH 2 -O-H.)

  The dihydroxy compound is not particularly limited as long as a part of the molecular structure is represented by the general formula (9). Specifically, 9,9-bis (4- (2 -Hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9, 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phen Ruphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6 -Methylphenyl) fluorene 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene or the like, an ether having an aromatic group in the side chain and bonded to the aromatic group in the main chain And compounds having a group.

  From the viewpoint of heat resistance, a compound having a cyclic ether structure such as spiroglycol can be preferably used. Specifically, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane (common name: spiroglycol), 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.

  Other polycarbonate resins may contain structural units derived from dihydroxy compounds other than the above-mentioned dihydroxy compounds (hereinafter sometimes referred to as “other dihydroxy compounds”), and 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-hexanediol Aliphatic dihydroxy compounds such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalindi Methanol, 1,5-decalin Alicyclic dihydroxy compounds such as methanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 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- -Nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy) Phenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 9,9-bis Aromatics such as (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene Bisphenols are mentioned.

  At least four layers of the resin layer C formed of the thermoplastic resin composition c, the resin layer A formed of the acrylic resin a, the resin layer B formed of the curable resin composition b, and the protective film D In the resin laminate with a protective film, which is laminated in order, the absolute value of the difference between the glass transition temperatures of the resin layer A and the resin layer C is set within 30 ° C. Even when exposed to the above environment, the warpage of the present resin laminate can be suppressed, which is preferable. From this viewpoint, the absolute value of the difference between the glass transition temperatures of the resin layer A and the resin layer C is more preferably 25 ° C. or less, and further preferably 20 ° C. or less.

Examples of the method for setting the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C to be within 30 ° C. include the following methods.
(1) In the thermoplastic resin composition a and / or the thermoplastic resin composition c, by blending thermoplastic resins having different glass transition temperatures, a mixture of at least two kinds of thermoplastic resins is obtained. A method of adjusting the difference in glass transition temperature between A and the resin layer C within 30 ° C. Here, as the two or more types of thermoplastic resins having different glass transition temperatures, the same or different types of thermoplastic resins can be used as long as the glass transition temperatures are different. The thermoplastic resin blended here is compatible with the thermoplastic resin composition a or the thermoplastic resin composition c.
(2) About the thermoplastic resin composition a and / or the thermoplastic resin composition c, the difference between the glass transition temperatures of the resin layer A and the resin layer B is within 30 ° C. by using a copolymer with other components. How to adjust.
(3) About thermoplastic resin composition a and / or thermoplastic resin composition c, by mixing additives such as plasticizer, the difference in glass transition temperature between resin layer A and resin layer C is within 30 ° C. How to adjust.

  Further, as another method for suppressing the warp of the laminate by a method other than setting the absolute value of the difference between the glass transition temperatures of the resin layer A and the resin layer C within 30 ° C., for example, the thermoplastic resin composition a and In the thermoplastic resin composition c, there may be mentioned a method of preparing a mixture comprising at least two types of incompatible thermoplastic resins.

  Of the methods in which the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is within 30 ° C., the example of the above (1) is that the thermoplastic resin a is mainly composed of an acrylic resin, and the thermoplastic resin The case where the composition c consists of a mixture of a polycarbonate resin and other thermoplastic resins will be described in detail.

  As described above, the thermoplastic resin composition c in the present invention can be a mixture composed of two or more thermoplastic resins. For example, when the thermoplastic resin composition a has an acrylic resin as a main component and the thermoplastic resin composition c has a polycarbonate resin as a main component, the absolute value of the difference between the glass transition temperatures is 30 ° C. or less. In order to reduce the glass transition temperature of the polycarbonate resin, the other polycarbonate resin is mixed with the latter polycarbonate resin. That is, a method of lowering the glass transition temperature of a polycarbonate resin by melt blending (; mixing and heat-melting) a polycarbonate resin and another thermoplastic resin to form a polymer alloy.

  In general, the glass transition temperature of polycarbonate resin is around 150 ° C, which is higher by 50 ° C than the typical glass transition temperature of acrylic resin, 100 ° C, so other thermoplastic resins are mixed with polycarbonate resin. Thus, the glass transition temperature of the polycarbonate resin is lowered. From this viewpoint, preferred examples of other thermoplastic resins include aromatic polyesters and polyester resins having a cyclic acetal skeleton.

(Aromatic polyester d1)
Examples of the aromatic polyester d1 that can be used as another thermoplastic resin include a resin obtained by condensation polymerization of an aromatic dicarboxylic acid component and a diol component.

  Here, representative examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. Further, a part of terephthalic acid may be substituted with another dicarboxylic acid component. Examples of other dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentylic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, p-oxybenzoic acid, and the like. These may be one kind or a mixture of two or more kinds, and the amount of other dicarboxylic acids to be substituted can be appropriately selected.

  On the other hand, typical examples of the diol component include ethylene glycol, diethylene glycol, triethylene glycol, and cyclohexanedimethanol. A part of ethylene glycol may be substituted with another diol component. Other diol components include propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, trimethylol, methoxypolyethylene Examples include alkylene glycol. These may be one kind or a mixture of two or more kinds, and the amount of other diols to be substituted can be appropriately selected.

  Specific examples of the aromatic polyester include polyethylene terephthalate obtained by condensation polymerization of terephthalic acid and ethylene glycol, and polybutylene terephthalate obtained by condensation polymerization of terephthalic acid or dimethyl terephthalate and 1,4-butanediol. Moreover, the copolyester containing other dicarboxylic acid components other than terephthalic acid and / or other diol components other than ethylene glycol can also be mentioned as a preferred aromatic polyester.

  Among them, as a preferable example, a part of ethylene glycol in polyethylene terephthalate, preferably a copolyester having a structure obtained by substituting 55 to 75 mol% with cyclohexanedimethanol, or a part of terephthalic acid in polybutylene terephthalate, preferably May include a copolyester having a structure obtained by substituting 10 to 30 mol% with isophthalic acid, or a mixture of these copolyesters.

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

  From such a viewpoint, a copolymerized polyester having a structure in which 50 to 75 mol% of ethylene glycol, which is a diol component of polyethylene terephthalate, is substituted with 1,4-cyclohexanedimethanol (1,4-CHDM) (so-called “ PCTG "), or a copolyester having a structure obtained by substituting a part of terephthalic acid of polybutylene terephthalate, preferably 10 to 30 mol% with isophthalic acid, or a mixture thereof is the most preferable example. These copolyesters are known to be completely compatible and polymerized by melt blending with a polycarbonate-based resin, and the glass transition temperature can be effectively lowered.

(Polyester resin d2 having a cyclic acetal skeleton)
The polyester resin d2 having a cyclic acetal skeleton that can be used as another thermoplastic resin is a polyester resin that includes a dicarboxylic acid unit and a diol unit, and 1 to 60 mol% of the diol unit is a diol unit having a cyclic acetal skeleton. is there. The diol unit having a cyclic acetal skeleton is preferably a unit derived from a compound represented by the following general formula (10) or (11).

  R1, R2, and R3 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic carbon group having 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of hydrogen groups.

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

  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, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentane. Aliphatic diols such as diol, 1,6-hexanediol, diethylene glycol, propylene glycol and neopentyl glycol; polyether diols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 1,3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 1,2-decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5-de Cycloaliphatic diols such as hydronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydro naphthalene diethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol Bisphenols such as 4,4 ′-(1-methylethylidene) bisphenol, methylene bisphenol (bisphenol F), 4,4′-cyclohexylidene bisphenol (bisphenol Z), 4,4′-sulfonyl bisphenol (bisphenol S), etc. Alkylene oxide adducts of the above bisphenols; hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydipheny Aromatic dihydroxy compounds such as benzophenone; and alkylene oxide adducts of the above aromatic dihydroxy compounds can be exemplified. Ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol are preferable from the viewpoint of mechanical performance and economical efficiency of the polyester resin of the present invention, and ethylene glycol is particularly preferable. The exemplified diol units can be used alone or in combination.

  In addition, the dicarboxylic acid unit of the polyester resin d2 having a cyclic acetal skeleton used in the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane. Aliphatic dicarboxylic acids such as dicarboxylic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, 1, Examples include aromatic dicarboxylic acids such as 4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetralindicarboxylic acid. From the viewpoint of mechanical performance and heat resistance of the film of the present invention, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalene Aromatic dicarboxylic acids such as dicarboxylic acids are preferred, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are particularly preferred. Among these, terephthalic acid is most preferable from the viewpoint of economy. The illustrated dicarboxylic acids can be used alone or in combination.

Whether or not the melt-blended mixed resin composition is a polymer alloy, in other words, whether or not it is completely compatible, is determined by, for example, a glass transition temperature measured at a heating rate of 10 ° C./min by differential scanning calorimetry. It can be judged by whether it becomes one. Here, that the glass transition temperature of the mixed resin composition is single means that the glass transition temperature of the mixed resin composition is determined using a differential scanning calorimeter at a heating rate of 10 ° C./min in accordance with JIS K-7121. It means that only one peak indicating the glass transition temperature appears when measured.
Further, when the mixed resin composition was measured by dynamic viscoelasticity measurement (dynamic viscoelasticity measurement of JIS K-7198A method) at a strain of 0.1% and a frequency of 10 Hz, the maximum loss tangent (tan δ) was obtained. It can also be determined whether there is one value.
If the mixed resin composition is completely compatible (polymer alloying), the blended components are compatible with each other on the nanometer order (molecular level).

  As a means for polymer alloying, a compatibilizer, a secondary block polymerization or a graft polymerization, or a means of dispersing one polymer in a cluster form can be employed.

  The mixing ratio of the polycarbonate resin and the polyester d1 or d2 described above is such that the absolute value of the difference in glass transition temperature between the polycarbonate resin composition obtained by mixing and the acrylic resin is within 30 ° C. Although it does not restrict | limit, it is preferable that it is polycarbonate-type resin: polyester d1 or d2 = 20: 80-90: 10 by a mass ratio from a viewpoint of transparency maintenance, and especially polycarbonate-type resin: polyester d1 or d2 = 30. : 70 to 80:20, in particular, polycarbonate resin: polyester d1 or d2 = 40: 60 to 75:25 is preferable.

  Next, among the methods in which the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is within 30 ° C., the thermoplastic resin composition a is mainly composed of an acrylic resin as the example of 3) above. 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 polycarbonate resin is around 150 ° C., which is nearly 50 ° C. higher than the typical glass transition temperature of acrylic resin of 100 ° C. In order to make the absolute value of within 30 ° C., there is a method in which the latter polycarbonate resin is mixed with a plasticizer to lower the glass transition temperature of the polycarbonate resin.

  Examples of the plasticizer that can be used in the laminate include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate. Phosphate compounds such as 2-ethylhexyl diphenyl phosphate; phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl phthalate), diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate Acid ester compounds; trimellitic acid ester compounds such as tris (2-ethylhexyl) trimellitate; Til adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisodecyl adipate, bis (butyldiglycol) adipate, bis (2-ethylhexyl) azelate, dimethyl sebacate, dibutyl sebacate, Aliphatic dibasic acid ester compounds such as bis (2-ethylhexyl) sebacate and diethyl succinate; Ricinoleic acid ester compounds such as methylacetylricinoleate; Acetic acid ester compounds such as triacetin and octyl acetate; N-butylbenzenesulfone And sulfonamide compounds such as amides. In particular, when the resin component is a polycarbonate resin, among the plasticizers described above, a phosphoric acid ester-based compound is preferable because of its good compatibility with the polycarbonate resin and good transparency of the resin after the compatibility. In particular, cresyl diphenyl phosphate and tricresyl phosphate are more preferable.

  When the thermoplastic resin composition c is a mixture of a polycarbonate resin and a plasticizer, the ratio of both is a mass ratio, preferably polycarbonate resin: plasticizer = 70: 30 to 99: 1. It is more preferable that the system resin: plasticizer = 90: 10 to 98: 2. When the amount of the plasticizer is less than the above-described ratio, the effect of lowering the glass transition temperature due to plasticization becomes insufficient, and the absolute value of the difference in glass transition temperature between the resin layer A and the thermal resin layer C is within 30 ° C. As a result, it may be difficult to suppress warpage of the obtained laminate. On the other hand, when the amount of the plasticizer is larger than the above-described ratio, the fluidity of the thermoplastic resin composition c containing the polycarbonate resin is remarkably increased. For example, the laminate can be obtained by coextrusion molding with the thermoplastic resin composition a. When doing so, the appearance may be impaired.

(Other ingredients)
In addition to the resin component, the thermoplastic resin composition c forming the resin layer C includes, for example, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant such as a silicone compound, a filler, glass fiber, Various additives such as impact modifiers can be contained within a range not impairing the effects of the present invention.

  As described above, the resin layer C plays a role of imparting secondary workability such as excellent impact resistance or punchability to the laminate by being laminated with the resin layer A and the resin layer B. From this point of view, it is important that the thickness of the resin layer C is set based on the ratio with the total thickness of the resin layer A and the resin layer B, and the thickness ratio is determined by the resin layer C thickness / (resin layer A (Thickness + resin layer B thickness) is preferably 2 or more, and more preferably 4 or more. A thickness ratio of 2 or more is preferable because secondary workability such as excellent impact resistance or punchability can be imparted to the laminate.

(Protective film D)
In the present resin laminate, the protective film D has a predetermined water vapor permeability to suppress moisture absorption of the resin layer A, the resin layer B, and the resin layer C constituting the resin laminate during storage. And it plays a role which prevents appearance troubles, such as curvature and a wave | undulation, in this resin laminated body.
Therefore, for example, when the molded body is obtained by thermoforming the resin laminate, even if the resin laminate is stored for a long time before thermoforming, there is no problem during molding due to deformation. At this time, the protective film D of the present resin laminate may be thermoformed while being laminated, or may be thermoformed after peeling. If the protective film D is still laminated at the time of thermoforming, it has the advantage that the surface is less likely to be scratched or dusted before the molded body is used, so that it is preferably used as a molded body with a protective film. be able to.
In addition, when the protective film D has a high elastic modulus at a high temperature, the waist of the protective film is appropriately maintained even when exposed to a high temperature during thermoforming. Can be suppressed. Furthermore, the resin layer B formed from the curable resin composition b is disposed on both surfaces of the resin layer C formed from the thermoplastic resin composition c and the resin layer A formed from the thermoplastic resin composition a, Further, when the protective film D is laminated on both surfaces, the protective film D does not extend or compress the resin layer B in close contact with the adhesive layer when the resin laminate is molded. It plays a role of binding. When thermoforming, if the resin layer B is constrained by the protective film D and the resin layer B does not stretch or compress in the surface direction, the resin layer B is not likely to be whitened or cracked, and has an appearance. A beautiful molded body can be obtained.
Thus, the protective film D can exhibit an excellent effect even when the resin laminate is thermoformed and used as a molded body. In the molded body thermoformed with the protective film D laminated, when the molded body is used, the protective film may be peeled off and used.

  In the present invention, the protective film D includes at least a base material layer and an adhesive layer.

(Base material layer)
Any appropriate material can be adopted as a material for forming the base material layer depending on the application. For example, plastic, paper, a metal film, a nonwoven fabric, etc. are mentioned, Preferably it is a plastic. The base material layer may be formed from one kind of material, or may be formed from two or more kinds of materials. For example, you may form from 2 or more types of plastics.

Examples of the plastic include a vinyl chloride resin, a vinylidene chloride resin, a polyester resin, a polyamide resin, a polyolefin resin, and an acrylic resin. The water vapor permeability of the protective film D is within a predetermined range. In order to adjust to the above, a plastic having few hydrophilic groups or a plastic not containing a hydrophilic group can be mentioned as a preferable one. Here, examples of the hydrophilic group include a hydroxyl group (—OH), a carboxyl group (—COOH), and an amino group (—NH ₂ ). As a plastic having few hydrophilic groups or a plastic not containing a hydrophilic group, For example, polyester resins and polyolefin resins can be mentioned as preferable examples.

The water vapor permeability (25 ° C., 90% RH) of the polyester resin and the polyolefin resin is 25 g / (m, respectively) according to “New Food Packaging Film” (published by Nikkan Publishing Co., Ltd. 2004). ² · 24 h) and 5 to 17 g / (m ² · 24 h), both of which make it easy to adjust the water vapor permeability of the protective film D to a predetermined range in the present invention. It can use preferably as a material which forms a layer.

  When the base layer of the protective film is formed of the polyester resin, the elastic modulus is appropriately maintained even at high temperatures as described above, that is, the stiffness of the protective film is appropriately maintained. Even if the body is exposed to a high temperature during storage or thermoforming, it is preferable in that the deformation of the resin layer A, the resin layer C, particularly the resin layer B may be appropriately suppressed.

  Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid. Examples of the polyolefin resin include olefin monomer homopolymers, olefin monomer copolymers, and the like. Specific examples of the polyolefin-based resin include, for example, homopolypropylene; block-type, random-type, and graft-type propylene copolymers having an ethylene component as a copolymerization component; reactor TPO; low density, high density, linear Ethylene polymers such as low density and ultra-low density; ethylene / propylene copolymer, poly-1-butene, poly-4-methyl-1-pentene, cyclic olefin resin, ethylene / methyl acrylate copolymer, And ethylene / ethyl acrylate copolymers, ethylene / butyl acrylate copolymers, ethylene / methacrylic acid copolymers, ethylene copolymers such as ethylene / methyl methacrylate copolymers, and the like.

  The base material layer may contain any appropriate additive as required. Examples of the additive that can be contained in the base material layer include an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a plasticizer, a filler, and a pigment. The kind, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material forming the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration. From the viewpoint of improving weather resistance and the like, particularly preferred additives include antioxidants, ultraviolet absorbers, light stabilizers, and fillers.

Any appropriate thickness can be adopted as the thickness of the base material layer depending on the application. The thickness of a base material layer becomes like this. Preferably it is 10-200 micrometers, More preferably, it is 20-100 micrometers, More preferably, it is 30-80 micrometers.
If the thickness of the base material layer in the protective film D is 10 μm or more, the upper limit value of the water vapor permeability of the protective film D can be adjusted to a preferable range, which is preferable. On the other hand, if the thickness of the base material layer is 200 μm or less, the handling property of the protective film D is ensured and the workability is improved, which is preferable.

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

(Adhesive layer)
The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive. One type of pressure-sensitive adhesive may be used, or two or more types may be used.

The pressure-sensitive adhesive preferably contains a high molecular compound as a main component. Here, the polymer compound may be a crosslinked polymer compound.
The content of the polymer compound in the pressure-sensitive adhesive is preferably 50% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more.

  Arbitrary appropriate adhesives can be employ | adopted for the adhesive which comprises an adhesive layer. Examples of such adhesives include olefin-based adhesives, silicone-based adhesives, urethane-based adhesives, acrylic-based adhesives, polyester-based adhesives, rubber-based adhesives, and the like. From the standpoint of further manifesting the effects of the present invention, the pressure-sensitive adhesive is preferably an olefin-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or a urethane-based pressure-sensitive adhesive.

  Any appropriate additive may be contained in the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. Examples of such additives include softeners, tackifiers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, heat stabilizers, polymerization inhibitors, silane cups. Examples include ring agents, lubricants, inorganic or organic fillers, metal powders, pigments, and solvents. However, in the present invention, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer preferably does not contain a plasticizer. When a pressure-sensitive adhesive layer to which a plasticizer is added is used, wettability is improved, but the adherend may be contaminated by the plasticizer.

  The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer can be produced by any appropriate method. As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, for example, a polymerization method generally used as a polymer synthesis method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, polymerization by ultraviolet rays (UV), etc. is used. It can be produced by adopting an appropriate crosslinking method and using any appropriate additive as required.

  The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer preferably has a lower content of low molecular weight components in the sol component. If the content ratio of the low molecular weight component is small, it can be estimated that stable reworkability can be obtained with little contamination to the adherend.

  The thickness of the pressure-sensitive adhesive layer in the protective film D is preferably 1 to 100 μm, more preferably 3 to 50 μm, and further preferably 5 to 30 μm. A thickness of the pressure-sensitive adhesive layer of 1 μm or more is preferable because it is easy to uniformly adjust the thickness of the pressure-sensitive adhesive layer and a stable adhesive force can be secured. Moreover, if the thickness of an adhesive layer is 100 micrometers or less, since an adhesive force does not increase excessively and it becomes possible to adjust to an optimal adhesive force, it is preferable.

  The protective film D that can be used in the present invention is a method of laminating a material that will be a melt-kneaded pressure-sensitive adhesive layer on one side of a pre-formed base material layer, or a coextrusion molding such as a T-die method or an inflation method. Can be obtained by a method of simultaneously laminating the base material layer and the pressure-sensitive adhesive layer.

  The method of laminating the protective film D is not particularly limited. For example, a laminate in which the resin layer C, the resin layer A, and the resin layer B are laminated in this order is manufactured in advance. And a method of laminating the pressure-sensitive adhesive layer surface of the protective film D and the surface of the resin layer B, or a method of thermocompression bonding using a hot press, a hot metal roll, a hot rubber roll, or the like.

(Configuration of this resin laminate)
The present resin laminate has a configuration in which at least four layers of a resin layer C, a resin layer A, a resin layer B, and a protective film D are laminated in this order, but a multilayer configuration of five or more layers including other layers. It may be. For example, the protective layer D is laminated on the surface of the resin layer C opposite to the surface on which the resin layer A is laminated, and more specifically, the protective film D / resin layer C / resin layer A. A six-layer structure such as: / resin layer B / protective film D, or protective film D / resin layer B / resin layer C / resin layer A / resin layer B / protective film D.

(Thickness)
The thickness of the resin laminate is not particularly limited, and is preferably 0.1 mm to 1.5 mm, for example, and is particularly about 0.2 mm to 1.0 mm or less in consideration of practical handling. Is preferred.
For example, the surface protection panel used by being arranged on the front side of the image display device preferably has a thickness of 0.2 mm to 1.2 mm. For example, a front cover such as a mobile phone or a liquid crystal pen tablet having a touch panel function The material preferably has a thickness of 0.3 mm to 1.0 mm.

FIG. 1 illustrates a configuration of an embodiment of the present resin laminate. In FIG. 1A, a resin layer C (12), a resin layer A (13), a resin layer B (14), And the resin laminated body (11) formed by laminating four layers in the order of the protective film D (15) is illustrated.
Further, in FIG. 1B, a configuration in which a protective film D (15) is laminated on both surfaces of a laminate composed of a resin layer C (12), a resin layer A (13), and a resin layer B (14). The resin laminate (16) is illustrated. According to this structure, since it is the structure by which the protective film D (15) was coat | covered also to the resin layer C (12), there exists an advantage that it can suppress that a process damage | wound generate | occur | produces on the resin layer C (12) surface. Have. In addition, the protective film D (15) coated on the resin layer C (12) side may be different from the protective film D (15) on the resin layer A (13) side.
Furthermore, in (c) of FIG. 1, the protective film D is provided on both surfaces of a laminate composed of four layers of the resin layer B (14), the resin layer C (12), the resin layer A (13), and the resin layer B (14). The resin laminated body (17) of the structure which laminated | stacked (15) is illustrated. 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. Furthermore, when the protective film D (15) is laminated on both surfaces of the laminate, the protective film D (15) may be different between the front and back of the laminate.

<Explanation of terms>
In general, "film" refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japan) (Industrial standard JIS K-6900), “sheet” generally refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.

In the present invention, when expressed as “X to Y” (X and Y are arbitrary numbers), “X is preferably greater than X” and “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It means “smaller”.
Further, in the present invention, when expressed as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and “Y or less” (Y is an arbitrary number). ) Includes the meaning of “preferably smaller than Y” unless otherwise specified.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples, and various applications are possible without departing from the technical idea of the present invention.

<Measurement and evaluation method>
The measurement method and evaluation method of various physical property values of the resin layers, laminates, and resin laminates obtained in Examples and Comparative Examples will be described.

(Glass transition temperature (Tg) of resin layer)
The resin layers obtained in Examples and Comparative Examples were subjected to dynamic viscoelasticity measurement according to JIS K-7198A method using the following apparatus, the peak temperature of loss tangent (tan δ) was read, and the glass transition of the resin layer The temperature (Tg) was used.
Apparatus: Dynamic viscoelasticity measuring apparatus DVA-200 (made by IT Measurement Control Co., Ltd.)
Distance between chucks: 25mm
Distortion: 0.1%
Temperature range: -50 ° C to 250 ° C
Temperature increase rate: 3 ° C / min
Frequency: 10Hz

(Pencil hardness of resin layer)
About the resin layer obtained by the Example and the comparative example, the measurement of the surface pencil hardness was performed based on JISK-5600-5-4. The load applied during the test was 750 gf.

(Scratch resistance on the surface of the resin layer B)
With respect to the surface of the resin layer B obtained in Examples and Comparative Examples, the number of reciprocations until a scratch was generated was examined using the following apparatus and conditions. The obtained measured values were evaluated for scratch resistance based on the following evaluation criteria. However, the symbol “Δ” is also above the practical level.
Equipment: Friction fastness tester Gakushin type (manufactured by Daiei Scientific Instruments)
Steel wool count: # 0000
Test load: 500gf
Test speed: 30 reciprocations / minute Test stroke: 120 mm

◎: Number of reciprocations until the scratch occurs ≧ 500 times ○: 50 times ≦ Number of reciprocations until the scratch occurs <500 times Δ: Number of reciprocations until the scratch occurs <50 times

(Water vapor permeability of protective film D)
About the protective film D used in an Example, the water-vapor-permeation rate was measured according to JISK-7129 (B method) using the following apparatus.
Apparatus: PERMATRAN-W3 / 31MG (manufactured by MOCON; infrared sensor method)
Transmission area: 50 cm ²
Set temperature: 40 ° C
Setting humidity: 90% RH
Carrier gas / flow rate: Nitrogen gas / 50 ml / min

(Dimensional stability of resin laminate)
The dimensional stability of this resin laminate was evaluated by the value of “environmental warp”. The environmental warpage is determined by the difference between the warpage after the environmental test (LA) and the warpage before the environmental test (LB). Here, the warpage (LA) after the environmental test was carried out at room temperature after leaving the resin laminate with a protective film cut to 100 mm square for 3 hours in a constant temperature and humidity chamber adjusted to 85 ° C. and 85% RH. It is a numerical value obtained by performing measurement and calculation in the extracted state.
On the other hand, the warpage (LB) before the environmental test was annealed by leaving it to stand in a thermostat adjusted to 130 ° C. for 1 hr with the upper and lower sides of the resin laminate with protective film cut into 100 mm squares sandwiched between iron plates. It is a numerical value obtained by performing measurement and calculation in a state of being taken out at room temperature. For the annealing treatment, an iron plate having a size of 330 mm square, 2 mm thickness, and 1.6 kg weight was used.
In addition, the value of the warp before the environmental test and after the environmental test is that the resin laminated body with the protective film cut to 100 mm square is allowed to stand on the surface plate in the direction in which the four corners float, It is obtained by measuring the height and determining the average value. Here, the height from the standard when the resin layer B is on the convex side is distinguished as a positive value, and conversely, the height from the standard when the resin layer C is on the convex side is distinguished as a negative value.
Based on the numerical value of the obtained environmental warpage, the dimensional stability was evaluated based on the following evaluation criteria. However, the symbols “◯” and “Δ” are above the practical level.
○: Environmental warpage <1.5 (mm)
Δ: 1.5 (mm) ≦ environment warp <2.5 (mm)
×: 2.5 (mm) ≦ environment warpage

<Example 1>
(Preparation of resin composition a)
A pellet of acrylic resin A (manufactured by Arkema, trade name “Altglas HT121”, containing hard dispersed phase) was used as resin composition a as it was.

(Preparation of resin composition c)
Pellets of polycarbonate resin (manufactured by Sumika Stylon; trade name “CALIBER 301-4”), pellets of polycarbonate resin (manufactured by Sumika Stylon; trade name “SD Polycarbonate SP3030”), and polyester resin (SK Chemical) The product composition “SKYGREEN J2003”) was mixed at a mass ratio of 55:25:20, and then pelletized using a twin screw extruder heated to 260 ° C. to produce a resin composition c. did.

(Production of single-layer film constituting each resin layer)
For the single-layer sheet for evaluation, for the A layer and the C layer, the resin composition a or c was supplied to an extruder equipped with a single-layer T die, and 240 ° C. and 260 ° C. in each extruder. Then, a sheet-like sample having a single-layer structure having a thickness of 200 μm was obtained.
About the obtained sheet-like sample of each resin layer, glass transition temperature was evaluated. The results are shown in Table 1.

(Production of laminate)
The resin compositions a and c are respectively supplied to the extruders A and B. In each extruder, after melt-kneading at 240 ° C. and 260 ° C., the T-die for two types and two layers heated to 250 ° C. is used. It was made to merge, extruded into a sheet shape so as to have a two-layer structure of resin layer A / resin layer C, and cooled and solidified to obtain an intermediate laminate having a thickness of 600 μm (resin layer A: 80 μm, resin layer C: 520 μm). . Pencil hardness was evaluated about the surface of the resin layer A of the obtained laminated body. The results are shown in Table 1.

Further, an organic / inorganic hybrid ultraviolet curable resin composition b (manufactured by MOMENTIVE, trade name “UVHC7800FS”) was applied to the surface of the intermediate laminate on the resin layer A side using a bar coater, and then at 90 ° C. for 1 minute. After drying, exposure was performed at an exposure amount of 500 mJ / cm ² to obtain a laminate including a resin layer B having a thickness of 10 μm. Here, the concentration of the reactive functional group-containing silica in the resin layer B was 46% by mass. The surface of the resin layer B of the obtained laminate was evaluated for pencil hardness and scratch resistance. The results are shown in Table 1.

(Preparation of resin laminate 1 with protective film)
On the surface of the resin layer B of the laminate and the surface of the resin layer C, the pressure-sensitive adhesive layer surface of the protective film D-1 (ethylene / propylene copolymer substrate layer; thickness 30 μm, polyethylene pressure-sensitive adhesive layer; thickness 3 μm) is formed. Lamination was performed by passing through a laminating roll (two rolls, upper rubber roll, lower rubber roll, laminating pressure 0.5 MPa) to obtain a resin laminate 1 with a protective film. About the obtained resin laminated body 1 with a protective film, evaluation of dimensional stability was performed. The results are shown in Table 1.

<Example 2>
(Preparation of resin laminate 2 with protective film)
In the production of the resin laminate 1 with a protective film of Example 1, a protective film D-2 (polyethylene base layer; thickness 50 μm, acrylic pressure-sensitive adhesive layer, thickness 4 μm) was used instead of the protective film D-1. Except for the above, a resin laminate 2 with a protective film was obtained in the same manner as in Example 1. Evaluation was performed in the same manner as in Example 1 using the obtained resin laminate 2 with a protective film. The results are shown in Table 1.

<Reference Example 1>
In Example 1, the dimensional stability was evaluated in a state where the protective film D was not laminated. The results are shown in Table 1.

  As is clear from Table 1, in the resin laminates of the present invention of Examples 1 and 2, the surface of the resin layer B has an excellent hardness of 5H or more, and the environmental warpage is 1.5 (mm) or less. And dimensional stability was found to be particularly excellent.

  Since the resin laminate proposed by the present invention has excellent surface hardness and dimensional stability, it has a surface protection panel, particularly a touch panel function, which is used by being arranged on the front side (viewing side) of the image display device. It is suitably used for front cover materials such as mobile phones and liquid crystal pen tablets.

11, 16, 17: This laminated body 12: Resin layer C
13: Resin layer A
14: Resin layer B
15: Protective film D

Claims (11)

At least four layers of resin layer C formed from thermoplastic resin composition c, resin layer A formed from thermoplastic resin composition a, resin layer B formed from curable resin composition b, and protective film D In the resin laminate with a protective film formed by laminating in this order,
Resin layer with a protective film having a pencil hardness on the surface of the resin layer B of 5H or more and a water vapor permeability of the protective film D of 3 g / (m ² · 24h) or more and 40 g / (m ² · 24h) or less body. 2. The resin with a protective film according to claim 1, wherein a difference between the warp after the environmental test (LA) and the warp before the environmental test (LB) is −2.0 mm or more and 2.0 mm or less. Laminated body.
(Environmental test): Leave in a constant temperature and humidity chamber adjusted to 85 ° C. and 85% RH for 3 hours.   The absolute value of the difference of the glass transition temperature of the said resin layer A and the said resin layer C is less than 30 degreeC, The resin laminated body with a protective film of Claim 1 or 2 characterized by the above-mentioned.   The resin laminate with a protective film according to any one of claims 1 to 3, wherein a pencil hardness of the surface of the resin layer A is 3H or more.   The resin laminate with a protective film according to any one of claims 1 to 4, wherein the thermoplastic resin composition a contains an acrylic resin as a main component.   The resin laminate with a protective film according to any one of claims 1 to 5, wherein the thermoplastic resin composition c contains a polycarbonate-based resin as a main component.   7. The resin laminate with a protective film according to claim 1, wherein the resin layer B has a thickness of 5 μm to 20 μm.   The thickness of the base material layer in the protective film D is 10-200 micrometers, The resin laminated body with a protective film of any one of Claim 1 to 7 characterized by the above-mentioned.   The molded object with a protective film obtained by thermoforming the resin laminated body with a protective film of any one of Claim 1 to 8.   A molded product obtained by thermoforming the resin laminate with protective film according to any one of claims 1 to 9, and then peeling the protective film.   The resin laminated body with a protective film of any one of Claim 1 to 10 WHEREIN: The molded object obtained by peeling after forming a protective film and thermoforming.

Images