JP2015189175A - laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate comprising a plastic using isosorbide being a plant-derived monomer, as a raw material, which has surface hardness equivalent to or higher than a polycarbonate resin of a homopolymer using only the isosorbide as a dihydroxy compound constitutional unit and has excellent adhesion and impact resistance.SOLUTION: The laminate comprises a layer (layer A) comprising a polycarbonate resin and a layer (layer B) other than the Layer A, the polycarbonate resin having a structural unit (a) derived from a dihydroxy compound having a specific structure and a structural unit (b) derived from the other dihydroxy compound. The layer B comprises a resin having a structural unit derived from a polyfunctional acrylate.

Description

  The present invention is a laminate having a layer obtained by curing an active energy ray-curable resin composition on a substrate such as a film, a sheet, or a molded product. It has the characteristics of excellent surface hardness and adhesion. Such a laminated body is suitable as a display body protective cover for industrial electronic devices such as mobile phones. Specifically, the present invention relates to a laminate having excellent surface hardness and adhesion, good dimensional stability (low curling property), excellent impact resistance, and good wet heat resistance.

  Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, ABS, MS resin, AS resin and other styrene resins, vinyl chloride resin, cellulose acetate such as triacetyl cellulose, etc. Lightweight, easy processability, impact resistance, etc. are especially excellent, so containers, instrument panels, packaging materials, various housing materials, optical disk substrates, plastic lenses, liquid crystal displays, plasma displays, and other display device substrates It is used for various uses.

  In industrial electronic devices with display bodies such as mobile phones and devices with optical lenses, with the diversification of design, thinning, and large area, there is an increasing demand for thinning the display cover. At present, acrylic resin sheets and polycarbonate resin sheets are generally used. In the case of a polycarbonate resin sheet, although impact resistance is high, there is a disadvantage that pencil hardness is low. On the other hand, the acrylic resin sheet has a drawback that it has a higher pencil hardness than polycarbonate but is easily broken by impact.

  In addition, these plastic substrates have a surface hardness lower than that of glass and are easily damaged. Transparent resins such as polycarbonate and acrylic have the disadvantage that the original transparency or appearance of the resin is significantly impaired. It makes it difficult to use plastic substrates in fields that require wear. For this reason, there is a need for an active energy ray-curable hard coat material (coating material) that imparts wear resistance to the surface of these plastic substrates.

  By the way, polyacrylate resin, polycarbonate resin and the like are generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the depletion of petroleum resources, and provision of materials from plastics using raw materials obtained from biomass resources such as plants is required. In addition, since there is a concern that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, etc., plastics made from plant-derived monomers that are carbon neutral in disposal after use Development of materials from is required.

  Conventionally, it has been proposed to obtain a polycarbonate resin by transesterification with diphenyl carbonate using isosorbide as a plant-derived monomer (see, for example, Patent Document 1). Attempts have also been made to improve the rigidity of homopolycarbonate resins made of isosorbide by copolymerizing isosorbide and an aliphatic dihydroxy compound (see, for example, Patent Document 2).

Among them, many polycarbonates obtained by polymerizing 1,4-cyclohexanedimethanol or the like, which is an alicyclic dihydroxy compound, have been proposed (see, for example, Patent Documents 3 to 5). In the above-mentioned patent document, a polycarbonate resin using isosorbide has been proposed.
Furthermore, a resin molded product obtained by injection-molding a polycarbonate resin composition containing a carbonate having a structural unit derived from isosorbide and an antioxidant into a sheet shape and applying a hard coat treatment to at least one surface (Patent Document 6) Have been proposed).

British Patent No. 1079686 International Publication No. 04/111106 Pamphlet JP-A-6-145336 Japanese Patent Publication No. 63-12896 JP 2008-24919 A JP 2009-102537 A

However, the polycarbonates as described in the references 1 to 5 are required to have further hardness depending on the intended use, and the molded product needs to maintain the hardness and the shape. Further, as in Cited Document 6, a laminate in which a homopolymer polycarbonate resin containing only isosorbide as a dihydroxy compound structural unit and subjected to a hard coat treatment on the surface has insufficient adhesion between the polycarbonate resin and the hard coat. Therefore, it was not suitable for use as a surface protection member or optical glass.
Therefore, the problem to be solved by the present invention is to provide a laminate having improved hardness, good adhesion, and excellent impact resistance as compared with the polycarbonate resin alone containing isosorbide as in the above patent document. is there.

As a result of intensive studies to solve the above problems, the present inventors have found that a laminate having the structure of the present invention can solve the above problems. That is, the present invention is as follows.
[1] A layer containing a polycarbonate resin having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound ( A layer)
And a laminate having a layer (B layer) obtained by curing an active energy ray-curable resin composition containing polyfunctional (meth) acrylate.

(However, the case where the structure represented by the general formula (1) is a part of —CH ₂ —OH is excluded.) [2] The structural unit (b) in the polycarbonate resin is an aliphatic dihydroxy compound and The laminate according to [1], which is a structural unit derived from at least one compound selected from the group consisting of alicyclic dihydroxy compounds.
[3] The dihydroxy compound having a structure represented by the general formula (1) is a compound represented by the following general formula (2), according to any one of [1] or [2] Laminated body.

[4] The layered product according to any one of [1] to [3], wherein the B layer is cured by active energy rays.
[5] The active energy ray-curable resin composition is an active energy ray-curable resin composition containing an acrylic copolymer (α),
The acrylic copolymer (α) is a layer formed by curing an active energy ray-curable resin composition obtained by adding the compound (γ) to the following copolymer (β). The laminate according to any one of [1] to [4], wherein:
Copolymer (β): Copolymer compound (γ) of silicone monomer (A) represented by structural formula (I), (meth) acrylate (B) having an epoxy group and other copolymerizable monomer (C) ): Compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each a methyl group or a phenyl group, n is an integer of 10 to 100, and R ³ And R ⁴ may be the same as or different from each other, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.
[6] The laminate according to [5], wherein the active energy ray-curable resin composition contains 0.05 to 10% by weight of the acrylic copolymer (α).
[7] The monomer (C) that can be copolymerized with the acrylic copolymer (α) of the active energy ray-curable resin composition is at least one selected from linear or branched alkyl (meth) acrylates having 4 to 22 carbon atoms. The laminate according to [5] or [6], comprising one (meth) acrylate selected.
[8] A display front plate comprising the laminate according to any one of [1] to [7].
[9] A front plate of a tablet personal computer comprising the laminate according to any one of [1] to [7].
[10] A front panel of a vehicle-mounted display comprising the laminate according to any one of [1] to [7].

According to the present invention, a laminate having not only low optical distortion but also excellent impact resistance, hard coat adhesion, surface hardness, and wet heat resistance can be obtained, and injection of electrical / electronic parts, automotive parts, etc. It becomes possible to provide resin molded products that can be applied to a wide range of fields such as molding applications, camera lenses, finder lenses, lenses such as CCD and CMOS lenses, and optical applications such as optical disks, optical materials, and optical components.

In the following, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. .
In the present specification, the (meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group. The same applies to (meth) acryl and (meth) acrylate.
Further, in the present specification, “to” is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value.

1. Laminate The laminate of the present invention is as follows.
Layer (A layer) containing a polycarbonate resin having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound
And a laminate having a layer (B layer) obtained by curing an active energy ray-curable resin composition containing polyfunctional (meth) acrylate.

(However, the case where the structure represented by the general formula (1) is a part of —CH ₂ —OH is excluded.)

Arbitrary forms and shapes can be adopted as the A layer of the present invention, and examples thereof include a film, a sheet, and a molded body.
The A layer of the present invention preferably has a thickness of 0.05 mm or more, more preferably 0.075 mm or more, and more preferably 0.1 mm or more when importance is placed on the lightweight compact. Most preferred. For example, in order to reduce the thickness when used as a display body, it is preferably 8 mm or less, more preferably 6 mm or less, and most preferably 4 mm or less.

The B layer in the present invention is a layer formed by curing the active energy ray-curable resin composition, but the thickness of the layer after curing is preferably 2 μm or more from the viewpoint of ensuring high hardness, More preferably, it is 5 μm or more, and most preferably 8 μm or more. Further, it is preferably 100 μm or less from the viewpoint that the distortion (crack) of the layer due to curing shrinkage is unlikely to occur, and the destruction (crack) of the B layer in a humid heat environment is unlikely to occur.
It is more preferably 0 μm or less, and most preferably 25 μm or less.

  In the laminate of the present invention, the arrangement of the A layer and the B layer is not particularly limited. Each layer may be formed so as to be directly adjacent to each other, and may have other layers such as a primer layer for further improving the adhesion between the layers. In order to obtain the effect of the present invention, the B layer needs to be the outermost surface layer.

2. Layer A The layer A of the present invention is a polycarbonate having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound. It is a layer containing a resin.

(However, the case where the structure represented by the general formula (1) is part of —CH ₂ —OH is excluded.) (1) Polycarbonate resin and resin composition based thereon Polycarbonate resin according to the present invention is obtained below. The polycarbonate resin and the resin composition based thereon will be described in detail.

[Polycarbonate resin]
<Raw material>
(Dihydroxy compound)
The polycarbonate resin used in the present invention (hereinafter sometimes referred to as “resin used in the present invention”) is a dihydroxy compound having a structure represented by the following general formula (1) as a part of the structure (hereinafter referred to as “ At least the structural unit (a) derived from “dihydroxy compound used in the present invention”. That is, the dihydroxy compound used in the present invention includes two hydroxyl groups and at least a structure represented by the following general formula (1) in a part of the structure.

(However, the case where the structure represented by the general formula (1) is a part of —CH 2 —O—H is excluded.)

The dihydroxy compound used in the present invention is not particularly limited as long as it has a structure represented by the above general formula (1) in a part of the structure, but specifically, diethylene glycol, triethylene glycol Oxyalkylene glycols such as tetraethylene glycol, 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-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene 9,9-bis (4- (3-hydroxy- 2,2-dimethylpropoxy) phenyl) fluorene and the like, compounds having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain, and dihydroxy compounds represented by the following general formula (2) Although the compound which has cyclic ether structures, such as the anhydrosugar alcohol represented and the spiroglycol represented by following General formula (3), is mentioned, From the viewpoints of ease of handling, handling, reactivity during polymerization, and hue of the polycarbonate resin obtained, diethylene glycol and triethylene glycol are preferred. From the viewpoint of heat resistance, anhydrous sugar alcohols and compounds having a cyclic ether structure are preferred. preferable.
These may be used alone or in combination of two or more depending on the required performance of the resin to be obtained.

Examples of the dihydroxy compound represented by the general formula (2) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. It may be used.
Of these dihydroxy compounds, it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the light resistance of the resin. Among them, it is produced from various starches that are abundant as plant-derived resources and are easily available. Isosorbide obtained by dehydrating and condensing sorbitol is most preferable from the viewpoints of availability and production, light resistance, optical properties, moldability, heat resistance, and carbon neutral.

  The resin used in the present invention may contain a structural unit (b) derived from a dihydroxy compound other than the dihydroxy compound used in the present invention (hereinafter sometimes referred to as “other dihydroxy compound”). Examples of the dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, Aliphatic dihydroxy compounds such as 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin Methanol, 2,3-decalin methanol, 2,3-norbornane methanol, 2,5-norbornane methanol, 1,3-adamantane dimethanol, dihydroxy compound alicyclic hydrocarbon and the like and the like.

2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5- Dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1 , 1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) Enyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 ′ -Dichlorodiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2) Aromatic bisphenols such as -methylphenyl) fluorene can also be used.

  The structural unit (b) in the polycarbonate resin is preferably a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound. That is, from the viewpoint of the light resistance of the resin, at least one compound selected from the group consisting of an aliphatic dihydroxy compound that is a dihydroxy compound having no aromatic ring structure in the molecular structure and an alicyclic hydrocarbon dihydroxy compound is used. As the aliphatic dihydroxy compound, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are particularly preferable. As the alicyclic hydrocarbon dihydroxy compound, 1,4 is particularly preferable. -Cyclohexanedimethanol and tricyclodecanedimethanol are preferred.

  By using these other dihydroxy compounds, it is possible to obtain effects such as improvement in flexibility of the resin, improvement in heat resistance, improvement in moldability, etc., but inclusion of structural units derived from other dihydroxy compounds If the ratio is too large, mechanical properties and heat resistance may be reduced. Therefore, the dihydroxy compound having a structure represented by the general formula (1) as a part of the structure with respect to all dihydroxy compounds. The ratio of the derived structural unit (a) is preferably 50 mol% or more, more preferably 55 mol% or more, and most preferably 60 mol% or more. On the other hand, the upper limit is preferably 95 mol% or less, more preferably 85 mol% or less, and particularly preferably 75 mol% or less. If this ratio is too small, the moisture and heat resistance properties tend to decrease, while if too large, the impact resistance tends to deteriorate.

  One of the characteristics of the resin molded product of the present invention is that, as described above, a structural unit derived from a dihydroxy compound having a structure represented by the general formula (1) as a part of the structure for all dihydroxy compounds (a ) In the specific range as described above. Thereby, the optical distortion generally expressed by the birefringence or retardation of the resin can be made lower than that of a molded product using a conventional polycarbonate resin.

The dihydroxy compound used in the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer, etc. Since the dihydroxy compound used in the invention is easily altered, it is preferable to include a basic stabilizer. Basic stabilizers include Group 1 or Group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites in the Long Periodic Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium Basic ammonium compounds such as um hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole And amine compounds such as aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferred, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferred because of their effects and ease of distillation removal described below.

  Although there is no restriction | limiting in particular in content in the dihydroxy compound used for this invention of these basic stabilizers, if there is too little, there exists a possibility that the effect which prevents the quality change of the dihydroxy compound used for this invention may not be acquired, and too much. Since it may cause modification of the dihydroxy compound used in the present invention, it is usually 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound used in the present invention. It is.

  Further, when the dihydroxy compound used in the present invention containing these basic stabilizers is used as a raw material for producing polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. It is preferable to remove the basic stabilizer by ion exchange or distillation before using it as a raw material for producing the resin in order to deteriorate the initial hue and consequently deteriorate the light resistance of the molded product.

  When the dihydroxy compound used in the present invention has a cyclic ether structure such as isosorbide, it is easily oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen scavenger or handle under a nitrogen atmosphere. When isosorbide is oxidized, decomposition products such as formic acid may be generated. For example, when isosorbide containing these decomposition products is used as a raw material for the production of polycarbonate resin, the resulting resin may be colored, and not only the physical properties may be significantly degraded, but also the polymerization reaction may be affected. This is not preferable because a high molecular weight polymer may not be obtained.

  The dihydroxy compound used in the present invention is preferably subjected to distillation purification in order to remove the oxidative decomposition product and the above-mentioned basic stabilizer. The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress thermal denaturation, it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of ℃ or less.

  By such distillation purification, the dihydroxy compound used in the present invention is made to have a formic acid content in the dihydroxy compound used in the present invention of 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less. When a dihydroxy compound containing is used as a resin production raw material, it is possible to produce a resin excellent in hue and thermal stability without impairing polymerization reactivity. The formic acid content is measured by ion chromatography.

(Carbonated diester)
The polycarbonate resin used in the present invention can be obtained by polycondensation by a transesterification reaction using the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester as raw materials.
As a carbonic acid diester used, what is normally represented by following General formula (4) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

(In General Formula (4), A1 and A2 are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group, and A1 and A2 May be the same or different.)

Examples of the carbonic acid diester represented by the general formula (4) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Diphenyl carbonate and substituted difel carbonate are preferable, and diphenyl carbonate is particularly preferable. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting resin. It is preferable to use one.
The resin used in the present invention is a polycarbonate resin having the specific structural unit (a), and the resin may be used as a polycarbonate resin composition by adding other additives within a range not impairing the gist of the present invention. Good.

<Transesterification reaction catalyst>
The resin used in the present invention can be produced by transesterifying the dihydroxy compound containing the dihydroxy compound used in the present invention with a carbonic acid diester as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

The transesterification reaction catalyst (hereinafter sometimes simply referred to as “catalyst” or “polymerization catalyst”) that can be used in the production of the resin used in the present invention affects the light transmittance at a wavelength of 350 nm and the yellow index value. Can give.
The catalyst used is not limited as long as the light resistance can be satisfied, that is, the light transmittance at a wavelength of 350 nm or the yellow index can be set to a predetermined value. Basic compounds such as metal compounds of Group 2 (hereinafter simply referred to as “Group 1” and “Group 2”), basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds, and the like. It is done. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.

It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.
In addition, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

Examples of the Group 1 metal compound include sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, sodium acetate, sodium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, disodium hydrogen phosphate, phenyl phosphoric acid. 2
Sodium, sodium alcoholate or phenolate, sodium compounds such as disodium salt of bisphenol A, potassium hydroxide, potassium bicarbonate, potassium carbonate, potassium acetate, potassium stearate, potassium borohydride, potassium borohydride, benzoic acid Potassium acid, dipotassium hydrogen phosphate, dipotassium phenyl phosphate, potassium alcoholate or phenolate, potassium compounds such as dipotassium salt of bisphenol A, lithium hydroxide, lithium hydrogen carbonate, lithium carbonate, lithium acetate, stearic acid Lithium, lithium borohydride, lithium phenyl borohydride, lithium benzoate, dilithium hydrogen phosphate, dilithium phenyl phosphate, lithium alcoholate or phenolate, bisphenol A 2 Lithium compounds such as thium salts, cesium hydroxide, cesium bicarbonate, cesium carbonate, cesium acetate, cesium stearate, cesium borohydride, cesium phenyl borohydride, cesium benzoate, 2 cesium hydrogen phosphate, 2 cesium phenyl phosphate Cesium compounds such as alcoholate or phenolate of cesium, dicesium salt of bisphenol A, and the like, among which lithium compounds are preferable.

  Examples of the Group 2 metal compound include calcium compounds such as calcium hydroxide, calcium bicarbonate, calcium carbonate, calcium acetate, and calcium stearate, and barium such as barium hydroxide, barium bicarbonate, barium carbonate, barium acetate, and barium stearate. Compounds, magnesium compounds such as magnesium hydroxide, magnesium hydrogen carbonate, magnesium carbonate, magnesium acetate, magnesium stearate, strontium hydroxide, strontium hydrogen carbonate, strontium carbonate, strontium acetate, strontium stearate, etc. Of these, magnesium compounds, calcium compounds and barium compounds are preferred. From the viewpoint of polymerization activity and the hue of the obtained polycarbonate resin, magnesium compounds are preferred. And at least one metal compound is more preferably selected from the group consisting of calcium compound, most preferably a calcium compound.

  Examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.

Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole,
Examples include 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

  The amount of the polymerization catalyst used is preferably 0.1 μmol to 300 μmol, preferably 0.5 μmol to 100 μmol per 1 mol of all dihydroxy compounds used in the polymerization. Among these, from lithium and a metal of Group 2 of the long-period periodic table When using at least one metal compound selected from the group consisting of, in particular, when using at least one metal compound selected from the group consisting of a magnesium compound and a calcium compound, the amount of metal per 1 mol of the total dihydroxy compound used, Usually, it is 0.1 μmol or more, preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more. Further, the upper limit is usually 20 μmol, preferably 10 μmol, more preferably 3 μmol, particularly preferably 1.5 μmol, and most preferably 1.0 μmol.

  If the amount of the catalyst is too small, the polymerization rate will slow down. As a result, when trying to obtain a resin with the desired molecular weight, the polymerization temperature will have to be increased, and the hue and light resistance of the resulting resin will deteriorate. The unreacted raw material volatilizes during the polymerization, and the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention to the carbonic acid diester represented by the general formula (4) may collapse, and may not reach the desired molecular weight. is there. On the other hand, when the amount of the polymerization catalyst used is too large, the hue of the resulting resin is deteriorated, and the light resistance of the resin may be deteriorated.

Further, Group 1 metals, especially lithium, sodium, potassium and cesium, especially sodium, potassium and cesium, may have a bad influence on the hue when contained in the resin in large quantities, and the metal is only from the catalyst used. However, the total amount of these compounds in the resin is usually 20 ppm by weight or less, preferably 2 ppm by weight or less, more preferably 1.5 wt. ppm or less, more preferably 1.2 ppm by weight or less, particularly preferably 0.8 ppm by weight or less, and most preferably 0.7 ppm by weight or less.
The amount of metal in the resin can be measured using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) after recovering the metal in the resin by a method such as wet ashing.

<Manufacturing method>
The polycarbonate resin used in the present invention is obtained by polycondensation of a dihydroxy compound containing the dihydroxy compound used in the present invention and a carbonic acid diester by a transesterification reaction. The raw material dihydroxy compound and the carbonic acid diester are converted before the transesterification reaction. It is preferable to mix uniformly in the raw material preparation tank. Moreover, the raw material uniformly mixed in the raw material preparation tank or the like may be subjected to a transesterification reaction after being stored in the raw material storage tank or the like.

  The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated. The hue of the polycarbonate resin thus obtained may deteriorate, which may adversely affect light resistance.

The operation of mixing the dihydroxy compound containing the dihydroxy compound used in the present invention, which is the raw material of the resin used in the present invention, and the carbonic acid diester is an oxygen concentration of 10 vol% or less, more preferably 0.0001 vol% to 10 vol%, and more preferably 0.0001 vol% to It is preferable to carry out in an atmosphere of 5 vol%, particularly 0.0001 vol% to 1 vol%, from the viewpoint of preventing hue deterioration.

In order to obtain the polycarbonate resin used in the present invention, the carbonic acid diester represented by the general formula (4) is 0.90 to 1.0 with respect to all dihydroxy compounds including the dihydroxy compound used in the present invention used in the reaction. The molar ratio is preferably 20 and more preferably 0.95 to 1.10.
When this molar ratio is reduced, the amount of terminal hydroxyl groups of the produced resin increases, the thermal stability of the polymer deteriorates, coloring occurs during molding, the rate of transesterification reaction decreases, the desired high molecular weight The body may not be obtained.

Moreover, when this molar ratio becomes large, the rate of the transesterification reaction may decrease or it may be difficult to produce a resin having a desired molecular weight. The decrease in the transesterification reaction rate may increase the thermal history during the polymerization reaction, and may deteriorate the hue and light resistance of the resulting resin.
Furthermore, when the molar ratio of the carbonic acid diester represented by the general formula (4) is increased with respect to all the dihydroxy compounds including the dihydroxy compound used in the present invention, the amount of residual carbonic acid diester in the resulting resin increases. These may be unfavorable because they may absorb ultraviolet rays and deteriorate the light resistance of the resin. The concentration of the carbonic acid diester represented by the general formula (4) remaining in the resin used in the present invention is preferably 60 ppm by weight or less, more preferably 50 ppm by weight or less, and particularly preferably 40 ppm by weight or less. . In reality, the resin may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.

In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.
In the initial stage of polymerization, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum, but the jacket temperature at each molecular weight stage. Appropriate selection of the internal temperature and pressure in the reaction system is important from the viewpoints of hue and light resistance. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention may not be achieved.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80 to 150 ° C, particularly preferably 100 to 130 ° C. If the temperature of the refrigerant is too high, the amount of reflux decreases and the effect is reduced. On the other hand, if the temperature is too low, the distillation efficiency of the monohydroxy compound that should be distilled off tends to decrease. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, while keeping the hue, thermal stability, light resistance, etc. of the finally obtained polycarbonate resin, The selection of the quantity is important.
The resin used in the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is that at the initial stage of the polymerization reaction, Since there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate. In the late stage of the polymerization reaction, in order to shift the equilibrium to the polymerization side, This is because it is important to sufficiently distill off the produced monohydroxy compound. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

The reactor used in the production of the polycarbonate resin used in the present invention may be at least two or more as described above, but from the viewpoint of production efficiency, three or more, preferably 3 to 5, particularly preferably. Are four groups.
If there are two or more reactors, a plurality of reaction stages with different conditions may be set in the reactor, or the temperature and pressure may be continuously changed.

The polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or directly to the polymerization tank. From the viewpoint of supply stability and control of the polymerization reaction, the raw material line supplied to the polymerization tank is used. It is preferable to install and supply a catalyst supply line in the middle. The state of the polymerization catalyst to be supplied includes a solid and a liquid. From the viewpoint of quantitative supply, a liquid is preferable.
If the temperature of the polymerization reaction is too low, the productivity decreases due to a decrease in the reaction rate or the reaction time, and if it is too high, not only the evaporation of the monomer is caused but also the decomposition and coloring of the resin may be promoted. .

  Specifically, the reaction in the first stage is performed at 140 to 270 ° C., preferably 180 to 240 ° C., more preferably 200 to 230 ° C. as the maximum internal temperature of the polymerization reactor. The monohydroxy compound generated is removed from the reaction system at a pressure of 1 kPa, preferably 70 kPa to 5 kPa, more preferably 30 kPa to 10 kPa (absolute pressure) for 0.1 hours to 10 hours, preferably 0.5 hours to 3 hours. Carried out while distilling.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. 200 Pa or less, maximum internal temperature of 210 ° C. to 270 ° C., preferably 220 ° C. to 250 ° C., usually 0.1 hour to 10 hours, preferably 1 hour to 6 hours, particularly preferably 0.5 hour. Perform for ~ 3 hours.

In particular, in order to suppress resin coloring and thermal deterioration and obtain a resin having good hue and light resistance, the maximum internal temperature in all reaction stages is preferably less than 250 ° C., particularly 225 ° C. to 245 ° C.
In order to suppress the decrease in the polymerization rate in the latter half of the polymerization reaction and minimize degradation due to thermal history, it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.

If the polymerization temperature is increased and the polymerization time is excessively long in order to obtain a resin having a predetermined molecular weight, the ultraviolet transmittance of the obtained resin decreases and the yellow index (YI) value tends to increase.
The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
The polycarbonate resin obtained as described above is usually cooled and solidified after polycondensation and pelletized with a rotary cutter or the like.

The method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or from the final polymerization reactor in a molten state, uniaxial or biaxial extrusion. The resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again Alternatively, a method may be mentioned in which resin is supplied to a biaxial extruder, melt-extruded, cooled and solidified, and pelletized.

At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.
The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the resin, but is usually 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C, and more preferably 230 ° C to 260 ° C. When the melt kneading temperature is lower than 150 ° C., the melt viscosity of the resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the thermal deterioration becomes severe, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

  When producing the polycarbonate resin used in the present invention, it is desirable to install a filter in the extruder in order to prevent foreign substances from entering. The filter installation position is preferably on the downstream side of the extruder, and the foreign matter removal size (opening) of the filter is preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 μm or less, more preferably 10 μm or less.

Extrusion of the resin used in the present invention is preferably carried out in a clean room having a higher degree of cleanliness than Class 6 as defined in JIS B 9920 (2002), and more preferably in a clean room in order to prevent foreign matter from being mixed after extrusion. It is desirable.
Further, when cooling the extruded resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

The molecular weight of the resin used in the present invention thus obtained can be represented by a reduced viscosity, and the lower limit of the reduced viscosity is 0.10 dL / g or more, preferably 0.20 dL / g or more, and More preferably, it is 30 dL / g or more. The upper limit of the reduced viscosity is more preferably 0.45 dL / g or less and 0.40 dL / g or less.
If the reduced viscosity of the resin is too low, the mechanical strength of the molded product may be small, and if it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease.

The reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent and precisely preparing a resin concentration of 0.6 g / dL.
Furthermore, the lower limit of the concentration of the terminal group represented by the following general formula (5) (referred to as “terminal phenyl group concentration”) of the resin used in the present invention is preferably 20 μeq / g, more preferably 40 μeq / g, particularly preferably Is 50 μeq / g, while the upper limit is preferably 160 μeq / g, more preferably 140 μeq / g, particularly preferably 100 μeq / g.

If the concentration of the terminal group represented by the following general formula (5) is too high, even if the hue at the time of polymerization or at the time of molding is good, the hue after UV exposure may be deteriorated. Thermal stability may be reduced.
In order to control the concentration of the terminal group represented by the following general formula (5), the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention as the raw material and the carbonic acid diester represented by the general formula (4) is set. In addition to controlling, a method for controlling the kind and amount of the catalyst at the time of the transesterification reaction, the polymerization pressure and the polymerization temperature can be used.

  When using the substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate as the carbonic acid diester represented by the general formula (4) to produce the resin used in the present invention, phenol and substituted phenol are by-produced in the resin. Although it cannot be avoided, phenol and substituted phenols also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, and may also cause odor during molding. . The resin contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction, it is devolatilized. It is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less using a horizontal reactor having excellent performance or an extruder with a vacuum vent. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight.

These aromatic monohydroxy compounds may have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.
When the equivalent number of hydrogen atoms (H) bonded to the aromatic ring of the resin used in the present invention is (A) and the equivalent number of hydrogen atoms (H) bonded to other than the aromatic ring is (B), the aromatic ring The ratio of the number of equivalents of hydrogen atoms (H) bonded to the number of equivalents of all hydrogen atoms (H) is represented by A / (A + B), but the light resistance has an ultraviolet absorbing ability as described above. Since the aromatic ring may influence, the value of A / (A + B) is preferably 0.05 or less, more preferably 0.03 or less, particularly preferably 0.02 or less, suitably 0.01 or less. A / (A + B) can be quantified by 1H-NMR.

[Other additives]
As described above, the polycarbonate resin used in the present invention is generally used as a polycarbonate resin composition by adding other additives to the extent that the gist of the present invention is not impaired.
Examples of such additives include antioxidants, acidic compounds, ultraviolet absorbers, light stabilizers, inorganic fillers, and the like.
The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, phosphite antioxidants and sulfur antioxidants, and phenolic antioxidants and / or phosphites. More preferred are system antioxidants.

Examples of the phenolic antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-
Hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) Compounds such as undecane are listed.

  Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, preferably pentaerythris Lithyl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is more preferred.

  Examples of the phosphite antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-) tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaeri Li diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

  Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and tris (2,4-di-tert-butylphenyl) phosphite is more preferred.

  Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3 -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

The content of the antioxidant is preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more, particularly preferably 0.05 parts by weight or more, on the other hand, preferably 100 parts by weight of the polycarbonate resin. 1 part by weight or less, more preferably 0.7 part by weight or less, particularly preferably 0.5 part by weight or less. If the content of the antioxidant is excessively small, the coloring suppression effect during molding may be insufficient. Also, if the content of the antioxidant is excessively large, the amount of deposits on the mold during injection molding increases or the number of deposits on the roll increases when forming a film by extrusion. The surface appearance of the product may be damaged.

  Examples of acidic compounds include hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid Acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid , Bronsted acids such as picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof.

Among these acidic compounds or derivatives thereof, sulfonic acids or esters thereof are preferable, and p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.
These acidic compounds can be added in the production process of the resin composition as compounds that neutralize the basic transesterification catalyst used in the above-described resin polycondensation reaction.

  The compounding amount of the acidic compound is 0.00001 part by weight or more and 0.1 part by weight or less, preferably 0.0001 part by weight or more and 0.01 part by weight or less, based on 100 parts by weight of the resin. Preferably they are 0.0002 weight part or more and 0.001 weight part or less. If the blending amount of the acidic compound is excessively small, it may not be possible to sufficiently suppress coloring when the residence time of the resin composition in the injection molding machine becomes long during injection molding. Moreover, when there are too many compounding quantities of an acidic compound, the hydrolysis resistance of a resin composition may fall remarkably.

The content in the case of using an ultraviolet absorber or a light stabilizer is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the resin.
Examples of the inorganic filler include glass fiber, glass milled fiber, glass flake, glass bead, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc, mica, and wallast. Calcium silicate such as knight; carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whisker, etc. It is done. Among these, glass fiber filler, glass powder filler, glass flake filler; carbon fiber filler, carbon powder filler, carbon flake filler; various whiskers, mica Talc is preferred. More preferably, glass fiber, glass flake, glass milled fiber, carbon fiber, wollastonite, mica and talc are mentioned.

The compounding amount of the inorganic filler is usually 1 part by weight or more and 100 parts by weight or less, preferably 3 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the resin. When the blending amount of the inorganic filler is excessively small, the reinforcing effect is small, and when it is excessively large, the appearance tends to deteriorate.
The resin composition used in the present invention includes, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS and other synthetic resins, polylactic acid, polybutylene succin It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as nate and rubber.

In order to produce the above resin composition, the above components are mixed simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, extruder, etc. be able to. Furthermore, a nucleating agent, a flame retardant, an inorganic filler, an impact modifier, a foaming agent, a dye / pigment and the like that are usually used in the resin composition may be contained within a range not impairing the object of the present invention.
The resin composition preferably contains at least one metal compound selected from the group consisting of a lithium compound and a metal of Group 2 of the long-period periodic table, and the content of the metal compound is the amount of metal. Is preferably 0.1 ppm by weight or more, more preferably 0.5 ppm by weight or more, and particularly preferably 0.7 ppm by weight or more. Further, the upper limit is preferably 20 ppm by weight, more preferably 10 ppm by weight, particularly preferably 3 ppm by weight, most preferably 1.5 ppm by weight, and most preferably 1.0 ppm by weight.

(2) Resin molded product <Physical properties and characteristics>
The resin molded product of the present invention is obtained by molding the resin composition used in the present invention according to a conventional method.

  In the resin molded product of the present invention, for example, the ratio of the area where the maximum phase difference in the plate-like portion of the molded product is 250 nm or less and the phase difference in the same portion is 150 nm or less is based on the total area of the molded product. Thus, a molded product having a small optical distortion as a whole can be obtained. A smaller optical distortion is more suitable for use in optical applications, but there is generally a limit to reducing the optical distortion.

  The molded product of the present invention can be used for liquid crystal display devices such as televisions, computer monitors, various touch panels, displays, and tablet personal computers. In such applications, the molded product is flat or curved. Often used as a member.

  Further, for example, in a molded product in which such a flat plate and a frame (bezel) are combined, or a molded product in which the housing and the flat plate are integrally formed by two-color molding or the like, the flat plate portion It is important to reduce the optical distortion.

  Further, for example, when used in a liquid crystal display device such as a television, a computer monitor, and various touch panels, it may be used as a curved curved member instead of a flat surface from the viewpoint of visibility and design. In this case, the upper part of the plate in the present invention shows a curved curved part.

<Manufacturing method>
The molded article of the present invention can be produced by various methods.
Manufacture of the molded article of the present invention can also be performed by an injection molding method. In the case of injection molding, a resin molded product having a complicated shape can be manufactured by using a mold corresponding to the shape of the molded product. Injection molding is performed by an injection molding machine, and suitable molding conditions are appropriately set according to the resin composition to be used and the product shape. The molding conditions include cylinder temperature, mold temperature, injection pressure, holding pressure, screw rotation speed, cushion amount, injection speed, injection time, pressure holding time, cooling time, and the like.

  In the production of the molded article of the present invention by the injection molding method, the cylinder temperature is preferably 200 ° C. to 300 ° C., more preferably 210 ° C. to 280 ° C., particularly preferably 220 ° C. to 270 ° C., most preferably 230 ° C. to 260 ° C. If the cylinder temperature is too high, the resin composition tends to thermally decompose and the resin molded product tends to be colored. On the other hand, if the cylinder temperature is too low, the melt viscosity of the resin composition increases, resulting in molding defects and increased optical distortion. It tends to be.

The mold temperature is preferably 40 ° C to 120 ° C, more preferably 50 ° C to 100 ° C, and particularly preferably 60 ° C to 80 ° C. If the mold temperature is too high, the productivity of the molded product tends to decrease, while if too low, the optical distortion tends to increase.

  As a means for obtaining the molded product of the present invention, as described above, the ratio of the structural unit (a) derived from the dihydroxy compound to the total dihydroxy compound is within a specific range, and the cylinder temperature and the mold temperature are set as described above. It is mentioned to be a specific range. The molded article of the present invention can be produced by combining these means alone or in an appropriate combination.

  The production of the molded product of the present invention can also be performed by an extrusion molding method. In the case of extrusion molding, a film or sheet having a desired thickness and width can be produced by appropriately selecting the shape of the discharge cap (die) and the clearance between cooling rolls. Extrusion molding is performed by an extrusion molding machine, and suitable molding conditions are appropriately set according to the resin composition to be used and the product shape. Examples of molding conditions include cylinder temperature, roll temperature, screw rotation speed, screw configuration (shape), and discharge rate.

  In the production of the molded article of the present invention by the extrusion extrusion method, the cylinder temperature is preferably 200 ° C. to 300 ° C., more preferably 210 ° C. to 280 ° C., particularly preferably 220 ° C. to 270 ° C., most preferably 230 ° C. ~ 260 ° C. If the cylinder temperature is too high, the resin composition tends to thermally decompose and the resin molded product tends to be colored. On the other hand, if the cylinder temperature is too low, the melt viscosity of the resin composition increases, resulting in molding defects and increased optical distortion. It tends to be.

  The roll temperature is preferably 40 ° C to 160 ° C, more preferably 60 ° C to 145 ° C, and particularly preferably 80 ° C to 130 ° C. If the roll temperature is too high, the productivity of the molded product tends to decrease, while if it is too low, the optical distortion tends to increase.

  By the above manufacturing method, the molded product of the present invention is molded as a molded product having a thickness of 0.05 mm or more and 8 mm or less. When the thickness is within this range, it can be easily used as a molded product having a thickness suitable for optical applications. The thickness of the molded product is preferably 0.075 mm to 6 mm, more preferably 0.01 mm to 4 mm. If the thickness of the molded product is too thin, the moldability may decrease, and the surface hardness and impact resistance may decrease. On the other hand, if the thickness of the molded product is too thick, the molded product may become heavy, optical distortion may increase, and the transparency of the molded product may decrease.

  The molded product of the present invention may have a decorative film layer or a printing layer laminated on at least one surface thereof. By providing the decorative film layer and the printed layer, excellent effects such as improving the appearance of the molded product and improving the scratch resistance of the surface on which the decorative film layer and the printed layer are present are obtained. Lamination | stacking of the decoration film in a metal mold | die and a printing layer can be performed by a conventionally well-known method.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body shape | molded using the polycarbonate resin composition excellent in surface hardness and impact resistance can be provided. This laminate can be used for many purposes as described above, and is particularly suitable for optical applications.

3. B layer B layer of this invention is characterized by being a layer formed by hardening | curing the active energy ray-curable resin composition containing the polyfunctional (meth) acrylate which is an active energy ray-curable compound.

"Active energy ray-curable resin composition"
<Active energy ray-curable compound>
The polyfunctional (meth) acrylate of the present invention is preferably a polyfunctional (meth) acrylate that reacts with the acrylic copolymer (α) from the viewpoint of pencil hardness and adhesion. Furthermore, the polyfunctional (meth) acrylate of the present invention is a compound other than the acrylic copolymer (α) of the present invention described later. Moreover, it is preferable that it is a compound containing two or more (meth) acryloyl groups in a molecule | numerator. Further, the number of functional groups of the (meth) acryloyl group in the polyfunctional (meth) acrylate is preferably 3 or more from the viewpoint of good hardness and scratch resistance of the cured film and high reactivity at the time of curing. 4 or more are particularly preferable. Moreover, 9 or less are preferable from the point which the resin viscosity before hardening is suitable for coating, and 6 or less is especially preferable.

  The polyfunctional (meth) acrylate of the present invention is specifically a polyfunctional (meth) acrylate composed of one or more selected from polyfunctional (meth) acrylate and its urethane-modified product, ester-modified product, and carbonate-modified product. An acrylate derivative. More specifically, the following can be exemplified, but the present invention is not limited thereto as long as the active energy ray-curable resin composition of the present invention can be obtained.

  For example, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate adduct to succinic anhydride, dipentaerythritol to succinic anhydride Polyfunctional acrylates such as pentaacrylate adducts; polyesters such as polyester oligomers (specifically, M8030, M7100, etc., manufactured by Toagosei Co., Ltd.) having side chains or side chain and terminal (meth) acryloyl groups Acrylates: Isophorone diisocyanate (IPDI) isocyanurate, polytetramethylene glycol (PTMG) and hydroxyethyl acrylate ( EA), polyfunctional urethane (meth) acrylates such as hexamethylene diisocyanate (HDI) isocyanate and PTMG reaction product of pentaerythritol triacrylate; oligoesters using polycarbonate diol and pentaerythritol tris Polyester (meth) acrylates having a carbonate bond such as a reaction product of acrylate; Polyurethane (meth) acrylates having a carbonate bond such as a reaction product of IPDI and polycarbonate diol and a reaction product of HEA; Acrylic acid adduct of bisphenol A (Specifically, polyepoxy (meth) acrylates such as EA-1025 manufactured by Shin-Nakamura Chemical Co., Ltd .; triethoxyisocyanuric acid diacrylate, triethoxyisocyanuric acid triac (Specifically, manufactured by Toagosei Co., Ltd. of Aronix M315, M313) Rate triethoxy (meth) acrylates having an isocyanurate ring such as; and their alkylene oxide modification products; polycaprolactone-modified products; and the like. Moreover, these may be used independently and may use 2 or more types together.

  Among them, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, due to viscosity and curability, hardness of the resulting cured film surface, etc. And dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, an alkylene oxide modified product, a caprolactone modified product, and the like are particularly preferable.

<Acrylic copolymer>
The active energy ray-curable resin composition of the present invention is an active energy ray-curable resin composition containing an acrylic copolymer and an active energy ray-curable compound, from the viewpoint of pencil height and adhesiveness. preferable. An acrylic resin (α) is an active energy ray-curable resin composition obtained by adding a compound (γ) to the following copolymer (β). More preferably.

Copolymer (β): Copolymer compound (γ) of silicone monomer (A) represented by structural formula (I), (meth) acrylate (B) having an epoxy group and other copolymerizable monomer (C) ): Compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each a methyl group or a phenyl group, n is an integer of 10 to 100, and R ³ And R ⁴ may be the same as or different from each other, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.

The active energy ray-curable resin composition of the present invention preferably contains 0.05% by weight or more of the acrylic copolymer, and sufficiently exhibits surface slipperiness in the cured film. From the viewpoint of good wool scratch resistance, it is preferably 0.1% by weight or more, particularly preferably 1% by weight or more. Further, it is preferably contained in an amount of 10% by weight or less, the compatibility with the photocurable compound that reacts with the acrylic copolymer is ensured, and the transparency of the cured film is good. However, it is preferably 9% by weight or less, particularly preferably 8% by weight or less, from the viewpoint that the relatively soft acrylic copolymer is not unevenly distributed on the surface and hardness and scratch resistance can be secured.
The acrylic copolymer and the active energy ray-curable compound will be described.

<Acrylic copolymer (α)>
The acrylic copolymer (α) of the present invention is obtained by adding a compound (γ) to the following copolymer (β).

[Copolymer (β)]
The copolymer (β) of the present invention comprises a copolymer of the silicone monomer (A) represented by the structural formula (I), the (meth) acrylate (B) having an epoxy group and other copolymerizable monomers (C). It is a coalescence.
(Silicone monomer (A) represented by structural formula (I))
The silicone monomer (A) of the present invention is a compound represented by the following structural formula (I).

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each a methyl group or a phenyl group, n is an integer of 10 to 100, and R ³ And R ⁴ may be the same as or different from each other, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.
R ¹ is characterized by being a hydrogen atom or a methyl group. From the point that the glass transition temperature (hereinafter sometimes abbreviated as Tg) of the copolymer is increased, and the hardness of the cured film surface is increased. It is preferably a group.

R ² is characterized by being an alkylene group having 1 or more carbon atoms, and is preferably 2 or more, and particularly preferably 3 or more, from the viewpoint of relatively easy availability of raw materials and production (reaction). Moreover, it is characterized by being 12 or less alkylene group, 10 or less is preferable and 8 or less is preferable.
R ³ and R ⁴ are each a methyl group or a phenyl group, and are preferably a methyl group from the viewpoint of relatively easy acquisition and production (reaction) of raw materials. In addition, n is an integer of 10 or more, and 25 or more is preferable and 50 or more is particularly preferable from the viewpoint of sufficient surface slipperiness and satisfactory slipperiness in the cured film. Further, it is characterized by being an integer of 100 or less, preferably 90 or less from the viewpoint of good solubility in the solvent of the raw material and the acrylic copolymer and compatibility with the photocurable compound, 80 or less is particularly preferable.

R ⁵ is characterized by being an alkyl group having 1 or more carbon atoms, and is preferably 2 or more, and particularly preferably 3 or more, from the viewpoint of relatively easy availability of raw materials and production (reaction). Further, the alkyl group is 12 or less, preferably 10 or less, and more preferably 8 or less.

  The specific structure is not particularly limited as long as the effects of the present application can be obtained, but those having polydimethylsiloxane are preferable. For example, polydimethylsiloxane having a methacryloyl group at one end (for example, “Silaplane manufactured by JNC Co., Ltd.). FM0711 "," Silaplane FM0721 "," Silaplane FM0725 ") and other radical-polymerizable monomers. These compounds may be used individually by 1 type, and may use 2 or more types. In addition, among the silicone monomers (A) in the present application, the number average molecular weight (g / mol) of the compound having the highest number average molecular weight is the number having the highest number average molecular weight when two or more kinds of (A) are used. Mean average molecular weight (g / mol).

  Among the silicone monomers (A), the number average molecular weight (g / mol) of the compound having the highest number average molecular weight is not particularly limited, but is usually 1,000 or more, and the surface slipperiness in the cured film is good. In view of (low friction coefficient), 2,000 or more is preferable, and 3,000 or more is more preferable. Moreover, since it is normally 50,000 or less and compatibility with a solvent and an active energy ray hardening compound is favorable, 20,000 or less are preferable and 10,000 or less are more preferable. In particular, it is particularly preferably 4,000 or more and 7,000 or less because the antifouling property is specifically improved.

((Meth) acrylate (B) having epoxy group)
Examples of the (meth) acrylate having an epoxy group of the present invention include (meth) acrylate having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate; 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3 , 4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate and the like (meth) acrylate in which an epoxy group is directly bonded to an alicyclic structure.

  Among these, glycidyl methacrylate and 3,4-epoxycyclohexyl are easy to obtain and easy to modify with a compound (γ) having a carboxyl group and one or more (meth) acryloyl groups in the molecule described later. Particularly preferred are acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and the like. These compounds may be used individually by 1 type, and may use 2 or more types.

  The weight ratio (%) of the (meth) acrylate (B) having an epoxy group in the copolymer (β) is not particularly limited, but is usually 1% by weight or more, and the durability of the surface slipperiness of the cured film is not limited. From the viewpoint of good properties, it is preferably 10% by weight or more, more preferably 20% by weight or more, still more preferably 40% by weight or more, and particularly preferably 50% by weight or more. In addition, the solubility of the acrylic copolymer in a solvent is good, and it is usually 99.9% by weight or less because gelation is difficult to occur during the epoxy-acid reaction of the copolymer (β). 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 70% by weight or less.

(Other copolymerizable monomer (C))
The “other copolymerizable monomer (C)” used in the present invention is not particularly limited as long as the effects of the present application can be obtained, but preferably the reactivity with the epoxy group is low, and the stability of the produced polymer is improved. A monomer that does not decrease, or a structure derived from a monomer that has a rigid skeleton and does not decrease the hardness. Examples of the monomer include (meth) acrylate having a linear or branched alkyl having 1 to 22 carbon atoms, styrene, or a lower alkyl group of styrene (for example, an alkyl group having 1 to 4 carbon atoms) or lower Substituted derivatives of alkenyl groups (for example, alkenyl groups having 2 to 4 carbon atoms), perfluoroalkyl (meth) acrylates, alkyl (meth) acrylamides, and cycloalkyls having 5 to 20 carbon atoms (poly) cycloalkyl side chains ( Examples thereof include meth) acrylate and (meth) acrylamides, and one kind may be used alone or two or more kinds may be used in combination.

For example, the following compounds are mentioned.
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) Acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, n-tridecyl (meth) acrylate, stearyl methacrylate , Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) ) Acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and a modified product thereof with a cationizing agent, diethylaminoethyl (meth) acrylate and a modified product with a cationizing agent, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate such as methoxypolypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2 Hydroxyethyl phthalate, (meth) acrylic acid, 2-acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanate Ethyl (meth) acrylate, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyltrimethoxysilane, and 3- (meth) acryloyloxypropylmethyltriethoxysilane, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, vinylidene cyanide and the like Lilonitrile compound, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-ethyl (meth) acrylamide, N-methoxy (meth) acrylamide, N, N -Dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-ethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) Acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N, N-ethylenebis (meth) acrylamide, etc. Acrylamide compound Things.

  Among these, the linear or branched alkyl group having 1 to 22 carbon atoms is used because the Tg of the copolymer is increased, the hardness of the cured film surface is increased, and the hardness of the cured surface is increased. (Meth) acrylate having, that is, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate , Sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, n-tridecyl (Meth) acrylate and stearyl methacrylate are preferred, copolymerized From the point that the hardness of the cured film surface is increased and the solubility of methyl (meth) acrylate and copolymer in the solvent is improved, 2-ethylhexyl (meth) acrylate and octyl (meth) A structure using acrylate, lauryl (meth) acrylate or stearyl methacrylate is particularly preferable. These structures may contain 1 type independently, and 2 or more types may contain them.

  In addition, the other copolymerizable monomer (C) preferably has a molar ratio in the acrylic copolymer of 1% by weight or more from the viewpoint that the solubility of the copolymer in a solvent is improved. % By weight is more preferred, 10% by weight or more is more preferred, 20% by weight or more is particularly preferred, and 30% by weight or more is most preferred. In addition, from the viewpoint of good slipperiness, scratch resistance of the coating film after curing and solubility of the acrylic copolymer, it is preferably 99% by weight or less, more preferably 95% by weight or less, and 90% by weight. % Or less is more preferable, 80% by weight or less is particularly preferable, and 70% by weight or less is most preferable.

  In the present invention, among the silicone monomers (A), the number average molecular weight (g / mol) of the compound having the highest number average molecular weight and the (meth) acrylate (B) having an epoxy group in the copolymer (β) ) Is preferably 250,000 or more multiplied by the weight ratio (%). Here, the larger the number average molecular weight of the silicone monomer (A), the better the slipping property of the cured film, and the larger the weight ratio (%) in the copolymer (β) of the (meth) acrylate having an epoxy group, the harder the curing. From the viewpoint of preventing the copolymer (α) from falling off in the film and improving the durability of slipperiness, it is preferably 250,000 or more, more preferably 270,000 or more, and particularly preferably 300,000 or more. Further, the smaller the number average molecular weight of the silicone monomer (A) and the smaller the weight ratio (%) in the copolymer (β) of the (meth) acrylate having an epoxy group, the gelation in the acid-epoxy reaction at the time of synthesis. Is preferably 1,000,000 or less, more preferably 900,000 or less, and particularly preferably 700,000 or less.

Of the silicone monomers (A), the number average molecular weight (g / mol) of the compound having the highest number average molecular weight and the (meth) acrylate having an epoxy group in the copolymer (β) (
In order to adjust the value obtained by multiplying the weight ratio (%) of B), the number average molecular weight (g / mol) of the silicone monomer (A) is selected, or the epoxy group in the copolymer (β) is selected. It can adjust by selecting the weight ratio (%) of (meth) acrylate (B) to have.

[Compound (γ)]
The compound (γ) of the present invention is a compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule.

(Compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule)
Examples of the compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule include (meth) acrylic acid and a reaction product of a hydroxyl group-containing polyfunctional acrylate and an acid anhydride. For example, (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipentaerythritol pentaacrylate maleic acid monoester, pentaerythritol Triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol Pentaacrylate tetrahydrophthalic acid monoester, and the like.

  When the total amount (total weight) of the components of the acrylic copolymer (α) and the active energy ray-curable compound is 100 parts by weight, the weight ratio of the acrylic copolymer (α) is usually 0.1 weight. %, But when the weight ratio of the acrylic copolymer (α) is increased, the slidability of the cured film surface is improved, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, More preferably, it is 1.0% by weight or more. In addition, the amount is usually 10% by weight or less, but since the amount of the copolymer (α) unevenly distributed in the vicinity of the surface decreases as the weight ratio of the acrylic copolymer (α) decreases, the surface hardness increases and the scratch resistance. Is preferably 5% by weight or less, more preferably 3% by weight or less, and particularly preferably 2.5% by weight or less. The weight ratio of the acrylic copolymer (α) is not particularly limited as long as the desired physical properties are satisfied, and depends on the structure of the acrylic copolymer (α), particularly the molecular weight and content of the silicone monomer (A). It can be adjusted as appropriate.

<Photopolymerization initiator>
As the photopolymerization initiator contained in the active energy ray-curable resin composition of the present invention, known ones can be widely used. Preferably, α-hydroxyacetophenone (α-hydroxyphenyl ketone), α-aminoacetophenone is used. Alkylphenone type compounds such as benzyl ketals; acyl phosphine oxide type compounds; oxime ester compounds; oxyphenyl acetates; benzoin ethers; aromatic ketones (benzophenones); ketone / amine compounds; Such ester derivatives.

Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoylformic acid, methyl benzoylformate, Zoirugi ethyl are preferred. Two or more of these photopolymerization initiators can be used in combination as appropriate.

  Among these, 2-hydroxy-2-methylpropio is used as at least a part of the photopolymerization initiator because it is possible to minimize a decrease in curability, is easily available, and hardly causes coloring and the like. It is preferable to use α-hydroxyphenyl ketones such as phenone and 1-hydroxycyclohexyl phenyl ketone.

  In order to obtain an active energy ray-curable resin composition having particularly good curability, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethyl Α-aminophenyl ketones such as amino-1- (4-morpholinophenyl) -butan-1-one; benzophenones such as benzophenone, Michler's ketone, 2-chlorothioxanthone, isopropylthioxanthone, and 2,4-diethylthioxanthone Benzoyl formates (esters) such as methyl benzoylformate, benzoylformate, ethyl benzoylformate; oxime esters such as CGI242 (manufactured by Ciba) and OXE01 (manufactured by Ciba) are preferred. Further, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzophenone, More preferably, methyl benzoylformate or the like is used, and 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one and methyl benzoylformate are particularly preferred.

  When the total amount (total weight) of the components of the photocurable compound that reacts with the acrylic copolymer is 100 parts by weight, the photopolymerization initiator is 2 to 6.5 parts by weight, preferably 2.5. It is not less than 5.5 parts by weight. If it is less than 2 parts by weight, the curability of the obtained active energy ray-curable resin composition is inferior, and if it is 6.5 parts by weight or more, the physical properties of the cured film may be lowered.

  In addition, when an active energy ray is irradiated to the active energy ray-curable resin composition of the present invention to obtain a cured film, ultraviolet rays, soft X-rays, etc. are used as the active energy ray in the composition of the present invention. Although it is preferable to contain a photopolymerization initiator as described above, it is not necessary to contain a photopolymerization initiator when an electron beam or a hard X-ray having a relatively high energy is used.

<Inorganic particles>
The active energy ray-curable resin composition of the present invention can contain inorganic particles. By containing the inorganic particles and the (meth) acryloyl copolymer having a high crosslinking density, an active energy ray-curable resin composition capable of forming a hard coat having higher hardness can be provided.

  The average primary particle diameter of the inorganic particles is preferably 1 nm to 200 nm, more preferably 150 nm or less, and more preferably 100 nm or less from the viewpoint of good transparency of the cured film. Although a lower limit is not specifically limited, Usually, 1 nm or more is preferable, From the point that the acquisition of a raw material is easy, More preferably, it is 5 nm or more, More preferably, it is 10 nm or more.

On the other hand, since the movement of inorganic particles in the above range is governed by thermal diffusion rather than sedimentation by gravity, it becomes possible to disperse particles stably in the hard coat liquid, and when the hard coat film is formed, the surface is effectively exposed to the surface. Inorganic particles can be present. Moreover, there exists a tendency for an optical characteristic to become favorable, so that the average primary particle diameter of an inorganic particle is small.
The average primary particle diameter of the inorganic particles in the present invention refers to a diameter obtained by averaging the particle sizes observed with an electron microscope such as TEM.

  Examples of inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide) / Tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide and the like. These inorganic particles may be contained alone or in combination of two or more. Among these, silica (including organosilica sol) is preferably used because it is easy to obtain raw materials, the surface of the particles can be easily modified, and the dispersion stability is easily secured.

The colloidal silica in which silica is dispersed in water is preferably a surface-modified colloidal silica from the viewpoint of transparency of the coating film, weather resistance of the laminate, and laminate.
For the modification of colloidal silica, a compound having a hydrolyzable silicon group or a compound having a silicon group to which a hydroxyl group is bonded can be used. Each of these compounds may be one kind or two or more kinds. In a compound having a hydrolyzable silicon group, silanol groups are generated by hydrolysis, and these silanol groups react with and bind to silanol groups present on the surface of the colloidal silica to form surface-modified colloidal silica.

  Examples of the silicon group-containing compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and β- (meth) acryloyloxyethyltri. Methoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinyl orimethoxysilane, vinyltriethoxysilane, vinyl Methyldimethoxysilane, p-vinylphenyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimeth Shishiran, .gamma.-aminopropyltrimethoxysilane, .gamma. styryltrimethoxysilane, p- styryl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, and 3-mercaptopropyl trimethoxysilane.

Alternatively, a derivative obtained by adding a polyfunctional (meth) acrylate or a high molecular weight (meth) acrylate to a silane having a mercapto group or a derivative obtained by adding a polyfunctional (meth) acrylate having a hydroxyl group to a silane having an isocyanate group is modified. Silicon group-containing compounds may be used.
The surface modification of colloidal silica can be performed by reacting colloidal silica with a hydrolyzable silicon group-containing compound, catalyst, and water at 20 to 100 ° C. for 1 to 40 hours.

Examples of the catalyst used in the surface modification reaction include inorganic acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid; formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, acrylic Acids, organic acids such as methacrylic acid; alkalis; aluminum acetylacetone, aluminum 2,2,6,6, -tetramethyl-3,5-heptanedionate, aluminum diisopropoxide ethyl acetoacetate, aluminum diisobutoxide ethyl aceto Acetate, butoxide borate, dibutyltin dilaurate, dibutyltin dioctate. The amount of these catalysts used is preferably 0.0001 to 5 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of colloidal silica and hydrolyzable silicon group-containing compound. It is more preferable. Moreover, it is preferable that it is 0.5-100 equivalent with respect to a hydrolysable silicon group, and, as for the quantity of the water in the said surface modification reaction, it is more preferable that it is 1-30 equivalent.

The colloidal silica is preferably acidic colloidal silica among acidic or basic colloidal silica.
The inorganic particles used in the present invention are preferably contained in an amount of 5 parts by weight or more, more preferably 10 parts by weight or more, based on 100 parts by weight of the active energy ray-curable resin composition (I) of the present invention. More preferably, it is 20 parts by weight or more. Further, it is preferably 70 parts by weight or less, more preferably 50 parts by weight or less, and still more preferably 40 parts by weight or less.

<Preparation method>
The method for preparing the active active energy ray-curable resin composition (I) of the present invention is not particularly limited. For example, a (meth) acryloyl copolymer and a polyfunctional (meth) acrylate are optionally mixed with a solvent or a polymer. It can prepare by mixing together with an initiator, an additive, etc.
The solvent used in the preparation of the active energy ray-curable resin composition (I) of the present invention is not particularly limited, and becomes a (meth) acryloyl copolymer, a polyfunctional (meth) acrylate, and a base for coating. The material is appropriately selected in consideration of the material of the base material and the coating method of the composition. Specific examples of the solvent that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol. Ether solvents such as dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; dimethylformamide, Amide solvents such as diethylformamide and N-methylpyrrolidone; methyl Cellosolve, ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, propanol, isopropanol, alcohol solvents such as butanol; and the like; dichloromethane, halogenated solvents such as chloroform.

These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.
Various additives can be added to the active energy ray-curable resin composition (I) of the present invention as necessary. Examples of such additives include conventional additives such as leveling agents, antistatic agents, plasticizers, surfactants, antioxidants, and ultraviolet absorbers.

  Examples of the leveling agent include a compound containing a perfluoroalkyl group or a perfluoroalkylene skeleton, a compound containing a polydimethylsiloxane structure, and the like. The content of the leveling agent in the active energy ray-curable resin composition (I) is preferably 0 to 5 parts by mass from the viewpoint of transparency, coating appearance, adhesion, and hardness, and 0 to 2 parts by mass. It is more preferable that it is 0-1 mass part.

Moreover, when the base material described later includes a functional group that can be cured by light or heat, it may be more preferable to cure the base material by irradiation with active energy rays or heating. The substrate may be in the form of a molded article (article), or another layer may be interposed between the substrate and the coated surface.
The application method of the active energy ray-curable resin composition of the present invention is not particularly limited, and spin coating, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, air knife coating, etc. Preferable examples can be given.

After the coating film is formed on the substrate by the above coating method, the cured film is obtained by such means as removing volatile components by heat drying and then irradiating the coating film with active energy rays. The cured film of the active energy ray-curable resin composition (I) thus obtained is referred to as a B layer in the present invention.
When using an active energy ray when obtaining a cured film, the irradiation method includes ultraviolet rays emitted from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like. Examples thereof include active energy rays (electron beams, EB) such as electron beams, α rays, β rays, and γ rays that are usually extracted from a particle accelerator of 20 to 2000 kV. A cured film cured with such active energy rays is particularly preferable because of its excellent balance between productivity and physical properties.

  The B layer in the laminate of the present invention is a layer formed by curing the above-described active energy ray-curable resin composition (I), but the thickness of the layer after curing is not limited. The lower limit is usually 2 μm or more from the viewpoint of ensuring high hardness, more preferably 5 μm or more, and most preferably 8 μm or more. Further, the upper limit is preferably 100 μm or less from the viewpoint of dimensional stability and wet heat resistance, more preferably 60 μm or less, further preferably 40 μm or less, and most preferably 25 μm or less. .

4). Rolled film laminate The laminate of the present invention forms, for example, a B layer formed by curing the active energy ray-curable resin composition (I) of the present invention on the A layer, and is wound into a roll. Can be manufactured.
<Reason why the present invention is effective>
The reason why the present invention is effective is inferred as follows.

（但し、上記一般式（１）で表される構造が−ＣＨ_２−ＯＨの一部である場合を除く。） That is, the laminate of the present invention is a polycarbonate having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound. A layer (B layer) formed by curing a resin-containing layer (A layer) itself having both surface hardness and impact resistance and further containing an active energy ray-curable resin composition containing polyfunctional (meth) acrylate. By having it, a better pencil hardness is given. In addition, the A layer has not only a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) but also a structural unit (b) derived from another dihydroxy compound, whereby B It is presumed that the affinity with the layer can be increased and high adhesion can be given, and the effects of the present invention can be achieved.

(However, the case where the structure represented by the general formula (1) is a part of —CH ₂ —OH is excluded.)

<Display device>
The present invention further relates to a display device including the laminate of the present invention and a light source. In this case, it is desirable that the base material included in the laminate is a translucent base material. Moreover, it is preferable that a light source is arrange | positioned on the back surface of a base material, ie, the surface on the opposite side to the fine uneven | corrugated layer of a base material, and irradiates light toward a base material there.
In addition, although the thickness of a translucent base material can be selected timely according to a use, generally it is used at about 10-2000 micrometers.

  The light source that can be combined with the laminate is not particularly limited as long as it can emit light. Examples of the light source include a light emitting diode, a cold cathode tube, a hot cathode tube, and an EL. . The display device of the present invention may further include a retardation plate, a brightness enhancement film, a light guide plate, a light diffusing plate, a light diffusing sheet, a light collecting sheet, a reflecting plate, and the like. Further, a liquid crystal module, a backlight unit, or the like may be used as the light source.

  As the light transmissive member, various light transmissive plates, light transmissive films, and the like can be used. For example, tempered glass, acrylic plate, triacetyl cellulose plate, polyethylene terephthalate plate, diacetylene cellulose plate, acetate butyrate cellulose plate, polyethersulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plate , Polyether plate, polymethylpentene plate, polyether ketone plate, (meth) acrylonitrile plate and the like. Examples of the light transmissive film include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, Examples include a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyether ketone film, a (meth) acrylonitrile film, and a cycloolefin polymer (COP) film. As the light transmissive member, an acrylic plate, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a cycloolefin polymer (COP) film, and tempered glass are more preferably used. In addition, although the thickness of a light transmissive member can be selected timely according to a use, it is generally used at about 25-1000 micrometers.

In the case of a liquid crystal module, the light source is included, and a polarizing plate / liquid crystal cell / polarizing plate is arranged in this order on the light source. The liquid crystal cell is not particularly limited as long as it is generally used in a liquid crystal display device. For example, TN (Twisted Ne
magic) type liquid crystal cell, STN (Super Twisted Nematic) type liquid crystal cell, HAN (Hybrid Alignment Nematic) type liquid crystal cell, IPS (In Plane Switching) type liquid crystal cell, VA (Vertical Ali)
and a liquid crystal cell such as a multiple vertical alignment liquid crystal cell and an OCB (optically compensated bend) liquid crystal cell.

  The display device of the present invention is applied to a flat panel display such as a liquid crystal display device (liquid crystal display), LED (light emitting diode display), ELD (electroluminescence display), VFD (fluorescent display), PDP (plasma display panel), etc. can do. Moreover, since the active energy ray-curable composition of the present invention that can be used for the production of the display device of the present invention has weather resistance in addition to anti-blocking properties, the display device can be used outdoors. Is possible. For example, it can be installed outdoors or semi-outdoors as a panel display for the purpose of posting information such as advertisements.

  In addition, the outdoor or semi-outdoor use of the display device of the present invention includes a touch panel, which has a mechanism for operating equipment by holding down the display on the screen, for example, bank ATM, vending Machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, information displays installed in facilities such as museums and department stores, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), This is useful in mobile phones, railway vehicle monitoring devices, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In the following examples, “parts” means “parts by weight”.
The physical properties of the laminates obtained in the following examples and the like were evaluated by the following methods.

(1) Measurement of reduced viscosity A sample of a polycarbonate resin composition was dissolved using methylene chloride as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dL. Measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde viscometer manufactured by Moriyu Rika Kogyo Co., Ltd., and the relative viscosity ηrel is obtained from the following equation from the solvent passage time t0 and the solution passage time t. Specific viscosity ηsp from viscosity
Asked.
ηrel = t / t0
ηsp = (η−η0) / η0 = ηrel−1

  The reduced viscosity ηsp / c was determined by dividing the specific viscosity by the concentration c (g / dL). The higher this value, the higher the molecular weight.

(2) Measurement of the structural unit ratio derived from each dihydroxy compound in the polycarbonate resin composition The structural unit ratio derived from each dihydroxy compound in the polycarbonate resin composition was obtained by weighing 30 mg of the polycarbonate resin composition, It melt | dissolved in 0.7 mL, it was set as the solution, this was put into the tube for NMR of 5 mm in internal diameter, and 1H NMR spectrum was measured at normal temperature using JNM-AL400 (resonance frequency 400MHz) by JEOL. The structural unit ratio derived from each dihydroxy compound was determined from the signal intensity ratio based on the structural unit derived from each dihydroxy compound.

(3) Molding of the resin composition layer (A layer) An injection molding machine with a clamping force of 200 tons made by Meiki Seisakusho Co., Ltd., a cavity having a width of 100 mm, a length of 100 mm and a wall thickness of 1.0 mm, and a gate width A mold having a fan gate gate with 40 mm and a gate thickness of 0.8 mm is mounted, mold temperature is 80 ° C., injection pressure is 180 to 250 MPa, holding pressure is 60 to 80 MPa, holding pressure is 2 seconds, and cooling time is A plate was molded in 30 seconds to obtain a resin composition layer (A layer) in the present invention.

(4) Synthesis, blending and coating method of active energy ray curable resin composition (B layer) <Synthesis Example 1>
A reactor equipped with a stirrer, a reflux condenser, and a thermometer, 20 parts by weight of a polydimethylsiloxane having one end methacryloyl group having a number average molecular weight of 10,000 (“Sylaplane FM-0725” manufactured by JNC), glycidyl methacrylate ("Acryester G" manufactured by Mitsubishi Rayon Co., Ltd.) 30 parts by weight, 40 parts by weight of methyl methacrylate ("Acryester M" manufactured by Mitsubishi Rayon Co., Ltd.), 10 parts by weight of stearyl methacrylate ("Acryester S" manufactured by Mitsubishi Rayon Co., Ltd.), methyl 150 parts by weight of isobutyl ketone (MIBK) was charged, and after starting stirring, the system was purged with nitrogen, and the temperature was raised to 55 ° C. 0.06 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), 0.09 part by weight of 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.) Then, the system was heated to 65 ° C. and stirred for 3 hours, and then 0.06 part by weight of V-65 was further added and stirred at 65 ° C. for 3 hours. The temperature inside the system is raised to 100 ° C. and stirred for 30 minutes, 68.8 parts by weight of MIBK is added, and the temperature inside the system is again raised to 100 ° C. After adding 0.05 parts by weight of p-methoxyphenol (manufactured by Wako Pure Chemical Industries) and 2.3 parts by weight of triphenylphosphine (manufactured by Wako Pure Chemical Industries), acrylic acid (manufactured by Mitsubishi Chemical Corporation) 15.5 Part by weight was added, the temperature was raised to 110 ° C., and the mixture was stirred for 6 hours. After cooling, 253 parts of MIBK was added to obtain a solution of copolymer (F1). The composition of the reaction solution was (F1) / MIBK = 20/80 (weight ratio).

<Formulation example I>
The solution of the copolymer (F1) obtained in Synthesis Example 1, the curable monomer DPHA, and Aronix M313 were blended at a solid content ratio of 2:12:86, and 1-hydroxy was used as a photopolymerization initiator. After adding 4.0 parts by weight of cyclohexyl phenyl ketone (“Irgacure 184” manufactured by BASF) and 0.5 part by weight of α-aminophenyl ketone photopolymerization initiator (“Irgacure 907” manufactured by BASF), propylene glycol monomethyl ether / Methyl isobutyl ketone = 1/1 (weight ratio) was diluted so that the solid content would be 40%, to obtain Formulation Liquid I.

<Coating method of active energy ray-curable resin composition (B layer)>
The obtained compounded liquid I was applied onto the A layer obtained in the above (3) with a bar coater so that the coating film after drying had a film thickness described in the table, and the coating liquid I at 80 ° C. The coating was dried by heating for a minute. Next, using a high-pressure mercury lamp with an output of 120 W / cm, irradiation with 450 mW / cm ² and 500 mJ / cm ² of ultraviolet rays was performed to obtain a laminate having a cured film coated thereon. For each of the examples and comparative examples, as shown in Table 1, a film having a changed thickness of the B layer was prepared.

(5) Pencil hardness:
About the laminated body which coat | covered the A layer obtained by said (3), and the cured film obtained by said (4), using a JIS-compliant pencil hardness meter (made by Dazai Equipment Co., Ltd.), JIS K-5400 The measurement was performed based on the conditions, and the evaluation was made with the hardest pencil count without scratches. About the laminated body, the pencil hardness of the surface which has a hard-coat layer was measured. The pencil hardness of the laminate is 3H or higher, and the laminate has two or more levels of hardness compared to the hardness of the A layer (for example, from F to 2H, etc.)
It is preferable to improve. When the pencil hardness is less than 3H, there is a possibility that the obtained molded product is easily damaged and the appearance is liable to be damaged. Moreover, when the hardness improvement of a laminated body is less than 2 steps | paragraphs compared with the hardness of a base material, there exists a possibility that the problem that the cost effectiveness at the time of coating a hard-coat layer may be impaired easily is produced. The pencil hardness is expressed in the order of 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, and 4B in order from the hardest. In the present invention, 2H or more was considered acceptable.

(6) Adhesiveness After obtaining the laminated body which coat | covered the cured film with an active energy ray curable resin composition by the method of said (4), the cross-cut peel test (number of cross-cuts: 100 pieces of JIS K-5400) Table 1 shows the number of grids that were not peeled off.

(7) Dimensional stability (low curl)
After obtaining the laminated body which coat | covered the cured film by an active energy ray curable resin composition by the method of said (4), a laminated body is set | placed on a flat desk and four corners (desk) part from the desk surface The distance (warping amount) was measured to obtain an average value, and evaluated according to the following criteria.
○: The amount of warpage is less than 1.5 mm.
(Triangle | delta): The curvature amount is 1.5 mm or more and less than 3 mm.
X: The amount of warpage is 3 mm or more.

(8) Impact resistance After obtaining the laminated body which coat | covered the cured film with an active energy ray curable resin composition by the method of said (4), 100 g of using DuPont impact tester (Toyo Seiki Seisakusho). The weight was dropped from the height of 30 cm onto the laminate, and the impact resistance was evaluated. At this time, the surface on the cured film (B layer) side was used as the contact surface with the hitting core. In addition, as evaluation, (circle) shows that the laminated body was not broken, and x shows that the laminated body was cracked.

(9) Moisture and heat resistance After obtaining a laminate coated with a cured film of an active energy ray-curable resin composition by the method of (4) above, in a constant temperature and humidity chamber adjusted to a temperature of 80 ° C. and a humidity of 90% This was left on a metal shelf for 120 hours (with the B layer on top and flat) and then taken out, and the presence or absence of cracks in the cured film (B layer) was confirmed. The moisture and heat resistance of the resin in which no cracks were observed in the cured film (B layer) was marked with ◯, and the moisture and heat resistance of the laminate with cracks in the cured film (B layer) was marked with ×.

The abbreviations of the compounds used in the description of the following examples are as follows.
(Dihydroxy compound)
・ ISB: Isosorbide (Rocket Fleure, trade name: POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Rika Co., Ltd., trade name: SKY CHDM)
TCDDM: TCDDM: Tricyclodecane dimethanol (carbonic acid diester)
・ DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
(Heat stabilizer)
AS2112: Compound name, tris (2,4-di-t-butylphenyl) phosphite (manufactured by ADEKA)
(Antioxidant)
IRGANOX 1010: Compound name, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd.)
(Release agent)
E-275: Compound name, ethylene glycol distearate (manufactured by NOF Corporation)
(Bisphenol A polycarbonate: BPA PC)
NOVAREX 7022R: aromatic polycarbonate resin having a structure derived only from 2,2-bis- (4-hydroxyphenyl) propane, viscosity average molecular weight 22,000 (manufactured by Mitsubishi Engineering Plastics)
(PMMA)
・ Acrypet VH: Polymethyl methacrylate resin (Mitsubishi Rayon Co., Ltd.)

[Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, in a molar ratio. ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 −6, and sufficiently purged with nitrogen (oxygen concentration 0.0005 vol% -0.001 vol%). Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes. The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.

  The content thus oligomerized is once restored to atmospheric pressure, and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes. Thereafter, the internal temperature was set at 228 ° C. and the pressure at 133 Pa or less over 20 minutes, and when the predetermined stirring power was reached, the pressure was restored, and a molten polycarbonate resin was obtained from the outlet of the polymerization reactor.

Further, the melted polycarbonate resin was continuously supplied to a twin-screw extruder provided with 3 vents and water injection equipment, and “Irganox 1010” and “AS2112” were used as antioxidants so as to have the compositions shown in Table 1. In addition to continuously adding “E-275” as a mold release agent at a predetermined ratio, low-molecular weight substances such as phenol are devolatilized under reduced pressure at each vent section provided in the twin-screw extruder, and then a pelletizer is used. Pelletization was performed to obtain polycarbonate resin composition pellets.
Table 1 shows various evaluation results of the laminate obtained by coating the obtained resin composition and a cured film of the active energy ray-curable resin composition.

[Example 2]
In Example 1, except that the charge composition was changed so that ISB / CHDM / DPC / calcium acetate monohydrate = 0.90 / 0.10 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of a carbonate copolymer resin composition were obtained. Table 1 shows various evaluation results of the laminate obtained by coating the obtained resin composition and a cured film of the active energy ray-curable resin composition.

[Example 3]
In Example 1, except that the charging composition was changed to ISB / TCDDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of a carbonate copolymer resin composition were obtained. Table 1 shows various evaluation results of the laminate obtained by coating the obtained resin composition and a cured film of the active energy ray-curable resin composition.

[Example 4]
In Example 1, except that the charge composition was changed to ISB / TCDDM / DPC / calcium acetate monohydrate = 0.80 / 0.20 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of a carbonate copolymer resin composition were obtained. Table 1 shows various evaluation results of the laminate obtained by coating the obtained resin composition and a cured film of the active energy ray-curable resin composition.

[Comparative Example 1]
In Example 1, carbonate was changed in the same manner as in Example 1 except that the charged composition was changed to ISB / DPC / calcium acetate monohydrate = 0.10 / 1.00 / 1.3 × 10 ^−6. Polymer resin composition pellets were obtained. Table 1 shows various evaluation results of the laminate obtained by coating the obtained resin composition and a cured film of the active energy ray-curable resin composition.

[Comparative Example 2]
Table 1 shows various evaluation results of a laminate in which a commercially available bisphenol A-based polycarbonate, NOVAREX 7022R (manufactured by Mitsubishi Engineering Plastics) and a cured film coated with an active energy ray-curable resin composition are coated.

[Comparative Example 3]
Table 1 shows various evaluation results of a laminate in which a commercially available PMMA, ACRYPET VH (manufactured by Mitsubishi Rayon Co., Ltd.) and a cured film made of an active energy ray-curable resin composition are coated.

The laminated body of the invention shown in Examples 1 to 4 is superior to the molded product shown in the comparative example without x or rejection in each characteristic evaluation, when the evaluation items such as hardness impact resistance and adhesion are combined. there were. Among them, Examples 1 and 3 are particularly excellent in surface hardness (the pencil hardness of the laminate is 3H or more, and the hardness of the laminate is improved by two or more steps compared to the hardness of the A layer). Examples 1, 2, and 3 (excluding Examples 3-5) and 4 are particularly excellent in dimensional stability (low curl properties) and moisture and heat resistance (the B layer does not crack in the wet heat test). Met.
On the other hand, Comparative Example 1 is a molded product having a structure derived only from the structural unit (a), has insufficient impact resistance, and has poor adhesion.

  Comparative Example 2 is a laminate using a commercially available bisphenol A-based polycarbonate, but the pencil hardness of the laminate is F to H, and the molded product may be easily damaged. Although the comparative example 3 is a molded article using commercially available PMMA, although the surface hardness is good, the impact resistance is insufficient and the laminate may be easily broken.

  The laminate molded using the polycarbonate resin composition of the present invention is excellent in impact resistance and adhesion, and has low optical distortion. For example, it can be used as a resin molded product for optical applications such as liquid crystal display devices. Can be used.

Claims (10)

Layer (A layer) containing a polycarbonate resin having a structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1) and a structural unit (b) derived from another dihydroxy compound
And a laminate having a layer (B layer) obtained by curing an active energy ray-curable resin composition containing polyfunctional (meth) acrylate.

(However, the case where the structure represented by the general formula (1) is a part of —CH ₂ —OH is excluded.)   The structural unit (b) in the polycarbonate resin is a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound. Laminated body. The laminate according to claim 1 or 2, wherein the dihydroxy compound having a structure represented by the general formula (1) is a compound represented by the following general formula (2).

  The layered product according to any one of claims 1 to 3, wherein the B layer is cured by active energy rays. The active energy ray-curable resin composition is an active energy ray-curable resin composition containing an acrylic copolymer (α),
The acrylic copolymer (α) is a layer formed by curing an active energy ray-curable resin composition obtained by adding the compound (γ) to the following copolymer (β). The laminate according to any one of claims 1 to 4, wherein:
Copolymer (β): Copolymer compound (γ) of silicone monomer (A) represented by structural formula (I), (meth) acrylate (B) having an epoxy group and other copolymerizable monomer (C) ): Compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each a methyl group or a phenyl group, n is an integer of 10 to 100, and R ³ And R ⁴ may be the same as or different from each other, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.   The laminate according to claim 5, wherein the active energy ray-curable resin composition contains 0.05 wt% to 10 wt% of the acrylic copolymer (α).   The monomer (C) that can be copolymerized with the acrylic copolymer (α) of the active energy ray-curable resin composition is at least one selected from linear or branched alkyl (meth) acrylates having 4 to 22 carbon atoms. The laminate according to claim 5 or 6, comprising (meth) acrylate.   A front panel of a flat panel display comprising the laminate according to any one of claims 1 to 7.   A front plate of a tablet personal computer, comprising the laminate according to any one of claims 1 to 7.   A front plate of a vehicle-mounted display comprising the laminate according to any one of claims 1 to 7.