Laminated body and manufacturing method therefor

Abstract

To acquire a laminated body with an excellent surface hardness, an excellent scratch resistance, an excellent adhesion between a base material and a hard-coat layer, and an excellent weather resistance.SOLUTION: A laminated body is used, which has: a layer (A layer) containing polycarbonate resin having a structural unit derived from a dihydroxy compound having a prescribed structure; and a hardened layer (B layer) of an active energy ray-curable resin composition containing mono- or poly-pentaerythritol-poly (meth)acrylate with a prescribed structure, a (meth)acrylate compound with three or more functions having an isocyanuric ring, and inorganic fine particles coated with an organic functional group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polycarbonate resin film, sheet, molded article, or other substrate, A laminate having a layer obtained by curing an active energy ray-curable resin composition, and Regarding the manufacturing method. [Background technology]

[0002] Polycarbonate resin is excellent in transparency, heat resistance, and mechanical strength, and is therefore used in automobile parts, Medical parts, films, sheets, containers such as bottles, building materials, various housing materials for mobile phones, etc. It is widely used in the fields of optical disc substrates and plastic lenses. However, polycarbonate resin has a lower surface hardness than glass, so it is prone to scratches. This has the drawback of significantly impairing the transparency or appearance of the resin. This makes it difficult to use plastic substrates in areas where scratch resistance is required. Therefore, in order to solve the abrasion resistance of these polycarbonate resin surfaces, isosorbide was used. Polycarbonate with high surface hardness is produced by transesterification with diphenyl carbonate. It has been proposed to obtain a resin by the reaction of isosorbide with alicyclic dihydroxybenzoates (Patent Document 1). A method for obtaining polycarbonate resin by copolymerizing a silicon compound has been proposed ( Patent document 2). However, these polycarbonate resins have excellent optical properties, processability, mechanical properties, and light resistance. However, the scratch resistance of these polymers was not satisfactory. A laminated body in which a hard coat layer is laminated has been proposed to improve the scratch resistance of carbonate resin. (Patent Documents 3 and 4). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6349866

[0004] [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-24919

[0005] [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-102537

[0006] [Patent Document 4] Japanese Patent Application Laid-Open No. 2016-68438 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the laminates described in Patent Documents 3 and 4 have a hard coat layer formed thereon. Although the surface hardness and scratch resistance were improved, the adhesion after the weather resistance test was insufficient. The present invention provides a coating film having surface hardness, scratch resistance, adhesion between the substrate and the hard coat layer, and weather resistance. The present invention aims to provide a laminate having excellent properties and a method for producing the same. [Means for solving the problem]

[0008] As a result of extensive research conducted by the present inventors to solve the above problems, it has been found that the laminate having the configuration of the present invention It has been found that the above problems can be solved. That is, the present invention is as follows. [1] Layer A containing a polycarbonate resin and a curable layer of an active energy ray-curable resin composition a laminate having a layer B made of a fluorine-containing compound, and at least one outermost layer is the layer B, The polycarbonate resin is a dihydroxycarbonate having a structure represented by the following general formula (1): having a structural unit (a1) derived from a compound, The active energy ray-curable resin composition comprises (b1) represented by the following general formula (2) and a tri- or higher functional (meth)acrylate compound (b2) represented by the general formula (3), and inorganic fine particles (b3) coated with an organic functional group.

[0009] [ka]

[0010] [ka]

[0011] [In formula (2), "4+2n" Xs each independently represent a (meth)acryloyloxy group. (That is, a group represented by CH2=CR-COO-, where R represents a hydrogen atom or a methyl group. ), (meth)acryloyloxy groups modified with caprolactone (i.e., CH 2=CR-CO(O(CH2)5C=O) y is a group represented by -O-, where R is a hydrogen atom or represents a methyl group, and y represents an integer of 1 to 5.) and a hydroxy group. In addition, n is an integer of 0 to 4.

[0012] [ka]

[0013] [In formula (3), Y1, Y2, and Y3 each independently contain a (meth)acryloyl group, At least two of these are (meth)acryloyl groups, and Z1, Z2 and Z3 are It represents an oxyalkylene group having 1 to 4 carbon atoms and an alkyl group having 2 to 10 carbon atoms.] [2] The active energy ray-curable resin composition forming the layer B contains a (meth)acryloyl group. a polymer having at least one functional group selected from the group consisting of an epoxy group and a vinyl group;

[0023] The present invention relates to a siloxane oligomer (b4) having a weight-average molecular weight of 200 to 3,000. 1] The laminate according to claim 1. [3] The trifunctional or higher functional (meth)acrylate compound (b2) represented by the general formula (3) , a urethane (meth)acrylate compound having a nurate skeleton, [1] or [2] The laminate according to claim 1. [4] At least one of X in the formula (2) is modified with caprolactone (methacrylamide). The laminate according to any one of [1] to [3], wherein the aryl group is an acryloyloxy group. [5] The inorganic fine particles (b3) whose surfaces are coated with organic functional groups are (meth)acrylonitrile-butadiene-based fine particles. At least one functional group selected from the group consisting of an aryl group, an epoxy group, and a vinyl group. The laminate according to any one of [1] to [4], which is inorganic fine particles that have been subjected to a coating treatment. [6] In the active energy ray-curable resin composition, Mono- or polypentaerythritol represented by the following general formula (2) based on the total solid content of the composition: 10 to 90% by mass of poly(meth)acrylate (b1) and 3 represented by the following general formula (3) The (meth)acrylate compound (b2) having a functionality of 10 to 90% by mass, the surface of which is coated with an organic functional group 5 to 50 mass % of inorganic fine particles (b3) coated with (meth)acryloyl groups, epoxy groups having at least one functional group selected from the group consisting of an oxy group and a vinyl group, and a weight average Contains 1 to 10% by mass of siloxane oligomer (b4) having a molecular weight of 200 to 3,000 The laminate according to any one of [1] to [5]. [7] The active energy ray-curable resin composition forming the layer B contains an ultraviolet absorber (c1) and and a hindered amine light stabilizer (c2), The laminate according to any one of claims 1 to 14. [8] After applying an active energy ray-curable resin composition to at least one surface of the layer A,

[0023] Any one of [1] to [7], which comprises a step of irradiating the layer B with active energy rays. Item 1. A method for producing the laminate described in item 1. [9] Automobiles including plastic glass, plastic grilles, headlight covers, and taillight covers from the group consisting of eyeglass parts, eyeglass frames, and eyeglass parts including sunglasses The product according to any one of [1] to [7], which is used for at least one or more purposes. Layered body. [Effects of the Invention]

[0014] According to the present invention, in addition to the surface hardness, scratch resistance, and abrasion resistance, the substrate (layer A) and the hard coat A laminate having excellent adhesion to (layer B) and weather resistance is obtained, and it is suitable for use in automobile parts, medical parts, film Films, sheets, containers such as bottles, building materials, various housing materials for smartphones, optical We offer resin molded products that can be applied to a wide range of fields, including screen substrates, plastic lenses, and eyeglass components. It will be possible to provide DETAILED DESCRIPTION OF THE INVENTION

[0015] The following describes in detail the embodiments of the present invention. The above description is a representative example of an embodiment of the present invention, and the present invention is not limited to these contents. isn't it. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group and a methacryloyl group. This is a general term for the aryl group. About "(meth)acrylic" and "(meth)acrylate" The same is true. In this specification, a numerical range expressed by "to" means the numerical values ​​before and after it. The numerical ranges disclosed herein include the lower and upper limits. Any combination can be used to create a new range of values.

[0016] [1. Laminate] The laminate of the present invention comprises a layer (layer A) containing the following specific polycarbonate resin, and It is a laminate having a layer (layer B) formed by curing a certain active energy ray-curable resin composition. . The layer A is a dihydroxy compound (hereinafter referred to as "dihydroxy compound") having a structure represented by the following general formula (1): The compound (a1) may be referred to as "hydroxy compound (1)." This is a layer containing a polycarbonate resin.

[0017] [ka]

[0018] The layer B is a mono- or polypentaerythritol polymer represented by the following general formula (2): a trifunctional or higher (meth)acrylate represented by the following general formula (3): Acrylate compound (b2), inorganic fine particles (b3) whose surfaces are coated with organic functional groups, ( One or more of the following groups in the structure: meth)acryloyl group, glycidyl group, and vinyl group and (b4) a siloxane oligomer having a molecular weight of 200 to 3,000. This layer is formed by curing an active energy ray-curable resin composition.

[0019] [ka]

[0020] In formula (2), "4+2n" Xs each independently represent a (meth)acryloyloxy group. (That is, a group represented by CH2=CR-COO-, where R represents a hydrogen atom or a methyl group. ), (meth)acryloyloxy groups modified with caprolactone (i.e., CH 2=CR-CO(O(CH2)5C=O) y is a group represented by -O-, where R is a hydrogen atom or represents a methyl group, and y represents an integer of 1 to 5.) and a hydroxy group. In addition, n is an integer of 0 to 4.

[0021] [ka]

[0022] In formula (3), Y1, Y2, and Y3 each contain a (meth)acryloyl group, and At least two of Z1, Z2 and Z3 are (meth)acryloyl groups, and Z1, Z2 and Z3 are each a group having 1 to 4 carbon atoms. It represents an oxyalkylene group and an alkyl group having 2 to 10 carbon atoms.

[0023] The layer A in the laminate of the present invention can have any shape and form. Examples of the form include a film, a sheet, and a molded article. In the laminate of the present invention, in order to obtain the effects of the present invention such as chemical resistance and scratch resistance on the surface, Therefore, at least one of the outermost layers must be layer B. The other arrangement of layers A and B There is no particular limitation on the thickness of the layers. The layers may be formed adjacent to each other, or may be further bonded to each other. It may also have other layers such as a primer layer to improve the properties.

[0024] [2.A layer] The polycarbonate resin (A) constituting the layer A is derived from a dihydroxy compound (1). Dihydroxy compounds other than the dihydroxy compound (1) having the structural unit (a) It is preferred that the copolymer further comprises a structural unit (b) derived therefrom.

[0025] The polycarbonate resins used to obtain the laminate of the present invention and polycarbonates based thereon are as follows: The nate resin composition will now be described in detail. <Raw materials> (Dihydroxy compound (1)) The polycarbonate resin used in the present invention (hereinafter referred to as "polycarbonate resin (A)") The compound (1) has a structure derived from the dihydroxy compound (1) in at least a part of its structure. Includes construction unit (a). Dihydroxy compounds (1) include isosorbide, isomers, and Among these dihydroxy compounds (1), the resources and Sorbitol is an abundant and readily available starch that is produced from various starches. isosorbide obtained by dehydration condensation of I wish. These dihydroxy compounds (1) may be used singly or in combination of two or more. They may also be used in combination.

[0026] The polycarbonate resin (A) may contain, as part of its structure, a dihydroxy compound derived from another dihydroxy compound. It is preferable that the structural unit (b) is an aliphatic dihydroxy group. compounds, alicyclic dihydroxy compounds, and heterocyclic dihydroxy compounds. It is more preferable that the structural unit is derived from at least one compound.

[0027] Among the other dihydroxy compounds, in particular, those derived from aliphatic dihydroxy compounds It is preferable that the structural unit derived from the alicyclic dihydroxy compound is In this case, the resulting polycarbonate resin (A) is provided with flexibility. can be given

[0028] (aliphatic dihydroxy compounds) The aliphatic dihydroxy compound may be a straight-chain aliphatic dihydroxy compound or a branched aliphatic dihydroxy compound. The linear aliphatic dihydroxy compound may be any of the following: Number of carbon atoms: 2 to 30, more preferably 3 to 20, and even more preferably 3 to 10 A straight chain aliphatic dihydroxy compound is used. A branched aliphatic dihydroxy compound and Preferably, the carbon number is 3 to 30, more preferably 3 to 20, and even more preferably 10 to 20 carbon atoms. A branched aliphatic dihydroxy compound having a prime number of 4 to 12 is used.

[0029] Specific examples of the linear aliphatic dihydroxy compound include ethylene glycol, 1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol Sandiol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, 1,11-undecanediol, 1,12-decanediol Examples include decanediol, hydrogenated dilinoleyl glycol, and hydrogenated dioleyl glycol. Among them, 1,3-propanediol, 1,4-butanediol, 1,6-pentanediol, Tandanediol and 1,9-nonanediol are preferred in terms of heat resistance, polymerizability and availability.

[0030] Specific examples of branched aliphatic dihydroxy compounds include 1,3-butylene glycol, 2-Methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,6 -Hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,2,4- Trimethyl-1,6-hexanediol, 2-n-butyl-2-ethyl-1,3-propanediol 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5 -Pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2- Ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol , 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, etc. Among them, neopentyl glycol, 2-n-butyl ether, etc. 2,2-Diethyl-1,3-propanediol, 2,2-Diethyl-1,3-propanediol ol, 2,4-diethyl-1,5-pentanediol are preferred in terms of heat resistance, polymerizability, and availability. preferable.

[0031] (alicyclic dihydroxy compounds) The alicyclic dihydroxy compound is not particularly limited, but usually has a five-membered ring structure or a six-membered ring structure. The alicyclic dihydroxy compound may have a five-membered ring structure or a six-membered ring structure. This structure may result in the polycarbonate resin (A) having high heat resistance. The six-membered ring structure may be fixed in a chair or boat shape by a covalent bond. The number of carbon atoms contained in the dihydroxy compound of the formula is usually 70 or less, preferably 50 or less, The number of carbon atoms is preferably 30 or less. If the number of carbon atoms is too large, the heat resistance increases, but synthesis becomes difficult. It tends to be difficult to purify and expensive. The higher the purity, the easier it tends to be to refine and obtain.

[0032] Specific examples of the alicyclic dihydroxy compound containing a five-membered ring structure or a six-membered ring structure include cyclohexyl hydroxybenzoates, Cyclohexanedimethanols, tricyclodecane dimethals, pentacyclopentadeca dimethanols, decalin dimethanols, tricyclotetradecane dimethanols, Norbornane dimethanols, adamantane dimethanols, cyclohexanediols , tricyclodecanediols, pentacyclopentadecanediols, decalindiols diols, tricyclotetradecanediols, norbornanediols, adamantanediols Examples include alcohols.

[0033] Among the specific examples of the alicyclic dihydroxy compounds mentioned above, cyclohexane dimethanols, Tricyclodecane dimethanols, adamantanediols, pentacyclopentadecane Dimethanols are preferred, and from the viewpoints of availability and ease of handling, 1, 4-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, 1,2-Cyclohexanedimethanol Particularly preferred are tricyclohexanedimethanol and tricyclodecanedimethanol. The above-exemplified compounds are examples of other dihydroxy compounds that can be used in the present invention. However, the present invention is not limited to these. These other dihydroxy compounds include One type may be used alone, or two or more types may be used in combination.

[0034] When the polycarbonate resin (A) has the structural unit (b), the polycarbonate resin ( The molar ratio of the structural unit (a) to the structural unit (b) in A) can be set to any desired ratio. By adjusting the molar ratio, impact strength (e.g., notched Charpy impact strength) can be improved. Furthermore, it is possible to obtain a polycarbonate resin (A) having a desired glass transition temperature. It is possible to do this. The ratio of the structural unit (a) in the polycarbonate resin (A) is the total dihydroxy compounds. The content of the structural units derived from the above is preferably 25 to 95 mol %, more preferably 30 to 90 mol %. It is preferable that the content is 40 to 80 mol %.

[0035] (carbonate diester) The polycarbonate resin (A) is a dihydroxy compound containing the dihydroxy compound (1). It can be obtained by polycondensation using a carbonic acid diester as the raw material through an ester exchange reaction. .

[0036] Examples of the carbonic acid diesters that can be used include diphenyl carbonate and ditolyl carbonate. Substituted diphenyl carbonates such as carbonate, dimethyl carbonate, diethyl carbonate Among these, diphenyl carbonate is preferred. Carbonates and substituted diphenyl carbonates, particularly preferably diphenyl carbonate. Carbonate diesters may contain impurities such as chloride ions. These impurities may inhibit the polymerization reaction or deteriorate the color of the resulting polycarbonate resin (A). If necessary, use purified products by distillation, etc. preferable.

[0037] The amount of carbonic acid diesters is 0.90 to 1.0% of the total dihydroxy compounds used in the melt polymerization. It is preferable to use it at a molar ratio of 0.20, and it is preferable to use it at a molar ratio of 0.95 to 1.10. More preferably, the molar ratio is 0.96 to 1.10, and even more preferably 0.98 It is particularly preferred to use a molar ratio of up to 1.04.

[0038] If this molar ratio is 0.90 or more, the terminals of the produced polycarbonate resin (A) The hydroxyl groups do not increase too much, improving the thermal stability of the polymer and making it less likely to discolor during molding. In addition, the rate of the transesterification reaction is less likely to decrease, making it easier to obtain a desired high molecular weight product.

[0039] In addition, if this molar ratio is 1.20 or less, the rate of transesterification reaction will be This improves the molecular weight of the polycarbonate resin (A), making it easier to produce a polycarbonate resin (A) having a desired molecular weight. The amount of residual carbonate diester in the produced polycarbonate resin (A) is reduced. Carbonate diesters can be undesirable as they can cause odors during molding or in molded products. The heat history during the polymerization reaction is increased, and the color and Therefore, if the amount of residual carbonate diester decreases, This is preferable in that the above-mentioned problems are less likely to occur.

[0040] Furthermore, as the molar ratio of the carbonic acid diester to the total dihydroxy compounds increases, The amount of residual carbonate diester in the polycarbonate resin (A) increases, and these are absorbed by ultraviolet light. This is undesirable because it may absorb light and deteriorate the light resistance of the polycarbonate resin (A). .

[0041] The concentration of the carbonic acid diester remaining in the polycarbonate resin (A) is preferably 200 mass %. ppm by mass or less, more preferably 100 ppm by mass or less, particularly preferably 60 ppm by mass or less However, in reality, the polycarbonate resin (A) may contain unreacted carbonic acid diester, and the unreacted carbonic acid diester in the polycarbonate resin (A) may The lower limit of the carbonic acid diester concentration in the reaction is usually 1 ppm by mass.

[0042] <Method for producing polycarbonate resin (A)> The polycarbonate resin (A) is a dihydroxy compound containing the dihydroxy compound (1). It is obtained by polycondensation of ethylenediamine and a carbonic acid diester through an ester exchange reaction. The dihydroxy compound and the carbonate diester are prepared in a raw material preparation tank before the transesterification reaction. It is preferable to mix them uniformly.

[0043] The mixing temperature is usually 80°C or higher, preferably 90°C or higher, and the upper limit is usually 250°C. The temperature is preferably 200°C or less, and more preferably 150°C or less. If the mixing temperature is above the lower limit, a sufficient dissolution rate can be achieved. The resulting mixture is easy to obtain, the solubility is unlikely to be insufficient, and problems such as solidification are unlikely to occur. If the content is equal to or less than the upper limit, the dihydroxy compound is less susceptible to thermal degradation, and the resulting The color of the polycarbonate resin is less likely to deteriorate, and the light resistance is less likely to be adversely affected.

[0044] The polycarbonate resin (A) is melt-polymerized in multiple stages using multiple reactors in the presence of a catalyst. The reason for carrying out the melt polymerization in a plurality of reactors is that At the beginning of the reaction, the reaction solution contains a large amount of monomer, so the required polymerization rate is maintained. It is important to suppress the evaporation of the monomer while maintaining the polymerization temperature. In order to shift the balance to the polymerization side, the monohydroxy compound produced as a by-product must be distilled off sufficiently. In this way, in order to set different polymerization reaction conditions, From the viewpoint of production efficiency, it is preferable to use a plurality of reactors. As mentioned above, at least two or more are sufficient, but from the viewpoint of production efficiency, it is preferable to have three. More preferably, there are three to five of these, and particularly preferably four.

[0045] The reaction type can be batch type, continuous type, or a combination of batch type and continuous type. This method is also acceptable.

[0046] Furthermore, in order to suppress the amount of distilled monomer, a reflux condenser is used in the polymerization reactor. This is particularly effective in a reactor in the early stage of polymerization where there is a large amount of unreacted monomer components. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected depending on the monomer used. However, the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 1 The reduction temperature is 80°C, preferably 80 to 150°C, and particularly preferably 100 to 130°C. If the temperature of the refrigerant introduced into the flow condenser is equal to or lower than the upper limit, the amount of reflux increases, and the effect is When the distillation efficiency is equal to or greater than the lower limit, the efficiency of distillation of the monohydroxy compounds that should be distilled off is improved. It tends to be upward.

[0047] As the refrigerant, hot water, steam, heat transfer oil, etc. are used, with steam and heat transfer oil being preferred.

[0048] The final polycarbonate can be obtained by maintaining an appropriate polymerization rate and suppressing the distillation of monomers. In order to avoid impairing the color, thermal stability, light resistance, etc. of the carbonate resin (A), The selection of the type and amount of catalyst is important.

[0049] In producing the polycarbonate resin (A), if there are two or more reactors, In the reactor, there are multiple reaction stages with different conditions, and the temperature and pressure are continuously changed. It is also possible to implement something like this.

[0050] <Physical properties of polycarbonate resin (A)> Preferred physical properties of the polycarbonate resin (A) are shown below. (glass transition temperature) The glass transition temperature (Tg) of the polycarbonate resin (A) is preferably lower than 155°C. If the glass transition temperature of the polycarbonate resin (A) is less than 155°C, it is less likely to be discolored. In this case, the impact strength can be easily improved. When transferring the surface shape to the molded product, the mold temperature can be set to a certain degree. There are fewer restrictions on the temperature controllers that can be selected, and the transferability of the mold surface is improved.

[0051] The glass transition temperature of the polycarbonate resin (A) is more preferably lower than 145°C, and even more preferably lower than 145°C. Preferably it is below 135°C. The glass transition temperature of the polycarbonate resin (A) is usually 90°C or higher, and Mostly above 95°C.

[0052] As a method for making the glass transition temperature of the polycarbonate resin (A) less than 155°C, By reducing the proportion of structural unit (a) in polycarbonate resin (A), Other dihydroxy compounds used in the production of resin (A) include alicyclic dihydroxy compounds with low heat resistance. Selecting hydroxy compounds, bisphenol compounds in polycarbonate resin (A), etc. Examples of methods include reducing the proportion of structural units derived from aromatic dihydroxy compounds. It can be obtained.

[0053] (Polycarbonate resin composition) In forming the A layer, the polycarbonate resin (A ) may be blended with additives to form a polycarbonate resin composition. Examples of additives used in polycarbonate resin compositions include ultraviolet absorbers, light stabilizers, and the like. agent, release agent, lubricant, antioxidant, flame retardant, flame retardant assistant, hydrolysis inhibitor, antistatic agent, foaming agent fillers such as inorganic fillers, and colorants such as dyes and pigments.

[0054] (Manufacturing method of polycarbonate resin molded product (layer A)) The polycarbonate resin molded article (hereinafter simply referred to as "molded article") that is layer A of the laminate of the present invention The production of the polycarbonate resin (A) and the polycarbonate resin (B) may be carried out by Resin compositions (hereinafter collectively referred to as "polycarbonate resin compositions, etc.") This can be done in a variety of ways. Molded articles can also be produced by injection molding. By using a mold that matches the shape, it is possible to manufacture molded products with complex shapes. The molding is carried out using an injection molding machine, and the molding is carried out appropriately depending on the resin composition used and the shape of the product. The molding conditions are set as follows: cylinder temperature, mold temperature, injection pressure, and holding pressure. These include screw rotation speed, cushion amount, injection speed, injection time, pressure holding time, and cooling time. can be done.

[0055] In the production of molded products by injection molding, the cylinder temperature is preferably 200°C to 300°C, more preferably 210°C to 280°C, particularly preferably 220°C to 270°C, The cylinder temperature is preferably 230°C to 260°C. The resin composition is less likely to be thermally decomposed and the molded product is less likely to be discolored. If the melt viscosity of the polycarbonate resin composition is not too high, molding defects and optical distortion can be prevented. This tends to make it less likely to occur.

[0056] The mold temperature is preferably 40°C to 120°C, more preferably 50°C to 100°C, and particularly preferably Preferably, the temperature is 60 to 80° C. If the mold temperature is equal to or lower than the upper limit, the productivity of molded products is improved. On the other hand, if the value is equal to or greater than the lower limit, optical distortion tends to be small. .

[0057] As a means for obtaining the molded article (layer A) in the present invention, as described above, a total dihydroxylation The ratio of the structural unit (a) derived from the dihydroxy compound (1) to the total of the compound is within a specific range. In addition, the cylinder temperature and mold temperature may be set within the above-mentioned specific ranges. The molded article of the present invention can be produced by any of these means alone or in combination. It is possible.

[0058] The molded article of the present invention may have a decorative film layer or a printed layer laminated on at least one surface thereof. By providing a decorative film layer or a printed layer, the appearance of the molded product can be improved. This has the excellent effect of improving the scratch resistance of the surface where the rubber layer and the printed layer are present. The lamination of the inner decorative film and the printed layer can be carried out by a conventionally known method.

[0059] According to the present invention, a polycarbonate resin composition having excellent surface hardness and impact resistance is used. It is possible to provide a formed laminate. This laminate can be used for various purposes as described above, and is particularly suitable for optical applications. It is a material that can be used, and is particularly suitable for optical applications.

[0060] [3.B layer] The B layer in the laminate of the present invention is a mono- or polypentaerythritol poly(meth)acrylate (b1) represented by the following general formula (2) (hereinafter, sometimes simply referred to as the "(b1) component"). There is such a thing.) And a trifunctional or higher functional (meth)acrylate compound ( b2) (hereinafter, sometimes simply referred to as the "(b2) component"), inorganic fine particles (b3) whose surface is coated with an organic functional group ( hereinafter, sometimes simply referred to as the "(b3) component"), A siloxane oligomer (b4) having at least one of (meth)acryloyl group, glycidyl group, and vinyl group in its structure and having a molecular weight of 200 to 3,000 ( hereinafter, sometimes simply referred to as the "(b4) component") and an active energy ray curable resin composition (hereinafter, sometimes simply referred to as the "curable resin composition"). It is a layer formed by curing. .

[0061] [Chemical formula] <000​​​​​​​​​​​​​​represents a methyl group, and y represents an integer of 1 to 5.) and a hydroxy group. In addition, n is an integer of 0 to 4.

[0063] [ka]

[0064] In formula (3), Y1, Y2, and Y3 each contain a (meth)acryloyl group, and At least two of Z1, Z2 and Z3 are (meth)acryloyl groups, and Z1, Z2 and Z3 are each a group having 1 to 4 carbon atoms. It represents an oxyalkylene group and an alkyl group having 2 to 10 carbon atoms.

[0065] <Mono- or polypentaerythritol poly(meth)acrylate (b1)> The component (b1) is a component that is contained in the curable resin composition for forming the layer B and is irradiated with active energy rays. It is a type of curable compound. By using the component (b1), the curable resin composition can be cured by irradiation with active energy rays. It exhibits good curing properties and has a high crosslink density, making it scratch-resistant, abrasion-resistant, and chemical-resistant. It is possible to form a cured film (layer B) with excellent properties.

[0066] Specific examples of the component (b1) include pentaerythritol tri(meth)acrylate, E O-modified pentaerythritol tri(meth)acrylate, PO-modified pentaerythritol Tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate acrylate, pentaerythritol tetra(meth)acrylate, EO modified pentaerythritol Pentaerythritol tetra(meth)acrylate, PO modified pentaerythritol tetra(meth)acrylate acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, diphenyl Dipentaerythritol tri(meth)acrylate, EO modified dipentaerythritol tri( meth)acrylate, PO modified dipentaerythritol tri(meth)acrylate, Cap Lactone-modified dipentaerythritol tri(meth)acrylate, dipentaerythritol Dipentaerythritol tetra(meth)acrylate, EO modified dipentaerythritol tetra(meth)acrylate acrylate, PO-modified dipentaerythritol tetra(meth)acrylate, caprolactone Modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol pentaerythritol Penta(meth)acrylate, EO modified dipentaerythritol penta(meth)acrylate PO modified dipentaerythritol penta(meth)acrylate, caprolactone modified Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa( meth)acrylate, EO modified dipentaerythritol hexa(meth)acrylate, P O-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol Taerythritol hexa(meth)acrylate, Tripentaerythritol tetra(meth)acrylate ) acrylate, EO modified tripentaerythritol tetra(meth)acrylate, PO Modified tripentaerythritol tetra(meth)acrylate, caprolactone modified tripentaerythritol tetra(meth)acrylate Tripentaerythritol tetra(meth)acrylate, Tripentaerythritol penta(meth)acrylate meth)acrylate, EO modified tripentaerythritol penta(meth)acrylate, P O-modified tripentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol penta(meth)acrylate Pentaerythritol penta(meth)acrylate, tripentaerythritol hexa( meth)acrylate, EO modified tripentaerythritol hexa(meth)acrylate, PO modified tripentaerythritol hexa(meth)acrylate, caprolactone modified tripentaerythritol hexa(meth)acrylate Tripentaerythritol hexa(meth)acrylate, Tripentaerythritol heptaacrylate (Meth)acrylate, EO modified tripentaerythritol hepta(meth)acrylate , PO-modified tripentaerythritol hepta(meth)acrylate, caprolactone-modified Tripentaerythritol hepta(meth)acrylate, Tripentaerythritol octaacrylate Tripentaerythritol octa(meth)acrylate EO modified tripentaerythritol octa(meth)acrylate , PO-modified tripentaerythritol octa(meth)acrylate, caprolactone-modified Tripentaerythritol octa(meth)acrylate, etc. "PO" means propylene oxide. Two or more types can be used in combination. Among these, dipentaerythritol polyacrylate is the most suitable from the viewpoint of the balance between weather resistance and scratch resistance of the cured film. Poly(meth)acrylate is preferred, and caprolactone-modified dipentaerythritol poly( Dipentaerythritol poly(meth)acrylate is more preferred. As a cured film, dipentaerythritol penta(meth)acrylate is used from the viewpoint of weather resistance of the cured film. Dipentaerythritol hexa(meth)acrylate is preferred, and caprolactone is preferred. Caprolactone-modified dipentaerythritol penta(meth)acrylate and caprolactone-modified dipentaerythritol penta(meth)acrylate Pentaerythritol hexa(meth)acrylate is more preferred.

[0067] In the general formula (2), the compound modified with caprolactone is preferred from the viewpoint of scratch resistance of the cured film. (Meth)acryloyl group (CH2=CR-CO(O(CH2)5C=O)y -O-) The value of y is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. The number of (meth)acryloyl groups modified with caprolactone is Per molecule of modified mono- or polypentaerythritol poly(meth)acrylate The average is 1 or more and 2n+2 or less, but the lower limit is preferably 2 or more from the viewpoint of weather resistance. The upper limit is preferably 2n+1, more preferably 2n, from the viewpoint of the scratch resistance and weather resistance of the cured film. stomach.

[0068] The amount of the component (b1) to be blended is 10% based on the total solid content of the active energy ray-curable resin composition. % by mass or more is preferable, 25% by mass or more is more preferable, and 40% by mass or more is particularly preferable. In addition, it is preferably 90% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less. It is particularly preferable that the content of the component (b1) is less than 10% by mass. Furthermore, if the content of component (b1) exceeds 90 mass %, the cured film will not have any cracks. For example, cracks will occur in the cured film after a durability test. The amount of the component (b1) blended is preferably within the range of the upper limit mentioned above, and the greater the amount, the better the durability of the cured film. The amount of the component (b1) blended is not less than the lower limit mentioned above. The lower the content, the better the weather resistance and adhesion of the cured film.

[0069] <Tri- or higher functional (meth)acrylate compound (b2)> The component (b2) is a component that is contained in the curable resin composition for forming the layer B and is irradiated with active energy rays. A type of curable compound that contains three or more (meth)acryloyl groups in one molecule. By using the component (b2), the curable resin It can impart toughness to the cured film of the composition, improve adhesion, and further improve the weather resistance of the cured film (layer B). It can improve sexuality. The component (b2) may be an isocyanuric skeleton-containing (meth)acrylate compound (B1), and a polyisocyanate (B2) having three or more isocyanate groups and one or more ( Hydroxy(meth)acrylate having a meth)acryloyloxy group and a hydroxy group (B3) and the resulting urethane (meth)acrylate compound (hereinafter simply referred to as "( B23) ingredient).

[0070] ((B1) component) (B1) is bis(2-acryloyloxyethyl)hydroxyethylisocyanate. urate, tris(2-acryloyloxyethyl) isocyanurate, bis(2-acryloyloxyethyl) Tris(2-acryloyloxypropyl)hydroxyethyl isocyanurate, These may be used alone or in combination. Among these, the component (B1) is preferably a catalyst having good polymerization activity and high polymerization activity. From the viewpoint of excellent abrasion resistance, bis(2-acryloyloxyethyl)hydroxyethylisocyanide isocyanurate and tris(2-acryloyloxyethyl)isocyanurate are preferred .

[0071] (Component (B23)) The polyisocyanate (B2) may be a polyisocyanate having the skeleton represented by the above formula (3) in its structure. There are no particular limitations as long as the isocyanurate is aliphatic, alicyclic or aromatic isocyanurate. Among them, cyanate derivatives are preferred from the viewpoint of weather resistance and excellent hardness of the cured coating film. , hexamethylene diisocyanate, isophorone diisocyanate-derived isocyanates An anurate derivative of isocyanate is preferred. Duranate TPA-100, TKA-100, MHG-80B, etc. manufactured by Tosoh Corporation Coronate HX, 2715, etc., Stabio D-370N, D-375 manufactured by Mitsui Chemicals, Inc. N, EVONIK's VESTANAT T-1890, etc. can be used. They may be used alone or in combination of two or more.

[0072] Hydroxy(meth)acryloyloxy group having one or more (meth)acryloyloxy groups and hydroxy groups The acrylate (B3) is not particularly limited, and examples thereof include hydroxy(meth)acrylates. In addition to acrylate (d2), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Dialkyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, etc. Among these, 2-hydroxyethyl (meth)acrylate is the most popular due to its excellent surface hardness and adhesion. acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate ) acrylate, dipentaerythritol penta(meth)acrylate, etc. are more preferred. These hydroxy(meth)acrylates (B3) may be used alone or in combination of two or more. They may be used in combination.

[0073] Furthermore, as a raw material for the above urethane (meth)acrylate compound, A diol having a silyl group may be used. There is no particular limitation on the diol to be used. , for example, low molecular weight diols, polyether diols, polycaprolactone dipolyols , polycarbonate dipolyols, etc.

[0074] The method for synthesizing component (B23) is not particularly limited, and known polyurethane synthesis methods can be used. For example, polyisocyanate (B2) can be mixed with a polyurethane-forming catalyst. Then, hydroxy(meth)acrylate (B3) is added dropwise at 50 to 90°C to react. This allows the (B23) component to be obtained.

[0075] As the polyurethane-forming catalyst, an amine catalyst, an organometallic catalyst, or the like can be used. Amine catalysts include triethylamine, N,N-dimethylcyclohexylamine, dimethylamine, As the organometallic catalyst, an organotin compound is preferably used. Stannous octoate, stannous laurate, dibutyltin dilaurate, Djibutanol dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate, etc. These may be used alone or in combination of two or more. From the viewpoint of obtaining a high catalytic effect, organometallic catalysts are preferred, and dibutyltin dilaurate is preferred. It is more preferable. In addition, it facilitates temperature control during synthesis and reduces the viscosity of the resulting component (d). For the purpose of improving workability, the reaction solution may be diluted with a solvent or the like as needed.

[0076] The weight average molecular weight of the component (B23) is preferably 5,500 to 60,000. When the weight average molecular weight of the component (B23) is within the above range, the abrasion resistance of the resulting cured film is improved. It becomes easy to achieve both scratch resistance and weather resistance. The weight average molecular weight of component (B23) is 5, It is more preferable that it is 500 to 30,000, and it is 5,500 to 25,000. When the weight average molecular weight is 5,500 or more, the weather resistance of the obtained cured film is improved. It will get better.

[0077] The weight average molecular weight of component (B23) was determined by gel permeation chromatography. Weight average molecular weight measured by GPC method under the following conditions, converted into standard polystyrene. (Mw). Apparatus: Tosoh Corporation high-speed GPC instrument HLC-8320GPC UV detector: Tosoh UV-8320 ·Flow rate: 0.35mL / min ·Inlet temperature: 40℃ Oven temperature: 40℃ ·RI temperature: 40℃ ·UV wavelength: 254nm Sample injection volume: 10 μL · Columns: Three columns connected in the order of (1) to (3). (1) Tosoh Corporation TSKgel superHZM-M (4.6mm ID x 15cm) mL) (2) Tosoh Corporation TSKgel superHZM-M (4.6mm ID x 15cm) mL) (3) Tosoh Corporation TSKgel HZ2000 (4.6 mm ID x 15 cm L) Guard column: TSKguardcolumn SuperHZ-L manufactured by Tosoh Corporation (4.6mm ID x 3.5cm L) Solvent: THF (tetrahydrofuran) (stabilizer: BHT (dibutylhydroxytoluene) ) Sample concentration: Adjusted to 0.2% resin by mass

[0078] The amount of component (b2) blended is 10 mass % based on the total solid content of the active energy ray-curable resin composition. % by mass or more, more preferably 15% by mass or more, and even more preferably 30% by mass or more. It is particularly preferable that the content is 90% by mass or less, and more preferably 70% by mass or less. If the content of the (b2) component is less than 10% by mass, sufficient A cured film having good adhesion cannot be obtained. In addition, when the content of component (b2) exceeds 90% by mass, If the temperature is too high, a cured film having sufficient scratch resistance cannot be obtained. The higher the amount of component (b2) blended, the stronger the toughness of the cured film, provided it does not exceed the upper limit mentioned above. In addition, the blending amount of component (b2) is preferably at least the above lower limit. The lower the content, the better the coating hardness and chemical resistance of the cured film.

[0079] <Inorganic fine particles whose surfaces are coated with organic functional groups (b3)> The component (b3) is a component that is contained in the curable resin composition for forming the layer B and is irradiated with active energy rays. The component (b3) is a type of curable compound. By using the component (b3), a curable resin composition In the cured film, component (b3) is less likely to aggregate and has excellent transparency, and the crosslinking density with the inorganic fine particles is high. By incorporating a (meth)acryloyl copolymer with a high hardness, a hardness of It is possible to provide a curable resin composition capable of forming a hard coat layer.

[0080] The average primary particle diameter of the inorganic fine particles is preferably 1 nm to 200 nm, and the transparency of the cured film is good. From the viewpoint of the efficiency, the thickness is more preferably 150 nm or less, and even more preferably 100 nm or less. The lower limit of the average primary particle size of the fine particles is preferably 5% or less, because raw materials are readily available. nm or more, and more preferably 10 nm or more.

[0081] The movement of inorganic fine particles in the above range is governed by thermal diffusion rather than sedimentation due to gravity, so that the curing property is It is possible to stably disperse particles in the resin composition, which is also effective when forming a cured film (layer B). In addition, the inorganic fine particles can be present on the surface of the inorganic fine particles. The smaller the thickness, the better the optical properties tend to be. The average primary particle size of inorganic fine particles is the size of particles observed using an electron microscope such as a TEM. The average diameter of the above.

[0082] Examples of inorganic particles include silica (including organosilica sol), alumina, titania, Zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride Magnesium, smectite, synthetic smectite, vermiculite, ITO (indium oxide) antimony / tin oxide), ATO (antimony / tin oxide), tin oxide, indium oxide, aluminum oxide These inorganic particles may be contained in one kind or in two or more kinds. Among them, silica (including organosilica sol) is difficult to obtain as a raw material. It is preferred because it is easy to modify the particle surface and to ensure dispersion stability. It is used.

[0083] The inorganic fine particles (b3) whose surfaces are coated with organic functional groups may be commercially available. Alternatively, inorganic fine particles may be used which are produced by coating the surfaces of the inorganic fine particles with organic functional groups. The inorganic fine particles coated with organic functional groups are inorganic fine particles having organic functional groups on the surface. It is also possible to use a material that has been coated with an organic functional group.

[0084] Colloidal silica, which is silica dispersed in water, is a surface-modified colloidal silica. This is preferable from the viewpoints of the transparency of layer B, the weather resistance of the laminate, and the laminate itself. The colloidal silica can be modified with compounds having hydrolyzable silicon groups or hydroxy groups. These compounds can be used as the compounds having a silicon group bonded thereto. In the case of a compound having a hydrolyzable silicon group, the compound may be one or more of the following: Silanol groups are generated and these silanol groups are transferred to the silanols present on the colloidal silica surface. The surface-modified colloidal silica is produced by reacting with and bonding to the alkyl groups.

[0085] Examples of the silicon group-containing compound include tetramethoxysilane and tetraethoxysilane. Silane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane Lanthanum, dimethyldimethoxysilane, trimethylmethoxysilane, β-(meth)acryloyl hydroxyethyltrimethoxysilane, γ-(meth)acryloyloxypropyltrimeth oxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane ) Acryloyloxypropylmethyldimethoxysilane, vinyl dimethoxysilane, vinyl dimethoxysilane Nyltriethoxysilane, vinylmethyldimethoxysilane, p-vinylphenyltrimethysilane hydroxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ- Glycidyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane , γ-styryltrimethoxysilane, p-styryltrimethoxysilane, 3-mercapto Examples include propylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. It can be obtained.

[0086] In addition, silane having a mercapto group is combined with a polyfunctional (meth)acrylate or a high molecular weight (meth)acrylate. p) Derivatives with acrylate added, silane with isocyanate group and hydroxy group added A modified silicon group-containing compound such as a derivative to which a polyfunctional (meth)acrylate having It may be used.

[0087] Among these, the preferred silane compounds (silane coupling agents) are those which are readily available. From this point of view, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxy Propyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane is an example.

[0088] The surface modification of colloidal silica is carried out by combining colloidal silica with a compound containing hydrolyzable silicon groups. The reaction can be carried out by reacting the compound, the catalyst and water at 20 to 100°C for 1 to 40 hours. do.

[0089] Examples of the catalyst used in the surface modification reaction include hydrochloric acid, hydrofluoric acid, and hydrobromic acid. inorganic acids such as sulfuric acid, nitric acid, phosphoric acid; formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, Acrylic acid, methacrylic acid and other organic acids; alkali; acetylacetone aluminum, aluminum Aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate, aluminum diisocyanate Aluminum diisobutoxide ethyl acetoacetate, Aluminum diisobutoxide ethyl acetoacetate acetate, boric acid butoxide, dibutyltin dilaurate, and dibutyltin dioctate. can be done.

[0090] The amount of these catalysts used is the total amount of colloidal silica and the hydrolyzable silicon group-containing compound. The amount is preferably 0.0001 to 5 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass. preferable. The amount of water in the surface modification reaction is 0.5 to 10 times the amount of the hydrolyzable silicon group. 0 equivalents is preferred, and 1 to 30 equivalents is more preferred. The colloidal silica is preferably acidic or basic colloidal silica. Preferably it is loidal silica.

[0091] The content of the inorganic fine particles (b3) in the curable resin composition is determined by the active energy ray curing agent. The content is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the mixture. It is preferably 20% by mass or more, and more preferably 50% by mass or less. It is more preferably 0% by mass or less, and particularly preferably 35% by mass or less. If the content of the (b3) component is less than 10 mass %, a cured film having sufficient abrasion resistance cannot be obtained. Furthermore, if the content of component (b3) exceeds 50% by mass, the transparency of the cured film may decrease to such an extent that For example, cracks may occur in the cured film after the durability test. do. The amount of component (b3) blended is preferably within the above upper limit, and the greater the amount, the better the abrasion resistance of the cured film. The amount of component (b3) to be added may be as small as possible, provided that it does not fall below the lower limit mentioned above. The less the temperature is, the better the adhesion and weather resistance of the cured film will be.

[0092] <About Siloxane Oligomer (b4)> The component (b4) is selected from the group consisting of a (meth)acryloyl group, an epoxy group, and a vinyl group. A carbon black having at least one functional group and a weight average molecular weight of 200 to 3,000. It is a xanthane oligomer.

[0093] The siloxane oligomer is a silane compound (silane copolymer) represented by the following general formula (4): and at least one selected from the group consisting of a silane compound C represented by the following general formula (5): It is preferable that the silane compound is a condensation product of at least one silane compound (including at least silane compound A). I wish.

[0094] Silane compound C (silane coupling agent): (R 1 ) n (R 2 ) m Si(OR 3 ) 4-n-m (4) (In the formula, R 1 When a plurality of groups are present, they may be the same or different, and may be (meth)acryloyl groups. , an epoxy group, or a vinyl group; R 2 When there are multiple R 3 When there are multiple They may be the same or different and represent an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms. where n is an integer from 1 to 3, m is an integer from 0 to 2, and n+m is an integer from 1 to 3.

[0095] Silane Compound D: (R 2 ) n Si(OR 3 ) 4-n (5) (In the formula, R 2 When there are multiple groups, they may be the same or different and are organic groups having 1 to 12 carbon atoms. and R 3 When there are a plurality of groups, they may be the same or different and are alkyl groups having 1 to 5 carbon atoms. group or an acyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 3.

[0096] The hydrolysis condensation products (siloxane oligomers) of the above silane compounds may be used alone or in any combination. Any two or more of these may be used in combination, but the silanized silanol represented by the general formula (5) Siloxane oligomers consisting only of Compound D are not included in this component.

[0097] Here, the hydrolysis condensation product of the silane compound (siloxane oligomer) is a silane compound. 1 to 3 contained in the item OR 3 It is not necessary for all groups to be hydrolyzed; for example, if only one Hydrolyzed 1 or more of the above, or a mixture of these It may also be a mixture.

[0098] The siloxane oligomer is a siloxane compound in a hydrolyzate produced by hydrolysis of the silane compound. The lanol groups were condensed by dehydration or dealcoholization to form Si-O-Si bonds. In the embodiment of the present invention, it is not necessary for all silanol groups to be condensed, and The condensation product may be a product in which only a small portion of the silanol groups have condensed, or a product in which most (including all) of the silanols have condensed. The term also includes those in which the alkyl group is condensed, and mixtures thereof.

[0099] In general formula (4), R 1 Examples of the organic group include a vinyl group, an allyl group, a glycidyl group, and the like. epoxycycloalkyl groups (e.g., 3,4-epoxycyclohexyl groups), (methyl p) acryloyloxy groups, as well as substituted derivatives of these groups. do. In general formula (4), R 1 When there are a plurality of, they may be the same or different.

[0100] Also, R 3 Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n- Propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentanol Examples of the acyl group having 1 to 6 carbon atoms include acetyl. Examples of the aryl group include a propionyl group, a butyryl group, a valeryl group, and a caproyl group. . Multiple R's present in general formula (4) 3 may be the same or different from each other.

[0101] In general formulas (4) and (5), R 2 Examples of the monovalent organic group having 1 to 12 carbon atoms include For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl butyl group, sec-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, etc. Alkyl group; acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, thiazolinol group acyl groups such as thioyl groups and caproyl groups; phenyl groups, ureido groups, amide groups, fluoro groups, Examples include acetamide groups, isocyanate groups, and substituted derivatives of these groups. It is possible.

[0102] R 2 Substituents in the substituted derivatives of the formula (I) include, for example, halogen atoms, substituted or unsubstituted Substituted amino group, hydroxyl group, mercapto group, isocyanate group, ureido group, ammonium salt However, R groups consisting of these substituted derivatives can also be used. 3 The number of carbon atoms in The number of carbon atoms in the substituents is 12 or less. In the general formulas (4) and (5), R 2 When there are multiple, they may be the same or different. stomach.

[0103] Specific examples of such silane compounds C (silane coupling agents) include 2-(meth) Acryloyloxyethyltrimethoxysilane, 2-(meth)acryloyloxyethyl Triethoxysilane, 2-(meth)acryloyloxyethylmethyldimethoxysilane, 2-(meth)acryloyloxyethylmethyldiethoxysilane, 3-(meth)acrylo Acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane Ethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3 -(meth)acryloyloxypropylmethyldiethoxysilane, 4-(meth)acryloyloxypropylmethyldiethoxysilane Acryloyloxybutyltrimethoxysilane, 4-(meth)acryloyloxybutyltriethoxy methyldimethoxysilane, 4-(meth)acryloyloxybutylmethyldimethoxysilane, 4-(meth)acryloyloxybutylmethyldimethoxysilane p) Silanes having a (meth)acryloyl group, such as acryloyloxybutylmethyldiethoxysilane Silane coupling agent; 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Silane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, etc. Silane coupling agents containing epoxycycloalkyl groups; 3-glycidoxypropyl Glycidyl groups such as trimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane Silane coupling agents having the formula: vinyltrimethoxysilane, vinyltriethoxysilane and the like.

[0104] In addition, R in general formula (5) 3 Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, Ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group Examples of the acyl group having 1 to 6 carbon atoms include an acyl group, an n-pentyl group, and the like. Examples include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. It is possible. In general formula (5), R 3 When there are a plurality of, they may be the same or different.

[0105] Examples of silane compounds represented by general formula (5) include those having one non-hydrolyzable group and three hydroxyl groups. Examples of silane compounds substituted with decomposable groups include methyltrimethoxysilane, methyltrimethoxysilane, Ethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyl Trimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane silane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane Ethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, 2-ethylhexyl n-Dodecyltrimethoxysilane, n-Decyltrimethoxysilane, n-Dodecyltrimethoxysilane vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane Silane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyl Triethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltri Ethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3- Trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2- Hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2 -Hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane , 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethylsilane Triethoxysilane, 3-Isocyanatopropyltriethoxysilane, 3-Ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, methyltriacetylsilane Examples include trialkoxysilanes such as xysilane.

[0106] In addition, examples of the silane compound represented by the general formula (5) include a silane compound having two non-hydrolyzable groups and two Examples of silane compounds substituted with the hydrolyzable group include dimethyldimethoxysilane, dimethyldimethoxysilane, and dimethyldimethoxysilane. Diethyldiethoxysilane, Diethyldimethoxysilane, Diethyldiethoxysilane, Di-n -propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldi Methoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane , di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldimethoxysilane Di-n-hexyldiethoxysilane, Di-n-hexyldimethoxysilane, Di-n-hexyldiethoxysilane Silane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di -n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-decyl Dimethoxysilane, di-n-dodecyldimethoxysilane, di-n-cyclohexyldimeth Dimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, In addition to dialkoxysilanes such as diphenyldiethoxysilane, dimethyldiacetylsilane Examples include xysilane.

[0107] In addition, examples of silane compounds represented by general formula (5) include those having three non-hydrolyzable groups and one Examples of the silane compounds substituted with the hydrolyzable group include tributylmethoxysilane, tributylsilane, Methylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, trif Examples of suitable silanes include phenylmethoxysilane and triphenylethoxysilane.

[0108] In an embodiment of the present invention, the siloxane oligomer (component (b4)) is a siloxane oligomer represented by the above formula (4) The hydrolysis condensation reaction was carried out using only one silane compound C (silane coupling agent) represented by the formula: However, a combination of two or more silane compounds C (silane coupling agents) may be used. Hydrolysis condensation product or one or more kinds of silane compound C (silane coupling agent) and the above A hydrolysis condensation product in which one or more silane compounds D represented by formula (5) are used in combination may also be used. stomach.

[0109] In an embodiment of the present invention, the siloxane oligomer (component (C)) is a commercially available polysiloxane. Although the silane may be used as it is, the silane compound (at least one of silane compounds C and D) may be used as the silane compound. In this case, a silane compound (including a silane compound C) can be prepared, and its hydrolysis and condensation product can be used. In this case, a silane compound previously prepared by hydrolysis and condensation may be used. 3) When preparing the silane compound (silane compounds C and D, at least silane compound C is included) ) and the siloxane oligomers made from the silane compounds generated during this process are used as they are. You may do so.

[0110] (Method of producing component (b4)) Hydrolysis of silane compounds (silane compounds C and D, including at least silane compound C) The condensation conditions are such that at least a portion of the silane compound is hydrolyzed to convert the hydrolyzable group into a silane compound. There are no particular limitations on the type of hydroxyl group, as long as it is converted into a hydroxyl group or undergoes a condensation reaction. However, as an example, it can be implemented as follows.

[0111] (Water used for hydrolysis) The water used for hydrolysis of the silane compound represented by the above formula (4) or (5) is obtained by reverse osmosis. It is preferable to use water that has been purified by a method such as membrane treatment, ion exchange treatment, or distillation. By using such purified water, side reactions are suppressed and the reactivity of hydrolysis is improved. It is possible.

[0112] The amount of water used is determined by the hydrolysis of the silane compound (-OR 2 ) for 1 mole of the total amount of Preferably, the amount is 0.1 to 3 mol, more preferably 0.3 to 2 mol, and even more preferably 0.3 to 1 mol. By using such an amount of water, the hydrolysis reaction rate can be increased to the desired level. The reaction conditions can be optimized by adjusting the reaction temperature.

[0113] (organic solvent) There are no particular limitations on the solvents that can be used in the hydrolysis and condensation reaction of silane compounds. Preferred examples of such solvents include propyl alcohol, butyl alcohol, Alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoaromatic alkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol Cholesterol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol Examples include glycol monoalkyl ether acetate and propionate esters. Among these solvents, propyl alcohol, methyl isobutyl ketone, diethylene glycol Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, and methyl 3-methoxypropionate are preferred, One selected from these may be used alone or two or more may be used in combination.

[0114] (catalyst) There are no particular limitations on the catalysts that can be used in the hydrolysis and condensation reaction of silane compounds. Preferred examples of such catalysts include acid catalysts (e.g., hydrochloric acid, sulfuric acid, etc.). , nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acid, acidic ion exchange resins, various Lewis acids), base catalysts (e.g., ammonia, primary amines, Nitrogen-containing compounds such as amines, secondary amines, tertiary amines, and pyridine; basic ion-exchange resins Fats; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate; sodium acetate, etc. carboxylic acid salts; various Lewis bases), or alkoxides (e.g., zirconium alkoxides) oxide, titanium alkoxide, aluminum alkoxide). As the aluminum alkoxide, tetra-i-propoxyaluminum is used. The amount of catalyst used is determined based on the molar ratio of the silane compound from the viewpoint of promoting the hydrolysis reaction. The amount of the hydroxybenzoate can be set to preferably 0.2 moles or less per mole of the monomer, and can be set to 0.00001 to 0.1 moles. Molar is more preferred.

[0115] (Reaction conditions) The reaction temperature and reaction time for the hydrolysis and condensation of the silane compound can be set appropriately. For example, For example, the following conditions can be used: The reaction temperature is preferably 40 to 200°C, more preferably The reaction temperature is 50 to 150° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 By using such a reaction temperature and reaction time, the hydrolysis reaction This hydrolysis and condensation reaction can be carried out most efficiently. The reaction may be carried out in one step by adding the silane compound, water and catalyst at once, or The hydrolysis and condensation reactions are carried out by adding the substance, water, and catalyst to the reaction system in several portions. The reaction may be carried out in multiple stages. After the hydrolysis and condensation reaction, a dehydrating agent is added, and then If necessary, evaporation is carried out to remove water and the produced alcohol from the reaction system. can be removed from

[0116] (Molecular weight of component (b4)) From the viewpoint of compatibility with the resin composition, the siloxane oligomer constituting component (b4) is Its weight average molecular weight (hereinafter referred to as "Mw") is in the range of 200 to 3,000. It is preferably 300 to 2,500, more preferably 500 to 2,000.

[0117] In the present invention, the weight average molecular weight (Mw) is determined by the gel permeation chromatography (GPC) method. The measurement was carried out by the gel permeation chromatography (GPC) method. A tetrahydrofuran solution (concentration: 0.3% by mass) of the above was prepared. Columns (TSKgel Super HM-H*4, TSKguardcolumn S The measurement conditions were as follows: Injection volume of the above solution: 20 μl, flow rate: 0.6 ml / min, eluent: tetrahydrofuran (Stabilizer: BHT: 2,6-di-tert-butyl-p-cresol), column temperature: 40°C. From the measurement results, the weight average molecular weight (Mw) was calculated in terms of standard polystyrene.

[0118] (Content of component (b4)) Content of siloxane oligomer (b4) in active energy ray-curable resin composition From the viewpoint of improving the dispersibility of the component (b3) in the cured film and improving the scratch resistance of the cured film, It is preferably 1% by mass or more, and more preferably 2% by mass or more, based on 100% by mass of the energy ray-curable compound. It is more preferable that the content is 2.5 mass % or more, and even more preferable that the content is 2.5 mass % or more. It is more preferable that the content is 10 mass % or less, and even more preferable that the content is 9 mass % or less. The content of the component (b4) is preferably 1 mass % or less, and more preferably 8 mass % or less. If the content is less than 100%, the dispersibility of component (b3) in the cured film will be insufficient, resulting in a deterioration in the appearance of the cured film. Furthermore, if the content of component (b4) exceeds 10 mass %, the abrasion resistance of the coating film decreases. In addition, the silane compound that was not used to coat the inorganic fine particles when synthesizing component (b3) It is not easy to completely remove the hydrolysis condensation products (siloxane oligomers) of It is preferable to prepare a synthesis recipe taking into account the amount of component (b4) produced in the preparation stage of component (b3). It's nice.

[0119] <Other Monomers> The active energy ray-curable resin composition of the present invention comprises (b1), (b2), (b3), and (b4). In addition to component b4), other active energy ray-curable compounds include (b1) and (b2) (b1), (b2), and (b3) may contain (meth)acrylate compounds other than the components (b1), (b2), and (b3). . Examples of the other active energy ray-curable compounds include polymers such as (meth)acrylates. a monofunctional (meth)acrylate or a polyfunctional (meth)acrylate having a carboxylic unsaturated bond; Examples include polyester (meth)acrylate and epoxy (meth)acrylate. The material may be selected appropriately depending on the required performance of the membrane. Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethylenediamine di ... butyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl ( meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Acrylate, Lauryl (meth)acrylate, Stearyl (meth)acrylate, Morpho (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy Dipropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin Dimethylaminoethyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, Diethylamino Polyethyl (meth)acrylate, Tricyclodecane (meth)acrylate, Polyethylene Glycol mono(meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofuran Drofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyl Clopentenyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate meth)acrylate, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate acrylate, phenoxyethyl (meth)acrylate, phenyl (meth)acrylate, etc. (meth)acrylate, phthalic anhydride and 2-hydroxyethyl (meth)acrylate Examples include additions of the above.

[0120] Examples of the polyfunctional (meth)acrylate include neopentyl glycol di(meth)acrylate. ) acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol (Number of repeating units (hereinafter referred to as "n") = 2 to 15) di(meth)acrylate, poly Propylene glycol (n=2-15) di(meth)acrylate, polybutylene glycol (n=2-15) di(meth)acrylate, 2,2-bis(4-(meth)acryloxy) Ethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, (2-(meth)acryloyl)propane, trimethylolpropane diacrylate, bis(2-(meth)acryloyl)propane hydroxyethyl)-hydroxyethyl-isocyanurate, trimethylolpropane tri(methyl acrylate, tris(2-(meth)acryloxyethyl)isocyanurate, pentaerythritol Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Dipentaerythritol tetra(meth)acrylate, Dipentaerythritol Dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Examples include:

[0121] Examples of polyester poly(meth)acrylate include trimethylolethane and copoly(meth)acrylate. Polyester (meth)acrylate obtained by reacting vinyl acid and (meth)acrylic acid, tri Methylolpropane is reacted with succinic acid, ethylene glycol, and (meth)acrylic acid. Examples of the polyester include polyester (meth)acrylate. Epoxy (meth)acrylates include glycidyl (meth)acrylate, 2-hydroxybenzoate, 2-Hydroxypropyl (meth)acrylate glycidyl ether, 2-hydroxypropyl (meth)acrylate ) acrylate glycidyl ether, 2-hydroxybutyl (meth)acrylate glycidyl Diethyl ether and the like. These can be used alone or in combination of two or more.

[0122] <Ultraviolet absorber (c1)> The curable resin composition preferably contains an ultraviolet absorber (c1) from the viewpoint of weather resistance. In view of the fact that a large amount of the benzophenone-based ultraviolet absorber is contained in the curable resin composition, In addition, from the viewpoint of preventing yellowing of the A layer, triazine or benzotriazoline is more preferable. A methylol-based ultraviolet absorber is more preferred.

[0123] Examples of the ultraviolet absorber (c1) include triazine compounds, benzophenone compounds, benzophenone compounds, benzoic acid phenyl compounds, salicylic acid phenyl compounds, cyclohexyl benzoate compounds, Examples thereof include oxalic acid anilide compounds. Examples of triazine compounds include 2-[4-{(2-hydroxy-3-dodecyl) 4,6-bis(2,4-dimethylamino)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylamino)-2-hydroxyphenyl phenyl)-1,3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyl) {2-hydroxyphenyl}-4,6-bis(2,4-dimethylamino)-4,6-bis(2-hydroxy-propyl)oxy 2-(4-(octylphenyl)-1,3,5-triazine, 2-(4-(octyl-2-methylethanoic acid) hydroxy-2-hydroxyphenyl-4,6-{bis(2,4-dimethylphenyl) }-1,3,5-triazine, 2-[4-{(2-hydroxy-3-dodecyloxy- 4,6-bis(2,4-dimethylphenyl)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-4,6-bis(2-hydroxy ... )-1,3,5-triazine, 2-[4-{(2-hydroxy-3-tridesiloxy- 4,6-bis(2,4-dimethylphenyl)-4,6-bis(hydroxyphenyl)-2-hydroxyphenyl (triazine), and the like.

[0124] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2 -hydroxy-4-methoxy-benzophenone and the like. Examples of benzotriazole compounds include 2-(2H-benzotriazole-2 -yl)-4,6-bis(I-methyl-1-phenylethyl)phenol, 2-(2H- Benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1, 1,3,3-tetramethylbutyl)phenol and the like.

[0125] Examples of phenyl benzoate compounds include phenyl salicylate, p-tert- Butylphenyl salicylate, p-(1,1,3,3-tetramethylbutyl)phenyl salicylate lysates, etc.

[0126] Examples of the phenyl salicylate compounds include phenyl salicylates and 3-hydroxybenzoates. hydroxyphenyl benzoate, phenylene-1,3-dibenzoate, etc.

[0127] Examples of oxalic acid anilide compounds include 2-ethoxy-2'-ethyloxalanilide. oxalanilide, 2-ethoxy-2'-dodecyloxalanilide, and the like.

[0128] Among these, the curable resin composition has good curability and can produce a cured film with high surface hardness. From the viewpoint of the ease of use, triazine compounds or oxalic acid anilide compounds are preferred, and 2- [4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxypropyl phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxy phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2 -ethoxy-2'-dodecyloxalanilide is more preferred. These can be used alone or in combination of two or more.

[0129] Furthermore, from the viewpoint of scratch resistance of the cured film, 2-[4-{(2-hydroxy-3-dodecyloxy -propyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) phenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyl 4,6-bis(2,4-dimethylamino)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylamino)-2-hydroxyphenyl It is preferable to use a combination of 1,3,5-triazine and 1,3,5-triazinyl benzoate.

[0130] The content of the ultraviolet absorber (c1) in the curable resin composition is preferably higher from the viewpoint of weather resistance. It is preferable that the thickness is low from the viewpoint of scratch resistance. The content of the ultraviolet absorber (c1) in the curable resin composition is determined by the active energy ray curing property. The amount is preferably 0.5 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the compound, and more preferably 0.5 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the compound. More preferably, the amount is from 1 part to 5 parts by mass.

[0131] <Hindered amine light stabilizer (c2)> The curable resin composition contains a hindered amine light stabilizer (c2) from the viewpoint of weather resistance. These may be used alone or in combination of two or more. Examples of the hindered amine light stabilizer (c2) include 1, 2, 3, manufactured by ADEKA Corporation. ,4-Butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidino β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro) [5,5] undecane) condensation product with diethanol (trade name: ADK STAB (registered trademark) The same applies below.)LA-63P) 1,2,3,4-butanetetracarboxylic acid and 2,2,6, 6-Pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2 ,4,8,10-tetraoxaspiro[5,5]undecane) condensation product with diethanol (Product name: ADK STAB LA-68P), 1,1-dimethylethyl hydrochloride manufactured by BASF Condensation product of peroxide with octane, decanedioic acid bis(2,2,6,6-tetramethyl- 1-(octyloxy)-4-piperidinyl) ester, 1,1-dimethylethyl hydrochloride Reaction products of peroxide and octane (e.g., Tinuvin (trade name; the same applies below)) 123 ), 2-butyl-2-[3,5-di(tert-butyl)-4-hydroxybenzyl]malon Bis(1,2,2,6,6-pentamethyl-4-piperidyl)phosphate (trade name: Tinuvin 1) 44), 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6- Tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)- 1,3,5-triazine (trade name: Tinuvin 152), bis(1,2,2,6) sebacate ,6-pentamethylpiperidin-4-yl) and methyl sebacate (1,2,2,6,6- pentamethylpiperidin-4-yl) (trade name: Tinuvin 292) and the like. can be.

[0132] Among these, the curable resin composition has good curability and can maintain weather resistance for a long period of time. From this point of view, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-penta Methyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8, 10-Tetraoxaspiro[5,5]undecane) condensation product with diethanol (trade name: ADK STAB (registered trademark, the same applies hereinafter) LA-63P), 1,1-dimethylethyl hydrochloride Condensation product of peroxide with octane, decanedioic acid bis(2,2,6,6-tetramethyl- 1-(octyloxy)-4-piperidinyl) ester, 1,1-dimethylethyl hydrochloride Reaction products of peroxide and octane (e.g., Tinuvin (trade name; the same applies below)) 123 ), bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate and sebacate Mixture of methyl (1,2,2,6,6-pentamethylpiperidin-4-yl) cinnamate ( Product name: Tinuvin 292) is preferred.

[0133] The content of the hindered amine light stabilizer (c2) in the curable resin composition is determined by the active energy The amount is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the energy ray-curable compound. Parts by mass are more preferred.

[0134] <Photopolymerization initiator> After applying the curable resin composition to the A layer, it is cured by irradiating it with active energy rays such as light. , forming layer B.

[0135] When relatively high-energy electron beams or hard X-rays are used as active energy rays, In this case, the curable resin composition can be cured without adding a photopolymerization initiator. On the other hand, when other active energy rays, such as ultraviolet rays or soft X-rays, are used for curing, In this case, it is preferable to add a photopolymerization initiator to the curable resin composition.

[0136] When a photopolymerization initiator is contained in the curable resin composition, a known photopolymerization initiator may be used. Although a wide variety of compounds can be used, α-hydroxyacetophenone (α-hydroxyphenone) is preferred. alkylphenyl ketones, α-aminoacetophenones, benzyl ketals, etc. Non-type compounds; Acylphosphine oxide type compounds; Oxime ester compounds; Oxif Phenyl acetate esters; Benzoin ethers; Aromatic ketones (benzophenones); Ketone / amine compounds; benzoylformic acid and its ester derivatives, etc.

[0137] Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzoin dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxysilane Cyclohexyl phenyl ketone, benzophenone, 2,4,6-trimethylbenzoin dif Phenylphosphine oxide, 2-methyl-[4-(methylthio)phenyl]-2-morph Morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholino) (phenyl)-butan-1-one, Michler's ketone, N,N-dimethylaminobenzoic acid Soamyl, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoyl guanidine These photopolymerization initiators include benzoylformate, methyl benzoylformate, and ethyl benzoylformate. One type may be used alone, or two or more types may be used in combination.

[0138] Among these, it is possible to minimize the decrease in hardening property, and it is easy to obtain and easy to wear. Since it is difficult to cause color, etc., 2-hydroxy-2-methylpropanol is used as at least a part of the photopolymerization initiator. -methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, etc. It is preferable to use hydroxyphenyl ketones.

[0139] In particular, in order to improve the curability of the curable resin composition, 2-methyl-[4-(methyl Thio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethyla α-aminophenylketones such as α-amino-1-(4-morpholinophenyl)-butan-1-one Tons; Benzophenone, Michler's ketone, 2-chlorothioxanthone, isopropyl Thioxanthone, 2,4-diethylthioxanthone and other benzophenones; benzoylformic acid (esters) such as methyl benzoylformate, benzoylformic acid, and ethyl benzoylformate; Oxime esters such as CGI242 (manufactured by Ciba) and OXE01 (manufactured by Ciba) are preferred. Furthermore, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanol Non-, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane It is more preferable to use 2-1-one, benzophenone, methyl benzoylformate, etc. -methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one It is particularly preferred to use methyl benzoylformate.

[0140] When a photopolymerization initiator is contained in the curable resin composition, the content of the photopolymerization initiator is The amount is preferably 2 to 6.5 parts by mass, more preferably 2.5 to 6.5 parts by mass, based on 100 parts by mass of the energy ray-curable compound. When the content of the photopolymerization initiator is equal to or greater than the lower limit, the curability is improved. The resin composition has excellent curability, and if the content is equal to or less than the upper limit, the physical properties of the cured film (layer B) are improved. .

[0141] <Preparation method> The method for producing the curable resin composition involves mixing and stirring the above-mentioned components using a conventional mixer. If necessary, a solvent, a polymerization initiator, an additive, etc. may be mixed. It can be prepared by mixing

[0142] The solvent used in the preparation of the curable resin composition is not particularly limited, and may be (meth) Acryloyl copolymer, multifunctional (meth)acrylate, the material of the substrate that serves as the base for coating, and The solvent to be used is selected appropriately taking into consideration the composition and the method of application of the composition. Examples of suitable solvents include aromatic solvents such as toluene and xylene; methyl ethyl ketone, acetone, Ketone solvents such as methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl alcohol, Propyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, propylene glycol monomethyl ether, Ether solvents such as nisol, phenetole, etc.; ethyl acetate, butyl acetate, isopropyl acetate ester solvents such as ethylene glycol diacetate; dimethylformamide, diethylene glycol diacetate; Amide solvents such as methylformamide and N-methylpyrrolidone; methyl cellosolve, ethyl Cellosolve solvents such as cellosolve and butyl cellosolve; methanol, ethanol, propane alcoholic solvents such as dichloromethane, chloromethane, isopropanol, and butanol; halogen-based solvents such as formaldehyde;

[0143] These solvents may be used alone or in combination of two or more. Among these, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used. It is used.

[0144] Various additives can be added to the curable resin composition as needed. Additives such as antioxidants, anti-yellowing agents, bluing agents, pigments, leveling agents, extinguishing agents, Included are conventional additives such as foaming agents, thickeners, anti-settling agents, anti-static agents and anti-fogging agents.

[0145] The leveling agent may be, for example, a perfluoroalkyl group or a perfluoroalkyl group. Examples of the compound include a compound containing an alkylene skeleton and a compound containing a polydimethylsiloxane structure. can be done. The content of the leveling agent in the curable resin composition affects transparency, coating appearance, adhesion, hardness, etc. From this viewpoint, the amount is preferably 0 to 5 parts by mass relative to 100 parts by mass of the active energy ray-curable compound. The amount is more preferably 0 to 2 parts by mass, and even more preferably 0 to 1 part by mass.

[0146] In addition, when the layer A contains a functional group that can be cured by light or heat, the layer A is irradiated with active energy rays or It may be more preferable to cure the layer A by heating. The layer A and the layer B may have another layer interposed between them.

[0147] The method for applying the curable resin composition is not particularly limited, but may be spin coating, dip coating, or the like. Coating, flow coating, spray coating, bar coating, gravure coating, roll coating, The coating method is preferably a blade coating method, an air knife coating method, or the like. In order to ensure the smoothness and uniformity of the coating film and the adhesion of the cured film (layer B) to layer A, an organic solvent is added. It is preferable to heat the curable resin composition before application in order to reduce the viscosity. Alternatively, the solution may be diluted with a subcritical fluid.

[0148] After forming a coating film on at least one surface of the A layer by the above coating method, it is dried by heating as necessary. The volatile components are removed by drying, and then the coating film is irradiated with active energy rays, etc. A layer consisting of a cured film, i.e., layer B, is obtained.

[0149] When using active energy rays to obtain a cured film, the irradiation method is xenon lamp. low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, carbon arc lamp UV light emitted from a light source such as a tungsten lamp, or particles of 20 to 2000 kV Active energy rays (electron beams), such as electron beams, alpha rays, beta rays, and gamma rays, are extracted from electron accelerators. As for active energy rays, those with good curing properties and productivity are For this reason, ultraviolet light is preferred. A high-pressure mercury lamp, a metal halide lamp, etc., is used as the ultraviolet light source. UV rays are 100mJ / cm2, with wavelengths between 100nm and 400nm. 2 More than 5000mJ / cm 2 It is preferable to irradiate the active energy rays so that the following occurs: The atmosphere for irradiation may be air or an inert gas such as nitrogen or argon.

[0150] The thickness of the B layer after curing is preferably 2 μm or more, and more preferably 3 μm or more, in order to ensure high hardness. The thickness of the layer B is preferably 4 μm or more, and more preferably 4 μm or more. From the viewpoint of dimensional stability, which makes it difficult for distortion (cracks) to occur in layer B, and in a humid and hot environment From the viewpoint of moisture and heat resistance, which makes it difficult for distortion (cracks) to occur in the B layer, it is preferable that the thickness is 40 μm or less. It is preferably 30 μm or less, more preferably 25 μm or less, and particularly preferably 20 μm or less. I wish.

[0151] The laminate may have the B layer formed on only one side of the A layer, or may have the B layer formed on both sides. Alternatively, the B layer may be laminated directly on the A layer. In the production of the laminate, the application and curing of the curable resin composition may be carried out only once. The application and curing of the curable resin composition may be repeated multiple times. This can prevent warping. [Example]

[0152] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples. means "parts by mass." The physical properties of the laminates obtained in the following examples were evaluated by the following methods.

[0153] (1) Molding of polycarbonate resin (manufacturing of layer A) A 100mm wide, 100mm long injection molding machine with a clamping force of 200 tons manufactured by Meiki Seisakusho Co., Ltd. mm, 1.0 mm wall thickness cavity, gate width 40 mm, gate thickness 0.8 mm A mold with one gate is installed, and the mold temperature is 80°C and the injection pressure is 180-250MPa. The polycarbonate resin was subjected to the following conditions: 60-80 MPa holding pressure, 2 seconds holding time, and 30 seconds cooling time. The resins (A-1) to (A-2) were used to form plates, and polycarbonate resin molded products (A layer) was obtained.

[0154] (2) Synthesis of urethane (meth)acrylate compound (component (b2)) [Synthesis Example 1] Synthesis of urethane (meth)acrylate compound (UA1) A four-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and an air inlet was filled with isopropyl alcohol. Phoron diisocyanate trimer 333.5 parts (0.50 moles), ethyl acetate 558.3 300 ppm of dibutyltin dilaurate was added and heated to 70°C to dissolve. After introducing air into the liquid, 703.4 parts (1.58 molar) of pentaerythritol triacrylate 1.06 parts of methyl ethyl hydroquinone were added and reacted at the same temperature for 5 hours. The reaction was terminated after confirming that the remaining isocyanate group was 0.3%, and a 9-functional urethane The solid content of the resulting mixture was 65% by mass. .

[0155] [Comparative Synthesis Example 1] Synthesis of urethane (meth)acrylate compound (UA2) Four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and a dropping funnel with heat retention function 265 parts (1.00 moles) of dicyclohexylmethane diisocyanate, dilaurin 300 ppm of di-n-butyltin acetate was added and heated to 50°C. Polycarbonate diol (trade name: Kuraray Polyol C-770, manufactured by Kuraray Co., Ltd.) 800 g (1 mol) of the polymer (weight average molecular weight 800) was added dropwise over 4 hours. The mixture was stirred at 50°C for 2 hours and then heated to 70°C over 1 hour. 232 g (2 mol) of ethyl acrylate (HEA) was added dropwise over 2 hours, and then the mixture was stirred for another 2 hours. The reaction was stopped when it was confirmed that the residual isocyanate group was 0.3%. A functional urethane acrylate compound (UA2) was obtained.

[0156] (3) Synthesis of inorganic particles (component (b3)) whose surfaces are coated with organic functional groups [Synthesis Example 2] Synthesis of surface-modified inorganic fine particle solution In a 200 ml three-neck flask equipped with a stirrer, thermometer, and condenser, As inorganic oxide fine particles, isopropanol-dispersed silica sol (IPA-ST (trade name), Japan) Sankagaku Co., Ltd.; Dispersion medium: isopropanol, SiO2 concentration: 30% by mass, average primary particle size Diameter: 15 nm, hereinafter abbreviated as "IPA-ST". Dipropyltrimethoxysilane (KBM-503 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd., formula (4) and R 1 = 3-methacryloyloxypropyl group, n = 1, R 2 = (This corresponds to the case of a methyl group. Hereafter abbreviated as "KBM-503") Add 22.9 g of As soon as reflux of the volatile components began, 8.3 g of deionized water was added and the mixture was refluxed. The hydrolysis and dehydration condensation reactions were carried out at room temperature for 2 hours with stirring. When the solid content reached approximately 60% by mass, 72 g of toluene was added. The alcohol, water, etc. were azeotropically distilled off together with toluene while stirring under reflux for 3 hours. The reaction was carried out at about 110°C for 4 hours while distilling off the toluene. The resulting toluene solution containing surface-modified inorganic oxide particles was yellow and had the permeability of a Newtonian fluid. The solid content of the heating residue was 60% by mass.

[0157] [Confirmation of the amount of components in a solution containing surface-modified inorganic particles] Component (b3) (hereinafter referred to as "component (CS-1)") contained in the solution prepared by the above method, and The amount of component (b4) (hereinafter referred to as "component (Oligo-1)") was confirmed by the following procedure. While stirring 500 ml of the solution, slowly add 50 g of solution (CS-1) to re-precipitate. After solid-liquid separation, the hexane solution was concentrated under reduced pressure to obtain the component (Oligo-1) contained in the solution. The mass was measured. The content of the component (Oligo-1) in the solution was 26 mass% ((b 3) / (b4) was 1.3). In addition, the results of GPC measurement under the above conditions were The Mw of the component (Oligo-1) was 1,533.

[0158] [Confirmation of the amount of components in a solution containing surface-modified inorganic fine particles (Comparative Example)] While stirring 500 ml of hexane, MEK-AC-2140Z solvent (Nissan Chemical Co., Ltd.) After the solid-liquid separation, the hexane solution was concentrated under reduced pressure to remove the precipitate. An attempt was made to measure the components contained in the liquid, but no components were found to be present in the solution.

[0159] (4) Synthesis of siloxane oligomer (component (b4)) [Synthesis Example 3] Synthesis of siloxane oligomer (Oligo-2) In a 200 ml three-neck flask equipped with a stirrer, thermometer, and condenser, Add 84g of isopropyl alcohol and 46g of "KBM-503" and heat while stirring. As soon as reflux of the volatile components began, 16.7 g of deionized water was added and the mixture was stirred under reflux for 2 hours. Hydrolysis and dehydration condensation reactions were carried out while the volatile components such as alcohol and water were removed under normal pressure. When the solid content reached approximately 60% by mass, 72 g of toluene was added and the mixture was refluxed for 3 hours. The alcohol, water, etc. were azeotropically distilled together with toluene while stirring for a period of time to obtain a toluene solution. The reaction was further carried out at about 110°C for 4 hours while distilling off toluene. The toluene solution of xanthane oligomer (Oligo-2) is a transparent liquid, and the solid concentration is the heating residue. In addition, the result of GPC measurement under the above conditions was that the component (Ol The weight average molecular weight Mw of igo-2) was 1,992.

[0160] (5) Preparation of active energy ray-curable resin composition [Formulation Example 1] Preparation of active energy ray-curable resin composition Kayarad DPHA (in the structure of formula (2), n=1, 6 X Of these, five Xs are "(meth)acryloyloxy groups" and the remaining are "(meth)acryloyl Mono- or polypentaerythritol poly(meth)acrylate with oxy and hydroxy groups Aronix M315 (manufactured by Toagosei Co., Ltd.), the composition obtained in Synthesis Example 2 A solution of surface-modified inorganic particles (a mixture of CS-1 and Oligo-1) was added at a solids ratio of 23 : 46: 17.6: 13.4, and for a total of 100 parts of the solids 2.4 parts of methylbenzophenone as a photopolymerization initiator and Omnirad TPO- 1.8 parts of L (manufactured by iGM RESINS), 1.8 parts of Tinuvin 400 (BA) as an ultraviolet absorber SF Co., Ltd.) as a hindered amine light stabilizer, ADK STAB LA-63P ( ADEKA Co., Ltd.) 3.6 parts, and BYK-333 (BYK-Chemie Co., Ltd.) as a leveling agent. After adding 0.1 parts of propylene glycol monomethyl ether, dilute with 100 parts of propylene glycol monomethyl ether. Thus, an active energy ray-curable resin composition (B-1) was obtained.

[0161] (6) Method for applying active energy ray-curable resin composition The obtained active energy ray-curable resin composition (B-1) was used for the layer A obtained in (1) above. The film was then coated with an air spray so that the thickness of the dried film was 8 μm, and the film was then placed in an oven for 80 The coating was dried by heating at 100°C for 3 minutes. UV light with wavelengths between 340nm and 380nm was used at 100mW / cm 2 , 1000 mJ / cm 2 The laminate was then irradiated with light at a wavelength of 1000 nm to obtain a laminate coated with a cured film (layer B).

[0162] (7) Appearance The appearance of the laminate obtained in (6) above was visually observed and evaluated according to the following criteria: . ○: Transparent with no whitening ×: bleached

[0163] (8) Adhesion The adhesion of the laminate obtained in (6) above was evaluated by the following procedure. 11 scratches were made vertically and horizontally at 1.5 mm intervals, reaching the substrate, for a total of 100 samples. Make holes and press cellophane adhesive tape (25mm wide, manufactured by Nichiban Co., Ltd.) into the holes. The adhesiveness is evaluated by dividing the number of remaining squares by the total number of squares (100) and visually inspecting the adhesive. The results were judged based on the following criteria: ○: 100 / 100 (no peeling or chipping). △: 100 / 100 (no peeling, chipping around the notch). ×: 0 / 100 to 99 / 100 (peeling occurs).

[0164] (9) Hot water resistance The laminate obtained in (6) was left to stand in a warm bath adjusted to a temperature of 80°C for 8 hours, and then taken out. The adhesion between the cured film (layer B) and the substrate (layer A) was evaluated by the method (8) above. ◯: 100 / 100 of the cured film remained after the cross-cut peel test △: The number of remaining cured films after the cross-cut peel test was 100 / 100 (no peeling). chipping occurs). ×: The number of cured films remaining after the cross-cut peel test was 99 / 100 or less

[0165] (10)Pencil hardness: The laminate obtained in (6) above was measured using a JIS pencil hardness tester (manufactured by Taiyu Kizai Co., Ltd.). Measurements were carried out based on the conditions of JIS K-5400 using the hardest pencil that does not scratch. The pencil hardness was evaluated by the grit size. The pencil hardness of the laminate is preferably 2H or more, and the hardness of the laminate is higher than that of the A layer. It is preferable that the pencil hardness is improved by two or more steps (for example, from F to 2H). In this case, the molded product obtained may be easily damaged and its appearance may be impaired. In addition, if the hardness of the laminate is improved by less than two stages compared to the hardness of layer A, There is a risk that the cost-effectiveness of forming the coating layer (layer B) may be compromised. The pencil hardness is 7H, 6H, 5H, 4H, 3H, 2H, in order from hardest to hardest. It is expressed in the order of H, F, HB, B, 2B, 3B, and 4B. The above was considered a pass.

[0166] (11) Scratch resistance 150 g / cm2 on the surface of the cured film of the laminate obtained in (6) 2 A steel sheet with a load of Scratch tests were carried out by moving wool #0000 back and forth 20 times. The haze value was measured before and after the scratch test using a M-65W (manufactured by Murakami Color Research Institute Co., Ltd.). The scratch resistance was evaluated based on the following criteria. ◎: Increased haze value is 0% or more and less than 0.5% ◯: The increased haze value is 0.5% or more and less than 1.0%. △: The increased haze value is 1.0% or more and less than 2.0%. ×: The increased haze value is 2.0% or more.

[0167] (12) Abrasion resistance The surface of the cured film of the laminate obtained in (4) above was subjected to abrasion testing using a Taber type abrasion tester. The cured film of the laminate was abraded 500 times with a CS-10F abrasive wheel and a load of 500gf (4.90N). After that, it was washed with a neutral detergent and then washed according to JIS K7136:2000. The haze value was measured, and the increase in haze value before and after the abrasion test was calculated. The abrasion resistance was evaluated according to the following criteria: . ◎: Increase in haze value = less than 7%. ○: Increased haze value = 7% or more and less than 10%. ×: Increase in haze value = 10% or more.

[0168] The abbreviations for compounds used in the following examples are as follows: (Polycarbonate resin) A-1: Isosorbide / 1,4-cyclohexanedimethanol = 70 / 30 mol% Polymerized polycarbonate (Mitsubishi Chemical Corporation: Durabio D7340R) A-2: Bisphenol A polycarbonate (Teijin Ltd., PANLITE L- 1225Z) DPHA: Dipentaerythritol penta / hexaacrylate DPCA20: Caprolactone 2mol modified pentaerythritol tri / tetraacrylate rate PGM: Propylene glycol monomethyl ether

[0169] [Example 1] The layer A is formed by the method (1) using the polycarbonate resin (A-1), and the active element is Layer B is formed on the surface of layer A using the energy wire resin composition (B-1) by the method (6) above. The laminate thus obtained was evaluated according to the methods (7) to (12) above. Shown in Table 1.

[0170] [Examples 2 to 10, Comparative Examples 1 to 8] The following polycarbonate resins and active energy ray ray resin compositions shown in Tables 1 and 2 were used. Other than that, a laminate was obtained in the same manner as in Example 1. The evaluation results of the obtained laminate are shown in Tables 1 and 2. vinegar.

[0171] [Table 1]

[0172] [Table 2]

[0173] The laminates of Examples 1 to 10 were evaluated in terms of adhesion, durability, hardness, and weather resistance. In the evaluation of each characteristic, there were no △ or × marks, and the laminate was superior to the laminate shown in the comparative example. Among them, Examples 5 and 7 are particularly excellent in scratch resistance and abrasion resistance, and Examples 4 and 7 are excellent in lead resistance. The writing hardness was particularly excellent. On the other hand, the active energy ray-curable resin compositions of Comparative Examples 1 and 2 do not contain the component (b3). In Comparative Examples 3 and 4, either the component (b1) or the component (b2) was used. Since it does not contain any adhesive, the adhesion between the (A) layer and the (B) layer is insufficient, especially after the hot water resistance test. In addition, in Comparative Examples 5 and 6, the structural unit derived from the dihydroxy compound was The laminate is made of bisphenol A polycarbonate that does not contain the unit (a), but The pencil hardness of the body is F, which makes the molded product easily scratched. Also, after the hot water resistance test, the adhesion with the (B) layer was poor. The wearability was also insufficient. [Industrial Applicability]

[0174] A layer (A layer) containing the polycarbonate resin of the present invention and a layer (B layer) containing the polycarbonate resin represented by the general formula (2) Mono- or polypentaerythritol poly(meth)acrylate and the general formula (3) (Meth)acrylate compounds with three or more functional groups, inorganic compounds coated with organic functional groups It has a layer (layer B) formed by curing an active energy ray-curable resin composition containing fine particles. The laminate has excellent appearance, surface hardness, and adhesion between layers A and B, and is used in automobile parts, eyeglass parts, medical products, etc. Medical parts, films, sheets, containers such as bottles, building materials, various housing materials for mobile phones, etc. We provide resin molded products that can be used in a wide range of fields, such as optical disc substrates and plastic lenses. It is possible to do this.

Claims

1. Layer A containing a polycarbonate resin and a cured product of an active energy ray-curable resin composition A laminate having a layer B consisting of: The polycarbonate resin is a dihydroxycarbonate having a structure represented by the following general formula (1): having a structural unit (a1) derived from a compound, The active energy ray-curable resin composition comprises a compound (b1) represented by the following general formula (2): ) and a trifunctional or higher functional (meth)acrylate compound (b2) represented by the following general formula (3), and inorganic fine particles (b3) whose surfaces are coated with organic functional groups. 【Chemical 1】 【Chemistry 2】 [In formula (2), "4+2n" Xs each independently represent a (meth)acryloyloxy group. (i.e. CH ２ =CR-COO-, where R represents a hydrogen atom or a methyl group. ), (meth)acryloyloxy group modified with caprolactone (i.e., CH ２ =CR-CO(O(CH ２ ) ５ C=O) ｙ -O-, where R is a hydrogen atom or represents a methyl group, and y represents an integer of 1 to 5. In addition, n is an integer of 0 to 4.] 【Chemistry 3】 [In formula (3), Y1, Y2, and Y3 each independently represent at least two or more (meth)aryl groups. Z1, Z2 and Z3 are oxyalkylene groups or carbon atoms having 1 to 4. It represents an alkylene group having 2 to 10 prime numbers.]

2. The active energy ray-curable resin composition is a (meth)acryloyl group, an epoxy group, and vinyl groups, and has a weight average molecular weight of 20 2. The laminate according to claim 1, containing a siloxane oligomer (b4) having a molecular weight of 0 to 3,000. body.

3. The (meth)acrylate compound (b2) is a urethane (meth)acrylate having a nurate skeleton. The laminate according to claim 1 or 2, wherein the compound is an acrylate compound.

4. At least one of X in the formula (2) is a (meth)acrylate modified with caprolactone. The laminate according to claim 1 or 2, wherein the group is an acryloxy group.

5. The inorganic fine particles (b3) are composed of (meth)acryloyl groups, epoxy groups and vinyl groups. and (iii) inorganic fine particles coated with at least one functional group selected from the group consisting of: Item 1 or 2. The laminate according to item 1 or 2.

6. In the active energy ray-curable resin composition, (b1) represented by the general formula (2) is 10 to 90% by mass based on the total solid content, 10 to 90 mass % of a trifunctional or higher functional (meth)acrylate compound (b2) represented by formula (3) %, 5 to 50 mass % of inorganic fine particles (b3) whose surfaces are coated with organic functional groups, (meta) At least one functional group selected from the group consisting of an acryloyl group, an epoxy group, and a vinyl group a siloxane oligomer (b4) having a functional group and a weight average molecular weight of 200 to 3,000; The laminate according to claim 1 or claim 2, wherein the content is 1 to 10 mass %.

7. The active energy ray-curable resin composition contains an ultraviolet absorber (c1) and a hindered amine The laminate according to claim 1 or 2, further comprising at least one of a hydroxybenzoate-based light stabilizer (c2) and a hydroxybenzoate-based light stabilizer (c3). 。

8. After applying an active energy ray curable resin composition to at least one surface of the layer A, 3. The method according to claim 1 or 2, further comprising a step of forming a layer B by irradiating the layer with a reactive energy ray. Method for manufacturing a layered body.

9. The laminated body is used for resin glass, resin grilles, headlight covers, and tail lamp covers. or eyeglasses parts including eyeglass frames and sunglasses. The laminate according to claim 1, which is used for at least one of the following purposes:

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