JP5104788B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate having a cured layer excellent in appearance, abrasion resistance, scratch resistance, adhesion to a substrate and weather resistance.

In general, plastics are used in various applications because they are excellent in lightness, easy processability, impact resistance, and the like. For example, polycarbonate, methacrylic resin, polyethylene terephthalate, vinyl chloride resin, ABS resin, cellulose acetate, polypropylene and the like are known.
Particularly in recent years, polycarbonate, polymethyl methacrylate, epoxy resin, cellulose acetate are used as an alternative to glass for products that use light-transmitting properties such as optical recording media, magneto-optical recording media, lenses, optical filters, and display parts of displays. There is a demand for using transparent resins such as cycloolefin polymers. Among them, for example, a polycarbonate resin is excellent in transparency, impact resistance, and processability, and thus is used as a window glass for automobiles and contributes to an improvement in fuel consumption by reducing the weight of the automobile.

However, these plastic molded products are easily scratched because of their low surface hardness, and may deteriorate easily when used outdoors for a long time, resulting in damage to physical properties and appearance. In order to impart durability and wear resistance, a technique for forming a laminate in which a hardened layer that increases surface hardness is formed on a substrate is known.
Such a hardened layer can form a high-hardness film on the plastic surface, but has a drawback that cracks are likely to occur for various reasons. Therefore, as a method for solving these disadvantages, a laminate in which a film made of an acrylic resin having functional groups and silica is formed on the substrate surface, and a hard coat layer made of an alkoxysilane hydrolysis condensate and silica is formed thereon. A body has been proposed (Patent Document 1). Further, there has been proposed a laminate in which a primer layer having a reactive silyl group on the protective surface of the substrate and a silicone hard coat layer formed thereon are formed (Patent Document 2). And the laminated body which has the hard-coat layer which consists of an alkoxysilane hydrolyzate and a silica as a 2nd layer is proposed on the surface of a transparent plastic base material as a 1st layer containing a hydroxyl-containing acrylic resin and isocyanate ( Patent Document 3). Furthermore, a laminate has been proposed in which an active energy ray-curable resin is used for the inner layer in contact with the outermost layer, and a hard coat layer is formed on the outermost layer (Patent Document 4).

JP-A-2-284930 JP 11-217519 A JP 2003-342403 A Japanese Patent Laid-Open No. 11-221873

However, a laminate in which a hard coat layer is formed on a film made of an acrylic resin having a functional group has a drawback that the film or the hard coat layer is whitened or cracks are generated. In addition, since the cross-linking reaction of the cured layer proceeds with time, the coating is apt to be distorted, the hard coat layer is cracked, and the hard coat layer is easily peeled off. It was insufficient for maintaining the weather resistance. Further, since the hardness of the resin in the laminated body layer is too high, there is a problem that the adhesion with the outermost layer is insufficient and peeling is likely to occur.

The present invention has been made in view of the above problems, and is excellent in appearance, abrasion resistance, scratch resistance, substrate adhesion, heat resistance, moist heat resistance and weather resistance, and generation of cracks and peeling. It is an object of the present invention to provide a laminate having a cured layer without any problem.

The inventors of the present invention have intensively studied to solve such problems, and contain a resin obtained by polymerizing a monomer compound having a specific structure between the base material and the cured layer, and with respect to the base material. It has been found that by having a resin layer having specific physical properties, a laminate having very excellent performance can be obtained, and the present invention has been completed.
That is, the first gist of the present invention includes a substrate made of a thermoplastic resin and a cured layer, and at least selected from the group of compounds having a (meth) acryloyl group between the substrate and the cured layer. A laminate having a resin layer containing a resin obtained by polymerizing one kind of compound, wherein the resin layer has a water absorption ratio Q to the substrate of less than 4, and the glass transition of the resin layer The laminate has a temperature (Tg) of 60 ° C. or higher (Claim 1), the resin layer has a thickness of 2 μm or more and 20 μm or less, and a light transmittance at 300 nm of 5%. The following is preferable (claim 2).

  The second gist of the present invention is that the resin layer is an unsaturated monomer (a-1) represented by the following formula (1): 5 to 40% by weight,

CH ₂ = C (R ¹ ) COOR ² (1)
(R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkyl group which may have a branch having 8 to 30 carbon atoms)
1 to 70% by weight of an unsaturated monomer (a-2) having an ultraviolet absorbing group, and at least one monomer selected from the group represented by (a-1) and (a-2) It contains a copolymer (A) having a number average molecular weight of 1,000 to 1,000,000 obtained by copolymerizing 1 to 94% by weight of a polymerizable unsaturated monomer (a-3). (3).

  Furthermore, the third gist of the present invention is an active energy ray containing an unsaturated compound (B) in which the cured layer has two or more unsaturated groups, an ultraviolet absorber (C), and a photopolymerization initiator (D). A laminate obtained by curing a curable composition with active energy rays (Claim 4), and preferably the cured layer contains colloidal silica (E) having a volume average particle diameter of 1 nm to 200 nm. (Claim 5) Preferably, the cured layer contains a hydrolysis-condensation product (F) of alkoxysilane represented by the following formula (2) (Claim). Item 5).

R ³ _r R ⁴ _s Si (OR ⁵ ) _4-rs (2)
R ³ and R ⁴ in the formula (2) are each selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloyl group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. an alkyl group having 1 to 3 carbons substituted with or more functional groups, ^{R 5} is an alkyl group having 1 to 4 carbon atoms, r, s is an integer of 0 to 3, r + s is 0 It is an integer of 3.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the laminated body which has the cured layer excellent in base-material adhesiveness, and was excellent in an external appearance, adhesiveness, abrasion resistance, scratch resistance, and a weather resistance. In addition, since the laminate of the present invention has excellent appearance, abrasion resistance, scratch resistance, and weather resistance, it can be suitably used for headlamp covers, windshield materials, window materials, roof materials, etc. for vehicles. It is also useful for window glass for buildings, exterior wall materials for buildings, soundproof walls for roads, face plates for displays, and members for mobile phones.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of the embodiments of the present invention, and is appropriately modified and implemented without departing from the spirit of the present invention. can do. In the present invention, the description “(meth) acryloyl” means “at least one selected from the group consisting of acryloyl and methacryloyl”, and the description “(meth) acrylate” consists of “acrylate and methacrylate”. Means at least one selected from the group ".

The laminate of the present invention has a substrate and a cured layer, has a resin layer between the substrate and the cured layer, and the ratio Q of the water absorption rate of the resin layer to the substrate is less than 4. It will be. Here, Q is a value obtained by dividing the water absorption rate of the cured layer by the water absorption rate of the substrate.
The physical properties of the laminate of the present invention are not particularly limited as long as the physical properties described above are provided, and are arbitrary according to the use of the laminate of the present invention. However, it is desirable to further have the following physical properties.

[1. Laminate]
[1-1. Physical properties of laminates]
・ Mechanical strength
Although there is no restriction | limiting in particular about the mechanical strength requested | required of the laminated body of this invention, It is preferable to have the intensity | strength required according to the use of a laminated body. Properties of each layer of the laminate, such as its durability and weather resistance, will be described later.

[1-2. Structure of laminate]
The laminate of the present invention has a specific relationship between the water absorption rate of the base material and the water absorption rate of the resin layer, and the resin layer is usually formed on the base material in contact with the base material. The substrate and the resin layer do not necessarily have to be in contact with each other, and another type of layer may be formed between the substrate and the resin layer.

  Even if the base material and the resin layer are not in contact with each other, the reason why a specific excellent effect is manifested in the present invention is not certain, but the elastic deformation rate of the base material and the resin layer and the expansion of each layer due to temperature and humidity changes It is thought that the influence of the shape change due to the shrinkage reaches even if it passes through another kind of layer. However, the effect of the present invention is particularly remarkable when the resin layer is formed on the base material so as to be in contact with the base material. Therefore, in the laminate of the present invention, the resin layer is formed so as to be in contact with the base material. It is preferable.

[2. Base material]
[2-1. Physical properties of substrate]
・ Moisture content
The water absorption rate of the base material according to the laminate of the present invention was measured by the following method.
A test piece with a side of 50 mm and a thickness of 1 mm is press-molded at a mold temperature of 280 ° C., dried in a constant temperature layer at 50 ° C. for 24 hours, and allowed to cool in a desiccator containing silica gel as a desiccant. did.

The sample was taken out after being immersed in pure water at 50 ° C. for 24 hours, and the weight of the test specimen before immersion in pure water was compared with the weight after immersion, and the weight after immersion relative to the weight before immersion in pure water was compared. The water absorption was determined as the ratio of the increase.
In the present invention, if the ratio Q of the water absorption rate of the resin layer as defined above to the substrate is less than 4, the value of the water absorption rate of the resin layer is not particularly limited, but preferably 2.0 wt. % Or less, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less.

[2-2. Structure of base material]
The base material according to the laminate of the present invention is not particularly limited as long as the ratio of the water absorption ratio of the resin layer to the base material is within the range defined by the present invention, and a resin material that is generally widely used can be used. .
Among these, a thermoplastic resin is preferably used from the viewpoint of ease of processing, and a polymer having a carbonyl group is more preferable from the viewpoint of adhesiveness with the resin layer according to the present invention. Further, from the viewpoint of preferably satisfying the physical properties of the substrate, polyester, polyarylate, polycarbonate, and cellulose acetate are preferable, and polycarbonate is particularly preferable.

As the monomer unit constituting the polymer having a carbonyl group suitable for the base material, any conventionally known monomer unit can be used, but two monomer units commonly used as a monomer unit of polyester resin, polyarylate resin, and polycarbonate resin can be used. It is preferable to use a monohydric alcohol.
Specifically, hydroquinone, resorcinol, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene Bifunctional phenolic compounds such as 2,7-dihydroxynaphthalene;
4,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl, 3,3′-di (t-butyl) -4,4′-dihydroxy-1,1 '-Biphenyl, 3,3', 5,5'-tetramethyl-4,4'-dihydroxy-1,1'-biphenyl, 3,3 ', 5,5'-tetra (t-butyl) -4, 4′-dihydroxy-1,1′-biphenyl, 2,2 ′, 3,3 ′, 5,5′-hexamethyl-4,4′-dihydroxy-1,1′-biphenyl, 2,4′-biphenol, 3,3′-dimethyl-2,4′-dihydroxy-1,1′-biphenyl, 3,3′-di (t-butyl) -2,4′-dihydroxy-1,1′-biphenyl, 2,2 '-Biphenol, 3,3'-dimethyl-2,2'-dihydroxy-1,1'-biphenyl, 3,3'-di (t-butyl) -2, '- biphenol compounds such as dihydroxy-1,1'-biphenyl;
Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4- Hydroxyphenyl) hexane, 3,3-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) bisphenol compounds having no substituents on the aromatic rings such as cyclohexane;
Bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2 A bisphenol compound having an aryl group as a substituent on an aromatic ring such as bis (3-phenyl-4-hydroxyphenyl) propane;
Bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 2,2 -Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane, 1,1-bis ( 4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4
-Hydroxy-3-ethylphenyl) propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis ( 4-hydroxy-3- (sec-butyl) phenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2 , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy-3,6-dimethylphenyl) Methane, 1,1-bis (4-hydroxy-3,6-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,6-di) Tilphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ethane, 2,2-bis (4- Hydroxy-2,3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) A bisphenol compound having an alkyl group as a substituent on an aromatic ring such as phenylethane or 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane;
Bis (4-hydroxyphenyl) (phenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4- A bisphenol compound in which a divalent group connecting aromatic rings such as hydroxyphenyl) (diphenyl) methane and bis (4-hydroxyphenyl) (dibenzyl) methane has an aryl group as a substituent;
Bisphenol compounds in which aromatic rings such as 4,4′-dihydroxydiphenyl ether and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl ether are linked by an ether bond; 4,4′-dihydroxydiphenyl sulfone Bisphenol compounds in which aromatic rings such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone are connected by sulfone bonds; 4,4′-dihydroxydiphenyl sulfide, 3,3 ′, A bisphenol compound in which aromatic rings such as 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide are linked by a sulfide bond;
Examples thereof include bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, and phenolphthalein.

[2-3. Base material form]
There is no restriction | limiting in particular about the form of the base material which concerns on this invention, Any form, such as a sheet form, a film form, a molded object, may be sufficient.
[3. Resin layer]
[3-1. Physical properties of resin layer]
・ Water absorption
The water absorption rate of the resin layer according to the present invention can be measured by the same method as the water absorption rate of the substrate. In the present invention, if the ratio Q of the water absorption rate of the resin layer to the base material is less than 4, the value of the water absorption rate of the resin layer is not particularly limited, but is preferably 2% by weight or less, more preferably Is 1.0% by weight or less, particularly preferably 0.5% by weight or less.
・ Resin layer thickness
In order to improve the weather resistance of the laminate, the thickness of the resin layer used in the laminate of the present invention is usually 1 μm or more, preferably 5 μm or more, more preferably 8 μm or more, and further preferably 10 μm or more. Is usually not more than 50 μm, preferably not more than 20 μm, more preferably not more than 15 μm, for the reason that it is excellent in drying properties when it is formed by applying and drying a coating solution using a solvent.
・ Light transmittance
The light transmittance at a wavelength of 300 nm of the resin layer according to the present invention is measured by a spectrophotometer, and is generally 10% or less, preferably from the viewpoint of improving weather resistance, regardless of the thickness of the resin layer. 5% or less, more preferably 2% or less.
・ Haze
Although there is no restriction | limiting in particular in the haze of the resin layer which concerns on this invention, When using the laminated body of this invention for a glass substitute use, it is preferable that the haze of a resin layer is low. Specifically, the haze measured by a test method based on JIS K7136: 2000 is preferably 15% or less, more preferably 5% or less, and particularly preferably 2% or less.

[3-2. Composition of resin layer]
The resin layer according to the present invention contains a resin obtained by polymerizing at least one compound selected from the group of compounds having a (meth) acryloyl group. This is because polymerization is performed using a heavy bond. For technical reasons, the compound group having a (meth) acryloyl group has an acryloyl group or a methacryloyl group, or an acryloyl group and a methacryloyl group. Any compound, if any, is included.

  A resin formed by polymerizing at least one compound selected from the group of compounds having a (meth) acryloyl group is a plurality of types selected from the group of compounds having a (meth) acryloyl group in order to adjust the physical properties of the resin layer. The copolymer is preferably a compound. The type of the compound having a (meth) acryloyl group used in this case and the copolymerization ratio are not particularly limited, but in order to obtain the effects of the present invention, the compound having a (meth) acryloyl group as described later is used. It is appropriately selected based on the technical idea related to the characteristics.

However, if the molecular weight of the compound is too large, it becomes difficult to produce a polymer. Therefore, the number of carbon atoms of the compound is preferably 50 or less, more preferably 40 or less, and particularly preferably 35 or less.
In the present invention, as the compound having a (meth) acryloyl group, a compound represented by the following formula (1) is typically used.

CH ₂ = C (R ¹ ) COOR ² (1)
In the formula (1), R ¹ and R ² represent an organic substituent.
In order to define the characteristics of the resin layer according to the laminate of the present invention in the present invention, R ¹ and R ² are appropriately adjusted in consideration of the characteristics described below. Preferably, R ¹ and R ² are an alkyl group which may have a substituent, and the alkyl group may have a branched or cyclic structure. Furthermore, R ¹ is more preferably an alkyl group having 5 or less carbon atoms, and even more preferably a linear alkyl group having 5 or less carbon atoms.

In order to facilitate the adjustment of the mechanical strength, adhesiveness, and water absorption of the resin layer, R ¹ and R ² are preferably linear alkyl groups. In particular, R ² greatly affects the properties of the resin contained in the resin layer. When adjusting the mechanical strength, adhesiveness, and water absorption of the resin layer, the carbon number is preferably 30 or less. For the same reason, R ¹ is preferably a linear alkyl group having 5 or less carbon atoms, particularly a hydrogen atom, a methyl group or an ethyl group.

In the laminate, from the viewpoint of enhancing the adhesion between the resin layer and the other layer, the alkyl group represented by R ² preferably has 3 or less carbon atoms, and particularly preferably a methyl group.
On the other hand, in order to adjust the water absorption rate of the resin layer, R ² is preferably an alkyl group having 8 or more carbon atoms, and the carbon number of the alkyl group is more preferably 10 or more, and still more preferably. It is 12 or more, particularly preferably 16 or more carbon atoms, preferably 30 or less carbon atoms, more preferably 25 or less carbon atoms. Among them, in the formula (1), R ¹ is a hydrogen atom, a methyl group or an ethyl group, and R ² is an alkyl group which may have a branch having 8 to 30 carbon atoms. A compound having a (meth) acryloyl group (hereinafter sometimes referred to as an unsaturated monomer (a-1)) is preferred.

  In the present invention, as the unsaturated monomer (a-1), more specifically, for example, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (Meth) acrylate, isostearyl (meth) acrylate, cetyl (meth) acrylate, behenyl (meth) acrylate, etc. can be mentioned.

In addition, as described above for the physical properties of the resin layer, from the viewpoint of improving the weather resistance of the laminate, the light transmittance of 300 nm light may be below a certain level for the entire resin layer regardless of the thickness of the resin layer. Preferably, in order to adjust the light transmittance of 300 nm light, the substituent represented by R ² is preferably a group that absorbs or blocks light in the vicinity of 300 nm. A compound having a (meth) acryloyl group having a so-called ultraviolet absorbing group derived from a compound used as an absorbent (hereinafter sometimes referred to as an unsaturated monomer (a-2)) is preferred.

In order to adjust the light transmittance of 300 nm light of the resin layer, the ultraviolet absorbing group used for the organic substituent represented by R ² includes a group having a benzophenone skeleton such as 2,4-dihydroxybenzophenone, triazine A group having a skeleton, a group having a benzotriazole skeleton such as 2- (5′-methyl-2′-hydroxyphenyl) benzotriazole, and a cyanoacrylate skeleton such as ethyl-2-cyano-3,3′-diphenylacrylate A group having a salicylate skeleton such as phenyl salicylate or a group having a benzylidene malonate skeleton such as diethyl-p-methoxybenzylidene malonate is preferably used. Among these, a group having a benzophenone skeleton, a group having a triazine skeleton, and a group having a benzotriazole skeleton are preferable, and a group having a benzotriazole skeleton is particularly preferably used.

  More specifically, the compound having a (meth) acryloyl group used for adjusting the light transmittance of 300 nm light of the resin layer has, for example, a benzotriazole skeleton represented by the formula (3). Examples thereof include compounds, compounds having a benzophenone skeleton represented by formula (4), and compounds having a triazine skeleton represented by formula (5).

In formula (3), X represents a hydrogen atom or a chlorine atom, and R ⁶ represents a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms. R ⁷ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and R ⁸ represents a hydrogen atom or a methyl group. n represents 0 or 1.
Equation (4) Medium ^{R 8} has the same meaning as ^{R 8} in formula (3), ^{R 9} represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ¹⁰ represents a hydrogen atom or a hydroxyl group, and R ¹¹ represents a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

Medium ^{R 8} has the formula (5) represent the same meaning as ^{R 8} in formula ^{(3), R 12} is a direct _bond, -CH 2 _CH 2 O- or _{-CH 2 CH (OH) -CH 2} O- and represent, m represents an integer of 1 to 5. R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group, o represents an integer of 0 to 4, and p and q each independently represents an integer of 0 to 5. .
The resin layer according to the present invention contains a resin obtained by polymerizing at least one compound selected from the group of compounds having a (meth) acryloyl group, and the resin includes a plurality of types of (meth) acryloyl. It may be a copolymer using a compound selected from a group of compounds having a group.

Among them, the unsaturated monomer (a-1) is 5 to 40% by weight, the unsaturated monomer (a-2) is 5 to 70% by weight, and (a-1) and ( 1 to 94 weight percent of unsaturated monomer (a-3) characterized in that it can be copolymerized with at least one unsaturated monomer selected from the group represented by a-2) The resin (A) obtained by copolymerization in the range of% is preferred.

An unsaturated monomer (a-) characterized in that it can be copolymerized with at least one unsaturated monomer selected from the group represented by (a-1) and (a-2). Examples of 3) include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, alkyl vinyl ether, alkyl vinyl ester, styrene, and derivatives thereof.

  Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, butoxyethyl ( (Meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, alkoxypolyalkylene glycol (meth) acrylate such as methoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- Acryloyloxyethyl-2-hydroxyethyl phthalate, (meth) acrylic acid, 2-acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl Oxahydrophthalate, 2- (meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanatoethyl (meth) acrylate, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxy Examples thereof include propylmethyltrimethoxysilane and 3- (meth) acryloyloxypropylmethyltriethoxysilane.

Specific examples of (meth) acrylonitrile include α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, and vinylidene cyanide.
Specific examples of (meth) acrylamide derivatives include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-ethyl (meth) acrylamide, N -Methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-ethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N -(2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N, N-ethylenebis (meth) acrylic Mention may be made of the bromide and the like.

Specific examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and the like.
Specific examples of the alkyl vinyl ester include vinyl formate, vinyl acetate, vinyl acrylate, vinyl butyrate, vinyl caproate, and vinyl stearate.
Specific examples of the styrene derivative include styrene, P-styryltrimethoxysilane, α-methylstyrene, vinyltoluene, chloromethylstyrene, and the like.

Furthermore, the resin obtained by polymerizing at least one compound selected from the group of compounds having a (meth) acryloyl group may be a copolymer with another repeating unit having no (meth) acryloyl group. Absent. In this case, the copolymerization ratio of at least one compound selected from the group of compounds having a (meth) acryloyl group and other repeating units is not particularly limited, but in order to obtain the effects of the present invention sufficiently, The ratio of the repeating unit is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 10 mol% or less.
·solvent
The resin layer according to the present invention may contain a solvent for the purpose of improving the convenience when synthesizing the resin and the coating property when employing the coating forming method when forming the resin layer. .

  Examples of the solvent used include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2 -Ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, Ether esters such as 2-methoxypropyl acetate and 2-butoxyethyl acetate; aromatic hydrocarbons such as toluene and xylene; ethyl acetate, proacetate Le, esters such as ethyl acetate and butyl acetate; and the like, may further be a mixture in any proportion of these solvents.

[3-2-2. Other ingredients]
The resin layer according to the present invention includes a stabilizer (for example, a hindered amine-based stabilizer), an antioxidant (for example, a phenol-based, sulfur-based, phosphorus-based antioxidant), an anti-blocking agent, a leveling agent, a silane coupling agent, and the like. The various additives blended in this type of composition can be blended in an amount of 0.01 to 10 parts by weight based on the weight of the film-forming component.

・ Light stabilizer
Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl)
Diphenylmethane-p, p′-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-disulfonate, bis (2,2,6,6-tetramethyl-4) Hindered amines such as -piperidyl) phenyl phosphite, nickel complexes such as nickel bis (octylphenyl sulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate These agents may be used alone or in combination of two or more.

·Silane coupling agent
Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N -Vinylbenzylaminoethyl)
-Γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyl Examples include dimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltriethoxysilane, and the like, and partial hydrolysis condensates of the above silane coupling agents can also be used. By adding such an agent, the adhesion between the polycarbonate base material and the first layer and between the first layer and the second layer is maintained for a long time. These agents may be used alone or in combination of two or more.

[3-3. Method for forming resin layer]
The resin layer may be formed by any conventionally known method, but it is usually performed by coating and forming a composition for forming a resin layer because of the advantage of easy mass production.
The coating method for coating formation is not particularly limited, and dip coating method, flow coating method, spray method, spin coating method, bar coating method, curtain coating method, die coating method, gravure coating method, roll coating method, blade coating method. The coating can be carried out by any of the conventionally known coating methods such as the method and the air knife coating method.

  At this time, if the thickness of the finally formed resin layer is a desired thickness, the thickness of the applied resin layer forming composition layer is not limited, but usually 10 μm or more, preferably It is applied so as to be 30 μm or more, more preferably 50 μm or more, and usually 300 μm or less, preferably 200 μm or less, more preferably 120 μm or less. The application may be performed in one step or divided into two or more steps. However, it is usually more economical and preferable to perform the application once.

When a solvent is optionally used for the resin layer according to the present invention, a composition layer for forming a resin layer is applied and formed, and then dried to remove the solvent. The preferred drying conditions vary depending on the boiling point of the solvent, the material of the base material, the coating amount, etc., but in general, the drying is performed at 30 to 150 ° C. for 1 to 60 minutes, preferably at 80 to 120 ° C. for 1 to 10 minutes. Do.
[4. Cured layer]
[4-1. Curable compound]
The cured layer according to the present invention is a layer made of a resin that has been cross-linked and cured by a cross-linking material typified by a polyisocyanate compound or a trialkoxysilane hydrolyzate. A hardened layer may be used. Further, as a method for crosslinking and curing the cured layer, any conventionally known crosslinking curing method such as curing by heat or curing by irradiation with active energy rays may be used. However, since a thermoplastic resin is used for the base material, there is a risk of deterioration of the base material or deformation due to softening, so that it is cured by irradiation with active energy rays rather than a method of curing by heat. Is preferred.

More specifically, a monomer and / or oligomer having at least one selected from the group consisting of a (meth) acrylate group, a cyclic ether group, and a vinyl ether group can be used as the curable compound used in the cured layer.
Monomers and oligomers having a (meth) acrylate group can be radically polymerized by irradiation with active energy rays. Therefore, when the resin layer composition contains a monomer or oligomer having a (meth) acrylate group, it can be cured by radical polymerization if the resin layer composition is irradiated with active energy rays. .

The cured layer according to the present invention is preferably an active energy ray-curable composition containing an unsaturated compound (B) having two or more unsaturated groups, an ultraviolet absorber (C), and a photopolymerization initiator (D). It is formed by curing an object with active energy rays.
More preferably, the hardened layer contains a colloidal silica (E) having a volume average particle diameter of 1 nm or more and 200 nm or less. In particular, the hardened layer is a hydrolyzed alkoxysilane represented by the following formula (2). It is preferable to contain a decomposition condensate (F).

R ³ _r R ⁴ _s Si (OR ⁵ ) _4-rs (2)
R ³ and R ⁴ in the formula (2) are each selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloyl group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. an alkyl group having 1 to 3 carbons substituted with or more functional groups, ^{R 5} is an alkyl group having 1 to 4 carbon atoms, r, s is an integer of 0 to 3, r + s is 0 It is an integer of 3.

・ Unsaturated compounds having two or more unsaturated groups (B)
The unsaturated compound (B) having two or more unsaturated groups used in the cured layer according to the present invention is not particularly limited as long as it is an unsaturated compound usually used in the cured layer. 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol Adipate di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, EO (ethylene oxide) modified bisphenol A di (meta) Acu Rate, EO (ethylene oxide) modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) aurate, isocyanuric acid ethoxy modified di (meth) acrylate, isocyanuric acid ethoxy modified tri (meth) acrylate, trimethylolpropane di (meta) ) Acrylate and other di (meth) acrylates, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, PO (propylene oxide) modified trimethylolpropane tri (meth) acrylate, Lith (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol tetra (meth) acrylate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolaclone modified dipentaerythritol hexa (meta) ) Trifunctional or higher functional (meth) acrylate such as acrylate; Hydrolyzed condensate of colloidal silica and / or silicate of the above trifunctional or higher functional (meth) acrylate and an adduct of γ-mercaptopropyltrimethoxysilane; Copolymers of hydroxyl group-containing acrylates such as acrylates, pentaerythritol triacrylates, dipentaerythritol pentaacrylates, and adducts of isocyanate propyltriethoxysilane. Hydrolyzed condensate of idal silica and / or silicate; alicyclic skeleton isocyanate compounds such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; (poly) butadiene diol, (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene After adding hydroxyl groups of one or more compounds such as glycol, (poly) ester diol, (poly) caprolactone-modified diol, (poly) carbonate diol, (poly) spiroglycol, etc., -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl acrylate, pentaerythritol Urethane poly (meth) acrylates reacted with (meth) acrylate having a hydroxyl group such as triacrylate; bisphenol A diglycidyl ether, novolac type epoxy resins; trisphenol methane triglycidyl ether, 1,4-butanediol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, propylene glycol diglycidyl ether, 2,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3 , 4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dio Examples include epoxy (meth) acrylates modified with xylene, bis (2,3-epoxycyclopentyl) ether, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin) with (meth) acrylic acid, and the like. It is done.
These unsaturated compounds having two or more unsaturated groups can be used alone or in combination of two or more.

・ Ultraviolet absorber (C)
Examples of the ultraviolet absorber (C) include benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based ultraviolet absorbers. Specific examples thereof include 2- (2-hydroxy-5-methyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole,
2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy) -3 ', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole-2 -Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2'hydroxy-3 ', 5'-t-pentylbenzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3, -tetramethylbutyl)] benzotriazole, 2- (2'hydroxy-3'-s-butyl-5'-t-butylbenzotriazole, 2- (2'-hydroxy- 3-dodecyl-5 ' Methylbenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 , 2-methylenebis [4-1,1,3,3-tetramethylbutyl] -6- (2H-benzotriazol-2-yl) phenol], 3- [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate and polyethylene glycol, 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 -Hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydride Xylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, phenyl salicylate, p-tert-butylphenyl salicylate 3-hydroxyphenylbenzoate, phenylene-1,3-benzoate, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, 2- (4 6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, etc. These ultraviolet absorbers can be used alone or in combination of two or more. The amount added is 100 weights of the composition in terms of the hardness of the coating. Preferably 10 parts by weight or less with respect to part.

・ Polymerization initiator (D)
Examples of the photopolymerization initiator (D) include, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2 , 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxy Ethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1- (4-morpholino Eniru) -1-acetophenones, such as butanone; 2-methyl anthraquinone, 2-ethylanthraquinone, 2-tertiary butyl anthraquinone, 1-chloro anthraquinone, anthraquinones such as 2-amyl anthraquinone.

  Further, thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenones such as benzophenone or xanthone , Α-amino ketones such as 2-benzyl-2-dimethylamino 1-1 (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) Feni Examples thereof include ruthenium, η5-cyclopentadienyl-η6-cumenyliron (1 +)-hexafluorophosphate (1-), etc. These photopolymerization initiators are used alone or in combination of two or more. The addition amount of the photopolymerization initiator is preferably 0.1 to 20 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the composition from the viewpoint of the hardness of the coating.

  Examples of the radical scavenger (D) include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyl. Oxy-2,2,6,6-tetramethylpiperidine, 4-steayloxy-2,2,6,6-tetramethylpiperidine, succinic acid-bis (2,2,6,6-tetramethylpiperidine), Sebacic acid-bis (2,2,6,6-tetramethylpiperidine), sebacic acid-bis (1,2,2,6,6-pentamethyl-4-piperidine), 8-acetyl-3-dodecyl-7, 7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, N-methyl-3-dodecyl-1-(-2,2,6,6-tetra Methyl-4-pi Lysinyl) pyrrolidine-2,5-dione, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidine), trimesic acid-tris (2,2,6,6- Tetramethyl-4-piperidyl) and the like. These light stabilizers can be used alone or in combination of two or more. The addition amount of the light stabilizer is preferably 10 parts by weight or less with respect to 100 parts by weight of the composition from the viewpoint of the hardness of the coating.

・ Colloidal silica (E)
As the colloidal silica (E) having a volume average particle system of 1 nm or more and 200 nm or less preferably used for the cured layer of the present invention, a colloidal solution of inorganic silicic acid fine particles is used. Also, powdered fine particle silica containing no dispersion medium can be used in the present invention. Examples of the colloidal silica dispersion medium include alcohols such as water, methanol, ethanol, isopropanol, n-butanol and n-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, ethylene glycol monomethyl ether, and ethylene glycol mono Derivatives of polyhydric alcohols such as ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, toluene, xylene, etc. Aromatic hydrocarbons and amides such as dimethylacetamide are preferred.

These colloidal silicas can be used by selecting those having the above particle diameters from those manufactured and marketed by a known method. For example, trade names Snowtex O, AK, methanol silica sol, IPA-ST, MEK-ST, MIB commercially available from Nissan Chemical Co., Ltd.
K-ST, PMA-ST, trade names Cataloid-SN, OSCAL1432, etc. commercially available from Catalyst Kasei Co., Ltd. Examples of the powdery fine particle silica include trade name OSCAP commercially available from Catalyst Kasei Co., Ltd., trade name Nanotech commercially available from C.I. Although the colloidal silica of the present invention is available in an acidic or basic form, it is preferable to use the acidic form in the method for producing the active energy ray-curable composition of the present invention.

・ Hydrolysis condensate of alkoxysilane (F)
The alkoxysilane hydrolysis condensate (F) preferably used in the cured layer of the present invention is preferably an alkoxysilane hydrolysis condensate represented by the following formula (2).

R ³ _r R ⁴ _s Si (OR ⁵ ) _4-rs (2)
R ³ and R ⁴ in the formula (2) are each selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloyl group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. an alkyl group having 1 to 3 carbons substituted with or more functional groups, ^{R 5} is an alkyl group having 1 to 4 carbon atoms, r, s is an integer of 0 to 3, r + s is 0 It is an integer of 3.

  More specifically, for example, tetramethoxysilane, tetraethoxysilane, tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetraisobutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, ethyl tri Methoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylto Tokishishiran, 3-methacryloxypropyl methyl dimethoxysilane, 3-glycidoxypropyl main Hill dimethoxysilane, 3-glycidoxypropyl Mehi distearate silane, 3-aminopropyl methyl diethoxy silane, and the like.

[4-2. Other ingredients]
Other components include, for example, stabilizers such as antioxidants, heat stabilizers, light absorbers; fillers such as glass fibers, glass beads, mica, talc, kaolin, metal fibers, metal powders; carbon fibers, carbon black, graphite, carbon nanotube, carbon materials such as fullerene such as C ₆₀ (fillers such, such as fullerenes collectively is referred to as inorganic filler component); antistatic agents, plasticizers, mold release agents, antifoaming agents , Leveling agents, anti-settling agents, surfactants, thixotropy imparting agents, etc .; pigments, dyes, color modifiers such as hue control agents; curing agents necessary for the synthesis of monomers and / or their oligomers or inorganic components And catalysts, curing accelerators and the like.
Furthermore, although the usage-amount of these components is arbitrary unless the effect of this invention is impaired remarkably, normally it is desirable to use only 20 weight% or less of the composition for resin layers.

[4-3. Method for forming cured layer]
The cured layer according to the present invention is formed by applying a cured layer composition to form a cured layer composition layer, and then curing the layer. It is preferable to cure by irradiation.

  The coating method of the hardened layer is not particularly limited, and includes a dip coating method, a flow coating method, a spray method, a spin coating method, a bar coating method, a curtain coating method, a die coating method, a gravure coating method, a roll coating method, a blade coating method, and It can be applied by any coating method such as an air knife coating method. In this case, the thickness of the applied composition for the cured layer is not limited, but is usually 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more, and usually 300 μm or less, preferably 200 μm or less. Preferably it is 120 μm or less. The coating may be performed once or may be performed in two or more times. However, it is usually more economical and preferable to perform the coating once.

When a solvent is used as desired in the cured layer according to the present invention, the resin layer is supplied to the substrate and then dried to remove the solvent. The preferred drying conditions vary depending on the boiling point of the solvent, the material of the base material, the coating amount, etc., but in general, the drying is performed at 30 to 150 ° C. for 1 to 60 minutes, preferably at 80 to 120 ° C. for 1 to 10 minutes. Do.
As the solvent used for the cured layer, the same type of solvent as used for the resin layer can be used.

[4-4. Curing of composition for cured layer]
Although there is no restriction | limiting in particular in the hardening method at the time of hardening the composition for hardened layers which became the layer, and forming a resin layer as a hardened | cured material of the composition for hardened layers, Preferably it is based on irradiation of an active energy ray.
When curing with active energy rays, the cured layer composition is irradiated with radiation (active energy rays or electron beams) to initiate the polymerization reaction of monomers and oligomers in the resin layer composition (hereinafter referred to as radiation curing). Sometimes).

The radiation is an electromagnetic wave (gamma ray, X-ray, ultraviolet ray, visible ray, infrared ray, microwave, etc.) that acts on a polymerization initiator that initiates a necessary polymerization reaction to generate a chemical species that initiates the polymerization reaction. ) Or particle beam (electron beam, α-ray, neutron beam, various atomic beams, etc.).
For example, as an example of radiation that is preferably used, ultraviolet rays, visible rays, and electron beams are preferable, and ultraviolet rays and electron beams are more preferable because energy and a general-purpose light source can be used.

In the case of using ultraviolet rays, a method is generally employed in which a photo radical initiator that generates radicals by ultraviolet rays is used as a polymerization initiator and ultraviolet rays are used as radiation. At this time, you may use said photosensitizer together as needed. As the ultraviolet ray, light having an arbitrary wavelength can be used as long as the composition for a cured layer can be cured. For example, the wavelength is usually 200 nm or more, preferably 250 nm or more, and usually 400 nm or less. Can be used.

  Furthermore, any device can be used as the device for irradiating ultraviolet rays. For example, a known arbitrary device such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet lamp having a structure for generating ultraviolet rays by microwaves is preferably used. it can. The output of the apparatus is normally 10 to 200 W / cm, and when the apparatus is installed at a distance of 5 to 80 cm with respect to the irradiated object, the light deterioration, thermal deterioration, and thermal deformation of the irradiated object. Etc. are preferable.

  Moreover, the composition for cured layers can be preferably cured by an electron beam as described above, whereby a cured product having excellent mechanical properties, particularly tensile elongation properties, can be obtained. When an electron beam is used, the light source and irradiation device are expensive, but are preferably used because the use of an initiator can be omitted and the polymerization is not inhibited by oxygen, and therefore the degree of surface hardening is good. There is a case. The electron beam irradiation apparatus used for the electron beam irradiation is not particularly limited, and any apparatus can be used. Examples thereof include a curtain type, an area beam type, a broad beam type, and a pulse beam type. Furthermore, the acceleration voltage at the time of electron beam irradiation is usually preferably 10 to 1000 kV.

Furthermore, the intensity of the radiation to be irradiated during the radiation curing is optional so long as capable of curing the curable layer composition, usually 0.1 J / cm ² or more is irradiated preferably 0.2 J / cm ² or more energy Is desirable. The irradiation is usually performed at an energy range of 20 J / cm ² or less, preferably 10 J / cm ² or less, more preferably 5 J / cm ² or less, further preferably 3 J / cm ² or less, and particularly preferably ² J / cm ² or less. Is desirable. If the intensity of the radiation is within this range, it can be appropriately selected depending on the type of the composition for the cured layer.

  Further, the irradiation of radiation may be performed in one stage, or may be performed in two or more stages. As the radiation source, a diffusion radiation source in which radiation spreads in all directions is usually used.

  Synthesis examples and examples will be described below to further illustrate the present invention. The components, ratios, procedures, and the like described in the following synthesis examples and examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples described below. In the synthesis examples and examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

(Synthesis Example 1)
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 300 g of propylene glycol monomethyl ether, 150 g of methyl methacrylate, 40 g of stearyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H— 10 g of benzotriazole (RUVA93 manufactured by Otsuka Chemical Co., Ltd.) and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours. Further, 2,2′-azobis (2, 1 g of 4-dimethylvaleronitrile) was added and reacted for 3 hours to obtain a copolymer (A-1) having a nonvolatile content of 40% and a number average molecular weight of 180,000. The number average molecular weight of the copolymer was determined by gel permeation chromatography. Used to determine by polystyrene conversion.

(Synthesis Example 2)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 140 g of methyl methacrylate, 40 g of stearyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H-benzo 20 g of triazole (RUVA93, manufactured by Otsuka Chemical Co., Ltd.) and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours, and further 2,2′-azobis (2,4-dimethyl). 1 g of valeronitrile) was reacted for 3 hours to obtain a copolymer (A-2) having a non-volatile content of 40% and a number average molecular weight of 190000. The number average molecular weight of the copolymer was measured by gel permeation chromatography using polystyrene. Determined by conversion.

(Synthesis Example 3)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 140 g of methyl methacrylate, 40 g of lauryl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H-benzo 20 g of triazole (RUVA93, manufactured by Otsuka Chemical Co., Ltd.) and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours, and further 2,2′-azobis (2,4-dimethyl). 1 g of valeronitrile) was reacted for 3 hours to obtain a copolymer (A-3) having a non-volatile content of 40% and a number average molecular weight of 180,000. The number average molecular weight of the copolymer was measured by gel permeation chromatography using polystyrene. Determined by conversion.

(Synthesis Example 4)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 150 g of methyl methacrylate, 40 g of tridecyl methacrylate,
10 g of (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H-benzotriazole (RUVA93 manufactured by Otsuka Chemical Co., Ltd.) and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) The mixture was further reacted at 65 ° C. for 3 hours, and 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours to react with a copolymer having a nonvolatile content of 40% and a number average molecular weight of 170000 (A-4). The number average molecular weight of the copolymer was determined in terms of polystyrene using gel permeation chromatography.

(Synthesis Example 5)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 14 g of methyl methacrylate, 40 g of behenyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H-benzo 20 g of triazole (RUVA93, manufactured by Otsuka Chemical Co., Ltd.) and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours, and further 2,2′-azobis (2,4-dimethyl). 1 g of valeronitrile) was added and reacted for 3 hours to obtain a copolymer (A-5) having a nonvolatile content of 40% and a number average molecular weight of 160000. The number average molecular weight of the copolymer was measured by gel permeation chromatography using polystyrene. Determined by conversion.

(Synthesis Example 6)
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 300 g of propylene glycol monomethyl ether, 148 g of methyl methacrylate, 40 g of stearyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H-benzo 10 g of triazole (RUVA93 manufactured by Otsuka Chemical Co., Ltd.), 2 g of 2-methacryloyloxyethyl phosphate and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours. -1 g of azobis (2,4-dimethylvaleronitrile) was added and reacted for 3 hours to obtain a copolymer (A-6) having a nonvolatile content of 40% and a number average molecular weight of 150,000. It calculated | required by polystyrene conversion using the permeation chromatography.

(Synthesis Example 7)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 180 g of methyl methacrylate, (2, [2′-hydroxy-5′-
(Methacryloxyethyl) phenyl] -2H-benzotriazole (RUV manufactured by Otsuka Chemical Co., Ltd.)
A93) 20 g and 2,2′-azobis (2,4-dimethylvaleronitrile) 2 g were added and reacted at 65 ° C. for 3 hours. Further, 2,2′-azobis (2,4-dimethylvaleronitrile) 1 g was added. The mixture was reacted for 3 hours to obtain a copolymer (A-7) having a nonvolatile content of 40% and a number average molecular weight of 148,000. The number average molecular weight of the copolymer was determined in terms of polystyrene using gel permeation chromatography.

(Synthesis Example 8)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 140 g of methyl methacrylate, 40 g of n-butyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl]- 20 g of 2H-benzotriazole (RUVA93 manufactured by Otsuka Chemical Co., Ltd.) and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours, and further 2,2′-azobis (2, 1 g of 4-dimethylvaleronitrile) was added and reacted for 3 hours to obtain a copolymer (A-8) having a nonvolatile content of 40% and a number average molecular weight of 180,000. The number average molecular weight of the copolymer was determined by gel permeation chromatography. Used to determine by polystyrene conversion.

(Synthesis Example 9)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 130 g of methyl methacrylate, 60 g of cyclohexyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H— 10 g of benzotriazole (RUVA93 manufactured by Otsuka Chemical Co., Ltd.) and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours, and 2,2′-azobis (2,4- 1 g of dimethylvaleronitrile) was added and reacted for 3 hours to obtain a copolymer (A-9) having a nonvolatile content of 40% and a number average molecular weight of 160000. The number average molecular weight of the copolymer was determined by gel permeation chromatography. Obtained by polystyrene conversion.

(Synthesis Example 10)
In a flask equipped with a thermometer, stirrer and reflux condenser, 300 g of propylene glycol monomethyl ether, 190 g of isobutyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H-benzotriazole (Otsuka Chemical) RUVA93) (10 g) and 2,2′-azobis (2,4-dimethylvaleronitrile) 2 g were added and reacted at 65 ° C. for 3 hours. Further, 2,2′-azobis (2,4-dimethylvaleronitrile) 1 g Was added and reacted for 3 hours to obtain a copolymer (A-10) having a nonvolatile content of 40% and a number average molecular weight of 130000. The number average molecular weight of the copolymer was determined in terms of polystyrene using gel permeation chromatography. .

(Measurement method of physical properties)
The results of measuring the physical properties of the copolymers (A-1) to (A-10) of Synthesis Examples 1 to 10 according to the following measurement methods are summarized in Table 1.
・ Glass transition point (Tg): A test piece having a side of 50 mm and a thickness of 1 mm was molded by a press, and a test piece having a thickness of 50 mm × 4 mm and a thickness of 1 mm was cut out from the molded product, and a rheometer (TA Instruments RSA) was obtained. -III), the elastic modulus of storage (E ') and the elastic modulus of loss (E ") at a frequency of 20 Hz in tensile mode and a temperature of 2 mm per minute from 25 ° C to 250 ° C with a test piece chuck of 40 mm Tan δ was determined from the ratio, and the peak value of tan δ was defined as the glass transition point (Tg).

  -Water absorption: A test piece with a side of 50 mm square and a thickness of 1 mm was molded with a press, dried in a constant temperature layer at 50 ° C. for 24 hours, and allowed to cool to room temperature in a desiccator containing a desiccant (silica gel). Later, the weight of the test piece was measured (hereinafter, this weight may be referred to as the original weight of the test piece). Further, the test piece was immersed in pure water at 50 ° C. for 24 hours and then taken out. The water adhering to the surface was completely absorbed and removed by water supply paper (manufactured by Nippon Paper Crecia Co., Ltd .: Kimwipe S-200). (Hereinafter, sometimes referred to as the weight after water immersion). The water absorption was determined from the ratio of the weight increase between the original weight of the test piece and the weight after immersion in water to the original weight of the test piece.

  ・ Transmittance: A film with a thickness of 5 μm is formed on a quartz plate by a solvent casting method, and the difference in light transmittance of 300 nm from a quartz cell that does not form a film using a spectrophotometer (JASCO UV 570) It was measured.

実施例１
脱脂処理を行ったポリカーボネート板（厚さ３ｍｍ、ヘーズ０．１％、吸水率０．４１４％）にフィルムアプリケータを用いて乾燥後の塗膜が１０μｍになるように、表２の実施例１に示した樹脂層形成用の組成物を（ただし、各使用成分の量は共重合体を１００重量部とした場合の重量部）塗布し、１２０℃で２分間加熱乾燥し、樹脂層を形成した。

Example 1
Example 1 in Table 2 so that the coating film after drying was 10 μm using a film applicator on a degreased polycarbonate plate (thickness 3 mm, haze 0.1%, water absorption 0.414%). The composition for forming a resin layer shown in (1) is applied (however, the amount of each component used is 100 parts by weight of the copolymer) and dried by heating at 120 ° C. for 2 minutes to form a resin layer. did.

Furthermore, the composition for cured layers shown in Example 1 in Table 2 (however, the amount of each used component is 100 parts by weight of the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). Parts by weight) was applied using a bar coater so that the coating thickness after drying was 5 μm, dried by heating at 80 ° C. for 2 minutes, and then applied to this coating plate using a 120 W / cm ² high-pressure mercury lamp to 2000 mJ A cured layer was formed by irradiating with / cm ² of ultraviolet rays. The evaluation results of this sample are shown in Table 2.

Example 2
Except for the resin layer forming composition shown in Example 2 in Table 2 (however, the amount of each used component is parts by weight when the sum of copolymer, UVA and PGM is 100 parts by weight) Form a resin layer in the same manner as in Example 1, and set the composition for the cured layer as Example 2 in Table 2 (however, the amount of each used component is the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). A hardened layer was formed in the same manner as in Example 1 except that the weight was 100 parts by weight. The evaluation results of this sample are shown in Table 2.

Example 3
The resin layer forming composition was the same as in Example 1 except that the composition shown in Example 3 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer) was used. Then, the resin layer was formed, and the composition for the cured layer was made into Example 3 of Table 2 (however, the amount of each used component was 100 parts by weight of the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). A hardened layer was formed in the same manner as in Example 1 except that it was shown in the case of “parts by weight”. The evaluation results of this sample are shown in Table 2.

Example 4
The resin layer forming composition was the same as that of Example 1 except that the composition shown in Example 4 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer). Then, a resin layer was formed, and the composition for the cured layer was changed to Example 4 in Table 2 (however, the amount of each used component was PE3A, TAI
A hardened layer was formed in the same manner as in Example 1 except that the weight of C, NPGDA, IPA-ST, and PGM was 100 parts by weight. The evaluation results of this sample are shown in Table 2.

Example 5
The composition for forming the resin layer was the same as that of Example 1 except that the composition shown in Example 5 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer). Then, a resin layer was formed, and the composition for the cured layer was made into Example 5 of Table 2 (however, the amount of each used component was 100 parts by weight of the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). A hardened layer was formed in the same manner as in Example 1 except that it was shown in the case of “parts by weight”. The evaluation results of this sample are shown in Table 2.

Example 6
The resin layer forming composition was the same as that of Example 1 except that the composition shown in Example 6 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer). Then, a resin layer was formed, and the composition for the cured layer was made into Example 6 of Table 2 (however, the amount of each used component was 100 parts by weight of the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). A hardened layer was formed in the same manner as in Example 1 except that it was shown in the case of “parts by weight”. The evaluation results of this sample are shown in Table 2.

Example 7
The resin layer forming composition was the same as in Example 1 except that the composition shown in Example 7 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer) was used. Then, the resin layer was formed, and the composition for the cured layer was made into Example 7 in Table 2 (however, the amount of each used component was 100 parts by weight of the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). A hardened layer was formed in the same manner as in Example 1 except that it was shown in the case of “parts by weight”. The evaluation results of this sample are shown in Table 2.

Example 8
For the resin layer formation shown in Example 8 of Table 2 so that the coated film after drying using a film applicator is 10 μm on a degreased polycarbonate plate (thickness 3 mm, haze 0.1%) (However, the amount of each component used is 100 parts by weight of the copolymer), and dried by heating at 120 ° C. for 2 minutes to form a resin layer.

Furthermore, the cured layer composition shown in Example 8 in Table 2 (however, the amount of each component used is 100 parts by weight of the silicone resin) is applied to the coating after drying using a bar coater. The film was applied to a thickness of 5 μm and left at room temperature for 5 minutes, and then dried by heating at 120 ° C. for 60 minutes to form a cured layer. The evaluation results of this sample are shown in Table 2.
Comparative Example 1
The composition for forming the resin layer was the same as in Example 1 except that the composition was shown in Comparative Example 1 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer). Then, a resin layer was formed, and the composition for the cured layer was prepared as Comparative Example 1 in Table 2 (however, the amount of each used component was 100 parts by weight of the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). A hardened layer was formed in the same manner as in Example 1 except that it was shown in the case of “parts by weight”. The evaluation results of this sample are shown in Table 2.

Comparative Example 2
The composition for forming the resin layer was the same as in Example 1 except that the composition was shown in Comparative Example 2 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer). Then, a resin layer was formed, and the composition for the cured layer was made into Comparative Example 2 in Table 2 (however, the amount of each used component was PE3A, TAI
A hardened layer was formed in the same manner as in Example 1 except that the weight of C, NPGDA, IPA-ST, and PGM was 100 parts by weight. The evaluation results of this sample are shown in Table 2.

Comparative Example 3
The resin layer forming composition was the same as in Example 1 except that the composition shown in Comparative Example 3 in Table 2 (however, the amount of each component used was 100 parts by weight when the copolymer was 100 parts by weight) was used. Then, a resin layer was formed, and the composition for the cured layer was made into Comparative Example 3 in Table 2 (however, the amount of each used component was 100 parts by weight of the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). A hardened layer was formed in the same manner as in Example 1 except that it was shown in the case of “parts by weight”. The evaluation results of this sample are shown in Table 2.

Comparative Example 4
The composition for forming the resin layer was the same as in Example 1 except that the composition was shown in Comparative Example 4 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer). Then, a resin layer was formed, and the composition for the cured layer was made into Comparative Example 4 in Table 2 (however, the amount of each used component was 100 parts by weight of the sum of PE3A, TAIC, NPGDA, IPA-ST, and PGM). A hardened layer was formed in the same manner as in Example 1 except that it was shown in the case of “parts by weight”. The evaluation results of this sample are shown in Table 2.

Comparative Example 5
The composition for forming the resin layer was the same as that of Example 1 except that the composition was shown in Comparative Example 5 in Table 2 (however, the amount of each component used was 100 parts by weight of the copolymer). Then, a resin layer was formed, and the composition for the cured layer was as shown in Comparative Example 5 in Table 2 (however, the amount of each component used was 100 parts by weight of the silicone resin). Except for the above, a cured layer was formed in the same manner as in Example 1. The evaluation results of this sample are shown in Table 2.

(Test piece evaluation method)
Appearance: The appearance of the coating film of the sample was visually observed, and a sample having a uniform coating film was marked with ◯, and a sample having no uniform coating film was marked with ×.
-Haze: According to JIS K-7105, haze value (%) was evaluated using HM-65W made by Murakami Coloring Company.

・ Abrasion resistance: Taber abrasion test (Rotary Abrasion Tester manufactured by Toyo Seiki Co., Ltd.) was performed under conditions of wear wheel CS-10F, load 500 g, rotation speed 100 cycles, and the difference ΔH% in haze values before and after the test was measured. .
-Adhesiveness: JIS K 5600-5-6: 1999 General test methods for paints-Part 5: Mechanical properties of coating films-Section 6: 2 mm intervals between test pieces according to adhesion (cross-cut method) 100 cell meshes were made, and cellophane adhesive tape (Cello Tape (registered trademark) width 24 mm, manufactured by Nichiban Co., Ltd.) was pressed and peeled off, and the remaining grids were counted. The case where there was no peeling was marked as ◯, and the case where even one peeled off was marked as x.

Heat resistance: left in a hot air dryer at 110 ° C. for 360 hours, visually observed for changes in coating appearance, ○ when no peeling or cracking is seen, ○ when peeling or cracking is seen .
-Humidity and heat resistance: After standing in a constant temperature and humidity machine at 50 ° C. and 95% for 360 hours, an adhesion test was carried out and evaluated in the same manner as the adhesion test.

  -Weather resistance: 1 cycle using SUV (Iwasaki Electric Eye Super UV Tester UV Fluorescent Lamp Weather Meter), UV irradiation time 20 hours (black panel temperature 63 ° C), wet 4 hours (atmosphere temperature 50 ° C, humidity 95%) As follows, the change in the appearance of the film after 20 cycles was visually observed.

In addition, each symbol in Table 2 was used in the following meaning.
PE3A: Pentaerythritol triacrylate
TAIC: Tris (2-acryloyloxyethyl) isocyanurate
NPGDA: Neopentyl glycol diacrylate
IPA-ST: Organo silica sol (30% solution) manufactured by Nissan Chemical Co., Ltd.
UVA1: Triazine ultraviolet absorber
Ciba Specialty Chemicals: TINUVIN400
UVA2: Benzotriazole ultraviolet absorber
Ciba Specialty Chemicals: TINUVIN213
HALS1: hindered amine light stabilizer
Sankyo LS765
HALS2: hindered amine light stabilizer
Ciba Specialty Chemicals: TINUVIN123
PI1: manufactured by Ciba Specialty Chemicals: Irgacure 184
Silicone resin: Momentive Performance Materials
Tosgard 510 (solids concentration 20.5%)
PGM: Propylene glycol monomethyl ether

表２の結果から、本発明の樹脂層を有する積層体は耐摩耗性が高いだけでなく、同時に密着性、耐熱性、耐湿熱性、耐候性も優れたものとなることが分かる。

From the results in Table 2, it can be seen that the laminate having the resin layer of the present invention has not only high wear resistance, but also excellent adhesion, heat resistance, moist heat resistance, and weather resistance.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the laminated body which has a hardened layer excellent in base-material adhesiveness, and was excellent in an external appearance, adhesiveness, abrasion resistance, scratch resistance, and a weather resistance. In addition, since the laminate of the present invention has excellent appearance, abrasion resistance, scratch resistance, and weather resistance, it can be suitably used for headlamp covers, windshield materials, window materials, roof materials, etc. for vehicles. It can also be suitably used for building window glass, building exterior wall materials, road soundproof walls, display faceplates, mobile phone members, and the like.

Claims (6)

  A resin obtained by polymerizing at least one compound selected from the group of compounds having a (meth) acryloyl group between a base material made of a thermoplastic resin and a cured layer, and between the base material and the cured layer In the laminate having the resin layer containing the resin layer, the water absorption ratio Q of the resin layer to the base material is less than 4, and the glass transition temperature (Tg) of the resin layer is 60 ° C. or higher. Characteristic laminate   2. The laminate according to claim 1, wherein the resin layer has a thickness of 2 μm or more and 20 μm or less, and the light transmittance of 300 nm of the layer is 5% or less. A resin obtained by polymerizing at least one compound selected from the group of compounds having a (meth) acryloyl group between a base material made of a thermoplastic resin and a cured layer, and between the base material and the cured layer In the laminate having a resin layer containing the unsaturated monomer (a-1) represented by the following formula (1) 5 to 40% by weight,
CH ₂ = C (R ¹ ) COOR ² (1)
(R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkyl group which may have a branch having 8 to 30 carbon atoms)
1 to 70% by weight of an unsaturated monomer (a-2) having an ultraviolet absorbing group, and at least one monomer selected from the group represented by (a-1) and (a-2) It contains a copolymer (A) having a number average molecular weight of 1,000 to 1,000,000 obtained by copolymerizing 1 to 94% by weight of a polymerizable unsaturated monomer (a-3). Laminate   An active energy ray-curable composition in which the cured layer contains an unsaturated compound (B) having two or more unsaturated groups, an ultraviolet absorber (C), and a photopolymerization initiator (D) is used as an active energy ray. The laminate according to any one of claims 1 to 3, wherein the laminate is cured by the method.   The laminate according to any one of claims 1 to 4, wherein the hardened layer contains colloidal silica (E) having a volume average particle diameter of 1 nm to 200 nm. The laminate according to any one of claims 1 to 5, wherein the cured layer contains a hydrolysis condensate (F) of alkoxysilane represented by the following formula (2).
R ³ _r R ⁴ _s Si (OR ⁵ ) _4-rs (2)
Wherein R ³ and R ⁴ are each one or more functional groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloyl group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. An alkyl group having 1 to 3 carbon atoms substituted with a group, R ⁵ is an alkyl group having 1 to 4 carbon atoms, r and s are each an integer of 0 to 3, and r + s is an integer of 0 to 3 Is)