JP2010215843A - Active energy ray-curable composition and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which has excellent appearance, wear resistance, scratch resistance, adhesion to the base material, heat resistance, wet heat resistance, and weatherability, and does not cause cracking nor peeling. <P>SOLUTION: The laminate has a primer layer composed of an acrylic resin and a hard coat layer composed of an active energy ray-curable composition at least one side of the base material in this order. The active energy ray-curable composition consists of (A), (B), and (C) below. (A) Multifunctional (meth)acrylate of 50-90 pts.wt. (B) Urethane (meth)acrylate obtained by reacting (b-1) a diol having an alicyclic structure, (b-2) a lactone, (b-3) a polyisocyanate, and a hydroxyl group-containing (meth)acrylate of 10-50 pts.wt. (C) Ultraviolet absorber of 0.1-20 pts.wt. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is an active energy ray-curable composition that can be cured by irradiation with an active energy ray and can form a hard coat layer having excellent appearance, scratch resistance, adhesion to a substrate and weather resistance, and an acrylic resin. The present invention relates to a laminate having a primer layer and a hard coat layer obtained by curing the active energy ray-curable composition, a resin window comprising the laminate, and an automobile window material.

  Polycarbonate resins have the advantages of excellent transparency, heat resistance, mechanical strength, and easy processability, and are therefore widely used in electrical, automotive, medical applications and the like. However, polycarbonate has the disadvantages that the surface hardness is insufficient and the scratch resistance is insufficient, and that yellowing occurs when used outdoors for a long time. In order to improve these drawbacks, a method for coating the surface of a polycarbonate molded article with various coating agents has been proposed. However, although the hard coating agent can form a high hardness film on the plastic surface, it has a drawback that cracks are likely to occur because the hardness is too high.

  As a method for solving these problems, an ultraviolet curable hard coat agent composed of colloidal silica, a hydrolyzable product of alkoxysilyl acrylate, hexanediol diacrylate, a branched or carbocyclic monofunctional acrylate ester has been proposed. (Patent Document 1). Further, a coating composition (Patent Document 2) comprising a bifunctional acrylate having a cardo structure, a urethane acrylate having three or more acryloyl groups, a lactone-modified polypentaerythritol polyacrylate, colloidal silica, and an ultraviolet absorber has been proposed. . Further, a hard coating agent (Patent Document 3) containing a polymerizable monomer and polymerizable benzophenone or polymerizable benzotriazole has been proposed.

JP-A-5-306374 JP 7-247382 A Japanese Patent Laid-Open No. 10-60307

Conventionally, coating compositions known in patent literatures, etc., increase the difunctional acrylate to make the surface hardness insufficient, or conversely reduce the bifunctional acrylate to easily generate cracks. It was difficult to satisfy.
In addition, for example, when a polymerizable ultraviolet absorber is used for the purpose of forming a coating layer having ultraviolet absorptivity in order to prevent the base material from being deteriorated by ultraviolet rays, the polymerizable ultraviolet absorber is converted into an acrylic monomer. Since the solubility was insufficient, there was a drawback that cracks were likely to occur due to the unreacted ultraviolet absorber.

  And in the laminated body which formed the hard-coat layer on the layer which consists of acrylic resins, this layer and this hard-coat layer had the fault that a whitening or a crack generate | occur | produces. In addition, since the cross-linking reaction of the cured layer proceeds with time, the coating film is likely to be distorted, the hard coat layer is cracked, and the hard coat layer is easily peeled off. It was insufficient to maintain the weather resistance of the period. Furthermore, since the hardness of the resin of 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 to solve the above-mentioned problems, and is an active energy ray-curable composition that can form a hard coat layer excellent in appearance, abrasion resistance, weather resistance, and substrate adhesion, Laminated body having a hard coat layer made of the active energy ray-curable composition, appearance, abrasion resistance, weather resistance, resin window having a hard coat layer excellent in substrate adhesion, and appearance, abrasion resistance, An automobile window material having a hard coat layer excellent in weather resistance and substrate adhesion is provided.

As a result of intensive studies to solve the problems, the present inventors have found that a composition capable of forming a hard coat layer having extremely excellent performance can be obtained by containing a specific material. The headline and the present invention were completed.
That is, the first gist of the present invention is an active energy ray-curable composition for forming a hard coat layer that can be cured by active energy rays, from the following (A), (B), and (C): The present invention resides in an active energy ray-curable composition (claim 1).

(A) Polyfunctional (meth) acrylate: 50 to 90 parts by weight (B) Diol (b-1) having an alicyclic structure, lactones (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meta ) Urethane (meth) acrylate obtained by reacting acrylate: 10 to 50 parts by weight (C) UV absorber 0.1 to 20 parts by weight Further, the active energy ray-curable composition further has a volume average particle diameter of 200 nm. The following (D) colloidal silica is preferably included (Claim 2), and the colloidal silica is preferably surface-modified with a compound having a hydrolyzable silicon group (Claim 3).

Moreover, it is preferable that the diol (b-1) which has the said alicyclic structure is tricyclodecane dimethanol (Claim 4), and also the said active energy ray curable composition is (E) hindered amine type light stability. It is preferable to contain 0.1 to 10 parts by weight of the agent (Claim 5), and (F) 0.1 to 10 parts by weight of the photopolymerization initiator is further preferably contained (Claim 6).
The second gist of the present invention resides in a laminate having at least one surface of a base material in the order of a primer layer made of an acrylic resin and a hard coat layer made of the active energy ray-curable composition on at least one surface of the substrate ( It is preferable that the molded body is formed by injection molding of polycarbonate resin (Claim 8), and the laminate is preferably used for a resin window (Claim 9).

  And the third gist of the present invention is a laminate having at least one surface of a base material in this order, a primer layer made of an acrylic resin, and a hard coat layer made of an active energy ray-curable composition. The active energy ray-curable composition resides in an automotive window material comprising a laminate, which is a composition comprising the following (A), (B), and (C) (Claim 10).

(A) polyfunctional (meth) acrylate (B) diol (b-1) having an alicyclic structure, lactone (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meth) acrylate are reacted. Urethane (meth) acrylate obtained (C) UV absorber

  The laminate of the present invention has a coating film excellent in appearance, abrasion resistance, weather resistance, and substrate adhesion, and has a hard coat layer cured by active energy rays, and therefore has low heat resistance. It can also be applied to plastic substrates to obtain a high performance laminate. The laminate of the present invention is excellent in appearance, wear resistance, weather resistance, and substrate adhesion, and is a headlamp cover, windshield, vehicle window glass, vehicle roofing material, building window glass, and building. It is useful for exterior wall materials, road noise barriers, display faceplates, mobile phone members, and the like. Furthermore, it is a laminate having high wear resistance, weather resistance and substrate adhesion while maintaining high transparency, and is suitable as a resin window material. In particular, it is suitable as a window material for automobiles that are used outdoors and exposed to temperature changes, humidity changes, ultraviolet irradiation, and infrared irradiation over a long period of time.

  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 composition of this invention is a composition for forming the hard-coat layer which can be hardened | cured with an active energy ray, Comprising: It consists of following (A) (B) (C).
(A) Polyfunctional (meth) acrylate: 50 to 90 parts by weight (B) Diol (b-1) having an alicyclic structure, lactones (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meta ) Urethane (meth) acrylate obtained by reacting acrylate: 10 to 50 parts by weight (C) Ultraviolet absorber 0.1 to 20 parts by weight The laminate of the present invention is acrylic on at least one surface of the substrate. It has at least a primer layer made of resin and a hard coat layer made of the active energy ray-curable composition in this order, and the resin window of the present invention is made of the laminate of the present invention.

  Furthermore, the window material for automobiles of the present invention has a primer layer made of an acrylic resin, (A) a polyfunctional (meth) acrylate, and (B) a diol (b-1) having an alicyclic structure on at least one surface of a substrate. ), Lactones (b-2), a polyisocyanate (b-3) and a urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate, and (C) an active energy ray curable composition comprising an ultraviolet absorber. It consists of a laminated body which has the hard-coat layer which consists of a composition at least in this order.

[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 primer layer and a hard coat layer made of an active energy ray-curable composition at least in this order on at least one surface of the substrate, and the primer layer is usually in contact with the substrate. Although formed, the base material and the primer layer may not necessarily be in contact with each other, and another kind of layer may be formed between the base material and the primer layer.

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

  Similarly, the relationship between the primer layer and the hard coat layer comprising the active energy ray-curable composition may or may not be in contact with the primer layer and the hard layer comprising the active energy ray-curable composition. Since it becomes particularly prominent when it is formed so as to be in contact with the coat layer, it is preferable that the laminate of the present invention is formed so that the primer layer and the hard coat layer made of the active energy ray-curable composition are in contact with each other. .

[2. Base material]
[2-1. Structure of base material]
There is no restriction | limiting in particular in the base material which concerns on the laminated body of this invention, Usually, the plastic material currently used widely can be used.
As the plastic material, it is preferable to use a thermoplastic resin for ease of processing. For example, an acrylic resin such as polycarbonate or polymethyl methacrylate, a polyester resin such as polyethylene terephthalate, a styrene resin such as vinyl chloride resin or polystyrene, or cellulose acetate. Polypropylene can be used, but from the viewpoint of adhesiveness with the primer layer according to the present invention, a polymer having a carbonyl group is more preferable. Further, from the viewpoint of preferably satisfying the physical properties of the substrate, polyester, polyarylate, polycarbonate, and cellulose acetate are preferable, polycarbonate is more preferable, and aromatic polycarbonate is particularly preferable.

  The aromatic polycarbonate according to the present invention is a resin obtained by reacting a carbonate precursor with an interfacial method or a melting method using dihydric phenol as a dihydric alcohol, and is a mixture of two or more kinds of polycarbonates. May be. Examples of the carbonate precursor include carbonyl halides such as phosgene, carbonyl esters such as diphenyl carbonate, and haloformates. The aromatic polycarbonate according to the present invention preferably has a number average molecular weight of about 15,000 to 50,000 in terms of polystyrene by the GPC method. Further, the polycarbonate resin contains various additives such as a mold release agent, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a colorant, a whitening agent, and a flame retardant within a range not impairing the object of the present invention. Also good.

  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 a dihydric alcohol usually used as a monomer unit of polyester, polyarylate, or polycarbonate is used. It is preferable to use it.

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-dimethylphenyl) propane, bis (4-hydroxy-2,3, 5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ethane, 2,2-bis (4-hydroxy-) , 3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) phenylethane, A bisphenol compound having an alkyl group as a substituent on an aromatic ring such as 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 connected 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.

[2-2. 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. Primer layer]
[3-1. Physical properties of primer layer]
Although there is no restriction | limiting in particular in the water supply rate of the primer layer which concerns on this invention, The direction which is hard to receive to the influence of the humidity fluctuation of an environment is preferable, and the one where water absorption is especially low is preferable.

  In order to improve the weather resistance of the laminate, the thickness of the primer 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, 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.

The light transmittance at a wavelength of 300 nm of the primer layer according to the present invention is measured by a spectrophotometer, and is usually 10% or less, preferably from the viewpoint of improving the weather resistance, regardless of the thickness of the primer layer. 5% or less, more preferably 2% or less.
Although there is no restriction | limiting in particular in the haze of the primer layer which concerns on this invention, When using the laminated body of this invention for glass substitute use, for example, it is preferable that the haze of a primer 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 primer layer]
The primer layer according to the present invention is made of an acrylic resin and 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 carbon-carbon double bond at the end of the compound. For technical reasons, the compound group having a (meth) acryloyl group has an acryloyl group or a methacryloyl group, Any compound having an acryloyl group and a methacryloyl group 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 primer 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 prescribe the properties of the primer 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 properties 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 easily adjust the mechanical strength, adhesiveness, and water absorption of the primer 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 primer layer, and when the mechanical strength, adhesiveness, and water absorption of the primer layer are adjusted, 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 primer layer and other layers, 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 of the primer layer is preferably R ² is alkyl group having 8 or more carbon atoms, the carbon number of the alkyl group, and more preferably 10 or more carbon atoms, 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 is preferred.

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) Examples include acrylate and behenyl (meth) acrylate.
In addition, as described above for the physical properties of the primer 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 as a whole primer layer regardless of the thickness of the primer layer. preferred, in order to adjust the light transmittance of the light of 300nm is preferably a substituent represented by R ² is a group that absorbs or blocks the light of 300nm vicinity, more specifically, usually ultraviolet A compound having a (meth) acryloyl group having a so-called ultraviolet absorbing group derived from a compound used as an absorbent is preferable.

In order to adjust the light transmittance of 300 nm light of the primer 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 primer 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 primer 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.
Examples of unsaturated monomers that can be copolymerized when the resin is a copolymer include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, and (meth) acrylamide. , Alkyl vinyl ethers, alkyl vinyl esters, styrene or derivatives thereof.

  Among these, specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and 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 group Alkoxypolyalkylene glycol (meth) acrylate such as coal (meth) acrylate, 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) acryloyl Oxyethyl hexahydrophthalate, 2- (meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanatoethyl (meth) acrylate, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) Examples include acryloyloxypropylmethyltrimethoxysilane 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.

The primer layer according to the present invention can 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 primer 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.

[3-3. Other ingredients]
The primer layer according to the present invention includes a stabilizer (for example, a hindered amine 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-tetra Methylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1 , 3-disulfonate, hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) phenyl phosphite, nickel bis (octylphenyl ester) Nickel complexes such as fido, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, etc. These agents may be used alone or in combination of two or more. May be.

Silane coupling agent As the silane coupling agent, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N -Β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-anilino Examples include propyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltriethoxysilane, and the like. Can 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.

[3-4. Method for forming primer layer]
The primer layer may be formed by any conventionally known method, but is usually performed by coating and forming a primer layer forming composition from 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 finally formed primer layer has a desired thickness, there is no limitation on the thickness of the applied primer layer forming composition layer, 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 used as desired for forming the primer layer according to the present invention, a composition layer for forming a primer 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. Hard coat layer]
[4-1. Active energy ray curable composition]
The hard coat layer according to the present invention is a layer made of a resin that is cross-linked and cured by a cross-linking material typified by a polyisocyanate compound or a trialkoxysilane hydrolyzate, and the active energy ray-curable composition is converted into an active energy ray. Is cured by irradiation.

(A) Polyfunctional (meth) acrylate As (A) polyfunctional (meth) acrylate used for the active energy ray-curable composition of the present invention, for example,
1,4-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, neo Pentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) Modified bisphenol A di (meth) acrylate, EO-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) aurate, isocyanuric acid ethoxy modified di ( ) Acrylate, isocyanuric acid ethoxy modified tri (meth) acrylate, trimethylolpropane di (meth) acrylate and other di (meth) acrylate, 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, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acrylic) Roxyethyl) isocyanurate, propionic acid modified dipentaerythritol tetra (meth) acrylate, propionic acid modified dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Kapurorakuron modified dipentaerythritol hexa (meth) acrylate such as trifunctional or more (meth) acrylate;

An adduct of the above trifunctional (meth) acrylate and γ-mercaptopropyltrimethoxysilane, colloidal silica and / or silicate hydrolysis condensate;
An adduct of a hydroxyl group-containing acrylate such as glycerin diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and isocyanatepropyltriethoxysilane, colloidal silica and / or silicate hydrolysis condensate;
To alicyclic skeleton isocyanate compounds such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, (poly) butadiene diol, (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) ester diol, (poly) After adding hydroxyl groups of one or more compounds such as caprolactone-modified diol, (poly) carbonate diol, (poly) spiroglycol, etc., 2-hydroxyethyl (meth) acrylate, 2-hydroxy is added to the remaining isocyanate groups. (Meth) acrylate having a hydroxyl group such as propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl acrylate, pentaerythritol triacrylate Urethane poly (meth) acrylates obtained by response;
Bisphenol A diglycidyl ether, novolak 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-dioxane, bis (2,3-epoxycyclopentyl) ether, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) Modified epoxy (meth) acrylates with cycloaliphatic epoxy resin) (meth) acrylic acid and the like.

An acrylate having two or more (meth) acryloyl groups in these molecules may be used alone or in combination of two or more.
In the active energy ray-curable composition of the present invention, the content of (A) polyfunctional (meth) acrylate is (A) polyfunctional (meth) acrylate and (B) urethane (meth) acrylate for reasons of scratch resistance. When the total amount of the components is 100 parts by weight, it is preferably 50 to 90 parts by weight, more preferably 60 to 90 parts by weight, and still more preferably 60 to 80 parts by weight.

(B) Urethane (meth) acrylate According to the present invention, the diol (b-1), lactone (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meth) acrylate having an alicyclic structure are reacted. As (B) urethane (meth) acrylate obtained in this way, for example, those synthesized using the following raw materials can be used.

Examples of the diol (b-1) having an alicyclic structure include compounds in which indene, naphthalene, azulene, anthracene and the like are hydroxyalkylated; bicyclo [5,3,0] decandimethanol, bicyclo [4,4,0 ] decane dimethanol, bicyclo [4,3,0] nonane methanol, norbornanedimethanol, tricyclodecanedimethanol, 1,3-adamantane-diol (1,3-dihydroxy-tricyclo [3,3,1,1 ^{3 , 7} ] decane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, isosorbide, hydrogenated bisphenol A, 1, 4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol

Examples of the lactones (b-2) include β-propiolactone, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, α, β, γ-trimethoxy-δ-valerolactone, β -Methyl- [epsilon] -isopropyl- [epsilon] -caprolactone, lactide, glycolide and the like.
Examples of the polyisocyanate (b-3) include tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, trimethylhexamethylene. Examples thereof include diisocyanate, 1,5 naphthalene diisocyanate, norbornene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and lysine diisocyanate.

  As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. are mentioned.

  The (B) urethane (meth) acrylate according to the present invention synthesizes a caprolactone-modified diol having an alicyclic structure, and further reacts with the diisocyanate at 20 to 100 ° C., preferably 40 to 80 ° C. for 1 to 20 hours. It can be obtained by synthesizing a diisocyanate and reacting a hydroxyl group-containing (meth) acrylate at 20 to 100 ° C. for 1 to 20 hours. For example, when a caprolactone-modified diol having an alicyclic structure uses tricyclodenkanedimethanol as the diol (b-1) having an alicyclic structure and ε-caprolactone as the lactone (b-2), In the presence, it can be synthesized by performing an addition reaction by heating to 50 to 220 ° C, preferably 100 to 200 ° C. At this time, the reaction rate is low at low temperatures, and thermal decomposition occurs at high temperatures, which is not preferable. As the catalyst used in this reaction, inorganic salts, inorganic acids, organic alkali metals, tin compounds, titanium compounds, aluminum compounds, zinc compounds, tungsten compounds, molybdenum compounds, and zirconium compounds can be used.

  In the reaction of diol and dicyanate, or dicyanate and hydroxyl group-containing (meth) acrylate, it is preferable to use a catalyst to accelerate the reaction. As a catalyst which can be used here, tertiary amine compounds such as organic tin compounds typified by dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin diacetate, and triethylamine can be used.

  In the active energy ray-curable composition of the present invention, the content of (B) urethane (meth) acrylate is (A) polyfunctional (meth) acrylate and (B) urethane (meth) acrylate component for reasons of weather resistance. When the total amount is 100 parts by weight, it is preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight, still more preferably 20 to 40 parts by weight.

(C) Ultraviolet absorber (C) Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based ultraviolet absorbers.
Specific examples thereof include, for example, 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- [
Benzotriazoles such as 3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate and a reaction product of polyethylene glycol, 2-
Hydroxybenzophenone, 5-chloro 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2, Benzophenones such as 2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2- (4,6-diphenyl-1, 3,5-triazin-2-yl) -5-[(methyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(ethyl) oxy]- Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl -[(Propyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(butyl) oxy] -phenol, 2- (4,6-diphenyl) Triazines such as -1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, salicylates such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl 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 are used alone. Others may be used in combination of two or more.

  In the active energy ray-curable composition of the present invention, the content of the (C) ultraviolet absorber is the sum of (A) polyfunctional (meth) acrylate and (B) urethane (meth) acrylate component for reasons of weather resistance. When the amount is 100 parts by weight, it is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 0.5 to 5 parts by weight.

(D) Colloidal silica (D) Examples of colloidal silica include water, methanol, isopropanol, n-butanol, isobutanol, ethylene glycol, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, and methyl. Silica having an average particle size of 1 to 200 nm is preferable, and an average particle size of 5 to 50 nm is more preferable, using isobutyl ketone, dimethylacetamide, xylene and a mixed solvent thereof as a dispersion medium. The average particle size was measured using a scanning electron microscope (JSM-7401F manufactured by JEOL Ltd.), and the 50 particles of this image were measured using image analysis software ImageProPlus (MediaMedianets). The colloidal silica used in the present invention is contained in an amount of 10 to 40% by weight when the total amount of the (A) polyfunctional (meth) acrylate and (B) urethane (meth) acrylate component is 100 parts by weight as a solid content. It is preferable to do. In particular, when colloidal silica dispersed in an organic solvent is used, it is preferable because it exhibits high transparency when formed into a coating film. Typically, an organo dispersed in a solvent having a hydroxyl group or a polar solvent having a ketone group is used. It is preferable to use silica sol. Specifically, “IPA-ST” (IPA-dispersed organosilica sol, Nissan Chemical), “MEK-ST” (MEK-dispersed organosilica sol, Nissan Chemical), “MIBK-ST” (MIBK-dispersed organosilica sol, Nissan Chemical), etc. Or a sol (for example, PGM-dispersed organosilica sol) obtained by replacing these with a solvent having another hydroxyl group as a raw material.

  As the colloidal silica, either a surface-modified one or an unmodified one may be used, but a surface-modified colloidal silica is preferably used. For the modification of colloidal silica, a hydrolyzable silicon group or a compound having a silicon group to which a hydroxyl group is bonded can be used. Hydrolyzable silicon groups generate silanol groups by hydrolysis, and these silanol groups react with and bind to silanol groups present on the surface of the colloidal silica to produce surface-modified colloidal silica. Used to modify colloidal silica.

  Examples of the silicon group-containing compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and β- (meth) acryloyloxyethyltrimethoxy. Silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinylolimethoxysilane, vinyltriethoxysilane, vinylmethyl Dimethoxysilane, p-vinylphenyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxy Orchids, .gamma.-aminopropyltrimethoxysilane, .gamma., P- styryltrimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, can be mentioned 3-mercaptopropyl trimethoxysilane. A silicon group containing compound can be used individually or in combination of 2 or more types.

As a surface modification method of colloidal silica, it can be synthesized by reacting colloidal silica with a hydrolyzable silicon group-containing compound, a catalyst, and water at 20 to 100 ° C. for 1 to 40 hours.
The catalyst used in this reaction is inorganic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid; formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, acrylic acid, methacrylic acid, etc. Organic acid; alkali; acetylacetone aluminum, aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate, aluminum diisopropoxide ethyl acetoacetate, aluminum diisobutoxide ethyl acetoacetate, butanoic acid borate Dibutyltin dilaurate, dibutyltin dioctate and the like can be used. The amount of these catalysts used is 0.0001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total amount of colloidal silica and hydrolyzable silicon group-containing compound. The amount of water required for hydrolysis is 0.5 to 100 equivalents, preferably 1 to 30 equivalents, relative to the hydrolyzable silicon group.
As the colloidal silica used in this reaction, colloidal silica in an acidic or basic dispersion form can be used, and acidic colloidal silica is preferred.

(E) Hindered amine light stabilizer (E) Examples of the hindered amine light stabilizer include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2,6,6. -Tetramethylpiperidine, 4-octanoyloxy-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-tetramethyl-4-piperidinyl) 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.

(F) Photopolymerization initiator (F) Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and 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-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- Examples include acetophenones such as (4-morpholinophenyl) -1-butanone; and anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone.

  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 content 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.

Solvent The active energy ray-curable composition of the present invention can contain a solvent from the viewpoint of handling the composition. For example, 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-butoxyethanol, 1 Ethers such as 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, 2-butoxyethyl acetate, 3 -Ether esters such as methoxypropyl acetate; Aromatic hydrocarbons such as toluene and xylene; Ethyl acetate, propyl acetate, butyl acetate, etc. Ester compounds; and the like. These solvents can be used alone or in combination of two or more.

In addition, the base material to which the curable composition of the present invention is applied can be subjected to surface treatment in advance for the purpose of improving adhesion, smoothing, patterning and the like. Examples of the surface treatment include plasma treatment, corona discharge treatment, ultraviolet irradiation treatment, flame treatment, chemical treatment, degreasing, oxidation treatment, vapor deposition treatment, blast treatment, ion treatment and the like.
It does not specifically limit as a method of apply | coating the said active energy ray curable composition to a base material, A well-known and usual method can be used. As the coating method, for example, any method such as dipping method, flow coating method, spray method, spin coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, offset method, bar coating method, etc. Can also be applied. It can also be applied like an image by printing or the like.

In addition, although it does not restrict | limit in particular about an application quantity, It is preferable to apply so that the film thickness of the film hardened | cured by irradiation of the active energy ray may be 0.1-50 micrometers, Preferably it is 1-10 micrometers.
When a solvent is used in the curable composition of the present invention as desired, the curable composition is supplied to the substrate and then dried to remove the solvent. The preferable 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 120 ° C. for 1 to 30 minutes, preferably at 50 to 100 ° C. for 1 to 5 minutes Do.

Next, it is cured by irradiation with active energy rays. Active energy rays include ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps, usually electron beams extracted from particle accelerators of 20 to 2000 kV, α A line, a beta ray, a gamma ray, etc. can be used.
The laminate of the present invention uses, for example, a plastic film having a film thickness of 200 μm or less, more preferably 5 to 150 μm as the substrate, and the active energy ray of the present invention is applied to the surface of the film according to the above method. It can produce by forming the film which consists of a curable composition.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples. The components, ratios, procedures, and the like described in the following production 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 addition, “parts” and “%” described in the production examples and examples mean “parts by mass” and “% by mass”, respectively.

(Production Example 1: Surface-modified colloidal silica)
100 g of colloidal silica (silica content 30%, volume average particle size 14 nm) dispersed in 2-propanol, 5 g of 3-mercaptopropyltrimethoxysilane, acetylacetone aluminum, in a flask equipped with a thermometer, stirrer and reflux condenser 0.35 g, 1 g of water, and 11.5 g of propylene glycol monomethyl ether were added and the mixture was heated and stirred at 70 ° C. for 6 hours and then aged at room temperature for 12 hours to obtain a surface-modified colloidal silica (hereinafter referred to as 30% nonvolatile content). , Sometimes referred to as silica 2).

(Production Example 2: Polymer for forming primer layer)
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 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours. Further, 2,2′-azobis (2, 4-Dimethylvaleronitrile) 2 g was added and reacted for 3 hours to obtain a copolymer (P-1) having a nonvolatile content of 40% and a weight average molecular weight of 68,000.

(Production Example 3: Urethane acrylate 2)
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 168.2 g of hexamethylene diisocyanate, 344 g of polycaprolactone monoacrylate (Placcel FA2D hydroxyl value 163 KOHmg / g, manufactured by Daicel Chemical Industries), 0.8 g of dibutyltin laurate and hydroquinone monomethyl ether After adding 0.8 g and heating and stirring at 70 ° C. for 5 hours, 128.5 g of propylene glycol monomethyl ether was added to the reaction solution to obtain urethane acrylate 2 (nonvolatile content: 80%).

(Production Example 4: Urethane acrylate 1)
After adding 39.3 g of tricyclodecane dimethanol, 46.6 g of ε-caprolactone and 0.1 g of tetraoctyltin to a flask equipped with a thermometer, a stirrer and a reflux condenser, the mixture was heated and stirred at 180 ° C. for 15 hours under a nitrogen stream. , 88.9 g of isophorone diisocyanate, 46.5 g of 2-hydroxyethyl acrylate, 55.3 g of phenoxydiethylene glycol acrylate, 0.2 g of dibutyltin laurate and 0.1 g of hydroquinone monomethyl ether were heated and stirred at 80 ° C. for 5 hours in an air stream. Urethane acrylate 1 was obtained.

Example 1
A copolymer (P-) produced in Production Example 2 using a film applicator on a degreased polycarbonate plate (thickness 3 mm, haze 0.1%) so that the coating thickness after drying is 10 μm. 1) was applied and dried with a hot air dryer at 120 ° C. for 5 minutes to form a primer layer.

  Kayrad DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional acrylate, 23.4 parts, urethane acrylate 1 produced in Production Example 4 as a urethane acrylate, 23.4 parts, and tinuvin 400 (manufactured by Ciba Specialty Chemicals) as a UV absorber 2.3 parts, 0.5 part of Tinuvin 123 (manufactured by Ciba Specialty Chemicals) as a stabilizer, 0.5 part of Tinuvin 184 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and 50 parts of propylene glycol monomethyl ether Were mixed and stirred well to obtain an active energy ray-curable composition.

On this primer layer, this active energy ray-curable composition was applied using a bar coater so that the coating thickness after drying was 6 μm, and dried by heating at 80 ° C. for 5 minutes. Next, this coating film was irradiated with ultraviolet rays so as to obtain an integrated light amount of 3 J / cm ² at an irradiation intensity of 400 mW / cm ² using a high-pressure mercury lamp with an output of 120 w / cm ^{2 as} a light source, and the coating film was cured to harden the hard coat layer. To form a laminate.

(Examples 2-8 and Comparative Examples 1-5)
A hard coat layer was formed in the same manner as in Example 1 except that active energy ray-curable compositions having the compositions (units: parts by weight) shown in Tables 1 and 2 below were used. Examples 2 to 8 And the laminated body of Comparative Examples 1-5 was produced.

表−１および表−２中の各記号は下記材料の意味であり、−はそれを使用していないことを示す。

Each symbol in Table-1 and Table-2 means the following material, and-indicates that it is not used.

Multifunctional acrylate 1: Dipentalysitol manufactured by Nippon Kayaku Co., Ltd. (trade name: Kayarad D
PHA)
Multifunctional acrylate 2: Pentaerythritol triacrylate manufactured by Osaka Organic Chemical Co., Ltd.
(Product name: Biscote 300)
Multifunctional acrylate 3: Isocyanuric acid EO-modified acrylate (product of Toagosei Co., Ltd.)
Name: Aronix M313)
Multifunctional acrylate 4: Caprolactone-modified isocyanuric acid acrylate, manufactured by Toagosei Co., Ltd.
(Product name: Aronix A9300-3CL
Multifunctional acrylate 5: Tricyclodecane dimethanol acrylate manufactured by Shin-Nakamura Chemical Co., Ltd.
(Product name: NK Ester A-DCP)
Multifunctional acrylate 6: Caprolactone-modified dipentaerythritol manufactured by Nippon Kayaku Co., Ltd.
Xaacrylate (trade name: Kayarad DPCA60)
Urethane acrylate 1: Urethane acrylate produced in Production Example 4 Urethane acrylate 2: Urethane acrylate produced in Production Example 3 Silica 1: Organosilica sol manufactured by Nissan Chemical Co., Ltd. (trade name: IPA-ST
(Average particle size 13 nm 30% 2-propanol solution)
Silica 2: Surface-modified colloidal silica produced in Production Example 1 UVA1: Triazine-based UV absorption manufactured by Ciba Specialty Chemicals
Collection agent (trade name: TINUVIN400)
UVA2: Benzotriazole series manufactured by Ciba Specialty Chemicals
Ultraviolet absorber (trade name: TINUVIN213)
HALS1: Hindered amine light from Ciba Specialty Chemicals
Stabilizer (trade name: TINUVIN123)
PGM: Propylene glycol monomethyl ether Photopolymerization initiator 1: Ciba Specialty Chemicals (trade name: Irgac
A)

(Evaluation methods)
The laminate produced as described above was evaluated according to the following evaluation method. The results are shown in Table-3 and Table-4.
Haze: The haze value (H%) was evaluated according to JIS K-7105.
Abrasion resistance: According to JIS K5600, a Taber abrasion test was performed under the conditions of an abrasion wheel CS-10F, a load of 500 g, and a rotation speed of 500 cycles, and a haze value difference ΔH% before and after the test was measured.
Scratch resistance: A load of 500 g is applied on steel wool # 0000 using a Gakushin abrasion tester.
Ten reciprocations were made, and the state of the scratch was judged visually.
◎: No scratches are observed. ○: 1 to 5 scratches are observed. Δ: 5 to 10 scratches are applied. ×: 10 or more scratches are applied. Initial adhesion: 100 pieces at intervals of 2 mm on the test piece. Make your eyes more cellophane tape (Nichi
24 mm) was peeled and peeled upward, and the peeling was observed visually. ○: No peeling ×: With peeling Heat and heat resistance: After leaving the test piece in a constant temperature and humidity chamber at 50 ° C. and a humidity of 98% for 360 hours, 2
According to the following adhesion evaluation method after standing for 24 hours in an environment of 3 ° C. and 50%.
Evaluated.
Weather resistance: Set the test piece on a xenon weather meter (Ci4000 manufactured by Atlas)
UV irradiation intensity 180mW / m2, black panel temperature 63 ℃
In a cycle of 102 minutes and rainfall of 18 minutes, the cumulative UV irradiation dose is 1000 MJ / m
Were tested to reach ^2, the adhesion and appearance evaluation method described below, evaluation and
It was.
Adhesiveness: Make 100 grids at 2mm intervals on the test piece and use cellophane tape (Nichiban)
24 mm) was pressure-bonded and peeled upward, and the peeling was visually observed.
○: No peeling Δ: No more than 3rd peeling ×: More than 4th peeling Appearance: Observed cracks visually ○: No change ×: Any crack, peeling or whitening observed

  From the above results, according to the present invention, it is possible to obtain a high-quality laminate having no evaluation item x. In addition, it is particularly excellent in weather resistance and has a preferable performance when applied to articles used outdoors, and is suitable as a resin window material and particularly preferable when used as an automobile window material.

Claims (10)

An active energy ray-curable composition for forming a hard coat layer that can be cured by active energy rays, comprising the following (A), (B), and (C): Composition (A) Polyfunctional (meth) acrylate: 50 to 90 parts by weight (B) Diol (b-1) having alicyclic structure, lactone (b-2), polyisocyanate (b-3) and hydroxyl group-containing Urethane (meth) acrylate obtained by reacting (meth) acrylate: 10 to 50 parts by weight (C) UV absorber 0.1 to 20 parts by weight   The active energy ray-curable composition according to claim 1, wherein the active energy ray-curable composition further comprises (D) colloidal silica having a volume average particle diameter of 200 nm or less.   The active energy ray-curable composition according to claim 1 or 2, wherein the (D) colloidal silica is surface-modified with a compound having a hydrolyzable silicon group.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the diol (b-1) having an alicyclic structure is tricyclodecane dimethanol.   The active energy ray-curable composition according to any one of claims 1 to 4, wherein the active energy ray-curable composition further contains 0.1 to 10 parts by weight of (E) a hindered amine light stabilizer. Sex composition.   The active energy ray-curable composition according to any one of claims 1 to 5, wherein the active energy ray-curable composition further contains 0.1 to 10 parts by weight of (F) a photopolymerization initiator. Composition. The laminated body which has the primer layer which consists of an acrylic resin, and the hard-coat layer which consists of the said active energy ray curable composition at least in this order on the at least 1 surface of a base material. The laminate according to claim 7, wherein the base material is formed by injection molding of a polycarbonate resin.   A resin window comprising the laminate according to claim 7 or 8. A laminate having at least one surface of a base material made of an acrylic resin and a hard coat layer made of an active energy ray-curable composition on at least one surface in this order, the active energy ray-curable composition comprising: (A) Polyfunctional (meth) acrylate (B) Diol (b) having an alicyclic structure, comprising a laminate characterized by being a composition comprising the following (A), (B) and (C) -1) Urethane (meth) acrylate obtained by reacting lactones (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meth) acrylate (C) UV absorber