KR101441851B1 - Laminate and use thereof - Google Patents

Abstract

A cured resin layer (II) having a contact angle with water of 100 ° or more is formed on at least one surface of a resin molded article (I) obtained by curing the photo-curable composition (i) in a laminate having excellent antifouling properties and high surface hardness and transparency, Respectively.

Description

Laminate and its use {Laminate and use thereof}

The present invention relates to a laminate having an antifouling function imparted to a transparent resin molded article obtained by curing a photo-curing composition, more particularly to a laminate having excellent antifouling properties and excellent transparency, abrasion resistance and heat resistance, To a laminate useful as a substrate for a touch panel.

Conventionally, as a protective sheet for displays, glass has been widely used, and chemical tempered glass or a very thin glass film has been used in addition to ordinary sheet glass having a general thickness of 0.5 to 1 mm.

The protective sheet referred to here is located on the outermost surface of a display such as a cellular phone or a PC, and plays a role of protecting an internal device. Such a protective sheet may also be referred to as a cover, a window, or a cover window. In the case of the touch panel display, since the film or sheet located on the outermost surface of the touch panel also serves as the protective sheet, it is naturally required to have excellent strength and abrasion resistance. Further, such a protective sheet should be transparent, but also has a haze value of some degree from the viewpoint of the anti-glare effect, the hiding property of scars and fouling, and / or the finger sliding property.

On the other hand, in recent years, an anti-fouling function is required for such a protective sheet. Contamination of sebum, sweat, and sewage adhered to the protective sheet not only deteriorates the cleanliness but also lowers the visibility of the image. In addition, when dirty with a magic ink or the like, it does not fall even when wiped with waste, and the visibility is remarkably deteriorated.

In addition, contaminants such as sebum and sweat are liable to cause propagation of bacteria causing food poisoning and infection in the inside of the room, in a touch panel that a plurality of people input with their fingers. Therefore, it is necessary to quickly wipe the attached contaminants, and it is required that the protective sheet can easily wipe the contaminants.

In order to impart the antifouling function to the protective sheet, a method of increasing the contact angle of the sheet surface by using a fluorine-based material, a silicon-based material, or the like is generally used. For example, there can be mentioned a method of treating glass with a silane coupling agent containing a fluorinated alkyl group or a method of providing a cured coating of a polysiloxane-containing urethane (meth) acrylate composition on a glass surface (see, for example, Patent Document 1 Reference.). However, in the former method, there is a problem in durability because only a thin fluorine film can be formed, and in the latter method, there is a problem in adhesion between the glass and the cured coating.

On the other hand, a protective sheet made of plastic has also been used for the purpose of manufacturing a flexible display from the viewpoint of safety improvement such as light weight thinning of display and difficulty of cracking. Specifically, polymethyl methacrylate (PMM) , Polycarbonate, or a film or sheet of polyethylene terephthalate (PET).

However, these protective sheets made of plastic can not satisfy satisfactory performance such as mechanical properties such as surface hardness and flexural modulus, thermal characteristics such as heat resistance, hygroscopicity, chemical resistance and solvent resistance, and low retardation, With respect to surface hardness, even if a hard coat layer is provided on the surface of these plastic substrates, since the hardness of the substrate itself is low, it is a current state that a sufficient hardness can not be secured as a protective sheet.

Accordingly, in order to satisfy these properties, a large number of resins have been proposed regardless of thermoplastic or thermosetting properties, and in recent proposals, a molded article obtained by photo-curing a specific photopolymerizable composition is also noticeable. For example, it has been disclosed that a photopolymerizable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure and a polyfunctional (meth) acrylate having an alicyclic structure gives a resin molding having a high pencil hardness (Meth) acrylate having an alicyclic structure, a polyfunctional (meth) acrylate having an alicyclic structure, and a polyfunctional (meth) acrylate having an alicyclic structure, (Meth) acrylate-based compound, a specific aliphatic tetrafunctional (metha) acrylate-based compound, and a specific alicyclic tetrafunctional (meth) acrylate compound, ) Acrylate compound and a polyfunctional urethane (meth) acrylate compound having a molecular weight of 200 to 2000 and having a cycloaliphatic skeleton, (For example, refer to Patent Document 4).

JP2006-45504A JP2006-193596A JP2007-204736A JP2007-56180A

However, even with these starting techniques, it is difficult to say that all the performances are satisfied, and a plastic protective sheet having a high antifouling function and a high surface hardness is required. Particularly, regarding the application of the antifouling function, a laminate having an antifouling layer excellent in adhesion and durability is preferable.

Therefore, the object of the present invention is to provide a laminate having excellent antifouling property, high surface hardness and transparency under the background.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, they have found that a cured resin layer having a high contact angle with water formed by curing a photo-curing composition is formed on a resin molding obtained by curing a photo- Has excellent adhesion with the cured resin layer, and thus has excellent antifouling properties, and is excellent in transparency, surface hardness and abrasion resistance. Thus, the present invention has been completed.

That is, the gist of the present invention relates to a laminate in which a cured resin layer having a contact angle of 100 ° or more with water is formed on at least one surface of a resin molded article obtained by curing a photo-curable composition.

The present invention also provides a protective sheet for display and a touch panel using the laminate.

In addition, it is difficult to use the antifouling agent such as a fluorine-based material or a silicon-based material generally used for a photocured resin molded article because of the problem of adhesion, and it is difficult to use the antifouling layer obtained by photocuring As a result, it has been surprisingly found that a laminate excellent in antifouling property and excellent in transparency, surface hardness and abrasion resistance is obtained as described above. The reason why the adhesion is good as described above is unclear, but it is not clear whether the photocurable composition forming the cured resin layer having a contact angle of 100 DEG or more with the surface of the base resin obtained by curing the photocurable composition is physically and / or chemically compatible It is presumed that it is high.

According to the present invention, a laminate excellent in adhesion between a resin molded article and a cured resin layer and having excellent antifouling properties and excellent in transparency, surface hardness and abrasion resistance can be obtained. It is very suitable as a panel.

Hereinafter, the present invention will be described in detail.

In the present invention, "(meth) acrylate" is a generic name of acrylate and methacrylate, and "(meth) acrylic" is a generic term of acrylic and methacryl. The term polyfunctional as used herein means having two or more (meth) acryloyl groups in the molecule.

The laminate of the present invention is a laminate in which a cured resin layer [II] having a contact angle with water of at least 100 ° is formed on at least one surface of a resin molded article [I] obtained by curing the photo-curable composition (i).

First, the resin molded article [I] will be described.

The resin molded article [I] is obtained by curing the photo-curable composition (i). As the photo-curable composition (i), for example, known compositions such as acrylic, epoxy, and thiol / ene systems can be used. Among these, the photo-curing composition (i) is preferably a composition containing (A1), (A2) and (A3) as described below in terms of adhesion with a cured resin layer desirable.

(A1) polyfunctional urethane (meth) acrylate compound

(A2) a polyfunctional (meth) acrylate-based compound containing a cycloaliphatic skeleton

(A3) A photopolymerization initiator

Since the polyfunctional urethane (meth) acrylate compound (A1) is polyfunctional, a crosslinked resin is formed by curing, and a resin molded article having high surface hardness and heat resistance can be obtained. Further, since the resin molded article having a urethane bond in the molecule has a suitable toughness by hydrogen bonding, a resin molded article having a high flexural modulus and high strength can be obtained.

Since the alicyclic skeleton-containing polyfunctional (meth) acrylate compound (A2) is polyfunctional, it is possible to form a crosslinked resin by curing to obtain a resin molded article having high surface hardness and heat resistance. In addition, since the resin has the alicyclic skeleton, the absorption rate of the resin molded article can be reduced.

The polyfunctional urethane (meth) acrylate compound (A1) is obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound. The polyisocyanate compound is not particularly limited, Polyisocyanates such as aliphatic, alicyclic, alicyclic and the like. Among them, tolylene diisocyanate, diphenylmethane diisocyanate, hydrolyzed diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, (Isocyanatomethyl) cyclohexane, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, , Polyisocyanates such as phenylene diisocyanate, lydidine diisocyanate, lidine triisocyanate and naphthalene diisocyanate, or trimer compounds or multimer compounds of these polyisocyanates, biuret type polyisocyanates, water dispersed polyisocyanates (for example, Nippon Polyurethane "Arcanate 100", "Arcanate 110", "Arcanate 200", "Arcanate 210", etc.) produced by Koyo Co., Ltd. or reaction products of these polyisocyanates and polyols. These may be used alone or in combination of two or more. Among these, alicyclic polyisocyanates such as hydrolyzed diphenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane are preferable because they can reduce the absorption rate of the resin molded article .

Examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxyethyl (meth) acrylate, 2- Acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified (meth) acrylate, caprolactone modified (meth) acrylate, Caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, Acrylic Ray And the like. These may be used alone or in combination of two or more. Of these, acrylates are preferred from the viewpoint of quick curability, and carbon atoms such as 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate Carbon chain) is relatively short in that the flexural modulus of the resin molded article can be improved.

Examples of the alicyclic skeleton-containing polyfunctional (meth) acrylate compound (A2) include bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane di (meth) acrylate, bis (hydroxy) Tricyclo [5.2.1.0 ^2,6 ] decane acrylate methacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane di (meth) acrylate, bis (hydroxymethyl) tri Acrylate methacrylate, cyclo [5.2.1.0 ^2,6 ] decane acrylate methacrylate, bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] pentadecane di acrylate, bis (hydroxymethyl) penta-cyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] pentadecane = acrylate methacrylate, bis (hydroxy-methyl) penta-cyclo [6.5.1.1 ^{3, 6.0 2,7} .0 ^9,13] pentadecane = di (meth) acrylate, bis (hydroxymethyl) penta-cyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] pentadecane Acrylate methacrylate, 2,2-bis [4- (β-meth) acryloyloxyethoxy Cyclohexyl] propane, 1,3-bis ((meth) acryloyloxymethyl) cyclohexane, 1,3-bis ((meth) acryloyloxyethyl) cyclohexane, 1,4- (Meth) acryloyloxymethyl) cyclohexane and 1,4-bis ((meth) acryloyloxyethyl) cyclohexane ^{; 6]} decane = tri (meth) acrylate, tris (hydroxymethyl) tricyclo [5.2.1.0 ^2,6] decane = tri (meth) acrylate, tris (hydroxymethyl) penta seek [6.5.1.1 ^{3, 6.0 2,7} .0 ^9,13] pentadecane = tri (meth) acrylate, tris (hydroxymethyl) penta-cyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] pentadecane (Meth) acryloyloxyethyl) cyclohexane such as 1,3,5-tris (meth) acrylate, 1,3,5-tris (Meth) acrylate. Of these, bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane di (meth) acrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] Decane-di (meth) acrylate is preferable. The above-mentioned alicyclic skeleton-containing polyfunctional (meth) acrylate compound (A2) may be used in combination of two or more kinds, or acrylate and methacrylate may be used in combination.

In the present invention, the content of the polyfunctional urethane (meth) acrylate compound (A1) is preferably 5 to 50% by weight, more preferably 8 to 40% by weight based on the total amount of the component (A1) %, And 10 to 30 wt%. When the content of the component (A1) is too low, the surface hardness of the resin molded article tends to decrease. On the other hand, if the content is too large, the water absorbency of the resin molded article tends to increase.

The content of the alicyclic skeleton-containing polyfunctional (meth) acrylate compound (A2) is preferably from 50 to 95% by weight, more preferably from 60 to 92% by weight based on the sum of the components (A1) %, More preferably 70 to 90% by weight. If the content of the component (A2) is too small, the water absorption of the resin molded article tends to increase. On the other hand, if it is too large, the surface hardness of the resin molded article tends to decrease.

As the photopolymerization initiator (A3), known compounds can be used, and examples thereof include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6- Dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. Of these, radical-series photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl diphenyl phosphine oxide are preferred. These photopolymerization initiators (A3) may be used alone or in combination of two or more.

The content of the photopolymerization initiator (A3) is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, particularly 0.3 to 3 parts by weight, based on 100 parts by weight of the total of the components (A1) and (A2). If the content is too large, the amount of the blockage of the resin molded article tends to increase and yellowing tends to occur. If the content is too small, the polymerization rate decreases and there is a fear that polymerization does not proceed sufficiently.

The photo-curable composition (i) used in the present invention may contain small amounts of auxiliary components to the extent that the surface hardness and heat resistance of the resin molded product [I] are not impaired. For example, A chain transfer agent, an antioxidant, an ultraviolet absorber, a thermal polymerization initiator, a polymerization inhibitor, a defoaming agent, a labeling agent, a blue ink, a salt pigment, a filler and the like.

Examples of the monomer having an ethylenic unsaturated bond other than the components (A1) and (A2) include methyl methacrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylate such as ethyleneglycol di (meth) acrylate, cyclohexyl (meth) acrylate, ethyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di Diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (Meth) acrylate such as 2-hydroxy-1,3-di (meth) acryloxypropane, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, trimethylolpropane tri (Meth) acrylate, acrylamide, methacrylate (Meth) acrylic acid derivatives such as methacrylonitrile and methacrylonitrile, styrene compounds such as styrene, chlorostyrene, divinylbenzene and? -Methylstyrene, and the like.

The content of the monomer having an ethylenically unsaturated bond other than the components (A1) and (A2) is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, particularly preferably 20 parts by weight or less, Is preferably 10 parts by weight or less. If the content is too large, the surface hardness and heat resistance of the resin molded article [I] tend to decrease.

As the chain transfer agent, a polyfunctional mercaptan compound is preferable. As the polyfunctional mercaptan compound, for example, pentaerythritol tetraquistioglycolate, pentaerythritol tetraquistiophosphate and the like can be given. These polyfunctional mercaptan compounds are preferably used in a proportion of usually not more than 10 parts by weight, preferably not more than 5 parts by weight, particularly not more than 3 parts by weight, based on 100 parts by weight of the total of the components (A1) and (A2) Or less. If the amount is too large, the surface hardness and rigidity of the obtained resin molded article [I] tends to be lowered.

Examples of the antioxidant include 2, 6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4,6- Butyl-4-s-butylphenol, 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl-? - (4'- (N, N-dimethylaminomethyl) phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate (N-octylthio) -6- (4-hydroxy-3 ', 5'-di-t-butyl anilino) -1,3,5-triazine, (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis (2,6-di-t-butylphenol), 2,2-thiodiethylene bis [3- (3,5- , N'-hexamethylene bis- (3,5-di-t-butyl-4-hydroxyhydrocinnamide, N, N'-bis - (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, calcium (3,5- , 3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5- Tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,5-di-t-butyl -Butyl-4-hydroxybenzylphosphite-diethyl ester, etc. These compounds may be used alone or in combination of two or more. Among them, tetraques [methylene 3- (3 ' Di-t-butyl-4-hydroxyphenyl) propionate] methane is particularly preferable in that the effect of suppressing color is enhanced.

The content of the antioxidant is preferably 0.001 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the total of the components (A1) and (A2). When the amount of such an antioxidant is too small, the heat resistance of the resin molded product [I] tends to deteriorate, while when it is too much, the light transmittance tends to decrease.

The ultraviolet absorber is not particularly limited as long as it is soluble in the (meth) acrylate compound, and various ultraviolet absorbers can be used. Specific examples thereof include a salicylic ester type, benzophenone type, triazole type, hydroxybenzoate type, and cyanoacrylate type. A plurality of these ultraviolet absorbers may be used in combination. Among them, from the viewpoint of compatibility with the (meth) acrylate compound, benzophenone or triazole compounds, specifically, (2-hydroxy-4-octyloxyphenyl) -phenylmethanone, 2-benzotriazole 2-yl-4-t-octyl-phenol and the like. The content of the ultraviolet absorber is preferably 0.001 to 1 part by weight, particularly preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the total of the components (A1) and (A2). If the amount of such ultraviolet absorber is too small, the light resistance tends to decrease. If it is too much, it may take time to cure the photocurable composition or there is a possibility that sufficient curing can not be performed.

As the thermal polymerization initiator, known compounds can be used, and examples thereof include hydroperoxides such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide and 1,3,3-tetramethylbutyl hydroperoxide. Dialkyl peroxides such as hydroperoxide, di-t-butyl peroxide and dicumyl peroxide, peroxy esters such as t-butyl peroxybenzoate and t-butyl peroxy (2-ethylhexanoate) Peroxides such as diacyl peroxide such as peroxide, peroxycarbonate such as diisopropyl peroxycarbonate, and peroxides such as peroxyketal and ketone peroxide.

In the present invention, the resin molded article [I] is prepared by curing the photo-curing composition (i), but specifically, the resin molded article is prepared by the following method.

That is, for example, the photo-curing composition (i) may be provided on a flat frame or between two flat frames, and irradiated with ultraviolet rays of active energy rays, particularly ultraviolet rays having a wavelength of 200 to 400 nm, It is preferable to photo-cure in the range of light quantity of 1 to 100 J / cm < 2 >. A more preferable range of the irradiation light amount is 5 to 70 J / cm 2, more preferably 10 to 50 J / cm 2. If the irradiation light amount is too small, the polymerization tends to be insufficient, while if too large, the productivity tends to decrease. The illuminance of ultraviolet rays is usually 10 to 5000 mW / cm 2, preferably 100 to 1000 mW / cm 2. If the roughness is too small, it tends to be hard enough to cure into the inside of the resin molded product, and if the roughness is too large, the polymerization tends to be congested and the clogs tend to increase.

The material of the shape is not particularly limited as long as at least one frame is capable of emitting an active energy ray, and glass, metal, or resin can be used. Among these, in view of light transmittance of an active energy ray, a form of glass or transparent resin is preferable. When an opaque form is used, a frame made of a transparent material is used for the frame on the opposite side, and the active energy line is irradiated on the opposite side.

At the time of irradiation with ultraviolet rays, irradiation with a plurality of divided portions is preferable because a resin molding having a smaller amount of an obstruction can be obtained. For example, a method of irradiating about 1/100 to 1/10 of the total amount of irradiation in the first time and inspecting the necessary amount in the second and subsequent steps can be mentioned.

Examples of the ultraviolet radiation source include a metal halide lamp, a high-pressure mercury lamp, and a mercury-free lamp. It is also possible to use a filter for blocking infrared rays or a mirror which does not reflect infrared rays, in order to prevent the polymerization from being runaway due to infrared rays generated from the light source.

The resin molded product obtained in the present invention may be subjected to heat treatment for better improvement in polymerization degree or to open stress strain, and particularly preferably to heat treatment at 100 占 폚 or higher.

In the present invention, the thickness of the resin molded article [I] directly affects the rigidity of the protective sheet, preferably 0.1 to 3 mm. If the thickness is too thin, the curvature or the ratio tends to make it difficult to protect the internal device. Conversely, if it is too thick, it tends to make it difficult to reduce the weight of the entire display. The preferable range of the thickness is 0.2 to 2 mm, more preferably 0.3 to 1.5 mm, and particularly preferably 0.4 to 1 mm.

The resin molded article [I] of the present invention preferably has a glass transition temperature of 100 ° C or more from the viewpoint of heat resistance. If the glass transition temperature is too low, there is a tendency for waves to occur or color deterioration. The glass transition temperature is preferably in the range of 100 to 500 캜, more preferably 150 to 400 캜, and still more preferably 200 to 300 캜. In order to adjust the glass transition temperature to the above range, a method of properly controlling the kind of the photo-curable composition (i) and the content of the component is mentioned. For example, a combination of an acrylate-based compound and a methacrylate-based compound together with a methacrylate-based compound in proportion to the mixing ratio can be cited.

The resin molded article [I] of the present invention is preferably a pencil hardness of 3H or more in view of surface hardness. The pencil hardness is more preferably 3H to 10H, particularly preferably 4H to 8H. When the pencil hardness is adjusted to the above range, a method of appropriately controlling the kind and content of the above-mentioned photopolymerizable composition (i) can be mentioned. For example, a polyfunctional urethane (meth) acrylate-based compound having 3 to 6 functional groups can be used.

The resin molded article [I] of the present invention preferably has a flexural modulus of 3 GPa or more. If the flexural modulus is too low, the rigidity tends to decrease. The flexural modulus of elasticity is more preferably from 3 to 5 GPa, and still more preferably from 3.5 to 4 GPa. When the flexural modulus is adjusted to the above range, a method of appropriately controlling the kind of the photo-curing composition (i) and the content of the component is mentioned. Examples of the polyfunctional urethane (meth) acrylate compound (A1) include those using 3 to 6 functional groups and the like.

The resin molded article [I] of the present invention preferably has a total light transmittance of 80% or more, more preferably 85% or more and 90% or more.

Next, the cured resin layer [II] will be described.

In the present invention, it is the largest feature that a cured resin layer [II] having a contact angle with water of at least 100 ° is formed on at least one surface of the resin molded article [I] so as to impart an antifouling function to the resin molded article [I] . The contact angle with water is preferably from 100 to 150 deg., More preferably from 105 to 140 deg., And particularly preferably from 110 to 120 deg. In view of the antifouling function. If the contact angle is too small, the antifouling property is lowered. In addition, when the contact angle is too large, the adhesion to the substrate (specifically, the resin molded article [I] or the cured resin layer [III] described later) tends to decrease.

The cured resin layer [II] may be one which is photo-cured by using a known material such as a fluorine-based or silicone-based material if the contact angle is 100 ° or more. In particular, the following components (B1), (B2) ) Is preferably cured from the viewpoint of adhesion with the resin molded article.

(B1) a urethane (meth) acrylate compound containing a polysiloxane structure

(B2) a reactive fluorine-containing compound represented by the following general formula (1)

(B3) a photopolymerization initiator

[Wherein R1, R2, R3, and R4 are each independently a hydrogen atom or a methyl group. X ₁ is an alkylene group, X ₂ is an arylene group, X ₃ is a substituent represented by the following formula 2 or 3, X ₄ is an alkylene group or an oxyalkylene group, X ₅ is an alkylene group, X ₆ is a hydrogen atom or an ester bond Lt; / RTI > a and b each represent an integer of 1 to 30, and c and d each represent an integer of 0 to 60 (provided that the order of combining constituent units is optional).

The urethane (meth) acrylate compound (B1) containing a polysiloxane structure may contain a polysiloxane structure in its structure. Among them, a polysiloxane compound having a hydroxyl group at one end represented by the following formula (4) (Meth) acrylate compound (B1-1) obtained by using the urethane (meth) acrylate compound (B1-1) obtained by using the polysiloxane compound having a hydroxyl group at both terminals represented by the following formula Do.

The urethane (meth) acrylate compound (B1) containing a polysiloxane structure may have a structural moiety derived from both of the formulas (4) and (5).

Wherein R ¹ represents an alkyl group, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and R ³ represents an organic group containing a hydrocarbon group or an oxygen atom. a is an integer of 1 or more, and b is an integer of 1 to 3.]

Wherein R ¹ and R ³ represent an organic group containing a hydrocarbon group or an oxygen atom, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, a represents an integer of 1 or more, b and c represent an integer of 1 to 3 .

First, the urethane (meth) acrylate compound (B1-1) obtained by using the polysiloxane compound having a hydroxyl group at one end represented by the above formula (4) will be described.

Such a urethane (meth) acrylate compound (B1-1) is obtained by reacting a polysiloxane compound (x1) having a hydroxyl group at one end and a polyisocyanate compound (x2) (X3) and, if necessary, the polyol compound (x4).

For such a polysiloxane-based compound (x1), R ¹ in Chemical Formula 4 is an alkyl group, and the number of carbon atoms of the alkyl group is preferably relatively small. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ² in Formula 4 is independently an alkyl group, a cycloalkyl group, or a phenyl group. The number of carbon atoms in the alkyl group is preferably relatively small. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

The number of carbon atoms of the cycloalkyl group is usually from 3 to 10, preferably from 5 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a norbornyl group.

The above alkyl group, cycloalkyl group and phenyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group and a heteroaryl group. When such a substituent has a carbon atom, the carbon atom is not included in the carbon number defined in the description of R ² above.

R ³ in the general formula (4) is an organic group containing a hydrocarbon group or an oxygen atom.

The hydrocarbon group is usually a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and a divalent or trivalent hydrocarbon group.

As the divalent hydrocarbon group, an alkylene group can be exemplified. The number of carbon atoms of the alkylene group is preferably from 1 to 10, particularly preferably from 1 to 4, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.

Examples of organic groups containing an oxygen atom include oxyalkylene groups and polyoxyalkylene groups.

A in the general formula (4) is an integer of 1 or more, preferably 5 to 200, particularly preferably 5 to 120. [ b is an integer of 1 to 3, preferably an integer of 1 to 2.

The weight average molecular weight of the polysiloxane compound (x1) used in the present invention is preferably 100 to 50,000, more preferably 500 to 10,000 and 1,000 to 10,000. When the weight average molecular weight is too small, the antifouling performance tends to decrease. When the weight average molecular weight is too large, the hardness and abrasion resistance of the cured resin layer (hereinafter also referred to as "coating film") tend to decrease.

Specific examples of the polysiloxane compound (x1) represented by the general formula (4) include X-22-170 BX, X-22-170 DX, X-22-176 DX, X-22-176 F, SIRA PLAIN FM-0411, SIRA PLAIN FM-0421, SIRA PLAIN FM-0425, SIRA PLAIN FM-DA11 , "Sara Plain FM-DA21" and "Sara Plain FM-DA26".

Examples of the polyisocyanate compound (x2) used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate , Aromatic polyisocyanates such as phenylene diisocyanate and naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lydidine diisocyanate and lidine triisocyanate, hydrolyzed diphenylmethane diisocyanate, Alicyclic polyisocyanates such as xylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane, and alicyclic polyisocyanates such as polyisocyanates (For example, "Arcanate 100" manufactured by Nippon Polyurethane Industry Co., Ltd., "Arcanate 110" manufactured by Nippon Polyurethane Industry Co., Ltd.), a polymerizable compound , &Quot; Arcanate 200 ", " Arcanate 210 ", etc.). These may be used alone or in combination of two or more.

Of these, isocyanate-based compounds having three or more isocyanate groups in one molecule, especially trimer or multimer compounds of polyisocyanate, are preferred because of their hardness, abrasion resistance, solvent resistance and unreacted low It is more preferable that the molecular weight component can be reduced.

Examples of the hydroxyl group-containing (meth) acrylate compound (x3) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (Meth) acrylate such as hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl Caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene (Meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl -3-acryl Caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, (Meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, and ethylene oxide-modified dipentaerythritol penta (meth) acrylate. These may be used alone or in combination of two or more. Of these, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable in that a coating film of high hardness can be obtained.

Further, the polyol compound (x4) may be used as long as the effect of the present invention is not impaired. Examples of the polyol compound (x4) include a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, a polybutadiene polyol, and a (meth) acrylic polyol.

Examples of the polyether-based polyol include polyether-based polyols having an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol; Or block copolymers.

Examples of the polyester-based polyol include a polycondensation reaction product of a polyhydric alcohol and a polyvalent carboxylic acid; A ring-opening polymer of cyclic ester (lactone), a reaction product of three kinds of components of polyhydric alcohol, polyvalent carboxylic acid and cyclic ester, and the like. Examples of the polyhydric alcohol include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl- Cyclohexanediol, etc.), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol), and the like can be given. .

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and the like; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, paraphenylene dicarboxylic acid and trimellitic acid; .

Examples of the cyclic ester include propiolactone, beta -methyl-delta-valerolactone-epsilon -caprolactone, and the like.

The weight average molecular weight of the polyol compound (x4) is preferably from 50 to 8000, particularly preferably from 50 to 5,000, and more preferably from 600 to 3,000. If the weight average molecular weight of the polyol compound (x4) is too large, the mechanical properties such as hardness of the coating film tends to decrease at the time of curing, while if it is too small, the curing shrinkage tends to greatly decrease in stability.

The urethane (meth) acrylate compound (B1-1) is preferably one having at least one ethylenic unsaturated group, particularly preferably at least three ethylenically unsaturated groups in view of the hardness of the cured coating film , And those having at least 6 ethylenic unsaturated groups. The upper limit of the ethylenic unsaturated group contained in the urethane (meth) acrylate compound (B1-1) is usually 30, preferably 25 or less.

The method for producing the urethane (meth) acrylate compound (B1-1) is not particularly limited, and for example,

(A) a polyisocyanate compound (x2) obtained by reacting a polysiloxane compound (x1), a polyisocyanate compound (x2) (if necessary, a polyisocyanate compound (x2) A method in which the compound (x3) is added all at once,

(B): a method of reacting a polysiloxane compound (x1) with a polyisocyanate compound (x2) (if necessary, a polyisocyanate compound (x2) previously reacted with a polyol compound (x4) (Meth) acrylate compound (x3)

(Meth) acrylate compound (x3) with a polyisocyanate compound (x2) (if necessary, a polyisocyanate compound (x2) previously reacted with a polyol compound (x4) Followed by reacting the polysiloxane compound (x1)

(X2) (a polyisocyanate compound (x2) previously reacted with a polyol compound (x4)) and a part of a hydroxyl group-containing (meth) acrylate compound (x3) (Meth) acrylate compound (x3) is reacted with the other hydroxyl group-containing (meth) acrylate compound (x3)

Among them, the method (b) or (d) is preferable, and the method (b) is particularly preferable in view of the stability of the reaction control.

When the polyol compound (x4) is reacted with the polyisocyanate compound (x2) in advance, it may be suitably used, for example, according to a production example of a urethane-based polyol.

In the method (b), the hydroxyl group of the polysiloxane compound (x1) and the isocyanate group of the polyisocyanate compound (x2) are reacted under the condition that the isocyanate group remains, and then the remaining isocyanate of the polyisocyanate compound (x2) Group is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (x3).

The reaction molar ratio of the polysiloxane compound (x1) to the polyisocyanate compound (x2) is, for example, a ratio of the isocyanate group of the polyisocyanate compound (x2) to the hydroxyl group of the hydroxyl group-containing (meth) (X1): polyisocyanate compound (x2) is about 0.001 to 1: 1, the number of isocyanate groups of the polyisocyanate compound (x2) is 3, the content of the hydroxyl group-containing (meth) (x3) is 1, the polysiloxane compound (x1): polyisocyanate compound (x2) should be about 0.001 to 2: 1.

In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (x3), the reaction is terminated when the residual isocyanate group in the reaction system becomes 0.5% by weight or less. Thus, the urethane (meth) B1-1) is obtained.

The weight of the structural part derived from the polysiloxane compound (x1) contained in 100 parts by weight of the urethane (meth) acrylate compound (B1-1) is preferably 0.1 to 80 parts by weight within the above-mentioned molar ratio .

As for such a reaction, it is also preferable to use a catalyst for the purpose of promoting the reaction. Examples of such catalysts include organic metals such as dibutyltin dilaurate, trimethyltin hydroxide, tetra- A metal salt such as zinc octoate, tin octoate, cobalt naphthenate, stannous chloride, and stannic chloride; a metal salt such as triethylamine, benzyldiethylamine, 1,4-diazabicyclo [ 2-tert-butoxycyclo [5,4,0] undecene, N, N, N'-tetramethyl-1,3-butanediamine, N- Organic bismuth compounds such as dibutylbismuth dilaurate and dioctylbismuth dilaurate, and organic bismuth compounds such as 2-ethylhexanoic acid bismuth salt, bismuth naphthenate, bismuth naphthenate, and the like, in addition to the catalyst, bismuth acetate, bismuth bromide, bismuth bismuth and bismuth sulfide, Isodecanoic acid bismuth salt, neodecanoic acid bismuth salt, lauryl A bismuth-based catalyst such as an organic acid bismuth salt such as a bismuth acid salt, a bismuth maleate salt, a bismuth stearate salt, a bismuth oleate salt, a bismuth linoleate salt, a bismuth acetate salt, a bismuth bisneodecanoate, a bismuth dissalicylate salt or a bismuth salt of di- Among them, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are very suitable.

In such a reaction, an organic solvent having no functional group reactive with an isocyanate group, for example, an ester such as ethyl acetate or butyl acetate, a ketone such as methyl ethyl ketone or methyl isobutyl ketone, an aromatic ketone such as toluene or xylene An organic solvent such as water or the like can be used.

The reaction temperature for such a reaction is usually 30 to 100 占 폚, preferably 40 to 90 占 폚, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

The weight average molecular weight of the urethane (meth) acrylate compound (B1-1) thus obtained is preferably 500 to 50,000, more preferably 500 to 30,000. If the weight average molecular weight is too small, the curing shrinkage tends to shrink greatly and the physical properties such as hardness and abrasion resistance of the cured resin layer tend to decrease. When the weight average molecular weight is too high,

The above weight average molecular weight was a weight average molecular weight in terms of standard polystyrene molecular weight, and it was measured by high performance liquid chromatography (Shodex GPC system-11 type, manufactured by Showa Denko K.K.) using a column: Shodex GPC KF-806 L (Exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical number of steps: 10,000 pieces / filler material: styrene-divinylbenzene copolymer, filler particle diameter: 10 μm) .

Hereinafter, the measurement of the weight average molecular weight of the urethane (meth) acrylate compound to be described later is carried out in the same manner as described above.

The viscosity of the urethane (meth) acrylate compound (B1-1) at 60 ° C is preferably 500 to 150,000 mPa · s, more preferably 500 to 120,000 mPa · s, S. When the viscosity is outside the above range, the coating property tends to decrease.

The viscosity is measured by an E-type viscometer.

The urethane (meth) acrylate compound (B1-1) may be used singly or in combination of two or more.

Next, the urethane (meth) acrylate-based compound (B1-2) obtained by using the polysiloxane-based compound having a hydroxyl group at both terminals represented by the above formula (5) will be described.

[Chemical Formula 5]

Wherein R ¹ and R ³ represent an organic group containing a hydrocarbon group or an oxygen atom, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, a represents an integer of 1 or more, b and c represent an integer of 1 to 3 .

Such a urethane (meth) acrylate compound (B1-2) is a compound having a hydroxyl group-containing polysiloxane compound (y1), a polyisocyanate compound (y2) and hydroxyl group-containing (meth) (Y3), and if necessary, the polyol compound (y4).

For such a polysiloxane compound (y1), R ¹ and R ³ in the general formula (5) are organic groups containing a hydrocarbon group or an oxygen atom.

The hydrocarbon group is usually a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and a divalent or trivalent hydrocarbon group.

As the divalent hydrocarbon group, an alkylene group can be exemplified. The number of carbon atoms of the alkylene group is preferably from 1 to 10, particularly preferably from 1 to 4, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.

Examples of organic groups containing an oxygen atom include oxyalkylene groups and polyoxyalkylene groups.

R ² in Formula 5 are each independently an alkyl group, a cycloalkyl group, or a phenyl group. The number of carbon atoms in the alkyl group is preferably relatively small. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

The number of carbon atoms of the cycloalkyl group is usually from 3 to 10, preferably from 5 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a norbornyl group.

The above alkyl group, cycloalkyl group and phenyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group and a heteroaryl group. When such a substituent has a carbon atom, the carbon atom is not included in the carbon number specified in the description of R ² above.

A in the general formula (5) is an integer of 1 or more, preferably 5 to 200, particularly preferably 5 to 120. [ b and c are integers of 1 to 3, preferably 1 to 2.

The weight average molecular weight of the polysiloxane compound (y1) is preferably 100 to 50,000, more preferably 500 to 10,000 and 1,000 to 10,000. If the weight average molecular weight is too small, the antifouling performance is lowered And if it is too large, transparency and abrasion resistance tend to deteriorate.

Specific examples of the polysiloxane compound (y1) include "X-22-160 AS", "KF-6001", "KF-6002", "KF-6003" manufactured by Shin-Etsu Chemical Co., Sara Plain FM-4421 ", " Sara Plain FM-4425 ", and " Macromonomer HK-20 " manufactured by Touka Kosei Co.,

Examples of the polyisocyanate compound (y2) include those exemplified as the polyisocyanate compound (x2) in the description of the urethane (meth) acrylate compound (B1-1).

Examples of the hydroxyl group-containing (meth) acrylate compound (y3) include a hydroxyl group-containing (meth) acrylate compound (x3) The same can be said.

The polyol compound (y4) may be used as long as the effect of the present invention is not impaired. For example, the polyol compound (x4) may be used among the descriptions of the urethane (meth) ) Can be mentioned.

The urethane (meth) acrylate compound (B1-2) is preferably one having at least two ethylenically unsaturated groups, and particularly preferably at least four ethylenically unsaturated groups in terms of the hardness of the cured resin layer And also has at least 6 ethylenic unsaturated groups.

The upper limit of the ethylenic unsaturated group contained in the urethane (meth) acrylate compound (B1-2) is usually 30, preferably 25 or less.

The method for producing the urethane (meth) acrylate compound (B1-2) is not particularly limited, and for example,

(A): a polyisocyanate compound (y2) obtained by reacting a polysiloxane compound (y1), a polyisocyanate compound (y2) (if necessary, with a polyol compound (y4) A method of collectively adding the compound (y3)

(B): A method of reacting a polysiloxane compound (y1) and a polyisocyanate compound (y2) (if necessary, a polyisocyanate compound (y2) previously reacted with a polyol compound (y4) Methacrylate compound (y3) are reacted,

(Meth) acrylate compound (y3) with a polyisocyanate compound (y2) (optionally, a polyisocyanate compound (y2) previously reacted with a polyol compound (y4) A method of reacting the polysiloxane-based compound (y1)

(C) a polyisocyanate compound (y2) (optionally, a polyisocyanate compound (y2) previously reacted with the polyol compound (y4)) and a part of the hydroxyl group-containing (meth) acrylate compound (Meth) acrylate compound (y3) is reacted with the remaining hydroxyl group-containing (meth) acrylate compound (y3)

Among them, the method (b) or (d) is preferable, and the method (b) is particularly preferable in view of the stability of the reaction control and compatibility.

When the polyol compound (y4) is reacted with the polyisocyanate compound (y2) in advance, it may be suitably used, for example, according to a production example of a urethane-based polyol.

In the method (b), the hydroxyl group of the polysiloxane compound (y1) and the isocyanate group of the polyisocyanate compound (y2) are reacted under the condition that an isocyanate group remains, and then the remaining isocyanate of the polyisocyanate compound (y2) Is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (y3).

The reaction molar ratio of the polysiloxane compound (y1) and the polyisocyanate compound (y2) is, for example, the ratio of the isocyanate group of the polyisocyanate compound (y2) (Y1): polyisocyanate compound (y2) in an amount of about 0.001 to 1: 1, the number of isocyanate groups of the polyisocyanate compound (y2) is three, the content of the hydroxyl group-containing (meth) acrylate When the hydroxyl group of the compound (y3) is 1, the polysiloxane compound (y1): polyisocyanate compound (y2) should be about 0.001 to 2: 1.

With respect to the addition reaction of the reactive organics with the hydroxyl group-containing (meth) acrylate compound (y3), the reaction is terminated when the residual isocyanate group in the reaction system becomes 0.5% by weight or less, whereby the urethane (meth) (B1-2) is obtained.

The weight of the structural part derived from the polysiloxane compound (y1) contained in 100 parts by weight of the urethane (meth) acrylate compound (B1-2) is preferably 0.1 to 80 parts by weight within the above-mentioned molar ratio .

In such a reaction, it is also preferable to use a catalyst for the purpose of promoting the reaction. Examples of such a catalyst include the catalysts described above.

In such a reaction, an organic solvent having no functional group reactive with an isocyanate group, for example, an ester such as ethyl acetate or butyl acetate, a ketone such as methyl ethyl ketone or methyl isobutyl ketone, an aromatic ketone such as toluene or xylene An organic solvent such as water or the like can be used.

The reaction temperature for such a reaction is usually 30 to 100 占 폚, preferably 40 to 90 占 폚, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

The weight average molecular weight of the urethane (meth) acrylate compound (B1-2) thus obtained is preferably 500 to 50,000, more preferably 500 to 30,000. If the weight average molecular weight is too small, the curing shrinkage tends to shrink greatly and the physical properties such as hardness and abrasion resistance of the cured resin layer tend to decrease. When the weight average molecular weight is too high, viscosity tends to be lowered and handling property is lowered.

The viscosity of the urethane (meth) acrylate compound (B1-2) at 60 ° C is preferably 500 to 150,000 mPa · s, more preferably 500 to 120,000 mPa · s, mPa • s. When the viscosity is outside the above range, the coating property tends to decrease.

The viscosity is measured by an E-type viscometer.

The urethane (meth) acrylate compound (B1-2) may be used alone, or two or more kinds thereof may be used in combination.

As the urethane (meth) acrylate compound (B1) containing a polysiloxane structure, it is preferable to use the urethane (meth) acrylate compound (B1-1) and / or the urethane (meth) acrylate compound However, it is particularly preferable to use the urethane (meth) acrylate compound (B1-1) in view of excellent antifouling performance.

When the urethane (meth) acrylate compounds (B1-1) and (B1-2) are used in combination, the urethane (meth) acrylate compound (B1-1) and the urethane (meth) (B1-1) / (B1-2) = 5/95 to 95/5, particularly preferably (B1-1) / (B1-2) = 20/80 to 80/20.

Next, the reactive fluorine-containing compound (B2) represented by the following formula (1) will be described.

[Chemical Formula 1]

　　

　

[Wherein,

R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom or a methyl group.

X ₁ represents an alkylene group,

X ₂ represents an allylene group,

X ₃ represents a substituent represented by the following formula (2) or (3)

X ₄ represents an alkylene group, or an oxyalkylene group,

X ₅ represents an alkylene group

X < ₆ > is a hydrogen atom or an ester bond residue.

a and b each represent an integer of 1 to 30, and c and d each represent an integer of 0 to 60 (provided that the order of combining constituent units is optional).

The reactive fluorine-containing compound (B2) represented by the general formula (1) is characterized by containing a fluorine atom-containing structural moiety represented by X ₃ and a (meth) acryloyl group in its structure. As a result, when used together with the urethane (meth) acrylate compound (B1), excellent antifouling performance can be exhibited. Particularly when X ₄ is an oxyalkylene group, the compatibility with the urethane (meth) acrylate compound (B1) is particularly preferably improved.

R 1 to R 4 in the general formula (1) are each independently a hydrogen atom or a methyl group.

X ₁ in the general formula (1) is an alkylene group, and the number of carbon atoms of the alkylene group is usually 1 to 12, preferably 1 to 8, and particularly preferably 1 to 4. Specific examples thereof include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.

X ₂ in the general formula (1) is an arylene group, and the number of carbon atoms of the arylene group is usually 6 to 12, preferably 6. Specific examples thereof include a phenylene group and a naphthylene group.

X ₃ in the general formula (1) is a fluorine atom-containing substituent represented by the following general formula (2) or (3).

(2)

(3)

In the case where a is 2 or more in the reactive fluorine-containing compound (B2), the reactive fluorine-containing compound (B2) may contain both substituents represented by formulas (2) and (3) or may contain only one of them.

X ₄ in the general formula (1) is an alkylene group or an oxyalkylene group.

The number of carbon atoms of the alkylene group is usually 1 to 12, preferably 1 to 8, and particularly preferably 1 to 4. Specific examples thereof include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.

In the case of an oxyalkylene group, it may be a structure represented by the following general formula (7). In the case of a polyoxyalkylene group having 2 or more, a homopolymer of the same oxyalkylene chain may be used, and different oxyalkylene chains may be randomly or block- It may be.

(7)

(Wherein Y is an alkylene group and n is an integer of 1 or more).

Y in formula (7) is an alkylene group, and the number of carbon atoms of the alkylene group is usually 1 to 12, preferably 1 to 8, and particularly preferably 1 to 4. Specific examples thereof include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.

In the general formula (7), n is an integer of 1 or more, preferably 1 to 30, particularly preferably 2 to 20, and more preferably 5 to 15.

Formula X ₅ in 1 is an alkylene group, as the number of carbon atoms of the alkylene group, usually 1 to 12, preferably from 1 to 8, especially preferably 1 to 4. Specific examples thereof include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.

X ₆ in the general formula (1) is a hydrogen atom or an ester bond residue.

Examples of the ester bond residue include a saturated hydrocarbon group or an aryl group having one valence.

The monovalent saturated hydrocarbon group usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Specific examples include linear alkyl groups such as methyl and ethyl, branched alkyl groups such as isooctyl and 2-ethylhexyl, and alicyclic alkyl groups such as cyclohexyl, isobonyl and dicyclopentanyl.

The aryl group is usually an aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms. Specific examples include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, and a naphthyl group.

In addition, the _{X 1, X 2, X 4} , X 5, X 6 is optionally has a substituent, examples of such a substituent, for example, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfamoyl group, A vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group. When such a substituent has a carbon atom, the carbon atom is not included in the carbon number defined in the description of X ₁ , X ₂ , X ₄ , X ₅ , and X _{6 above} .

In the general formula (1), a and b are each an integer of 1 to 30, and c and d are an integer of 0 to 60, respectively. Also,

the ratio of a and b + c + d is preferably 0.1 a / b + c + d 10, particularly preferably 0.1 a / b + c + d 8,

the ratio of c and (b + c) is preferably 0? c / (b + c) <0.95, particularly preferably 0? c /

the ratio of d to (a + b + c) is preferably 0? d / (a + b + c? 5, particularly preferably 0? d / (a + b + c)?

In the case where a to d in the general formula (1) are an integer of 2 or more, the [] in the general formula [1] and the structure of the parenthesized structure may be repeats of the same structure,

The weight average molecular weight of the reactive fluorine-containing compound (B2) is usually from 1,000 to 100,000, preferably from 2, 500 to 40,000, particularly preferably from 3,000 to 30,000.

The production method of the reactive fluorine-containing compound (B2) may be carried out according to a known method for producing a fluorine-containing compound, for example, according to the method described in JP-A-2010-47680.

The content of the reactive fluorine-containing compound (B2) is preferably 0.5-500 parts by weight, particularly preferably 2-200 parts by weight, more preferably 2-20 parts by weight, per 100 parts by weight of the urethane (meth) acrylate- Preferably 5 to 100 parts by weight. If the content is too large, compatibility tends to deteriorate and phase separation may occur or the cured resin layer tends to become opaque. When the content is too small, the antifouling performance tends to be insufficient.

In the present invention, an ethylenically unsaturated compound [but excluding (B1) and (B2) is added in addition to the urethane (meth) acrylate compound (B1) and the reactive fluorine- ] (B4) is preferable in that the hardness and abrasion resistance of the cured resin layer are excellent.

The content of the ethylenically unsaturated compound (B4) is preferably 0 to 99% by weight, particularly preferably 25 to 98% by weight, particularly preferably 25 to 99% by weight, based on the total of the components (B1) By weight, more preferably 50 to 97% by weight, and still more preferably 75 to 96% by weight. If the content of the ethylenically unsaturated compound (B4) is too large, sufficient antifouling performance tends not to be obtained. When the amount of the ethylenically unsaturated compound (B4) is too small, the hardness and abrasion resistance of the cured resin layer tend to decrease.

The ethylenically unsaturated compound (B4) is preferably, for example, a urethane (meth) acrylate compound (B4-1) and / or an ethylenically unsaturated monomer (B4-2).

The urethane (meth) acrylate compound (B4-1) is preferably a urethane (meth) acrylate compound (B4-1-1) represented by the following general formula (6) In view of easiness of giving.

[Chemical Formula 6]

Wherein R ₁ is a urethane bond residue of a polyvalent isocyanate compound, R ₂ is a urethane bond residue of a hydroxyl group-containing (meth) acrylate compound, and a is an integer of 2 to 50.

The urethane (meth) acrylate compound (B4-1-1) represented by the above formula (6) is obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound.

A in the above formula (6) may be an integer of 2 to 50, preferably 2 to 20, and particularly preferably 2 to 10.

Examples of such a polyisocyanate compound include those exemplified as the polyisocyanate compound (x2) in the description of the urethane (meth) acrylate compound (B1-1), the polyisocyanate compound And a compound obtained by reacting the compound (x2) with the polyol compound (x4).

Examples of such a hydroxyl group-containing (meth) acrylate compound include, for example, in the description of the urethane (meth) acrylate compound (B1-1) And so on.

The method for producing the urethane (meth) acrylate compound (B4-1-1) may be produced in accordance with a known method for producing a urethane (meth) acrylate compound. For example, a compound such as the polyisocyanate compound (x2) and a compound such as the hydroxyl group-containing (meth) acrylate compound (x3) may be used in a batch or separately in the reactor.

The reaction molar ratio of the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound is, for example, such that the isocyanate group of the polyisocyanate compound is 2 and the hydroxyl group of the hydroxyl group-containing (meth) (Meth) acrylate compound is about 1: 2 to 3, the isocyanate group of the polyisocyanate compound is 3, and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound is 1 , The polyisocyanate compound: hydroxyl group-containing (meth) acrylate compound is about 1: 3 to 4.

In the addition reaction of the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound, the reaction is terminated when the residual isocyanate group content in the reaction system becomes 0.5 wt% or less, whereby the urethane (meth) (B4-1-1) is obtained.

The number of the ethylenic unsaturated groups contained in the urethane (meth) acrylate compound (B4-1-1) obtained above is preferably from 2 to 30, particularly preferably from 3 to 20, more preferably from 6 ~ 15.

If the number of the ethylenic unsaturated groups is too small, the hardness and abrasion resistance of the coating film tends not to be obtained. If too large, the hardening shrinkage of the coating film tends to be large and the adhesion of the substrate tends to deteriorate or the coating film tends to be retreated.

The weight-average molecular weight of the urethane (meth) acrylate compound (B4-1) is preferably 700 to 50,000, more preferably 800 to 30,000, particularly preferably 1000 to 10,000. If the weight average molecular weight is too small, it tends to make it difficult to maintain the balance between the hardness and shrinkage resistance of the cured resin layer or the wettability to the substrate. If the weight average molecular weight is too large, Of the polyfunctional oligomer tends to be difficult to maintain abrasion resistance and hardness.

The viscosity of the urethane (meth) acrylate compound (B4-1) at 60 ° C is preferably 200 to 150,000 mPa · s, more preferably 500 to 120,000 mPa · s, mPa &amp;bull; s. When the viscosity is outside the above range, the coating property tends to decrease.

The viscosity is measured by an E-type viscometer.

Examples of the ethylenically unsaturated monomer (B4-2) include an ethylenically unsaturated monomer having at least one ethylenic unsaturated group in one molecule (provided that the urethane (meth) acrylate-based compound (excluding B4-1) For example, monofunctional monomers, bifunctional monomers and trifunctional or higher monomers can be mentioned.

The monofunctional monomer may be a monomer containing one ethylenic unsaturated group, and examples thereof include styrene, vinyltoluene, chlorostyrene,? -Methylstyrene, methyl (meth) acrylate, ethyl (meth) (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl Hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, (Meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylate, n-butyl (meth) acrylate (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (Meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (Meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate and butoxyethyl (meth) acrylate of a phthalic acid derivative such as 2- (Meth) acrylate, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acrylamide, ) Acryloyloxyethyl acrylate And the like can be de-phosphate monoester.

In addition to the monofunctional monomers mentioned above, there can also be mentioned a Michael addition product of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester. Examples of the Michael addition product of acrylic acid include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimmer, Acrylic acid tetramer, methacrylic acid tetramer, and the like. Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, Acryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester and the like . Also, oligoester acrylates can be mentioned.

The bifunctional monomer may be a monomer containing two ethylenic unsaturated groups, and examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol (meth) acrylate, polyethylene Acrylate, propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol (meth) acrylate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A Diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diol ethylene oxide modified di (meth) acrylate, glycerin di (Meth) acrylate, hydroxypivalic acid-modified neopentylglycidyl di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di Isocyanuric acid ethylene oxide-modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester and the like.

The monomer having three or more functional groups may be any monomer containing three or more ethylenic unsaturated groups. Examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxy trimethylol propane, glycerin polyglycidyl Ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (metha) acrylate, ethylene oxide modified polyoxyethylene (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, (Meth) acrylate modified with ethylene oxide, pentaerythritol tetra (meth) acrylate modified with ethylene oxide, caprolactone Caprolactone-modified pentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) (Meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, and the like.

These ethylenically unsaturated monomers (B4-2) may be used alone or in combination of two or more.

The ethylenically unsaturated monomer (B4-2) is preferably a monomer containing two or more ethylenically unsaturated groups and more preferably at least one ethylenically unsaturated group containing at least three ethylenically unsaturated groups It is a monomer.

Specific examples thereof include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Is preferable because a hard cured resin layer is obtained.

(B4-1) and (B4-2) in the case of using the urethane (meth) acrylate compound (B4-1) and the ethylenically unsaturated monomer (B4-2) as the ethylenically unsaturated compound (B4-1): (B4-2) = 5: 95 to 95: 5, and particularly preferably (B4-1) :( B4-2) = 20: 80 to 80:20.

In the present invention, it may further contain a photopolymerization initiator (B3).

Examples of such a photopolymerization initiator (B3) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4- (2- Methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2- Acetophenones such as dimethylamino-1- (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- -Diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethanium bromide, (4-benzoylbenz Trimethylammonium chloride), benzophenones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Thioxanthones such as 4-propoxythioxanthone and 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone- (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Acylphosphine oxides such as oxalic acid, and the like. These photopolymerization initiators (B3) may be used singly or in combination of two or more.

These preparations can also be exemplified by triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Mihira ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid isoylmethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, It is also possible to use isopropylthioxanone and the like.

The content of the photopolymerization initiator (B3) is preferably such that the total amount of the urethane (meth) acrylate compound (B1), the reactive fluorine compound (B2) and the ethylenically unsaturated compound More preferably from 1 to 8 parts by weight, and particularly preferably from 1 to 5 parts by weight, based on the weight of the composition. If the content is too small, the curing rate in the case of ultraviolet curing tends to be extremely slow, and if too much, the curing property is not improved and it is inefficient.

In the present invention, in addition to the above components (B1) to (B4), it is also possible to use a filler, an electrolyte salt, a salt pigment, oil, plasticizer, wax, drier, dispersant, wetting agent, emulsifier, gelling agent, stabilizer, A thixotropic agent, an antioxidant, a flame retardant, a filler, a reinforcing agent, a gloss-erasing agent, a crosslinking agent and the like may be blended.

In addition to these, for the purpose of suppressing the hardening shrinkage ratio of the coating film, it is possible to use an unsaturated polyester resin, a vinyl urethane resin, a vinyl ester urethane resin, a polyisocyanate, a polyepoxide, an acrylic resin, an alkyd resin, a urea resin, Polymers such as polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers, nitrocellulose, and cellulose derivatives such as cellulose acetate butyrate may be added.

Thus, the urethane (meth) acrylate compound (B1) containing the polysiloxane structure of the present invention, the reactive fluorine-containing compound (B2) and the photopolymerization initiator (B3), preferably the ethylenically unsaturated compound (Ii) is further obtained.

The photo-curable composition (ii) may be blended with an organic solvent and adjusted in viscosity, if necessary. Usually, the photo-curable composition (ii) is diluted to 10 to 70% by weight, preferably 20 to 60% Can be applied.

Examples of such an organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, , Aromatic hydrocarbons such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetic acid esters such as ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone, or two or more of them may be used in combination.

The photopolymerizable composition (ii) of the present invention can also be produced by reacting a urethane (meth) acrylate compound (B1), a reactive fluorine compound (B2), a photopolymerization initiator (B3), an ethylenically unsaturated compound (B1) to (B4) may be blended in various orders. First, (B1) and (B4) are prepared in the same reaction system, and then (B2 ) (B3) may be added. When an organic solvent such as ethyl acetate or methyl isobutyl ketone is used, an organic solvent may be added to the mixture, or each compound may be dissolved in an organic solvent and then mixed.

Among them, a method of adding (B3) at the end after blending (B1), (B2) and (B4) is preferably used.

In the present invention, the photo-curable composition (ii) is prepared by coating (at least one side of the resin molded article [I]) after coating (when the composition diluted with an organic solvent is coated, To be cured as a cured resin layer [II]. The coating method is not particularly limited, and wet coating methods such as spraying, showering, dipping, roll, spinning, screen printing and the like can be mentioned.

The thickness after curing of the cured resin layer [II] is preferably 1 to 50 탆, and particularly preferably 3 to 30 탆.

Examples of such active energy rays include, but are not limited to, light rays such as deep ultraviolet rays, ultraviolet rays, near ultraviolet rays and infrared rays, electromagnetic waves such as X-rays and gamma rays, electron beams, , The ease of obtaining the irradiation apparatus, and the cost, it is advantageous to cure by ultraviolet irradiation.

As a method of curing by ultraviolet irradiation, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, or the like is used as a high-pressure mercury lamp, ultra-high pressure mercury lamp or carbon arc lamp emitting light in a wavelength range of 150 to 450 nm, 3000 mJ / cm &lt; 2 &gt;

After irradiation with ultraviolet rays, heating may be carried out as necessary to achieve complete curing.

Thus, a cured resin layer [II] is formed on at least one surface of the resin molded article [I].

In the present invention, a cured resin layer [i] is obtained by curing a photocurable composition (iii) containing the following components (C1), (C2) and (C3) between a resin molding [I] and a cured resin layer [ III] is formed, thereby improving the adhesion between the resin molded article [I] and the cured resin layer [II].

(C1) Acrylic resin

(C2) an unsaturated compound containing two or more ethylenic unsaturated groups

(C3) a photopolymerization initiator

[Acrylic resin (C1)]

The acrylic resin (C1) in the present invention is obtained by polymerizing a monomer component containing a (meth) acrylic monomer, and the acrylic resin (C1) can be used singly or in combination of two or more.

The acrylic resin (C1) preferably contains a (meth) acrylate monomer (c1) as a main component and a monomer (c2) containing a functional group and other copolymerizable monomers It may be a copolymerization component.

Examples of such a (meth) acrylic ester monomer (c1) include aliphatic (meth) acrylic acid ester monomers such as (meth) acrylic acid alkyl esters, aromatic (meth) acrylic acid Ester-based monomers.

Examples of such aliphatic (meth) acrylic acid ester monomers include (meth) acrylic acid alkyl esters having an alkyl group having a carbon number of usually from 1 to 12, particularly preferably from 1 to 10, and more preferably from 1 to 8, , And (meth) acrylic acid esters having an alicyclic structure.

Specific examples of such (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i- (Meth) acrylate, n-hexyl (meth) acrylate, n-butyl (meth) acrylate, Acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, and stearyl (meth) acrylate.

Specific examples of the (meth) acrylate ester having an alicyclic structure include cyclohexyl (meth) acrylate and isobonyl (meth) acrylate.

Examples of the aromatic (meth) acrylate monomer include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyldiethylene glycol (Meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, nonylphenol ethylene oxide adduct (meth) acrylate And the like.

Examples of other (meth) acrylic ester monomers include tetrahydroperfuryl (meth) acrylate and the like. These may be used singly or in combination of two or more.

Of these (meth) acrylic ester monomers (c1), methyl (meth) acrylate, n-butyl (meth) acrylate and the like are preferable from the viewpoints of copolymerization, excellent film strength, ease of handling, Isobornyl (meth) acrylate is particularly preferably used, and methyl (meth) acrylate is particularly preferable.

Examples of the functional group-containing monomer (c2) include a monomer having a hydroxyl group, a carboxyl group-containing monomer, an alkoxy group or a phenoxy group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a nitrogen-containing monomer, a glycidyl group- , Sulfonic acid group-containing monomers, and the like. These may be used singly or in combination of two or more.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylic acid hydroxyalkyl (meth) acrylate such as (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl Ester, caprolactone-modified 2-hydroxyethyl (meth) acrylate and the like, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N- (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy- Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate (Meth) acrylate, and 2, 2-dimethyl-2-hydroxyethyl (meth) acrylate; .

Examples of the nonionic surfactant include polyethylene glycol derivatives such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol- An oxyalkylene-modified monomer such as poly (meth) acrylate, poly (ethylene glycol tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol tetramethylene glycol) mono (meth) acrylate may be used.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic acid, itaconic acid, fumaric acid, acrylamide-N-glycolic acid, cinnamic acid, (Meth) acryloyloxyethyl dicarboxylic acid monoester (e.g., methacrylic acid dimer, methacrylic acid dimmer, methacrylic acid trimmer, tetramer acid acrylate, tetramer methacrylate, etc.) Acryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2- Acryloyloxyethylhexahydrophthalic acid monoester, 2-methacryloyloxyethylhexasahydrophthalic acid monoester, etc.), and the like. The carboxyl group-containing monomer may be used in the form of a salt or in the form of a salt neutralized with an alkali.

Examples of the alkoxy group-containing monomer include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate, stearoxypolyethylene glycol (Meth) acrylic esters of aliphatic type such as acrylate and the like.

Examples of the amide group-containing monomer include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N- ) Acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkyl acrylamide, Amides and the like.

Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternary cargo thereof.

Examples of the nitrogen-containing monomer include acryloylmorpholine and the like.

Examples of the glycidyl-containing monomer include glycidyl (meth) acrylate, allyl glycidyl ether, and the like.

Examples of the phosphoric acid group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate and bis (2- (meth) acryloyloxyethyl) acid phosphate such as polyethylene glycol monomethacrylate (For example, &quot; Sipomer PAM100 &quot; or &quot; Sipomer PAM4000 &quot; manufactured by Rhodia Nikka Corporation), phosphoric acid esters of polyethylene glycol monoacrylate (e.g., &quot; Sipomer PAM5000 &quot; Phosphate ester of glycol monomethacrylate (e.g., &quot; Sipomer PAM200 &quot; manufactured by RhodiaIyhara), phosphoric ester of polypropylene glycol monoacrylate (e.g., &quot; Sipomer PAM300 &quot; (Meth) acrylate of polyalkylene glycol mono (meth) acrylate such as methylene (meth) acrylate phosphate, trimethylene (meth) acrylate It can be given site, phosphoric propylene (meth) acrylate, phosphoric tetramethylene (meth) acrylate such as a phosphate-alkylene (meth) acrylate and the like.

Examples of the sulfonic acid group-containing monomer include olefin sulfonic acids such as ethylene sulfonic acid, aryl sulfonic acid and methallylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, styrene sulfonic acid, .

These functional group-containing monomers (c2) may be used singly or in combination of two or more.

Examples of the other copolymerizable monomer (c3) include acrylonitrile, methacrylonitrile, styrene,? -Methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, But are not limited to, vinyltoluene, vinylpyridine, vinylpyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, acryl chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone And the like.

In order to increase the molecular weight, it is possible to use ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di A compound having two or more ethylenic unsaturated groups such as propylene glycol di (meth) acrylate and divinylbenzene, or the like may be used in combination.

In the acrylic resin (C1), the content ratio of the (meth) acrylate monomer (c1), the functional group containing monomer (c2) and the other copolymerizable monomer (c3) Preferably 10 to 100% by weight, particularly preferably 20 to 95% by weight, the functional group-containing monomer (c2) is preferably 0 to 90% by weight, particularly preferably 5 to 80% by weight, (c3) is preferably 0 to 50% by weight, particularly preferably 0 to 40% by weight.

The acrylic resin (C1) in the present invention is preferably a polymer comprising a (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms in the alkyl group as a polymerization component, and more preferably a polymer containing methyl (meth) , And is preferably a polymer containing methyl methacrylate as a polymerization component, and more preferably, polymethyl methacrylate is preferable in that the strength of the cured resin layer is excellent.

In the polymerization of the acrylic resin (C1), conventionally known methods such as solution radical polymerization, suspension polymerization, bulk polymerization and emulsion polymerization can be employed. (Meth) acrylate monomer (c1), functional group-containing monomer (c2) and other copolymerizable monomer (c3), polymerization initiator (azobisisobutyronitrile, Azobisisobalonitrile, benzoyl peroxide, etc.) are mixed or dropped, and the mixture is polymerized in a reflux state or at 50 to 90 占 폚 for 2 to 20 hours.

The glass transition temperature (Tg) of the acrylic resin (C1) is usually from 0 to 180 캜, preferably from 15 to 175 캜, particularly preferably from 50 to 130 캜. If the glass transition temperature is too high, the relaxation effect of heat shrinkage of the cured product tends to deteriorate. If the glass transition temperature is too low, the thermal durability of the cured product tends to deteriorate.

The weight average molecular weight of the acrylic resin (C1) thus obtained is usually from 10,000 to 500,000, and preferably from 10,000 to 100,000.

If the weight average molecular weight is too large, the strength of the cured resin layer tends to decrease. If the weight average molecular weight is too small, the adhesion to various substrates such as glass substrates and plastic substrates and the appearance of the coating film tends to deteriorate.

The dispersion degree (weight average molecular weight / number average molecular weight) of the acrylic resin (C1) is usually 1 to 4, preferably 1.5 to 2.5.

The above weight average molecular weight and number average molecular weight are based on standard polystyrene molecular weight conversions and are shown in Table 1 by high performance liquid chromatography (Waters 2695 (main body) and Waters 2414 (detector), manufactured by Nippon Waters Co., Shodex GPCKF-806 L (exclusion limit molecular weight: 2 x 10 ⁷ , separation range: 100 to 2 x 10 ⁷ , theoretical number of stages: 10,000 stages / filler material: styrene-divinylbenzene copolymer, , And the degree of dispersion can be determined by weight average molecular weight and number average molecular weight. The glass transition temperature is calculated from the Fox equation.

[Unsaturated compound (C2) containing two or more ethylenic unsaturated groups]

The unsaturated compound (C2) containing two or more ethylenic unsaturated groups in the present invention (hereinafter also referred to as "polyfunctional unsaturated compound (C2)") has preferably two or more ethylenic unsaturated groups in one molecule, Containing group is 2 to 15, particularly preferably 3 to 6, and the phosphoric acid group-containing ethylenically unsaturated compound (C4), which will be described later, is excluded. The polyfunctional unsaturated compound (C2) may be used alone or in combination of two or more. For example, bifunctional monomers, trifunctional or higher functional monomers, urethane (meth) acrylate compounds, epoxy (meth) acrylate compounds and polyester (meth) acrylate compounds can be used.

The bifunctional monomer is a monomer containing two ethylenic unsaturated groups, and examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylates such as methylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A Diol di (meth) acrylate, 1,6-hexanediol ethylene oxide modified di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10- (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di , Diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified Diacrylate, and the like.

The monomer having three or more functional groups is a monomer containing three or more ethylenic unsaturated groups, and examples thereof include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri Acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxy trimethylol propane, ethoxylated glycerin tri (meth) acrylate, glycerin polyglycidyl ether poly ) Acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate,? -Caprolactone modified tris (2-acryloxyethyl) isocyanurate, ethylene oxide modified diphenyl (Meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra Acrylate, caprolactone-modified pentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (metha) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone Modified pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, and the like.

The urethane (meth) acrylate compound is a (meth) acrylate compound having a urethane bond in the molecule, and a (meth) acrylic compound containing a hydroxyl group and a polyisocyanate compound , And those which can be obtained by reacting by the method of the general public, and the weight average molecular weight is usually 300 to 50,000.

Examples of the polyfunctional unsaturated compound (C2) in the present invention include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) (Meth) acrylate, and particularly preferably a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate in view of excellent film strength.

The content of the polyfunctional unsaturated compound (C2) is usually from 10 to 900 parts by weight, preferably from 10 to 500 parts by weight, particularly preferably from 15 to 100 parts by weight, based on 100 parts by weight (in terms of solid content) More preferably 20 to 150 parts by weight, still more preferably 30 to 100 parts by weight.

If the content of the polyfunctional unsaturated compound (C2) is too large, the adhesion to the resin molded article [I] tends to deteriorate, while if it is too small, the strength of the cured resin layer tends to decrease.

Examples of the photopolymerization initiator (C3) used in the present invention include those exemplified as the photopolymerization initiator (B3).

Such a preparation may be the same as exemplified as the preparation of the photopolymerization initiator (B3).

Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy- 2-methyl-1-phenylpropan-1-one is preferably used.

The content of the photopolymerization initiator (C3) is preferably from 0.1 to 20 parts by weight, more preferably from 1 to 18 parts by weight, based on 100 parts by weight (in terms of solid content) of the total of the component (C2) Particularly preferably 2 to 15 parts by weight.

If the content of the photopolymerization initiator (C3) is too small, the curing tends to be defective. If it is too much, mechanical properties such as hardness tend to decrease, and problems of embrittlement and coloring tend to occur.

In the present invention, it is preferable that the photocurable composition (iii) further contains a phosphoric acid group-containing ethylenically unsaturated compound (C4) in view of further improving adhesion with the resin molded article [I].

[Phosphorus group-containing ethylenically unsaturated compound (C4)]

The phosphoric acid group-containing ethylenically unsaturated compound (C4) in the present invention contains one or more phosphoric acid groups in one molecule, preferably 1 to 5, and contains one or more ethylenic unsaturated groups, preferably 1 to 3 Containing unsaturated compounds. The phosphoric acid group-containing ethylenically unsaturated compound (C4) may be used singly or in combination of two or more.

Examples of the phosphoric acid group-containing ethylenically unsaturated compound (C4) include 2-acryloyloxyethyl acid phosphate (e.g., "Light Acrylate P-1 A" manufactured by Kyowa Chemical Co., Ltd.) 2-acryloyloxyethyl) acid phosphate (e.g., &quot; LIGHT ACRYLATE P-2 A &quot; manufactured by Kyowa Chemical Co., Ltd.), 2-methacryloyloxyethyl acid phosphate 2-methacryloyloxyethyl) acid phosphate (e.g., &quot; Lite Ester P-2M &quot; manufactured by Kyoeisha Chemical Co., Ltd., EM39 manufactured by Tunnel Chemical Co., Ltd., "KAYAMER PM-2" manufactured by Nippon Kayaku Co., Ltd.), reaction products of 6-hexanol adduct of 2-hydroxyethyl methacrylate and anhydrous phosphoric acid (for example, KAYAMER PM-21 &quot; manufactured by Kayaku Co., Ltd.), trisacryloyloxyethylphosphate (For example, "Viscot # 3 PMA" manufactured by Osaka Organic Chemical Industry Co., Ltd., etc.), tris (methacryloyloxyethyl phosphate) (For example, "Sipomer PAM100" or "Sipomer PAM4000" manufactured by Rhodia Nikka Co., Ltd.), phosphoric acid ester of polyethylene glycol monoacrylate (for example, manufactured by Rhodia Nikka Co., (For example, &quot; Sipomer PAM5000 &quot;, etc.) of polypropylene glycol monomethacrylate, phosphoric acid esters of polypropylene glycol monomethacrylate (E.g., &quot; Sipomer PAM300 &quot; manufactured by Nikkasa), phosphoric acid esters of polyalkylene glycol mono (meth) acrylate such as methylene (meth) (Meth) acrylates such as trimethylene (meth) acrylate, trimethylene (meth) acrylate, propylene (meth) acrylate phosphate and tetramethylene (meth) acrylate phosphate. These phosphoric esters can be used alone or in combination of two or more of monoesters, diesters and triesters.

Examples of the organic acid include vinylphosphonic acid, dimethylvinylphosphonic acid, diethylvinylphosphonic acid, diisopropylvinylphosphonic acid, diisobutylvinylphosphonic acid, dibutylvinylphosphonic acid, phenylvinylphosphonic acid, p-vinylbenzenephosphonic acid, etc. (Diethyl vinyl) phosphonic acid, bis (diisopropyl vinyl) phosphonic acid, (diisobutylvinyl) phosphine, bis (dimethyl vinyl) phosphonic acid, Phosphonic acid group-containing diethylenically unsaturated compounds such as phosphonic acid, (dibutylvinyl) phosphonic acid and bis (phenylvinyl) phosphonic acid. These vinyl compounds may be used alone or in combination of two or more.

As the phosphate group-containing ethylenically unsaturated compound (C4), bis (2- (meth) acryloyloxyethyl) acid phosphate and 2- (meth) acryloyloxyethyl acid phosphate are preferable, and one or two Species can be used together.

The content of the phosphate group-containing ethylenically unsaturated compound (C4) is usually 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight (in terms of solid content) of the acrylic resin (C1) 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight.

If the content of the phosphoric acid group-containing ethylenically unsaturated compound (C4) is too large, the adhesion of the base material with the resin molded article [I] and the strength of the cured resin layer tend to be lowered.

The photo-curable composition (iii) used in the present invention contains the acrylic resin (C1), the polyfunctional unsaturated compound (C2), the photopolymerization initiator (C3), and preferably the ethylenically unsaturated compound , And a silane coupling agent (C5).

[Silane coupling agent (C5)]

Examples of the silane coupling agent (C5) include an epoxy group-containing silane coupling agent, a (meth) acryloyl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a hydroxyl group-containing silane coupling agent, Containing silane coupling agent, an amide group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent. Of these, the (meth) acryloyl group-containing silane coupling agent is most suitable. These may be used singly or in combination of two or more.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3- 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriacetate, (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-mercaptomethyldimethoxysilane and 3-mercaptotriethoxysilane, and preferably 3- (meth) acryloxypropyltrimethoxysilane.

The content of the silane coupling agent (C5) is usually 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight (in terms of solid content) By weight, more preferably 1 to 5 parts by weight. If the content of the silane coupling agent (C5) is too large, the strength and external appearance of the cured resin layer tend to decrease. If the content is too low, the adhesion of the base material with the resin molded article [I] tends to decrease.

The photo-curable composition (iii) used in the present invention may also contain other additives such as filler, electrolyte salt, salt pigment, oil, plasticizer, wax, drier, dispersant, wetting agent, emulsifier, gelling agent, stabilizer, defoamer, A polymerization inhibitor, an antioxidant, a flame retardant, a filler, a reinforcing agent, a delustering agent, a crosslinking agent, an ultraviolet absorber, and a light stabilizer. In order to impart antistatic property and conductivity, a conductive filler such as a metal salt such as a lithium salt, a metal oxide, a conductive polymer, an antistatic agent and the like may be contained.

However, the photo-curable composition (iii) used in the present invention is preferably free of inorganic fine particles such as silica from the viewpoints of transparency of the cured resin layer and stability and compatibility of the photo-curing composition (iii).

The photo-curable composition (iii) used in the present invention may contain an organic solvent, if necessary, and adjust the viscosity thereof. Examples of such an organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, Etc., glycol ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, acetic acid esters such as ethyl acetate and butyl acetate, diacetone alcohol and the like. . These organic solvents may be used singly or in combination of two or more.

When two or more of them are used in combination, a combination of acetic acid ester homologues such as ethyl acetate and butyl acetate, a combination of acetic acid ester homologues such as ethyl acetate and butyl acetate, and aromatics such as toluene, a combination of methyl ethyl ketone and methyl isobutyl ketone And a combination of alcohols such as methanol and propyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol and propyl alcohol, and a combination of aromatics such as toluene and the like, Which is preferable in terms of appearance.

The photo-curable composition (iii) used in the present invention can be applied by diluting to 10 to 60% by weight, preferably 20 to 40% by weight, of the above organic solvent.

The photopolymerizable composition (iii) of the present invention preferably contains an acrylic resin (C1), a polyfunctional unsaturated compound (C2), a photopolymerization initiator (C3), preferably a phosphoric acid group-containing ethylenically unsaturated compound (C4) (C5) are mixed, various methods can be adopted.

For example, the acrylic resin (C1) and the polyfunctional unsaturated compound (C2) are mixed to add a phosphate group-containing ethylenically unsaturated compound (C4), followed by adding a silane coupling agent (C5) (C1) and a polyfunctional unsaturated compound (C2) are dissolved in an organic solvent such as ethyl acetate or toluene, and a solution obtained by dissolving an acrylic resin (C1) and a polyfunctional unsaturated compound A method of mixing with the unsaturated compound (C4), again mixing the silane coupling agent (C5) with the photopolymerization initiator (C3) in this order is employed.

In the present invention, the photo-curing composition (iii) can be cured by applying an active energy ray after coating the resin molding [I], and a cured resin layer [III] is formed on the resin molding [I] . Then, the above-mentioned cured resin layer [II] is formed on the cured resin layer [III], and the resin molded product [I] and the cured resin layer [II] are strengthened.

In this case, it is preferable that the cured resin layer [III] is formed on the resin molded article [I], then the photo-curable composition (ii) is coated thereon to cure it to form the cured resin layer [II] The formation of the resin layer [II] can be carried out in accordance with the method for forming the cured resin layer [II] on the resin molded article [I].

Examples of the coating method include wet coating methods such as spraying, showering, dipping, flow coating, gravure coating, roll coating, spin coating, and screen printing.

As such an active energy ray, it is possible to use an electromagnetic wave such as a deep ultraviolet ray, ultraviolet ray, near ultraviolet ray, infrared rays, an electromagnetic wave such as an X ray or a? The curing by ultraviolet irradiation is advantageous in terms of cost and the like.

As a method of curing by ultraviolet irradiation, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, or the like is used as a high-pressure mercury lamp, ultra-high pressure mercury lamp or carbon arc lamp emitting light in a wavelength range of 150 to 450 nm , And a method of irradiating about 30 to 3000 mJ / cm 2.

After irradiation with ultraviolet rays, heating may be carried out as necessary to achieve complete curing.

The thickness of the cured resin layer [III] after curing is preferably 1 to 30 μm, and particularly preferably 2 to 20 μm. If the film thickness is too large, the thermal load such as the boiling water immersion test becomes large, and the thermal shrinkage of the cured resin layer [III] tends to increase in such durability test, and the adhesion to the substrate tends to decrease. On the other hand, if it is too thin, a desired surface hardness can not be obtained as an ultraviolet cured film.

Thus, in the present invention, a laminate having a cured resin layer [II] formed on a resin molded article [I] or a laminate having a cured resin layer [II] formed on a resin molded article [I] through a cured resin layer [III] Can be obtained.

The pencil hardness of the surface of the cured resin layer [II] of the laminate of the present invention is preferably 3H or more from the viewpoint of durability of the protective sheet. The pencil hardness is more preferably 3H to 10H, particularly preferably 4H to 8H. In order to adjust the pencil hardness to the above range, a method of appropriately controlling the type of the cured resin layer [II] and the amount of the components to be blended can be mentioned.

The laminate of the present invention can be formed into a pressure-sensitive adhesive layer protective sheet by forming a pressure-sensitive adhesive layer on one side. The material of the pressure-sensitive adhesive layer is not particularly limited, and an acrylic or silicone pressure-sensitive adhesive is suitably used.

Further, the laminate of the present invention can be formed into a touch panel by forming a transparent conductive film on one surface. The material of the transparent electrode is not particularly limited, and examples thereof include inorganic conductive films such as ITO and IGZO, and organic conductive films such as PEDOT. The surface resistance value of the transparent conductive film is preferably 1000? /?, More preferably 10-900? / ?, still more preferably 200-800? /? Or less. If the surface resistance value is too high, the conductivity tends to become insufficient.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

In the examples, &quot; part &quot; and &quot;% &quot; mean weight basis unless otherwise specified.

In addition, evaluation was carried out as follows.

(1) Antifouling property

(Ink extractability)

The surface of the resin molded article was scratched with a blue magic ink, left standing for 24 hours, wiped off by a mop, and the appearance was visually observed and evaluated as follows.

  ○ ... It was excerpts beautifully.

△ ... trace of line of excerpt remains.

× ... can not be extracted.

(Ink elasticity)

A line was drawn with the blue magic ink on the surface of the resin molded article and the trace of the magic ink was visually observed and evaluated as follows.

○ · · · The ink is being repelled and the trace of the line becomes dotted

△ ... the ink is being repelled and the trace of the line becomes thinner

× · · · Does not repel the ink.

(2) Pencil hardness

The pencil hardness of the side of the cured resin layer [II] side of the laminate was measured according to JIS K 5600-5-4.

(3) Transparency (%)

The total light transmittance (%) was measured using a haze meter &quot; NDH-2000 &quot; manufactured by Nippon Denshoku Co.,

(4) Adhesion

Evaluation was carried out by the checkerboard tape method in accordance with JIS K 5400 (1990 edition) at the initial stage and at 65 ° C and 95% RH for 48 hours.

&Lt; Reference Example 1 &

[Preparation of photocurable composition (i)] [

10 parts of the following 6-functional urethane acrylate as the polyfunctional urethane (meth) acrylate compound (A1) and 10 parts of bis (hydroxymethyl) tricyclo [5.2. 1.0 ^2,6] decane = dimethacrylate (produced by Shin-Nakamura car flexors manufacture "DCP"), 90 parts of a photopolymerization initiator (A3) as a 1-hydroxycyclohexyl phenyl ketone (Ciba Chemicals LTD. Made Chari tea manufacture "Irgacure184") Was stirred at 60 캜 until it became homogeneous, and then filtered through a 50 탆 filter to obtain a photocurable composition (i).

[6-functional urethane acrylate]

To a flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet were added 192.0 g (0.86 mol) of isophorone diisocyanate and 18.0 g of pentaerythritol triacrylate (pentaerythritol triacrylate and pentaerythritol tetraacryl (Hydroxyl value of 120 mg KOH / g)] as a polymerization initiator, 0.01 g of hydroquinone methyl ether as a polymerization inhibitor and 0.01 g of dibutyltin dilaurate as a reaction catalyst were placed, The reaction was terminated when the residual isocyanate group became 0.3% or less to obtain hexafunctional urethane acrylate.

[Production of resin molded article [I]

The photo-curable composition (i) was injected at 23 占 폚 into a molding frame having a 0.2 mm-thick silicon plate as a spacer with the two optical polishing glasses facing each other, and a metal halide lamp was used. Respectively. The resin sheet obtained by demolding was heated in a vacuum oven at 150 캜 for 2 hours to obtain a resin molded article [I] having a length of 400 mm, a width of 300 mm and a thickness of 0.2 mm. The obtained resin molded product [I] had a total light transmittance of 92%, a glass transition temperature of 250 캜 or higher, a pencil hardness of 5H and a flexural modulus of 4 GPa.

[Preparation of urethane (meth) acrylate compound (B1) containing polysiloxane structure]

A flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet was charged with 90.6 g of a trimer (y2) of hexamethylene diisocyanate (isocyanate group content: 21.0%), 30 g of a polysiloxane- R ¹ = -C ₂ H ₄ OC ₃ H ₆ -, R ² = methyl group, R ³ = -C ₃ H ₆ OC ₂ H ₄ -, a = 9, b = 1, c = 120 mg KOH / g), dipentaerythritol pentaacrylate (y3) [a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate acrylate (hydroxyl value: 50 mg KOH / g), 0.10 g of dibutyltin dilaurate and 500 g of methyl ethyl ketone were charged and reacted at 60 ° C for 3 hours. When the residual isocyanate group became 0.76%, again, dipentaerythritol penta (Y3) [a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value: 50 mg KOH / g) , And 0.4 g of 2,6-di-t-butylcresol were added dropwise over about 1 hour, and the reaction was continued as it was to terminate the reaction at the time when the isocyanate groups disappeared. Thus, a polysiloxane group-containing urethane (meth) B1) solution (solid concentration 50%).

[Adjustment of photo-curable composition (ii)] [

(B2) shown in Table 1 was prepared as a reactive fluorine-containing compound (weight average molecular weight: 20,000).

(100 parts in terms of solid content) and the reactive fluorine-containing compound (B2) (1 part in terms of solid content) as the urethane (meth) acrylate-containing urethane (meth) acrylate structure-containing polysiloxane structure Irgacure 184 &quot; (4 parts in terms of solid content) were blended in the ratios shown in Table 2 to obtain a solution of the photo-curable composition (ii).

[Preparation of laminate]

The solution of the photo-curing composition (ii) was coated on the resin molding [I] using a 50 탆 applicator so as to have a thickness of 15 탆 after drying, and dried at 60 캜 for 5 minutes. 1, etc., and a 2-pass ultraviolet ray irradiation (cumulative dose: 450 mJ / cm 2) was carried out from a height of 18 cm at a conveyor speed of 5.1 m / min to form a cured resin layer [II] .

Each performance of the obtained laminate was evaluated as described above. The evaluation results are shown in Table 2.

&Lt; Example 1 &gt;

[Adjustment of photo-curing composition (iii)] [

100 parts of polymethylmethacrylate (weight average molecular weight: 43,000) as the acrylic resin (C1), 2 parts of an unsaturated compound (C2) containing at least two ethylenic unsaturated groups, dipentaerythritol pentaacrylate Acrylate and dipentaerythritol hexacrylate) (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerization initiator (C3), 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Corporation, Irgacure 184 ) Were mixed and diluted with a mixed solvent of ethyl acetate / acetic acid partly (73/27) to have a solid concentration of 35% to obtain a photocurable composition (iii) solution.

[Preparation of laminate]

The photo-curable composition (iii) solution was coated on the resin molded article [I] so as to have a film thickness of 5 mu m after curing using Barcoat No. 7, and dried at 80 DEG C for 3 minutes. Thereafter, a 2-pass ultraviolet ray irradiation (cumulative dose: 500 mJ / cm 2) was applied from a height of 18 cm to a conveyor speed of 5.1 m / min using a high pressure mercury lamp 80 W, .

Subsequently, a photo-curing composition (ii) solution was coated on the cured resin layer [III] using an applicator having a thickness of 50 탆 so as to have a film thickness after drying of 15 탆, dried at 60 캜 for 5 minutes, (80 mW / cm &lt; 2 &gt;) at a conveyor speed of 5.1 m / min from a height of 18 cm to obtain a cured resin layer (II) .

Each performance was evaluated for the obtained laminate (resin molded article [I] / cured resin layer [III] / cured resin layer [II]) as described above. The evaluation results are shown in Table 2.

&Lt; Example 2 &gt;

[Adjustment of photo-curing composition (iii)] [

100 parts of polymethylmethacrylate (weight average molecular weight: 43,000) as the acrylic resin (C1), 2 parts of dipentaerythritol pentaacrylate (dipentaerythritol pentaacrylate) as an unsaturated compound (C2) containing two or more ethylenic unsaturated groups 46.2 parts of a mixture of lithol pentaacrylate and dipentaerythritol hexaacrylate ("KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Co., (2-methacryloxyethyl) acid phosphate ("Light Ester P-2M", manufactured by Kyoeisha Chemical Co., Ltd.) as the phosphoric acid group-containing ethylenically unsaturated compound (C4) , A photocurable composition (iii) solution was obtained in the same manner as in Example 2.

[Preparation of laminate]

A cured resin layer [III] was formed in the same manner as in Example 1, using the photo-curable composition (iii) solution.

Subsequently, a cured resin layer [II] was formed on the cured resin layer [III] in the same manner as in Example 1.

Each performance of the obtained laminate (resin molded article [I] / cured resin layer [III] / cured resin layer [II]) was evaluated as described above. The evaluation results are shown in Table 2.

&Lt; Comparative Example 1 &

In Reference Example 1, the performance of each resin molded article [I] was evaluated as described above without forming the cured resin layer [II]. The evaluation results are shown in Table 2.

From the above evaluation results, the antifouling property can not be obtained even if the resin molded article [I] is used as it is. However, the resin molded article [I] can be obtained through the laminate or the cured resin layer [III] in which the cured resin layer [II] It is found that the laminate having the cured resin layer [II] formed thereon is excellent in adhesion, has excellent antifouling property, and has high surface hardness and transparency.

While the present invention has been shown and described with reference to specific embodiments thereof, it is to be understood that these embodiments are merely illustrative and not restrictive. Various modifications apparent to those skilled in the art are intended to be within the scope of the present invention.

(Industrial availability)

The laminate of the present invention can be advantageously used for various optical materials and electronic materials. For example, a protective sheet, a touch panel, a liquid crystal substrate, a substrate for organic / inorganic EL, a substrate for PDP, , A phase difference plate, an optical filter, various display members, storage and recording applications including optical disk substrates, energy use for thin film battery substrates and solar cell substrates, optical communication applications such as optical waveguides, · Can be used for seat applications. In addition to optical materials and electronic materials, they can also be used for automobile materials, building materials, medical materials, stationery, and the like.

Claims (12)

A cured resin layer [II] having a contact angle with water of 100 ° or more is formed on at least one side of the resin molded article [I] obtained by curing the photo-curable composition (i), and the resin molded article [I] and the cured resin layer [II (III) formed by curing a photocurable composition (iii) containing the following components (C1), (C2) and (C3)
(C1) an acrylic resin;
(C2) an unsaturated compound containing two or more ethylenically unsaturated groups;
(C3) a photopolymerization initiator. The method according to claim 1,
The photo-curing composition (i) comprises the following components (A1), (A2) and (A3)
(A1) a polyfunctional urethane (meth) acrylate compound;
(A2) a multifunctional (meth) acrylate compound containing a alicyclic skeleton;
(A3) a photopolymerization initiator. The method according to claim 1 or 2,
The cured resin layer (II) is obtained by curing a photocurable composition (ii) containing the following components (B1), (B2) and (B3)
(B1) a urethane (meth) acrylate compound containing a polysiloxane structure;
(B2) a reactive fluorine-containing compound represented by the following formula (1);
(B3) a photopolymerization initiator.
[Chemical Formula 1]

[Wherein,
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a methyl group,
X ₁ represents an alkylene group,
X ₂ represents an allylene group,
X ₃ represents a substituent represented by the following formula (2) or (3)
X ₄ represents an alkylene group, or an oxyalkylene group,
X &lt; ₅ &gt; is an alkylene group,
X ₆ is a hydrogen atom or an ester bond residue,
a and b each represent an integer of 1 to 30, and c and d each represent an integer of 0 to 60 (provided that the order of combining constituent units is optional).
(2)

(3)

The method according to claim 1 or 2,
And the pencil hardness of the surface of the cured resin layer (II) of the laminate is 3H or more. The method according to claim 1 or 2,
A laminate characterized in that the photo-curing composition (iii) further comprises the following component (C4):
(C4) a phosphoric acid group-containing ethylenically unsaturated compound. The method according to claim 1 or 2,
And a thickness of 0.1 to 3 mm. The method according to claim 1 or 2,
Characterized in that a pressure-sensitive adhesive layer is formed on one side of the laminate. The method according to claim 1 or 2,
Characterized in that the laminate is used as a protective sheet of a display. A protective sheet for a display, characterized by comprising the laminate according to claim 8. The method according to claim 1 or 2,
A laminate characterized by being used as a substrate for a touch panel. Wherein the laminate according to claim 10 is used as a substrate. delete