JP2019206636A - Resin composition, and sheet - Google Patents

Abstract

To provide an active energy ray-curable compound composition having excellent water repellency, stain resistance, repeating stain resistance, and weather resistance.SOLUTION: A resin composition comprising a resin (A) having a structural unit (a) containing an epoxy group, a structural unit having polysiloxane (b), and at least one UV-absorption structure (c) selected from the group consisting of a benzotriazole group, a benzophenone group, and a triazine group, an active energy ray curable compound (B), and a liquid medium (C).SELECTED DRAWING: None

Description

  The present invention relates to a novel resin composition. More specifically, the resin composition of the present invention forms a coating film excellent in antifouling properties and weather resistance, and can be suitably used in applications such as paints and coating agents.

  Conventionally, various paints and coating agents have been proposed for the purpose of protecting the surface of various objects, imparting aesthetics, and imparting special functions. In recent years, the demand for outdoor use is increasing, and not only weather resistance and light resistance, but also antifouling properties are important for maintaining beauty.

So far, weather resistance has been evaluated for resin compositions and cured films made of resins modified with acrylic acid and introduced with photoreactive groups into resins made of copolymers having a polydimethylsiloxane structure and an epoxy skeleton in the side chain. However, there is no description of the antifouling property of the coating film. (Patent Document 1)

On the other hand, a coating film made of a resin comprising a copolymer having a polydimethylsiloxane structure and an epoxy skeleton in the side chain and modified with acrylic acid and introduced with a photoreactive group has a water repellency, oil repellency, weather resistance, It has the characteristic of having contamination etc. (patent document 2)

Patents relating to compounds in which a photoreactive group is introduced by modifying acrylic resin into a resin comprising a copolymer having a monomer having an ultraviolet absorber skeleton and an epoxy skeleton have also been reported. (Patent Document 3)

  As shown in the above-mentioned patent, it is characterized in that weather resistance and antifouling properties are expressed by curing with energy at the time of preparing a coating film by introducing a crosslinkable group into the resin skeleton.

JP 2007-191703 A Japanese Patent Laid-Open No. 2007-077188 JP 2007-238823 A

The present invention has a radically polymerizable double bond in a copolymer containing at least one ultraviolet absorbing structure selected from the group consisting of a polysiloxane skeleton, an epoxy skeleton, and a benzotriazole group, a benzophenone group, and a triazine group. Even if it does not, it aims at providing the coating film which can make higher pollution resistance and weather resistance compatible.

As a result of intensive studies, the inventors of the present invention include (meth) acrylate containing an epoxy group and polysiloxane mono (meth) acrylate as polymerization components, and the group consisting of a benzotriazole group, a benzophenone group, and a triazine group. It has been found that the above-mentioned problems can be solved by coating a resin having at least one selected ultraviolet-absorbing structure (c) as a resin composition, and the present invention has been completed.

The present invention is a resin composition containing a resin (A), an active energy ray-curable compound (B), and a liquid medium (C),
The resin (A) has at least one ultraviolet absorbing property selected from the group consisting of a structural unit (a) containing an epoxy group, a structural unit (b) having a polysiloxane, and a benzotriazole group, a benzophenone group, and a triazine group. It is related with the resin composition characterized by being resin (A) which has a structure (c).

Moreover, this invention relates to the said resin composition characterized by the resin (A) containing the piperidyl structure (d) represented by General formula (1).
General formula (1)

(In General Formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. ⁴ and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R ² and R ³ each independently represents a methyl group, an ethyl group, or a phenyl group, and “*” represents a bond.)

Moreover, this invention relates to the said resin composition characterized by the resin (A) containing the structural unit represented by General formula (2).
General formula (2)

(In General Formula (2), R ⁵ represents H or CH ₃ , A represents an alkyleneoxy group having 1 to 8 carbon atoms, — (CH ₂ CH ₂ —O—) _m —, —O—CH ₂ CH ( -OH) _-CH 2 -R ⁶ -, or _{-O-CH 2 CH (CH 2} OH) -R 6 - represents, m is an integer from 2 to 5, ^{R 6} are, -NH-, group or -O-, and X is at least one ultraviolet absorbing structure (c) selected from the group consisting of a benzotriazole group, a benzophenone group, and a triazine group, or a piperidyl structure (d) represented by the general formula (1) .)

The present invention, A in the general formula (2) _{is, -O-CH 2 CH (-OH} ) -CH 2 -R 6 -, or _{-O-CH 2 CH (CH 2} OH) -R 6 - in The present invention relates to the resin composition as described above,

The present invention also relates to the resin composition as described above, wherein the active energy ray-curable resin (B) is urethane acrylate or acrylic acrylate.

It is related with the said resin composition whose relative evaporation rate of a liquid medium (C) is 50-180.

Moreover, this invention relates to the coating sheet which has a resin layer formed from the said resin composition.

  By using the resin of the present invention in a composition for a coating agent, it is possible to provide an extremely excellent coating film that achieves both high weather resistance and high antifouling properties.

In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy” are particularly expressed, Unless otherwise stated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, and “acryloyloxy and / or methacryloyloxy”, respectively. ". The active energy ray-curable resin composition may be described as a resin composition.

<Resin (A)>
The resin (A) contains a structural unit containing polysiloxane, a structural unit containing an epoxy group, and at least one ultraviolet absorbing structure selected from the group consisting of a benzotriazole group, a benzophenone group, and a triazine group. Resin. By including a structural unit having a polysiloxane structure in the resin skeleton, when an active energy ray-curable resin composition is applied to form a coating film, an ultraviolet absorber structure copolymerized on the surface of the coating film and When the polysiloxane structure is unevenly distributed, both the stain resistance and the weather resistance of the coating film can be achieved.
Further, since the structural unit having an epoxy group is present in the resin (A), at least selected from the group consisting of a hydrophilic epoxy group, a hydrophobic polysiloxane unit, a benzotriazole group, a benzophenone group, and a triazine group. Resin (A) containing a polysiloxane unit is likely to float on the outermost surface of the coating film after coating due to repulsion with one UV-absorbing structure due to the hydrophilic-hydrophobic interaction. More improved.

Examples of the monomer containing an epoxy group used for constituting the resin (A) include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, α-n-propyl (meth) acrylic acid. Glycidyl, glycidyl α-n-butyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-3,4- Epoxy butyl, (meth) acrylic acid-6,7-epoxypentyl, α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4 -Epoxycyclohexyl, lactone-modified (meth) acrylic acid-3,4-epoxycyclohexyl, vinylcyclohexene oxide, etc. Can be mentioned. These may be used alone or in combination of two or more. Preferably, it is a (meth) acrylate containing an epoxy group, and glycidyl (meth) acrylate is preferable from the viewpoint of availability.

  Due to the presence of the epoxy group-containing monomer, the resin (A) is unevenly distributed on the outermost surface of the coating film in the coated film, and the outermost surface of the coating film made of the resulting resin composition is resistant to contamination and weathering. Sex is imparted.

The epoxy group-containing monomer is desirably contained in an amount of 30 to 90% by weight, more preferably 50 to 80% by weight, and particularly preferably 60 to 75% by weight in 100% by weight of the monomer.
When the said preferable range is shown by the equivalent of an epoxy group, 150-500 are preferable, 180-300 are more preferable, 190-250 are especially preferable.

(Epoxy equivalent)
The epoxy equivalent is shown as “mass of resin containing 1 equivalent of an epoxy group”, and was calculated from the following formula in this specification.
[Epoxy equivalent] = [Total charged monomer mass (g) + Initiator mass (g)] / [Mole number of monomer having epoxy group (mol)]

  The polysiloxane mono (meth) acrylate used for constituting the resin (A) is not particularly limited as long as it has one (meth) acryloyl group and an organopolysiloxane unit in one molecule. However, the compound represented by the following general formula (1) is preferable in terms of availability, production cost, and performance.

General formula (3)

(In General Formula (3), R ⁷ is a hydrogen atom or a methyl group, R ^{8 to} R ¹¹ are each independently an alkyl group having 1 to 4 carbon atoms, and R ¹² is an alkyl group having 1 to 4 carbon atoms. An alkyl group, a hydroxyl group, an alkoxy group, or a hydrogen atom, L ¹ is a substituted or unsubstituted linear alkylene group, branched alkylene group, cycloalkylene group, or arylene group, and n is 1 to 300. (It is an integer.)

As the alkyl group having 1 to 4 carbon atoms of R ^{8 to} R ¹¹ in the general formula (3), a methyl group, an ethyl group, a propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, an isobutyl group, or A secondary butyl group is mentioned.

Examples of the substituted or unsubstituted linear alkylene group, branched alkylene group, or cycloalkylene group represented by L ¹ in the general formula (3) include a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, and a tetramethylene group. , Hexamethylene group, octamethylene, 1,2-cyclohexene group, 1,3-cyclohexene group, 1,4-cyclohexene group, 2-methylpropene group and the like.

Examples of the substituted or unsubstituted arylene group as L ¹ in the general formula (3) include a phenylene group, a nonylphenylene group, and a paracumylphenylene group.

Due to the presence of the polysiloxane mono (meth) acrylate, the surface of the resulting resin composition coating film is imparted with stain resistance and repeated stain resistance.

In the polysiloxane mono (meth) acrylate represented by the general formula (3), a preferable range of n is n = 5 to 200, preferably n = 5 to 170, and more preferably n = 30 to 100. It is. Within the above range, the stain resistance is excellent.

As polysiloxane mono (meth) acrylate represented by the general formula (3), trade names “X-22-174DX” (manufactured by Shin-Etsu Silicone) “X-22-2426” (manufactured by Shin-Etsu Silicone), trade names “ X-22-174ASX "(manufactured by Shin-Etsu Silicone Co., Ltd.), trade name" Silaplane FM-0721 "(manufactured by JNC Corporation), trade name" Silaplane FM-0711 "(manufactured by JNC Corporation), commodity It can be easily obtained under the name “Silaplane FM-0725” (manufactured by JNC Corporation). These monomers may be used alone or in combination.

The polysiloxane mono (meth) acrylate is preferably contained in an amount of 1 to 70% by weight, more preferably 3 to 50% by weight, and particularly preferably 5 to 30% by weight in 100% by weight of the monomer.

The ultraviolet absorbing structure (c) used for constituting the resin (A) is a structure selected from at least one selected from the group consisting of a benzotriazole group, a benzophenone group, and a triazine group.

Specifically, in order to construct the resin (A), the ultraviolet absorbing structure (c) is introduced by the reaction of an epoxy group of (meth) acrylate containing an epoxy group copolymerized with the resin (A), and reaction. And an ethylenically unsaturated monomer having a UV-absorbing structure, or an addition reaction with a compound having a UV-absorbing structure (c) having a substituent. Preferably, it is a method of forming by an addition reaction between an epoxy group of (meth) acrylate containing an epoxy group copolymerized with resin (A) and a compound containing an ultraviolet absorbing structure (c) having a reactive substituent. is there.

As a preferable reason, a hydroxyl group is introduced between the main chain of the resin (A) and the ultraviolet absorbing structure (c) by forming a structure represented by the general formula (2) by an addition reaction. . Thereby, a hydrophilic substituent is introduced into the resin side chain, and hydrophilicity-hydrophobicity between the polysiloxane mono (meth) acrylate and the ultraviolet absorbing structure (c) which are the hydrophobic units constituting the resin (A). It is presumed that high antifouling properties and weather resistance can be achieved by the interaction between the hydrophobic components that are likely to be unevenly distributed at the air interface on the resurface of the coating film when the coating film is formed.

As a specific introduction method of the addition reaction between the epoxy group of (meth) acrylate containing an epoxy group copolymerized with the resin (A) and the piperidyl structure-containing compound having a reactive substituent, a resin (A ) Is a reaction of a compound having an ultraviolet-absorbing structure (c) having an amino group, a hydroxyl group, or an acid group with an epoxy substituent of (meth) acrylate containing an epoxy group copolymerized with (a). The details can be synthesized by the method described in Reference 1, and the conditions are not particularly limited. The addition reaction product thus obtained contains a structure represented by the general formula (2).

Reference 1
"Cross-linking reaction handbook by Masaharu Nakayama Maruzen Publishing"

General formula (2)

(In General Formula (2), R ⁵ represents H or a methyl group, A represents an alkyleneoxy group having 1 to 8 carbon atoms, — (— CH ₂ CH ₂ —O—) _m , —O—CH ₂ CH ( -OH) _-CH 2 -R ⁶ -, or _{-O-CH 2 CH (CH 2} OH) -R 6 - represents, m is an integer from 2 to 5, ^{R 5} is, -NH-, group or , -O-, and X is at least one ultraviolet absorbing structure (c) selected from the group consisting of a benzotriazole group, a benzophenone group, and a triazine group, or a piperidyl structure (d) represented by the general formula (1) ).)

Examples of the alkyleneoxy group having 1 to 8 carbon atoms of A in the general formula (2) include an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutene group, an oxypentene group, an oxyheptene group, and an oxyoctene group.

A reaction between the epoxy substituent of (meth) acrylate containing an epoxy group copolymerized with the resin (A) and a compound having an ultraviolet-absorbing structure (c) having an amino group or a hydroxyl group is preferred, and A is —O It is preferably —CH ₂ CH (—OH) —CH ₂ —R ⁶ — or —O—CH ₂ CH (CH ₂ OH) —R ⁶ —.

Specific examples of the compound having an ultraviolet-absorbing structure (c) having an amino group, a hydroxyl group, or an acid group include
2- [4,6-Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropyl] phenyl (manufactured by BASF TINUVIN 400 "), 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester There is no particular limitation as long as it is a compound containing an ultraviolet absorbing structure such as a product (“TINUVIN405” manufactured by BASF) and an amino group, a hydroxyl group, and an acid group.

More specifically, a polymerizable benzotriazole compound of the following general formula (4), a polymerizable benzotriazine compound of the following general formula (5), a polymerizable benzophenone compound of the following general formula (6), and the like can be given.

General formula (4)

(In General Formula (4), Z is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an alkoxyl group having 1 to 6 carbon atoms or a halogen atom, R ¹³ is a hydrogen atom, and 1 to 3 carbon atoms. 8 alkyl groups and cyclic alkyl groups, cumyl groups or alkoxy groups having 1 to 4 carbon atoms, R ¹⁴ represents a hydrogen atom or a methyl group, and B represents an alkyleneoxy group having 1 to 8 carbon atoms.)

Examples of the alkyl group having 1 to 6 carbon atoms of Z in the general formula (4) include methyl group, ethyl group, propyl group, isopropyl group, normal propyl group, tertiary butyl group, isobutyl group, secondary butyl group, and normal pentyl. Group, isopentyl group, neopentyl group, n-hexyl group, and isohexyl group.

The aryl group of Z in the general formula (4) means a monocyclic or polycyclic aryl group. In the case of a polycyclic aryl group, a group having a partially saturated ring in addition to a fully unsaturated ring is also included. . Specific examples include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, a tetralinyl group, and the like, and an aryl group having 6 to 10 carbon atoms is preferable.

Examples of the aralkyl group of Z in the general formula (4) include aralkyl groups having 7 to 10 carbon atoms such as benzyl group and phenethyl.

Specific examples of the alkoxyl group having 1 to 6 carbon atoms of Z in the general formula (4) include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t- And a butoxy group.

As the alkyl group having 1 to 8 carbon atoms of R ¹³ in the general formula (4), methyl group, ethyl group, propyl group, isopropyl group, normal propyl group, tertiary butyl group, isobutyl group, secondary butyl group, normal Examples include a pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, a heptyl group, and an octyl group.

The cyclic alkyl group represented by R ¹³ in the general formula (4) is a cycloalkyl group having 3 to 8 carbon atoms, and specifically includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Group, cyclooctyl group and the like.

The alkoxy group having 1 to 4 carbon atoms of R ¹³ in the general formula (4) has the same meaning as the alkoxy group having 1 to 6 carbon atoms described in Z in the general formula (4).

Examples of the alkyleneoxy group having 1 to 8 carbon atoms of B in the general formula (4) include an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutene group, an oxypentene group, an oxyheptene group, and an oxyoctene group.

General formula (5)

In the general formula (5), R ¹⁵ , R ¹⁶ and R ¹⁷ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms, and R ¹⁸ represents a hydrogen atom or a methyl group. , -E- alkyleneoxy group having 1 to 8 carbon _{atoms, - (- CH 2 CH 2} -O-) indicated by p-p is 2 to 5 _groups, -CH 2 CH (-OH) -CH _2- O-). )

The alkyl group having 1 to 6 carbon atoms of R ¹⁵ , R ¹⁶ and R ^{17 in} the general formula (5) has the same definition as the alkyl group having 1 to 6 carbon atoms in Z in the general formula (4).

The alkoxy group having 1 to 6 carbon atoms of R ¹⁵ , R ¹⁶ and R ^{17 in} the general formula (5) has the same meaning as the alkoxy group having 1 to 6 carbon atoms in the general formula (4).

The alkyleneoxy group having 1 to 8 carbon atoms in E in the general formula (5) has the same meaning as the alkyleneoxy group having 1 to 8 carbon atoms in B in the general formula (4).

General formula (6)

(In General Formula (6), R ¹⁹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms, R ²⁰ is a hydrogen atom or a methyl group, and -F- is 1 carbon atom. An alkyleneoxy group of ˜8, a group represented by — (CH ₂ CH ₂ —O—) r—, wherein r is 2 to 5, and —CH ₂ CH (—OH) —CH ₂ O) —. )

The alkyl group having 1 to 6 carbon atoms of —R ¹⁹ in the general formula (6) has the same meaning as the alkyl group having 1 to 6 carbon atoms of Z in the general formula (4).

The alkoxy group having 1 to 6 carbon atoms of —R ¹⁹ in the general formula (6) has the same meaning as the alkoxy group having 1 to 6 carbon atoms of Z in the general formula (4).

The alkyleneoxy group having 1 to 8 carbon atoms in F in the general formula (6) has the same meaning as the alkyleneoxy group having 1 to 8 carbon atoms in F in the general formula (4).

  Specific examples of the polymerizable benzotriazole compound of the general formula (4) include, for example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′- Hydroxy-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyl Oxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-tert- Chill -5 '- (meth) acryloyloxyethyl phenyl) -5-chloro -2H- it can be mentioned benzotriazole.

  Specific examples of the polymerizable triazine compound of the general formula (5) include 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -s-triazine, 2,4 -Bis (2-methylphenyl) -6- [2-hydroxy-4- (3-acryloyloxy-2-hydroxypropyloxy) phenyl] -s-triazine, 2,4-bis (2-methoxyphenyl) -6 -[2-Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -s-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) Phenyl] -s-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl Enyl] -s-triazine, 2,4-diphenyl-6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -s-triazine, 2,4-bis (2-methylphenyl) -6 And [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -s-triazine.

  Specific examples of the polymerizable benzophenone compound of the general formula (6) include 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4- (2-acryloyloxy) ethoxybenzophenone. 2-hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methyl-2-acryloyloxy) ethoxybenzophenone, and the like.

  Any of these UV-absorbing group-containing unsaturated monomers may be used alone, or two or more of them may be used in combination.

The compound having the ultraviolet absorbing structure (c) is preferably contained in an amount of 1 to 5% by weight, more preferably 1 to 3% by weight, based on the solid content in the resin (A). .

The resin (A) can further contain a piperidyl structure (d) represented by the general formula (1).

General formula (1)

(In General Formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. ⁴ and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R ² and R ³ each independently represents a methyl group, an ethyl group, or a phenyl group, and “*” represents a bond.)

In the general formula (1), examples of the alkyl group having 1 to 18 carbon atoms of R ¹ and R ⁴ include linear, branched, and cyclic alkyl groups. Group, normal propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like.

In the general formula (1), examples of the aryl group having 6 to 20 carbon atoms of R ¹ and R ⁴ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

In the general formula (1), examples of the aralkyl group having 7 to 12 carbon atoms of R ¹ and R ⁴ include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specific examples include benzyl group, phenethyl group, α-methylbenzyl group, 2-phenylpropan-2-yl group and the like.

In the general formula (1), examples of the acyl group of R ¹ and R ⁴ include alkanoyl groups having 2 to 8 carbon atoms and aroyl groups, and specific examples include acetyl groups and benzoyl groups. I can do it.
In the present invention, R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an oxy radical group, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

As a method for introducing the piperidyl structure (d) represented by the general formula (1) to specifically configure the resin (A), an epoxy group copolymerized with the resin (A) is contained (meth). Forming by an addition reaction between an epoxy group of acrylate and a piperidyl structure-containing compound having a reactive substituent, or an ethylenically unsaturated monomer having a piperidine skeleton represented by the general formula (1) It is done. Preferably, it is a method of forming by an addition reaction between an epoxy group of (meth) acrylate containing an epoxy group copolymerized with the resin (A) and a piperidyl structure-containing compound having a reactive substituent.

The reason why it is preferable and the specific introduction method of the addition reaction are the same as those described for the ultraviolet absorbing structure.

Reaction of the epoxy substituent of (meth) acrylate containing an epoxy group copolymerized with the resin (A) and a compound having an amino group or a piperidyl structure having a hydroxyl group is preferred, and A represents —O—CH ₂ CH ( -OH) _-CH 2 -R ⁶ -, or _{-O-CH 2 CH (CH 2} OH) -R 6 - is preferably.

Specific examples of the compound having an amino group, a hydroxyl group, or an acid group and having a piperidyl structure include 4-amino-1,2,2,6,6, -pentamethylpiperidine, 4-hydroxy-1,2,2, 6,6, -Pentamethylpiperidine is preferred.

The ethylenically unsaturated monomer having a piperidine skeleton represented by the general formula (1) is preferably contained in an amount of 1 to 5% by weight based on the solid content in the resin (A), and further 1% by weight. It is preferable to contain 3 to 3 weight%.

Specific examples of the ethylenically unsaturated monomer having a piperidyl skeleton are preferably 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate. 2,2,6,6-pentamethylpiperidyl methacrylate.

  From the group consisting of (meth) acrylate (a), polysiloxane (meth) acrylate (b) containing an epoxy group, and benzotriazole group, benzophenone group, and triazine group, which are used for constituting the resin (A) From the viewpoint of compatibility with at least one selected UV-absorbing structure (c), another monomer can be added as a constituent monomer of the resin (A) in order to increase the compatibility.

In preparing the resin (A), other monomers that can be used are not particularly limited as long as they are polysiloxane mono (meth) acrylate and (meth) acrylate capable of radical polymerization with an epoxy group-containing monomer. It can select suitably according to a use. For example,

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, octyl ( (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl Linear or branched alkyl (meth) acrylates such as (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;

Cyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate Or (meth) acrylates having a heterocyclic ring such as 3-methyl-3-oxetanyl (meth) acrylate;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;

2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or (Meth) acrylates having a hydroxyl group such as caprolactone adducts of these monomers (immol number is 1 to 5);

Methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, Phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol mono (meth) acrylate, Nonylphenoxy polypropylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol polypro Lenglycol mono (meth) acrylate, phenoxypolyethyleneglycol mono (meth) acrylate, methoxypolyethyleneglycol (meth) acrylate, n-butoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, 2-methoxyethyl (meth) (Meth) acrylates having an ether group such as acrylate and 2-ethoxyethyl (meth) acrylate;

3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-hexyloxetane (Meth) acrylates having;
Alternatively, a mixture thereof can be mentioned.

The other polymerizable monomer is selected from the group consisting of (meth) acrylate (a) having an epoxy group, polysiloxane mono (meth) acrylate (b), and benzotriazole group, benzophenone group, and triazine group. Alkyl (meth) acrylates are preferred from the viewpoints of polymerizability with at least one ultraviolet-absorbing structure (c) and compatibility between the monomers.

Alkyl (meth) acrylates are not particularly limited, but linear alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) Acrylate is preferred.

As the branched alkyl (meth) acrylates, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isostearyl (meth) acrylate are preferable.

In addition to the above, other polymerizable monomers can also be used. As a polymerizable monomer,
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
N-substituted types such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ) Acrylamides;
Nitriles such as (meth) acrylonitrile;

Vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Etc.

These monomers are desirably contained in an amount of 10 to 50% by weight, more preferably 10 to 30% by weight, and particularly preferably 10 to 20% by weight in 100% by weight of the monomer.

  The weight average molecular weight (polystyrene conversion) of the resin (A) is preferably 10,000 to 100,000, and more preferably 10,000 to 30,000. In this specification, the weight average molecular weight indicates a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The resin (A) can be synthesized by a known method, for example, solution polymerization. Solvents used during polymerization include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyls such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether, aromatics such as benzene, toluene, xylene, and cumene, and acetic acid. Esters such as ethyl and butyl acetate can be used. Two or more solvents may be mixed and used, but from the viewpoint of expressing the function of the outermost surface of the coating, it is possible to use normal butyl acetate and methyl isobutyl ketone shown in the liquid medium (C) described later. preferable.

  As a polymerization initiator at the time of synthesizing the resin (A), an ordinary peroxide or an azo compound, for example, benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butyl peroxide, t -Butyl perbenzoate, t-butyl peroctoate, cumene hydroxy peroxide and the like are used, and the polymerization temperature is preferably 50 to 140 ° C, more preferably 70 to 140 ° C.

<Active energy ray-curable compound (B)>
The active energy ray-curable compound (B) is a compound having a radical reactive unsaturated group in the compound and polymerized by irradiation with active energy rays. The active energy ray-curable compound in the present invention means a compound having at least one skeleton capable of radical polymerization in the molecule. These have chemical forms of liquid or solid monomers, oligomers or polymers at normal temperature and pressure.

C = C bond equivalent is a measure of the amount of double bonds contained in the molecule. If the compounds have the same molecular weight, the smaller the C = C bond equivalent value, the more the amount of double bonds introduced. Become more.
The C = C bond equivalent was calculated by the following formula.
[C = C bond equivalent] = [molecular weight of active energy ray curable compound] / [number of functional groups of active energy ray curable compound]

Examples of such active energy ray-curable compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, acid amides, acid anhydrides. In addition, urethane (meth) acrylate, epoxy (meth) acrylate, acrylic (meth) acrylate, ester (meth) acrylate acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides , Unsaturated polyurethane and the like, but are not limited thereto. Below, the specific example of the active energy ray hardening compound in this invention is given.

The active energy ray-curable compound (B) is not particularly limited, but includes epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, and the like. Among them, acrylic (meth) acrylate and urethane (meth) acrylate are preferable, and polyfunctional (meth) acrylate and polyfunctional urethane (meth) acrylate are more preferable.

As a particularly preferred active energy ray-curable compound (B), the C = C bond equivalent is 550 or less, or the active energy ray-curable compound (B) has a C = C functional group number of 4 or more (meth). Preferred are acrylates and tetrafunctional or higher urethane (meth) acrylates.

Specific examples of the active energy ray-curable compound (B) in the present invention are given below.

Examples of acrylates:
Examples of monofunctional acrylates:
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, benzyl acrylate. 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3 -Tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO addition acrylate, 2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate , Butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol Acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, p-nonylphenoxyethyl acrylate, p-nonylphenoxy polyethylene glycol Chryrate, glycidyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone Modified-2-acryloyloxyethyl acid phosphate, 2-hydroxy-1-acryloxy-3-methacryloxypropane.

Examples of bifunctional acrylates:
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 Diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neo Pentyl glycol diacrylate, ne Pentyl glycol PO-modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO Hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromobisphenol A diacrylate, tricyclodecane dimethylol Diacrylate, isocyanuric acid EO-modified diacrylate, 2-hydroxy-1,3-diacryloxypropane.

Examples of trifunctional acrylates:
Glycerin PO modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane PO modified triacrylate, isocyanuric acid EO modified triacrylate, isocyanuric acid EO modified ε-caprolactone modified triacrylate, 1,3 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetrafunctional or higher acrylates:
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate.

Examples of methacrylates:
Examples of monofunctional methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, -Hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoro Isopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl Methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate, 2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate Methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, methacrylic acid-2- (vinyloxyethoxy) ethyl, ethoxydiethylene glycol methacrylate, 2 -Ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, cresyl polyethylene glycol methacrylate, p-nonylphenoxyethyl methacrylate, p-nonylphenoxy polyethylene Glycol methacrylate, glycidyl methacrylate, dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyl Oxyethyl acid phosphate, caprolactone-modified-2-methacryloyloxyethyl acid phosphate, etc.

Examples of bifunctional methacrylates:
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopenty Glycol dimethacrylate, neopentyl glycol PO-modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct dimethacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3- (Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane , Bisphenol A dimethacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate, PO modified bisphenol F dimethacrylate, EO modified Tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane.

Examples of trifunctional methacrylates:
Glycerin PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate.

Examples of arylates:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

Examples of acid amides:
Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

Examples of styrenes:
Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene 2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds:
Vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone etc.

Said radically polymerizable compound can be easily obtained as a commercial product of the manufacturer shown below. For example, `` Light acrylate '', `` Light ester '', `` Epoxy ester '', `` Urethane acrylate '' and `` Highly functional oligomer '' series manufactured by Kyoeisha Yushi Chemical Co., Ltd., Shin Nakamura Chemical Co., Ltd. "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Co., Ltd., manufactured by Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. “Kayarad” and “Kayamar” series manufactured by Nippon Kayaku Co., Ltd. “Acrylic acid / methacrylic acid ester monomer” series manufactured by Nippon Shokubai Co., Ltd., Nippon Synthetic Chemical Industry Made in "Nichigo-UV Shiko urethane acrylate oligomer" series, Shin-Etsu vinyl acetate Co., Ltd. "carboxylic vinyl ester monomers" series include Co. Kohjin Co. "functional monomer" series, and the like.

Moreover, the cyclic compound shown below is also mentioned as a radically polymerizable compound.
Examples of three-membered ring compounds:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Vol. 17, 3169 (1979), vinylcyclopropanes, Macromolecular Chemie Rapid Communication (Makromol. Chem. Rapid Commun.), Volume 5, p. 63 (1984), 1-phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition ( J. Polym. Sci. Polym. Chem. Ed.), 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed. 21), 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 (1985) Mounting No 2,3-vinyl oxirane.

Examples of cyclic ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Volume 20, p. 3021 (1982) and Journal of Polymer Science Polymer Letter Edition (J.Polym.Sci.Polym.Lett.Ed.), Vol. 21, 373 (1983), 2-methylene-1,3-dioxepane, polymer pre-prints (Polym. Preprints), No. 34, 152 (1985), dioxolanes, Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), 20, 361 (1982) 2) described in Macromolecular Chemie, 183, 1913 (1982) and Macromolecular Chem., 186, 1543 (1985). -Methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, polymer described in Macromolecules, Vol. 15, page 1711 (1982) -5,6-benzo-2-methylene-1,3-diosepane described in Polypre. Preprints, Vol. 34, page 154 (1985).

Furthermore, the polymeric compound (B) can also mention the thing as described in the literature shown below. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyoto Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Association, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

Only one kind of active energy ray-curable compound (B) may be used, or a mixture of two or more kinds in any ratio may be used in order to improve desired properties.

As the active energy ray-curable compound (B), in addition to the above monomers, those called oligomers and prepolymers can be used. Specifically, “Ebecryl 230, 244, 245, 270, 280 / 15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, 294 / 35HD, manufactured by Daicel UCB, 1259, 1264, 4866, 9260, 8210, 1290.1290K, 5129, 2000, 2001, 2002, 2100, KRM7222, KRM7735, 4842, 210, 215, 4827, 4849, 6700, 6700-20T, 204, 205, 6602, 220, 4450, 770, IRR567, 81, 84, 83, 80, 657, 800, 805, 808, 810, 812, 1657, 1810, IRR302, 450, 670, 830, 835, 870, 1 30, 1870, 2870, IRR267, 813, IRR483, 811, 436, 438, 446, 505, 524, 525, 554W, 584, 586, 745, 767, 1701, 1755, 740 / 40TP, 600, 601, 604, 605, 607, 608, 609, 600 / 25TO, 616, 645, 648, 860, 1606, 1608, 1629, 1940, 2958, 2959, 3200, 3201, 3404, 3411, 3412, 3415, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3703, 3702, RDX63182, 6040, IRR419 ", manufactured by Sartomer CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN971, CN972, CN9782, CN981, CN9873, CN991, "Laromar EA81L, F87" manufactured by BASF LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, LR8967, LR8981, LR8982, LR8992, LR9004, LR8956, LR8985, LR8987, UP35D, UA19T, LR9005, PO83F, PO33F, L8489, L9489 LR8996, LR9013 LR9019, PO9026V, PE9027V "manufactured by Cognis" Photomer 3005, 3015, 3016, 3072, 3982, 3215, 5010, 5429, 5430, 5432, 5662, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6572, 3660 "," Art Resin UN-9000HP, 9000PEP, 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T, manufactured by Negami Kogyo Co., Ltd. "1200TPK, 6060PTM, 6060P", "Nippon Gosei Co., Ltd." "purple light UV-6630B, 7000B, 7510B, 7461TE, 3000B, 3200" B, 3210EA, 3310B, 3500BA, 3520TL, 3700B, 6100B, 6640B, 1400B, 1700B, 6300B, 7550B, 7605B, 7610B, 7620EA, 7630B, 7640B, 2000B, 2010B, 2250EA, 2750B, “Kayarad” R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, C-0011, TCR-1234, ZFR-1122, UX-2201, UX-2301, UX3204, UX-3301, UX-4101, UX-6101, UX-7101, MAX-5101, MAX-5100, MAX-3510, UX-4101 "and the like.

Examples of acrylic (meth) acrylates:
“Orestar RA3055, OlesterRA3050, OlesterRA3081, OlesterRA3091, OlesterRA5000, OlesterRA3030, OlesterRA5000” manufactured by Mitsui Chemicals, Inc. (“Miramer SC9050” manufactured by MIWON, etc.) .

Examples of urethane (meth) acrylates:
“Ebecryl 220, 4500, 4200, 4666, 8210, 8405, 1290, 5129, 8254, 8301R, KRM8200, 8452” manufactured by Daicel UCB, “purple light 1700B, 6300B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B "," KAYARAD DPHA-40H, UX-5000, UX-5102D-M20, UX-5103D, UX-5005 "manufactured by Nippon Kayaku Co., Ltd." Art Resins UN-3320HA, 3320HC, 3320HS, 904 "manufactured by Negami Kogyo Co., Ltd. , 906S, 901T, 905, 952 ”,“ U-6LPA, U-10HA, U-10PA, UA-1100H, U-15HA ”manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

  Only one kind of active energy ray-curable compound (B) may be used, or a mixture of two or more kinds in any ratio may be used in order to improve desired properties.

<Liquid medium (C)>
The liquid medium (C) is preferably an organic solvent, and is used by blending it in the energy ray curable composition from the viewpoints of dispersion stability, adhesion to the substrate, smoothness of the coating, uniformity, and the like. .

The organic solvent used in the liquid medium (C) is preferably an organic solvent having a relative evaporation rate of 50 to 180 when n-butyl acetate is 100, more preferably 80 to 160, and 100 to 150. Further preferred.

  When the relative evaporation rate is 50 or more, the resin (A) is likely to float on the surface of the coating film, so that the amount of polysiloxane on the outermost surface is increased and contamination resistance and weather resistance are easily developed. Further, when the relative evaporation rate is 180 or less, the resin (A) is present on the outermost surface before the composition is thickened, and the stain resistance is easily exhibited.

The relative evaporation rate is an evaporation rate measured according to ASTM-D3539, and is a numerical value represented by the following formula (1). Specifically, it is defined as the value of the ratio between the evaporation time of n-butyl acetate and the evaporation time of each solvent at 25 ° C. in dry air.
Relative evaporation rate = (time required for normal butyl acetate to evaporate) / (time required for each solvent to evaporate) × 100 (1)

Examples of the solvent having a relative evaporation rate of 50 to 180 include alcohols such as normal propanol, isopropyl alcohol, 2-heptanol, and 3-heptanol, normal butyl acetate, isobutyl acetate, and esters such as propyl propionate, 2 A combination of one or two or more nonpolar solvents such as hexanone, 3-hexanone, and ketones such as methyl isobutyl ketone, toluene, and 1,4-dioxane may be used.

  The liquid medium (C) includes the liquid medium contained in the product of the organic solvent and active energy ray-curable compound used in the synthesis of the resin (A), but the relative evaporation in the total amount of the liquid medium (C). The speed may be within the above range.

In addition, the relative evaporation rates of various solvents can be obtained by software developed by Charles Hansen et al. (Software name: Hansen Solubility Parameter in Practice (HSPIP) Version 4.1.07). When combining two or more kinds of solvents, the relative evaporation rate of the mixed solvent can be approximately determined by the following formula.
Formula [Relative evaporation rate of the two mixed solvents] = [Relative evaporation rate of the liquid medium a] × [Ratio of the liquid medium a in the total liquid medium (volume%)] + [Relative evaporation rate of the liquid medium b] × [Ratio (volume%) of the liquid medium b in the total liquid medium]

<Resin composition>
Next, the manufacturing method of a resin composition (active energy ray curable composition) is demonstrated.
The production method is not particularly limited, but the resin (A) and the active energy ray-curable compound (B) are mixed in a part of the liquid medium (C), and after stirring, the liquid medium (C) is further added, It is preferred to dilute.

  The viscosity of the resin composition is a value measured using a rotary viscometer under the condition of 25 ° C., and can be measured according to JIS Z 8803 (2011). As the rotary viscometer, measurement with a B-type viscometer, an E-type viscometer, and an EMS viscometer is preferable.

The measurement condition of the viscosity of the resin composition of the present application is a value measured under the condition of 25 ° C. Examples include a rheometer that calculates the viscosity from the proportional coefficient between the shear rate and the shear stress, and an EMS viscometer that calculates the viscosity from the rotation speed of the metal sphere in the sample solution.

The measured viscosity of the resin composition is preferably 80 mPa · s or less. When the viscosity is higher than 80 mPa · s, the mobility of the resin (A) is lowered when the resin composition is formed into a coating film, and the resin (A) is less likely to float on the outermost surface of the coating film after coating. For this reason, the proportion of polysiloxane on the outermost surface is reduced, so that the stain resistance is not exhibited. 3 to 70 mPa · s is more preferable, and 3 to 50 mPa · s is still more preferable.

The active energy ray-curable compound (B) is preferably used in an amount of 20 to 95% by weight based on the total amount of solids in the resin composition. If it is less than 20% by weight, the physical properties of the film are deteriorated.

As a ratio of the resin (A) and the active energy ray-curable compound (B), a weight ratio of 1: 3 to 1: 100 is preferable. When the amount of the resin (A) is insufficient, satisfactory stain resistance and repeated stain resistance are not expressed, and when the amount of the resin (A) is large, it causes cissing at the time of coating and it causes the cured skin to be distorted. There is.

As the active energy ray used for curing the resin composition, any of ultraviolet rays, electron beams and the like may be used, for example. When the resin composition is cured with an electron beam or the like, a photopolymerization initiator is not required, but when cured with ultraviolet rays, the photopolymerization initiator is usually 1 to 15 weights per 100 parts by weight of the resin composition. About parts can be contained. As the photopolymerization initiator, various known types such as Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 754 (all manufactured by Ciba Specialty Chemicals), Esacure ONE (Lamberti), benzophenone, and the like. Can be used.

As an ultraviolet ray generation source, an ultraviolet lamp is generally used in terms of practicality and economy, and specific examples include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a metal halide lamp. In the case of an electron beam, the irradiation atmosphere must be in an inert gas such as nitrogen, but in the case of ultraviolet light, the atmosphere may be air or an inert gas such as nitrogen or argon.

<Coating sheet>
If the coating sheet of this invention has a base material and the resin layer (cured film) is formed using the photosensitive composition of this invention, there will be no restriction | limiting in particular.

  The resin composition of the present invention is provided as an antifouling hard coat sheet by applying it to a substrate sheet and curing it. Examples of the base sheet include transparent resin films such as polyethylene terephthalate and polycarbonate. The base sheet may be colored or uncolored. The thickness of the base sheet is preferably about 25 to 200 μm.

  Further, in the resin composition of the present invention, if necessary, a light stabilizer, an ultraviolet absorber, a catalyst, a colorant, an antistatic agent, a lubricant, a leveling agent, an antifoaming agent, a polymerization accelerator, an antioxidant, It is optional to include additional components such as a flame retardant, an infrared absorber, a surfactant, and a surface modifier.

  In order to apply the resin composition of the present invention to a substrate, methods such as brush coating, spray coating, dip coating, spin coating, and curtain coating are used. As a coating amount of the radiation curable composition, the film thickness of the cured film is 3 to 10 μm, preferably 5 to 25 μm, particularly preferably 8 to 20 μm. If the film thickness of the cured film is less than 3 μm, sufficient wear resistance cannot be obtained, and if it exceeds 30 μm, the adhesion to the substrate is lowered or cracks are likely to occur in the film.

The Si element density | concentration of the outermost surface of the coating sheet which consists of a resin composition of this application is measured on condition of the following by K-Alpha + (made by Thermo Scientific) by X-ray photoelectron spectroscopy.
X-ray source: Monochrome (Al)
X-ray irradiation range: 400 μm × 250 μm (ellipse)
Measurement elements: Si, C, O, N

The ratio of Si element on the outermost surface of the coating film was calculated by the following formula.
[Surface Si element concentration] = [Si peak area] / [total sum of Si, C, N, and O peak areas] × 100
It is preferable that Si element density | concentration of the outermost surface of a cured film is the range of 8.0-13.5, and it is excellent in stain resistance and a weather resistance. More preferably, it is 9.0-13.0.

  In the examples, the term “parts” means parts by mass.

<Synthesis of copolymer (A-1)>
15 parts of one-end methacryloxy group-containing polysiloxane compound ("Syla Plain FM-0721" manufactured by JNC), 67 parts of glycidyl methacrylate, 15 parts of methyl methacrylate, 200 parts of methyl isobutyl ketone (MIBK), cooling tube, stirring device, thermometer Was added to a four-necked flask equipped with a nitrogen gas stream, heated to 90 ° C. with stirring under a nitrogen stream, added with 3 parts of azobisisobutyronitrile and subjected to a polymerization reaction for 2 hours. Further, azobisisobutyronitrile 1 Polymerization was carried out for 2 hours by adding a portion. Then 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropyl] in the flask 3 parts of phenyl (“TINUVIN400” manufactured by BASF) and 0.1 part of t-butoxypotassium were added, and the reaction was performed at 60 ° C. for 5 hours. The resulting copolymer A-1 had a weight average molecular weight of about 13,000.

<Synthesis of copolymer (A-2)>
15 parts of one-terminal methacryloxy group-containing polysiloxane compound ("Syla Plain FM-0721" manufactured by JNC), 65 parts of glycidyl methacrylate, 15 parts of butyl methacrylate, 200 parts of methyl isobutyl ketone (MIBK), cooling tube, stirring device, thermometer Was added to a four-necked flask equipped with a nitrogen gas stream, heated to 90 ° C. with stirring under a nitrogen stream, added with 3 parts of azobisisobutyronitrile and subjected to a polymerization reaction for 2 hours. Further, azobisisobutyronitrile 1 Polymerization was carried out for 2 hours by adding a portion. In the flask, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and oxirane {especially [(C10-C16, Reaction product (mainly C12-C13 alkyloxy) methyl] oxirane} (“TINUVIN 400” manufactured by BASF), 2 parts 4-amino-1,2,2,6,6-pentamethylpiperidine, And 0.1 part of t-butoxypotassium were added and reacted at 60 ° C. for 5 hours. The weight average molecular weight of the obtained copolymer A-2 was about 13,000.

<Synthesis of copolymer (A-3)>
One-terminal methacryloxy group-containing polysiloxane compound ("Cylaplane FM-0721" manufactured by JNC) 15 parts, 67 parts of glycidyl methacrylate, 15 parts of butyl methacrylate, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl ] Phenyl] -2H-benzotriazole ("RUVA-93" manufactured by Otsuka Chemical Co., Ltd.) 3 parts and 200 parts of methyl isobutyl ketone (MIBK) were charged into a four-necked flask equipped with a condenser, a stirrer, and a thermometer, and nitrogen While stirring under an air stream, the temperature was raised to 90 ° C., 3 parts of azobisisobutyronitrile was added to conduct a polymerization reaction for 2 hours, and 1 part of azobisisobutyronitrile was further added to carry out the polymerization for 2 hours. The weight average molecular weight of the obtained copolymer A-3 was about 15,000.

<Synthesis of copolymer (A-4)>
15 parts of polysiloxane compound containing one-end methacryloxy group ("Syla Plain FM-0721" manufactured by JNC), 65 parts of glycidyl methacrylate, 15 parts of methyl methacrylate, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl ] Phenyl] -2H-benzotriazole ("RUVA-93" manufactured by Otsuka Chemical Co., Ltd.) 3 parts, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate ("LA-82" manufactured by ADEKA) 2 parts , 200 parts of methyl isobutyl ketone (MIBK) was charged into a four-necked flask equipped with a condenser, a stirrer, and a thermometer, heated to 90 ° C. with stirring under a nitrogen stream, and 3 parts of azobisisobutyronitrile. Was added to carry out the polymerization reaction for 2 hours, and 1 part of azobisisobutyronitrile was further added to carry out the polymerization for 2 hours. The weight average molecular weight of the obtained copolymer A-4 was about 16,500.

<Synthesis of copolymer (A-5)>
One-terminal methacryloxy group-containing polysiloxane compound ("Syla Plain FM-0721" manufactured by JNC) 30 parts, glycidyl methacrylate 50 parts, methyl methacrylate 15 parts, methyl isobutyl ketone (MIBK) 200 parts are cooled, stirrer, thermometer Was added to a four-necked flask equipped with a nitrogen gas stream, heated to 90 ° C. with stirring under a nitrogen stream, added with 3 parts of azobisisobutyronitrile and subjected to a polymerization reaction for 2 hours. Further, azobisisobutyronitrile 1 Polymerization was carried out for 2 hours by adding a portion. Reaction reaction of 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester in the flask 3 parts of a product (“TINUVIN405” manufactured by BASF), 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 0.1 part of t-butoxy potassium were added at 60 ° C. The reaction was performed for 5 hours. The weight average molecular weight of the obtained copolymer A-5 was about 13,000.

<Synthesis of copolymer (A-6)>
One-end methacryloxy group-containing polysiloxane compound ("Syla Plain FM-0721" manufactured by JNC) 5 parts, 75 parts of glycidyl methacrylate, 15 parts of methyl methacrylate, 200 parts of methyl isobutyl ketone (MIBK), condenser, stirrer, thermometer Was added to a four-necked flask equipped with a nitrogen gas stream, heated to 90 ° C. with stirring under a nitrogen stream, added with 3 parts of azobisisobutyronitrile and subjected to a polymerization reaction for 2 hours. Further, azobisisobutyronitrile 1 Polymerization was carried out for 2 hours by adding a portion. In the flask, in the flask, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid 3 parts of an ester reaction product (“TINUVIN405” manufactured by BASF), 2 parts of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine and 0.1 part of t-butoxypotassium were added, Reaction was performed at 60 degreeC for 5 hours. The weight average molecular weight of the obtained copolymer A-6 was about 13,000.

<Synthesis of Resin (A-7)>
15 parts of one-terminal methacryloxy group-containing polysiloxane compound ("Syla Plain FM-0721" manufactured by JNC), 70 parts of glycidyl methacrylate, 15 parts of methyl methacrylate, 200 parts of methyl isobutyl ketone (MIBK), cooling tube, stirring device, thermometer Was added to a four-necked flask equipped with a nitrogen gas stream, heated to 90 ° C. with stirring under a nitrogen stream, added with 3 parts of azobisisobutyronitrile and subjected to a polymerization reaction for 2 hours. Further, azobisisobutyronitrile 1 Polymerization was carried out for 2 hours by adding a portion. The weight average molecular weight of Resin A-7 obtained was about 15,000.

<Synthesis of Resin (A-8)>
15 parts of one-terminal methacryloxy group-containing polysiloxane compound ("Syla Plain FM-0721" manufactured by JNC), 70 parts of glycidyl methacrylate, 15 parts of methyl methacrylate, 200 parts of methyl isobutyl ketone (MIBK), cooling tube, stirring device, thermometer Was added to a four-necked flask equipped with a nitrogen gas stream, heated to 90 ° C. with stirring under a nitrogen stream, added with 3 parts of azobisisobutyronitrile and subjected to a polymerization reaction for 2 hours. Further, azobisisobutyronitrile 1 Polymerization was carried out for 2 hours by adding a portion. Thereafter, the temperature was raised to 100 ° C., the inflowing gas was changed from nitrogen to air, 0.7 part of dimethylbenzylamine was added, 35 parts of acrylic acid was dropped in about 10 minutes, and the reaction was carried out for 10 hours after the dropping. The obtained resin A-8 had a weight average molecular weight of about 15,000.

<Synthesis of Resin (A-9)>
15 parts of one-terminal methacryloxy group-containing polysiloxane compound ("Syla Plain FM-0721" manufactured by JNC), 68 parts of glycidyl methacrylate, 15 parts of methyl methacrylate, 200 parts of methyl isobutyl ketone (MIBK), cooling tube, stirring device, thermometer Was added to a four-necked flask equipped with a nitrogen gas stream, heated to 90 ° C. with stirring under a nitrogen stream, added with 3 parts of azobisisobutyronitrile and subjected to a polymerization reaction for 2 hours. Further, azobisisobutyronitrile 1 Polymerization was carried out for 2 hours by adding a portion. In the flask, 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 0.1 part of t-butoxypotassium were added and reacted at 60 ° C. for 5 hours. The weight average molecular weight of Resin A-9 obtained was about 13,000.

Table 1 shows the composition of Resin A.

<Creation of resin composition>
Example 1
Using a mixer having a stirring blade, 3.1 parts of Esacure ONE (Lambarti) and 0.8 parts of Irgacure 907 (BASF) were added to 25 parts of a normal butyl acetate / isopropyl alcohol = 28/72 (weight ratio) solution. Dissolved. In the obtained solution, 44.8 parts of UV-6300B (manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate, C = C functional group number: 7, C = C bond equivalent: 530) as an energy ray curable compound (B). Dissolved. Thereafter, 1.3 parts of the resin (A-1) as a solid content was added and mixed by stirring. 24.0 parts of the mixed solution prepared in the normal butyl acetate / isopropyl alcohol = 28/72 solution was added to the obtained mixed solution and mixed by stirring to obtain a resin composition.

(Examples 2 to 6)
The resin (A-1) used in Example 1 was changed in the same manner as in Examples 2 to 6, except that the resin (A-2) to resin (A-6) were used. 2 to 6 resin compositions were prepared.

(Example 7)
In Example 1, the active energy resin (B) was changed from UV-6300B to Laromer DPHA (manufactured by BASF, acrylic acrylate, C = C functional group number: 6, C = C bond equivalent: 96). Thus, a resin composition was prepared.

(Example 8)
A resin composition was prepared in the same manner as in Example 1 except that the normal butyl acetate / isopropyl alcohol = 28/72 solution was changed to isopropyl alcohol.

Example 9
An active energy ray-curable compound composition was prepared in the same manner as in Example 1 except that the normal butyl acetate / isopropyl alcohol = 28/72 solution was changed to normal butyl acetate.

(Example 10)
An active energy resin composition was prepared in the same manner as in Example 1 except that UV-6300B was changed to UV-1700B (manufactured by Nippon Synthetic Chemical Co., Ltd.).

(Example 11)
An active energy ray-curable compound composition was prepared in the same manner as in Example 1 except that the normal butyl acetate / isopropyl alcohol = 28/72 solution was changed to methanol.

(Example 12)
An active energy ray-curable compound composition was prepared in the same manner as in Example 1 except that the normal butyl acetate / isopropyl alcohol = 28/72 solution was changed to 1-butanol.

(Example 13)
An active energy ray-curable compound composition was prepared in the same manner as in Example 1, except that the normal butyl acetate / isopropyl alcohol = 28/72 solution was changed to N, N-dimethylformamide.

(Example 14)
Using a mixer having a stirring blade, 4.0 parts of Esacure ONE (Lambarty) and 1.0 part of Irgacure 907 (BASF) were dissolved in 25 parts of a normal butyl acetate / isopropyl alcohol = 28/72 solution. In the obtained solution, 58.3 parts of UV-6300B (manufactured by Nippon Synthetic Chemical Co., Ltd.) was dissolved as the energy ray curable resin (B). Thereafter, 1.7 parts of the resin (A-1) was added as a solid content, and the mixture was stirred and mixed. To the obtained mixed solution, 8.7 parts of a mixed solution prepared in a normal butyl acetate / isopropyl alcohol = 28/72 solution was added and mixed by stirring to obtain a resin composition.

(Comparative Examples 1-3)
A resin composition was produced in the same manner as in Example 1, except that the resin (A-1) was changed to the resin (A-7) to the resin (A-9) in Comparative Examples 1 to 3, respectively.

<Viscosity measurement>
Measurement was performed with an EMS viscometer (manufactured by Kyoto Electronics Industry Co., Ltd.) under the measurement conditions of a measurement temperature of 25 ° C., a motor rotation speed of 1000 rpm, and a spherical probe Al of 2 mm.

<Creation of a coating sheet using a resin composition>
The active energy ray-curable compound composition prepared above was applied to a 100 μm thick corona-treated PET base material (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) with a bar coater # 8, and dried at 40 ° C. for 30 seconds. Then, active energy rays from a metal halide lamp were irradiated at 50 mJ / cm ² to obtain a coating sheet made of a resin composition.

The Si element concentration on the outermost surface of the sheet made of the coated product was measured by X-ray photoelectron spectroscopy using K • Alpha + (manufactured by Thermo Scientific) under the following conditions. The evaluation results are shown in Table 1.
X-ray source: Monochrome (Al)
X-ray irradiation range: 400 μm × 250 μm (ellipse)
Measurement elements: Si, C, O, N

The ratio of Si element on the outermost surface of the coating film was calculated by the following formula.
[Surface Si element concentration] = [Si peak area] / [total sum of Si, C, N, and O peak areas] × 100

Table 2 shows the composition of the resin composition, the viscosity of the resin composition, the stain resistance of the resin composition coating film evaluated by the following method, and the repeated stain resistance evaluation.

Abbreviations in Table 2 are shown below.
nBAc: normal butyl acetate IPA: isopropyl alcohol MeOH: methanol 1-BuOH: 1-butanol DMF: dimethylformamide

<Contamination resistance evaluation>
After writing with oil-based magic (Terani Chemical Co., Ltd. Magic Ink Black No. 500) on the coating surface of the resin composition coating, it was dried at room temperature for 30 seconds, and then wiped off with tissue paper. Evaluated.
Evaluation criteria ○: After wiping lightly with dry wipe, there is no remaining residue. ○ △: After wiping lightly with dry wipe, white paper is placed under the coated material. △ +: After lightly wiping with dry wipe △: The writing mark remains thin. △: Lightly wipes off with dry wiping, and the writing mark remains. X: After wiping off with dry wiping, the practical level that cannot be wiped off is ◯.

<Repetitive stain resistance evaluation>
Number of times the paint surface of the resin composition coating was wiped with tissue paper after writing with oil-based magic (Terani Chemical Co., Ltd. Magic Ink Black No. 500) and drying for 30 seconds at room temperature. It was evaluated with.
Evaluation criteria ◎: Number of wipes 15 or more ○: Number of wipes 10-14 times ○ △: Number of wipes 8-9 times Δ +: Number of wipes 6-7 times Δ: Wipe The number of removals is 3 to 5 times: The number of removals is 0 to 2 The practical level is Δ or more.

The weather resistance of the resin composition coating film was evaluated by the following method and shown in Table 3.

<Weather resistance evaluation>
About the sheet | seat which consists of the obtained coating material, the test according to JISA1415 is performed with the ultraviolet-carbon-arc type | formula weathering tester (made by Suga Test Instruments Co., Ltd.) of JIS B7751 regulation, and 1200 hours Table 2 shows the results of confirming the deterioration state after the lapse of the following test items.

[Gloss maintenance rate]

Using a gloss meter VG-7000 (Nippon Denshoku Industries Co., Ltd.), the 60-degree gloss value of the coating film was measured.
The gloss retention rate was determined by the following formula.

Gloss maintenance rate (%) = (Gloss value after accelerated test / Initial gloss value) × 100

(Evaluation criteria)
○: 95% or more Δ: 85% or more and less than 94% ×: less than 94%

[transparency]
Using a haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the change in turbidity (ΔHz) of the coating film was measured.
(Evaluation criteria)
○: ΔHz is less than 1 Δ: ΔHz is 1 or more and less than 3 ×: ΔHz is 3 or more

[Yellowing]
Using a color difference meter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the yellowing change (Δb * value) of the coating film was measured.

(Evaluation criteria)
◎: Δb is 1 or less ○: Δb is 1 or more and less than 3 Δ: Δb is 3 or more and less than 10 ×: Δb is 10 or more

[Residual film rate]
Kapton tape was applied to a part of the coating film or the cured film, and was peeled off after the acceleration test. Using the position protected by the tape as a reference, the step (μm) from the unprotected surface was measured using a film thickness meter F20-UV (manufactured by Filmetrics). The remaining film rate was determined by the following formula.

Residual film ratio (%) = {(initial film thickness−step difference) / initial film thickness} × 100

As described above, the initial film thickness was 10 μm in this example.

(Evaluation criteria)

◎: 98 or more ○: 94% or more and less than 98%

As described above, the results shown in Tables 2 and 3 show that the weather resistance of the obtained sheet is significantly lowered with the resin (A) not containing the ultraviolet absorbing structure (c) as shown in Comparative Example 1. It was done.
In Comparative Example 2, the resin A is a resin (A-8) obtained by reacting acrylic acid with a (meth) acrylate containing an epoxy group as a crosslinkable group, but the antifouling property is relatively high. Although good, gloss retention, transparency, and yellowing are inferior.
Furthermore, in Comparative Example 3, although the resin resin (A-9) contains the piperidyl structure (d) represented by the general formula (1), it is sufficient because it does not contain the ultraviolet absorbing structure (c). It has not yet shown weather resistance.
The coating film (Examples 1 to 14) obtained by crosslinking the composition using the resin (A) of the present invention was a coating film (Comparative Example 1) obtained by photocuring a composition using a resin having a structure outside the present invention. It became clear that the physical properties such as the antifouling property and various weather resistances, such as gloss maintenance rate, transparency, yellowing, and remaining film rate, are clearly superior to those of ˜3).

Claims (7)

A resin composition containing a resin (A), an active energy ray-curable compound (B), and a liquid medium (C),
The resin (A) has at least one ultraviolet absorbing property selected from the group consisting of a structural unit (a) containing an epoxy group, a structural unit (b) having a polysiloxane, and a benzotriazole group, a benzophenone group, and a triazine group. A resin composition, which is a resin (A) having a structure (c). Resin (A) contains the piperidyl structure (d) represented by General formula (1), The resin composition of Claim 1 characterized by the above-mentioned.
General formula (1)

(In General Formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. ⁴ and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R ² and R ³ each independently represents a methyl group, an ethyl group, or a phenyl group, and “*” represents a bond.) Resin (A) contains the structural unit represented by General formula (2), The resin composition of Claim 1 or 2 characterized by the above-mentioned.
General formula (2)

(In General Formula (2), R ⁵ represents H or CH ₃ , A represents an alkyleneoxy group having 1 to 8 carbon atoms, — (CH ₂ CH ₂ —O—) _m —, —O—CH ₂ CH ( -OH) _-CH 2 -R ⁶ -, or _{-O-CH 2 CH (CH 2} OH) -R 6 - represents, m is an integer from 2 to 5, ^{R 6} are, -NH- or - X is a piperidyl structure (d) represented by at least one ultraviolet absorbing structure (c) or general formula (1) selected from the group consisting of a benzotriazole group, a benzophenone group, and a triazine group .) A in the general formula (2) is —O—CH ₂ CH (—OH) —CH ₂ —R ⁶ — or —O—CH ₂ CH (CH ₂ OH) —R ⁶ —. The resin composition according to claim 3. The resin composition according to any one of claims 1 to 4, wherein the active energy ray-curable compound (B) is urethane acrylate or acrylic acrylate. The resin composition according to any one of claims 1 to 5, wherein a relative evaporation rate of the liquid medium (C) is 50 to 180. The coating sheet which has a base material and the resin layer formed from the resin composition in any one of Claims 1-6.