JP2013023548A - Photocurable resin composition, wet area member and functional panel using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition capable of improving performance such as water repellency and slippage over a long term.SOLUTION: The photocurable resin composition includes: a dimethyl silicone (meth)acrylate oligomer (A) obtained by using at least a specific silicone polyol (a) and a (meth)acrylate monomer (b) having a functional group, which can react with a hydroxyl group, at the end; a photopolymerizable oligomer (B) and/or a photopolymerizable monomer (C) copolymerizable with the dimethyl silicone (meth)acrylate oligomer (A); a fluorine-containing compound (D); and a photoinitiator (E).

Description

  The present invention relates to a photocurable resin composition, a water-surrounding member using the same, and a functional panel, and in particular, to improve slipperiness (slidability capable of easily removing water droplets on the surface). The present invention relates to a possible photocurable resin composition, and a water-surrounding member and a functional panel using the same.

  Functional panels as building materials are members that are arranged as the wall surface, floor surface, or ceiling wall surface of a building. Depending on the location, various functions such as soundproofing and humidity control are provided. Has been. Such functional panels are required to have various characteristics such as water repellency and slipperiness that can withstand more severe use environments, particularly when used as a water component in a bathroom, washroom or kitchen in a house. It is done.

  In contrast, by blending a low surface free energy compound with a low surface free energy, a composition having a reduced surface free energy is applied to the surface of the member to give the member good water repellency and become soiled. Attempts have been made to make this difficult, and as such low surface free energy compounds, hydrophobic materials such as fluororesins and silicone compounds are used.

  For example, Patent Document 1 below discloses a water-circulating member having a cured coating material containing a low surface free energy compound on its surface. Further, as the low surface free energy compound, a silicone resin compound and a fluororesin compound are used. It is disclosed.

  Patent Document 2 below discloses a resin molded body in which a low surface free energy layer is formed on the surface of the base resin, and the surface of the molded body is a surface having a low surface free energy compared to the surface of the base resin. Further, it is disclosed that the contact angle between the surface of the resin molded body and water is 90 degrees or more and 170 degrees or less, and the falling angle between the surface of the resin molded body and water is 1 degree or more and 80 degrees or less.

JP 2002-69378 A JP 2000-233156 A

  However, although the low surface free energy surface produced using the low surface free energy compound repels water and forms spherical water droplets on the surface, the water droplets often adhere strongly to the surface and do not fall. It can be seen. Attempts have been made to roughen the surface and make the contact angle of the surface as large as possible in order to drop the attached water droplets from the surface, but the roughening of the surface requires man-hours. However, there is a problem in that the cost is high and dirt is easily attached.

  Then, the objective of this invention is providing the photocurable resin composition which can solve said problem and can improve slipperiness. Another object of the present invention is to provide a water-surrounding member and a functional panel which have an application layer formed by curing such a photo-curable resin composition and have good slipperiness.

  As a result of intensive studies to achieve the above object, the present inventors have been able to react with (A) at least (a) a silicone polyol and (b) a hydroxyl group at the terminal as constituents of the photocurable resin composition. Water droplets on the surface can be easily removed by using a dimethyl silicone (meth) acrylate oligomer obtained by using a (meth) acrylate monomer having various functional groups, and (D) a fluorine-containing compound. The inventors have found that a water-sliding surface can be formed, and have completed the present invention.

  In addition, as a result of intensive studies to achieve the above object, the present inventors have found that the equivalent ratio of (i) (c) isocyanate group (—NCO) in isocyanate and (a) hydroxyl group (—OH) in silicone polyol By setting (—NCO / —OH) to less than 1 (0/100 or more and less than 100/100), a prepolymer having a hydroxyl group at the terminal can be produced. (Ii) Thereafter, at the terminal of the prepolymer For example, a monomer having an isocyanate group and a (meth) acryloyl group can be reacted with a hydroxyl group to produce a dimethylsilicone (meth) acrylate oligomer having a (meth) acryloyl group at the terminal, (iii) Fluorine-containing compound against the produced dimethyl silicone (meth) acrylate oligomer Found that it is possible to improve the sliding properties by binding, thereby completed the present invention.

但し、前記一般式（１）中、ｎは、前記（Ａ）ジメチルシリコーン（メタ）アクリレートオリゴマーの数平均分子量が７００〜４００００となるように任意に選択される整数を表し、Ｒは、総炭素数１〜３０のアルキレン基、又は、エーテル結合を有する総炭素数１〜３０の官能基を表す。 That is, the photocurable resin composition of the present invention is
(A) Dimethyl silicone obtained by using at least (a) a silicone polyol represented by the following general formula (1) and (b) a (meth) acrylate monomer having a functional group capable of reacting with a hydroxyl group at the terminal. (Meth) acrylate oligomer, copolymerizable with (A) dimethyl silicone (meth) acrylate oligomer, (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer, (D) fluorine-containing compound, and (E) A photopolymerization initiator is contained.

However, in said general formula (1), n represents the integer arbitrarily selected so that the number average molecular weight of said (A) dimethyl silicone (meth) acrylate oligomer may be set to 700-40000, R represents total carbon. A C1-C30 alkylene group or a C1-C30 functional group having an ether bond is represented.

  In a preferred example of the photocurable resin composition of the present invention, the (A) dimethyl silicone (meth) acrylate oligomer comprises (a) a silicone polyol represented by the general formula (1), (c) an isocyanate, The (b) terminal is obtained by reacting a (meth) acrylate monomer having a functional group capable of reacting with a hydroxyl group at the terminal.

  In another preferable example of the photocurable resin composition of the present invention, an equivalent ratio (isocyanate group) of the isocyanate group in the (c) isocyanate and the hydroxyl group in the silicone polyol represented by the (a) general formula (1). / Hydroxyl group) is less than 100/100.

  In another preferable example of the photocurable resin composition of the present invention, the (c) isocyanate is a polyisocyanate compound having a cyclic skeleton in the molecular structure.

  In another preferable example of the photocurable resin composition of the present invention, the functional group capable of reacting with a hydroxyl group in the (b) (meth) acrylate monomer is an isocyanate group.

In another preferable example of the photocurable resin composition of the present invention, the solubility parameter (SP value) of the (C) photopolymerizable monomer is 20.0 (J / cm ³ ) ^1/2 or less.

The (C) photopolymerizable monomer may be used alone or in combination of two or more. In addition, SP value at the time of using 2 or more types of photopolymerizable monomers is the SP value of each monomer in the SP value of each monomer, and the blending ratio (ratio of each monomer when the total amount of monomers is 1). ) And the sum of these values. For example, when a photopolymerizable monomer having an SP value of 19.0 is blended in an amount of 3/4 and a photopolymerizable monomer having an SP value of 21.0 in an amount of 1/4 with respect to the total amount of photopolymerizable monomers, the following formula ( According to X), the SP value of the entire photopolymerizable monomer used is determined.
SP value of photopolymerizable monomer = (19.0 × 3/4) + (21.0 × 1/4) = 19.5 (X)

In another preferable example of the photocurable resin composition of the present invention, the (C) photopolymerizable monomer is a compound represented by the following general formula (A).
^{_{(CH 2 = CR 1 COO)}} n R 2 ··· formula (A)
However, the above general formula (A), ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} represents an n-valent hydrocarbon group having 5 to 20 carbon atoms, n is in the range of 1-4 Represents an integer.

  In another preferable example of the photocurable resin composition of the present invention, the (B) photopolymerizable oligomer is a (meth) acrylate oligomer having a 1,2-polybutylene oxide unit.

  In another preferable example of the photocurable resin composition of the present invention, the content of the (A) dimethyl silicone (meth) acrylate oligomer is (B) the photopolymerizable oligomer and / or (C) the photopolymerizable monomer. It is 0.05 mass%-10 mass% with respect to it.

  In another preferable example of the photocurable resin composition of the present invention, the (D) fluorine-containing compound has a photopolymerizable functional group.

  In another preferable example of the photocurable resin composition of the present invention, the ratio of the solid content of the (A) dimethyl silicone (meth) acrylate oligomer to the solid content of the (D) fluorine-containing compound (A / D) is 0.2-10.

  In another preferable example of the photocurable resin composition of the present invention, the ratio of the solid content of the (A) dimethyl silicone (meth) acrylate oligomer to the solid content of the (D) fluorine-containing compound (A / D) is 0.4-3.

Moreover, the water-surrounding member of the present invention is characterized by comprising a coating layer formed by curing the photocurable resin composition of the present invention and a base material layer.
Moreover, the functional panel of the present invention is characterized by comprising a coating layer formed by curing the photocurable resin composition of the present invention and a base material layer.

  According to the present invention, (A) at least (a) a silicone polyol represented by the general formula (1) and (b) a (meth) acrylate monomer having a functional group capable of reacting with a hydroxyl group at the terminal are used. A dimethylsilicone (meth) acrylate oligomer obtained in this way, (B) a photopolymerizable oligomer and / or (C) a photopolymerizable monomer, (D) a fluorine-containing compound, and (E) a photopolymerization initiator, It is possible to provide a photocurable resin composition capable of improving the resistance. Moreover, the coating layer formed by hardening | curing this photocurable resin composition is provided, and the water surrounding member and functional panel with favorable slipperiness | lubricating property can be provided.

(Photocurable resin composition)
The present invention is described in detail below. The photocurable resin composition of the present invention comprises (A) a dimethyl silicone (meth) acrylate oligomer, (B) a photopolymerizable oligomer and / or (C) a photopolymerizable monomer, (D) a fluorine-containing compound, ( E) a photopolymerization initiator, and (F) other components as required.

  In the photocurable resin composition of the present invention, (D) the photocuring is caused by a synergistic effect of high water repellency due to the low surface energy of the fluorine-containing compound and high slipperiness of the (A) dimethyl silicone (meth) acrylate oligomer. The slipperiness of the water-surrounding member and the functional panel having a coating layer derived from the functional resin composition can be improved.

  And in the photocurable resin composition of this invention, as a result that (A) dimethyl silicone (meth) acrylate oligomer and (D) fluorine-containing compound segregate on the surface over a long period of time, this photocurable resin composition The water repellent member having the coating layer derived from the water and the performance of the functional panel such as water repellency and slipperiness can be improved over a long period of time.

<(A) Dimethyl silicone (meth) acrylate oligomer>
The (A) dimethyl silicone (meth) acrylate oligomer used in the photocurable resin composition of the present invention is obtained using at least (a) a silicone polyol and (b) a (meth) acrylate monomer. The (A) dimethyl silicone (meth) acrylate oligomer is prepared by, for example, reacting (a) a silicone polyol and (c) an isocyanate to synthesize a prepolymer having a hydroxyl group at a part or all of the terminals, It is obtained by adding (b) (meth) acrylate monomer to the hydroxyl group in the prepolymer obtained from (a) silicone polyol.
By using isocyanates to obtain dimethylsilicone (meth) acrylate oligomers, it is possible to synthesize prepolymers with any number of repetitions, thereby allowing molecular weight or physical properties of the resulting oligomers (flexibility, strength, adhesion) In addition to being able to adjust the properties, etc., there is an advantage that compatibility design with the base resin is easy because any number of highly polar urethane bonds can be included in the molecule.
There is no restriction | limiting in particular as a number average molecular weight of the said (A) dimethyl silicone (meth) acrylate oligomer, Although it can select suitably according to the objective, 1000-40000 are preferable. The number average molecular weight can be obtained from a retention time of a sample by preparing a calibration curve from a polystyrene standard by GPC. Tetrahydrofuran or chloroform can be used as the moving bed solvent for GPC. Moreover, a refractometer (RI), a UV detector, etc. can be used for a detector. If the number average molecular weight obtained by using such a method is less than 1000, the relative amount of dimethylsiloxane sites in the (A) dimethylsilicone (meth) acrylate oligomer will decrease, so that a sufficient effect can be exhibited. Therefore, it is necessary to increase the amount of addition. On the other hand, if the number average molecular weight exceeds 40,000, the compatibility between (A) dimethyl silicone (meth) acrylate oligomer and polymerizable (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer is significantly reduced. As a result, the film surface becomes soft and the surface is easily damaged.
(A) A dimethyl silicone (meth) acrylate oligomer has (a) a silicone polyol component represented by the general formula (1), (c) an isocyanate component, and (b) a functional group capable of reacting with a hydroxyl group at the terminal (meta In addition to the acrylate monomer component, (d) other polyol components may be included. In that case, (a) silicone polyol, (d) other polyol, and (c) isocyanate are copolymerized to synthesize a prepolymer having hydroxyl groups at some or all of the ends, (A) It is obtained by adding (b) a (meth) acrylate monomer having a functional group capable of reacting with a hydroxyl group to the hydroxyl group in the prepolymer obtained from the silicone polyol represented by the general formula (1).
(d) By containing other polyol components, water repellency, compatibility with the base resin, hardness of the cured product, and the like can be arbitrarily adjusted.

There is no restriction | limiting in particular as content of the said (A) dimethyl silicone (meth) acrylate oligomer, Although it can select suitably according to the objective, (B) Photopolymerizable oligomer and / or (C) Photopolymerizability. It is preferable that it is 0.05 mass%-10 mass% with respect to the sum total with the monomer (whole resin), and 0.1 mass%-5.0 mass% are more preferable. Here, the content of the (A) dimethyl silicone (meth) acrylate oligomer is the amount of the active ingredient (solid content) of the (A) dimethyl silicone (meth) acrylate oligomer.
When the content is less than 0.05% by mass, the lubricity of the article coated with the photocurable composition of the present invention may not be sufficiently improved, and if it is more than 10% by mass, The compatibility with (B) the photopolymerizable oligomer and / or (C) the photopolymerizable monomer may deteriorate, and a uniform cured product may not be obtained. On the other hand, when the content of the (A) dimethyl silicone (meth) acrylate oligomer is within the more preferable range, surface segregation of the (A) dimethyl silicone (meth) acrylate oligomer becomes remarkable, and the photocurable resin of the present invention. The lubricity of the article coated with the composition can be expressed over a longer period. Moreover, since the addition effect is almost saturated at 5.0%, it is advantageous from the viewpoint of cost to make the content of the (A) dimethyl silicone (meth) acrylate oligomer within the more preferable range.

但し、前記一般式（１）中、ｎは、前記（Ａ）ジメチルシリコーン（メタ）アクリレートオリゴマーの数平均分子量が７００〜４００００となるように（前記シリコーンポリオールの数平均分子量が５００〜４００００となるように）任意に選択される整数を表す限り、特に制限はなく、目的に応じて適宜選択することができる。
また、前記一般式（１）中、Ｒとしては、総炭素数１〜３０のアルキレン基、又は、エーテル結合を有する総炭素数１〜３０の官能基である限り、特に制限はなく、目的に応じて適宜選択することができる。
前記総炭素数１〜３０のアルキレン基としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、メチレン、エチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン、へプチレン、オクチレン、などのエーテル結合を有しない総炭素数１〜３０のアルキレン基が挙げられる。
また、前記エーテル結合を有する総炭素数１〜３０の官能基としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、−Ｃ_３Ｈ_６−Ｏ−Ｃ_２Ｈ_４−、−Ｃ_３Ｈ_６−（ＯＣ_２Ｈ_４）_ｍ−：ｍは総炭素数が３０を超えないような整数、−Ｃ_２Ｈ_４−Ｏ−Ｃ_２Ｈ_４−、−Ｃ_３Ｈ_６−Ｏ−Ｃ_３Ｈ_６−、などが挙げられる。
Ｒの総炭素数を３０以下としたのは、ジメチルシリコーン濃度、耐熱性等の観点からである。Ｒとしては、市場での入手のしやすさの観点から、プロピレン基、又は、−Ｃ_３Ｈ_６−Ｏ−Ｃ_２Ｈ_４−が好ましい。 -(A) Silicone polyol-
The (a) silicone polyol used as one of the starting materials for the (A) dimethyl silicone (meth) acrylate oligomer is represented by the following general formula (1).

However, in the general formula (1), n is such that the number average molecular weight of the (A) dimethyl silicone (meth) acrylate oligomer is 700 to 40000 (the number average molecular weight of the silicone polyol is 500 to 40000). As long as it represents an arbitrarily selected integer, there is no particular limitation, and it can be appropriately selected according to the purpose.
In the general formula (1), R is not particularly limited as long as it is an alkylene group having 1 to 30 carbon atoms in total or a functional group having 1 to 30 carbon atoms having an ether bond. It can be appropriately selected depending on the case.
The alkylene group having 1 to 30 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene and octylene. Examples include an alkylene group having 1 to 30 carbon atoms that does not have an ether bond.
The functional group having 1 to 30 carbon atoms having an ether bond is not particularly limited and may be appropriately selected depending on the intended purpose. For example, —C ₃ H ₆ —O—C ₂ H ₄ — _{, -C 3 H 6 - (OC} 2 H 4) m -: m is as the total number of carbon atoms does not exceed 30 _{integer, -C 2 H 4 -O-C} 2 H 4 -, - C 3 H 6 - _O-C 3 _{H 6} -, and the like.
The reason why the total number of carbon atoms in R is 30 or less is from the viewpoint of dimethyl silicone concentration, heat resistance, and the like. R is preferably a propylene group or —C ₃ H ₆ —O—C ₂ H ₄ — from the viewpoint of easy availability in the market.

但し、前記一般式（２）中、ｎは、前記（Ａ）ジメチルシリコーン（メタ）アクリレートオリゴマーの数平均分子量が７００〜４００００となるように（前記シリコーンポリオールの数平均分子量が５００〜４００００となるように）任意に選択される整数を表し、ｐは、０〜９の範囲内の整数を表し、ｑは、３〜９の範囲内の整数を表す。
前記（ａ）シリコーンポリオールの市販品としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ＤＭＳ−Ｃ１６（Ｇｅｌｅｓｔ社製：数平均分子量≒７００：ｐ＝０、ｑ＝３）、ＦＭ−４４１１（チッソ株式会社製：数平均分子量≒１，０００：ｐ＝１、ｑ＝３）、ＦＭ−４４２１（チッソ株式会社製：数平均分子量≒５，０００：ｐ＝１、ｑ＝３）、ＦＭ−４４２５（チッソ株式会社製：数平均分子量≒１０，０００：ｐ＝１、ｑ＝３）、ＫＦ−６００１（信越化学工業株式会社製：数平均分子量≒１，７００：ｐ＝１、ｑ＝３）、ＫＦ−６００２（信越化学工業株式会社製：数平均分子量≒３，０００：ｐ＝１、ｑ＝３）、ＫＦ−６００３（信越化学工業株式会社製：数平均分子量≒５，５００：ｐ＝１、ｑ＝３）、Ｘ−２２−４９５２（信越化学工業株式会社製：数平均分子量≒４，０００：ｐ≒５、ｑ＝３）などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
前記一般式（２）中、ｐ及びｑは、上記の範囲内の整数を表す。これらの長さを変えることでベース樹脂との相溶性を変化させることができる一方、長すぎると構造中のシリコーン濃度が相対的に低下するために、十分な機能を発揮することができない。ｐ及びｑが上記範囲内にあれば、本発明の目的である撥水性及び滑り性（表面の水滴を容易に除去することができる滑水性）を長期に渡って向上させるという目的への影響はなく、機能を十分に発現することができる。 Furthermore, the following general formula (2) is mentioned as an example of the general formula (1).

However, in the said General formula (2), n is the number average molecular weight of the said (A) dimethyl silicone (meth) acrylate oligomer becoming 700-40000 (The number average molecular weight of the said silicone polyol will be 500-40000). And so on) represents an arbitrarily selected integer, p represents an integer in the range of 0-9, and q represents an integer in the range of 3-9.
There is no restriction | limiting in particular as a commercial item of said (a) silicone polyol, According to the objective, it can select suitably, For example, DMS-C16 (Gelest company: number average molecular weight ≒ 700: p = 0, q = 3), FM-4411 (manufactured by Chisso Corporation: number average molecular weight≈1,000: p = 1, q = 3), FM-4421 (manufactured by Chisso Corporation: number average molecular weight≈5,000: p = 1, q = 3), FM-4425 (manufactured by Chisso Corporation: number average molecular weight≈10,000: p = 1, q = 3), KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd .: number average molecular weight≈1,700: p = 1, q = 3), KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd .: number average molecular weight≈3,000: p = 1, q = 3), KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd .: number average) Molecular weight≈5,500: p = 1, q = 3 , X-22-4952 (Shin-Etsu Chemical Co., Ltd .: number average molecular weight ≒ 4,000: p ≒ 5, q = 3), and the like. These may be used individually by 1 type and may use 2 or more types together.
In said general formula (2), p and q represent the integer within said range. By changing these lengths, the compatibility with the base resin can be changed. On the other hand, if the length is too long, the silicone concentration in the structure is relatively lowered, so that a sufficient function cannot be exhibited. If p and q are within the above ranges, the influence on the purpose of improving the water repellency and slipperiness (slidability capable of easily removing water droplets on the surface), which is the object of the present invention, over a long period of time is as follows. And the function can be fully expressed.

The (a) silicone polyol can be produced, for example, by addition reaction of a terminal Si—H group-containing dimethylpolysiloxane and a compound having a hydroxyl group and an alkenyl group at each terminal with a platinum catalyst.

The number average molecular weight (Mn) of the (a) silicone polyol is not particularly limited as long as it is 500 to 20000, and can be appropriately selected according to the purpose. The number average molecular weight can be obtained from a retention time of a sample by preparing a calibration curve from a polystyrene standard by GPC. Tetrahydrofuran or chloroform can be used as the moving bed solvent for GPC. Moreover, a refractometer (RI), a UV detector, etc. can be used for a detector.
When the number average molecular weight is less than 500, the relative amount of dimethylsiloxane sites in the structure decreases, so in order to exert a sufficient effect, it is necessary to increase the amount of addition, and if it exceeds 20000, (A) Compatibility with dimethyl silicone (meth) acrylate oligomer and polymerizable (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer is significantly reduced and separated, and the crosslinking density is reduced. By doing so, the film surface becomes soft and the surface is easily damaged.

-(C) Isocyanate-
The (c) isocyanate that can be used as one of the starting materials for the (A) dimethyl silicone (meth) acrylate oligomer is not particularly limited and may be appropriately selected depending on the intended purpose. A polyisocyanate compound having a skeleton is preferred.

  When the (c) isocyanate is a polyisocyanate compound having a cyclic skeleton in the molecular structure, the (A) dimethyl silicone (meth) acrylate oligomer itself derived from the (c) isocyanate also has a cyclic skeleton in the molecular structure. The cyclic skeleton present in the molecular structure of the (A) dimethylsilicone (meth) acrylate oligomer may become steric hindrance, and the (A) dimethylsilicone (meth) acrylate oligomer may sink into the photocurable resin composition. And (A) dimethyl silicone (meth) acrylate oligomer segregates on the surface for a long time.

The polyisocyanate compound (c) having a cyclic skeleton in the molecular structure is particularly limited as long as it has a cyclic skeleton (cyclic structure portion) in the molecular structure and a plurality of isocyanate groups (NCO groups). And can be appropriately selected according to the purpose. For example, naphthalene diisocyanate (NDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), paraphenylene diisocyanate (PPDI), tolidine diisocyanate (TODI), dianisidine diisocyanate (DADI), dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis (isocyanatomethyl) cyclohexa (H6XDI), tetramethyl xylene diisocyanate (TMXDI), norbornene diisocyanate (NBDI), and NCO-terminated urethane prepolymer containing these structures, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, naphthalene diisocyanate (NDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), and isophorone diisocyanate (IPDI) are preferable.

The amount of the (a) silicone polyol and (c) isocyanate used can be appropriately changed. (C) The equivalent ratio of the isocyanate group (—NCO) in the isocyanate to the hydroxyl group in the (a) silicone polyol (—NCO) // OH) is preferably in the range of 0/100 or more and less than 100/100.
In the synthesis of the (A) dimethyl silicone (meth) acrylate oligomer, a urethane prepolymer having hydroxyl groups at some or all of the ends is synthesized by reacting (c) isocyanate with hydroxyl groups in (a) silicone polyol. In this case, the equivalent ratio (-NCO / -OH) of the isocyanate group (-NCO) in (c) isocyanate and the hydroxyl group in (a) silicone polyol may be less than 1.
Thus, the equivalent ratio (-NCO / -OH) of the isocyanate group (-NCO) in (c) isocyanate and the hydroxyl group (-OH) in (a) silicone polyol is less than 1 (0/100 or more and less than 100/100). ), It is possible to synthesize a prepolymer having hydroxyl groups at both ends, and the hydroxyl group can be used to react with a functional group (for example, an isocyanate group) in the (b) (meth) acrylate monomer. .

In the reaction of (a) silicone polyol and (c) isocyanate, it is preferable to use a catalyst for urethanization reaction.
The urethanization reaction catalyst is not particularly limited and may be appropriately selected depending on the intended purpose.For example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, Organotin compounds such as tin octenoate and monobutyltin oxide; inorganic tin compounds such as stannous chloride; organic lead compounds such as lead octenoate; cyclic amines such as triethylenediamine; p-toluenesulfonic acid, methanesulfonic acid, Organic sulfonic acids such as fluorosulfuric acid; inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid; bases such as sodium alcoholate, lithium hydroxide, aluminum alcoholate and sodium hydroxide; tetrabutyl titanate, tetraethyl titanate, tetraisopropyl Titanium compounds such as titanate; bismuth compounds; quaternary ammonium salts; These may be used individually by 1 type and may use 2 or more types together.
Among these, an organotin compound is preferable.
There is no restriction | limiting in particular as the usage-amount of the said catalyst for urethanation reaction, Although it can select suitably according to the objective, It is 0.001 mass part-2. with respect to 100 mass parts of said (a) silicone polyol. 0 parts by mass is preferred.

-(B) (Meth) acrylate monomer-
The (b) (meth) acrylate monomer used as one of the starting materials for the (A) dimethyl silicone (meth) acrylate oligomer is not particularly limited as long as it has a functional group capable of reacting with isocyanate at the terminal. For example, 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz MOI), 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI), 1,1- (Bisacryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, Karenz BEI), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these, 2-acryloyloxyethyl isocyanate (made by Showa Denko KK, Karenz AOI), 1,1- (bisacryloyloxymethyl) ethyl isocyanate (Showa Denko Co., Ltd.) from the viewpoint of the high reactivity of the functional group. Manufactured by Karenz BEI).

There is no restriction | limiting in particular as a functional group which can react with the said hydroxyl group, According to the objective, it can select suitably, For example, an isocyanate group, a chloro group, etc. are mentioned.
Among these, an isocyanate group is preferable because a coating film excellent in balance between flexibility and strength of the coating film can be obtained by including a urethane bond in the skeleton.
There is no restriction | limiting in particular as reaction with the said hydroxyl group, According to the objective, it can select suitably, For example, dehydration esterification with (meth) acrylic acid, transesterification method using lower (meth) acrylate, ( And a method of reacting with (meth) acrylic anhydride.

  The use amount of the (b) (meth) acrylate monomer can be appropriately changed, and (a) the functional group in the (b) (meth) acrylate monomer with respect to the hydroxyl group (—OH) in the prepolymer obtained from the silicone polyol. The equivalent (functional group / hydroxyl group) of (for example, an isocyanate group) may be used more than 1 equivalent.

  (B) The (meth) acrylate monomer may have both a functional group capable of reacting with isocyanate and a photopolymerizable (meth) acryloyl group in the structure. Any number of the (meth) acryloyl groups can be used, but the larger the number (polyfunctional), the more the (A) dimethyl silicone (meth) acrylate oligomer becomes polyfunctional. In general, the reactivity with (B) the photopolymerizable oligomer or (C) the photopolymerizable monomer increases as the number of functional groups increases. However, if the number of functional groups is too large, the reaction rate may decrease due to steric hindrance. In consideration of these, the number of functional groups is preferably between 2 and 10, and a larger number is more preferable (closer to 10) between them. During this period, the larger the number of functional groups, the more dense the cross-linking, which is preferable because it can be segregated on the surface stably for a long time and the surface hardness can be increased.

<(B) Photopolymerizable oligomer and / or (C) Photopolymerizable monomer>
The (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer used in the photocurable resin composition of the present invention is a radical polymerizable reactive group such as a (meth) acryloyl group [CH ₂ ═CHCO— or _{CH 2 = C (CH 3)} CO-] or the like containing. In the present invention, the above (A) dimethyl silicone (meth) acrylate oligomer is excluded from the (B) photopolymerizable oligomer.

  Moreover, the compounding quantity of (B) photopolymerizable oligomer and (C) photopolymerizable monomer is 100: 0-0: 100 by mass ratio, Preferably it is 80: 20-20: 80, More preferably, it is 30: It is the range of 70-70: 30. (C) If the blending amount of the photopolymerizable monomer is too small, the viscosity of the resulting photocurable composition may be increased and the coating property may be deteriorated, and physical properties such as chemical resistance and dye resistance are sufficient. May not be secured. Moreover, when there are too many compounding quantities of a photopolymerizable monomer, the softness | flexibility of a coating film will fall and it exists in the tendency for brittleness to become high.

-(B) Photopolymerizable oligomer-
As the (B) photopolymerizable oligomer is not particularly limited and may be appropriately selected depending on the intended purpose, acryloyloxy group _[CH 2 = CHCOO-] or methacryloyloxy group _[CH 2 = C _{(CH 3} ) A (meth) acrylate oligomer having at least one COO-] is preferred, and a (meth) acrylate oligomer having a 1,2-polybutylene oxide unit is particularly preferred. Since the (meth) acrylate oligomer having the 1,2-polybutylene oxide unit has low polarity, it has good compatibility with (A) dimethyl silicone (meth) acrylate oligomer, and (A) dimethyl silicone (meth) acrylate over a wide range It is possible to add oligomers. Therefore, even when the amount of (A) dimethyl silicone (meth) acrylate oligomer added is large, it is possible to suppress white turbidity, layer separation, etc., uniform properties after curing, and good appearance of the coating film. The used water-surrounding member and the functional panel can also form good physical properties and appearance. In addition, since the resin obtained by curing the photocurable resin composition has high hydrophobicity, it is highly resistant to water and stains such as detergents and hair colors used around the water, is not easily soiled, and is not slippery. Aqueous long-term stability becomes better.
Further, the low polarity of the (meth) acrylate oligomer (A) can be specifically expressed by a value of n-heptane tolerance, and such a value is preferably 0.5 g / 10 g or more, more preferably. Is 0.7 g / 10 g or more. In addition, n-heptane tolerance means the value of the amount (g) of n-heptane that can be added until n-heptane is dropped into the resin 10 g while keeping 10 g of the resin at 25 ° C., and is organic. It becomes an index of solubility in a solvent, and the larger the value, the lower the polarity.

  There is no restriction | limiting in particular as said (meth) acrylate oligomer, According to the objective, it can select suitably, For example, a urethane type (meth) acrylate oligomer, an epoxy-type (meth) acrylate oligomer, an ether type (meth) acrylate oligomer , Ester (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, silicone (meth) acrylate oligomers, and the like. These (meth) acrylate oligomers include polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, bisphenol A type epoxy resin, phenol novolac type epoxy resin, adducts of polyhydric alcohol and ε-caprolactone, (meth) It can be synthesized by reaction with acrylic acid or by urethanizing a polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group.

  The photopolymerizable oligomer (B) may be a monofunctional oligomer, a bifunctional oligomer, or a polyfunctional oligomer, and is multifunctional from the viewpoint of realizing an appropriate crosslinking density of the resulting photocurable resin composition. An oligomer is preferable.

Among the (B) photopolymerizable oligomers, urethane (meth) acrylate oligomers excellent in chemical resistance are preferable from the viewpoint of imparting suitable characteristics as a water-surrounding member and a functional panel.
The urethane-based (meth) acrylate oligomer may be, for example, a urethane prepolymer synthesized from (i) a polyol and (ii) polyisocyanate, and (iii) a compound having a functional group capable of reacting with isocyanate in the urethane prepolymer, For example, it can be produced by adding a (meth) acrylate having a hydroxyl group.

-(I) Polyol--
The polyol used for the synthesis of the urethane prepolymer is not particularly limited as long as it is a compound having a plurality of hydroxyl groups (—OH), and can be appropriately selected according to the purpose. For example, polyether polyol, polyester polyol, Examples thereof include polytetramethylene glycol, polybutadiene polyol, alkylene oxide-modified polybutadiene polyol, and polyisoprene polyol. These may be used individually by 1 type and may use 2 or more types together.

  The polyether polyol can be obtained by addition polymerization. For example, an alkylene oxide such as ethylene oxide or propylene oxide is added to a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, or sorbitol. It is also possible to obtain a polyether polyol by ring-opening polymerization. The polyether polyol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran (THF).

  The polyester polyol can be obtained by addition polymerization, for example, a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, trimethylolethane, trimethylolpropane, and the like. And a polyvalent carboxylic acid such as adipic acid, glutaric acid, succinic acid, sebacic acid, pimelic acid, and suberic acid, and a polyester polyol can also be obtained by ring-opening polymerization. There is no restriction | limiting in particular as said polyester polyol, According to the objective, it can select suitably, For example, the lactone polyester polyol obtained by the ring-opening polymerization of (epsilon) -caprolactone, etc. are mentioned.

  By using a butylene oxide-modified polyol as the (i) polyol, the (meth) acrylate oligomer having the 1,2-polybutylene oxide unit can be produced. The butylene oxide-modified polyol is a polyether polyol obtained by addition polymerization of 1,2-butylene oxide (BO) to a polyhydric alcohol in the presence of an alkali catalyst. Further, it may be a polyether polyol obtained by addition polymerization of not only 1,2-butylene oxide (BO) but also other alkylene oxides such as propylene oxide (PO). In this case, the molar ratio of 1,2-butylene oxide (BO) to other alkylene oxide is 20:80 to 100: 0, preferably 50:50 to 100: 0. The number average molecular weight by GPC of these butylene oxide modified polyols is usually 100 to 15000, preferably 500 to 5000.

-(Ii) Polyisocyanate--
The polyisocyanate is not particularly limited as long as it is a compound having a plurality of isocyanate groups (—NCO), and can be appropriately selected according to the purpose. For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) , Crude diphenylmethane diisocyanate (crude MDI), isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hexamethylene diisocyanate (HDI), their isocyanurate modified products, carbodiimide modified products, glycol modified products, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

-Catalyst for urethanization reaction-
In the synthesis of the urethane prepolymer, it is preferable to use a catalyst for urethanization reaction. The urethanization reaction catalyst is not particularly limited and may be appropriately selected depending on the intended purpose.For example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, Organotin compounds such as tin octenoate and monobutyltin oxide; inorganic tin compounds such as stannous chloride; organic lead compounds such as lead octenoate; cyclic amines such as triethylenediamine; p-toluenesulfonic acid, methanesulfonic acid, Organic sulfonic acids such as fluorosulfuric acid; inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid; bases such as sodium alcoholate, lithium hydroxide, aluminum alcoholate and sodium hydroxide; tetrabutyl titanate, tetraethyl titanate, tetraisopropyl Titanium compounds such as titanate; bismuth compounds; quaternary ammonium salts; These may be used individually by 1 type and may use 2 or more types together.
Among these, an organotin compound is preferable.
There is no restriction | limiting in particular as the usage-amount of the said catalyst for urethanation reaction, Although it can select suitably according to the objective, 0.001 mass part-2.0 with respect to 100 mass parts of said (i) polyols. Part by mass is preferred.

-(Iii) Compound having functional group capable of reacting with isocyanate--
In addition, the compound having a functional group capable of reacting with isocyanate (iii) to be added to the urethane prepolymer has at least one functional group (for example, hydroxyl group) capable of reacting with isocyanate, and exhibits a photopolymerizability ( It is a compound having one or more (meth) acryloyloxy groups [CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—]).
The compound having a functional group capable of reacting with (iii) isocyanate can be added to the isocyanate group in the urethane prepolymer.
The compound having a functional group capable of reacting with (iii) isocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta ) Acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 3-ethyl-3-hydroxymethyloxetane, 2- (meth) acryloyloxyethyl succinate, phthalic acid Examples thereof include monohydroxyethyl (meth) acrylate, (meth) acrylic acid ester whose side chain is a 1-aminoethyl group, (meth) acrylic acid ester whose side chain is a 1-aminopropyl group, and the like. These may be used individually by 1 type and may use 2 or more types together.

  By blending such a photopolymerizable oligomer (B), the glass transition temperature exhibited by the coating layer obtained by curing the photocurable resin composition can be optimized, and an effect excellent in slipperiness can be obtained. The photocurable composition which can be exhibited can be obtained.

-(C) Photopolymerizable monomer-
Examples of (C) a photopolymerizable monomer is not particularly limited and may be appropriately selected depending on the purpose, (meth) acryloyloxy group _[CH 2 = CHCOO-, or _{CH 2 = C (CH 3)} COO A (meth) acrylate monomer having one or more-] is preferable, and any of (i) a monofunctional monomer, (ii) a bifunctional monomer, and (iii) a polyfunctional monomer may be used.

In addition, the (C) photopolymerizable monomer may be used alone or in combination of two or more. When using two or more kinds of photopolymerizable monomers, the SP value is the SP value of each monomer and the SP value of each monomer is the blending ratio (the ratio of each monomer when the total amount of monomers is 1). Multiplication means the value obtained by adding these. For example, when a photopolymerizable monomer having an SP value of 19.0 is blended in an amount of 3/4 and a photopolymerizable monomer having an SP value of 21.0 in an amount of 1/4 with respect to the total amount of photopolymerizable monomers, According to X), the SP value of the entire photopolymerizable monomer used is determined.
SP value of photopolymerizable monomer = (19.0 × 3/4) + (21.0 × 1/4) = 19.5 (X)

-(I) Monofunctional monomer-
The monofunctional monomer (i) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate , Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) Acrylate, stearyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyoxyethylene nonylphenyl ether acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene Glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3, 7-dimethyloctyl (meth) acrylate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

-(Ii) Bifunctional monomer-
The (ii) bifunctional monomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, di (meth) acrylate of bisphenol A alkylene oxide addition diol ,water Di (meth) acrylate of alkylene oxide addition diol of bisphenol A, epoxy obtained by adding diglycidyl ether (meth) acrylates of bisphenol A (meth) acrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

-(Iii) Multifunctional monomer-
There is no restriction | limiting in particular as said (iii) polyfunctional monomer, According to the objective, it can select suitably, For example, a trimethylol propane tri (meth) acrylate, an ethoxylated trimethylol propane tri (meth) acrylate, propoxy Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol monohydroxypenta (Meth) acrylate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a solubility parameter (SP value) of the said photopolymerizable monomer, Although it can select suitably according to the objective, 20.0 (J / cm < ³ >) ^0.5 or less is preferable, 19 .6 (J / cm ³ ) ^0.5 or less is more preferable. Moreover, there is no restriction | limiting in particular as a lower limit of the said SP value, However, 17.0 (J / cm < ³ >) ^0.5 or more is preferable normally. Low SP value improves compatibility with (A) dimethylsilicone (meth) acrylate oligomer and (D) fluorine-containing compound, and (A) dimethylsilicone (meth) acrylate oligomer and (D) fluorine-containing over a wide range It is possible to add compounds. Therefore, even when the addition amount of (A) dimethyl silicone (meth) acrylate oligomer and (D) fluorine-containing compound is large, white turbidity, layer separation, etc. can be suppressed, and the appearance after curing is good. The functional panel can also form a good appearance.
Here, the SP value (δ) is generally expressed by the following formula from the molar evaporation energy (ΔEv) and the molar volume (V) of the liquid:
SP value (δ) = (ΔEv / V) ^0.5
Defined by Furthermore, the SP value can be estimated only from the chemical structure according to the Fedors method (see “Solubility Parameter Values”, Polymer Handbook, 4th edition (edited by J. Brandrup et al.)). . In the present specification, the SP value means a value calculated by the Fedors method, and the lower the value, the lower the polarity of the photopolymerizable monomer (C).

Moreover, as said (C) photopolymerizable monomer, following general formula (A):
^{_{(CH 2 = CR 1 COO)}} n R 2 ··· formula (A)
The monomer represented by these is preferable. In General Formula (A), R ¹ is a hydrogen atom or a methyl group, R ² is an n-valent hydrocarbon group having 5 to 20 carbon atoms, does not include a hetero atom, and is cyclic even if it is a chain. There may be. Further, —CH ₂ — in the group may be replaced with —CH═CH—. n is an integer of 1-4.

That is, In the general formula (A), for example if it is a saturated monomer a chain, R ² when n = 1 becomes a alkyl group having 5 to 20 carbon atoms, R ² when n = 2 the carbon It becomes an alkylene group of formula 5-20. Further, in the case of a chain and a saturated monomer, when n = 3, R ² is an alkanetriyl group having 5 to 20 carbon atoms, and when n = 4, R ² is an alkane having 5 to 20 carbon atoms. Tetrayl group. Examples of such R ² include —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) CH ₃ , cyclohexyl group, cycloheptane group, cyclooctane group, cyclononane group, cyclodecane group, and the like. An alkyl group, an alkylene group such as —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, etc., and CH ₃ CH ₂ C (CH ₂ —) ₃ And alkanetriyl groups such as those represented by C (CH ₂ —) ₄ .

When the carbon number of R ² is less than 5, in the case of a chain hydrocarbon group, the SP value of the monomer tends to increase, and (A) a dimethyl silicone (meth) acrylate oligomer and (D) a fluorine-containing compound The compatibility with the above is lowered, and in the case of a cyclic hydrocarbon group, it is difficult to obtain it. Further, the number of carbon atoms of R ² exceeds 20, crosslinking density of the photocurable composition obtained tends to decrease. If the crosslink density is lowered more than necessary, a dye such as a hair color tends to be leached into the coating layer, and the panel may be dyed.

Specific examples of the monomer represented by the general formula (A) include, for example, isobornyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, and isoamyl (meta). ) Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, cyclohexanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.
Among these, since it has a more suitable SP value, it tends to exhibit good low polarity, and not only has compatibility with (A) dimethyl silicone (meth) acrylate oligomer and (D) fluorine-containing compound, but also has chemical resistance. 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, dimethylol in that it is possible to further improve the properties and dyeing resistance. Tricyclodecane di (meth) acrylate is preferable, and 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, and 1,9-nonanediol di (meth) acrylate are more preferable.

The photopolymerizable monomer having the solubility parameter (SP value) of 20.0 (J / cm ³ ) ^0.5 or less, in particular, the monomer represented by the general formula (A) has a low polarity. ) Good compatibility with dimethylsilicone (meth) acrylate oligomer and (D) fluorine-containing compound, and it is possible to add (A) dimethylsilicone (meth) acrylate oligomer and (D) fluorine-containing compound over a wide range. Therefore, even when the addition amount of (A) dimethyl silicone (meth) acrylate oligomer and (D) fluorine-containing compound is large, white turbidity, layer separation, etc. can be suppressed, and the appearance after curing is good. The functional panel can also form a good appearance. In addition, since the resin obtained by curing the photocurable composition has high hydrophobicity, it is highly resistant to water and stains such as detergents and hair colors used around the water, is difficult to get dirty, and is slippery. The long-term stability of is better.

  Moreover, the number of functional groups of the photopolymerizable monomer is usually 1 to 6, and preferably 1 to 4. In addition, when the number of functional groups is 1, the crosslinking density tends to decrease. However, by using a monomer having a cyclic skeleton, the glass transition temperature becomes high and good film properties can be maintained. Moreover, since it exists in the tendency which can hold | maintain the crosslinking reaction of a photocurable composition moderately as the number of functional groups is 2-6, Preferably it is 2-4, especially a dyeing agent leaches out in the coating layer inside. It is presumed that the phenomenon in which the water-surrounding member and the functional panel are dyed can be more effectively suppressed. Therefore, in this case as well, a water-surrounding member and a functional panel in which a coating layer having suitable curability is formed while effectively retaining not only good antifouling properties but also chemical resistance and dyeing resistance are provided. Can be obtained.

 The (B) photopolymerizable oligomer and the (C) photopolymerizable monomer may be used only as an oligomer or as a monomer, but it is preferable to use a combination of the oligomer and the monomer.

<(D) Fluorine-containing compound>
The photocurable composition of the present invention further comprises (D) a fluorine-containing compound. By including the (D) fluorine-containing compound, the water repellency and water slidability of the photocurable composition can be improved.

Any fluorine-containing compound can be used as the fluorine-containing compound. Considering durability, photocuring containing (A) dimethyl silicone (meth) acrylate oligomer, (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer, and (E) photopolymerization initiator. The fluorine-containing compound (D) preferably has a photopolymerizable functional group (reactive group) in the structure in the sense that it is immobilized in the system by reacting with the functional composition.
There is no restriction | limiting in particular as said (D) fluorine-containing compound, According to the objective, it can select suitably, For example, perfluoroalkyl group containing photopolymerizable compounds, such as perfluoro octyl ethyl acrylate, are mentioned.
There is no restriction | limiting in particular as a commercial item of the said (D) fluorine-containing compound, According to the objective, it can select suitably, For example, light acrylate FA-108 (made by Kyoeisha Chemical Co., Ltd.), RS-75 (DIC stock) Company-made), OPTOOL DAC-HP (manufactured by Daikin Industries, Ltd.), Modiper F200, F600, F3035 (manufactured by NOF Corporation), Hypertech FA-200 (manufactured by Nissan Chemical Industries, Ltd.) These may be used individually by 1 type and may use 2 or more types together.

 The mass ratio (A / D) of the solid content of the (A) dimethyl silicone (meth) acrylate oligomer to the solid content of the (D) fluorine-containing compound is preferably in the range of 0.2 to 10.0. A range of 0.4 to 3.0 is more preferable. Here, the mass ratio (A / D) is an effective component ratio (solid content ratio) of (A) dimethylsilicone (meth) acrylate oligomer and (D) fluorine-containing compound in the photocurable composition. If the mass ratio (A / D) is 0.2 or more, both (D) fluorine-containing compound-derived high water repellency and (A) dimethylsilicone (meth) acrylate oligomer-derived water repellency can be expected, If it is 0.4 or more, the concentration of the surface fluorine-containing compound and (A) dimethylsilicone (meth) acrylate oligomer will be high, so the above-described effects can be expected more. , (B) a photopolymerizable oligomer and / or (C) a photopolymerizable monomer that can be copolymerized with the photopolymerizable monomer. It is possible.

 In the photocurable composition of the present invention, the content of the (D) fluorine-containing compound is 0.05 mass relative to a total of 100 mass parts of the (B) photopolymerizable oligomer and (C) photopolymerizable monomer. Part to 5.0 parts by mass is preferable, and a range from 0.1 to 3.0 parts by mass is more preferable. Here, the content of the fluorine-containing compound (D) is the amount (the amount of solid content) of the active ingredient of the fluorine-containing compound (D). (D) If the content of the fluorine-containing compound is 5.0 parts by mass or less, a sufficient improvement effect on water repellency and water slidability can be exhibited, while blending more than 5.0 parts by mass is a characteristic aspect, There is no point in terms of cost, and if it is 3.0 parts by mass or less, a sufficient effect of improving water repellency and water slidability with no practical problem can be expected. Moreover, if the content rate of (D) fluorine-containing compound is 0.1 mass part or more, the effect of improving the water repellency and water slidability of a photocurable composition will become very large.

<(E) Photopolymerization initiator>
The (E) photopolymerization initiator used in the photocurable resin composition of the present invention is the above-described (A) dimethyl silicone (meth) acrylate oligomer and (B) photopolymerizable when irradiated with light such as ultraviolet rays. It has the effect | action which starts superposition | polymerization of an oligomer and / or (C) photopolymerizable monomer.
The (E) photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy- Benzophenone derivatives such as 2-phenylacetophenone, acetophenone diethyl ketal, alkoxy acetophenone, benzyldimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 4,4-diaminobenzophenone, benzoylbenzoic acid Alkyl, bis (4-dialkylaminophenyl) ketone, benzyl derivatives such as benzyl and benzylmethyl ketal, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropyl Piophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, xanthone, thioxanthone and thioxanthone derivatives, fluorene, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone-1, and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a compounding quantity of the said (E) photoinitiator in the photocurable resin composition of this invention, Although it can select suitably according to the objective, (A) Dimethyl silicone (meth) acrylate The range of 0.1-10 mass parts is preferable with respect to a total of 100 mass parts of an oligomer and (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer (D) fluorine-containing compound. If the blending amount of the (E) photopolymerization initiator is 0.1 parts by mass or more, the polymerization reaction can be sufficiently started. On the other hand, if it exceeds 10 parts by mass, the effect of initiating the polymerization reaction is saturated. On the other hand, coloring becomes remarkable, and the cost of the raw material of the photocurable resin composition increases.

<(F) Other ingredients>
-Photosensitizer-
The photocurable resin composition of the present invention may further contain a photosensitizer as necessary in consideration of the required curing reactivity and stability. The photosensitizer absorbs energy when irradiated with light, and the energy or electrons move to the polymerization initiator to initiate polymerization. Examples of the photosensitizer include p-dimethylaminobenzoic acid isoamyl ester. These photosensitizers are blended in a total amount of 100 parts by mass of (A) a photopolymerizable silicone oligomer, (B) a photopolymerizable oligomer and / or (C) a photopolymerizable monomer, and (D) a fluorine-containing compound. The range of 0.1 to 10 parts by mass is preferable.

-Polymerization inhibitor-
Furthermore, the photocurable resin composition of the present invention may contain a polymerization inhibitor as necessary in consideration of the required curing reactivity and stability. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-p-cresol, butylhydroxyanisole, Examples include 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like. These polymerization inhibitors are added in a total amount of 100 parts by mass of (A) dimethyl silicone (meth) acrylate oligomer and (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer (D) fluorine-containing compound. On the other hand, the range of 0.1-10 mass parts is preferable.

-Organic solvent-
Moreover, the photocurable resin composition of the present invention may contain an organic solvent such as ether, ketone or ester as a diluent solvent. Examples of the organic solvent include propylene glycol monomethyl ether acetate (PMA), methyl ethyl ketone ( MEK), methyl isobutyl ketone (MIBK), acetone, butyl lactate and the like. These dilution solvents may be used individually by 1 type, and may use 2 or more types together.

  As described above, the photocurable resin composition of the present invention can be applied to the surface of the substrate as a coating liquid using a diluting solvent as necessary. The method for applying is not particularly limited, and a known method can be employed. For example, gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, Examples thereof include wire bar coating, curtain coating, extrusion coating, and spin coating.

(Water-related parts)
The water-surrounding member includes an application layer formed by curing the photocurable composition of the present invention and a base material layer. The water-surrounding member is a member that requires water drainage on the surface. The water-surrounding member is not particularly limited and may be appropriately selected depending on the purpose. For example, the kitchen sink, kitchen wall material, wash basin, bathroom wall material, bathtub, bathroom ceiling material, bathroom use Floor materials, bathroom counters, toilets, water storage tanks, etc.

(Functional panel)
The functional panel of the present invention comprises a coating layer formed by curing the photocurable resin composition of the present invention and a base material layer, for example, the coating layer is formed on the base material layer. Is preferred.
There is no restriction | limiting in particular as thickness of the whole functional panel of this invention, Although it can select suitably according to the objective, Usually, 2.5 mm or more is preferable. In addition, there is no restriction | limiting in particular as an upper limit of the thickness of the whole functional panel of this invention, According to the objective, it can select suitably. The coating layer may be formed on both the front surface and the back surface of the base material layer, and if necessary, in addition to the base material layer and the coating layer, a multilayer in which an intermediate layer made of various materials is formed between these layers. It is good also as a structure. In this case, since the coating layer has excellent slipperiness as described above, it is desirable to form the coating layer as the outermost surface layer of the functional panel. The intermediate layer is not particularly limited and may be appropriately selected depending on the purpose. For example, the undercoat layer for improving the adhesion between the base material layer and the coating layer, the design of the functional panel Examples thereof include a decorative layer provided with a pattern or color for improvement.

  The functional panel of the present invention thus obtained has excellent slipperiness due to the formation of the coating layer on the base material layer, and has abrasion resistance, chemical resistance, warm water resistance and dyeing resistance. It is also excellent in properties, and it is difficult to cause alteration or deterioration even by the use of a highly irritating cleaning agent containing acid or alkali while effectively suppressing the adhesion of various types of dirt typified by scale. Further, discoloration and dyeing hardly occur even when a dyeing agent such as a hair color is used. Therefore, the functional panel of the present invention is particularly suitable as a functional panel disposed in a bathroom or kitchen in a house.

<Coating layer>
An application layer can be formed on a base material layer by applying the photocurable resin composition of the present invention on a base material, and then making it photocure. As a method of photocuring, a method of irradiating light such as ultraviolet rays is common. The surface on the base material layer forming the coating layer may be only one surface or both surfaces of the front surface and the back surface, and may be appropriately selected as necessary. In addition, the irradiation amount of light at the time of curing the photocurable resin composition of the present invention is not particularly limited and can be appropriately selected according to the purpose. When ultraviolet rays are employed, the irradiation intensity is usually 20 mW / cm ² ~2000mW / cm ^2, an irradiation amount ^{100mJ / cm 2 ~5000mJ / cm 2} , thereby, the photocurable resin composition of the present invention is cured in the usual several seconds to several tens of seconds. Thus, since it can be hardened in a short time, the productivity of the functional panel obtained can be improved.

  There is no restriction | limiting in particular as thickness of the said application layer, Although it can select suitably according to the objective from the grade of the designability or chemical-resistance requested | required, it is the thickness of the range of 1 micrometer-200 micrometers normally. It is assumed.

In addition, when irradiating with ultraviolet rays, since the ultraviolet curing reaction is a radical reaction, it is susceptible to inhibition by oxygen. Therefore, after apply | coating the said photocurable resin composition to a base material, you may harden this composition in nitrogen atmosphere so that a contact with oxygen can be avoided. The surface free energy of the coating layer formed by photocuring, in view of sufficiently ensuring good sliding property, it is desirable generally ^{12mJ / m 2 ~30mJ / m 2} .

<Base material layer>
The material of the base material layer used in the functional panel of the present invention is not particularly limited and can be appropriately selected according to the purpose. For example, slate, concrete, metal, calcium silicate, calcium carbonate, glass, etc. Inorganic materials; wood materials; organic materials such as polypropylene, polystyrene, polycarbonate, and unsaturated polyester resin; and composite materials thereof.
Among these, a material obtained by adding glass fiber or carbon fiber to an organic material, so-called FRP (fiber reinforced plastic) is preferable. The FRP is not particularly limited and can be appropriately selected depending on the purpose. For example, the FRP is a sheet-like sheet molding compound (SMC) containing an unsaturated polyester resin, a filler and glass fiber or carbon fiber, SMC, Examples of the composite material include a bulk bulk molding compound (BMC) including short fibers. The FRP generally contains a thermosetting resin, an organic peroxide (curing agent), a filler, a low shrinkage agent, an internal mold release agent, a reinforcing material, a crosslinking agent, a thickener, and the like. These are used by being put in a mold set at a predetermined temperature and pressurized, and formed into a shape corresponding to a place to be arranged as a building material. Among these, the FRP containing unsaturated polyester as a thermosetting resin, a filler, and glass fiber or carbon fiber as a reinforcing material can further improve the strength and durability of the entire functional panel obtained. it can.

  The unsaturated polyester includes unsaturated polybasic acids such as maleic anhydride and fumaric acid, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, trimethylpentanediol, neopentyl glycol, trimethylpropane mono It is produced from polyhydric alcohols such as allyl ether, hydrogenated bisphenol and bisphenol dioxypropyl ether.

  There is no restriction | limiting in particular as said filler, According to the objective, it can select suitably, For example, calcium carbonate, aluminum hydroxide, etc. are mentioned. Among these, calcium carbonate is preferable from the viewpoint of cost reduction, and aluminum hydroxide is preferable from the viewpoint of improving the chemical resistance of FRP itself. However, as described above, if the coating layer is formed, the chemical resistance of the entire functional panel can be sufficiently improved even if FRP using calcium carbonate as a filler is used as a base material. A functional panel having a base material layer made of low-cost FRP can be easily realized.

  The glass fiber and carbon fiber as the reinforcing material are not particularly limited and may be appropriately selected depending on the intended purpose, but those having a fiber length of about 20 mm to 50 mm and a fiber diameter of about 5 μm to 25 μm are preferable. It is preferably used and contained in the FRP in an amount of 10% by mass to 70% by mass. The FRP used as the base material layer is manufactured as an FRP having a predetermined thickness and size by mixing these components and using an FRP manufacturing apparatus or the like.

  In addition, there is no restriction | limiting in particular as thickness of the said base material layer, Although it may fluctuate | variate with the use of a functional panel, Usually, it is 2.5 mm or more. There is no restriction | limiting in particular as an upper limit of the thickness of the said base material layer, According to the objective, it can select suitably.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Production Example 1>
Silicone polyol having a number average molecular weight of 1,000 (Silaplane FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation) and 0.3 mol of dibutyltin dilaurate and 0.06 g of dibutyltin are added to the reaction vessel. Stir. Next, 0.2 mol of isophorone diisocyanate (VESTANAT IPDI, manufactured by Evonik Degussa) was added at room temperature. This was heated to 70 ° C. and reacted at 300 rpm for 2 and a half hours to obtain a urethane prepolymer solution. 0.2 mol of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI) was added to the total amount of the resulting prepolymer solution, and the mixture was further stirred for 4 hours to complete the reaction. ) An acrylate oligomer was obtained.

<Production Example 2>
In Production Example 1, instead of using a silicone polyol having a number average molecular weight of 1,000 (Silaplane FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation), a number average molecular weight of about 700 is used. Dimethylsilicone having a number average molecular weight of about 3000 in the same manner as in Production Example 1 except that the following silicone polyol (DMS-C16, general formula (2), p = 0, q = 3, manufactured by Gelest) was used. A (meth) acrylate oligomer was obtained.

<Production Example 3>
In Production Example 1, instead of using a silicone polyol having a number average molecular weight of 1,000 (Silane Plan FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation), a number average molecular weight of about 5000 Dimethyl silicone having a number average molecular weight of about 7000, in the same manner as in Production Example 1, except that the silicone polyol (FM-4421, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation) was used. A (meth) acrylate oligomer was obtained.

<Production Example 4>
In Production Example 1, instead of using a silicone polyol having a number average molecular weight of 1,000 (Silaplane FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation), a number average molecular weight of about 10,000 Dimethyl silicone having a number average molecular weight of about 12,000 in the same manner as in Production Example 1 except that the following silicone polyol (FM-4425, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation) was used. A (meth) acrylate oligomer was obtained.

<Production Example 5>
In Production Example 1, instead of using a silicone polyol having a number average molecular weight of 1,000 (Silaplane FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation), a number average molecular weight of about 1700 Dimethylsilicone having a number average molecular weight of about 4000 in the same manner as in Production Example 1 except that the following silicone polyol (KF6001, general formula (2), p = 1, q = 3, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A (meth) acrylate oligomer was obtained.

<Production Example 6>
In Production Example 1, instead of using a silicone polyol having a number average molecular weight of 1,000 (Silaplane FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation), a number average molecular weight of about 3000 Dimethylsilicone having a number average molecular weight of 5000 in the same manner as in Production Example 1 except that the following silicone polyol (KF6002, general formula (2), p = 1, q = 3, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A (meth) acrylate oligomer was obtained.

<Production Example 7>
In Production Example 1, instead of using a silicone polyol having a number average molecular weight of 1,000 (Silaplane FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation), a number average molecular weight of about 5500 is used. Dimethyl silicone having a number average molecular weight of about 7500 in the same manner as in Production Example 1 except that the following silicone polyol (KF6003, general formula (2), p = 1, q = 3, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A (meth) acrylate oligomer was obtained.

<Production Example 8>
In Production Example 1, instead of using a silicone polyol having a number average molecular weight of 1,000 (Silaplane FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation), a number average molecular weight of about 4000 In the same manner as in Production Example 1 except that the silicone polyol (X-22-4952, general formula (2), p≈5, q = 3, manufactured by Shin-Etsu Chemical Co., Ltd.) was used, 7500 dimethyl silicone (meth) acrylate oligomers were obtained.

<Production Example 9>
Silicone polyol having a number average molecular weight of 1,000 (Silaplane FM-4411, general formula (2), p = 1, q = 3, manufactured by Chisso Corporation) and 0.2 mol of dibutyltin dilaurate and 0.06 g of dibutyltin are added to the reaction vessel. Stir. Next, 0.4 mol of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI) was added and stirred for 4 hours to complete the reaction, and a dimethyl silicone (meth) acrylate oligomer having a number average molecular weight of about 2000 was obtained.

<Production Example 10>
In Production Example 1, instead of adding 2-acryloyloxyethyl isocyanate (Showa Denko, Karenz AOI), 1,1- (bisacryloyloxymethyl) ethyl isocyanate (Showa Denko, Karenz BEI) was added. A dimethylsilicone (meth) acrylate oligomer having a number average molecular weight of about 3000 was obtained in the same manner as in Production Example 1 except that it was added.

<Production Example 11>
In Production Example 1, instead of adding 2-acryloyloxyethyl isocyanate (Showa Denko KK, Karenz AOI), except that 2-methacryloyloxyethyl isocyanate (Showa Denko KK, Karenz MOI) was added, In the same manner as in Production Example 1, a dimethyl silicone (meth) acrylate oligomer having a number average molecular weight of about 3000 was obtained.

<Production Example 12>
In Production Example 1, instead of adding 2-acryloyloxyethyl isocyanate (produced by Showa Denko KK, Karenz AOI), the resulting prepolymer was reacted with acrylic acid using toluene as a solvent under a paratoluenesulfonic acid catalyst. I let you. The reacted reaction product was neutralized to pH 11 with a 10% aqueous sodium hydroxide solution and the acid component was removed to obtain a dimethyl silicone (meth) acrylate oligomer having a number average molecular weight of about 3000.

<Production Example 13>
Instead of adding isophorone diisocyanate (VESTANAT IPDI, manufactured by Evonik Degussa) in Production Example 1, hexamethylene diisocyanate as a polyisocyanate compound having no cyclic skeleton in the molecular structure (trade name: HDI, manufactured by Evonik Degussa) A dimethylsilicone (meth) acrylate oligomer having a number average molecular weight of about 3000 was obtained in the same manner as in Production Example 1, except that was added.

<Preparation and Evaluation of Photocurable Resin Composition>
In accordance with the formulation shown in Tables 1 to 7, each component was added to and mixed in a stirrer to prepare a photocurable resin composition. The obtained photocurable resin composition was apply | coated so that it might become thickness 20 micrometers on the upper surface of the base material which consists of FRP (Deckmat (trademark) 2415, DIC Kako Co., Ltd. product). Next, UV irradiation (1000 mW / cm ² , 4000 mJ / cm ² ) was performed to cure the photocurable resin composition, thereby obtaining a sample. The following methods evaluated the slipperiness and chemical resistance, and obtained the results shown in Tables 1 to 7.

(1) Sliding property The slipping property was evaluated by measuring the falling angle of water. For the evaluation of slipperiness, DM-500 and DM-SA manufactured by Kyowa Interface Science Co., Ltd. were used. A 30 μL water droplet was dropped on the substrate, the stage was tilted at a speed of 7.5 degrees / second, and the angle at which the water droplet began to move was taken as the value of the falling angle. The measurement was performed twice, and the average value was taken as the value of the sliding angle.

(2) Chemical resistance (dyeability)
The sample was immersed in a commercially available hair dye (GATSBY black hair restoration (registered trademark): mixture of 1 agent and 2 agents, manufactured by Mandom Co., Ltd.) for 24 hours and then washed with water. The Lab color difference (ΔE) between the immersed part and the non-immersed part was determined based on the following formula using a color difference meter (SpectroEye, manufactured by Sakata Inx Engineering Co., Ltd.).
ΔE = (Δa ² + Δb ² + ΔL ² ) ^1/2
The smaller the value, the better the drug resistance.
ΔE = less than 3.0: ◎
ΔE = 3.0 or more and less than 5.0: ○
ΔE = 5.0 or more and less than 10.0: Δ
ΔE = 10.0 or more: ×

但し、一般式（３）中、Ｒはアルキル基を表し、Ｍｅはメチル基を表し、ｎは任意の整数を表す。ここで、Ｒは末端の反応性をなくす為にアルキル基とし、本発明に本質的な寄与はない。
＊２４ チッソ株式会社製、「ＦＭ−７７１１」、両末端メタクリル変性ジメチルシリコーンオイル、数平均分子量（Ｍｎ）１０００、比重０．９８、屈折率１．４１９、粘度２０ｍｍ^２／ｓ、下記一般式（４）で表される請求項範囲外の化合物

但し、一般式（４）中、Ｍｅはメチル基を表し、ｎは任意の整数を表す。 * 1 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 1 * 2 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 2 * 3 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 3 * 4 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 4 * 5 Urethane acrylate oligomer having 1,2-polybutylene oxide unit synthesized by the following method * 5-2 Kyoeisha Chemical Co., Ltd. UF-8001
* 6 Kyoeisha Chemical Co., Ltd. 1,6-hexanediol diacrylate, SP value = 19.6 (J / cm ³ ) ^0.5
* 7 manufactured by Kyoeisha Chemical Co., Ltd., 1,9-nonanediol diacrylate, SP value = 19.2 (J / cm ³ ) ^0.5
* 8 manufactured by Kyoeisha Chemical Co., Ltd., isobornyl acrylate, SP value = 18.9 (J / cm ³ ) ^0.5
* 9 Shin-Nakamura Kogyo Co., Ltd., 2-acryloyloxyethyl succinate, SP value = 22.7 (J / cm ³ ) ^0.5
* 10 DIC Corporation, reactive fluorine oligomer * 11 Nissan Chemical Industries, Ltd., reactive fluorine oligomer * 12 Kyoeisha Chemical Co., Ltd., perfluorooctylethyl acrylate * 12-2 Daikin Industries, Ltd. Molecular weight PTFE)
* 13 Ciba Specialty Chemicals, “IRGACURE184”, 1-hydroxy-cyclohexyl-phenyl-ketone * 14 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 5 * 15 Dimethylsilicone obtained in Production Example 6 ( (Meth) acrylate oligomer * 16 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 7 * 17 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 8 * 18 Dimethylsilicone (meth) obtained in Production Example 9 Acrylate oligomer * 19 Dimethyl silicone (meth) acrylate oligomer obtained in Production Example 10 * 20 Dimethyl silicone (meth) acrylate oligomer obtained in Production Example 11 * 21 Dimethyl obtained in Production Example 12 Ricone (meth) acrylate oligomer * 22 Dimethyl silicone (meth) acrylate oligomer obtained in Production Example 13 * 23 “FM-0711” manufactured by Chisso Corporation, methacryl-modified dimethyl silicone oil having one terminal, number average molecular weight (Mn) 1000 And a compound outside the scope of claims represented by the following general formula (3):

However, in General formula (3), R represents an alkyl group, Me represents a methyl group, and n represents arbitrary integers. Here, R is an alkyl group in order to eliminate terminal reactivity, and has no essential contribution to the present invention.
* 24 “FM-7711” manufactured by Chisso Corporation, methacryl-modified dimethyl silicone oil at both ends, number average molecular weight (Mn) 1000, specific gravity 0.98, refractive index 1.419, viscosity 20 mm ² / s, the following general formula ( 4) a compound outside the scope of claims

However, in General formula (4), Me represents a methyl group and n represents arbitrary integers.

<Method for synthesizing urethane acrylate oligomer having 1,2-polybutylene oxide unit>
Polyol was obtained by adding 12 mol of butylene oxide to 1 mol of propylene glycol (manufactured by Kanto Chemical Co., Ltd.) at a reaction temperature of 110 ° C. using potassium hydroxide as a catalyst. To the polyol, 2 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours. Next, 4 mol of 2-hydroxyethyl acrylate and a small amount of dibutyltin dilaurate as a catalyst were gradually added, and further reacted at 70 ° C. for 15 hours to obtain a 1,2-butylene glycol unit-containing urethane acrylate oligomer having a number average molecular weight of about 1500. . The n-heptane tolerance value of the urethane acrylate oligomer having 1,2-polybutylene oxide units thus obtained was 1.0 g / 10 g.

  From the results of Examples and Comparative Examples in Tables 1 to 7, (A) at least (a) a silicone polyol represented by the general formula (1) (general formula (2)), and (b) a hydroxyl group at the terminal By using a dimethyl silicone (meth) acrylate oligomer obtained by using a (meth) acrylate monomer containing a functional group capable of reacting with benzene, and (D) a fluorine-containing compound, long-term performance such as slipperiness is achieved. It turns out that the photocurable resin composition which can be improved over is obtained.

Claims (14)

(A) Dimethyl silicone obtained by using at least (a) a silicone polyol represented by the following general formula (1) and (b) a (meth) acrylate monomer having a functional group capable of reacting with a hydroxyl group at the terminal. (Meth) acrylate oligomers,
(B) a photopolymerizable oligomer and / or (C) a photopolymerizable monomer copolymerizable with the (A) dimethyl silicone (meth) acrylate oligomer,
(D) a fluorine-containing compound, and
(E) A photocurable resin composition comprising a photopolymerization initiator.

However, in said general formula (1), n represents the integer arbitrarily selected so that the number average molecular weight of said (A) dimethyl silicone (meth) acrylate oligomer may be set to 700-40000, R represents total carbon. A C1-C30 alkylene group or a C1-C30 functional group having an ether bond is represented.   The (A) dimethyl silicone (meth) acrylate oligomer comprises (a) a silicone polyol represented by the general formula (1), (c) an isocyanate, and (b) a functional group capable of reacting with a hydroxyl group at the terminal. The photocurable resin composition according to claim 1, wherein the photocurable resin composition is obtained by reacting a (meth) acrylate monomer.   The equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in (c) isocyanate and the hydroxyl group in the silicone polyol represented by (a) general formula (1) is less than 100/100. 2. The photocurable resin composition according to 2.   The photocurable resin composition according to claim 2 or 3, wherein the (c) isocyanate is a polyisocyanate compound having a cyclic skeleton in the molecular structure.   The photocurable resin composition according to any one of claims 1 to 4, wherein the functional group capable of reacting with a hydroxyl group in the (b) (meth) acrylate monomer is an isocyanate group. 6. The photocuring according to claim 1, wherein the solubility parameter (SP value) of the (C) photopolymerizable monomer is 20.0 (J / cm ³ ) ^1/2 or less. Resin composition. The photocurable resin composition according to any one of claims 1 to 6, wherein the photopolymerizable monomer (C) is a compound represented by the following general formula (A).
_{^{(CH 2 = CR 1 COO)}} n R 2 ··· formula (A)
However, the above general formula (A), ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} represents an n-valent hydrocarbon group having 5 to 20 carbon atoms, n is in the range of 1-4 Represents an integer.   The photocurable resin composition according to any one of claims 1 to 7, wherein the (B) photopolymerizable oligomer is a (meth) acrylate oligomer having a 1,2-polybutylene oxide unit.   Content of said (A) dimethyl silicone (meth) acrylate oligomer is 0.05 mass%-10 mass% with respect to the sum total with said (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer. The photocurable resin composition according to claim 1, wherein the photocurable resin composition is provided.   The photocurable resin composition according to claim 1, wherein the fluorine-containing compound (D) has a photopolymerizable functional group.   The ratio (A / D) of the solid content of the (A) dimethyl silicone (meth) acrylate oligomer to the solid content of the (D) fluorine-containing compound is 0.2 to 10. The photocurable resin composition in any one of Claim 1 to 10.   The ratio (A / D) of the solid content of the (A) dimethyl silicone (meth) acrylate oligomer to the solid content of the (D) fluorine-containing compound is 0.4-3. The photocurable resin composition according to claim 11.   A water-surrounding member comprising: a coating layer formed by curing the photocurable resin composition according to claim 1; and a base material layer.   A functional panel comprising: a coating layer formed by curing the photocurable resin composition according to claim 1; and a base material layer.