TW201317304A - Light-curing resin composition, and plumbing member and functional panel using same - Google Patents

Abstract

Provided is a light-curing resin composition that exhibits improved characteristics such as slipperiness. This light-curing resin composition contains the following: a (A) dimethyl silicone (meth)acrylate oligomer obtained by reacting (a) a silicone polyol represented by general formula (1), (b) isocyanate, and a (c) (meth)acrylate monomer that has a terminal functional group that can react with isocyanate; a (B) photopolymerizable oligomer and/or (C) photopolymerizable monomer that can copolymerize with the aforementioned (A) dimethyl silicone (meth)acrylate oligomer; a (D) fluorine-containing compound; and a (E) photopolymerization initiator. In general formula (1), n represents an integer selected discretionarily so as to bring the number-average molecular weight of the (A) dimethyl silicone (meth)acrylate oligomer to between 700 and 40,000, inclusive; and R represents a C1-30 alkylene group or a C1-30 functional group having an ether bond.

Description

Photocurable resin composition, water-using member and functional panel using the same (2)

The present invention relates to a photocurable resin composition, and a water-repellent member and a functional panel using the same, and more particularly to a photocurable resin composition capable of improving water slidability (slip water which can easily remove surface water droplets) And the water-using member and functional panel using the same.

The functional panel as a building material is a member that is disposed as a wall surface of a building, a floor surface, or a wall surface of a ceiling, and is provided with various functions such as sound insulation effect and humidity adjustment property in accordance with the place where it is disposed. When such a functional panel is used as a water-using member such as a bathroom, a washstand, or a kitchen in a house, it is required to have various characteristics such as water repellency and water slick which can withstand a more severe use environment.

On the other hand, it has been tried to apply a low surface free energy compound having a small surface free energy and a composition having a reduced surface free energy to the surface of the member to impart good water repellency to the member to make the dirt difficult to adhere. The low surface free energy compound is a hydrophobic material such as a fluororesin or a polyoxyalkylene compound.

For example, Patent Document 1 below discloses a water-repellent member having a hardened material of a coating having a low surface free energy compound on its surface, and further discloses that the low surface free energy compound is a polyoxyalkylene resin compound or a fluororesin compound.

Further, Patent Document 2 below discloses a surface shape of a substrate resin. a resin molded body having a low surface free energy layer to make the surface of the molded body lower than the surface of the base resin and having a low surface free energy surface, and further revealing that the contact angle of the surface of the resin molded body with water is 90 degrees or more 170 degrees or less, the roll-off angle of the surface of the resin molded body and water is 1 degree or more and 80 degrees or less.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-69378

Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-233156

However, although water may bounce off the surface of the low surface free energy produced by using the above low surface free energy compound to form spherical water droplets on the surface, it is common that the water droplet strongly adheres to the surface without falling. In order to make the attached water droplets fall from the surface, it is attempted to roughen the surface to increase the contact angle of the surface as much as possible. However, the roughening of the surface has the problems of labor, high cost, and easy adhesion of dirt. .

Therefore, an object of the present invention is to provide a photocurable resin composition which can solve the above problems and improve water slidability. Further, another object of the present invention is to provide a water-repellent member and a functional panel which have a coating layer formed by curing the photocurable resin composition and which have excellent water slidability.

The inventors of the present invention have conducted further studies to achieve the above object, and as a result, it has been found that (A) a polyoxyalkylene polyol, (b) an isocyanate, and (c) a terminal having an isocyanate-reactive functional group are used (A). Dimethyl polyoxane (methyl) propyl obtained by reacting a methyl acrylate monomer The olefinic acid ester oligomer and the (D) fluorine-containing compound are used as constituent components of the photocurable resin composition to form a water-sliding surface capable of easily removing water droplets on the surface, and the present invention has been completed. Further, in the present specification, "(meth) acrylate" means acrylate or methacrylate.

Further, the inventors of the present invention found that by making the equivalent ratio (-NCO/-OH) of the isocyanate group (-NCO) in the (b) isocyanate to the hydroxyl group (-OH) in the (a) polyoxyalkylene polyol When it is more than 100/100 but less than 300/100, a prepolymer having an isocyanate group at the end can be produced, and thereafter, with respect to the isocyanate group at the end of the prepolymer, for example, it has a hydroxyl group and a (meth) acrylonitrile group. By reacting the monomer with it, a dimethylpolysiloxane (meth) acrylate oligomer having a high water repellency at the terminal (meth) acrylonitrile group can be produced, and the present invention can be completed.

In other words, the photocurable resin composition of the present invention comprises (A) a dimethyl polyoxyalkylene (meth) acrylate oligomer, wherein (a) is represented by the following formula (1). a polyoxyalkylene polyol, (b) an isocyanate, and (c) a (meth) acrylate monomer having a functional group capable of reacting with an isocyanate; (B) a photopolymerizable oligomer and/or Or (C) a photopolymerizable monomer copolymerizable with the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer; (D) a fluorine-containing compound; and (E) photopolymerization initiation Agent

In the above formula (1), n is an arbitrarily selected integer such that the number average molecular weight of the (A) dimethylpolyoxyalkylene (meth) acrylate oligomer is from 700 to 40,000, and the R system An alkylene group having a total carbon number of 1 to 30 or a functional group having a total carbon number of 1 to 30 having an ether bond.

In a preferred embodiment of the photocurable resin composition of the present invention, the equivalent ratio of the isocyanate group in the (b) isocyanate to the hydroxyl group in the polyoxane polyol represented by the formula (1) (Isocyanate group / hydroxyl group) is greater than 100/100 but 300/100 or less.

In another preferred embodiment 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, the SP value in the case of using two or more kinds of photopolymerizable monomers means that the SP value of each monomer is multiplied by each addition ratio (mass ratio) (in the case where the total amount of monomers is 1) The ratio of the monomers), and then sum the values. For example, a photopolymerizable monomer having an SP value of 19.0 is added in an amount of 3/4, and a photopolymerizable monomer having an SP value of 21.0 is added in an amount of 1/4 of the total amount of the photopolymerizable monomer. The SP value of the entire photopolymerizable monomer to be used was determined according to the following formula (X).

SP value of photopolymerizable monomer = (19.0 × 3 / 4) + (21.0 × 1/4) = 19.5 ... (X)

In another preferred embodiment of the photocurable resin composition of the present invention, the (C) photopolymerizable monomer is a compound represented by the following formula (A): (CH ₂ =CR ¹ COO) _n R ² .... General formula (A)

In the above formula (A), R ¹ represents a hydrogen atom or a methylalkyl group, R ² represents an n-valent hydrocarbon group having 5 to 20 carbon atoms, and n represents an integer in the range of 1 to 4.

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

In another preferred embodiment of the photocurable resin composition of the present invention, the functional group reactive with the isocyanate group in the (c) (meth) acrylate monomer is a hydroxyl group.

In another preferred embodiment of the photocurable resin composition of the present invention, the content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is relative to the (B) photopolymerizable oligomer. And/or (C) the photopolymerizable monomer is 0.05% by mass to 10% by mass.

In another preferred embodiment of the photocurable resin composition of the present invention, the (D) fluorine-containing compound is a photopolymerizable functional group.

In another preferred embodiment of the photocurable resin composition of the present invention, the solid content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is relative to the (D) fluorochemical The solid content ratio (A/D) is 0.2 to 10.

In another preferred embodiment of the photocurable resin composition of the present invention, the solid content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is contained The ratio (A/D) of the amount to the solid content of the (D) fluorine-containing compound is 0.4 to 3.

Moreover, the water-repellent member of the present invention is characterized in that it has 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 in that it has a coating layer formed by curing the photocurable resin composition of the present invention, and a base material layer.

According to the present invention, there can be provided a compound comprising (A) a polyoxyalkylene polyol represented by (a) formula (1), (b) an isocyanate, and (c) a terminal having an isocyanate-reactive function. a dimethyl polyoxyalkylene (meth) acrylate oligomer obtained by reacting a (meth) acrylate monomer, (B) a photopolymerizable oligomer, and/or (C) photopolymerizable property A photocurable resin composition which is a monomer, a (D) fluorine-containing compound, and (E) a photopolymerization initiator and which can improve water slidability. Moreover, a water-repellent member and a functional panel having a coating layer formed by curing the photocurable resin composition and having good water slidability can be provided.

(Photocurable resin composition)

Hereinafter, the present invention will be described in detail. The photocurable resin composition of the present invention comprises (A) dimethyl polyoxyalkylene (meth) acrylate oligomer, (B) photopolymerizable oligomer, and/or (C) photopolymerizable single The body, the (D) fluorine-containing compound, and the (E) photopolymerization initiator may contain (F) other components as needed.

In the photocurable resin composition of the present invention, (D) a high water repellency due to a low surface energy of the fluorine-containing compound and (A) dimethyl polyoxyalkylene (meth) acrylate oligomer The synergistic effect of the high water slidability improves the water slidability of the water absorbing member and the functional panel having the coating layer derived from the photocurable resin composition, for example.

Then, in the photocurable resin composition of the present invention, as a result of segregation of (A) dimethyl polyoxyalkylene (meth) acrylate oligomer and (D) fluorinated compound on the surface, for example, The performance of the water-repellent member of the coating layer of the photocurable resin composition and the water slidability of the functional panel.

<(A) dimethyl polyoxyalkylene (meth) acrylate oligomer>

The (A) dimethyl polyoxyalkylene (meth) acrylate oligomer used in the photocurable resin composition of the present invention is such that (a) a polyoxyalkylene polyol component, (b) an isocyanate component, and c) The (meth) acrylate monomer component is obtained by a reaction. The (A) dimethylpolyoxyalkylene (meth) acrylate oligomer, for example, is such that (a) a polyoxyalkylene polyol is reacted with (b) an isocyanate to synthesize a part or all of the terminal having an isocyanate The polyoxyalkylene polyol prepolymer is obtained, followed by the isocyanate group addition (c) (meth) acrylate monomer in the polyoxyalkylene polyol prepolymer.

By using an isocyanate to obtain a dimethyl polyoxyalkylene (meth) acrylate oligomer, it is possible to synthesize a prepolymer having an arbitrary repeat amount, thereby, in addition to adjusting the molecular weight, or obtaining a low In addition to the physical property values (softness, strength, adhesion, etc.) of the polymer, The inclusion of any number of highly polar urethane bonds therein has the advantage of being easier to design with the base resin.

The number average molecular weight of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is not particularly limited, and may be appropriately selected depending on the purpose, but is preferably from 700 to 40,000. The number average molecular weight can be determined from the polystyrene standard by GPC, and is determined from the holding time of the sample. The mobile layer solvent of GPC may be tetrahydrofuran or chloroform. Further, the detector may use a refractometer (RI), a UV detector, or the like. If the number average molecular weight obtained by the above method is less than 1,000, since the relative amount of the dimethyloxane moiety in the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is lowered, To achieve sufficient results, it is necessary to make more additions. On the other hand, if the number average molecular weight exceeds 40,000, (B) photopolymerizable oligomer and (C) polymerizable with (A) dimethyl polyoxyalkylene (meth) acrylate oligomer The compatibility of the photopolymerizable monomer is markedly lowered and separated, and the crosslinking density is lowered to cause the surface of the film to become soft or to be damaged.

(A) a dimethyl polyoxyalkylene (meth) acrylate oligomer, in addition to (a) a polyoxyalkylene polyol represented by the formula (1), (b) an isocyanate, and (c) terminal In addition to the (meth) acrylate monomer of the functional group reactive with isocyanate, (d) other polyol component may be contained. In this case, (a) a polyoxyalkylene polyol, (d) another polyol, and (b) an isocyanate are copolymerized to synthesize a polyoxyalkylene polyol prepolymer having a part or all of an isocyanate group at the terminal. Substance, then, the polyoxyalkylene The isocyanate group addition (c) terminal in the polyol prepolymer is obtained by a (meth) acrylate monomer having a functional group reactive with isocyanate.

By including (d) another polyol component, the water repellency, the compatibility with the base resin, the hardness of the cured product, and the like can be arbitrarily adjusted.

The content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is not particularly limited, and may be appropriately selected depending on the purpose, but is preferably relative to (B) photopolymerizable oligomer. And/or (C) the total amount of the photopolymerizable monomer (the entire resin) is 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5.0% by mass. Here, the content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is the active ingredient amount of the (A) dimethyl polyoxy siloxane (meth) acrylate oligomer ( The amount of solid part).

When the content is less than 0.05% by mass, the water slidability of the article coated with the photocurable composition of the present invention may not be sufficiently improved, and if it exceeds 10% by mass, the photopolymerizability is low and (B) The compatibility of the polymer and/or the (C) photopolymerizable monomer is deteriorated, and a uniform cured product cannot be obtained. On the other hand, if the content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is within the above preferred range, (A) dimethyl polyoxy siloxane (meth) acrylate The surface segregation of the ester oligomer becomes remarkable, and the water slidability of the article coated with the photocurable resin composition of the present invention can be achieved. Further, since the addition effect is almost saturated at 5.0%, it is also advantageous from the cost side to make the content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer within the above preferred range. .

- (a) polyoxyalkylene polyol -

As the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer The (a) polyoxyalkylene polyol used in one of the starting materials is represented by the following formula (1).

In the above formula (1), n is such that the number average molecular weight of the (A) dimethylpolyoxyalkylene (meth) acrylate oligomer is 700 to 40,000 (the polypyrone is made). The number average molecular weight of the polyol is arbitrarily selected from 500 to 40000), and is not particularly limited, and may be appropriately selected depending on the purpose.

Further, in the above formula (1), R is not particularly limited as long as it is an alkylene group having a total carbon number of 1 to 30 or a total of 1 to 30 carbon atoms having an ether bond, and may be appropriately used depending on the purpose. Ground selection.

The alkylene group having 1 to 30 total carbon atoms is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include methylene, ethylene, propylene, butene, pentene, hexene, heptene, octene, and the like. The alkylene group having a total carbon number of 1 to 30 without an ether bond.

Further, the functional group having 1 to 30 total carbon atoms of the ether bond is not particularly limited, and may be appropriately selected depending on the purpose, for example, -C ₃ H ₆ -OC ₂ H ₄ -, -C ₃ H ₆ -( OC ₂ H ₄ ) _m -: m is an integer having a total carbon number of not more than 30, and examples thereof include -C ₂ H ₄ -OC ₂ H ₄ -, -C ₃ H _6- OC ₃ H ₆ - and the like.

The total carbon number of R is 30 or less because of the viewpoint of the concentration of dimethyl polysiloxane, heat resistance, and the like. R is preferably a propylene group or -C ₃ H ₆ -OC ₂ H ₄ - from the viewpoint of ease of market availability.

Further, as an example of the above formula (1), the following formula (2) is exemplified.

In the above formula (2), n represents that the number average molecular weight of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is 700 to 40,000 (the polypyroxyne is made plural) The number average molecular weight of the alcohol is an arbitrary integer selected from 500 to 40000), p is an integer in the range of 0 to 9, and q is an integer in the range of 3 to 9.

The commercial product of the (a) polyoxyalkylene polyol is not particularly limited and may be appropriately selected depending on the purpose. For example, DMS-C16 (manufactured by Gelest Co., Ltd.: number average molecular weight ≒700: p=0, q) is exemplified. =3), FM-4411 (manufactured by CHISSO Co., Ltd.: number average molecular weight ≒1,000: p = 1, q = 3), FM-4421 (manufactured by CHISSO Co., Ltd.: number average molecular weight ≒ 5,000: p = 1, q) =3), FM-4425 (manufactured by CHISSO Co., Ltd.: 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 (letter Yue Chemical Industry Co., Ltd.: number average molecular weight ≒ 4,000: p ≒ 5, q = 3) and so on. These may be used alone or in combination of two or more.

In the above formula (2), p and q represent an integer within the above range. The compatibility with the base resin can be changed by changing the lengths. On the other hand, if the length is too long, the concentration of polysiloxane in the structure is relatively lowered, so that a sufficient function cannot be exhibited. As long as p and q are in the above range, there is no influence on the purpose of improving the water slidability (water repellency of the water droplets which can easily remove the surface) as the object of the present invention, so that the function can be sufficiently achieved.

Further, the (a) polyoxyalkylene polyol can be reacted, for example, with a platinum-based catalyst to form a terminal Si-H group-containing dimethyl polyoxyalkylene with a compound having a hydroxyl group and an alkenyl group at each terminal. Manufacturing.

The number average molecular weight (Mn) of the (a) polyoxyalkylene polyol is not particularly limited as long as it is 500 to 20,000, and can be appropriately selected depending on the purpose. The number average molecular weight can be determined from the polystyrene standard by GPC, and is determined from the holding time of the sample. GPC's move As the layer solvent, tetrahydrofuran or chloroform can be used. Further, the detector may use a refractometer (RI), a UV detector, or the like.

If the number average molecular weight is less than 500, since the relative amount of the dimethyloxane moiety in the structure is lowered, in order to exhibit sufficient effects, it is necessary to increase the amount of addition, and if it exceeds 20,000, it is compatible with ( A) The compatibility of the (B) photopolymerizable oligomer and/or (C) photopolymerizable monomer in which the dimethyl polyoxyalkylene (meth) acrylate oligomer is polymerized is markedly lowered and separated. Further, the crosslink density is lowered, and the surface of the film becomes soft or becomes a surface that is easily damaged.

- (b) isocyanate -

The (b) isocyanate used as one of the starting materials of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is not particularly limited, and may be appropriately selected depending on the purpose. However, a polyisocyanate compound having a cyclic skeleton in a molecular structure is preferred.

If the (b) isocyanate is a polyisocyanate compound having a cyclic skeleton in a molecular structure, the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer derived from an isocyanate itself may have a molecular structure. Ring skeleton. Then, the cyclic skeleton present in the molecular structure of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer becomes a steric hindrance, so that (A) dimethyl polyoxy siloxane (A) The immersion of the acrylate oligomer into the interior of the photocurable resin composition is suppressed, resulting in segregation of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer on the surface.

The (is) isocyanate is a polyisocyanate compound having a cyclic skeleton in a molecular structure, as long as it has a cyclic skeleton in a molecular structure. (Acyclic structure portion), and a plurality of isocyanate groups (NCO groups) are not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include naphthalene diisocyanate (NDI), toluene diisocyanate (TDI), and Toluene diisocyanate (XDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate (PPDI), tolidine diisocyanate (TODI), dianisidine diisocyanate (DADI) ), dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis(isocyanatemethyl)cyclohexane (H6XDI), tetramethylxylene diisocyanate (TMXDI), norbornene diisocyanate (NBDI), and A urethane prepolymer or the like having an NCO terminal of such a structure. These may be used alone or in combination of two or more. Among them, naphthalene diisocyanate (NDI), toluene diisocyanate (TDI), xylene diisocyanate (XDI), and isophorone diisocyanate (IPDI) are preferred.

The amount of the (a) polyoxyalkylene polyol and (b) isocyanate may be appropriately changed, and (b) the equivalent of the isocyanate group (-NCO) in the isocyanate and the (a) hydroxyl group in the polyoxyalkylene polyol. The ratio (-NCO/-OH) is preferably in the range of more than 100/100 but 300/100 or less.

Further, when the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is synthesized, (b) an isocyanate is reacted with a hydroxyl group in (a) a polyoxyalkylene polyol to synthesize an end. a part or all of the isocyanate-based urethane prepolymer, as long as it is an equivalent ratio of the isocyanate group (-NCO) in the (b) isocyanate to the hydroxyl group in the (a) polyoxyalkylene polyol (-NCO/-OH) is greater than 1.

Thus, by making (b) an isocyanate group in the isocyanate When the equivalent ratio (-NCO/-OH) of (-NCO) to (a) the hydroxyl group in the polyoxyalkylene polyol is more than 1, a prepolymer having an isocyanate group at both ends can be synthesized, and the isocyanate group can be utilized. It is reacted with a functional group (for example, an isocyanate group) in the (c) (meth) acrylate monomer.

In the reaction of the (a) polyoxyalkylene polyol and the (b) isocyanate, a catalyst for the urethanization reaction is preferably used. The catalyst for the urethanization reaction is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include dibutyltin dilauryl ester, dibutyltin diacetate, dibutyltin thiocarboxylate, and Organotin compounds such as butyltin dimaleate, dioctyltin thiocarboxylate, tin octenate, monobutyltin oxide; inorganic tin compounds such as stannous chloride; organic lead compounds such as lead octenate; a cyclic amine such as ethylene diamine; an organic sulfonic acid such as p-toluenesulfonic acid, methanesulfonic acid or fluorosulfuric acid; an inorganic acid such as sulfuric acid, phosphoric acid or perchloric acid; a sodium alkoxide, lithium hydroxide, aluminum alkoxide or hydrogen; a salt such as sodium oxide; a titanium compound such as tetrabutyl titanate, tetraethyl titanate or tetraisopropyl titanate; an anthracene compound; a quaternary ammonium salt. These may be used alone or in combination of two or more. Among these, organotin compounds are preferred. The amount of the catalyst for the urethanation reaction is not particularly limited, and may be appropriately selected depending on the intended purpose, but it is preferably 0.001% by mass based on 100% by mass of the (a) polyfluorene oxide polyol. Mass%~2.0% by mass.

-(c) (meth) acrylate monomer -

(c) (meth) acrylate monomer used as one of the starting materials of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer, as long as it is contained at the end a functional group reactive with isocyanate It is not particularly limited and may be appropriately selected depending on the purpose.

The functional group reactive with the isocyanate is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include a hydroxyl group (-OH), a carboxyl group (-COOH), a 1-stage amine group, and a 2-stage amine group.

Among these, a hydroxyl group is preferable from the viewpoint of the goodness of reactivity with the isocyanate or the variety of commercially available products and easy availability.

The (meth) acrylate monomer having the hydroxy group (-OH) is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include 2-hydroxyethyl (meth)acrylate and (meth)acrylic acid 2 -hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (meth)acrylic acid 4 - Hydroxycyclohexyl ester, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.

The (meth) acrylate monomer having the carboxyl group (-COOH) is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include, for example, 2-(meth)acryloyloxyethyl succinate, 2- Acryloxyethyl-succinic acid, monohydroxyethyl (meth) acrylate, and the like.

The (meth) acrylate monomer having the amine group is not particularly limited and may be appropriately selected depending on the purpose, and for example, a (meth) acrylate having a 1-aminoethyl group as a side chain and a side chain are exemplified. 1-aminopropyl (meth) acrylate or the like.

(c) The (meth) acrylate monomer may contain a functional group reactive with isocyanate and a photopolymerizable (meth) acrylonitrile group in the structure. By. Although the number of the (meth)acrylinyl group may be any number, if the amount is more (multifunctional), the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer may become more Functional. In general, the higher the number of reactive functional groups of the (meth) acrylate monomer and the (B) photopolymerizable oligomer or the (C) photopolymerizable monomer, the higher the number of functional groups is. There is a case where the reaction rate is lowered due to a steric obstacle. The number of functional groups of the (meth) acrylate monomer is preferably from 2 to 10 in consideration of such factors, and more preferably (close to 10). In the meantime, as the number of functional groups of the (meth) acrylate monomer increases, the crosslinking becomes dense, so that it can be stably segregated on the surface and the surface hardness can be improved, which is preferable.

The (c) (meth) acrylate monomers may be used alone or in combination of two or more.

The amount of the (c) (meth) acrylate monomer used may be appropriately changed, and it is composed of (a) a polyoxyalkylene polyol and (b) an isocyanate which is a polyisocyanate compound having a cyclic skeleton in a molecular structure. The isocyanate group (-NCO) in the reaction product (urethane prepolymer), (c) the equivalent of the functional group reactive with isocyanate in the (meth) acrylate monomer (functional group /- NCO) may be used in an amount of more than one equivalent.

<(B) Photopolymerizable oligomer and/or (C) photopolymerizable monomer>

The (B) photopolymerizable oligomer used in the photocurable resin composition of the present invention and/or the (C) photopolymerizable single system contains a radical polymerizable reactive group such as a (meth) acrylonitrile group. [CH ₂ =CHCO- or CH ₂ =C(CH ₃ )CO-] or the like. Further, in the present invention, the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is removed from the (B) photopolymerizable oligomer.

Further, the mass ratio of the (B) photopolymerizable oligomer to the (C) photopolymerizable monomer is from 100:0 to 0:100, preferably from 80:20 to 20:80, more preferably 30. : Range of 70~70:30. When the amount of the (C) photopolymerizable monomer added is too small, the viscosity of the photocurable composition obtained increases, and the coating property in the case of application is deteriorated, and the drug resistance cannot be sufficiently ensured. The possibility of physical properties such as sex and dye resistance. In addition, when the amount of the photopolymerizable monomer is too large, the flexibility of the coating film is lowered, and the friability tends to be high.

- (B) Photopolymerizable oligomer -

The (B) photopolymerizable oligomer is not particularly limited, and may be appropriately selected depending on the intended purpose, but preferably has one or more acryloxy groups [CH ₂ =CHCOO-] or methacryl oxime. A (meth) acrylate oligomer of oxygen [CH ₂ =C(CH ₃ )COO-], particularly preferably a (meth) acrylate oligomer having a 1,2-polybutylene oxide unit. Since the (meth) acrylate oligomer having the 1,2-polybutylene oxide unit has a low polarity, it is oligomerized with (A) dimethyl polyoxyalkylene (meth) acrylate. The compatibility is good, and (A) dimethyl polyoxyalkylene (meth) acrylate oligomer can be added in a wide range. Therefore, even when the amount of (A) dimethyl polyoxyalkylene (meth) acrylate oligomer added is large, white turbidity, layer separation, and the like can be suppressed, and the properties after hardening can be made uniform. The appearance of the coating film is good, and the water-using member and the functional panel using the same can form good physical properties and appearance. Further, since the resin obtained by curing the photocurable resin composition has high hydrophobicity, it is highly resistant to stains such as detergents or hair dyes used in water and water, and dirt is difficult to be used. Adhesion and water slidability will be more stable.

Further, the (meth) acrylate oligomer (A) has a low polarity, and can be specifically represented by an n-heptane allowable value, and the value is preferably 0.5 g/10 g or more, more preferably 0.7 g/10 g. the above. Further, the n-heptane allowable value means a value obtained by continuously adding n-heptane to the amount of n-heptane (g) while dropping 10 g of the resin at 25 ° C until it is cloudy, which is relative to the organic solvent. The indicator of solubility, if the value is larger, indicates that the polarity is weaker.

The (meth) acrylate oligomer is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include an amine ester (meth) acrylate oligomer and an epoxy (meth) acrylate. Polymer, ether (meth) acrylate oligomer, ester (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, polyoxyalkylene (methyl) Acrylate oligomers, etc. The (meth) acrylate oligomers can be synthesized in the following manner: polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, bisphenol A epoxy resin, phenol novolac epoxy The resin, the adduct of the polyol and ε-caprolactone, and the like are reacted with (meth)acrylic acid; or the polyisocyanate compound and the (meth) acrylate compound having a hydroxyl group are subjected to amine esterification.

The (B) photopolymerizable oligomer may be any of a monofunctional oligomer, a difunctional oligomer, and a polyfunctional oligomer, from achieving an appropriate crosslinking density of the obtained photocurable resin composition. From the viewpoint of the above, a polyfunctional oligomer is preferred.

Among the (B) photopolymerizable oligomers, an amine ester-based (meth) acrylate oligomer excellent in chemical resistance is obtained from the viewpoint of imparting good characteristics as a water-retaining member and a functional panel. It is better.

The amine ester (meth) acrylate oligomer can be synthesized by, for example, (i) a polyol and (ii) a polyisocyanate, and then prepolymerized with the urethane. The compound is produced by a compound having a functional group reactive with (iii) isocyanate, for example, a (meth) acrylate having a hydroxyl group.

--(i) Polyol--

The polyol to be 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 may be appropriately selected depending on the purpose, and for example, polyether polyol is exemplified. , polyester polyol, polytetramethylene glycol, polybutadiene polyol, alkylene oxide modified polybutadiene polyol, polyisoprene polyol, and the like. These may be used alone or in combination of two or more.

The polyether polyol can be obtained by addition polymerization, for example, an addition of a polyol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol or sorbitol to ethylene oxide or propylene oxide. Obtained by oxyalkylene, and polyether polyol can also be obtained by ring-opening polymerization. The polyether polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran (THF) may, for example, be mentioned.

The polyester polyol can be obtained by addition polymerization, for example, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, trishydroxyl Polyols such as ethyl ethane and trimethylolpropane are obtained with polybasic acids such as adipic acid, glutaric acid, succinic acid, azelaic acid, pimelic acid, and suberic acid, and may also be opened by ring opening. Polymerization to obtain a polyester polyol. The polyester polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a lactone-based polyester polyol obtained by ring-opening polymerization of ε-caprolactone is exemplified.

As the (i) polyol, a (meth) acrylate oligomer having the above 1,2-polybutylene oxide unit can be produced by using a butylene oxide-modified polyol. The butylene oxide-modified polyol is a polyether polyol obtained by adding 1,2-butylene oxide (BO) to a polyol in the presence of a basic catalyst. Further, a polyether polyol obtained by adding polyoxyalkylene such as propylene oxide (PO) to a poly(1,2-butylene oxide (BO)) may be added. In this case, the ratio of 1,2-butylene oxide (BO) to other alkylene oxide is 20:80 to 100:0, preferably 50:50 to 100:0 in terms of a molar ratio. The GPC-based arithmetic mean molecular weight of these butylene oxide-modified polyols is usually from 100 to 15,000, preferably from 500 to 5,000.

--(ii) Polyisocyanate --

The polyisocyanate is not particularly limited as long as it is a compound having a plurality of isocyanate groups (-NCO), and may be appropriately selected according to the purpose, and examples thereof include toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). , crude diphenylmethane diisocyanate (Crude MDI), isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hexamethylenic diisocyanate (HDI); or the same Cyanuric acid modified material, carbodiimide modified product, glycol modified substance, and the like. These can be used alone or in combination 2 or more types.

- Catalyst for urethane reaction --

In the synthesis of the urethane prepolymer, a catalyst for the urethanization reaction is preferably used. The catalyst for the urethanization reaction is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, and dimaleic acid. Organotin compounds such as dibutyltin, dioctyltin thiocarboxylate, tin octenate, monobutyltin oxide; inorganic tin compounds such as stannous chloride; organic lead compounds such as lead octenate; and triethylenediamine Amines; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid; inorganic acids such as sulfuric acid, phosphoric acid, perchloric acid; sodium alkoxide, lithium hydroxide, aluminum alcoholate, sodium hydroxide, etc. a base; a titanium compound such as tetrabutyl titanate, tetraethyl titanate or tetraisopropyl titanate; an oxime compound; a quaternary ammonium salt. These may be used alone or in combination of two or more.

Among these, organotin compounds are preferred.

The amount of the catalyst for the urethanation reaction is not particularly limited, and may be appropriately selected depending on the intended purpose, but is preferably 0.001% by mass based on 100% by mass of the (i) polyol. 2.0% by mass.

-- a compound having a functional group reactive with (iii) isocyanate --

Further, the compound having a functional group reactive with (iii) isocyanate in the urethane prepolymer is one having one or more functional groups (for example, a hydroxyl group) reactive with isocyanate, and has one or more A compound exhibiting a photopolymerizable functional group ((meth)acryloxyloxy group [CH ₂ =CHCOO- or CH ₂ =C(CH ₃ )COO-])). A compound having a functional group reactive with the (iii) isocyanate may be added to the isocyanate group in the urethane prepolymer.

The compound having a functional group reactive with the (iii) isocyanate is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include 2-hydroxyethyl (meth)acrylate and 2-hydroxy (meth)acrylate. Propyl ester, pentaerythritol tri(meth)acrylate, 2-hydroxyethyl vinyl ether vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 3-ethyl-3-hydroxyl Methyl propylene oxide, 2-(meth) propylene oxirane ethyl succinate, monohydroxyethyl (meth) acrylate phthalate, 1-aminoethyl group (methyl) The acrylate and the side chain are 1-aminoethyl (meth) acrylate and the like. These may be used alone or in combination of two or more.

By adding the above (B) photopolymerizable oligomer, the glass transition temperature exhibited by the coating layer obtained by curing the photocurable resin composition can be optimized, and excellent water slidability can be obtained. A photohardenable composition of effect.

-(C) Photopolymerizable monomer -

The (C) photopolymerizable monomer is not particularly limited, and may be appropriately selected depending on the intended purpose, but preferably has one or more (meth) propylene fluorenyloxy groups [CH ₂ =CHCOO- or CH ₂ a (meth) acrylate monomer of =C(CH ₃ )COO-], which may also be (i) a monofunctional monomer, (ii) a bifunctional monomer, and (iii) a polyfunctional monomer. One.

Further, the (C) photopolymerizable monomer may be used alone or in combination of two or more. The SP value in the case of using two or more kinds of photopolymerizable monomers means the SP value of each monomer multiplied by each addition ratio (mass ratio) (the ratio of each monomer in the case where the total amount of monomers is 1), and the total value is added. For example, a photopolymerizable monomer having an SP value of 19.0 is added in an amount of 3/4, and a photopolymerizable monomer having an SP value of 21.0 is added in an amount of 1/4 of the total amount of the photopolymerizable monomer. The SP value of the entire photopolymerizable monomer to be used was determined according to the following formula (X).

SP value of photopolymerizable monomer = (19.0 × 3 / 4) + (21.0 × 1/4) = 19.5 ... (X)

- (i) monofunctional monomer -

The (i) monofunctional monomer is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include isodecyl (meth)acrylate, decyl (meth)acrylate, and tricyclo(meth)acrylate. Anthracene ester, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate; benzyl (meth)acrylate, 4-butyl (meth)acrylate Cyclohexyl ester, (meth) propylene morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (methyl) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (methyl) Tert-butyl acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, (methyl) Isooctyl acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate Base ester, dodecyl (meth)acrylate (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth Iso-octadecyl acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, polyoxyethylene Nonylphenyl ether acrylate, phenoxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxy (meth)acrylate Glycol ester, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dimethylamine (meth)acrylate Ethyl ethyl ester, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

- (ii) bifunctional monomer -

The (ii) bifunctional monomer is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and Triethylene glycol (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, di(meth)acrylic acid- 1,9-decanediol ester, neopentyl glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecane dimethanol (Meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, dialkyl (meth) acrylate of bisphenol A alkylene glycol addition diol, hydrogenated bisphenol A ring An oxyalkylene-added di(meth) acrylate of a diol, an epoxy (meth) acrylate obtained by adding a (meth) acrylate to a diglycidyl ether of bisphenol A, or the like. These may be used alone or in combination of two or more.

- (iii) Polyfunctional monomer -

The (iii) polyfunctional monomer is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include trimethylolpropane tri(meth)acrylate and ethoxylated trimethylolpropane tris(A). Acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Bis(trimethylolpropane)tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, and the like. These may be used alone or in combination of two or more.

The solubility parameter (SP value) of the photopolymerizable monomer is not particularly limited, and may be appropriately selected depending on the purpose, but is preferably 20.0 (J/cm ³ ) ^0.5 or less, more preferably 19.6 (J/cm). ³ ) ^0.5 or less. Further, the lower limit of the SP value is not particularly limited, but is usually preferably 17.0 (J/cm ³ ) of ^0.5 or more. When the SP value is low, compatibility with (A) dimethyl polyoxyalkylene (meth) acrylate oligomer and (D) fluorochemical is good, and (A) dimethyl group can be widely added. A polyoxyalkylene (meth) acrylate oligomer and (D) a fluorine-containing compound. Therefore, even when the amount of (A) dimethyl polyoxyalkylene (meth) acrylate oligomer and (D) fluorinated compound is large, it is possible to suppress white turbidity, layer separation, etc., after hardening. The appearance is good, and the water-using member and the functional panel using the same can also form a good appearance.

Here, the SP value (δ) is generally defined by the Mohr evaporating energy (ΔEv) and the Mohr volume (V) of the liquid, and is defined by the following formula: SP value (δ) = (ΔEv/V) ^0.5 .

Furthermore, according to the Fedors method, the SP value can be estimated only by the chemical structure (refer to "Solubility Parameter Values", Polymer Handbook, 4th edition (J.Brandrup et al.). Further, in the present specification, the SP value means a value calculated according to the Fedors method, and the lower the value, the weaker the polarity of the photopolymerizable monomer (C).

Further, the (C) photopolymerizable monomer is preferably represented by the following formula (A): (CH ₂ = CR ¹ COO) _n R ² ... (A)

The monomer represented. In the formula (A), R1 is a hydrogen atom or a methylalkyl group, and R ² is an n-valent hydrocarbon group having 5 to 20 carbon atoms, but does not contain a hetero atom, and may be a chain or a ring. Further, -CH ₂ - in the group may be substituted by -CH=CH-. n is an integer from 1 to 4.

That is, in the general formula (2), for example, in the case of a chain-like saturated monomer, when n=1, R ² is an alkyl group having 5 to 20 carbon atoms, and when n=2, R ² is a carbon number of 5 to 20 Alkylene group. Further, in the case of a chain-saturated monomer, when n=3, R ² is a cyanide trialkyl having 5 to 20 carbon atoms, and when n=4, R ² is a carbon number of 5 to 20. Alkane tetrayl. The above R ^{2 is,} for example, an alkyl group such as -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH(CH ₃ )CH ₃ , cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclodecyl. Alkyl group such as -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ -, a trisubstituted alkyl group represented by CH ₃ CH ₂ C(CH ₂ -) ₃ Or a tetrasubstituted alkyl group represented by C(CH ₂ -) ₄ or the like.

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) dimethyl polyoxyalkylene (meth) acrylate oligomer The compatibility of the (D) fluorine-containing compound is lowered, and when it is a cyclic hydrocarbon group, it becomes difficult to obtain itself. Further, when the carbon number of R ² exceeds 20, the crosslinking density of the obtained photocurable composition tends to decrease. Assuming that the crosslink density is excessively lowered as much as necessary, since the dye such as a hair dye easily penetrates into the inside of the coating layer, the wall may be dyed.

Specific examples of the monomer represented by the formula (A) include, for example, isodecyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dimethylol tricyclodecane. (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, 18 (meth) acrylate Alkyl ester, 3-methyl-1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, two 1,9-nonanediol (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like.

Among these, there is a tendency to exhibit a good low polarity due to a preferred SP value, not only with (A) dimethyl polyoxyalkylene (meth) acrylate oligomer and (D) fluorochemical From the viewpoint of compatibility, and further improvement of chemical resistance or dyeing resistance, 1,9-nonanediol di(meth)acrylate and 1,6-hexane di(meth)acrylate Alcohol ester, isodecyl (meth)acrylate, dimethylol tricyclodecane di(meth) acrylate, more preferably 1,6-hexanediol di(meth)acrylate, (methyl) Isodecyl acrylate and 1,9-nonanediol di(meth)acrylate are preferred.

Since the solubility parameter (SP value) is 20.0 (J/cm ³ ) ^0.5 or less photopolymerizable monomer, especially the monomer represented by the formula (A) has a weak polarity, and thus (A) dimethyl The polyoxyalkylene (meth) acrylate oligomer and the (D) fluorochemical have good compatibility, and the (A) dimethyl polyoxy siloxane (meth) acrylate oligomerization can be widely added. And (D) a fluorine-containing compound. Therefore, even when the amount of (A) dimethyl polyoxyalkylene (meth) acrylate oligomer and (D) fluorinated compound is large, white turbidity, layer separation, etc. can be suppressed, and after hardening The appearance is good, and the water-using member and the functional panel using the same can form a good appearance. Further, since the resin obtained by curing the photocurable composition has high hydrophobicity, it is highly resistant to a dye such as a detergent or a hair dye used in water and water, and the dirt is less likely to adhere. The stability of water skating will be better.

Further, the number of functional groups of the photopolymerizable monomer is usually from 1 to 6, preferably from 1 to 4. Further, when the number of functional groups is 1, the crosslinking density tends to decrease, but by using a monomer having a cyclic skeleton, the glass transition temperature is improved, and good film physical properties can be maintained. In addition, when the number of functional groups is from 2 to 6, preferably from 2 to 4, since the crosslinking reaction of the photocurable composition can be appropriately maintained, it is presumed that the dyeing agent can be more effectively suppressed. Penetration into the interior of the coating layer causes staining of the water-using member and the functional panel. Therefore, in this case, it is also possible to obtain a water-removing member and a functional body which are not only excellent in antifouling property but also have a coating layer having a preferable hardenability while effectively maintaining chemical resistance or dyeing resistance. panel.

(B) Photopolymerizable oligomer and (C) Photopolymerizable monomer It is preferred to use an oligomer alone or a monomer alone, but it is preferred to use an oligomer and a monomer in combination.

<(D) Fluorine-containing compound>

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

As the fluorine-containing compound, any fluorine-containing compound can be used. When durability is considered, it is possible to contain (A) dimethyl polyoxyalkylene (meth) acrylate oligomer, (B) photopolymerizable oligomer, and/or (C) photopolymerizable monomer. (E) In the sense that the photocurable composition of the photopolymerization initiator reacts and is immobilized in the system, it is preferred that the (D) fluorine-containing compound also has a photopolymerizable functional group in the structure (reactive group) ).

The (D) fluorine-containing compound is not particularly limited, and may be appropriately selected depending on the intended purpose. For example, a perfluoroalkyl group-containing photopolymerizable compound such as perfluorooctylethyl acrylate is exemplified.

The commercially available product of the (D) fluorine-containing compound is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include LIGHT ACRYLATE FA-108 (manufactured by Kyoeisha Chemical Co., Ltd.) and RS-75 (DIC shares). Co., Ltd.), OPTOOL DAC-HP (manufactured by DAIKIN Industries Co., Ltd.), MODIPER F200, F600, F3035 (manufactured by Nippon Oil Co., Ltd.), HYPERTECH FA-200 (manufactured by Nissan Chemical Industries, Ltd.), etc. These may be used alone or in combination of two or more.

The mass ratio (A/D) of the solid content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer to the solid content of the (D) fluorochemical is preferably 0.2. The range of 10.0 is more preferably in the range of 0.4 to 3.0. Here, the mass ratio (A/D) is (A) dimethyl polyoxyalkylene (meth) acrylate oligomer and (D) fluorochemical in the photocurable composition. Active ingredient ratio (solids ratio). When the mass ratio (A/D) is 0.2 or more, high water repellency derived from (D) fluorine-containing compound and (A) dimethyl polyoxyalkylene (meth) acrylate oligomer can be expected. When the effect of both of the water repellency is 0.4 or more, since the concentration of the fluorine-containing compound on the surface and the (A) dimethyl polyoxyalkylene (meth)acrylate oligomer becomes high, the above-mentioned ratio can be further expected. When the effect is as described above, the compatibility with (B) photopolymerizable oligomer and/or (C) photopolymerizable monomer can be obtained, and if it is 3.0 or less, it can be obtained. More good compatibility.

In the photocurable composition of the present invention, the content of the (D) fluorine-containing compound is preferably 0.05% by mass based on 100% by mass of the total of the (B) photopolymerizable oligomer and the (C) photopolymerizable monomer. The range of the mass % to 5.0% by mass is more preferably in the range of 0.1% by mass to 3.0% by mass. Here, the content of the (D) fluorine-containing compound is (D) the amount of the active ingredient of the fluorine-containing compound (the amount of the solid portion). When the content of the (D) fluorine-containing compound is 5% by mass or less, the effect of improving the water repellency and the water slidability can be sufficiently exhibited. On the other hand, when the content is more than 5% by mass, the surface of the characteristic surface and the cost are obtained. If it is 3.0% by mass or less, it is expected that the water repellency and the water skating property which are not problematic in practical use can be sufficiently improved. In addition, when the content of the (D) fluorine-containing compound is 0.1% by mass or more, the effect of improving the water repellency and the water slidability of the photocurable resin composition is greatly improved.

<(E) Photopolymerization initiator>

The (E) photopolymerization initiator used in the photocurable resin composition of the present invention has the above (A) dimethyl group by irradiating light such as ultraviolet rays. The polymerization of a polyoxyalkylene (meth) acrylate oligomer, (B) a photopolymerizable oligomer, and/or (C) a photopolymerizable monomer.

The (E) photopolymerization initiator is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include 4-dimethylamino benzoic acid, 4-dimethylamino benzoate, and 2,2-. Dimethoxy-2-phenylethene phenol, ethylene phenol diethyl ketal, alkoxyvinyl phenol, benzyl dimethyl ketal, benzophenone, and 3,3-dimethyl-4-methyl a benzophenone derivative such as oxybenzophenone, 4,4-dimethoxybenzophenone or 4,4-diaminobenzophenone, benzhydryl benzoic acid alkyl ester, double ( Benzyl derivatives such as 4-dialkylaminophenyl)one, benzyl and benzyl methyl ketal, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropenylbenzene, 1-hydroxy-cyclohexyl-phenyl-one, xanthone, thioxanthone and thioxanthone derivatives, anthracene, 2,4,6-trimethylbenzene Methyldiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-tri Methyl benzhydryl)-phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-? Phenyl) - butanone-1, etc. These may be used alone or in combination of two or more.

The amount of the (E) photopolymerization initiator to be added to the photocurable resin composition of the present invention is not particularly limited, and may be appropriately selected depending on the purpose, but is relative to (A) dimethyl polyoxyalkylene (A) The acrylate oligomer, the (B) photopolymerizable oligomer, and/or the (C) photopolymerizable monomer (D) and the fluorine-containing compound are 100% by mass in total, preferably 0.1% by mass to 10% by mass. The range of %. When the amount of the (E) photopolymerization initiator added is 0.1% by mass or more, The polymerization reaction can be sufficiently started. On the other hand, when it exceeds 10 masses, the effect of starting the polymerization reaction is saturated, and the coloring becomes conspicuous, and the raw material cost of the photocurable resin composition becomes high.

<(F) Other ingredients> -Light sensitizer -

The photocurable resin composition of the present invention may further contain a photosensitizer as needed in consideration of the required hardening reactivity, stability, and the like. The photosensitizer absorbs light by being irradiated with light, and the energy or electrons move toward the polymerization initiator to initiate polymerization. The photosensitizer is exemplified by isoamyl p-dimethylamine benzoate or the like. The amount of the photosensitizer added is preferably relative to (A) photopolymerizable fluorene oligomer, (B) photopolymerizable oligomer, and/or (C) photopolymerizable monomer, (D) The total amount of the fluorine compound is 100% by mass, and is in the range of 0.1% by mass to 10% by mass.

- Polymerization inhibitors -

Further, the photocurable resin composition of the present invention may contain a polymerization inhibitor as needed in consideration of required curing reactivity, stability, and the like. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and butyl. Hydroxyanisole, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like. The amount of the polymerization inhibitor added is preferably relative to (A) dimethyl polyoxyalkylene (meth) acrylate oligomer, (B) photopolymerizable oligomer, and/or (C) photopolymerization. The total amount of the monomer and the (D) fluorine-containing compound is 100% by mass, and is in the range of 0.1% by mass to 10% by mass.

-Organic solvents-

Further, the photocurable resin composition of the present invention may contain an organic solvent such as an ether, a ketone or an ester as a diluent solvent, and examples of the organic solvent include propylene glycol monomethyl ether acetate (PMA), methyl ethyl ketone (MEK), and methyl group. Butyl ketone (MIBK), acetone, butyl lactate, and the like. These diluent solvents may be used alone or in combination of two or more.

The photocurable resin composition of the present invention can be applied to a surface of a substrate by using a diluent solvent as described above, as needed, as described above. The coating method is not particularly limited, and a known method can be employed, and examples thereof include, for example, a gravure coating, a roll coating method, a reverse coating method, and a knife coating method (knife). Coating), die coating, lip coating, doctor coating, extrusion coating, slide coating A wire bar coating method, a curtain coating method, an extrusion coating method, a spin coating method, or the like.

(watering member)

The water-repellent member is characterized by having a coating layer formed by curing the photocurable composition of the present invention and a base material layer. The water application member is a member that requires dehydration of the surface. The water-repellent member is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a flow table, a kitchen wall material, a wash table, a wall material for a bathroom, a bathtub, a bathroom ceiling material, a bathroom floor panel, and a bathroom. Counters, toilets, tanks for water storage, etc.

(functional panel)

The functional panel of the present invention has a coating layer formed by curing the photocurable resin composition of the present invention, and the substrate layer is preferably formed on the substrate layer, for example, the coating layer. The thickness of the entire functional panel of the present invention is not particularly limited, and may be appropriately selected depending on the purpose, but is usually preferably 2.5 mm or more. Further, the upper limit of the thickness of the entire functional panel of the present invention is not particularly limited and may be appropriately selected depending on the purpose. The coating layer may be formed on both sides of the surface and the inner surface of the substrate layer, and an intermediate layer formed of various materials may be formed between the layers in addition to the substrate layer and the coating layer as needed. Multi-layer structure. At this time, since the coating layer has excellent water slidability as described above, it is preferable to form the coating layer as the outermost layer of the functional panel. The intermediate layer is not particularly limited and may be appropriately selected depending on the purpose, and for example, an undercoat layer for improving the adhesion between the substrate layer and the coating layer, or a pattern for improving the functional panel, and a pattern, Decorative layers of color, etc.

Since the functional panel of the present invention thus obtained has the above coating layer formed on the base material layer, it has excellent water slidability, and is excellent in abrasion resistance, chemical resistance, temperature resistance, and dye resistance. It is possible to effectively suppress the adhesion of various kinds of dirt represented by scale, and it is less likely to be deteriorated or deteriorated even if a highly irritating detergent containing an acid or a base is used. Further, even if a dye such as a hair dye is used, discoloration and dyeing are unlikely to occur. 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>

The coating layer can be formed on the substrate layer by applying the photocurable resin composition of the present invention to a substrate and then photocuring the composition. The method of hardening the light is generally a method of irradiating light such as ultraviolet rays. The surface on the substrate layer for forming the coating layer may be only one of the surface or the back surface, or may be double-sided, and may be appropriately selected as needed. Further, the amount of light irradiation when the photocurable resin composition of the present invention is cured is not particularly limited, and may be appropriately selected depending on the purpose. When ultraviolet rays are used, generally, the irradiation intensity is 20 mW/cm ² to 2000 mW/cm ^{2 .} The irradiation amount is from 100 mJ/cm ² to 5000 mJ/cm ² , whereby the photocurable resin composition of the present invention is usually cured in a few seconds to several tens of seconds. Since it can be hardened in a short time in this way, the productivity of the obtained functional panel can be improved.

The thickness of the coating layer is not particularly limited, and may be appropriately selected depending on the desired degree of pattern and chemical resistance. However, it is usually estimated to be in the range of 1 μm to 200 μm.

Further, in the case of ultraviolet irradiation, since the ultraviolet curing reaction is a radical reaction, it is easily blocked by oxygen. Therefore, after the photocurable composition is applied to the substrate, the composition can be cured in a nitrogen atmosphere in order to avoid contact with oxygen. Further, from the viewpoint of sufficiently ensuring good water slidability, the surface free energy of the coating layer formed by photocuring is usually from ¹² mJ/m ² to 30 mJ/m ² .

<Substrate layer>

The material of the base material layer used in the functional panel of the present invention is not particularly limited and may be appropriately selected depending on the purpose, for example, asbestos tile is exemplified. (slate), inorganic materials such as concrete, metal, calcium silicate, calcium carbonate, glass, etc.; organic materials such as wood materials, polypropylene, polystyrene, polycarbonate, unsaturated polyester resin; Wait.

Among these, a material obtained by adding fibers such as glass fibers and carbon fibers to an organic material, that is, a so-called FRP (fiber reinforced plastic) is preferred. The above FRP is not particularly limited and may be appropriately selected depending on the purpose, and for example, a sheet molding compound (SMC) containing an unsaturated polyester resin, a filler, and glass fiber or carbon fiber, or a composite of SMC is used. A material including a short fiber in the form of a bulk molding compound (BMC). In general, the FRP is added with a thermosetting resin, an organic peroxide (hardener), a filler, a low shrinkage agent, an internal mold release agent, a reinforcing material, a crosslinking agent, and a tackifier. This is placed in a mold set to a specific temperature, and then pressurized to form a shape suitable as a position for building materials. Among these, as long as it contains an unsaturated polyester as a thermosetting resin, a filler, and FRP of glass fiber or carbon fiber as a reinforcing material, the strength and durability of the entire functional panel obtained can be further improved. .

The above unsaturated polyester may be an unsaturated acid of a polybasic acid such as maleic anhydride or fumaric acid, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, trimethylpentanediol, and neopentyl Polyols such as diol, trimethylpropane monoallyl ether, hydrogenated bisphenol, bisphenol dioxypropyl ether, etc.

The above filler is not particularly limited and may be appropriately selected depending on the purpose. For example, calcium carbonate, aluminum hydroxide, etc. are mentioned. Among these, calcium carbonate is preferred from the viewpoint of cost reduction, but aluminum hydroxide is preferred from the viewpoint of improving the chemical resistance of the FRP itself. However, if the coating layer is formed as described above, even if FRP using calcium carbonate is used as the substrate for the filler, the chemical resistance of the entire functional panel can be sufficiently improved, so that it is easy to realize low cost. A functional panel of a substrate layer composed of FRP.

The glass 繊 dimension and the carbon 繊 dimension of the reinforcing material are about 20 mm to 50 mm, and the diameter of the bismuth dimension is preferably from 5 μm to 25 μm, and it is desirable to contain 10% by mass to 70% by mass of the FRP. The FRP having the specific thickness and size is produced by an FRP production apparatus or the like by mixing the components using the FRP as the base material layer.

Further, although the thickness of the above-mentioned base material layer changes depending on the use of the functional panel, it is usually 2.5 mm or more. The upper limit of the thickness of the base material layer is not particularly limited and may be appropriately selected depending on the purpose.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited.

<Manufacturing Example 1>

A polyoxane polyol having a number average molecular weight of 1,000 (SILAPLANE FM-4411, formula (2), p = 1, q = 3, (the total carbon number of R in the formula (1) is 5), CHISSO 0.1 mol, 0.1 mol of polyethylene glycol (PEG #1000, Nippon Oil Co., Ltd.) and 0.06 g of dibutyltin dilaurate The container should be stirred and stirred. Next, 0.3 mol of isophorone diisocyanate (VESTANATIPDI, manufactured by Evonik Degussa Japan Co., Ltd.) was added at room temperature. This was warmed to 70 ° C and reacted at 300 rpm for 2 hours and a half to obtain a urethane prepolymer solution. 0.2 mol of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) was added to the total amount of the prepolymer solution obtained, and the reaction was further stirred for 4 hours to obtain a number average molecular weight of about 3,000. Dimethyl polyoxyalkylene (meth) acrylate oligomer.

<Manufacturing Example 2>

Instead of using the polyoxonane polyol having a number average molecular weight of 1,000 in Production Example 1 (SILAPLANE FM-4411, Formula (2), p=1, q=3, (Total carbon number of R in Formula (1) 5), manufactured by CHISSO Co., Ltd., except that a polyoxyalkylene polyol having a number average molecular weight of about 700 (DMS-C16, formula (2), p=0, q=3, (formula (1)) In the same manner as in Production Example 1, except that the total carbon number of R was 3) (manufactured by Gelest Co., Ltd.), a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 3,000 was obtained.

<Manufacturing Example 3>

Instead of using the polyoxonane polyol having a number average molecular weight of 1,000 in Production Example 1 (SILAPLANE FM-4411, Formula (2), p=1, q=3, (Total carbon number of R in Formula (1) 5), manufactured by CHISSO Co., Ltd., except that a polyoxane polyol having a number average molecular weight of about 5,000 (FM-4421, formula (2), p=1, q=3, (formula (1)) In the case of R, the total carbon number is 5), other than CHISSO Co., Ltd.) In the same manner as in Example 1, a dimethylpolysiloxane (meth) acrylate oligomer having a number average molecular weight of about 7,000 was obtained.

<Manufacturing Example 4>

Instead of using the polyoxonane polyol having a number average molecular weight of 1,000 in Production Example 1 (SILAPLANE FM-4411, Formula (2), p=1, q=3, (Total carbon number of R in Formula (1) 5), manufactured by CHISSO Co., Ltd., except that a polyoxyalkylene polyol having a number average molecular weight of about 10,000 (FM-4425, formula (2), p=1, q=3, (formula (1)) In the case where R has a total carbon number of 5), which is manufactured by CHISSO Co., Ltd., the same as in Production Example 1, and a dimethylpolysiloxane (meth) acrylate oligomer having a number average molecular weight of about 12,000 is obtained. Things.

<Manufacturing Example 5>

Instead of using the polyoxonane polyol having a number average molecular weight of 1,000 in Production Example 1 (SILAPLANE FM-4411, Formula (2), p=1, q=3, (Total carbon number of R in Formula (1) 5), manufactured by CHISSO Co., Ltd., except that a polyoxyalkylene polyol having a number average molecular weight of about 1700 (KF6001, formula (2), p=1, q=3, (in the formula (1)) The total carbon number of R is 5), except for Shin-Etsu Chemical Co., Ltd., and the others are the same as in Production Example 1, and a dimethylpolysiloxane (meth) acrylate oligomer having a number average molecular weight of about 4,000 is obtained. Things.

<Manufacturing Example 6>

Instead of using the polyoxonane polyol having a number average molecular weight of 1,000 in Production Example 1 (SILAPLANE FM-4411, Formula (2), p=1, q=3, (Total carbon number of R in Formula (1) 5), CHISSO Co., Ltd. In addition to the use of a polyoxane polyol having a number average molecular weight of about 3,000 (KF6002, formula (2), p = 1, q = 3, (the total carbon number of R in the formula (1) is 5) Other than the production example 1, except that manufactured by Shin-Etsu Chemical Co., Ltd., a dimethylpolysiloxane (meth) acrylate oligomer having a number average molecular weight of about 5,000 was obtained.

<Manufacturing Example 7>

Instead of using the polyoxonane polyol having a number average molecular weight of 1,000 in Production Example 1 (SILAPLANE FM-4411, Formula (2), p=1, q=3, (Total carbon number of R in Formula (1) 5), manufactured by CHISSO Co., Ltd., except that a polyoxane polyol having a number average molecular weight of about 5,500 (KF6003, formula (2), p=1, q=3, (in the formula (1)) The total carbon number of R is 5), except for Shin-Etsu Chemical Co., Ltd., and the others are the same as in Production Example 1, and a dimethylpolysiloxane (meth) acrylate oligomer having a number average molecular weight of about 7,500 is obtained. Things.

<Manufacturing Example 8>

Instead of using the polyoxonane polyol having a number average molecular weight of 1,000 in Production Example 1 (SILAPLANE FM-4411, Formula (2), p=1, q=3, (Total carbon number of R in Formula (1) 5), manufactured by CHISSO Co., Ltd., except for the use of a polyoxane polyol having a number average molecular weight of about 4000 (X-22-4952, formula (2), p≒5, q=3, (formula ( 1) The total carbon number of R in R) (13), manufactured by Shin-Etsu Chemical Co., Ltd., was the same as in Production Example 1, and a dimethyl polyoxyalkylene (methyl) having a number average molecular weight of about 6,000 was obtained. Acrylate oligomer.

<Manufacturing Example 9>

In place of the addition of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) in the production example 1, except that 2-hydroxyethyl acrylate (trade name: LIGHTESTER HOA, manufactured by Kyoeisha Chemical Co., Ltd.) was added, The others were the same as in Production Example 1, and a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 3,000 was obtained.

<Manufacturing Example 10>

In addition to the addition of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) in the production example 1, except that dipropylene glycol acrylate (trade name: DPGA, manufactured by Dai-ichi Kogyo Co., Ltd.) was added, The same as in Example 1, was obtained to obtain a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 3,000.

<Manufacturing Example 11>

In place of the production example 1, pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.), 2-propenyloxyethyl succinate (trade name: A-SA, manufactured by Shin-Nakamura Chemical Co., Ltd.) was added. The same procedure as in Production Example 1 was carried out, and a dimethylpolysiloxane (meth) acrylate oligomer having a number average molecular weight of about 3,000 was obtained.

<Manufacturing Example 12>

In place of the production example 1, isophorone diisocyanate (VESTANATIPDI, manufactured by Evonik Degussa Japan Co., Ltd.) was added, except that hexadecenyl diisocyanate which is a polyisocyanate compound having no cyclic skeleton in a molecular structure was added (trade name: HDI, Evonik) The same procedure as in Production Example 1 was carried out except for the production of Degussa Japan, and a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 3,000 was obtained.

<Manufacturing Example 13>

In place of the addition of 0.3 mol of isophorone diisocyanate in Production Example 1, except that polyethylene glycol (PEG #1000, Nippon Oil Co., Ltd.) having a number average molecular weight of 1,000 was not added, and isophorone diisocyanate was added in an amount of 0.2 mol. The same procedure as in Production Example 1 was carried out, and a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 2,000 was obtained.

<Manufacturing Example 14>

In place of the addition of 0.3 mol of isophorone diisocyanate in Production Example 1, except that 0.22 mol of isophorone diisocyanate was added, the same procedure as in Production Example 1 was carried out, and dimethylpolysiloxane having a number average molecular weight of about 40,000 was obtained. Base) acrylate oligomer.

<Modulation and evaluation of photocurable resin composition>

According to the formulation of Tables 1-1 to 1-7 and Table 2, the components were poured into a stirring device and mixed to prepare a photocurable resin composition. The photocurable resin composition obtained was applied onto a substrate made of FRP (DECK MAT (registered trademark) 2415, manufactured by DIC Chemical Co., Ltd.) to a thickness of 20 μm. Next, UV (1000 mW/cm ² , 4000 mJ/cm ² ) was irradiated to harden the photocurable resin composition to obtain a sample. The water repellency and chemical resistance were evaluated by the following methods, and the results shown in Table 1-1 to Tables 1-7 and Table 2 were obtained.

(1) Water slidability

The evaluation of the water slick is carried out by measuring the roll angle of the water. In addition, the evaluation of the water slick was performed by DM-500 and DM-SA manufactured by Kyowa Interface Science Co., Ltd. 30 μL of water droplets were dropped on the substrate, and the pedestal was tilted at a speed of 7.5 degrees/second, and the angle at which the water droplets began to move was used as the value of the roll angle. The measurement system was performed twice, and the average value was used as the value of the roll-off angle.

(2) Chemical resistance (dyeability)

The sample was immersed in a commercially available hair dye (GATSBY return 黒髪 (registered trademark): a mixture of 1 dose and 2 doses, manufactured by MANDOM Co., Ltd.), and washed with water 24 hours later. For the degree of change, a color difference (ΔE) between the impregnated portion and the unimpregnated portion was determined using a color difference meter (SpectroEye, SAKATA INX ENG) and according to the following formula.

△E=(△a ² +Δb ² +△L ² ) ^1/2

The smaller the value, the better the resistance to chemicals.

△ E = less than 3.0: ◎

△E=3.0 or more, less than 5.0:○

△E=5.0 or more, less than 10.0: △

△E=10.0 or more: ×

*1 (a) (q=3) represented by the formula (1) (the total carbon number of R in the formula (1) is 3), poly (oxyalkylene polyol), and (b) iso isocyanate Reaction of sulfone diisocyanate (IPDI) and (c) (meth) acrylate monomer to obtain dimethyl polyoxyalkylene (meth) acrylate oligomer ("SIU1300", manufactured by Miwon Co., Ltd., number average molecular weight : about 7000, functional base 6)

*2 (a) (q=3) represented by the formula (1) (the total carbon number of R in the formula (1) is 3), polyoxyalkylene polyol, and (b) isocyanate Reaction of sulfone diisocyanate (IPDI) and (c) (meth) acrylate monomer to obtain dimethyl polyoxyalkylene (meth) acrylate oligomer ("SIU1500", manufactured by Miwon Co., Ltd., number average molecular weight : about 8000, functional base 10)

*3 (a) (q = 3) polydecane polyol represented by the formula (1), (b) isophorone diisocyanate (IPDI) as an isocyanate, (c) (meth)acrylic acid The ester monomer is reacted to obtain a dimethyl polyoxyalkylene (meth) acrylate oligomer ("SIU 2400", manufactured by Miwon Co., Ltd., number average molecular weight: about 7,000, functional group number 10)

*4 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 1

*4-2 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 2

*4-3 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 3

*4-4 dimethyl polyoxane (methyl) obtained in Production Example 4 Acrylate oligomer

*4-5 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 5

*4-6 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 6

*4-7 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 7

*4-8 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 8

*4-9 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 9

*4-10 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 10

*4-11 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 11

*4-12 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 12

*4-13 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 13

*4-14 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 14

*5 CHISSO Co., Ltd., "FM-0711", one-side terminal methacryl-modified dimethyl polysiloxane oil, the number average molecular weight (Mn) is 1000, and the application represented by the following formula (3) Compounds outside the scope of the patent

In the formula (3), R represents an alkyl group, Me represents a methyl group, and n represents an arbitrary integer. Here, R is an alkyl group for eliminating the reactivity of the terminal, and does not contribute substantially to the present invention.

*6 CHISSO Co., Ltd., "FM-7711", two-end methacryl-modified dimethyl polysiloxane oil, number average molecular weight (Mn) 1000, specific gravity 0.98, refractive index 1.419, viscosity 20mm ² /s , the following compounds outside the scope of the patent application represented by the general formula (4)

In the formula (4), Me represents a methyl group, and n represents an arbitrary integer.

*7 A urethane acrylate oligomer having a 1,2-polybutylene oxide unit synthesized by the following method

*7-2 UF-8001, manufactured by Kyoeisha Chemical Co., Ltd.

*8, 1,6-hexanediol diacrylate, manufactured by Gongrongshe Chemical Co., Ltd., SP value = 19.6 (J/cm ³ ) ^0.5

*9, 1,9-nonanediol diacrylate, manufactured by Gongrongshe Chemical Co., Ltd., SP value = 19.2 (J/cm ³ ) ^0.5

*10 manufactured by Gongrongshe Chemical Co., Ltd., isodecyl acrylate, SP value = 18.9 (J/cm ³ ) ^0.5

*11 2-Acryloxyethyl succinate, manufactured by Shin-Nakamura Co., Ltd., SP value = 22.7 (J/cm ³ ) ^0.5

*12 DIC Corporation, reactive fluoro oligomer

*13 Nissan Chemical Industry Co., Ltd., reactive fluoro oligomer

*14 Perfluorooctyl Ethyl Acrylate, manufactured by Gongrongshe Chemical Co., Ltd.

*14-2 LEBLOND (Low Molecular Weight PTFE) manufactured by DAIKIN Industrial Co., Ltd.

*15 manufactured by Ciba Specialty Chemicals Inc., "IRGACURE 184", 1-hydroxy-cyclohexyl-phenyl-ketone

<Synthesis method of urethane acrylate oligomer having 1,2-polybutylene oxide unit>

Using a potassium hydroxide as a catalyst and adding 12 mol of butylene oxide to propylene glycol (manufactured by Kanto Chemical Co., Ltd.) at a reaction temperature of 110 ° C to obtain a polyol. 2 mol of 2,4-toluene diisocyanate was introduced into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer, and a cooling tube, and reacted with the polyol at 70 ° C for 2 hours. Next, a small amount of dibutyltin dilaurate as a catalyst is slowly added to 2-hydroxyethyl propyl The olefin ester 4 mol was further reacted at 70 ° C for further 15 hours to obtain a urethane acrylate oligomer containing a 1,2-butanediol unit having a number average molecular weight of about 1,500. The n-heptane allowable value of the urethane acrylate oligomer having a 1,2-polybutylene oxide unit thus obtained was 1.0 g/10 g.

From the results of the examples and comparative examples of Tables 1-1 to 1-7 and Table 2, it can be known that (A) (a) is a polyoxane which is represented by the formula (1) by using a dimethyl polyoxyalkylene (meth) acrylate oligomer obtained by reacting an alcohol, (b) an isocyanate, and (c) a (meth) acrylate monomer having a functional group reactive with isocyanate, and (D) A fluorine-containing compound, a photocurable resin composition which can improve the performance of water slidability and the like can be obtained.

Claims (13)

A photocurable resin composition comprising: (A) a dimethyl polyoxyalkylene (meth) acrylate oligomer, wherein (a) is represented by the following formula (1) Obtaining an alkyl polyol, (b) an isocyanate, and (c) a (meth) acrylate monomer having a functional group capable of reacting with an isocyanate; In the above formula (1), n is an arbitrarily selected integer such that the number average molecular weight of the (A) dimethylpolyoxyalkylene (meth) acrylate oligomer is from 700 to 40,000, and the R system An alkylene group having a total carbon number of 1 to 30, or a functional group having a total carbon number of 1 to 30 having an ether bond; (B) a photopolymerizable oligomer and/or (C) a photopolymerizable monomer, which may Copolymerization with the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer; (D) a fluorine-containing compound; and (E) a photopolymerization initiator. The photocurable resin composition of claim 1, wherein the (b) isocyanate group in the isocyanate is equivalent to the hydroxyl group in the polyoxane polyol represented by the formula (1). The ratio (isocyanate group / hydroxyl group) is greater than 100/100 but 300/100 or less. The photocurable resin composition according to claim 1 or 2, wherein the (C) photopolymerizable monomer has a solubility parameter (SP value) of 20.0 (J/cm ³ ) ^1/2 or less. The photocurable resin composition according to any one of claims 1 to 3, wherein the (C) photopolymerizable monomer is a compound represented by the following formula (A): (CH ₂ = CR ¹ COO) _n R ^{2 In the} above formula (A), R ¹ represents a hydrogen atom or a methylalkyl group, and R ² represents an n-valent hydrocarbon group having 5 to 20 carbon atoms, and n represents An integer in the range 1~4. The photocurable resin composition according to any one of claims 1 to 4, wherein the (B) photopolymerizable oligomer is a (meth)acrylic acid having a 1,2-polybutylene oxide unit. Ester oligomer. The photocurable resin composition according to any one of claims 1 to 5, wherein the (b) isocyanate is a polyisocyanate compound having a cyclic skeleton in a molecular structure. The photocurable resin composition according to any one of claims 1 to 6, wherein the functional group reactive with the isocyanate group in the (c) (meth) acrylate monomer is a hydroxyl group. The photocurable resin composition according to any one of claims 1 to 7, wherein the content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is relative to the (B) The total of the photopolymerizable oligomer and/or the (C) photopolymerizable monomer is 0.05% by mass to 10% by mass. Photocuring tree as claimed in any one of claims 1 to 8 A lipid composition in which the (D) fluorine-containing compound has a photopolymerizable functional group. The photocurable resin composition according to any one of claims 1 to 9, wherein the solid content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is relative to the D) The ratio of the solid content of the fluorine-containing compound (A/D) is 0.2 to 10. The photocurable resin composition of claim 10, wherein the solid content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is relative to the (D) fluorochemical The solid content ratio (A/D) is 0.4 to 3. A water-repellent member comprising: a coating layer formed by curing a photocurable resin composition according to any one of claims 1 to 11; and a substrate layer. A functional panel comprising: a coating layer formed by curing a photocurable resin composition according to any one of claims 1 to 11; and a substrate layer.