TWI500641B - A photohardenable resin composition, and a water-absorbing member and a functional panel (1) - Google Patents

Description

Photocurable resin composition, water-using member and functional panel using the same (1)

The present invention relates to a photocurable resin composition, a water-using member using the same, and a functional panel, and particularly relates to a photocurable resin which has been improved for a long period of time in water repellency and slidability (sliding water which can easily remove surface water droplets) The composition, the water-using member using the same, and the functional panel.

The functional panel which is a building material is a member which is disposed as a wall surface, a floor surface or a ceiling wall surface of a building, and provides various functions such as sound insulation effect and humidity adjustment property depending on the arrangement place. When such a functional panel is used particularly as a water-using member such as a bathroom, a washstand, or a kitchen in a home, it is desirable to have various characteristics such as water repellency and slidability that can withstand a more severe use environment.

In this regard, attempts have been made to apply a composition that reduces the surface free energy by a low surface free energy compound having a small surface free energy to the surface of the member, thereby imparting good water repellency to the member and making the dirt difficult to adhere, and the correlation is low. As the surface free energy compound, a hydrophobic material such as a fluororesin or a polyoxyalkylene compound is used.

For example, Patent Document 1 listed below discloses a water-retaining member having a surface-cured material (containing a low-surface free-energy compound) on the surface, and further discloses a polyoxyalkylene resin compound and a fluororesin in terms of a low-surface free-energy compound. Compound.

Further, Patent Document 2 listed below discloses formation on the surface of a substrate resin. a low surface free energy layer, such that the surface of the molded body becomes a resin molded body having a low surface free energy surface than the surface of the base resin, and further, the contact angle of the surface of the resin molded body with water is 90 degrees or more and 170 degrees or less, and The roll angle of the surface of the resin molded body and water is 1 degree or more and 80 degrees or less.

Prior technical literature

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

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

However, among the low surface free energy surfaces produced by using the low surface free energy compound, the surface made using the fluororesin compound can be dialed with water to form spherical water droplets on the surface, but the water droplets are strongly adhered to the surface. On the surface without falling. On the other hand, even if the initial rolling angle is small, the surface prepared by using the polyoxyalkylene resin compound tends to have a lower surface slidability and a larger rolling angle. Therefore, it has been attempted to roughen the surface or the like to increase the surface contact angle as much as possible so that the adhered water droplets fall from the surface. However, such a roughened surface has problems in terms of durability and easy adhesion of dirt.

Furthermore, the above-mentioned low surface free energy compounds generally have a problem of poor compatibility with the base resin.

Therefore, an object of the present invention is to solve the above problems and to provide a photocurable resin composition which can improve water repellency and slidability for a long period of time. Further, another object of the present invention is to provide a water-repellent member and a functional panel comprising a coating layer which is cured by a photocurable resin composition, and has excellent water repellency and slidability for a long period of time.

In order to achieve the above object, the inventors of the present invention have found that (a) poly (a) polyoxyalkylene polyol, (b) isocyanate, and (c) terminal are used in the composition of the photocurable resin composition. The dimethyl polyoxyalkylene (meth) acrylate oligomer obtained by reacting a (meth) acrylate monomer reactive with an isocyanate-reactive group has good compatibility with the base resin and can be formed. The present invention has been completed by easily removing the water-sliding surface of the surface water droplets and forming a film which can withstand the durability of long-term use.

Further, the term "(meth) acrylate" as used herein means acrylate or methacrylate.

Further, the present inventors have found that an equivalent ratio (-NCO/-OH) of the isocyanate group (-NCO) in (b) isocyanate to (a) a hydroxyl group (-OH) in (a) polyoxaxane polyol is found. When it is more than 100/100 and 300/100 or less, a prepolymer having an isocyanate group at the end can be produced, and thereafter, an isocyanate group at the terminal of the prepolymer can be used, for example, to have a hydroxyl group and a (meth) acrylonitrile group. The reaction was carried out to prepare a dimethyl polyoxyalkylene (meth) acrylate oligomer having a high water repellency at the terminal (meth) acrylonitrile group, thereby completing the present invention.

That is, the photocurable resin composition of the present invention contains: (A) a dimethyl polyoxyalkylene (meth) acrylate oligomer, such that (a) is represented by the following formula (1) a polyoxyalkylene polyol, (b) isocyanate, and (c) a (meth) acrylate monomer having a functional group capable of reacting with an isocyanate at a terminal;

In the formula (1), n represents an integer arbitrarily selected such that the number average molecular weight of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is from 700 to 40000, and R represents 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 Copolymerization with the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer; and (D) photopolymerization initiator.

In a preferred embodiment of the photocurable resin composition of the present invention, the isocyanate group in the above (b) isocyanate and the hydroxyl group in the polyoxanol polyol represented by the above formula (1). The equivalent ratio (isocyanate group / hydroxyl group) is more than 100/100 and is 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.

Further, the aforementioned (C) photopolymerizable monomer These may be used alone or in combination of two or more. Here, the SP value in the case of using two or more kinds of photopolymerizable monomers is the SP value of each monomer multiplied by the respective mixing ratio (mass ratio) (each monomer in the case where the total amount of the monomers is 1) The ratio is added after the ratio). For example, in the case where the photopolymerizable monomer having an SP value of 19.0 and the photopolymerizable monomer having an SP value of 19.0 is blended in an amount of 1/4 with respect to the total amount of the photopolymerizable monomer of 19.0, the amount is based on the following formula. (X) The SP value of the whole photopolymerizable monomer used was computed.

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 single system contains a compound represented by the following formula (A).

(CH ₂ =CR ¹ COO) _n R ² .........Formula (A)

In the above formula (A), R1 represents a hydrogen atom or a methyl group, R2 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-polyoxybutylene unit.

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

In another preferred embodiment of the photocurable resin composition of the present invention, the functional group which can react 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 (B) photopolymerizable oligomer. And / or (C) the total amount of the photopolymerizable monomer is 0.05% by mass to 10% by mass.

Further, the water-absorbing member of the present invention has a coating layer obtained by curing the photocurable resin composition, and a substrate layer.

Furthermore, the functional panel of the present invention has: the light of the present invention The coating layer formed by curing the curable resin composition and the substrate layer.

According to the present invention, there can be provided a photocurable resin composition comprising: (A) a dimethyl polyoxyalkylene (meth) acrylate oligomer, wherein (a) is represented by the formula (1) a polyoxyalkylene polyol, (b) an isocyanate, (c) a terminal having a (meth) acrylate monomer reactive with an isocyanate-reactive functional group; (B) a photopolymerizable oligomer and / or (C) photopolymerizable monomer; and (D) photopolymerization initiator; can improve water repellency and slidability for a long time. Further, a water-receiving member and a functional panel can be provided, and a coating layer obtained by curing a photocurable resin composition can be provided, and water repellency and slidability can be maintained well for a long period of time.

(Photocurable resin composition)

The invention is described in detail below. The photocurable resin composition of the present invention contains: (A) dimethyl polyoxyalkylene (meth) acrylate oligomer, (B) photopolymerizable oligomer, and/or (C) photopolymerizable property The monomer and (D) photopolymerization initiator further contain (E) other components as necessary.

In the photocurable resin composition of the present invention, (A) a dimethyl polyoxyalkylene (meth) acrylate oligomer is used as one of the starting materials for (a) a polyoxyalkylene polyol. Since the surface energy of the dimethyloxane moiety is low, a low surface free energy compound can be produced, and a water-repellent member having a coating layer derived from the photocurable resin composition and a functional panel can be improved. Water repellency and slidability.

Further, in the photocurable resin composition of the present invention, the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is segregated on the surface for a long time. As a result, for example, water repellency and slidability of the water-repellent member having the coating layer derived from the photocurable resin composition and the functional panel can be improved for a long period of time.

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

The (A) dimethyl polyoxyalkylene (meth) acrylate oligomer used in the photocurable resin composition of the present invention is (a) a polydecane polyol component, (b) an isocyanate component, (c) A reaction obtained by reacting a (meth) acrylate monomer component. The (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is, for example, obtained by reacting (a) a polyoxyalkylene polyol with (b) an isocyanate to form a part or all of the terminal. An isocyanate-based polyoxyalkylene polyol prepolymer, and secondly, an isocyanate group addition (c) (meth) acrylate monomer of the polyoxyalkylene polyol prepolymer.

By using an isocyanate to obtain a dimethyl polyoxyalkylene (meth) acrylate oligomer, a prepolymer having an arbitrary number of counters can be synthesized, whereby the molecular weight can be adjusted, or the physical property value of the obtained oligomer can be adjusted. (softness, strength, adhesion, etc.), and any number of highly polar urethane bonds in the molecule can be contained, and the compatibility with the base resin is easy to design, which is an advantage.

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, and is preferably from 1,000 to 40,000. The number average molecular weight is determined by GPC and a reference line is prepared from the standard of polystyrene, and is obtained from the holding time of the sample. As the mobile layer solvent of GPC, 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 obtained by such a method is less than 1,000, the relative amount of the dimethyloxoxane moiety in the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is lowered in order to exhibit sufficient effect. Must increase the amount added. on the other hand, If the number average molecular weight exceeds 40,000, (B) photopolymerizable oligomer and (C) photopolymerizable can be polymerized with (A) dimethyl polyoxyalkylene (meth) acrylate oligomer. The compatibility of the monomer is remarkably lowered and separated, and the surface of the film becomes soft due to a decrease in the crosslinking density, which becomes a surface which is easily scratched.

(A) The dimethyl polyoxyalkylene (meth) acrylate oligomer contains (a) a polyoxyalkylene polyol represented by the formula (1), (b) an isocyanate, and (c) terminal In addition to the (meth) acrylate monomer which may react with the 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 terminal portion or all of the isocyanate groups. And, secondly, a (meth) acrylate monomer having a functional group capable of reacting with an isocyanate at the terminal (c) of the polyoxyalkylene polyol prepolymer is obtained.

By containing (d) another polyol component, the water repellency, the compatibility with respect to 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 with respect to (B) photopolymerizable oligomer and The total amount of the (C) photopolymerizable monomer is preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5.0% by mass. Here, the content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is the amount of the active ingredient of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer. (Amount of solid component).

When the content is less than 0.05% by mass, the water repellency and the water slidability of the article coated with the photocurable resin composition of the present invention may not be sufficient. When the amount is more than 10% by mass, the compatibility with the (B) photopolymerizable oligomer and/or the (C) photopolymerizable monomer may be deteriorated, and a uniform cured product may not 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 (methyl) The surface segregation of the acrylate oligomer becomes more remarkable, and the water repellency and water slidability of the article coated with the photocurable resin composition of the present invention can be exhibited for a longer period of time. Further, since the addition effect is substantially saturated at 5.0%, the content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer falls within the above-described preferable range from the viewpoint of cost.

- (a) polyoxyalkylene polyol -

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

In the above formula (1), n represents a mode in which the number average molecular weight of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is from 700 to 40,000 (the aforementioned polyoxane The number average molecular weight of the alcohol is from 500 to 40,000. The arbitrarily selected integer is not particularly limited and may be appropriately selected depending on the purpose. Further, in the above formula (1), as long as R is an alkylene group having a total carbon number of 1 to 30, or an official having a total carbon number of 1 to 30 having an ether bond The energy base can be any, and is not particularly limited, and can be appropriately selected depending on the purpose.

The alkylene group having a total carbon number of from 1 to 30 is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a methylene group, an ethylene group, a propylene group, a butyl group, a pentylene group, and a hexyl group. Alkylene group having a total carbon number of 1 to 30 which does not have an ether bond, such as a phenyl group, a heptyl group or a octylene group.

Further, the functional group having a total carbon number of 1 to 30 having an ether bond is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include -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, -C ₂ H ₄ -OC ₂ H ₄ -, -C ₃ H ₆ -OC ₃ H ₆ - or the like.

The reason why the total carbon number of R is set to 30 or less is based on the viewpoints of the concentration of dimethyl polysiloxane and heat resistance. In terms of R, based on the market availability, it is preferred to use propylene or -C ₃ H ₆ -OC ₂ H ₄ -.

In addition, an example of the above formula (1) is exemplified by the following formula (2).

In the above formula (2), n represents a mode in which the number average molecular weight of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is from 700 to 40,000 (the aforementioned polyoxane The number average molecular weight of the alcohol is 500 to 40,000) an arbitrarily selected integer, 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 above (a) polyoxyalkylene polyol is not particularly limited and may be appropriately selected depending on the purpose, and for example, DMS-C16 (manufactured by Gelest Corporation: number average molecular weight ≒700: p=0, q) =3), FM-4411 Manufactured by Kyrgyzstan Co., Ltd.: number average molecular weight ≒1,000: p = 1, q = 3), FM-4421 (manufactured by Soko Co., Ltd.: number average molecular weight ≒ 5,000: p = 1, q = 3), FM-4425 (Manufactured by Soji 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 (manufactured by Shin-Etsu Chemical Co., Ltd.: number average molecular weight ≒ 4,000: p ≒ 5, q = 3) and the like. 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. By changing these lengths, the compatibility with the base resin can be changed. On the other hand, if the length is too long, the concentration of the polyoxyalkylene in the structure is relatively lowered, and a sufficient function cannot be exhibited. When p and q are in the above range, the function can be sufficiently exhibited without impairing the object of the present invention, that is, the water repellency and the slidability (easily removing the water repellency of the surface water droplets) can be improved for a long period of time.

Further, the aforementioned (a) polyoxyalkylene polyol may, for example, be such that a terminal Si-H group-containing dimethyl polyoxyalkylene and a compound having a hydroxyl group and an alkenyl group at each terminal are subjected to an addition reaction using a platinum-based catalyst. To manufacture.

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

If the above-mentioned number average molecular weight is less than 500, since the relative amount of the dimethyloxane moiety in the structure is lowered, in order to exert sufficient effects, it is necessary to increase the addition amount, and if it exceeds 20,000, it can be combined with (A) dimethyl polyfluorene. The compatibility of the (A) photopolymerizable oligomer (B) photopolymerizable oligomer and/or (C) photopolymerizable monomer in the polymerization of the oxyalkyl (meth) acrylate oligomer is remarkably lowered, and the crosslinking density is lowered. The surface of the film becomes soft and becomes a surface that is easily scratched.

- (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, but in the form of a molecule. A polyisocyanate compound having a cyclic skeleton in the 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 isocyanate itself may also be in a molecular structure. Has a ring skeleton. Therefore, the cyclic skeleton existing in the molecular structure of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer becomes a steric hindrance, and (A) dimethyl polydecane can be suppressed ( Methyl acrylate oligomer immersed in photohardenability The inside of the resin composition causes (A) dimethyl polyoxyalkylene (meth) acrylate oligomer to segregate on the surface for a long period of time.

The (is) isocyanate is a polyisocyanate compound having a cyclic skeleton in a molecular structure, and is not particularly limited as long as it has a cyclic skeleton (annular structure portion) in the molecular structure and a complex isocyanate group (NCO group). It can be suitably selected according to the purpose, and examples thereof include naphthalene diisocyanate (NDI), toluene diisocyanate (TDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), and diphenylmethane diisocyanate. (MDI), p-phenylene diisocyanate (PPDI), benzidine diisocyanate (TODI), diphenylamine diisocyanate (DADI), dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis (isocyanate A) Base) cyclohexane (H6XDI), tetramethylxylene diisocyanate (TMXDI), decene diisocyanate (NBDI), and an NCO terminal urethane prepolymer having such a structure. These may be used alone or in combination of two or more.

Among these, naphthalene diisocyanate (NDI), toluene diisocyanate (TDI), xylene diisocyanate (XDI), and isophorone diisocyanate (IPDI) are preferred.

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

Further, in the synthesis of the above (A) dimethyl polyoxyalkylene (meth) acrylate oligomer, when the (b) isocyanate and the (a) polyoxyalkylene polyol are subjected to a hydroxyl group Reaction to synthesize a part or all of the urethane prepolymer having an isocyanate group, (b) isocyanate The equivalent ratio (-NCO/-OH) of the isocyanate group (-NCO) to the (a) polyoxyalkylene polyol in the polyoxyalkylene polyol may be more than 1.

Thus, if the equivalent ratio (-NCO/-OH) of the isocyanate group (-NCO) in the (b) isocyanate to the hydroxyl group in the (a) polyoxyalkylene polyol is greater than 1, both ends can be synthesized. It is an isocyanate-based prepolymer which can be reacted with a functional group (for example, an isocyanate group) in (c) a (meth) acrylate monomer.

In the reaction of the above (a) polyoxaxane polyol and (b) isocyanate, it is preferred to use a catalyst for the urethanization reaction. The catalyst for the urethanation reaction is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include dibutyltin dilauryl ester, dibutyltin diacetate, dibutyltin thiocarboxylate, and dibutyltin. Organotin compounds such as dimaleate, dioctyltin thiocarboxylate, tin octoate, monobutyltin peroxide; inorganic tin compounds such as stannous chloride; organic lead compounds such as lead octenate; triethylenediamine Such as cyclic 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 alkoxide, sodium hydroxide, etc. a titanium compound such as tetrabutyl titanate, tetraethyl titanate or tetraisopropyl titanate; an anthracene compound; a quaternary ammonium salt or the like. 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 purpose, and is 0.001 parts by mass to 2.0 parts by mass based on 100 parts by mass of the above (a) polyfluorene oxide polyol. It is better.

-(c) (meth) acrylate monomer -

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

The functional group which can be reacted 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 primary amine group, a secondary amine group, and the like. .

Among these, a hydroxyl group is preferred because of the good compatibility with the above-mentioned isocyanate and the viewpoint that it is abundant in a commercially available variety and is easily available.

The (meth) acrylate monomer having the above-mentioned hydroxyl group (-OH) is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include 2-hydroxyethyl (meth)acrylate and (methyl). 2-hydroxypropyl acrylate, 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 intended purpose, and examples thereof include 2-(meth)acryloyloxyethyl succinate and succinic acid. 2-propenyloxyethyl ester, monohydroxyethyl (meth) acrylate, and the like.

The (meth) acrylate monomer having the above amine group is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a (meth) acrylate having a 1-aminoethyl group in the side chain and a side chain. 1-aminopropyl (meth) acrylate or the like.

(c) The (meth) acrylate monomer may also contain a functional group reactive with an isocyanate and a photopolymerizable (meth) acrylonitrile in the structure. base. The amount of the (meth)acryl fluorenyl group may be any, but the more the amount (polyfunctional), the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer also becomes a polyfunctional substance. In general, the reactivity of a (meth) acrylate monomer and (B) a photopolymerizable oligomer or (C) a photopolymerizable monomer increases because the number of functional groups increases, but the number of functional groups is too large. Being a steric obstacle sometimes reduces the response rate. In view of this factor, the number of functional groups is preferably from 2 to 10, and more preferably (close to 10). In the meantime, since the (meth) acrylate monomer is crosslinked by a large number of functional groups, it can be segregated on the surface stably for a long period of time, and the surface hardness can be improved, so that it is preferred.

The (c) (meth) acrylate monomer 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 (a) a reaction of a polyoxyalkylene polyol and (b) an isocyanate with respect to a polyisocyanate compound having a cyclic skeleton in a molecular structure. The equivalent (functional group /-NCO) of the functional group in which the isocyanate group (-NCO) in the product (urethane prepolymer) can react with the isocyanate in the (c) (meth) acrylate monomer More than one equivalent can be used.

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

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

Further, the blending amount of the (B) photopolymerizable oligomer and the (C) photopolymerizable monomer is from 100:0 to 0:100, preferably from 80:20 to 20:80 by mass ratio, more preferably 30:70~70:30 range. When the amount of the (C) photopolymerizable monomer is too small, the viscosity of the photocurable resin composition may increase, the coating property may deteriorate during coating, and the chemical resistance and dyeing resistance may not be sufficiently ensured. Sexuality and other physical properties. Further, when the amount of the photopolymerizable monomer is too large, the flexibility in the case of forming a coating film tends to decrease, and the brittleness tends to become high.

- (B) Photopolymerizable oligomer -

The photopolymerizable oligomer (B) is not particularly limited and may be appropriately selected depending on the purpose, and may have one or more acryloxy groups [CH ₂ =CHCOO-] or methacryloxy groups [CH A (meth) acrylate oligomer of ₂ = C(CH ₃ )COO-] is preferred, and a (meth) acrylate oligomer having a 1,2-polyoxybutylene unit is particularly preferred. The (meth) acrylate oligomer having 1,2-polyoxybutylene unit has good compatibility with respect to (A) dimethyl polyoxyalkylene (meth) acrylate oligomer due to low polarity Further, (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 properties after hardening can be made uniform, and the appearance of the coating film can be further improved. Good, so the water-using members and functional panels can be used to form good physical properties and appearance. Further, the resin obtained by curing the photocurable resin composition has high water repellency, and is highly resistant to water and a dyeing agent such as a detergent or a hair dye used for water application, and is not easily attached with dirt, thereby enabling water repellency. Long-term stability is better.

Further, the above (meth) acrylate oligomer (A) is low in polarity, and specifically, it can be represented by an n-heptane tolerance value, and the correlation value is preferably 0.5 g/10 g or more, more preferably 0.7 g/10 g or more. In addition, the n-heptane tolerance is that the resin is kept at 25 ° C, and n-heptane is dropped thereto until the amount of n-heptane (g) which can be added before the white turbidity becomes a solubility in an organic solvent. Indicator, the larger the value, the more low polarity.

The (meth) acrylate oligomer is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include an urethane-based (meth) acrylate oligomer and an epoxy (meth) group. Acrylate oligomer, ether (meth) acrylate oligomer, ester (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, polyoxyalkylene ( A methyl acrylate oligomer or the like. These (meth) acrylate oligomers can be made of polyethylene glycol, polyglycol propylene glycol, polytetramethylene ether glycol, bisphenol A type epoxy resin, novolak type epoxy resin, polyol It is synthesized by reacting with an adduct of ε-caprolactone or the like with (meth)acrylic acid, or a polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group to form a urethane. Synthesis and synthesis.

The (B) photopolymerizable oligomer may be one of a monofunctional oligomer, a bifunctional oligomer, and a polyfunctional oligomer, based on the viewpoint of achieving a moderate crosslinking density of the resulting photocurable resin composition. Polyfunctional oligomers are preferred.

Among the above-mentioned (B) photopolymerizable oligomers, urethane-based (meth) acrylate oligomers excellent in drug resistance are provided from the viewpoint of imparting better properties to the water-using member and the functional panel. Things are better.

The urethane-based (meth) acrylate oligomer can be synthesized, for example, by synthesizing a urethane prepolymer composed of (i) a polyol and (ii) a polyisocyanate. a urethane prepolymer addition (iii) a compound having a functional group reactive with an isocyanate (for example, having a hydroxyl group) Base) Acrylate).

--(i) polyol --

The polyol to be used in the synthesis of the urethane prepolymer is not particularly limited as long as it has a complex hydroxyl group (-OH), and may be appropriately selected depending on the purpose, and for example, Polyether polyols, polyester polyols, polytetramethylene glycols, polybutadiene polyols, alkylene oxide-denatured polybutadiene polyols, polyisoamyl polyols, 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, ethylene oxide, propylene oxide, etc. can be added to a polyol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol or sorbitol. The alkylene oxide is obtained, and in addition, the polyether polyol can also be obtained by ring-opening polymerization. The polyether alcohol is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran (THF).

The polyester polyol can be obtained by addition polymerization, and examples thereof include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, and trishydroxymethyl B. a polyhydric alcohol such as an alkane or a trimethylolpropane, and a polycarboxylic acid such as adipic acid, glutaric acid, succinic acid, sebacic acid, pimelic acid or suberic acid, or by ring-opening polymerization. A polyester polyol is obtained. The polyester is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include a lactone-based polyester polyol obtained by ring-opening polymerization of ε-caprolactone.

The above (i) polyol can produce a (meth) acrylate oligomer having 1,2-polyoxybutylene units by denaturation of a polyol using butylene oxide. The oxidized butene-denatured polyol is a polyether polyol obtained by addition-polymerizing 1,2-butylene oxide (BO) to a polyol in the presence of a base catalyst. In addition, it can also be There are 1,2-butylene oxide (BO) and a polyether polyol of other alkylene oxide such as propylene oxide (PO) which is simultaneously polymerized. In this case, the ratio of 1,2-butylene oxide (BO) to other alkylene oxides is from 20:80 to 100:0, preferably from 50:50 to 100:0 in terms of a molar ratio. The number average molecular weight of these oxidized butene-denatured polyols is usually from 100 to 15,000, preferably from 500 to 5,000, depending on the GPC.

--(ii) Polyisocyanate --

The polyisocyanate is not particularly limited as long as it has a compound having a complex isocyanate group (-NCO), and may be appropriately selected depending on the intended 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, hexamethylene diisocyanate (HDI), such trimer Isocyanate denatured, carbodiimide denatured, diol denatured, and the like. These may be used alone or in combination of two or more.

- Catalyst for urethane reaction --

In the synthesis of the aforementioned urethane prepolymer, a catalyst for the urethanization reaction is preferably used. The catalyst for the urethanation reaction is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include dibutyltin dilauryl ester, dibutyltin diacetate, dibutyltin thiocarboxylate, and dibutyltin. Organotin compounds such as dimaleate, dioctyltin thiocarboxylate, tin octenate, monobutyltin oxide; inorganic tin compounds such as stannous chloride; lead octenoate and other organic lead compounds; Cyclic amines such as amines; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and fluorosulfuric acid; inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid; sodium alkoxide, lithium hydroxide, aluminum alkoxide, sodium hydroxide, etc. Salt; titanium such as tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate a compound; a hydrazine compound; a quaternary ammonium salt or the like. 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 purpose, and is preferably 0.001 parts by mass to 2.0 parts by mass based on 100 parts by mass of the above (i) polyol.

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

Further, (iii) a compound having a functional group reactive with an isocyanate added to the urethane prepolymer has at least one functional group (for example, a hydroxyl group) reactive with an isocyanate. Further, it has one or more compounds having a photopolymerizable functional group ((meth)acryloxyloxy group [CH ₂ =CHCOO- or CH ₂ =C(CH ₃ )COO-])).

The above (iii) a compound having a functional group reactive with an isocyanate may be added to the isocyanate group in the aforementioned urethane prepolymer. The compound (iii) having a functional group reactive with an isocyanate is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include 2-hydroxyethyl (meth)acrylate and 2-(meth)acrylic acid. Hydroxypropyl ester, pentaerythritol tri(meth)acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 3-ethyl-3-hydroxymethyl oxygen heterocycle Butane, 2-(meth)acryloyloxyethyl succinate, monohydroxyethyl (meth) acrylate, side chain 1-aminoethyl (meth) acrylate, side The chain is a 1-aminopropyl (meth) acrylate or the like. These may be used alone or in combination of two or more.

By blending such a (B) photopolymerizable oligomer, the glass transition temperature exhibited by the cured coating layer of the photocurable resin composition can be optimized, and excellent water repellency and slidability can be obtained. An effect photocurable resin composition.

-(C) Photopolymerizable monomer -

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

In addition, the (C) photopolymerizable monomer may be used alone or in combination of two or more. Here, the SP value in the case where two or more types of photopolymerizable monomers are used is the SP value of each monomer multiplied by the respective molar ratio (mass ratio) (the case where the total amount of the monomers is 1) The ratio of the body) and add the value obtained. For example, when the amount of photopolymerizable monomer having an SP value of 19.0 is 3/4 and the photopolymerizable monomer having an SP value of 21.0 is 1/4 of the total amount of the photopolymerizable monomer, The SP value of the entire photopolymerizable monomer to be used is determined by the above formula (X). 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, and examples thereof include isobornyl (meth)acrylate, decyl (meth)acrylate, and tricyclo(meth)acrylate. Anthracene ester, dicyclopentanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-butyl ring (meth)acrylate Hexyl ester, (meth) propyl Iridyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, (methyl) Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, (a) Ethyl acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (a) 2-ethylhexyl acrylate, decyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, (meth) acrylate Dodecyl ester, lauryl (meth)acrylate, stearyl (meth)acrylate, myristyl (meth)acrylate, palmitate (meth)acrylate, isostearyl (meth)acrylate, ( Tetrahydrofurfuryl methacrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth) acrylate, polyoxyethylene nonylphenyl ether acrylate, (meth)acrylic acid Phenoxyethyl ester, polyethyl b Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy ethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxy polyethylene Glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (methyl) 7-Amino-3,7-dimethyloctyl acrylate or the like. These may be used alone or in combination of two or more.

-(ii) 2-functional 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 three. Ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, 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, bisphenol A oxyalkylene addition diol di(meth) acrylate, plus A bis(meth) acrylate of an alkylene oxide addition diol of hydrogen bisphenol A, an epoxy (meth) acrylate of a bisphenol A diglycidyl ether addition (meth) acrylate, or the like. These may be used alone or in combination of two or more.

- (iii) Polyfunctional monomer -

The polyfunctional monomer (iii) is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include trimethylolpropane tri(meth)acrylate and ethoxylated trimethylolpropane tri ( Methyl)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate , ditrimethylolpropane 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, and is preferably 20.0 (J/cm ³ ) ^0.5 or less, and is 19.6 (J/cm ³ ) ^0.5 or less. For better. Further, under the limit of the SP value is not particularly limited, typically to 17.0 (J / cm ^{3) 0.5} or more is preferable. When the SP value is low, the compatibility with the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer becomes good, and (A) dimethyl polyoxy siloxane can be added in a wide range ( Methyl) acrylate oligomer. In the case where the amount of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer added is large, white turbidity, layer separation, and the like can be suppressed, and the appearance after curing is good, and the water-using member using the same is used. And the functional panel also forms a good appearance.

The SP value (δ) referred to here is generally the liquid Mohr evaporation energy (ΔEv) and the Mohr volume (V) according to the following formula: SP value (δ) = (ΔEv/V) ^0.5

To define. 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 (J. Brandrup, etc.)). Further, the SP value referred to in the present specification means a value calculated by the Fedors method, and the lower the value, the more polar the photopolymerizable monomer (C) is.

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

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

That is, in the general formula (A), for example, in the case of a chain and a saturated monomer, when n = 1, R ² becomes an alkyl group having 5 to 20 carbon atoms, and when n = 2, R ² becomes An alkylene group having 5 to 20 carbon atoms. Further, in the case of a chain and a saturated monomer, when n=3, R ^{2 is} an alkanetriyl group having a carbon number of 5 to 20, and when n=4, R ^{2 is} an alkanetetrayl group having a carbon number of 5 to 20. . Such R ² has 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. ; alkanetriyl represented by -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ -, and CH ₃ CH ₂ C(CH ₂ -) ₃ An alkanetetrayl group represented by C(CH ₂ -) ₄ or the like.

If the R ² carbon number is less than 5, in the case of a chain hydrocarbon group, the SP value of the monomer has an increasing tendency, and its compatibility with the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer It is difficult to obtain itself in the case of a cyclic hydrocarbon group. Further, when the number of carbon atoms of R ² exceeds 20, the crosslinking density of the resulting photocurable resin composition tends to decrease. If the crosslink density is lowered more than necessary, the dyeing agent such as a hair dye becomes easy to bleed out into the inside of the coating layer, and the panel is dyed.

Specific examples of the monomer represented by the formula (A) include isodecene (meth) acrylate, 1,6-hexanediol di(meth) acrylate, and dimethylol tricyclodecane. Di(meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, hard (meth)acrylate a fatty ester, 3-methyl-1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, 1, 9-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like.

Among them, there is a tendency to exhibit a good low polarity due to a better SP value, and compatibility with (A) dimethyl polyoxyalkylene (meth) acrylate oligomer and chemical resistance, From the viewpoint of further improvement in dye resistance, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, isodecene (meth)acrylic acid Ester, dimethylol tricyclodecane di(meth) acrylate is preferred, 1,6-hexanediol di(meth) acrylate, isodecene (meth) acrylate, 1,9- The decanediol di(meth) acrylate is more preferred.

The photopolymerizable monomer having a solubility parameter (SP value) of 20.0 (J/cm ³ ) ^0.5 or less, particularly a monomer represented by the general formula (A), is low in polarity, so it is combined with (A) dimethyl group. The polyoxyalkylene (meth) acrylate oligomer has good compatibility, and (A) dimethyl polyoxyalkylene (meth) acrylate oligomer can be added in a wide range. In the case where the amount of (A) dimethyl polyoxyalkylene (meth) acrylate oligomer added is large, white turbidity, layer separation, and the like can be suppressed, and the appearance after curing is good, and the water-using member using the same is used. And the functional panel also forms a good appearance. In addition, since the resin obtained by curing the photocurable resin composition has high water repellency, it is highly resistant to dyes such as detergents and hair dyes used for water and water application, and is less likely to adhere to dirt, and the water repellency is long-term stable. Sex becomes 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, although the crosslinking density tends to decrease, by using a cyclic skeleton monomer, the glass transition temperature becomes high, and good film physical properties can be maintained. Further, it is presumed that if the number of functional groups is 2 to 6, preferably 2 to 4, the crosslinking reaction of the photocurable resin composition tends to be moderately maintained, and in particular, the dyeing agent can be more effectively inhibited from oozing out to the coating layer. Internally, the water-supplying member and the functional panel are stained. Therefore, in this case, a water-receiving member and a functional panel can be obtained, which can form a coating layer which not only maintains good antifouling properties, but also can be preferably provided in the case of effectively maintaining chemical resistance and dyeing resistance. The hardenability.

(B) Photopolymerizable Oligomer and (C) Photopolymerizable Monomer An oligomer may be used singly or as a monomer alone, but it is preferred to use an oligomer and a monomer in combination.

<(D) Photopolymerization initiator>

The (D) photopolymerization initiator used in the photocurable resin composition of the present invention has the above (A) dimethyl polyoxyalkylene (meth) acrylate oligomerized when exposed to light such as ultraviolet rays. The polymerization of the material, (B) photopolymerizable oligomer, and/or (C) photopolymerizable monomer begins. The (D) photopolymerization initiator is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include 4-dimethylamino benzoic acid, 4-dimethylaminobenzoate, and 2,2. -Dimethoxy-2-phenylacetophenone, acetophenone diethyl ketal, alkoxyacetophenone, benzyldimethylketal, benzophenone, and 3,3-dimethyl a benzophenone derivative such as 4-methoxybenzophenone, 4,4-dimethoxybenzophenone or 4,4-diaminobenzophenone, or an alkyl benzoquinone benzoate, Benzyl derivatives such as bis(4-dialkylaminophenyl) ketone, benzyl and benzyl methyl ketal, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxyl -2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl-one, xanthonone, thioxanone and thioxanthene derivatives, hydrazine, 2,4,6-trimethylbenzene Diphenylphosphine oxide, bis(2,6-dimethoxyphenylhydrazine)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylphenylhydrazine) )-Phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl)-butyl 1 and the like. These may be used alone or in combination of two or more.

The amount of the (D) photopolymerization initiator to be used in the photocurable resin composition of the present invention is not particularly limited and may be appropriately selected depending on the purpose, with respect to (A) dimethylpolyoxane (methyl). 100 mass total of acrylate oligomer and (B) photopolymerizable oligomer and/or (C) photopolymerizable monomer The fraction is preferably in the range of 0.1 part by mass to 10 parts by mass. When the amount of the (D) photopolymerization initiator is 0.1 part 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 the polymerization reaction is saturated, but on the other hand, The coloring becomes remarkable, and the raw material cost of the photocurable resin composition becomes high.

<(E) Other ingredients>

-Light sensitizer -

The photocurable resin composition of the present invention may further contain a photosensitizer as necessary in consideration of the required curing reactivity, stability, and the like. The photo sensitizer has a function of absorbing energy by irradiation, and the energy or electrons move toward the polymerization initiator to start polymerization. The photo sensitizer may, for example, be p-dimethylamino benzoic acid isoamyl ester or the like. The total amount of the photo-sensitizer is 100 mass in total with respect to (A) photopolymerizable polyoxyalkylene oligomer and (B) photopolymerizable oligomer and/or (C) photopolymerizable monomer. The fraction is preferably in the range of 0.1 part by mass to 10 parts by mass.

- Polymerization inhibitors -

Further, the photocurable resin composition of the present invention may further contain a polymerization inhibitor as necessary in consideration of the required curing reactivity, stability, and the like. The polymerization inhibitor may, for example, be hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol or 2,6-di-t-butyl-pair. Cresol, butyl hydroxyanisole, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like. The amount of these polymerization inhibitors is relative to (A) dimethyl polyoxyalkylene (meth) acrylate oligomer and (B) photopolymerizable oligomer and/or (C) photopolymerizable single The total mass of the body is preferably in the range of 0.1 part by mass to 10 parts 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 in terms of a diluent solvent, and examples of the organic solvent include propylene glycol monomethyl ether acetate (PMA) and methyl ethyl ketone. (MEK), methyl isobutyl ketone (MIBK), acetone, butyl lactate, and the like. These diluting solvents may be used alone or in combination of two or more.

The photocurable resin composition of the present invention can be applied to the surface of the substrate in a liquid form by application of a diluent solvent as necessary, as described above. The coating method is not particularly limited, and a known method can be employed, and examples thereof include gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, blade coating, extrusion coating, slip coating, and wire rod. Coating, curtain coating, extrusion coating, spin coating, and the like.

(watering member)

The water-repellent member is characterized by comprising a coating layer obtained by curing the photocurable resin composition of the present invention, and a substrate layer. The water-using member is a member that requires water-cutting of the surface. The water-using member is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a kitchen flow table, a kitchen wall material, a wash table, a bathroom wall material, a bathtub, a bathroom ceiling material, and a bathroom floor panel. Bathroom counters, toilets, water storage tanks, etc.

(functional panel)

The functional panel of the present invention comprises a coating layer obtained by curing the photocurable resin composition of the present invention and a substrate layer, and for example, the coating layer is preferably formed on the substrate layer.

The overall thickness of the functional panel of the present invention is not particularly limited, and may be appropriately selected depending on the purpose, and is usually preferably 2.5 mm or more. In addition, this The upper limit of the thickness of the entire functional panel of the invention is not particularly limited and may be appropriately selected depending on the purpose. The coating layer may be formed on both the upper surface and the inner surface of the base material layer, and may be formed into a multilayer structure in addition to the base layer and the coating layer and the intermediate layer formed of various materials between the layers. At this time, since the coating layer has excellent water repellency and slidability as described above, it is desirable 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 examples thereof include an undercoat layer for improving the adhesion between the substrate layer and the coating layer, and an application pattern for improving the functional panel pattern or Decorative layers of color, etc.

Since the functional panel of the present invention obtained as described above has the coating layer formed on the base material layer, it has excellent water repellency and slidability, and is resistant to abrasion, chemical resistance, temperature resistance, and dyeing resistance. It is also excellent, and it can effectively suppress the adhesion of various contaminants represented by scale, and it is less likely to deteriorate or deteriorate even if a highly irritating detergent containing an acid or a base is used. Further, discoloration or dyeing is less likely to occur even when a dye such as a hair dye is used. Thus, the functional panel of the present invention is particularly suitable as a functional panel for a bathroom or kitchen disposed in a home.

<coating layer>

The photocurable resin composition of the present invention can be applied onto a substrate, and then photocured to form a coating layer on the substrate layer. The photohardening method generally irradiates light such as ultraviolet rays. The surface on the substrate layer on which the coating layer is formed may be one of the surface and the inner surface, or both surfaces, and may be appropriately selected as necessary. 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, and when ultraviolet rays are used, the irradiation intensity is usually 20 mW/cm ² to 2000 mW/cm. ² , the irradiation amount is 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. In this way, since the curing can be performed in a short time, the productivity of the obtained functional panel can be improved.

The thickness of the coating layer is not particularly limited, and can be appropriately selected depending on the desired pattern and the degree of chemical resistance, and is usually assumed 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 resin composition is applied to the substrate, the composition can be cured in a nitrogen atmosphere so as not to come into contact with oxygen. In addition, the free energy of the surface of the coating layer formed by photo-curing, based on sufficient water repellency and ensuring good slidability of view, usually ^{12mJ / m 2 ~ 30mJ / m} 2 for the desired person.

<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, and examples thereof include inorganic materials such as slate, concrete, metal, calcium silicate, calcium carbonate, and glass; Materials; organic materials such as polypropylene, polystyrene, polycarbonate, unsaturated polyester resin; these composite materials.

Among these, it is preferable that the organic material is added to a material such as glass fiber or carbon fiber, that is, a so-called FRP (fiber reinforced plastic). The FRP is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include an unsaturated polyester resin, a filler, and glass fiber or carbon fiber. The sheet-like sheet molding compound (SMC) and the SMC are a composite material, and a block-shaped dough-forming plastic (BMC) containing short fibers is used. The FRP is generally formulated 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 an adhesion promoter. The metal mold of a predetermined temperature is pressurized, and is formed into a shape suitable for the place where it is placed in the form of a building material. Among these, in the case of an FRP containing an unsaturated polyester as a thermosetting resin, a filler, and a glass fiber or a carbon fiber as a reinforcing material, the strength and durability of the entire functional panel can be improved. .

The 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, trimethyl diol, trimethyl pentane diol, and neopentyl It is produced by a polyol such as a diol, trimethylpropane monoallyl ether, hydrogenated bisphenol or bisphenol dioxypropyl ether.

The filler is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include calcium carbonate and aluminum hydroxide. Among these, calcium carbonate is preferred from the viewpoint of cost reduction, and aluminum hydroxide is preferred from the viewpoint of improving the chemical resistance of FRP itself. However, as described above, as long as the coating layer is formed, even if FRP using calcium carbonate as a base material is used as a base material, the chemical resistance of the entire functional panel can be sufficiently improved, and the cost can be easily achieved. A functional panel of a substrate layer composed of FRP.

The glass fiber and the carbon fiber as the reinforcing material are not particularly limited, and may be appropriately selected depending on the purpose, and preferably have a fiber length of about 20 mm to 50 mm, a fiber diameter of 5 μm to 25 μm, and a FRP of 10 mass. The amount of %~70% by mass is desired. The FRP used as the base material layer is mixed with these components and manufactured by FRP. Set to produce an FRP of a given thickness and size.

Further, the thickness of the base material layer is not particularly limited and may vary depending on the use of the functional panel, and 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 polyoxynonane polyol having a number average molecular weight of 1,000 (Salapu-linked FM-4411, formula (2), p=1, q=3, (total carbon number of R of formula (1) 5), 0.1 mol, 0.1 mol of polyethylene glycol (PEG #1000, Nippon Oil Co., Ltd.) having a number average molecular weight of 1,000, and 0.06 g of dibutyltin dilauryl ester were added to a reaction vessel and stirred. Next, 0.3 mol of isophorone diisocyanate (VESTANAT IPDI, manufactured by Abbott Decker) was added at room temperature. The mixture was heated to 70 ° C and reacted at 300 rpm for 2 hours and a half to obtain a urethane prepolymer solution. To the total amount of the prepolymer solution obtained, 0.2 mol of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) was further added, and the reaction was completed by stirring for 4 hours to obtain a dimethyl group having a number average molecular weight of about 3,000. A siloxane (meth) acrylate oligomer.

<Manufacturing Example 2>

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

<Manufacturing Example 3>

In Production Example 1, a polyoxynonane polyol having a number average molecular weight of 1,000 (Salapulian FM-4411, Formula (2), p=1, q=3, (R of Formula (1)) was used instead. Total carbon number 5), manufactured by Soko Co., Ltd., using a polyoxane polyol having a number average molecular weight of about 5,000 (FM-4421, formula (2), p=1, q=3, (general formula (1) In the same manner as in Production Example 1, except that the total carbon number of R in R) was 5), a dimethylpolysiloxane (meth) having a number average molecular weight of about 7,000 was obtained. Acrylate oligomer.

<Manufacturing Example 4>

In Production Example 1, a polyoxynonane polyol having a number average molecular weight of 1,000 (Salapulian FM-4411, Formula (2), p=1, q=3, (R of Formula (1)) was used instead. Total carbon number 5), manufactured by Soko Co., Ltd., using polyoxanol polyol having a number average molecular weight of about 10,000 (FM-4425, formula (2), p=1, q=3, (general formula (1) In the same manner as in Production Example 1, except that the total carbon number of R was 5 (manufactured by Sothes Co., Ltd.), a dimethyl polyoxane (methyl) having a number average molecular weight of about 12,000 was obtained. Acrylate oligomer.

<Manufacturing Example 5>

In Production Example 1, a polyoxynonane polyol having a number average molecular weight of 1,000 (Salapulian FM-4411, Formula (2), p=1, q=3, (R of Formula (1)) was used instead. Total carbon number 5), manufactured by Soko Co., Ltd., using a polyoxyl alkanol polyol having a number average molecular weight of about 1700 (KF6001, formula (2), p=1, q=3, (formula (1) ) The total carbon number of R is 5), Shin-Etsu Chemical Industry Co., Ltd. In the same manner as in Production Example 1, a dimethyl polysiloxane (meth) acrylate oligomer having a number average molecular weight of about 4,000 was obtained in the same manner as in Production Example 1.

<Manufacturing Example 6>

In Production Example 1, a polyoxynonane polyol having a number average molecular weight of 1,000 (Salapulian FM-4411, Formula (2), p=1, q=3, (R of Formula (1)) was used instead. Total carbon number 5), manufactured by Soko Co., Ltd., changed to polyoxane polyol with a number average molecular weight of about 3,000 (KF6002, formula (2), p = 1, q = 3, (formula (1) In the same manner as in Production Example 1, except that the total carbon number of R was 5) (manufactured by Shin-Etsu Chemical Co., Ltd.), a dimethyl polysiloxane (meth)acrylic acid having a number average molecular weight of about 5,000 was obtained. Ester oligomer.

<Manufacturing Example 7>

In Production Example 1, a polyoxynonane polyol having a number average molecular weight of 1,000 (Salapulian FM-4411, Formula (2), p=1, q=3, (R of Formula (1)) was used instead. Total carbon number 5), manufactured by Soko Co., Ltd., using polyoxanol polyol having a number average molecular weight of about 5,500 (KF6003, formula (2), p=1, q=3, (formula (1) In the same manner as in Production Example 1, except that the total carbon number of R was 5) (manufactured by Shin-Etsu Chemical Co., Ltd.), a dimethyl polysiloxane (meth)acrylic acid having a number average molecular weight of about 7,500 was obtained. Ester oligomer.

<Manufacturing Example 8>

In Production Example 1, a polyoxynonane polyol having a number average molecular weight of 1,000 (Salapulian FM-4411, Formula (2), p=1, q=3, (R of Formula (1)) was used instead. Total carbon number 5), made by Soji Co., Ltd.) Polyoxane polyol with a molecular weight of about 4,000 (X-22-4952, formula (2), p≒5, q=3, (total total carbon number of formula (1) ≒13), Shin-Etsu Chemical Industry In the same manner as in Production Example 1, a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 6,000 was obtained in the same manner as in Production Example 1.

<Manufacturing Example 9>

In the production example 1, a pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) was added instead of 2-hydroxyethyl acrylate (trade name: Leyte ester HOA, manufactured by Kyoeisha Chemical Co., Ltd.). In the same manner as in Production Example 1, a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 3,000 was obtained.

<Manufacturing Example 10>

In the production example 1, a pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) was added instead, and dipropylene glycol acrylate (trade name: DPGA, manufactured by Dai-ichi Pharmaceutical Co., Ltd.) was added instead. In the same manner as in Production Example 1, a dimethyl polysiloxane (meth) acrylate oligomer having a number average molecular weight of about 3,000 was obtained.

<Manufacturing Example 11>

In Production Example 1, a pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) was added instead of 2-propenyloxyethyl succinate (trade name: A-SA, Shin-Nakamura Chemical Co., Ltd.) In the same manner as in Production Example 1, a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 3,000 was obtained in the same manner as in Production Example 1.

<Manufacturing Example 12>

In Production Example 1, substituting isophorone diisocyanate (VESTANAT IPDI, manufactured by Albuquerque Dexsa), hexamethylene diisocyanate (trade name: HDI, manufactured by Albenik Dexsa), which is a polyisocyanate compound having no cyclic skeleton in its molecular structure, is added. In the same manner as in Production Example 1, a dimethyl polyoxyalkylene (meth) acrylate oligomer having a number average molecular weight of about 3,000 was obtained.

<Manufacturing Example 13>

In Production Example 1, polyethylene glycol (PEG #1000, Nippon Oil Co., Ltd.) having a number average molecular weight of 1,000 was not added, and 0.3 mol of isophorone diisocyanate was added instead, and isophorone diisocyanate was added instead. A dimethylpolysiloxane (meth) acrylate oligomer having a number average molecular weight of about 2,000 was obtained in the same manner as in Production Example 1 except for the above.

<Manufacturing Example 14>

In Production Example 1, a dimethyl group having a number average molecular weight of about 40,000 was obtained in the same manner as in Production Example 1, except that 0.3 mol of isophorone diisocyanate was added and 0.22 mol of isophorone diisocyanate was added instead. Polyoxyalkylene (meth) acrylate oligomer.

<Manufacturing Example 15>

Polyoxymethane compound which is condensed into a diol at one side of polydimethyl methoxy oxane (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-176DX) 30.0 g, isodecene acrylate 132.6 g, dibutyltin 0.03 g of dilauryl ester was added to the reaction vessel and stirred. Next, 3.14 g of hexamethylene diisocyanate (HDI) [manufactured by Albuquerque Dexsa] was added at room temperature. The mixture was heated to 50 ° C and reacted at 100 rpm for 3 hours to obtain a urethane prepolymer solution. To the obtained prepolymer solution, 2.24 g of 2-hydroxyethyl acrylate was added in a total amount, and the reaction was completed by stirring for 6 hours to obtain a polyoxyalkylene oligomer.

<Modulation and evaluation of photocurable resin composition>

According to the formulations shown in Tables 1 to 6, the components were placed in a stirring device and mixed to prepare a photocurable resin composition. The obtained photocurable resin composition was applied onto a substrate composed of FRP (Dickmart (registered trademark) 2415, manufactured by DIC Chemical Co., Ltd.) so as to have a thickness of 20 μm. Next, the photocurable resin composition was cured by UV irradiation (1000 mW/cm ² , 4000 mJ/cm ² ) to obtain a sample. The water repellency and slidability were evaluated by the following methods, and the results shown in Tables 1 to 6 were obtained. Further, in Tables 1 to 6, the initial meaning means that immediately after the preparation of the sample, the term "endurance test" means after immersion in water at 50 ° C for 50 hours.

(1) Compatibility

The evaluation of compatibility was carried out by visual observation. Addition of (A) dimethyl polyoxyalkylene (meth) acrylate oligomer to (B) photopolymerizable oligomer and/or (C) photopolymerizable monomer as base resin The compatibility is judged according to the following criteria.

○: transparent

△: slightly white turbid

×: Obviously turbid

(2) Water repellency

The evaluation of the water repellency was carried out by measuring the water contact angle. Further, the contact angle was measured using DM-500 manufactured by Kyowa Interface Science Co., Ltd. 1.5 μL of water droplets were dropped on the substrate, and the water contact angle immediately after the dropping and after the endurance test was measured. The measurement was carried out 3 times, and the average value thereof was used as the value of the contact angle.

(3) Slidability

The evaluation of the slidability was carried out by measuring the roll angle of water. In addition, slip The evaluation of the motility was carried out using DM-500 and DM-SA manufactured by Kyowa Interface Science Co., Ltd. 30 μL of water droplets were dropped on the substrate, and the platform 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 was carried out twice, and the average value thereof was the value of the roll-off angle.

*1 (a) (q = 3) represented by the formula (2) (total carbon number of R of the formula (1) 3) polyfluorene oxide polyol and (b) isophorone diisocyanate as an isocyanate (IPDI) dimethyl methacrylate (meth) acrylate oligomer obtained by reacting (c) (meth) acrylate monomer ("SIU1300", manufactured by Miwon Co., Ltd., number average molecular weight: about 7000 , functional group number 6)

*2 (a) (q = 3) represented by the formula (2) (total carbon number of R of the formula (1) 3) polyfluorene oxide polyol and (b) isophorone diisocyanate as an isocyanate (IPDI) dimethyl methoxide (meth) acrylate oligomer obtained by reacting (c) (meth) acrylate monomer ("SIU1500", manufactured by Miwon Co., Ltd., number average molecular weight: about 8,000 , functional group number 10)

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

*3-2 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 2

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

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

*3-5 The dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 5

*3-6 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 6

*3-7 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 7

*3-8 dimethyl polyoxyalkylene (meth) acrylate obtained in Production Example 8. Oligomer

*3-9 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 9.

*3-10 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 10.

*3-11 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 11

*3-12 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 12

*3-13 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 13

*3-14 dimethyl polyoxyalkylene (meth) acrylate oligomer obtained in Production Example 14.

*4 The polyoxyalkylene oligomer obtained in Production Example 15

*5, manufactured by Soko Co., Ltd., "FM-0711", single-end methacrylic acid-modified dimethylpolysiloxane oil, with a number average molecular weight (Mn) of 1000, which is 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 in order to eliminate terminal reactivity, and does not contribute substantially to the present invention.

*6 Sochi Co., Ltd., "FM-7711", methacrylic acid-modified dimethyl polysiloxane oil at both ends, with a number average molecular weight (Mn) of 1000, a specific gravity of 0.98, a refractive index of 1.419, and a viscosity of 20 mm ² / s, a compound outside the scope of the patent application represented by the following formula (4)

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

*7 A urethane acrylate oligomer having 1,2-polyoxybutylene units synthesized by the following method

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

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

*9 New Nakamura Industrial Co., Ltd., 2-propenyloxyethyl succinate, SP value = 22.7 (J/cm ³ ) ^0.5

*10 Gigabit Chemical, "IRGACURE 184", 1-hydroxy-cyclohexyl-phenyl-ketone

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

Using potassium hydroxide as a catalyst, 1 mol of propylene glycol (manufactured by Kanto Chemical Co., Ltd.) was added to 12 mol of butylene oxide at a reaction temperature of 110 ° C to obtain a polyol. In a reaction vessel having a nitrogen gas introduction tube, a stirrer, and a cooling tube, 2 mol of 2,4-toluene diisocyanate was added to the polyol, and the mixture was reacted at 70 ° C for 2 hours. Next, 4 mol of 2-hydroxyethyl acrylate and a small amount of dibutyltin dilauryl ester as a catalyst were gradually added, and further reacted at 70 ° C for 15 hours to obtain a 1,2-butanediol unit having a number average molecular weight of about 1,500. Urethane acrylate oligomer.

The n-heptane tolerance value of the urethane acrylate oligomer having a 1,2-polyoxybutylene unit thus obtained was 1.0 g/10 g.

From the results of the examples and the comparative examples of Tables 1 to 6, it is understood that (a) the (a) polypyroxyne polyol represented by the above formula (1), (b) isocyanate, (c) is used by using (A). a dimethyl polyoxyalkylene (meth) acrylate oligomer obtained by reacting a (meth) acrylate monomer capable of reacting with an isocyanate-reactive functional group, which can be obtained in water repellency and slidability A long-term enhanced photocurable resin composition.

Claims (9)

A photocurable resin composition comprising: (A) a dimethyl polyoxyalkylene (meth) acrylate oligomer, wherein (a) the polyoxane represented by the following formula (1) Alkane polyol, (b) isocyanate, (c) a terminal having a (meth) acrylate monomer reactive with an isocyanate-reactive functional group; In the formula (1), n represents an integer arbitrarily selected such that the number average molecular weight of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is from 700 to 40000, and R represents a (1) photopolymerizable oligomer and (C) a photopolymerizable monomer, (A) dimethylpolyoxyalkylene (meth) acrylate oligomer copolymerization; and (D) photopolymerization initiator; the (B) photopolymerizable oligomer having 1,2-poly A (meth) acrylate oligomer of a butylene oxide unit. The photocurable resin composition of claim 1, wherein the (b) isocyanate group in the isocyanate and the (a) hydroxyl group in the polyoxyalkylene polyol represented by the formula (1) The equivalent ratio, that is, the isocyanate group/hydrogenoxy group is more than 100/100 and is 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 claim 1 or 2, wherein the (C) photopolymerizable single system contains a compound represented by the following formula (A): (CH ₂ =CR ¹ COO) _n R ² ‧‧‧ Formula (A) wherein, in the 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, and n represents a range of 1 to 4 The integer inside. The photocurable resin composition according to claim 1 or 2, wherein the (b) isocyanate-based polyisocyanate compound having a cyclic skeleton in a molecular structure. The photocurable resin composition according to claim 1 or 2, wherein the functional group in the (c) (meth) acrylate monomer which can react with the isocyanate group is a hydroxyl group. The photocurable resin composition according to claim 1 or 2, wherein the content of the (A) dimethyl polyoxyalkylene (meth) acrylate oligomer is relative to the (B) photopolymerizable property. The total of the oligomer and/or the (C) photopolymerizable monomer is 0.05% by mass to 10% by mass. A water-receiving member comprising: a coating layer obtained by curing a photocurable resin composition according to any one of claims 1 to 7; and a substrate layer. A functional panel comprising: a coating layer obtained by curing a photocurable resin composition according to any one of claims 1 to 7; and a substrate layer.