JP2004115793A - Thermosetting resin composition having hydrophilicity, molding obtained from the composition, and producing method of the molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having excellent water drainability, and to provide a molding comprising the composition and a producing method of the molding. <P>SOLUTION: The composition comprises at least one hydrophilic compound selected from the group consisting of a hydrophilic compound having a molecular weight of ≤1,000 and a boiling point of ≥140°C and dissolving ≥7 g in water of 100 ml at 25°C, and a hydrophilic compounds having a molecular weight of greater than 1,000 and dissolving ≥7 g in water of 100 ml at 25°C, and a thermosetting resin. A cured product of the composition has a water drain off time of ≤30 min when it is measured by a mirror plane structured draining tester with a 700 mm long, a 700 mm wide, and a slant degree of 3°. A hydrophilic structural component comprising the cured product of the composition includes a floor covering for a bathroom, an indoor floor tile, an outdoor floor tile, a wash stand decorative board, and the like. <P>COPYRIGHT: (C)2004,JPO

Description

{Circle over (1)} The present invention relates to a thermosetting resin composition having hydrophilicity, molded articles obtained from this composition, and methods for producing these molded articles.

Conventionally, unsaturated polyester resin or the like that does not contain hydrophilicity has been used for the floor of a bathroom washroom and the decorative panel of a washbasin. However, in recent years, there has been an increasing demand for drainage of floors and veneers in bathrooms. In particular, there is a remarkable demand for improving the drainage of a bathroom washing place.

For this purpose, paints or the like for draining are applied to molded products. However, it has to be worked again after molding, which makes the operation complicated, and new materials have to be used, which tends to be expensive.

Therefore, there has been a demand for the appearance of a member having excellent drainage properties, which can be obtained by an inexpensive and simpler method.

An object of the present invention is to provide a thermosetting resin composition having excellent drainage properties, which can be used as a floor material or a wall material at a place where water is used, molded articles obtained from the composition, and methods for producing these molded articles Is to provide.

The thermosetting resin composition according to the present invention has a molecular weight of 1,000 or less, a boiling point of 120 ° C. or more, a hydrophilic compound soluble in 7 g or more in 100 ml of water at 25 ° C. and a molecular weight exceeding 1000, and 100 ml of water at 25 ° C. And at least one hydrophilic compound selected from the group consisting of hydrophilic compounds soluble in 7 g or more, and a thermosetting resin. In a composition containing a compound having a solubility of less than 7 g in 100 ml of water, a molded article obtained therefrom may not have sufficient drainage.

熱 The thermosetting resin composition according to the present invention is characterized by containing a hydrophilic compound in an amount of 0.5 to 50% by weight.

Examples of the hydrophilic compound include a compound having a pyrrolidone skeleton, a hydrophilic oligomer and a hydrophilic polymer compound.

熱 The thermosetting resin composition according to the present invention is characterized by containing a hydrophilic compound having a pyrrolidone skeleton in an amount of 0.1% by weight or more and 50% by weight or less.

硬化 The cured product of the thermosetting resin composition according to the present invention is characterized by containing a thermosetting resin in which the proportion of the pyrrolidone skeleton in the polymer molecule is from 0.1% by weight to 50% by weight.

In addition, the cured product of the thermosetting resin composition according to the present invention has a drainage time of 60 minutes or less as measured by a drainage tester having a mirror structure having a length of 700 mm, a width of 700 mm and an inclination of 3 °. It is characterized by.

Furthermore, the cured product of the thermosetting resin composition according to the present invention is characterized in that the contact angle with water is 80 ° or less.

親水 The hydrophilic member according to the present invention is characterized by being made of a cured product of the thermosetting resin composition. Examples of the hydrophilic member include bathroom floor materials, bathroom wall materials, indoor tiles, outdoor floor tiles, bathroom wall materials, washbasin facings, and the like. 2. Description of the Related Art Conventionally, bathroom flooring materials have a feature that a geometric pattern such as a rock surface pattern, a tile pattern, a lattice shape, and irregularities is provided.

The method for producing a hydrophilic member according to the present invention includes producing the hydrophilic member by molding the thermosetting resin composition by a molding method such as press molding, casting molding, spray-up molding, and hand-lay-up molding. It is characterized by.

From the thermosetting resin composition according to the present invention, a molded article having excellent hydrophilicity can be produced.
The molded article obtained from the thermosetting resin composition according to the present invention has excellent hydrophilicity.

Hereinafter, the thermosetting resin composition having hydrophilicity according to the present invention, a molded article comprising the same, and a method for producing the same will be described.

[Thermosetting resin composition]
The thermosetting resin composition according to the present invention comprises a hydrophilic compound and a thermosetting resin.

(Hydrophilic compound)
In the present invention, as a hydrophilic compound, a hydrophilic compound having a molecular weight of 1000 or less and a boiling point of 120 ° C. or more and soluble in 100 ml of water at 25 ° C. in a quantity of 7 g or more and a molecular weight exceeding 1000 and soluble in water 100 ml at 25 ° C. of 7 g or more at 25 ° C. At least one compound selected from the group consisting of hydrophilic compounds is used. In a composition containing a compound having a solubility in 100 ml of water at 25 ° C. of less than 7 g, a molded article obtained therefrom may not show sufficient drainage.
The hydrophilic compound having a molecular weight of 1,000 or less and a boiling point of 120 ° C. or more preferably has a solubility in water of 25 (g / 100 ml water) or more, more preferably 45 (g / 100 ml water) or more, It is particularly preferably 160 (g / 100 ml water) or more. The hydrophilic compound having a molecular weight of 1000 or less is desirably large in molecular weight because it has an effect of improving drainage with a small amount as the molecular weight is large, preferably has a molecular weight of 90 or more, more preferably 150 or more, and particularly preferably 200 or more. It is.

The hydrophilic compound having a molecular weight exceeding 1000 preferably has a solubility in water of 10 (g / 100 ml of water) or more, more preferably 25 (g / 100 ml of water) or more, and 80 (g / 100 ml of water). It is particularly preferable that the above is satisfied.

When the solubility of the hydrophilic compound in water is within the above range, the molded article (cured product) obtained from the thermosetting resin composition has excellent hydrophilicity and tends to exhibit sufficient drainage performance, and the boiling point is as described above. When it is in the range, there is no problem in appearance when the thermosetting resin composition is cured by heating. In the case of a composition containing a compound that does not dissolve in an amount of 7 g or more in 100 ml of water, a molded article obtained therefrom may not have sufficient drainage. When the boiling point of the hydrophilic compound is lower than 120 ° C., the appearance of the molded article may be deteriorated in the process of thermosetting.
The solubility of the hydrophilic compound in water is measured as follows.

The compound is added to 100 ml of distilled water at a predetermined temperature (25 ± 0.5 ° C.), stirred with a high-speed mixer or a kneader, and left in a constant temperature water bath at 25 ± 0.5 ° C. for 24 hours to precipitate the compound. It is defined as the ratio of the minimum weight (g / 100 ml of water) to start.
In the case of a high molecular weight polymer, it may be better to dissolve it using a kneader in some cases.

Examples of the hydrophilic compound having a molecular weight of 1,000 or less, a boiling point of 120 ° C. or more, and a solubility of 7 g or more in 100 ml of water at 25 ° C. include a compound having a pyrrolidone skeleton such as pyrrolidone or a derivative thereof, a hydrophilic oligomer, and a surfactant (electrically resistant). And a silane compound. Examples of the hydrophilic compound having a molecular weight of more than 1000 and soluble at least 7 g in 100 ml of water at 25 ° C. include a hydrophilic polymer compound.

As the compound having a pyrrolidone skeleton,
2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 250 ° C.),
N-methyl-2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 204 ° C.),
N-vinyl-2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 215 ° C.),
N-ethyl-2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 212 ° C.),
N-octyl-2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 307 ° C.),
N- (2-hydroxyethyl) -2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 309 ° C.),
N-cyclohexyl-2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 292 ° C.),
N-dodecyl-2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 361 ° C),
N-isopropyl-2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 219 ° C.),
N- (n-butyl) -2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 244 ° C.),
N- (t-butyl) -2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 221 ° C.),
N-hexyl-2-pyrrolidone (solubility: 148 g / 100 ml water, boiling point: 276 ° C.), N- (3-hydroxypropyl) vinyl-2-pyrrolidone (solubility: 148 g / 100 ml water, boiling point: 319 ° C.),
N- (2-methoxyethyl) -2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 252 ° C.),
N- (3-methoxypropyl) -2-pyrrolidone (solubility: 160 g / 100 ml or more water, boiling point: 272 ° C.),
N-benzyl-2-pyrrolidone (solubility: 160 g / 100 ml water or more, boiling point: 319 ° C.)
And the like. These compounds having a pyrrolidone skeleton are sold, for example, by BASF and can be obtained from the market.

Surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, fatty acid salts, formalin naphthalene sulfonate Condensates, anionic surfactants other than the above, such as polymeric surfactants; polyoxyethylene alkyl esters, polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene derivatives, sorbitan Fatty acid ester, sorbitan alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan alkyl ester, glycer Nonionic surfactants such as fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines and alkylalkanolamides; cationic interfaces such as alkylamine salts and quaternary ammonium salts Activator; an amphoteric surfactant such as alkyl betaine and amine oxide.

These surfactants can be obtained from the market. Examples of the anionic surfactant include Kao Corporation's Emal 0, 10 powder, 10 needle, 2F paste, 2F needle, 2F-30, 40 paste. 40 powder, 71, TD, AD-25R, Emar 20C, E-27C, 270J, 20CM, D-3-D, D-4-D, 20T, Latemul E-118B, E-150, Levenol WX, Latemul WX , Neoperex GS, G-15, G-25, G-65, No6F powder, Perex NB-L, Perex OT-P, TR, CS, TA, Perex SS-L, SS-H, NS soap, SS- 40N, KS soap, OS soap, FR-14, FR-25, Electrostripper F, Latemul S-180, S-180A, ASK PS, Demol N, NL, RN, RN-L, T, T-45, MS, SN-B, SS-L, SC-30, EP, Poise 520, 521, 530, 532A, homogenol L-18, L -1820, L-95, and L-100 (trade names).

Examples of nonionic surfactants include Emulgen 103, 104P, 105, 106, 108, 109P, 120, 123P, 147, 150, 130K, Emulgen 210P, 220, Emulgen 306P, 320P, and Emulgen 404 manufactured by Kao Corporation. 408, 409P, 420, 430, Emulgen 705, 707, 709, Emulgen 1108, 1118S-70, 1135S-70, 1150S-70, Emulgen 4085, 2020G-HA, 2025G, Emulgen LS-106, LS-110, LS- 114, MS-110, Emulgen A-60, A-90, A-500, B-66, PP-290, Rheodol SP-L10, SP-P10, SP-S10V, SP-S30V, SP-O10V, SP- O30V, Leodor Super SP-L10, Reodol AS-10, AO-10, AO-15V, Emazole L-10 (F), P-10 (F), S-10V, O-10V, Emazole Super L-10 (F), Emazole O-15R, S-20, Rheodor TW-L120, TW-L106, TW-P120, TW-S120V, TW-S106, Rheodor TW-S320V, TW-O120V, TW-O106V, TW-320V, Rheodor TW- IS399C, Reodol Super TW-L120, Emazole O-105R, Reodol 430, 440, 460, Reodol MS-50, MS-60, MO-60, MS-165V, Emazole MO-50, Exel T-95, VS- 95, O-95R, Exel 150, 200, 300, 84, 122, P 40S, Emanone 1112, 3199, 3299, 3299R, 4110, Emanone CH-25, CH-40, CH-60 (K), CH-80, Amate 105, 320, Aminone PK-02S, L-02, Electrostripper TS -2B, TS-3B, TS-5, TS-6B, TS-7B, TS-8B, HS-12N, EA, PC (trade names), Nissan Nonion L-4, P- 6, S-6, S-10, S-15.4, S-40, O-6, Nissan Nonion K-220, K-230, P-208, P-210, P-213, P-223, P-240, E-212, E-215, E-230, S-211, S-215, S-220, S-230, T-208.5, Nissan Nonion HS-210, HS-215
, HS-220, HS-240, NS-210, NS-212, NS-215, NS-2
20, NS-230, NS-240, NS-270, Nissan Nonion LT-221, ST-221, OT-221, Unilube 34S-23, 10MS-250KB, Uniox HC-40, HC-60, Nissan Naimin L-202, L-207, S-202, S-204, S-210, S-215, S-220, T 2 -210, T 2 -230, T 2
-260, DT-208 (all trade names) and the like.

The Nissan Naimeen (trade name) is a compound represented by the following general formula. As X, Y, and Z in the following formulas are larger, the hydrophilicity is improved.

Examples of the cationic surfactant include Kao Corporation's acetamine 24, 86, coatamine 24P, 86P conc, 60W, 86W, D86P, Sanizole C, B-50 (trade name) and the like.

Examples of the amphoteric surfactant include Amphitol 20BS, 24B, 86B, 20YB and Amphitol 20N (trade names) of Kao Corporation.
The above-listed commercially available surfactants have a molecular weight of 1,000 or less, a boiling point of 120 ° C. or more, and are dissolved in 100 ml of water at 20 ° C. in an amount of 7 g or more.

Examples of the silane compound include silane coupling agent A-1100, silane monomer A-1230, primers APZ-6601, APZ-6633, silicone foam stabilizers SZ-1111, SZ-1136, L-580, manufactured by Nippon Unicar Co., Ltd. SZ-1127, SZ-1919, SZ-1142, SZ-1162, SZ-1105, SZ-1605, SZ-1642, SZ-1649, L-5420, SZ-1675, SZ-1710, SZ-1627, L- 5340, SZ-1671, and SZ-1711 (all trade names).
The commercially available silane compound exemplified above has a molecular weight of 1,000 or less, a boiling point of 120 ° C. or more, and is dissolved in 100 ml of water at 25 ° C. in an amount of 7 g or more.

For a hydrophilic compound having a molecular weight of 1,000 or less, the boiling point is preferably 120 ° C. or more. It is preferably at least 150 ° C, more preferably at least 180 ° C. When the boiling point of the hydrophilic compound is lower than 120 ° C., the appearance of the molded article may be deteriorated.
As the hydrophilic polymer compound,
Polyvinyl alcohol (solubility: 25 g / 100 ml water or more),
Polyvinylpyrrolidone (solubility: 80 g / 100 ml water or more),
Cationized water-soluble polymer (cationized starch, cationized guar gum, cationized polyacrylamide (solubility: 7.5 g / 100 ml water), cationized polyacrylic acid ester (solubility: 7 g / 100 ml water or more), cationized vinyl formamide Cationized polyamine (solubility: 7.5 g / 100 ml water)),
Anionized water-soluble polymer (anionized polyacrylamide (solubility: 7 g / 100 ml water or more), anionized sodium polyacrylate (solubility: 7 g / 100 ml water or more))
Polyacrylate,
Organopolysiloxane (solubility: 230 g / 100 ml or more water),
Polyvinyl alcohol-polyvinyl acetate copolymer,
Vinyl acetate-polyvinylpyrrolidone copolymer,
Polysiloxane (solubility: 7g / 100ml water or more),
Urethane,
Amino group-containing condensate,
Hydroxyalkoxycellulose,
Hydroxyalkyl cellulose,
A copolymer of polyvinylpyrrolidone and acryl is exemplified.

Such a hydrophilic polymer compound can be produced by a conventionally known method, or can be obtained from the market.
Examples of polyvinyl alcohol include Poval C-05GP, C-10GP, C-25GP, PA-10GP, PA-15GP of Shin-Etsu Chemical Co., Ltd .; PVA-217, PVA-224 (Kuraray Co., Ltd.) Name).

Examples of polyvinylpyrrolidone include Kollidon 12PF, 17PF, 2
5, 30, 90F, VA64; Luvitec K17, K30, K60, K80, K85, K90, K115 (all trade names).
Examples of the cationized water-soluble polymer include cationized starch such as Hymax NC-10 and PC-6500 from Hymo Co., Ltd .; and cationized guar gum as Meprobond 9806 from Sansei Co., Ltd. as cationized acrylamide. Are polymalon 351 and 360, polystron 311 and 619, and ALAFIX 251 of Arakawa Chemical Industries, Ltd .; and as cationized polyacrylic acid esters, Hymoloc MP-184, MP-284, and MP-384 of Hymo Corporation. MP-484, MP-584, MP-684, MP-784, MP-984, MP-173H, MP-373H, MP-373L, MP-473H, MP-405, MP-180, MP-380, MP -558, MS-882, MS-884, MX-0120, MX-0210, M -8170, MX-8130, MX-6170, MX-6144, MX-4173, MX-2100, MX-4054, MX-3310, MX-2050, E-305, E-315, E-195, E-395 , E-775, E-755, E-555, E-950, E-513, E-515, E-510; as cationized vinylformamide, Hymoloc ZP-700 of Hymo Co., Ltd .; cationized polyacrylamide Examples of the cationized polyamine include Hymoloc Q-101, Q-311, and Q-501 (trade names) available from Hymo Corporation.

Examples of the anionized water-soluble polymer include, as anionized polyacrylamide, Hymoloc SS-200H, SS-200, SS-300, SS-500, SS-100, SS-120, SS-130 manufactured by Himo Co., Ltd. , SS-140, AP-105, AP-107, AP-115, AP-120, V-330, V-320, V-310, OK-107, OK-307, OK-507, L-113, Neo -200; Examples of anionized sodium polyacrylate include Hymoloc SS-190 (trade name) of Hymo Corporation.
Examples of the polyacrylic acid ester include Hymoloc DR-1500, DR-8500, DR-3015, DR-5700, DR-3600, and DR-7300 (trade names) of Hymo Corporation.

Examples of the organopolysiloxane include a polyoxyethylene / methylpolysiloxane copolymer and a (polyoxyethylene / polyoxypropylene) methylpolysiloxane copolymer.
As the (polyoxyethylene / polyoxypropylene) methylpolysiloxane copolymer, specifically, for example, the following formula

(In the formula, R is an alkyl group or H.)
The compound represented by is mentioned. These can be obtained from the market. For example, SILWET L-77, L-720, L-7002, L-7604, and F-7L manufactured by Nippon Unicar Co., Ltd.
Z-2101, FZ-2105, FZ-2118, FZ-2161, FZ-2162, FZ-2163, FZ-2164, and FZ-2166 (all trade names).

Examples of hydrophilic ethylene oxide / propylene oxide block copolymers include Adeka Pluronic L-44, L-62, L-72, and P-84 (trade name) of Asahi Denka Kogyo Co., Ltd. ) Epane 410, 420, 710, 740 and the like.

Also, -SO ₃ H as a hydrophilic polymer _{compound, -SO 3 M, -OSO 3 M} , -COOM,
_{-NR 3 X, -COOH, -NH 2} , -CN, -OH, -NHCONH 2, - (OCH 2 CH 2) a polymer of at least one hydrophilic group of the _n groups are introduced (wherein, R : Alkyl group, M: alkali metal, or —NH ₄ , X: halogen).

Among these hydrophilic polymer compounds, for example, when sold as an aqueous solution such as Polymalon 351 and 360, Polystron 311 and 619, and Alafix 251 (trade name) manufactured by Arakawa Chemical Industries, Ltd. After drying to remove water, it may be added to a predetermined thermosetting resin. Even in this case, the obtained drainage member exhibits good drainage properties.

Among the hydrophilic polymer compounds, the cationized hydrophilic polymer can express a high drainage property to the drainage member, but the cationized powder is obtained by cationizing the acidic polymer with ammonia or the like. You may get it. In addition, when a cellulose resin (for example, Metroose manufactured by Shin-Etsu Chemical Co., Ltd.) is used, the obtained drainage member exhibits good drainage properties.

Examples of the hydrophilic oligomer include a low polymer having a molecular weight of 1,000 or less composed of the constituent units forming the hydrophilic polymer.
The hydrophilic compound may have a functional group capable of reacting with a polymerizable monomer or a thermosetting resin (for example, N-vinyl-2-pyrrolidone, etc.) or may have no functional group capable of reacting. . In any case, a high drainage function can be imparted to the drainage member obtained from the thermosetting resin composition. A hydrophilic compound having a functional group capable of reacting is more excellent in the durability of the drainage function.

Among these hydrophilic compounds, hydrophilic compounds having a pyrrolidone skeleton, such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and polyvinylpyrrolidone, are preferable in terms of appearance, balance between physical properties and hydrophilicity. .
It is desirable that the hydrophilic compound be completely dissolved in the thermosetting resin, but the drainage function is exhibited even when the hydrophilic compound is not completely dissolved.
The hydrophilic compounds can be used alone or in combination of two or more.

The hydrophilic compound can be appropriately selected according to a molding method, a use to be used, and a member.
Such a hydrophilic compound is contained in the composition in an amount of 0.5% by weight or more and 50% by weight or less, preferably 100% by weight, based on a total amount of the thermosetting resin and the hydrophilic compound of 100 (excluding the thermoplastic polymer). It is desirable that it be contained in an amount of 2.5% by weight to 40% by weight, more preferably 5.0% by weight to 30% by weight, particularly preferably 10.0% by weight to 20% by weight.

When the hydrophilic compound is contained in the thermosetting resin composition in an amount within the above range, a molded article (cured product) obtained from the thermosetting resin composition has excellent hydrophilicity. If the amount of the hydrophilic compound is less than 0.5% by weight, the molded article may not show sufficient drainage. If the amount of the hydrophilic compound exceeds 50% by weight, the appearance of the molded product may be poor in gloss.
(Thermosetting resin)
Examples of the thermosetting resin used in the present invention include an unsaturated polyester resin, a vinyl ester resin, an acrylic resin, a urethane resin, a phenol resin, an epoxy resin, and a melamine resin. Of these, unsaturated polyester resins, vinyl ester resins, and acrylic resins are preferred, and unsaturated polyester resins are particularly economical. As the unsaturated polyester resin, DCPD resins, isophthalic acid resins, and hydrogenated bisphenol A resins are preferable.

熱 These thermosetting resins are not particularly limited, and conventionally known ones can be used.

As the unsaturated polyester resin, for example, polybasic acids using maleic acid, fumaric acid and the like, polyhydric alcohols using ethylene glycol and the like, and polymerizable vinyl monomers using styrene and the like can be preferably used. Examples of the polymerizable vinyl monomer include styrene, α-methylstyrene, methyl (meth) acrylate, α-ethylstyrene, and vinyl toluene, and the vinyl monomer (c) includes methyl (meth) acrylate, (meth) ) Ethyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl Lauryl acrylate, alkyl (meth) acrylate (12 or 13 carbon atoms), tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acryl Acid isobornyl, glycidyl (meth) acrylate, tetrahydro (meth) acrylate Furfuryl, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) Dimethylaminoethyl acrylate, dimethylaminoethyl methyl chloride (meth) acrylate, dimethylaminoethyl benzyl chloride (meth) acrylate, diethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, (meth) Monofunctional acryl molybdenum such as heptadecafluorodecyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate Mer: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (n = 4 to 23), propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (n = 4 to 10), 2-butyl-2-ethyl-1,3-propanediol di (meth) Acrylate, 2-hydroxy-1,3-propanediol di (meth) acrylate, butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate (N = 8,9), neopentyl glycol di (meth) acrylate, pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (Meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol di (meth) acrylate, dipentol di (meth) acrylate, sorbitol di (meth) acrylate, trishydroxyethyl isocyanurate, Nonanediol di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] propane (n = 3 to 30), 2 Polyfunctional acrylic monomers such as -hydroxy-1-acryloxy-3-methacryloxypropane; and dicyclopentadiene-based compounds represented by the following formula (1) or (2).

(Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ may be the same or different, and represent a lower alkylene group having 2 to 5 carbon atoms such as ethylene and butylene; m may be the same or different, and represents an integer of 0 to 5)
As the vinyl ester resin, for example, an epoxy acrylate resin, a urethane acrylate resin, or the like can be preferably used. As the polymerizable vinyl monomer, the same as the unsaturated polyester can be used.

As the urethane resin, for example, toluene diisocyanate, diphenylmethane diisocyanate, and the like, and polyol and the like can be preferably used. Further, urethane-modified unsaturated polyester resins and urethane-modified vinyl ester resins obtained from isocyanates and the unsaturated polyester resin or the vinyl ester resin are also preferably used.
Such a thermosetting resin is 50% by weight or more and 99.5% by weight or less, preferably 60% by weight, based on the total amount of 100 (excluding the thermoplastic polymer) of the thermosetting resin and the hydrophilic compound. It is contained in an amount of at least 97.5% by weight, more preferably at least 70% by weight and at most 95% by weight, particularly preferably at least 80% by weight and at most 90% by weight.

When the thermosetting resin is contained in the thermosetting resin composition in an amount within the above range, a molded product (cured product) obtained from the thermosetting resin composition can be obtained without deteriorating conventional physical properties. Hydrophilicity can be imparted.
(Other ingredients)
The thermosetting resin composition according to the present invention contains the hydrophilic compound and the thermosetting resin as essential components, but usually further includes a filler, a curing catalyst, a thickener, and other additives. And so on.

Examples of the filler include an organic filler and an inorganic filler.
Examples of the organic filler include known regenerated fibers, synthetic fibers, and natural fibers. For example, regenerated fibers such as rayon, aliphatic polyamides such as nylon 6, nylon 66, polyethylene terephthalate (PET), and acrylic fibers (PAN) , Polyvinyl alcohol (PVA), polypropylene (PP), polyvinyl chloride (PVC), polyethylene (PE), synthetic fibers such as vinylon, polyphenylene sulfide (PPS), ultra-high molecular weight polyethylene (UHMWPE), polyoxymethylene (POM) Fibers made of so-called high heat-resistant polymer such as aramid fiber, wholly aromatic polyester, so-called high elastic modulus such as polyimide, fiber made of high-strength polymer, jute fiber, and natural fiber such as bamboo fiber. Can be

Examples of the inorganic filler include carbon fiber, glass fiber, aluminum hydroxide, calcium carbonate, glass balloon, silica, fused silica, Aerosil (trade name), clay, mica, magnesium hydroxide, and cold water.
Of these, inorganic fillers are preferably used, but may be used in combination with organic fillers.

In the present invention, in order to improve the strength, it is preferable to use an organic filler or an inorganic filler having a large aspect ratio (500 or more), for example, glass fiber or carbon fiber. Further, a glass fiber or the like having a large aspect ratio and an organic or inorganic filler having a small aspect ratio (500 or less) such as calcium hydroxide, calcium carbonate, aluminum hydroxide, mica, clay, talc, and ceramic (hereinafter, referred to as “glass fiber, Also referred to as "a filler other than carbon fiber.").

As the filler, a surface-treated, coated or plated filler can be used.
These fillers can be used alone or in combination of two or more.
Such a filler is 5-1,000 parts by weight, preferably 50-700 parts by weight, more preferably 100-500 parts by weight, particularly preferably 130-400 parts by weight, based on 100 parts by weight of the thermosetting resin. It is desirable to use in the range of parts.

When Aerosil (trade name) is used as the filler, the thermosetting resin 1
It is used in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, more preferably 1 part by weight or less based on 00 parts by weight.
When the filler is contained in such a range, shrinkage generated during molding can be suppressed to a low level, and the molded article can have more excellent mechanical strength such as impact resistance.

Curing Catalyst The curing catalyst has a 10-hour half-life temperature of 130 ° C. or lower, preferably 110 ° C. or lower, more preferably 105 ° C. or lower, further preferably 100 ° C. or lower, particularly preferably 98 ° C. or lower, and 10 hours. It is desirable that the half-life temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. If the 10-hour half-life temperature exceeds 130 ° C., the curing time becomes longer, and if it is lower than 40 ° C., the compound life may be shortened.

The curing catalyst can be appropriately selected according to the thermosetting resin to be used and the molding temperature. For example, in the case of an acrylic resin, an unsaturated polyester resin, a vinyl ester resin or the like, the following may be mentioned.
Specific examples include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, alkyl perester, and percarbonate. Among these, it is preferable to use diacyl peroxide and alkyl perester, and it is particularly preferable to use alkyl perester.

Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide and the like.
Examples of the hydroperoxide include 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and the like.

Examples of the diacyl peroxide include isobutyryl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, and m-toluyl-benzoyl peroxide. And the like.
Examples of the dialkyl peroxide include succinic peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 1,3-bis (t-butylperoxyisopropyl). Benzene, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, tris (t-butylperoxy) triazine, etc. Is mentioned.

Examples of the peroxyketal include 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-hexylperoxy-3,3,5-trimethylcyclohexane, , 1-Di-t-butylperoxycyclohexane, 2,2-bis (4,
4-di-t-butylperoxycyclohexyl) propane, 2,2-di (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclododecane, 4,4-di (t- (Butylperoxy) valeric acid-n-butyl ester.

Examples of the alkyl perester include 1,1,3,3-tetramethylbutylperoxyneodecanate, α-cumylperoxyneodecanate, t-hexylperoxyneodecanate, and t-hexylperoxyneodecanate. Cyclohexyl-1-methylethyl peroxyneodecanate, t-butylperoxyneodecanate, t-butylperoxyneoheptane, t-hexylperoxy-2-ethylhexanate, 1,1,3,3 −
Tetramethylbutylperoxy-2-ethylhexanate, 1,1,3,3-tetramethylbutylperoxy-3,5,5-trimethylhexanate, t-amylperoxy-2-ethylhexanate, t- Butyl peroxy-2-ethylhexanate, t-amyl peroxy-3,5,5-trimethyl hexanate, t-butyl peroxy-3,5,5-trimethyl hexanate, t-butyl peroxyisobutyrate , Di-t-butylperoxyhexahydroterephthalate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, t-butylperoxymaleic acid, t-butylperoxy Acetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyl adipate And the like.

Examples of the percarbonate include di-3-methoxybutyl peroxycarbonate, di-3-methylhexyl peroxycarbonate, bis (4-t-butylcyclohexyl) peroxycarbonate, diisopropyl peroxycarbonate, and t-butylperoxyisopropyl carbonate , T-butyl peroxy 2-ethylhexyl carbonate, 1,
6-bis (t-butylperoxycarbonyloxy) hexane, diethyleneglycol-bis (t-butylperoxycarbonate) and the like.

Among these, among the percarbonates, 1,1,3,3-tetramethylbutylperoxyisopropyl carbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di- n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) Dicarbonate and the like are preferred.

Among the diacyl peroxides, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide (62 ° C.), lauroyl peroxide, stearoyl peroxide (62 ° C.), benzoyl peroxide, m-toluyl -Benzoyl peroxide (62 ° C.) and the like are preferable.

As the dialkyl peroxide, succinic peroxide and the like are preferable.

Among the alkyl peresters, 1,1,3,3-tetramethylbutylperoxyneodecanate, t-hexylperoxyneodecanate, t-hexylperoxyneodecanate, 1-cyclohexyl-1-methyl Ethyl peroxy neodecanate, t-butyl peroxy neodecanoate, t-hexyl peroxy-2-ethyl hexanate, 1,1,3,3-tetramethylbutyl peroxy-2-ethyl hexanate, t- Amyl peroxy-2-ethyl hexanate, t-butyl peroxy-2-ethyl hexanate), t-butyl peroxy isobutyrate, 2,4-dichlorobenzoyl peroxide, t
-Hexylperoxypivalate, t-butylperoxypivalate and the like are preferred, and 1,1,3,3-tetramethylbutylperoxyneodecanate, t-hexylperoxyneodecanate, t-hexylperoxyneodenate Decanoate, 1-cyclohexyl-1-methylethylperoxyneodecanate, t-butylperoxyneodecanate, t-hexylperoxy-2-ethylhexanate, 1,1,3,3-tetramethylbutylperate Oxy-2-ethyl hexanate, t-amyl peroxy-2-ethyl hexanate, 2,4-
Dichlorobenzoyl peroxide, t-hexyl peroxypivalate, t-butyl peroxypivalate and the like are more preferred.

Examples of the percarbonate include diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di (2 -Ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate and the like are preferable.

These can be used alone or in combination of two or more.
In the thermosetting resin composition according to the present invention, such a curing catalyst includes a thermosetting resin 10
0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, particularly preferably 0 to 0 parts by weight.
. It is desirable to use in the range of 7 to 2 parts by weight.
When the content of the curing catalyst is less than 0.1 part by weight, it takes too much time for curing, which is not practical, and when the content is more than 5 parts by weight, it is not economical.

Thickener Examples of the thickener include oxides or hydroxides of divalent metals such as magnesium, calcium, zinc, and strontium.
In the thermosetting resin composition according to the present invention, the thickener of the oxide or hydroxide of the divalent metal is, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermosetting resin. , Preferably in the range of 0.5 to 5 parts by mass.

ア ク リ ル Further, as another thickener, an acrylic polymer described in JP-A-5-171022 can be preferably used. For example, an acrylic polymer containing methyl methacrylate as a main component, other (meth) acrylic monomers such as ethyl (meth) acrylate, butyl (meth) acrylate, ethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. ) A copolymer of a polyfunctional crosslinking monomer such as acrylate may be used. An acrylic polymer having a methyl methacrylate content of preferably 90% by weight or more and a polyfunctional crosslinked polymer content of preferably 5% by weight or less.

In the thermosetting resin composition according to the present invention, such an acrylic polymer thickener is used in an amount of, for example, 2 to 50 parts by mass, preferably 3 to 25 parts by mass, based on 100 parts by mass of the thermosetting resin. It is desirable to use it.
Thickeners such as the oxide or hydroxide of the divalent metal and the acrylic polymer can be used alone or in combination.

Other additives The thermosetting resin composition according to the present invention further includes, if necessary, a release agent such as zinc stearate and a liquid wax, a pot life, and a known method for adjusting the rise of the curing reaction. Polymerization inhibitors, known low-shrinkage agents for adjusting molding shrinkage (for example, polystyrene, polyethylene, polyvinyl acetate, cross-linked polystyrene, polyvinyl acetate-polystyrene block copolymer, SBS (rubber), etc.), flame retardants, Antibacterial agents (organic and / or inorganic), viscosity reducing agents, low-shrinking agents antiseparation agents, silane coupling agents, antistatic agents, lubricating dispersants, thixo-providing agents, thixo-stabilizing agents, pigments, dyes, etc. Additives such as a coloring agent, a polymerization accelerator, and a patterning agent (decorative grains) can be added.

As the patterning agent, aluminum oxide, PET film, mica, ceramic and those coated with a coloring agent, surface treatment agent, etc., plated, thermosetting resin, inorganic filler, coloring agent, etc. And pulverized.

[Cured product of thermosetting resin composition and method for producing the same]
The cured product (molded product) of the thermosetting resin composition is obtained by injecting the thermosetting resin composition into a mold such as a mold, a resin mold, or a glass mold, or applying the composition on a target mold, and applying pressure or pressure. It can be obtained by curing under normal pressure in a specific temperature range.

Specifically, for example, a thermosetting resin composition thickened by adding a thickener is obtained as a sheet molding compound (SMC), a tic molding compound (TMC), a bulk molding compound (BMC), or the like. Molding by curing the thermosetting resin composition which is SMC, TMC or BMC using a known compression molding method, injection molding method, etc., in a heated mold while appropriately applying pressure. Can be a body.

シ ー ト Alternatively, the thermosetting resin composition to which no thickener is added may be poured into a mold and cured by heating to obtain a sheet-like molded product. The molded product obtained by BMC or casting is also reinforced by spraying, hand lay-up from the back, or reinforced with wood or the like.

(4) The temperature of heat curing is desirably in the range of less than 180 ° C., preferably 75 ° C. to less than 170 ° C., more preferably 80 ° C. to less than 160 ° C., and particularly preferably 85 ° C. to 150 ° C.

If the heating temperature is lower than 75 ° C., the curing rate may be too low to be practical, and if the heating temperature is higher than 180 ° C., the hydrophilicity of the molded article may be reduced or the product appearance may be reduced. Further, the upper mold and the lower mold may be heated with a temperature difference within the above temperature range.

The heating time can be appropriately selected depending on the 10-hour half-life temperature of the polymerization initiator, the thickness of the molded product, and the like, and is not limited.
Conventionally known conditions can be adopted for the mold clamping speed, vacuum conditions, and the like.
When pressurizing at the time of heat molding, the pressure applied to the molded product is preferably set to about 0.3 to 20 MPa, more preferably about 2 to 15 MPa.

When a compound having a pyrrolidone skeleton is used as the hydrophilic compound, the cured product of the thermosetting resin composition produced as described above is a thermosetting resin when the compound having a pyrrolidone skeleton in the composition is cured. The cured thermosetting resin may contain a group having a pyrrolidone skeleton. At this time, the cured thermosetting resin preferably contains a group having a pyrrolidone skeleton at a ratio of 0.1% by weight or more and 50% by weight or less.

The cured product (molded product) of the thermosetting resin composition thus obtained is excellent in hydrophilicity. For example, (1) a drainage tester having a mirror structure of 700 mm in length, 700 mm in width and 3 ° incline. (2) The contact angle with water is not more than 80 °, preferably not more than 75 °, more preferably not more than 60 minutes, more preferably not more than 10 minutes, more preferably not more than 10 minutes. It is preferable that at least one of 70 ° or less be satisfied, and it is particularly preferable that both (1) and (2) be satisfied at the same time. The smaller the contact angle with water, the more excellent the molded body is in drainage.
The drainage time is measured as follows. 1 and 2 show a drainage tester used for measuring drainage time.

After the drainage tester as shown in FIGS. 1 and 2 is formed, it is removed from the mold, and the molded product is left at 25 ° C. for 3 hours or more. Sprinkle 50 liters of water (25 ± 0.5 ° C.) so that the entire surfaces a, b and c of the drainage tester become wet. The time measurement is started after the watering is completed, and the time until the water droplets on the a-plane, the b-plane, and the c-plane completely disappear is measured (rounded down to seconds). The presence or absence of water droplets is checked visually. A dye may be added to water so that the presence or absence of water droplets can be easily checked. The measurement is performed at 25 ± 0.5 ° C. and 50% RH. The mirror surface structure means that a hard chrome plating is finished and polished with an oil whetstone # 1000.
The drainage tester is manufactured by various methods for molding a thermosetting resin as described below.

The method for measuring the contact angle of the cured product (molded product) of the thermosetting resin composition with water will be described later in Examples.
Examples of the molded body produced by curing the thermosetting resin composition as described above include floors and floors of water-wound parts such as floors of bathrooms, washbasin veneers, and kitchen floors of Japanese restaurants. And a hydrophilic member used for a veranda floor or the like.

Specific examples of the hydrophilic member include a bathtub, a bathroom wall material, a bathroom floor material, a bathroom grating,
Bathroom ceiling, shower hook, bathtub handgrip, bathtub apron, bathtub drain plug, bathroom window frame, drainage pit, bathroom door, bathroom door frame, bathroom window bar, bathroom door bar, scoop, mat, soap holder , Pail, bath chair, transfer board, bathroom storage shelf, bathroom handrail, bath lid, bathroom towel rail, shower chair, basin rest, etc .; kitchen kitchen back, kitchen flooring, sink , Kitchen counters, drain baskets, range hoods, ventilation fans, stove knobs and other kitchen components; urinals, toilet bowls, toilet traps, toilet plumbing, toilet flooring, toilet wall materials, toilet ceilings, ball taps , Stopcocks, cigarettes, toilet seats, lifting toilet seats, toilet doors, toilet towel rails, toilet lids, toilet railings, toilet counters, flush valves, tanks, stools with cleaning functions Toilet components such as water spout nozzles; wash bowls, wash traps, wash cabinets, drain cocks, toothbrush stands, wash counters, water soap dispensers, wash basins, mouth washes, hand dryers, rotating tiles, etc. Parts for washing; washing tub, washing machine lid, washing machine pan, dehydration tub, air conditioner filter, touch panel, cover for human body detection sensor, shower hose, shower head, shower spout, sealant; outdoor chairs for stadiums, etc. Bench, tableware tray, decorative board and the like. Among these applications requiring drainage, there is a strong need for drainage for bathroom flooring materials and bathroom wall materials, and especially for bathroom flooring materials.

Specific examples of the method for producing the hydrophilic member according to the present invention from the thermosetting resin composition include a press molding method, a casting method, an RTM (resin transfer) molding method, and a spray-up method which are conventionally known methods. Method, a hand lay-up method, a flow coater method, and the like. In these molding methods, it is possible to manufacture using a conventionally known apparatus under the same conditions as conventionally known manufacturing conditions. A press molding method excellent in productivity is particularly preferred.

The press molding method is a compression molding method in which a material is heated and pressed to form a pair of male and female molds equipped with a hydraulic press. Preform MMD method, SMC molding method, TMC molding method, BMC molding method are categorized. As the press molding method, an SMC molding method, a TMC molding method, and a BMC molding method which are excellent in productivity are preferable. The hydrophilic member manufactured by the press molding method has a reinforcing rib structure on the back surface of the product, and the mold is released from the mold more quickly by the push-up pin and / or the air valve.
Examples of the hydrophilic member manufactured by the press molding method include a bathtub, a bathroom floor material, a bathroom grating, a bathroom ceiling material, a bathtub apron, a bathtub drainage plug, a bathroom window frame, a floorboard, a bathroom storage shelf, and a sink. , Kitchen counters, washbasins, veneers, outdoor chairs, benches and the like.

Cast molding is a method in which a thermosetting resin composition is injected into a mold, polymerized, and the shape of the mold is transferred to a cured product to obtain a desired molded product. , Vacuum casting, continuous casting, encapsulation casting, and the like.
Examples of the hydrophilic member manufactured by the casting method include a bathtub, a bathroom flooring material, a sink, a kitchen counter, a washbasin, a washbasin, a decorative board, an outdoor chair, and a bench.

The spray-up method includes a device for continuously and quantitatively cutting glass roving into a predetermined length, and a device for continuously and quantitatively spraying a thermosetting resin composition in a required variable amount. This is a method of performing a laminating step using a basic spray-up machine.
Examples of the hydrophilic member manufactured by the spray-up method include those exemplified as the above-mentioned hydrophilic member.

In the hand lay-up method, a thermosetting resin composition is manually impregnated with a brush or a roller into a mold in which organic or inorganic fibers (for example, glass fibers) have been previously subjected to a mold release treatment. This is a method of obtaining a molded product after curing by lamination.
Examples of the hydrophilic member manufactured by the hand lay-up method include those exemplified above as the hydrophilic member.

[Example]
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

80 parts by weight of unsaturated polyester resin (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: POLYDAR 5410S; DCPD system), low-shrinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: POLYMER 9965 (containing 60% of styrene monomer) Polystyrene solution)) 20 parts by weight, (Sumitomo Seika Co., Ltd., trade name: UF-20) 2 parts by weight, N-methyl-2-pyrrolidone (manufactured by BASF) 5 parts by weight, calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd.) 80 parts of aluminum hydroxide (manufactured by Showa Denko KK, trade name: Heidilite H-32) 80 parts, internal release agent (zinc stearate, manufactured by NOF Corporation) 5 parts, 1 part of curing agent (manufactured by NOF Corporation, TBPB), 0.04 part by weight of polymerization inhibitor (parabenzoquinone: PBQ), and 5 parts of gray toner (manufactured by Toyo Ink Manufacturing Co., Ltd.) Was stirred for 5 minutes at over, it was sufficiently uniform dispersion of the raw materials. To this paste was added 4 parts of a thickener (Polymer thickener: 24% magnesium oxide paste manufactured by Mitsui Takeda Chemical Co., Ltd.), and after stirring for 2 minutes, immediately supplied to a conventional impregnating machine for SMC, and cut by 1 inch. 90 parts by weight of the obtained glass fiber (Nippon Electric Glass Co., Ltd. S235) was sufficiently impregnated to prepare SMC. This SMC was aged at 40 ° C. for 48 hours and adjusted to a tack-free moldable hardness.

In order to obtain a drainage tester having the shape shown in FIGS. 1 and 2, SMC was 8.0 kg, the mold temperature was 145 ° C. on the product side, 130 ° C. on the back side, and heat compression molding was performed at a surface pressure of 10 MPa. Cured in 10 minutes to obtain a molded product.
The SMC was molded in a 300 mm square mold under the same conditions as above to obtain a flat plate having a thickness of 3 mm. Using this, various physical properties were measured. The results are shown in Tables 1 and 2.
The physical property measuring method is as follows.

[Glossy]
The glossiness was measured under the conditions of an incident angle of 60 degrees and a detection angle of 60 degrees according to JIS K7105 5.2.

[Bending characteristics]
The bending characteristics were determined by performing a bending test under the following conditions in accordance with JIS K7055 to obtain a bending elastic modulus.
<Test conditions>
Test piece: 6.4 mm (thickness) x 12.7 mm (width) x 127 mm (length)
Between spans: 100mm
Bending speed: 2 mm / min Measurement temperature: 23 ° C
[Izod impact strength]
The Izod impact strength was determined by performing an impact test under the following conditions in accordance with JIS K7110.
<Test conditions>
Test piece: 12.7 mm (width) x 6.4 mm (thickness) x 64 mm (length)
Notch: Machining Measurement temperature: 23 ° C
[Drainage]
The drainability was evaluated by the presence or absence of water droplets after 60 minutes using our test model (area: 700 mm x 700 mm, mirror surface structure inclined to the drain port).

○: No water drop ×: Water drop [Contact angle]
The contact angle was measured by a droplet method. That is, a test piece was prepared according to JIS K7100 JIS Class 1, a water drop was dropped on the surface of the test piece, and the contact angle after one second was measured with an automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd.
<Test atmosphere>
Room temperature 23 ° C, humidity 50%

Except that the amount of N-methyl-2-pyrrolidone (manufactured by BASF) was changed from 5 parts by weight to 7 parts by weight, a drainage tester and a test piece were molded in the same manner as in Example 1 to obtain various physical properties. It was measured. The results are shown in Tables 1 and 2.

A drainage tester and test were performed in the same manner as in Example 1 except that 5 parts by weight of N-methyl-2-pyrrolidone (manufactured by BASF) was changed to 7 parts by weight of N-vinyl-2-pyrrolidone (manufactured by BASF). Pieces were molded and various physical properties were measured. The results are shown in Tables 1 and 2.

100 parts by weight of vinyl ester resin (produced KSV-16 manufactured by Mitsui Takeda Chemical Co., Ltd.), 15 parts by weight of N-methyl-2-pyrrolidone (manufactured by BASF), 0.04 parts by weight of polymerization inhibitor (hydroquinone), hydroxylation 250 parts by weight of aluminum (Heidilite H-32 manufactured by Showa Denko KK), 2 parts by weight of an internal mold release agent (zinc stearate, manufactured by NOF Corporation), 5 grey toner (manufactured by Toyo Ink Mfg. Co., Ltd.) (Parts by weight) The mixture was stirred for 5 minutes with a high-speed mixer to sufficiently uniformly disperse each raw material. To this paste was added 1.5 parts of a curing agent (Perhexyl HO, manufactured by NOF Corporation), stirred for 2 minutes, and poured into a mold to obtain a molded product. In order to obtain a molded product for evaluation (700 mm × 700 mm) in the drawing, 9.0 kg of the paste was poured into an injection mold, and the mold temperature was 100 ° C. on the product side and 90 ° C. on the back side, and was cured in 30 minutes. A sex tester was obtained.

Also, two 300 mm square glass plates were prepared, and an injection mold was prepared using a 3 mm thick spacer, and a 300 mm square flat plate was obtained under the above conditions. Using this, various physical properties were measured. The results are shown in Tables 1 and 2.

Acrylic resin (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Acrest HKY-100) 80 parts by weight, low shrinkage agent (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Polymer 9965), 20 parts by weight, N-methyl- 15 parts by weight of 2-pyrrolidone (manufactured by BASF), 300 parts by weight of aluminum hydroxide (manufactured by Showa Denko KK, trade name: Heidilite H-32), internal mold release agent (zinc stearate, manufactured by NOF Corporation) 5 parts by weight, 5 parts by weight of gray toner (manufactured by Toyo Ink Mfg. Co., Ltd.), 1.5 parts by weight of curing agent (manufactured by NOF Corporation, trade name: Perhexyl HO), and 0. polymerization inhibitor (hydroquinone). 04 parts by weight, thickener (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Polymeric thickener: 24% magnesium oxide paste) 4 parts by weight, 3 mm chopped strand glass (Nippon Sheet Glass ( ) Trade name: RES03X-BM) by kneading 20 parts by weight double-arm kneader to prepare a dough-like BMC. This BMC was aged at 40 ° C. for 24 hours and adjusted to a tack-free moldable hardness.

In order to obtain a molded product for evaluation (700 mm × 700 mm) shown in FIGS.
. Heat compression molding was performed at 5 kg and a mold temperature of 120 ° C. on the product side and 110 ° C. on the back side at a surface pressure of 10 MPa. Cured in 10 minutes to obtain a drainage tester.

Ｂ Further, BMC was molded in a 300 mm square mold under the same conditions as above to obtain a flat plate having a thickness of 3 mm. Using this, various physical properties were measured. The results are shown in Tables 1 and 2.

5 parts by weight of N-methyl-2-pyrrolidone (manufactured by BASF) was added to Nonion S-40 (trademark,
A drainage tester and a test piece were molded in the same manner as in Example 1 except that the weight was changed to 5 parts by weight (manufactured by NOF CORPORATION), and various physical properties were measured. The results are shown in Tables 1 and 2.

[Comparative Example 1]
In Example 1, a drainage tester and a test piece were molded in the same manner as in Example 1 except that N-methyl-2-pyrrolidone (manufactured by BASF) was not added, and various physical properties were measured. The results are shown in Tables 1 and 2.

[Comparative Example 2]
In Example 4, a drainage tester and a test piece were molded in the same manner as in Example 4 except that N-methyl-2-pyrrolidone (manufactured by BASF) was not added, and various physical properties were measured. The results are shown in Tables 1 and 2.

[Comparative Example 3]
In Example 5, a drainage tester and a test piece were molded in the same manner as in Example 5 except that N-methyl-2-pyrrolidone (manufactured by BASF) was not added, and various physical properties were measured. The results are shown in Tables 1 and 2.

A resin composition in which 30 parts by weight of N-vinyl-2-pyrrolidone is added to 100 parts by weight of Esther R2150 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd., unsaturated polyester resin) (concentration of hydrophilic compound: 23.1%) In addition, 0.65 parts by weight of a curing accelerator Ester EP430 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.) and a hardening agent Permec N (trade name, manufactured by NOF Corporation, MEKP
O) A gel coat resin liquid having a composition of 1.3 parts by weight and stirred so as to be uniform was sprayed up to a lower mold (product surface side) of a mold used for manufacturing a molded article for evaluation in Example 1. . The composition was cured at room temperature for 10 minutes, after-cured in a curing oven at 60 ° C. for 20 minutes, and allowed to cool to form a gel coat layer of about 0.5 mm. Next, 1 ply of glass mat # 450 (manufactured by Nitto Bo) is laid on the gel coat layer as an intermediate layer, and 100 parts by weight of Ester R257 (manufactured by Mitsui Takeda Chemical Co., Ltd., unsaturated polyester resin) is used as a curing agent Permec N (Japan). A liquid stirred to be uniform with a composition of 1.0 part by weight (oil and fat, MEKPO) was sprayed up. Cured for 1 hour at room temperature. Finally, as a reinforcing layer, 2 mats of glass mat # 450 (manufactured by Nitto Bo) are laid on the intermediate layer, and 100 parts by weight of Esther R235 (manufactured by Mitsui Takeda Chemical Co., Ltd., unsaturated polyester resin) is added to a curing agent Permec N ( A liquid stirred with a composition of 1.0 part by weight (manufactured by NOF Corporation, MEKPO) was sprayed up. As in the case of the intermediate layer, the composition was cured at room temperature for 1 hour, and further cured in a curing oven at 60 ° C. for 1 hour. After being taken out of the furnace, allowed to cool, and then released from the mold, a drainage tester having a thickness of about 6 mm as shown in FIGS. 1 and 2 was obtained.

(4) The drainage time was measured in the same manner as in Example 1 using the obtained drainage tester, and water droplets disappeared in 4 minutes. The evaluation of the drainage property is ○.

The sample for measuring physical properties was prepared in the same manner as described above except that the sample was laminated on a smooth film. As a result of measurement in the same manner as in Example 1, the gloss was 85, the bending strength was 150 MPa, and the Izod impact strength was 70 KJ / m ² .

[Comparative Example 4]
A drainage tester and a test piece were formed in the same manner as in Example 6, except that N-vinyl-2-pyrrolidone was not added.

(5) The drainage time was measured in the same manner as in Example 1 using the obtained drainage tester, and it was found that water droplets adhered for 180 minutes or more and became wet. The evaluation of drainage is x.

As a result of measuring the physical properties of the test piece in the same manner as in Example 1, the gloss was 84, the bending strength was 150 MPa, and the Izod impact strength was 68 KJ / m ² , which were almost equivalent to the physical properties of Example 7. .

It is explanatory drawing which shows a drainage tester. FIG. 2 is a sectional view taken along line A-A ′ and a sectional view taken along line B-B ′ of the plan view of FIG. 1.

Claims (11)

From the group consisting of a hydrophilic compound having a molecular weight of 1,000 or less and a boiling point of 120 ° C. or more and soluble in 100 ml of water at 25 ° C. in a quantity of 7 g or more and a hydrophilic compound having a molecular weight of more than 1000 and soluble in 100 ml of water at 25 ° C. in a quantity of 7 g or more. A thermosetting resin composition comprising at least one selected hydrophilic compound and a thermosetting resin. The thermosetting resin composition according to claim 1, wherein the hydrophilic compound is contained in an amount of 0.5% by weight or more and 50% by weight or less. The thermosetting resin composition according to claim 1 or 2, wherein the hydrophilic compound is a compound having a pyrrolidone skeleton, a hydrophilic oligomer, or a hydrophilic polymer compound. (4) A thermosetting resin composition comprising a hydrophilic compound having a pyrrolidone skeleton in an amount of 0.1% by weight or more and 50% by weight or less. (4) A cured product of a thermosetting resin composition, comprising a thermosetting resin in which a proportion of a pyrrolidone skeleton in a polymer molecule is from 0.1% by weight to 50% by weight. (4) A cured product of a thermosetting resin composition having a contact angle with water of 80 ° or less. (4) A cured product of a thermosetting resin composition, wherein a drainage time is 60 minutes or less as measured by a drainage tester having a mirror structure having a length of 700 mm, a width of 700 mm, and an inclination of 3 °. A hydrophilic member comprising a cured product of the thermosetting resin composition according to claim 6. 9. The hydrophilic member according to claim 8, which is a bathroom floor material, an indoor floor tile, an outdoor floor tile, a bathroom wall material, or a washbasin decorative panel. (5) A method for producing a hydrophilic member, comprising molding the thermosetting resin composition according to any one of (1) to (4) to produce a hydrophilic member. The method for producing a hydrophilic member according to claim 10, wherein the molding method is press molding.

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