WO2015025592A1

WO2015025592A1 - Method for producing resin molded article

Info

Publication number: WO2015025592A1
Application number: PCT/JP2014/065443
Authority: WO
Inventors: 大谷　和男; 三浦　賢治
Original assignee: 昭和電工株式会社
Priority date: 2013-08-22
Filing date: 2014-06-11
Publication date: 2015-02-26
Also published as: JPWO2015025592A1; JP6312334B2

Abstract

This method for producing a resin molded article is characterized in that a curable resin composition containing an organosilicon compound is molded and cured with use of a molding die that is surface-treated with a baking-type mold release agent containing a silicone. The organosilicon compound used for a resin molded article according to the present invention can be at least one compound that is selected from the group consisting of organic silane compounds, organo-modified siloxane compounds and silicon-modified acrylic compounds. The present invention is able to provide a method for producing a resin molded article, which exhibits excellent scale adhesion prevention effect and scale removal effect for a long period of time.

Description

Manufacturing method of resin molding

The present invention relates to a method for producing a resin molded product. Specifically, the present invention relates to a pipe used in hot springs, geothermal power generation, and the like, and a method for producing a resin molded product used as a watering member such as a bathtub, bath unit, and washstand.

Pipes used in hot springs and geothermal power generation (for example, binary power generation) have scales (for example, calcium scale and silica scale) attached to the inside as time passes. The scale attached to the pipe can be removed by washing with a strong acid or strong alkali. However, metal pipes may have problems such as opening holes when washed with strong acid or the like. Therefore, when washing with a strong acid or the like, it is necessary to use a resin pipe (for example, an FRP pipe or the like) that prevents the retention of the strong acid or the like and has excellent chemical resistance. In addition, resin pipes are said to be less likely to have scales attached than metal pipes, but scales cannot be prevented sufficiently.

Also in water-related members such as bathtubs, bath units, and washstands, when water accumulates on the surface and evaporates, a scale (also called “water red”) is formed. This scale cannot be easily removed once it has adhered, and must be scraped off with a scrubber or brush using various detergents.

Various methods have been proposed as a method for preventing adhesion of scale and a method for facilitating removal of scale.
For example, a method is known in which a base material to which a scale adheres is coated with a material such as a fluorine resin or a silicon resin. According to this method, since the surface free energy of the base material is lowered, the adhesion of the scale can be prevented. However, although this method has a good initial scale prevention effect after coating treatment, the adhesion between the substrate and the coating film is low, so the coating film is peeled off during use or production. Sometimes. As a result, there has been a problem that a long-term scale adhesion preventing effect cannot be obtained sufficiently.

In addition, a method has been proposed in which a silicone resin is transferred onto the surface of a base resin by placing the base resin in a molding die coated with a silicone resin and curing the base resin (see, for example, Patent Documents 1 and 2). ). According to this method, scale adhesion can be prevented by the silicone resin transferred to the surface of the base resin. However, this method also has a problem that a long-term scale adhesion preventing effect cannot be sufficiently obtained because of low adhesion between the base resin and the silicone resin.

Furthermore, a method of forming an uneven portion on the surface of a molded product using a wet honing process or a mold having uneven portions has been proposed (see, for example, Patent Document 3). According to this method, it is possible to easily remove the dirt attached to the surface of the molded product. However, this method is not necessarily effective for attaching the scale, and there is a problem that the manufacturing cost increases because it is necessary to use a special mold or the like.

JP 2001-323088 A JP 2006-305367 A Japanese Patent Laid-Open No. 2003-213897

The present invention has been made in view of the above situation, and an object of the present invention is to provide a method for producing a resin molded product which has an excellent effect of preventing adhesion of scale and removing effect of scale over a long period of time.

As a result of diligent research to solve the above problems, the present inventors have surface-treated a mold with a baking mold release agent containing silicone, and an organosilicon compound having an affinity for the baking mold release material Can be formed into a curable resin composition and molded and cured to localize the organosilicon compound on the surface of the resin molded product and form a surface on which the scale is difficult to adhere and the scale can be easily removed. The headline, the present invention has been reached.

That is, the present invention includes the following [1] to [7].
[1] A method for producing a resin molded product, comprising molding and curing a curable resin composition containing an organosilicon compound using a molding die surface-treated with a baking mold release agent containing silicone.
[2] The resin-molded product according to [1], wherein the organosilicon compound is at least one selected from the group consisting of an organosilane compound, an organo-modified siloxane compound, and a silicon-modified acrylic compound. Method.
[3] In [1] or [2], the content of the organosilicon compound in the curable resin composition is 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable resin. The manufacturing method of the resin molding of description.

[4] The curable resin composition includes at least one curable resin selected from the group consisting of a radical polymerizable resin, an epoxy resin, and a phenol resin. The manufacturing method of the resin molding as described in any one.
[5] The method for producing a resin molded product according to [4], wherein the radical polymerizable resin is a vinyl ester resin.
[6] The method for producing a resin molded product according to any one of [1] to [5], wherein the curable resin composition further includes a fiber reinforcing material.
[7] A resin molded product obtained by the method for producing a resin molded product according to any one of [1] to [6].

According to the present invention, it is possible to provide a method for producing a resin molded product that is excellent in scale adhesion prevention effect and scale removal effect over a long period of time.

The method for producing a resin molded product of the present invention is characterized in that a curable resin composition containing an organosilicon compound is molded and cured using a molding die surface-treated with a baking mold release agent containing silicone. .

The organic silicon compound added to the curable resin composition is not particularly limited, and those known in the art such as an organic silane compound, an organic modified siloxane compound, and a silicon modified acrylic compound can be used. Examples of organosilane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxy Examples include silane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like. Examples of organically modified siloxane compounds include polyether modified polydimethylsiloxane, polyester modified polydimethylsiloxane, polyester modified polymethylalkylsiloxane, aralkyl modified polymethylalkylsiloxane, polyether modified siloxane, polyester modified hydroxyl group-containing polydimethylsiloxane, and the like. Can be mentioned. Examples of the silicon-modified acrylic compound include silicon-modified acryl and hydroxyl group-containing silicon-modified acryl. Among these, an organic silicon compound having a hydroxyl group is particularly preferable because it has a high affinity with a baking mold release agent containing silicone and is excellent in the effect of localizing the organic silicon compound on the surface of the resin molded product. Moreover, these compounds can be used individually or in combination of 2 or more types.

The organosilicon compounds exemplified above are commercially available, for example, KBM-1003, KBE-1003, KBM-303, KBM-403, KBM-1403, KBM-503, KBM manufactured by Shin-Etsu Chemical Co., Ltd. -5103, KBM-602, KBM-603, KBE-603, KBM-573; BYK (registered trademark) -300, BYK (registered trademark) -302, BYK (registered trademark) -306 manufactured by Big Chemie Japan KK BYK (R) -307, BYK (R) -310, BYK (R) -313, BYK (R) -315, BYK (R) -320, BYK (R) -322, BYK ( Registered trademark) -323, BYK (registered trademark) -330, BYK (registered trademark) -331, BYK (registered trademark) -3. 3, BYK (registered trademark) -342, BYK (registered trademark) -345, BYK (registered trademark) -346, BYK (registered trademark) -347, BYK (registered trademark) -348, BYK (registered trademark) -349, BYK (registered trademark) -370, BYK (registered trademark) -3550, BYK (registered trademark) -SILCLEAN 3700, BYK (registered trademark) -SILCLEAN 3720, and the like can be used.

The content of the silicon compound in the curable resin composition is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, most preferably 100 parts by mass of the curable resin. The amount is preferably 1 to 5 parts by mass. When the content of the silicon compound is less than 0.1 parts by mass, the effect of preventing adhesion of the scale of the resin molded product and the effect of removing the scale may not be sufficiently obtained. On the other hand, when the content of the silicon compound exceeds 10 parts by mass, the ratio of the resin component decreases, and a resin molded product having desired characteristics may not be obtained.

It does not specifically limit as a curable resin composition containing an organosilicon compound, What is necessary is just to select an appropriate thing according to the use of the resin molding formed from a curable resin composition.
It does not specifically limit as curable resin used for curable resin composition, A well-known thing can be used in the said technical fields, such as a radically polymerizable resin, an epoxy resin, and a phenol resin.

The radical polymerizable resin is not particularly limited, and examples thereof include unsaturated polyester resins, vinyl ester resins, polyester (meth) acrylate resins, urethane (meth) acrylate resins, and the like. These resins can be used alone or in combination of two or more.

Unsaturated polyester resin dissolves condensation product (unsaturated polyester) by esterification reaction of polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid if necessary) in polymerizable monomer such as styrene. It is a thing. The unsaturated polyester resin is not particularly limited, and is described in “Polyester Resin Handbook” (published by Nikkan Kogyo Shimbun, 1988) or “Paint Glossary of Terms” (edited by Color Material Association, published in 1993). Can be used. Moreover, unsaturated polyester resin is marketed, for example, "Rigo rack (trademark)" series etc. by Showa Denko KK can be used.

Vinyl ester resin (also referred to as “epoxy acrylate resin”) is produced by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. The compound having a polymerizable unsaturated bond (vinyl ester) is dissolved in a polymerizable monomer such as styrene. The vinyl ester resin is not particularly limited, and those described in “Polyester Resin Handbook” (published by Nikkan Kogyo Shimbun, 1988) or “painting glossary” (edited by Color Material Association, published in 1993), etc. Can be used. Vinyl ester resins are commercially available, and for example, “Lipoxy (registered trademark)” series manufactured by Showa Denko KK can be used.

The polyester (meth) acrylate resin is obtained by dissolving polyester (meth) acrylate in a polymerizable monomer such as styrene. The polyester (meth) acrylate is not particularly limited, but (1) α, β- is added to the terminal carboxyl group of the polyester obtained by the esterification reaction of a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol. Polyester (meth) acrylate obtained by reacting an epoxy compound containing an unsaturated carboxylic acid ester group, (2) Saturated polybasic acid and / or obtained by esterification reaction of unsaturated polybasic acid and polyhydric alcohol Polyester (meth) acrylate obtained by reacting a terminal carboxyl group of polyester with a hydroxyl group-containing acrylate, or (3) Polyester obtained by esterification reaction of saturated polybasic acid and / or unsaturated polybasic acid and polyhydric alcohol Obtained by reacting (meth) acrylic acid with the terminal hydroxyl group of Ter (meth) acrylate can be used.

Urethane (meth) acrylate resin is obtained by dissolving urethane (meth) acrylate in a polymerizable monomer such as styrene. The urethane (meth) acrylate is not particularly limited, but an isocyanate compound having two or more isocyanate groups in one molecule, a (meth) acrylic compound having one or more hydroxyl groups in one molecule, polyethylene glycol, A urethane (meth) acrylate obtained by reacting a polyol selected from polyether polyol and adipate-based polyester polyol can be used.

The polymerizable monomer used in the radical polymerizable resin is not particularly limited, and those known in the technical field can be used. Examples of polymerizable monomers include styrene; styrene monomers such as vinyltoluene and divinylbenzene; methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate And (meth) acrylic acid esters such as phenoxyethyl (meth) acrylate. In addition, in the molecule such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate It is also possible to use a (meth) acrylic acid ester compound having two or more (meth) acryloyl groups. Among these, styrene is preferable from the viewpoints of workability, cost, and curability. Moreover, these polymerizable monomers can be used individually or in combination of 2 or more types.

The content of the polymerizable monomer in the radical polymerizable resin is not particularly limited, but is preferably 20% by mass to 80% by mass, more preferably 25% by mass to 70% by mass, and most preferably 30% by mass to 60% by mass. is there. When the compounding amount of the polymerizable monomer is less than 20% by mass, workability may decrease due to an increase in the viscosity of the radical polymerizable resin composition. On the other hand, when the compounding quantity of a polymerizable monomer exceeds 80 mass%, the resin molding which has a desired characteristic may not be obtained.

A curable resin composition containing a radical polymerizable resin (hereinafter referred to as “radical polymerizable resin composition”) generally contains a curing agent in addition to the radical polymerizable resin.
It does not specifically limit as a hardening | curing agent, What is necessary is just to select suitably according to various hardening methods, such as normal temperature hardening, heat hardening, and photocuring.

The curing agent used for normal temperature curing is not particularly limited, and those known in the technical field can be used. Examples of the curing agent used for room temperature curing include a combination of ketone peroxide, hydroperoxide or diacyl peroxide and a reducing agent. Examples of the reducing agent include cobalt salts such as cobalt naphthenate and cobalt octylate, vanadium compounds such as vanadium pentoxide, and amines such as dimethylaniline. Among these, a combination of a peroxyester and a cobalt salt is particularly effective from the viewpoint of pot life and the like. Alternatively, known radical polymerization initiators such as ketone peroxide, peroxyketal, hydroperoxide, diallyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, and azo compound may be used. These can be used alone or in combination of two or more. The amount of the reducing agent used is not particularly limited, but is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the curing agent.

The curing agent used for heat curing is not particularly limited, and those known in the technical field can be used. Examples of curing agents used for heat curing include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 1,1-bis (t-butyl Peroxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 3-isopropyl hydroperoxide, t-butyl hydroperoxide, dic Milperoxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, Lauryl par Kisaido, azobisisobutyronitrile, and azobis carboxamido like. These can be used alone or in combination of two or more. Further, these curing agents may be combined with the above-described reducing agent to perform intermediate temperature curing at 50 to 80 ° C. The kind and amount of the reducing agent used are the same as described above.

It does not specifically limit as a hardening | curing agent used for photocuring, A well-known thing can be used in the said technical field. Among them, as the curing agent used for photocuring, a photopolymerization initiator having photosensitivity in an arbitrary region within the range from the ultraviolet light region to the visible light region is effective, and a known ultraviolet polymerization initiator or visible light is effective. It is preferable to use a polymerization initiator.
Examples of the ultraviolet polymerization initiator include acetophenone-based, benzyl ketal-based, and (bis) acylphosphine oxide-based ultraviolet polymerization initiators. These ultraviolet polymerization initiators can be used alone or in combination of two or more. In addition, short wavelength ultraviolet rays have low light transmittance with respect to a radically polymerizable resin composition (FRP) containing a fiber reinforcing material, so that they have photosensitivity to a relatively long wavelength, preferably to a visible light region of 380 nm or more. It is preferable to use an ultraviolet polymerization initiator such as (bis) acylphosphine oxide.

Examples of visible light polymerization initiators include Yamaoka et al., “Surface”, 27 (7), 548 (1989), Sato et al., “Summary of the 3rd Polymer Material Forum”, 1BP18 (1994). Single initiator systems such as quinone, benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, biscyclopentadienyltitanium-di (pentafluorophenyl); organic peroxide catalyst / dye system, diphenyliodonium salt / dye, biphenyl Imidazole / keto compound, hexaarylbiimidazole compound / hydrogen donating compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye, hexaarylbiimidazole / radical generator described in JP-B-45-37777, etc. Initiator system etc. It is. These can be used alone or in combination of two or more.

The blending amount of the curing agent in the radical polymerizable resin composition is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass with respect to 100 parts by mass of the radical polymerizable resin. Most preferably, it is 0.5 to 4 parts by mass. When the blending amount of the curing agent is less than 0.1 parts by mass, the curing reaction may not proceed sufficiently. On the other hand, when the compounding quantity of a hardening | curing agent exceeds 10 mass parts, the resin molding which has a desired characteristic may not be obtained.

The epoxy resin is not particularly limited, and those known in the technical field can be used. Examples of epoxy resins include bisphenol A type diglycidyl ether and its high molecular weight homologue, novolac type polyglycidyl ether and its high molecular weight homologue, aliphatic glycidyl ether such as 1,6 hexanediol diglycidyl ether, alicyclic ring Formula epoxy compounds can be used. In addition, you may use an aliphatic glycidyl ether etc. and an alicyclic epoxy compound as a diluent.

The curable resin composition containing an epoxy resin (hereinafter referred to as “epoxy resin composition”) generally contains a curing agent in addition to the epoxy resin.
It does not specifically limit as a hardening | curing agent of an epoxy resin, A well-known thing can be used in the said technical field. Examples of epoxy resin curing agents include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like. More specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, and imidazole. Examples of amide compounds include polyamide resins synthesized from dicyandiamide, a dimer of linolenic acid, and ethylenediamine. In addition, as acid anhydride compounds, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexa And hydrophthalic anhydride. In addition, as phenolic compounds, phenol novolak resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins, resorcinol novolac resins and polyvalent hydroxy compounds and formaldehyde Polyphenol novolak resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin Polyphenols such as biphenyl-modified naphthol resin, aminotriazine-modified phenol resin and alkoxy group-containing aromatic ring-modified novolak resin. Lumpur compounds. These hardening | curing agents can be used individually or in combination of 2 or more types.

The amount of the epoxy resin and the curing agent to be used in the epoxy resin composition is not particularly limited as long as the amount corresponding to the kind thereof is used, but generally, it reacts with the epoxy group with respect to 1 equivalent of epoxy group in the epoxy resin. The equivalent of functional groups in the curing agent to be used is preferably 0.3 to 2.0 equivalents, more preferably 0.4 to 1.5 equivalents, and most preferably 0.5 to 1.2 equivalents. That's fine. If the equivalent of the functional group in the curing agent that reacts with the epoxy group is less than 0.3 equivalent or exceeds 2.0 equivalent, the curing becomes incomplete and a resin molded product having desired characteristics cannot be obtained.

It does not specifically limit as a phenol resin, A well-known thing can be used in the said technical field. Examples of the phenol resin include a resol type phenol resin and a novolac type phenol resin. Among them, it is preferable to use a resol type phenolic resin that can be cured by adding heat and acid.
It does not specifically limit as a resole type phenol resin, A well-known thing can be used in the said technical field. The resol type phenol resin can be generally produced using a phenol compound such as phenol, bisphenol, cresol, PTBP, resorcin, naphthol, dihydroxynaphthalene as a raw material.
The phenol resin is generally used in a form diluted with a solvent such as water. The content of the solvent in the diluted phenol resin is not particularly limited, but is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. The preferred resol-type phenol resin dilution has a viscosity of 500 to 8000 mPa · s (25 ° C.), a specific gravity of 1.15 to 1.30, a pH of 6.6 to 7.2, and a non-volatile content of 68 to 80%. It is an adjusted liquid resol type phenol resin. Such a liquid resol type phenol resin is commercially available, and for example, Shonor (registered trademark) BRL-240, BRL-1017 manufactured by Showa Denko KK and the like can be used.

A curable resin composition containing a phenolic resin (hereinafter referred to as “phenolic resin composition”) generally contains an acidic curing agent in addition to the phenolic resin when curing with an acid.
It does not specifically limit as an acidic hardening | curing agent of a phenol resin, A well-known thing can be used in the said technical field. As an acidic hardening | curing agent, a well-known thing can be used in the said technical field. Examples of acidic curing agents include organic acids or inorganic acids such as benzene sulfonic acid, paratoluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, sulfuric acid and phosphoric acid. These can be used alone or in combination of two or more. Such acidic curing agents are generally commercially available, and for example, FRH-50 manufactured by Showa Denko KK can be used.

The amount of the phenolic resin and the acidic curing agent used in the phenolic resin composition is not particularly limited as long as the amount corresponding to the type thereof is used. Generally, from the viewpoint of achieving both curability and stability of the phenol resin composition, the amount of the acidic curing agent used is preferably 1 to 20 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the phenol resin dilution. The amount may be 3 to 15 parts by mass, most preferably 5 to 12 parts by mass. When the amount of the acidic curing agent used is less than 1 part by mass, it may take a long time to cure and may not be practical. On the other hand, when the usage-amount of an acidic hardening | curing agent exceeds 20 mass parts, it is easy to gelatinize in a short time and sufficient pot life may not be obtained.

The curable resin composition such as the radical polymerizable resin composition, the epoxy resin composition, and the phenol resin composition as described above includes a fiber reinforcing material from the viewpoint of improving the strength and impact resistance of the resin molded product. Can do.
It does not specifically limit as a fiber reinforcement, A well-known thing can be used in the said technical field. Examples of the fiber reinforcement include inorganic fibers and organic fibers. More specifically, glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, high density polyethylene fiber, nylon fiber, vinylon fiber and the like can be mentioned. These can be used alone or in combination of two or more. Further, the shape of the fiber material is not particularly limited, and a material such as roving, tape, or mat can be used.

The amount of the fiber reinforcement used is not particularly limited, but is preferably 5 to 400 parts by weight, more preferably 50 to 350 parts by weight, and most preferably 50 to 300 parts by weight with respect to 100 parts by weight of the curable resin composition. It is. When the amount of the fiber reinforcing material used is less than 5 parts by mass, desired strength may not be obtained. On the other hand, if the amount of the fiber reinforcement used exceeds 400 parts by mass, the impact resistance may be lowered.

In the curable resin composition, additives known in the technical field may be blended within a range that does not impair the properties of the resin molded product. Examples of known additives include UV absorbers, antioxidants, dyes, pigments, thixotropic agents, flame retardants, low shrinkage agents, inorganic and organic fillers, diluent solvents, surface treatment agents, wetting agents, and curing accelerators. Agents, release agents and the like. The blending ratio of these additives is not particularly limited as long as it does not impair the effects of the present invention.

The curable resin composition containing the above components can be produced by kneading the above components using a method usually performed in the art, for example, a kneader. Moreover, when using a fiber reinforcing material, after preparing components by kneading components other than the fiber reinforcing material, the curable resin composition may be produced by impregnating the fiber reinforcing material with the compound.

The type of mold for molding and curing the curable resin composition is not particularly limited, and may be appropriately selected according to the molding method of the curable resin composition. Examples of types of molds that can be used include mandrels, injection molds, blow molds, compression molds, vacuum molds, and extrusion molds.
The material of the mold is not particularly limited as long as it can be surface-treated with a baking mold release agent containing silicone, and materials known in the technical field can be used. Examples of the material of the mold include metal, glass, FRP and the like.

Specifically, when manufacturing a resin molded product for a pipe, a metal mandrel or the like is used, and when manufacturing a resin molded product for a watering member such as a bathtub, a bath unit, and a wash basin, An FRP compression mold or the like is used.

The surface of the mold for molding and curing the curable resin composition is treated with a baking mold release agent containing silicone. Since the mold is surface-treated with a baking mold release agent containing silicone, the organosilicon compound contained in the curable resin composition is compatible with the baking mold release agent on the mold surface. During the molding and curing, the organosilicon compound can be localized on the surface of the resin molding. If the baking mold release agent does not contain silicone, the organosilicon compound cannot be localized on the surface of the resin molding. In addition, when the mold release agent is not a baked mold, the mold release agent is absorbed by the curable resin composition when the curable resin composition is applied to the mold, and the organosilicon compound is sufficiently absorbed on the surface of the resin molded product. Cannot be localized. Therefore, it is difficult to form a surface on which the scale is difficult to adhere and the scale can be easily removed.

The silicone used for the baking mold release agent is not particularly limited, and those known in the technical field can be used, but oily ones are preferable from the viewpoint of applicability by brush or spray. In general, silicone is obtained by hydrolyzing and polymerizing an organosilicon compound, and is a compound in which an organic group is bonded to the main skeleton of a siloxane chain (Si—O—Si) in which silicon and oxygen are bonded alternately.

The content of silicone in the baking mold release agent is not particularly limited, but is generally 3 to 20% by mass. The baking mold release agent contains a solvent such as toluene and xylene in addition to silicone.

Baking mold release agents containing silicone as described above are commercially available, for example, KS-702, KS-726, KS-707, KS-700, KS-7201, KS- manufactured by Shin-Etsu Chemical Co., Ltd. 7200, SEPA-COAT, KF-96SP, KF-965SP, KF-412SP, RELEASE, SEPA-COAT SP, and the like can be used.

The method of treating the surface of the mold with the baking mold release agent is not particularly limited, but after the baking mold release agent is uniformly applied to the surface of the molding mold, the solvent is volatilized by heating at room temperature or low temperature. The baking process may be performed. The baking temperature is not particularly limited, but is generally 50 to 200 ° C.
In addition, when the mold is soiled with oils and fats, dust, etc., the baking mold release agent cannot be uniformly applied to the surface of the mold, so it is preferable to wash the surface of the mold in advance.

The method for molding and curing the curable resin composition using the molding die is not particularly limited, and may be appropriately selected according to the type of the curable resin composition to be used and the molding method.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these.
Example 1
A baking mold release agent (silicone SEPA-COAT (registered trademark) SP manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-coated on a 3 mm thick glass plate from which oils and fats had been removed by washing with acetone, and dried at room temperature (25 ° C.). Then, the glass plate was surface-treated with a baking mold release agent by heating at 150 ° C. for 30 minutes in a dryer.
Next, 100 parts by mass of vinyl ester resin (Lipoxy (registered trademark) R-806 (Styrene content: 45% by mass) manufactured by Showa Denko KK) was added to hydroxyl group-containing silicon-modified acrylic (BYK (registered trademark) manufactured by Big Chemie Japan Co., Ltd.). ) -SILCLEAN 3700) 3 parts by weight and 0.2 parts by weight of polyester-modified polydimethylsiloxane (BYK (registered trademark) -310 manufactured by Big Chemie Japan Co., Ltd.) were added and mixed, and then 0.3 parts by weight of naphthenic acid Co Further, 1.5 parts by mass of Permec (registered trademark) N (Nippon Yushi Co., Ltd. methyl ethyl ketone peroxide) was further added and mixed to prepare a room temperature curable vinyl ester resin composition.

Next, a mold having a thickness of 3 mm was prepared using two glass plates surface-treated with a baking mold release agent and a silicon rubber spacer having a height of 3 mm, and then the above vinyl ester was added to the mold. When the resin composition was injected and allowed to stand at room temperature, it gelled and cured in 30 minutes. After leaving this to stand for 24 hours, after-curing was performed at 120 ° C. for 2 hours, and the mold was returned to room temperature and removed to obtain a resin molded product.

(Comparative Example 1)
Vinyl ester resin (Lipoxy (registered trademark) R-806 (Styrene content 45% by mass) manufactured by Showa Denko KK), 100 parts by mass of naphthenic acid Co, Parmec (registered trademark) N (Nippon Yushi Co., Ltd.) (Methyl ethyl ketone peroxide) 1.5 parts by mass was added and mixed to prepare a room temperature curable vinyl ester resin composition.
Next, a mold having a thickness of 3 mm was prepared using two glass plates with a PET film and a silicon rubber spacer having a height of 3 mm, and then the above vinyl ester resin composition was applied to the mold. Was allowed to stand at room temperature and gelled and cured in 30 minutes. After leaving this to stand for 24 hours, after-curing was performed at 120 ° C. for 2 hours, and the mold was returned to room temperature and removed to obtain a resin molded product.

(Comparative Example 2)
A glass release plate (Daikin Kogyo Co., Ltd., Daifree (registered trademark) GF500) is spray-coated on a 3 mm thick glass plate from which oils and fats have been removed by washing with acetone, and dried at room temperature (25 ° C.). The plate was surface treated with a fluorinated mold release agent. Here, the fluorine-based mold release agent is a mold release agent that does not contain silicone and is not a baking type.
Next, a mold having a thickness of 3 mm was prepared using two glass plates surface-treated with a fluorine-based mold release agent and a spacer having a height of 3 mm, and then the vinyl prepared in Example 1 was applied to this mold. When the ester resin composition was injected and allowed to stand at room temperature, it gelled and cured in 30 minutes. After leaving this to stand for 24 hours, after-curing was performed at 120 ° C. for 2 hours, and the mold was returned to room temperature and removed to obtain a resin molded product.

The following evaluation was performed about the resin molding obtained by said Example and comparative example.
(Evaluation of water and oil repellency angles)
The water repellent angle was measured by dropping 2 μL of water onto the surface of the resin molding and measuring the contact angle of water with a contact angle meter (contact angle meter CA-DT type manufactured by Kyowa Interface Science).
The oil repellency angle was measured by dropping 2 μL of oleic acid onto the surface of the resin molding and measuring the oil contact angle with a contact angle meter (contact angle meter CA-DT type manufactured by Kyowa Interface Science).

(Evaluation of scale removal)
Acidic Kusatsu hot spring water (PH: 1.95, Kusatsu Town, Gunma Prefecture), alkaline Onogami hot spring water (PH: 8.9, Shibukawa City, Gunma Prefecture), tap water (Isezaki City, Gunma Prefecture) 0.4 mL) was dropped and allowed to dry for 24 hours in an environment of 23 ° C. and 50% humidity. This operation was repeated seven times at the same location to form a scale on the surface of the resin molded product.
Next, the scale was wiped off by applying a load of 30 g / cm ² to the sponge containing water, and the number of times the scale was completely removed by wiping was measured.
The evaluation results are shown in Table 1.

As shown in Table 1, the resin molded product of Example 1 had both a high water repellency angle and an oil repellency angle, was difficult to adhere to water and oil, and had high scale removability. On the other hand, the resin moldings of Comparative Examples 1 and 2 had both low water repellency angles and oil repellency angles, were easily attached to water and oil, and had low scale removability.

(Example 2)
A baking mold release agent (silicone SEPA-COAT (registered trademark) SP manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-coated on a 3 mm thick glass plate from which oils and fats had been removed by washing with acetone, and dried at room temperature (25 ° C.). Then, the glass plate was surface-treated with a baking mold release agent by heating at 150 ° C. for 30 minutes in a dryer.
Next, 100 parts by mass of a phenol resin dilution (Shonol (registered trademark) BRL-240 (water content: 30% by mass) manufactured by Showa Denko KK) was added to a curing agent (FRH-50 manufactured by Showa Denko KK) 10 3 parts by mass and 3 parts by mass of a hydroxyl group-containing silicon-modified acrylic (BYK (registered trademark) -SILCLEAN 3700, manufactured by BYK Japan) and polyester-modified polydimethylsiloxane (BYK (registered trademark) -310, manufactured by BYK Japan) After adding 0.2 parts by mass and mixing, a glass cloth (# 200) was impregnated to prepare a phenol resin composition. Here, content of the glass cloth in a phenol resin composition was 70 mass%.

Next, the above phenol resin composition (10 ply) is placed on a glass plate surface-treated with a baking mold release agent, heated at 60 ° C. for 2 hours, and then heated at 80 ° C. for 3 hours to be cured. The resin molded product was obtained by returning to room temperature and removing the mold.

(Comparative Example 3)
As a comparative product of Example 2, the same procedure as in Example 2 was used except that a carbon steel plate and a stainless steel plate from which surface oils and fats were removed by washing with acetone were used instead of the glass plate surface-treated with a baking mold release agent. Thus, a resin composition was obtained.

For the resin moldings obtained in the above examples and comparative examples, the scale removability was evaluated in the same manner as in Example 1. The results are shown in Table 2.

As shown in Table 2, the resin molded product of Example 2 had high scale removability, whereas the carbon steel plate and stainless steel plate of Comparative Example 3 had low scale removability.

Example 3
A spray-type mold release agent (silicone SEPA-COAT (registered trademark) SP manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-coated on a filament winding molding mandrel from which oils and fats were removed by acetone washing, and dried at room temperature (25 ° C.). Then, the mandrel was surface-treated with a baking mold release agent by heating at 150 ° C. for 30 minutes in a dryer.
Next, 100 parts by mass of a phenol resin dilution (Shonol (registered trademark) BRL-240 (water content: 30% by mass) manufactured by Showa Denko KK) was added to a curing agent (FRH-50 manufactured by Showa Denko KK) 10 3 parts by mass and 3 parts by mass of a hydroxyl group-containing silicon-modified acrylic (BYK (registered trademark) -SILCLEAN 3700, manufactured by BYK Japan) and polyester-modified polydimethylsiloxane (BYK (registered trademark) -310, manufactured by BYK Japan) After adding 0.2 parts by mass and mixing, a glass cloth (# 200) was impregnated to prepare a phenol resin composition. Here, content of the glass cloth in a phenol resin composition was 70 mass%.

Next, the above-mentioned phenol resin composition (10 ply) is wrapped around a mandrel surface-treated with a baking mold release agent, heated at 60 ° C. for 2 hours, then cured by heating at 80 ° C. for 3 hours, and brought to room temperature. By returning and demolding, a pipe-shaped resin molded product was obtained.

Example 4
A spray-type mold release agent (silicone SEPA-COAT (registered trademark) SP manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-coated on a filament winding molding mandrel from which oils and fats were removed by acetone washing, and dried at room temperature (25 ° C.). Then, the mandrel was surface-treated with a baking mold release agent by heating at 150 ° C. for 30 minutes in a dryer.
Next, 100 parts by mass of vinyl ester resin (Lipoxy R-806 (Showa Denko Co., Ltd.) (styrene content: 45 mass%)) and hydroxyl-containing silicon-modified acrylic (BYK (registered trademark) -SILCLEAN 3700 manufactured by Big Chemie Japan Co., Ltd.) ) 3 parts by mass and 0.2 parts by mass of polyester-modified polydimethylsiloxane (BYK (registered trademark) -310 manufactured by Big Chemie Japan Co., Ltd.) were added and mixed, and then 0.3 parts by mass of Naphthenic acid Co and Parmec (registered) A vinyl ester resin composition was prepared by further adding 1.5 parts by mass of N) (Methyl Ethyl Ketone Peroxide manufactured by NOF Corporation) and impregnating the mixture with glass cloth (# 200). Here, the content of the glass cloth in the vinyl ester resin composition was 75% by mass.

Next, the above-mentioned vinyl ester resin composition (10 ply) was wound around a mandrel surface-treated with a baking mold release agent, cured while rotating at room temperature for 30 minutes, and allowed to stand for 24 hours. Next, this was demolded and after-curing at 120 ° C. for 2 hours to obtain a pipe-shaped resin molded product.

(Example 5)
A spray-type mold release agent (silicone SEPA-COAT (registered trademark) SP manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-coated on a filament winding molding mandrel from which oils and fats were removed by acetone washing, and dried at room temperature (25 ° C.). Then, the mandrel was surface-treated with a baking mold release agent by heating at 150 ° C. for 30 minutes in a dryer.
Next, 100 parts by mass of a phenol resin dilution (Shonol (registered trademark) BRL-240 (water content: 30% by mass) manufactured by Showa Denko KK) was added to a curing agent (FRH-50 manufactured by Showa Denko KK) 10 3 parts by mass and 3 parts by mass of a hydroxyl group-containing silicon-modified acrylic (BYK (registered trademark) -SILCLEAN 3700, manufactured by BYK Japan) and polyester-modified polydimethylsiloxane (BYK (registered trademark) -310, manufactured by BYK Japan) After adding 0.2 parts by mass and mixing, a glass cloth (# 200) was impregnated to prepare a phenol resin composition. Here, content of the glass cloth in a phenol resin composition was 70 mass%.

Next, the above-mentioned phenol resin composition (10 ply) is wrapped around a mandrel surface-treated with a baking mold release agent, heated at 60 ° C. for 2 hours, then cured by heating at 80 ° C. for 3 hours, and brought to room temperature. Returned. Next, a visible light curable vinyl ester resin Lipoxy (registered trademark) LC-760 (manufactured by Showa Denko KK) was impregnated into a T glass roving (RST-220PA manufactured by Nittobo Co., Ltd.), which was subjected to a filament winding method. First, the helical winding was wound to a layer thickness of 0.98 mm, and then the hoop winding was wound to a thickness of 0.6 mm (fiber content: 50% by volume). After the winding, three 600W metal halide lamps, which are visible light sources including ultraviolet rays, are arranged, and light is irradiated while rotating the compact so that the light intensity of 380 to 450 nm on the irradiated surface is 20 mW / cm ^2. After being cured, the mold was removed to obtain a pipe-shaped resin molded product.

(Comparative Example 4)
As a comparative product of Example 5, a baking mold release agent (silicone SEPA-COAT (registered trademark) SP manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-applied to a filament winding molding mandrel from which fats and oils were removed by acetone washing, and room temperature ( A pipe-shaped resin composition was obtained in the same manner as in Example 5 except that a mandrel that had been subjected to a surface treatment that was only dried at 25 ° C. and not subjected to a baking treatment was used.

(Comparative Example 5)
As a comparative product of Example 5, a pipe-shaped resin was used in the same manner as in Example 5 except that an untreated mandrel coated with a polyethylene terephthalate film was used instead of a mandrel surface-treated with a baking mold release agent. A composition was obtained.

(Comparative Example 6)
A spray-type mold release agent (silicone SEPA-COAT (registered trademark) SP manufactured by Shin-Etsu Chemical Co., Ltd.) was spray-coated on a filament winding molding mandrel from which oils and fats were removed by acetone washing, and dried at room temperature (25 ° C.). Then, the mandrel was surface-treated with a baking mold release agent by heating at 150 ° C. for 30 minutes in a dryer.
Next, 100 parts by mass of vinyl ester resin (Lipoxy (registered trademark) R-806 (Styrene content: 45% by mass) manufactured by Showa Denko KK), 0.3 parts by mass of naphthenic acid Co, Parmeck (registered trademark) N (Japan) 1.5 parts by mass of Methyl Ethyl Ketone Peroxide manufactured by Yushi Co., Ltd. was added and mixed, and this was impregnated into glass cloth (# 200) to prepare a vinyl ester resin composition. Here, the content of the glass cloth in the vinyl ester resin composition was 75% by mass.
Next, the vinyl ester resin composition (10 ply) was wound around a mandrel surface-treated with a baking mold release agent, cured while rotating at room temperature for 30 minutes, and allowed to stand for 24 hours. Next, this was demolded and after-curing at 120 ° C. for 2 hours to obtain a pipe-shaped resin molded product.

(Comparative Example 7)
100 mass parts of vinyl ester resin (Lipoxy (registered trademark) R-806 (Styrene content 45 mass%) manufactured by Showa Denko KK) and silicon-modified acrylic (BYK (registered trademark) -SILCLEAN 3700 manufactured by Big Chemie Japan Co., Ltd.) 3 parts by mass and 0.2 parts by mass of polyester-modified polydimethylsiloxane (BYK (registered trademark) -310 manufactured by Big Chemie Japan Co., Ltd.) were added and mixed, and then 0.3 parts by mass of Naphthenic acid Co and Parmec (registered trademark) ) 1.5 parts by mass of N (Methyl ethyl ketone peroxide manufactured by NOF Corporation) was added and mixed, and a glass cloth (# 200) was impregnated to prepare a vinyl ester resin composition. Here, the content of the glass cloth in the vinyl ester resin composition was 75% by mass.
Next, after applying FRP release agent BONLYSE (registered trademark) (H) (manufactured by Keiyo Kasei Co., Ltd.) to the mandrel, the above vinyl ester resin composition (10 ply) is wound and rotated at room temperature for 30 minutes. The mixture was cured while being left for another 24 hours. Here, the FRP mold release agent Bon Lease (H) is a wax-type mold release agent that does not contain silicone and is not baked. Next, this was demolded and after-curing at 120 ° C. for 2 hours to obtain a pipe-shaped resin molded product.

The pipe-shaped resin moldings obtained in the above examples and comparative examples are installed in the well water line in Showa Denko Co., Ltd. Isesaki Office, and the scale adhesion on the inner surface is 1 month later, 3 months later and 6 months later Observed later. The results are shown in Table 3.

As shown in Table 3, in the pipe-shaped resin molded products of Examples 3 to 5, no scale adhesion was confirmed even after 6 months, whereas the pipe-shaped resin of Comparative Example 5 was confirmed. Scale adhesion was confirmed after 3 months for the molded product and after 1 month for the pipe-shaped resin molded products of Comparative Examples 4, 6, and 7.

As can be seen from the above results, according to the present invention, it is possible to provide a method for producing a resin molded product that is excellent in scale adhesion prevention effect and scale removal effect over a long period of time.

This international application claims priority based on Japanese Patent Application No. 2013-172512 filed on August 22, 2013, and the entire contents of this Japanese patent application are incorporated herein by reference. To do.

Claims

A method for producing a resin molded product, comprising molding and curing a curable resin composition containing an organosilicon compound using a molding die surface-treated with a baking mold release agent containing silicone.
The method for producing a resin molded product according to claim 1, wherein the organosilicon compound is at least one selected from the group consisting of an organosilane compound, an organomodified siloxane compound, and a silicon modified acrylic compound.
3. The resin molded product according to claim 1, wherein the content of the organosilicon compound in the curable resin composition is 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable resin. Manufacturing method.
The curable resin composition includes at least one curable resin selected from the group consisting of a radical polymerizable resin, an epoxy resin, and a phenol resin. The manufacturing method of the resin molding of description.
The method for producing a resin molded product according to claim 4, wherein the radical polymerizable resin is a vinyl ester resin.
The method for producing a resin molded product according to any one of claims 1 to 5, wherein the curable resin composition further contains a fiber reinforcing material.
A resin molded product obtained by the method for producing a resin molded product according to any one of claims 1 to 6.