WO2005063894A1 - Composition de resine thermodurcissable et son procede de production, article forme et son procede de production, et agent de demoulage - Google Patents

Composition de resine thermodurcissable et son procede de production, article forme et son procede de production, et agent de demoulage Download PDF

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Publication number
WO2005063894A1
WO2005063894A1 PCT/JP2004/019256 JP2004019256W WO2005063894A1 WO 2005063894 A1 WO2005063894 A1 WO 2005063894A1 JP 2004019256 W JP2004019256 W JP 2004019256W WO 2005063894 A1 WO2005063894 A1 WO 2005063894A1
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Prior art keywords
thermosetting resin
resin composition
mass
raw material
parts
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PCT/JP2004/019256
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English (en)
Japanese (ja)
Inventor
Takeyuki Nakai
Fumio Kurihara
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Techno Polymer Co., Ltd
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Publication of WO2005063894A1 publication Critical patent/WO2005063894A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

  • Thermosetting resin composition method for producing the same, molded article, method for producing the same, and release agent
  • the present invention relates to a thermosetting resin composition, a method for producing the same, a molded article, a method for producing the same, and a release agent. More specifically, a thermosetting resin composition and molded article having permanent hydrophilicity and antifouling properties on the surface thereof, and a thermosetting resin composition having the above properties and a production method for efficiently producing the molded article And a release agent.
  • artificial marble has been widely used as a so-called "water circulating" product such as a wash counter, a kitchen counter, a bathtub, a member for a toilet, and the like.
  • This artificial marble is manufactured from a composition mainly composed of a thermosetting resin such as polyester resin, acrylic resin and vinyl ester resin.
  • a thermosetting resin such as polyester resin, acrylic resin and vinyl ester resin.
  • composition containing a thermosetting resin, a filler, a curing agent, and a silicone oil is used (see Patent Document 1).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2001-234079
  • the present invention utilizes the hydrophilicity of silanol groups, and has a thermosetting resin composition and a molded article having permanent hydrophilicity and antifouling properties on the surface thereof, and a thermosetting resin having the above properties.
  • An object of the present invention is to provide a method for efficiently producing a resin composition and a molded product by reducing contamination of a mold, and a release agent.
  • thermosetting resin composition formed from a raw material composition containing (A) a thermosetting resin and (B) an alkoxysilane and a condensate thereof at least one selected from silane compounds.
  • the content in terms of SiO of the (B) silane conjugate was 100 parts by mass of the cured polymer.
  • thermosetting resin composition 0.1 to 50 parts by mass of the thermosetting resin composition.
  • thermosetting resin composition according to 1 above wherein the (A) thermosetting resin is at least one selected from polyester resins, vinyl ester resins, and acrylic resins.
  • thermosetting resin composition containing a thermosetting resin, an alkoxysilane and a condensate thereof, at least one selected silane compound, and a curing agent at a temperature of 10 ° C. or less
  • a method for producing a thermosetting resin composition comprising a curing step of heating and curing the composition.
  • thermosetting resin composition obtained by the method described in 3 above.
  • the content of the silani conjugate in terms of SiO is 100 cured polymers.
  • thermosetting resin composition according to the above item 4 wherein the amount is 0.1 to 50 parts by mass with respect to parts by mass.
  • thermosetting resin composition according to 1 above 6.
  • thermosetting resin composition as described in 2 above.
  • thermosetting resin composition according to 4 above 8. A molded article comprising the thermosetting resin composition according to 4 above.
  • thermosetting resin composition according to 5 above 9. A molded article comprising the thermosetting resin composition according to 5 above.
  • a method for producing a molded article comprising: a casting step of injecting an object into a mold having a predetermined shape; and a curing step of heating and curing the raw material composition in the mold.
  • the content in terms of SiO of the silane conjugate in the molded product is 100 mass of the cured polymer.
  • thermosetting resin composition of the present invention comprises a raw material composition containing (A) a thermosetting resin, and (B) at least one silane conjugate selected from alkoxysilanes and condensates thereof. Since it is formed in a flat manner and contains a predetermined amount of the silane conjugate (B), It has continuous hydrophilicity and antifouling properties. These properties are due to the silanol groups on the surface. This silanol group oozes out to the surface when the thermosetting resin composition is allowed to stand in the air at a temperature around room temperature of about 10-30 ° C or under heating at about 30-50 ° C (bleeding). Out), the silane conjugate (B) is hydrolyzed to form.
  • a silane compound in a preparation step contains a predetermined amount of a silane compound that does not react with a curing agent, and is hydrophilic on its surface. It is possible to efficiently and easily obtain a thermosetting resin composition having water resistance and stain resistance.
  • the molded article of the present invention has permanent hydrophilicity and antifouling properties on its surface. Therefore, when used as a "water-around" product, even if dirt adheres to or adheres to the surface, it can be washed away instantly without leaving dirt by washing with water, etc. Is held.
  • a molded article containing a predetermined amount of a silane compound that does not react with a curing agent in a preparation step and having a surface having hydrophilicity and antifouling property can be easily prepared.
  • the curing speed is high, the mold is not contaminated, the releasability is excellent, and no unevenness or wrinkles are formed on the surface of the molded product.
  • the release agent of the present invention can be diluted with a solvent such as alcohol which has relatively low toxicity and little effect on the environment, so that it is easy to handle and a molded article can be obtained without contaminating the mold. Further, the performance of the molded article is not reduced.
  • a solvent such as alcohol which has relatively low toxicity and little effect on the environment
  • thermosetting resin composition of the present invention comprises (A) a thermosetting resin (hereinafter also referred to as “component (A)”), and (B) an alkoxysilane and a condensate thereof.
  • component (A) a thermosetting resin
  • component (B) an alkoxysilane and a condensate thereof.
  • Amount is 100 mass of cured polymer
  • the raw material composition usually contains the component (A) and its curing agent, and the component (B). Therefore, various additives are blended as necessary.
  • the “cured polymer” is formed by mainly curing a thermosetting resin by heat treatment (heating or the like) of the raw material composition.
  • the curing agent is a polymer or the like
  • the cured polymer is a reaction product between the thermosetting resin and the polymer or the like.
  • “sio conversion” refers to alkoxysilane and
  • the component (A) blended in the raw material composition is an uncured polymer, oligomer, or the like, and is not particularly limited as long as it can be cured by heat at 20 ° C or higher.
  • Unsaturated polyester resin, unsaturated alkyd resin, etc. vinyl ester resin, acrylic resin, epoxy resin, phenol resin, melamine resin, urethane resin, urea resin, silicone resin, polyimide Resin, bismaleimide 'triazine resin, furan resin, xylene resin, guanamine resin, dicyclopentadiene resin and the like.
  • polyester resins, vinyl ester resins and acrylic resins are preferred.
  • the polyester resin is obtained by subjecting a dibasic acid containing a, ⁇ unsaturated dibasic acid such as maleic anhydride and a saturated dibasic acid such as ⁇ or phthalic anhydride to a condensation reaction with glycols. It is not particularly limited as long as it is synthesized and has an unsaturated bond and an ester bond in the molecule.
  • Compounds having an unsaturated bond capable of reacting with the above monomer component unsaturated monobasic acid, (meth) acrylic acid ester conjugate, aromatic vinyl compound, cyclopentadiene compound, Or a polyester resin obtained using a cyclopentadiene-based compound!
  • Examples of the a, ⁇ unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like. These can be used alone or in combination of two or more.
  • Saturated dibasic acids include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hydroterephthalic acid, Hexahydroisophthalenoic acid, Succinic acid, Malonic acid, Gunoletanoleic acid, Adipic acid, Sebacic acid, 1,12-dode force 2,2,6 naphthalenedicarboxylic acid, 2,7 naphthalenedicarboxylic acid, 2,3 naphthalenedicarboxylic acid, 2,3 naphthalenedicarboxylic anhydride, 4,4'-biphenyldicarboxylic acid, etc. No. These can be used alone or in combination of two or more.
  • glycols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, and neopentyl.
  • Glycol hydrogenated bisphenol A 1,4 butanediol, bisphenol A and a mixture of propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1, 3 Propanediol, 1,2-cyclohexane glycolone, 1,3-cyclohexane glycolone, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, para-xylene glycol, 2, 6 —Decaling recall, 2, 7—Deca Phosphorus glycol and the like. These can be used alone or in combination of two or more.
  • unsaturated monobasic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, monomethino Examples include remalate, monopropynolemalate, monobutynolemalate, and mono (2-ethynolehexyl) malate. These can be used alone or in combination of two or more.
  • Examples of the (meth) acrylate ester conjugate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylate.
  • Aromatic vinyl compounds include styrene, chlorostyrene, bromostyrene, dichlorostyrene, ⁇ -methylstyrene, t-butylstyrene, vinyltoluene, and divinylbenzene. And the like. These can be used alone or in combination of two or more.
  • cyclopentadiene compound and the dicyclopentadiene compound examples include cyclopentadiene, dicyclopentadiene, and derivatives thereof, such as tricyclodecyl maleate, tricyclodecyl fumarate, and adipic acid.
  • glycerin monoallyl ether trimethylol propane monolinoleate ethere, trimethylolone propane diarynoateatenole, trimethylonole ethane monoarynoleate ether, trimethylonoleatene diethanolate
  • pentaerythritol monoallyl ether pentaerythritol diaryl ether, pentaerythritol triallyl ether, 1,2,6-hexanetriol monoaryl ether, 1,2,6-hexanetriol diaryl ether
  • polyhydric alcohol aryl ether units such as ethylene glycol, sorbitan monoaryl ether and sorbitan diaryl ether; ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) Tallylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohex
  • examples of the vinyl ester resin include a bisphenol-type vinyl ester resin, a novolak-type vinyl ester resin, and the like. These can be used alone or in combination of two or more.
  • the bisphenol-type vinyl ester resin is an addition reaction product of a bisphenol-type epoxy resin and an acid, and each has a reactive unsaturated group only at both terminals.
  • the bisphenol type epoxy resin various types such as bisphenol A type, bisphenol AD type, bisphenol S type and bisphenol F type can be used.
  • a styrene monomer, an acrylic monomer, or the like may be blended in the bullet ester resin as a crosslinking agent.
  • acrylic resin what is generally called an acrylic syrup composed of a mixture of two or more of methyl methacrylate, polyfunctional (meth) acrylate, a prepolymer and a polymer is used. Can be.
  • polyester resin butyl ester resin and acrylic resin
  • component (A) the properties of each resin and the filler Interaction or the ability to determine the optimal blending that matches the desired product quality
  • the blending ratio is not particularly limited.
  • the water content of the component (A) is preferably 3% by mass or less, more preferably 3 to 0.01% by mass, and still more preferably 0.5 to 0.01% by mass. If the water content is too high, the hydrolysis of the component (B) proceeds in the raw material composition, and the hydrolysis product is dispersed in the thermosetting resin composition formed thereafter. Thereby, hydrophilicity and antifouling property are reduced. There is a case. Also, if the water content is too high, the polymerization reaction of the thermosetting resin may be stopped halfway during thermosetting, and a low molecular weight polymer may be generated, which may cause mold contamination. The water content can be measured by a method such as the Karl Fischer method.
  • This component (B) is at least one selected from the group consisting of alkoxysilanes and condensates thereof.
  • the alkoxysilane is a compound represented by the following general formula (I).
  • R 1 is each independently a linear or branched hydrocarbon group having 10 to 10 carbon atoms
  • R 2 is each independently a halogen atom or an organic group.
  • N is 0, 1 or 2 o]
  • R 1 in the above general formula (I) is a hydrocarbon group, and the hydrocarbon group may be an aliphatic, alicyclic or aromatic group.
  • Aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, and n- Xyl groups, n-heptyl groups, n-octyl groups, 2-ethylhexyl groups and the like.
  • Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.
  • aromatic hydrocarbon group examples include an aryl group, a xylyl group, and a naphthyl group.
  • the hydrocarbon group may be a hydrocarbon group which may have a substituent, such as a halogen atom, a hydroxyl group or an ether group.
  • each R 1 when there are a plurality of R 1 , each R 1 may be the same hydrocarbon group or different hydrocarbon groups.
  • R 2 in the general formula (I) is an organic group, and examples of the organic group include a hydrocarbon group, an alkoxyl group (including a cycloalkoxyl group and an aryloxy group).
  • the hydrocarbon group may be any of aliphatic, alicyclic, and aromatic, and those exemplified above may be applied.
  • OR 1 represented by using the above R 1 can be applied. Note that the hydrocarbon group and the alkoxyl group may be a hydrocarbon group and an alkoxyl group having a halogen atom, a hydroxyl group, an ether group or the like which may have a substituent.
  • R 1 in the above general formula (I) is an aliphatic hydrocarbon group
  • R 2 is an organic group
  • n l, methyltrimethoxysilane, methyltriethoxysilane, ethylethyl Alkyl trialkoxysilanes such as methoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane; phenyl Aryltrialkoxysilanes such as trimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2aminoethyl) 3-aminopropyltrieth
  • R 1 in the general formula (I) is an aliphatic hydrocarbon group
  • R 2 is an organic group
  • n 2
  • dialkyl dialkoxy silanes such as toxic silane.
  • R 1 in the general formula (I) is an aliphatic hydrocarbon group
  • R 2 is an organic group
  • n l.
  • the above-mentioned alkoxysilanes can be used alone or in combination of two or more as the silane conjugate (B).
  • the condensate of the above-mentioned alkoxysilane is usually an alkoxysilane represented by the above general formula (I).
  • R 3 in this general formula ( ⁇ ) can be the same as R 1 in the above general formula (I) .R 3 in the above general formula ( ⁇ ), each R 3 may be the same hydrocarbon group. Or different hydrocarbon groups.
  • the degree of condensation is usually 2 to 10 mer, preferably 2 to 6 mer, and more preferably 2 to 4 mer.
  • the number of carbon atoms in the hydrocarbon group of R 3 is 3 to 6, it is usually 2 to 10 mer, preferably 2 to 8 mer, and more preferably 4 to 8 mer.
  • a part of R 3 in the general formula ( ⁇ ⁇ ⁇ ⁇ ) may be a hydrogen atom.
  • the content ratio of such a silanol group is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less, based on the total amount of the alkoxyl group before condensation.
  • the condensate of the alkoxysilane may be a product obtained by further performing a transesterification reaction and modified into an ester of an alcohol having a higher carbon number.
  • a transesterification reaction can be performed on a portion of the methyl ester to give a condensate modified to a butyl ester.
  • a compound in which R 3 in the above general formula ( ⁇ ) is a hydrocarbon group having 3 to 6 carbon atoms and is a 418-mer is preferable.
  • the weight average molecular weight of the condensate of the alkoxysilane is usually 300 to 3000, preferably 400 to 2500, more preferably 400 to 2500 in terms of standard polypropylene glycol by gel permeation chromatography (GPC). Or 400-2000. Within the above range, the silanol groups are formed efficiently and have excellent hydrophilicity. If the weight average molecular weight is too low, it tends to easily become a nitric acid silicon by heat, while if it is too high, it may be difficult to exude to the surface.
  • the condensate of the above alkoxysilane may be used alone or as a silane compound ( ⁇ ). More than one species can be used in combination.
  • a condensate of an alkoxysilane is preferable. When this condensate is used, the production stability of the cured resin composition is excellent.
  • an alkoxysilane and a condensate of the alkoxysilane can be used in combination.
  • the content (in terms of SiO) of the raw material composition is preferably 0.1 to 100 parts by mass of the component (A).
  • component (B) It is 50 parts by mass, more preferably 0.5-10 parts by mass, and even more preferably 115 parts by mass.
  • component (B) the mixing ratio of each component is not particularly limited.
  • the amount of the component (B) is less than 0.1 part by mass, the surface of the finally formed cured composition tends to be less likely to exhibit hydrophilicity and antifouling properties. If the amount is more than parts by mass, the above-mentioned component (B) itself reacts (condensation and the like) to easily produce a gelled product, and as a result, hydrophilicity is reduced, which is not preferable.
  • the raw material composition may contain other silane conjugates in addition to the component (B)!
  • Other silane compounds include alkyltrichlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, hexyltrichlorosilane, phenyltrichlorosilane, methylsilyltriisocyanate, dimethylsilyldisilane Examples include isocyanate, butylsilyl triisocyanate, dimethylvinylmethoxysilane, and dimethylvinylchlorosilane. These other silani conjugates can be used alone or in combination of two or more.
  • the compounding amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, in terms of the amount of SiO, relative to 100 parts by mass of the above component (A).
  • It is preferably 10 parts by mass or less.
  • Additives to be added to the raw material composition include a curing agent of component (A), a curing accelerator, a catalyst for promoting hydrolysis of component (B), a diluent, a release agent, and an antioxidant.
  • a curing agent of component (A) a curing accelerator
  • a catalyst for promoting hydrolysis of component (B) a diluent
  • a release agent a diluent
  • an antioxidant e.g., a diluent, a release agent, and an antioxidant.
  • Thickener lubrication Agents, fillers, metal powders, reinforcing agents, plasticizers, compatibilizers, heat stabilizers, light stabilizers, ultraviolet absorbers, coloring agents (dyes, pigments, etc.), antistatic agents, flame retardants, antibacterial agents, etc.
  • the catalyst is not particularly limited as long as it can promote the hydrolysis of component (B).
  • the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic carboxylic acids such as formic acid, acetic acid, benzoic acid, phthalic acid, and maleic acid; benzenesulfonic acid, toluenesulfonic acid, and xylenesulfonic acid.
  • Organic sulfonic acids such as ethylbenzenesulfonic acid; inorganic alkali catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia; organic amine compounds; organic metal compounds; Metal alkoxide conjugates such as organic aluminum compounds, organic titanium compounds and organic zirconium compounds; boron compounds such as boron tri-n-butoxide and boric acid;
  • the compounding amount is as follows: Component (B) equivalent force Total SiO calculated 100 mass
  • Parts by weight preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 5 parts by mass. If the amount of the catalyst is too small, the effect of promoting hydrolysis may not be sufficient.
  • the diluent is used for diluting the component (B), and can suppress the condensation reaction.
  • the diluent is not particularly limited, but is preferably a diluent having a hydroxyl group.
  • glycol solvents such as ethylene glycol and propylene glycol; having 8 or more carbon atoms, preferably 12 or more, more preferably 18 or more Higher alcohols and the like can be mentioned.
  • these diluents can be used alone or in combination of two or more.
  • the amount of the mixture is calculated based on the total amount of SiO calculated from the components (B) and the like.
  • the amount is preferably from 100 to 50,000 parts by mass, more preferably from 150 to 10,000 parts by mass, and still more preferably from 200 to 5,000 parts by mass, per 2 parts by mass.
  • the release agent is suitably used when a mold release step is provided in mold molding or the like. That is, by the addition of the release agent, the molded article after molding is released smoothly without sticking to the mold.
  • the releasing agent include long-chain fatty acids such as stearic acid and behenic acid; Metal salts of long-chain fatty acids, such as zinc stearate and calcium stearate; ester waxes, such as carnauba tastes, montan wax, and partially saponified esters of montanic acid; long-chain fatty acid amides, such as stearylethylenediamide; polyethylene wax Paraffin and the like. These release agents can be used alone or in combination of two or more.
  • release agents are roughly classified into those that are blended into the raw material composition (internal release agent) and those that are applied to the inner surface of the mold before casting (external release agent).
  • internal release agent those that are applied to the inner surface of the mold before casting
  • release agent corresponds to an internal release agent.
  • the amount of the release agent is preferably 1 to 100 parts by mass of the component (A).
  • the above-mentioned raw material composition preferably does not contain water.
  • polyester resin or the like is used as the component (A)
  • water produced by the condensation reaction may remain in the production stage, and the raw material composition may contain a slight amount of water. It becomes.
  • the water content is more preferably 0.5 01-0. 5 mass 0/0.
  • the raw material composition containing each of the above components can be prepared by a known method, such as component (A), the type of curing agent, and the like.
  • thermosetting resin composition is thermoset in accordance with the properties and the like, and a thermosetting resin composition having high hydrophilicity and antifouling property on the surface can be formed.
  • thermosetting resin composition of the present invention the content of the above component (B) is
  • the surface When expressed as 2, it is 0.1 to 50 parts by mass, preferably 0.1 to 40 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the cured polymer.
  • the content of the component (B) By setting the content of the component (B) within this range, the surface can have permanent hydrophilicity and antifouling property. If the content of the component (B) is too small, it tends to be difficult to efficiently exhibit hydrophilicity and antifouling properties. On the other hand, if the content is too large, the gelled ridge produced by the reaction of the component) itself is contained, and as a result, the hydrophilicity tends to be reduced.
  • thermosetting resin composition of the present invention contains a cured polymer obtained by curing the component (A) and the component (B). However, depending on the production method and production conditions, the component (B) is homogeneous. Concentration distribution between the surface layer and the inside, especially when the There are cases. The same applies to the molded article of the present invention.
  • the composition (B) is oozed out by allowing the composition to stand in the air at a temperature around room temperature of about 10 to 30 ° C or under heating at about 30 to 50 ° C (bleeding). Then, the component (B) is hydrolyzed by, for example, contacting with water, whereby silanol groups can be efficiently produced, and hydrophilicity and antifouling properties are imparted.
  • the surface layer of the composition is rich in silanol group-containing compounds produced by hydrolysis of component (B), and as it is, hydrophilicity and antifouling properties on the surface Excellent.
  • thermosetting resin composition of the present invention when the thermosetting resin composition of the present invention is formed into a molded product or the like by processing such as cutting, the component (B) is oozed out on the renewed surface by the same method as described above (by bleeding out). ), A silanol group can be efficiently generated by hydrolysis, and hydrophilicity and antifouling property can be imparted or restored.
  • the bleed out of the component (B) on the renewed surface is the difference between the solubility parameter ( s ) of the cured polymer derived from the component (A) and the solubility parameter ( s ) of the component (B).
  • the above solubility parameter is based on the Smart equation.
  • thermosetting resin composition of the present invention comprises a thermosetting resin, at least one silane conjugate selected from alkoxysilanes and condensates thereof, and a curing agent. It is characterized by comprising a preparation step of preparing a raw material composition at a temperature of 10 ° C. or lower, and a curing step of heating and curing the raw material composition.
  • thermosetting resin and the silane compound constituting the raw material composition were respectively the same as the component (A) and the component (B). ) Can be applied.
  • the blending amount of the silane ligated product is such that the content in terms of SiO is 100 parts by mass of the cured polymer.
  • the above-mentioned curing agent is heated to a specific temperature (decomposition temperature of the curing agent) or more, it is thermally cured.
  • a specific temperature decomposition temperature of the curing agent
  • the resin can be cross-linked, and examples thereof include organic peroxides, azoi conjugates, and the like. These can be used alone or in combination of two or more.
  • organic peroxides examples include lauroyl peroxide, bis (4t-butylcyclohexyl) peroxydicarbonate, dimethoxybutyl butyl xydicarbonate, t-hexylsiloxyloxy-2-ethylhexanoate, and benzoyl peroxide.
  • Luperoxide 1,1 bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, acetylacetone peroxide, t-amylperoxybenzoate, methylethylketone Peroxide, cyclohexane peroxide, t-butyl perotate and the like can be mentioned.
  • the azo compounds include 2,2-azobisisobutymouth-tolyl and 2-phenylazo 2,4
  • the amount of the curing agent is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the thermosetting resin. Department.
  • the above-mentioned raw material composition can contain various additives exemplified above in predetermined amounts.
  • the method of compounding the additive is not particularly limited.
  • the catalyst may be dissolved or dispersed in a solvent or the like and then mixed with the raw material composition.
  • solvent examples include alcohols, glycol derivatives, hydrocarbons, esters, ketones, and ethers. These can be used alone or in combination.
  • alcohols examples include methanol, ethanol, n- propanol, isopropanol, n-butanol, isobutanol, and anhydrides of acetylacetone alcohol.
  • glycol derivatives examples include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether ether, propylene glycol, propylene glycol monomethyl methyl ether ether, propylene glycol monomethyl ethyl ether ether, and diethylene glycol monomethyl ether ether.
  • hydrocarbons examples include hexane, benzene, toluene, xylene, kerosene and the like.
  • esters examples include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl acetate acetate, ethyl acetate acetate, butyl acetate acetate and the like.
  • ketones include acetone, methylethyl ketone, methyl isobutyl ketone, and acetyl acetone.
  • ethers examples include ethyl ether, butyl ether, methoxyethanol, ethoxyethanol, dioxane, furan, and tetrahydrofuran.
  • the raw material composition preferably contains no water, but when it contains water, the water content is preferably 1% by mass or less.
  • the water content is more preferably 0.01 to 0.5% by mass.
  • the raw material composition can be used as a thermosetting resin composition, and is preferably stored at a temperature of 10 ° C or lower.
  • the raw material composition is prepared at a temperature of 10 ° C or less in the above-mentioned preparation step, and the preferred temperature is 0-10 ° C, more preferably 0-10 ° C. 5 ° C. If the preparation temperature of the raw material composition is too high, the silane compound may react with the curing agent, and the effect of blending the curing agent may be reduced.
  • the heating temperature is selected in consideration of the types and properties of the thermosetting resin and the curing agent contained in the raw material composition! You can do it.
  • the heating temperature is usually 20 ° C or higher, preferably 20-50 ° C.
  • the heating time is usually 0.5-5 hours, more preferably 113 hours.
  • thermosetting resin composition obtained by the method of the present invention is obtained by converting the silane conjugate to SiO conversion.
  • 100 parts by mass of the cured polymer preferably 0.1 to 50 parts by mass, more preferably 0.1 One 40 parts by mass, more preferably 0.5 to 30 parts by mass, particularly preferably 0.5 to 20 parts by mass.
  • thermosetting resin composition having excellent hydrophilicity and antifouling properties can be easily obtained.
  • the raw material components do not adhere to the mold, so that mold contamination is reduced.
  • a concentration distribution of the silane conjugate is generated between the surface layer and the inside, and in particular, the concentration may be high in the inside.
  • the raw material composition contains a trace amount of water derived from the thermosetting resin, and in the curing step, the silani conjugate moves toward the surface (the higher the heating temperature is, the faster), and Simultaneously with the oozing, hydrolysis with a small amount of water proceeds to produce a silanol group-containing conjugate.
  • thermosetting resin composition when this thermosetting resin composition is processed into a molded product or the like, the silane-bonded product oozes (bleeds out) on the renewed surface, and thus comes into contact with water when used.
  • the silani conjugate is hydrolyzed, silanol groups are efficiently generated, and hydrophilicity can be imparted to the surface.
  • the molded article of the present invention is characterized by containing the above thermosetting resin composition. That is, the molded article of the present invention may be a strong one only from the above-mentioned thermosetting resin composition, or may have another member such as a net on the surface and inside for the purpose of reinforcement or the like. You may. Further, depending on the production conditions, the molded article of the present invention has a case where the component (B) is uniformly dispersed and contains a concentration distribution between the surface layer and the inside. Sometimes.
  • the molded article of the present invention can have a shape according to the purpose, application, and the like.
  • the method for producing a molded article of the present invention provides a raw material composition (thermoplastic resin) containing a thermosetting resin, at least one silane compound selected from alkoxysilanes and condensates thereof, and a curing agent. (Fat composition) at a temperature of 10 ° C or lower, a casting step of injecting the raw material composition into a mold having a predetermined shape, and a curing step of heating and curing the raw material composition in the mold. And a step.
  • the molding method can be selected according to the form of the raw material composition (thermoplastic resin composition), the shape of the molded product, etc. Pressing method (SMC method, BMC method), hand lay-up method, spraying An up method, an injection method, a filament winding method, an autoclave method, a lamination method and the like can be mentioned.
  • the preparation step can be the same as the method described in the method for producing a thermosetting resin composition.
  • a raw material composition is poured into a mold having a predetermined shape according to the purpose, application, and the like.
  • the temperature of the mold in the casting step or the ambient temperature is not particularly limited, but is usually 10 ° C. or lower, preferably 0 to 10 ° C., which is preferably lower.
  • the mold is usually made of metal, but a mold whose inner surface is coated with a fluorine resin may be used. Further, an external mold release agent may be applied to the inner surface of the mold as necessary.
  • the process may proceed to the curing step immediately, or may be maintained for a certain period of time.
  • the member is previously installed at a predetermined position in the mold.
  • the curing step is performed at a heating temperature selected in consideration of the types and properties of the thermosetting resin and the curing agent contained in the raw material composition, as in the above-described method for producing the thermosetting resin composition. It can be carried out.
  • the heating temperature is usually 20 ° C or higher, preferably 20-50 ° C.
  • the heating time is usually 0.5 to 5 hours, more preferably 113 hours.
  • the molded product molded in the curing step is taken out of the mold in the demolding step.
  • This demolding may be performed when the temperature of the mold is in a heated state, or may be performed after the mold is cooled. Since the raw material composition according to the present invention is imparted with excellent releasability without blending a release agent, it has a desired shape, size, size, etc., and is excellent in appearance. Goods.
  • the molded product obtained by the method of the present invention is obtained by subjecting the silane conjugate to curing polymerization in terms of SiO.
  • 0.1 to 50 parts by mass more preferably 0.1 to 40 parts by mass, per 100 parts by mass of the body Parts by mass, more preferably 0.5 to 30 parts by mass, particularly preferably 0.5 to 20 parts by mass.
  • the molded article of the present invention may be left standing in the air at a temperature around room temperature of about 10 to 30 ° C, or may be appropriately heated to about 10 to 30 ° C to form a surface cover.
  • the silane drip oozes out (bleeds out). The degree of this bleed-out depends on the compatibility between the thermoset resin component and the silane compound, the type and properties (crystallinity, glass transition point) of the thermoset resin, and other additives (for example, fillers). Etc.).
  • bleed out can be promoted by blending a silane conjugate having a small molecule, a silane conjugate having an alkoxyl group having a small number of carbon atoms, and the like into the raw material composition.
  • the raw material composition contains a silane compound having a large molecule, a silane compound having an alkoxyl group having a large number of carbon atoms, etc. Out relatively slow. The latter case is remarkable when, for example, a filler such as zeolite is used. Therefore, the bleed-out can be controlled by appropriately adjusting the above factors, and as a result, the hydrophilicity and the antifouling property of the molded product can be adjusted.
  • the hydrophilicity can be evaluated by a contact angle with water, and can be preferably 60 degrees or less, more preferably 50 degrees or less, and further preferably 40 degrees or less.
  • the above-mentioned "contact angle” means that a water droplet of 0.2 ml is dropped on a horizontal surface of a molded article at 23 ° C in the air, and the dropping force is a contact angle measured by a known contact angle measuring method after 30 seconds. means.
  • the method of contact with the aqueous medium and the catalyst, the conditions are not particularly limited, and may be immersion, spraying, coating, or the like.
  • the surface of the molded article may be washed and dried with pure water or the like.
  • the drying method may be natural drying, hot air drying, drying by infrared heating, or the like.
  • the drying temperature is preferably 5 to 80 ° C, more preferably 10 to 70 ° C, and still more preferably 20 to 60 ° C.
  • the molded article of the present invention When the molded article of the present invention is used, all the surfaces thereof become silanol groups by hydrolysis. In some cases, some alkoxyl groups may remain.
  • the proportion of the exposed silanol groups is usually at least 20%, preferably at least 30%, more preferably at least 40%, based on the total amount of alkoxyl groups contained in the silane compound compounded.
  • the dirt can be lifted by digging under the dirt.
  • the surface of the molded product can be instantly cleaned. As a result, good appearance is always maintained.
  • the molded article of the present invention may exhibit hydrophilicity and antifouling properties on the surface by bleeding out the silane compound and further hydrolyzing the silane compound.
  • the radiation treatment can be performed by using a known device including an electron gun, an ultraviolet ray source, an ion gun, and the like.
  • the corona discharge treatment can also be performed using a known device. In any case, the processing conditions are not particularly limited!
  • surface modification is performed by irradiating an excimer lamp.
  • the above treatment (such as contact with water) may be performed.
  • the release agent of the present invention is an internal release agent that is blended in a raw material composition (thermoplastic resin composition) used for forming a thermosetting resin composition, and contains the silane compound.
  • the release agent may contain only the above-mentioned alkoxysilane, may contain only the above-mentioned condensate, or may contain these in combination.
  • the release agent of the present invention is used as a solution in a medium (anhydrous alcohol or the like) in which the silane compound is dissolved, and is used as a mixture with the glycol-based solvent exemplified as the diluent. You may.
  • the mold release agent of the present invention is easy to handle, provides a molded article having a good appearance without contaminating the mold, and does not lower the performance of the molded article.
  • thermosetting resin composition (i) A mold for molding whose inner surface is coated with tetrafluoroethylene is previously set at a low temperature (20 ° C), and the thermosetting resin composition (i) is poured into the mold and stored at a constant temperature of 2 ° C. It was left in the refrigerator for 15 hours. Thereafter, the temperature in the thermostatic storage is set at 30 ° C, and the thermosetting resin composition (i) is cured to obtain a plate-like molded body (100 mm long, 100 mm wide and 3 mm thick) (thermosetting resin composition). ) Was removed from the mold.
  • a hardening agent trade name “HB-PEM100”, manufactured by Huckle Born
  • the cured product of the thermosetting resin composition adheres to the inner surface of the mold. was evaluated.
  • the molded plate can be removed from the mold without resistance, If the surface is smooth by inspection, “ ⁇ ” indicates the mold force. Rated "X”.
  • thermosetting resin composition was produced and evaluated in the same manner as in Example 1 except that the resin composition (ii) was used. The results are shown in Table 1.
  • thermosetting resin composition (iii) into the mold and leave it in a constant temperature storage at 30 ° C. for 2 hours to cure the thermosetting resin composition (iii). After obtaining a plate-shaped molded product (thermosetting resin composition) having a width of 100 mm and a thickness of 3 mm, the resultant was demolded. Thereafter, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.
  • thermosetting resin composition was produced and evaluated in the same manner as in Example 3, except that the thermosetting resin composition (iv) in which the blending amount of the tetra-n-butyl silicate was 8 parts was used. The results are also shown in Table 1.
  • thermosetting resin composition was produced and evaluated in the same manner as in Example 1 except that the thermosetting resin composition (V) containing no tetra-n-butyl silicate was used. The results are shown in Table 1.
  • thermosetting resin composition was produced and evaluated in the same manner as in Example 3, except that the thermosetting resin composition (V) was used. The results are shown in Table 1.
  • an oil compound type silicone release agent (GE Toshiba Silicone Co., Ltd.) ) was prepared and evaluated in the same manner as in Comparative Example 1 except that the composition was uniformly applied to the inner surface of the mold. The results are shown in Table 1.
  • Comparative Examples 1 and 2 did not contain the silane conjugate, mold contamination was observed, and the mold releasability was insufficient.
  • the contact angles of the cured products were all 75 degrees, which was inferior in hydrophilicity.
  • Comparative Example 3 was an example in which an external mold release agent was used, and although mold release was good and mold release was good, the surface was poor in hydrophilicity.
  • Examples 1 and 2 are examples in which a thermosetting resin composition was prepared at 2 ° C., and until the curing of the thermosetting resin composition started, the silylated conjugate and the curing agent reacted. Therefore, the blended silani ligated product could be contained as it was.
  • thermosetting resin composition was prepared at 23 ° C. At the time of preparation, the silane compound and the curing agent contained in the thermosetting resin composition slightly reacted, However, the contact angles are 58 degrees and 55 degrees, respectively, and the effect is practically recognized.
  • thermosetting resin composition and the molded article of the present invention have permanent hydrophilicity and antifouling properties, they can be used in civil engineering and architectural structures such as beams, houses, buildings, transportation equipment such as automobiles, and home appliances. For products, windows, signs, etc. that are installed outdoors, or for the components that make up these It can be applied to the way.
  • it also has the property of exhibiting permanent hydrophilicity and antifouling properties by hydrolysis, so it can be used as a ⁇ water-around '' product that comes into contact with water, a product that is installed outdoors, and It can be used suitably for the parts of.
  • it is suitable for housing and housing-related parts such as artificial marble, flooring and wall materials for wash counters, kitchen counters, bathtubs, toilet members, and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition thermodurcissable et un article formé présentant une hydrophilicité permanente et une propriété antisalissure sur la surface. L'invention concerne également des procédés destinés à produire efficacement une composition thermodurcissable et un article formé présentant ces propriétés. L'invention se rapporte en outre à un agent de démoulage. Un procédé destiné à produire cette composition de résine thermodurcissable comprend une étape de préparation consistant à préparer une composition de matière brute contenant une résine thermodurcissable, au moins un composé silane choisi parmi des alcoxysilanes et des condensés correspondants, et un agent de durcissement, à une température inférieure ou égale à 10 °C, ainsi qu'une étape de durcissement consistant à durcir la composition de matière brute par chauffage. Par conséquent, on peut obtenir une composition de résine thermodurcissable contenant entre 0,1 et 50 parties en masse du composé silane en termes de SiO2 pour 100 parties en masse du polymère durci.
PCT/JP2004/019256 2003-12-25 2004-12-22 Composition de resine thermodurcissable et son procede de production, article forme et son procede de production, et agent de demoulage WO2005063894A1 (fr)

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JP2003-431420 2003-12-25

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09208839A (ja) * 1996-02-07 1997-08-12 Dainippon Ink & Chem Inc 熱硬化性樹脂組成物
JPH09241424A (ja) * 1996-03-13 1997-09-16 Shin Etsu Chem Co Ltd 樹脂組成物及びその製造方法並びに人工大理石
JPH11293013A (ja) * 1998-04-08 1999-10-26 Nippon Paint Co Ltd プラスチック成形体の表面処理方法及びプラスチック成形体
JP2000109709A (ja) * 1998-10-06 2000-04-18 Hitachi Ltd 熱硬化性樹脂材料およびその製造方法
JP2002322343A (ja) * 2001-04-24 2002-11-08 Hitachi Chem Co Ltd 熱硬化性樹脂組成物及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09208839A (ja) * 1996-02-07 1997-08-12 Dainippon Ink & Chem Inc 熱硬化性樹脂組成物
JPH09241424A (ja) * 1996-03-13 1997-09-16 Shin Etsu Chem Co Ltd 樹脂組成物及びその製造方法並びに人工大理石
JPH11293013A (ja) * 1998-04-08 1999-10-26 Nippon Paint Co Ltd プラスチック成形体の表面処理方法及びプラスチック成形体
JP2000109709A (ja) * 1998-10-06 2000-04-18 Hitachi Ltd 熱硬化性樹脂材料およびその製造方法
JP2002322343A (ja) * 2001-04-24 2002-11-08 Hitachi Chem Co Ltd 熱硬化性樹脂組成物及びその製造方法

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