JP4667017B2 - Curable resin composition containing colloidal silica-containing monomer and cured resin - Google Patents

Description

The present invention relates to a colloidal silica-containing monomer used in producing a coating agent or molding material having high hardness, high elasticity, and high heat resistance, and a curable resin composition mainly composed of the colloidal silica-containing monomer. And a cured resin product thereof.
Specifically, by reacting colloidal silica with a compound containing a (meth) acryloyl group and an isocyanate group in the molecule, the hydroxyl group of colloidal silica and the isocyanate group of the compound are reacted and bonded via a urethane bond. Cured resin obtained by homopolymerizing a curable resin composition containing a colloidal silica-containing monomer, or curable by mixing a curable resin composition containing a colloidal silica-containing monomer and a polymerizable compound resin cured product obtained resin composition copolymerized with, and, among the compounds having two or more isocyanate groups in the molecule, obtained by reacting a compound having at least one isocyanate group polymerizable unsaturated group a polymerizable unsaturated group introduced isocyanate compound, an average particle diameter of 100nm or less of the colloidal silica dispersed in an organic solvent And in a temperature range of 0 ° C. to 80 ° C., homopolymerization curable resin composition comprising a colloidal silica-containing monomer comprising an isocyanate group of a hydroxyl group and the isocyanate compound of the colloidal silica is bound via urethane bonds It relates to a cured resin obtained by copolymerizing a cured resin composition obtained by mixing a curable resin composition containing a colloidal silica-containing monomer and a polymerizable compound.

  Conventionally, various methods of mixing inorganic compounds have been attempted as means for improving the elasticity, hardness, and heat resistance of organic resins.

  For example, the compositions described in JP-B-4-48832, JP-B-5-40796, JP-A-5-287217, JP-A-6-199917, JP-B-7-94620, and JP-A-6-322036. In the manufacturing method of the product, colloidal silica and an organic resin or a monomer thereof are mixed and then combined by polymerization or heteroaggregation. However, these composite compositions are effective in modifying the surface condition and the like, but cannot improve the elasticity, hardness, and heat resistance of the molded product itself.

  JP-A-11-124501 and JP-A-10-45867 disclose a composite resin in which a blocked isocyanate or an amino resin and an organosilica sol are reacted with a polyol resin. It has been difficult to achieve both elasticity and high hardness.

Furthermore, in the field of radiation curable coatings, Japanese Patent Application Laid-Open Nos. 2002-235018, 2002-69333, 2002-67238, and 2001-113649 disclose that two or more ethylenic polymers in a dispersed state. Although a film obtained by radiation-curing a composition containing a saturated group, polyisocyanate and colloidal silica has been disclosed, in the production of this type of film, it is difficult to control at the time of curing, polymerization in a solution state or There is a problem that it cannot be obtained by a simple production method such as emulsion polymerization.
As a UV curable resin similar to the above, JP-A 09-157315 discloses a urethane acrylic monomer having a (meth) acryloyloxy group in one molecule and an acrylic monomer having a hydroxyl group, a cyclic ether bond and a chain ether bond. In this composition, colloidal silica is dispersed in urethane (meth) acrylate, and colloidal silica and urethane (meth) acrylate are disclosed. Therefore, the desired high elasticity and high heat resistance cannot be obtained.

  The composition described in JP-A-10-298265 disperses a silica-based polycondensate obtained by hydrolysis and polycondensation of colloidal silica and a specific silane compound in a hydroxyl group-containing radical polymerizable vinyl compound. A hydroxyl group-containing radical-polymerizable vinyl compound and a compound having two or more isocyanate groups in the molecule to give a urethane bond-containing radical-polymerizable vinyl compound. Silica-based polycondensates obtained by hydrolysis and polycondensation of silane compounds are difficult to control, and the reproducibility of the molecular weight of compounds centering on target hydroxyl group-containing radical polymerizable vinyl compounds is difficult. Therefore, desired high elasticity and high heat resistance cannot be obtained.

Japanese Patent Publication No. 4-48832 Japanese Patent Publication No. 5-40796 Japanese Patent Laid-Open No. 5-287217 JP-A-6-199917 Japanese Patent Publication No. 7-94620 JP-A-6-322036 JP-A-11-124501 Japanese Patent Laid-Open No. 10-45867 JP 2002-233501 A JP 2002-69333 A JP 2002-67238 A JP 2001-113649 A JP 09-157315 A JP-A-10-298265

  An object of the present invention is a resin cured product having high hardness, high elasticity, and high heat resistance that cannot be obtained by an organic compound alone or an inorganic compound alone, and cannot be obtained by mixing an organic compound and an inorganic compound as described above. Is to provide.

As a result of diligent research to solve the above problems, the present inventors have found that colloidal silica formed by urethane bonding of colloidal silica dispersed in an organic solvent and a compound containing a (meth) acryloyl group and an isocyanate group in the molecule. A curable resin composition containing a silica-containing monomer, or a colloidal silica and an isocyanate compound in which a polymerizable unsaturated group is introduced into at least one isocyanate group of a polyisocyanate having two or more isocyanate groups in the molecule. Resin curing obtained by using a curable resin composition containing a combined colloidal silica-containing monomer, polymerizing alone or copolymerizing a curable resin composition that is a mixture of this and a polymerizable compound We have found that the product is excellent in high elasticity, high hardness and high heat resistance.

  As described above in detail, since the present invention uses a monomer as a raw material, the molecular design is easy, and the obtained cured product is not a single organic synthetic resin or a material in which colloidal silica is simply dispersed. Various coating materials that have high elasticity, high hardness, and excellent heat resistance that cannot be obtained, and that can retain high transparency while containing colloidal silica. And molding materials can be realized.

The colloidal silica used in the present invention is not particularly limited, and various commercial products having an average particle diameter of 100 nm or less and an organic solvent as a dispersion medium can be used. When colloidal silica having a larger particle size is used, not only storage stability is deteriorated, but there is a problem that the transparency of the obtained cured product is lowered, and the good elasticity intended in the present invention, Since hardness and heat resistance cannot be expressed at the same time, those having an average particle diameter of 5 to 50 nm are more preferable.
Here, as for colloidal silica, it is desirable to use colloidal silica having a hydrophobic group dispersible in an organic solvent in which a part of hydroxyl groups present on the silica surface is chemically modified. More preferably, a hydrophobic organic material having a water solubility of 0.1 to 12% by weight, wherein a part of hydroxyl groups on the surface of colloidal silica is modified with a silylating agent such as a disiloxane compound and / or a monoalkoxysilane compound. It is desirable that it is colloidally dispersed in a solvent.

Examples of the organic solvent used as a dispersion medium for colloidal silica include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, n-butyl acetate, diisopropyl ether, and dibutyl ether.
Moreover, as a compound containing the (meth) acryloyl group and isocyanate group used for the colloidal silica containing monomer which concerns on this invention, acryloyl isocyanate, methacryloyl isocyanate, acrylic acid 2-isocyanate ethyl, methacrylic acid 2-isocyanate Examples include natoethyl.
Here, the colloidal silica colloidally dispersed as described above and the compound containing the (meth) acryloyl group and the isocyanate group are mixed and stirred to react the hydroxyl group remaining on the surface of the colloidal silica with the isocyanate group. The temperature during the treatment is preferably 0 ° C. to 80 ° C., more preferably a temperature range of 10 ° C. to 30 ° C., and the reaction can actually be performed at a temperature of about 20 ° C.

Examples of the compound containing two or more isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1 , 5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane triisocyanate, 3, 3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-toe Methyl hexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate 2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, trimethylolpropane adduct of triethylene diisocyanate, isocyanurate of triethylene diisocyanate, diphenylmethane-4,4'- Diisocyanate oligomer, hexamethylene diisocyanate biuret, hexamethylene diisocyanate isocyanurate, hexamethyl The diisocyanate uretdione, isocyanurate and the like of isophorone diisocyanate.
Moreover, these polyisocyanates can be used individually or in combination of 2 or more types.

The compound having a polymerizable unsaturated group to be introduced into at least one isocyanate group in the polyisocyanate includes a polymerizable unsaturated compound having a hydroxyl group, a polymerizable unsaturated compound having a carboxyl group, and a polymerizable compound having an amino group. Examples include unsaturated compounds and polymerizable compounds having an epoxy group.
Specifically, examples of the polymerizable unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- Phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) Acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol pen Data (meth) acrylate.
Examples of the polymerizable unsaturated compound having a carboxyl group include (meth) acrylic acid, itaconic acid, cinnamic acid, maleic acid, fumaric acid, 2- (meth) acryloxypropylhexahydrogen phthalate, 2 -Unsaturated aliphatic carboxylic acids such as (meth) acryloxyethyl hexahydrogen phthalate; 2- (meth) acryloxypropyl phthalate, 2- (meth) acryloxypropyl ethyl phthalate, etc. And unsaturated aromatic carboxylic acids.
Furthermore, examples of the polymerizable unsaturated compound having an amino group include (meth) acrylamide, 2-acrylamidoethylamine, 3-methacrylamidopropylamine, 3-crotonamide-3,3-dimethylpropylamine, allylamine, isopentenyl. Examples include amine, 5-hexenylamine, 11-dodecenylamine, vinyloxyethylamine, vinyl oxide decylamine, allyloxypropylamine, 2-methylallyloxyhexylamine, and vinyloxy- (2-hydroxy) butylamine.
Examples of the polymerizable compound having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 9,10-epoxystearyl (meth) acrylate, methyl glycidyl (meth) acrylate, Examples include 3,4-epoxycyclohexylmethyl (meth) acrylate.
In addition, these compounds can be used individually or in combination of 2 or more types.
In the case where the polyisocyanate is n-functional (n ≧ 2), when the polymerizable unsaturated group is introduced into the polyisocyanate, n mole of the polyisocyanate and the polymerizable unsaturated compound (n− 1) It is desirable to react with mol. In this case, the molar ratio of the polymerizable unsaturated compound and the polyisocyanate is (n-1) / n.
The reaction temperature for introducing the polymerizable unsaturated group into the polyisocyanate is preferably 0 ° C. to 80 ° C., more preferably a temperature range of 10 ° C. to 30 ° C. The reaction can be carried out at a temperature around 0 ° C.

  In order to promote the reaction for introducing a polymerizable unsaturated group into the polyisocyanate and the reaction between the colloidal silica and the isocyanate group, a catalyst may be added. For example, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] It is preferable to use 0.01 to 1 part by weight of a urethanization catalyst such as octane with respect to 100 parts by weight of the total amount of reactants.

Further, in the reaction of the isocyanate group with colloidal silica, methyl alcohol, ethyl alcohol, isopropyl alcohol are used to block the unreacted isocyanate group while confirming the reaction of the isocyanate group by infrared absorption spectroscopy (IR) or the like. You may add alcohols, such as these, and the compound which can react with the said isocyanate group. The reaction in this case can be performed at a temperature of 100 ° C. or lower.

In addition, as a polymerizable compound to be mixed and copolymerized with a curable resin composition containing a colloidal silica-containing monomer, acrylic acid or methacrylic acid alkyl ester, urethane (meth) acrylate, unsaturated nitrile monomer, unsaturated It is a compound having a reactive double bond in the molecular chain such as carboxylic acid, amide group-containing monomer, methylol group-containing monomer, alkoxymethyl group-containing monomer, epoxy group-containing monomer, polyfunctional monomer, vinyl ester, olefin. Examples of alkyl esters of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl Examples include methacrylate, isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl itaconate and the like. Radical polymerizable monomers other than those described above may be combined as necessary. Amide group-containing monomers such as acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide, methylol group-containing monomers such as N-methylol acrylamide, N-methylol methacrylamide, dimethylol acrylamide, dimethylol Methacrylamide, alkoxymethyl group-containing monomers such as N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, Methyl glycidyl acrylate, methyl glycidyl methacrylate, polyfunctional monomer Divinylbenzene, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, penta Erythritol tetraacrylate, pentaerythritol tetramethacrylate, mono or diester of α, β-ethylenically unsaturated dicarboxylic acid such as mono or dibutyl maleate, mono or dioctyl fumarate, vinyl ester such as vinyl acetate, vinyl propionate, olefin such as butadiene, Isoprene, chlorine-containing vinyl monomers such as vinyl chloride, vinylidene chloride, chloride Or the like can be mentioned Puren. Other examples include styrene and styrene derivatives. These vinyl compounds may be used alone or in combination of two or more.

The homopolymerization of the curable resin composition containing the colloidal silica monomer or the copolymerization with the polymerizable compound can be reacted in a solution. Examples of the solvent used include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate and carbitol acetate, ether compounds such as dibutyl ether, and alcohol solvents such as n-butanol and isobutanol can be used. A mixed solvent of the above solvents can also be used.

Examples of the copolymerization initiator include peroxides and azobis compounds. Examples of peroxides include dibutyl peroxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and the like. 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis ( 2-methylpropionamidine) dihydrochloride and the like.
Here, when the polymerization is carried out using the above-described polymerization initiator, the polymerization reaction temperature may be 100 ° C. or lower.

  Moreover, radiation polymerization is also possible, and it is also possible to use a radiation polymerization initiator. Examples of the radiation polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chloro. Benzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chloro Oxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like, and as commercially available products Irgacure 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61 (above, manufactured by Ciba-Geigy); Lucirin LR8728 ( BASF); Darocur 1116, 1173 (above, Merck); Ubekrill P36 (UCB), and the like.

  Further, microgel polymerization, emulsion polymerization, dispersion polymerization, suspension polymerization, and the like are possible. In two-stage swelling polymerization, there are polymerization methods such as emulsion monomer premix dropping or monomer direct dropping or charging in a monomer polymerization system in advance.

  Surfactants that can be used in these polymerizations include ionic and nonionic surfactants, and examples of ionic surfactants include anionic surfactants, cationic surfactants, and amphoteric surfactants. There are no particular restrictions. Examples of the anionic surfactant include fatty acids, higher alcohol sulfates, liquid fatty oil sulfates, aliphatic amines and amide sulfates, fatty alcohol phosphates, dibasic fatty acid esters. Examples of cationic surfactants include primary amine salts, secondary amine salts, tertiary amine salts, quaternary ammonium salts, and the like. Examples of the amphoteric surfactant include a carboxylate salt type, a sulfate ester salt type, a sulfonate salt type, and a phosphate ester salt. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, and the like. In addition to the non-reactive surfactants listed above, reactive surfactants can also be used. The reactive surfactant has a radical polymerizable functional group in one molecule and has one or more functional groups selected from a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid group, and a sulfonic acid ester base, Or it has a radically polymerizable functional group in one molecule and has polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene composite type alkyl ether or alcohol. These surfactants may be used alone or in combination with two or more.

  In emulsion polymerization, pH adjusters such as sodium hydrogen phosphate and sodium hydrogen carbonate, molecular weight adjusters such as t-dodecyl mercaptan, n-dodecyl mercaptan and low molecular halogen compounds, chelating agents, plasticizers, and organics as necessary. Solvents and the like can be added in the first, middle and later stages of emulsion polymerization. The polymerization temperature is, for example, 0 to 150 ° C., particularly preferably 30 to 90 ° C., and the polymerization is performed in an inert atmosphere, under normal pressure, or under pressure as necessary. As needed, natural latex such as acrylic latex, styrene butadiene latex, chloroprene latex, urethane latex, ethylene vinyl acetate latex, vinyl acetate latex, rosin, rosin derivative, terpene resin, terpene derivative, etc. And petroleum resin, styrene resin, coumarone indene resin, phenol resin, xylene resin synthetic resin tackifier, liquid nitrile rubber, silicone rubber and other rubber components, barium hydroxide, magnesium hydroxide, Besides extender pigments such as aluminum hydroxide, silicon oxide, titanium oxide, calcium sulfate, barium sulfate, calcium carbonate, basic zinc carbonate, basic lead carbonate, silica sand, clay, talc, silica compound, titanium dioxide, antimony trioxide , (Bactericides, preservatives Defoamers, plasticizers, flow control agents, thickeners, pH modifiers, surfactants, coloring pigments, extender pigments, may be added to anticorrosive pigments and the like). Furthermore, (inorganic acid, low molecular organic acid, carboxylic acid polymer, etc.) may be added to achieve a balance between pot life and room temperature curability. Moreover, you may add antioxidant and a ultraviolet absorber for the purpose of light resistance improvement.

  Hereinafter, a description will be given based on specific examples. The test methods employed in the examples and comparative examples are as follows.

[Test method]
Mechanical test: JISK7171 compliant Vickers hardness: JISZ2244 compliant Heat resistance: Dynamic Mechanical Analysis (DMA)
DMA measuring device for DMS-200 manufactured by Seiko Electronics Industry Co., Ltd.
Measurement of Glass Transition Temperature (Tg) by Light Transmittance: UV / Vis Spectrometer V-5 manufactured by JASCO Corporation
20 is used to measure the transmittance (%) of each cured product (sample thickness 2 mm) at a wavelength of 500 nm.

  2-methacryloyloxyethyl isocyanate (MOI) (molecular weight 155 / manufactured by Showa Denko KK) and ethyl acetate solvent-dispersed colloidal silica (SiO2 component 30%, average particle size 20 nm / manufactured by Nissan Chemical Co., Ltd.) 400 0.05 parts by weight of dilauric acid di-n-butyltin (DBTDL) as a catalyst was added and stirred at room temperature (20 ° C.) for 24 hours. The reaction of the isocyanate group was confirmed by infrared spectroscopy (IR) (confirmation of disappearance of the isocyanate group and the presence of the urethane bond), and the solvent was removed with an evaporator to obtain a colloidal silica-containing monomer. Next, 1 part by weight of benzoyl peroxide (BPO) as an initiator was added to 100 parts of the colloidal silica-containing monomer, and bulk polymerization was carried out at 80 ° C. for 12 hours to obtain the test piece (resin cured product) of Example 1. Obtained.

2-Methacryloyloxyethyl isocyanate (MOI) (molecular weight 155 / manufactured by Showa Denko KK) and 100 parts by weight of methyl isobutyl ketone (MIBK) solvent-dispersed colloidal silica (SiO2 component 30%, average particle size 20 nm / Nissan Chemical Co., Ltd.) (Manufactured) 330 parts by weight, 0.04 part by weight of di-n-butyltin dilaurate (DBTDL) as a catalyst was added, and the mixture was stirred at room temperature (20 ° C.) for 24 hours. To the reaction solution, MOI and equimolar or more isopropanol were added and stirred for 3 hours. The reaction of the isocyanate group was confirmed by IR (confirmation of the disappearance of the isocyanate group and the presence of the urethane bond), and an unreacted isopropyl alcohol and an evaporator. The solvent was removed to obtain a colloidal silica-containing monomer. Next, 20 parts by weight of MMA and 1 part by weight of benzoyl peroxide (BPO) initiator were added to 80 parts by weight of the colloidal silica-containing monomer, and bulk polymerization was carried out at 80 ° C. for 12 hours to obtain the test piece (resin of Example 2 Cured product) was obtained.

  59 parts by weight of equimolar 2-hydroxyethyl methacrylate (HEMA) and 0.07 parts by weight of DBTDL as a catalyst were added to 100 parts by weight of isophorone diisocyanate (IPDI) to obtain a HEMA-IPDI monomer. This monomer was added to 530 parts by weight of MIBK-dispersed colloidal silica (SiO2 component 30%, average particle size 20 nm / Nissan Chemical Co., Ltd.) and stirred for 24 hours at room temperature (20 ° C.), and then isopropyl alcohol was added. The reaction of the isocyanate group was confirmed by IR (confirmation of disappearance of the isocyanate group and the presence of the urethane bond), and unreacted isopropyl alcohol was removed with an evaporator to obtain a colloidal silica-containing monomer. 1 part by weight of BPO as an initiator was added to 100 parts by weight of the obtained colloidal silica-containing monomer, and bulk polymerization was performed at 80 ° C. for 12 hours to obtain a test piece (cured resin product) of Example 3.

  59 parts by weight of equimolar 2-hydroxyethyl methacrylate (HEMA) and 0.07 parts by weight of DBTDL as a catalyst were added to 100 parts by weight of isophorone diisocyanate (IPDI) to obtain a HEMA-IPDI monomer. This monomer was added to 530 parts by weight of MIBK-dispersed colloidal silica (SiO2 component 30%, average particle size 20 nm / Nissan Chemical Co., Ltd.) and stirred for 24 hours at room temperature (20 ° C.), and then isopropyl alcohol was added. The reaction of the isocyanate group was confirmed by IR (confirmation of disappearance of the isocyanate group and the presence of the urethane bond), and unreacted isopropyl alcohol was removed with an evaporator to obtain a colloidal silica-containing monomer. 20 parts by weight of MMA and 1 part by weight of BPO as an initiator were added to 80 parts by weight of the obtained colloidal silica-containing monomer, and bulk polymerization was performed at 80 ° C. for 12 hours to obtain a test piece (cured resin product) of Example 4. It was.

(Comparative Example 1)
100 parts by weight of 2-methacryloyloxyethyl isocyanate (MOI) (molecular weight 155 / manufactured by Showa Denko KK) and equimolar or more of isopropyl alcohol, and 0.04 parts by weight of DBTDL as a catalyst were added. The reaction of the isocyanate group was confirmed by IR (confirmation of disappearance of the isocyanate group and the presence of a urethane bond), and unreacted isopropyl alcohol was removed by an evaporator to obtain a urethane acrylic monomer. 1 part by weight of benzoyl peroxide (BPO) as an initiator was added to 100 parts of this urethane acrylic monomer, and bulk polymerization was carried out at 80 ° C. for 12 hours to obtain a test piece (cured resin product) of Comparative Example 1.

(Comparative Example 2)
100 parts by weight of 2-methacryloyloxyethyl isocyanate (MOI) (molecular weight 155 / manufactured by Showa Denko KK) and equimolar or more of isopropyl alcohol, and 0.04 parts by weight of DBTDL as a catalyst were added. The reaction of the isocyanate group was confirmed by IR (confirmation of disappearance of the isocyanate group and the presence of a urethane bond). Thereafter, 30 parts by weight of methyl isobutyl ketone (MIBK) solvent-dispersed colloidal silica (SiO2 component 30%, average particle size 20 nm / manufactured by Nissan Chemical Co., Ltd.) is mixed, unreacted isopropyl alcohol and solvent are removed with an evaporator, and urethane acrylic is removed. A mixture of monomer and colloidal silica was obtained. To 80 parts by weight of this mixture, 20 parts by weight of MMA and 1 part by weight of initiator benzoyl peroxide (BPO) were added, and bulk polymerization was carried out at 80 ° C. for 12 hours to obtain a test piece (cured resin product) of Comparative Example 2.

(Comparative Example 3)
59 parts by weight of equimolar 2-hydroxyethyl methacrylate (HEMA) and 0.07 parts by weight of DBTDL as a catalyst were added to 100 parts by weight of isophorone diisocyanate (IPDI) to obtain a HEMA-IPDI monomer. Thereafter, equimolar or more isopropyl alcohol was added to IPDI, and the reaction of isocyanate groups was confirmed by IR (disappearance of isocyanate groups and presence of urethane bonds were confirmed). 530 parts by weight of MIBK-dispersed colloidal silica (SiO2 component 30%, average particle size 20 nm / manufactured by Nissan Chemical Co., Ltd.) was added to the urethane acrylic monomer and stirred at room temperature for 24 hours. Unreacted isopropyl alcohol was removed with an evaporator to obtain a mixture of urethane acrylic monomer and colloidal silica. 20 parts by weight of MMA and 1 part by weight of BPO as an initiator were added to 80 parts by weight of the obtained mixture, and bulk polymerization was performed at 80 ° C. for 12 hours to obtain a test piece (cured resin product) of Comparative Example 3.

(Comparative Example 4)
59 parts by weight of equimolar 2-hydroxyethyl methacrylate (HEMA) and 0.07 parts by weight of DBTDL as a catalyst were added to 100 parts by weight of isophorone diisocyanate (IPDI) to obtain a HEMA-IPDI monomer. After this, add equimolar or more of isopropyl alcohol to IPDI, confirm the reaction of the isocyanate group by IR (confirm the disappearance of the isocyanate group and the presence of the urethane bond), and remove the unreacted isopropyl alcohol with an evaporator. A urethane acrylic monomer was obtained. 20 parts by weight of MMA and 1 part by weight of BPO as an initiator were added to 80 parts by weight of the obtained urethane acrylic monomer, and bulk polymerization was performed at 80 ° C. for 12 hours to obtain a test piece (cured resin product) of Comparative Example 4. .

  The test results are shown in Table 1.

Table 1 Properties of cured resin Sample Mechanical test Vickers hardness Heat resistance Permeability
Elastic modulus (GPa) Tg (℃) (%)
Example 1 4.4 32.1 180 88.2
Example 2 6.0 38.9 160 86.3
Example 3 5.4 39.7 150 89.3
Example 4 6.3 38.5 130 89.7
Comparative Example 1 3.3 23.0 80 88.7
Comparative Example 2 3.9 27.8 90 83.1
Comparative Example 3 3.7 27.5 100 85.3
Comparative Example 4 3.3 25.7 90 89.1

  When paying attention to the elastic modulus measured in the mechanical test in Table 1, the elastic modulus of the cured resin products of Comparative Examples 1 to 4 is a value of 3.9 (GPa) or less. On the other hand, in the resin cured products of Examples 1 to 4, the elastic modulus is a value of 4.4 (GPa) or more. This is because in Comparative Examples 1 and 4, the colloidal silica is not contained and only the resin matrix is used. In Comparative Examples 2 and 3, the colloidal silica is merely dispersed in the resin matrix. In contrast, the elastic modulus is low and the mechanical properties are poor, whereas in Examples 1 to 4, a urethane bond is formed between the hydroxyl group and the isocyanate group of colloidal silica. It is thought that the characteristic was obtained.

  Further, focusing on the Vickers hardness in Table 1, in Comparative Examples 1 to 4, only a value of 28 or less was obtained, whereas in Examples 1 to 4, a value of 32 or more was obtained. Thus, the higher hardness is obtained with the resin cured products according to Examples 1 to 4, as in the case described above, in Examples 1 to 4, a urethane bond is formed between the hydroxyl group and the isocyanate group of colloidal silica. This is thought to be based on the formation of

  Furthermore, when focusing on the glass transition temperature (Tg) measured as an index representing heat resistance, the glass transition temperatures in Comparative Examples 1 to 4 are as low as 100 ° C. or lower and inferior in heat resistance. It turns out that the glass transition temperature in Examples 1-4 is as high as 130 degreeC or more, and is excellent in heat resistance. Thus, the resin cured products according to Examples 1 to 4 are more excellent in heat resistance, as in the case described above, in Examples 1 to 4, urethane between the hydroxyl group and the isocyanate group of colloidal silica. This is thought to be based on the fact that a bond is formed.

Further, focusing on the light transmittance in Table 1, Comparative Examples 1 and 4 do not contain colloidal silica, and thus high transmittances of 88.7% and 89.1% are obtained. In Examples 2 and 3, since the colloidal silica is contained in the resin matrix in a dispersed state, the transmittance tends to be as low as 83.1% and 85.3%, respectively.
Moreover, in Examples 1-4, since colloidal silica does not exist in a dispersed state, it exists uniformly in a state in which a urethane bond is formed between a hydroxyl group and an isocyanate group of colloidal silica. It can be seen that the rates are as high as 88.2%, 86.3%, 89.3%, and 89.7%, respectively. These transmittance values are higher than the transmittance values in Comparative Examples 2 and 3 in which colloidal silica is present in a dispersed state, and are equivalent to the values in Comparative Examples 1 and 4 in which no colloidal silica is contained. It has become. Thus, in Examples 1 to 4, it is clear that the same transparency as Comparative Examples 1 and 4 can be ensured despite the presence of colloidal silica.

Claims (10)

Colloidal silica dispersed in an organic solvent with an average particle size of 100 nm or less and a compound containing a (meth) acryloyl group and an isocyanate group in the molecule in a temperature range of 0 ° C. to 80 ° C. and the compound And an isocyanate group of
A curable resin containing a colloidal silica-containing monomer, wherein if necessary, a compound capable of reacting with an isocyanate group is added and an unreacted isocyanate group in the compound that has not reacted with a hydroxyl group of the colloidal silica is blocked. Composition.   A curable resin composition obtained by mixing the curable resin composition containing the colloidal silica-containing monomer of claim 1 and a polymerizable compound.   A cured resin obtained by homopolymerizing the curable resin composition containing the colloidal silica-containing monomer according to claim 1.   A cured resin obtained by copolymerizing the curable resin composition containing the colloidal silica-containing monomer according to claim 1 and the polymerizable compound. A polymerizable unsaturated group-introduced isocyanate compound obtained by reacting at least one isocyanate group with a compound having a polymerizable unsaturated group among compounds having two or more isocyanate groups in the molecule, and dispersed in an organic solvent. A colloidal silica having an average particle size of 100 nm or less is bonded to a hydroxyl group of colloidal silica and an isocyanate group of the isocyanate compound via a urethane bond in a temperature range of 0 ° C. to 80 ° C.,
Curable resin containing colloidal silica-containing monomer, wherein the blocking unreacted isocyanate groups in the isocyanate compound that has not reacted with the hydroxyl groups of the colloidal silica with the addition of a compound capable of reacting with isocyanate groups as required Composition.   A curable resin composition obtained by mixing a curable resin composition containing the colloidal silica-containing monomer of claim 5 and a polymerizable compound.   A cured resin obtained by homopolymerizing the curable resin composition containing the colloidal silica-containing monomer according to claim 5.   A cured resin obtained by copolymerizing the curable resin composition containing the colloidal silica-containing monomer of claim 5 and the polymerizable compound.   The curable resin composition containing the colloidal silica-containing monomer according to claim 5, wherein the introduction of the polymerizable unsaturated group into the isocyanate group is performed by a reaction between an isocyanate group and a hydroxyl group, The curable resin composition and the resin cured product according to claim 7 or 8.   The curable resin composition containing a colloidal silica-containing monomer, wherein the colloidal silica-containing monomer has an average particle diameter in the range of 5 to 50 nm.