KR101075220B1 - Colloidal Silica Inclusion Monomer, Hardening Resin Composition And The Resin Cue Thing - Google Patents

Abstract

With respect to the high hardness, high elasticity, and high heat resistance required for the coating agent and the molding material, at the same time having high hardness, high elasticity, and high heat resistance not obtained from the organic compound alone, the inorganic compound alone, or the mixture of the organic compound and the inorganic compound, Provided is a resin cured product having high transparency.

Colloidal silica dispersed in an organic solvent and a compound containing a (meth) acryloyl group and an isocyanate group in the molecule is a colloidal silica-containing monomer, or a colloidal silica and a molecule in the molecule is bonded through a urethane bond The isocyanate compound which introduce | transduced the polymerizable unsaturated group into the at least 1 isocyanate of the polyisocyanate which has more than one isocyanate group superposed | polymerized independently, or this and a polymerizable compound using the colloidal silica containing monomer couple | bonded through the urethane bond. Copolymerize.

Description

Colloidal silica-containing monomer, curable resin composition and cured resin thereof {Colloidal Silica Inclusion Monomer, Hardening Resin Composition And The Resin Cue Thing}

The present invention relates to a colloidal silica-containing monomer used for producing a coating material having high hardness, high elasticity, and high heat resistance, and a molding material, and a curable resin composition containing the colloidal silica-containing monomer as a main component and its resin diameter. It's about cargo.

Specifically, a colloid formed by reacting a colloidal silica with a compound containing a (meth) acryloyl group and an isocyanate group in a molecule to bond the hydroxyl group of the colloidal silica and the isocyanate group of the compound through a urethane bond. Cured resin obtained by homopolymerizing a (colloidal) silica-containing monomer or a cured resin composition obtained by copolymerizing a curable resin composition obtained by mixing a colloidal silica-containing monomer and a polymerizable compound, and two or more present in the molecule. By reacting an isocyanate compound having a polymerizable unsaturated group with at least one isocyanate group and a colloidal silica in the isocyanate group, the hydroxyl group of the colloidal silica and the isocyanate group of the compound are urethane-bonded. It relates to a cured resin obtained by homopolymerizing a colloidal silica-containing monomer formed by bonding through a copolymer or a cured resin composition obtained by copolymerizing a curable resin composition obtained by mixing a colloidal silica-containing monomer and a polymerizable compound. .

Conventionally, various methods of mixing an inorganic compound have been performed as a means of improving elasticity, hardness, and heat resistance of an organic resin.

For example, the compositions described in JP-A 4-48832, JP-A 5-40796, JP-A-5-287217, JP-A 6-199917, JP-A 7-94620, and JP-A 6-322036. In the production method thereof, after the colloidal silica is mixed with the organic resin or the monomer, it has been complexed by polymerization or heteroaggregation. However, these composite compositions are effective in modifying the surface state and the like, but it is impossible to improve the elasticity, hardness, and water resistance of the molding itself.

Further, Japanese Patent Laid-Open Nos. 11-124501 and 10-45867 disclose composite resins for reacting a polyol resin with a block isocyanate or amino resin and an organic silica sol. However, such composite resins have high elasticity and high hardness. It was difficult to make them compatible.

In particular, in the field of radiation-curable coatings, Japanese Patent Application Laid-Open Nos. 2002-235018, 2002-69333, 2002-67238, and 2001-113649 disclose two or more ethylenically unsaturated groups and polyisocyanates in a dispersed state. Films obtained by radiation-curing a composition containing colloidal silica have been disclosed. However, in the production of this kind of film, it is difficult to control the curing. There is a problem that cannot be obtained.

In addition, Japanese Unexamined Patent Application Publication No. 09-157315 discloses an acrylic monomer having a urethane acryl monomer having a (meth) acryloyloxy group, a hydroxyl group, a cyclic ether bond, and a chain ether bond in one molecule. UV curable resin raw material compositions comprising and colloidal silica have been disclosed, but in such a composition, the colloidal silica is dispersed in urethane (meth) acrylate, and colloidal silica and urethane (meth) Since it does not involve a chemical bond with)), preferable high elasticity and high heat resistance cannot be obtained.

The composition described in JP 10-298265 A disperses a silica-based polycondensate obtained by hydrolyzing and polycondensing colloidal silica and a specific silane compound in a hydroxyl group-containing radically polymerizable vinyl compound, and containing a hydroxyl group. Although a composition is disclosed in which a radical polymerizable vinyl compound and a compound having two or more isocyanate groups in a molecule are added and reacted to form a urethane bond-containing radical polymerizable vinyl compound, a composition obtained by hydrolyzing and polycondensing a silane compound is disclosed. The silica-based polycondensate is difficult to control the reaction, and the reproducibility such as the molecular weight of the compound centered on the target hydroxyl group-containing radically polymerizable vinyl compound is difficult, and the desired high elasticity and high heat resistance are not obtained.

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

MEANS TO SOLVE THE PROBLEM The present inventors discovered that colloidal silica which the colloidal silica disperse | distributed in the organic solvent and the compound containing a (meth) acryloyl group and an isocyanate group in a molecule | numerator urethane bond is contained. By using a colloidal silica-containing monomer formed by a urethane bond between a monomer or a colloidal silica and at least one isocyanate group of a polyisocyanate having two or more isocyanate groups in a molecule, a polymerizable unsaturated group is introduced. It was discovered that the resin cured product obtained by superposing | polymerizing in or copolymerizing curable resin composition which is a mixture of this and a polymeric compound is excellent in high elasticity, high hardness, high heat resistance, etc.

Although it does not specifically limit as colloidal silica used for this invention, Various commercial items which have an average particle diameter of 100 nm or less and which use the organic solvent as a dispersion medium can be used. In the case of using colloidal silica having a larger particle diameter than this, not only the storage stability is deteriorated, but also the transparency of the resulting cured product is lowered, and at the same time, the good elasticity, hardness, and heat resistance of the present invention are at the same time. Since it cannot express, Preferably it is preferable that the average particle diameter is 5-50 nm.

Here, as the colloidal silica, it is preferable to use colloidal silica having a hydrophobic group which is partially chemically modified by a hydroxyl group present on the surface of silica and can be dispersed in an organic solvent. More preferably, a part of the hydroxyl groups on the surface of the colloidal silica is modified with a silylating agent such as a disiloxane compound and / or a monoalkoxysilane compound and the like, and the colloid in a hydrophobic organic solvent having a water solubility of 0.1 to 12% by weight. (colloidal) It is preferable to disperse.

In addition, as an organic solvent used as a dispersion medium of colloidal silica, it is preferable to use methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, ethyl acetate, n-butyl acetate, diisopropyl ether, dibutyl ether, or the like. Do.

Moreover, as a compound containing the (meth) acryloyl group and the isocyanate group used for the colloidal silica containing monomer which concerns on this invention, acryloyl isocyanate, methacryloyl isocyanate, 2-acrylic-acid isocyanate ethyl, methacrylic acid 2-isocyanate ethyl and the like.

Here, as described above, the colloidal silica in which the colloidal is dispersed and the compound containing the above-mentioned (meth) acryl group and isocyanate group are mixed and stirred, and the hydroxyl group remaining on the surface of the colloidal silica is mixed. As for the temperature at the time of making an isocyanate group react, 0 degreeC-80 degreeC is preferable, More preferably, the temperature range of 10 degreeC-30 degreeC is preferable, and can actually react at temperature around 20 degreeC.

As the compound containing two or more isocyanates, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1, 5-naphthalene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, 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, methylenebis (4-cyclohexyl isocyanate) , 2,2,4, -trimethylhexamethylene diisocyanate, bis (2-isocyanate ethyl) fumaric acid, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenation Diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, tetramethyl xylene diisocyanate, trimethylol propane of 2,5 (or 6) -bis (isocyanate methyl) -bicyclo [2.2.1] heptane, triethylene diisocyanate Adduct, isocyanurate of triethylene diisocyanate, oligomer of diphenylmethane-4,4'- diisocyanate, biuret of hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate, hexamethylene di Urethane, isocyanurate, isophorone diisocyanate, and the like.

Moreover, these polyisocyanate can also be used individually or in combination of 2 or more types.

The compound having a polymerizable unsaturated group 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, a polymerizable unsaturated compound having an amino group, and a polymerizable compound having an epoxy group. Etc.

Specifically, as a polymerizable unsaturated compound which has a hydroxyl group, 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, neoheptyl glycol mono (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, and the like.

Moreover, as a polymerizable unsaturated compound which has a carboxyl group, it is (meth) acrylic acid, itaconic acid, cinnamic acid, maleic acid, fumaric acid, 2- (meth) acryloxypropyl hexahydro phthalate, 2- ( Unsaturated aliphatic carboxylic acids such as meta) acryloxyethyl hexahydrophthalphthalate; Unsaturated aromatic carboxylic acids such as 2- (meth) acryloxypropyl phthalate and 2- (meth) acryloxypropyl ethyl phthalate.

On the other hand, as a polymerizable unsaturated compound which has an amino group, it is (meth) acrylamide, 2-acrylamide ethylamine, 3-methacrylamide propylamine, 3-crotonic acid amide-3,3-dimethylpropylamine, Allylamine, isopentenylamine, 5-hexenylamine, 11-dodecenylamine, vinyloxyethylamine, vinyloxydodecylamine, aryloxypropylamine, 2-methylaryloxyhexylamine, vinyloxy- (2- Hydroxy) butylamine and the like.

Moreover, as a polymeric compound which has an epoxy group, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl methyl (meth) acrylate, 9, 10- epoxy stearyl (meth) acrylate, Methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like.

In addition, these compounds can be used individually or in combination of 2 or more types.

Here, when the said polyisocyanate is n functional (n≥2), when introduce | transducing the said polymerizable unsaturated group with respect to this polyisocyanate, n mol of polyisocyanate and (n-1) mol of a polymerizable unsaturated compound are made to react. It is preferable. In this case, the molar ratio of the polymerizable unsaturated compound and polyisocyanate is set to (n-1) / n.

Moreover, as reaction temperature at the time of introducing the said polymerizable unsaturated group with respect to polyisocyanate, 0 degreeC-80 degreeC is preferable, More preferably, the temperature range of 10 degreeC-30 degreeC is preferable, and actually about 20 degreeC Can be reacted with temperature.

A catalyst may be added to promote the reaction for introducing the polymerizable unsaturated group into the polyisocyanate and the reaction of the colloidal silica with the isocyanate group. For example, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-butyl lauryl acid, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl- It is preferable to use 0.01-1 weight part of urethanization catalysts, such as 1, 4- diazabicyclo [2.2.2] octane, with respect to 100 weight part of total amounts of a reactant.

In addition, in the reaction between the isocyanate group and the colloidal silica, in order to block excess isocyanate groups while confirming the reaction of the isocyanate group by infrared absorption spectroscopy (IR) or the like, methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. It is preferable to add an alcohol and a compound which can react with the isocyanate group. Reaction in this case can be performed at the temperature of 100 degrees C or less.

Moreover, as a polymeric compound mixed and copolymerized with a colloidal silica containing monomer, the alkyl ester of acrylic acid or methacrylic acid, a urethane (meth) acrylate, an unsaturated nitrile monomer, an unsaturated carboxylic acid, the monomer containing an amino group, methyl It is a compound which has a reactive double bond in molecular chains, such as a monomer containing a roll group, the monomer containing an alkoxy methyl group, the monomer containing an epoxy group, a polyfunctional monomer, vinyl ester, and an olefin. Examples of alkyl esters of acrylic acid or methacrylic acid are 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 methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate , 2-ethylhexyl methacrylate, lauryl acrylate, and the like. Examples of unsaturated nitrile monomers include acrylonitrile, methacrylonitrile and the like. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, monoalkylitaconate, and the like. You may combine radical polymerizable monomers other than the above as needed. Examples of the monomer containing an amino group include acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimido, and methylol groups. Examples of the monomer containing N-methylol methacrylamide, dimethylol acrylamide, dimethylol methacrylamide, and an alkoxymethyl group include N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-butoxy. As a monomer containing methyl acrylamide, N-butoxymethyl methacrylamide, and an epoxy group, for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycine Examples of cyl methacrylate and polyfunctional monomers include divinylbenzene, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate and polyoxy. Lohylene diacrylate, polyoxypropylene dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate Rates, mono or diesters of α, β-ethylenically unsaturated dicarboxylic acids such as mono or dibutyl maleate, mono or dioctyl fumarate, vinyl esters such as vinyl acetate, vinyl propionate, olefins Butadiene, isoprene, chlorine-containing vinyl monomers, for example, vinyl chloride, vinylidene chloride, chloroprene and the like can be selected. In addition, styrene, a styrene derivative, etc. can also be used. You may use these vinyl compounds individually or in combination of 2 or more types.

The homopolymerization of the colloidal silica monomer or copolymerization with the polymerizable compound can be reacted in a solution. Examples of the solvent used may include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and acetic acid. Ester solvents, such as ethyl, butyl acetate, and carbitol acetate, ether compounds, such as dibutyl ether, and alcohol solvents, such as n-butanol and isobutanol, are used. In addition, a mixed solvent of the solvent may also be used.

As a polymerization initiator of copolymerization, a peroxide, an azobis compound, etc. are used, As an azobis compound, such as dibutyl peroxide, benzoyl peroxide, lauroyl peroxide, cumene high peroxide, for example, 2, 2'-azobisisobutylonitrile, 2,2'-azobis-2-methylbutylonitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis ( 2-methylpropionamidine) dihydrochloride and the like are used.

Here, when superposing | polymerizing using the said polymerization initiator, the polymerization reaction temperature is possible also at the temperature of 100 degrees C or less.

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-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl thioxanthone, 2-isopropylthioxone, 2-chlorothioxone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2,4,6-trimethylbenzoyldi Phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. are used, As a commercial item, Irgacure184, 369, 651, 500, 907, CGI1700, CGI1750, CGI1850 , CG24-61 (above, Chiba Chemical products); Lucirin LR8728 from BASF; Darocure 1116, 1173 (above, from Merck); Kobecryl (UCB) etc. are used.

In particular, microgel polymerization, emulsion polymerization, dispersion polymerization, suspension polymerization, and the like are also possible. In the two-step swelling polymerization, there is a polymerization method such as dropping an emulsion monomer premix or direct dropping of a monomer or dropping into a monomer polymerization system in advance.

Surfactants that can be used in these polymerizations include ionic and nonionic surfactants, and as ionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used, and there is no particular limitation. . Examples of the anionic surfactant include fatty acid, sulfate ester salts of higher alcohols, sulfate ester salts of liquid fatty oils, sulfates of aliphatic amines and aliphatic amides, phosphate esters of aliphatic alcohols, sulfonates of these basic fatty acid esters and aliphatic amides. Sulfonate, alkylallyl sulfonate, etc. are used, As a cationic surfactant, a primary amine salt, a second amine salt, a third amine salt, a quaternary ammonium salt, a pyridinium salt, etc. are used, and a cationic interface is used, for example. As the activator, for example, a carboxylate type, a sulfate ester salt type, a sulfonate type, a phosphate ester salt or the like is used. As the nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester and the like are used. Moreover, in addition to the non-reactive surfactant used above, a reactive surfactant can also be used. The reactive surfactant may have a radical polymerizable functional group in one molecule or one or more functional groups selected from a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid base, a sulfonic acid ester base group, or have a radical polymerizable functional group in a molecule or a poly Oxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene complex type alkyl ether or alcohol. You may use these surfactant in one type or in combination of two or more types.                     

In emulsion polymerization, if necessary, pH regulators such as sodium hydrogen phosphate and sodium hydrogen carbonate, molecular weight regulators such as t-dodecyl mercaptan, n-dodecyl mercaptan and low molecular halogen compounds, chelating agents, reversible agents, organic solvents, and the like. Can be added to the first, the middle, and the late stage of emulsion polymerization. The polymerization temperature is, for example, preferably in the range of 0-150 ° C and in the range of 30-90 ° C, and is carried out in an inert atmosphere under normal pressure or under pressure as necessary. Natural tackifiers such as acryl latex, styrene butadiene latex, chloroprene latex, urethane latex, ethylene vinyl acetate latex, vinyl acetate latex, rosin, rosin derivatives, terpene resins, terpene derivatives, and the like; Tackifiers of petroleum resins, styrene resins, cumarone indene resins, phenolic resins, synthetic resins of xylene resins, rubber components such as liquid nitrile rubber and silicone rubber, barium hydroxide, magnesium hydroxide, aluminum hydroxide, silicon oxide, titanium oxide Other than sieving pigments such as calcium sulfate, barium sulfate, calcium carbonate, basic zinc carbonate, basic lead carbonate, silica sand, clay, tar, silica compounds, titanium dioxide, antimony trioxide, etc., (disinfectants, preservatives, antifoams, reversible agents, fluids) Regulators, thickeners, pH regulators, surfactants, colored pigments, extender pigments, rust preventive pigments, and the like) may be added. In particular, (inorganic acid, low molecular weight organic acid, carboxylic acid polymer, etc.) may be added in order to show the pot-life and the normal temperature curability. Moreover, you may add antioxidant and a ultraviolet absorber for the purpose of improving light resistance.

Hereinafter, a description will be given based on specific examples. The test method employ | adopted by the present Example and the comparative example is as follows.

[Test Methods]                     

Mechanics test: conforms to JISK7171

Vickers hardness: JISZ2244 conformity

Heat resistance: Dynamic Mechanical Analysis (DMA) Measurement of glass transition temperature (Tg) by DMA measuring device of DMS-200 manufactured by Seiko Electronics Industry Co., Ltd.

Light Transmittance: Each cured product (measured transmittance (%) of sample thickness 2 mm) at a wavelength of 500 nm using a UV / Vis spectrometer V-520 manufactured by Nippon Co., Ltd.

Example 1

Colloidal silica (30% of SiO ₂ component, dispersed in ethyl acetate solvent) in 100 parts by weight of 2-methacryloyloxyethyl isocyanate (MOI) (molecular weight 155 / Digestion Co., Ltd.), average particle diameter 20nm 0.05 parts by weight of dilauric acid di-n-butyltin (DBTDL) was added as 400 parts by weight of Ilsan Chemical Co., Ltd.) and a catalyst, and the mixture was stirred at room temperature (20 ° C) for 24 hours. The reaction of the isocyanate group was confirmed by infrared spectroscopy (IR) (the loss of the isocyanate group and the presence of the urethane bond) was confirmed, the solvent was removed by an evaporator, and a colloidal silica-containing monomer was obtained. Subsequently, 1 part by weight of benzoyl peroxide (BPO) was added as an initiator to 100 parts of the colloidal silica-containing monomer, followed by polymerization in a lump form at 80 占 폚 for 12 hours to prepare the test piece (resin cured product) of Example 1. Got it.

Example 2                     

Colloidal silica (SiO ₂ component 30%) dispersed in methyl isobutyl ketone (MIBK) solvent in 100 parts by weight of 2-methacryloyloxyethyl isocyanate (MOI) (molecular weight 155 / Digestion Co., Ltd.) 0.04 weight part of dilauric acid di- n-butyltin (DBTDL) was added as a 330 weight part of average particle diameters 20nm / Ilsan Chemical Co., Ltd. product, and a catalyst, and it stirred at room temperature (20 degreeC) for 24 hours. MOI and equimolar or more isopropanol were added to the reaction solvent and stirred for 3 hours, and IR confirmed the reaction of the isocyanate group. And a colloidal silica-containing monomer were obtained. Subsequently, 20 parts by weight of MMA and 1 part by weight of benzoyl peroxide (BPO) as an initiator were added to 80 parts by weight of the colloidal silica-containing monomer, followed by polymerization in a lump form at 80 占 폚 for 12 hours to test the specimen of Example 2. (Resin cured product) was obtained.

Example 3

59 parts by weight of equimolar 2-hydroxyethyl methacrylate (HEMA) and 0.07 parts by weight of DBTDL were added as a catalyst 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 (30% of SiO ₂ component, average particle diameter of 20 nm / manufactured by Ilsan Chemical Co., Ltd.), and stirred at room temperature (20 ° C.) for 24 hours. Propyl alcohol was added. The reaction of the isocyanate group was confirmed by IR (the loss of the isocyanate group and the presence of urethane bond) was confirmed, and unreacted isopropyl alcohol was removed by an evaporator to obtain a colloidal silica-containing monomer. To 100 parts by weight of the obtained colloidal silica-containing monomer, 1 part by weight of BPO was added as an initiator and polymerized in a lump form at 80 占 폚 for 12 hours to obtain a test piece (resin cured product) of Example 3.

Example 4

59 parts by weight of equimolar 2-hydroxyethyl methacrylate (HEMA) and 0.07 parts by weight of DBTDL were added as a catalyst 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 (30% of SiO ₂ component, average particle diameter of 20 nm / manufactured by Ilsan Chemical Co., Ltd.), and stirred at room temperature (20 ° C.) for 24 hours. Propyl alcohol was added. The reaction of the isocyanate group was confirmed by IR (the loss of the isocyanate group and the presence of urethane bond) was confirmed, and unreacted isopropyl alcohol was removed by 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 polymerization was carried out in agglomerates at 80 ° C for 12 hours to prepare the test piece (resin cured product) of Example 4. Got it.

[Comparative Example 1]

100 parts by weight of 2-methacryloyloxyethyl isocyanate (MOI) (molecular weight 155 / Digestion Co., Ltd. product), equimolar or more isopropyl alcohol, and 0.04 part by weight of DBTDL as a catalyst were added. The reaction of the isocyanate group was confirmed by IR (the loss of the isocyanate group and the presence of the urethane bond) was confirmed, and unreacted isopropyl alcohol was removed by an evaporator to obtain a urethane acryl monomer. To 100 parts of the urethane acryl monomer, 1 part by weight of benzoyl peroxide (BPO) was added as an initiator and polymerized in a lump form at 80 占 폚 for 12 hours to obtain a test piece (resin cured product) of Comparative Example 1.

Comparative Example 2

100 parts by weight of 2-methacryloyloxyethyl isocyanate (MOI) (molecular weight 155 / Digestion Co., Ltd. product), equimolar or more isopropyl alcohol, and 0.04 part by weight of DBTDL as a catalyst were added. The reaction of the isocyanate group was confirmed by IR (the loss of the isocyanate group and the presence of urethane bonds were confirmed). Then, 30 parts by weight of methyl isobutyl ketone (MIBK) solvent-dispersed colloidal silica (30% of SiO ₂ component, average particle diameter of 20 nm / manufactured by Ilsan Chemical Co., Ltd.) was mixed, and unreacted isopropyl alcohol was evaporated by an evaporator. The excess solvent was removed to obtain a mixture of urethane acryl monomer and colloidal silica. To 80 parts by weight of this mixture, 20 parts by weight of MMA and 1 part by weight of benzoyl peroxide (BPO) were added as an initiator and polymerized in a lump form at 80 ° C for 12 hours to obtain a test piece (resin cured 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 were added as a catalyst to 100 parts by weight of isophorone diisocyanate (IPDI) to obtain a HEMA-IPDI monomer. Thereafter, equimolar or more isopropyl alcohol was added to the IPDI, and IR confirmed the reaction of the isocyanate group (the loss of the isocyanate group and the presence of the urethane bond). 530 parts by weight of MIBK dispersed colloidal silica (30% of SiO ₂ component, 20 nm / average particle diameter / manufactured by Ilsan Chemical Co., Ltd.) was added to the urethane acryl monomer, followed by stirring at room temperature for 24 hours. Unreacted isopropyl alcohol was removed by an evaporator to obtain a mixture of a urethane acryl monomer and colloidal silica. 20 parts by weight of MMA and 1 part by weight of BPO were added as an initiator to 80 parts by weight of the obtained mixture, followed by polymerization in a lump form at 80 占 폚 for 12 hours to obtain a test piece (resin cured 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 were added as a catalyst to 100 parts by weight of isophorone diisocyanate (IPDI) to obtain a HEMA-IPDI monomer. Thereafter, equimolar or more isopropyl alcohol is added to the IPDI, and IR confirms the reaction of the isocyanate group (confirms the loss of the isocyanate group and the presence of urethane bonds), and removes unreacted isopropyl alcohol by an evaporator to remove the urethane acryl monomer. Got. 20 parts by weight of MMA and 1 part by weight of BPO were added as an initiator to 80 parts by weight of the urethane acryl monomer thus obtained, followed by polymerization in a lump form at 80 占 폚 for 12 hours to obtain a test piece (resin cured product) of Comparative Example 4.

The test results are shown in Table 1.

[Table 1] Properties of Cured Resin

Sample Mechanics test
Modulus of elasticity (GPa) Vickers hardness Heat resistance
(Tg) Permeability
(%) 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

In Table 1, looking at the elastic modulus measured in the mechanical test, in the cured resin of Comparative Example 1-4, the elastic modulus is less than 3.9 (GPA). In contrast, in the cured resin of Example 1-4, the elastic modulus is a value of 4.4 (Gpa) or more. In Comparative Examples 1 and 4, this is only a resin matrix containing no colloidal silica, and in Comparative Examples 2 and 3, since colloidal silica is simply dispersed in the resin matrix, the elastic modulus is low. In comparison with the poor mechanical properties, in Example 1-4, since a urethane bond is formed between the hydroxyl group and the isocyanate group of the colloidal silica, it is considered that excellent mechanical properties with high elastic modulus are obtained.

In addition, looking at Vickers hardness in Table 1, in Comparative Example 1-4, only the value of 28 or less is obtained, whereas in Example 1-4, the value of 32 or more is obtained. In this way, the higher hardness of the cured resin according to Example 1-4 is obtained. In Example 1-4, the urethane bond is formed between the hydroxyl group and the isocyanate group of the colloidal silica. It is believed to be based on what is there.

In addition, looking at the glass transition temperature (Tg) measured as an indicator indicating the heat resistance, in Comparative Example 1-4, the glass transition temperature is lower than 100 ℃ low heat resistance is poor, whereas in Example 1-4 the glass transition It turns out that temperature is high beyond 130 degreeC and is excellent in heat resistance. In this way, the cured resin according to Example 1-4 is more excellent in heat resistance, as in the case of Example 1-4, in which the urethane bond is formed between the hydroxyl group and the isocyanate group of the colloidal silica. It is considered based on the thing.

In addition, looking at the light transmittance in Table 1, since Comparative Examples 1 and 4 do not contain colloidal silica, a high transmittance of 88.7% and 89.1% is obtained, but in Comparative Examples 2 and 3, the resin matrix Since colloidal silica is contained in the dispersed state, the transmittance tends to be low at 83.1% and 85.3%, respectively.

In Example 1-4, colloidal silica is not present in a dispersed state, and since the urethane bond is uniformly formed between the hydroxyl group and the isocyanate group of the colloidal silica, the transmittances are respectively. 88.2%, 86.3%, 89.3%, 89.7%. These transmittance values are higher than those of Comparative Examples 2 and 3 in which colloidal silica is present in a dispersed state, and are almost similar to those of Comparative Examples 1 and 4 containing no colloidal silica. Do. Thus, in Example 1-4, even if colloidal silica exists, it turns out that transparency similar to the comparative examples 1 and 4 can be ensured.

As described in detail above, the present invention is easy for molecular design in order to use a monomer as a raw material, and the obtained cured product is not obtained by simply dispersing a single organic synthetic resin and colloidal silica therein. It is possible to realize various coating materials and molding materials which are excellent in high elasticity, high hardness, and heat resistance, and which contain colloidal silica and have high transparency, and which require more scratch resistance and heat resistance.

Claims (11)

A colloidal silica dispersed in an organic solvent and a compound containing a (meth) acryloyl group and an isocyanate group in a molecule are reacted, A colloidal silica-containing monomer, characterized in that the hydroxyl group of the colloidal silica and the isocyanate group of the compound are bonded via a urethane bond. Curable resin composition obtained by mixing the colloidal silica containing monomer of Claim 1, and the compound which has a reactive double bond in a molecular chain. A cured resin obtained by homopolymerizing the colloidal silica-containing monomer according to claim 1. A cured resin obtained by copolymerizing a colloidal silica-containing monomer according to claim 1 and a compound having a reactive double bond in the molecular chain. An isocyanate compound having a polymerizable unsaturated group introduced therein with at least one isocyanate group of two or more isocyanate groups present in a molecule reacts with a colloidal silica dispersed in an organic solvent, and the hydroxyl group and the isocyanate compound of the colloidal silica. Colloidal silica-containing monomer, characterized in that the isocyanate group bonded through a urethane bond. The method of claim 5, A colloidal silica-containing monomer, wherein the polymerizable unsaturated group is introduced by a reaction of an isocyanate group with a hydroxyl group. Curable resin composition obtained by mixing the colloidal silica containing monomer of Claim 5, and the compound which has a reactive double bond in a molecular chain. The method of claim 7, wherein Curable resin composition which introduce | transduces a polymerizable unsaturated group by the said isocyanate group is performed by reaction of an isocyanate group and a hydroxyl group. A cured resin obtained by homopolymerizing the colloidal silica-containing monomer according to claim 5. A cured resin obtained by copolymerizing a colloidal silica-containing monomer according to claim 5 and a compound having a reactive double bond in the molecular chain. 11. The method according to claim 9 or 10, Introducing a polymerizable unsaturated group into the said isocyanate group is performed by reaction of an isocyanate group and a hydroxyl group, The resin cured material characterized by the above-mentioned.