JP2009074046A - Organic-inorganic composite material and composition thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent resin composition containing an organic-inorganic composite material having adequate inorganic particle dispersive properties and transparency and useful as an additive for contributing toward improving various physical properties of a transparent resin. <P>SOLUTION: The organic-inorganic composite material comprises an inorganic material to which a polymer of a specific structure bonds chemically. The transparent resin composition comprises the organic-inorganic composite material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic / inorganic composite material and a composition containing the same. More specifically, the present invention relates to an organic / inorganic composite material composed of a polymer having a specific structure and an inorganic material, and a composition containing the organic / inorganic composite material.

  Inorganic compound particles or particles having at least a surface inorganic compound (hereinafter referred to as inorganic particles) are generally used as additives for improving physical properties of various plastics, films, paints and the like. Such inorganic particles have been conventionally marketed as powders. On the other hand, particle miniaturization (nanoparticle formation) has been progressing recently. Finely divided inorganic particles are known to have low dispersibility due to their large cohesive energy. In addition, since inorganic particles have a hydrophilic surface, dispersion into a hydrophobic substance is particularly difficult. For this reason, the inorganic particles are often supplied as an aqueous dispersion or a hydrophilic organic solvent dispersion such as alcohol. For these reasons, inorganic particles cannot be added directly to a hydrophobic monomer, thermosetting or various energy ray curable monomer compositions, oligomer compositions, etc., and dispersed or blended uniformly. Further, it is difficult to disperse even in melt mixing with a thermoplastic resin or the like. Therefore, the surface of the inorganic particles (inorganic material) having such a hydrophilic surface is modified (composited) with a polymer to make the surface hydrophobic, thereby making the surface hydrophobic, hydrophobic monomers and hydrophobic thermoplastics. It is necessary to improve compatibility and affinity dispersibility with resins and the like.

  Various attempts have been made for this. For example, a method of dispersing the surface by a method of dispersing in a hydrophobic organic solvent using a super-dispersant (Solsperse, manufactured by Avisia) on the particle surface, a method of polymer-grafting the particles (polymer coating method), etc. Etc. As the polymer coating method, a microhybridization method and a microencapsulation method are known. Examples of the microhybridization method include a mechanochemical method (for example, see Patent Document 1), a heteroaggregation method (for example, see Patent Document 2), and a spray drying method (for example, see Patent Document 3). They attach the polymer particles to the surface of the material by electrostatic or ionic attraction, and then apply physical (mechanical) or thermal energy to fuse the polymer particles, thereby fusing the surface of the material. This is a method for producing polymer-coated composite particles formed by coating with a polymer layer. The spray drying method is a method in which inorganic particles are dispersed in an aqueous dispersion of spherical organic fine powders prepared by a soap-free polymerization method, etc., and then applied to the outer periphery of the inorganic particles by a spray dryer. is there. However, it has been difficult to precisely control and modify (coat) the surface of an inorganic material with an organic polymer compound.

Japanese Patent Publication No. 7-75665 (page 1-2) JP 2002-131757 A (page 1-2) JP-A-5-112429 (page 1-2)

  The present invention has been made in view of the above-mentioned present situation, and has sufficient inorganic material dispersibility and transparency, and particularly useful as an additive for contributing to an increase in mechanical strength and physical properties. It is an object of the present invention to provide a composite material and a transparent resin composition containing the organic / inorganic composite material.

  The present inventor conducted various studies on additives used for improving physical properties of various plastic materials and the like, and found that the constituent monomer used when organically modifying the surface of the inorganic material greatly affects the dispersibility of the inorganic material. I found it. Therefore, an inorganic material obtained by organically modifying an inorganic material using a constituent monomer having a specific structure is excellent in various properties such as dispersibility and water resistance, and is suitable as an additive for improving physical properties of various plastic materials. I found. It has been found that a transparent resin composition comprising these organically modified inorganic materials and dispersions thereof is very useful in various fields, and has reached the present invention.

  That is, the present invention relates to the general formula (1);

A polymer having a structural unit represented by:
It is an organic / inorganic composite material made of inorganic materials.
The inorganic material is preferably nanoparticles.
The present invention is also a transparent resin composition containing the organic-inorganic composite material.

  The organic / inorganic composite material of the present invention has the above-described structure, has sufficient dispersibility and mechanical properties, and is suitable as an additive for improving physical properties in various plastic materials. In the case of a thermoplastic resin, the transparent resin composition containing the organic / inorganic composite material of the present invention can be used as various application materials by injection molding, extrusion molding, stretching, and the like.

  The present invention is described in detail below.

The organic / inorganic composite material of the present invention comprises a polymer having a structural unit represented by the general formula (1) and an inorganic material. The “organic / inorganic composite material” in the present invention is preferably a composite in which an organic component and an inorganic component are chemically bonded. “Chemically bonded” may be any of a covalent bond, a coordination bond, an ionic bond, and the like, and is not particularly limited, but is particularly preferably a covalent bond. As a method for compounding the inorganic material and the polymer having the structural unit represented by the general formula (1), the structural unit represented by the general formula (1) is treated after treating the inorganic material with a coupling agent or the like. After making a polymer having a structural unit represented by the general formula (1) having a functional group that can be chemically bonded to an inorganic material, a method of making a composite with the polymer having, and then making a composite with the inorganic material A method is mentioned. The production method preferably includes at least one of the following steps (a) to (c).
(B) A step of treating an inorganic material with a polymerizable double bond-containing modifier without substantially using a surfactant (b) A step of dispersing the treated inorganic material in a well-dispersed solvent (c) In the above production process (A), the inorganic material is an inorganic substance serving as the nucleus of the organic / inorganic composite material. In the present specification, the inorganic material may be fine particles, nanoparticles, or ultrafine particles. In the step (b), the case where the good dispersion solvent is composed only of monomers containing a specific monomer is also included.

  Examples of the inorganic material include particles of metal oxide, metal sulfide, metal nitride, metal selenide, and the like, and one kind or two or more kinds can be used.

  Examples of the metal oxide include zirconia compounds such as zirconia and silica-coated zirconia; titanium compounds such as titania, silica-coated titania, alumina-coated titania, zinc oxide-coated titania, and composite coated titania thereof; zinc oxide and silica Examples thereof include zinc oxide-based compounds such as coated zinc oxide, alumina-coated zinc oxide, zirconia-coated zinc oxide, tin oxide-coated zinc oxide, and silica / alumina-coated composite coated zinc oxides, and ceria-based compounds. Among these, zirconia is preferable.

  Such an inorganic material may have a layered structure of two or more layers. That is, the organic / inorganic composite material may be obtained by organically modifying the surface of an inorganic material having two or more layered structures.

  As the inorganic material having two or more kinds of layered structures, when the inorganic material is composed of a core part and a shell part, for example, one kind of core part is used, such as silica-coated titania and alumina-coated titania described above. The shell portion may have a layered structure of one kind, or may have a layered structure of one kind of core part and two or more kinds of shell parts such as silica / alumina-coated titania. The seed or two or more types and the shell part may have one layered structure, the core part may have two or more types, and the shell part may have two or more layered structures. Examples of each layer include a metal layer, a layer containing a non-metal layer metal, and the like.

  The layered structure of the inorganic material also has a form having a core portion and a shell portion so that one layer covers the other layer, one layer does not cover the other layer, and each layer overlaps. It may be a form.

  The size of the inorganic material is preferably 30 nm or less, particularly preferably 20 nm or less, and more preferably 10 nm or less (hereinafter referred to as 30 nm or less inorganic material) as measured by a TEM (transmission electron microscope). (Also called “nanoparticles”). It is preferable that an inorganic material of 30 nm or less can be uniformly dispersed in, for example, a transparent plastic because the friction resistance, heat resistance, optical characteristics, etc. of the plastic can be improved.

  Specific examples of such inorganic materials include NANOFINE-50A, which is ZnO particles encapsulated by a silica layer and an alumina layer manufactured by Sakai Chemical Co., Ltd., sold as NANO FINE, and ultrafine titanium oxide STR-60C (20 nm). ), Transparent conductive zinc oxide SC-18 doped with Al; silica coated zinc oxide ZnO-350SiO2 (5) manufactured by Sumitomo Osaka Cement Co., Ltd .; silica coated titanium oxide manufactured by Showa Denko Co., Ltd. sold under the trademark of Maxlite And zinc oxide. In particular, nano zirconia particles (average particle diameter of 4 to 10 nm) produced via zirconium neodecanoate are particularly preferable.

  In the production method of (1) above, for example, the inorganic material is treated with a coupling agent. In this specification, “treating an inorganic material with a coupling agent” means on the surface of the inorganic fine material. Coupling the coupling agent.

  The treatment with the coupling agent may be performed without using a surfactant, for example, by adding a coupling agent to an inorganic material dispersion in which an inorganic material is dispersed in a solvent. Is preferred.

  In the inorganic material dispersion, the inorganic material concentration is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass with respect to 100% by mass including the hydrophilic solvent.

  The coupling agent has a substituent capable of reacting with an inorganic material and a substituent having a double bond so that a polymer graft or a coating layer can be formed on the upper layer (surface) of the inorganic material. If it has, it will not specifically limit, For example, the coupling agent which has a vinyl group, the coupling agent which has an allyl group, etc. are mentioned. More preferred is a coupling agent having a vinyl group.

  Examples of the coupling agent having a vinyl group include alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, dimethylvinylmethoxysilane; vinyltrichlorosilane, dimethylvinylchlorosilane, and the like. Chlorosilanes; methacryloxysilanes such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane; N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl trimethoxysilane Quaternary ammonium salts of the following: titanates such as isopropyl dimethacrylisostearoyl titanate and isopropyl diacrylisostearoyl titanate; p-styryltrimethoxysilane and the like. These can use 1 type (s) or 2 or more types. Preferred is γ-methacryloxypropyltrimethoxysilane.

  Examples of the coupling agent having an allyl group include allyldimethylpiperidinomethylsilane, allylchlorodimethylsilane, allyltriethoxysilane, allyltrichlorosilane, and allyltrimethylsilane. These can use 1 type (s) or 2 or more types.

  The amount of the coupling agent used is an inorganic material (note that the amount of the inorganic material here indicates the amount of the inorganic material in the raw material dispersion, that is, the solid content of the inorganic material dispersion as the raw material) 100. It is preferable that it is 0.01-50 weight part with respect to a weight part. If the amount is less than 0.01 parts by weight, there is a possibility that sufficient double bonds may not be introduced on the surface of the inorganic material. It takes time and effort. More preferably, it is 0.02-30 weight part, More preferably, it is 0.05-20 weight part.

  In the treatment with the coupling agent, “substantially without using a surfactant” means that the surfactant is dispersed in an inorganic material in a hydrophilic solvent in the above production method, or the coupling agent treatment. This means that it is not used for the later dispersion of inorganic materials and dispersion of monomers.

  The above surfactants are generally used surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, reactive surfactants, polymer dispersants, polymer stabilizers. Means containing additives used for normal particle dispersion and monomer dispersion, such as an agent and a hydrophilic monomer. The polymer stabilizer and the polymer dispersant are collectively referred to as “polymer dispersion stabilizer”.

  Here, non-polymerizable low molecular weight (molecular weight of 500 or less) organic compounds (stabilizers, crystal growth inhibitors, surfactant decomposition products, etc.) that can be used in producing the inorganic material dispersion. Is not included in the “surfactant” here.

Examples of the anionic surfactant include alkali metal salts (soap) of higher fatty acids such as sodium laurate, sodium stearate, and sodium oleate; higher alcohol sulfate sodium such as lauryl sulfate sodium salt and cetyl sulfate sodium salt Salts; higher alkyl ether sulfates such as lauryl alcohol ethylene oxide adduct sulfates; sulfated oils, sulfated fatty acid esters, sulfated fatty acids, sulfated olefins, sodium alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate; Alkyl aryl sulfonates, formalin condensed naphthalene sulfonates, α-olefin sulfonates, alkyl (N-methyl) taurides such as oleyl (N-methyl) tauride Sulfosuccinic acid diester type surfactants such as sodium di-2-ethylhexyl sulfosuccinate; higher alcohol phosphate monoester disodium salt; higher alcohol phosphate diester monosodium salt; phosphate ester salt of higher alcohol ethylene oxide adduct; dialkyl Zinc dithiophosphate; and the like.
Examples of the nonionic surfactant include polyoxyethylene alkyl and phenyl ethers, polyoxyethylene group-containing activators such as polyoxyethylene ethers of sorbitan esters and polyethylene glycol fatty acid esters; glycerin fatty acid esters and propylene glycol esters. Ester type; and the like.

  Examples of the cationic surfactant include fatty acid amine salts and quaternary ammonium salts thereof, aromatic quaternary ammonium salts (such as benzalkonium chloride), imidazolinium salts, and the like.

  As the above-mentioned reactive surfactant, dimethylaminoethyl methacrylate, its quaternized salt, sodium undecylate, allyl group, propenyl group, methacryl group and the like having a copolymerizable group, a hydrophobic part and a hydrophilic part Etc. Moreover, the thing with a very small hydrophobic part like sodium styrenesulfonate may be included in this class.

  Examples of the polymer dispersion stabilizer include proteins such as gelatin, colloidal albumin, and casein; sugar derivatives such as agar, sodium alginate and starch derivatives; cellulose compounds such as carboxymethyl cellulose and hydroxymethyl cellulose; polyvinyl alcohol; Group-modified polyvinyl alcohol, N-vinylpyrrolidone, acrylic acid, methacrylic acid, maleic acid, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, vinyl alcohol, methyl vinyl ether, vinyl acetate, acrylamide, methacrylamide, diacetone acrylamide , Homopolymers or copolymers having an ethylenically unsaturated monomer such as vinylimidazole as a constituent, polyoxyethylene, polyoxypropylene, poly-2-methyl Examples include synthetic hydrophilic polymers such as tiloxazoline. Further, the polymer dispersion stabilizer may be a graft polymer or block polymer in which an anchor group and a dispersion stabilizing group are separated, or a macromer (dispersion stabilizer precursor) type. Typical examples are polyvinylpyrrolidone polymer, polyvinyl alcohol, polyacrylic acid, and polymethacrylic acid. In addition, there is Solsperse (consisting of various molecular shapes consisting of a cationic adsorbing part and a methyloxirane polymer) sold by Nippon Lubrizol as a superdispersant.

  Examples of the hydrophilic monomer include (meth) acrylic acid and salts thereof, acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid chloride, allyl acetic acid, and allyl alcohol. , Allylamide, vinyl sulfonic acid and its salt, allyl sulfonic acid and its salt, (meth) acrylic acid amide propane sulfonic acid and its salt, etc., such as carboxylic acid group, amide group, sulfonic acid group, hydroxyl group and generating hydroxyl group after reaction And water-soluble monomers having a glycidyl group.

  In the production step (ii), it is preferable to wash the inorganic material after the treatment with the coupling agent described above in order to remove the unreacted coupling agent. Thereby, it can prevent that coupling agent reacts at the following superposition | polymerization process, and produces | generates a coarse particle (bridge | crosslinking) copolymer particle | grain. Thereafter, it is preferable that the inorganic material is sufficiently dispersed in a good dispersion solvent substantially free of water, and then a hydrophobic monomer is added for polymerization.

  In the production process (b), the inorganic material is dispersed in a good dispersion solvent. The dispersion step in such a good dispersion solvent is preferably performed by adding a good dispersion solvent to, for example, the reaction solution obtained by the coupling agent treatment step or the reaction solution that has undergone the washing step. It is preferable to sufficiently disperse the inorganic material in the solvent using a technique such as stirring or ultrasonic irradiation.

  The good dispersion solvent is not particularly limited as long as the inorganic material to which the coupling agent is bonded can be dispersed. For example, alcohols such as methanol, ethanol, isopropanol, n-propyl alcohol, and various butyl alcohols Ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone; esters such as methyl formate, ethyl formate, methyl acetate, and butyl acetate; and aromatic solvents such as toluene. These can use 1 type (s) or 2 or more types. Preferably, a solvent selected from lower alcohols such as ethanol, isopropanol, and t-butyl alcohol, a mixture thereof, or a solvent selected from methyl ethyl ketone, ethyl acetate, toluene, etc., in particular, methyl ethyl ketone, ethyl acetate, acetic acid which are hydrophobic solvents A single solvent of butyl and toluene, and a mixed solvent such as methyl ethyl ketone, ethyl acetate, butyl acetate and toluene are preferable.

  In addition, it is also possible to use commercially available inorganic materials such as nano zirconia manufactured by Sumitomo Osaka Cement, which have a surface treated with a coupling agent having a polymerization group and dispersed in a hydrophobic solvent. Toluene such as nano titania, methyl ethyl ketone dispersion, and the like can also be used (eg, product name “nano zirconia MEK dispersion” (NZD-8E61)).

  Furthermore, an inorganic material obtained by a production method as shown in the examples of the present specification is particularly preferable. Among them, the organic weight loss including the coupling agent at the time of drying is most preferably 25% by weight or less, more preferably 20% by weight or less.

  In the production process (c), the polymerization treatment is then performed in the presence of a hydrophobic monomer. An initiator is preferably used for the polymerization.

  In the present invention, the general formula (1);

A polymer having a structural unit represented by
In General formula (1), Preferably they are a hydrogen atom and a C1-C18 alkyl group, More preferably, they are a hydrogen atom and a C1-C8 alkyl group.
R2 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group, more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and most preferably a hydrogen atom or a methyl group.
R3 is a hydrogen atom, or

It is. Preferably, a hydrogen atom, the above formula R7 is a hydrogen atom, a methyl group, or an ethyl group, n is 1, and m is an integer of 1-5. More preferably, it is a hydrogen atom, said formula R7 is a hydrogen atom, n is 1, and m is 1-3.

  In the present invention, the polymer having the structural unit represented by the general formula (1) may be a homopolymer or a copolymer, and may be a homopolymer or a modified product of the copolymer. good. In the case of a copolymer, the structural unit represented by the general formula (1) is preferably 5 to 80 mol% in all monomer components. More preferably, it is 5-50 mol%, More preferably, it is 10-30 mol%.

  As a monomer for obtaining a polymer having the structural unit represented by the general formula (1), the following formula (1 ′) can be used.

Specific examples when R6 is a hydrogen atom include, for example, methyl-α-hydroxymethyl acrylate, ethyl-α-hydroxymethyl acrylate, n-butyl-α-hydroxymethyl acrylate, 2-ethylhexyl-α-hydroxymethyl acrylate, Examples include alkyl-α-hydroxyalkyl acrylates such as methyl-α- (1-hydroxyethyl) acrylate, ethyl-α- (1-hydroxyethyl) acrylate, and 2-ethylhexyl-α- (1-hydroxyethyl) acrylate. . Among these compounds, methyl-α-hydroxymethyl acrylate, ethyl-α-hydroxymethyl acrylate, n-butyl-α-hydroxymethyl acrylate, 2-ethylhexyl-α-hydroxymethyl acrylate exhibit the effects of the present invention more. This is particularly preferable.

  As a monomer for obtaining the polymer having the structural unit represented by the general formula (1), when R3 is represented by the following general formula (2), the compound is not particularly limited. The repeating structure of the oxyalkylene group represented by -CH2 (CHR7) nO- has the following structure. That is, the substituent represented by R7 below may be independently composed of a hydrogen atom or an organic residue for each oxyalkylene group, and these oxyalkylene groups may be bonded in a block or randomly. Good. R 7 is preferably a hydrogen atom, a methyl group or an ethyl group. The substituent represented by R1 is preferably an alkyl group having 1 to 18 carbon atoms, and the substituent represented by R2 is preferably a hydrogen atom.

In addition, the synthesis | combining method of the monomer for obtaining the polymer which has a structural unit represented by General formula (1) is not specifically limited.

  Examples of the copolymerizable hydrophobic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, Isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid behenyl, (meth) acrylic acid adamantyl, (meth) acrylic acid decahydro-2-naphthyl, (meth) acrylic acid naphthyl, (meth) acrylic acid octylphenyl, (meth) acrylic acid benzyl, C1-C18 monohydric alcohol (including aromatic) and (meth) acrylic acid (Meth) acrylates that do not have hydrophilic groups such as esters; special esters such as (meth) acrylic acid caprolactone-modified tetrahydrofurfuryl; aromatic vinyl-based monomers such as styrene, methylstyrene, divinylbenzene, and N-vinylcarbazole 1-olefins such as butene, pentene and hexene; alkenes such as isobutylene and cyclohexene; dienes such as butadiene and cyclopentadiene; aliphatic vinyl monomers such as vinyl acetate; nitriles such as methacrylonitrile Group-containing vinyl monomers; halogen group-containing vinyl monomers such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride; trifluoroethyl (meth) acrylate, trifluoropropyl (meth) acrylate, (meta ) Acrylic acid perfluoroalkyl ester, H, IH, 5H-Octal fluoropentyl (meth) fluorine-containing acrylates such as (meth) acrylate; fluorinated olefin; but like, but is not particularly limited. These may be used alone or in combination of two or more.

In the above polymerization treatment, the amount of the (hydrophobic) monomer used is preferably 3 to 100 parts by weight with respect to 100 parts by weight of the solid content of the inorganic material. More preferably, it is 5-50 weight part, More preferably, it is 10-25 weight part.
Further, in the above polymerization treatment, the polymerization is preferably performed in a polymerization system in which the weight ratio of (particle solid content + charged monomer) / solvent is 0.5 or less, more preferably 0.3 or less, and most preferably 0.8. 2 or less.

  In the polymerization treatment, examples of the initiator include azo polymerization initiators, organic peroxides such as t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, and perfluoroalkyl peroxide.

  Examples of the azo polymerization initiator include azoamidine compounds, azonitrile compounds, azoamide compounds, 2,2′-azobis (alkyl azo compounds such as 2,4,4-trimethylpentane, Wako Pure Chemical 2,2′-azobis (2 -Methylpropionamidine) dihydrochloride: V-50, azobisisobutyronitrile: V-60, 2,2'-azobis (2,4-dimethylvaleronitrile: V65, 1,1'-azobis (cyclohexane) -1-carbonitrile: V40, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile): V70, 2,2′-azobis (2-cyclopropylpropionitrile): V68, 2, 2′-azobis (2-methylbutylnitrile): V59, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile V19, and the like.

  In the above polymerization treatment, a water-soluble initiator and / or an oil-soluble initiator can be used, but t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, perfluoroalkyl peroxide, azobisiso Butyronitrile: V-60), 2,2'-azobis (2,4-dimethylvaleronitrile): V65, 1, 1'-azobis (cyclohexane-1-carbonitrile): V40, 2, 2'- Azobis (4-methoxy-2,4-dimethylvaleronitrile): V70, 2,2′-azobis (2-cyclopropylpropionitrile): V68, 2,2′-azobis (2-methylbutylnitrile): V59 , 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile: Use an oil-soluble initiator such as V19. Preferred.

  Although the usage-amount of the said initiator can be set arbitrarily, it is preferable that it is 0.001-20 mass% with respect to preparation monomer mass. When the amount is less than 0.001% by mass, the polymerization does not proceed well. When the amount is 20% by mass or more, the graft chain becomes too short and the surface becomes insufficiently hydrophobic. More preferably, it is 0.01-10 mass%, Most preferably, it is 0.1-5 mass%.

  In order to measure the organic coating amount after the above polymerization treatment, it is preferable to perform washing with a solvent such as alcohol, methyl ethyl ketone, and toluene (washing step after the polymerization treatment) after centrifugal sedimentation. In this case, the dried and pulverized product obtained through the washing step after centrifugal sedimentation has an organic matter adhesion amount of the dried product by thermal analysis of 0. It is preferably 5 to 60% by mass. If it is less than 0.5% by mass, the surface may not be sufficiently coated, and if it exceeds 60% by mass, a crosslinked product may be formed. More preferably, it is 1-50 mass%, More preferably, it is 2-40 mass%.

  In addition, the said organic substance means the organic substance which mainly consists of an inorganic material and the organic component which coat | covers the surface, for example, the polyalkyl (meth) acrylate etc. which are the polymers of the said monomer are mentioned.

  The amount of organic matter (for example, polymer) attached to the organic / inorganic composite material can be measured by the following method. That is, when TG-DTA (thermogravimetric-differential thermal analysis) was used to measure the organic material adhesion or the mass reduction rate of the organic / inorganic composite material when the temperature was raised to 800 ° C. at a rate of 10 ° C./min in an air atmosphere The weight reduction rate is the amount of organic matter attached.

  The optical resin additive and the method for producing the transparent resin composition are not particularly limited as long as the organic / inorganic composite material and the dispersion thereof are included. The dried inorganic composite material can also be obtained simply or after sufficiently pulverizing with a mortar or the like and then directly melt-kneaded into the desired transparent resin. It can also be obtained by sufficiently dispersing organic / inorganic composite material powder in a good solvent for transparent resin by ultrasonic irradiation etc., then mixing with solvent solution for transparent resin, and then removing the solvent. Can do. Furthermore, the solvent may be removed after mixing the polymer solution with the polymer dispersion containing the solvent.

  In this way, the physical properties such as refractive index, hardness, and adhesiveness of the transparent resin can be arbitrarily adjusted by adding the organic / inorganic composite material.

  The transparent resin composition used in the present invention contains the organic-inorganic composite material and the transparent resin. The transparent resin is not particularly limited, and for example, acrylic, polystyrene, polyolefin, polycarbonate, polyethylene terephthalate, or the like can be used. These dispersed transparent resins may be used alone or in a mixture of two or more. When used in a mixture of two or more, they are preferably thermodynamically compatible. This means that the polymer obtained by polymerizing the monomer using a thermodynamically compatible monomer composition is compatible with the transparent resin to be dispersed, and confirmation that it is thermodynamically compatible is obtained. It can be confirmed by measuring the glass transition point (Tg) of the thermoplastic resin composition. Specifically, in each resin mixture, the glass transition point measured by a differential scanning calorimeter is observed at one point, thereby confirming that they are thermodynamically compatible with each other. In addition, it is possible to visually determine that a film or molded product formed from a mixture has transparency, or to evaluate transparency by measuring optical properties such as total light transmittance by a predetermined method. It can be confirmed that they are thermodynamically compatible. Among these, it is more preferable to use a monomer having the same composition as the resin that finally functions as an additive (in the case of a monomer or oligomer, a resin after polymerization).

  Among these, heat-resistant acrylic is preferable, and a copolymer of 2- (hydroxymethyl) acrylic acid ester and methacrylic acid ester, or a modified product of the copolymer is particularly preferable.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

  In addition, the measuring method of each physical property is as follows.

<Powder X-ray diffraction>
The crystal structure of the zirconium oxide nanoparticles was measured using a fully automatic multipurpose X-ray diffractometer (Specter Pro, manufactured by Spectris). The measurement conditions are as follows.

X-ray source: CuKα (0.154 nm)
X-ray output setting: 45kV, 40mA
Step size: 0.017 °
Scan step time: 5.08 seconds Measurement range: 5-90 °
Measurement temperature: 25 ° C
Further, the obtained X-ray diffraction chart was analyzed with analysis software (XRay Crystal), and a C value indicating crystallinity was calculated from the formula (1).

<Average particle size>
The zirconium oxide nanoparticles were observed with an ultra-high resolution field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation). Arbitrarily 100 particles observed to be enlarged were selected, the length of each particle in the major axis direction was measured, and the average value was taken as the average particle diameter.

<Polymerization reaction rate, polymer composition analysis>
The reaction rate during the polymerization reaction and the content of the specific monomer unit in the polymer were determined by gas chromatography (manufactured by Shimadzu Corporation, apparatus name: GC17A) based on the amount of unreacted monomer in the obtained polymerization reaction mixture. ) And measured.

<Dynamic TG>
The polymer (or polymer solution or pellet) is once dissolved or diluted in tetrahydrofuran, poured into excess hexane or methanol for reprecipitation, and the taken out precipitate is vacuum dried (1 mmHg (1.33 hPa), 80 ° C. Volatile components and the like were removed by conducting the reaction for 3 hours or more, and the obtained white solid resin was analyzed by the following method (dynamic TG method).

Measuring apparatus: Thermo Plus2 TG-8120 Dynamic TG (manufactured by Rigaku Corporation)
Measurement conditions: Sample amount 5 to 10 mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 200ml / min
Method: Step-like isothermal control method (controlled at a weight reduction rate value of 0.005% / sec or less between 60 ° C and 500 ° C)
<Dealcoholization reaction rate and proportion of lactone ring structure>
First, from the polymer composition obtained by polymerization, on the basis of the weight loss that occurs when all the hydroxyl groups are dealcoholated as methanol, before decomposition of the polymer starts at 150 ° C. before the weight reduction starts in dynamic TG measurement. From the weight loss due to the dealcoholization reaction up to 300 ° C., the dealcoholization reaction rate was determined.

That is, in the dynamic TG measurement of a polymer having a lactone ring structure, the weight reduction rate between 150 ° C. and 300 ° C. is measured, and the obtained actual weight reduction rate is defined as (X). On the other hand, from the composition of the polymer, all the hydroxyl groups contained in the polymer composition are involved in the formation of the lactone ring, so that the alcohol is converted into alcohol, and the theoretical weight reduction rate (ie, in the composition) The weight reduction rate calculated on the assumption that a 100% dealcoholization reaction has occurred is defined as (Y). The theoretical weight reduction rate (Y) is more specifically the molar ratio of raw material monomers having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material in the polymer composition. It can be calculated from the monomer content. These values (X, Y) are calculated from the dealcoholization formula:
1- (actual weight reduction rate (X) / theoretical weight reduction rate (Y))
Substituting into, the value is obtained and expressed in% to obtain the dealcoholization reaction rate.

<Weight average molecular weight>
The weight average molecular weight of the polymer was determined by polystyrene conversion of GPC (GPC system manufactured by Tosoh Corporation). Chloroform was used as the developing solution.

<Thermal analysis of resin>
Thermal analysis of the acrylic resin was performed using DSC (manufactured by Rigaku Corporation, apparatus name: DSC-8230) under the conditions of a sample of about 10 mg, a heating rate of 10 ° C./min, and a nitrogen flow of 50 cc / min. . The glass transition temperature (Tg) was determined by the midpoint method according to ASTM-D-3418.

<Melt flow rate>
The melt flow rate was measured at a test temperature of 240 ° C. and a load of 10 kg based on JIS-K7210.

<Melt viscosity>
The melt viscosity of the sufficiently dried acrylic resin pellets was measured using a capillary rheometer RH10 manufactured by Borin Instruments.

<Production Example 1>
Production of zirconium oxide nanoparticles coated with neodecanoic acid and 3-methacryloxypropyltrimethoxysilane Sodium hydroxide (80 g, manufactured by Kishida Chemical Co., Ltd., special grade) was added to pure water (640 g) at 40 ° C. with dissolution. did. Next, neodecanoic acid (396.9 g, manufactured by Japan Epoxy Resin Co., Ltd.) was added with stirring to prepare a sodium neodecanoate aqueous solution. Next, the solution was heated to 80 ° C., and with stirring, zirconium oxychloride (585.99 g, ZrOCl 2 · 8
H2O, manufactured by Daiichi Kagaku Kagaku Kogyo Co., Ltd., and Zircosol ZC-20) were added over 20 minutes. When stirring was continued at 80 ° C. for 1.5 hours, white and viscous zirconium neodecanoate was produced. After removing the aqueous phase, the zirconium neodecanoate was sufficiently washed with pure water. Next, tetradecane (92 g) was added to the zirconium neodecanoate and stirred.

  Pure water (400 g) was mixed with the obtained zirconium neodecanoate-tetradecane solution. The mixture was charged into an autoclave equipped with a stirrer, and the atmosphere in the reaction vessel was replaced with nitrogen gas. Thereafter, the reaction mixture was heated to 180 ° C. and reacted for 3 hours to synthesize zirconium oxide particles. The pressure in the container when reacted at 180 ° C. was 0.9 MPa. The solution after the reaction was taken out, and the precipitate accumulated at the bottom was filtered off, washed with acetone and dried. When the precipitate (80 g) after drying was dispersed in toluene (800 mL), a cloudy solution was obtained. Next, it filtered again with the quantitative filter paper (Advantech Toyo Co., Ltd. No.5C) as a refinement | purification process, and removed the coarse particle etc. in a deposit. Next, white zirconium oxide nanoparticles were recovered by removing toluene obtained by concentrating the filtrate under reduced pressure.

  The obtained zirconium oxide nanoparticles (10 g) were dispersed in toluene (90 g) to prepare a transparent solution. To the solution, 3-methacryloxypropyltrimethoxysilane (1.5 g, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was added as a surface treatment agent, and the mixture was heated to reflux at 90 ° C. for 1 hour. Next, n-hexane was added to the solution after the reflux treatment to agglomerate the dispersed particles to make the solution cloudy. Aggregated particles were separated from the white turbid solution with a filter paper and then vacuum dried at room temperature to prepare zirconium oxide nanoparticles surface-treated with neodecanoic acid and 3-methacryloxypropyltrimethoxysilane.

  When the crystal structure of the obtained coated zirconium oxide nanoparticles was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction lines, it was confirmed that the crystal structure was mainly tetragonal and slightly monoclinic. Moreover, when the particle diameter of the said zirconium oxide nanoparticle was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, when analyzed by an infrared absorption spectrum, absorption derived from Si—O—C was observed in addition to absorption derived from C—H and absorption derived from COOH. These absorptions are considered to be derived from neodecanoic acid and 3-methacryloxypropyltrimethoxysilane covering the zirconium oxide nanoparticles. Further, when the mass reduction rate of the zirconium oxide nanoparticles was measured by TG-DTA (thermogravimetric-differential thermal analysis) at a rate of 10 ° C./min in an air atmosphere to 800 ° C., 18 mass% Decrease rate. Therefore, it was confirmed that neodecanoic acid and 3-methacryloxypropyltrimethoxysilane, which had coated the zirconium oxide nanoparticles, accounted for 18% by mass of the whole particles.

  In addition, the total C content in the nanoparticles was measured with a CHN coder analyzer, the amount of neodecanoic acid derived from the amount of neodecanoic acid was calculated by subtracting the amount of C derived from 3-methacryloxypropyltrimethoxysilane, and the amount of neodecanoic acid in the coating layer Asked. As a result, the abundance ratio of 3-methacryloxypropyltrimethoxysilane to neodecanoic acid in the coating layer was 1.5 in terms of molar ratio.

  Further, the particle size distribution is measured, and the coefficient of variation is obtained from the formula: σ / x × 100 [where σ is the standard deviation of the particle size distribution of the particles, and x is the 50% cumulative diameter (nm) of the particles]. As a result, it was 20%. Therefore, it was found that there was little variation in the particle size of the nanoparticles.

<Production Example 2>
MHMA-MMA Copolymer Production Method Into a 1 m2 reaction kettle equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe, 136 kg of methyl methacrylate (MMA), 34 kg of methyl 2- (hydroxymethyl) acrylate (MHMA) 166 kg of toluene was charged and heated to 105 ° C. while passing nitrogen therein. When refluxed, 187 g of tertiary amyl peroxyisononanoate (trade name: Lupazole, manufactured by Atofina Yoshitomi) was used as a polymerization initiator. 570) is added and at the same time, solution polymerization is carried out under reflux (about 105 to 110 ° C.) while dropping a solution comprising 374 g of a polymerization initiator and 3.6 kg of toluene over 2 hours, and further over 4 hours. Aging was performed to obtain a polymer solution (A).

  170 g of stearyl phosphate / distearyl phosphate mixture (manufactured by Sakai Chemicals, product name: Phoslex A-18) is added to the polymer solution (A), and cyclized under reflux (about 90 to 110 ° C.) for 5 hours. A condensation reaction was performed. Subsequently, the polymer solution obtained by the cyclization condensation reaction was subjected to a vent having a barrel temperature of 250 ° C., a rotation speed of 150 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent of 1 and a forevent of 4 It is introduced into a type screw twin screw extruder (φ = 42 mm, L / D = 42) at a processing rate of 13 kg / hour in terms of resin amount, and is subjected to cyclization condensation reaction and devolatilization in the extruder and extruded. Thus, a transparent pellet was obtained.

  When the obtained pellet was measured by dynamic TG, a mass decrease of 0.15% by mass was detected. The lactone ring-containing polymer has a mass average molecular weight of 147,000, a melt flow rate of 11.0 g / 10 min, a glass transition temperature of 130 ° C., a viscosity of 270 ° C. and a shear rate of 100 (1 / s) at a viscosity of 470 Pa.・ It was s.

<Example 1>
In a separable flask, 300 parts by weight of methyl ethyl ketone, 300 parts by weight of butyl acetate and 300 parts by weight of toluene were added to 100 parts by weight of the zirconia nanoparticle powder obtained in Production Example 1 and dispersed therein. 32 parts by weight of MMA and 8 parts by weight of MHMA were added to this, and after blowing nitrogen gas, 0.2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile (Wako Pure Chemical) was used as a polymerization initiator. The product was polymerized for 4 hours in a warm water bath at 70 ° C. After the polymerization, a translucent polymer solution (1) was obtained, and this polymer solution (1) was added with n-hexane. The product was allowed to settle and washed by repeating solvent separation in a centrifuge and redispersion in toluene twice to obtain a wet product (1), a portion of which was vacuum dried overnight at room temperature, The amount of organic matter deposited on the mortar was 43% by weight.
A polymer solution in which 100 parts by weight of the lactone ring-containing polymer obtained in Production Example 2 was dissolved in 900 parts of toluene was added to and uniformly mixed with the wet product (1) redispersed in 900 parts by weight of toluene. . The solvent was removed by distillation under reduced pressure to obtain a transparent resin. The refractive index was 1.687.

<Example 2>
In a separable flask, 600 parts by weight of toluene was added to 100 parts by weight of the zirconia nanoparticle powder obtained in Production Example 1 and dispersed therein. To this, 16 parts by weight of MMA and 4 parts by weight of MHMA were added, and after blowing nitrogen gas, 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile (Wako Pure Chemical) was used as a polymerization initiator. The product was polymerized for 4 hours in a warm water bath at 70 ° C. After the polymerization, a translucent polymer solution (2) was obtained. Similarly, the amount of organic matter deposited after washing, drying and grinding was 25% by weight.
This polymerization liquid (2) was mixed with 100 parts by weight of the polymer solution (A) obtained in Production Example 2, and a cyclization reaction was performed in the same manner as in Production Example 2 to obtain transparent pellets by devolatilization. The refractive index was 1.735.

<Example 3>
In a separable flask, 600 parts by weight of toluene was added to 100 parts by weight of the zirconia nanoparticle powder obtained in Production Example 1 and dispersed therein. 8 parts by weight of MMA and 2 parts by weight of MHMA were added to this, and after blowing nitrogen gas, 0.1 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile (Wako Pure Chemical) was used as a polymerization initiator. The product was polymerized for 4 hours in a warm water bath at 70 ° C. After the polymerization, a translucent polymer solution (3) was obtained. Similarly, the amount of organic matter deposited after washing, drying and grinding was 25% by weight.
This polymerization liquid (3) was mixed with 100 parts by weight of the polymer solution (A) obtained in Production Example 2, and a cyclization reaction was performed in the same manner as in Production Example 2 to obtain transparent pellets by devolatilization. The refractive index was 1.750.

<Example 4>
MEZ dispersion NZD-8E61 of nano zirconia (manufactured by Sumitomo Osaka Cement Co., Ltd .: solid content concentration 17.1% by weight, ash content 12.3% by weight, organic matter adhesion amount of dry pulverized product 28% by weight, zirconia average particle size 3 nm) 32 parts by weight of MMA and 4 parts by weight of MHMA were added to parts by weight (containing 663 parts of methyl ethyl ketone), and after blowing nitrogen gas, 0.1 parts by weight of 2,2′-azobis (2,4,4) was used as a polymerization initiator. -Dimethylvaleronitrile (manufactured by Wako Pure Chemical Industries, Ltd .: V65) was added and polymerized for 4 hours in a warm water bath at 70 ° C. After polymerization, a translucent polymerization solution (3) was obtained.
A part of the polymerization solution (3) was similarly washed, dried and pulverized, and the organic matter adhesion amount was 59% by weight.
This was mixed with 100 parts by weight of the polymer solution (A) obtained in Production Example 2, and subjected to a cyclization reaction in the same manner as in Production Example 2 to obtain transparent pellets by devolatilization. The refractive index was 1.660.

<Comparative Example 1>
100 parts by weight of the same zirconia nanoparticle powder as in Example 1 was dispersed in 300 parts by weight of methyl ethyl ketone. To this was added a polymer solution prepared by dissolving 300 parts by weight of the lactone ring-containing polymer obtained in Production Example 2 in 2700 parts of MEK and mixed uniformly. A dispersion with a slight haze was obtained. When this solvent was air-dried and then dried under reduced pressure, a dried product having a white opaque portion was obtained, and it was clear that nanoparticles were aggregated.

In order to confirm the dispersibility of the zirconia nanoparticle powder, a part of the dry sample embedded in an epoxy resin and cut with a microtome was observed with an FE-SEM. As shown in FIG. It was confirmed that the dispersion was uneven. (* In the figure, the zirconia nanoparticles are displayed as black spheres. The wide white part at the end is outside the microtome cutting surface, that is, the part of the base outside the sample.)
<Example 5>
100 parts by weight of the same zirconia nanoparticle powder as in Example 1 was dispersed in 300 parts by weight of methyl ethyl ketone. 240 parts by weight of MMA and 60 parts by weight of MHMA were added to this, and after blowing nitrogen gas, 2.5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile (Wako Pure Chemical) was used as a polymerization initiator. The product was polymerized for 4 hours in a warm water bath at 70 ° C. After the polymerization, a translucent soft gel-like material (organic / inorganic composite material) separated from the solvent was obtained. Therefore, it was considered that zirconia nanoparticles having a plurality of polymerizable groups function as a crosslinking agent.

In order to confirm the dispersibility of the zirconia nanoparticle powder, a part of the translucent organic / inorganic composite material was subdivided into a clean sample container and dried under reduced pressure to obtain a flaky organic / inorganic composite material. When the cross section obtained by embedding the thin piece sample with an epoxy resin and cutting with a microtome was observed with FE-SEM, it was confirmed that zirconia was uniformly dispersed as shown in FIG. (* In the figure, the zirconia nanoparticles are displayed as black spheres. The wide white part at the end is outside the microtome cutting surface, that is, the part of the base outside the sample.)
<Example 6>
Nano zirconia MEK dispersion NZD-8E61 (manufactured by Sumitomo Osaka Cement Co., Ltd .: solid content concentration: 117.1% by weight, ash content: 12.3% by weight, organic matter adhesion amount of dry ground product: 28% by weight) 240 parts by weight MMA and 60 parts by weight of MHMA were added, and after nitrogen gas was blown, 2.5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile (manufactured by Wako Pure Chemicals: V65)) was used as a polymerization initiator. The resulting mixture was polymerized for 4 hours in a hot water bath at 70 ° C. After polymerization, a whitish semi-transparent soft gel (organic / inorganic composite material) separated from the solvent was obtained. Therefore, zirconia nanoparticles having a plurality of polymerizable groups were considered to function as a crosslinking agent.

  In order to confirm the dispersibility of the zirconia nanoparticle powder, a part of the translucent organic / inorganic composite material was subdivided into a clean sample container and dried under reduced pressure to obtain a flaky organic / inorganic composite material. When the cross section obtained by embedding the thin piece sample with an epoxy resin and cutting with a microtome was observed with an FE-SEM, it was confirmed that zirconia was uniformly dispersed as shown in FIG. (* In the figure, the zirconia nanoparticles are displayed as black spheres. The wide white part at the end is outside the microtome cutting surface, that is, the part of the base outside the sample.)

FIG. 1 is a cross-sectional photograph taken by FE-SEM of the zirconia nanoparticle powder-dispersed lactone ring-containing polymer of Comparative Example 1. (Magnification: 200,000) FIG. 2 is a cross-sectional image taken by FE-SEM of the zirconia nanoparticle powder-dispersed lactone ring-containing polymer of Comparative Example 1. (Magnification: 400,000) FIG. 3 is a cross-sectional photograph taken by FE-SEM of the dried organic / inorganic composite material of Example 5. (Magnification: 200,000) FIG. 4 is a cross-sectional photograph taken by FE-SEM of the dried organic / inorganic composite material of Example 6. (Magnification: 300,000)

Claims (3)

General formula (1);

A polymer having a structural unit represented by:
Organic / inorganic composite materials made of inorganic materials. The organic / inorganic composite material according to claim 1, wherein the inorganic material is nanoparticles. A transparent resin composition comprising the organic / inorganic composite material according to claim 1.

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