JP2001002746A - Inorganically modified polyurethane emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inorganically modified polyurethane emulsion that has very high water dispersion stability, can give a urethane coating film having excellent physical properties, for example, hardness, durability, and the like, and is useful in coating materials, adhesives, and the like, by dispersing a specific urethane polymer in water in the presence of inorganic particles and/or a silane compound. SOLUTION: (A) A urethane polymer bearing hydrolyzable silyl groups is dispersed in water in the presence of (B) inorganic particles and/or (C) a silane compound. The weight ratio of the component (A) to the component (B+C) is preferably 0.001-100, and the weight ratio of the component B to the component C is preferably 0.01-100. In a preferred embodiment, the component A is a reaction product from (i) a compound bearing 2 or more isocyanate groups, (ii) a compound bearing active hydrogen groups that are reactive with the isocyanate groups, (iii) a silane coupling agent bearing active hydrogen group reactive with the isocyanate groups and/or (iv) a silane coupling agent bearing isocyanate group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic modified polyurethane emulsion which is useful as a paint, an undercoating or finishing material for building materials, an adhesive, a paper processing agent, or a finishing agent for woven or nonwoven fabrics. The present invention relates to an inorganic modified polyurethane emulsion which can be used for various applications as a clear coat agent, a top coat agent, a paint, an undercoat agent, a cloth or paper impregnating agent, an adhesive, a fiber treatment agent and the like.

[0002]

2. Description of the Related Art In recent years, aqueous emulsions have attracted attention in the field of coating as a conversion material from an organic solvent system to an aqueous system. In particular, polyurethane emulsions have excellent film-forming properties and have abrasion resistance, adhesiveness, rubber elasticity and the like. It is widely used for applications such as paints or adhesives, fiber treatment agents, coating agents, etc., because it gives a coating film having the same. However, it has not yet exhibited sufficient physical properties in terms of hardness, durability and the like, which are required particularly in the fields of paints and coating agents.

To solve these problems, for example, Japanese Patent Laid-Open No. 7-1
38649 and JP-A-7-138524 disclose an aqueous polyurethane composition in which an alkoxysilane derivative is introduced as a crosslinking group into polyurethane molecules. However, in this case, the molecular weight of the urethane prepolymer becomes extremely small in a design in which the silicon content is increased, and physical properties as polyurethane cannot be expressed.
Naturally, the silicon content in the composition is limited to very low values. Therefore, with this method, it is almost impossible to improve the hardness, durability, and the like of the coating film having the properties of urethane.

[0004] For example, JP-A-7-216340 and JP-A-8-73830 propose a polyurethane emulsion synthesized by synthesizing a urethane prepolymer in the presence of inorganic particles and then making it aqueous. I have. However, since the polyurethane emulsion obtained by this method has no interaction between the inorganic particles and the urethane-based polymer, the resulting coating film has poor uniformity and insufficient physical properties such as durability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an inorganic modified polyurethane emulsion capable of obtaining a urethane-based coating film having excellent physical properties such as hardness and durability.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have found that a urethane polymer having a hydrolyzable silyl group is dispersed in water in the presence of inorganic particles and / or a silane compound. The present inventors have found that the inorganic modified polyurethane emulsion is very effective in solving the above-mentioned problems, and have reached the present invention. Hereinafter, the present invention will be described in detail.

In the present invention, the hydrolyzable silyl group refers to a group in which a hydrolyzable substituent is bonded to a silicon atom. Examples of the hydrolyzable group include a hydrogen atom,
Examples include a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group that is easy to handle is preferable.

Further, the urethane polymer having a hydrolyzable silyl group in the present invention refers to a urethane polymerization reaction in the presence of a compound that generates the silyl group, or a reaction between the compound that generates the silyl group and the urethane polymer. A compound having two or more isocyanate groups (a), a compound having active hydrogen capable of reacting with isocyanate groups (b), and a silane coupling having active hydrogen groups capable of reacting with isocyanate groups A reaction product derived from the agent (c) and / or the silane coupling agent (d) having an isocyanate group is exemplified.

As the compound (a) having two or more isocyanate groups, for example, 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), dimethylcyclohexane diisocyanate (hydrogenated XDI) Alicyclic diisocyanate and hexamethylene diisocyanate (H
Aliphatic diisocyanate such as DI), furthermore, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and a mixture thereof (TDI), diphenylmethane-4,4 ′ diisocyanate (MDI), naphthalene-1,5 diisocyanate (NDI), 3,3-dimethyl-4,4-biphenylene diisocyanate (TO
DI), crude TDI, polymethylene polyphenyl diisocyanate, aromatic diisocyanate such as crude MDI,
Examples include aromatic alicyclic diisocyanates such as xylylene diisocyanate (XDI) and phenylene diisocyanate, and combinations thereof. Among these isocyanate compounds, aliphatic and / or alicyclic isocyanate compounds are preferable from the viewpoint of weather resistance, heat yellowing and the like.

As the compound (b) having an active hydrogen capable of reacting with the isocyanate group, polyols are typical. In addition, a hydroxyl group and / or an amino group having a number average molecular weight of 400 or less may be used. Examples thereof include low molecular weight compounds, active hydrogen compounds having a nonionic and / or ionic hydrophilic group (or a group that can be subsequently converted to a hydrophilic group), and combinations of these compounds. First, as the polyols, polycarbonate polyols, polyether polyols, polyester polyols, polybutadiene glycols and the like can be used alone or in combination of two or more.
Among these, polycarbonate polyols are preferred from the viewpoints of heat yellowing, water resistance, solvent resistance, weather resistance and the like.

[0011] Among the above polyols, first, as a polycarbonate polyol, a dihydric alcohol is used in the presence or absence of a catalyst with a carbonate agent selected from phosgene, dialkyl carbonate, diallyl carbonate and alkylene carbonate. A product obtained by the reaction is mentioned. Examples of these dihydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,3- Pentanediol, 1,6-hexanediol, and the like, or a combination of two or more of these. The polycarbonate polyol obtained can be used alone or in combination of two or more. Among these polycarbonate polyols, JP-A-2-28-28
Amorphous polycarbonate polyols described in U.S. Pat. No. 9616, JP-A-4-25264 and the like are preferable, and polytetramethylene carbonate diol produced in the presence of an acidic substance from the viewpoint of solvent resistance, hardness, etc. 4
-258748) is preferred.

Next, specific examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene-oxypropylene (random and / or block) glycol, polyoxyethylene-oxytetramethylene (random and And / or block) glycol, polyoxypropylene-oxytetramethylene (random and / or block) glycol, polyhexamethylene glycol and the like, and a combination of two or more thereof.

Further, specific examples of polyester polyols include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate,
Examples include polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol, and the like, and a combination of two or more of these.

Further, the polybutadiene glycols include polybutadiene homopolymer type and polybutadiene copolymer type (styrene butadiene copolymer, acrylonitrile butadiene copolymer, etc.) having hydroxyl groups at both ends, and a part or all of these unsaturated double bonds. Examples thereof include hydrogenated ones and a combination of two or more of them. In order to further improve the properties such as heat softening temperature and flexibility and hardness of the obtained polyurethane, a part of the polyols may be used, if necessary, with a hydroxyl group and / or amino group having a number average molecular weight of usually 400 or less. It may be a low molecular compound having a group.

Examples of these low-molecular compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, Dihydric alcohols such as 1,3-pentanediol, 1,6-hexanediol, hydrogenated bisphenol A, cyclohexanedimethanol, trihydric or higher alcohols such as glycerin, trimethylolpropane and pentaerythritol, monoethanolamine, Amino alcohols such as diethanolamine, aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, isophoronediamine, 4,4-methylenebis (cyclohexylamine)
And the like, and a combination of two or more of these.

If necessary, a part of the compound (b) having active hydrogen may be combined with an active hydrogen compound having a nonionic and / or ionic hydrophilic group (or a group which can be converted into a hydrophilic group later). By doing so, the obtained polyurethane can be made into a self-emulsifying type. The use of a self-emulsifying type is preferred from the viewpoint of improving the dispersion stability of the polyurethane emulsion and the water resistance of a film obtained therefrom.

First, examples of the ionic hydrophilic group include an anionic group such as a tertiary amine salt of a carboxylic acid and a cationic group such as a quaternary ammonium salt. Examples of the active hydrogen compound having an anionic group (or a group that can be converted into an anionic group later) include, for example, α, α′-dimethylolpropionic acid, α, α′-dimethylolacetic acid, α, α′-dimethylolbutyric acid, α, α α, α 'such as α'-dimethylolvaleric acid
-Dimethylolalkanoic acids, aminosulfonic acids such as taurine and the like, and combinations thereof. Of these, α, α'-dimethylolpropionic acid is preferred. The acid groups of these active hydrogen compounds can be converted to anionic groups by neutralizing with a base during the synthesis or emulsification of the urethane prepolymer. As the base used for neutralization,
Amine compounds such as triethylamine, ammonia, diethanolamine, dimethylaminoethanol, methyldiethanolamine and dibutylamine; KOH, N
Examples include hydroxides of alkali metals such as aOH and LiOH, and combinations thereof.

Examples of the active hydrogen compound having a cationic group (or a group that can be converted into a cationic group later) include N-alkyldialkanolamines such as N-methyldiethanolamine and N-butyldiethanolamine, triethanolamine, and tripropanol. Trialkanolamines such as amines; N, N- such as N, N-dimethylethanolamine and N, N-diethylethanolamine;
These include alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, etc.), such as dialkyl monoalkanolamines, and combinations thereof. The tertiary amino group of these active hydrogen compounds can be converted to a cationic group during the synthesis or emulsification of the urethane prepolymer by neutralization with an acid or quaternization with an alkylating agent. Examples of the acid used for neutralization include acetic acid, lactic acid, hydrochloric acid, phosphoric acid, sulfuric acid and the like, and a combination thereof. Examples of the alkylating agent include dimethyl sulfate, diethyl sulfate, methyl chloride, methyl iodide, benzyl chloride and the like.

Next, examples of the nonionic hydrophilic group include a suspended polyoxyalkylene group, particularly a polyoxyethylene group. Examples of active hydrogen compounds having these groups include diols having a suspended polyoxyethylene chain as described in US Pat. No. 3,905,929.

The silane coupling agent (c) having an active hydrogen group capable of reacting with an isocyanate group in the present invention.
Examples thereof include silane coupling agents having a mercapto group, a hydroxyl group, an amino group, and the like. Among them, first, as the silane coupling agent having a mercapto group, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ
-Mercaptopropylmethyldiethoxysilane.

Next, as the compound having an amino group,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-
Examples include aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane. These silane coupling agents can be used alone or in combination of two or more. Further, as the silane coupling agent (d) having an isocyanate group in the present invention, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane and the like can be mentioned.

The urethane polymer having a hydrolyzable silyl group of the present invention comprises, for example, the compound (a) having two or more isocyanate groups, the compound (b) having an active hydrogen group capable of reacting with the isocyanate group, and the isocyanate group. The silane coupling agent (c) having an active hydrogen group and / or the silane coupling agent (d) having an isocyanate group capable of reacting with urethane under a substantially anhydrous condition at a temperature of about 0 ° C. to about 130 ° C. It is obtained by a chemical reaction. At this time, (a) and (b) may be reacted first to obtain a urethane prepolymer, and then (c) and / or (d) may be reacted, or all may be reacted simultaneously. Here, the equivalent ratio between the NCO group of the isocyanate compound (total of (a) and (d)) and the active hydrogen in the compound having active hydrogen (total of (b) and (c)) is 0.2 to 0.2%. 5.0: 1.0, preferably 0.5-2.0:
1.0.

In producing the urethane polymer having a hydrolyzable silyl group of the present invention, a catalyst can be used if necessary. Specific examples of the catalyst include salts of metals such as dibutyltin dilaurate, stannous octylate, lead octylate and organic and inorganic acids, and organic metal derivatives; organic tertiary amines such as triethylamine and triethylenediamine; Bicycloundecene-based catalysts and the like can be mentioned.

The production of a polyurethane having a hydrolyzable silyl group can be carried out without a solvent or in a solvent. As the solvent, those which are inert to the isocyanate group or have lower activity than the reaction components can be used. Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; amide solvents such as dimethylformamide and dimethylacetamide; N-methyl-2-pyrrolidone Lactam solvents such as dimethyl sulfoxide; ester solvents such as ethyl acetate and cellosolve acetate; t-butanol;
Examples thereof include alcohols such as diacetone alcohol, aromatic hydrocarbon solvents such as toluene xylene, aliphatic hydrocarbon solvents such as n-hexane, and the like, and combinations thereof. Among them, acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, and tetrahydrofuran are particularly preferable from the viewpoint of emulsifying dispersibility in water and the like. These solvents may remain in the inorganic modified polyurethane emulsion described below,
After the emulsion is formed, it can be removed by distillation by heating under normal pressure or reduced pressure.

The modified inorganic polyurethane emulsion in the present invention is produced by dispersing the urethane polymer in water in the presence of inorganic particles and / or a silane compound. At this time, it is possible to obtain an inorganic modified polyurethane emulsion in which the inorganic component and the polyurethane are complexed by an interaction such as a chemical bond between the hydrolyzable silyl group introduced into the urethane polymer and the inorganic particles and / or the silane compound. .

Examples of the inorganic particles include oxides such as silica, titanium oxide, alumina, zirconia, zinc oxide, magnesium oxide, antimony trioxide, iron oxide, dolomite, and manganese oxide; magnesium carbonate, calcium carbonate, and zinc carbonate. Carbonates, aluminum silicate, magnesium silicate, calcium silicate, zircon silicate, kaolin, clay, bentonite, talc, mica, silicates such as zeolite, asbestos, sericite, hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfuric acid Calcium, barium sulfate, natural gypsum, calcium sulfite, titanates such as barium titanate, water glass,
Dawsonite, carbon black, silicon carbide, molybdenum disulfide and the like. These may be used alone or in combination of two or more.

These inorganic particles have an average particle size of 1 to 100.
In the range of 00 nm, the particles themselves or those obtained by dispersing these particles in water or an appropriate organic solvent are used. From the viewpoint of the dispersion stability of the resulting inorganic modified urethane emulsion, the average particle size of the inorganic particles used is 1 to 200 nm.
Is preferred in the form of an inorganic organosol.

Examples of the silane compound used in the present invention include compounds having a hydrolyzable silyl group. Specific examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane , Ethyltrimethoxysilane, ethyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, octamethylcyclotetrasiloxane and oligomers derived from at least one compound selected from these compounds, etc. Alkoxysilanes, methyltrichlorosilane, ethyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldi A halosilane such as chlorosilane, a repeating unit represented by the following general formula (A), a repeating unit represented by the following general formula (B), and a terminal group X in the molecule; And a silicone compound bonded to the silicon atom in the repeating unit via the above oxygen atom.

[0029]

Embedded image

(In the formulas (A) and (B), R1
Is selected from the following substituents. X
Is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, -Si
R ₂ R ₃ R ₄ (R ₂ , R ₃ , and R ₄ may be the same or different from each other, and may be a hydrogen atom or a group having 1 to 3 carbon atoms.
Represents 0 hydrocarbon groups. At least one selected from
Represents two groups.

A hydrogen atom having 1 to 3 carbon atoms which may or may not have a substituent;
At least one hydrophobic group selected from the group consisting of a monovalent group containing 0 hydrocarbon groups and a monovalent group containing a fluoroalkyl group having 1 to 30 carbon atoms, a monovalent group containing a carboxyl group Containing a phosphate group
At least one hydrophilic group selected from the group consisting of a monovalent group, a monovalent group containing a sulfone group, and a polyoxyalkylene group, a monovalent group containing an epoxy group, a monovalent group containing an acryloyl group, and methacryloyl A monovalent group containing a group, a monovalent group containing a cyclic acid anhydride, a monovalent group containing a carbonyl group,
A monovalent group containing a hydroxyl group, a monovalent group containing an amino group, an alkoxy group, and at least one reactive group selected from the group consisting of a hydroxyl group) These silane compounds may be used alone or in combination of two or more. Used.

In order to obtain an inorganic modified polyurethane emulsion by dispersing the urethane polymer having a hydrolyzable silyl group in the presence of these inorganic particles and / or a silane compound, the hydrolyzable silyl group is converted to The coexistence ratio (weight ratio: (e) / ((f) + (g))) of the urethane polymer (e) and the above-mentioned inorganic particles (f) and / or silane compound (g) is 0.00.
It is 1-100, preferably 0.01-20, more preferably 0.05-5. When the inorganic particles (f) and the silane compound (g) are used in combination, the mixing ratio (weight ratio:
(F) / (g)) is 0.01 to 100, preferably 0.05 to 20.

The method of causing the urethane polymer having a hydrolyzable silyl group to coexist with an inorganic particle and / or a silane compound includes the following methods: (1) mixing the inorganic particle and / or the silane compound with the urethane polymer having a hydrolyzable silyl group; How to let. (2) a method of synthesizing a urethane polymer having a hydrolyzable silyl group in the presence of inorganic particles and / or a silane compound.

As a method for dispersing the urethane polymer having a hydrolyzable silyl group in water in the coexistence of inorganic particles and / or a silane compound, the urethane polymer having a hydrolyzable silyl group and the inorganic particles and / or a silane compound may be used. A method in which water is added to a coexisting substance with moderate stirring to disperse the water. The coexistence of a urethane polymer having a hydrolyzable silyl group and inorganic particles and / or a silane compound,
A method in which water is added to water and dispersed in water under appropriate stirring, and the like can be given. At this time, the applied temperature condition is 0 ° C to 120 ° C.
° C, preferably 5 ° C to 90 ° C.

In the present invention, when a silane coupling agent having an amino group is used as a silane coupling agent for introducing a hydrolyzable silyl group into a urethane polymer, the silane coupling agent has two or more isocyanate groups. An isocyanate group-containing urethane prepolymer obtained by reacting a compound (a) with a compound (b) having an active hydrogen capable of reacting with an isocyanate group under conditions in which the isocyanate group is greater than the active hydrogen group is added to the inorganic particles and / or
Alternatively, a silane compound is made to coexist in the above-described method ((1) and (2)), and a process of dispersing in water, or after dispersing in water, adding a silane coupling agent having an amino group,
You may make it react.

When the urethane polymer having a hydrolyzable silyl group is dispersed in water in the coexistence of inorganic particles and / or a silane compound, a chain extender may be used if necessary. As a chain extender, ethylenediamine,
Propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, various diamines such as isophoronediamine, polyethylenepolyamines such as diethylenetriamine, hydrazine, Adipic dihydrazide and the like, and a combination thereof can be mentioned.

Further, a surfactant may be added at an optional stage for the purpose of assisting or adding to the dispersibility and dispersion stability of the inorganic modified polyurethane emulsion formed as required. When a cationic or anionic hydrophilic group is introduced into the urethane prepolymer, the surfactant may be the same ionic group or nonionic.

The resin content of the inorganic modified polyurethane emulsion of the present invention can be 0.1 to 95% by weight, but is preferably 10 to 50% by weight in terms of production. In addition, various additives may be added for the purpose of improving weather resistance and the like, if necessary, in producing the inorganic modified polyurethane emulsion of the present invention. When an additive is used, it is usually added at the time of synthesizing the urethane prepolymer. However, when the additive is water-soluble or reacts with a reaction component such as an isocyanate component, it is preferably added as a dispersion. As additives, hindered phenol-based, phosphite-based, thioether-based antioxidants, benzophenone-based, benzotriazole-based, salicylate-based ultraviolet absorbers,
Examples include light stabilizers such as hindered amines, flame retardants such as organic halogens, antistatic agents, water repellents and the like, and combinations thereof.

The inorganic modified polyurethane emulsion obtained according to the present invention may contain, if necessary, a crosslinking agent, a pigment, a filler, a dispersant, a wetting agent, a thickener, a rheology control agent, an antifoaming agent, a plasticizer, a film-forming auxiliary, Rust inhibitors, etc. are selected, combined and compounded according to the purpose of each, and clear coat agents, top coat agents, paints, undercoat agents,
It can be used for various uses as an impregnating agent for fabric or paper, a fiber treatment agent, various adhesives, and the like.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. In the following description, “parts” after numerical values mean “parts by weight”.

[0041]

[Reference Example 1] The hydroxyl value was 54.7 and the number average molecular weight was 197.
9 polycarbonate diol (CX-4 manufactured by Nissei Chemical Co., Ltd.)
920) 186.9 parts, isophorone diisocyanate (IPDI) 64 parts, triethylamine (TEA) 9.
57 parts, dimethylolpropionic acid (DMPA)
7 parts, 282.1 parts of methyl ethyl ketone (MEK) and 0.165 parts of dibutyltin dilaurate (BTL) were placed in a reactor having a reflux condenser, a thermometer and a stirrer.
The urethane reaction was carried out at 0 ° C. for 22 hours to obtain an NCO group-terminated urethane prepolymer solution.

The obtained urethane prepolymer solution 430
Part into a reaction group having a thermometer and a stirrer, and γ-
Aminopropyltrimethoxysilane (KB made by Shin-Etsu Chemical Co., Ltd.)
(M-903) 23 parts of MEK dissolved in 23 parts of MEK were added dropwise at room temperature over 1 hour to obtain a urethane polymer having a hydrolyzable silyl group.

[0043]

[Reference Example 2] The hydroxyl value was 57.3 and the number average molecular weight was 195.
4 polycarbonate diol (CX-5 manufactured by Nissei Chemical Co., Ltd.)
520) 200.7 parts, isophorone diisocyanate (IPDI) 82.5 parts, triethylamine (TEA)
12.3 parts, dimethylolpropionic acid (DMPA) 1
6.5 parts, 392 parts of tetrahydrofuran (THF) and 0.206 parts of dibutyltin dilaurate (BTL) are placed in a reactor having a reflux condenser, a thermometer and a stirrer.
The urethane reaction was carried out at 0 ° C. for 24 hours to obtain a urethane prepolymer solution having NCO group terminals.

[0044]

Reference Example 3 To 353 parts of the urethane prepolymer solution synthesized in Reference Example 2, 23.3 parts of γ-aminopropyltrimethoxysilane (KBM903 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to THF2.
The solution dissolved in 3.3 parts was dropped at room temperature over 1 hour to obtain a urethane polymer having a hydrolyzable silyl group.

[0045]

Reference Example 4 To 177 parts of the urethane prepolymer solution synthesized in Reference Example 2, 5.8 parts of γ-aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to THF.
The solution dissolved in 5.8 parts was added dropwise at room temperature over 1 hour to obtain a urethane prepolymer having an isocyanate group and a hydrolyzable silyl group.

[0046]

Example 1 42.8 parts of a urethane polymer solution having a hydrolyzable silyl group synthesized in Reference Example 1 were used as inorganic particles (f) as an organosilica sol having a solid content of 30% (MEK-ST manufactured by Nissan Chemical Industries, Ltd.). ) 100 parts and 30 parts of ethanol were placed in a reaction vessel having a reflux condenser, a thermometer and a stirrer and mixed at room temperature. The obtained mixture is heated at 40 ° C.
Then, 150 parts of water was added dropwise over 1 hour, and the mixture was further heated to 80 ° C. and stirred for 2 hours to obtain an inorganic modified polyurethane emulsion. The obtained inorganic-modified polyurethane emulsion was applied on a glass plate so as to have a film thickness of 30 μm, and was allowed to stand at a temperature of 20 ° C. and a humidity of 65% for one week. As a result, a very hard film having good transparency was obtained. .

[0047]

Example 2 67.4 parts of the urethane prepolymer solution synthesized in Reference Example 3 was used as the inorganic particles (f).
Organo silica sol (MEK-S manufactured by Nissan Chemical Industries, Ltd.)
T) 50 parts were placed in a reaction vessel having a reflux condenser, a thermometer and a stirrer and mixed at room temperature. The resulting mixture is
After heating to 150C and dropping 150 parts of water over 1 hour, the mixture was further heated to 80C and stirred for 2 hours to obtain an inorganic modified polyurethane emulsion. The obtained inorganic-modified polyurethane emulsion was applied on a glass plate so as to have a thickness of 30 μm, and was left at a temperature of 20 ° C. and a humidity of 65% for 1 week. The film had good transparency, and was hard and flexible. was gotten.

[0048]

Example 3 67.4 parts of the urethane prepolymer solution synthesized in Reference Example 4 was used as the inorganic particles (f) to have a solid content of 30%.
Organosilica sol (MEK-ST, Nissan Chemical Co., Ltd.)
25 parts, as a silane compound (g), methyltrimethoxysilane (KBM-13 manufactured by Shin-Etsu Chemical Co., Ltd.) 10.13
Part, dimethyldimethoxysilane (KB manufactured by Shin-Etsu Chemical Co., Ltd.)
M-22) 4.1 parts and ethanol 5 parts were put into a reaction vessel having a reflux condenser, a thermometer and a stirrer, and mixed at room temperature. The resulting mixture is heated to 40 ° C. and water 117
And N-β (aminoethyl) γ-aminopropyltrimethoxysilane (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.)
After dropping 5.5 parts over 1 hour, the mixture was further heated to 80 ° C. and stirred for 2 hours to obtain an inorganic modified polyurethane emulsion. The obtained inorganic-modified polyurethane emulsion was applied on a glass plate so as to have a thickness of 30 μm, and was left at a temperature of 20 ° C and a humidity of 65% for 1 week.
A hard and flexible film having good transparency was obtained.

[0049]

Example 4 As a silane compound (g), 48.6 parts of the urethane prepolymer solution synthesized in Reference Example 3 was methyltrimethoxysilane (KBM-13 manufactured by Shin-Etsu Chemical Co., Ltd.) 2
0.3 parts, dimethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
32.4 parts of KBM-22) and 10 parts of ethanol were placed in a reaction vessel having a reflux condenser, a thermometer and a stirrer, and mixed at room temperature. Heating the resulting mixture to 40 ° C.,
After 150 parts of water was added dropwise over 1 hour, the mixture was further heated to 80 ° C. and stirred for 2 hours to obtain an inorganic modified polyurethane emulsion. The obtained inorganic-modified polyurethane emulsion was applied on a glass plate so as to have a thickness of 30 μm, and was left at a temperature of 20 ° C. and a humidity of 65% for 1 week. The film had good transparency, and was hard and flexible. was gotten.

[0050]

Comparative Example 1 42.8 parts of the urethane prepolymer solution synthesized in Reference Example 2 was used as the inorganic particles (f), and the solid content was 30%.
Organosilica sol (Nissan Chemical Industries, Ltd. MEK-S)
T) 100 parts were placed in a reaction vessel having a reflux condenser, a thermometer and a stirrer and mixed at room temperature. The resulting mixture is
After heating to 0 ° C. and dropping 150 parts of water over 1 hour,
The mixture was further heated to 80 ° C. and stirred for 2 hours, but no polyurethane emulsion was obtained, and the mixture was gelled.

[0051]

According to the present invention, the inorganic modified polyurethane emulsion produced by the present invention has very good water dispersion stability, and the resulting coating film has excellent transparency and a balance between hardness and elasticity. Therefore, according to the present invention, an excellent inorganic modified polyurethane emulsion that can be used for various applications as a clear coat agent, a top coat agent, a paint, an undercoat agent, a cloth or paper impregnating agent, a fiber treatment agent, various adhesives, and the like. Can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08J 3/075 CFF C08L 75/04 C08K 3/00 C09D 175/04 C08L 75/04 C09J 175/04 // C09D 175/04 C08J 3/03 CFF C09J 175/04 F term (reference) 4F070 AA50 AA53 AA60 AC04 AC14 AC15 AC16 AC20 AC22 AC23 AC27 AC28 AC52 AD10 AE01 CA01 CA18 CB01 CB13 4J002 CK02W CK05W DA036 DE076 DE126 DE126 DE0909 DE236 DE246 DG026 DG046 DG056 DJ006 DJ016 DJ036 DL006 GH00 GH01 GJ01 4J034 BA08 BA10 CA01 CA04 CB03 DA01 DB04 DD01 DD03 DD11 DG03 DG04 DN03 HA01 HA04 HA07 HA13 HA14 HA15 HB16 HC03 JA02 JA03 JA1 K04 MA1 DG12 MA041 DG131 DG191 DG271 DG281 DG291 DL022 DL032 GA01 GA02 GA03 GA06 GA08 GA09 GA12 GA13 HA026 HA156 HA166 HA266 HA356 HA376 HA436 HA446 HA456 JC31 JC32 KA08 KA20 MA08 MA10 MA14 NA03 NA04 NA11 NA26 4J040 EF051 EF061 EF111 EF121 EF131 EF181 EF291 EF301 EF311 EK022 EK032 GA01 GA03 GA05 HA07 GA26 GA24 HA356 HD31 HD32 JA03 KA23 KA42 LA03 LA05 LA06 LA07 LA10 MA09 MA10

Claims (4)

[Claims] An inorganic modified polyurethane emulsion obtained by dispersing a urethane polymer having a hydrolyzable silyl group in water in the presence of inorganic particles and / or a silane compound. 2. A urethane polymer having a hydrolyzable silyl group, a compound (a) having two or more isocyanate groups, a compound (b) having an active hydrogen capable of reacting with an isocyanate group, and a compound capable of reacting with an isocyanate group A silane coupling agent having an active hydrogen group (c) and / or a silane coupling agent having an isocyanate group (d)
The inorganic modified polyurethane emulsion according to claim 1, which is a reaction product with the above. 3. The inorganic modified polyurethane emulsion according to claim 1, wherein the inorganic particles are an inorganic organosol. 4. The inorganic modified polyurethane emulsion according to claim 2, wherein the compound (b) is a polycarbonate diol.