JP3444287B2 - Alkoxy group-containing silane-modified polyurethane resin, resin composition and polyurethane resin-silica hybrid - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an alkoxy group-containing silane-modified polyurethane resin, the resin composition and a polyurethane resin-silica hybrid.

[0002]

2. Description of the Related Art Polyurethane resins have been widely used in various fields because they have rubber elasticity. The rubber elasticity of such a polyurethane resin is exhibited because the hard segment having toughness is insolubilized from the matrix of the soft segment having flexibility to form a domain. However, the polyurethane resin is generally a material having low heat resistance, and normally, there is a problem that the rubber elasticity disappears due to melting of the hard segment at 100 to 160 ° C., resulting in liquefaction. Particularly in recent years, due to the diversification of technology, improvement in performance has been required also in the coating field, and polyurethane resins having rubber elasticity even at high temperatures are desired.

As a method for improving the heat resistance of the polyurethane resin, there are a method of increasing the proportion of hard segments and a method of introducing many urea bonds into the hard segments. However, such a method is not preferable because it causes insolubilization of the polyurethane resin in a solvent or an increase in viscosity.

As a method of imparting heat resistance to a polyurethane resin, there is a method of applying a sol-gel method to synthesize a hybrid with an inorganic glass. That is, by utilizing hydrolysis and polycondensation of hydrolyzable alkoxysilane such as tetraethoxysilane, a hybrid body in which an inorganic glass is dispersed in a polyurethane resin by a so-called filler effect is manufactured. According to the sol-gel method, the diameter of glass particles produced is as small as several nm, and therefore the transparency of the organic polymer is not lost even when the glass particles are dispersed in the polyurethane resin.

However, when an organic / inorganic hybrid body of a polyurethane resin is produced by the sol-gel method, performances such as heat resistance are improved due to the filler effect, while glass particles are dispersed throughout the polyurethane resin, which is unique to the polyurethane resin. The soft segment of the is lost and becomes brittle. For example, JP-A-6-136321 discloses an organic / inorganic hybrid body using an alcohol sol solution obtained by dissolving a hydrophilic soft segment polyurethane resin, a hydrolyzable alkoxysilane, and optionally a catalyst in a lower alcohol. Although the manufacturing method is described,
The resulting organic / inorganic hybrid has no flexibility,
It was brittle and its heat resistance was not sufficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to mechanical strength,
An object of the present invention is to provide an alkoxy group-containing silane-modified polyurethane resin and a resin composition capable of producing a polyurethane resin-silica hybrid body (cured product) having excellent heat resistance and high temperature durability.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a reaction product containing a specific polyurethane resin and a specific silane compound as constituent components is used. The inventors have found that the above object can be achieved and have completed the present invention.

That is, according to the present invention, a polyurethane resin (1) obtained from a high molecular weight polyol, a diisocyanate and a chain extender and having a functional group reactive with an epoxy group (1) and one hydroxyl group in one molecule Epoxy compound (A) (hereinafter simply abbreviated as epoxy compound (A))
And an alkoxy group-containing alkoxysilane partial condensate (2) obtained by dealcoholization reaction of the alkoxysilane partial condensate (B) with the alkoxy group-containing silane-modified polyurethane resin; And a polyurethane resin-silica hybrid body obtained by curing the alkoxy group-containing silane-modified polyurethane resin or the resin composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polyurethane resin (1) used in the present invention comprises a soft segment composed of a polymer polyol, and a hard segment composed of a diisocyanate, a chain extender and optionally a chain length terminating agent. It is a thing.

The polymer polyol is not particularly limited, and various known ones such as polyester polyol, polycarbonate polyol, polyether polyol and polyolefin polyol can be mentioned. The polymer polyol has a number average molecular weight in the range of 500 to 10,000 and preferably has a hydroxyl group at the molecular end. When the number average molecular weight is less than 500, stability tends to decrease with the decrease in solubility, and when it exceeds 10,000, elasticity tends to decrease. Considering the mechanical properties of the cured product, it is preferably in the range of 1000 to 6000. Also, from the viewpoint of various resistance such as high temperature durability of the finally obtained polyurethane-silica hybrid,
Among the above-mentioned polymer polyols, polyester polyol and / or polycarbonate polyol are particularly suitable.

As the polyester polyol, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,
3-propanediol, 1,3-butanediol, 1,
4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, octanediol, 1,4
-Saturated or unsaturated known low-molecular-weight glycols such as butynediol and dipropylene glycol, or n
-Alkyl glycidyl ethers such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, and terephthalic acid ,
Dibasic acids such as succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, or their corresponding acid anhydrides, dimer acids, castor oil and its fatty acids are dehydrated and condensed. And polyester polyols obtained by ring-opening polymerization of a cyclic ester compound. In the case of a polymer polyol obtained from a low molecular glycol and a dibasic acid, up to 5 mol% of the glycols can be replaced with the following various polyols. Examples thereof include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol and pentaerythritol.

Further, as the polycarbonate polyol, generally known are the demethanol condensation reaction of polyhydric alcohol and dimethyl carbonate, the deurethane condensation reaction of polyhydric alcohol and diphenyl carbonate, or the deethylene glycol condensation reaction of polyhydric alcohol and ethylene carbonate. Obtained by reaction. Examples of the polyhydric alcohol used in these reactions include 1,6-hexanediol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1, 5-
Saturated or unsaturated various known low molecular weight glycols such as pentanediol, octanediol, 1,4-butynediol and dipropylene glycol, and alicyclic rings such as 1,4-cyclohexanediglycol and 1,4-cyclohexanedimethanol Group glycol etc. are mentioned.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol and the like obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran and the like.

Examples of the polyolefin polyols include polybutadiene polyol having a hydroxyl group at the terminal, polyisoprene polyol, and hydrogenated products thereof.

As the diisocyanate compound which is a constituent of the polyurethane resin (1), various known aromatic, aliphatic or alicyclic diisocyanates can be used. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1, 4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, hydrogen Xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, Cyclohexyl-4,4 '
Typical examples thereof include diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexanediisocyanate, m-tetramethylxylylene diisocyanate, and dimerisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group.

The chain extender used in the polyurethane resin (1) is, for example, a low molecular weight glycol, dimethylolpropionic acid, dimethylolbutanoic acid or the like having a carboxyl group in the molecule described in the section of the polyester polyol. , Ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine,
Polyamines such as dimer diamine, which is obtained by converting the carboxyl group of dimer acid into amino group, polyamines having a carboxyl group in the molecule such as L-lysine and L-arginine
Is mentioned.

A polymerization terminator may be used in the polyurethane resin of the present invention to control the molecular weight. Examples of the polymerization terminator include alkyl monoamines such as di-n-butylamine and n-butylamine,
Examples thereof include monoamines having a carboxyl group in the molecule such as D-alanine and D-glutamic acid, alcohols such as ethanol and isopropyl alcohol, alcohols having a carboxyl group in the molecule such as glycolic acid.

As the method for producing the polyurethane resin (1) used in the present invention, a one-step method of reacting a polymer polyol, a diisocyanate compound, a chain extender and / or a polymerization terminator at once in a suitable solvent, A molecular polyol and a diisocyanate compound are reacted under conditions of excess isocyanate groups to prepare a prepolymer having an isocyanate group at the terminal of the polymer polyol, which is then chain-extended in a suitable solvent and, if necessary, Examples thereof include a two-step method of reacting with a polymerization terminator. The two-step method is preferred for the purpose of obtaining a uniform polymer solution. In these production methods, the solvent used is usually an aromatic solvent such as benzene, toluene or xylene; an ester solvent such as ethyl acetate or butyl acetate; methanol, ethanol, isopropanol, n-butanol, diacetone alcohol or the like. Alcohol-based solvent; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and other solvents such as dimethylformamide, dimethylacetamide, ethylene glycol dimethyl ether, tetrahydrofuran, and cyclohexanone can be used alone or in combination.

The functional group having reactivity with the epoxy group in the polyurethane resin (1) is the polyurethane resin (1).
It may be present at either the terminal or the main chain. Examples of the epoxy group-reactive functional group include a carboxyl group, a sulfone group, an acidic group such as a phosphoric acid group, an amino group, a hydroxyl group, and a mercapto group, but usually, reactivity with an epoxy group and functional group addition From the viewpoint of easiness, an acidic group and an amino group are preferable. The method of imparting an acidic group to the polyurethane resin (1) is not limited, but, for example, of the above chain extenders and polymerization terminators, one having a carboxyl group can be easily imparted with a carboxyl group. The method of imparting an amino group to the polyurethane resin (1) is not limited, but for example, polyamines may be reacted so that the amino group becomes excessive with respect to the terminal isocyanate group of the prepolymer. The amount of the epoxy group-reactive functional group in the polyurethane resin (1) is not particularly limited, but is usually 0.1 to 20.
It is preferably KOH mg / g. 0.1 KOHm
If it is less than g / g, the flexibility and heat resistance of the resulting polyurethane resin-silica hybrid will decrease,
If it exceeds OHmg / g, the water resistance of the polyurethane resin-silica hybrid tends to decrease.

The epoxy group-containing alkoxysilane partial condensate (2) of the present invention is obtained by dealcoholation reaction of the epoxy compound (A) and the alkoxysilane partial condensate (B) as described above.

As the epoxy compound (A), 1
The number of epoxy groups is not particularly limited as long as it is an epoxy compound having one hydroxyl group in the molecule. Further, as the epoxy compound (A), a compound having a carbon number of 15 or less is preferable because the smaller the molecular weight, the better the compatibility with the alkoxysilane partial condensate (B) and the higher the effect of imparting heat resistance and adhesion. It is suitable. Specific examples thereof include monoglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting epichlorohydrin with water, dihydric alcohol or phenols; epichlorohydrin and glycerin, pentaerythritol, etc. Polyglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting with polyhydric alcohol having 3 or more valences; one hydroxyl group at the molecular end obtained by reacting epichlorohydrin and aminomonoalcohol Epoxy compound having; alicyclic hydrocarbon monoepoxide having one hydroxyl group in the molecule (for example, epoxidized tetrahydrobenzyl alcohol) and the like. Of these epoxy compounds, glycidol is the most excellent in the heat resistance imparting effect, and is also most suitable because it has high reactivity with the alkoxysilane partial condensate (2).

Further, an alkoxysilane partial condensate (B)
Then, the general formula (a): R¹ _pSi (OR²)_4-p (In the formula, p represents 0 or 1. R¹Is directly on the carbon atom
A lower alkyl group which may have a bonded functional group, ari
Group or unsaturated aliphatic residue. R²Is a methyl group
Or an ethyl group, R²Even though they are the same, they are different
It may be. ) Hydrolyzable alkoxy
Hydrolysis of silane monomer in the presence of acid or alkaline water
However, those obtained by partial condensation are used.

Specific examples of such a hydrolyzable alkoxysilane monomer include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetraisopropoxysilane.
Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyl Examples include trialkoxysilanes such as triethoxysilane. As the alkoxysilane partial condensate (B), those exemplified above can be used without particular limitation, but when two or more kinds of these exemplified substances are mixed and used, tetramethoxysilane is used.
The one synthesized by using 70 mol% or more of all alkoxysilane monomers constituting the alkoxysilane partial condensate (B) is preferable.

The alkoxysilane partial condensate (B) is represented by, for example, the following general formula (b) or (c). General formula (b):

[0025]

[Chemical 1]

(In the formula, R ¹ represents a lower alkyl group, an aryl group or an unsaturated aliphatic residue which may have a functional group directly bonded to a carbon atom. R ² represents a methyl group or an ethyl group. , R ² may be the same or different.)

General formula (c):

[0028]

[Chemical 2]

[0029] (In the general formula (c), R ² is Formula (b) the same as R ² in.)

The alkoxysilane partial condensate (B) has a number average molecular weight of about 230 to 2000, and in the general formulas (c) and (d), the average number of repeating units n is 2 to 11.
Is preferred. When the value of n exceeds 11, the solubility of the epoxy group-containing alkoxysilane partial condensate (2) deteriorates, the compatibility with the urethane resin (1) significantly decreases at the reaction temperature, and the reactivity tends to decrease. It is not preferable because it is present. When n is less than 2, it is not preferable because it is distilled out together with alcohol out of the reaction system during the dealcoholization reaction reaction with the epoxy compound (A).

The epoxy group-containing alkoxysilane partial condensate (2) can be obtained by subjecting the epoxy compound (A) and the alkoxysilane partial condensate (B) to a dealcoholization (ester exchange) reaction. The ratio of the epoxy compound (A) and the alkoxysilane partial condensate (B) to be used is not particularly limited as long as the alkoxy group substantially remains, but is usually equivalent to the hydroxyl group of the epoxy compound (A). / The alkoxysilane partial condensate (B) and the epoxy compound (A) are dealcoholized at a charging ratio such that the alkoxyl group equivalent of the alkoxysilane condensate (B) = 0.01 / 1 to 0.7 / 1. It is preferable. Since the proportion of the alkoxysilane partial condensate (B) which is not modified with epoxy increases as the charging ratio decreases, the charging ratio is preferably 0.03 or more / 1. Further, when the charging ratio becomes large, the epoxy groups of the epoxy group-containing alkoxysilane partial condensate (2) become polyfunctional, and gelation easily occurs during the synthesis of the silane-modified urethane resin, so the charging ratio is 0.5 or less /
It is preferably 1.

The reaction between the alkoxysilane partial condensate (B) and the epoxy compound (A) is carried out, for example, by charging each of the above-mentioned components and removing the alcohol produced by heating to carry out a dealcoholization reaction. The reaction temperature is about 50 to 150 ° C, preferably 70 to 110 ° C, and the total reaction time is 1
It is about 15 hours. In addition, the dealcoholization reaction
If carried out at a temperature higher than 0 ° C., the molecular weight of the reaction product will be too high due to the condensation of the alkoxysilane in the reaction system,
It tends to be highly viscous and gel. In such a case, increasing the viscosity and preventing gelation can be prevented by, for example, stopping the dealcoholization reaction during the reaction.

Further, in the dealcoholization reaction of the above-mentioned alkoxysilane partial condensate (B) and epoxy compound (A), a conventionally known catalyst which does not open the epoxy ring is used to accelerate the reaction. be able to. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium and manganese. , These oxides, organic acid salts, halides, alkoxides and the like. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate, tin octylate and the like are effective.

The above reaction can also be carried out in a solvent. The solvent is not particularly limited as long as it dissolves the alkoxysilane condensate (B) and the epoxy compound (A) and is inert to the epoxy group of the epoxy compound (A). As such an organic solvent, it is preferable to use the solvent used for producing the polyurethane resin (1).

The alkoxy group-containing silane-modified polyurethane resin which is the object of the present invention is obtained by reacting the polyurethane resin (1) with the epoxy group-containing alkoxysilane partial condensate (2). Urethane resin (1)
The use ratio of the epoxy group-containing alkoxysilane partial condensate (2) and the epoxy group-containing alkoxysilane partial condensate (2) is not particularly limited, but is equivalent to the epoxy group of the epoxy group-containing alkoxysilane partial condensate (2) / epoxy group reactivity of the polyurethane resin (1). The total equivalent amount (equivalent ratio) of the functional groups is preferably in the range of 0.30-5. When it is less than 0.30, the obtained alkoxy group-containing silane-modified polyurethane resin cannot sufficiently exert the effect of the present invention, and when it is more than 5, unreacted epoxy group-containing alkoxysilane partial condensation in the alkoxy group-containing silane modified polyurethane resin. It is not preferable because the ratio of the item (2) increases.

In the production of such a silane-modified polyurethane resin composition containing an alkoxy group, for example, the above components are charged and the reaction is carried out by heating in a substantially anhydrous state. The main purpose of this reaction is to react the acidic group and / or amino group of the polyurethane resin (1) with the oxirane group of the above-mentioned epoxy group-containing alkoxysilane partial condensate (2). It is necessary to suppress the formation of silica due to the sol-gel reaction of the alkoxysilyl moiety of the partial condensate (2). Therefore, the reaction temperature is room temperature to about 150 ° C., preferably 40 to 120 ° C., and the total reaction time is preferably about 1 to 10 hours.

In addition, a catalyst is not particularly required for the above reaction, but a conventionally known catalyst can be used to accelerate the reaction. For example, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine,
Tertiary amines such as dimethylaminoethanol and tris (dimethylaminomethyl) urethane; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4
-Imidazoles such as methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4- Examples thereof include tetraphenylboron salts such as methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. The reaction catalyst may be used in a proportion of 0.01 to 5 parts by weight based on 100 parts by weight of the solid content of the polyurethane resin (1).

The above reaction can be carried out in a solvent or without a solvent depending on the purpose of use. The solvent is not particularly limited as long as it dissolves the polyurethane resin (1) and the epoxy group-containing alkoxysilane partial condensate (2). As such a solvent, the one used at the time of producing the polyurethane resin (1) or the epoxy group-containing alkoxysilane partial condensate (2) can be used.

The alkoxy group-containing silane-modified polyurethane resin of the present invention thus obtained has an alkoxy group derived from the alkoxysilane partial condensate (B) in its molecule. The content of the alkoxy group is not particularly limited, but the alkoxy group is bound to each other by sol-gel reaction or dealcohol condensation by evaporation of solvent or heat treatment or by reaction with water (humidity). Since it is necessary for forming a cured product, the silane-modified polyurethane resin containing an alkoxy group usually contains 50 to 95 mol%, preferably 60 to 90 mol%, of unreacted alkoxy groups of the alkoxysilane partial condensate (B). It is good to keep it as it is.

The cured product obtained from the alkoxy group-containing silane-modified polyurethane resin has a gelled fine silica site (higher-order network structure of siloxane bonds). The alkoxy group-containing silane-modified polyurethane resin of the present invention is mainly composed of a polyurethane resin in which a part of the epoxy group-reactive functional groups in the polyurethane resin (1) is silane-modified. The modified polyurethane resin may contain an unreacted alkoxysilane partial condensate (B), an epoxy group-containing alkoxysilane partial condensate (2), a solvent and a catalyst used for the reaction. The unreacted alkoxysilane partial condensate (B) and epoxy group-containing alkoxysilane partial condensate (2) are cured by silica by hydrolysis and polycondensation during curing, and are integrated with the alkoxy group-containing silane-modified polyurethane resin.

The alkoxy group-containing silane-modified polyurethane resin composition of the present invention may contain the alkoxy group-containing silane-modified polyurethane resin, and the other components are not particularly limited and are conventionally known depending on the application. Polymer materials can be appropriately used together. Examples of such polymer material include acrylic resin, epoxy resin, polystyrene and the like. In addition, the resin composition of the present invention is the same as Si in the solid residue in the silane-modified resin composition.
The content is preferably 0.5 to 30% by weight in terms of silica weight. The Si content in terms of silica weight in the solid residue referred to here is the silica moiety when the alkoxysilyl moiety of the silane-modified polyurethane resin undergoes a sol-gel curing reaction to cure into a silica moiety (general formula (d)). Is the weight percent of. If it is less than 0.5% by weight, heat resistance,
It becomes difficult to obtain the effects of the present invention such as strength, and 30% by weight
If it exceeds, the cured product tends to be too brittle and the strength tends to decrease. The concentration of the resin composition can be appropriately adjusted with a solvent according to the purpose of use. Any solvent can be used without particular limitation as long as it can dissolve the alkoxy group-containing silane-modified polyurethane resin. When it is necessary to adjust the Si content in the solid residue for the purpose of adjusting the mechanical strength and heat resistance of the cured product, the alkoxy group partial condensate (B ) Or polyurethane resin (1) may be blended. In addition, various curing agents which are conventionally used for curing polyurethane resins may be used in the alkoxy group silane modified resin composition.

Further, the silane-modified resin composition contains a conventionally known acid or basic catalyst, a sol-gel curing catalyst such as a metal catalyst, or water for the purpose of accelerating the silica curing reaction at a low temperature. good. In addition, in addition to the above, the alkoxy group silane-modified resin composition may contain a filler, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, if necessary, within a range that does not impair the effects of the present invention. , An antibacterial agent, an antifungal agent, a leveling agent, an antifoaming agent, a coloring agent, a stabilizer, a coupling agent and the like may be added.

The alkoxy group-containing silane-modified polyurethane resin and resin composition of the present invention can be used for various plastics,
Glass, metal, leather material, mortar, wood, paper, concrete, concrete, leather material, wood, paper, rubber, woven cloth,
It can be used as a coating agent, adhesive, and impregnating agent for various base materials such as non-woven fabrics and printed wiring boards. Further, alkoxy group-containing silane-modified urethane resins and resin compositions are used as potting agents for electronic devices, ICs, optical devices, paints such as magnetic paints, conductive pastes, printing inks such as resist inks and special gravure inks, floors. It can be used in various fields as a binder for materials, waterproof materials, fiber processing agents, paper processing agents, and the like. When the silane-modified urethane resin composition or the resin composition is used as a paint, an ink or various coating agents, a conventionally known pigment is used for 100 parts by weight of the solid residue of the alkoxy group-containing silane-modified polyurethane resin composition. Is used by blending 0 to 150 parts by weight. The coating material is coated on the base material using a conventionally known coating equipment such as a sprayer or a coater, and then baked at 60 ° C. or higher to form a coating film. The amount of the catalyst used can be appropriately determined depending on the activity of the catalyst used. Usually, the molar ratio to the alkoxy group of the silane-modified polyurethane resin used is about 0.01 to 5 mol% for paratoluenesulfonic acid or tin octylate having a high catalytic ability, and 0 for formic acid or acetic acid having a low catalytic ability. 0.1 to 50 mol% is used. Further, a curing agent such as polyisocyanate may be blended for the purpose of softening and strengthening the cured film.

In the cured product formed from the alkoxy group-containing silane-modified polyurethane resin, almost all silica produced by sol-gel curing of the alkoxysilyl moiety derived from the alkoxysilane partial condensate (B) is a polyurethane resin. It combines with the hard segment of to form a composite domain of the hard segment and silica. That is, the alkoxy group-containing silane-modified urethane resin forms a hybrid body in which the composite domain and the soft segment have a two-layer separated (sea-island) structure. Due to such a two-layer separated (sea-island) structure, the soft segment of polyurethane constituting the matrix of the hybrid body does not contain silica and therefore retains its flexibility. On the other hand, in the hard segment of the polyurethane, since only the domain can be toughened by the composite domain with silica, it is presumed that the cured product obtained has improved mechanical strength, heat resistance and the like.

[0045]

According to the present invention, it is possible to provide a polyurethane resin-silica hybrid body (cured product) having excellent flexibility, mechanical strength, heat resistance and high temperature durability. Further, according to the present invention, an alkoxy group-containing silane-modified polyurethane resin and a resin composition capable of producing the polyurethane resin-silica hybrid body can be provided.

The present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. In each example,% is based on weight unless otherwise specified.

Production Example 1 (Production of Epoxy Group-Containing Alkoxysilane Partial Condensate (2)) A reactor equipped with a stirrer, a water divider, a thermometer and a nitrogen gas inlet tube was placed in a glycidol (manufactured by NOF Corporation) Trade name "Epiol OH") 1400 g and tetramethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd., trade name "methyl silicate 51", average number of Si is 4) 8957.9
After charging g, the temperature was raised to 90 ° C. with stirring under a nitrogen stream, and 2.0 g of dibutyltin dilaurate as a catalyst was added and reacted. During the reaction, methanol was distilled off using a water separator, and when the amount reached about 630 g, the mixture was cooled. The time required for cooling after the temperature was raised was 5 hours. Then, about 80 g of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes. In this way, an epoxy group-containing alkoxysilane partial condensate (2A) was obtained.
The equivalent of the hydroxyl group of the epoxy compound (A) / the equivalent of the alkoxyl group of the alkoxysilane condensate (B) (equivalent ratio) = 0.10 at the time of charging, and the epoxy equivalent is 512 g / e.
q.

Production Example 2 (Production of Epoxy Group-Containing Alkoxysilane Partial Condensate (2)) Glycidol 250.0 was charged in the same reactor as in Production Example 1.
g and tetramethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 56”, average number of Si is 10) 2675.4 g were charged, and a nitrogen stream was used.
After heating to 90 ° C. with stirring, 0.5 g of dibutyltin dilaurate as a catalyst was added and reacted. During the reaction, methanol was distilled off using a water separator, and the amount was about 1
When it reached 25 g, it was cooled. The time required for cooling after raising the temperature was 6.5 hours. Subsequently, about 5 g of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes. Thus, an epoxy group-containing alkoxysilane partial condensate (2B) was obtained. The equivalent of the hydroxyl group of the epoxy compound (A) at the time of charging / the equivalent of the alkoxyl group of the alkoxysilane condensate (B) (equivalent ratio) = 0.0
5, the epoxy equivalent is 830 g / eq.

Example 1 (Production of alkoxy group-containing silane-modified polyurethane resin) A polycarbonate diol (manufactured by Daicel Chemical Co., Ltd.) was placed in a reactor equipped with a stirrer, a thermometer and a nitrogen gas inlet tube.
Product name "Plaxel CD220", number average molecular weight 2
000) 1000 g and isophorone diisocyanate 27
8 g was charged and reacted under a nitrogen stream at 100 ° C. for 6 hours to obtain a prepolymer having a free isocyanate value of 3.44%. To this, 548 g of methyl ethyl ketone was added to prepare a uniform solution of a urethane prepolymer. Then, 71.8 g of isophoronediamine, 4.0 of di-n-butylamine.
g, 906 g of methyl ethyl ketone, and 603 g of isopropyl alcohol in the presence of a mixture of 1000 g of the urethane prepolymer solution, and the mixture was reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as polyurethane resin 1A) had a resin solid content concentration of 30% and an amine value of 1.2 KOHmg / g. Furthermore, after heating 500 g of the above polyurethane resin 1A to 50 ° C. in the same reactor, the epoxy group-containing alkoxysilane partial condensate (2A) 1 obtained in Production Example 1 was obtained.
0.95 g was added and reacted at 60 ° C. for 4 hours under a nitrogen stream to obtain an alkoxy group-containing silane-modified polyurethane resin. The epoxy group equivalent of the epoxy group-containing alkoxysilane partial condensate (2A) / polyurethane resin (1
The equivalent weight (equivalent ratio) of the amino group of A) = 2, and the Si content in the solid residue in the alkoxy group-containing silane-modified polyurethane resin was 3.3% in terms of silica weight.

Example 2 (Production of alkoxy group-containing silane-modified polyurethane resin) In Example 1, "Plaxel CD220" was changed to polyester polyol (Kuraray Co., Ltd., "Kuraray Polyol P2010", number average molecular weight 2000). Other than that, the reaction was performed in the same manner as in Example 1 to obtain a polyurethane resin solution (hereinafter referred to as polyurethane resin (1B)). The polyurethane resin (1B) had a resin solid content of 30% and an amine value of 1.2 KOHmg / g. Further, in the same reactor, 500 g of the above polyurethane resin 1A is added to 50 g.
After heating to 0 ° C., 17.75 g of the epoxy group-containing alkoxysilane partial condensate (2B) obtained in Production Example 2 was added and reacted at 60 ° C. for 4 hours under a nitrogen stream to give an alkoxy group-containing silane-modified polyurethane resin. Obtained. Incidentally, the epoxy group equivalent of the epoxy group-containing alkoxysilane partial condensate (2B) / amino group equivalent of the urethane resin (1B) (equivalent ratio) = 2, Si in the solid residue in the alkoxy group-containing silane-modified polyurethane resin The content was 6.0% in terms of silica weight.

Example 3 (Production of alkoxy group-containing silane-modified polyurethane resin) The same reactor as in Example 1 was charged with "Placcel CD22.
0 "1000 g and isophorone diisocyanate 278
g, and react under a nitrogen stream at 100 ° C. for 6 hours,
A prepolymer having a free isocyanate value of 3.44% was prepared, and 548 g of methyl ethyl ketone was added to the prepolymer to prepare a uniform solution of the urethane prepolymer. Then, 77.6 g of isophoronediamine, 2.4 g of di-n-butylamine,
1000 g of the urethane prepolymer solution was added in the presence of a mixture of 913 g of methyl ethyl ketone and 607 g of isopropyl alcohol, and the mixture was reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as polyurethane resin (1C)) had a resin solid content concentration of 30% and an amine value of 2.4 KOHmg / g. Furthermore, after heating 500 g of the above polyurethane resin 1A to 50 ° C. in the same reactor, the epoxy group-containing alkoxysilane partial condensate (2A) 1 obtained in Production Example 1 was obtained.
8.54 g was added, and the mixture was reacted under a nitrogen stream at 60 ° C. for 4 hours to obtain an alkoxy group-containing silane-modified polyurethane resin. The epoxy group equivalent of the epoxy group-containing alkoxysilane partial condensate (2A) / polyurethane resin (1
The equivalent weight (equivalent ratio) of the amino group of C) = 2, and the Si content in the solid residue in the alkoxy group-containing silane-modified polyurethane resin was 6.4% in terms of silica weight.

Example 4 (Production of alkoxy group-containing silane-modified polyurethane resin) The same reactor as in Example 1 was charged with "Kuraray Polyol P2".
010 "1000 g and dimethylolbutanoic acid 40 g,
Isophorone diisocyanate (342 g) was charged and reacted at 100 ° C. for 6 hours under a nitrogen stream to form a prepolymer having a free isocyanate value of 3.28%. To this, 593 g of methyl ethyl ketone was added to prepare a uniform solution of a urethane prepolymer. Then, 59.7 g of isophorone diamine,
Di-n-butylamine 9.9 g, methyl ethyl ketone 8
1000 of the above urethane prepolymer solution in the presence of a mixture consisting of 97 g and 599 g of isopropyl alcohol.
g was added and reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as polyurethane resin (1D)) had a resin solid content concentration of 30% and an acid value of 3.0 KOHmg / g. Further, after heating 500 g of the above polyurethane resin 1A to 50 ° C. in the same reaction apparatus, 18.54 g of the epoxy group-containing alkoxysilane partial condensate (2A) obtained in Production Example 1 was added, and the mixture was placed under a nitrogen stream. The reaction was carried out at 60 ° C. for 4 hours to obtain an alkoxy group-containing silane-modified urethane resin. Incidentally, the epoxy group equivalent of the epoxy group-containing alkoxysilane partial condensate (2A) / the equivalent of the carboxylic acid group of the urethane resin (1D) (equivalent ratio) =
2. Si content in the solid residue in the alkoxy group-containing silane-modified polyurethane resin is 7.8% in terms of silica weight.
Met.

Examples 5 to 8 (Production of Resin Composition and Polyurethane Resin-Silica Hybrid) The alkoxy group-containing silane-modified polyurethane resins of Examples 1 to 4 were methyl ethyl ketone / isopropanol = 1 /
1 (weight ratio) was diluted to prepare a resin composition having a solid residue of 12.5%, respectively. Furthermore, containers coated with these resin compositions in a fluororesin (length x width x depth = 10 cm)
(× 10 cm × 1.5 cm) and allowed to stand for 3 days to cure, followed by drying at 100 ° C. for 1 hour to remove the residual solvent to prepare a polyurethane resin-silica hybrid body (film thickness: about 0.6 mm). ).

Example 9 (Production of Resin Composition and Polyurethane Resin-Silica Hybrid) To 100 g of the alkoxy group-containing silane-modified polyurethane resin of Example 1, 2.4 g of methyl silicate 51 and 0.24 g of tin octylate were blended. Dilute the mixed solution with methyl ethyl ketone / isopropanol = 1/1 (weight ratio),
A resin composition having a solid residue of 12.5% was prepared. Further, a polyurethane resin-silica hybrid body was prepared in the same manner as in Examples 5-8.

Example 10 (Production of Resin Composition and Polyurethane Resin-Silica Hybrid) To 100 g of the alkoxy group-containing silane-modified polyurethane resin of Example 1 was added 6.0 g of methyl silicate 51 and 0.24 g of tin octylate. Dilute the mixed solution with methyl ethyl ketone / isopropanol = 1/1 (weight ratio),
A resin composition having a solid residue of 12.5% was prepared. Further, a polyurethane resin-silica hybrid body was prepared in the same manner as in Examples 5-8. Table 1 shows the constitution of the resin composition.

Comparative Example 1 The polyurethane resin solution (1A) produced in Example 1 was diluted with methyl ethyl ketone / isopropanol = 1/1 (weight ratio) to prepare a resin composition having a solid residue of 12.5%. Further, a cured product was prepared in the same manner as in Examples 5-8.

Comparative Example 2 The polyurethane resin solution (1B) prepared in Example 2 was diluted with methyl ethyl ketone / isopropanol = 1/1 (weight ratio) to prepare a resin composition having a solid residue of 12.5%. Further, a cured product was prepared in the same manner as in Examples 5-8.

Comparative Example 3 Polyurethane resin solution (1A) 10 produced in Example 1
2.00g of methyl silicate 51 was mixed with 0g, and methyl ethyl ketone / isopropanol = 1/1 (weight ratio)
And a resin composition with a solid residue of 12.5% was prepared. Further, a cured product was prepared in the same manner as in Examples 5-8.

Comparative Example 4 Polyurethane resin solution (1B) 10 prepared in Example 2
3.42 g of methyl silicate 56 was mixed with 0 g, and methyl ethyl ketone / isopropanol = 1/1 (weight ratio)
And a resin composition with a solid residue of 12.5% was prepared. Further, a cured product was prepared in the same manner as in Examples 5-8.

Comparative Example 5 A reactor similar to that used in Example 1 was charged with 489.9 g of polytetramethylene glycol (number average molecular weight 2000) and 107.6 g of isophorone diisocyanate, and the mixture was reacted at 100 ° C. for 6 hours under a nitrogen stream. A prepolymer having a free isocyanate value of 3.28% was prepared, and 1085 g of methyl ethyl ketone was added to this to prepare a uniform solution of a urethane prepolymer. Then, 37.34 g of isophorone diamine
And 10 parts of the above urethane prepolymer solution in the presence of a mixture of 3.27 g of di-n-butylamine, 897 g of methyl ethyl ketone and 599 g of isopropyl alcohol.
00 g was added, and the mixture was reacted at 50 ° C. for 3 hours. The polyurethane resin solution thus obtained (hereinafter referred to as polyurethane resin (1E)) had a resin solid content concentration of 30% and an acid value or amine value of 0. 4.11 g of methyl silicate 51 was added to 100 g of the polyurethane resin solution (1A).
Blended, methyl ethyl ketone / isopropanol = 1 /
1 (weight ratio) was diluted to prepare a resin composition having a solid residue of 12.5%. Further, a cured product was prepared in the same manner as in Examples 5-8.

[0061]

[Table 1] MS51: Methyl silicate 51, MS-56: Methyl silicate 56

(Appearance) Examples 5 to 10 and Comparative Examples 1 to 5
The appearance of the cured film obtained in 1. was evaluated according to the following criteria. The results are shown in Table 2. ◯: The film is transparent. X: The film is clouded. The polyurethane-silica hybrid bodies of the respective examples were transparent. On the other hand, the films of Comparative Examples 3 and 4 were brittle and were cloudy.

(Mechanical Strength, Flexibility) The cured films prepared in Examples 5 to 10 and Comparative Examples 1 to 5 were cut out with dumbbell No. 1, and a Tensilon tester (trade name UCT-500 manufactured by Orientec Co., Ltd.) was used. The film was stretched at a pulling speed of 50 cm / min, and the stress at 100% elongation, the film elongation before breaking, and the strength at breaking were measured. A tensile test was conducted 3 times at 25 ° C. by the same method, and the average value is shown in Table 2.

(High temperature durability) Examples 5 to 10 and Comparative Example 1
After incubating the cured film prepared in ~ 5 at 150 ° C for 30 hours, it is cooled to 25 ° C and the same as in the item of film strength, 10
0% stress and breaking strength / breaking elongation were measured. Table 2 shows the retention rates of 100% stress and rupture strength / elongation before and after heat retention.
Shown in.

[0065]

[Table 2]

Examples 5 to 10 showed higher strength than Comparative Examples 1 to 4 while maintaining elongation. Further, Comparative Examples 1 to 4 are in a molten state at a temperature of 150 ° C., and Comparative Example 5 has a significantly lower breaking strength and elongation retention, whereas all the urethane / silica hybrids of Examples are films at 150 ° C. Shape is maintained, and 10
The 0% stress, the breaking strength, and the elongation exhibited high retention rates.

(Evaluation of Viscoelasticity) The cured films obtained in Examples 5, 9, 10 and Comparative Examples 1, 3 were 6 mm × 25 m.
Cut to m, viscoelasticity measuring instrument (Rheology Co., trade name "DVE-V4", measuring condition amplitude 1 μm, frequency 10H
z, slope 3 ° C./min) was used to measure the dynamic storage elastic modulus E ′ to evaluate heat resistance. The measurement results are shown in FIG.

The polyurethane-silica hybrid bodies of the respective examples maintained a high elastic modulus even at 150 ° C. or higher. On the other hand, the films of Comparative Examples 1 and 3 were in a molten state at 150 ° C. or higher, and the elastic modulus was significantly lowered.

[Brief description of drawings]

1 is an evaluation result of dynamic (tensile) viscoelasticity of cured films obtained in Examples 5, 9 and 10 and Comparative Examples 1 and 3. FIG.

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Claims (8)

(57) [Claims] 1. A polyurethane resin (1) obtained from a polymer polyol, a diisocyanate and a chain extender and having a functional group reactive with an epoxy group, and 1 in 1 molecule.
An alkoxy group characterized by reacting an epoxy group-containing alkoxysilane partial condensate (2) obtained by dealcoholization reaction of an epoxy compound (A) having one hydroxyl group with an alkoxysilane partial condensate (B). Silane-modified polyurethane resin containing. 2. The alkoxy group-containing silane-modified polyurethane resin according to claim 1, wherein the polymer polyol is a polyester polyol and / or a polycarbonate polyol. 3. The alkoxy group-containing silane-modified polyurethane resin according to claim 1, wherein the alkoxysilane partial condensate (B) is a tetramethoxysilane partial condensate. 4. The alkoxy group-containing silane-modified polyurethane resin according to claim 1, wherein the epoxy compound (A) having one hydroxyl group in one molecule is glycidol. 5. The alkoxy group-containing silane-modified polyurethane resin according to claim 1, wherein the polyurethane resin (1) is obtained by chain extending an isocyanate group-terminated urethane prepolymer with a diamine. 6. The equivalent of the oxirane ring of the epoxy group-containing alkoxysilane partial condensate (2) / the equivalent of the epoxy group-reactive functional group of the polyurethane resin (1) (equivalent ratio) is in the range of 0.30 to 5. The alkoxy group-containing silane-modified polyurethane resin according to claim 1. 7. A resin composition comprising the alkoxy group-containing silane-modified polyurethane resin according to any one of claims 1 to 6. 8. A polyurethane resin-silica hybrid body obtained by curing the alkoxy group-containing silane-modified polyurethane resin composition according to claim 7.