JPH10245482A - Silicone-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicone-based resin composition safe and friendly to the environment, bondable in an extremely short time, showing excellent storage stability in preservation, by compounding a silicone-based resin with a tin-based catalyst and a specific alkoxysilane. SOLUTION: This composition is obtained by compounding (A) a silicone- based resin, which is a silicone resin prepared by urethane forming reaction of (i) a polyoxypropylenepolyol having 500-30,000 number-average molecular weight with (ii) an isocyanate substituted type trialkoxysilane compound containing one isocyanate group in the molecule, and comprises a main chain substantially composed of a polyoxypropylene and a group of the formula (R is a 1-4C alkyl; (n) is 1-5) bonded to the end of the main chain with (B) a curing catalyst and (C) an amino group-substituted alkoxysilane. A polyoxypropylenediol having 5,000-20,000 number-average molecular weight is preferably used as the component (i).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silicone resin composition.

[0002]

2. Description of the Related Art Currently, a one-pack, room-temperature-curing type instant adhesive which is commercially available as an instant adhesive mainly contains cyanoacrylate. This is called an α-cyanoacrylate adhesive and is used for a wide range of applications. A cyanoacrylate is a low molecular compound having a cyano group in a molecule, and has a property of being polymerized in a very short time by moisture in the air. Since cyanoacrylate can adhere to an adherend in several seconds to about one minute depending on the use conditions,
It is called instant adhesive. However, since cyanoacrylate is a low molecular weight compound having a cyano group in the molecule, it is highly irritating to mucous membranes and also has flammability. It remains a solution. Furthermore, since this adhesive adheres in a few seconds depending on the adherend, it is difficult to obtain flexibility in the adhesive work such as positioning adjustment due to the deviation of the object to be adhered, and it must be used under extremely limited use conditions. Had.

[0003] On the other hand, one-part cold-setting adhesives using high-risk / hazardous high-molecular compounds are based on the property that a liquid polymer is crosslinked mainly by moisture curing. Is available on the market, but the time to cure takes several tens of minutes to several hours, and there is no such thing as α-cyanoacrylate adhesive that enables bonding in a very short time. is the current situation.

[0004]

DISCLOSURE OF THE INVENTION The present invention is a safe alternative to α-cyanoacrylate-based adhesives, which have high danger and harmfulness and, depending on the use conditions, literally adhere instantaneously, which makes slashing work and the like harmful. It is an object of the present invention to develop a liquid polymer type one-part cold curing type adhesive which is environmentally friendly, can bond in a very short time, and can exhibit excellent storage stability during storage.

[0005]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and found that the following specific silicone resins have the above-mentioned desired properties. . However, unfortunately, when such a silicone resin is mixed with a tin-based catalyst, which is a usual curing catalyst, to prepare an adhesive, the storage stability is significantly impaired because of the tin-based catalyst, and the adhesive is It was also found that the viscosity of the solution was remarkably increased, and it was not possible to obtain the desired liquid polymer type one-part cold curing adhesive. The present inventor has continued his research.As a result, when an amino group-substituted alkoxysilane is added to a silicone resin together with a tin catalyst which is a usual curing catalyst, an increase in the viscosity of the adhesive solution can be avoided. It has been found that a desired liquid polymer-type one-part cold-setting adhesive having fast curing properties and excellent storage stability can be obtained. The present invention has been completed based on such findings.

That is, the present invention relates to (1) a compound having a number average molecular weight of 5
A silicone resin obtained by a urethanization reaction of a polyoxypropylene polyol having a molecular weight of from 0.000 to 30000 and an isocyanate-substituted trialkoxysilane compound having one isocyanate group in the molecule, wherein the main chain is substantially a polyoxypropylene polyol. Made of propylene, with a group at the molecular end of the main chain

[0007]

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[R is a C _1-4 alkyl group, and n is 1 to 5
Indicates an integer. ] -Bonded silicone resin, (2)
The present invention relates to a silicone resin composition containing a curing catalyst and (3) an amino-substituted alkoxysilane.

The silicone resin of the present invention is safe, environmentally friendly, can be bonded in a very short time, and can be used as a resin component of a liquid polymer type one-part cold curing type adhesive which does not have any adverse effects such as slipping work. is there.

In particular, when a polyoxypropylene diol having a number average molecular weight of 5,000 to 20,000 is used as the polyoxypropylene polyol, a silicone resin composition having the above-mentioned properties, especially storage stability, which is further improved, can be obtained. I found

Therefore, according to the present invention, (1) a urethanization reaction between a polyoxypropylene diol having a number average molecular weight of 5,000 to 20,000 and an isocyanate-substituted trialkoxysilane compound having one isocyanate group in the molecule. Wherein the main chain is substantially composed of polyoxypropylene, and a group is attached to a molecular terminal of the main chain.

[0012]

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[R is a C _1-4 alkyl group, and n is 1-5
Indicates an integer. ] -Bonded silicone resin, (2)
A silicone-based resin composition containing a curing catalyst and (3) an amino-substituted alkoxysilane is provided.

The number average molecular weight is 5,000 to 2,000.
It has been found that the same effect as described above is exhibited even when a part of the polyoxypropylene diol which is 0 is replaced with a polyoxypropylene polyol other than the polyoxypropylene diol.

Therefore, according to the present invention, (1) 100 parts by weight of polyoxypropylene diol having a number average molecular weight of 5,000 to 20,000 and a number average molecular weight of 500 to 30,000
Polyoxypropylene polyol (number average molecular weight 50
A silicone resin obtained by a urethanization reaction of a mixture of 1 to 200 parts by weight with an isocyanate-substituted trialkoxysilane compound having one isocyanate group in a molecule (excluding a polyoxypropylene diol of 00 to 20,000). , The main chain of which is substantially composed of polyoxypropylene,

[0016]

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[R is a C _1-4 alkyl group, and n is 1-5
Indicates an integer. ] -Bonded silicone resin, (2)
A silicone-based resin composition containing a curing catalyst and (3) an amino-substituted alkoxysilane is provided.

Further, when γ-isocyanatoalkyltrimethoxysilane is used as the isocyanate-substituted trialkoxysilane compound having one isocyanate group in the molecule, a silicone resin composition having further excellent rapid curability can be obtained. I found

Therefore, according to the present invention, there is provided (1) a silicone resin obtained by a urethanization reaction between a polyoxypropylene polyol having a number average molecular weight of 500 to 30,000 and γ-isocyanatoalkyltrimethoxysilane, The main chain is substantially composed of polyoxypropylene, and a group is

[0020]

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[N represents an integer of 1 to 5; ], A silicone resin composition comprising (2) a curing catalyst and (3) an amino-substituted alkoxysilane.

According to the present invention, there is also provided (1) a silicone resin obtained by a urethanization reaction of polyoxypropylene diol having a number average molecular weight of 5,000 to 20,000 and γ-isocyanatoalkyltrimethoxysilane, The main chain is substantially composed of polyoxypropylene, and a group is

[0023]

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[N represents an integer of 1 to 5; ], A silicone resin composition comprising (2) a curing catalyst and (3) an amino-substituted alkoxysilane.

According to the present invention, (1) 100 parts by weight of a polyoxypropylene diol having a number average molecular weight of 5,000 to 20,000 and a number average molecular weight of 500 to 300
A polyoxypropylene polyol (excluding a polyoxypropylene diol having a number average molecular weight of 5,000 to 20,000) of 1 to 200 parts by weight and a urethanization reaction of γ-isocyanatoalkyltrimethoxysilane with a silicone resin, , The main chain of which is substantially composed of polyoxypropylene,

[0026]

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[N represents an integer of 1 to 5. ], A silicone resin composition comprising (2) a curing catalyst and (3) an amino-substituted alkoxysilane.

Conventional silicone-based liquid polymers in which the silicone-reactive group is a trialkoxysilyl group and the main chain has a substantially polyoxypropylene structure are disclosed, for example, in JP-B-45-36319 and JP-B-46-12154.
Gazette, JP-B-49-32673, JP-A-50-1
It is manufactured by various methods described in JP-A-56599, JP-A-51-73561 and JP-A-54-6096. Specifically, a method for synthesizing a hydroxytrialkoxysilane such as hydroxytrimethoxysilane by a Michael addition reaction to polyoxypropylene having an allylated molecular terminal and a polyoxypropylene having an isocyanate at the molecular terminal, N-phenyl- capable of reacting with the isocyanate group
This is a method of synthesizing using an amino group-substituted silane compound such as γ-aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane, or a mercapto group-substituted silane compound such as γ-mercaptopropyltrimethoxysilane. However, when synthesized by such a conventionally known method, a large amount of time for polymer synthesis, the number of steps, not only complicated operations such as removal of the catalyst are required,
Even if a silicone liquid polymer is obtained using a polyoxypropylene polyol in the range used in the present invention as a starting material,
The desired silicone resin as in the present invention cannot be obtained.

On the other hand, the silicone resin used in the present invention is produced by a method different from the above-mentioned conventional method. That is, the silicone resin of the present invention is produced by directly urethane-forming an isocyanate-substituted trialkoxysilane compound in a molecule with respect to a hydroxyl group of a polyoxypropylene polyol. The desired liquid polymer type one-part cold curing adhesive having the above properties can be obtained only by using the silicone-based resin obtained by such a method and using an amino group-substituted alkoxysilane together with a curing catalyst. it can.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The silicone resin of the present invention is obtained by subjecting a polyoxypropylene polyol having a number average molecular weight of 500 to 30,000 to an isocyanate-substituted trialkoxysilane compound having one isocyanate group in the molecule to undergo a urethanization reaction. It is manufactured by causing

In the present invention, the polyoxypropylene polyol is a polymer polyol having oxypropylene as a unit, and has a number average molecular weight of 500 to 3 from a commercially available urethane raw material which is conventionally widely used.
What is 0000 may be selected. Specifically, copolymerization of polyoxypropylene polyols such as polyoxypropylene diol, polyoxypropylene triol, polyoxypropylene tetraol, and polyoxypropylene such as polyoxy (propylene / ethylene) copolymerized polyol with other alkylenes. Polyols having an oxypropylene unit content of more than 50 mol% (in the case of copolymerized polyols of this polyoxypropylene and other alkylenes, even if they are block polymers, polyoxypropylene polyols may contain other alkylene oxides) May be added), and substantial polyoxypropylene polyols polymerized by jumping the polyoxypropylene polyol with a diisocyanate or the like.
In the present invention, these polyoxypropylene polyols need to have a hydroxyl group at the molecular terminal.
Those having excellent inner-speed curability and storage stability are polyoxypropylene diols having a number average molecular weight of 5,000 to 20,000, and specific examples include Preminol 4010 and Preminol 4019 (both manufactured by Asahi Glass Co., Ltd.). . Using a polyoxypropylene diol other than the above,
As a method for setting the number average molecular weight to 5,000 to 20,000, in the case of low molecular weight polyoxypropylene diol, a method of performing a jumping reaction using diisocyanate can be mentioned. It can be suitably used in the invention.

In the present invention, an isocyanate-substituted trialkoxysilane compound has the structural formula OCN- (C
H ₂ ) _n -Si (OR) ₃ . Here, n is an integer of 1 to 5, and R is a C _1-4 alkyl group (preferably a methyl group or an ethyl group). As the isocyanate-substituted trialkoxysilane compound used in the present invention, specifically, γ-isocyanatomethyltrimethoxysilane, γ-isocyanatoethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatebutyltrimethoxysilane ,
γ-isocyanate pentyltrimethoxysilane, γ-
Examples include isocyanate methyl triethoxy silane, γ-isocyanate ethyl triethoxy silane, γ-isocyanate propyl triethoxy silane, γ-isocyanate butyl triethoxy silane, and γ-isocyanate pentyl triethoxy silane. Among these,
γ-isocyanatomethyltrimethoxysilane, γ-isocyanateethyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatebutyltrimethoxysilane and γ-isocyanatepentyltrimethoxysilane are preferred, and γ-isocyanatepropyltrimethoxysilane is preferred. Particularly preferred.

In the urethanization reaction between the polyoxypropylene polyol and the isocyanate-substituted trialkoxysilane compound, the mixing ratio of the two is not particularly limited. The ratio of the trimethoxysilane compound to the number of isocyanate groups (hereinafter referred to as “NCO / OH ratio”) is usually 0.6 to
It is good to mix both so as to be in the range of 1.2, preferably 0.8 to 1.0. Specifically, a molecular weight of 500 to
If one kind of polyoxypropylene polyol selected from the range of 30,000 is used, the hydroxyl value of the polyol is calculated. If two or more kinds of polyoxypropylene polyol are used, the hydroxyl value of the mixed polyol is calculated by a weighted average. The amount of the isocyanate-substituted trimethoxysilane compound to be reacted is calculated so that the NCO / OH ratio falls within the above range per part by weight.

In determining the amount of the isocyanate-substituted trialkoxysilane compound relative to the polyol, NC
When the O / OH ratio is smaller than 0.6, the resulting silicone resin tends to have a low curability, and
Residual hydroxyl groups tend to lower water resistance, which is not preferred. On the other hand, if the NCO / OH ratio is larger than 1.2, the isocyanate-substituted trimethoxysilane compound remains, which tends to lower the storage stability, which is not preferable. When the polyoxypropylene polyol and the isocyanate-substituted trialkoxysilane compound are blended so that the NCO / OH ratio is in the range of 0.8 to 1.0, rapid curing properties, storage stability, water resistance, and the like are remarkable. An excellent silicone resin can be obtained.

In performing the above urethanation reaction,
A predetermined amount of the polyoxypropylene polyol and the isocyanate-substituted trialkoxysilane compound may be mixed and stirred under heating, for example, at 60 to 100 ° C. for several hours. This reaction is desirably performed in an inert gas such as nitrogen gas. Also, a slight amount of a urethane polymerization catalyst such as dibutyltin dilaurate may be added at the beginning or during the reaction to promote the urethanization reaction. Completion of the reaction can be determined by using a point close to the theoretical NCO amount or the theoretical hydroxyl value calculated from the NCO / OH ratio as the reaction end point.

When a mixture of a polyoxypropylene diol having a specific molecular weight and a polyoxypropylene polyol other than the polyoxypropylene diol is used as the polyoxypropylene polyol, the mixture is reacted with an isocyanate-substituted trialkoxysilane compound and a urethanization reaction. The silicone-based resin of the present invention may also be used, or a polyoxypropylene diol having a specific molecular weight and a polyoxypropylene polyol other than the polyoxypropylene diol are individually urethanized with an isocyanate-substituted trialkoxysilane compound, The obtained urethane compound may be mixed to obtain the silicone resin of the present invention. The mixing ratio of the polyoxypropylene diol having a specific molecular weight to the polyoxypropylene polyol other than the polyoxypropylene diol is preferably 5 to 200 parts by weight per 100 parts by weight of the former. Within this range, properties such as storage stability and rapid curability of the obtained silicone resin will not be impaired.

The structure of the silicone resin of the present invention thus obtained has a trialkoxysilyl group as a silicone-reactive group, and a methylene linkage and one It has a urethane bond and its main chain is substantially polyoxypropylene.

Among the silicone resins of the present invention, the silicone resins having the fastest curing properties and excellent storage stability are those of polyoxypropylene diol having a number average molecular weight of 5,000 to 20,000 and γ-isocyanatoalkyltrimethoxysilane. It is a polymer obtained by the reaction and represented by the following chemical formula.

[0039]

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[N represents an integer of 1 to 5. The polyoxypropylene structural portion corresponds to m + p, where m and p are positive integers, and satisfy 86 <m + p <344. When the number-average molecular weight is substantially 5,000 to 20,000 by performing a jumping reaction with a low-molecular-weight polyoxypropylene diol and a diisocyanate, the main chain structure portion may have one or more ether bonds such as urethane bonds. Although it may be through a chemical bond other than the bond, the molecular terminal is a hydroxyl group, and finally, the hydroxyl group of the jumped polyoxypropylene diol and the isocyanate group of the γ-isocyanatoalkyl trialkoxysilane react to form a tri group. If a silicone resin having an alkoxysilyl group can be obtained, this silicone resin is also included in the silicone resin of the present invention.

A curing catalyst is added to the silicone resin composition of the present invention in order to promote curing with moisture.
As the curing catalyst, conventionally known silanol condensation catalysts can be widely used. Specific examples thereof include titanium esters such as tetrabutyl titanate and tetrapropyl titanate; tin carboxyls such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, tin laurate, and tin ferzaticate. Acid salts; reaction products of dibutyltin oxide and phthalic acid esters; dibutyltin diacetylacetonate; organic aluminum compounds such as aluminum triacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylethylacetoacetate; zirconium tetraacetylacetonate , Chelate compounds such as titanium tetraacetylacetonate; lead octylate; iron naphthenate; bismuth-tris (neodecanoate) Bismuth - it can be exemplified metallic catalysts bismuth compounds such as tris (2-ethylhexoate). These metal catalysts may be used alone or in combination of two or more.
Further, a known amine catalyst such as laurylamine may be used. In the present invention, among the above curing catalysts, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate,
Tin carboxylate salts such as tin laurate and tin ferzatic acid; reaction products of dibutyltin oxide and phthalic acid esters; tin catalysts such as dibutyltin diacetylacetonate are particularly preferred.

The curing catalyst is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the silicone resin composition.
It is preferable that 5 to 5 parts by weight, more preferably 1 to 3 parts by weight be blended.

The silicone resin composition of the present invention contains an amino group-substituted alkoxysilane (hereinafter sometimes abbreviated as "aminosilane") together with the above curing catalyst. As aminosilanes, conventionally known ones can be widely used. Specific examples thereof include monoaminosilanes, diaminosilanes, triaminosilanes, terminal alkoxysilanes, and complex reactive aminosilanes. Monoaminosilanes can be broadly classified into primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Examples of diaminosilanes include compounds having one primary amine and one secondary amine in the molecule, compounds having two secondary amines in the molecule, and the like. As terminal trialkoxyaminosilanes,
Examples thereof include compounds having an alkoxysilyl structure at both ends and having a secondary amine in the molecule. Specific examples of these various amino-substituted alkoxysilanes are shown in Tables 1 to 4 below.
Shown in Examples of the complex reactive aminosilanes include aminosilanes having two secondary amino groups and a styrenic unsaturated group in the molecule, and more specifically, one or more amino groups (1 And secondary and tertiary) and olefinically unsaturated groups.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

The amino-substituted alkoxysilanes used in the present invention may be those obtained by reacting an epoxysilane compound or an acryloylsilane compound with the amino-substituted alkoxysilane. Table 5 below shows specific examples of the epoxysilane compound and the acryloylsilane compound.

[0049]

[Table 5]

The reaction of the above-mentioned amino-substituted alkoxysilane with an epoxysilane compound or a methacryloxysilane compound is performed by mixing the former 1 mol with 0.2 to 5 mol of the latter, and reacting the mixture at room temperature to 180 ° C. with 1 to 1 mol. This can be easily performed by stirring for 8 hours.

Preferred examples of the above-mentioned amino-substituted alkoxysilanes are as follows. Among monoaminosilanes and diaminosilanes, compounds in which the amine at the molecular end is a primary amine and the alkoxysilyl group is a trimethoxysilyl group, a methyldimethoxysilyl group or a triethoxysilyl group have rapid curing properties. It is preferable in the point shown. Particularly preferred amino-substituted alkoxysilanes are shown in Table 6 below. These compounds are not only fast-curing,
It has the advantage of providing excellent storage stability.

[0052]

[Table 6]

The above-mentioned aminosilanes are incorporated in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the silicone resin composition. .

The resin composition of the present invention may further contain a silane coupling agent such as vinyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane in order to further improve adhesion and storage stability. Can be.

Further, the resin composition of the present invention may optionally contain an epoxy resin and its curing agent, a filler, a plasticizer, a viscosity improver, and other additives as necessary.

As the epoxy resin, conventionally known epoxy resins can be widely used, for example, flame-retardant epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ether of tetrabromobisphenol A, and novolak type epoxy resin. Hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, diglycidyl-p-oxybenzoic acid, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, etc. Diglycidyl phthalate epoxy resin, m-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N N- diglycidyl aniline,
N, N-Diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohol such as glycerin, epoxidized unsaturated polymer such as hydantoin type epoxy resin, petroleum resin, etc. Can be mentioned. Among these epoxy resins, those containing at least two epoxy groups in the molecule are preferable in terms of high reactivity upon curing and easy formation of a three-dimensional network in the cured product. More preferred epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin and diglycidyl phthalate epoxy resin.

As the epoxy resin curing agent, conventionally known curing agents for epoxy resins can be widely used, such as triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, and the like. Amines such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6-tris (dimethylaminomethyl) phenol, tertiary amine salts, polyamide resins, ketimines, aldimines, enamine And other latent curing agents, imidazoles,
Dicyandiamides, boron trifluoride complex compounds, carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecinyl succinic anhydride, pyromellitic anhydride, and chlorenic anhydride , Alcohols, phenols, carboxylic acids and the like.

As the filler, conventionally known fillers can be widely used, and specifically, fumed silica, precipitated silica,
Fillers such as silicic anhydride, hydrous silicic acid and carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth,
Filling materials such as calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc flower, hydrogenated castor oil and glass balloon, and fibrous filling such as asbestos, glass fiber and filament Materials can be exemplified.

As the plasticizer, conventionally known plasticizers can be widely used, and specifically, phthalic esters such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate; dioctyl adipate, isodecyl succinate, sebacin Aliphatic carboxylic acid esters such as dibutyl acrylate and butyl oleate; glycol esters such as pentaerythritol ester; phosphoric esters such as trioctyl phosphate and tricresyl phosphate; epoxy plastics such as epoxidized soybean oil and epoxy benzyl stearate Agents: chlorinated paraffins and the like can be used alone or in a mixture of two or more. In addition, polyoxypropylene monol, polyoxypropylene diol, and a terminal-modified product thereof can also be used. Examples of the terminal modified product include a compound in which a terminal hydroxyl group is modified to an alkoxy group or an alkenyloxy group, a compound blocked by a hydrocarbon group via a urethane bond, an ester bond, a urea bond, or a carbonate bond.

Examples of the viscosity improver include gelling agents such as dibenzylidene sorbitol and tribenzylidene sorbitol, and fatty acid amidates such as amide wax.

Other additives include, for example, pigments, various antioxidants, ultraviolet absorbers and the like.

The mixing ratio of each of the above components to be mixed in the silicone resin composition of the present invention is not particularly limited.
1 to 100 parts by weight of the epoxy resin (preferably 10 to 1
00 parts by weight) and a curing agent for epoxy resin
1 to 200 parts by weight (preferably 50 to 100 parts by weight)
100 parts by weight), 0.1 to 200 parts by weight of a filler, 1 to 50 parts by weight of a plasticizer, and 0.1 to 10 parts by weight of a viscosity improver.

[0063]

The present invention will be further clarified with reference to the following examples. In the following, “parts” means “parts by weight” and “%” means “% by weight”.

Production Example 1 A stirrer, dropping funnel, reflux tube, thermometer, nitrogen gas flow device,
Polyoxypropylene diol (number average molecular weight (hereinafter abbreviated as "Mn") = 10000, hydroxyl value (hereinafter abbreviated as "OHV") = 11.2 in a 2-liter four-neck separable flask equipped with a decompression device, Number of hydroxyl groups per molecule: 2, Preminol 4010, Asahi Glass Co., Ltd.
Manufactured at 1000C and 10 to 20 mm
Dehydration was performed by performing distillation under reduced pressure at Hg for 1 hour,
40.9 parts of γ-isocyanatopropyltrimethoxysilane was added so that NCO / OH = 1.0, the temperature was increased under a nitrogen stream, and stirring was continued at 80 to 90 ° C. for 8 hours. When the NCO content was measured,
Since it was 3% (theoretical value 0%), it was taken out after cooling. The viscosity of this silicone-based liquid polymer is 210 Pa ·
s / 23 ° C. This is designated as modified silicone A of the present invention.

Production Example 2 In the same apparatus and method as in Production Example 1, polyoxypropylene diol (Mn =
4000, OHV = 29.5, 2 hydroxyl groups per molecule, trade name Preminol 4002, manufactured by Asahi Glass Co., Ltd.)
Per 1000 parts of γ-isocyanatopropyltrimethoxysilane so that NCO / OH = 1.0.
7.7 parts were charged, and after the reaction under the same conditions, the NCO content was 0.07.
%, And a liquid polymer having a viscosity of 76 Pa · s / 23 ° C. was obtained.
This is designated as modified silicone B of the present invention.

Production Example 3 In the same apparatus and method as in Production Example 1, polyoxypropylene triol (Mn) was used instead of the polyol used in Production Example 1.
= 10000, OHV = 16.8, 3 hydroxyl groups per molecule, trade name Preminol 3010, Asahi Glass Co., Ltd.
Per 1000 parts), and 71.9 parts of γ-isocyanatopropyltrimethoxysilane were added so that NCO / OH = 1.0.
A liquid polymer having a viscosity of 6% and a viscosity of 550 Pa · s / 23 ° C. was obtained. This is designated as modified silicone C of the present invention.

Production Example 4 Using the same apparatus and method as in Production Example 1, using the same polyoxypropylene diol as in Production Example 1, NCO / OH = 1.
In place of the isocyanate compound used in Production Example 1, 49.3 parts of γ-isocyanatopropyltriethoxysilane was added so that the reaction became 0, and after reaction under the same conditions, the NCO content was 0.10%, and the viscosity was 85 Pa · s. / 23 ° C was obtained. This is designated as modified silicone D of the present invention.

Reference Production Example 1 The same polyoxypropylene diol as in Production Example 1 was dehydrated in the same apparatus as in Production Example 1, and then NCO / OH was added at 50 ° C.
Then, 34.7 parts of 2.4-toluene diisocyanate was added so as to be 2.0, and the mixture was allowed to react for 24 hours while stirring at 80 to 90 ° C. under a nitrogen stream, and the NCO-terminated urethane prepolymer was once used. Was synthesized (this was regarded as one step). The next day, the prepolymer was once cooled to 40 ° C., mixed with 50.9 parts of N-phenyl-γ-aminopropyltrimethoxysilane, and further stirred for 24 hours.
After reaction for an hour, NCO content 0.12%, viscosity 300Pa
-The liquid polymer of s / 23 degreeC was obtained. This is designated as modified modified silicone E by a conventional method.

Reference Production Example 2 An NCO-terminated urethane prepolymer was once synthesized in the same manner as in Reference Production Example 1 using the same polyol and diisocyanate (this was taken as one step). This was once cooled to 50 ° C. the next day in the same manner as in Comparative Example 1, 62.6 parts of γ-mercaptopropyl triisocyanate was added, and the mixture was reacted for 24 hours while stirring was continued. As a result, the NCO content was 0.5%. The reaction was continued for another 24 hours, the NCO content was 0.25%, and the viscosity was 340 Pa · s.
/ 23 ° C was obtained. This is designated as modified modified silicone F by a conventional method.

Test Example 1 100 g of each of the modified silicones A to F obtained above.
And sealed in a glass bottle, and then stored in a 50 ° C. incubator to conduct a storage stability test. The storage stability was stored under the same conditions at 50 ° C. × 30 days, then allowed to cool to 23 ° C. in a sealed state again, and the viscosity was measured immediately. Table 7 shows the results.

[0071]

[Table 7]

The total reaction time is the time from charging to taking out.

Thickening ratio = 50 ° C. × viscosity value after 30 days−initial viscosity value / initial viscosity value × 100 (%) From Table 7, the following can be seen. That is, in Production Examples 1 to 4, the number of steps was small and synthesis could be performed in a much shorter time, and the storage stability was good as compared with the method according to the conventional method (Reference Production Example 1 and Reference Production Example 2). Among the silicone resins of the present invention, those having the highest storage stability were Production Example 1 (modified modified silicone A) and Production Example 4 (modified modified silicone D).

A mixture of the modified silicones A to F and a curing catalyst (dibutyltin dilaurate) (the mixing ratio of the former: the latter = 100: 2 (weight ratio)) was 1
A 100 g glass bottle was filled, and a storage stability test was performed in the same manner as described above. Table 8 shows the results.

[0075]

[Table 8]

Examples 1-4 and Comparative Examples 1-2 Each of the modified silicones A-F obtained above, a curing catalyst (dibutyltin dilaurate) and amino-substituted alkoxysilanes (N- (β-amino A mixture of (ethyl) -γ-aminopropyltrimethoxysilane) (the blending ratio is the former: the latter = 100: 2: 2 (weight ratio)) was packed in a 100 g glass bottle to obtain each adhesive. Incidentally, for example, an adhesive using the modified silicone A is referred to as a modified silicone adhesive A, and
F and the modified denatured silicone adhesives A to F correspond to each other. Further, a storage stability test was conducted in the same manner as described above. Table 9 shows the results.

[0077]

[Table 9]

Test Example 2 Using the modified and modified silicone adhesives A to F obtained above, the respective effects were confirmed by the following methods.

(I) Measurement of sticking time: An aluminum plate of 300 mm square (thickness 3 mm) was cut in an atmosphere of 23 ° C. and 50% relative humidity on a plane of a piece of wood (Asada wood) cut into a 25 mm square (thickness 10 mm). Each adhesive was applied so that the thickness of the adhesive layer was about 0.2 mm, and the wood pieces were pressed on an aluminum plate to measure how long it could be fixed. The measurement was performed every minute, and the time at which the finger did not move easily with the finger was taken as the fixing time.

(Ii) Measurement of rise time of initial adhesive strength: Each adhesive is applied to a 300 mm square plywood with a bar coater to a thickness of about 0.1 mm in an atmosphere of 23 ° C. and 50% relative humidity. A polyester transparent film (thickness: 50 μm) immediately subjected to corona discharge treatment was laminated and pressed with a rubber roll, and the film was applied to the film.
A cut having a width of mm was made, and the peel strength was measured over time using a spring balance. The measurement was performed every minute, and the time when the maximum strength exceeded 2 kg · f was defined as the end point, and the time was recorded.

(Iii) Measurement of tensile shear bond strength after 30 minutes: 100 m length in an atmosphere of 23 ° C. and 50% relative humidity
m, width 25 mm, width 5 mm, and a 5 mm thick asada material (wood), the bonding area is 25 mm × 25 mm, and the bonding layer is 0.1 mm.
Each adhesive was applied on one side so as to have a thickness of about 2 mm, immediately superposed and adhered, left for 30 minutes, and the tensile shear adhesive strength was measured. The tensile speed at the time of measurement was 5 mm /
, And the number of test pieces was 5, and the average value of the maximum adhesive strength was defined as the adhesive strength. Test equipment is Autograph A
G5000 (manufactured by Shimadzu Corporation) was used (unit: N / c
m ² ).

Table 10 shows the results.

[0083]

[Table 10]

As is clear from Table 10, Production Examples 1 to 4
The adhesive using the silicone-based resin obtained in (1) was superior in storage stability to the adhesive using the silicone-based resin obtained in Reference Production Example 1 or 2. Production example 1 which has the best storage stability and can be bonded in a very short time
(Modified silicone A).

Example 5 The polypropylene diol used in Production Example 1 (Mn = 10
000, OHV = 11.2) and 500 parts of polypropylene triol (Mn = 4000, OH) used in Production Example 2.
V = 29.5) 200 parts, polypropylene triol of Production Example 3 (Mn = 10000, OHV = 16.8) 3
OHV of the mixed polyol of 00 parts = 16.5 and NC
Production Example 1 was charged with 60.3 parts of γ-isocyanatopropyltrimethoxysilane so that O / OH = 1.0.
The urethanization reaction was carried out in the same manner as described above, and the NCO content =
A silicone liquid polymer having a viscosity of 0.08% and a viscosity of 280 Pa · s / 23 ° C. was obtained. This was subjected to a storage stability test in the same manner as in Test Example 1, and the same test as in Test Example 2 was performed using an adhesive as in Examples 1 to 4.

As a result of the storage stability test, when the curing catalyst (dibutyltin dilaurate) was blended, the thickening rate was 16%.
When 8%, a curing catalyst (dibutyltin dilaurate) and an amino-substituted alkoxysilane (N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane) were blended, the viscosity increase rate was 25%. . The results of the adhesion test were comparable to those of the adhesive of Example 1 (adhesive using modified modified silicone A).

Claims (9)

[Claims] (1) The number average molecular weight is 500 to 3000
Polyoxypropylene polyol which is 0 and 1 in the molecule
A silicone resin obtained by a urethanation reaction with an isocyanate-substituted trialkoxysilane compound having two isocyanate groups, wherein the main chain is substantially composed of polyoxypropylene, and a group is attached to a molecular terminal of the main chain. ] [R represents a C _1-4 alkyl group, and n represents an integer of 1 to 5. ], A silicone resin composition comprising (2) a curing catalyst and (3) an amino-substituted alkoxysilane. 2. The silicone resin according to claim 1, wherein the polyoxypropylene polyol has a number average molecular weight of 5,000 to 2,000.
The silicone resin composition according to claim 1, which is a silicone resin obtained by using a polyoxypropylene diol of 0. 3. The silicone resin according to claim 1, wherein the polyoxypropylene polyol has a number average molecular weight of 5,000 to 2,000.
Silicone obtained by using a mixture of 100 parts by weight of polyoxypropylene diol of 0 and 1 to 200 parts by weight of polyoxypropylene polyol having a number average molecular weight of 500 to 30,000 (excluding polyoxypropylene diol having a number average molecular weight of 5,000 to 20,000) The silicone resin composition according to claim 1, which is a resin. 4. The silicone resin according to claim 1, wherein the silicone resin is obtained by using γ-isocyanatoalkyltrimethoxysilane as an isocyanate-substituted trialkoxysilane compound having one isocyanate group in a molecule. Silicone resin composition. 5. The silicone resin according to claim 2, wherein the silicone resin is obtained by using γ-isocyanatoalkyltrimethoxysilane as an isocyanate-substituted trialkoxysilane compound having one isocyanate group in a molecule. Silicone resin composition. 6. The silicone resin according to claim 3, wherein the silicone resin is obtained by using γ-isocyanatoalkyltrimethoxysilane as an isocyanate-substituted trialkoxysilane compound having one isocyanate group in a molecule. Silicone resin composition. 7. The silicone resin composition according to claim 1, wherein the curing catalyst is a tin-based curing catalyst. 8. The method according to claim 1, wherein the amino-substituted alkoxysilane is N-
(Β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
The silicone resin composition according to claim 7, which is at least one member selected from the group consisting of N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane and γ-aminopropylmethyldimethoxysilane. 9. The composition according to claim 1, wherein 0.1 to 10 parts by weight of a curing catalyst and 0.1 to 15 parts by weight of an amino group-substituted alkoxysilane are blended in 100 parts by weight of the silicone resin composition.
7. The silicone resin composition according to any one of items 1 to 6.