JPH10245484A - Silicone-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicone-based resin composition useful as an adhesive little in danger and harmfulness, capable of bonding in an extremely short time, by using a mixture of silicone-based resins containing specific silicone reactive groups, respectively. SOLUTION: This composition is constituted by blending a silicone-based resin containing a polyalkoxy silyl group as a silicone reactive group at the end of the molecule and a main chain having a substantially polyoxyalkylene structure. The resin is a mixture of (A) 10-90wt.% of a silicone-based resin containing a trialkoxysilyl group as the silicone reactive group and a main chain having a substantially polyoxyalkylene structure, and (B) 90-10wt.% of a silicone-based resin containing an alkyldialkoxysilyl group as the silicone reactive group and a main chain having a substantially polyoxyalkylene structure. Preferably the trialkoxysilyl group is a (R<1> O)3 Si group (R<1> is a 1-5C alkyl) and the oxyalkylene group of the component A is a 1-6C oxyalkylene group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silicone resin composition. The silicone resin composition of the present invention,
It can be used in the fields of adhesives, sealants, coatings, paints, etc. having a moisture curing function.

[0002]

2. Description of the Related Art Conventionally, the only commercially available silicone resin (liquid polymer) having a polyalkoxylyl group as a silicone-reactive group at the molecular terminal and having a substantially polyoxyalkylene structure in the main chain structure. Silicone resins are limited to those in which the silicone reactive group is an alkylene dialkoxysilyl group.

[0003] Originally, there are three types of polyalkoxysilyl groups which are silicone-reactive groups, namely, dialkylmonoalkoxysilyl groups, alkyldialkoxysilyl groups and trialkoxysilyl groups. The polyalkoxysilyl group is easily hydrolyzed by water to be silanolized, and then causes a condensation reaction between silanols to form a siloxane bond, leading to crosslinking. However, currently, the only commercially available silicone resins are the above-mentioned liquid polymers having an alkyldialkoxysilyl group. The reason is considered as follows. That is, a dialkyl monoalkoxysilyl group having one cross-linking point has a very low curing rate, and the polymer obtained by cross-linking has an extremely insufficient cohesive force, so that it cannot find an industrial value and has not yet been marketed. . Also, the trialkoxysilyl group having three crosslinking points has the property that the curing rate is very fast, but the polymer obtained by crosslinking is very hard and brittle, which is a disadvantage of the silicone resin. In addition to having physical properties with low tear strength (this property is called "brittiness"), trialkoxysilyl groups are easily affected by moisture, and the storage stability of the liquid polymer itself is unstable, and it tends to thicken. No industrial value has been found and it has not been commercialized.

The above liquid polymer having an alkyl dialkoxysilyl group having two crosslink points has a lower curing speed than a trialkoxysilyl group, but has an insufficient cohesive force like a dialkyl monoalkoxysilyl group. It is known that the polymer does not give a brittle property unlike a trialkoxysilyl group, and thus provides excellent polymer properties which are flexible and tough. Also, unlike the trialkoxysilyl group, it has excellent storage stability. For this reason,
Only the above-mentioned liquid polymers having an alkyldialkoxysilyl group have found industrial value, and this liquid polymer has been the only commercially available. Accordingly, the term "modified silicone" is given to a liquid polymer having an alkyl dialkoxysilyl group having two crosslinking points as a silicone reactive group and having a main chain structure substantially a polyalkylene structure. In this specification, the above liquid polymer having an alkyldialkoxysilyl group is referred to as "commercially modified silicone".

[0005] Commercially modified silicones usually include a curing catalyst, a silane coupling agent, an inorganic filler, a viscosity improver,
Further, other liquid resins such as an epoxy resin and a curing agent thereof are blended as required, and are widely used in the fields of adhesives, sealants, paints, coating agents and the like. In particular, in the case of adhesives and sealants, the use of one liquid can give the property of curing with atmospheric moisture at room temperature, and the cured product exhibits elasticity and flexibility without using an organic solvent. Since it maintains the fluidity that allows the coating operation, it has recently been receiving attention as a safe, convenient, and easy-to-use one-part normal-temperature, moisture-curable adhesive.

[0006] However, although resin compositions containing commercially available modified silicones are widely used in the various fields described above, there is no technique for dramatically improving the curing speed.
Therefore, requests for labor saving and productivity improvement by shortening the working time have not been solved yet.

[0007]

At present, there is an α-cyanoacrylate-based adhesive in a moisture-curable resin which can be bonded in a very short time by curing it at room temperature with one liquid. It is a well-known fact that the agent is a low molecular weight monomer having a cyano group as its main component, and the danger and harmfulness such as flammability and mucous membrane irritation are much higher than liquid polymer type adhesives with high molecular weight. It is.

On the other hand, liquid polymer type adhesives such as urethane type and epoxy type, including the above-mentioned modified silicone type, have little danger and harmfulness such as flammability and mucous membrane irritation, but all of them take several tens of minutes. It takes several hours to reach curing, and has a fatal defect in curing speed.

Thus, there is little danger / harmfulness and α
-At present, a resin composition suitable for an application such as an adhesive capable of bonding in a very short time, such as a cyanoacrylate adhesive, has not yet been developed.

[0010]

SUMMARY OF THE INVENTION In view of the above situation, the present invention provides a low-molecular-weight monomer-type adhesive using a liquid polymer-type material without relying on highly hazardous and harmful low-molecular-weight monomer-type materials. The task is to develop an instant adhesive.

The present inventors first synthesized a liquid polymer having a trialkoxysilyl group as a silicone-reactive group, and blended a curing catalyst, an adhesion-imparting agent, and the like with the liquid polymer. In about 1 to 5 minutes. However, the liquid polymer is inferior in storage stability and has hard and brittle physical properties (brittle property) after curing, so that the adhesive strength is poor and practically insufficient. Next, the inventor blends a commercially available modified silicone having only a stable and commercially available alkyldimethoxysilyl group into a polymer composition containing a liquid polymer having a trialkoxysilyl group as a silicone-reactive group. I imagined that. In contrast to unstable and highly reactive trialkoxysilyl groups, the combined use of a commercially available modified silicone with a less reactive and stable alkyldimethoxysilyl group improves storage stability and reduces brittleness. It is easily anticipated that the essential quick-curing property will decrease. Thus, when a commercially available modified silicone having an alkyldimethoxysilyl group was blended with a polymer composition containing a liquid polymer having a trialkoxysilyl group as a silicone-reactive group, the inventors predicted the initial expectation. An unexpected effect of overturning was developed. That is,
When a liquid polymer having a trialkoxysilyl group and a modified silicone having an alkyldimethoxysilyl group are blended, it is expected that the brittle properties, storage stability and curing speed are improved on average. However, although the relaxation of the brittle property is as expected, the storage stability of the modified silicone having an alkyldimethoxysilyl group can be maintained almost as it is when the modified silicone having the alkyldimethoxysilyl group is present. It has been found that the fast-curing property exhibited when a liquid polymer having only an alkoxysilyl group is present can be maintained almost as it is, and the fast-curing property hardly decreases. Such a phenomenon is a peculiar phenomenon that overturns the chemical wisdom of those skilled in the art, and it must be said that the controlling factor that gives storage stability and the controlling factor that leads to rapid curing are completely different. The present invention has been completed based on such findings.

That is, the present invention provides a resin composition containing a silicone-based resin in which the silicone-reactive group at the molecular end is a polyalkoxysilyl group and the main chain is substantially a polyoxyalkylene structure. The silicone resin is (1) a silicone-reactive group is a trialkoxysilyl group, and the main chain is substantially 10 to 90% by weight of a silicone resin having a polyoxyalkylene structure; and (2) the silicone-reactive group is an alkyldialkoxy. The present invention relates to a silicone resin composition comprising a mixture of 90 to 10% by weight of a silicone resin having a silyl group and a main chain substantially having a polyoxyalkylene structure.

The silicone resin composition of the present invention satisfies all the above-mentioned conventional needs. That is, since the silicone resin composition of the present invention is a polymer compound, it has almost no danger or harm such as flammability and mucous membrane irritation. Further, the silicone resin composition of the present invention is excellent in storage stability, and is remarkably excellent in quick curing. Furthermore, since the silicone resin composition of the present invention also has reduced brittle properties, it can impart excellent polymer properties that are flexible and tough. Therefore, if such characteristics are utilized, it can be suitably used in a wide range of fields such as sealants, coating agents, paints, etc., having unprecedented quick-setting properties.

The mixing ratio of the silicone resin of (1) and the silicone resin of (2) is set as follows:
80:80 to 20 (weight ratio), especially the former: the latter = 30 to
By setting the ratio to 70:70 to 30 (weight ratio), the effects of the present invention are more remarkably exhibited.

In the present invention, as the silicone resin (1), a trialkoxysilyl group has (R ¹ O) ₃ S
i-groups (where R ¹ is a C _1-5 alkyl group); a silicone resin in which an oxyalkylene group as a constituent unit of a polyoxyalkylene structure is an oxyalkylene group having 1 to 6 carbon atoms; ) As a silicone resin, an alkyldialkoxysilyl group is a (R ¹ O) ₂ (R ² ) Si group (where R ¹ is a C _1-5 alkyl group, and R ² is a C _1-20 alkyl group); When a silicone-based resin in which the oxyalkylene group, which is a constituent unit of the oxyalkylene structure, is an oxyalkylene group having 1 to 6 carbon atoms is used, the quick-curing properties are further improved.

Therefore, according to the present invention, the trialkoxysilyl group of ( ¹ ) is a (R ¹ O) ₃ Si group [where R ¹
Is a C _1-5 alkyl group], the oxyalkylene group which is a constituent unit of the polyoxyalkylene structure is an oxyalkylene group having 1 to 6 carbon atoms, and the alkyl dialkoxysilyl group of the above (2) is (R ¹ O ) ₂ (R ² ) Si group [where R ¹
Is a C _1-5 alkyl group, R ² is a C _1-20 alkyl group], wherein the oxyalkylene group as a constituent unit of the polyoxyalkylene structure is an oxyalkylene group having 1 to 6 carbon atoms. Things are provided.

In the present invention, a silicone resin having a trimethoxysilyl group and a oxypropylene group as a structural unit of the polyoxyalkylene structure is used as the silicone resin (1), and an alkyl resin is used as the silicone resin (2). When a dialkoxysilyl group is a methyldimethoxysilyl group, and a silicone resin in which the constituent unit of the polyoxyalkylene structure is an oxypropylene group,
Fast curing and transparency are further improved.

Therefore, according to the present invention, the trialkoxysilyl group of (1) is a trimethoxysilyl group, the structural unit of the polyoxyalkylene structure is an oxypropylene group, and the alkyldialkoxysilyl group of (2) is Is a methyldimethoxysilyl group, and the constituent unit of the polyoxyalkylene structure is an oxypropylene group.

If the silicone resin (1) having a number average molecular weight of 500 to 30,000 and the silicone resin (2) having a number average molecular weight of 1,000 to 30,000 is used, storage stability can be improved. It is possible to obtain a silicone-based resin composition having excellent properties, rapid curability and the like.

Therefore, according to the present invention, the number average molecular weight of the silicone resin (1) is 500 to 30,000 and the number average molecular weight of the silicone resin (2) is 10
The aforementioned silicone resin composition having a molecular weight of from 00 to 30,000 is provided.

If a resin obtained by a urethane reaction between a polyoxypropylene polyol and an isocyanate-substituted trialkoxysilane compound is used as the silicone resin (1), the silicone resin having further improved storage stability can be obtained. A resin composition can be obtained. In the urethane reaction between the polyoxypropylene polyol and the isocyanate-substituted trialkoxysilane compound, the ratio of the number of isocyanate groups of the isocyanate-substituted trialkoxysilane compound to the number of hydroxyl groups of the polyoxypropylene polyol (NCO / OH
Ratio) is set to 0.6 to 1.2, and the urethanization reaction is desirably performed.

Therefore, according to the present invention, the silicone resin composition according to the above (1), wherein the silicone resin is a resin obtained by a urethane reaction between a polyoxypropylene polyol and an isocyanate-substituted trialkoxysilane compound. Is provided.

According to the present invention, the ratio of the number of isocyanate groups in the isocyanate-substituted trialkoxysilane compound to the number of hydroxyl groups in the polyoxypropylene polyol (NCO /
(OH ratio) is 0.6 to 1.2, and the silicone resin composition is a resin obtained by a urethanization reaction.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The silicone resin, which is the active ingredient of the silicone resin composition of the present invention, comprises (1) a silicone-reactive group having a trialkoxysilyl group and a main chain having a substantially polyoxyalkylene structure. It is a mixture of a certain silicone resin and (2) a silicone resin in which the silicone reactive group is an alkyldialkoxysilyl group and the main chain is substantially a polyoxyalkylene structure.

The silicone resin (1) and (2)
Are all publicly known. These silicone resins are described, for example, in JP-B-45-363.
No. 19, JP-B-46-12154, JP-B-49
JP-A-32673, JP-A-50-156599, JP-A-51-73561, JP-A-54-60
No. 96, etc. Specifically, a method of synthesizing a hydroxyalkyldialkoxysilane such as hydroxymethyldimethoxysilane or a hydroxytrialkoxysilane such as hydroxytrimethoxysilane by a Michael addition reaction to a polyoxyalkylene having an allylated molecular terminal, For polyoxyalkylenes whose terminals are isocyanated,
N-phenyl-γ- capable of reacting with the isocyanate group
Aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyldimethoxysilane, γ-
Aminopropyltrimethoxysilane, amino-substituted silane compounds such as γ-aminopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane,
Examples include a method of synthesizing using a mercapto group-substituted silane compound such as γ-mercaptopropyltrimethoxysilane.

The silicone resin (1) is
It can also be synthesized by reacting a polyoxypropylene having a hydroxyl group at a molecular terminal with an isocyanate-substituted silane compound such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropyltrimethoxysilane, which can react with the hydroxyl group. When this isocyanate-type substituted silane compound is used, the number of isocyanate groups in the compound is determined based on the number of hydroxyl groups in the polyoxyalkylene polyol by an NCO / OH ratio of 0.6 to 1.
In this case, it is only necessary to make the number 2 work. According to this method,
The number of steps and the process time of the conventional synthesis method can be significantly reduced,
Not only does a complicated operation such as removal of impurities be unnecessary, but also the storage stability of the obtained silicone resin is superior to that of the silicone resin obtained by the conventional method. Therefore, in the present invention, it is preferable to use a silicone resin obtained by this production method.

In the present invention, as the silicone resin (1), a silicone resin produced according to each of the above methods is used.

In the present invention, as the silicone resin (1), a trialkoxysilyl group is an (R ¹ O) ₃ Si group (where R ¹ is a C _1-5 alkyl group), and a structural unit of a polyoxyalkylene structure Is an oxyalkylene group having 1 to 6 carbon atoms
It is preferable to use a silicone-based resin that is an oxyalkylene group, and a trialkoxysilyl group is a trimethoxysilyl group, and a polyoxyalkylene structure is preferably a silicone-based resin having an oxypropylene group. It is particularly preferable in terms of compatibility, rapid curing, and transparency. The number average molecular weight of the silicone resin (1) is 500 to 30,000, preferably 5000 to 20,000.
It is good.

In the present invention, as the silicone resin (2), a silicone resin produced according to each of the above methods may be used, but it is more convenient to use a commercially available modified silicone. Commercially available modified silicones specifically include MS polymer S203, MS polymer S303,
Examples include MS polymer 15A, Cyril SAT030, Cyril SAT200, Cyril SAX400 (manufactured by Kanegafuchi Chemical Industry Co., Ltd.), Exester S2410, Exester S2420, Exester S3430 (all manufactured by Asahi Glass Co., Ltd.), and the like.

In the present invention, the alkyl dialkoxysilyl group is (R ¹ O) as the silicone resin (2).
₂ (R ² ) Si group [where R ¹ is a C _1-5 alkyl group, R ²
Is a C _1-20 alkyl group], and a silicone resin in which the oxyalkylene group, which is a constituent unit of the polyoxyalkylene structure, is an oxyalkylene group having 1 to 6 carbon atoms is preferably used, and the alkyl dialkoxysilyl group is methyl. It is particularly preferable to use a silicone resin having a dimethoxysilyl group or a polyoxyalkylene structure whose structural unit is an oxypropylene group in terms of compatibility with other resins, rapid curability, and transparency. The number average molecular weight of the silicone resin (2) is 1,000 to 30,000, preferably 5,000 to 2,000.
It is better to be 0000.

The silicone resin of the present invention can be obtained by using the above (1)
And a mixture of the silicone resin of (2) and the silicone resin of (2). In the present invention, a method of separately producing these two types of silicone resins and mixing them is adopted, but the method is not limited thereto. For example, hydroxytrialkoxysilanes and / or hydroxyalkyldialkoxysilanes may be added simultaneously or stepwise to polyoxyalkylenes whose terminals are allylated, or polyalkylene polyols may be previously prepared using diisocyanate. A mercapto-substituted trialkoxysilane compound and / or a mercapto-substituted alkyldialkoxysilane compound may be added simultaneously or stepwise as an NCO-terminated urethane prepolymer. According to this method, a mixture of the silicone resin (1) and the silicone resin (2) can be prepared at once.

In the present invention, a commercially available modified silicone having an alkyldialkoxysilyl group of a methyldimethoxysilyl group and a main chain of substantially polyoxypropylene is used as the silicone resin of the above (2). Number average molecular weight of 500 to 30,000 as a system resin
It is preferable to use a silicone-based resin obtained from the above polypropylene polyol and a γ-isocyanate-substituted alkoxysilane compound because a resin composition having excellent curability, storage stability and compatibility can be obtained. In this preferred composition, a polypropylene polyol having a number average molecular weight of 5,000 to 20,000 and γ-isocyanatopropyltrimethoxysilane of the γ-isocyanate-substituted alkoxysilane compound with an NCO / OH ratio of 0.6 with respect to a commercially available modified silicone. Incorporation of a silicone resin having a trimethoxysilyl group obtained by reacting at -1.2 provides excellent storage stability, compatibility, transparency and the fastest-curing resin composition For,
Particularly preferred.

The silicone resin which is an active ingredient of the silicone resin composition of the present invention comprises 10 to 90% by weight of the silicone resin (1) and the silicone resin 90 (2).
-10% by weight of the mixture. When the mixing ratio of the silicone resin of (1) is larger than the above range, the change in viscosity over time exceeds 50% when stored at 50 ° C. × 30 days, and when processed into an adhesive, the thickening rate further increases. Therefore, good storage stability cannot be obtained. When the mixing ratio of the silicone resin of (1) is less than the above range, the quick-curing property approaches the characteristics of the silicone resin of (2), and when this silicone resin composition is processed into an adhesive, it takes a short time. It becomes impossible to bond.

In the present invention, the preferred ranges of excellent compatibility, storage stability and adhesion in a very short time are 20 to 80% by weight of the silicone resin (1) and the silicone resin (2). 80 to 20% by weight of the resin, the characteristics of which are most remarkably mixed in the silicone resin 3 of (1)
0 to 70% by weight and the silicone resin (2) of 70 to 3
0% by weight.

The silicone resin composition of the present invention may contain a curing catalyst for accelerating the 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; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, tin laurate, tin ferzaticate, and the like. Tin carboxylate; a reaction product of dibutyltin oxide and phthalate;
Dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum triacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; octylic acid Lead; iron naphthenate; and metal-based catalysts such as bismuth compounds such as bismuth-tris (neodecanoate) and bismuth-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.

The silicone-based resin composition of the present invention contains N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane and γ-aminopropyltrimethoxy for the purpose of improving adhesiveness and storage stability. Silane, γ-aminopropyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
A silane coupling agent such as N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane can be blended.

Further, the silicone resin composition of the present invention may contain, if necessary, an epoxy resin and its curing agent, a filler,
A plasticizer, a viscosity improver, other additives and the like can be appropriately compounded.

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, novolak type epoxy resin, and the like. 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 butyl benzyl phthalate; dioctyl adipate, isodecyl succinate, sebacine 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.
0.1 to 10 parts by weight (preferably 0.5 to 5 parts) of the curing catalyst
Parts by weight, particularly preferably 1 to 3 parts by weight, and 0.1 to 15 parts by weight of the silane coupling agent (preferably 0.5 to 1 part by weight).
0 parts by weight, particularly preferably 1 to 5 parts by weight), 1 to 100 parts by weight (preferably 10 to 50 parts by weight) of epoxy resin, and 1 to 200 parts by weight of epoxy resin curing agent per 100 parts by weight of epoxy resin ( Preferably 10 to 100 parts by weight), 0.1 to 200 parts by weight of filler, and 1 to 1 part of plasticizer.
It is preferable to add 50 parts by weight and about 0.1 to 10 parts by weight of a viscosity improver.

[0045]

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”.

Reference Example 1 A stirrer, dropping funnel, reflux tube, thermometer, nitrogen gas flow device,
Polyoxypropylene triol (number average molecular weight = 10000, hydroxyl value = 16.8, number of hydroxyl groups per molecule = 3, trade name: Preminol 3010, Asahi Glass) 1000 parts) and 10-2 at 100 ° C.
Dehydration was performed by distillation under reduced pressure at 0 mgHg for 1 hour, and this was cooled to 50 ° C. 7-isocyanatopropyltrimethoxysilane was added to NCO / OH = 1.0.
1.9 parts are charged, and the temperature is increased under a nitrogen stream, and 80 to 90 ° C.
The stirring was continued for 8 hours, and the NCO content was measured. As a result, it was 0.06% (theoretical value: 0%). The viscosity of this silicone liquid polymer was 550 Pa · s / 23 ° C. The modified silicone having a trialkoxysilyl terminal thus obtained is referred to as “modified silicone A”.

REFERENCE EXAMPLE 2 In the experimental apparatus of Reference Example 1, as a polymer having an alkyldialkoxysilyl group, a commercially available modified silicone (where the silicone-reactive group is a methyldimethoxysilyl group and the main chain is substantially polyoxypropylene) Kaneka MS Polymer S303, designed molecular weight 10,000, viscosity 200 Pa.
s / 23 ° C., the number of methyldimethoxysilyl per molecule is about 3, 1000 parts of Kanebuchi Chemical Industry Co., Ltd.) are charged, and the mixture is dehydrated by vacuum distillation at 100 ° C. and 10-20 mmHg for 1 hour. Then, it was cooled and taken out under a nitrogen stream. The modified silicone having an alkyldialkoxysilyl terminal thus obtained is referred to as “modified silicone B”.

Test Example 1 In a dry box, modified silicone A and modified silicone B were blended at the ratio shown in Table 1 below, and a storage stability test was conducted. That is, the modified silicone A produced in Reference Example 1
The modified silicone B produced in Reference Example 2 was packed in a glass bottle of 100 g, subjected to nitrogen purging, sealed, sealed, and then stored in a 50 ° C. incubator to perform a storage stability test. First, the viscosity (initial viscosity) at 23 ° C. of the mixture of the modified silicone A and the modified silicone B was measured. Next, the mixture was stored under the condition of 50 ° C. × 30 days, and then allowed to cool to 23 ° C. in a sealed state again, and the viscosity was measured immediately. From these viscosity values, the thickening rate (%)
I asked. The results are shown in Table 1.

[0049]

[Table 1]

As is apparent from Table 1, except for Comparative 1 (modified silicone A having a trimethoxysilyl group terminal alone) and Comparative 2, the thickening rate was 50% or less.

Example 1 An adhesive was prepared using a mixture of the modified silicone A and the modified silicone B blended in the ratio shown in Table 1 above.
That is, using a 2 liter planetary mixer (manufactured by Inoue Seisakusho), each modified silicone mixture 10
Per 100 parts, 300 parts of heavy calcium carbonate from which water was removed by heating and drying, 30 parts of a curing catalyst (dibutyltin dilaurate), and aminosilane (N-
20 parts of (β-aminoethyl) -γ-aminopropyltrimethoxysilane and 50 parts of dioctyl adipate as a diluent were blended to obtain respective adhesives.

The adhesive containing the silicone resin of Comparative Example 1 is referred to as the adhesive of Comparative Example 1, and the adhesive containing the silicone resin of Examples 1 to 7 is referred to as the adhesive of Examples 1 to 7. did. Accordingly, the present inventions 1 to 7 and Comparatives 1 to 4 correspond to the compounding ratios of the modified silicones in Table 1 above.

Using these adhesives, the respective effects were confirmed by the following methods.

(I) Measurement of sticking time: A 300 mm square (thickness 3 mm) aluminum plate was cut into a 25 mm square (10 mm thick) wooden piece (Asada wood) in an atmosphere of 23 ° C. and 50% relative humidity. 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 thickness of about 0.1 mm on a 300 mm square plywood with a bar coater in an atmosphere of 23 ° C. and a relative humidity of 50%. 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 every minute with the passage of time using a spring balance. 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 adhesive strength after 30 minutes: length 100 m 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 ).

(Iv) Storage stability test The adhesives of Examples 1 to 7 and Comparative Examples 1 to 4 were packed in 100 g glass bottles, purged with nitrogen, hermetically sealed and placed in a 50 ° C. incubator. A storage stability test was performed. First, the viscosity at 23 ° C. (initial viscosity) of each adhesive was measured. Next, each adhesive was stored under the condition of 50 ° C. × 30 days, then allowed to cool to 23 ° C. in a sealed state again, and the viscosity was measured immediately. From these viscosity values, the thickening rate (%) was determined.

Table 2 shows the results.

[0059]

[Table 2]

As is clear from Table 1, the adhesives of the present inventions 1 to 7 having excellent storage stability and capable of bonding in a very short time were used.

Claims (8)

[Claims] 1. A resin composition containing a silicone-based resin in which a silicone-reactive group at a molecular end is a polyalkoxysilyl group and a main chain of which is substantially a polyoxyalkylene structure, wherein the silicone-based resin is (1) Silicone resin 10 in which the silicone-reactive group is a trialkoxysilyl group and the main chain is substantially a polyoxyalkylene structure
90 to 90% by weight and (2) 90 to 10% by weight of a silicone resin in which the silicone reactive group is an alkyldialkoxysilyl group and the main chain is substantially a polyoxyalkylene structure.
A silicone resin composition characterized by being a mixture of 2. The silicone resin composition according to claim 1, wherein the silicone resin is a mixture of 20 to 80% by weight of the silicone resin (1) and 80 to 20% by weight of the silicone resin (2). 3. The silicone resin composition according to claim 1, wherein the silicone resin is a mixture of 30 to 70% by weight of the silicone resin (1) and 70 to 30% by weight of the silicone resin (2). 4. The (1) trialkoxysilyl group is a (R ¹ O) ₃ Si group (where R ¹ is a C _1-5 alkyl group);
An oxyalkylene group which is a constituent unit of the polyoxyalkylene structure is an oxyalkylene group having 1 to 6 carbon atoms,
The alkyl dialkoxysilyl group of the above (2) is (R)
¹ O) ₂ (R ² ) Si group [where R ¹ is a C _1-5 alkyl group, R ² is a C _1-20 alkyl group], and the oxyalkylene group, which is a structural unit of the polyoxyalkylene structure, is carbon Number 1
The silicone resin composition according to any one of claims 1 to 3, wherein the composition is an oxyalkylene group. 5. The (1) trialkoxysilyl group is a trimethoxysilyl group, the structural unit of the polyoxyalkylene structure is an oxypropylene group, the (2) alkyldialkoxysilyl group is a methyldimethoxysilyl group, The silicone resin composition according to any one of claims 1 to 3, wherein the constituent unit of the polyoxyalkylene structure is an oxypropylene group. 6. The method according to claim 4, wherein the silicone resin of (1) has a number average molecular weight of 500 to 30,000 and the silicone resin of (2) has a number average molecular weight of 1,000 to 30,000. Silicone resin composition. 7. The silicone resin according to claim 1, wherein the silicone resin (1) is a resin obtained by a urethane reaction between a polyoxypropylene polyol and an isocyanate-substituted trialkoxysilane compound. Resin composition. 8. The silicone resin according to (1), wherein the ratio of the number of isocyanate groups of the isocyanate-substituted trialkoxysilane compound to the number of hydroxyl groups of the polyoxypropylene polyol (NCO / OH ratio) is 0.6 to 0.6.
The silicone resin composition according to claim 7, which is a resin obtained by a urethanization reaction as 1.2.