JP3286749B2 - Silicone resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silicone resin composition. Its purpose is to be fast-curing,
An object of the present invention is to provide a silicone resin composition having excellent storage stability, internal curability, adhesiveness and adhesive strength.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open Nos. 63-112,842 and 63-65086, as typical processes, have a methyldimethoxysilyl group as a silicone-reactive group, and the main chain is substantially made of polyoxypropylene. Certain silicone-based liquid polymers (hereinafter referred to as “methyldimethoxysilyl-type modified silicone”) and acrylic copolymers having polyalkoxysilyl groups such as trimethoxysilyl groups and / or methyldimethoxysilyl groups as silicone-based reactive groups ( The so-called acryl-modified silicone blended with this “hereinafter referred to as“ polyalkoxysilyl group-containing acrylic copolymer ”) is widely marketed as a one-part cold curing adhesive base. The acrylic modified silicone is mixed with a curing catalyst, a silane coupling agent, an adhesive modifier such as a filler, and the like, and used as a moisture-curable adhesive.

[0003] This modified acrylic silicone has an excellent initial tack compared with a commercially available modified silicone not containing the acrylic copolymer (methyldimethoxysilyl-type modified silicone), and has good adhesion and adhesion strength to various adherends (these are referred to as “modified silicone”). (Hereinafter referred to as “adhesion function”), but has the disadvantage that, due to the highly hydrophobic acrylic polymer, it has poor internal curability compared to methyldimethoxysilyl-modified silicone and has a slow curing speed. are doing. In this acrylic modified silicone, a polyalkoxysilyl group is introduced into the molecule of the acrylic polymer in order to promote sensitivity to moisture by the highly hydrophobic acrylic polymer component. It has not been improved enough. That is, although commercially available acrylic modified silicones are widely used as adhesive bases having excellent adhesive functions and storage stability, technical problems to be solved in terms of internal curability and curing speed remain.

On the other hand, a modified silicone having a trimethoxysilyl group instead of a methyldimethoxysilyl group as a silicone-reactive group and having a main chain of polyoxypropylene (hereinafter referred to as "trimethoxysilyl-type modified silicone")
Is a polyoxypropylene in which the trimethoxysilyl group is more reactive than the methyldimethoxysilyl group and the main chain is hydrophilic, so that the internal curability is excellent and the curing speed is very fast. Has characteristics.
However, the modified trimethoxysilyl-type silicone has poor storage stability and an inferior adhesive function to a commercially available modified methyldimethoxysilyl-type silicone, and thus has not been recognized as having industrial value and has not been marketed.

[0005] Thus, to date, storage stability is excellent,
In addition, a modified silicone having excellent internal curability and a very high curing speed and excellent adhesive function has not yet been found.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to develop a silicone resin composition having excellent storage stability, excellent internal curability, extremely high curing speed, and excellent adhesive function. As an issue.

[0007]

SUMMARY OF THE INVENTION Even if an acrylic modified silicone contains an acrylic copolymer in which a highly reactive trimethoxysilyl group is introduced as a polyalkoxysilyl group, the acrylic modified silicone has a hydrophobic main chain acrylic copolymer. Since the sensitivity to moisture is hindered, the internal curability is poor, and the time required for curing is usually about 30 minutes in the air at room temperature. More specifically, JP-A-63-11264
Modified acrylic silicone (polyalkoxysilyl group-containing acrylic copolymer: methyldimethoxysilyl-type modified silicone = 50: 50) produced according to JP-A-2
Even when stored at 0 ° C. for about one month, there is almost no change in viscosity, and the storage stability is good. However, when a curing catalyst and a silane coupling agent are blended to form an adhesive, the curing takes 30 minutes at room temperature. Need.

On the other hand, the modified trimethoxysilyl-type silicone has a synergistic effect based on the hydrophilicity of the highly reactive trimethoxysilyl group and the polyoxypropylene as the main chain.
The curing speed is as fast as about 1 to 5 minutes at room temperature, but the storage stability is poor. More specifically, a modified trimethoxysilyl-type silicone synthesized from, for example, polyoxypropylene triol and γ-isocyanatopropyltrimethoxysilane can be stored at 50 ° C. for about one month to have a viscosity about twice as high as the initial viscosity (viscosity increase). (% = 127%), but when this is used as an adhesive as described above, the curing time is only 1 to 5 minutes at room temperature. Here, the viscosity increase (%) means the viscosity value (23 ° C.) after 50 ° C. × 30 days−initial viscosity value (23 ° C.) / Initial viscosity value (23 ° C.) × 10.
It is represented by 0.

If a modified trimethoxysilyl type silicone having a poor storage stability and a high curing speed and an acrylic modified silicone having a good storage stability and a low curing speed are blended,
It is believed that the storage stability is improved on average, but the cure speed is also slowed on average. That is, regarding the curing speed, if the modified silicone of the former is 1 to 5 minutes and the modified silicone of the latter is 30 minutes, the curing speed of the mixture is expected to be about 15 minutes, and the storage stability is estimated to be about 15 minutes. If the silicone is slightly more than twice the initial viscosity (127% thickening) and the latter modified silicone hardly thickens with time, the thickening of the mixture is about 1.5 times (about 50% thickening). It is expected to calm down. However, in fact, when 50 to 100 parts by weight of a modified trimethoxysilyl type silicone was blended with respect to 100 parts by weight of the modified acrylic silicone, the mixture was stable and thickened even after 1 month at 50 ° C. The rate was found to stop within 20%. Further, when this mixture was blended with a curing catalyst and a silane coupling agent and processed into an adhesive, it was found that the mixture exhibited a rapid curing time of 1 to 5 minutes, which is almost the same as that of the modified trimethoxysilyl type silicone. That is, such a phenomenon is a specific phenomenon that overturns the common sense of chemistry of those skilled in the art,
The controlling factor that leads to fast curing and the controlling factor that provides storage stability are completely different. In addition, it has been found that this adhesive exhibits an initial tackiness and an adhesive function close to those of an adhesive processed using only an acrylic-modified silicone as an adhesive base.

On the basis of such findings, the present inventors have conducted intensive studies on the mixing ratios of the methyldimethoxysilyl-modified silicone, the trimethoxysilyl-modified silicone and the polyalkoxysilyl group-containing acrylic copolymer and the production method thereof. In the past, we found a region that gives rapid curing properties and good storage stability that is indispensable as an adhesive base, and provides an excellent adhesive function when used as an adhesive, and here we have completed the present invention. Reached.

That is, the present invention provides a silicone resin wherein the resin component is (a) a silicone-reactive group is a trimethoxysilyl group and / or a triethoxysilyl group and the main chain is substantially a polyoxypropylene structure; b) a silicone resin in which the silicone-reactive group is a methyldimethoxysilyl group and / or a methyldiethoxysilyl group, and the main chain of which is substantially a polyoxypropylene structure; and (c) 0.1 to 20% by weight in the molecule. Containing an alkoxy group having 1 to 20 carbon atoms in the alkyl group and having at least one selected from the group consisting of acrylates and methacrylates having 1 to 20 carbon atoms in the alkyl group. Combination of the silicone resin (a) with the silicone resin (b) If the former: the latter = 10 to 90:
A silicone resin of (a) having an acrylic resin content of (c) of 90 to 10 (weight ratio) and (b)
5 to 200% by weight based on the total amount of silicone resin
The present invention relates to a silicone resin composition containing the following resin:

According to the present invention, there is provided a silicone resin composition having excellent storage stability, excellent internal curability, very high curing speed, and excellent adhesive function.

According to the present invention, the resin component comprises (a)
A silicone resin wherein the silicone-reactive group is a trimethoxysilyl group and the main chain is substantially a polyoxypropylene structure; (b) the silicone-reactive group is a methyldimethoxysilyl group and the main chain is substantially a polyoxypropylene The silicone resin having the structure and (c) 0.5 to 1 in the molecule.
It contains 0% by weight of trimethoxysilylmethyl and / or dimethoxysilyl groups, and the alkyl group has 2 to 17 carbon atoms.
Consisting of an acrylic resin having a silicone-reactive group obtained by copolymerizing an acrylate ester and methyl methacrylate and / or tetrahydrofuran methacrylate, wherein the silicone resin of (a) and the silicone of (b) The ratio of the former to the latter is 10 to 90:90 to 10 (weight ratio), and the proportion of the acrylic resin (c) is the silicone resin (a) and the silicone resin (b). The present invention provides a silicone resin composition containing a resin in an amount of 5 to 200% by weight based on the total amount of the resin. This silicone resin composition is particularly excellent in fast curing.

Further, according to the present invention, the above silicone wherein the mixing ratio of the silicone resin (a) and the silicone resin (b) is the former: the latter = 20-80: 80-20 (weight ratio). A resin composition is provided. This silicone-based resin composition is particularly excellent in quick curing and storage stability.

Further, according to the present invention, the acrylic resin (c) is mixed with the silicone resin (a) and the silicone resin (b).
The silicone resin composition is provided in an amount of 10 to 100% by weight based on the total amount of the silicone resin. This silicone-based resin composition is particularly excellent in fast-curing properties, storage stability and transparency, and is also excellent in imparting low viscosity.

Further, according to the present invention, 0.1 to 2
A solution polymerization of at least one selected from the group consisting of acrylates and methacrylates containing 0% by weight of a polyalkoxysilyl group and having 1 to 20 carbon atoms in the alkyl group in an organic solvent ( A method for producing the above-mentioned silicone-based resin is provided, wherein the acrylic-based resin of (c) is obtained, and then the silicone-based resin of (a) and the silicone-based resin of (b) are added thereto, and then the organic solvent is removed.

Further, according to the present invention, in the presence of the silicone-based resin (a) and the silicone-based resin (b), an alkyl group containing 0.1 to 20% by weight of a polyalkoxysilyl group in the molecule, A method for producing the silicone resin is provided, wherein at least one selected from the group consisting of acrylates and methacrylates having 1 to 20 carbon atoms is polymerized.

Further, according to the present invention, there is provided an adhesive comprising the above-mentioned various silicone resin compositions.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The resin component, which is an active ingredient of the silicone resin composition of the present invention, comprises (a) a silicone-reactive group having a trimethoxysilyl group and / or a triethoxysilyl group, and a main chain having substantially a main chain. A silicone-based resin having a polyoxypropylene structure, (b) a silicone-based resin having a silicone-reactive group of a methyldimethoxysilyl group and / or a methyldiethoxysilyl group and a main chain of substantially a polyoxypropylene structure, and ( c) 0.1-20 in the molecule
At least one selected from the group consisting of acrylates and methacrylates containing 1% to 20% by weight of a polyalkoxysilyl group and having 1 to 20 carbon atoms in the alkyl group;
A mixture of acrylic resins having a silicone-reactive group obtained by polymerizing a seed as a main component,
The mixing ratio of the silicone resin (a) and the silicone resin (b) is the former: the latter = 10-90: 90-1
0 (weight ratio), and the mixing ratio of the acrylic resin (c) is 5 to 200% by weight based on the total amount of the silicone resin (a) and the silicone resin (b). Resin.

The silicone resin (a) and (b)
Are all publicly known. These silicone resins are described, for example, in JP-B-45-363.
No. 19, JP-B-46-12154, JP-B-4
9-32673, JP-A-50-156599, JP-A-51-73561, JP-A-54-60
No. 96, JP-A-3-160022 and the like.

Specifically, a method of synthesizing a polyoxyalkylene which is allylated with a molecular terminal by subjecting a hydroxysilane such as hydroxymethyldimethoxysilane, hydroxytrimethoxysilane, or hydroxytriethoxysilane to a Michael addition reaction, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxy which can react with the isocyanate group of polyoxyalkylene having a molecular terminal isocyanated Silane, amino-substituted silane compounds such as γ-aminopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, etc. A method of adding and synthesizing a rucapto-substituted silane compound, for a polyoxyalkylene having a hydroxyl group at a molecular end, for γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, etc. A method of adding an isocyanate group-substituted silane compound and synthesizing the compound can be exemplified.

Among these, the only commercially available silicone resin is a silicone resin having a methyldimethoxysilyl group at the molecular end and a polyoxypropylene main chain (the silicone resin (b) in the present invention). And the synthesis method is also limited to the above-mentioned Michael reaction addition method using allylated polyoxypropylene and hydroxymethyldimethoxysilane.

Commercially available silicone resins (b) include MS polymer S20.
3, MS polymer S303, MS polymer 15A, Cyril SAT030, Cyril SAT200, Cyril S
AX400 (all manufactured by Kaneka Corporation), Exester S2410, Exester S2420 and Exester S3430 (all manufactured by Asahi Glass Co., Ltd.).

On the other hand, the silicone resin (a) is not commercially available, and can be synthesized according to the various known methods described above.

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

In the present invention, it is particularly preferable to use, as the silicone resin (a), a silicone resin in which the silicone-reactive group is a trimethoxysilyl group and the main chain is substantially a polyoxypropylene structure. The number average molecular weight of the silicone resin (a) is preferably from 500 to 30,000, more preferably from 5,000 to 20,000.

In the present invention, as the silicone resin (b), a silicone resin produced according to each of the above methods may be used, but it is more convenient to use the commercially available modified silicone.

In the present invention, it is particularly preferable to use, as the silicone resin (b), a silicone resin in which the silicone-reactive group is a methyldimethoxysilyl group and the main chain is substantially a polyoxypropylene structure. (B)
The number average molecular weight of the silicone resin is 1000 to 300
00, preferably 5,000 to 20,000.

In the present invention, a method of separately producing two kinds of silicone resins, ie, the silicone resin (a) and the silicone resin (b), and mixing them is adopted. It is not something to be done. 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 (a) and the silicone resin (b) can be prepared at once.

In the present invention, a commercially available modified silicone having a silicone-reactive group of methyldimethoxysilyl group and a main chain of substantially polyoxypropylene is used as the silicone resin (b). When a silicone-based resin obtained from a polypropylene polyol having a number average molecular weight of 500 to 30,000 and a γ-isocyanate-substituted alkoxysilane compound is used as the resin, a resin composition having excellent curability, storage stability, compatibility and the like can be obtained. It is preferable because it 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 among γ-isocyanate-substituted alkoxysilane compounds are added to a commercially available modified silicone by NC.
By blending a silicone resin having a trimethoxysilyl group obtained by reacting at an O / OH ratio of 0.6 to 1.2, a resin composition having excellent storage stability and the fastest curing property can be obtained. It is particularly preferable because it can be obtained.

In the present invention, the silicone resin 10 (a)
To 90% by weight and the silicone resin of (b) 90 to 10
% By weight of the mixture. When the mixing ratio of the silicone-based resin (a) is more than the above range, the change in viscosity over time is 50.
When the temperature exceeds 50% after storage at about 30 ° C. for about 30 days, when processed into an adhesive, the thickening rate is further increased, so that good storage stability cannot be obtained. When the mixing ratio of the silicone resin (a) is less than the above range, the quick-curing property approaches the characteristics of the silicone resin (b), 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 (a) and the silicone resin (b). 80 to 20% by weight of the resin, the characteristics of which are most remarkably mixed with the silicone resin 3 (a)
0 to 70% by weight and the silicone resin (b) 70 to 3
0% by weight.

The acrylic resin (c), which is one of the resin components of the present invention, is a resin containing 0.1 to 20% by weight of a polyalkoxysilyl group in the molecule.
It is obtained by polymerizing at least one selected from the group consisting of acrylates and methacrylates having 1 to 20 carbon atoms in the alkyl group as a main component. Such acrylic resins are also known.

Examples of the acrylate having an alkyl group having 1 to 20 carbon atoms include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate and tertiary acrylate.
t-butyl, n-hexyl acrylate, 2-acrylate
Ethylhexyl, lauryl acrylate, myristyl acrylate, stearyl acrylate, and the like,
Among these, acrylates having an alkyl group having 2 to 17 carbon atoms are preferred. Examples of the methacrylate having an alkyl group having 1 to 20 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, and methacrylic acid. N-hexyl acid, 2-ethylhexyl methacrylate, lauryl methacrylate, myristyl methacrylate,
Examples thereof include stearyl methacrylate and tetrahydrofuran methacrylate. Of these, methyl methacrylate and tetrahydrofuran methacrylate are preferred.

The acrylic resin (c) is obtained by copolymerizing at least one monomer selected from the group consisting of the above-mentioned acrylates and methacrylates with a comonomer having a polyalkoxysilyl group, or It is produced by polymerizing in the presence of a chain transfer agent having a silyl group.

Examples of comonomers having a polyalkoxysilyl group include γ-methacryloxyalkylpolyalkoxysilanes such as γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane. And γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-acryloxyalkylpolyalkoxysilane such as γ-acryloxypropyltriethoxysilane.

Examples of the chain transfer agent having a polyalkoxysilyl group include γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and the like.

In the present invention, the above acrylate and methyl methacrylate and / or tetrahydrofuran methacrylate are combined with a polyalkoxysilyl group (preferably a trimethoxysilyl and / or methyldimethoxysilyl group).
It is preferable to carry out the copolymerization in the presence of a comonomer having the formula (I) or a chain transfer agent having a polyalkoxysilyl group (preferably a trimethoxysilyl and / or methyldimethoxysilyl group).

The compounding amount of the acrylic resin (c) is as follows:
5 to 200% by weight, preferably 10% by weight, based on the total amount of the silicone resin (a) and the silicone resin (b)
It is preferably from 100 to 100% by weight, particularly preferably from 20 to 80% by weight.

In the present invention, the silicone resin (a), the silicone resin (b) and the acrylic resin (c) obtained above are separately produced, and these are mixed at a predetermined ratio. Alternatively, a mixture of the silicone resin (a) and the silicone resin (b) and the acrylic resin (c) may be separately manufactured, and these may be mixed at a predetermined ratio. Further, the acrylic resin of (c) may be added to a mixture of the silicone resin of (a) and the silicone resin of (b), or the silicone resin of (b) and the acrylic resin of (c) may be added. May be added to the mixture of (a).

The mixture of the silicone resin (b) and the acrylic resin (c) is produced by a known method or a method similar thereto. For example, JP-B-63-65086, JP-B-2-42367, JP-B-2-35793, JP-B2-44845, and JP-B-2-5293.
No. 5, Japanese Patent Publication No. 4-56066, Japanese Unexamined Patent Publication No.
1122642, JP-A-7-238144,
JP-A-8-67707 and other publications disclose techniques for blending the silicone resin (b) and the acrylic resin (c). The mixture of the silicone resin (b) and the acrylic resin (c) thus obtained is, for example, Silyl MA430, Silyl MA440, Silyl MA447, or Silyl MAX45.
0 (all manufactured by Kanegafuchi Chemical Industry Co., Ltd.) and the like.

The silicone resin (a), the silicone resin (b) and the acrylic resin (c), which are the resin components of the present invention, are produced by mixing known resins as described above. However, if a preferable manufacturing method is shown, for example, the film is manufactured by the following method.

In the first method, a polyalkoxysilyl group is contained in the molecule in an amount of 0.1 to 20% by weight, and the alkyl group has 1 to 20 carbon atoms. The at least one selected is solution-polymerized in an organic solvent to obtain an acrylic resin (c), and then a silicone resin (a) and (b)
And then removing the organic solvent after blending the silicone resin.

The second method is to contain a polyalkoxysilyl group of 0.1 to 20% by weight in the molecule in the presence of the silicone resin (a) and the silicone resin (b), Is a method of polymerizing at least one selected from the group consisting of acrylic esters and methacrylic esters having 1 to 20 carbon atoms.

The first method is described in detail in JP-A-63-1.
As described in No. 12642, for example, in an organic solvent such as xylene, toluene, acetone, methyl ethyl ketone, ethyl acetate, and butyl acetate, a polymerizable monomer having a polyalkoxysilyl group in the molecule and an acrylate ester, A general method is to obtain a polymerizable monomer such as methacrylic acid ester by polymerization in the presence of a known radical polymerization initiator such as azobisisobutyronitrile. In this case, a compound having a polyalkoxysilyl group in the molecule such as γ-mercaptopropyltrimethoxysilane may be introduced as a chain transfer agent, or may be introduced using a compound having a polyalkoxysilyl group as an initiator. You may. The polymer (acrylic resin of (c)) solution thus obtained is mixed with the silicone resin of (a) or the silicone resin of (b), and the organic solvent is removed by vacuum distillation or the like as necessary. do it.
When the silicone resin of (a) or the silicone resin of (b) is blended, the silicone resin of (a) and the silicone resin of (b) are blended simultaneously, or (b)
It is desirable to compound the silicone resin of (a) after mixing the silicone resin of (a). It should be noted that if the silicone resin of (b) is blended after blending the silicone resin of (a), the storage stability of the resulting resin mixture may be reduced.

The second method is specifically described in JP-B-63-6-6.
As described in Japanese Patent No. 5086, etc., instead of solution polymerization in advance, a known polymerization initiator and a polymerization regulator are used in the silicone resin (a) or the silicone resin (b). There is also a method of radical polymerization using In this case, a comonomer having a polyalkoxysilyl group in the molecule, a polymerization initiator having a polyalkoxysilyl group, a chain transfer agent having a polyalkoxysilyl group, or the like is used as the monomer, initiator, and polymerization regulator. Needless to say. Also in this method, the silicone resin (a) and the silicone resin (b) may be simultaneously present in the reaction system, or only the silicone resin (b) may be present. In the case where the polymerization is performed by allowing only the silicone resin (a) to be present in the reaction system,
Care must be taken since the storage stability of the resulting resin mixture may be reduced.

A curing catalyst can be 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; 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.

Further, the silicone resin composition of the present invention contains N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane and γ-aminopropyltrimethoxy for 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.

The silicone resin composition of the present invention may further comprise an epoxy resin and a 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, 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. 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, and 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 added to 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.

[0057]

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 An acrylic polymer having a trimethoxysilyl group as a silicone-reactive group was produced according to Synthesis Example 4 described in JP-A-63-112642.

That is, 257 parts of xylene dehydrated with a molecular sieve was charged into a 2-liter four-neck separable flask equipped with a stirrer, a dropping funnel, a reflux tube, a thermometer, a nitrogen gas flow device, and a decompression device. The temperature was raised, and the monomer mixture was treated with 29.1 parts of γ-methacryloxypropyltrimethoxysilane and 7.4 parts of butyl acrylate.
Part, 447 parts of methyl methacrylate, 117 parts of stearyl methacrylate (manufactured by Mitsubishi Rayon), γ as a polymerization regulator
-12.0 parts of mercaptopropyltrimethoxysilane,
After dissolving 30.0 parts of azobisbutyronitrile as a polymerization initiator, the solution is transferred to a dropping funnel, and is heated to 110 to 110 under a nitrogen stream.
After dropping continuously at 115 ° C. over 6 hours, the mixture was aged for 2 hours at the same temperature, cooled to 50 ° C., and taken out to obtain an acrylic polymer solution having a silicone-reactive group. The evaporation residue of this solution was 68.5%, and the number average molecular weight by GPC was 4,300 (in terms of polystyrene). This polymer is referred to as "trimethoxysilyl group-containing acrylic copolymer solution A".

Production Example 2 In a pressure-resistant reaction vessel equipped with a stirrer (manufactured by Pressure-resistant Glass KK), a number average molecular weight of 8 in which an allyl ether group was introduced at 97% of all terminals.
They were charged 800 parts of polyoxypropylene 000, 19 parts of hydroxyethyl _{dimethoxysilane, (2 O H 2 PtCl 6} · 6H) 20 parts of isopropanol, 9 parts of chloroplatinic acid catalyst solution was dissolved in 180 parts of tetrahydrofuran solution) 0. After adding 4 parts, the mixture was reacted at 80 to 85 ° C for 6 hours. After the reaction, this was cooled to 50 ° C. and taken out.
As a result of structural analysis using R, a modified silicone having about 1.7 methyldimethoxysilyl groups per molecule at the molecular terminal was obtained. This polymer was compared with a commercially available modified silicone (Kaneka MS Polymer S203, designed molecular weight 8,000, manufactured by Kaneka Chemical Industry) by IR.
The R spectrum is shown. This is referred to as "methyldimethoxy-modified silicone B". The polymer solution was purged with nitrogen and stored in a sealed glass bottle at 50 ° C. for 30 days, and the viscosity was measured. The initial viscosity was 180 Pa · s / 2.
3 ° C. was 190 Pa · s / 23 ° C., and the thickening rate was about 6%, indicating good storage stability.

Production Example 3 Using the experimental apparatus used in Production Example 1, dehydrated polyoxypropylene triol at 50 ° C. (number average molecular weight 10,000, hydroxyl value 16.8, number of hydroxyl groups per molecule, 3 Preminol 3010, manufactured by Asahi Glass)
The number of NCOs and the number of OHs are the same per 00 parts (NCO / O
H = 1.0), 71.9 parts of γ-isocyanatopropyltrimethoxysilane was added and heated, and reacted at 80 to 90 ° C. for 8 hours under a nitrogen stream, and the NCO content was 0.06. % (Theoretical value: 0%), and was taken out after cooling to 50 ° C. This was subjected to structural analysis using NMR, and it was confirmed that the modified silicone had about 3.0 trimethoxysilyl groups per molecule at the molecular terminal. This is called "trimethoxy-modified silicone C". This polymer was purged with nitrogen and stored in a sealed glass bottle at 50 ° C. for 30 days, and the viscosity was measured. The initial viscosity was 550 Pa · s / 23 ° C., and the initial viscosity was 1250 Pa · s / 23.
The viscosity increased to 127 ° C., and the thickening rate was 127%, and storage stability was lacking.

Example 1 Using the experimental apparatus used in Production Example 1, 300 parts of a trimethoxysilyl group-containing acrylic copolymer solution A (polymer content: 205.5 parts), 200 parts of a modified methyldimethoxy-type silicone B and 200 parts of a modified trimethoxy-type silicone C200
The parts were mixed at 50 ° C. under a nitrogen stream, and xylene was removed by vacuum distillation using a rotary evaporator to obtain a viscous liquid polymer. The liquid polymer was a trimethoxysilyl group-containing acrylic copolymer A:
Methyldimethoxysilyl-type modified silicone B: Trimethoxysilyl-type modified silicone C = 103: 100: 10
0 (weight ratio). This mixture is referred to as “silicone resin composition I” of the present invention.

Example 2 Using the experimental apparatus used in Production Example 1, 300 parts of a trimethoxysilyl group-containing acrylic copolymer solution A (205.5 parts of polymer), 100 parts of a methyldimethoxysilyl-type modified silicone B and 100 parts of a trimethoxysilyl-type modified silicone 100 parts of the modified silicone C were mixed at 50 ° C. under a nitrogen stream, and xylene was removed in the same manner as in Example 1 to obtain a viscous liquid polymer. The liquid polymer was a trimethoxysilyl group-containing acrylic copolymer A: methyldimethoxysilyl-modified silicone B: trimethoxysilyl-modified silicone C = 103: 50: 50 (weight ratio). This mixture is referred to as “silicone resin composition II” of the present invention.

Comparative Example 1 Using the experimental apparatus used in Production Example 1, 300 parts of a trimethoxysilyl group-containing acrylic copolymer solution A (polymer content: 205.5 parts) and 200 parts of a methyldimethoxy-type modified silicone B were mixed with nitrogen at 50 ° C. The mixture was mixed under an air stream, and xylene was removed in the same manner as in Example 1 to obtain a viscous liquid polymer. The liquid polymer is a trimethoxysilyl group-containing acrylic copolymer: methyldimethoxysilyl-type modified silicone B = 103: 100 (weight ratio).

Comparative Example 2 Using the experimental apparatus used in Production Example 1, 300 parts of a trimethoxysilyl group-containing acrylic copolymer solution A (polymer content: 205.5 parts) and trimethoxy-modified silicone C
200 parts were mixed at 50 ° C. under a nitrogen stream, and xylene was removed in the same manner as in Example 1 to obtain a viscous liquid polymer. The liquid polymer was a trimethoxysilyl group-containing acrylic copolymer: trimethoxysilyl-type modified silicone C = 103: 100 (weight ratio).

Test Example 1 To check the storage stability of each of the mixed modified silicones obtained above, each was transferred to a 100 g mayonnaise bottle, purged with nitrogen, sealed completely, and then placed in an incubator at 50 ° C. × It was stored for 30 days, returned to 23 ° C., and immediately after opening, the viscosity was measured. Table 1 shows the results.

[0067]

[Table 1]

Test Example 2 As is clear from Table 1, except for Comparative Example 2, the others showed good storage stability. Dibutyltin laurylate (hereinafter abbreviated as "DBTDL") as a curing catalyst per 100 parts of each modified silicone showing good storage stability
2 parts of aminosilane (N- (β-aminoethyl) -γ-propyltrimethoxysilane) was blended as an adhesion-imparting agent to prepare each adhesive, and the following tests were performed.

(I) Measurement of fixation time: A 300 mm square (thickness 3 mm) aluminum plate was cut in an atmosphere of 23 ° C. and 50% relative humidity on a plane of a 25 mm square (10 mm thick) piece of wood (Asada wood). 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: The thickness of each adhesive is about 0.1 mm by a bar coater on a 300 mm square plywood 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 is performed every minute, and when the maximum strength exceeds 2 kg · f, the end point is determined.
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) Measurement of internal curability: In a 50 cc PP pudding cup in an atmosphere of 23 ° C. and 50% relative humidity,
After blending each resin composition so as to be heaped, the surface was scraped off with a putty knife so as to be uniform, and a test specimen was obtained. Twenty-four hours later, the cured portion of the surface of the test piece was peeled off so as to peel off the skin, and the uncured adhered portion was thoroughly wiped off. The thickness of the specimen was measured at five points with a vernier caliper, and the average value was defined as the degree of deep curing (single mm). ).

(V) Measurement of tensile shear bond strength of various materials 25 m in an atmosphere of 23 ° C. and 50% relative humidity
An aluminum plate having a length of 100 mm and a thickness of 3 mm (described as aluminum), a rigid polyvinyl chloride plate (described as PVC), and a polycarbonate plate (described as polycarbonate) were bonded to each other. The adhesive area is 25 mm x 25 mm, each adhesive is applied to one side so that the adhesive layer is about 0.2 mm, and about 30 seconds after application, one of the test pieces is overlapped and adhered to each other for 7 days under the same conditions. After standing, the tensile shear bond strength was measured. The tensile speed at the time of measurement was 5 mm / min, the number of test pieces was 5, and the average value of the respective maximum adhesive strengths was defined as the adhesive strength. Test equipment is Autograph AG5000
(Manufactured by Shimadzu Corporation) was used (unit: N / cm ² ).

[0074]

[Table 2]

Example 3 Using the same experimental apparatus as in Production Example 1, 300 parts of modified methyldimethoxysilyl-type silicone B and 700 parts of modified trimethoxysilyl-type silicone C were charged, the temperature was raised to 90 ° C., and a methacrylic acid mixture was obtained as a monomer mixture. Methyl 150
Part, 2-ethylhexyl acrylate 150 parts, γ-methacryloxypropyltrimethoxysilane 30 parts, γ-mercaptopropyltrimethoxysilane 3 as a polymerization regulator
Parts, and a monomer mixture of 3 parts of azobisisobutyronitrile as an initiator was added dropwise at 90 to 100 ° C. over 3 hours, followed by aging at 95 ° C. for 3 hours. Then 10m at 100 ° C to remove residual monomer and mixed water
Vacuum distillation was performed under reduced pressure of mHg, and the pressure was reduced to 50
After cooling to ℃, it was taken out to obtain a viscous liquid polymer. This polymer is a trimethoxysilyl group-containing acrylic copolymer: methyldimethoxysilyl-modified silicone B: trimethoxysilyl-modified silicone C = 33:
30:70. This mixture is referred to as “silicone resin composition III” of the present invention.

Example 4 The procedure was performed except that γ-methacryloxypropylmethyldimethoxysilane was used instead of γ-methacryloxypropyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane was used instead of γ-mercaptopropyltrimethoxysilane. A viscous liquid polymer was obtained in the same manner as in Example 3. This polymer is a methyldimethoxysilyl group-containing acrylic copolymer: methyldimethoxysilyl-modified silicone B: trimethoxysilyl-modified silicone C = 33: 30: 70.

This mixture is referred to as “silicone resin composition IV” of the present invention.

Example 5 A viscous liquid polymer was obtained in the same manner as in Example 3, except that 700 parts of the modified methyldimethoxysilyl type silicone B and 300 parts of the modified trimethoxysilyl type silicone C were used. This polymer is a trimethoxysilyl group-containing acrylic copolymer: methyldimethoxysilyl-modified silicone B: trimethoxysilyl-modified silicone C = 3
3:70:30. This mixture is referred to as “silicone resin composition V” of the present invention.

Comparative Example 4 A viscous liquid polymer was obtained in the same manner as in Example 3 except that the modified amount of the methyldimethoxysilyl-type modified silicone B was used without using the modified trimethoxysilyl-type silicone C. This polymer is a trimethoxysilyl group-containing acrylic copolymer: methyldimethoxysilyl-type modified silicone B = 33: 100 (weight ratio).

Comparative Example 5 Without using the methyldimethoxysilyl-type modified silicone B,
A viscous liquid polymer was obtained in the same manner as in Example 3 except that the total amount of the modified trimethoxysilyl-type silicone C was used. This polymer is a trimethoxysilyl group-containing acrylic copolymer: trimethoxysilyl-type modified silicone C =
33: 100 (weight ratio).

Test Example 3 In order to check the storage stability of each of the mixed modified silicones obtained above, each was transferred to a 100 g mayonnaise bottle, purged with nitrogen, sealed completely, and then placed in an incubator at 50 ° C. × It was stored for 30 days, returned to 23 ° C., and immediately after opening, the viscosity was measured. Table 3 shows the results.

[0082]

[Table 3]

As is clear from Table 3, except for Comparative Example 5, the others showed good storage stability. For each 100 parts of the modified silicone showing good storage stability, 2 parts of DBTDL as a curing catalyst and 2 parts of aminosilane (N- (β-aminoethyl) -γ-propyltrimethoxysilane) as an adhesion promoter were blended. Each adhesive was produced, and various tests were performed in the same manner as in Test Example 2. Table 4 shows the results.

[0084]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C09J 143/04

Claims (7)

(57) [Claims] 1. A silicone resin wherein the resin component is (a) a silicone-reactive group is a trimethoxysilyl group and / or a triethoxysilyl group and the main chain is substantially a polyoxypropylene structure, and (b) a silicone reaction A silicone resin having a methyldimethoxysilyl group and / or a methyldiethoxysilyl group and a main chain having a substantially polyoxypropylene structure; and (c) 0.1 to 20% by weight of a polyalkoxysilyl in the molecule. Acrylic having a silicone-reactive group obtained by polymerizing at least one selected from the group consisting of acrylates and methacrylates having an alkyl group having 1 to 20 carbon atoms and having a main group, (A)
The blending ratio of the silicone resin of (b) to the silicone resin of (b) is the former: the latter = 10 to 90:90 to 10 (weight ratio), and the blending ratio of the acrylic resin of (c) is (a) A silicone resin composition comprising 5 to 200% by weight based on the total amount of the silicone resin of (b) and the silicone resin of (b). 2. The resin component (a) is a silicone resin in which the silicone-reactive group is a trimethoxysilyl group and the main chain is substantially a polyoxypropylene structure. (B) The silicone-reactive group is a methyldimethoxysilyl group. A silicone resin having a main chain substantially of a polyoxypropylene structure; and (c) a carbon containing an alkyl group containing 0.5 to 10% by weight of trimethoxysilyl and / or methyldimethoxysilyl group in the molecule. It is composed of an acrylic resin having a silicone-reactive group obtained by copolymerizing an acrylate having a number of 2 to 17 with methyl methacrylate and / or tetrahydrofuran methacrylate. The blending ratio with the silicone resin of (b) is the former: the latter = 10 to 90:90
A resin having a mixing ratio of the acrylic resin of (c) of 5 to 200% by weight based on the total amount of the silicone resin of (a) and the silicone resin of (b). The silicone resin composition according to claim 1, comprising: 3. The silicone resin of (a) and (b)
The former and the latter have a compounding ratio with the silicone resin of 20:
The silicone resin composition according to claim 1 or 2, wherein the ratio is 80:80 to 20 (weight ratio). 4. The composition according to claim 1, wherein the mixing ratio of the acrylic resin (c) is 10 to 100% by weight based on the total amount of the silicone resin (a) and the silicone resin (b). The silicone resin composition according to claim 2 or 3. 5. A polyalkoxysilyl group of 0.1 to 20% by weight in a molecule, wherein the alkyl group has 1 to 2 carbon atoms.
A solution of at least one selected from the group consisting of an acrylate ester and a methacrylate ester, which is 0, in an organic solvent is obtained to obtain the acrylic resin (c), and then the silicone resin (a) and The method for producing a silicone resin according to claim 1, wherein the organic solvent is removed after blending the silicone resin (b). 6. In the presence of the silicone resin (a) and the silicone resin (b), a polyalkoxysilyl group of 0.1 to 20% by weight is contained in the molecule, and the carbon number of the alkyl group is The method for producing a silicone resin according to claim 1, wherein at least one selected from the group consisting of acrylic acid esters and methacrylic acid esters of 1 to 20 is polymerized. 7. An adhesive comprising the silicone resin composition according to claim 1.