JP5383088B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition mainly used as an adhesive, and more particularly to a curable resin composition that exhibits high adhesive strength against twisting.

  Conventionally, as a curable resin composition used as an adhesive, there is one called a curable silicone resin. There are various types of curable silicone resins, and the main chain is mainly composed of an oxyalkylene polymer, and the terminal is mainly composed of a vinyl polymer, and the main chain is mainly composed of a vinyl polymer. Some have hydrolyzable silicon groups bonded to the terminal. Any of these curable silicone resins functions as an adhesive by condensing and curing hydrolyzable silicon groups with moisture present in the environment. That is, the curable silicone resin is frequently used because it can be used as a moisture curable one-component adhesive.

  The curable silicone resin can adopt any main chain, so the physical properties after curing can be adjusted arbitrarily. Besides the adhesive, the sealant that requires elasticity and the hardness are required. It is also used for various applications such as paints.

  Moreover, in order to adjust the physical properties after curing, not only the main chain is changed, but plural kinds of curable silicone resins may be mixed. For example, Patent Documents 1 to 3 mainly describe a curable silicone resin whose main chain is mainly composed of an oxyalkylene polymer and a main chain mainly composed of a vinyl polymer in order to improve the weather resistance after curing. Mixing with a curable silicone resin is performed.

JP 59-122541 A JP 60-31556 A Japanese Unexamined Patent Publication No. Sho 63-112642

  The curable resin compositions described in Patent Documents 1 to 3 are excellent in peel strength and are preferable. As shown in FIG. 1, which is a side view of the adhesion state between adherends, the peel adhesion strength represents the bond strength when an external force is applied in the peeling direction between adherends. is there. Therefore, as shown in FIG. 2, which is a plan view of the adhesion state between the adherends, the adhesion strength when an external force is applied in the torsional direction between the adherends (hereinafter, this adhesion strength). This is not called “twisting bond strength”). However, the curable resin compositions described in Patent Documents 1 to 3 are not sufficient in terms of torsional adhesive strength.

  An object of the present invention is to provide a curable resin composition having improved torsional adhesive strength that could not be solved by the techniques described in Patent Documents 1 to 3.

  The present invention comprises a curable silicone resin containing a silicon atom derived from a hydrolyzable silicon group in a low proportion, a main chain mainly composed of an oxyalkylene polymer, and a hydrolyzable bonded to a side chain and a terminal. By mixing a specific proportion of a curable silicone resin containing a high percentage of silicon atoms derived from silicon groups and the main chain of which is a vinyl polymer, the torsional adhesive strength after curing is improved. A highly curable resin composition is obtained. That is, in the present invention, the main chain is mainly composed of an oxyalkylene polymer and a hydrolyzable silicon group is bonded to the terminal, and the silicon atom content derived from the hydrolyzable silicon group is 0.35 to 2.00 mass. % Curable silicone resin A, the main chain is mainly composed of a vinyl polymer, hydrolyzable silicon groups are bonded to the ends and side chains, and the silicon atom content derived from the hydrolyzable silicon group is 2 20 to 11.50% by mass of curable silicone resin B is blended at a ratio of curable silicone resin A: curable silicone resin B = 30 to 80:70 to 20 (mass ratio). The present invention relates to a curable resin composition.

[Curable silicone resin A]
In the curable silicone resin A, the main chain is mainly composed of an oxyalkylene polymer, and a hydrolyzable silicon group is bonded to the terminal, and the content of silicon atoms derived from the hydrolyzable silicon group is 0.35 to 2.00. % By mass.

（式中、Ｙは加水分解性基を示し、Ｚは加水分解しない不活性基を示し、ａは１、２又は３を示す。） The hydrolyzable silicon group is a group in which a hydrolyzable group is bonded to a silicon atom, and is represented by the following general formula (2).

(In formula, Y shows a hydrolysable group, Z shows the inactive group which does not hydrolyze, and a shows 1, 2, or 3.)

  As the hydrolyzable group Y, an alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group is generally used. In addition, conventionally known hydrolyzable groups such as halogen groups and mercapto groups can also be used. As the inert group Z, a hydrocarbon group is generally used, and an alkyl group such as a methyl group or an ethyl group is preferably used. Therefore, hydrolyzable silicon groups include trihydroxysilyl groups, monoalkyldihydroxysilyl groups, trialkoxysilyl groups, monoalkyldialkoxysilyl groups, trihalosilyl groups, monoalkyldihalosilyl groups, trimercaptosilyl groups, or monoalkyls. A dimercaptosilyl group or the like is used. Among these, a trialkoxysilyl group or a monoalkyl dialkoxysilyl group is preferable because it is relatively easy to handle.

  In particular, it is preferable to employ a trialkoxysilyl group as the hydrolyzable silicon group. The trialkoxysilyl group is fast-curing and trifunctional, so that the torsional adhesive strength after curing can be further increased. Therefore, among all silicon atoms derived from hydrolyzable silicon groups, the silicon atomic ratio derived from trialkoxysilyl groups is preferably 10 to 100% by mass, and particularly preferably 30 to 100% by mass. When the silicon atomic ratio derived from the trialkoxysilyl group is 10% by mass or more, the crosslinked state becomes dense, and further improvement in torsional adhesive strength can be realized.

  The main chain of the curable silicone resin A is mainly composed of an oxyalkylene polymer. As what consists only of an oxyalkylene polymer, a polyethylene oxide, a polypropylene oxide, a polytetramethylene oxide etc. are employ | adopted, for example. Among these, polyethylene oxide and polypropylene oxide are particularly preferable. Moreover, the composition ratio (molar ratio) is preferably propylene oxide: ethylene oxide = 100 to 10: 0 to 90, more preferably 99 to 20: 1 to 80, and particularly preferably 98 to 50: 2 to 50. When the composition ratio (molar ratio) of ethylene oxide exceeds propylene oxide: ethylene oxide = 10: 90, the viscosity becomes too high due to the high crystallinity of the polyethylene oxide chain, or the hydrophilicity of the polyethylene oxide chain. From the height, the water resistance of the cured product tends to decrease.

  Further, as the main chain of the curable silicone resin A, a polymer in which a linking group having a polar group such as a urethane bond in the molecule is introduced into the oxyalkylene polymer can also be used. The presence of polar groups such as urethane bonds in the molecule increases the interaction between the curable silicone resins A and further increases the torsional adhesive strength. The synthesis of a reactive silicon group-containing oxyalkylene polymer having a polar group such as a urethane bond in the molecule may be performed by a conventionally known method. For example, it can be easily synthesized by the method described in Japanese Patent No. 33177353, Japanese Patent No. 3030020 or Japanese Patent Application Laid-Open No. 2005-054174.

  As curable silicone resin A, what is marketed as a modified silicone resin can also be used. As commercial products, trade names of Kaneka Corporation; S203, S303, S810, SAT010, SAT030, SAT070, SAT200, SAT350, SAT400, S203, S810, S911, S943, EST200, EST250, ESX280, SAT070, SAX720, SAX725, and SAX725 SAX770 etc., Asahi Glass Co., Ltd. brand name; ES-S2410, ES-S2420, ES-S3430, ES-S3630, ES-G3440ST, ES-G2430ST, etc. can be used.

  The molecular weight of the curable silicone resin A is not particularly limited, but the number average molecular weight is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 20,000. If it is less than 1,000, the cured product tends to become brittle and twist and bond strength tends to be low. On the other hand, if it exceeds 100,000, the viscosity of the curable silicone resin A will be high, and the workability may be inferior.

  The curable silicone resin A has a hydrolyzable silicon group bonded to the end. The method of introducing a hydrolyzable silicon group at the terminal can be performed based on a well-known technique. In this invention, the silicon atom content rate derived from the hydrolyzable silicon group couple | bonded with the terminal is 0.35-2.00 mass%, Preferably it is 0.40-1.50 mass% More preferably, it is good that it is 0.45-1.00 mass%. The silicon atom content is the mass of silicon atoms derived from hydrolyzable silicon groups with respect to the total mass of the curable silicone resin A. Such a silicon atom content can be obtained by calculating the mass of silicon atoms with respect to the amount charged when the curable silicone resin A is produced. If the silicon atom content is less than 0.35% by mass, the torsional adhesive strength is lowered, which is not preferable. On the other hand, if the silicon atom content exceeds 2.00% by mass, the amount of shrinkage during curing increases, which is not preferable.

[Curable silicone resin B]
In the curable silicone resin B, the main chain is mainly composed of a vinyl polymer, hydrolyzable silicon groups are bonded to terminals and side chains, and the silicon atom content derived from the hydrolyzable silicon group is 2.20. 11.50% by mass.

  The hydrolyzable silicon group is the same as in the case of the curable silicone resin A, and is a group in which a hydrolyzable group is bonded to a silicon atom, and is represented by the general formula (2). The specific example of the hydrolyzable silicon group is the same as that of the curable silicone resin A. Furthermore, the preferable kind of hydrolyzable silicon group and the silicon atomic ratio of the trialkoxysilyl group are the same as those of the curable silicone resin A.

  The main chain of the curable silicone resin B is mainly composed of a vinyl polymer. Since the curable silicone resin B has a hydrolyzable silicon group bonded to the side chain, for example, a vinyl polymerizable unsaturated group-containing compound containing a hydrolyzable silicon group is polymerized when the main chain is obtained. May be. That is, the main chain of the curable silicone resin B is polymerized with a vinyl polymerizable unsaturated group-containing compound not containing a hydrolyzable silicon group and a vinyl polymerizable unsaturated group-containing compound containing a hydrolyzable silicon group. It may be obtained. Examples of vinyl polymerizable unsaturated group-containing compounds that do not contain hydrolyzable silicon groups include methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, isobornyl methacrylate, t-butyl methacrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, morpholine acrylate, butyl acrylate, lauryl acrylate, lauryl methacrylate, stearyl methacrylate, a styrene compound, an acrylonitrile compound, or the like can be used. Among these, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate or tetrahydrofurfuryl methacrylate having a homopolymer Tg of 60 ° C. or higher is preferable, methyl methacrylate or ethyl methacrylate is more preferable, and methyl methacrylate is particularly preferable. By using a vinyl polymerizable monomer having a Tg of homopolymer of 60 ° C. or higher, a curable resin composition having high twisting adhesive strength can be obtained. In particular, methyl methacrylate has good polymerization stability because of its high compatibility with other copolymerization components, and has a relatively high torsional adhesive strength because of its extremely high Tg of the homopolymer. Most useful in the invention.

  As the vinyl polymerizable unsaturated group-containing compound containing a hydrolyzable silicon group, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or the like can be used. Furthermore, hydrolyzable silicon groups obtained by the method described in the pamphlet of WO2002 / 102812, JP2003-238895, JP2003-268229, JP2004-035591, JP2006-052321, etc. A vinyl polymerizable unsaturated group-containing compound can also be used.

  In the curable silicone resin B, the mass ratio of the vinyl polymerizable unsaturated group-containing compound not containing a hydrolyzable silicon group and the vinyl polymerizable unsaturated group-containing compound containing a hydrolyzable silicon group is arbitrary. However, in general, the former is preferably blended in an amount of 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. If a vinyl polymerizable unsaturated group-containing compound that does not contain a hydrolyzable silicon group is not used, or if it is less than 10% by mass, the torsional adhesive strength tends to decrease.

  Further, the main chain of the curable silicone resin B includes a vinyl polymerizable unsaturated group-containing compound that does not contain a hydrolyzable silicon group and a vinyl polymerizable non-polymerizable group having a reactive group capable of introducing a hydrolyzable silicon group. It may be obtained by polymerizing a saturated group-containing compound. Examples of vinyl polymerizable unsaturated group-containing compounds having reactive groups capable of introducing hydrolyzable silicon groups include those having an epoxy group such as glycidyl acrylate, glycidyl methacrylate, hydroxybutyl acrylate glycidyl ether, or allyl glycidyl ether. Representative. And after superposition | polymerization, hydrolyzability, such as (gamma) -aminopropyltrimethoxysilane, (gamma) -aminopropylmethyldimethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, or 4-amino-3-dimethylbutylmethyldimethoxysilane An amino group or the like of a compound having a silicon group may be reacted with an epoxy group to obtain a main chain having a hydrolyzable silicon group in the side chain.

  The curable silicone resin B has a hydrolyzable silicon group bonded to its terminal. There are various methods for introducing a hydrolyzable silicon group at the terminal. Generally, when a main chain is obtained by polymerizing a vinyl polymerizable unsaturated group-containing compound, the hydrolyzable silicon group contains a hydrolyzable silicon group. This is carried out by reacting a chain transfer group-containing compound. Specific examples of the chain transfer group-containing compound having a reactive silicon group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Moreover, what was described in Unexamined-Japanese-Patent No. 2006-052168 or Unexamined-Japanese-Patent No. 2005-054174 can also be used.

  The curable silicone resin B has a silicon atom content derived from a hydrolyzable silicon group of 2.20 to 11.50% by mass, preferably 2.20 to 9.50% by mass. More preferably, the content is 2.20 to 7.50% by mass. Of the silicon atom content, the silicon atom content derived from the hydrolyzable silicon group bonded to the side chain of the curable silicone resin B is from the viewpoint of improving torsional adhesive strength. It is preferable that it is 80 mass% or more. For example, when the content of silicon atoms derived from the hydrolyzable silicon group as a whole of the curable silicone resin B is the lower limit of 2.20% by mass, silicon derived from the hydrolyzable silicon group bonded to the side chain The atomic content is preferably about 1.00% by mass, and when the upper limit is 11.50% by mass, it is preferably about 8.00% by mass. The meaning of the silicon atom content and the calculation method thereof are the same as in the case of the curable silicone resin A. If the silicon atom content derived from the hydrolyzable silicon group bonded to the side chain and the terminal of the curable silicone resin B is less than 2.20% by mass, the torsional adhesive strength is decreased. Absent. On the other hand, if the silicon atom content exceeds 11.50% by mass, the amount of shrinkage at the time of curing increases and the torsional adhesive strength also decreases, which is not preferable.

  The blending ratio (mass ratio) of the curable silicone resin A and the curable silicone resin B is A: B = 30-80: 70-20. Preferably it is A: B = 40-70: 60-30, More preferably, it is 50-60: 50-40. When the blending ratio of the curable silicone resin A is less than 30% by mass, the cured product becomes brittle and the torsional adhesive strength is lowered, which is not preferable. When the blending ratio of the curable silicone resin A exceeds 80% by mass, the blending amount of the curable silicone resin B is relatively decreased, and the twisting adhesive strength is lowered, which is not preferable. Moreover, when mix | blending curable silicone resin A and curable silicone resin B, the silicon atomic ratio derived from a trialkoxy silyl group is 10 to 10 among all the silicon atoms derived from a hydrolyzable silicon group in both resin. It is preferably 100% by mass, particularly preferably 30 to 100% by mass. When the silicon atomic ratio derived from the trialkoxysilyl group is 10% by mass or more, as described above, the cross-linked state becomes dense, and further improvement in torsional adhesive strength can be realized. A method of mixing and mixing the curable silicone resin A and the curable silicone resin B is arbitrary. For example, a method of mixing a separately manufactured curable silicone resin A and a separately manufactured curable silicone resin B, a method of manufacturing a curable silicone resin B in the curable silicone resin A, a curable silicone resin Examples thereof include a method for producing a curable silicone resin A in the resin B.

（式中、Ｘはビニル基、炭素数１〜１８のアルキル基及び炭素数１〜６のアルコキシ基よりなる群から選ばれる基を表し、Ｒは各々独立して炭素数１〜６のアルキル基を表す。） [Alkoxysilane monomer and alkoxysilane oligomer]
The curable resin composition according to the present invention may contain an alkoxysilane monomer and / or an alkoxysilane oligomer. Alkoxysilane is a compound represented by the following general formula (1).

(In the formula, X represents a group selected from the group consisting of a vinyl group, an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and each R independently represents an alkyl group having 1 to 6 carbon atoms. Represents.)

  Examples of the alkoxysilane monomer include vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, methyldiethoxymethoxysilane, vinylethoxydimethoxysilane, diethoxydimethoxysilane, and KBM- manufactured by Shin-Etsu Chemical Co., Ltd. 3063, KBE-3063 or KBM-3103, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, KBM-04 or KBE-04 manufactured by Shin-Etsu Chemical Co., Ltd., ethyl silicate 28 or N- Propyl silicate or the like is used.

  The alkoxysilane oligomer is a hydrolysis polymer obtained by polycondensation of an alkoxysilane monomer by hydrolysis. Examples of such alkoxysilane oligomer include KC-89S, KR-500, KR-510, X-41-1056 or X-41-1810 manufactured by Shin-Etsu Chemical Co., Ltd., DC3037 manufactured by Toray Dow Corning Co., Ltd. SR2402, MS3301 or MS3302 manufactured by Chisso Corporation, methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485 or SS-101 manufactured by Colcoat Co., Ltd. are used.

  By blending an alkoxysilane monomer or an alkoxysilane oligomer in the curable resin composition, curing is promoted, and a cured product with higher twisting adhesive strength can be obtained, which is preferable. The blending ratio of the alkoxysilane monomer and the like is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass with respect to a total of 100 parts by mass of the curable silicone resin A and the curable silicone resin B. 1.0 to 15 parts by mass is preferable.

[Aminosilane compound]
An aminosilane compound may also be blended in the curable resin composition according to the present invention. The aminosilane compound has one or more amino groups and one or more hydrolyzable silicon groups in the molecule. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBM603, KBM602 or KBM903, SZ6023 manufactured by Toray Dow Corning Silicone Co., etc. are used.

  By blending an aminosilane compound into the curable resin composition, curing is accelerated, and a cured product having higher twisting adhesive strength is obtained, which is preferable. The blending ratio of the aminosilane compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the curable silicone resin A and the curable silicone resin B. 1.0-15 mass parts is especially preferable.

[Curing catalyst]
The curable resin composition according to the present invention may further contain a curing catalyst for promoting the curing reaction of the curable silicone resin A and the curable silicone resin B. As the curing catalyst, a compound composed of boron trifluoride and / or a complex thereof, an organometallic compound such as an organic tin compound, or the like is used. As the compound composed of boron trifluoride and / or its complex, boron trifluoride amine complex, alcohol complex, ether complex, thiol complex, sulfide complex, carboxylic acid complex, water complex and the like are used. Among the boron trifluoride complexes, amine complexes having both stability and catalytic activity are particularly preferred. Examples of organic tin compounds include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, dibutyltin oxide, dibutyltin oxide and phthalic acid diester And U-303, U-700 or U-700ES manufactured by Nitto Kasei Co., Ltd. are used.

  The blending ratio of the curing catalyst is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 7.0 parts by mass with respect to 100 parts by mass in total of the curable silicone resin A and the curable silicone resin B. 0.05 to 5.0 parts by mass is preferable.

[Filler]
In the curable resin composition according to the present invention, it is preferable that a filler is further blended in order to obtain a tough cured product. As the filler, hydrophilic or hydrophobic silica powder, calcium carbonate powder, clay powder, acrylic organic powder, organic / inorganic balloon, or the like is used.

[Other ingredients]
In the curable resin composition according to the present invention, other conventionally known components may be blended in order to obtain desired physical properties. Other components include anti-aging agents such as hindered phenolic compounds, thixotropic agents such as amide wax, tackifiers such as phenolic resins, dehydrating agents such as calcium oxide, diluents, plasticizers, flame retardants , Hindered amine compounds, ultraviolet absorbers, pigments, titanate coupling agents, aluminum coupling agents or drying oils.

  The curable resin composition according to the present invention is generally used as an adhesive because the cured product is excellent in twisting adhesive strength. Further, in many cases, the curable resin composition according to the present invention has a hardness of 50 or more with a durometer A hardness meter after curing for 3 days under conditions of 50 ° C. and 95% relative humidity. Yes. Therefore, it can also be used as a coating material or paint. Furthermore, it can be used as a sealant or the like by adjusting fluidity, curing speed, and the like.

  The curable resin composition according to the present invention includes a curable silicone resin A having a lower silicon atom content than the curable silicone resin B and a cured resin having a higher silicon atom content than the curable silicone resin A. This is a combination of the functional silicone resin B. By such a combination, the cured product obtained by curing the curable resin composition has an effect of high twisting adhesive strength.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not necessarily limited to an Example. The present invention combines a curable silicone resin A having a relatively low silicon atom content with a curable silicone resin B having a relatively high silicon atom content, thereby providing high torsional adhesive strength. It should be construed as being based on the knowledge that a cured product can be obtained.

Synthesis example 1
[Production of Curable Silicone Resin A]
First, a silylating agent for introducing a hydrolyzable silicon group at the terminal was obtained by the following method. That is, while stirring N- (2-aminopropyl) -3-aminopropylmethyldimethoxysilane (206.4 g, 1.0 mol) at room temperature under a nitrogen atmosphere in a reaction vessel, methyl acrylate (172.2 g, 2.0 mol) was added dropwise over 1 hour and further reacted at 40 ° C. for 7 days to obtain a silylating agent having a methyldimethoxysilyl group and a secondary amino group in the molecule.

  Separately, in the reaction vessel, “Actocol P-21” (manufactured by Mitsui Chemicals Polyurethanes, polyoxypropylene polyol, number average molecular weights 2,000, 1,000 g), isophorone diisocyanate (221.4 g) and dioctyltin diversa Tate (50 mg) was charged and reacted at 80 ° C. for 3 hours with stirring and mixing under a nitrogen atmosphere to obtain a urethane resin having a main chain of an oxyalkylene polymer and an isocyanate group in the molecule. Then, the silylating agent (377.5 g) obtained above was added to the reaction vessel and reacted at 80 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere. As a result, a curable silicone resin A having a main chain mainly composed of an oxyalkylene polymer, a urethane bond and a substituted urea bond in the main chain, and a methyldimethoxysilyl group bonded to the terminal was obtained. This curable silicone resin A had a silicon atom content of 1.75% by mass derived from a methyldimethoxysilyl group. The viscosity of the curable silicone resin A at 23 ° C. was 32,000 mPa · s (BH viscometer, No. 7 rotor, 10 rotations), and the appearance was light yellow and transparent.

[Production of curable silicone resin B in curable silicone resin A]
In a reaction vessel, 200 g of the curable silicone resin A was put and heated to 80 ° C. in a nitrogen atmosphere. There, 75 g of methyl methacrylate, 50 g of lauryl methacrylate, 14 g of 3-acryloxypropyltrimethoxysilane, 14 g of 3-mercaptopropyltrimethoxysilane and 1.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) A monomer mixed solution in which was added dropwise over 30 minutes to carry out a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.34 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was dropped to conduct a polymerization reaction. Then, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.17 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after making it react at 80 degreeC for 30 minutes, 154 g of curable silicone resin B in curable silicone resin A was obtained by depressurizingly distilling methyl ethyl ketone. The resulting curable silicone resin B had a content of silicon atoms derived from trimethoxysilyl groups of 2.32% by mass. Furthermore, the silicon atom content rate derived from the trimethoxysilyl group bonded to the side chain of the curable silicone resin B was 1.02% by mass.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B154 g was obtained. This mixture had a viscosity at 23 ° C. of 200,000 mPa · s (BH viscometer, No. 7 rotor, 10 revolutions), and the appearance was light yellow and transparent.

Synthesis example 2
[Production of Curable Silicone Resin A]
Instead of N- (2-aminopropyl) -3-aminopropylmethyldimethoxysilane (206.4 g, 1.0 mol), N- (2-aminopropyl) -3-aminopropyltrimethoxysilane (222.4 g, A silylating agent was obtained in the same manner as in Synthesis Example 1 except that 1.0 mol) was used.

  “Actocol P-21” (manufactured by Mitsui Chemicals Polyurethanes, polyoxypropylene polyol, number average molecular weights 2,000, 1,000 g) is referred to as “Actocol P-28” (manufactured by Mitsui Chemicals Polyurethanes, polyoxypropylene polyols). The number average molecular weight was 4,000, 1,000 g), and the urethane resin was obtained in the same manner as in Synthesis Example 1 except that isophorone diisocyanate was changed from 221.4 g to 117.3 g. And using this urethane resin, the silylation agent (208.4g) obtained above was made to react like the synthesis example 1, and the curable silicone resin A was obtained. This curable silicone resin A had a silicon atom content derived from a trimethoxysilyl group of 1.12% by mass. When the viscosity was measured under the same conditions as in Synthesis Example 1, it was 32,000 mPa · s and the appearance was light yellow and transparent.

[Production of curable silicone resin B in curable silicone resin A]
Using said curable silicone resin A, it carried out similarly to the synthesis example 1, and obtained curable silicone resin B154g. Therefore, the silicon atom content of the curable silicone resin B is the same as in the case of Synthesis Example 1.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B154 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 180,000 mPa · s and the appearance was light yellow and transparent.

Synthesis example 3
[Production of Curable Silicone Resin A]
“Accor P-21” (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 2,000, 1,000 g) and “PMLS3011” (manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10) , 1,000 g), and a urethane resin was obtained in the same manner as in Synthesis Example 1 except that isophorone diisocyanate was changed from 221.4 g to 65.8 g. And using this urethane resin, the silylating agent (116.7g) obtained by the synthesis example 2 was made to react similarly to the synthesis example 1, and the curable silicone resin A was obtained. This curable silicone resin A had a content of silicon atoms derived from trimethoxysilyl groups of 0.70% by mass. In addition, when the viscosity was measured on the same conditions as the case of the synthesis example 1, it was 380,000 mPa * s and the external appearance was colorless and transparent.

[Production of curable silicone resin B in curable silicone resin A]
Using said curable silicone resin A, it carried out similarly to the synthesis example 1, and obtained curable silicone resin B154g. Therefore, the silicon atom content of the curable silicone resin B is the same as in the case of Synthesis Example 1.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B154 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 575,000 mPa · s, and the appearance was light yellow and transparent.

Synthesis example 4
[Production of Curable Silicone Resin A]
“Actocol P-21” (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., polyoxypropylene polyol, number average molecular weights 2,000, 1,000 g) was changed to “PMLS4012” (Asahi Glass Urethane Co., Ltd., polyoxypropylene polyols, number average molecular weight 10). , 950, 950 g) and “PR-3007” (produced by Asahi Denka Kogyo Co., Ltd., random copolymer polyol of propylene oxide and ethylene oxide, number average molecular weight 3,000, 50 g) and isophorone diisocyanate from 221.4 g A urethane resin was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 53.5 g. And using this urethane resin, the silylation agent (95.0g) obtained by the synthesis example 2 was made to react similarly to the synthesis example 1, and the curable silicone resin A was obtained. This curable silicone resin A had a content of silicon atoms derived from trimethoxysilyl groups of 0.59% by mass. In addition, when the viscosity was measured on the same conditions as the case of the synthesis example 1, it was 96,000 mPa * s and the external appearance was cloudy.

[Production of curable silicone resin B in curable silicone resin A]
Using said curable silicone resin A, it carried out similarly to the synthesis example 1, and obtained curable silicone resin B154g. Therefore, the silicon atom content of the curable silicone resin B is the same as in the case of Synthesis Example 1.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B154 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 150,000 mPa · s, and the appearance was pale yellow translucent.

Synthesis example 5
[Production of Curable Silicone Resin A]
A urethane resin was obtained by the same method as in Synthesis Example 4. Then, using this urethane resin, the silylating agent (91.1 g) obtained in Synthesis Example 1 was reacted in the same manner as in Synthesis Example 1 to obtain a curable silicone resin A. This curable silicone resin A had a silicon atom content of 0.59% by mass derived from a methyldimethoxysilyl group. In addition, when the viscosity was measured on the same conditions as the case of the synthesis example 1, it was 95,000 mPa * s and the external appearance was cloudy.

[Production of curable silicone resin B in curable silicone resin A]
In addition to the above curable silicone resin A, 3-acryloxypropylmethyldimethoxysilane and 3-mercaptopropylmethyldimethoxysilane are used instead of 3-acryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. Obtained 154 g of curable silicone resin B in the same manner as in Synthesis Example 1. The resulting curable silicone resin B had a content of silicon atoms derived from methyldimethoxysilyl groups of 2.50% by mass. Furthermore, the silicon atom content rate derived from the methyldimethoxysilyl group couple | bonded with the side chain of the curable silicone resin B was 1.09 mass%.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B154 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 160,000 mPa · s, and the appearance was pale yellow translucent.

Synthesis Example 6
[Preparation of Curable Silicone Resin A]
A commercially available modified silicone resin “Excestar G3440ST” (manufactured by Asahi Glass Co., Ltd.) was prepared as a curable silicone resin A. The silicon atom content derived from the trimethoxysilyl group of the curable silicone resin A was 0.45% by mass. In addition, when the viscosity was measured on the same conditions as the case of the synthesis example 1, it was 12,000 mPa * s and the external appearance was light yellow translucent.

[Production of curable silicone resin B in curable silicone resin A]
Using said curable silicone resin A, it carried out similarly to the synthesis example 1, and obtained curable silicone resin B154g. Therefore, the silicon atom content of the curable silicone resin B is the same as in the case of Synthesis Example 1.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B154 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 29,000 mPa · s and the appearance was light yellow and transparent.

Synthesis example 7
[Preparation of Curable Silicone Resin A]
The curable silicone resin A obtained in Synthesis Example 4 was prepared.

[Production of curable silicone resin B in curable silicone resin A]
Using the above curable silicone resin A, the charging amount of 3-acryloxypropyltrimethoxysilane was changed from 14 g to 4.0 g, the charging amount of 3-mercaptopropyltrimethoxysilane was changed from 14 g to 8.0 g, and lauryl was further added. 6.0 g of mercaptan was added, and the charge of the first 2,2′-azobis (2,4-dimethylvaleronitrile) was changed from 1.02 g to 0.95 g, and the second 2,2′-azobis. The amount of (2,4-dimethylvaleronitrile) charged was changed from 0.34 g to 0.32 g, and the amount of the second 2,2′-azobis (2,4-dimethylvaleronitrile) charged was decreased from 0.17 g to 0. A curable silicone resin B144g was obtained in the same manner as in Synthesis Example 1 except that it was changed to .16 g. The resulting curable silicone resin B had a content of silicon atoms derived from trimethoxysilyl groups of 1.11% by mass. Furthermore, the silicon atom content rate derived from the trimethoxysilyl group couple | bonded with the side chain of the curable silicone resin B was 0.31 mass%.

  As described above, a mixture of curable silicone resin A 200 g and curable silicone resin B 144 g was obtained. With respect to this mixture, the viscosity was measured under the same conditions as in Synthesis Example 1. As a result, it was 120,000 mPa · s and the appearance was pale yellow translucent.

Example 1
10 parts by mass of 3-aminopropyltrimethoxysilane (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound is added to 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 1. And 0.5 parts by mass of dibutyltin dimethoxide as a curing catalyst were blended to obtain a curable resin composition.

Example 2
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 1, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 2 is used. Otherwise, a curable resin composition was obtained in the same manner as in Example 1.

Example 3
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 1, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 3 is used. A curable resin composition was prepared in the same manner as in Example 1 except that 0.1 parts by mass of monoethylamine complex of boron trifluoride was added instead of 0.5 parts by mass of dibutyltin ditomethoxide as a curing catalyst. Obtained.

Example 4
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 1, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 4 is used. A curable resin composition was prepared in the same manner as in Example 1 except that 0.1 parts by mass of monoethylamine complex of boron trifluoride was added instead of 0.5 parts by mass of dibutyltin ditomethoxide as a curing catalyst. Obtained.

Example 5
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 1, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 5 is used. A curable resin composition was obtained in the same manner as in Example 1 except that 0.1 part by mass of boron trifluoride monoethylamine complex was further added as a curing catalyst.

Example 6
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 1, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 6 is used. Otherwise, a curable resin composition was obtained in the same manner as in Example 1.

Comparative Example 1
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 1, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 7 is used. A curable resin composition was prepared in the same manner as in Example 1 except that 0.1 parts by mass of monoethylamine complex of boron trifluoride was added instead of 0.5 parts by mass of dibutyltin ditomethoxide as a curing catalyst. Obtained.

Comparative Example 2
To 100 parts by mass of the curable silicone resin A obtained in Synthesis Example 4, 10 parts by mass of 3-aminopropyltrimethoxysilane (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound, and boron trifluoride as a curing catalyst 0.1 mass part of monoethylamine complex was mix | blended and the curable resin composition was obtained.

Comparative Example 3
A commercially available modified silicone resin “SAT200” (manufactured by Kaneka Corporation), 10 parts by mass of 3-aminopropyltrimethoxysilane (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound, and 0.5 mass of dibutyltin dimethoxide as a curing catalyst The curable resin composition was obtained. The commercially available modified silicone resin “SAT200” corresponds to the curable silicone resin A, and the silicon atom content derived from the methyldimethoxysilyl group was 0.30 mass%. Further, this modified silicone resin was measured for viscosity under the same conditions as in Synthesis Example 1, and as a result, it was 30,000 mPa · s, and the appearance was pale yellow translucent.

[Torsion bond strength test]
Two asada materials having a width of 25 mm, a length of 100 mm, and a thickness of 5 mm were prepared. And as shown in FIG. 2, it orthogonally crossed and the superposition | polymerization location was adhere | attached using the curable resin composition obtained in Examples 1-6 and Comparative Examples 1-3. The application amount of the adhesive was 160 g / m ² , the adhesive was adhered under the condition of 23 ° C. and 50% relative humidity, and cured and cured for 1 day under the same condition. Thereafter, under the same conditions, a load was applied in the direction of the arrow in FIG. 2, and the maximum load was measured. This value was used as the twisting adhesive strength (kN), and the results are shown in Table 1.

[Hardness test]
The curable resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were poured into a tray and cured and cured at 50 ° C. and 95% relative humidity for 3 days to obtain a film having a thickness of about 6 mm. . Then, the durometer A hardness tester was applied to the surface of the coating under the condition of 23 ° C. and relative humidity of 50%, and the hardness was measured. The results are shown in Table 1.

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━
Torsional bond strength Hardness ━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 0.35 55
Example 2 0.38 65
Example 3 0.37 71
Example 4 0.30 57
Example 5 0.35 52
Example 6 0.33 53
Comparative Example 1 0.18 35
Comparative Example 2 0.12 58
Comparative Example 3 0.09 36
━━━━━━━━━━━━━━━━━━━━━━━━━━

  As is clear from the comparison between Examples 1 to 6 and Comparative Example 1, the curable silicone resin B has a hydrolyzable silicon group as compared with a high content of silicon atoms derived from the hydrolyzable silicon group. It can be seen that the torsional bond strength is halved when a silicon atom having a low content is derived. Further, as is clear from the comparison between Examples 1 to 6 and Comparative Examples 2 and 3, it can be seen that when the curable silicone resin B is not used, the torsional adhesive strength is further reduced.

Synthesis example 8
[Preparation of Curable Silicone Resin A]
The curable silicone resin A obtained in Synthesis Example 4 was prepared.

[Production of curable silicone resin B in curable silicone resin A]
In a reaction vessel, 200 g of the curable silicone resin A was put and heated to 80 ° C. in a nitrogen atmosphere. There, 50 g of methyl methacrylate, 20 g of lauryl methacrylate, 20 g of 3-acryloxypropylmethyldimethoxysilane, 9.0 g of 3-mercaptopropylmethyldimethoxysilane and 2,2′-azobis (2,4-dimethylvaleronitrile) 0 A monomer mixture mixed with .66 g was added dropwise over 30 minutes to conduct a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.22 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was dropped to conduct a polymerization reaction. Next, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.11 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after making it react at 80 degreeC for 30 minutes, 100 g of curable silicone resin B was obtained in the curable silicone resin A by depressurizingly distilling methyl ethyl ketone. The resulting curable silicone resin B had a content of silicon atoms derived from methyldimethoxysilyl groups of 3.81% by mass. Furthermore, the silicon atom content rate derived from the methyldimethoxysilyl group couple | bonded with the side chain of the curable silicone resin B was 2.41 mass%.

  As described above, a mixture of curable silicone resin A 200 g and curable silicone resin B 100 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 83,200 mPa · s, and the appearance was pale yellow and translucent.

Synthesis Example 9
[Preparation of Curable Silicone Resin A]
The curable silicone resin A obtained in Synthesis Example 4 was prepared.

[Production of curable silicone resin B in curable silicone resin A]
Preparation amount of methyl methacrylate from 50 g to 70 g, Preparation amount of lauryl methacrylate from 20 g to 50 g, Preparation amount of 3-acryloxypropylmethyldimethoxysilane from 20 g to 100 g, Preparation of 3-mercaptopropylmethyldimethoxysilane The amount was changed from 9.0 g to 30 g, the first charge of 2,2′-azobis (2,4-dimethylvaleronitrile) was changed from 0.66 g to 1.67 g, and the second charge of 2,2′- The amount of azobis (2,4-dimethylvaleronitrile) charged from 0.22 g to 0.56 g, and the amount of the second 2,2′-azobis (2,4-dimethylvaleronitrile) charged from 0.11 g. A curable silicone resin B252g was obtained in the curable silicone resin A in the same manner as in Synthesis Example 8 except that the amount was changed to 0.28 g. The resulting curable silicone resin B had a content of silicon atoms derived from methyldimethoxysilyl groups of 6.63% by mass. Furthermore, the silicon atom content rate derived from the methyldimethoxysilyl group couple | bonded with the side chain of the curable silicone resin B was 4.78 mass%.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B252 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 32,000 mPa · s, and the appearance was pale yellow and translucent.

Synthesis Example 10
[Preparation of Curable Silicone Resin A]
The curable silicone resin A obtained in Synthesis Example 4 was prepared.

[Production of curable silicone resin B in curable silicone resin A]
The amount of methyl methacrylate charged from 50 g to 10 g, the amount of 3-acryloxypropylmethyldimethoxysilane charged from 20 g to 120 g, and the amount of 3-mercaptopropylmethyldimethoxysilane charged from 9.0 g to 40 g, Of 2,2'-azobis (2,4-dimethylvaleronitrile) from 0.66 g to 1.27 g, the second charge of 2,2'-azobis (2,4-dimethylvaleronitrile) Synthetic Example 8 except that the amount was changed from 0.22 g to 0.42 g, and the third charge of 2,2′-azobis (2,4-dimethylvaleronitrile) was changed from 0.11 g to 0.21 g. In the same manner as above, 192 g of curable silicone resin B was obtained in curable silicone resin A. The resulting curable silicone resin B had a content of silicon atoms derived from methyldimethoxysilyl groups of 10.79% by mass. Furthermore, the silicon atom content rate derived from the methyldimethoxysilyl group couple | bonded with the side chain of the curable silicone resin B was 7.55 mass%.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B192 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 7,800 mPa · s and the appearance was pale yellow translucent.

Synthesis Example 11
[Production of Curable Silicone Resin A]
In a reaction vessel, “PMLS4012” (manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000, 1000 g), isophorone diisocyanate (47.5 g) and dioctyltin diversate (50 mg) were charged, and a nitrogen atmosphere Under stirring and mixing, the reaction was carried out at 80 ° C. for 3 hours to obtain a urethane resin having a main chain of an oxyalkylene polymer and an isocyanate group in the molecule. Then, the silylating agent (42.2 g) obtained in Synthesis Example 2 was added to the reaction vessel and reacted at 80 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere. Since only 0.5 molar equivalent of the terminal isocyanate group was silylated with this silylating agent, excess methanol was added to urethanize the terminal. As a result, a curable silicone resin A having a main chain mainly composed of an oxyalkylene polymer, a urethane bond and a substituted urea bond in the main chain, and a trimethoxysilyl group bonded to the terminal was obtained. This curable silicone resin A had a content of silicon atoms derived from trimethoxysilyl groups of 0.27% by mass. The viscosity of the curable silicone resin A at 23 ° C. was 96,000 mPa · s (BH viscometer, No. 7 rotor, 10 rotations), and the appearance was transparent.

[Production of curable silicone resin B in curable silicone resin A]
Preparation amount of methyl methacrylate from 50 g to 75 g, Preparation amount of lauryl methacrylate from 20 g to 50 g, Preparation amount of 3-acryloxypropylmethyldimethoxysilane from 20 g to 10 g, Preparation of 3-mercaptopropylmethyldimethoxysilane From 9.0 g to 14 g, the first charge of 2,2′-azobis (2,4-dimethylvaleronitrile) was changed from 0.66 g to 0.99 g, and the second charge of 2,2′- The amount of azobis (2,4-dimethylvaleronitrile) charged from 0.22 g to 0.33 g, and the amount of the second charged 2,2′-azobis (2,4-dimethylvaleronitrile) from 0.11 g A curable silicone resin B150 g was obtained in the curable silicone resin A in the same manner as in Synthesis Example 8 except that the amount was changed to 0.17 g. The resulting curable silicone resin B had a content of silicon atoms derived from methyldimethoxysilyl groups of 2.25% by mass. Furthermore, the silicon atom content rate derived from the methyldimethoxysilyl group couple | bonded with the side chain of the curable silicone resin B was 0.80 mass%.

  As described above, a mixture of 200 g of curable silicone resin A and 150 g of curable silicone resin B was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 150,000 mPa · s and the appearance was light yellow and transparent.

Synthesis Example 12
[Preparation of Curable Silicone Resin A]
A commercially available modified silicone resin “SAT200” (manufactured by Kaneka Corporation) was prepared as the curable silicone resin A. As described in Comparative Example 3 above, SAT200 "has a silicon atom content of 0.30 mass% derived from a methyldimethoxysilyl group.

[Production of curable silicone resin B in curable silicone resin A]
In a reaction vessel, 200 g of the curable silicone resin A was put and heated to 80 ° C. in a nitrogen atmosphere. There, 87.6 g of methyl methacrylate, 7.8 g of butyl acrylate, 17.5 g of stearyl methacrylate, 7.2 g of 3-acryloxypropylmethyldimethoxysilane, 9.3 g of 3-mercaptopropylmethyldimethoxysilane and 2,2 A monomer mixed solution in which 2.59 g of '-azobis (2,4-dimethylvaleronitrile) was mixed was dropped over 30 minutes to carry out a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.86 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Subsequently, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.43 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after making it react at 80 degreeC for 30 minutes, 133 g of curable silicone resin B was obtained in the curable silicone resin A by depressurizingly distilling methyl ethyl ketone. The resulting curable silicone resin B had a content of silicon atoms derived from methyldimethoxysilyl groups of 1.74% by mass. Furthermore, the silicon atom content rate derived from the methyldimethoxysilyl group couple | bonded with the side chain of the curable silicone resin B was 0.65 mass%.

  As described above, a mixture of curable silicone resin A 200 g and curable silicone resin B 133 g was obtained. When the viscosity of this mixture was measured under the same conditions as in Synthesis Example 1, it was 128,000 mPa · s and the appearance was yellow and transparent.

Synthesis Example 13
[Preparation of Curable Silicone Resin A]
The curable silicone resin A obtained in Synthesis Example 4 was prepared.

[Production of curable silicone resin B in curable silicone resin A]
In a reaction vessel, 200 g of the curable silicone resin A was put and heated to 80 ° C. in a nitrogen atmosphere. A monomer mixed solution in which 12.0 g of 3-acryloxypropylmethyldimethoxysilane, 4.0 g of 3-mercaptopropylmethyldimethoxysilane and 0.32 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed therewith. Was dropped over 30 minutes to carry out a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.11 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was dropped to conduct a polymerization reaction. Next, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.05 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after making it react at 80 degreeC for 30 minutes, curable silicone resin B16g was obtained in curable silicone resin A by distilling off methyl ethyl ketone under reduced pressure. The resulting curable silicone resin B had a content of silicon atoms derived from methyldimethoxysilyl groups of 12.60% by mass. Furthermore, the silicon atom content rate derived from the methyldimethoxysilyl group couple | bonded with the side chain of the curable silicone resin B was 8.82 mass%.

  As described above, a mixture of curable silicone resin A200 g and curable silicone resin B16 g was obtained. With respect to this mixture, the viscosity was measured under the same conditions as in Synthesis Example 1. As a result, it was 42,800 mPa · s, and the appearance was pale yellow translucent.

Example 7
10 parts by mass of 3-aminopropyltrimethoxysilane (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound was added to 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 8. Part and 0.3 part by weight of dibutyltin dimethoxide as a curing catalyst and 0.1 part by weight of monoethylamine complex of boron trifluoride were blended to obtain a curable resin composition.

Example 8
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 8, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 9 is used. A curable resin composition was obtained in the same manner as in Example 7.

Example 9
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 8, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 10 is used. A curable resin composition was obtained in the same manner as in Example 7.

Comparative Example 4
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 8, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 11 is used. A curable resin composition was obtained in the same manner as in Example 7.

Comparative Example 5
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 8, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 12 is used. A curable resin composition was obtained in the same manner as in Example 7.

Comparative Example 6
Instead of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 8, the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 13 is used. A curable resin composition was obtained in the same manner as in Example 7.

  The curable resin compositions obtained in Examples 7 to 9 and Comparative Examples 4 to 6 were subjected to a torsional adhesive strength test and a hardness test by the method employed in Example 1. The results are shown in Table 2.

[Table 2]
━━━━━━━━━━━━━━━━━━━━━━━━━━
Torsional bond strength Hardness ━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 7 0.49 95
Example 8 0.39 80
Example 9 0.49 95
Comparative Example 4 0.05 20
Comparative Example 5 0.09 25
Comparative Example 6 0.13 60
━━━━━━━━━━━━━━━━━━━━━━━━━━

  As is clear from the comparison between Examples 7 to 9 and Comparative Example 4, the curable silicone resin A is derived from a hydrolyzable silicon group as compared with those having a high silicon atom content derived from a hydrolyzable silicon group. It can be seen that the twisted bond strength is extremely reduced when the silicon atom content of is low. In addition, as is clear from the comparison between Examples 7 to 9 and Comparative Example 5, the curable silicone resin B is more hydrolyzable than the one having a high silicon atom content from the hydrolyzable silicon group. It can be seen that when a silicon group-derived silicon atom content is low, the torsional bond strength is extremely reduced. Further, as is clear from the comparison between Examples 7 to 9 and Comparative Example 6, when the curable silicone resin B having a too high silicon atom content derived from a hydrolyzable silicon group was used, It can be seen that the crease bond strength is reduced.

Synthesis Example 14
[Preparation of Curable Silicone Resin A]
The curable silicone resin A obtained in Synthesis Example 4 was prepared.

[Production of curable silicone resin B in curable silicone resin A]
In a reaction vessel, 200 g of the curable silicone resin A was put and heated to 80 ° C. in a nitrogen atmosphere. There, 75 g of methyl methacrylate, 50 g of lauryl methacrylate, 8.0 g of glycidyl methacrylate, 14 g of 3-acryloxypropyltrimethoxysilane, 14 g of 3-mercaptopropyltrimethoxysilane and 2,2′-azobis (2,4- A monomer mixed solution in which 1.07 g of dimethylvaleronitrile) was added dropwise over 30 minutes to conduct a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.36 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Next, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.18 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after making it react at 80 degreeC for 30 minutes, 162 g of precursors of curable silicone resin B in curable silicone resin A were obtained by depressurizingly distilling methyl ethyl ketone. When a viscosity of a mixture of 200 g of the curable silicone resin A and 162 g of the curable silicone resin B precursor was measured under the same conditions as in Synthesis Example 1, it was 160,000 mPa · s, and the appearance was a pale yellow half It was transparent.

  From a mixture of 200 g of curable silicone resin A and 162 g of curable silicone resin B precursor, 100 g is put into another reaction vessel, and 2.7 g of 3-aminopropyltrimethoxysilane (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) Was added and the temperature was raised to 50 ° C. in a nitrogen atmosphere. Furthermore, it stirred at 50 degreeC for 1 hour, the epoxy group contained in the precursor of curable silicone resin B, and the amino group of 3-aminopropyl trimethoxysilane were made to react, and 48 g of curable silicone resin B was obtained. The resulting curable silicone resin B had a content of silicon atoms derived from trimethoxysilyl groups of 2.99% by mass. Furthermore, the silicon atom content rate derived from the trimethoxysilyl group bonded to the side chain of the curable silicone resin B was 1.83% by mass.

  As described above, a mixture of curable silicone resin A55g and curable silicone resin B48g was obtained. The appearance of this mixture was pale yellow translucent.

Synthesis Example 15
[Preparation of Curable Silicone Resin A]
The curable silicone resin A obtained in Synthesis Example 3 was prepared.

[Production of curable silicone resin B in curable silicone resin A]
The precursor of the curable silicone resin B is obtained by the same method as in Synthesis Example 14 except that the curable silicone resin A is used. After that, the curable silicone resin B is obtained by the same method as in Synthesis Example 14. Got. The mixture of curable silicone resin A200 g and curable silicone resin B precursor 162 g was measured for viscosity under the same conditions as in Synthesis Example 1 except that the number of rotations of the rotor was changed to 4 rotations. It was 666,000 mPa · s, and the appearance was pale yellow translucent. The appearance of the mixture of curable silicone resin A55g and curable silicone resin B48g was light yellow and transparent.

Synthesis Example 16
[Preparation of Curable Silicone Resin A]
A commercially available modified silicone resin “Excestar G3440ST” (manufactured by Asahi Glass Co., Ltd.) was prepared as a curable silicone resin A.

[Production of curable silicone resin B in curable silicone resin A]
The precursor of the curable silicone resin B is obtained by the same method as in Synthesis Example 14 except that the curable silicone resin A is used. After that, the curable silicone resin B is obtained by the same method as in Synthesis Example 14. Got. A mixture of 200 g of curable silicone resin A and 162 g of curable silicone resin B precursor was measured for viscosity under the same conditions as in Synthesis Example 1, and found to be 37,000 mPa · s. It was transparent. The appearance of the mixture of curable silicone resin A55g and curable silicone resin B48g was light yellow and transparent.

Example 10
To 100 parts by mass of a mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 14, 3-aminopropyltrimethoxysilane (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) 7.3 as an aminosilane compound Part by mass and 0.1 part by mass of boron trifluoride monoethylamine complex as a curing catalyst were blended to obtain a curable resin composition.

Example 11
Instead of 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 14, the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 15 A curable resin composition was obtained in the same manner as in Example 10 except that 100 parts by mass of the mixture was used.

Example 12
Instead of 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 14, the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 16 Curing was carried out in the same manner as in Example 10 except that 100 parts by mass of the mixture was used, and 0.5 parts by mass of dibutyltin dimethoxide was blended instead of 0.1 parts by mass of boron trifluoride monoethylamine complex as a curing catalyst. A functional resin composition was obtained.

Comparative Example 7
Instead of 100 parts by mass of the mixture of curable silicone resin A and curable silicone resin B obtained in Synthesis Example 14, 100 parts by mass of curable silicone resin A obtained in Synthesis Example 3 was used, and an aminosilane compound was used. A curable resin composition was obtained in the same manner as in Example 10 except that the amount of 3-aminopropyltrimethoxysilane ("KBM903" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 10.0 parts by mass.

  The curable resin compositions obtained in Examples 10 to 12 and Comparative Example 7 were subjected to a torsional adhesive strength test and a hardness test by the method employed in Example 1. The results are shown in Table 3.

[Table 3]
━━━━━━━━━━━━━━━━━━━━━━━━━━
Torsional bond strength Hardness ━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 10 0.45 80
Example 11 0.39 87
Example 12 0.51 75
Comparative Example 7 0.05 69
━━━━━━━━━━━━━━━━━━━━━━━━━━

  As is clear from the comparison between Examples 10 to 12 and Comparative Example 7, when the curable silicone resin B is not used as compared with the case where the curable silicone resin A and the curable silicone resin B are used in combination. It can be seen that the torsional bond strength is extremely reduced.

Example 13
100 parts by mass of a mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 15, 10 parts by mass of n-propyl silicate as an alkoxysilane monomer, and 3-aminopropyltrimethoxysilane as an aminosilane compound 10 parts by mass (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.1 parts by mass of boron trifluoride monoethylamine complex as a curing catalyst were blended to obtain a curable resin composition.

Example 14
Instead of 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 15, the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 3 were used. A curable resin composition was obtained in the same manner as in Example 13 except that 100 parts by mass of the mixture was used.

Example 15
Instead of 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 15, the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 14 were used. A curable resin composition was obtained in the same manner as in Example 13 except that 100 parts by mass of the mixture was used.

Example 16
100 parts by mass of a mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 4, 10 parts by mass of n-propyl silicate as an alkoxysilane monomer, and 3-aminopropyltrimethoxysilane as an aminosilane compound 10 parts by mass (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.1 parts by mass of boron trifluoride monoethylamine complex as a curing catalyst were blended to obtain a curable resin composition.

Example 17
10 parts by mass of a silicone alkoxy oligomer (“KC-89S” manufactured by Shin-Etsu Chemical Co., Ltd.) as an alkoxysilane oligomer is added to 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 4. And 10 parts by mass of 3-aminopropyltrimethoxysilane (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound and 0.5 parts by mass of dibutyltin dimethoxide as a curing catalyst are obtained to obtain a curable resin composition. It was.

Example 18
A curable resin composition was obtained in the same manner as in Example 16 except that hexyltriethoxysilane was used in place of n-propyl silicate as the alkoxysilane monomer.

Example 19
A curable resin composition was obtained in the same manner as in Example 16 except that vinyltriethoxysilane was used instead of n-propyl silicate as the alkoxysilane monomer.

Example 20
The curable resin composition of Example 16 was further mixed with 40 parts by mass of specially baked clay (manufactured by Burgess Pigment, “Optiwhite”) as a filler to obtain a curable resin composition.

Example 21
Instead of 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 15, the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 6 were used. A curable resin composition was obtained in the same manner as in Example 13 except that 100 parts by mass of the mixture was used.

Comparative Example 8
Instead of 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 4, the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 7 A curable resin composition was obtained in the same manner as in Example 17 except that 100 parts by mass of the mixture was used.

Comparative Example 9
Instead of 100 parts by mass of the mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 15, 100 parts by mass of a commercially available modified silicone resin “SAT200” (manufactured by Kaneka Corporation) was used. In the same manner as in Example 13, a curable resin composition was obtained. The modified silicone resin “SAT200” corresponds to the curable silicone resin A as described in the comparative example 3.

  The curable resin compositions obtained in Examples 13 to 20 and Comparative Examples 8 to 9 were subjected to a torsional adhesive strength test and a hardness test by the method employed in Example 1. The results are shown in Table 4.

[Table 4]
━━━━━━━━━━━━━━━━━━━━━━━━━━
Torsional bond strength Hardness ━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 13 0.49 90
Example 14 0.61 80
Example 15 0.68 90
Example 16 0.52 81
Example 17 0.51 82
Example 18 0.52 81
Example 19 0.53 91
Example 20 0.43 92
Example 21 0.38 73
Comparative Example 8 0.19 41
Comparative Example 9 0.10 28
━━━━━━━━━━━━━━━━━━━━━━━━━━

  As is clear from the comparison between Examples 13 to 21 and Comparative Example 8, the curable silicone resin B has a hydrolyzable silicon group as compared with one having a high silicon atom content from the hydrolyzable silicon group. It can be seen that the twisted bond strength is reduced by half or less when a silicon atom having a low content of silicon is used. Further, as is clear from the comparison between Examples 13 to 21 and Comparative Example 9, the curable silicone resin B is not used as compared with the case where the curable silicone resin A and the curable silicone resin B are used in combination. In this case, it can be seen that the torsional bond strength is extremely reduced.

Example 22
To 100 parts by mass of a mixture of the curable silicone resin A and the curable silicone resin B obtained in Synthesis Example 4, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound was added. 10 parts by mass of “KBM603” manufactured by the company and 0.1 part by mass of monoethylamine complex of boron trifluoride as a curing catalyst were blended to obtain a curable resin composition.

Example 23
Instead of 10 parts by mass of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (“KBM603” manufactured by Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound, 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. “ KBM903 ") A curable resin composition was obtained in the same manner as in Example 22 except that 20 parts by mass was blended.

Example 24
Instead of 10 parts by mass of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (“KBM603” manufactured by Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound, 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. “ KBM903 ") A curable resin composition was obtained in the same manner as in Example 22 except that 5 parts by mass was blended.

Example 25
A curable resin composition was obtained in the same manner as in Example 22 except that the aminosilane compound was not used. However, the monoethylamine complex of boron trifluoride which is a curing catalyst was used by dissolving in 2 parts by mass of tetrahydrofuran.

Example 26
Instead of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (“KBM603” manufactured by Shin-Etsu Chemical Co., Ltd.) as an aminosilane compound, 3-aminopropyltrimethoxysilane (“KBM903” manufactured by Shin-Etsu Chemical Co., Ltd.)) A curable resin composition was prepared in the same manner as in Example 22 except that 0.5 parts by mass of dibutyltin dimethoxide was blended instead of 0.1 parts by mass of boron trifluoride monoethylamine complex as a curing catalyst. Got.

  The curable resin compositions obtained in Examples 22 to 26 were subjected to a torsional adhesive strength test and a hardness test by the method employed in Example 1. The results are shown in Table 5.

[Table 5]
━━━━━━━━━━━━━━━━━━━━━━━━━━
Torsional bond strength Hardness ━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 22 0.35 62
Example 23 0.54 80
Example 24 0.32 60
Example 25 0.33 58
Example 26 0.56 77
━━━━━━━━━━━━━━━━━━━━━━━━━━

  From the results of Examples 22 to 26, the curable resin composition using both the curable silicone resin A and the curable silicone resin B having a silicon atom content derived from a predetermined hydrolyzable silicon group is high. It can be seen that it has torsional bond strength.

It is typical sectional drawing for demonstrating the meaning of peeling adhesive strength. It is a schematic plan view for demonstrating the meaning of torsional adhesive strength.

Claims (8)

A curable silicone having a main chain mainly composed of an oxyalkylene polymer and having a hydrolyzable silicon group bonded to the terminal and a silicon atom content derived from the hydrolyzable silicon group of 0.35 to 2.00% by mass. Resin A,
Curing in which the main chain is mainly composed of a vinyl polymer and hydrolyzable silicon groups are bonded to the terminal and side chains, and the silicon atom content derived from the hydrolyzable silicon groups is 2.20 to 11.50% by mass. With a functional silicone resin B
A curable resin composition comprising: a curable silicone resin A: a curable silicone resin B = 30 to 80:70 to 20 (mass ratio). The curable silicone-based resin B has a homopolymer Tg of 60 ° C. or more and a vinyl polymerizable unsaturated group-containing compound that does not contain a hydrolyzable silicon group, and a vinyl polymerizable unsaturated group that contains a hydrolyzable silicon group. compound, a curable resin composition according to claim 1, wherein the chain transfer group-containing compound containing a hydrolyzable silicon group is made copolymerized.   At least a part of the hydrolyzable silicon group contained in the curable silicone resin A and / or the curable silicone resin B is a trialkoxysilyl group, and the trioxysilane group has a trialkoxysilyl group. The curable resin composition according to claim 1 or 2, wherein the silicon atomic ratio derived from the alkoxysilyl group is 10% by mass. An alkoxysilane monomer represented by the following general formula (1) and / or an alkoxy which is a hydrolysis polymer of the alkoxysilane monomer with respect to a total of 100 parts by mass of the curable silicone resin A and the curable silicone resin B The curable resin composition according to any one of claims 1 to 3, wherein 0.1 to 30 parts by mass of a silane oligomer is blended.

(In the formula, X represents a group selected from the group consisting of a vinyl group, an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and each R independently represents an alkyl group having 1 to 6 carbon atoms. Represents.)   With respect to a total of 100 parts by mass of the curable silicone resin A and the curable silicone resin B, 1.0 to 1.0 aminosilane compounds having one or more amino groups and one or more hydrolyzable silicon groups in the molecule. 30 parts by mass and 0.001 to 5.0 parts by mass of a curing catalyst for curing the curable silicone resin A and the curable silicone resin B are blended. The curable resin composition according to Item.   Furthermore, the curable resin composition as described in any one of Claims 1 thru | or 5 with which a filler is mix | blended.   The curable resin composition according to any one of claims 1 to 6, wherein the hardness of the cured product after curing for 3 days under a condition of 50 ° C and a relative humidity of 95% is 50 or more according to a durometer A hardness meter. .   A room temperature curable adhesive composition mainly comprising the curable resin composition according to any one of claims 1 to 7.

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