JP2013237837A - Silicone resin modifier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone resin having sufficient mechanical strength and excellent chemical resistance.SOLUTION: A silicone resin (D) is obtained by reacting an alkenyl ether compound (A) represented by general formula (1) with a silicon hydride compound (B). A silicone resin cured product is obtained by curing the resin (D). Preferably the alkenyl ether compound (A) represented by general formula (1) contains two or more 2-8C alkenyl groups in the molecule.

Description

  The present invention relates to a silicone resin modifier comprising an alkenyl ether compound represented by the general formula (1). More specifically, the present invention relates to a silicone resin modifier used as an intermediate for silicone resins, dispersants, urethane foam stabilizers, cosmetics, varnishes, insulating liquid die bonding agents and the like.

  Conventionally, compounds having an alkenyl group are copolymerized with other monomers and used as dispersants for cement and inorganic pigments. In addition, alkenyl compounds having a polyether group in the molecule have been proposed to be used as raw materials for urethane foam stabilizers, cosmetics, varnishes, insulating liquid die bonding agents and the like by hydrosilylation reactions (for example, patent documents). 1).

JP 2002-338683 A

  However, the cured silicone resin obtained by polymerization of the alkenyl compound described in Patent Document 1 has a low degree of polymerization, so that sufficient mechanical strength cannot be obtained, and chemical resistance against strong acids and strong alkalis is low. There were drawbacks. Therefore, an object is to provide a silicone resin modifier that imparts sufficient mechanical strength and good chemical resistance to a cured silicone resin.

［式中、Ｚは炭素数３〜２２の３価以上の多価アルコール、炭素数６〜２４の３価以上の多価フェノール、又は炭素数４〜２２の３価以上の多価カルボン酸からすべての活性水素原子を除いた残基；R₁は炭素数２〜８のアルケニル基；R₂は水素原子、炭素数１〜８のアルキル基、炭素数２〜８のアルケニル基及び炭素数２〜８のアシル基から選ばれる少なくとも１種の基；AＯは炭素数２〜４のアルキレンオキシ基；ｍ、ｎはアルキレンオキシ基の付加モル数を示し、ｍは１以上の整数、ｎは０以上の整数；ｑは２以上の整数であり、ｍ＋ｎ×ｑは１〜２００である。］ The inventor of the present invention has reached the present invention as a result of studies to achieve the above object.
That is, the present invention provides a silicone resin modifier comprising an alkenyl ether compound (A) represented by the general formula (1); a silicone resin obtained by reacting the silicone resin modifier with a silicon hydride compound (B); This is a cured silicone resin obtained by reacting the silicone resin.

[In the formula, Z is a trihydric or higher polyhydric alcohol having 3 to 22 carbon atoms, a trihydric or higher polyhydric phenol having 6 to 24 carbon atoms, or a trivalent or higher polyvalent carboxylic acid having 4 to 22 carbon atoms. Residues excluding all active hydrogen atoms; R ₁ is an alkenyl group having 2 to 8 carbon atoms; R ₂ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 2 carbon atoms At least one group selected from ˜8 acyl groups; AO is an alkyleneoxy group having 2 to 4 carbon atoms; m and n are the added moles of an alkyleneoxy group, m is an integer of 1 or more, and n is 0. Q is an integer of 2 or more, and m + n × q is 1 to 200. ]

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a silicone resin modifier capable of obtaining a resin having high mechanical strength and excellent chemical resistance. .

The silicone resin modifier of the present invention is characterized by comprising a compound (A) represented by the general formula (1).
As the alkenyl ether compound (A) in the present invention, a trihydric or higher polyhydric alcohol having 3 to 22 carbon atoms, a trihydric or higher polyhydric phenol having 6 to 24 carbon atoms, and a trihydric or higher trivalent having 4 to 22 carbon atoms. An alkylene oxide adduct (A1) is obtained by adding an alkylene oxide having 2 to 4 carbon atoms to at least one compound (a1) selected from the group consisting of polyvalent carboxylic acids, and then q + 1 pieces of (A1) Is substituted with an alkenyl group having 2 to 8 carbon atoms, and if necessary, the remaining active hydrogen is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 2 to 8 carbon atoms. It is a compound substituted with at least one group selected from acyl groups.

Z in the general formula (1) is a trihydric or higher polyhydric alcohol having 3 to 22 carbon atoms, a trihydric or higher polyhydric phenol having 6 to 24 carbon atoms, or a trihydric or higher polyvalent having 4 to 22 carbon atoms. It is a residue obtained by removing all active hydrogens from at least one compound (a1) selected from the group consisting of carboxylic acids.
The trivalent or higher polyhydric alcohol having 3 to 22 carbon atoms is preferably a 3 to 8 alcohol having 3 to 22 carbon atoms from the viewpoint of reactivity. Specifically, glycerin, 1,2,4-trihydroxybutane, 2,3,4-trihydroxypentane, 1,1,1-tris (hydroxymethyl) ethane, 1,2,6-trihydroxyhexane and Examples include 1,2,3-trihydroxyheptane, pentaerythritol, xylitol, arabitol, sorbitol, mannitol, and sucrose.
The trivalent or higher polyhydric phenol having 6 to 24 carbon atoms is preferably a 3 to 6 alcohol having 6 to 24 carbon atoms from the viewpoint of reactivity. Specific examples include pyrogallol, dihydroxynaphthylcresol and tris (hydroxyphenyl) methane pyrogallol, tetrahydroxybenzene, tetra (4-hydroxyphenyl) ethane, pentahydroxybenzene, hexahydroxybenzene and the like.
The trivalent or higher valent carboxylic acid having 4 to 22 carbon atoms is preferably a 3 to 8 valent carboxylic acid having 4 to 22 carbon atoms. Specifically, trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1 , 3-Dicarboxyl-2-methyl-2-methylenecarboxypropane and 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-tetracarboxyl-n-octane and pyromerit Examples include acid, 1,1,2,2,2-penta (carboxymethyl) ethane, pentacarboxylbenzene, 1,1,1,2,2,2-hexa (carboxymethyl) ethane, hexacarboxylbenzene and the like.
Compound (a1) has q + 1 active hydrogens. q is an integer of 2 or more, and is preferably 2 to 7 from the viewpoint of reactivity.
Among (a1), preferred from the viewpoint of reactivity with alkylene oxide are glycerin, 1,2,4-trihydroxybutane, 2,3,4-trihydroxypentane, 1,1,1-tris (hydroxy). Methyl) ethane, pentaerythritol, sorbitol, and sucrose, and more preferable are glycerin, pentaerythritol, sorbitol, and sucrose. These may be used alone or in combination of two or more.

AO in the general formula (1) is an alkyleneoxy group having 2 to 4 carbon atoms. Examples of the alkyleneoxy group having 2 to 4 carbon atoms include ethyleneoxy group, 1,2-propyleneoxy group, 1,3-propyleneoxy group, 1,2-butyleneoxy group and 1,4-butyleneoxy group. It is done. Of these, an ethyleneoxy group, a 1,2-propyleneoxy group, and a combination thereof are preferable, and an ethyleneoxy group is more preferable.

R ₁ in the general formula (1) is an alkenyl group having 2 to 8 carbon atoms.
Examples of the alkenyl group having 2 to 8 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, isobutenyl group, 1-pentenyl group and 2-pentenyl group. , 3-pentenyl group, isopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group and isohexenyl group. Among these, from the viewpoint of reactivity, a vinyl group, a 1-propenyl group or a 2-propenyl group is preferable.

R ₂ in the general formula (1) is selected from one or more of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms. Group.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, cyclohexyl group, octyl group, cyclooctyl group, and dimethylcyclohexyl group. It is done.
Examples of the alkenyl group having 2 to 8 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, isobutenyl group, 1-pentenyl group and 2-pentenyl group. , 3-pentenyl group, isopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group and isohexenyl group.
As the acyl group having 2 to 8 carbon atoms, one or more acyl groups among acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, benzoyl group, octanoyl group and the like can be used.
R ₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and more preferably a vinyl group, a 1-propenyl group or a 2-propenyl group from the viewpoint of chemical resistance.

In the general formula (1), m and n represent the number of added moles of the alkyleneoxy group with respect to Z, m is an integer of 1 or more, and n is an integer of 0 or more. From the viewpoint of improving the chemical resistance of the cured silicone resin, m is preferably 1 to 50, and more preferably 1 to 30. n is preferably 1 to 50, and more preferably 1 to 30.

Q in the general formula (1) is an integer of 2 or more, and is preferably an integer of 2 to 7 from the viewpoint of the resin strength of the cured silicone resin.

Although there is no restriction | limiting in particular as a manufacturing method of the alkylene oxide adduct (A1) which added the C2-C4 alkylene oxide to the compound (a1), For example, the following method is mentioned.
The compound (a1) is charged into a pressure-resistant reaction vessel, and an alkylene oxide having 2 to 4 carbon atoms is blown in the absence of a catalyst or in the presence of a catalyst, and the reaction is carried out in one step or multiple steps under normal pressure or pressure. Examples of the catalyst include alkali catalysts [eg hydroxides of alkali metals (lithium, sodium, potassium, cesium, etc.) and alkoxides (methoxide, ethoxide, propoxide, butoxide, etc.), acids [perhalogen acids (perchloric acid, perbromine, etc. Acid, periodic acid, etc.), sulfuric acid, phosphoric acid, nitric acid, etc.] and their salts [preferably divalent or trivalent metals (Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, Al, etc.) The reaction temperature is usually 50 to 200 ° C. and the reaction time is usually 2 to 20 hours After completion of the addition reaction of alkylene oxide, the catalyst is neutralized if necessary and treated with an adsorbent. Thus, the catalyst can be removed and purified.

It is preferable that the number of C2-C8 alkenyl groups which a compound (A) has is 3-8 from a viewpoint of the resin strength of a silicone resin hardened | cured material.

From the viewpoint of improving the chemical resistance of the cured silicone resin, m + n × q is 1 to 200, preferably 3 to 160, and more preferably 9 to 160.

As a manufacturing method of a compound (A), the well-known manufacturing method etc. which alkenyl-etherify an alkylene oxide adduct (A1) are mentioned. For example, an alkylene oxide adduct (A1), sodium borohydride, and a granular alkali catalyst [for example, hydroxides of alkali metals (lithium, sodium, potassium, cesium, etc.) are charged into a pressure-resistant reactor and purged with nitrogen under stirring. Thereafter, the pressure in the reaction system is reduced, and a haloalkene [eg, alkenyl (vinyl, 1-propenyl, 2-propenyl, etc.) chloride] is added dropwise to alkenyl etherify. The reaction temperature is usually 50 to 100 ° C., and the reaction time is usually 3 to 20 hours. After alkenyl etherification, ion-exchanged water is added to the crude product to dissolve excess alkali and product salts. Next, an alkali adsorbent [for example, KW-600 (manufactured by Kyowa Chemical Industry), KW-700 (manufactured by Kyowa Chemical Industry), etc.] is added to the upper layer and mixed. After mixing, the mixture is dehydrated under reduced pressure at 70 to 80 ° C. for 4 hours while bubbling nitrogen through the liquid, cooled to 40 ° C., and filtered under nitrogen pressure to obtain the alkenyl ether compound (A).
When an alkyl group is introduced, haloalkene and haloalkane [for example, alkyl (methyl, ethyl, propyl, etc.) chloride] may be used in combination.
When an acyl group is introduced, a haloalkene and an acid halide [eg, acyl (carbonyl, benzoyl, etc.) chloride] may be used in combination.

As a method for modifying the chemical resistance of a cured silicone resin, a silicone having a silyl group at at least one end by adding (B) to an alkenyl group of (A) in the presence of a catalyst (C). After obtaining resin (D), the method of obtaining a silicone resin hardened | cured material by exposing to air | atmosphere etc. are mentioned.

Examples of the silicon hydride compound (B) include halogenated silane, alkoxysilane, acyloxysilane, and ketoximate silane. Examples of the halogenated silane include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane. Can be mentioned.
Examples of the alkoxysilane include trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane.
Examples of acyloxysilane include methyldiacetoxysilane and phenyldiacetoxysilane.
Examples of the ketoximate silane include bis (dimethyl ketoximate) methyl silane and bis (cyclohexyl ketoximate) methyl silane.
Of these, halogenated silanes and alkoxysilanes are preferred, and halogenated silanes are more preferred.

The equivalent ratio of the alkenyl group (A) in the silicone resin (D) to the silane group of the silicon hydride compound (B) is preferably 1: 2 to 2: 1, more preferably 1: from the viewpoint of resin strength. It is 1.5 to 1.5: 1, particularly preferably 1: 1.2 to 1.2: 1.

As the catalyst (C), it is preferable to use a platinum catalyst, and it is more preferable to use a catalyst such as chloroplatinic acid, platinum metal, activated carbon with platinum, platinum chloride and a platinum olefin complex. The reaction temperature is preferably 30 to 150 ° C, more preferably 50 to 120 ° C. The reaction time is preferably 2 to 20 hours, more preferably 4 to 15 hours. Solvents may or may not be used, but when used, ether solvents (diethyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbon solvents (n-hexane, cyclohexane, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.) ), An inert solvent having no active hydrogen, such as a halogenated hydrocarbon solvent (carbon tetrachloride, trichloroethane, etc.) is preferred.

When the silicone resin (D) is exposed to the atmosphere, it reacts with moisture to form a three-dimensional network structure and is cured into a cured silicone resin. The curing rate varies depending on the atmospheric temperature, humidity, and type of hydrolyzable group.

A curing catalyst may be mixed with the silicone resin (D) for the purpose of increasing the curing rate. Curing catalysts include metal catalysts such as tin catalysts [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.], lead catalysts [olein Lead acid, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], other metal catalysts [metal naphthenate such as cobalt naphthenate, phenylmercuric propionate, alkyl titanate, organosilicon titanate] Salts, etc.]; and amine-based catalysts such as triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (manufactured by San Apro), Registered trademark)]]]]; dialkylamino Alkylamines [dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, etc.] or heterocyclic aminoalkylamines [2- (1-aziridinyl) ethylamine , 4- (1-piperidinyl) -2-hexylamine, etc.] carbonates and organic acid salts (formate, etc.), etc .; N-methylmorpholine, N-ethylmorpholine, triethylamine, diethylethanolamine, dimethylethanolamine, etc .; Other known catalysts such as acidic catalysts and basic catalysts; and a combination system of two or more of these may be used. A tin-based catalyst is preferred, and a tin carboxylate is particularly preferred. The amount of the curing catalyst varies depending on the type of the hydrolyzable functional group (D), the type of the curing catalyst, etc., but is preferably 0 to 8% by weight, more preferably 0.1 to 3% based on the weight of (D). % By weight, particularly preferably 0.3 to 2% by weight.

The silicone resin (D) can be mixed with other fillers, additives and the like in addition to the curing catalyst.
Examples of the filler include heavy calcium carbonate, calcium carbonate surface-treated with fatty acid, barium sulfate, alumina, silica, carbon black, calcium oxide, titanium oxide, diatomaceous earth, glass fiber and crushed material thereof (cut glass And inorganic fillers such as talc, mica, and shirasu balloon. The content of the filler is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, based on the weight of the silicone resin (D).

Additives include plasticizers, diluents, and thinning agents for the purpose of improving mixing and workability by reducing the viscosity before curing, and imparting elasticity and flexibility to the cured silicone resin after curing. One or more selected from the group consisting of a softening agent, an antioxidant, an ultraviolet absorber, and a thixotropic agent may be used. Examples of plasticizers used in the present invention include ester plasticizers [dibutyl phthalate, dioctyl phthalate, dioctyl adipate, polyethylene glycol (molecular weight: 200) diadipate, etc.]; tar plasticizers (tar, asphalt, etc.); petroleum Resin-based plasticizers may be mentioned. The content of the plasticizer is preferably 5 to 70% by weight, more preferably 15 to 50% by weight, based on the weight of the silicone resin (D). Diluents and thinning agents include the plasticizers and aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate, butyl acetate, and cellosolve acetate. And solvents of ketones such as acetone and methyl ethyl ketone, and ethers such as diethylene glycol dimethyl ether and ethylene glycol dibutyl ether. Content is 0-20 weight% based on the weight of a silicone resin (D), Preferably it is 0-5 weight%.

Examples of the softening agent include a polyether compound having an acyl group at a terminal, a polyether compound having an alkyl ether group at a terminal, and the like. The content of the softening agent is preferably 5 to 70% by weight, more preferably 15 to 50% by weight, based on the weight of the silicone resin composition (D). Antioxidants include hindered phenol antioxidants [Irganox 1010 (manufactured by BASF Japan), octadecyl-3- (3,5-di-t-butyl-4hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF Japan). And the like], hindered amine antioxidants [Sanol LS770 (manufactured by Sankyo Lifetech), 4-benzoyloxy-2,2,6,6, -tetramethylpiperidine (sanol LS-744, Sankyo Lifetech)]. . The content of the antioxidant is 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the weight of the silicone resin (D).

Examples of ultraviolet absorbers include triazole ultraviolet absorbers [2- (5-methyl-2-hydroxyphenyl) benzotriazole, tinuvin 320 (manufactured by BASF Japan), etc.], benzophenone ultraviolet absorbers [2-hydroxy-4-methoxy Benzophenone, Siasorb UV9 (manufactured by Cyanamid), etc.]. Content of a ultraviolet absorber is 0.001 to 10 weight% based on the weight of a silicone resin (D), Preferably it is 0.01 to 5 weight%. Examples of the thixotropic agent include colloidal silica, fine carbon black, fatty acid amide, and fatty acid metal soap. The content of the thixotropic agent is 0 to 50% by weight, preferably 0 to 20% by weight, based on the weight of the silicone resin (D).

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Below, a part shows a weight part.

<Example 1>
In a stainless steel pressure-resistant reaction vessel with a stirring device and a temperature control device with an internal volume of 2000 ml, alkylene oxide adduct (A1-1) [Sanniks GP-1000; manufactured by Sanyo Chemical Industries, Z is all activity from glycerin Residue from which hydrogen is removed, AO is a propyleneoxy group, m + n × q = 17] 500 g, sodium borohydride 0.02 g and sodium hydroxide 24.0 g are charged, and the temperature in the reaction vessel is adjusted to 40 to 50 ° C. To do. Thereafter, 39.0 g of allyl chloride was added dropwise over 2 hours while controlling the reaction temperature to be kept at 75 to 85 ° C., and then aged at 80 ° C. for 4 hours to obtain a crude product of polypropylene glycol monoallyl ether. Obtained.

Next, after adjusting the crude product obtained above to 50 to 60 ° C., 219.2 g of ion-exchanged water was added and stirred for 20 minutes to dissolve the remaining alkali and product salt in the crude product. After dissolving the salt, the mixture was allowed to stand for 30 minutes while maintaining the temperature in the reaction vessel at 50 to 60 ° C., and the separated lower layer water was extracted. Next, 3 parts of KW-600 (manufactured by Kyowa Chemical Industry) and 2 parts of KW-700 (manufactured by Kyowa Chemical Industry) were added to the upper layer and mixed. After mixing, dehydrated under reduced pressure at 70-80 ° C. for 4 hours while ventilating nitrogen in the liquid, cooled to 40 ° C., and filtered under nitrogen pressure to obtain 475.3 g of polypropylene glycol monoallyl ether (A-1). It was. The degree of unsaturation of (A-1) was 0.915 meq / g, and the hydroxyl value was 102.8. The degree of unsaturation was measured according to JIS K1557-1 (2007), and the hydroxyl value was measured according to JIS K1557-1 (2007).

<Example 2>
In Example 1, liquid polypropylene glycol diallyl ether (A-2) was used in the same manner as in Example 1 except that 48.0 g of sodium hydroxide, 78.0 g of allyl chloride, and 438.4 g of ion-exchanged water were used. 480.2 g was obtained. The degree of unsaturation of (A-2) was 1.77 meq / g, and the hydroxyl value was 49.6.

<Example 3>
In Example 1, except that 72.0 g of sodium hydroxide, 117.0 g of allyl chloride, and 657.7 g of ion-exchanged water were used, liquid polypropylene glycol triallyl ether (A-3) was used in the same manner as in Example 1. ) 482.9 g was obtained. The degree of unsaturation of (A-3) was 2.53 meq / g, and the hydroxyl value was 1.6.

<Comparative Example 1>
Example 1 except that 140 g of glycerin, 73.0 g of sodium hydroxide, 130.6 g of allyl chloride, and 667.2 g of ion-exchanged water are used instead of the alkylene oxide adduct (A1-1) in Example 1. In the same manner, 185.6 g of monoallyl ether (A′-1) of glycerin was obtained. The degree of unsaturation of (A′-1) was 7.75 meq / g, and the hydroxyl value was 869.8.

<Comparative example 2>
In Comparative Example 1, 185.6 g of glyceryl diallyl ether (A′-2) was obtained in the same manner as in Example 1 except that 146.1 g of sodium hydroxide, 261.3 g of allyl chloride, and 1334 g of ion-exchanged water were used. Obtained. The degree of unsaturation of (A′-2) was 11.8 meq / g, and the hydroxyl value was 332.0.

<Comparative Example 3>
In Comparative Example 1, 175.9 g of glyceryl triallyl ether (A′-3) was used in the same manner as in Example 1 except that 219.1 g of sodium hydroxide, 391.8 g of allyl chloride, and 2001 g of ion-exchanged water were used. Got. The degree of unsaturation of (A′-3) was 14.2 meq / g, and the hydroxyl value was 11.4.

<Example 4>
100 g of the alkenyl ether compound (A-1) obtained in Example 1 was placed in a 500 ml nitrogen-resistant pressure-resistant reaction vessel, and a chloroplatinic acid catalyst solution (H ₂ PtCl ₂ .6H ₂ O 2 g was added to 9 ml of isopropanol and tetrahydrofuran. After adding 0.05 ml of a solution dissolved in 82 ml) and 10.2 g of methyldimethoxysilane, the temperature is raised to 100 ° C., and the reaction is carried out at the same temperature for 8 hours. When the volatile matter was removed, a silicone resin (D-1) in which all terminal allyl groups of (A-1) were substituted with methyldimethoxysilylpropyl ether groups was obtained.

<Example 5>
In the same manner as in Example 4 except that 100 g of the alkenyl ether compound (A-2) obtained in Example 2 and 19.7 g of methyldimethoxysilane were used, the terminal allyl group of (A-2) was all methyl. A silicone resin (D-2) substituted with a dimethoxysilylpropyl ether group was obtained.

<Example 6>
In the same manner as in Example 4 except that 100 g of the alkenyl ether compound (A-3) obtained in Example 3 and 28.0 g of methyldimethoxysilane were used, all terminal allyl groups of (A-3) were methyl. A silicone resin (D-3) substituted with a dimethoxysilylpropyl ether group was obtained.

<Comparative example 4>
The terminal allyl group of (A′-1) was the same as in Example 4 except that 100 g of allyl ether of glycerin (A′-1) obtained in Comparative Example 1 and 86.4 g of methyldimethoxysilane were used. A silicone resin for comparison (D′-1) in which all were substituted with methyldimethoxysilylpropyl ether groups was obtained.

<Comparative Example 5>
The terminal allyl group of (A'-2) is all the same as in Example 4 except that 100 g of diallyl ether of glycerin (A'-2) obtained in Comparative Example 2 and 132 g of methyldimethoxysilane are used. A comparative silicone resin (D′-2) substituted with a methyldimethoxysilylpropyl ether group was obtained.

<Comparative Example 6>
The terminal allyl group of (A′-3) is the same as in Example 4 except that 100 g of triallyl ether (A′-3) of glycerin obtained in Comparative Example 3 and 158 g of methyldimethoxysilane are used. A comparative silicone resin (D′-3) was obtained that was all substituted with methyldimethoxysilylpropyl ether groups.

<Examples 7 to 9 and Comparative Examples 7 to 9>
Dioctyl phthalate with respect to 100 parts of silicone resins (D-1) to (D-3) and (D′-1) to (D′-3) obtained in Production Examples 4 to 6 and Comparative Examples 4 to 6 30 parts, fatty acid-treated calcium carbonate 30 parts, titanium oxide 25 parts, organic bentonite 3 parts, anhydrous silicic acid 5 parts, activated zinc 1 part, dibutyltin dilaurate 1.5 parts, dibutyldithiocarbamate nickel 0.5 parts, 2, 2 -Add 1 part of methylenebis (4-methyl-6-tertiarybutylphenol), 0.5 part of 2 (2'-hydroxy-3 ', 5'-di-dibutyltertiarybutylphenyl) -5-chlorobenzotriazole. After mixing with three rolls, a sheet having a thickness of 3 mm was prepared and cured at 25 ° C. and 65% RH for 7 days to obtain a cured silicone resin.

<Measuring method of mechanical strength>
Using the cured products obtained in Examples 7 to 9 and Comparative Examples 7 to 9, test dumbbells (JIS No. 3 type) were produced as test pieces. A tensile test was conducted by an autograph (manufactured by Shimadzu Corp., AG500C type) using a test dumbbell, and tensile properties were measured. The results are shown in Table 1.

<Chemical resistance evaluation method>
The chemical resistance was measured as follows. The cured product was cut into 50 mm length × 50 mm width × 3 mm height to prepare a test piece. After leaving the test piece for 1 day in an environment of 25 ° C. and 65% RH, the test piece was immersed in an aqueous solution of 37% by weight hydrochloric acid, 60% by weight nitric acid and 50% by weight sodium hydroxide at 25 ° C. for 3 days. After the test piece surface is wiped off at 25 ° C. and 65% RH for 3 days, the length, width and height of the test piece are measured. From this, the rate of change in volume (%) was calculated and determined as chemical resistance. The evaluation results are shown in Table 1.
[Chemical resistance evaluation criteria]
○: Volume change rate is less than 5%
Δ: Volume change rate is 5 or more and less than 10%
X: Volume change rate is 10% or more

From the results in Table 1, it was confirmed that the cured silicone resins obtained in Examples 7 to 9 were excellent in mechanical strength and chemical resistance.

  The cured silicone resin produced using the silicone resin modifier of the present invention is excellent in mechanical strength and chemical resistance, and is expected to have good adhesion to various adhesive substrates. The silicone resin of the present invention is useful as a silicone adhesive and is also useful as a silicone sealant.

Claims (4)

A silicone resin modifier comprising the alkenyl ether compound (A) represented by the general formula (1).

[In the formula, Z is a trihydric or higher polyhydric alcohol having 3 to 22 carbon atoms, a trihydric or higher polyhydric phenol having 6 to 24 carbon atoms, or a trivalent or higher polyvalent carboxylic acid having 4 to 22 carbon atoms. Residues excluding all active hydrogen atoms; R ₁ is an alkenyl group having 2 to 8 carbon atoms; R ₂ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 2 carbon atoms At least one group selected from ˜8 acyl groups; AO is an alkyleneoxy group having 2 to 4 carbon atoms; m and n are the added moles of an alkyleneoxy group, m is an integer of 1 or more, and n is 0. The above integers and q are integers of 2 or more, and m + n × q is a number satisfying 1 to 200. ] The silicone resin modifier according to claim 1, wherein the compound (A) has two or more alkenyl groups having 2 to 8 carbon atoms in the molecule. A silicone resin (D) obtained by reacting the silicone resin modifier according to claim 1 or 2 and a silicon hydride compound (B). A cured silicone resin obtained by reacting the silicone resin according to claim 3.