JP4631270B2 - Method for producing cyclic siloxane skeleton-containing compound having SiH group - Google Patents

Description

  The present invention relates to a method for producing a cyclic siloxane skeleton-containing compound having a SiH group, and more particularly to a method for producing a cyclic siloxane skeleton-containing compound having at least two SiH groups in one molecule.

  Hydrosilylation catalyst comprising cyclic siloxane compound (A) having at least two SiH groups in one molecule and compound (B) containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule (C) A cyclic siloxane skeleton-containing compound having at least two SiH groups in one molecule, wherein the reaction is carried out in the presence of a carbon-carbon double bond having reactivity with SiH groups in one molecule. Is useful as a curing agent for a compound containing at least two compounds (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5).

  Examples of cyclic siloxane compounds having at least two SiH groups in one molecule of component (A) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclo Various things including pentasiloxane are known, but these are expensive and not easily available. There is known a method of obtaining a cyclic siloxane-containing compound having at least two SiH groups in one molecule by decomposing an inexpensive and readily available SiH group-containing polysiloxane (for example, Patent Document 6, Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11, Non-Patent Document 1).

However, when a cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups as component (A) is used, at least two in one molecule obtained The cyclic siloxane skeleton-containing compound having a SiH group has a problem in storage stability such as thickening during storage.
JP-A-2-209957 JP-A-3-181565 JP-A-3-294320 JP-A-8-157720 JP 2002-241614 A JP-A-11-100309 JP-A-7-316167 JP-A-7-242678 JP-A-2-129192 JP 52-69500 A JP 47-13699 A Chem. Mater. 1993, 5,983

  The problem to be solved by the present invention is that a cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups, and a carbon-carbon having reactivity with SiH groups. A compound having at least two double bonds in one molecule is reacted in the presence of a hydrosilylation catalyst, and has at least two SiH groups in one molecule having low viscosity and excellent storage stability It is to provide a method for producing a cyclic siloxane skeleton-containing compound.

  As a result of intensive studies to solve such problems, the present inventor has obtained a cyclic siloxane compound (A) having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups, and SiH. By reacting a compound (B) having at least two carbon-carbon double bonds reactive with a group in one molecule in the presence of a hydrosilylation catalyst (C), at least two compounds in one molecule are reacted. When the cyclic siloxane skeleton-containing compound having a SiH group is produced, the above-mentioned problem is achieved by using a cyclic siloxane compound having a 1,3,5-trimethylcyclotrisiloxane content of 1% by weight or less as the component (A). The inventors have found that this can be solved and have reached the present invention.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶はメチル基、ｊは４〜１０００の数、ｋは０〜９９６の数であり、ｊ＋ｋは４〜１０００の数を表す。）で表される鎖状ポリシロキサンおよび／または下記一般式（ＩＩＩ）

（式中、Ｒ¹、Ｒ²、Ｒ³はメチル基。ｐは５〜１００の数、ｑは０〜９５の数であり、ｐ＋ｑは５〜１００の数を表す。）で表される環状ポリシロキサンからなるＳｉＨ基を有するポリシロキサンを分解することにより得られる１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン化合物（Ａ）と、ＳｉＨ基と反応性を有する炭素−炭素二重結合を１分子中に少なくとも２個有する化合物（Ｂ）をヒドロシリル化触媒（Ｃ）の存在下に反応させることによる、前記化合物（Ｂ）１分子に対して前記環状シロキサン化合物（Ａ）が少なくとも２分子結合してなり、反応生成物１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン骨格含有化合物の製造法であって、（Ａ）成分として１，３，５−トリメチルシクロトリシロキサンの含有量が１重量％以下である環状シロキサン化合物を用いることを特徴とする、１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン骨格含有化合物の製造法（請求項１）であり、
（Ａ）成分の環状シロキサン化合物が、ＳｉＨ基を有するポリシロキサンを金属アルコキシド触媒で分解することにより得られるものである請求項１に記載の１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン骨格含有化合物の製造法（請求項２）、であり、
１，３，５−トリメチルシクロトリシロキサンの含有量が１重量％以下である環状シロキサン化合物が、１，３，５−トリメチルシクロトリシロキサンの含有量が１重量％よりも高い（Ａ）成分を処理することにより得られたものである、請求項１あるいは２に記載の１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン骨格含有化合物の製造法（請求項３）である。
That is, the present invention
The following general formula (II)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are methyl groups, j is a number from 4 to 1000, k is a number from 0 to 996, and j + k is a number from 4 to 1000. A linear polysiloxane represented by the following general formula (III):

(Wherein R ¹ , R ² and R ³ are methyl groups, p is a number of 5 to 100, q is a number of 0 to 95, and p + q represents a number of 5 to 100). A cyclic siloxane compound (A) having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups composed of polysiloxane, and a carbon-carbon double bond having reactivity with SiH groups By reacting compound (B) having at least two per molecule in the presence of hydrosilylation catalyst (C), at least two molecules of cyclic siloxane compound (A) are present per molecule of compound (B). It becomes bonded to, a method of manufacturing a cyclic siloxane skeleton-containing compound having at least two SiH groups in the reaction product in one molecule, (a) 1,3,5 trimethylcyclotrisiloxane Shiroki as component Content of emissions is characterized by using a cyclic siloxane compound is less than 1 wt%, a method of producing the cyclic siloxane skeleton-containing compound having at least two SiH groups in a molecule (Claim 1),
2. The cyclic siloxane having at least two SiH groups in one molecule according to claim 1, wherein the cyclic siloxane compound of component (A) is obtained by decomposing polysiloxane having SiH groups with a metal alkoxide catalyst. A method for producing a skeleton-containing compound (claim 2),
The cyclic siloxane compound in which the content of 1,3,5-trimethylcyclotrisiloxane is 1% by weight or less is the component (A) in which the content of 1,3,5-trimethylcyclotrisiloxane is higher than 1% by weight. The method for producing a cyclic siloxane skeleton-containing compound having at least two SiH groups in one molecule according to claim 1 or 2 obtained by treatment (claim 3).

  According to the present invention, a cyclic siloxane compound (A) having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups, and a carbon-carbon double bond having reactivity with SiH groups By reacting the compound (B) having at least two per molecule in the presence of the hydrosilylation catalyst (C), at least two SiH groups in one molecule having low viscosity and excellent storage stability are obtained. The cyclic siloxane skeleton-containing compound can be produced.

Hereinafter, the present invention will be described in detail.
((A) component)
The component (A) of the present invention is a cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups.

  A cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups is represented by the following general formula (I):

（式中、Ｒ¹、Ｒ²、Ｒ³は同種または異種の炭素数１〜９の有機基を表し、ｍは２〜６の数、ｎは０〜４の数で、ｍ＋ｎは３〜６の数を表す。）で表される化合物が例示でき、通常複数成分の混合物として得られる。

Wherein R ¹ , R ² and R ³ represent the same or different organic group having 1 to 9 carbon atoms, m is a number of 2 to 6, n is a number of 0 to 4, and m + n is 3 to 6 The compound represented by this can be illustrated, and is usually obtained as a mixture of a plurality of components.

  From the viewpoint of the availability of polysiloxanes having SiH groups used for decomposition, cyclic siloxane compounds having at least two SiH groups in one molecule represented by the above general formula (I) are 1, 3, 5, 7 -Tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9,11-hexamethylcyclohexasiloxane are preferred, at least two per molecule Since it is easy to remove the unreacted cyclic siloxane compound under reduced pressure after synthesizing the cyclic siloxane-containing compound having SiH group, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 , 7,9-pentamethylcyclopentasiloxane is preferred.

  The cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing the polysiloxane having SiH groups as the component (A) is stable, reactive and easy to remove unreacted components. More preferably, 80% by weight or more of the cyclic siloxane compound having at least two SiH groups in one molecule is 1,3,5,7-tetramethylcyclotetrasiloxane, and 90% by weight or more is 1,3. , 5,7-tetramethylcyclotetrasiloxane, more preferably 95% by weight or more is 1,3,5,7-tetramethylcyclotetrasiloxane.

  The polysiloxane having a SiH group is not particularly limited, and various types can be used.

Examples of the polysiloxane having a SiH group include chain polysiloxanes represented by the general formula (II) and / or cyclic polysiloxanes represented by the general formula (III).

  From the point of availability, the following general formula (IV)

（式中、ｒは４〜１０００の数を表す。）が好ましい。

(Wherein r represents a number of 4 to 1000).

  The method for decomposing the polysiloxane having SiH groups is not particularly limited. Moreover, you may use a catalyst for decomposition | disassembly of the polysiloxane which has SiH group. The decomposition catalyst that can be used includes sulfuric acid, hydrochloric acid, alkylsulfonic acid, aluminum halide, acid halide, activated clay, cation exchange resin and other acidic catalysts, alkali metal hydroxide, alkaline earth metal hydroxide, alkali Neutral catalysts such as metal silanolates, alkali metal carbonates, ammonium hydroxide, phosphonium hydroxide, etc., alkali metal fluorides, metal alkoxides, metal alkoxides partially hydrolyzed and gelled Can be mentioned. Of these, metal alkoxides are preferred because gelation of the reaction system is unlikely to proceed.

  Specific examples of the metal alkoxide include aluminum triethoxide, aluminum triisopropoxide, aluminum tributoxide, aluminum trisecondary butoxide, aluminum diisopropoxysecondary butoxide, aluminum diisopropoxyacetylacetonate, aluminum disecondary. Butoxyacetylacetonate, Aluminum diisopropoxyethylacetoacetate, Aluminum di-secondary butoxyethylacetoacetate, Aluminum trisacetylacetonate, Aluminum trisethylacetoacetate, Aluminum acetylacetonate bisethylacetoacetate, Titanium tetraethoxy , Titanium tetraisopropoxide, titanium tetrabutoxide, titanium diisopropoxybisacetylacetona , Titanium diisopropoxybisethyl acetoacetate, titanium tetra-2-ethylhexyl oxide, titanium diisopropoxybis (2-ethyl-1,3-hexanediolate), titanium dibutoxybis (triethanolaminato), zirconium Tetrabutoxide, zirconium tetraisopropoxide, zirconium tetramethoxide, zirconium tributoxide monoacetylacetonate, zirconium dibutoxide bisacetylacetonate, zirconium butoxide trisacetylacetonate, zirconium tetraacetylacetonate, zirconium tributoxide monoethylacetoacetate Tartar, zirconium dibutoxide bisethyl acetoacetate, zirconium butoxide trisethylacetoacetate, zir Ni-tetraethylacetoacetate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetate, tin (II) diacetate, tin (II) dioctoate, tin (II) dilaurate, tin (II) bisacetylacetonate, tin (II) bisethylacetoacetate, zinc diacetate, magnesium diacetate, magnesium dimethoxide, magnesium diethoxide and the like. In addition, cyclic 1,3,5-triisopropoxycyclotrialuminoxane and the like can also be used. Of these, aluminum triisopropoxide, aluminum tri-secondary butoxide, aluminum diisopropoxyethyl acetoacetate, aluminum disecondary butoxyethyl acetoacetate, aluminum trisacetylacetonate, titanium tetraisopropoxide, titanium tetra Butoxide and zirconium tetrabutoxide are used. Most preferred is aluminum triisopropoxide.

  These decomposition catalysts may be used alone or in combination at any ratio.

In addition, a catalyst in which a decomposition catalyst is supported on a carrier such as silica gel, alumina, titania, zeolite, molecular sieve, graphite, metal, or glass by a method such as fusion, vapor deposition, or adsorption can also be used.

  The amount of the decomposition catalyst used can be variously selected depending on the reaction rate, but is generally 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.01 to 1 part by weight based on the starting polysiloxane. Part can be used. In the case of using a metal alkoxide supported or partially hydrolyzed, 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably based on the starting polysiloxane in terms of the original metal alkoxide. 0.01 to 1 part by weight can be used.

  The decomposition temperature may be any temperature at which the decomposition reaction proceeds. Generally, a temperature of 60 to 300 ° C. is used, but a temperature of 100 to 200 ° C. is preferable in order to suppress side reactions and allow the reaction to proceed efficiently. Moreover, in order to suppress the gelatinization of a decomposition liquid more, the temperature of 140-190 degreeC is further more preferable.

The decomposition reaction can be carried out at normal pressure or under reduced pressure, but it is preferably carried out under reduced pressure in order to efficiently distill off the decomposition products and advance the decomposition reaction efficiently at a relatively low temperature. In this case, for example, the reaction can be carried out under a reduced pressure of 10 to 300 mmHg. In addition, the composition of the decomposition product can be controlled by adjusting the temperature, the reflux ratio, and the degree of reduced pressure, and an appropriate solvent or additive can be used depending on the purpose such as gelation suppression of the decomposition solution. As the solvent, those having no chemical reactivity with a decomposition catalyst or SiH group and having a boiling point higher than that of the obtained cyclic siloxane compound can be used.

  For the cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing the polysiloxane having SiH groups as described above, 1,3,5-trimethylcyclotrisiloxane usually having a low boiling point is used. Containing.

  When a cyclic siloxane compound having a content of 1,3,5-trimethylcyclotrisiloxane higher than 1% by weight is used as a raw material for the component (A), the resulting molecule has at least two SiH groups. The viscosity of the cyclic siloxane skeleton-containing compound is high, and the viscosity tends to increase during storage. Therefore, the content of 1,3,5-trimethylcyclotrisiloxane in the component (A) needs to be 1% by weight or less.

  A cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups, wherein the content of 1,3,5-trimethylcyclotrisiloxane is 1% by weight or less The method for producing the cyclic siloxane compound is not particularly limited. The production of the cyclic siloxane compound having a 1,3,5-trimethylcyclotrisiloxane content of 1% by weight or less may be carried out by controlling the conditions for decomposing the polysiloxane having SiH groups. May be carried out using a tower, and after the production of a cyclic siloxane compound having a content of 1,3,5-trimethylcyclotrisiloxane higher than 1 wt% by decomposing a polysiloxane having SiH groups, May be performed by reducing the content of 1,3,5-trimethylcyclotrisiloxane to 1% by weight or less. Since the decomposition conditions and equipment are not complicated, after producing a cyclic siloxane compound having a content of 1,3,5-trimethylcyclotrisiloxane higher than 1 wt% by decomposing polysiloxane having SiH groups, A method of reducing the content of 1,3,5-trimethylcyclotrisiloxane to 1% by weight or less by performing the treatment is preferable.

  A treatment method for reducing the content of 1,3,5-trimethylcyclotrisiloxane in the cyclic siloxane compound higher than 1% by weight to 1% or less is not particularly limited, such as simple distillation or rectification. Examples thereof include a method in which 1,3,5-trimethylcyclotrisiloxane is reacted and converted into another compound and reduced by distillation, contact with water or acid, heating, or the like.

  Among the above-mentioned treatment methods, distillation is preferable because of easy operation, and rectification using a distillation column is more preferable because recovery of 1,3,5,7-tetramethylcyclotetrasiloxane can be increased. The treatment such as distillation may be performed as it is, or may be performed by adding a solvent that does not react with SiH groups. Distillation may be carried out after reacting 1,3,5-trimethylcyclotrisiloxane by contact with water or acid, heating, or the like.

To effectively separate 1,3,5-trimethylcyclotrisiloxane and 1,3,5,7-tetramethylcyclotetrasiloxane by distillation, 1,3,5-trimethylcyclotrisiloxane and 1,3,5 It is preferable to use a solvent having a boiling point between, 7-tetramethylcyclotetrasiloxane. Examples of preferable solvents include ethylene glycol diethyl ether, n-octane, n-butyl acetate, s-butyl acetate, and toluene, and toluene is more preferable. It is preferable to add 1 to 20 parts by weight with respect to 100 parts by weight of the cyclic siloxane compound having a content of 1,3,5-trimethylcyclotrisiloxane higher than 1% by weight, and to perform simple distillation or rectification, and more preferable addition The lower limit of the amount is 2 parts by weight, an even more preferable lower limit is 5 parts by weight, a more preferable upper limit of the addition amount is 15 parts by weight, and an even more preferable upper limit is 10 parts by weight. If the amount added is too small, the amount of 1,3,5,7-tetramethylcyclotetrasiloxane entrained with 1,3,5-trimethylcyclotrisiloxane, which is reduced, increases, and the recovery rate decreases. If the amount added is too large, the amount of the solvent contained in the cyclic siloxane compound having at least two SiH groups in one molecule increases, which makes handling difficult.
((B) component)
The compound having at least two carbon-carbon double bonds reactive with the SiH group as the component (B) in one molecule is not particularly limited, and any of inorganic, organic, and inorganic / organic mixed compounds Can also be used.

  Examples of inorganic compounds include silicone compounds containing siloxane units (Si—O—Si), and inorganic / organic mixed systems include organic polymers such as silicones and polyethers, polyesters, and poly (meth) acrylates described later. Examples include compounds in which the compound is chemically bonded as a block copolymer or graft copolymer.

  The component (B) is preferably an organic compound containing no siloxane unit (Si—O—Si) because of problems such as gas permeability, repellency, and contamination with a low molecular weight silicone compound.

  Organic compounds can be classified into organic polymer compounds and organic monomer compounds.

  Examples of organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (phenolic resin) ), Polyimide compounds can be used.

  Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: ethers: heterocyclic compounds. And mixtures thereof.

  (B) Although it does not specifically limit as a carbon-carbon double bond reactive with SiH group of a component, The following general formula (V)

（式中Ｒ⁷は水素原子あるいはメチル基を表す。）で示される基が反応性の点から好適である。また、原料の入手の容易さからは、

A group represented by the formula (wherein R ⁷ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. In addition, from the availability of raw materials,

示される基が特に好ましい。

The groups shown are particularly preferred.

  As the carbon-carbon double bond having reactivity with the SiH group of the component (B), the following general formula (VI)

（式中Ｒ⁸は水素原子あるいはメチル基を表す。）で示される脂環式の基が、硬化物の耐熱性が高いという点から好適である。また、原料の入手の容易さからは、

An alicyclic group represented by the formula (wherein R ⁸ represents a hydrogen atom or a methyl group) is preferable from the viewpoint that the heat resistance of the cured product is high. In addition, from the availability of raw materials,

示される脂環式の基が特に好ましい。

The alicyclic groups shown are particularly preferred.

  The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (B) or may be covalently bonded via a divalent or higher valent substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but preferably includes only C, H, N, O, S, and halogen as constituent elements. Examples of these substituents include

が挙げられる。また、これらの２価以上の置換基の２つ以上が共有結合によりつながって１つの２価以上の置換基を構成していてもよい。

Is mentioned. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

が挙げられる。

Is mentioned.

  Specific examples of the component (B) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2, -tetraallyloxy. Ethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably having a purity of 80 to 100% ), Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2) (The ratio is 50 to 100%) Allyl ether rack phenol, allylated polyphenylene oxide,

の他、従来公知のエポキシ樹脂のグルシジル基の一部あるいは全部をアリル基に置き換えたもの等が挙げられる。

In addition, there may be mentioned those in which part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group.

  As the component (B), it is also possible to use low molecular weight compounds that are difficult to express separately as described above for the skeleton and alkenyl groups. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  The component (B) preferably contains 0.001 mol or more of carbon-carbon double bond having reactivity with the SiH group per 1 g of the component (E) from the viewpoint that heat resistance can be further improved. What contains 0.005 mol or more per is more preferable, and what contains 0.008 mol or more is still more preferable.

  The number of carbon-carbon double bonds that are reactive with the SiH group of the component (B) should be on average at least two per molecule, but it may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it is 3 or more. In the case where the number of carbon-carbon double bonds having reactivity with the SiH group of component (B) is 1 or less per molecule, even if it reacts with component (A), only a graft structure is formed and Don't be.

  As the component (B), from the viewpoint of good reactivity, it is preferable that one or more vinyl groups are contained in one molecule, and two or more vinyl groups are contained in one molecule. Is more preferable. Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.

  The component (B) has a molecular weight of less than 900, preferably less than 700, from the viewpoint of high mechanical heat resistance and from the viewpoint of low formability of the raw material liquid and good moldability and handleability. More preferably, those less than 500 are more preferable.

  As the component (B), in order to obtain uniform mixing with other components and good workability, the viscosity is preferably less than 1000 poise at 23 ° C., more preferably less than 300 poise, More preferred is less than 30 poise. The viscosity can be measured with an E-type viscometer.

  As the component (B), those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of suppressing coloring, particularly yellowing. What does not contain the compound which has a derivative is preferable. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

  From the viewpoint of good optical properties such as low birefringence and low photoelastic coefficient and good weather resistance, the component weight ratio in the component (B) of the aromatic ring is 50 wt. % Or less, preferably 40% by weight or less, more preferably 30% by weight or less. Most preferred are those that do not contain an aromatic hydrocarbon ring.

  From the viewpoint that the obtained cured product is less colored, has high optical transparency, and has high light resistance, the component (B) includes vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, 2,2-bis (4 -Hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinylcyclohexane is preferred, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinyl Cyclohexane is particularly preferred.

  (B) As a component, you may have another reactive group. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.

  As the component (B), from the viewpoint of high heat resistance and transparency, the following general formula (VII)

（式中Ｒ⁹は炭素数１〜５０の一価の有機基を表し、それぞれのＲ⁹は異なっていても同一であってもよい。）で表される化合物が好ましい。

(Wherein R ⁹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ⁹ may be different or the same).

R ^{9 in the} general formula (VII) is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ⁹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

R ^{9 in the} general formula (VII) is a carbon in which at least one of the three R ^{9 s} contains one or more epoxy groups from the viewpoint that adhesion of the obtained cured product with various materials can be improved. A monovalent organic group of 1 to 50 is preferable,

で表されるエポキシ基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましい。これらの好ましいＲ⁹の例としては、グリシジル基、

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of these preferred R ⁹ include glycidyl group,

等が挙げられる。

Etc.

As R ^{9 in the} general formula (VII), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it contains 2 or less oxygen atoms, and C, H, O as constituent elements It is preferably a monovalent organic group having 1 to 50 carbon atoms, and more preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms. Examples of these preferable R ⁹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

As R ^{9 in the} general formula (VII), at least one of the three R ⁹ is from the viewpoint of good reactivity.

で表される基を１個以上含む炭素数１〜５０の一価の有機基であることが好ましく、下記一般式（ＶＩＩＩ）

It is preferable that it is a C1-C50 monovalent organic group containing 1 or more groups represented by general formula (VIII) below.

（式中Ｒ¹⁰は水素原子あるいはメチル基を表す。）で表される基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましく、
３つのＲ¹⁰のうち少なくとも２つが下記一般式（ＩＸ）

(Wherein R ¹⁰ represents a hydrogen atom or a methyl group), and more preferably a monovalent organic group having 1 to 50 carbon atoms and containing at least one group represented by:
At least two of the three R ¹⁰ are represented by the following general formula (IX)

（式中Ｒ¹¹は直接結合あるいは炭素数１〜４８の二価の有機基を表し、Ｒ¹²は水素原子あるいはメチル基を表す。）で表される有機化合物（複数のＲ¹¹およびＲ¹²はそれぞれ異なっていても同一であってもよい。）であることがさらに好ましい。

(Wherein R ¹¹ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ¹² represents a hydrogen atom or a methyl group) (a plurality of R ¹¹ and R ¹² are More preferably, they may be the same or different.

R ¹¹ in the above general formula (IX) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the obtained cured product can have higher heat resistance, the direct bond or carbon It is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably, it is a group. Examples of these preferred R ¹¹ include

等が挙げられる。

Etc.

As R ^{11 in the} general formula (IX), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, a direct bond or two or less oxygen atoms and C as a constituent element can be used. It is preferably a C1-C48 divalent organic group containing only H and O, more preferably a direct bond or a C1-C48 divalent hydrocarbon group. Examples of these preferred R ¹¹ include

が挙げられる。

Is mentioned.

R ^{12 in the} general formula (IX) is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of good reactivity.

  However, in the preferred examples of the organic compound represented by the general formula (IX) as described above, it is necessary to contain at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. is there. From the viewpoint that heat resistance can be further improved, an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule is more preferable.

  Preferred specific examples of the organic compound represented by the general formula (VII) as described above include triallyl isocyanurate,

等が挙げられ、トリアリルイソシアヌレートが特に好ましい。

And triallyl isocyanurate is particularly preferable.

  When triallyl isocyanurate is used as the component (B), it is preferable that the content of 1,3-diallylurea contained in triallyl isocyanurate is 700 ppm or less because a product having high curability and low colorability is obtained. 100 ppm or less is more preferable, and more preferably 10 ppm or less.

Component (B) can be used alone or in combination of two or more (component (C))
Component (C) is a hydrosilylation catalyst.

The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, a platinum simple substance, a support made of alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid, platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), platinum-vinyl Siloxane complexes (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phos Fight complexes _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents a methyl group, Bu a butyl group, Vi represents a vinyl group Ph represents a phenyl group, and n and m represent integers.), Dicarbonyldichloroplatinum, Karstedt catalyst, and also described in Ashby US Pat. Nos. 3,159,601 and 3,159,662. Platinum-hydrocarbon complexes, as well as platinum alcoholate catalysts described in Lamoreaux US Pat. No. 3,220,972. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the component (B) in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably from 10 ^-7 mol, preferable amount of the upper limit (B) 10 ^-1 moles per mole of the SiH group in component, more preferably 10 ^-2 moles.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

  A cyclic siloxane skeleton-containing compound having at least two SiH groups in one molecule produced by reacting the components (A) and (B) of the present invention in the presence of the component (C), Usually, it is a mixture of a plurality, and can be used as a curing agent for a compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule.

 The mixing ratio of the component (A) and the component (B) when the component (A) and the component (B) are hydrosilylated is not particularly limited, but the cyclic siloxane having at least two SiH groups in one molecule to be obtained Since the amount of SiH groups in the contained compound is small and the amount used as a curing agent is small, it is generally advantageous. And the total number (X) of reactive carbon-carbon double bonds is preferably Y / X ≧ 2, more preferably Y / X ≧ 3, and Y / X ≧ 5 Even more preferred. When it is desired to improve the compatibility as the curing agent, it is preferably 10 ≧ Y / X, and more preferably 5 ≧ Y / X.

  As a method of mixing the component (A), the component (B), and the component (C) that is a catalyst in the reaction, various methods can be used, and the component (C) that is a catalyst is added to the component (B). A method of mixing the mixture with component (A) is preferred. It is difficult to control the reaction by mixing the component (A) and the component (B) with the component (C) as a catalyst. When the method of mixing the component (B) with the mixture of the component (A) and the catalyst (C) is used, the time for heating only the component (A) in the presence of the catalyst (C) component Therefore, quality deterioration due to side reaction is likely to occur.

  The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  Various reaction times and pressures during the reaction can be set as required.

  A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

  In addition, various additives may be used for the purpose of controlling reactivity.

  After reacting the component (A) and the component (B), the solvent, the unreacted component (A), the unreacted component (B) and / or the component (C) can be removed. Examples of methods for removing these components include vacuum devolatilization, treatment with activated carbon, aluminum silicate, silica gel, and the like. By removing the volatile component, an organic compound having at least two SiH groups in one molecule having no volatile content can be obtained, and therefore, a carbon-carbon double having reactivity with SiH groups as a curing agent. In the case of curing with a compound having at least two bonds in the position molecule, the problem of voids and cracks due to volatilization of volatile matter is unlikely to occur. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 80 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

  The cyclic siloxane skeleton-containing compound having at least two SiH groups in one molecule obtained by reacting the component (A) and the component (B) in the presence of the component (C) improves storage stability. Therefore, a catalyst activity inhibitor can be added. Examples of the catalyst activity inhibitor include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination. . Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these catalyst activity inhibitors, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1 are used from the viewpoint of good suppression effect and good raw material availability. -Cyclohexanol is preferred.

When a catalyst activity inhibitor is added, it may be added at any stage immediately after completion of the reaction of the component (A) and the component (B), before vacuum devolatilization, or after vacuum devolatilization. However, the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 10 ³ mol, more preferably 60 mol.

  These catalyst activity inhibitors may be used alone or in combination of two or more.

A compound containing a cyclic siloxane skeleton having at least two SiH groups in one molecule obtained by reacting the components (A) and (B) in the presence of the component (C) with the SiH group. The curable composition obtained by using as a curing agent for compounds containing at least two carbon-carbon double bonds per molecule and a cured product obtained by curing the same can be used in various applications. It is. In addition to optical materials and electronic materials, general uses in which thermosetting resins such as epoxy resins are used include, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.) In addition to insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins, and the like.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.
(Distillation equipment)
A packed tower (outer diameter 20 mm, packed length 30 mm) packed with 6 mm McMahon in a 2 L eggplant-shaped flask, distillation head (refrigerant temperature 0 ° C.), receiver, cryogenic trap (dry ice / ethanol bath), pressure controller, A distillation apparatus equipped with a vacuum pump was assembled. This was designated as (Distillation apparatus A).

  A packed column (outer diameter 40 mm, packed length 30 mm) packed with 6 mm McMahon in a 2 L eggplant-shaped flask, distillation head (refrigerant temperature 0 ° C.), receiver, deep cold trap (dry ice / ethanol bath), pressure controller, A distillation apparatus equipped with a vacuum pump was assembled. This was designated as (Distillation apparatus B).

A distillation apparatus equipped with a bumper prevention ball, a receiver, a deep cold trap (dry ice / ethanol bath), a pressure controller, and a vacuum pump was assembled on a rotary evaporator. This was designated as (Distillation apparatus C).
(SiH group-containing polysiloxane)
The following general formula (IV)

で表されるＳｉＨ基を有するポリシロキサンとして
ＧＥ東芝シリコーン株式会社製のＴＳＦ４８４（（ポリシロキサンＡ）とする）および信越化学工業株式会社製のＫＦ９９(（ポリシロキサンＢ）とする）を用いた。
ポリシロキサンＡおよびポリシロキサンＢの¹Ｈ−ＮＭＲを測定し、末端メチル基の水素の積分値（０．１２ｐｐｍ）とＳｉＨ基の水素の積分値（４．７ｐｐｍ）の比より求めた上記一般式（ＩＶ）のｒの値は、ポリシロキサンＡが４５、ポリシロキサンＢが５１であった。
（製造例１）
（蒸留装置Ａ）を用い、（ポリシロキサンＡ）１８００ｇ、アルミニウムトリイソプロポキシド１．８ｇを２Ｌナス型フラスコに投入、磁気攪拌子で攪拌しながら減圧度５０ｔｏｒｒに調整し、１５０〜１５５℃の油浴中で加熱した。還流比１の状態で留出する留分を約２０時間かけて回収した。

As the polysiloxane having a SiH group, TF Toshiba Silicone Co., Ltd. TSF484 (referred to as (polysiloxane A)) and Shin-Etsu Chemical Co., Ltd. KF99 (referred to as (polysiloxane B)) were used.
¹ H-NMR of polysiloxane A and polysiloxane B was measured, and the above general formula was obtained from the ratio of the integral value of hydrogen at the terminal methyl group (0.12 ppm) and the integral value of hydrogen at the SiH group (4.7 ppm). The value of r in (IV) was 45 for polysiloxane A and 51 for polysiloxane B.
(Production Example 1)
(Distillation apparatus A), 1800 g of (polysiloxane A) and 1.8 g of aluminum triisopropoxide were put into a 2 L eggplant-shaped flask, adjusted to a degree of vacuum of 50 torr while stirring with a magnetic stirrer, and 150-155 ° C. Heated in an oil bath. A fraction distilled at a reflux ratio of 1 was collected over about 20 hours.

  The obtained fraction was 1020 g and was analyzed by gas chromatography. As a result, 4.1% by weight of 1,3,5-trimethylcyclotrisiloxane and 1,3,5,7-tetramethylcyclotetrasiloxane 91.4 were obtained. The mixture was 1.4% by weight of 1,3,5,7,9-pentamethylcyclopentasiloxane. This fraction was defined as (Fraction A1).

In addition, quantification of various fractions by gas chromatography was performed by adding LS-8660 manufactured by Shin-Etsu Chemical Co., Ltd. as an internal standard substance, and quantified based on a separately prepared calibration curve.
(Production Examples 2 to 8)
Using a polysiloxane having an SiH group shown in Table 1 and a distillation apparatus A or B, fraction collection was performed under substantially the same conditions as in Production Example 1. The temperature adjustment range of the oil bath was 150 to 160 ° C., the distillation time was 10 to 30 hours, and the distillation recovery rate was 55 to 65%. The recovered fractions were fractions A2 to A8, respectively. Gas chromatography of the content of 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7,9-pentamethylcyclopentasiloxane in the fraction The results analyzed in Table 1 are shown in Table 1.

（製造例９〜１３）
製造例４〜８で得られた留分（留分Ａ４〜Ａ８）を２Ｌナス型フラスコに投入し、減圧度５０ｔｏｒｒ水浴温５０〜６０℃程度でロータリーエバポレーター（蒸留装置Ｃ）を用いて１〜１２時間かけて１，３，５−トリメチルシクロトリシロキサンの含有量低減を目的とした留去を行なった。

(Production Examples 9 to 13)
The fractions obtained in Production Examples 4 to 8 (fractions A4 to A8) were put into a 2 L eggplant-shaped flask, and the rotary evaporator (distillation apparatus C) was used at a reduced pressure of 50 torr and a water bath temperature of about 50 to 60 ° C. Distillation was performed for the purpose of reducing the content of 1,3,5-trimethylcyclotrisiloxane over 12 hours.

  Cyclic siloxane compounds with reduced 1,3,5-trimethylcyclotrisiloxane content remaining in the flask were designated as (distilled fraction products B1 to B5), respectively.

  The recovery rate was about 70% in all cases.

  Results of gas chromatography analysis of 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane content Are shown in Table 2.

（製造例１４）
蒸留缶に（ポリシロキサンＡ）１００重量部に対してアルミニウムトリイソプロポキシド０．１重量部添加して５０〜７０ｔｏｒｒ、油浴温１５０〜１７０℃で揮発性成分を減圧留去することにより得られた１，３，５−トリメチルシクロトリシロキサン３．６重量％、１，３，５，７−テトラメチルシクロテトラシロキサン９３．２重量％、１，３，５，７，９−ペンタメチルシクロペンタシロキサン０．１重量％の混合物（留分Ａ９）１５００ｇを（蒸留装置Ａ）に投入し、磁気攪拌子で攪拌しながら減圧度５０ｔｏｒｒに調整、５５〜６２℃の油浴中で加熱した。還流比１の状態で約４時間かけて１，３，５−トリメチルシクロトリシロキサンの含有量低減を目的とした留去を行なった。フラスコに残った１，３，５−トリメチルシクロトリシロキサンの含有量の低減された環状シロキサン化合物を（留分精製品Ｂ６）とした。回収率は９０％であった。１，３，５−トリメチルシクロトリシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、１，３，５，７，９−ペンタメチルシクロペンタシロキサン含有量をガスクロマトグラフィーで分析した結果を表２に示した。
（製造例１５）
上述の（留分Ａ９）１０９０ｇとトルエン１１０ｇを２Ｌナス型フラスコに投入し、減圧度５０ｔｏｒｒ、水浴温５０〜６０℃程度でロータリーエバポレーター（蒸留装置Ｃ）を用いて６時間かけて１，３，５−トリメチルシクロトリシロキサンの含有量低減を目的とした留去を行なった。フラスコに残った１，３，５−トリメチルシクロトリシロキサンの含有量の低減された環状シロキサン化合物とトルエンの混合物を（留分精製品Ｂ７）とした。留分精製品中のトルエン含有量は５％であり、留分９由来の成分の回収率は８０％であった。トルエン含有量を考慮しない１，３，５−トリメチルシクロトリシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、１，３，５，７，９−ペンタメチルシクロペンタシロキサン含有量をガスクロマトグラフィーで分析した結果を表２に示した。
（製造例１６）
蒸留缶に（ポリシロキサンＢ）１００重量部に対してアルミニウムトリイソプロポキシド０．１重量部添加して５０〜７０ｔｏｒｒ、油浴温１５０〜１８０℃で揮発性成分を減圧留去することにより得られた１，３，５−トリメチルシクロトリシロキサン３．７重量％、１，３，５，７−テトラメチルシクロテトラシロキサン９３．２重量％、１，３，５，７，９−ペンタメチルシクロペンタシロキサン０．１重量％の混合物（留分Ａ１０）９００ｇ、トルエン９０ｇを（蒸留装置Ａ）に投入し、磁気攪拌子で攪拌しながら減圧度５０ｔｏｒｒに調整、５８〜６５℃の油浴中で加熱した。還流比１の状態で約５時間かけて１，３，５−トリメチルシクロトリシロキサンの含有量低減を目的とした留去を行なった。フラスコに残った１，３，５−トリメチルシクロトリシロキサンの含有量の低減された環状シロキサン化合物を（留分精製品Ｂ８）とした。留分精製品中のトルエン含有量は３％であり、留分１０由来の成分の回収率は９１％であった。トルエン含有量を考慮しない１，３，５−トリメチルシクロトリシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、１，３，５，７，９−ペンタメチルシクロペンタシロキサン含有量をガスクロマトグラフィーで分析した結果を表２に示した
（実施例１）
２Ｌオートクレーブにトルエン６８０ｇ、製造例１１で得たＳｉＨ基を有するポリシロキサンを分解することにより得られる１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン化合物であって１，３，５−トリメチルシクロトリシロキサン含有量０．６％である（留分精製品Ｂ３）５７６ｇを入れ、気相部を窒素で置換した後、ジャケット温１０５℃で加熱、攪拌した。気相部を酸素含有量３％の窒素混合ガスで置換した後、トリアリルイソシアヌレート（日本化成株式会社製）８０ｇ、トルエン１２０ｇ及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．５ｇの混合液を２５分かけて滴下した。滴下終了直後およびその後３０分間隔で気相部を酸素含有量３％の窒素混合ガスの置換と０．１ＭＰａの加圧を行ない反応を継続させた。滴下終了から７．５時間後に¹Ｈ−ＮＭＲでアリル基の反応率が９５％以上であることを確認し、冷却により反応を終了した。未反応のＳｉＨ基含有化合物及びトルエンを減圧留去し、透明の液体を得た。

(Production Example 14)
Obtained by adding 0.1 parts by weight of aluminum triisopropoxide to 100 parts by weight of (polysiloxane A) in a distillation can and distilling off volatile components under reduced pressure at 50 to 70 torr and an oil bath temperature of 150 to 170 ° C. 1,3,5-trimethylcyclotrisiloxane 3.6% by weight, 1,3,5,7-tetramethylcyclotetrasiloxane 93.2% by weight, 1,3,5,7,9-pentamethylcyclo 1500 g of a mixture of 0.1% by weight of pentasiloxane (fraction A9) was charged into (distillation apparatus A), adjusted to a degree of vacuum of 50 torr while stirring with a magnetic stirrer, and heated in an oil bath at 55 to 62 ° C. Distillation was carried out for the purpose of reducing the content of 1,3,5-trimethylcyclotrisiloxane over about 4 hours at a reflux ratio of 1. The cyclic siloxane compound in which the content of 1,3,5-trimethylcyclotrisiloxane remaining in the flask was reduced was designated as (Distillation Product B6). The recovery rate was 90%. Results of gas chromatography analysis of 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane content Are shown in Table 2.
(Production Example 15)
1090 g of the above (Fraction A9) and 110 g of toluene were put into a 2 L eggplant type flask, and the pressure was reduced to 50 torr and the water bath temperature was about 50 to 60 ° C. using a rotary evaporator (distillation apparatus C) over 1, 6 hours. Distillation was performed for the purpose of reducing the content of 5-trimethylcyclotrisiloxane. A mixture of the cyclic siloxane compound with reduced content of 1,3,5-trimethylcyclotrisiloxane remaining in the flask and toluene was used as (distilled product B7). The toluene content in the purified fraction product was 5%, and the recovery rate of the component derived from the fraction 9 was 80%. Gasses 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane content without considering toluene content The results of chromatographic analysis are shown in Table 2.
(Production Example 16)
Obtained by adding 0.1 parts by weight of aluminum triisopropoxide to 100 parts by weight of (polysiloxane B) in a distillation can and distilling off volatile components under reduced pressure at 50 to 70 torr and an oil bath temperature of 150 to 180 ° C. 1,3,5-trimethylcyclotrisiloxane 3.7% by weight, 1,3,5,7-tetramethylcyclotetrasiloxane 93.2% by weight, 1,3,5,7,9-pentamethylcyclo A mixture of 0.1% by weight of pentasiloxane (fraction A10) and 90 g of toluene were added to (distillation apparatus A), adjusted to a degree of vacuum of 50 torr while stirring with a magnetic stirrer, in an oil bath at 58 to 65 ° C. Heated. Distillation was performed for the purpose of reducing the content of 1,3,5-trimethylcyclotrisiloxane over about 5 hours at a reflux ratio of 1. The cyclic siloxane compound in which the content of 1,3,5-trimethylcyclotrisiloxane remaining in the flask was reduced was designated as (Distillation Product B8). The toluene content in the purified fraction product was 3%, and the recovery rate of the component derived from the fraction 10 was 91%. Gasses 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane content without considering toluene content The results analyzed by chromatography are shown in Table 2 (Example 1).
A cyclic siloxane compound having at least 2 SiH groups in one molecule obtained by decomposing the polysiloxane having SiH groups obtained in Production Example 11 in 680 g of toluene in a 2 L autoclave, and 1,3,5-trimethyl 576 g of a cyclotrisiloxane content of 0.6% (distilled product B3) was added, the gas phase portion was replaced with nitrogen, and then heated and stirred at a jacket temperature of 105 ° C. After replacing the gas phase part with a nitrogen mixed gas having an oxygen content of 3%, 80 g of triallyl isocyanurate (Nihon Kasei Co., Ltd.), 120 g of toluene and a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) 5 g of the mixture was added dropwise over 25 minutes. Immediately after completion of the dropping and at intervals of 30 minutes thereafter, the gas phase portion was replaced with a nitrogen mixed gas having an oxygen content of 3% and pressurized to 0.1 MPa to continue the reaction. 7.5 hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. Unreacted SiH group-containing compound and toluene were distilled off under reduced pressure to obtain a transparent liquid.

The transparent liquid obtained in Example 1 was suggested to be a mixture because a multimodal chromatogram was obtained by GPC measurement, and 8.6 mmol / g SiH group was observed in ¹ H-NMR measurement. It was found that it contained. The transparent liquid is composed of 1,3,5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate having the following structural formula as a main component based on GC / MS, GPC fractionation, and ¹ H-NMR measurement. And a cyclic siloxane skeleton-containing compound having at least two SiH groups in one molecule, and 1,3,5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate are 5: 2, 8 It was confirmed that a compound containing a cyclic siloxane skeleton having at least two SiH groups was also contained in one molecule reacted in 3: 3. The viscosity at 23 ° C. immediately after production of the transparent liquid was 2.1 Pa · s, and the viscosity after storage at 23 ° C. for 1 week was 2.5 Pa · s.

（実施例２〜６、比較例１〜７）
実施例１の、製造例１１で得たＳｉＨ基を有するポリシロキサンを分解することにより得られる１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン化合物であって１，３，５−トリメチルシクロトリシロキサン含有量０．６％である（留分Ｂ３）の替わりに、同含有量が０．５％である（留分Ｂ４）、同含有量が０．３％である（留分Ｂ５）、同含有量が０．５％である（留分Ｂ６）、同含有量が０．８％である（留分Ｂ７）、同含有量が０．１％である（留分Ｂ８）を用いたものをそれぞれ実施例２〜６、同含有量が４．１％である（留分Ａ１）、同含有量が５．０％である（留分Ａ２）、同含有量が６．１％である（留分Ａ３）、同含有量が３．９％である（留分Ｂ１）、同含有量が３．１％である（留分Ｂ２）、同含有量が３．６％である（留分Ａ９）、同含有量が３．７％である（留分Ａ１０）を用いたものをそれぞれ比較例１〜７とし、得られた透明の液体（１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン骨格含有化合物）の製造直後の２３℃での粘度と２３℃で１週間貯蔵した後の粘度を表３に示した。比較例１〜７で得られた透明の液体のＧＰＣクロマトグラムは、実施例１〜６で得られた透明の液体の場合と比較して、単分散ポリスチレン換算分子量で４，０００以上の成分の割合が高かった。

(Examples 2-6, Comparative Examples 1-7)
A cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing the polysiloxane having SiH groups obtained in Production Example 11 of Example 1, which is 1,3,5-trimethylcyclohexane Instead of the trisiloxane content of 0.6% (fraction B3), the content is 0.5% (fraction B4), and the content is 0.3% (fraction B5). The same content is 0.5% (fraction B6), the same content is 0.8% (fraction B7), and the same content is 0.1% (fraction B8). In each of Examples 2 to 6, the same content was 4.1% (fraction A1), the same content was 5.0% (fraction A2), and the same content was 6.1%. (Fraction A3), the same content is 3.9% (Fraction B1), the same content is 3.1% (Fraction B2), the same content is Of 6% (fraction A9) and the same content of 3.7% (fraction A10) were used as Comparative Examples 1 to 7, respectively, and the resulting transparent liquids (in one molecule) Table 3 shows the viscosity at 23 ° C. immediately after the production of the cyclic siloxane skeleton-containing compound having at least two SiH groups) and the viscosity after storage at 23 ° C. for 1 week. The GPC chromatograms of the transparent liquids obtained in Comparative Examples 1 to 7 have a molecular weight of 4,000 or more in terms of monodisperse polystyrene as compared with the transparent liquids obtained in Examples 1 to 6. The rate was high.

ＳｉＨ基を有するポリシロキサンを分解することにより得られる１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン化合物に１，３，５−トリメチルシクロトリシロキサン含有量１％以下のものを用いることにより、得られる１分子中に少なくとも２個のＳｉＨ基を有する環状シロキサン骨格含有化合物は低粘度でかつ貯蔵安定性に優れる。

By using a cyclic siloxane compound having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups and having a 1,3,5-trimethylcyclotrisiloxane content of 1% or less. The obtained cyclic siloxane skeleton-containing compound having at least two SiH groups in one molecule is low in viscosity and excellent in storage stability.

Claims (3)

The following general formula (II)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are methyl groups, j is a number from 4 to 1000, k is a number from 0 to 996, and j + k is a number from 4 to 1000. A linear polysiloxane represented by the following general formula (III):

(Wherein R ¹ , R ² and R ³ are methyl groups, p is a number of 5 to 100, q is a number of 0 to 95, and p + q represents a number of 5 to 100). A cyclic siloxane compound (A) having at least two SiH groups in one molecule obtained by decomposing a polysiloxane having SiH groups composed of polysiloxane, and a carbon-carbon double bond having reactivity with SiH groups By reacting compound (B) having at least two per molecule in the presence of hydrosilylation catalyst (C), at least two molecules of cyclic siloxane compound (A) are present per molecule of compound (B). It becomes bonded to, a method of manufacturing a cyclic siloxane skeleton-containing compound having at least two SiH groups in the reaction product in one molecule, (a) 1,3,5 trimethylcyclotrisiloxane Shiroki as component Content of emissions is characterized by using a cyclic siloxane compound is less than 1 wt%, the preparation of the cyclic siloxane skeleton-containing compound having at least two SiH groups in each molecule.   2. The cyclic siloxane having at least two SiH groups in one molecule according to claim 1, wherein the cyclic siloxane compound of component (A) is obtained by decomposing polysiloxane having SiH groups with a metal alkoxide catalyst. A method for producing a skeleton-containing compound.   The cyclic siloxane compound in which the content of 1,3,5-trimethylcyclotrisiloxane is 1% by weight or less is the component (A) in which the content of 1,3,5-trimethylcyclotrisiloxane is higher than 1% by weight. The process for producing a cyclic siloxane skeleton-containing compound having at least two SiH groups in one molecule according to claim 1 or 2 obtained by treatment.