JP6068965B2 - Modified polyhedral polysiloxane, curable composition containing the same, and method for producing modified polyhedral polysiloxane - Google Patents

Description

  The present invention provides, for example, a modified polyhedral polysiloxane having a low residual metal catalyst and good storage stability, a curable composition using the modified product, a cured product, and a method for producing the modified product from which the catalyst has been removed. It is possible.

  In recent years, optical materials such as sealing materials used for optical semiconductors such as LEDs and light receiving elements have been increasingly demanded for heat resistance and light resistance, and mainly developed based on silicone-based materials. One of the effective reactions for curing these silicone materials is a hydrosilylation reaction. The hydrosilylation reaction can smoothly proceed with the curing reaction, but the reaction may proceed during storage due to the remaining metal catalyst when the precursor is synthesized, and there is a problem in terms of long-term storage stability. For example, Patent Document 1 discloses a method using a heterogeneous metal catalyst such as a platinum-supported carbon catalyst. In this method, after completion of the reaction, the catalyst can be removed by a simple operation such as filtration, but it is difficult to store and handle the catalyst, and it is not practical from the viewpoint of industrial use. Patent Document 2 reports an example in which the catalyst is removed by using an adsorbent whose surface is treated with silane, such as silica or activated carbon, but selection and availability of an adsorbent suitable for the reaction system, or adsorbent. There is concern about the impact on cost increase due to an increase in the number of synthesis steps. For this reason, development of a simple removal method of a metal catalyst and a silicone material has been demanded.

JP-A-2005-298606 JP-A-11-343457

  Accordingly, an object of the present invention is to provide a polyhedral polysiloxane modified product having a small amount of residual metal catalyst and good storage stability, a curable composition using the modified product, a cured product, and a method for producing the modified product from which the catalyst has been removed. That is.

As a result of intensive studies, the present inventors have
Polyhedron obtained by hydrosilylation reaction of polyhedral polysiloxane compound (a) containing alkenyl group, compound (b) containing one carbon-carbon double bond in one molecule and compound (c) having hydrosilyl group It has been found that the above problems can be solved by a modified polyhedral polysiloxane obtained by treating a structural polysiloxane reactant with an alkali adsorbent (d) and a base (e).

  That is, the present invention has the following configuration.

  1). A polyhedral polysiloxane reaction product obtained by hydrosilylating a polyhedral polysiloxane compound (a) containing an alkenyl group and a compound (c) having a hydrosilyl group is treated with an alkali adsorbent (d) and a base (e). A polyhedral polysiloxane modified product characterized by comprising:

  2). Polyhedron obtained by hydrosilylation reaction of polyhedral polysiloxane compound (a) containing alkenyl group, compound (b) containing one carbon-carbon double bond in one molecule and compound (c) having hydrosilyl group The modified polyhedral polysiloxane according to 1), wherein the structural polysiloxane reactant is treated with an alkali adsorbent (d) and a base (e).

  3). The modified polyhedral polysiloxane according to any one of 1) to 2), wherein the alkali adsorbent (d) is an alkali inorganic adsorbent.

  4). The modified polyhedral polysiloxane according to any one of 1) to 3), wherein the base (e) is a base containing two or more nitrogen atoms in one molecule.

5). The polyhedral polysiloxane compound (a) containing an alkenyl group has the formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
The modified polyhedral polysiloxane according to any one of 1) to 4), wherein the modified polyhedral polysiloxane is an alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by:

  6). The modified polyhedral polysiloxane according to any one of 1) to 5), wherein the modified polyhedral polysiloxane has at least three hydrosilyl groups in the molecule.

7). The polyhedral polysiloxane modification is
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, or an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain And may be the same or different, provided that at least one of Y or Z is a hydrogen atom, and at least one is derived from the condensed ring compound (c) containing an alkenyl group. It has the structure of (3).
^{_{- [CH 2] l -R 5}} (3)
(1 is an integer of 2 or more; R ⁵ is a group having a condensed ring compound); R is an alkyl group or an aryl group) The structural unit is any one of 1) to 6) The polyhedral polysiloxane modified product.

  8). The modified polyhedral polysiloxane according to any one of 1) to 7), wherein the compound (c) having a hydrosilyl group is a cyclic siloxane or a linear siloxane containing a hydrosilyl group.

  9). A polyhedral polysiloxane composition comprising the modified polyhedral polysiloxane (A) according to any one of 1) to 8) and a compound (B) having at least one alkenyl group.

  10). 1. The modified polyhedral polysiloxane according to 1), wherein the modified polyhedral polysiloxane (A) is liquid at a temperature of 20 ° C.

  11). The polyhedral polysiloxane composition according to 9), wherein the compound (B) having an alkenyl group is a polysiloxane having at least two alkenyl groups in the molecule.

  12). The polyhedral polysiloxane composition according to any one of 9) to 11), further comprising a curing retarder.

  13). The polyhedral polysiloxane composition according to any one of 9) to 12), which contains an adhesion-imparting agent.

  14). A method for producing a modified polyhedral polysiloxane comprising a step of treating with the alkali adsorbent (d) and the base (e) according to 1) and 2).

It is possible to provide a modified polyhedral polysiloxane having a low residual metal catalyst and good storage stability, a curable composition using the modified, a cured product, and a modified product from which the catalyst has been removed.

The present invention is described in detail below.
<(A) Polyhedral polysiloxane>
The component (A) in the present invention is a polyhedral polysiloxane compound containing an alkenyl group, and the polysiloxane compound (a) in which the alkenyl group is bonded directly or indirectly to the Si atom forming the polyhedral skeleton. On the other hand, it may be a polyhedral polysiloxane obtained by modifying the compound (c) having a hydrosilyl group by hydrosilation. The (A) component is a polyhedral polysiloxane compound containing an alkenyl group, and the polysiloxane compound (a) and one molecule in which the alkenyl group is bonded directly or indirectly to the Si atom forming the polyhedral skeleton A polyhedral polysiloxane obtained by modifying a compound (c) having a hydrosilyl group by hydrosilation with respect to the compound (b) containing one carbon-carbon double bond therein is particularly preferable.

  Hereinafter, the polysiloxane compound (a) in which an alkenyl group is bonded directly or indirectly to the Si atom forming the polyhedral skeleton will be described.

<Polysiloxane compound containing alkenyl group (a)>
In the polysiloxane compound in which the alkenyl group is bonded directly or indirectly on the Si atoms forming the polyhedral skeleton used in the present invention, the number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24 Specifically, for example, silsesquioxane having a polyhedral structure represented by the following structure is exemplified (here, the number of Si atoms = 8 is exemplified as a representative example).

In the above formula, R ^{1 to} R ⁸ are alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom, methyl group Group, ethyl group, propyl group, alkyl group such as butyl group, cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group and tolyl group, or part or all of hydrogen atoms bonded to carbon atoms of these groups Is the same or different, preferably an unsubstituted group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. Or it is a substituted monovalent hydrocarbon group.

However, at least one of R ^{1 to} R ⁸ is an alkenyl group. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance, and when a group other than the alkenyl group is selected, a methyl group is preferable from the viewpoint of heat resistance.

The above-mentioned silsesquioxane having a polyhedral structure is, for example, RSiX ₃ (wherein R represents R ^{1 to} R ⁸ described above, and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by hydrolytic condensation reaction of the silane compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by the hydrolysis condensation reaction of RSiX ₃ , the ring is closed by reacting the same or different trifunctional silane compounds to form a polyhedral skeleton. A method for synthesizing silsesquioxane is also known.

  In the polysiloxane compound in which an alkenyl group is bonded directly or indirectly to a Si atom forming a polyhedral skeleton in the present invention, a more preferable example is a silylated silica having a polyhedral structure as shown by the following structure. An acid is exemplified (here, Si atom number = 8 is exemplified as a representative example). In the compound, since the Si atom and the alkenyl group forming the polyhedral skeleton are bonded via a siloxane bond, the resulting cured product is not too rigid and a good molded product can be obtained. .

In the above structure, R ^{9 to} R ³² are alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom A methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a part of hydrogen atoms bonded to carbon atoms of these groups Alternatively, they are the same or different organic groups selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group and the like, all of which are substituted with a halogen atom, a cyano group or the like. However, at least one of these R ^{9 to} R ³² is an alkenyl group. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance, and even when a group other than the alkenyl group is selected, a methyl group is preferable from the viewpoint of heat resistance and light resistance.

  The method for synthesizing the silylated silicic acid having a polyhedral structure is not particularly limited, and is synthesized using a known method. Specific examples of the synthesis method include a method in which a tetraalkoxysilane such as tetraethoxysilane is hydrolytically condensed in the presence of a base such as quaternary ammonium hydroxide.

  In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It becomes possible to obtain a polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded through a siloxane bond. In the present invention, silylated silicic acid having the same polyhedral structure can be obtained from a silica-containing substance such as silica or rice husk instead of tetraalkoxysilane.

  In the present invention, the number of Si atoms contained in the polyhedral skeleton is preferably 6 to 24, more preferably 6 to 10. Further, it may be a mixture of polysiloxanes having polyhedral skeletons having different numbers of Si atoms.

<Compound (b) containing one carbon-carbon double bond in one molecule>
Hereinafter, the compound (b) containing one carbon-carbon double bond in one molecule will be described.
In the present invention, the compound (b) containing one carbon-carbon double bond in one molecule undergoes a hydrosilylation reaction with the hydrosilyl group of the compound (c) having a hydrosilyl group. By using the component (b), the elastic modulus of the obtained sealant can be reduced, and the thermal shock resistance can be improved. Further, by using the component (b), the gas barrier property and light extraction efficiency of the obtained sealant are improved.
Examples of the group containing a carbon-carbon double bond include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

The component (b) in the present invention is preferably a silane, polysiloxane, or cyclic olefin compound from the viewpoints of heat resistance and light resistance. When the component (b) is a silane containing one carbon-carbon double bond in one molecule, specifically, for example, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethyl Examples include vinylsilane, diethylphenylvinylsilane, ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane, and the like. Among these, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance, and dimethylphenylvinylsilane and methyldiphenylvinylsilane are also preferable from the viewpoint of gas barrier properties and refractive index. Triphenylvinylsilane is a preferred example.
In addition, when the component (b) is a polysiloxane, a polysiloxane having a linear structure having one carbon-carbon double bond, a polysiloxane having one carbon-carbon double bond at the molecular end, and a carbon-carbon double Examples thereof include cyclic siloxane having one bond.
In the case where the component (b) is a polysiloxane having a linear structure containing one carbon-carbon double bond in one molecule, specifically, for example, a dimethylvinylsilyl group and a trimethylsilyl group each having one end each Blocked polydimethylsiloxane, polymethylphenylsiloxane blocked one by one with dimethylvinylsilyl group and trimethylsilyl group, polydiphenylsiloxane blocked one by one with dimethylvinylsilyl group and trimethylsilyl group, Copolymers of dimethylsiloxane units and methylphenylsiloxane units each blocked with a dimethylvinylsilyl group and a trimethylsilyl group, and dimethylsiloxanes each blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Units and Giffeni Copolymers of siloxane units, copolymers of terminal and methylphenylsiloxane units and diphenylsiloxane units are blocked one by one, respectively dimethylvinylsilyl group and trimethylsilyl group and the like.

In the case of a polysiloxane having one carbon-carbon double bond at the molecular end, specifically, for example, a polysiloxane having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group as exemplified above, SiO ₂ unit And at least one siloxane unit selected from the group consisting of SiO _3/2 units, SiO units, and SiO _1/2 units, and polysiloxane composed of one dimethylvinylsiloxane unit.

  When the component (b) is a cyclic siloxane containing one carbon-carbon double bond in one molecule, specifically, for example, 1-vinyl-1,3,3,5,5,7,7- Heptamethylcyclotetrasiloxane, 1-vinyl-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7, Examples include 7-pentamethylcyclotetrasiloxane and 1-vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.

When the component (b) is a cyclic olefin compound having one carbon-carbon double bond in one molecule, the carbon-carbon double bond may be any of a vinylene group, a vinylidene group, or an alkenyl group. Good. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.
In addition, the cyclic olefin compound preferably has an average molecular weight of 1000 or less from the viewpoint of reactivity with the component (c). Examples of such cyclic olefin compounds include aliphatic cyclic olefin compounds and substituted aliphatic cyclic olefin compounds.

  Specific examples of the aliphatic cyclic olefin compound include cyclohexene, cycloheptene, cyclooctene, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, allylcyclohexane, allylcycloheptane, allylcyclooctane, and methylenecyclohexane. It is done.

  Specific examples of the substituted aliphatic cyclic olefin compound include norbornene, 1-methylnorbornene, 2-methylnorbornene, 7-methylnorbornene, 2-vinylnorbornane, 7-vinylnorbornane, 2-allylnorbornane, 7-allylnorbornane, 2-methylene norbornane, 7-methylene norbornane, camphene, vinyl norcamphene, 6-methyl-5-vinyl-bicyclo [2,2,1] -heptane, 3-methyl-2-methylene-bicyclo [2,2,1 ] -Heptane, α-pinene, β-pinene, 6,6-dimethyl-bicyclo [3,1,1] -2-heptaene, 2-vinyladamantane, 2-methyleneadamantane and the like.

Among these, cyclohexene, vinylcyclohexane, norbornene, camphene, and pinene are preferable examples from the viewpoint of availability.
The amount of the compound (b) having one carbon-carbon double bond in one molecule is such that the carbon-carbon double bond of the component (b) per one hydrosilyl group of the compound (c) having a hydrosilyl group described later It is preferable to use so that the number may become 0.01-0.5. When the addition amount is small, the thermal shock resistance of the resulting cured product may be reduced, and when the addition amount is large, the resulting sealant may cause poor curing.
These compounds (b), which have one carbon-carbon double bond in one molecule, may be used alone or in combination of two or more.

Hereinafter, the compound (c) having a hydrosilyl group will be described.
<Compound (c) having hydrosilyl group>
The compound having a hydrosilyl group used in the present invention is not particularly limited as long as it is a compound having a hydrosilyl group, but is a siloxane compound having a hydrosilyl group from the viewpoint of the transparency, heat resistance, and light resistance of the resulting modified polysiloxane. A siloxane compound having a hydrosilyl group and a cyclic or linear structure is more preferable. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having a hydrosilyl group include poly or oligosiloxanes whose ends are blocked with dimethylhydrogensilyl groups, poly or oligosiloxanes having hydrosilyl groups in the side chains, and tetramethyldisiloxane. And hexamethyltrisiloxane.

  Examples of the cyclic siloxane containing a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydro. Gen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5- Trihydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexa Examples include hydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

  Hereinafter, the alkali adsorbent (d) will be described.

<Alkali adsorbent (d)>
As the alkali adsorbent (d) in the present invention, a synthetic resin adsorbent such as activated carbon or an ion exchange resin, an inorganic adsorbent such as zeolite, and the like can be suitably used depending on the base (e). Activated carbon is mostly carbonaceous charcoal and has high adsorptivity. Usually, it is powdery or granular, but either can be used.

  An ion exchange resin can be used as the synthetic resin-based adsorbent. As an ion exchange resin, you may use the general thing of a basic ion exchange resin. A chelate ion exchange resin may also be used.

Inorganic adsorbents generally have a solid acid and a solid base, and the particles have a porous structure, so the adsorbing ability is very high. Moreover, it can be used from low temperature to high temperature. The inorganic adsorbent is not particularly limited, and specifically includes, for example, a single or a combination of aluminum, magnesium, silicon and the like as main components. Specifically, for example, silicon dioxide, magnesium oxide, silica, alumina, silica alumina, diatomaceous earth, activated alumina, aluminum hydroxide, aluminum silicate, magnesium silicate, acid clay, activated clay, clay-based adsorbent, sodium aluminum silicate, etc. Examples thereof include zeolite adsorbents, dosonite compounds, hydrotalcite compounds, etc., which are collectively referred to as a hydrous aluminosilicate mineral group. There are natural and synthetic zeolites, and any of them may be used. Silicon dioxide includes crystalline, amorphous, amorphous, glassy, synthetic and natural products, but can be used in the present invention as long as it is in powder form. Examples of silicon dioxide include silicic acid made from clay minerals obtained by acid treatment of activated clay, synthetic silicic acid such as Carplex BS304, Carplex BS304F, Carplex # 67, Carplex # 80 (all of which are Shionogi Pharmaceutical). It is done. The aluminum silicate is obtained by replacing a part of silicon of silicic acid with aluminum, and specifically includes pumice, fly ash, kaolin, bentonite, activated clay, diatomaceous earth, and the like. Among these, synthetic aluminum silicate has a large specific surface area and high adsorption capacity. Examples of the synthetic aluminum silicate include KYOWARD 600 and 700 series (manufactured by Kyowa Chemical Industry Co., Ltd.). Hydrotalcite compounds are hydrated hydroxides of divalent metals (Mg, Mn, Fe, Co, Ni, Cu, Zn, etc.) and trivalent metals (Al, Fe, Cr, Co, In, etc.) Part of the hydroxyl group of the hydroxide is a negative ion such as halogen ion, NO ₃ ⁻ , CO ₃ ²⁻ , SO ₄ ²⁻ , Fe (CN) ₆ ³⁻ , CH ₃ CO ₂ ⁻ , oxalate ion, salicylate ion, etc. It was exchanged for ions. Among these, specific examples of the synthetic products include the Kyoto word 500 series, the Kyoto word 1000 series, and the Kyoto word 2000 series (all manufactured by Kyowa Chemical Co., Ltd.). Of these adsorbents, KYOWARD 600 and KYODWARD 700 are more preferable from the viewpoint of adsorbability of basic substances.
Although there is no restriction | limiting in particular as addition amount of an alkali adsorption agent (d), It is good to use in 0.0001 phr-50 phr with respect to 100 weight part of polyhedral structure polysiloxane reactant. Further, from the viewpoint of filterability, 0.1 phr to 30 phr is more preferable. If the addition amount is small, the adsorption capacity is lowered, so that the residual amount of the metal catalyst or base may be increased. If the addition amount is large, stirring may be difficult or removal by filtration may be difficult.

Hereinafter, the base (e) will be described.
The base (e) in the present invention is not particularly limited as long as it is a base containing two or more nitrogen atoms in one molecule. Bases containing two or more nitrogen atoms in one molecule include diamine compounds that can be represented by the following formula, triamine compounds that can be represented by the following formula, tetramine, pyrazine, pyrimidine, pyridazine, triazine, imidazole, benzimidazole, etc. And nitrogen-containing cyclic compounds exemplified in the above.

(Wherein R ³³ and R ³⁴ represent hydrogen or an organic group having 1 to 50 carbon atoms, and each of R ³³ and R ³⁴ may be different or the same. In the formula, x is 1 to 10) Indicates an integer up to.)
Among these, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrabutylethylenediamine, ethylenediamine, N, N, N ′, N′-tetramethylhexanediamine from the viewpoint of availability Hexanediamine, diethylenetriamine, 3,3′-diaminodipropylamine, bis (hexamethylene) triamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ″, Examples thereof include N ″ -tetrabutyldiethylenetriamine, N, N, N ″, N ″ -tetraisopropyldiethylenetriamine, and tetramine. From the viewpoint of adsorptivity to the adsorbent, N, N, N ′, N′-tetramethylethylenediamine, ethylenediamine, N, N, N ′, N′-tetramethylhexanediamine, hexanediamine, diethylenetriamine, bis (hexamethylene) ) Triamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, tetramine are more preferred.

  Although there is no restriction | limiting in particular as addition amount of a base (e), It is good to use in 0.1 to 10,000 times with respect to the addition mole number of the catalyst used at the time of polyhedral structure polysiloxane synthesis. Furthermore, 10 to 3000 times are preferable from the viewpoint of catalyst removal. If the addition amount is small, the adsorption capacity is lowered, so that the residual amount of the catalyst may be increased. If the addition amount is large, the base may not be completely removed and may adversely affect the subsequent process.

  Next, the treatment method using the alkali adsorbent (d) and the base (e) in the present invention will be described. In the method, the metal catalyst contained in the reaction solution can be effectively removed by mixing and contacting the alkali adsorbent (d) and the base (e) after synthesizing the polyhedral polysiloxane. The treatment method in the present invention may be carried out continuously after the synthesis of the polyhedral polysiloxane, or may be carried out after removing the solvent once and re-dissolving the reactant, and is not particularly limited. The order of addition of the alkali adsorbent (d) and the base (e) is not particularly limited, and the alkali adsorbent (d) and the base (e) may be added simultaneously, or the alkali adsorbent (d) may be added first. After the addition, the base (e) may be added. Further, the alkali adsorbent (d) may be added after the base (e) is added first.

  A method for treating a residue such as an adsorbent is not particularly limited, but a batch system, a continuous system using an adsorption tower, or the like can be preferably used. Specific examples of the batch system include a method in which an alkali adsorbent (d) and a base (e) are added to a solution after completion of the reaction, stirred and adsorbed, and then filtered. As the continuous type, specifically, for example, there is a method of pouring the solution after completion of the reaction into a column tower packed with an adsorbent. There is no limitation on the method of use in either a batch system or a continuous system using an adsorption tower. Specifically, for example, the polyhedral polysiloxane may be isolated and then dissolved in an organic solvent, and then the adsorbent treatment may be performed by the above-described method. Although it is not necessary to make it melt | dissolve in a solvent, when a viscosity is too high, you may dilute with an organic solvent according to a condition, and you may process. Furthermore, from the viewpoints of efficiency and productivity, it is preferable to add the alkali adsorbent (d) and the base (e) to the polyhedral polysiloxane solution in contact with the polyhedral polysiloxane solution after the reaction is completed.

  The temperature during the adsorbent treatment is not particularly specified, but is preferably 0 to 300 ° C, more preferably 10 to 200 ° C. If the temperature is too high or too low, the processing may be insufficient.

  After sufficiently mixing and contacting the adsorbent, the adsorbent can be easily removed by simple means such as filtration. The polyhedral polysiloxane after removal of the adsorbent may be used after the solvent is distilled off, or may be handled in a solution state.

  The amount of residual catalyst contained in the polyhedral polysiloxane after the above-described adsorption treatment is preferably 0.01 to 0.6 ppm from the viewpoint of coloring. Furthermore, from a viewpoint of long-term storage stability, it is desirable that it is 0.01-0.5 ppm. When the residual catalyst is large, the modified polyhedral polysiloxane and the composition thereof may be colored or thickened depending on the storage conditions and period.

Hereafter, the manufacturing method of (A) component is described.
The method for obtaining the modified polyhedral polysiloxane of the present invention is not particularly limited and can be variously set. However, the component (a) and the component (c) may be reacted in advance, and then the component (b) may be reacted. Then, after reacting the component (b) and the component (c) in advance, the component (a) may be reacted, or the component (a) and the component (b) coexist and reacted with the component (c). May be. After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of a compound containing only the component (b) and the component (c) and not including the component (a), the component (a) and the component (c) are reacted, and the unreacted (c) A method in which the component (b) is reacted after the component is distilled off is preferred. In the polyhedral polysiloxane modified product thus obtained, a part of the alkenyl group of the component (a) used for the reaction may remain.

The amount of component (c) may be added so that the number of hydrosilyl groups is 1 or more with respect to one alkenyl group of component (a), and further 2.5 to 20 is used. It is preferable. When the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the handleability of the modified polyhedral polysiloxane may be inferior, and when the addition amount is large, the physical properties of the cured product may be adversely affected.
Component (b) is preferably added so that the number of alkenyl groups is 0.01 to 0.5 with respect to one hydrosilyl group of component (c). When the addition amount is small, the thermal shock resistance of the resulting cured product may be lowered, and when the addition amount is large, a curing failure may occur in the resulting cured product.
Polyhedral polysiloxane is not particularly limited as amount of the hydrosilylation catalyst used during the synthesis of the modified product, used for the reaction (a) and component (b) component of the alkenyl group 1 mol per 10 ^-1 to 10 ^{- It} is good to use in the range of ¹⁰ mol. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  The polyhedral polysiloxane modified product thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and further, since hydrosilyl groups are introduced into the molecule, It becomes possible to make it react with the compound which has. Specifically, a cured product can be obtained by reacting with a polysiloxane having two or more alkenyl groups in one molecule described later.

The modified polyhedral polysiloxane in the present invention can be liquid at a temperature of 20 ° C. It is preferable that the polyhedral polysiloxane modified is in a liquid form because of excellent handling properties.

<(B) Compound having alkenyl group>
The component (B) in the present invention is a compound having an alkenyl group, preferably one containing at least two alkenyl groups in one molecule, a linear polysiloxane having an alkenyl group, and having an alkenyl group at the molecular end. Examples include polysiloxanes, cyclic siloxanes containing alkenyl groups, and isocyanuric acid derivatives having alkenyl groups. In the present invention, the compound having an alkenyl group is preferably a polysiloxane having an alkenyl group at the molecular terminal or an isocyanuric acid derivative having an alkenyl group from the viewpoint of the strength of the resulting cured product. The linear polysiloxane having an isocyanuric acid derivative having 2 or 3 alkenyl groups in one molecule is more preferable.

  Specific examples of the alkenyl group-containing polysiloxane having a linear structure include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Examples include copolymers, copolymers of methylphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having an alkenyl group at the molecular end include the polysiloxane whose end is blocked by the dimethylalkenyl group exemplified above, a dimethylalkenylsiloxane unit and a SiO ₂ unit, a SiO _3/2 unit, and a SiO unit. Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group.

  Examples of the cyclic siloxane compound containing an alkenyl group include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3. , 5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, , 3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9, Examples thereof include 11-hexamethylcyclosiloxane.

  Examples of isocyanuric acid derivatives containing alkenyl groups include triallyl isocyanurate, diallyl isocyanurate, monoallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl Examples include monoethyl isocyanurate, monoallyl diethyl isocyanurate, monoallyl monomethyl monoethyl isocyanurate and the like, from the viewpoint of heat resistance, light resistance, gas barrier properties, etc., triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, A preferred example is diallyl monoglycidyl isocyanurate. These compounds having an alkenyl group may be used alone or in combination of two or more.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

Although the addition amount of a hardening | curing agent can be set variously, it is the ratio which becomes 0.3-5 hydrogen atoms directly connected to the Si atom in (A) component per 1 alkenyl group, Preferably, it is 0.5-2. It is desirable to be.
If the ratio of the alkenyl group is too small, appearance defects due to foaming and the like are likely to occur, and if too large, the physical properties of the cured product may be adversely affected.

<(C) Hydrosilylation catalyst>
About the hydrosilylation catalyst which is (C) component of this invention, what is normally used as a hydrosilylation catalyst formation catalyst can be used, there is no restriction | limiting in particular, Arbitrary things can be used.

Specifically, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a support (alumina, silica, carbon black, etc.) supported on solid platinum; a platinum-vinylsiloxane complex {for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m }; platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ } (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m are integers. the represented), Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al Country Patent No. 3220972 No. platinum Arcola described in the specification - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

Although there is no restriction | limiting in particular as addition amount of a hydrosilylation catalyst, It is used in the range of 10 ^{< -1} > ^-10 < ^-10 > mol with respect to ¹ mol of alkenyl groups contained in the polysiloxane compound (a) in (A) component. Good. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas may be generated and the cured product may foam, so it is better not to use 10 ⁻¹ mol or more. When the hydrosilylation catalyst remains in the component (A) described above, the remaining hydrosilylation catalyst can be substituted as the component (C).

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC.

<(D) Adhesiveness imparting agent>
The component (D), the adhesion-imparting agent, is used for the purpose of improving the adhesion with the substrate of the composition of the present invention. An agent and an epoxy compound can be illustrated as a preferable thing.

  The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferable silane coupling agents are specifically 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 -Methacrylic groups such as acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, Alkoxysilanes having a drill group can be exemplified.

  The addition amount of the silane coupling agent is preferably 0.05 to 30% by weight, more preferably 0.1 to 10% by weight, based on the total weight of the component (A) and the component (B). If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl iso Cyanurate, mention may be made of diallyl monoglycidyl isocyanurate and the like.

  The addition amount of the epoxy compound can be variously set, but the lower limit of the preferable addition amount with respect to the total weight of the component (A) and the component (B) is 1% by weight, more preferably 3% by weight. The upper limit is 50% by weight, more preferably 25% by weight. If the addition amount is small, the effect of improving adhesiveness does not appear, and if the addition amount is large, the cured material properties may be adversely affected.

  Moreover, a silane coupling agent, an epoxy compound, etc. may be used independently and may be used together 2 types.

  In the present invention, a known adhesion promoter can be used to enhance the effect of the adhesion promoter. Examples of the adhesion promoter include, but are not limited to, boronic acid ester compounds, organoaluminum compounds, and organotitanium compounds.

<Composition>
The polysiloxane composition of the present invention comprises (A) a polyhedral polysiloxane, (B) a compound having an alkenyl group, (C) a hydrosilylation catalyst, and (D) an adhesion-imparting agent as essential components. The polysiloxane composition of the present invention can be made into a transparent liquid resin composition. By forming a liquid composition, it is possible to obtain a transparent film having excellent adhesion to the substrate by applying to the substrate and heating and curing, for example, various adhesives, coating agents, sealants Can be suitably used.
Moreover, this composition can also be obtained as a hardened | cured material by pouring into a molded object and heating.

  When adding temperature when making it harden | cure, Preferably it is 30-400 degreeC, More preferably, it is 40-250 degreeC. If the curing temperature is too high, the resulting cured product tends to have poor appearance, and if it is too low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.

  The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst used and the amount of hydrosilyl group, and other combinations of the composition of the present application. Is carried out for 10 minutes to 8 hours, a good cured product can be obtained.

  To the polysiloxane composition used in the present invention, in addition to the above essential components, fillers such as pulverized quartz, calcium carbonate, carbon and the like are added as an extender as necessary, as long as the effects of the present invention are not hindered. May be.

  In addition, various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, or a dispersant for a filler may be optionally added to the polysiloxane composition of the present invention as necessary. Can do.

  Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like.

In order to make the polysiloxane composition of the present invention flame-retardant and fire-resistant, known additives such as titanium dioxide, manganese carbonate, Fe ₂ O ₃ , ferrite, mica, glass fiber, glass flakes are added. May be. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  In the polysiloxane composition used in the present invention, the above-mentioned components are uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and subjected to heat treatment as necessary. Can be obtained.

  The polysiloxane composition of the present invention can be used as a molded article. As a molding method, any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding can be used.

  The molded product obtained from the polysiloxane composition according to the present invention is excellent in heat resistance and light resistance.

  The polysiloxane composition of the present invention can be used as a composition for optical materials. The optical material mentioned here refers to general materials used for the purpose of allowing light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material.

Specific uses of the composition and molded product obtained in the present invention include color filters, resist materials, substrate materials in the field of liquid crystal displays, passivation films, light guide plates, prism sheets, deflection plates, retardation plates, visual fields Examples include peripheral materials for liquid crystal display devices such as a liquid crystal film such as a corner correction film, an adhesive, and a polarizer protective film.
In addition, color PDP (plasma display) sealants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED element mold material used in the device, front glass protective film, front glass substitute material, adhesive, substrate material for plasma addressed liquid crystal (PALC) display, light guide plate, prism sheet, deflector plate, retardation plate, Viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various film substrates and front glass in field emission display (FED) Protective films, front glass substitute material, adhesives.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives.

  In the field of optical equipment, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

  In the field of optical components, fiber materials, lenses, waveguides, element sealants, adhesives and the like around optical switches in optical communication systems are exemplified. Examples include optical fiber materials, ferrules, sealants, adhesives and the like around the optical connector. Examples of optical passive components and optical circuit components include lenses, waveguides, LED element sealants, adhesives, and the like. Examples include substrate materials, fiber materials, element sealants, adhesives, and the like around an optoelectronic integrated circuit (OEIC).

  In the field of optical fibers, examples include sensors for industrial use such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in the home.

  Examples of the semiconductor integrated circuit peripheral material include resist materials for microlithography for LSI and VLSI materials.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Examples include rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, and glass substitutes. Moreover, the multilayer glass for rail vehicles is illustrated. Further, examples thereof include a toughness imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating.

  In the construction field, interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials are exemplified. In agriculture, a house covering film is exemplified.

  Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.

  Next, although the composition of this invention is demonstrated in detail based on an Example, this invention is not limited only to these Examples.

(SiH value)
The following SiH value is obtained by making a mixture of the compound and dibromoethane, dissolving in deuterated chloroform, and performing NMR measurement using 300 MHz NMR manufactured by Varian Technologies Japan Limited.
SiH value (mol / kg) = [integral value of peak attributed to SiH group of compound] / [integral value of peak attributed to methyl group of dibromoethane] × 4 × [weight of dibromoethane in mixture] / [Molecular weight of dibromoethane] / [weight of compound in mixture] (1)
Calculated using

(Measurement of platinum remaining amount)
With respect to the modified polyhedral polysiloxane shown in Production Example 2 described later and the modified polyhedral polysiloxane shown in Production Example 3, the residual amount of platinum was measured by IPC-MASS. The results are shown in Table 1.

(Curability test: gelation time)
One drop of a polyhedral polysiloxane composition blended as described below was dropped on a 150 ° C. hot plate, and the time (seconds) until gelation was measured while mixing. The results are shown in Table 1.

(Production Example 1)
To 1262 g of a 48% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), 1083 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1000 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  While vigorously stirring a solution of 537 g of dimethylvinylchlorosilane, 645 g of trimethylsilyl chloride and 1942 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, it is a polyhedral polysiloxane compound containing 16 Si atoms and an alkenyl group having 3 vinyl groups by washing the produced solid by vigorously stirring in methanol and filtering it off. 536 g of tris (vinyldimethylsiloxy) pentakis (trimethylsiloxy) octasilsesquioxane (Fw = 1166.2) was obtained as a white solid.

(Production Example 2)
25.0 g of tris (vinyldimethylsiloxy) pentakis (trimethylsiloxy) octasilsesquioxane, which is a polyhedral polysiloxane compound containing an alkenyl group obtained in Production Example 1, was dissolved in 37.5 g of toluene, and platinum was further added. 2.48 μL of a xylene solution of vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was dissolved. The solution thus obtained was treated with 25,54 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 38.12 g of diphenylmethylvinylsilane, 25.54 g of toluene. The solution was added dropwise over 3 hours, reacted at 105 ° C. for 3 hours, and cooled to room temperature.

  After completion of the reaction, 4.2 μl of ethynylcyclohexanol and 0.82 μl of dimethyl maleate were added, and toluene was distilled off to obtain 88.7 g of a liquid polyhedral polysiloxane modified product (SiH value 1.66 mmol / g). It was.

(Production Example 3)
After 10.00 g of the polyhedral polysiloxane modified product obtained in Production Example 2 is dissolved in 20 g of toluene, 0.002 g of N, N, N ′, N′-tetramethylethylenediamine is added and stirred at 40 ° C. for 30 minutes. , KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) 0.15 g was added, and the mixture was further stirred for 1 hour. After the reaction, the solid component was removed by filtration, and then the solvent was distilled off to obtain 10 g (SiH value 1.64 mmol / g) of a modified liquid polyhedral polysiloxane.

(Comparative Production Example 1)
10.00 g of the modified polyhedral polysiloxane obtained in Production Example 2 was dissolved in 20 g of toluene, and 0.002 g of N, N, N ′, N′-tetramethylethylenediamine was not added. Similarly, 10 g (SiH value 1.64 mmol / g) of a modified liquid polyhedral polysiloxane was obtained.

Example 1
To 8.20 g of the modified polyhedral polysiloxane of Production Example 3, 0.72 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, 1.08 g of diallylmethyl isocyanurate And stirred to prepare a polyhedral polysiloxane composition. Using the composition thus obtained and the modified polyhedral polysiloxane of Production Example 3 used, the various evaluations described above were performed, and the results are shown in Table 1.

(Comparative Example 1)
To 8.20 g of the modified polyhedral polysiloxane of Production Example 2, 0.72 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, 1.08 g of diallylmethyl isocyanurate And stirred to prepare a polyhedral polysiloxane composition. Using the composition thus obtained and the modified polyhedral polysiloxane of Production Example 2 used, the above-described various evaluations were performed, and the results are shown in Table 1.

(Comparative Example 2)
To 8.20 g of the modified polyhedral polysiloxane of Comparative Production Example 1, 0.72 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, diallylmethyl isocyanurate 1. 08 g was added and stirred to prepare a polyhedral polysiloxane composition. The gelation time of the composition thus obtained was measured, and the results are shown in Table 1.

As described above, the composition using the polyhedral polysiloxane modified body subjected to the adsorption treatment shown in Production Example 3 is compared with the composition using the untreated polyhedral polysiloxane modified body shown in Production Example 2, It is clear that the gel time is longer. Moreover, the gelation time of the composition using the polyhedral polysiloxane modified body treated only with the adsorbent shown in Production Comparative Example 1 was almost the same as that of the untreated Comparative Example 1. From these results, it is obvious that the combination of the adsorbent and the base has a catalyst removal effect. Further, from the analysis result of the residual amount of platinum by ICP-MS of the modified polyhedral polysiloxane, the adsorption treatment shown in Production Example 3 is performed. It can be seen that the platinum content of the modified polyhedral polysiloxane is reduced as compared with the untreated polyhedral polysiloxane shown in Production Example 2. From the above results, the polyhedral polysiloxane compound according to the present invention is excellent in long-term storage stability because the catalyst used in the synthesis can be reduced.

Claims (13)

A polyhedral polysiloxane reaction product obtained by hydrosilylating a polyhedral polysiloxane compound (a) containing an alkenyl group and a compound (c) having a hydrosilyl group is treated with an alkali adsorbent (d) and a base (e). A method for producing a modified polyhedral polysiloxane, comprising: Polyhedron obtained by hydrosilylation reaction of polyhedral polysiloxane compound (a) containing alkenyl group, compound (b) containing one carbon-carbon double bond in one molecule and compound (c) having hydrosilyl group The method for producing a modified polyhedral polysiloxane according to claim 1, wherein the structural polysiloxane reactant is treated with an alkali adsorbent (d) and a base (e). The method for producing a modified polyhedral polysiloxane according to any one of claims 1 to 2, wherein the alkali adsorbent (d) is an alkali inorganic adsorbent. The method for producing a modified polyhedral polysiloxane according to any one of claims 1 to 3, wherein the base (e) is a base containing two or more nitrogen atoms in one molecule. . The polyhedral polysiloxane compound (a) containing an alkenyl group has the formula [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
The method for producing a modified polyhedral polysiloxane according to any one of claims 1 to 4, which is an alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by formula (1). The method for producing a modified polyhedral polysiloxane according to any one of claims 1 to 5, wherein the modified polyhedral polysiloxane has at least three hydrosilyl groups in the molecule. The polyhedral polysiloxane modification is
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, or an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain And may be the same or different, provided that at least one of Y or Z is a hydrogen atom, and at least one is derived from the condensed ring compound (c) containing an alkenyl group. It has the structure of (3).
^{_{- [CH 2] l -R 5}} (3)
(L is an integer of 2 or more; radicals having R ⁵ are fused ring compounds); R is according to any one of claims 1 to 6, characterized in that the alkyl or aryl group) the structural unit A method for producing a modified polyhedral polysiloxane. The modified polyhedral polysiloxane according to any one of claims 1 to 7, wherein the compound (c) having a hydrosilyl group is a cyclic siloxane or a linear siloxane containing a hydrosilyl group. Production method. A polyhedral polysiloxane reaction product obtained by hydrosilylating a polyhedral polysiloxane compound (a) containing an alkenyl group and a compound (c) having a hydrosilyl group is treated with an alkali adsorbent (d) and a base (e). And the process of
A method for producing a polyhedral polysiloxane composition comprising a step of uniformly mixing the obtained polyhedral polysiloxane modified product (A) and a compound (B) having at least one alkenyl group. 2. The method for producing a modified polyhedral polysiloxane according to claim 1, wherein the modified polyhedral polysiloxane (A) is liquid at a temperature of 20 ° C. 3. The method for producing a polyhedral polysiloxane composition according to claim 9, wherein the compound (B) having an alkenyl group is a polysiloxane having at least two alkenyl groups in the molecule. The method for producing a polyhedral polysiloxane composition according to claim 9 or 11, comprising a curing retarder. 13. The method for producing a polyhedral polysiloxane composition according to any one of claims 9, 11 and 12, comprising an adhesiveness imparting agent .