JP2009298930A - Polysiloxane-based composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysiloxane-based composition excellent in heat resistance, light resistance, adhesiveness to substrates, and cohesiveness. <P>SOLUTION: The polysiloxane-based composition comprises a polyhedral structure polysiloxane obtained by modifying a polyhedral structure polysiloxane-based compound (a) containing alkenyl groups and/or hydrosilyl groups with a compound (b) having a hydrosilyl group and/or an alkenyl group and capable of hydrosilylation-reacting with the component (a), a curing agent, a hydrosilylation catalyst, and a polysiloxane having epoxy groups and hydrosilyl groups in the molecule. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a curable composition that maintains high transparency and is excellent in heat resistance, light resistance, adhesion to a substrate, and adhesion.

  Resin compositions containing polysiloxanes having a polyhedral skeleton are known. For example, a hydrosilylation curable composition of a functional group-containing polysiloxane having a polyhedral skeleton has been disclosed (for example, Non-Patent Document 1). In this technique, an example composed of a vinyl group-containing polysiloxane having a polyhedral skeleton and a hydrosilyl group-containing polysiloxane having a polyhedral skeleton is shown, and the material is excellent in heat resistance and light resistance, but is a rigid and extremely brittle material. Molding processability is poor and adhesion is low.

In addition, curable compositions using polysiloxanes having polyhedral skeletons containing epoxy groups (Patent Documents 1 and 2), and hybrid materials of polysiloxanes having a specific structure and linear polysiloxanes (patents) Although the disclosure of the material using the polysiloxane compound having a polyhedral skeleton such as Document 3) is seen, there is no example that maintains high transparency, has excellent heat resistance and light resistance, and has sufficient adhesiveness, The development of new materials has been desired.
J. et al. Am. Chem. Soc. 1998, 120, 8380-8391 Special table 2004-529984 JP 2004-359933 A JP 2006-22207 A

  Provided is a polysiloxane composition that maintains high transparency and is excellent in heat resistance, light resistance, adhesion to a substrate, and adhesion.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the component (a) and the hydrosilyl group have a polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group. A polyhedral polysiloxane obtained by modifying a compound having a hydrosilyl group and / or an alkenyl group capable of oxidization reaction, a curing agent, a hydrosilylation catalyst, an epoxy group in the molecule, and a polysiloxane containing a hydrosilyl group,
The present inventors have found that a polysiloxane composition comprising such components can solve the above-mentioned problems, and has reached the present invention.

  That is, the present invention has the following configuration.

1). (A) Compound (b) having a hydrosilyl group and / or an alkenyl group capable of undergoing a hydrosilylation reaction with the component (a) with respect to the polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group A polyhedral polysiloxane obtained by modifying
(B) a curing agent,
(C) a hydrosilylation catalyst,
(D) a polysiloxane containing an epoxy group and a hydrosilyl group in the molecule;
A polysiloxane composition comprising:

  2). The component (A) is a liquid at a temperature of 20 ° C., and the polysiloxane composition according to 1).

  3). The polysiloxane composition according to 1) or 2), wherein the compound (b) is a cyclic siloxane containing a hydrosilyl group and / or an alkenyl group.

  4). The polysiloxane composition according to 1) or 2), wherein the compound (b) is a linear siloxane containing an alkenyl group and / or a hydrosilyl group at the molecular end.

5). (A) component is
[XR ₂ SiO—SiO _3/2 ] _a [R ′ 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 is an alkyl group or an aryl group; R ′ is an alkyl group, an aryl group, or other polyhedral skeleton The group connected to the polysiloxane, X, has a structure represented by the following general formula (1) or general formula (2).

(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 Yes, they may be the same or different, provided that at least one of Y or Z is a hydrogen atom; and when there are a plurality of X, the structures of formula (1) or formula (2) are different. Or a structure of formula (1) or formula (2) may be mixed))) as a structural unit. Composition( Motomeko 5).

  6). (B) The polysiloxane composition according to any one of 1) to 5), wherein the component is a polysiloxane having a hydrosilyl group or an alkenyl group at the molecular end.

  7). The component (B) is a linear polysiloxane having a hydrosilyl group or an alkenyl group at both ends, and the polysiloxane composition according to any one of 1) to 6).

8). (D) component is
[SiO _4/2 ] _a [XR ₂ SiO _1/2 ] _b [YR ₂ SiO _1/2 ] _c [R ₃ SiO _1/2 ] _d
(A, b, c are integers of 1 or more, d is 0 or an integer of 1 or more; X is a hydrogen atom, Y is an organic group having an epoxy group, R is an organic group such as an alkyl group or an aryl group)
The polysiloxane composition according to any one of 1) to 7), which has the following composition:

9). (D) component is
[XSiO _3/2 ] _a [YSiO _3/2 ] _b [RSiO _3/2 ] _c
(A and b are integers of 1 or more, c is 0 or an integer of 1 or more; X is a hydrogen atom, a group having a hydrosilyl group, Y is a group having an epoxy group, R is an organic group such as an alkyl group, an aryl group, etc. is there)
The polysiloxane composition according to any one of 1) to 7), which has the following composition:

  10). (D) The polysiloxane composition according to any one of 1) to 9), wherein the component is a polyhedral polysiloxane.

  11). (D) The polysiloxane composition according to any one of 1) to 10), wherein the component is liquid at a temperature of 20 ° C.

  It is possible to provide a polysiloxane composition that maintains high transparency and is excellent in heat resistance, light resistance, adhesion to a substrate, and adhesion.

  The present invention is described in detail below.

<(A) Polyhedral polysiloxane>
In the present invention, the component (A) is a hydrosilyl group and / or alkenyl group capable of undergoing a hydrosilylation reaction with the component (a) with respect to the polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group. It is a polyhedral polysiloxane obtained by modifying the compound (b) having In the present invention, the polyhedral polysiloxane obtained does not gel during the synthesis of polysiloxane, and the resulting polyhedral polysiloxane can be made liquid at a temperature of 20 ° C. from the viewpoints of handling properties and moldability.

The preferred polyhedral polysiloxane in the present invention will be specifically described below.
A preferred polyhedral polysiloxane in the present invention is characterized by comprising a siloxane unit [XR ₂ SiO—SiO _3/2 ] as an essential unit, and if necessary, an arbitrary siloxane unit [R ' ₃ SiO-SiO _3/2 ] as a structural unit,
[XR ₂ SiO—SiO _3/2 ] _a [R ′ 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; X has a structure of either general formula (1) or general formula (2), and X is plural In some cases, the structure of general formula (1) or general formula (2) may be different and the structure of general formula (1) or general formula (2) may be mixed; R is an alkyl group or An aryl group; R ′ is an alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane)
A polyhedral polysiloxane composed of siloxane units represented by Here, on average, a is 1 or more, preferably 2 or more, and b is 0 or an integer of 1 or more. a + b is an integer of 6 to 24, preferably an integer of 6 to 12.

Below, siloxane units
[XR ₂ SiO-SiO _3/2 ]
Will be described.

The siloxane unit [XR ₂ SiO—SiO _3/2 ] is a unit that plays a role of generating or curing a crosslinking reaction with a curing agent by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later.

  Here, preferred X is not particularly limited as long as it is a group represented by any one of formulas (1) and (2), but m is preferably an integer of 1 to 7. , N is preferably an integer of 2-4.

(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 Yes, it may be the same or different, provided that at least one of Y or Z is an alkenyl group or a hydrogen atom; R is an alkyl group or an aryl group; 1) or the structure of formula (2) may be different, or the structure of formula (1) or formula (2) may be mixed)
The siloxane unit in the present invention preferably contains two or more siloxane units on average among all siloxane units constituting the polyhedral skeleton. That is, a in the general formula (1) is preferably 2 or more. When there are few siloxane units to contain, sclerosis | hardenability will become inadequate and there exists a possibility that the intensity | strength of the hardened | cured material obtained may fall.

Then any siloxane unit
_{[R '3 SiO-SiO 3/2} ]
Will be described.

The siloxane unit [R ′ ₃ SiO—SiO _3/2 ] is a unit for adjusting the physical properties of the polyhedral polysiloxane and the resulting cured product in the present invention. Since the present siloxane unit does not substantially contain a reactive substituent, it is possible to adjust the crosslinking density, improve the film property, leveling property, improve brittleness, and the like.

As R ′ in the siloxane unit, an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group connected to another polyhedral polysiloxane can be preferably used.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like. Furthermore, a part of the alkyl group may be replaced with a substituent that is not substantially reactive. Specific examples of the alkyl group partially substituted with a substituent having substantially no reactivity include, for example, a polysiloxanylalkyl group. Leveling properties and film properties, and a curing agent described later and Compatibility with a curing initiator can be imparted, and the properties of the compound can be made liquid.

<Method for producing modified polyhedral polysiloxane>
First, the polyhedral siloxane compound (a) will be described in detail.

Examples of the method for synthesizing the polyhedral siloxane compound (a) containing the alkenyl group and / or hydrosilyl group include R ¹ SiX ^a ₃ (wherein R ¹ represents an alkenyl group or a hydrogen atom, and X ^a represents , Which represents a hydrolyzable functional group such as a halogen atom or an alkoxy group).

Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolytic condensation reaction of R ¹ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds, and polyhedral Methods for synthesizing structural polysiloxanes are also known.

  As another method for synthesizing the polyhedral siloxane compound (a), for example, a tetraalkoxysilane such as tetraethoxysilane is replaced with a quaternary ammonium hydroxy such as trimethyl (2-hydroxyethyl) ammonium hydroxide or tetramethylammonium hydroxide. A silicate having a polyhedral structure is obtained by hydrolytic condensation reaction in the presence of a base such as a hydrogen atom, and the obtained silicate is further reacted with a silylating agent such as silyl chloride having an alkenyl group and / or a hydrosilyl group. Can be synthesized. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

As a preferable example of the polyhedral polysiloxane compound (a) in the present invention, specifically, for example, a polyhedral polysiloxane compound having an alkenyl group represented by the following formula:
[AR ² ₂ SiO—SiO _3/2 ] _a [R ³ 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 and / or a hydrogen atom provided that at least one is an alkenyl group;. R ² is An alkyl group or an aryl group; R ³ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) .

  When such a component (a) is used, by using a compound having a hydrosilyl group as the component (b), for example, to obtain a modified polyhedral polysiloxane by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later. Can do. At this time, all the alkenyl groups of the polyhedral siloxane compound (a) do not need to react and may partially remain. A plurality of polyhedral polysiloxane compounds (a) and a compound (b) having a plurality of hydrosilyl groups may react.

As other preferable examples of the polyhedral polysiloxane compound (a) in the present invention, specifically, for example,
[BR ² ₂ SiO—SiO _3/2 ] _a [R ³ 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; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. R ² is An alkyl group or an aryl group; R ³ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) .

  When such a component (a) is used, by using a compound having an alkenyl group as the component (b), for example, a modified polyhedral polysiloxane is obtained by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later. Can do. At this time, all the hydrogen atoms of the polyhedral siloxane-based compound (a) do not need to react and may partially remain. A plurality of polyhedral polysiloxane compounds (a) and a compound (b) having a plurality of hydrosilyl groups may react.

  Next, the compound (b) having a hydrosilyl group and / or an alkenyl group will be described.

  The compound having a hydrosilyl group has a hydrosilyl group (a hydrogen atom directly bonded to an Si atom) and reacts with the alkenyl group of the polyhedral siloxane compound (a) to form a new polyhedral polysiloxane molecule. It is a component for introducing a group having a reactive functional group.

  As a compound having a preferred hydrosilyl group in the present invention, specifically, for example, a compound having a hydrosilyl group (a hydrogen atom directly bonded to a Si atom) reacts with an alkenyl group of the polyhedral siloxane compound (a). And those that form X represented by any one of the general formula (1) and the general formula (2).

(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 Each of which may be the same or different, provided that at least one of Y or Z is a hydrogen atom; R is an alkyl group or an aryl group; The structure of formula (2) may be different, and the structure of formula (1) or formula (2) may be mixed)
Preferred examples of the compound having a hydrosilyl group include hydrosilyl group-containing siloxane compounds, specifically, for example, linear polysiloxanes having hydrosilyl groups at both ends, and cyclic siloxanes having hydrosilyl groups. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having hydrosilyl groups at both ends include poly or oligosiloxanes whose ends are blocked with dimethylhydrogensilyl groups, tetramethyldisiloxane, hexamethyltrisiloxane and the like. The

  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-trihydrogen- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydro Gen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen Examples include -1,3,5,7,9,11-hexamethylcyclosiloxane.

  The addition amount of the hydrosilyl group-containing siloxane compound is used so that the number of hydrogen atoms directly bonded to Si atoms is 2.5 to 20 per one alkenyl group of the polyhedral polysiloxane compound (a). Preferably, it depends on the compound. When the addition amount is small, gelation occurs due to a crosslinking reaction, resulting in a polysiloxane compound having poor handling properties. When the addition amount is too large, the physical properties of the cured product may be adversely affected. Furthermore, in order to allow an excessive amount of the hydrosilyl group-containing siloxane compound to exist, it is preferable to remove the unreacted hydrosilyl group-containing siloxane compound, for example, under reduced pressure and heating conditions.

  Other preferable compounds having hydrosilyl groups include hydrosilyl groups containing at least one reactive functional group selected from the group consisting of epoxy groups, hydrolyzable silyl groups, oxetanyl groups, (meth) acryloyl groups, and thiol groups. A compound can be illustrated.

  The amount of the hydrosilyl group-containing compound containing the reactive functional group is such that the number of hydrogen atoms directly bonded to Si atoms is 0.2 to 1.5 per one alkenyl group in the polyhedral siloxane intermediate. It is preferable to be used as such, but it depends on the compound. When the addition amount is small, the introduction rate of the reactive functional group is lowered, which may adversely affect the physical properties of the obtained cured product. Moreover, when there is too much addition amount, the hydrosilyl group containing compound containing an unreacted reactive functional group may remain, and it may have a bad influence on the physical property of hardened | cured material.

  The compound having an alkenyl group has an alkenyl group and reacts with the hydrosilyl group of the polyhedral siloxane compound (a) to introduce a new functional group into the polyhedral polysiloxane molecule. It is.

  Preferred examples of the compound having an alkenyl group include alkenyl group-containing siloxane compounds, specifically, for example, linear polysiloxanes having alkenyl groups at both ends, and cyclic siloxanes having alkenyl groups. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  The compound having an alkenyl group is a component for introducing a new functional group into the polyhedral polysiloxane molecule by reacting with the hydrosilyl group of the polyhedral polysiloxane compound (a).

  Preferred examples of the compound having an alkenyl group include alkenyl group-containing siloxane compounds, specifically, for example, linear polysiloxanes having alkenyl groups at both ends, and cyclic siloxanes having alkenyl groups. These compounds having an alkenyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having an alkenyl group at both ends include poly or oligosiloxane blocked with dimethylvinylsilyl groups, tetramethyldivinyldisiloxane, hexamethyldivinyltrisiloxane, etc. Is done.

  Examples of the cyclic siloxane containing an alkenyl group include 1,3,5,7-tetravinyl-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.

  The addition amount of the compound having an alkenyl group is preferably used so that the number of alkenyl groups is 2.5 to 20 per one hydrogen atom directly bonded to the Si atom of the polyhedral siloxane intermediate, but depends on the compound. . When the addition amount is small, gelation occurs due to a crosslinking reaction, resulting in a polysiloxane compound having poor handling properties. When the addition amount is too large, the physical properties of the cured product may be adversely affected.

  The addition amount of the alkenyl group-containing compound containing the reactive functional group is such that the number of hydrogen atoms directly bonded to Si atoms is 0.2 to 1.5 per one alkenyl group in the polyhedral siloxane intermediate. It is preferable to be used as such, but it depends on the compound. When the addition amount is small, the introduction rate of the reactive functional group is lowered, which may adversely affect the physical properties of the obtained cured product. Moreover, when there is too much addition amount, the alkenyl group containing compound containing an unreacted reactive functional group will remain, and it may have a bad influence on the physical property of hardened | cured material.

  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.

  The polyhedral polysiloxane compound of the present invention is preferably a liquid from the viewpoint of handling properties and the like when adjusting the cured product, and is preferably transparent from the viewpoint of the light transmittance of the molded body.

<(B) Curing agent>
The component (B) in the present invention is a compound having a hydrosilyl group or alkenyl group that can react with the polyhedral polysiloxane (A), and is a component that cures the polyhedral polysiloxane molecule.

  The compound having an alkenyl group preferably contains at least two alkenyl groups in one molecule, and contains a polysiloxane having a straight-chain structure having an alkenyl group, a polysiloxane having an alkenyl group at the molecular end, and an alkenyl group. Examples thereof include cyclic siloxane. In the present invention, the compound having an alkenyl group is preferably a polysiloxane having an alkenyl group at the molecular terminal from the viewpoint of the strength of the resulting cured product, and is a linear polysiloxane having an alkenyl group at both terminals. More preferably it is. These compounds having an alkenyl group may be used alone or in combination of two or more.

  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.

  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.

  The compound having a hydrosilyl group is not particularly limited as long as it is a compound having a hydrosilyl group, but preferably contains at least two hydrosilyl groups in one molecule. Siloxane compounds such as polysiloxane having a hydrosilyl group at the terminal and cyclic siloxane having a hydrosilyl group are particularly preferred. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of hydrosilyl group-containing polysiloxanes having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units. And a copolymer of a methylphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a polysiloxane having a terminal blocked with a dimethylhydrogensilyl group, and the like.

Specific examples of the polysiloxane having a hydrosilyl group at the molecular end include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups exemplified above, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units And a polysiloxane composed of at least one siloxane unit selected from the group consisting of SiO ₂ units, SiO _3/2 units, and SiO units.

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

Although the addition amount of the curing agent can be variously set, it is desirable that the amount of hydrogen atoms directly bonded to Si atoms is 0.3 to 5, preferably 0.5 to 2, per alkenyl group.
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) Polysiloxane containing epoxy group and hydrosilyl group in molecule>
The component (D) polysiloxane is used for the purpose of improving the adhesion to the substrate of the composition of the present invention, and is particularly a polysiloxane containing an epoxy group and a silyl group in the molecule. There is no limitation.

The polysiloxane containing an epoxy group and a hydrosilyl group in a preferred molecule in the present invention is a siloxane unit [XR ₂ SiO _1/2 ] having a hydrosilyl group, a siloxane unit [YR ₂ SiO _1/2 ] having an epoxy group, It is composed of tetrafunctional siloxane units [SiO _4/2 ] as essential units, and optionally contains siloxane units [R ₃ SiO _1/2 ] as physical property adjusting units as necessary. And the following formula:
[SiO _4/2 ] _a [XR ₂ SiO _1/2 ] _b [YR ₂ SiO _1/2 ] _c [R ₃ SiO _1/2 ] _d
(A, b, c are integers of 1 or more, d is 0 or an integer of 1 or more; X is a hydrogen atom, Y is an organic group having an epoxy group, R is an organic group such as an alkyl group or an aryl group)
The polysiloxane comprised from the siloxane unit represented by these is illustrated.

The siloxane unit [XR ₂ SiO _1/2 ] having a hydrosilyl group causes a crosslinking reaction with the polyhedral polysiloxane (A) or the curing agent (B) by the hydrosilylation reaction in the presence of the aforementioned hydrosilylation catalyst, or is cured. It is a unit that can play the role of bonding.

  The siloxane unit having a hydrosilyl group in the present invention preferably contains one or more of all siloxane units on average. That is, b is preferably 1 or more. When there are few siloxane units which have a hydrosilyl group to contain, there exists a possibility that hardening and adhesion may become inadequate.

Examples of Y in the siloxane unit [YR ₂ SiO _1/2 ] having an epoxy group include groups represented by the following general formula (3), 1 is an integer of 2 to 4, and an adhesive viewpoint with a substrate Therefore, Z can preferably use a group having an alicyclic epoxy group or a glycidyl group.

(L is an integer of 2 or more; Z is an organic group having at least one epoxy group)
The siloxane unit having an epoxy group in the present invention preferably contains one or more of all siloxane units on average. That is, c is preferably 1 or more. When there are few siloxane units which have an epoxy group to contain, there exists a possibility that adhesiveness may fall.

The tetrafunctional siloxane unit [SiO _4/2 ] is a unit for forming the main chain structure of the polysiloxane in the present invention, and preferably contains at least one of all siloxane units on average. That is, a is 1 or more, preferably 3 or more.

The arbitrary siloxane unit [R ₃ SiO _1/2 ] is a unit for adjusting the physical properties of the polysiloxane in the present invention. Since the present siloxane unit does not substantially contain a reactive substituent, it is possible to adjust the crosslinking density, improve the film property, leveling property, improve brittleness, and the like.

  R in the siloxane unit is not particularly limited as long as it is an organic group such as an alkyl group or an aryl group, and is preferably alkyl.

Other preferred examples of the polysiloxane containing molecule epoxy groups in and a hydrosilyl group, according to the present invention, siloxane units [XSiO _3/2] having a hydrosilyl group, siloxane units [YSiO _3/2] having an epoxy group The polysiloxane is characterized by being constituted as an essential unit, and contains an optional siloxane unit [RSiO _3/2 ] as a physical property adjusting unit as a constituent unit, if necessary.

As a preferable example of the polysiloxane, specifically, for example,
[XSiO _3/2 ] _a [YSiO _3/2 ] _b [RSiO _3/2 ] _c
(A and b are integers of 1 or more, c is 0 or an integer of 1 or more; X is a hydrogen atom, a group having a hydrosilyl group, Y is an organic group having an epoxy group, R is an organic group such as an alkyl group, an aryl group, etc. Is)
The siloxane unit [XSiO _3/2 ] having a hydrosilyl group generates a crosslinking reaction with the polyhedral polysiloxane (A) or the curing agent (B) by the hydrosilylation reaction in the presence of the hydrosilylation catalyst, or is cured. This unit is responsible for bonding.

  The siloxane unit having a hydrosilyl group in the present invention preferably contains one or more of all siloxane units on average. That is, a is preferably 1 or more. When there are few siloxane units which have a hydrosilyl group to contain, there exists a possibility that hardening and adhesion may become inadequate.

Examples of Y in the siloxane unit [YSiO _3/2 ] having an epoxy group include the group represented by the general formula (3).

  The siloxane unit having an epoxy group in the present invention preferably contains one or more of all siloxane units on average. That is, b is preferably 1 or more. When there are few siloxane units which have an epoxy group to contain, there exists a possibility that adhesiveness may fall.

The arbitrary siloxane unit [RSiO _3/2 ] is a unit for adjusting the physical properties of the polysiloxane in the present invention. Since the present siloxane unit does not substantially contain a reactive substituent, it is possible to adjust the crosslinking density, improve the film property, leveling property, improve brittleness, and the like.

  R in the siloxane unit is not particularly limited as long as it is an organic group such as an alkyl group or an aryl group, and is preferably alkyl.

  The polysiloxane containing an epoxy group and a silyl group in the molecule of the present invention is preferably a polyhedral polysiloxane in terms of compatibility and reactivity with the polyhedral polysiloxane (A) and the curing agent (B). It is also possible to give a cured product having high transparency.

As polyhedral polysiloxane, specifically, for example,
[SiO _4/2 ] _a [XR ₂ SiO _1/2 ] _b [YR ₂ SiO _1/2 ] _c [R ₃ SiO _1/2 ] _d
(A, b, c are integers of 1 or more, d is 0 or an integer of 1 or more; X is a hydrogen atom, Y is an organic group having an epoxy group, R is an organic group such as an alkyl group or an aryl group)
Polyhedral polysiloxane composed of siloxane units represented by Here, on average, a, b and c are 1 or more, preferably 2 or more, and d is 0 or an integer of 1 or more. a and b + c + d are an integer of 6 to 24, preferably an integer of 6 to 12.

As another preferable example of polyhedral polysiloxane, specifically, for example,
[XSiO _3/2 ] _a [YSiO _3/2 ] _b [RSiO _3/2 ] _c
(A and b are integers of 1 or more, c is 0 or an integer of 1 or more; X is a hydrogen atom, a group having a hydrosilyl group, Y is a group having an epoxy group, R is an organic group such as an alkyl group, an aryl group, etc. is there)
Polyhedral polysiloxane composed of siloxane units represented by Here, a, b, and c on average are preferably 1 or more, and preferably 2 or more. a + b + c is an integer of 6 to 24, preferably an integer of 6 to 12.

  Next, a method for producing a polyhedral polysiloxane containing an epoxy group and a silyl group in the molecule will be described.

  Examples of the method for synthesizing a polyhedral polysiloxane compound containing an epoxy group and a hydrosilyl group in the molecule include tetraalkoxysilane such as tetraethoxysilane, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetramethylammonium. A silicate having a polyhedral structure is obtained by hydrolysis condensation reaction in the presence of a base such as quaternary ammonium hydroxide such as hydroxide, and the resulting silicate is further converted into a silylating agent such as silyl chloride having a hydrosilyl group. In the presence of the above hydrosilylation catalyst and hydrosilylation with a compound having an alkenyl group and an epoxy group.

In the present invention, it is possible to obtain the same polyhedral polysiloxane from a substance containing silica such as silica or rice husk instead of tetraalkoxylane. The amount of polysiloxane added is (A) It is preferable that it is 0.05 to 30 weight% of the total weight of a component and (B) component, More preferably, it is 0.1 to 10 weight%. 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.

  The polysiloxane containing an epoxy group and a hydrosilyl group in the molecule of the present invention is preferably a liquid in terms of compatibility and handling properties, and is transparent in terms of light transmittance of a molded product obtained by curing. It is preferable that

<Composition>
The polysiloxane composition of the present invention essentially comprises (A) a polyhedral polysiloxane, (B) a cured product, (C) a hydrosilylation catalyst, (D) a polysiloxane containing an epoxy group and a hydrosilyl group in the molecule. Configured as an ingredient. 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 for organic EL (electroluminescence) display, front glass substitute material, adhesive, and various film substrates and front glass for 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.
(Adhesion test)
A polysiloxane composition (150 g / m ² ) is applied to one side of a glass chip (2 mm square), laminated on a glass epoxy plate (manufactured by Dazai Equipment Co., Ltd.), 3 hours at 60 ° C., 1 hour at 80 ° C., Heating was performed at 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. After cooling to room temperature, the bond strength between the glass chip and the glass epoxy plate was measured using a bond tester SERIES4000 (manufactured by Tage). The results are shown in Table 1.

(Heat resistance test)
In a hot air circulating oven set at 200 ° C., a 3 mm thick plate-shaped molded body is cured for 24 hours, and the appearance after curing is evaluated. When there is no change, ○, and when coloring is observed, ×. did.

(Light resistance test)
A metering weather meter (model M6T) manufactured by Suga Test Instruments Co., Ltd. was used. When the black panel temperature is 120 ° C, the irradiance is 0.53 kW / m ² , and the irradiated irradiance is 50 MJ / m ² , the appearance after irradiation is evaluated. X.

(Production Example 1)
A mixed solution of 1.12 g of allyl glycidyl ether, 0.55 μL of platinum vinylsiloxane complex (3% platinum, xylene solution), and 10 mL of methylcyclohexane is mixed with 2.00 g of octa (hydroxydimethylsiloxy) octasilsesquioxane and 10 mL of methylcyclohexane. The solution was added dropwise to the mixed solution, heated at 95 ° C. for 2 hours, and then cooled to room temperature. From the resulting reaction solution, methylcyclohexane and unreacted octa (hydroxydimethylsiloxy) octasilsesquioxane were distilled off to obtain 1.90 g of polysiloxane.

(Example 1)
A polysiloxane compound is added to 7.0 g of a polysiloxane compound, 11.69 g of a linear polydimethylsiloxane containing a vinyl group at the terminal (MVD8MV, manufactured by Clariant) and 0.58 g of the polysiloxane obtained in Production Example 1. I adjusted things. The obtained polysiloxane composition is poured into a mold and heated at 60 ° C. for 3 hours, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. And cured to obtain a molded product for evaluation having a thickness of 3 mm. The molded body thus obtained was subjected to a heat resistance test and a light resistance test. Moreover, the obtained composition was used for the adhesive test. The results are shown in Table 1.

(Comparative Example 1)
To 1.0 g of the polysiloxane compound obtained in Production Example 1, 1.65 g of linear polydimethylsiloxane (MVD8MV, manufactured by Clariant) containing a vinyl group at the terminal was added to prepare a polysiloxane composition. The obtained polysiloxane composition is poured into a mold and heated at 60 ° C. for 3 hours, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. And cured to obtain a molded product for evaluation having a thickness of 3 mm. The molded body thus obtained was subjected to a heat resistance test and a light resistance test. Moreover, the obtained composition was used for the adhesive test. The results are shown in Table 1.

As described above, the polyhedral polysiloxane compound of the present invention is excellent in heat resistance and light resistance, and excellent in adhesion to a substrate.

Claims (11)

(A) Compound (b) having a hydrosilyl group and / or an alkenyl group capable of undergoing a hydrosilylation reaction with the component (a) with respect to the polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group A polyhedral polysiloxane obtained by modifying
(B) a curing agent,
(C) a hydrosilylation catalyst,
(D) a polysiloxane containing an epoxy group and a hydrosilyl group in the molecule;
A polysiloxane composition comprising: The polysiloxane composition according to claim 1, wherein the component (A) is liquid at a temperature of 20 ° C. The polysiloxane composition according to claim 1 or 2, wherein the compound (b) is a cyclic siloxane containing a hydrosilyl group and / or an alkenyl group. The polysiloxane composition according to claim 1 or 2, wherein the compound (b) is a linear siloxane containing an alkenyl group and / or a hydrosilyl group at the molecular end. (A) component is
[XR ₂ SiO—SiO _3/2 ] _a [R ′ 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 is an alkyl group or an aryl group; R ′ is an alkyl group, an aryl group, or other polyhedral skeleton The group connected to the polysiloxane, X, has a structure represented by the following general formula (1) or general formula (2).
(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 Yes, they may be the same or different, provided that at least one of Y or Z is a hydrogen atom; and when there are a plurality of X, the structures of formula (1) or formula (2) are different. Or a structure of formula (1) or formula (2) may be mixed))) as a structural unit. Composition. The polysiloxane composition according to any one of claims 1 to 5, wherein the component (B) is a polysiloxane having a hydrosilyl group or an alkenyl group at the molecular end. The polysiloxane composition according to any one of claims 1 to 6, wherein the component (B) is a linear polysiloxane having hydrosilyl groups or alkenyl groups at both ends. (D) component is
[SiO _4/2 ] _a [XR ₂ SiO _1/2 ] _b [YR ₂ SiO _1/2 ] _c [R ₃ SiO _1/2 ] _d
(A, b, c are integers of 1 or more, d is 0 or an integer of 1 or more; X is a hydrogen atom, Y is an organic group having an epoxy group, R is an organic group such as an alkyl group or an aryl group)
The polysiloxane composition according to claim 1, wherein the polysiloxane composition has the following composition. (D) component is
[XSiO _3/2 ] _a [YSiO _3/2 ] _b [RSiO _3/2 ] _c
(A and b are integers of 1 or more, c is 0 or an integer of 1 or more; X is a hydrogen atom, a group having a hydrosilyl group, Y is a group having an epoxy group, R is an organic group such as an alkyl group, an aryl group, etc. is there)
The polysiloxane composition according to claim 1, wherein the polysiloxane composition has the following composition. (D) A component is polyhedral polysiloxane, The polysiloxane type composition of any one of Claims 1-9 characterized by the above-mentioned. The polysiloxane composition according to any one of claims 1 to 10, wherein the component (D) is liquid at a temperature of 20 ° C.