JPH0395267A - Organopolysiloxane composition - Google Patents

Abstract

PURPOSE:To obtain the title composition with a good long-term storage stability at room temperature by compounding a specified organopolysiloxane, a specified organohydrogenpolysiloxane, a platinum group metal catalyst, a specified amine, and an acetylenic alcohol. CONSTITUTION:The title composition comprises an organopolysiloxane wherein at least 0.05 mole % on average of the total organic groups bonded to the Si atoms are alkenyl groups, an organohydrogenpolysiloxane with two siloxy units of formula I (wherein R<1> is a hydrocarbon group other than an aliphatic unsaturated one) in its molecule, a platinum group metal catalyst, an amine selected from the compounds of formula II (wherein R<2> is 1-4C alkyl, R<3> is H or 1-4C alkyl, and R<4> is 2-4C alkylene) and formula III (wherein R<5> is 2-4C alkyl), and an acetylenic alcohol. This composition has a good stability even after being stored for a long time at room temperature and can be rapidly cured by heating.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an organoborisiloxane composition, and particularly to an organoborisiloxane composition having good long-term storage stability at room temperature.

[Prior Art] Conventionally, an organohydrogenpolysiloxane having a hydrogen atom (St-H) bonded to a silicon atom and an aliphatic unsaturated hydrocarbon group bonded to a silicon atom, for example, a vinyl group (St-H) have been used. A curable organopolysiloxane composition containing an organopolysiloxane having the following formula (Vi) and utilizing an addition reaction (hydrosilylation) of a 'l:St--H bond to a vinyl group, etc. is well known. Various reaction inhibitors are blended into such compounds to suppress the curing reaction at temperatures around room temperature to improve long-term storage stability, and at the time of use, heating accelerates the hydrosilylation reaction and cures. An organopolysiloxane A-type material that can be used has been proposed. For example, acetylene compounds (US Pat. No. 3,445,420) and sulfoxide compounds (US Pat. No. 3,45) are used as reaction inhibitors.
3,234) or an organoborisiloxane mtt blended with a hydroperoxide compound (US Pat. No. 4,061,609). However, organoborisiloxane 1 (I!) (R
' ) zsioo. When containing an organohydrodiene polysiloxane having an s unit (in the formula, the two R's are the same or different l-valent hydrocarbon groups), even if the above reaction inhibitor is added, this (H)(R'
)gsiO. ．． , Since hardening due to the hydrosilylation reaction between the hydrogen atoms of the unit and the aliphatic unsaturated hydrocarbon groups bonded to the silicon atoms at around room temperature cannot be effectively suppressed, the storage stability of organoborisiloxane & Il compounds is poor. It wasn't enough. On the other hand, as a reaction inhibitor, n- butylamine, N,N-
Dibutylanoprobilamine, N, N, N', N'
- It has been proposed to use an amine compound such as tetramethylethylenediamine.

(U.S. Patent Specification No. C58L361) [Problem to be Solved by the Invention] However, when the above amine compound is (H) (R') zs
ioo. Even when incorporated into an organoborisiloxane composition containing an organohydrodiene polysiloxane having s units, the resulting composition has poor long-term storage stability;
If an attempt is made to cure the material after storing it at room temperature for a long period of time, there are problems such as poor curing.

Therefore, the object of the present invention is to provide an organoborisiloxane m that has excellent long-term storage stability, does not cause curing failure even when stored at room temperature for a long period of time, and can be rapidly cured by heating. It consists in offering the precepts.

[Means to solve the problem]

In order to achieve the above object, the present inventors conducted extensive studies and found that the above problem could be solved by using an amine compound and acetylene alcohol together as a reaction inhibitor, thereby completing the present invention. That is, the present invention provides (A) an organoborisiloxane in which an average of 0.05 mol% or more of all organic groups bonded to silicon atoms contained in one molecule is an alkenyl group; (B) an organoborisiloxane of the formula (I ) Rl Maro H [In the formula, the two Rl's may be the same or different, and are substituted or non-N-substituted monovalent hydrocarbon groups that are not aliphatic unsaturated hydrocarbon groups]. an organohydrogenpolysiloxane containing at least two in one molecule, (C) a platinum group metal catalyst, (b) general formula (■): (R2)zN-R'-N(R')z (
It) [In the formula, the two R2s may be the same or different and are an alkyl group having up to 4 carbon atoms, the two R'' may be the same as Rz, and R4 is a hydrogen atom, and R4 is a carbon atom. is an alkylene group having 2 to 4 atoms] and general formula (■): R' Nu! (III)
[In the formula, R5 is an alkyl group having 2 to 4 carbon atoms] An organoborisiloxane composition containing at least one azen compound selected from the compounds represented by the following and (E) acetylene alcohol. It is something that provides something.

Organoborisiloxane, which is the component (A) of the composition of the present invention, has, for example, the following average composition formula (■): (r) - c
r) bsioj. PJL(rv) [wherein R1' is an alkenyl group, preferably an alkenyl group having 2 to 8 carbon atoms, such as vinyl group, allyl l, 1-butenyl l, t-hexenyl group, etc. R′? is a substituted or unsubstituted monovalent hydrocarbon group, or
R7 together form a lower alkylene group.

Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, probyl group, isoprobyl group, butyl group, and octyl group; cycloalkyl groups such as cyclobentyl group, cyclohexyl group, and cyclobutyl group; phenyl group; aryl groups such as tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl, phenylethyl, and phenylbrobyl groups; or a part or all of the hydrogen atoms bonded to these hydrocarbon groups. A group substituted with a halogen atom such as chlorine, fluorine, or bromine, or a cyano group,
For example, halogenated hydrocarbon groups such as chloromethyl group, trifluoroprobyl group, chlorophenyl group, dibromophenyl group, Te1-lachlorophenyl group, difluorophenyl group; β-cyanoethyl group, T-cyanoprobyl group,
Examples of the lower alkylene group formed from two R7s include ethylene group, trimethylene group, methylmethylene group, tetramethylene group, and hexamethylene group. Examples include groups.

In addition, a is a number of O<a<3, b is a number of O<b<3, provided that O<a+b<4], or a linear or branched organoborisiloxane, or It consists of a mixture of

The organoborisiloxanes represented by the average formula (TV) may be used alone or in combination of two or more.

This organoborisiloxane (A) is on average 0.05 mol% or more of all organic groups bonded to silicon atoms contained in one molecule, preferably 0.1 to 2 mol%.
is an alkenyl group. If the amount of alkenyl groups bonded to silicon atoms is less than 0.05 mol% on average of all organic groups bonded to silicon atoms in one molecule, the obtained composite material will not be cured sufficiently. There is a possibility that it will not become gel-like or elastomer-like. In addition, this alkenyl group may be bonded to either a silicon atom in the middle of the molecular chain or a silicon atom at the end of the molecular chain, but in terms of the curing speed of the resulting composite bottom, Preferably, they are bonded.

(A) The viscosity of the organoborisiloxane obtained by casting, botting, coating, impregnation, etc.
When used for adhesion, etc., it is usually 50 to 100,000 cP at 25 °C because it has appropriate fluidity before curing and exhibits stable physical properties after curing. It is preferable.

(A)rti. Specific examples of organoborisiloxanes include, for example, the following formula: (CH3StOs/x) p (5i-0) Ls 1 CH, 11 CI3 CHI (where 1Sms Q..P and q are each positive Indicating an integer), etc. are listed.

The organonohydrogenpolysiloxane which is the component (B) of the composition of the present invention contains at least two siloxy units represented by the above formula (I) in one molecule, for example, the following: Average group command formula (V): (II) c (R”) astOi+i(.V) [
In the formula, R1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms that is not an aliphatic unsaturated hydrocarbon group, or two R1s taken together form a lower alkylene group. For example, the same compounds as those exemplified for R7 in the above formula (IV) can be mentioned. C is a number of O<c≦2, d is a number of O<d≦3, provided that Q<c+d<4], and examples thereof include linear and branched ones.

In the present invention, (B
) organohydrogenpolysiloxanes may be used alone or in combination of two or more.

As a linear organohydrogenpolysiloxane for (B) tt, for example, the following general formula (■
): [In the formula, R3 is the same as above. Further, r is a positive integer, S is 0 or a positive integer].

(B) As a branching source of precepts, R'SiOazz
unit, Sing unit, Rll, etc.

(B) Bokimin's organohydrodiene polysiloxane has a viscosity of 1000 cP at 25°C for ease of synthesis.
The following are preferred.

The blending ratio of (B) boken in the &l1 precept of the present invention is based on the fact that the obtained cured product of the Mi precept has good physical properties such as heat resistance and mechanical strength, and does not foam during curing. usually,
(B) The number of hydrogen atoms bonded to silicon atoms contained in one molecule of the precept is 0.5 to 4.0 per alkenyl group possessed by the organopolysiloxane of the predetermined product (A), and The ratio is preferably 0.8 to 1.5.

The set of precepts of the present invention (C) 7i! Examples of platinum group metal catalysts include platinum, chloroplatinic acid, platinum-olefin complexes, platinum monoalcohol complexes, platinum coordination compounds, and the like.

The blending ratio of (C) a in the composition of the present invention is usually determined from the viewpoint that the resulting composition has good curability.
) 1 ppm or more, especially 3 to 100 ppm to the precepts
A ratio of .

The compound (D) of the composition of the present invention is
At least one compound selected from the compounds represented by formulas (n) and (II[) above. Formula (II) or (I[
In I), two R2 may be the same or different,
It is an alkyl group having 1 to 4 carbon atoms, two R3s may be the same or different, and R! is as defined above or a hydrogen atom, and R4 is an alkylene group having 2 to 4 carbon atoms.

As a specific example of the amine compound of the precept (D), for example, N,N,N'N'-tetramethylethylenediaξ
N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, N,N-dibutyl-1,3-propylenediamine
N,N-dimethyl-1,3-brobanediamine,
Examples include N,N,N',N'-tetraethylethylene diane, N,N-dibutyl-1,4-butane diane, and the like.

Among these, N,N,N',N'-tetramethylethylene diazine is preferred. The blending ratio of (D) 1 minute in the assembled sole of the present invention is (
C) Appropriately suppresses the catalytic action of the platinum group metal-based catalyst of Bokubun, and the resulting kumikaimono has good long-term stability, does not harden during storage, and has good curability during hardening. Usually, (C
) The ratio is preferably 1 mole or more, preferably 2 to 20 moles, per mole of platinum atoms in the platinum group metal catalyst.

Acetylene alcohol, which is the precept (E) of the composition of the present invention, is an unsaturated alcohol having an acetylene bond in the molecule, and examples include those described in U.S. Patent No. 3.445.420. It will be done.

Specific examples of this acetylene alcohol include 3-methyl-1-butyn-3-ol, 3-phenyl-1-butyn-3-ol, 1-ethynyl-1-hexanol, 3.
Examples include 5-dimethyl-1-hexyn-3-ol, 3-methyl-l-bentin-3-ol, and the like.

The blending ratio of (0) in a certain product of the present invention is usually determined from the viewpoint of curing speed, storage stability, etc. of the resulting composition, and the platinum content in the platinum group metal catalyst of (C) a certain product. The ratio is preferably 10 mol or more, particularly 50 mol or more per 1 mol of atoms.

The composition of the present invention has the above (^'), (B), (C
), (b) and (B) In addition to e, there are additional dimethylhydrogensiloxy units (CI!3) 2 (ll
) SiO. ．． ,, methylhydrogensiloxane unit (CH.) (H)Organovo 4J siloxane containing only one SiO in one molecule, and organohydrosiloxane that does not contain a siloxy unit represented by the formula (I) at the end of the molecule. Gembolysiloxane can also be blended as appropriate to an extent that does not impair the effects of the present invention.

In addition, the composite of the present invention may be blended with silicone oil such as dimethylborisiloxane or raw rubber in order to adjust or modify its flowability, the hardness of the cured product, etc. ．． Additionally, mechanical strength can be adjusted by adding an inorganic filler depending on the application. Inorganic fillers used include, for example, fumed silica, silica aerogel, precipitated silica, ground lime, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, alumina, aluminum nitride straw. Examples include carbon black, graphite, glassy carbon and the like. For coloring etc., various dyes such as anthraquinone dyes,
Azo dyes and the like can also be blended.

〔Example〕

Hereinafter, the present invention will be explained in detail by giving Examples and Comparative Examples. In the following, "parts" indicate "parts by weight."

Example 1 95 mol% dimethylsiloxane units, 0.7 mol% dimethylvinylsiloxy units, 1.
50 parts of an organoborisiloxane consisting of 3 mol% and 3 mol% of monomethylsiloxane units and having a viscosity of 1000 cP at 25°C, 9 dimethylsiloxane units.
4.5 mol%, 2.5 mol% of trimethylsiloxy units and 3 mol% of monomethylsiloxane units, 25
50 parts of an organoborisiloxane having a viscosity of 800 cP at C, a dimethylborisiloxane terminally capped with dimethylhydrodienesiloxy units and having a content of silicon-bonded hydrogen atoms of about 0.0681% by weight. 5. 5 parts chloroplatinic acid monovinylsiloxane complex (
Platinum content: ■wt%) 0.05 part, tetramethylethylenediamine 0.0012 part and 1-ethynyl-1
- 0.003 part of hexanol was mixed uniformly to obtain a combination.

The resulting composition was cured by heating at 150° C. for 60 minutes to obtain a transparent gel-like material. The penetration of this gel-like material was measured using a 1/4 scale needle size meter.

In addition, the curability of the composition immediately after blending at 120°C and the curability of the composite after being stored at room temperature for 6 months after blending were measured by the following methods, and the storage stability was evaluated. The results are shown in Table 1.

L-position rheovexi analyzer (manufactured by Iwamoto Seisakusho, RPX-7)
05) was used, the torque was measured under the conditions of temperature 120'C, swing angle 4°, frequency 0.1Hz, sweet time 30 minutes, and the torque after 30 minutes sweet time was taken as the maximum value (full torque). The time (T, .) from the start of curing until the torque reached 90% of the full torque was measured and used as an index of curability.

Further, after compounding, the curing properties (T9.') of the compositions were measured after being stored at room temperature for 6 months.

After the preparation and formulation, an increase in the viscosity of the composite proboscis was observed after storage at room temperature for 6 months.

Example 2 A composite was obtained in the same manner as in Example 1, except that the amount of 1-ethynyl-1-hexanol was changed to 0.03 parts. The penetration degree of the obtained group proboscis, &Il7i immediately after compounding! Curability of the composition at 120°C (T..) and cureability of the composition after compounding and storage at room temperature for 6 months (T,.')
were measured and storage stability was evaluated. The results are shown in Table 1. Example 3 A composite was obtained in the same manner as in Example 1, except that the amount of 1-ethynyl-1-hexanol was changed to 0.06 parts.

Needle size of the obtained composition, 120°C of the composition immediately after blending
The curability (T, .) of the composition was measured, and the curability (T, .') of the compound after being stored at room temperature for 6 months after blending was measured.
In addition, storage stability was evaluated. The results are shown in Table 1. Example 4 A composite material was obtained in the same manner as in Example 1, except that 0.02 part of 3-methyl-l-butyn-3-ol was used instead of (1)-ethynyl-1-hexanol.

The penetration degree of the obtained Kumikaimono, the hardening property (T,.) of the Kumikaimono at 120°C immediately after blending, and the hardening property of the Kumikaimono after being stored at room temperature for 6 months after blending (T,. q.′) was measured and storage stability was evaluated. The results are shown in Table I. Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that 1-ethynyl-1-hexanol was not used.

The needle size of the obtained kumikaimono, the curing property (T.,.) of the kumikaimono at 120°C immediately after blending, and the hardness of the kumikaimono at room temperature after blending.
After storage for several months, the curing properties (T..') of the U specimens were measured, and the storage stability was evaluated. The results are shown in Table 1.

Comparative Example 2 A composite product was obtained in the same manner as in Example 1, except that tetramethylethylenediamine was not used and the amount of l-ethynyl-1-hexanol was changed to 0.03 parts.

The penetration degree of the obtained proboscis, 120 of the Mi precept immediately after blending.
Curability (T,.) at ``C, and 6 at room temperature after compounding.
After storage for several months, the curing properties (T, .') of the composite materials were measured, and the storage stability was evaluated. The results are shown in Table 1.

〔Effect of the invention〕

The organoborisiloxane composition of the present invention has excellent long-term storage stability, exhibits good stability even when stored at room temperature for a long period of time, and can be rapidly cured by heating. It has great practical value.

Claims (1)

[Scope of Claims] (A) an organopolysiloxane in which an average of 0.05 mol% or more of all organic groups bonded to silicon atoms contained in one molecule are alkenyl groups; (B) an organopolysiloxane of the formula (I ): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, the two R^1s may be the same or different, and are substituted or unsubstituted monovalent groups that are not aliphatic unsaturated hydrocarbon groups. A hydrocarbon group] An organohydrodiene polysiloxane containing at least two siloxy units in one molecule, (C) a platinum group metal catalyst, (D) general formula (II): (R^ 2)_2N-R^4-N(R^3)_2(II) [
In the formula, two R^2 may be the same or different and are an alkyl group having 1 to 4 carbon atoms, two R^3 are the same as R^2 or a hydrogen atom, and R^ 4 is an alkylene group having 2 to 4 carbon atoms] and general formula (III): R^5-NH_2(III) [wherein R^5 is an alkyl group having 2 to 4 carbon atoms] An organopolysiloxane composition comprising at least one amine compound selected from the compounds shown below and (E) acetylene alcohol.