JP2017057386A - Condensation curable organopolysiloxane composition, condensation curable organopolysiloxane composition kit and silicone rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone rubber which is condensation-curable, having enhanced heat resistance of a siloxane chain while maintaining high reactivity of a side chain and excellent in heat resistance.SOLUTION: The invention relates to an organopolysiloxane composition capable of forming a condensation curable silicone rubber containing terminal silanol modified organopolysiloxane having weight average molecular weight (Mw) of 700 or more (A), a diphenylsilane-based crosslinking agent (B) of 1 pts.mass to 40 pts.mass based on 100 pts.mass of the terminal silanol modified organopolysiloxane (A), a silane-based crosslinking agent (C) of 0.2 pts.mass to 10 pts.mass based on 100 pts.mass of a mixture main agent of the terminal silanol modified organopolysiloxane (A) and the diphenylsilane-based crosslinking agent (B) and a condensation curing catalyst (D), a kit by dividing constitutional components of the composition into a plurality and a silicone rubber by curing the composition.SELECTED DRAWING: None

Description

  The present invention relates to a condensation-curable organopolysiloxane composition, a kit in which the components of the composition are divided into a plurality of parts, and a silicone rubber obtained by curing the composition.

  Silicone rubber is superior in heat resistance as compared with organic rubber having a siloxane bond (Si—O) as a skeleton and a C—C bond as a skeleton. For this reason, silicone rubber is used as an elastic material that can be used at high temperatures in various fields including the automobile industry, aviation industry, and medicine. The siloxane chain, which is the skeleton of the silicone rubber, is stable up to 200 ° C., but when the temperature exceeds 200 ° C., the hydrolysis reaction of the siloxane chain proceeds with moisture in the gas phase. Furthermore, it is known that the thermal oxidation reaction of the organic group in the side chain is caused by oxygen in the gas phase and the elasticity of the silicone rubber is lost (see Non-Patent Document 1). That is, it is considered that the factor that lowers the heat resistance of the silicone rubber is deterioration due to a thermal oxidation reaction of an organic factor (existing at a crosslinking point and a side chain) present in the inorganic network.

  Various technological developments have been made to improve the heat resistance of silicone rubber. For example, an organosilicon compound containing iron sesquioxide, an alkoxy group and an epoxy group is added to an addition reaction type organopolysiloxane composition. There is a known method (see Patent Document 1). In addition, as a countermeasure against thermal degradation of the side chain, a report that a phenyl group is introduced into the side chain to improve the heat resistance of the silicone rubber is also known (see Non-Patent Document 2).

Siska H, Claire L, Didier P, Jose'm, Francois G ELSEVIOR (2009) (465-495) N. GRASSIE & K. F. FRANCEY Polymer Degradation and stability 2 (1980) (53-66)

JP-A-11-106659

  Various methods for improving the heat resistance of the silicone rubber have been carried out as described above, but the present state has not yet been developed that can be used at a high temperature exceeding 200 ° C. Moreover, when a phenyl group is introduced into a part of the side chain, the heat resistance is certainly slightly improved, but as a compensation, it is difficult to increase the molecular weight due to the presence of the phenyl group.

  The present invention has been made in order to solve the above-described problems, and is a condensation-curing type silicone that improves the heat resistance of the siloxane chain while maintaining high side chain reactivity, and has excellent heat resistance. The object is to form rubber.

  As a result of diligent efforts to achieve the above object, the present inventors extended the polymer chain while introducing many phenyl groups into the siloxane chain, and then connected the linear inorganic polymer chains together to form a tertiary. By forming the original inorganic network, the present inventors succeeded in developing a condensation-curable organopolysiloxane composition having high heat resistance without reducing the polymerization, and reached the present invention. Specific problem solving means are as follows.

  One embodiment of the present invention is an organopolysiloxane composition capable of forming a condensation-curable silicone rubber, wherein the terminal silanol-modified organopolysiloxane (A) having a weight average molecular weight (Mw) of 700 or more, and a terminal silanol 1 to 40 parts by mass of a diphenylsilane-based crosslinking agent (B) with respect to 100 parts by mass of the modified organopolysiloxane (A) and at least one phenyl group in one molecule, and a terminal silanol-modified organo 0.2 to 10 parts by mass of a silane-based crosslinking agent (C) and a condensation curing catalyst (100 parts by mass) with respect to 100 parts by mass of the main component of the polysiloxane (A) and the diphenylsilane-based crosslinking agent (B). D) and a condensation-curable organopolysiloxane composition.

  In the condensation-curable organopolysiloxane composition according to another embodiment of the present invention, the terminal silanol-modified organopolysiloxane (A) may be both terminal silanol-modified polydimethylsiloxane.

  The condensation-curable organopolysiloxane composition according to another embodiment of the present invention may also include a monophenylsilane-based crosslinking agent in the silane-based crosslinking agent (C).

  In the condensation-curable organopolysiloxane composition according to another embodiment of the present invention, the silane-based crosslinking agent (C) may be 1 part by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the mixed main agent.

  The condensation-curable organopolysiloxane composition according to another embodiment of the present invention is 3 parts by mass or more and 20 parts by mass when the total amount of the mixing main agent and the silane-based crosslinking agent (C) is 100 parts by mass. The following metal phthalocyanine complex (E) may further be included.

  The condensation-curable organopolysiloxane composition according to another embodiment of the present invention may also contain at least one of cobalt phthalocyanine, iron phthalocyanine, copper phthalocyanine and derivatives thereof as the metal phthalocyanine complex (E). good.

  The condensation-curable organopolysiloxane composition according to another embodiment of the present invention may further include at least one of silica and calcium carbonate as a filler (F).

  One embodiment of the present invention is a kit in which components of an organopolysiloxane composition capable of forming a condensation-curable silicone rubber are divided into a plurality of components, and a terminal silanol-modified organo having a weight average molecular weight (Mw) of 700 or more. 1 part by mass or more and 40 parts by mass or less of a diphenylsilane-based crosslinking agent (B) with respect to 100 parts by mass of the polysiloxane (A), the terminal silanol-modified organopolysiloxane (A), and the terminal silanol-modified organopolysiloxane (A ) And a diphenylsilane-based cross-linking agent (B) and a cross-linking agent having at most one phenyl group in one molecule, and 0.2 parts by mass with respect to 100 parts by mass of the main mixing agent 10 parts by mass or less of the silane-based crosslinking agent (C), and the condensation curing catalyst (D) added simultaneously with or before the silane-based crosslinking agent (C). A condensation-curable organopolysiloxane composition kit comprising a.

  In the condensation-curable organopolysiloxane composition kit according to another embodiment of the present invention, the terminal silanol-modified organopolysiloxane (A) may be both terminal silanol-modified polydimethylsiloxane.

  The condensation-curable organopolysiloxane composition kit according to another embodiment of the present invention may also include a monophenylsilane-based crosslinking agent in the silane-based crosslinking agent (C).

  The condensation-curable organopolysiloxane composition kit according to another embodiment of the present invention may further include 1 part by mass or more and less than 5 parts by mass of the silane-based crosslinking agent (C) with respect to 100 parts by mass of the mixed main agent. .

  The condensation curable organopolysiloxane composition kit according to another embodiment of the present invention is also 3 parts by mass or more and 20 parts by mass when the total amount of the mixed main agent and the silane-based crosslinking agent (C) is 100 parts by mass. The metal phthalocyanine complex (E) may be further included in a part or less.

  The condensation-curable organopolysiloxane composition kit according to another embodiment of the present invention also includes at least one of cobalt phthalocyanine, iron phthalocyanine, copper phthalocyanine, and derivatives thereof as the metal phthalocyanine complex (E). But it ’s okay.

  The condensation-curable organopolysiloxane composition kit according to another embodiment of the present invention may further include at least one of silica and calcium carbonate as a filler (F).

  One embodiment of the present invention is a silicone rubber obtained by curing a component of any of the above-mentioned condensation-curable organopolysiloxane compositions or condensation-curable organopolysiloxane composition kits.

  According to the present invention, it is a condensation curable type, and it is possible to form a silicone rubber excellent in heat resistance by increasing the heat resistance of the siloxane chain while maintaining high reactivity of the side chain.

FIG. 1 shows the TG / DTA measurement results of Examples 1 and 2 and Comparative Example 1. FIG. 2 shows the TG / DTA measurement results of Examples 3 to 5. FIG. 3 shows the TG / DTA measurement results of Comparative Example 3, Examples 6 to 9, and Example 9-1. FIG. 4 shows the TG / DTA measurement results of Example 10 and Example 4 in which the weight loss with and without the metal phthalocyanine complex was compared. FIG. 5 shows the TG / DTA measurement results of Example 11 and Example 2 in which the weight loss due to the presence or absence of the metal phthalocyanine complex was compared. FIG. 6 shows TG / DTA measurement results of Examples 10, 11-1, 12 to 14 and Comparative Example 4 in which Mw of PDMS is 3000 and dimethoxydiphenylsilane is used as the crosslinking agent B-1. FIG. 7 shows TG / DTA measurement results of Examples 15 to 18 in which Mw of PDMS is 1000 and dichlorodiphenylsilane is used as the crosslinking agent B-1. FIG. 8 shows TG / DTA measurement results of Examples 11, 19, 20, 20-1, 20-2 and Comparative Example 6 in which Mw of PDMS is 3000 and dichlorodiphenylsilane is used as the crosslinking agent B-1. FIG. 9 shows TG / DTA measurement results of Examples 16, 21 to 25, 25-1, 25-2, 25, 3, 25-4 in which Mw of PDMS is 1000. FIG. 10 shows the TG / DTA measurement results of Examples 11 and 26 to 32 in which Mw of PDMS is 3000. FIG. 11 shows the TG / DTA measurement results of Examples 7, 12, and 33-36.

  Next, embodiments of the condensation curable organopolysiloxane composition according to the present invention, a kit in which the components of the composition are divided into a plurality of parts, and a silicone rubber obtained by curing the composition will be described. The embodiments described below do not limit the invention according to the claims, and all the elements and combinations thereof described in the embodiments are the means for solving the present invention. It is not always essential.

  The condensation curable organopolysiloxane composition according to an embodiment of the present invention is an organopolysiloxane composition capable of forming a condensation curable silicone rubber and has a weight average molecular weight (hereinafter referred to as “Mw”) of 700. 1 to 40 parts by mass of a diphenylsilane-based cross-linking agent (B) with respect to 100 parts by mass of the terminal silanol-modified organopolysiloxane (A) and the terminal silanol-modified organopolysiloxane (A), and 1 At least one phenyl group in the molecule and 0.2 to 10 parts by mass with respect to 100 parts by mass of the mixed main component of terminal silanol-modified organopolysiloxane (A) and diphenylsilane-based crosslinking agent (B) The following silane-based crosslinking agent (C) and a condensation curing catalyst (D) are included.

  In addition, the condensation curable organopolysiloxane composition kit according to the embodiment of the present invention is a kit in which the components of the organopolysiloxane composition capable of forming a condensation curable silicone rubber are divided into a plurality of components, and Mw is 700 or more terminal silanol-modified organopolysiloxane (A) and 1 to 40 parts by mass of a diphenylsilane-based crosslinking agent (B) with respect to 100 parts by mass of the terminal silanol-modified organopolysiloxane (A); A cross-linking agent having at most one phenyl group in one molecule, added to the main mixing agent of the terminal silanol-modified organopolysiloxane (A) and the diphenylsilane-based cross-linking agent (B), and 100 parts by mass of the main mixing agent 0.2 parts by mass or more and 10 parts by mass or less of the silane-based crosslinking agent (C) and the silane-based crosslinking agent (C) or Re containing a condensation cure catalyst (D) to be added before.

  In addition, the silicone rubber according to the embodiment of the present invention is obtained by curing the constituent components of any of the above-described condensation-curable organopolysiloxane compositions or condensation-curable organopolysiloxane composition kits.

  Hereinafter, the condensation curable organopolysiloxane composition, the condensation curable organopolysiloxane composition kit, and the silicone rubber will be described in detail.

I. Condensation-curable organopolysiloxane composition Terminal silanol-modified organopolysiloxane (A), diphenylsilane-based crosslinking agent (B), silane-based crosslinking agent (C) and condensation-curing contained in the condensation-curable organopolysiloxane composition The catalyst (D) is as follows.

(A) Terminal silanol-modified organopolysiloxane The terminal silanol-modified organopolysiloxane suitably used in this embodiment is a both-end silanol-modified organopolysiloxane represented by the following general formula (1) and the following general formula ( Any of the one-end silanol-modified organopolysiloxanes represented by 2) is included. In formula (1) and formula (2), R ¹ , R ² and R ³ are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a triorganosiloxy group. Or it is a cycloalkyl group. N is an integer of 2 or more. Specific examples of R ¹ , R ² and R ^{3 in} the above general formula include hydrogen, methyl group, ethyl group, cyclohexyl group, methoxy group, trimethylsiloxy group, methylene group, ethylene group and cyclopropyl group.

  As the terminal silanol-modified organopolysiloxane, both terminal silanol-modified organopolysiloxane is particularly preferable, and both terminal silanol-modified polydimethylsiloxane or both terminal silanol-modified polydiethylsiloxane is preferable. The most preferred terminal silanol-modified organopolysiloxane is a both-end silanol-modified polydimethylsiloxane.

  Further, the Mw of the terminal silanol-modified organopolysiloxane can be suitably used as long as it is 700 or more, preferably Mw is 800 or more, and more preferably Mw is 1000 or more. Moreover, if the upper limit of Mw is given, Mw is 50000 or less, Furthermore, 40000 or less, Furthermore, 30000 or less are preferable.

(B) Diphenylsilane-based cross-linking agent The diphenylsilane-based cross-linking agent preferably used in this embodiment has two phenyl groups bonded to a silicon element and is represented by the following general formula (3). It is a cross-linking agent. In formula (3), R ⁴ and R ⁵ are each independently hydrogen, a hydroxyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, a triorganosiloxy group, a cycloalkyl group, or a halogen group. It is. Specific examples of R ⁴ and R ^{5 in} the above general formula include hydrogen, hydroxyl group, methyl group, ethyl group, cyclohexyl group, methoxy group, trimethylsiloxy group, methylene group, ethylene group, cyclopropyl group, and chloro group. It is done.

  The amount of the diphenylsilane-based crosslinking agent is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the terminal silanol-modified organopolysiloxane. The amount of the diphenylsilane-based crosslinking agent may be 0.5 mol or more and 2 mol or less with respect to 1 mol of the terminal silanol-modified organopolysiloxane.

  Diphenylsilane-based crosslinking agents include dimethoxydiphenylsilane, diethoxydiphenylsilane, dipropoxydiphenylsilane, dimethyldiphenylsilane, diethyldiphenylsilane, dipropyldiphenylsilane, diphenylsilane, dihydroxydiphenylsilane, dichlorodiphenylsilane, and dibromodiphenylsilane. Etc. can be illustrated. Suitable diphenylsilane-based crosslinking agents include dimethoxydiphenylsilane and dichlorodiphenylsilane.

(C) Silane-based crosslinking agent The silane-based crosslinking agent preferably used in this embodiment has at most one phenyl group in one molecule, and when a phenyl group is present, the phenyl group is Bonds to silicon.

As the silane-based crosslinking agent, those having one phenyl group in one molecule (referred to as a monophenylsilane compound or a monophenylsilane-based crosslinking agent) can be used. The monophenylsilane-based crosslinking agent preferably used in this embodiment is represented by the following general formula (4). In formula (4), R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydroxyl group or a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, a triorganosiloxy group, a cycloalkyl group or It is a halogen group. Specific examples of R ⁴ and R ^{5 in} the above general formula include hydrogen, methyl group, ethyl group, cyclohexyl group, methoxy group, ethoxy group, trimethylsiloxy group, cyclopropyl group, and chloro group.

  As the silane-based crosslinking agent, alkylalkoxysilanes and alkoxysilanes can be suitably used. Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, trimethoxymethylsilane, trimethoxyethylsilane, triethoxymethylsilane, triethoxyethylsilane, trimethoxyisopropoxysilane, dimethoxydimethylsilane, dimethoxydiethylsilane , Methoxytrimethylsilane, methoxytriethylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltrimethylsilane, phenyltriethylsilane, phenyltripropylsilane, phenyldimethylethylsilane, Phenyldimethylpropylsilane, phenyldiethylmethylsilane, phenyldiethylpropylsilane, fluorine Nyldipropylmethylsilane, phenyldipropylethylsilane, phenyldimethoxymethylsilane, phenyldimethoxyethylsilane, phenyldimethoxypropylsilane, phenyldiethoxymethylsilane, phenyldiethoxyethylsilane, phenyldiethoxypropylsilane, phenyldipropoxymethylsilane Phenyldipropoxyethylsilane, phenyldipropoxypropylsilane, phenylmethoxytrimethylsilane, phenylmethoxytriethylsilane, phenylmethoxytripropylsilane, phenylethoxytrimethylsilane, phenylethoxytriethylsilane, phenylethoxytripropylsilane, phenylpropoxytrimethylsilane, Phenylpropoxytriethylsilane and phenylpropoxide Propyl silane can be suitably exemplified.

  Among these, in particular, phenyltrimethoxysilane or phenyltriethoxysilane, which is a monophenylsilane-based crosslinking agent, can be used more suitably.

  A suitable amount of the silane-based crosslinking agent is 1 part by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the mixed main component of the terminal silanol-modified organopolysiloxane and the diphenylsilane-based crosslinking agent.

(D) a condensation cure catalyst condensation cure catalyst is a silicone rubber capable of forming catalysts by radical polymerization of the Si-CH ₃ group, and is preferably an organic peroxide. Hereinafter, typical condensation curing catalysts will be exemplified.

(D.1) Organotin-based catalyst Examples of the organotin-based catalyst usable for the condensation curing catalyst include monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra-n-octyltin, and tetra-n. -Butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyltin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin Salt and silicate compounds, dioctyltin salt and silicate compounds, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylmalate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin Bi (Benzyl malate), dibutyltin bis (stearyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (o-phenylphenoxide), dibutyltin bis (2-ethylhexyl mercaptoacetate) , Dibutyltin bis (2-ethylhexyl mercaptopropionate), dibutyltin bis (isononyl-3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate) , Dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctate, dioctyltin didodecylmercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethylmalate), Octyl tin bis (octyl malate), dioctyl tin malate, dioctyl tin bis (isooctyl thioglycolate), dioctyl tin bis (2-ethylhexyl mercaptoacetate), dibutyl tin dimethoxide, dibutyl tin diethoxide, dibutyl tin dibutoxide, dioctyl tin dimethoxide , Dioctyltin diethyloxide, dioctyltin dibutoxide, tin octylate, tin stearate and the like.

(D.2) Metal chelating agent (1) Titanium chelate compound As the titanium chelate compound, titanium diethoxide bis (ethyl acetoacetate), titanium dieto bis (acetylacetonate), titanium diisopropoxide bis (ethylacetate) Acetate), titanium diisopropoxide bis (acetylacetonate), titanium isopropoxy (2-ethyl-1,3-hexanediolato), titanium diisopropoxybis (triethanolaminato), titanium dibutoxide bis (ethyl) Acetoacetate), titanium dibutoxide bis (acetylacetonate), titanium dibutoxybis (triethanolaminato), titanium oxobis (acetylacetonate), titanium hydroxybis ( Kutato), an ammonium salt of titanium hydroxy bis (lactato) titanium Vero Kiso ammonium citrate salts and the like.

(2) Zirconium chelate compound Examples of the zirconium chelate compound include triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, Tri-n-butoxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxymono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) Zirconium, di-n-propoxy bis (acetylacetonato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonate) Zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxy tris (acetyl) Acetonato) zirconium, mono-i-propoxy-tris (acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t -Butoxy-tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxy-mono (ethylacetoacetate) zirconium, tri-n-propoxy-mono (ethyla) Toacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) zirconium, tri-n-butoxymono (ethylacetoacetate) zirconium, tri-sec-butoxymono (ethylacetoacetate) zirconium, tri-t -Butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di -N-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, Noethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) Zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, mono (acetylacetonato) tris (ethyl acetoacetate) Zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium, etc. Can be illustrated.

(3) Aluminum chelate Aluminum chelate compounds include diisopropoxy (acetyl acetate) aluminum, di-n-butoxy (acetyl acetate) aluminum, tris (acetyl acetate) aluminum, tris (ethyl acetoacetate) aluminum, diisopropoxy ( Examples thereof include ethyl acetoacetate) aluminum, di-n-butoxy (ethylacetoacetate) aluminum, and n-butoxybis (ethylacetoacetate) aluminum.

  The range of addition amount of the condensation curing catalyst is not particularly limited as long as it is necessary for obtaining the condensation curable silicone rubber, but preferably a mixed main component of a terminal silanol-modified organopolysiloxane and a diphenylsilane-based crosslinking agent. It is 0.5 mass part or more and 5 mass parts or less with respect to 100 mass parts, More preferably, it is 1 mass part or more and 3 mass parts or less with respect to 100 mass parts of this mixing main ingredient.

(4) Others The metal chelating agent may be formed by adding a metal alkoxide such as titanium alkoxide, zirconium alkoxide or aluminum alkoxide and a ligand. The “ligand” in the present specification refers to a compound capable of coordinating to a metal of a metal alkoxide.

(E) Metal phthalocyanine complex In addition to the above (A), (B), (C) and (D), when a metal phthalocyanine complex is added, the heat resistance of the silicone rubber is higher, specifically, it can withstand 300 ° C. Can be done. The metal phthalocyanine complex suitably used in this embodiment is represented by the following general formula (5), and is broadly interpreted to include derivatives thereof in addition to metal phthalocyanine. A metal phthalocyanine complex has a structure in which a metal is coordinated to the center of a phthalocyanine ring. In the formula (5), M means a metal element, preferably from the group consisting of Cu, Fe, Co, Mn, Ni, Cr, Zn, Pb, Ti, Pt, Pd, Ru, Ce and V. One or more metals selected. In the formula (5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are preferably groups such as hydrogen, halogen group, hydroxyl group, alkyl group, nitro group, amino group, sulfonic acid group, carboxy group, alkoxy group, and the like. It is a group that may or may not have a substituent. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are all The same case, all different cases, or some overlapping cases may be used.

The metal phthalocyanine complex is preferably one or two of copper phthalocyanine, cobalt phthalocyanine, iron phthalocyanine and their derivatives represented by phthalocyanine blue and phthalocyanine green (chlorinated copper phthalocyanine, brominated copper phthalocyanine). The combination of the above can be mentioned. As specific cobalt phthalocyanine, iron phthalocyanine, copper phthalocyanine and derivatives thereof, M is a metal selected from iron, cobalt and iron, and when R ⁿ (n = 1 to 16), R is the same Or the phthalocyanine derivative shown by a different carboxy group, a sulfonic acid group, or an amino group is mentioned, It is more preferable that n is 1-8. In particular, phthalocyanine blue, phthalocyanine copper (II) (α-type), phthalocyanine copper (II) (β-type), phthalocyanine iron (II), phthalocyanine cobalt (II), cobalt phthalocyanine amine derivatives, iron phthalocyanine tetracarboxylic And one or a combination of two or more of acid, cobalt phthalocyanine monosulfonic acid, copper phthalocyanine monosulfonic acid, and iron phthalocyanine monosulfonic acid, and more preferably copper phthalocyanine (phthalocyanine blue, phthalocyanine green) , Phthalocyanine copper (II) (α-type), phthalocyanine copper (II) (β-type), copper phthalocyanine derivatives), cobalt phthalocyanine amine derivatives, and cobalt phthalocyanine monosulfide At least one of phosphate and the like.

  A suitable amount of the metal phthalocyanine complex is 3 masses when the total amount of the terminal silanol-modified organopolysiloxane (A), the diphenylsilane-based crosslinking agent (B), and the silane-based crosslinking agent (C) is 100 parts by mass. Part to 20 parts by mass, and a more suitable amount is 3 parts by mass to 15 parts by mass with respect to the total amount of 100 parts by mass. More than 15 parts by mass.

(F) Filler Optional fillers include inorganic oxides such as silica, titanium oxide, alumina and zirconia, carbonates such as calcium carbonate and magnesium carbonate, and barium sulfate. Or a fibrous filler can be illustrated. In particular, silica having a small particle size and good compatibility with the curable silicone rubber composition is preferable. The content of the filler is preferably 2 parts by mass or more and 99 parts by mass or less in 100 parts by mass of the condensation curable organopolysiloxane composition including the filler. Specific examples of the filler include fillers mainly added for the purpose of causing cross-linking and increasing the strength, for example, silica such as hydrophobic fumed silica, carbon black, and the like. The filler is preferably 2 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the condensation curable organopolysiloxane composition including the filler. Further, as a filler added mainly for the purpose of increasing the bulk, calcium carbonate without surface treatment can be mentioned, and as a filler added mainly for the purpose of increasing the strength and increasing the bulk, surface treatment was performed with a fatty acid or the like. An example is calcium carbonate. The filler is preferably 5 parts by mass or more and 30 parts by mass or less in 100 parts by mass of the condensation curable organopolysiloxane composition including the filler.

(G) Light Stabilizer A light stabilizer may be added to the condensation-curable organopolysiloxane composition according to this embodiment. The light stabilizer is effective for improving the weather resistance or providing thermal stability of the silicone rubber. As a light stabilizer, it can use without a restriction | limiting especially, A hindered amine type thing can be used suitably especially. Examples of hindered amine light stabilizers include dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1 , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2, 2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2,2,6,6-pentame Til-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl Malonate, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) Amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl) Examples include polycondensates of -4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, etc. Silanol-modified organopolysiloxane 1 It is 0.1 to 7 parts by mass, preferably 0.5 to 5 parts by mass, and more preferably 1 to 3 parts by mass with respect to 00 parts by mass.

(H) Ultraviolet absorber An ultraviolet absorber may be added to the condensation-curable organopolysiloxane composition according to this embodiment. The ultraviolet absorber has a function of absorbing ultraviolet rays and is effective in improving the weather resistance of the resin or imparting thermal stability. As an ultraviolet absorber, it can use without a restriction | limiting especially, For example, a benzotriazole type, a salicylic acid type, a benzophenone type, a cyanoacrylate type, and a triazine type can be used conveniently. Of these, benzophenone-based ultraviolet absorbers can be particularly preferably used.

  Examples of the benzotriazole series include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy- 5′-octylphenyl) -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- {2'-hydroxy-3 '-(3 ", 4", 5 ", 6 -Tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, 2,2-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol} Can be illustrated. Examples of the salicylic acid type include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate. The benzophenone series includes 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4- Examples include methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and bis (2-methoxy-4-hydroxy-5-benzophenone) methane. Examples of cyanoacrylates include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate. The triazine series includes 2- {4 ′, 6′-bis (2 ″, 4 ″ -dimethylphenyl) -1 ′, 3 ′, 5′-triazine-2′-yl} -5- (octyloxy) phenol. 2- (4 ′, 6′-diphenyl-1 ′, 3 ′, 5′-triazin-2′-yl) -5- (hexyloxy) phenol. The amount of the ultraviolet absorber is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass or less, more preferably 100 parts by mass of the terminal silanol-modified organopolysiloxane. 0.5 parts by mass or more and 2 parts by mass or less.

(I) Plasticizer A plasticizer may be added to the condensation-curable organopolysiloxane composition according to this embodiment. A plasticizer imparts flexibility to the material and helps to mix and disperse the formulation. Examples of the plasticizer include phthalate esters such as dioctyl phthalate and diisononyl phthalate, adipate esters such as dioctyl adipate and diisononyl adipate, trimellitic acid ester, and pyromellitic acid citrate ester. The amount of the plasticizer is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 2 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the terminal silanol-modified organopolysiloxane.

II. Condensation-curable organopolysiloxane composition kit The condensation-curable organopolysiloxane composition kit according to this embodiment is obtained by dividing the components constituting the condensation-curable organopolysiloxane composition into a plurality of components. Specifically, terminal silanol-modified organopolysiloxane (A), diphenylsilane-based crosslinking agent (B), silane-based crosslinking agent (C), condensation curing catalyst (D), and preferably a metal phthalocyanine complex (E) is separately sealed in a container, or (A), (B), (C), (D), preferably including (E), two or more of them are mixed. It is sealed in a container. However, the silane-based crosslinking agent (C) and the condensation curing catalyst (D) are preferably sealed separately from the terminal silanol-modified organopolysiloxane (A) and the diphenylsilane-based crosslinking agent (B). The composition kit may contain a filler, a light stabilizer, an ultraviolet absorber, or a plasticizer. The terminal silanol-modified organopolysiloxane (A) is preferably sealed in a separate container from the diphenylsilane-based crosslinking agent (B). The kit includes the above (A), (B), (C), (D), preferably (E), and more preferably a filler (F), a light stabilizer ( G), including one or more of the ultraviolet absorber (H) or the plasticizer (I), may be added separately or mixed with two or more, but the moisture and air are shut off and sealed. It is preferable.

III. Silicone rubber The silicone rubber according to this embodiment is obtained by curing a condensation curable organopolysiloxane composition (may be referred to as a component of a condensation curable organopolysiloxane composition kit). As the curing method, at least the terminal silanol-modified organopolysiloxane (A), the diphenylsilane-based crosslinking agent (B), the silane-based crosslinking agent (C), and the condensation curing catalyst (D) are mixed, A preferred method is heating. In addition to (A), (B), (C) and (D), a metal phthalocyanine complex (E) is added, and a filler (F), a light stabilizer (G), and an ultraviolet absorber (H). Alternatively, one or more of the plasticizers (I) may be added. Silicone rubber includes (A), (B), (C), (D) and preferably (E), and further includes a filler (F), a light stabilizer (G), an ultraviolet absorber (H ) Or a mixture obtained by adding one or more of the plasticizers (I) to water and / or oxygen. A more preferable process for producing silicone rubber is as follows. In the following steps, one or more of filler (F), light stabilizer (G), ultraviolet absorber (H) and plasticizer (I) are omitted.

  The terminal silanol-modified organopolysiloxane (A) and the diphenylsilane-based crosslinking agent (B) are mixed (stirred) (first step). Subsequently, the condensation curing catalyst (D) is mixed with the mixture obtained in the first step (second step). Thereby, a phenyl group can be introduced into the siloxane chain. Next, the silane-based crosslinking agent (C) is mixed in the mixture obtained in the second step (third step). Thereby, a three-dimensional inorganic network can be constructed. Next, preferably a metal phthalocyanine complex (E) is added (fourth step). Next, preferably, defoaming treatment is performed (fifth step). Finally, heating is performed at 150 to 300 ° C. (sixth step). This completes the production of silicone rubber. In addition, a 2nd process and a 3rd process may be performed simultaneously, and the order of a 3rd process and a 4th process may be replaced. Further, the fifth step is not necessarily required. In addition, a filler (F) may be added simultaneously with a metal phthalocyanine complex (E), and may be added at another process.

  Examples of the present invention will be described below. However, the present invention is not limited to the following examples.

I. Materials used (1) Silanol-modified polydimethylsiloxane at both ends (abbreviated as “PDMS”)
(1.1) X-21-5841 (Mw = 1000): manufactured by Shin-Etsu Chemical Co., Ltd. (1.2) KF-9701 (Mw = 3000): manufactured by Shin-Etsu Chemical Co., Ltd. (1.3) DMS -S12 (Mw = 400-700)): Gelest Co., Ltd. (1.4) DMS-S21 (Mw = 4200): Gelest Co., Ltd. (1.5) DMS-S27 (Mw = 18000): Gelest (1.6) DMS-S31 (Mw = 26000): Gelest Co., Ltd. (2) Crosslinking agent (2.1) Phenyltrimethoxysilane (abbreviation PhTMS): Tokyo Chemical Industry Co., Ltd. ( 2.2) Dimethoxydiphenylsilane (abbreviation DMDPhS): Tokyo Chemical Industry Co., Ltd. (2.3) Dichlorodiphenylsilane (abbreviation DChDPhS): Tokyo Chemical Industry Co., Ltd. (3) Catalyst (3) 1) Aluminum-s-butoxide (abbreviation: ALsB): Wako Pure Chemical Industries, Ltd. (3.2) Dibutyl tartrate (abbreviation: DBT): Tokyo Chemical Industry Co., Ltd. (3.3) Dibutyltin dilaurate (abbreviation) (DBTDL): Gelest Co., Ltd. (4) Metal phthalocyanine complex (4.1) Phthalocyanine blue (abbreviation PhCB): Wako Pure Chemical Industries, Ltd. (4.2) Cobalt phthalocyanine amine derivative ("a" in the examples) ): Daiwabo Noi Co., Ltd. (4.3) Iron phthalocyanine tetracarboxylic acid (referred to as “b” in the examples): Daiwabo Noi Co., Ltd. (4.4) Cobalt phthalocyanine monosulphonic acid (Implementation) (In the example, “c”): manufactured by Daiwabo Neu Co., Ltd. (4.5) Copper phthalocyanine monosulfonic acid (referred to as “d” in the examples): Dai (4.6) Iron phthalocyanine monosulfonic acid (referred to as “e” in the examples): Daiwabo Neu (4.7) phthalocyanine copper (II) (α-type) (Example) (Referred to as “f”): manufactured by Tokyo Chemical Industry Co., Ltd. (4.8) phthalocyanine copper (II) (β-type) (referred to as “g” in the examples): manufactured by Tokyo Chemical Industry Co., Ltd. (4) .9) Phthalocyanine iron (II) (referred to as “h” in the examples): manufactured by Tokyo Chemical Industry Co., Ltd. (4.10) Phthalocyanine cobalt (II) (referred to as “i” in the examples): Tokyo Chemical Industry (5) Filler (5.1) Dry Fumed Silica (RX50): Made by Nippon Aerosil Co., Ltd. (5.2) Calcium Carbonate (Shiraka Hana CCR): Shiraishi Kogyo Co., Ltd.

II. Evaluation method (1) Molecular weight (Mw)
The molecular weight of PDMS or the like was measured using a molecular weight measuring device (HLC-8220GPC) manufactured by Tosoh Corporation.
(2) Weight reduction rate As one of the heat resistance evaluation of the synthetic rubber, the weight reduction rate accompanying the temperature increase from room temperature to 400 ° C was evaluated. The weight reduction rate was quantified by TG / DTA measurement using Thermo Plus TG8120 manufactured by Rigaku Corporation.
(3) Rubber properties As rubber properties of the synthetic rubber, hardness, elongation at break (%) and strength at break (MPa) were evaluated. These evaluations were performed after being placed in an environment maintained at a predetermined temperature within a range of 250 to 300 ° C. for 72 hours in addition to room temperature. Hardness was evaluated using GS-754G type-OO manufactured by Teclock Co., Ltd. based on the durometer ASTM type (D2240). The elongation at break and strength at break were determined by measuring the elongation when the synthetic rubber was dumbbell-shaped No. 6 with a width of 4.0 mm, a thickness of 1.5 mm, and a parallel part length of 20 mm, and both ends were pulled in the opposite direction. The degree and strength were calculated from the following formula and evaluated. A tensile tester (RTC-1250A) manufactured by A & D Co., Ltd. was used as the tensile tester.
Elongation at break (%) = 100 × (length of test piece at break−length of original test piece) / length of original test piece Break strength at break (MPa) = test force at break (N ) / Cross-sectional area of test piece (mm ² )
In the heat resistance test evaluated after holding at 250 ° C. or 300 ° C. for 72 hours, the initial shape is maintained and there is no discoloration, shrinkage, bending, etc., and mechanical measurement is possible; Return to the original shape without cracks, cracks, etc .; Pass / fail was judged on the basis of extending 100% (twice) or more.

III. Experiment / Evaluation Results (1) Effect of diphenylsilane-based crosslinking agent Example 1
50 g of KF-9701 (Mw = 3000) was prepared as silanol-modified polydimethylsiloxane at both ends, which is one of the main ingredients of silicone rubber. Also, 5 g of dimethoxydiphenylsilane (referred to as crosslinker B-1), which is also one of the main agents, was prepared as the crosslinker. Next, 30 g of both-end silanol-modified polydimethylsiloxane and 2.44 g (corresponding to 0.01 mol) of dimethoxydiphenylsilane were mixed in a glove box (Galaxy manufactured by AS ONE Co., Ltd.) at room temperature (23 ° C.). Stir for 15 minutes. Next, 0.65 g of dibutyltin dilaurate as a catalyst (corresponding to 2 parts by mass when the total amount of both-end silanol-modified polydimethylsiloxane and cross-linking agent B-1 is 100 parts by mass) is added to the stirred main agent. The mixture was added and stirred at room temperature for 1 hour to cause a polymerization reaction. Next, the temperature was raised to 60 ° C. and stirring was continued for 7 days. Next, 0.66 g of phenyltrimethoxysilane (crosslinking agent B-2) as a silane-based crosslinking agent (corresponding to 2 parts by mass with respect to 100 parts by mass of the main agent) and 2 g of toluene are added to the stirred product, and 120 g The temperature was raised to ° C and stirring was continued for 3 hours. Then, after stirring was stopped and 15 g of the composition was developed on a Teflon petri dish, defoaming treatment was performed at 60 ° C. for 2 hours in a vacuum oven. Finally, the temperature was further raised at 150 ° C. for 6 hours in a dry oven, followed by baking at 200 ° C. for 12 hours to produce a silicone rubber.

Example 2
As the cross-linking agent B-1, 2.53 g (corresponding to 0.01 mol) of dichlorodiphenylsilane was used instead of dimethoxydiphenylsilane, and 12 hours at 250 ° C. instead of baking at 200 ° C. for 12 hours in a dry oven A silicone rubber was produced under the same conditions as in Example 1 except that the firing was performed.

Comparative Example 1
50 g of DMS-S31 (Mw = 26000) was prepared as both-end silanol-modified polydimethylsiloxane which is one of the main ingredients of silicone rubber. Further, 1 g of phenyltrimethoxysilane (crosslinking agent B-2) was prepared as the crosslinking agent. Next, 39 g of both-end silanol-modified polydimethylsiloxane and 0.198 g of phenyltrimethoxysilane (equivalent to 0.001 mol) were mixed in a glove box (Galaxy made by ASONE Co., Ltd.) at room temperature (23 ° C.). Stir for about 15 minutes. Next, 0.051 g (equivalent to 0.0001 mol) of a mixture of AlsB and DBT was added as a catalyst to the stirred mixture, and the mixture was stirred at 120 ° C. for 3 hours to cause a polymerization reaction. Next, stirring was stopped and 15 g of the composition was developed on a Teflon petri dish, and then heated at 150 ° C. for 6 hours and further heated at 200 ° C. for 12 hours in a dry oven to produce a silicone rubber.

  Table 1 shows the synthesis conditions of Examples 1 and 2 and Comparative Example 1 and the weight loss rate with increasing temperature. Table 2 shows the rubber properties of Examples 1 and 2 and Comparative Example 1 at room temperature and the results of heat resistance tests at 250 ° C. and 300 ° C. FIG. 1 shows the TG / DTA measurement results of Examples 1 and 2 and Comparative Example 1. In FIG. 1, “Synthesis method-1” indicates Comparative Example 1, “Synthesis method-2” indicates Example 1, and “Synthesis method-3” indicates Example 2.

  From FIG. 1, it can be seen that the silicone rubber of Comparative Example 1 to which no cross-linking agent B-1 has been added starts a large weight reduction at around 300 ° C. Further, when the silicone rubber of Comparative Example 1 was held at 250 ° C. for 72 hours, the elasticity was lost, and the elongation at break and the strength at break could not be measured.

  On the other hand, it can be seen from FIG. 1 that the silicone rubbers of Examples 1 and 2 to which the crosslinking agent B-1 was added did not show a significant weight reduction up to around 350 ° C. Further, from Table 2, it was determined that the silicone rubbers of Examples 1 and 2 had a heat resistance of 250 ° C. because good evaluation was obtained even in a heat resistance test at 250 ° C. However, at 300 ° C., although it was deteriorated to have poor elasticity and could not withstand mechanical property evaluation even if the shape of the rubber was maintained, heat resistance of 250 ° C. was recognized, but 300 ° C. It was judged that there was no heat resistance.

(2) Effect of addition of crosslinking agent B-2 (phenyltrimethoxysilane) Example 3
50 g of KF-9701 (Mw = 3000) was prepared as silanol-modified polydimethylsiloxane at both ends, which is one of the main ingredients of silicone rubber. Moreover, 5 g of dimethoxydiphenylsilane, which is also one of the main agents, was prepared as the crosslinking agent B-1. Next, 30 g of both-end silanol-modified polydimethylsiloxane and 2.44 g (corresponding to 0.01 mol) of dimethoxydiphenylsilane were mixed in a glove box (Galaxy manufactured by AS ONE Co., Ltd.) at room temperature (23 ° C.). Stir for 15 minutes. Next, 0.65 g of dibutyltin dilaurate as a catalyst (corresponding to 2 parts by mass when the total amount of both-end silanol-modified polydimethylsiloxane and cross-linking agent B-1 is 100 parts by mass) is added to the stirred main agent. The mixture was added and stirred at room temperature for 1 hour to cause a polymerization reaction. Next, the temperature was raised to 60 ° C. and stirring was continued for 7 days. Next, 0.33 g of phenyltrimethoxysilane (crosslinking agent B-2) (corresponding to 1 part by mass with respect to 100 parts by mass of the main agent) and 2 g of toluene are added to the stirred product, and the temperature is raised to 120 ° C. Stirring was continued for an hour. Then, stirring was stopped, and then stirring was stopped. After 15 g of the composition was developed on a Teflon petri dish, defoaming treatment was performed at 60 ° C. for 2 hours in a vacuum oven. Finally, the temperature was further raised at 150 ° C. for 6 hours in a dry oven, followed by baking at 200 ° C. for 12 hours to produce silicone rubber.

Example 4
Silicone rubber was produced under the same conditions as in Example 1.

Example 5
A silicone rubber was produced under the same conditions as in Example 3, except that 1.65 g (corresponding to 5 parts by mass with respect to 100 parts by mass of the main agent) of phenyltrimethoxysilane (crosslinking agent B-2) was used.

Comparative Example 2
A silicone rubber was produced under the same conditions as in Example 3 except that phenyltrimethoxysilane (crosslinking agent B-2) was not added.

  Table 3 shows the synthesis conditions of Examples 3 to 5 and Comparative Example 2 and the weight loss rate with temperature rise. Table 4 shows the rubber properties at room temperature of Examples 3 to 5 and Comparative Example 2 and the results of the heat resistance test at 250 ° C. Moreover, in FIG. 2, the TG / DTA measurement result of Examples 3-5 is shown.

  The silicone rubber of Comparative Example 2 in which the cross-linking agent B-2 was not added was not polymerized and did not have a rubber form. For this reason, the mechanical characteristics could not be evaluated. From this, it is thought that addition of the crosslinking agent B-2 is essential. On the other hand, from FIG. 2, no significant difference was observed between 1 to 5 parts by mass of the addition amount of the crosslinking agent B-2, but 2 parts by mass of the silicone rubber had a lower weight reduction rate. Moreover, from Table 4, all of the silicone rubbers having 1 to 5 parts by mass of the crosslinking agent were rubbers that can withstand heat evaluation at 250 ° C.

(3) Effect of PDMS on Mw Comparative Example 3
30 g of DMS-S12 (Mw = 590) was prepared as silanol-modified polydimethylsiloxane at both ends, which is one of the main ingredients of silicone rubber. Further, 10 g of dimethoxydiphenylsilane, which is also one of the main agents, was prepared as the crosslinking agent B-1. Next, 17.7 g of both-end silanol-modified polydimethylsiloxane and 7.33 g of dimethoxydiphenylsilane (equivalent to 0.03 mol) are mixed in a glove box (Galaxy manufactured by AS ONE Co., Ltd.) to room temperature (23 ° C.). And stirred for about 15 minutes. Thereafter, a silicone rubber was produced through the same steps as in Example 1.

Example 6
A silicone rubber was produced through the same process as Comparative Example 3 except that X-21-5841 (Mw = 1000) was mixed with dimethoxydiphenylsilane as both-end silanol-modified polydimethylsiloxane.

Example 7
A silicone rubber was produced through the same process as Comparative Example 3 except that KF-9701 (Mw = 3000) was mixed with dimethoxydiphenylsilane as both-end silanol-modified polydimethylsiloxane.

Example 8
A silicone rubber was produced through the same process as Comparative Example 3 except that DMS-S21 (Mw = 4200) was mixed with dimethoxydiphenylsilane as both-end silanol-modified polydimethylsiloxane.

Example 9
A silicone rubber was produced through the same process as Comparative Example 3 except that DMS-S27 (Mw = 18000) was mixed with dimethoxydiphenylsilane as both-end silanol-modified polydimethylsiloxane.

Example 9-1
A silicone rubber was produced through the same process as Comparative Example 3 except that DMS-S31 (Mw = 26000) was mixed with dimethoxydiphenylsilane as both-end silanol-modified polydimethylsiloxane.

  Table 5 shows the synthesis conditions of Comparative Example 3, Examples 6 to 9, and Example 9-1, and the weight loss rate associated with the temperature rise. Table 6 shows the rubber properties at room temperature of Comparative Example 3, Examples 6 to 9, and Example 9-1 and the results of the heat resistance test at 250 ° C. Moreover, in FIG. 3, the TG / DTA measurement result of the comparative example 3, Examples 6-9, and Example 9-1 is shown.

  As is clear from FIG. 3, the weight of each of Comparative Example 3, Examples 6 to 9, and Example 9-1 is less than that in the case where the crosslinking agent B-1 is not used (Synthesis method-1). There was a tendency for the temperature to decrease greatly. From Table 6, when Mw of PDMS was 590, it was not able to use for a 250 degreeC heat test.

  On the other hand, when the Mw of PDMS was 1000 or more, the rubber characteristics were maintained even in the heat resistance test at 250 ° C. for 72 hours. Therefore, it is considered necessary to use a heat resistant silicone rubber having a PDMS Mw exceeding 590.

(4) Effect of addition of metal phthalocyanine complex Example 10
50 g of KF-9701 (Mw = 3000) was prepared as silanol-modified polydimethylsiloxane at both ends, which is one of the main ingredients of silicone rubber. Moreover, 5 g of dimethoxydiphenylsilane, which is also one of the main agents, was prepared as the crosslinking agent B-1. Next, 30 g of both-end silanol-modified polydimethylsiloxane and 2.44 g (corresponding to 0.01 mol) of dimethoxydiphenylsilane were mixed in a glove box (Galaxy manufactured by AS ONE Co., Ltd.) at room temperature (23 ° C.). Stir for 15 minutes. Next, 0.65 g of dibutyltin dilaurate as a catalyst (2 masses when the total amount of the silanol-modified polydimethylsiloxane at both ends and the crosslinking agent B-1 (total amount of the main agent) is 100 parts by mass is added to the stirred main agent. And the mixture was stirred at room temperature for 1 hour to cause a polymerization reaction. Next, the temperature was raised to 60 ° C. and stirring was continued for 7 days. Next, 0.66 g of phenyltrimethoxysilane (crosslinking agent B-2) (corresponding to 2 parts by mass with respect to 100 parts by mass of the main agent) and 2 g of toluene are added to the stirring product, and the temperature is raised to 120 ° C. Stirring was continued for an hour. Next, 10 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount of the main agent and the crosslinking agent B-2, and planetary stirring was performed at a rotational speed of 2000 rpm for 5 minutes. Then, stirring was stopped, and then stirring was stopped. After 15 g of the composition was developed on a Teflon petri dish, defoaming treatment was performed at 60 ° C. for 2 hours in a vacuum oven. Finally, the temperature was further raised at 150 ° C. for 6 hours in a dry oven, followed by baking at 200 ° C. for 12 hours to produce a silicone rubber.

Example 11
Silicone rubber under the same conditions as in Example 10 except that the cross-linking agent B-1 was changed from dimethoxydiphenylsilane to dichlorodiphenylsilane and further changed from 200 ° C. for 12 hours to 250 ° C. for 12 hours in a dry oven. Was made.

  Table 7 shows the synthesis conditions of Examples 10 and 11 and the weight reduction rate with temperature increase in comparison with Example 2 and Example 4 (= Example 1). Table 8 shows the rubber properties at room temperature of Examples 10 and 11 and the results of the heat resistance test at 300 ° C. in comparison with Example 4 and Example 2. FIG. 4 shows the TG / DTA measurement results of Example 10 and Example 4 in which the weight loss due to the presence or absence of the metal phthalocyanine complex was compared. In FIG. 5, the TG / DTA measurement result of Example 11 and Example 2 which compared the weight reduction by the presence or absence of a metal phthalocyanine complex is shown.

  As shown in FIGS. 4 and 5, the silicone rubbers of Examples 2 and 4 to which no metal phthalocyanine complex was added caused a significant weight reduction near 350 ° C. For this reason, in the heat resistance test after holding at 300 ° C. for 72 hours, the silicone rubbers of Examples 2 and 4 could not withstand the test.

  On the other hand, the silicone rubbers of Examples 10 and 11 to which the metal phthalocyanine complex was added caused a large weight loss at a higher temperature than those of Examples 2 and 4, and were good in the heat resistance test after being held at 300 ° C. for 72 hours. It had mechanical properties. Even if the mechanical properties of the silicone rubbers of Examples 10 and 11 were compared, no significant difference was observed. Therefore, the heat resistance was improved solely by the addition of the metal phthalocyanine complex regardless of the type of the crosslinking agent B-1. It is considered a thing.

(5) Relationship between addition amount of metal phthalocyanine complex and performance Comparative Example 4
A silicone rubber was produced under the same conditions as in Example 10 except that 2 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount of the main agent and the crosslinking agent B-2.

Example 11-1
A silicone rubber was produced under the same conditions as in Example 10 except that 3 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount of the main agent and the crosslinking agent B-2.

Example 12
A silicone rubber was produced under the same conditions as in Example 10 except that 5 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount of the main agent and the crosslinking agent B-2.

Example 13
A silicone rubber was produced under the same conditions as in Example 10 except that 15 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Example 14
Silicone rubber was produced under the same conditions as in Example 10 except that 20 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Comparative Example 5
Silicone rubber was produced under the same conditions as in Example 10 except that 25 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Example 15
Silicone was used under the same conditions as in Example 11 except that dichlorodiphenylsilane was changed from Mw = 3000 to Mw = 1000 and phthalocyanine blue (PhCB) was added in an amount of 5 parts by mass relative to the total amount of 100 parts by mass. A rubber was prepared.

Example 16
A silicone rubber was produced under the same conditions as in Example 15 except that 10 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Example 17
A silicone rubber was produced under the same conditions as in Example 15 except that 15 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Example 18
Silicone rubber was produced under the same conditions as in Example 15 except that 20 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Comparative Example 6
Silicone rubber was produced under the same conditions as in Example 11 except that 2 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Example 19
Silicone rubber was produced under the same conditions as in Example 11 except that 3 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Example 20
A silicone rubber was produced under the same conditions as in Example 11 except that 5 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Example 20-1
A silicone rubber was produced under the same conditions as in Example 11 except that 15 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Example 20-2
Silicone rubber was produced under the same conditions as in Example 11 except that 20 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

Comparative Example 7
A silicone rubber was produced under the same conditions as in Example 11 except that 25 parts by mass of phthalocyanine blue (PhCB) was added to 100 parts by mass of the total amount.

  Table 9 shows the synthesis conditions of Examples 10 to 20, 20-1, and 20-2 and Comparative Examples 4 to 7 and the weight loss rate with increasing temperature. Table 10 shows the rubber properties at room temperature, heat resistance test at 250 ° C., and heat resistance test at 300 ° C. of Examples 10-20, 20-1, 20-2 and Comparative Examples 4-7. FIG. 6 shows the TG / DTA measurement results of Examples 10, 11-1, 12 to 14 and Comparative Example 4 in which Mw of PDMS is 3000 and dimethoxydiphenylsilane is used as the crosslinking agent B-1. FIG. 7 shows the TG / DTA measurement results of Examples 15 to 18 in which Mw of PDMS is 1000 and dichlorodiphenylsilane is used as the crosslinking agent B-1. FIG. 8 shows the TG / DTA measurement results of Examples 11, 19, 20, 20-1, 20-2 and Comparative Example 6 in which Mw of PDMS is 3000 and dichlorodiphenylsilane is used as the crosslinking agent B-1.

  As a general tendency, it was recognized that when the amount of phthalocyanine added was increased, the weight reduction rate in the TG / DTA measurement was decreased. When the crosslinking agent B-1 is dimethoxydiphenylsilane and the Mw of PDMS is 3000 (Examples 10, 11-1, 12-14 and Comparative Example 4), the addition amount of phthalocyanine is 250 ° C. in the range of 3-20 parts by mass. In addition, the heat resistance at 300 ° C. is lost in the case of 2 parts by mass, and even in the case of 25 parts by mass, uniform mixing of each component cannot be achieved. Could not be used for testing. Further, when the crosslinking agent B-1 is dichlorodiphenylsilane and the Mw of PDMS is 1000 (Examples 15 to 18), the heat resistance at 250 ° C. and 300 ° C. for 72 hours is within a range of 5 to 20 parts by mass of phthalocyanine. Satisfies the criteria for sex. Further, when the crosslinking agent B-1 is dichlorodiphenylsilane and the PDMS Mw is 3000 (Comparative Examples 6 and 7 and Examples 11, 19, 20, 20-1, and 20-2), the amount of phthalocyanine added is Within the range of 3 to 20 parts by mass, the heat resistance judgment standard for 300 hours at 300 ° C. was satisfied. Taking these results together, it is considered that the preferred amount of phthalocyanine added is in the range of 3 to 20 parts by mass.

(6) Relationship between type and performance of metal phthalocyanine complex Example 21
A silicone rubber was produced under the same conditions as in Example 16 except that the cobalt phthalocyanine amine derivative (a) was used instead of phthalocyanine blue.

Example 22
A silicone rubber was produced under the same conditions as in Example 16 except that iron phthalocyanine tetracarboxylic acid (b) was used instead of phthalocyanine blue.

Example 23
A silicone rubber was produced under the same conditions as in Example 16 except that cobalt phthalocyanine monosulfonic acid (c) was used instead of phthalocyanine blue.

Example 24
A silicone rubber was produced under the same conditions as in Example 16 except that copper phthalocyanine monosulfonic acid (d) was used instead of phthalocyanine blue.

Example 25
A silicone rubber was produced under the same conditions as in Example 16 except that iron phthalocyanine monosulfonic acid (e) was used instead of phthalocyanine blue.

Example 25-1
A silicone rubber was produced under the same conditions as in Example 16 except that phthalocyanine copper (II) (α-type) (f) was used instead of phthalocyanine blue.

Example 25-2
A silicone rubber was produced under the same conditions as in Example 16 except that phthalocyanine copper (II) (β-type) (g) was used instead of phthalocyanine blue.

Example 25-3
A silicone rubber was produced under the same conditions as in Example 16 except that phthalocyanine iron (II) (h) was used instead of phthalocyanine blue.

Example 25-4
A silicone rubber was produced under the same conditions as in Example 16 except that phthalocyanine cobalt (II) (i) was used instead of phthalocyanine blue.

Example 26
A silicone rubber was produced under the same conditions as in Example 11 except that the cobalt phthalocyanine amine derivative (a) was used instead of phthalocyanine blue.

Example 27
A silicone rubber was produced under the same conditions as in Example 11 except that iron phthalocyanine tetracarboxylic acid (b) was used instead of phthalocyanine blue.

Example 28
A silicone rubber was produced under the same conditions as in Example 11 except that iron phthalocyanine monosulfonic acid (e) was used instead of phthalocyanine blue.

Example 29
A silicone rubber was produced under the same conditions as in Example 11 except that phthalocyanine copper (II) (α-type) (f) was used instead of phthalocyanine blue.

Example 30
A silicone rubber was produced under the same conditions as in Example 11 except that phthalocyanine copper (II) (β-type) (g) was used instead of phthalocyanine blue.

Example 31
Silicone rubber was produced under the same conditions as in Example 11 except that phthalocyanine iron (II) (h) was used instead of phthalocyanine blue.

Example 32
A silicone rubber was produced under the same conditions as in Example 11 except that phthalocyanine cobalt (II) (i) was used instead of phthalocyanine blue.

  Table 11 shows the synthesis conditions of Examples 11, 16, 21 to 25, 25-1, 25-2, 25-3, 25-4, and 26 to 32, and the weight reduction rate with increasing temperature. Table 12 shows rubber properties at room temperature of Examples 11, 16, 21 to 25, 25-1, 25-2, 25-3, 25-4, and 26 to 32, and a heat resistance test at 300 ° C. Indicates. FIG. 9 shows the TG / DTA measurement results of Examples 16, 21 to 25, 25-1, 25-2, 25, 3, 25-4 in which Mw of PDMS is 1000. FIG. 10 shows the TG / DTA measurement results of Examples 11 and 26 to 32 in which Mw of PDMS is 3000.

  All phthalocyanines were able to pass the heat resistance test at 300 ° C. Among them, in particular, the heat resistance is extremely excellent in Example 16 using phthalocyanine blue when Mw of PDMS is 1000 and Example 25-1 using phthalocyanine copper (II) (α-type). Silicone rubber could be manufactured. Moreover, when the Mw of PDMS was 3000, silicone rubber having extremely excellent heat resistance could be produced in Example 29 using phthalocyanine copper (II) (α-type).

(7) Addition of filler and evaluation of heat resistance Example 33
A silicone rubber was produced under the same conditions as in Example 12 except that 2 parts by mass of dry fumed silica was added to 100 parts by mass of the total amount of the main agent and the crosslinking agent B-2 instead of phthalocyanine blue.

Example 34
In addition to phthalocyanine blue, a silicone rubber was produced under the same conditions as in Example 12 except that 2 parts by mass of dry fumed silica was added to 100 parts by mass of the total amount of the main agent and the crosslinking agent B-2.

Example 35
Instead of phthalocyanine blue, 2 parts by mass of dry fumed silica is added to 100 parts by mass of the total amount of the main agent and the crosslinking agent B-2, and calcium carbonate has a total amount of 100 masses of the main agent and the crosslinking agent B-2. Silicone rubber was produced under the same conditions as in Example 12 except that 5 parts by mass was added to the part.

Example 36
In addition to phthalocyanine blue, 2 parts by mass of dry fumed silica is added to 100 parts by mass of the main agent and the crosslinking agent B-2, and calcium carbonate is added to the total amount of the main agent and the crosslinking agent B-2 to 100. Silicone rubber was produced under the same conditions as in Example 12 except that 5 parts by mass was added to parts by mass.

  Table 13 shows the synthesis conditions of Examples 7, 12, and 33 to 36, and the weight reduction rate with increasing temperature. Table 14 shows the rubber properties at room temperature and heat resistance tests at 250 ° C. and 300 ° C. of Examples 7, 12, 33 to 36. Moreover, in FIG. 11, the TG / DTA measurement result of Example 7, 12, 33-36 is shown.

  In Example 33 in which dry fumed silica was added and in Example 35 in which dry fumed silica and calcium carbonate were added, the thermal weight loss rate at 400 ° C. was higher than that in Example 7 in which no additive was added. The elongation at break increased in a heat resistance test at 250 ° C. for 72 hours. Further, in Example 34 in which dry fumed silica and phthalocyanine blue were added and in Example 36 in which dry fumed silica, calcium carbonate and phthalocyanine blue were added, heat at 400 ° C. was higher than in Examples 7, 33 and 35. The weight reduction rate was further reduced, and higher characteristics were exhibited in a heat resistance test at 300 ° C. for 72 hours.

  The present invention can be used, for example, for rubber in a heat-resistant environment.

Claims (15)

An organopolysiloxane composition capable of forming a condensation-curable silicone rubber,
A terminal silanol-modified organopolysiloxane (A) having a weight average molecular weight (Mw) of 700 or more;
1 to 40 parts by mass of a diphenylsilane-based crosslinking agent (B) with respect to 100 parts by mass of the terminal silanol-modified organopolysiloxane (A);
0.2 parts by mass or more with respect to 100 parts by mass of the mixed main component of the terminal silanol-modified organopolysiloxane (A) and the diphenylsilane-based crosslinking agent (B), which contains at most one phenyl group in one molecule. 10 parts by mass or less of a silane-based crosslinking agent (C),
A condensation curing catalyst (D);
A condensation-curable organopolysiloxane composition comprising:   The condensation curable organopolysiloxane composition according to claim 1, wherein the terminal silanol-modified organopolysiloxane (A) is a silanol-modified polydimethylsiloxane having both ends.   The condensation curable organopolysiloxane composition according to claim 1, wherein the silane-based crosslinking agent (C) includes a monophenylsilane-based crosslinking agent.   The condensation curable organopoly of any one of claims 1 to 3, wherein the silane-based crosslinking agent (C) is 1 part by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the mixed main agent. Siloxane composition.   5. The metal phthalocyanine complex (E) further comprising 3 parts by mass or more and 20 parts by mass or less when the total amount of the mixed main agent and the silane-based crosslinking agent is 100 parts by mass. The condensation curable organopolysiloxane composition according to Item.   The condensation curable organopolysiloxane composition according to claim 5, wherein the metal phthalocyanine complex (E) contains at least one of cobalt phthalocyanine, iron phthalocyanine, copper phthalocyanine and derivatives thereof.   The condensation-curable organopolysiloxane composition according to any one of claims 1 to 6, further comprising at least one of silica and calcium carbonate as a filler (F). A kit in which the components of an organopolysiloxane composition capable of forming a condensation-curable silicone rubber are divided into a plurality of components,
A terminal silanol-modified organopolysiloxane (A) having a weight average molecular weight (Mw) of 700 or more;
1 to 40 parts by mass of a diphenylsilane-based crosslinking agent (B) with respect to 100 parts by mass of the terminal silanol-modified organopolysiloxane (A);
A crosslinking agent having at least one phenyl group in one molecule added to the mixed main agent of the terminal silanol-modified organopolysiloxane (A) and the diphenylsilane-based cross-linking agent (B), wherein the mixed main agent 0.2 to 10 parts by mass of a silane-based crosslinking agent (C) with respect to 100 parts by mass;
A condensation curing catalyst (D) added simultaneously with or before the silane-based crosslinking agent (C);
Condensation-curable organopolysiloxane composition kit.   The condensation curable organopolysiloxane composition kit according to claim 7, wherein the terminal silanol-modified organopolysiloxane (A) is a both-end silanol-modified polydimethylsiloxane.   The condensation curable organopolysiloxane composition kit according to claim 8 or 9, wherein the silane-based crosslinking agent (C) includes a monophenylsilane-based crosslinking agent.   The condensation curable organopoly of any one of claims 8 to 10, wherein the silane-based crosslinking agent (C) is 1 part by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the mixed main agent. Siloxane composition kit.   12. The metal phthalocyanine complex (E) further comprising 3 parts by mass or more and 20 parts by mass or less when the total amount of the mixed main agent and the silane-based crosslinking agent is 100 parts by mass. The condensation-curable organopolysiloxane composition kit according to Item.   The condensation curable organopolysiloxane composition kit according to claim 12, wherein the metal phthalocyanine complex (E) contains at least one of cobalt phthalocyanine, iron phthalocyanine, copper phthalocyanine and derivatives thereof.   The condensation curable organopolysiloxane composition kit according to any one of claims 8 to 13, further comprising at least one of silica and calcium carbonate as a filler (F).   A silicone rubber obtained by curing the condensation-curable organopolysiloxane composition according to any one of claims 1 to 7.