JPH09125048A - Gipper type gasket made of silicone-polyolefin-based organic rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gipper type gasket made of silicone-polyolefin-based organic rubber, having executability excellent in weather resistance, creep resistance and colorability, high in glass retentivity, excellent in strength of wind pressure resistance and stable to change in temperature of the whole year. SOLUTION: This gipper type gasket made of silicone-polyolefin-based organic rubber is obtained by vulcanizing and molding a silicone-polyolefin-based organic rubber comprising 100 pts.wt. of an ethylene propylene based organic polymer and/or an ethylene-propylene-diene-based organic polymer, 10 500 pts.wt. of a diorganopolysiloxane of the average composition formula R<1> n SiO(4-n)/2 (R<1> is the same or different nonsubstituted or substituted monofuntional hydrocarbon group; (n) is a positive number of 1.98-2.02), 10-120 pts.wt. of reinforcing silica powder having >=50m<2> /g specific surface area and 0.1-5 pts.wt. of an organic peroxide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silicone which is excellent in weather resistance and creep resistance, has a high glass holding power, is excellent in wind pressure resistance, and has stable workability against temperature changes throughout the year. The present invention relates to a polyolefin-based organic rubber zipper gasket.

[0002]

2. Description of the Related Art
As zipper gaskets for construction, those molded with rubber materials such as ethylene-propylene-diene rubber and chloroprene rubber are used, but these zipper gaskets are used for increasing the service life of buildings and gasket materials. It has become impossible to meet various demands for improvement such as weather resistance, creep resistance, colorability, and workability.

Therefore, in recent years, in order to improve such a zipper gasket, JP-A-5-132664 and 5-2.
No. 87205 proposes a zipper gasket made of silicone rubber. However, the zipper gasket made of silicone rubber is easily contaminated by low-molecular-weight siloxane, and if it is damaged during cutting or glass fitting for transportation, silicone rubber It is difficult to repair with adhesives because of its good releasability, and silicone rubber is inferior in breaking strength and rubber hardness as compared with chloroprene rubber and is not suitable for high-rise buildings. Had a problem.

Further, Japanese Patent Laid-Open No. 6-93249 discloses that
In order to improve the above-mentioned contamination to the surroundings, a gasket having a cured coating composed of ethylene-propylene-diene copolymer, organohydrogenpolysiloxane and platinum on the surface of the silicone rubber gasket body has been proposed. . However, it was difficult to manufacture this gasket efficiently, and the breaking strength was not sufficient.

Further, in the chloroprene type rubber gasket, there is a problem that the rubber becomes hard during construction in winter, and that the construction worker needs a great deal of force when inserting glass as compared with construction during summer. Therefore, development of a zipper gasket having more excellent properties is desired.

The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a zipper gasket which is excellent in weather resistance, creep resistance, and coloration, and which can be stably applied even when the temperature changes throughout the year.

[0007]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of earnest studies to achieve the above object, the present inventor has found that ethylene-propylene organic polymer and / or ethylene-propylene-diene organic polymer 100 parts by weight, 10 to 500 parts by weight of the diorganopolysiloxane represented by the average composition formula (1), and a specific surface area of 50 m ² / g
Silicone containing 10 to 150 parts by weight of the reinforcing silica powder and 0.1 to 5 parts by weight of organic peroxide
When a zipper gasket is formed by vulcanizing and molding a polyolefin organic rubber composition, it combines the properties of silicone rubber and polyolefin organic rubber, and has high strength and excellent wind pressure resistance, high glass holding power, and year-round temperature. Stable workability is obtained against changes and good colorability. Therefore, it has excellent weather resistance, creep resistance, and colorability, has high workability, and sufficiently meets the demands of the recent construction field. The inventors have found that a zipper gasket that can be obtained is obtained, and have completed the present invention.

Accordingly, the present invention provides (1) 100 parts by weight of an ethylene-propylene organic polymer and / or an ethylene-propylene-diene organic polymer (2 below average composition formula (1) R ¹ _n SiO _{(4-n) / 2} (1) (wherein R ¹ is the same or different, unsubstituted or substituted monovalent hydrocarbon group, and n is a positive number from 1.98 to 2.02). 10 to 500 parts by weight (3) Reinforcing silica powder having a specific surface area of 50 m ² / g or more 10 to 150 parts by weight (4) Organic peroxide 0.1 to 5 parts by weight Silicone-polyolefin organic rubber There is provided a zipper gasket obtained by vulcanizing and molding a composition.

The present invention will be described in more detail below. The silicone-polyolefin organic rubber zipper gasket of the present invention comprises an ethylene-propylene organic polymer and / or an ethylene-propylene-diene organic polymer and a diorganopolysiloxane. It is obtained by vulcanizing and molding a silicone-polyolefin-based organic rubber composition containing a reinforcing silica powder and an organic peroxide.

The first component organic polymer is an ethylene-propylene organic polymer (hereinafter referred to as EPM).
Abbreviated), an ethylene-propylene-diene-based organic polymer (abbreviated as EPDM hereinafter), or a mixture thereof.

Known EPMs and EPDMs can be used, but these are preferably those having an ethylene content of about 40 to 70% by weight, and EPD.
Examples of M include those using ethylidene norbornene, dicyclopentadiene, or 1,4-hexadiene as a diene monomer. The molecular weight is not particularly limited, but the Mooney viscosity (ML100 ° C.) is 20 due to processability.
Those of ˜120 are preferable. Also paraffinic oil,
It may be one to which a petroleum-based softening agent such as naphthenic oil is added.

The second component, diorganopolysiloxane, is added in order to improve the weather resistance and temperature change resistance of the first polyolefin organic polymer.
Average composition formula (1) R ¹ _n SiO _{(4-n) / 2} (1) (wherein R ¹ is the same or different, unsubstituted or substituted monovalent hydrocarbon group, and n is 1.98 to 2. A positive number of 02.) is used.

In the above formula (1), R ¹ is a methyl group,
Aliphatic unsaturated hydrocarbon groups such as alkyl groups such as ethyl, propyl and butyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl, allyl, butenyl and hexenyl. Group, phenyl group, aryl group such as tolyl group, or halogen such as chloromethyl group or trifluoropropyl group in which some or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atom, cyano group, etc. It is an unsubstituted or substituted monovalent hydrocarbon group preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which is the same or different and is selected from a substituted alkyl group, a cyano substituted alkyl group such as a cyanoethyl group and the like. R ¹ is 0.001 to 5 mol%, especially 0.01
It is preferable that ˜0.5 mol% is an alkenyl group, particularly a vinyl group. n is 1.98 to 2.02.

Further, the diorganopolysiloxane of the above formula (1) has a molecular chain terminal blocked with a trimethylsilyl group, a dimethylphenylsilyl group, a dimethylhydroxysilyl group, a dimethylvinylsilyl group, a trivinylsilyl group or the like. is there.

This type of organopolysiloxane is obtained by (co) hydrolyzing and condensing one or more selected organohalogenosilanes, or cyclic polysiloxane (trimer or tetramer of siloxane). Etc.) can be obtained by ring-opening polymerization using an alkaline or acidic catalyst. This is basically a linear diorganopolysiloxane, but two or more kinds having different molecular structures are used. It may be a mixture of. The organopolysiloxane preferably has a viscosity at 25 ° C. of 100 cs or more, particularly 100,
It is preferably from 000 to 10,000,000 cs.

The addition amount of the diorganopolysiloxane of the above formula (1) is 10 to 500 parts, preferably 3 parts with respect to 100 parts (part by weight, the same hereinafter) of the organic polymer as the first component.
0 to 300 parts, less than 10 parts is not sufficient to improve the weather resistance and temperature change resistance of the polyolefin-based organic polymer, and more than 500 parts, the molded zipper gasket is inferior in strength or hard. Is not enough.

The reinforcing silica powder as the third component is essential to obtain a silicone-polyolefin organic rubber having excellent mechanical strength, and for this purpose, the specific surface area is 50 m ² / g or more, preferably 100 to 4
It is necessary to make it 100 m ² / g. Specific surface area is 50
If it is less than m ² / g, the mechanical strength of the cured product will be low.

Examples of such reinforcing silica powder include fumed silica, precipitated silica, and silica whose surface is hydrophobized with chlorosilane, alkoxysilane, silazane, or the like.

The amount of the reinforcing silica powder added is 10 to 150 parts, preferably 30 to 100 parts, based on 100 parts of the organic polymer as the first component. If the amount is less than 10 parts, the effect is too small and sufficient. If it is not obtained and the amount is more than 150 parts, the workability becomes poor.

The organic peroxide as the fourth component is
A vulcanizing agent for heat-curing a silicone-polyolefin organic rubber composition, such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-bis (2,2
5-t-butylperoxy) hexane, 2,5-dimethyl-bis (2,5-t-butylperoxy) hexyne,
Di-t-butyl peroxide, t-butyl perbenzoate, t-butyl cumyl peroxide, 1,1-bis-t-butyl peroxy-3,3,5-trimethylcyclohexane and the like can be mentioned.

The amount of the organic peroxide added is 0.1 to 5 parts with respect to 100 parts of the first component organic polymer.

The silicone-polyolefin organic rubber composition according to the present invention is prepared by uniformly mixing the above-mentioned first to fourth components with a rubber kneader such as a two-roll, Banbury mixer, dough mixer (kneader mixer). It can be obtained by subjecting it to a heat treatment as necessary, but a rubber compounding agent known per se, which is appropriately compounded with rubber as necessary, may be added to such an extent that the effect of the present invention is not impaired. Good. For example, pulverized silica, diatomaceous earth, iron oxide, titanium oxide, carbon black, barium oxide, magnesium oxide, cerium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, fused silica powder and the like may be blended.

Further, if necessary, various additives such as colorants, heat resistance improvers, flame retardant aids, antistatic agents, antiaging agents, mold release agents, and dispersants for filling may be added. Although optional, diphenylsilanediol, various alkoxysilanes, carbon functional silanes, silanol group-containing low-molecular-weight siloxanes and the like used as the filling dispersant should be minimized so as not to impair the effects of the present invention. Is.

The silicone-polyolefin organic rubber composition thus obtained is molded by various molding methods such as cast molding, mold pressure molding and extrusion molding. When forming a gasket, extrusion molding is particularly preferably used. The vulcanization conditions include hot air vulcanization at 100 to 400 ° C. or 100 to 250 ° C., which is the decomposition temperature of the organic peroxide or higher.
The steam vulcanization (CV vulcanization) may be performed for about 10 seconds to 60 minutes, but if necessary, at 100 to 200 ° C. for 30 minutes to
Secondary vulcanization may be performed for 24 hours.

Since the silicone-polyolefin-based organic rubber zipper gasket of the present invention has the high strength of the polyolefin-based organic rubber, it is excellent in wind pressure resistance and has a high glass holding power, and in particular, contains a silicone polymer.
The ratio of the elastic modulus at 30 ° C / the elastic modulus at 30 ° C is 2
In the following, the range can be preferably in the range of 1 to 1.8, and when the elastic modulus ratio is larger than 2, stable workability may not be obtained against temperature changes throughout the year.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following examples, a part shows a weight part.

Example 1 100 parts of ethylene-propylene-diene-based organic polymer Esprene 567 (trade name of Sumitomo Chemical Co., Ltd.) was added to 99.825 mol% of dimethylsiloxane units and 0. 0% of methylvinylsiloxane units.
15 mol%, dimethylvinylsiloxane unit 0.025
43 parts by weight of methyl vinyl polysiloxane having an average degree of polymerization of 8,000, and 50 parts by weight of precipitating silica Nipsyl LP (trade name, manufactured by Nippon Silica Co., Ltd.) having a specific surface area of 230 m ² / g. Is 200 m ² / g, 30 parts of fumed silica Aerosil 200 (trade name of Nippon Aerosil Co., Ltd.), zinc flower 7 parts, stearic acid 2
Part and Irganox 1010 (trade name, manufactured by Ciba-Geigy Co., Ltd.) were added and kneaded with a pressure kneader to prepare a compound I.

To 100 parts of compound I was added 3.0 parts of dicumyl peroxide as a curing agent, and the mixture was kneaded with a two-roll mill to give a composition having a diameter of 40 mm and L / D = 12.
After extruding with the extruder, put it in the steam pot for 6.5k
Apply steam pressure of g / cm ² to cure and cure for 30 minutes,
Further, secondary vulcanization was carried out for 2 hours in a dryer at 150 ° C. to produce a silicone-polyolefin organic rubber zipper gasket having the shape shown in FIG.

Example 2 100 parts of ethylene-propylene-diene-based organic polymer Esprene 524 (trade name of Sumitomo Chemical Co., Ltd.) was added to 94.975 mol% of dimethylsiloxane units and 5.45% of methylvinylsiloxane units.
0 mol%, made 0.025 mol% dimethylvinylsiloxane units, average degree of polymerization 43 parts of methyl vinyl polysiloxane 8,000, fumed silica Aerosil 200 specific surface area of 200 meters ² / g (Nippon Aerosil ( Brand name) 75 parts, zinc white 7 parts, stearic acid 2 parts and Irganox 1010 (Ciba Geigy Co., Ltd.)
(Product name) was added and kneaded with a pressure kneader to prepare compound II.

To 100 parts of compound II was added 4.0 parts of t-butylcumyl peroxide as a curing agent,
The composition is kneaded with two rolls and the composition is 40 mm in diameter and L
/ D = 12 after extrusion with an extruder, continuous 300 ℃
It is vulcanized and cured through the hot air vulcanizing furnace (retention time of about 7
Min), and secondary vulcanization was further carried out for 2 hours in a dryer at 200 ° C. to prepare a silicone-polyolefin organic rubber zipper gasket having the shape shown in FIG.

[Comparative Example 1] 100 parts of ethylene-propylene-diene-based organic polymer Esprene 524 (trade name of Sumitomo Chemical Co., Ltd.) and a specific surface area of 230 m ² /
30 parts of fumed silica Aerosil 200 (trade name of Nippon Aerosil Co., Ltd.) having a specific surface area of 200 m ² / g. 7 parts of zinc white, 2 parts of stearic acid and 1 part of Irganox 1010 (trade name, manufactured by Ciba-Geigy Co., Ltd.) were added, and kneaded with a pressure kneader to prepare compound III.

A curing agent was added to 100 parts of Compound III in the same manner as in Compound I, and the mixture was molded and vulcanized to produce a polyolefin organic rubber zipper gasket having the shape shown in FIG.

Comparative Example 2 Dimethylsiloxane Unit 9
4.975 mol%, methyl vinyl siloxane unit 5.0
100 parts of methyl vinyl polysiloxane having an average degree of polymerization of 8,000 and a specific surface area of 200 m ² / g, fumed silica Aerosil 200 (Nippon Aerosil Co., Ltd.). ) Product name) 70 parts, 20 parts of terminal silanol group dimethylpolysiloxane (polymerization degree 10) are added and mixed with a kneader, and heat-treated at 200 ° C. for 1 hour to obtain compound IV.
made.

To 100 parts of Compound IV, 1.8 parts of 2,4-dichlorobenzoyl peroxide (50% silicone oil product) was added as a curing agent and kneaded with a two-roll mill to give a composition having a diameter of 40 mm, After extruding with an extruder of L / D = 12, it is continuously vulcanized and cured through a hot air vulcanizing furnace at 300 ° C. (residence time about 10 minutes), and further 20
Secondary vulcanization was carried out for 4 hours in a dryer at 0 ° C. to prepare a silicone zipper gasket having the shape shown in FIG.

FIG. 1 is a sectional view of the zipper gasket, and this zipper gasket is a gasket body 1
Is formed with a zipper 2 on the upper side, a glass plate fitting groove 3 is formed on one side surface, and an aluminum sash fitting groove 4 is formed on the other side surface.

Physical properties of the obtained rubber and 30 ° C and -30 ° C
The elastic modulus was measured by the following method. Physical property measurement: According to JIS-K-6301. Elastic modulus: Iwamoto Seisakusho, viscoelasticity spectrometer, frequency 30 Hz Further, the glass attachment work of FIG. 2 was performed in the freezer at -3 ° C., and the glass attachment work at low temperature was observed. Table 1 shows the above results.

In this case, FIG. 2 is a plan view and a cross-sectional view showing a mounting state of the glass plate 5 and the aluminum sash 6 using the zipper gasket of each example, and the glass plate fitting groove 3 of the gasket body 1 is shown. A glass plate 5 and an aluminum sash 6 are fitted in the aluminum sash fitting groove 4.

[0038]

[Table 1]

From the results shown in Table 1, it was found that the zipper gasket of the present invention was excellent in flexibility, weather resistance and workability.

[0040]

The silicone-polyolefin organic rubber zipper gasket of the present invention is excellent in weather resistance, creep resistance, and colorability, has high glass holding power, is excellent in wind pressure resistance, and is resistant to temperature changes throughout the year. It also has stable workability.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of a zipper gasket of the present invention.

FIG. 2 shows an example of glass attachment using the zipper gasket of the present invention, (A) is a plan view, and (B) is a sectional view.

[Explanation of symbols]

 1 Gasket body 2 Zipper 3 Glass plate fitting groove 4 Aluminum sash fitting groove 5 Glass plate 6 Aluminum sash

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsutomu Nakamura 1 Hitomi, Otomi, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (2)

[Claims] 1. An ethylene-propylene organic polymer and / or an ethylene-propylene-diene organic polymer 100 parts by weight (2) The following average composition formula (1) R ¹ _n SiO _{(4-n) / 2.} (1) (wherein R ¹ is the same or different, unsubstituted or substituted monovalent hydrocarbon group, and n is a positive number of 1.98 to 2.02) 10. 500 parts by weight (3) Reinforcing silica powder having a specific surface area of 50 m ² / g or more 10 to 150 parts by weight (4) Organic peroxide 0.1 to 5 parts by weight Silicone-polyolefin organic rubber composition containing A zipper gasket characterized by being vulcanized and molded. 2. The silicone-polyolefin organic rubber zipper gasket according to claim 1, wherein the ratio of elastic modulus at −30 ° C./elastic modulus at 30 ° C. is 2 or less.