JP2008013713A - Treating agent composition for glass fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone-based treating agent composition for a glass fiber product, having excellent penetrability to glass fiber, hardly foaming a rubber coating film at curing, and providing a cured product keeping the adhesiveness and rubber strength at good levels after curing. <P>SOLUTION: The treating agent composition of the glass fiber product contains (A) 100 pts.mass of an organopolysiloxane containing at least two alkenyl groups bound to silicon atoms in one molecule, (B) an organohydrogenpolysiloxane containing at least two SiH groups in one molecule in an amount in which the amount of the SiH group in the composition is 1-7 mol based on 1 mol of an alkenyl group bound to the silicon atom in the composition, (C) an effective amount of an addition reaction catalyst, and (D) 1-10 pts.mass of wet-process silica having ≥50 m<SP>2</SP>/g BET specific surface area, 1.0-1.3 ratio of the BET specific surface area to the CTAB specific surface area, and ≤4 mass% water content, and has ≤10,000 mPa s viscosity at 25°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a silicone-based treatment composition for glass fiber products such as glass fiber woven fabrics, glass fiber knitted fabrics, and glass fiber nonwoven fabrics, and in particular, a composition having good permeability to glass fibers and suppressing foaming during curing. Related to things.

It is known to use flexible silicone resins to treat glass fiber products such as glass fiber fabrics, glass fiber knitted fabrics, glass fiber nonwoven fabrics and the like. For example, an organopolysiloxane resin comprising units represented by the formulas: SiO _4/2 , R ₃ SiO _1/2 and R ₂ (CH ₂ ═CH) SiO _1/2 (R is a monovalent hydrocarbon group) is added. There is known an addition curing type liquid silicone composition for glass fiber treatment (Patent Document 1).

A silicone rubber composition for the purpose of forming a rubber film on the surface of a glass fiber product such as a glass fiber fabric needs to penetrate into the glass fiber and improve the convergence of the fiber itself. In the past, for example, the silicone rubber composition was diluted with a solvent to reduce the viscosity, thereby improving the permeability. In this method, there is a risk of adversely affecting the human body due to transpiration of the solvent used. In the solventless type, the amount of filler is reduced in order to lower the viscosity of the resulting composition, but the cured product has a problem that the rubber strength is extremely lowered. Furthermore, even when wet silica is used to lower the viscosity of the composition and increase the strength of the cured product, the rubber coating foams due to the influence of moisture present in the wet silica, resulting in poor electrical insulation. There are problems such as becoming unclear and poor appearance.
Japanese Patent Publication No.51-46880

  The present invention has been made in view of the above circumstances, has excellent permeability to glass fibers, suppresses foaming of the rubber coating during curing, and maintains a good level of adhesion and rubber strength after curing. An object of the present invention is to provide a silicone-based glass fiber product treating agent composition that provides a cured product.

As a result of intensive studies to achieve the above object, the present inventor has made the present invention. That is, the present invention
(A) Organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule: 100 parts by mass
(B) Organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule: silicon atoms in the composition with respect to 1 mol of alkenyl groups bonded to the silicon atoms in the composition An amount of 1 to 7 moles of hydrogen atoms bonded to
(C) addition reaction catalyst: effective amount, and (D) the BET specific surface area is 50 m ² / g or more, and the ratio of BET specific surface area / CTAB specific surface area (hereinafter referred to as “BET / CTAB”) is 1. Wet silica having a water content of 0 to 1.3 and a water content of 4% by mass or less: 1 to 100 parts by mass and a glass fiber product treating agent having a viscosity at 25 ° C. of 10,000 mPa · s or less A composition is provided.

  The glass fiber product treating agent composition of the present invention is excellent in permeability to glass fiber, so it can improve the convergence of the glass fiber product, foaming of the rubber coating is suppressed during curing, and adhesion to the fiber after curing Gives a cured product with good properties and rubber strength maintained at good levels. The composition of the present invention is excellent in coatability and is environmentally friendly because it can be used without blending a solvent.

  The composition of the present invention is applied to the surface of a glass fiber product such as a glass fiber woven fabric, a glass fiber knitted fabric, and a glass fiber nonwoven fabric, specifically, for example, the surface of a glass fiber tube, a glass fiber braided electric wire or the like and cured. By treating the surface, the convergence of the glass fiber product can be remarkably improved. Moreover, since the foamability at the time of hardening is suppressed, the composition of this invention can make the electrical insulation property and external appearance of hardened | cured material excellent.

Hereinafter, the present invention will be described in detail.
<Ingredients constituting the composition>
The glass fiber product treating agent composition of the present invention comprises the following components (A) to (D).

-(A) Organopolysiloxane-
The organopolysiloxane of component (A) is the base component (main agent) of the composition of the present invention, and is an alkenyl group (hereinafter referred to as “silicon”) bonded to at least 2, preferably 2 to 20, silicon atoms in one molecule. Containing an atom-bonded alkenyl group).

  The silicon-bonded alkenyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is preferable.

  The bonding position of the silicon atom-bonded alkenyl group in the organopolysiloxane molecule may be the molecular chain terminal, the molecular chain non-terminal (ie, molecular chain side chain), or both. Good.

  In the organopolysiloxane molecule of this component, an organic group bonded to a silicon atom other than the silicon atom-bonded alkenyl group (hereinafter referred to as “silicon atom-bonded organic group”) does not have an aliphatic unsaturated bond. For example, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms is preferable. Examples of the unsubstituted or substituted monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a cycloalkyl group such as a cyclohexyl group; Aryl groups such as a group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; some or all of hydrogen atoms of these hydrocarbon groups are halogens such as chlorine atom, fluorine atom and bromine atom Examples thereof include halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. substituted with atoms, preferably alkyl groups and aryl groups, more preferably A methyl group and a phenyl group;

  In this component, the content of the silicon-bonded alkenyl group is preferably 0.001 to 10 mol%, particularly preferably 0.01 to 5 mol%, based on all silicon-bonded organic groups in the component.

  The molecular structure of the organopolysiloxane of this component is not particularly limited, and examples thereof include a linear structure, a partially branched linear structure, a cyclic structure, a branched chain structure, and a three-dimensional network structure. It is preferably a linear diorganopolysiloxane in which the main chain basically consists of repeating diorganosiloxane units and both ends of the molecular chain are blocked with triorganosiloxy groups.

  The viscosity at 25 ° C. of this component is such that the physical properties such as the permeability of the composition to the fibers, the adhesion of the cured product to the fibers, and the rubber strength of the cured product, and the workability of the composition are superior. It is preferably 100 to 20,000 mPa · s, particularly preferably 300 to 5,000 mPa · s.

Examples of the organopolysiloxane of this component include an average composition formula (1):
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, R ² is the same or different alkenyl group, and a is from 0.00001 to 0.1. Number, b is a number from 1.7 to 2.1, provided that a + b satisfies 1.8 to 2.2)
The thing represented by is mentioned.

In the average composition formula (1), R ¹ preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms. Specific examples thereof include those exemplified as the silicon atom-bonded organic group other than the silicon atom-bonded alkenyl group.

R ² preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples thereof include those exemplified as the silicon atom-bonded alkenyl group.

  a is preferably a number from 0.0001 to 0.05, b is preferably a number from 1.9 to 2.0, and a + b preferably satisfies 1.95 to 2.05.

Specific examples of the organopolysiloxane of this component include a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both ends of a molecular chain, a trimethylsiloxy group-capped methylvinylpolysiloxane with a molecular chain at both ends, and a trimethylsiloxy group with both ends of a molecular chain. Blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / diphenylsiloxane copolymer, dimethylpolysiloxane / blocked dimethylvinylsiloxy group, molecular chain Dimethyl vinyl polysiloxane blocked with dimethylvinylsiloxy group blocked at both ends of chain, dimethylsiloxane / methylvinylsiloxane copolymer blocked with dimethylvinylsiloxy group blocked at both ends of molecular chain Vinylsiloxy-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, dimethylvinylsiloxy-blocked dimethylsiloxane / methylvinylsiloxane / diphenylsiloxane copolymer at both ends of the molecular chain, divinylmethylsiloxy-blocked dimethyl at both ends of the molecular chain Polysiloxane, Divinylmethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both ends of molecular chain, Trivinylsiloxy group-capped dimethylpolysiloxane with molecular chain at both ends, Trivinylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane with molecular chain at both ends Copolymer, siloxane unit represented by the formula: R ¹ ₃ SiO _1/2 (wherein R ¹ is as described above, hereinafter the same) and the formula: R ¹ ₂ R ² SiO _1/2 (formula among, ^{R 2} is the above-mentioned A cage, hereinafter the same) siloxane units being represented by formula: R 1 ² siloxane units and a small amount of the formula represented by _SiO: organosiloxane copolymers consisting of siloxane units represented by SiO _2, wherein: Organosiloxane copolymer comprising a siloxane unit represented by R ¹ ₃ SiO _1/2 and a siloxane unit represented by the formula: R ¹ ₂ R ² SiO _1/2 and a siloxane unit represented by the formula: SiO ₂ An organosiloxane comprising a siloxane unit represented by the formula: R ¹ ₂ R ² SiO _1/2 , a siloxane unit represented by the formula: R ¹ ₂ SiO and a small amount of a siloxane unit represented by the formula: SiO ₂ polymer of the ^formula: R ¹ R 2 siloxane units and a small amount of the formula represented by ^SiO: siloxane units or a small amount of the formula represented by ^{_{R 1 SiO 3/2: R 2 SiO}} 3 Organosiloxane copolymers consisting of siloxane units represented by _2, mixtures of two or more of these organopolysiloxanes.

  The (A) component organopolysiloxane may be used alone or in combination of two or more.

-(B) Organohydrogenpolysiloxane-
The (B) component organohydrogenpolysiloxane is a component that acts as a crosslinking agent in the addition curing reaction with the (A) component and further imparts adhesiveness to the cured product. The organohydrogenpolysiloxane has at least 2, preferably at least 3, hydrogen atoms bonded to silicon atoms in one molecule (hereinafter referred to as “silicon-bonded hydrogen atoms” (ie, SiH groups)). In this case, it is preferably one having no aliphatic unsaturated bond in the molecule. The upper limit of the number of silicon atom-bonded hydrogen atoms is preferably 500, more preferably 200, and still more preferably 100.

  The bonding position of the silicon atom-bonded hydrogen atom in the organohydrogenpolysiloxane molecule of this component may be the molecular chain terminal, the molecular chain non-terminal, or both.

  In this organohydrogenpolysiloxane molecule, the silicon atom-bonded organic group other than the silicon atom-bonded hydrogen atom is not particularly limited, but preferably has no aliphatic unsaturated bond, for example, unsubstituted or substituted. The monovalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Specific examples thereof include those exemplified as the silicon atom-bonded organic group other than the silicon atom-bonded alkenyl group in the description of the component (A), particularly methyl group, ethyl group, propyl group, phenyl group, 3, 3, Examples include 3-trifluoropropyl group and alkenyl groups such as vinyl group and allyl group.

  In this component, the content of the silicon atom-bonded hydrogen atoms is preferably 0.1 to 60 mol%, particularly preferably based on the total of all silicon atom-bonded organic groups and all silicon atom-bonded hydrogen atoms in the component. 1 to 50 mol%.

  The molecular structure of the organohydrogenpolysiloxane of this component is not particularly limited, and examples thereof include a linear structure, a cyclic structure, a branched structure, and a three-dimensional network structure (resinous structure). A structure or a cyclic structure is preferred.

  The viscosity at 25 ° C. of this component is such that the physical properties such as the permeability of the composition to the fibers, the adhesion of the cured product to the fibers, and the rubber strength of the cured product, and the workability of the composition are superior. A range that is liquid at room temperature (25 ° C.) satisfying the range of preferably 0.1 to 5,000 mPa · s, more preferably 0.5 to 1,000 mPa · s, and particularly preferably 5 to 500 mPa · s is desirable. When satisfying such viscosity, the number (or degree of polymerization) of silicon atoms in one molecule of the organohydrogenpolysiloxane is usually 2 to 1,000, typically 3 to 300, more typically 4 to 150.

Examples of the organohydrogenpolysiloxane of this component include an average composition formula (2):
R ³ _c H _d SiO _{(4-cd) / 2} (2)
Wherein R ³ is the same or different unsubstituted or substituted monovalent hydrocarbon group, c is a number from 0.7 to 2.1, d is a number from 0.001 to 1.0, provided that c + d is from 0.8 to 3.0)
The thing represented by is mentioned.

In the average composition formula (2), R ³ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. R ³ preferably does not have an aliphatic unsaturated bond such as an alkenyl group. Specific examples of R ³ include those exemplified as the silicon atom-bonded organic group other than the silicon atom-bonded alkenyl group in the description of the component (A), and alkenyl groups such as vinyl group and allyl group.

  c is preferably a number from 1.0 to 2.0, d is preferably a number from 0.01 to 1.0, and c + d is preferably a number from 1.5 to 2.5.

Specific examples of the organohydrogenpolysiloxane of this component include tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,1,3,3-tetramethyldisiloxane, 1,3, 5,7-tetramethylcyclotetrasiloxane, methylhydrogencyclopolysiloxane, dimethylsiloxane / methylhydrogensiloxane cyclic copolymer, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, molecular chain Both ends trimethylsiloxy group-capped methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped diester Methylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane with both molecular chains, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer with both molecular chains, A dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer having both ends of a molecular chain, a dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane having both ends of a molecular chain, represented by the formula: (CH ₃ ) ₂ HSiO _1/2 A copolymer comprising a siloxane unit and a siloxane unit represented by the formula: (CH ₃ ) ₃ SiO _1/2 and a siloxane unit represented by the formula: SiO _4/2 , a formula: (CH ₃ ) ₂ HSiO _{1 /} Siloxane represented by ₂ Examples thereof include a copolymer comprising a unit and a siloxane unit represented by the formula: SiO _4/2 , a mixture comprising two or more of these organopolysiloxanes, and the like.

Among them, (1) both ends of the molecular chain having no aliphatic unsaturated bond are represented by the formula: R ³ ₃ SiO _1/2 (wherein R ³ is as described above, and the same applies hereinafter). An organohydrogenpolysiloxane that is capped with a siloxane unit and the main chain is composed of repeating siloxane units represented by the formula: R ³ HSiO _2/2 , and (2) a molecular chain that does not have an aliphatic unsaturated bond Both ends are independently blocked with a siloxane unit represented by the formula: R ³ ₃ SiO _1/2 or a siloxane unit represented by the formula: R ³ ₂ HSiO _1/2 , and the main chain is represented by the formula: R ³ ₂ siloxane units of the formula represented by SiO ^_2/2: consisting random repetition of the siloxane units represented by R 3 _{HSiO 2/2,} union with the diorganosiloxane-organohydrogensiloxane copolymer So it is preferable. Specifically, (1) molecular chain both ends trimethylsiloxy group-capped methylhydrogenpolysiloxane, and (2) dimethylsiloxane methylhydrogen having both molecular chain ends blocked with trimethylsiloxy group or dimethylhydrogensiloxy group. A combination with a siloxane copolymer is preferred.

  (B) The compounding quantity of a component is as follows. The composition of the present invention can contain a component having a silicon atom-bonded alkenyl group other than the component (A) and / or a component having a silicon atom-bonded hydrogen atom other than the component (B). Therefore, the blending amount is an amount such that the silicon atom-bonded hydrogen atom in the composition is usually 1 to 7 mol, preferably 2 to 6 with respect to 1 mol of the silicon atom-bonded alkenyl group in the composition. However, in a typical example, 1 mol of silicon atom-bonded hydrogen atoms in component (B) is 1 to 7 mol per mol of silicon atom-bonded alkenyl group in component (A), The amount is 2 to 6 mol. This is because when the silicon-bonded hydrogen atom is less than 1 mole relative to 1 mole of the silicon-bonded alkenyl group, it is difficult to obtain a sufficient rubber strength of the cured product. This is because the heat resistance and rubber strength of the product are remarkably inferior. The ratio of silicon atom-bonded alkenyl groups in component (A) to the total silicon atom-bonded alkenyl groups in the composition is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 99. ~ 100 mol%. The proportion of silicon atom-bonded hydrogen atoms in component (B) in the total silicon-bonded hydrogen atoms in the composition is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, particularly preferably 99. ~ 100 mol%.

  The (B) component organohydrogenpolysiloxane may be used alone or in combination of two or more.

-(C) Addition reaction catalyst-
The addition reaction catalyst for component (C) is a component for promoting / promoting the hydrosilylation reaction between the silicon atom-bonded alkenyl group in component (A) and the silicon atom-bonded hydrogen atom in component (B). The addition reaction catalyst is not particularly limited, and examples thereof include platinum group metals such as platinum, palladium and rhodium; chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, vinyl siloxane or acetylene compounds. Platinum compounds such as coordination compounds, platinum group metal compounds such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, and the like are preferable, and platinum compounds are preferable.

  The compounding amount of the component (C) may be an effective amount as a catalyst, but is usually 0.1 to 1,000 ppm in terms of the mass of the platinum group metal with respect to the sum of the component (A) and the component (B). It is preferably 1 to 500 ppm, more preferably 10 to 100 ppm. When this blending amount is appropriate, the addition reaction can be promoted more effectively.

  (C) The addition reaction catalyst of a component may be used individually by 1 type, or may use 2 or more types together.

-(D) wet silica-
Component (D) wet silica improves the permeability of the composition of the present invention to glass fibers, imparts excellent convergence to the glass fibers, suppresses foaming during curing of the composition, It is a component that imparts mechanical strength (tensile strength, elongation at break, tear strength, etc.) to the cured product.

The wet silica of component (D) has a BET specific surface area of 50 m ² / g or more, preferably 100 m ² / g or more, particularly preferably 100 to 400 m ² / g, and BET / CTAB is 1.0 to 1.3. , Preferably 1.0 to 1.2, particularly preferably 1.0 to 1.1, and the water content is 4% by mass or less, preferably 3% by mass or less.

When the BET specific surface area is less than 50 m ² / g, the mechanical strength to the obtained cured product tends to be insufficient. Moreover, when BET / CTAB is out of the range of 1.0 to 1.3 and / or when the water content exceeds 4% by mass, the resulting composition is prone to foam during normal pressure hot air vulcanization. In addition, the silicone rubber obtained tends to have insufficient electrical characteristics.

  The BET specific surface area is a specific surface area according to the BET method, and can be calculated based on a measured value of nitrogen adsorption amount on wet silica. The CTAB specific surface area is a specific surface area according to the CTAB method, and can be calculated based on the measured value of the adsorption amount of N-cetyl-N, N, N-trimethylammonium bromide on wet silica. In wet silica, the closer BET / CTAB is to 1, the closer the ratio of internal pores to all pores is to 0, and the wet silica has a structure in which moisture is less likely to be adsorbed by internal pores. Such wet silica is easy to remove even if the apparent water content is large.

Moisture content measures the mass _{M Heated} wet silica after 2 hours of heat treatment at a mass _{M inital} and 110 ° C. of wet silica at 25 ° C., the following formula:
_{(M inital -M heated) / M} inital × 100 (%)
Is a value calculated by.

The surface of the wet silica of component (D) may be subjected to a hydrophobic treatment with a known treatment agent such as chlorosilane or hexamethyldisilazane as necessary.

  Examples of the available wet silica of component (D) include Zeosil (registered trademark) 172X (trade name, manufactured by Rhodia Japan).

  (D) The addition amount of the wet silica of a component is 1-100 mass parts with respect to 100 mass parts of (A) component, Preferably it is 10-70 mass parts, Most preferably, it is 30-60 mass parts. When the added amount is less than 1 part by mass, it is difficult to obtain a reinforcing effect by the component (D). On the other hand, when the added amount exceeds 100 parts by mass, the workability of the resulting composition tends to be poor, and the mechanical strength of the cured product of the composition tends to decrease.

  (D) The wet silica of component may be used individually by 1 type, or may use 2 or more types together.

-Optional component-
You may mix | blend the following components with the composition of this invention as needed other than the said (A)-(D) component. These optional components may be used alone or in combination of two or more.

Reaction control agent The reaction control agent is not particularly limited as long as it is a compound having an effect of adjusting the reaction rate of the curing reaction with respect to the addition reaction catalyst of the component (C), and a conventionally known one can also be used. . Specific examples thereof include phosphorus-containing compounds such as triphenylphosphine; compounds containing nitrogen atoms such as tributylamine, tetramethylethylenediamine, and benzotriazole; compounds containing sulfur atoms; acetylene-based compounds such as acetylene alcohols; 1-ethynylcyclohexanol; a compound containing 50 to 100 mol% of silicon atom-bonded alkenyl groups, such as methylvinylsiloxane cyclic, with respect to all silicon atom-bonded organic groups in the molecule; hydroperoxy compound; Can be mentioned.

  The blending amount of the reaction control agent is preferably adjusted to an optimum amount for each reaction control agent to be used, because the degree of action of adjusting the reaction rate of the curing reaction of the reaction control agent varies depending on its chemical structure. By blending an optimal amount of the reaction control agent, the composition has excellent curability.

Other components As other components, for example, a linear diorgano having a silicon atom-bonded alkenyl group or silicon atom-bonded hydrogen atom at one end of the molecular chain and the other end blocked with a trialkylsiloxy group Organopolysiloxane having one silicon atom-bonded hydrogen atom or one silicon atom-bonded alkenyl group in one molecule, such as polysiloxane, and having no other functional group; both ends of the molecular chain are trialkylsiloxy groups A non-reactive organopolysiloxane having no silicon atom-bonded hydrogen atom and silicon atom-bonded alkenyl group, such as a linear diorganopolysiloxane blocked with 1; a creep hardening inhibitor, a plasticizer, a thixotropic agent, In order to improve the rubber strength of a cured product, such as pigments, dyes, fungicides, etc., for example, the formula: R ³ ₃ SiO _1/2 (formula In which R ³ is the same as above, and a siloxane unit represented by the formula: SiO _4/2 , containing or not containing an alkenyl group, and a three-dimensional network-organopolysiloxane A resin or the like can be blended.

  The composition of the present invention can be suitably used without blending an organic solvent. When the composition is applied to various substrates, an organic solvent such as toluene or xylene may be used depending on conditions such as a coating apparatus. And may be used at a concentration that is easy to use.

<Preparation and use of composition>
The composition of the present invention can be prepared by mixing the above components (A) to (D) and optionally the components to be blended. The composition thus obtained is used as a treating agent for glass fiber products such as glass fiber fabrics (for example, glass sleeves, glass cloths, glass rovings, glass tapes, glass mats, etc.), glass fiber knitted fabrics, and glass fiber nonwoven fabrics. It is useful as a coating agent for sleeves.

  The composition of the present invention is preferably liquid at room temperature (25 ° C.) and has a low viscosity. Specifically, the viscosity at room temperature (25 ° C.) is 10,000 mPa · s or less, preferably 8,000 mPa.・ S or less. The lower limit of the viscosity is not particularly limited, but may be practically, for example, 10 mPa · s or more, preferably 100 mPa · s or more.

  What is necessary is just to perform the surface treatment of the glass fiber product using the composition of this invention by hardening, after apply | coating a composition to a glass fiber product, for example. Application | coating may be performed so that the thickness after hardening of a composition may be 0.1-500 micrometers, for example, Preferably it is 0.5-100 micrometers. Curing may be carried out according to conventionally known curing methods and conditions, for example, by heating at 120 to 220 ° C. for 0.1 to 10 minutes.

  If necessary, before applying and curing the composition, the glass fiber product may be preliminarily heat-treated or pretreated with a primer, a silane coupling agent, or the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all. “Parts” means “parts by mass” and the viscosity is a measured value at 25 ° C.

[Example 1]
100 parts of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain having a viscosity of 1,000 mPa · s
BET specific surface area 180 m ^{2 /} g, BET / CTAB 1.06, wet silica with a moisture content of 2.3% by mass (Zeosil 172X (trade name, manufactured by Rhodia Japan)): 40 parts,
Viscosity 50 mPa · s molecular chain both ends trimethylsiloxy group-blocked methyl hydrogen polysiloxane (content of silicon-bonded hydrogen atom = 0.38% by mass): 3.0 parts,
1-ethynylcyclohexanol: 0.05 part, and complex of chloroplatinic acid and divinyltetramethyldisiloxane: 30 ppm in terms of the mass of platinum metal with respect to the total of the dimethylpolysiloxane and the methylhydrogenpolysiloxane
Was uniformly mixed with a planetary mixer to prepare composition 1. In Composition 1, the amount of silicon atom-bonded hydrogen atoms per mole of silicon atom-bonded vinyl groups (hereinafter referred to as “SiH / SiVi”) was 2.0 mol.

[Comparative Example 1]
In Example 1, Composition C1 was prepared in the same manner as in Example 1, except that Zeosil 132 (trade name, manufactured by Rhodia Japan Co., Ltd.) was used instead of Zeosil 172X. The SiH / SiVi of composition C1 was 2.0 mol. The BET specific surface area, BET / CTAB, and water content of Zeosil 132 are as shown in Table 1.

[Example 2]
In Example 1, Composition 2 was prepared in the same manner as in Example 1 except that wet silica prepared by drying Zeosil 172X at 110 ° C. for 1 hour was used instead of Zeosil 172X. Composition 2 had a SiH / SiVi of 3.4 moles. The BET specific surface area, BET / CTAB, and water content of the wet silica used in Example 2 are as shown in Table 1.

[Comparative Example 2]
In Example 1, a composition C2 was prepared in the same manner as in Example 1 except that wet silica prepared by drying Zeosil 132 at 110 ° C. for 1 hour was used instead of Zeosil 172X. Composition C2 had SiH / SiVi of 3.4 mol. The BET specific surface area, BET / CTAB, and water content of the wet silica used in Comparative Example 2 are as shown in Table 1.

[Comparative Example 3]
A composition C3 was prepared in the same manner as in Example 1 except that Fine Seal (registered trademark) USF (trade name, manufactured by Tokuyama Corporation) was used instead of Zeosil 172X. Composition C3 had a SiH / SiVi of 3.4 moles. The BET specific surface area, BET / CTAB, and water content of the fine seal USF are as shown in Table 1.

[Measurement and testing]
About the composition obtained in each of said Example and comparative example, the physical-property characteristic measurement, the convergence test of glass fiber, and the foamability test at the time of normal pressure hardening were done. The obtained results are shown in Table 1.

<Measurement of physical properties>
The obtained composition is cured by heating at 150 ° C. for 5 minutes to obtain a cured product, and the cured product has hardness (durometer A), tensile strength, elongation at break, tearing according to JIS K 6249 Strength was measured.

<Glass fiber convergence test>
A glass fiber convergence test was performed by cutting the glass fiber perpendicularly with respect to the major axis direction with a cutter and visually confirming whether the cut portion (cut surface) was frayed. The convergence of the glass fiber was evaluated according to the following criteria. When the glass fiber was not frayed at all, it was evaluated that the convergence was good, and is indicated by “A” in Table 1. When the glass fiber frayed in part, it was evaluated that the convergence was slightly good, and is indicated by “B” in Table 1. When all the glass fibers were frayed, it was evaluated that the convergence was poor, and is indicated by “C” in Table 1.

<Foaming test at normal pressure curing>
The silicone rubber composition was poured into an aluminum container so that the thickness after curing was 10 mm, and cured by heating at 200 ° C. for 5 minutes, and the degree of foaming was visually observed. The degree of foaming was evaluated according to the following criteria. When the number of bubbles per unit volume was 1 / cm ³ or less, it was evaluated that almost no foaming was observed, and “1” is shown in Table 1. When the number was 2 to 5 / cm ³ , it was evaluated that foaming was slightly observed, and “2” is shown in Table 1. When the number was 6 pieces / cm ³ or more, it was evaluated that a large amount of foaming was observed.

Claims (2)

(A) Organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule: 100 parts by mass
(B) Organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule: silicon atoms in the composition with respect to 1 mol of alkenyl groups bonded to the silicon atoms in the composition An amount of 1 to 7 moles of hydrogen atoms bonded to
(C) addition reaction catalyst: effective amount, and (D) the BET specific surface area is 50 m ² / g or more, the ratio of BET specific surface area / CTAB specific surface area is 1.0 to 1.3, and the water content is 4% by mass or less of wet silica: A glass fiber product treating agent composition comprising 1 to 100 parts by mass and having a viscosity at 25 ° C. of 10,000 mPa · s or less. The composition according to claim 1, wherein the proportion of hydrogen atoms bonded to silicon atoms in component (B) in the hydrogen atoms bonded to silicon atoms in the composition is 90 to 100 mol%.