JP2698491B2 - Glass fiber fabric treatment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone-based treating agent for glass fiber fabric, and more particularly to a treating agent which is flexible, transparent and excellent in flame retardancy.

[0002]

BACKGROUND OF THE INVENTION The use of flexible silicone resins in the treatment of woven glass fiber products is known, and several methods are known for improving the flame retardancy of these silicone resins. For example, a composition using a vinyl group-containing resin (see Japanese Patent Publication No. 51-46880), a method using zinc carbonate powder and cerium oxide powder (Japanese Patent Publication No. 53-13)
No. 505). However, in the method using a vinyl group-containing resin, it is difficult to balance flame retardancy and flexibility, and when using zinc carbonate powder and cerium oxide powder, the composition becomes opaque and a transparent product is obtained. It is difficult.

[0003] Generally, as a method of imparting flame retardancy to silicone rubber, a method of adding a platinum compound, a method of adding a platinum compound, and the like.
There is a method of using titanium oxide powder or carbon black in combination with a platinum compound, but the method of adding a platinum compound does not have a sufficient flame-retardant effect, and the method of using titanium oxide powder or carbon black in combination with a platinum compound is transparent. It is difficult to obtain a product with excellent properties.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has excellent flame retardancy and excellent transparency.
Another object of the present invention is to provide a silicone resin-based treating agent for a glass fiber fabric product having flexibility.

[0005]

Means for Solving the Problems The present invention has solved the above-mentioned problems, and comprises : (a) a vinyl compound directly bonded to at least two silicon atoms in one molecule represented by [Chemical Formula 3]; A hydrogen atom directly bonded to at least two silicon atoms in one molecule of a vinyl group-containing organopolysiloxane having 5% by mole or less of an organic group having a vinyl group directly bonded to a silicon atom; An organohydrogenpolysiloxane in an amount sufficient to provide at least 0.5 hydrogen atoms directly bonded to the silicon atoms to one vinyl group in the component (a).

Embedded image [R ¹ represents an aliphatic unsaturated group which may be the same or different from each other ;
One or more selected from the group consisting of a monovalent hydrocarbon group not containing and an alkoxy group represented by R ³ O— (R ³ is an alkyl group having 1 to 6 carbon atoms), and R ² is an aliphatic group A monovalent hydrocarbon group having 2 to 8 carbon atoms having an unsaturated group;
An integer of 00, q is an integer of 1 to 100, and 0 ≦ p / q ≦ 1
And at least 25 mol% or more of the organic group directly bonded to the silicon atom is R ² , and n is an integer of 0 to 3. (D) a treating agent for a glass fiber fabric, which comprises a catalytic amount of platinum or a platinum compound.

That is, the inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an organopolysiloxane containing a vinyl group has an organohydrogen having at least two hydrogen atoms directly bonded to silicon atoms in one molecule. A composition obtained by blending a composition containing a polysiloxane and a platinum-based catalyst with a relatively low-molecular-weight organopolysiloxane containing a high proportion of aliphatic unsaturated groups in the molecule has a flexibility. It forms a transparent and flame-retardant film, and this film can be formed by heat treatment at a relatively low temperature and for a short time. The inventors have found that they exhibit heat resistance, and have reached the present invention.

Hereinafter, the present invention will be described in detail. As the component (A) of the treating agent of the present invention, at least 5% by mole of an organic group having a vinyl group directly bonded to at least two silicon atoms in one molecule and having a vinyl group directly bonded to a silicon atom. With the following general formula

Embedded image (Where R ⁴ is a monovalent hydrocarbon group or a hydroxyl group, R ⁵
Is a monovalent hydrocarbon group, at least two of R ⁴ and R ⁵ are vinyl groups, and m represents an integer. It is preferable to use a vinyl group-containing organopolysiloxane represented by the following formula), and by using such a compound,
It is possible to obtain a treatment agent for a glass fiber fabric product having a cured treatment film having a high flexibility. Here, R ⁴ and R ⁵ may be the same or different, and each monovalent hydrocarbon group may be substituted or unsubstituted. Specifically, examples of the monovalent hydrocarbon group of R ⁴ and R ⁵ include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group. Aryl groups, cycloalkyl groups such as cyclohexyl groups, and chloromethyl groups, fluoropropyl groups, and cyanomethyl groups in which some or all of the hydrogen atoms bonded to carbon atoms of these organic groups have been substituted with halogen atoms, cyano groups, and the like. Examples can be given.

Further, when this compound is used in combination with a branched compound, the mechanical strength of the treated film after curing can be increased. Also, the vinyl group-containing organopolysiloxane (a) has a viscosity at 25 ° C. of 100 to 10,000.
00,000 centistokes (hereinafter abbreviated as cs)
It is preferred that Viscosity is 10,000,000c
If it is larger than s, the workability may be poor when impregnating or applying a glass fiber fabric product as an electrical insulating material using the treatment agent of the present invention, and if it is smaller than 100 cs, the film formed by the treatment agent becomes brittle. There are cases.

The component (b) of the treating agent of the present invention is an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to one silicon atom in one molecule. Reacts with organopolysiloxane and crosslinks to form a cured film. The organohydrogenpolysiloxane of the component (b) may be linear, branched or cyclic.

Embedded image

Embedded image

Embedded image (Wherein, R ⁶ is one or more groups selected from a hydrogen atom, an alkyl group, and an aryl group, and two or more of R ^{6 in} one molecule are hydrogen atoms; Is a positive integer of 3 or more, and a is 1.5 to 2.), but is not limited thereto.

The amount of the component (b) used is such that the number of hydrogen atoms of the component (b) per one vinyl group in the component (a) is 0.1.
The amount is set to be 5 or more. When the amount of the hydrogen atom of the component (b) is less than the above amount, the effect as a curing agent is not sufficient, and the curability is poor, and the strength and electric insulation are reduced. Furthermore, the number of hydrogen atoms in the component (b) is (a)
Within a range not exceeding 100 times the number of vinyl groups in the component (b)
It is preferable to mix the components, and when the number of hydrogen atoms in the component (b) exceeds 100 times the number of vinyl groups in the component (a),
In some cases, the curability is reduced and the function of the treated film is reduced.

The treating agent of the present invention further contains the above component (c) as the third component. The component (c) is added for the purpose of enhancing the flame retardancy of the treating agent of the present invention, and has the general formula

Embedded image [R ¹ represents an aliphatic unsaturated group which may be the same or different from each other ;
One or more selected from the group consisting of a monovalent hydrocarbon group not containing and an alkoxy group represented by R ³ O— (R ³ is an alkyl group having 1 to 6 carbon atoms), and R ² is an aliphatic group A monovalent hydrocarbon group having 2 to 8 carbon atoms having an unsaturated group;
An integer of 00, q is an integer of 1 to 100, and 0 ≦ p / q ≦ 1
And at least 25 mol% or more of the organic groups directly bonded to the silicon atom are R ² , and n is an integer of 0 to 3]. Here, R ¹ may be the same or different from each other, and each monovalent hydrocarbon group may be substituted or unsubstituted.

Specific examples of the monovalent hydrocarbon group include:
Alkyl groups such as methyl group, ethyl group, propyl group and butyl group, aryl groups such as phenyl group and tolyl group, cycloalkyl groups such as cyclohexyl group, and part of hydrogen atoms bonded to carbon atoms of these organic groups Alternatively, a chloromethyl group, a fluoropropyl group, and a cyanomethyl group, all of which are substituted with a halogen atom, a cyano group, or the like, may be mentioned, but a methyl group or a phenyl group is industrially preferred. ² to 2 carbon atoms having an aliphatic unsaturated group contained in R 2
Examples of the monovalent hydrocarbon group of 8 include a vinyl group and an allyl group, but a vinyl group is industrially preferable.

The component (c) has a siloxane chain p of 0 to 10;
0 is an integer, q is an integer of 1 to 100, and 0 ≦ p / q ≦ 1
And n is an integer of 0 to 3, and at least 25 mol% or more, preferably 40% or more, of the organic group directly bonded to the silicon atom.
There is no particular limitation so long as the mole% or more is R ² , but those having a viscosity at 25 ° C. of 5 to 1000 centistokes are preferred in view of workability. As the component (c), an organopolysiloxane having a vinyl group content of 50 mol% or more is particularly preferred.

The amount of the component (c) is not particularly limited, but is preferably 0.01 to 10 parts by weight per 100 parts by weight of the component (a). When the amount is less than 0.01 part by weight, the effect of improving the flame retardancy is insufficient. When the amount is more than 10 parts by weight, the film becomes hard or reacts with the component (b).
This is because the effective cross-linking reaction between the component and the component (b) may be inhibited, and the treatment agent may not be cured. The component (C) having a (CH ₂ CHCH) ₃ —SiO— structure at the molecular terminal is particularly preferable for improving the flame retardancy. Although the detailed reason is unknown, due to the presence of many vinyl groups at the molecular end,
It is considered that the three-dimensional crosslinking when heated is effectively accelerated and the flame retardancy is improved.

Further, the treating agent of the present invention contains a platinum-based catalyst as component (d), and this platinum-based catalyst promotes the addition reaction between component (a) and component (b). Specific examples of the platinum-based catalyst include platinum alone, platinum alone adsorbed on a holding carrier, chloroplatinic acid, a platinum-olefin complex, and a platinum coordination compound. The amount of the platinum-based catalyst used is a catalytic amount, and is usually added and used in the range of 1 to 100 ppm as platinum metal with respect to the total weight of the components (a) and (b). If the amount is small, the curing is slow. On the other hand, if it is too large, the pot life is short and the cost may be disadvantageous.

The treating agent of the present invention preferably contains a silica filler as another component. By adding the silica filler to the treating agent of the present invention, a treated film having excellent mechanical strength can be obtained. A treating agent to be formed can be obtained.
In this case, examples of the silica-based filler include fumed silica, diatomaceous earth, and precipitated silica. Among them, fumed silica hydrophobized with a silane compound is preferably used. Furthermore, the average particle size is 50 mμ or less, particularly 30 mμ or less, and the specific surface area is 50 to 50 μm.
It is preferable to use a silica-based filler of 0 m ² / g.
The amount of the silica filler to be used is preferably from 0 to 100 parts by weight based on 100 parts by weight of the component (a). In some cases, the workability when processing a textile fabric product is deteriorated.

The treating agent of the present invention can be obtained by blending the above-mentioned components (a) to (d) and, if necessary, a silica-based filler and simply mixing these components. Can also be used. Other additives include acetylene alcohols having a function of extending the pot life, reaction retarders such as vinyl group-containing low molecular weight siloxanes, nitrile compounds, phosphate esters, iron oxide, aluminum hydroxide, and carbonate. A flame retardant such as zinc, mica powder, talc powder, potassium titanate, etc., and a heat resistance imparting agent can be blended.

The treating agent according to the present invention is impregnated with a glass fiber woven product or coated with a glass fiber woven product, and then heated to form a cured film on the glass fiber woven product. It is used by forming. In this case, the treating agent may be used without solvent, or may be dissolved and diluted in a solvent and used at a concentration and viscosity that are easy to use. The solvent is not particularly restricted but includes, for example, hydrocarbon solvents such as toluene, xylene, rubber volatile oil and naphtha, halogen solvents such as perchloroethylene and 1,1,1-trichloroethane, and esters. And polar solvents such as ketones, and one of these can be used alone or as a mixture of two or more.

When the glass fiber fabric product is treated with the treatment agent of the present invention by, for example, impregnation, coating, or the like, and a predetermined amount of the treatment agent is applied to the glass fiber fabric product, and then heat treatment is performed, the heat treatment conditions include Is 100 ~
The condition of treating at 250 ° C. for 1 to 30 minutes can be adopted. In this case, if necessary, the object to be processed is subjected to heat cleaning, primers,
It can be pretreated with a silane coupling agent, a low molecular hydrogen polysiloxane, or the like. The type of the glass fiber woven product treated with the treating agent of the present invention is not limited, and examples thereof include a glass sleeve, a glass cloth, a glass roving, a glass tape, a glass mat, and a glass nonwoven fabric.

[0020]

The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. A treating agent was prepared according to the formulation shown in Table 1 (the blending amount indicates parts by weight), and properties of the glass sleeve treated with the resulting treating agent were evaluated by the following methods. The results are also shown in Table 1. The components used in the formulations in Table 1 are as follows.

Organosiloxane 1: Viscosity of 10,000 cs in which both molecular chain terminals are blocked with dimethylvinylsilyl group
(25 ° C.) dimethylpolysiloxane organosiloxane 2: dimethylpolysiloxane having a viscosity of 5000 cs (25 ° C.) in which both ends of the molecular chain are blocked with trivinylsilyl groups Organosiloxane 3: both ends of the molecular chain are blocked with dimethylvinylsilyl groups Dimethylpolysiloxane with a viscosity of 1000cs (25 ° C)

Silica powder: fumed silica powder treated with trimethylchlorosilane (specific surface area: about 200 m
² / g)

Organohydrogensiloxane 1: Viscosity of both ends of molecular chain blocked by trimethylsilyl group: 20
cs (25 ° C.) of methylhydrogenpolysiloxane organohydrogensiloxane 2: for one SiO ₂ units (CH ₃₎ 0.5 or ₃ SiO _{1/2 units, (CH 3) 2 (H} ) SiO 1 Organohydrogenpolysiloxane having a ratio of 1.2 units _{/ 2} units

High alkenyl siloxane 1: average formula

Embedded image Methyl vinyl polysiloxane represented by the formula: High alkenyl siloxane 2: average formula

Embedded image Organovinylpolysiloxane represented by the formula: High alkenyl siloxane 3: average formula

Embedded image Organoalkenyl polysiloxane represented by the formula: alkenyl siloxane: average formula

Embedded image An organoalkenyl polysiloxane represented by

Platinum-based catalyst: containing 0.5% platinum, platinum /
Vinylsiloxane complex

The treatment of the glass sleeve with the treating agent (preparation of a test piece) and the measurement of the properties of the treated glass sleeve were performed as follows. Treatment of glass sleeve with treatment agent: The treatment agent of Examples 1 to 10 and Comparative Examples 1 to 4 was impregnated and applied to a glass sleeve having an inner diameter of 3 mm so as to have an adhesion amount of 3 to 3.5 g / m.
A heat treatment was performed at 50 ° C. for 15 minutes to form a silicone-coated glass sleeve, and the characteristics of the sleeve were measured. Amount of adhesion: The amount of adhesion per 1 m was obtained in units of g from the weight difference of the sleeve before and after the impregnation application. Tack: Presence or absence was judged by touch. Dielectric breakdown strength: Measured on a sleeve under normal conditions and after absorbing 90% RH / 24 Hrs moisture. (Unit KV) Flame retardancy: After a flame of an alcohol lamp was applied to the lower end of the vertically hung sleeve for 5 seconds, the time from when the flame was removed to when the sleeve no longer glows red was measured.

[0027]

[Table 1] In addition, the cured film of the treating agent in the example was excellent in transparency and flexibility.

[0028]

According to the present invention, excellent characteristics are provided.
That is, a novel silicone resin-based treating agent for glass fiber fabric products having excellent flame retardancy, excellent transparency, flexibility, and excellent electrical properties was provided. The treating agent of the present invention achieves excellent flame retardancy by a new formulation in place of a component that impairs transparency and flexibility, and has not been conventionally provided in that it has the above-mentioned properties.

Claims (2)

(57) [Claims] (1) 5 moles of an organic group having at least two vinyl atoms directly bonded to a silicon atom in one molecule represented by the following formula ( 3 ) and the vinyl group being directly bonded to a silicon atom: % Or less of a vinyl group-containing organopolysiloxane of 100 % or less
(B) one molecule has at least two hydrogen atoms directly bonded to a silicon atom in one molecule, and the hydrogen atom directly bonded to the silicon atom is added to each of the vinyl groups in the component (a) in an amount of 0.1% . An organohydrogenpolysiloxane in an amount sufficient to give 5 or more (c) general formula [R ¹ represents an aliphatic unsaturated group which may be the same or different from each other ;
One or more selected from the group consisting of a monovalent hydrocarbon group not containing and an alkoxy group represented by R ³ O— (R ³ is an alkyl group having 1 to 6 carbon atoms), and R ² is an aliphatic group A monovalent hydrocarbon group having 2 to 8 carbon atoms having an unsaturated group;
An integer of 00, q is an integer of 1 to 100, and 0 ≦ p / q ≦ 1
And at least 25 mol% or more of the organic group directly bonded to the silicon atom is R ² , and n is an integer of 0 to 3. A glass fiber fabric treating agent comprising 0.01 to 10 parts by weight (d) a catalytic amount of platinum or a platinum compound represented by the formula (1): 2. A monovalent hydrocarbon having 2 to 8 carbon atoms, wherein n of the component (c) is 3 and all R ² bonded to the molecular terminals of the component (c) have an aliphatic unsaturated group. The treatment agent for a glass fiber fabric according to claim 1, which is a base.