JP2006225794A - Perfluoropolyether fluorine-containing rubberized cloth - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber-coated cloth which can be used in wide fields such as electrical and electronic fields, starting with component maintenance associated with coating and machine and having large industrial utility value. <P>SOLUTION: The rubber-coated cloth is obtained by impregnating and/coating cloth with a perfluoropolyether-based fluorine-containing rubber. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a rubberized cloth impregnated and / or coated with a perfluoropolyether-based fluororubber having good solvent resistance, chemical resistance, heat resistance, and low temperature characteristics.

  Rubberized cloth is used in tents, rain gear, automotive airbags, various sealing materials, anti-slip sheets, cushion sheets, and the like. Examples of rubber materials used for these include natural rubber (NR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), butadiene rubber (BR), isoprene rubber (IR), and ethylene-propylene copolymer (EPM). ), Ethylene-propylene-nonconjugated diene terpolymer (EPDM), chloroprene rubber (CR), butyl rubber (IIR), urethane rubber, silicone rubber, chlorinated polyethylene rubber, fluoro rubber (FKM), acrylic rubber, epichlorohydrin rubber , Ethylene-acrylic rubber, etc., but when using a rubberized cloth for work such as slip prevention, when the organic solvent or various lubricating oils come into contact with the conventional rubberized cloth, the rubberized cloth will swell Due to this, there is a problem that it is deformed or becomes brittle.

  Also, when cleaning or washing using a solvent for the purpose of removing dirt adhering to the surface of the rubberized cloth, the conventional rubberized cloth has insufficient solvent resistance and is particularly excellent in cleaning properties. Such polar solvents such as those based on alcohols, lower alcohols, esters, and aromatics have the disadvantage of being easily deteriorated and inferior in durability.

In addition, the following is mentioned as a prior art relevant to this invention.
Japanese Patent No. 2990646 Japanese Patent No. 3077536 Japanese Patent No. 3329717 Japanese Patent No. 3413713 Japanese Patent Laid-Open No. 2004-10808

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a rubberized cloth excellent in solvent resistance, lubricating oil resistance, and chemical resistance.

As a result of intensive studies to achieve the above object, the present inventor has found that perfluoropolyether-based fluorine-containing rubber, in particular, the crosslinking site is Si—CH═CH ₂ and the crosslinking system is addition reaction crosslinking. When a cured product of a fluororubber composition, particularly a cured product of a crosslinkable fluororubber composition containing the following components (A) to (C), is impregnated or coated with a woven or non-woven fabric, the solvent resistance, It was found that a rubberized cloth excellent in lubricating oil resistance and chemical resistance was obtained, and the present invention was made.

［式中、Ｘは−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ−ＣＯ−（Ｙは−ＣＨ₂−又は下記構造式（Ｚ）

（ｏ，ｍ又はｐ位）で示される基）
で表される基、Ｒは水素原子、メチル基、フェニル基又はアリル基、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（Ｚ’）

（ｏ，ｍ又はｐ位）で示される基）
で表される基であり、Ｒは上記と同じである。ａは独立に０又は１、Ｌは２〜６の整数、ｂ及びｃはそれぞれ０〜２００の整数である。］
で表される直鎖状フルオロポリエーテル化合物であることを特徴とする請求項３記載のゴム引き布。 Accordingly, the present invention provides the following perfluoropolyether-based fluorine-containing rubberized cloth.
Claim 1:
A rubberized cloth impregnated and / or coated with a perfluoropolyether fluorine-containing rubber.
Claim 2:
The perfluoropolyether-based fluorine-containing rubber is obtained by curing a crosslinkable fluororubber composition in which a crosslinking site is Si—CH═CH ₂ and a crosslinking system is addition reaction crosslinking. Item 1. A rubberized cloth according to item 1.
Claim 3:
The perfluoropolyether fluorine-containing rubber is
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer obtained by adding the hydrosilyl group of a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule;
A crosslinkable fluororubber composition comprising (B) a reinforcing filler and (C) a crosslinking agent having a hydrosilyl group in the molecule and sufficient for curing the component (A). The rubberized cloth according to claim 2, wherein the rubberized cloth is cured.
Claim 4:
In the component (A), the alkenyl group-containing perfluoro compound before the hydrosilylation addition reaction is represented by the following general formula (1).

[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR-CO- (Y is -CH ₂ - or the following structural formula (Z)

(Group represented by o, m or p position)
R is a hydrogen atom, methyl group, phenyl group or allyl group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR—Y ′ — (Y 'Is -CH ₂ -or the following structural formula (Z')

(Group represented by o, m or p position)
R is the same as above. a is independently 0 or 1, L is an integer of 2 to 6, and b and c are integers of 0 to 200, respectively. ]
The rubberized cloth according to claim 3, which is a linear fluoropolyether compound represented by the formula:

  The rubberized cloth of the present invention is obtained by impregnating and / or coating a woven or non-woven fabric with a crosslinkable fluororubber composition that forms a perfluoropolyether-based fluororubber having excellent solvent resistance, and then heat-curing the composition. It is easily manufactured and can be used in a wide range of fields such as electrical and electronic parts maintenance, including paint-related and machine-related parts maintenance, and its industrial utility value is great.

The rubberized cloth of the present invention can be produced by impregnating and / or coating a crosslinkable fluororubber composition that forms a perfluoropolyether-based fluororubber on a woven fabric or non-woven fabric, followed by heat curing.
Examples of the woven or non-woven fabric (hereinafter referred to as “base material”) used for the rubberized fabric include cotton, cellulosic fiber, polyester fiber, polyethylene fiber, polypropylene fiber, polyvinyl alcohol fiber, nylon fiber, aramid fiber, and glass fiber. Woven fabrics or non-woven fabrics made of single or mixed blends of ceramic fibers, asbestos fibers and the like. Further, a primer may be applied to the surface of the base material in order to improve the adhesion between the base material and the perfluoropolyether-based fluorine-containing rubber.

  The thickness of the substrate is selected from the range of 10 μm to 1 mm, but if it is too thin, the strength as a support is lacking, and if it is too thick, the amount of the crosslinkable fluororubber composition that penetrates into the substrate increases. Since it is uneconomical, it is preferably in the range of 20 μm to 500 μm.

In the crosslinkable fluororubber composition forming the perfluoropolyether-based fluororubber used in the present invention, the crosslinking site is Si—CH═CH ₂ . It is preferable that the crosslinked system is a cured product of a crosslinkable fluororubber composition having addition reaction crosslinking. Such a composition is described in detail in Japanese Patent No. 2990646, Japanese Patent No. 3077536, Japanese Patent No. 3329717, Japanese Patent No. 3413713, etc., and trade name SIFEL series (Shin-Etsu Chemical Co., Ltd.). In general).

Among these, as perfluoropolyether type fluorine-containing rubber,
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer obtained by adding the hydrosilyl group of a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule;
A crosslinkable fluororubber composition comprising (B) a reinforcing filler and (C) a crosslinking agent having a hydrosilyl group in the molecule and sufficient for curing the component (A). It is preferable to be cured.

  In the component (A), the alkenyl group-containing perfluoro compound (i) before adding the compound having a hydrosilyl group may be a linear fluoropolyether compound represented by the following general formula (1). preferable.

［式中、Ｘは−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ−ＣＯ−（Ｙは−ＣＨ₂−又は下記構造式（Ｚ）

[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR-CO- (Y is -CH ₂ - or the following structural formula (Z)

（ｏ，ｍ又はｐ位）で示される基）
で表される基、Ｒは水素原子、メチル基、フェニル基又はアリル基、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（Ｚ’）

(Group represented by o, m or p position)
R is a hydrogen atom, methyl group, phenyl group or allyl group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR—Y ′ — (Y 'Is -CH ₂ -or the following structural formula (Z')

（ｏ，ｍ又はｐ位）で示される基）
で表される基であり、Ｒは上記と同じである。ａは独立に０又は１、Ｌは２〜６の整数、ｂ及びｃはそれぞれ０〜２００の整数であり、好ましくはｂ，ｃはそれぞれ独立に２〜１８０の整数であり、特に好ましくはｂ，ｃはそれぞれ独立に１０〜１５０の整数である。］

(Group represented by o, m or p position)
R is the same as above. a is independently 0 or 1, L is an integer of 2 to 6, b and c are each an integer of 0 to 200, preferably b and c are each independently an integer of 2 to 180, particularly preferably b. , C are each independently an integer of 10 to 150. ]

  To the linear fluoropolyether compound of the formula (1), a hydrosilyl group of a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule is added to a part of the alkenyl group of the compound. This is used as the component (A).

  The compound (ii) capable of undergoing addition reaction with an alkenyl group containing at least two hydrosilyl groups in the molecule includes those containing a hydrosilyl group in an organic compound and those containing a hydrosilyl group in an organosilicon compound. However, in consideration of dispersibility and heat resistance, a compound of the following formula (2) or formula (3) is desirable.

〔式中、Ｘ，Ｘ’，ａは上記と同様の意味を示す。Ｒｆは２価のパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基を示す。Ｙは下記一般式（４）

[Wherein X, X ′ and a have the same meaning as described above. Rf represents a divalent perfluoroalkylene group or a divalent perfluoropolyether group. Y is the following general formula (4)

（但し、Ｒ¹は置換又は非置換の一価炭化水素基、ｐは式（２）の化合物の場合は１，２又は３、式（３）の化合物の場合は２又は３である。）
で示される基を示す。〕

(Wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, p is 1, 2 or 3 in the case of the compound of formula (2), and 2 or 3 in the case of the compound of formula (3).)
The group shown by is shown. ]

  Specific examples of the formulas (2) and (3) include those described in Japanese Patent Application Laid-Open No. 2004-10808.

The amount of the component (ii) is such that the ratio of the component (i) to the component (ii) is such that the amount of hydrosilyl groups in the component (ii) / the amount of alkenyl groups in the component (i) is 0.1. It is the range which becomes -0.99, Preferably it becomes 0.3-0.8, (i) It is the quantity which the alkenyl group of a component remains.
That is, the component (A) has an average of at least two alkenyl groups in one molecule.

  Examples of the reinforcing filler of the component (B) include fumed silica, wet silica, pulverized silica, calcium carbonate, diatomaceous earth, carbon black, various metal oxide powders, and the like. It may be processed. Among these, fumed silica is particularly preferable from the viewpoint of improving mechanical strength, and further, fumed silica treated with a silane-based surface treatment agent is preferable from the viewpoint of improving dispersibility.

  (B) As an addition amount of the reinforcing filler of a component, 1-200 mass parts is preferable with respect to 100 mass parts of (A) component. In particular, 5 to 100 parts by mass is preferable from the viewpoint of stability of mechanical properties.

  Component (C) is a crosslinking agent that cures the polymer of component (A), and is a crosslinking agent capable of addition reaction having a hydrosilyl group in the molecule.

  Examples of the component (C) include organosilicon compounds such as organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and are compatible with the component (A). From the viewpoints of dispersibility and uniformity after curing, those having one or more fluorine-containing monovalent hydrocarbon groups in one molecule are preferred, and examples thereof include compounds such as component (ii) described above.

  Furthermore, it is preferable to use a catalyst that promotes the addition reaction between the alkenyl group and the hydrosilyl group in component (A). This hydrosilylation reaction catalyst is generally a noble metal compound and is expensive, Platinum group metal compounds such as platinum or platinum compounds that are readily available are often used.

  Component (C) may be added in an amount sufficient to cure the polymer of component (A). Usually, the molar ratio of hydrosilyl group in component (C) / alkenyl group in component (A) Is in a range of 0.5 to 2.0, more preferably 0.8 to 1.5. Platinum or a platinum group metal compound such as a platinum compound is a platinum group metal with respect to the mass of the component (A). 0.1 to 1,000 ppm, preferably 1 to 500 ppm.

  Examples of the addition reaction cross-linking perfluoropolyether-based fluororubber composition described above include SIFEL series (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by SIFEL661, SIFEL3155 and the like.

  When the composition form is a liquid rubber composition, the crosslinkable fluororubber composition can be impregnated with a substrate as it is or can be applied by coating. Although it depends on the conditions of impregnation and coating, if the viscosity at 23 ° C. is 300 Pa · s or less, it can be applied without solvent. You may use it, reducing.

  Although it does not restrict | limit especially about the coating method etc., You may apply | coat and shape | mold by methods, such as knife coating, roll coating, reverse coating, gravure coating, and screen coating.

The amount of the crosslinkable fluororubber composition applied to the substrate is appropriately selected, but is usually 20 to 2,000 g / m ² , particularly 50 to 1,000 g / m ² , and if it is too small, sufficient performance can be obtained. In some cases, the strength may be inferior, and it is uneconomical.

  The curing conditions after impregnation and coating are usually 100 to 200 ° C. for 30 seconds to 15 minutes, particularly 100 to 180 ° C. for 30 seconds to 15 minutes. Further, in order to make the curing more complete, after-curing may be performed at 120 to 200 ° C. for 30 minutes to 4 hours, but in this case, the heat resistance of the substrate must be taken into consideration.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Example 1]
A nylon fiber nonwoven fabric having a thickness of about 200 μm is fixed on a polytetrafluoroethylene (PTFE) sheet, and a perfluoropolyether fluorine-containing rubber composition; SIFEL661 (manufactured by Shin-Etsu Chemical Co., Ltd., liquid one-component addition reaction) Crosslinking type composition (containing components (A) to (C)) was knife-coated, cured at 120 ° C. for 5 minutes, and then aftercured at 120 ° C. for 1 hour to obtain a rubberized cloth. The obtained rubberized cloth was cut into a size of 50 mm × 25 mm, the cut test piece was immersed in various solvents shown in Table 1 at 40 ° C. for 24 hours, and the state after immersion was visually observed. The results are shown in Table 1.

[Example 2]
A glass fiber woven fabric having a thickness of about 300 μm is fixed on a PTFE sheet, and a perfluoropolyether-based fluorine-containing rubber composition SIFEL 3155 (manufactured by Shin-Etsu Chemical Co., Ltd., liquid one-component addition reaction crosslinking type composition, (A ) To (C) containing component) were knife coated and cured at 150 ° C. for 5 minutes to obtain a rubberized cloth. The obtained rubberized cloth was cut into a size of 50 mm × 25 mm, the cut test piece was immersed in various solvents shown in Table 1 at 40 ° C. for 24 hours, and the state after immersion was visually observed. The results are shown in Table 1.

[Comparative Example 1]
A glass fiber woven fabric having a thickness of about 300 μm is fixed on a PTFE sheet, and a silicone rubber composition; KE106 (manufactured by Shin-Etsu Chemical Co., Ltd., liquid one-component addition reaction crosslinking type composition) is knife coated, and 150 A rubberized cloth was obtained by curing at 10 ° C. for 10 minutes. The obtained rubberized cloth was cut into a size of 50 mm × 25 mm, the cut test piece was immersed in various solvents shown in Table 1 at 40 ° C. for 24 hours, and the state after immersion was visually observed. The results are shown in Table 1.

○：外観変化なし。基材との剥離なし。
△：一部基材とゴムとの剥離あり。
×：全体的に基材とゴムが剥離。

○: No change in appearance. No peeling from the substrate.
(Triangle | delta): There exists peeling of a one part base material and rubber | gum.
X: The base material and the rubber peeled as a whole.

Claims (4)

  A rubberized cloth impregnated and / or coated with perfluoropolyether fluorine-containing rubber. The perfluoropolyether-based fluorine-containing rubber is obtained by curing a crosslinkable fluororubber composition in which a crosslinking site is Si—CH═CH ₂ and a crosslinking system is addition reaction crosslinking. Item 1. A rubberized cloth according to item 1. The perfluoropolyether fluorine-containing rubber is
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer obtained by adding the hydrosilyl group of a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule;
A crosslinkable fluororubber composition comprising (B) a reinforcing filler and (C) a crosslinking agent having a hydrosilyl group in the molecule and sufficient for curing the component (A). The rubberized cloth according to claim 2, wherein the rubberized cloth is cured. In the component (A), the alkenyl group-containing perfluoro compound before the hydrosilylation addition reaction is represented by the following general formula (1).

[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR-CO- (Y is -CH ₂ - or the following structural formula (Z)

(Group represented by o, m or p position)
R is a hydrogen atom, methyl group, phenyl group or allyl group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR—Y ′ — (Y 'Is -CH ₂ -or the following structural formula (Z')

(Group represented by o, m or p position)
R is the same as above. a is independently 0 or 1, L is an integer of 2 to 6, and b and c are integers of 0 to 200, respectively. ]
The rubberized cloth according to claim 3, which is a linear fluoropolyether compound represented by the formula: