JPS60125664A - Manufacture of silicon elastomer coated cloth - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of making silicone elastomer coated fabrics. More specifically, the present invention relates to a method for producing a silicone elastomer-coated cloth in which an addition reaction-curable silicone elastomer and a cloth are firmly adhered to each other.

In recent years, silicone elastomer-coated fabrics have been coated with silicone elastomers for ski wear, golf wear, raincoats, firefighting suits, tents, diaper covers, etc., taking advantage of the excellent water vapor permeability, oxygen permeability, waterproofness, heat resistance, and weather resistance of silicone elastomer-coated fabrics. The use of cloth is being actively considered.

This silicone elastomer has various curing functions, and among them, silicone elastomer obtained by addition reaction curing function cures at low temperature and in a short time, has good productivity, and does not produce by-products during curing, so it has a sponge-like appearance. This silicone elastomer is most suitable as a silicone elastomer for coating fabrics because it does not smear or cause microvoids and has no tackiness.

However, this addition reaction-curable silicone elastomer has a weak adhesive strength with cloth, and has the drawback that the coating easily peels off and is easily damaged when worn or washed. Additionally, even if fabric is pretreated with aminosilane, epoxysilane, or mercaptosilane, and then coated with silicone elastomer, the resulting coated fabric will not only become rough and hard, but will have little effect on improving adhesive strength. It had drawbacks.

The inventors of the present invention have made extensive studies to overcome these drawbacks, and as a result have come up with a method for manufacturing a silicone elastomer-coated cloth in which the silicone elastomer and the cloth are firmly bonded.

That is, the present invention includes (A) 100 parts by weight of a silicone pressure sensitive adhesive (B)
Rn general formula 2', Si X (3n) (wherein, Z is an organic group or hydrogen atom having an aliphatic unsaturated group, A J:9 fabric is treated with a treatment agent consisting of 1 to 100 parts by weight of silane or its partially hydrolyzed condensate (n is 0.1 or 2), and an addition reaction-curable silicone elastomer composition is applied to the J:9 fabric. The present invention relates to a method for producing a silicone elastomer-coated fabric, which comprises coating an object and curing the fabric.

To explain this, component (A), together with component (B), is used to firmly adhere the silicone elastomer composition and cloth. A silicone pressure-sensitive adhesive is a silicone-based adhesive that sticks firmly to an adhesive object by just pressing it lightly.
Japanese Patent Publication No. 30-5186, Japanese Patent Publication No. 32-5099, Japanese Patent Publication No. 2881-1973, Japanese Patent Publication No. 47-33
Conventionally known silicone pressure-sensitive adhesives described in Japanese Patent Application Laid-Open No. 1989-138029, Japanese Patent Application Laid-Open No. 56-49778, and Japanese Patent Application Laid-Open No. 57-168974 can be used.

The main components are R'3sioo, 5, R' □S i
O.

R' S i O + , s, (wherein R1 is an unsubstituted-valent hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a vinyl group, a phenyl group, or a group in which these are substituted with a halogen atom, etc.) Ol/polysiloxane tIf fatty copolymer vehicle 5 consisting of one or more units selected from the above and S i 02 units, and having at least one hydroxyl group bonded to a silicon atom in its molecule. ~95 2 parts by weight, substantially 1: R3-5iO (R2, R'' is the same as R1 described above) units, and has a viscosity of at least 3-100 centistokes or more at 25°C. It is a silicone pressure sensitive adhesive consisting of 95 to 5 parts by weight of organopolysiloxane.

Component (B) is a silane or a partially hydrolyzed condensate thereof having a hydrolyzable group and an aliphatic unsaturated group or a hydrogen atom in one molecule, and the hydrolyzable group in component (B) and (A )
reacts with the hydroxyl groups in component (B) to crosslink it, and reacts with the aliphatic unsaturated groups or SiH in component (B) and the SiH or vinyl groups in the addition reaction curable silicone elastomer composition that is later coated; It imparts adhesive properties.

In the above general formula, Z is an organic group having an aliphatic unsaturated group or a hydrogen atom, and includes 11, CH2=CH-1
CH2=CI-CI+2-1CH.

CH2=C-Cl+□-1CH2=CI (C112)
2-1C112=C1l (C112)3-1C112
=CIl-C-0-(('II□)3-1 C11゜CH2=CC-0-(CH2)3- 〇4- 〇 etc. X is a hydrolyzable organic group, and For example, CH,0-1C21150-1C,H,0-1
C) an alkoxy group such as 130CH2Cf120-,
alkenyloxy groups such as impropenoxy groups, ct
+, coo-1c2t+, coo-1C3H7COO-
ft tof) 7 There are oxime groups such as O2115\C2H5-C=NO-.

R is an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

Preferred are methyl and ethyl groups. n is 0.1*
or 2, with 0 or 1 being common. Examples of such silanes include HSi(OCHs)+, ClI2=CH5i(OCHs)
)1, CH2=CHSi(OCH3)+, CH2=CH
-5i -OCllzC112=CII 5i(OC2
Ils)3, CH3 CH2=CH-3i (OCJ5)2, CH=CH-5i
(OCCH3) 3, 0 CH2=CHl C1125i (OCII3) 8, 11
3 C112”Cl-C112-5i (OC2115)2,
113 Cf12=CCO(CH2)3 5i(OCHs)3,
1 CH2=CHCO(CI(2)3 5i(QC1lsl
+, 1 CH2=CC-C-CH2CHCH2Si (OCI+3)
3, OC11゜CI2”CFI CCH2CHCH2SI (OCH3)
3, I, etc.

The cloth may be in the form of woven fabrics, knitted fabrics, nonwoven fabrics, or laminates thereof, and its materials include natural fibers such as cotton, hemp, wool, and silk, semi-synthetic fibers such as rayon and acetate, nylon, polyester, It may be 100% synthetic fiber such as polyacrylonitrile, inorganic fiber such as asbestos, glass fiber, or a mixture thereof.

The addition reaction curable silicone elastomer composition that coats the fabric is based on an aliphatic unsaturated group such as a vinyl group bonded to a silicon atom constituting an organopolysiloxane, another organohydrodiene polysiloxane, and a platinum group compound catalyst. It is cured by an addition reaction. Organopolysiloxanes containing aliphatic unsaturated groups such as vinyl groups include dimethylpolysiloxanes with vinyl dimethylsilyl groups at both ends, dimethylpolysiloxane/methylvinylpolysiloxane copolymers with vinyl 7-dimethylsilyl groups at both ends, vinyl methyl 7
There are dimethylpolysiloxane/methylphenylpolysiloxane copolymers blocked with enyl groups, and organohydrodiene polysiloxanes such as methylhydrodienepolysiloxanes with both ends blocked with trimethylsilyl groups,
Trimethylsilyl groups at both ends! Examples include chain dimethylpolysiloxane/methylhydrogenpolysiloxane copolymer, dimethylpolysiloxane/methylhydrogenpolysiloxane copolymer with dimethylsilyl groups endblocked at both ends, and methylhydrogencyclopolysiloxane.

Examples of platinum group compound catalysts include fine particulate platinum, chloroplatinic acid, complexes of platinum and olefins, complexes of platinum and vinyl siloxane, complexes of platinum and diketones, palladium compound catalysts, and rhodium compound catalysts. A platinum compound catalyst is preferred.

This silicone efstomer composition desirably contains a reinforcing inorganic filler, such as dry-processed silica, wet-processed silica, hydrophobized products of these silicas, or carbon black, and also contains a reaction-suppressing inorganic filler. It may also contain additives, pigments, heat stabilizers, etc.

The silicone elastomer-coated fabric of the present invention is first prepared by (A)
It can be produced by treating a cloth with a treatment agent consisting of 100 parts by weight of component and 1 to 100 parts by weight of component (B), coating it with an addition reaction-curable silicone elastomer composition, and curing it.

When producing this, 100 parts by weight of component (A) and (B
) A processing agent consisting of 1 to 100 parts by weight of components includes toluene,
Any amount can be dissolved in aromatic solvents such as xylene and benzene, chlorine solvents such as chlorocene and trichlene, or mixed solvents of these solvents and aliphatic solvents such as n-hexane and -hebutane. preferable. Further, the cloth can be treated with a hardening accelerator such as potassium hydroxide, sodium hydroxide, or organic tin salt by spraying, dipping, or rolling.

If the amount is too small, a sufficient effect may not be obtained, and if it is too large, the adhesion may be poor.The silicone content should be 0.05 to 5.0% by weight, preferably 0.1 to 5.0%. 3.
Deposit 0% by weight.

Since this treatment agent gradually hardens at room temperature, after the treatment, the solvent may be removed and the treatment agent may be left as it is, or it may be cured by heating.

To coat the addition reaction curable silicone elastomer composition, a cloth treated with a treatment agent consisting of components (A) and (11) is coated with a direct knife coating, reverse coating, wire round coating, gravure coating, air knife coating, etc. It can be coated by a method. In addition, after immersing the prepared cloth in a solution of a silicone elastomer composition diluted with toluene, xylonone, benzene, or chlorine-based solvents, it can be hardened by drying, or it can be applied externally by spraying. It may be cured and coated with three coats. Also, silicone elastomer is easily peeled off.
- The silicone elastomer composition may be coated with paper or Teflon film by the method described above, then a pretreated cloth is laminated, and after curing, the silicone elastomer composition is transferred to the cloth.

The thickness of the coated silicone elastomer is not particularly limited, but is generally 1 to 500μ, especially raincoats for clothing,
When used for ski wear etc., the thickness is preferably 5 to 10 ()μ.

The curing method for the silicone elastomer is appropriately selected from leaving it at room temperature, blowing hot air, irradiating it with radiation, and leaving it in heated air.The curing conditions are heating and curing by staying at 100 = 180°C for 10 to 2 minutes. It is preferable to obtain a void-free silicone elastomer. Incidentally, it is also effective to apply a fine powder such as talc, fine mica powder, titanium dioxide powder, zinc dioxide powder, or silica powder to the surface of the silicone elastomer in order to eliminate the tackiness of the elastomer.

The thus obtained silicone elastomer-coated cloth has excellent waterproof properties because the silicone elastomer and the cloth are firmly bonded to each other. In addition, the silicone elastomer does not peel off or get damaged when worn or washed, making it highly durable.

Moreover, silicone elastomer has good moisture permeability and oxygen permeability, and can be used for ski wear, golf wear, raincoats, firefighting suits, tents, diaper covers, etc.

Next, the present invention will be explained with reference to examples. In examples, “part”
"" means parts by weight, and measurements of viscosity, peeling resistance value, etc. were all carried out at 25°C.

The adhesive strength was determined by peeling 5 test pieces with a width of 3c+n at a peeling speed of 30.
It represents the average value when measured under the conditions of cm 1 minute and peeling angle 180'.

Example 1 (a) Preparation of silicone pressure-sensitive adhesive An organopolysiloxane resin consisting of s i O2'i' was prepared by the following procedure.

125 g of 35% concentrated hydrochloric acid and 432 g of water were placed in a Mitsuro flask, and 261 g of sodium silicate was gradually added dropwise from the dropping funnel while stirring, followed by the addition of 225 g of isopropyl alcohol. After about 10 minutes (C1l+)3Si
111 g of Cl was added, refluxed at 80° C. for 1 hour, and then cooled. 200 g of xylene was added to this, and the aqueous layer was separated using a separating funnel. Add 60g of isopropyl alcohol to this, remove part of the solvent at 135℃, and solid content 50g.
% by weight. This organopolysiloxane O
(The fat solution is made into IAl solution. Then, this [A] solution 12
0g xylene 20. Add 0 g of nomethylbolysiloxane 12-loxane, which has a viscosity of about 2 million centistokes and is capped with hydroxyl groups at both ends, and dissolve it uniformly while stirring slowly for about 4 hours to form a silicone pressure-sensitive material with a viscosity of about 2 million centistokes. An adhesive solution [B] was prepared.

(b) Preparation of treatment liquid and pretreatment A treatment liquid was prepared using the pressure-sensitive adhesive [B1] prepared in (a) above and the silanes listed in Table 1.

Polyester 10 which was desized and refined using the treatment liquid in Table 1
After immersing 0% tricot fabric (20x20c+n) for 10 seconds, it was drawn with a roller to a squeezing rate of 100%, dried at room temperature, and left for 20 days.

(c) Using an applicator on polyethylene laminated kraft paper coated with silicone elastomer, use dimethylpolysiloxane/methylvinylpolysiloxane copolymer raw rubber as the main ingredient, methylhydrotene polysiloxane (viscosity 40 centistokes) blocked at both ends with trimethylsilyl groups, and platinum. Addition reaction curing silicone elastomer composition dispersion [C1 (solid content 30% by weight) dispersed and dissolved in catalyst, reinforcing silica filler, and toluene
, viscosity 25,500 centistokes) was applied to a thickness of 100 μm. After standing for 1 minute, the treated fabrics prepared in (b) above were overlapped and pressed together using a rubber roller.

This was heated and cured as it was in a hot air circulation oven at 150° C. for 3 minutes to obtain a silicone elastomer coated fabric with kraft paper.

(d) Measurement of adhesive strength Silicone elastomer coated cloth 15- with kraft paper was cut into 3 cm width to prepare test pieces. Using a tensilon type tensile tester, the peel resistance between the cloth and the silicone coating with polyethylene laminated kraft paper was measured at a speed of 30 cm/min, and the adhesive strength (g/3c+n) between the cloth and the silicone elastomer was determined. Examined.

The results are shown in Table 2, and the silicone elastomer coated fabric obtained by the manufacturing method of the present invention was firmly adhered.

Table-2 16- Example 2 (C) of Example 1 was placed on a Teflon sheet with a thickness of 0.1 mm.
After similarly applying the silicone efstomer composition dispersion [C] used in Example 1 to a thickness of 100μ, the treated fabric prepared in Example 1 (B) was layered and heated in a hot air circulation oven at 150°C for 3 minutes. hardened. The Teflon sheet was then peeled off to obtain a 27 micron thick silicone elastomer coated cloth. The water resistance of the thus prepared coated fabric was measured before and after washing.

Washing (water washing 20 times): JIS l, -0217 (1,
Water resistance according to JIS l, -1092 (1
The state of the coating before and after washing was also observed with the naked eye and evaluated as follows.

○... Even after washing, the silicone elastomer remains firmly adhered as shown in Wash&7 f+tf.

Δ...The silicone elastomer is partially peeled off and floating.

×: The silicone elastomer has peeled off considerably.

The results are shown in Table-3.

Table 3 Example 3 A Burberry base fabric for a lane coat made of a blended yarn of 65% Tetoron and 35% cotton was cut into a size of 30 x 30c+o, treated with the preparation liquid No. 3 used in Example 1, and then left at room temperature. The solvent was evaporated, and the mixture was heated at 120° C. for 10 minutes.

Next, the dispersion [C] of the silicone elastomer V-composition (c) of Example 1 was diluted 15 times with chlorocene, and the treated fabric and untreated fabric for comparison were each diluted with
After being immersed for a second, it was immediately pulled up, squeezed with a roller to a squeezing rate of 100%, and dried at 100° C. for 3 minutes.

This was heated and cured at 130° C. for 2 minutes to produce 10 silicone elastomer coated fabrics, and their water resistance and wetting resistance before and after washing were examined.

Washing treatment (water washing): JIS L-0217 (197
According to 6).

Water resistance and water rinsing: , IIS L-1092 (197
According to 7).

The results are shown in Table-4.

In the coated fabric produced according to the present invention, since the silicone elastomer firmly covers the fiber surface, there was almost no decrease in water resistance and water resistance after washing 4110 times.

201 Example 4 As a silane for a pretreatment agent, treatment liquid No. of Example 1 was used.

The silane shown in Table 5 was used in place of the vinyltriacetoxysilane in No. 3, and a treatment liquid was prepared with the composition. The thickness of the silicone elastomer is 200μ, and the cloth is 1.75D.
(24 filament count) 100% nylon plain fiber Yu7
The adhesion strength was measured using the adhesive base, and the results are shown in Table 5.

Table 5 Example 5 A silicone pressure sensitive adhesive was prepared by changing the blending ratio of the organopolysiloxane resin solution [A] synthesized in Example 1 (a) and dimethylpolysiloxane gum as shown in Table 6. . Next, the adhesive strength was measured using the same formulation as that of treatment liquids No. 3 in Example 1. However, the cloth is Tetoron 50% cotton 5
0% twill material was used, and the thickness of the silicone elastomer was 200 μm.

The results are as shown in fi-6, and the adhesive strength of the silicone elastomer coated fabric according to the present invention was excellent.

23-Example 6 A mixed solution of 20 g of 0°001N hydrochloric acid aqueous solution and 20 g of methanol was slowly added dropwise to 100 g of vinyltrimethoxysilane while stirring while keeping the liquid temperature at 40 to 50°C. After the dropwise addition was completed, the mixture was heated and stirred at a liquid temperature of 60 to 65° C. for 5 hours.

Next, low volatile components were removed from this with 11 g of 25I*1ml at 100°C, and the mixture was cooled to room temperature and 0.0% of sodium carbonate was added. 2g was added to neutralize. This was purified by filtration to obtain a partially hydrolyzed condensate of vinyltrimethoxysilane. This liquid had a viscosity of 40es and approximately 35% methoxy residues.

The same procedure as in Example 1 was repeated except that 0.5 part of this partially hydrolyzed condensate was used in place of vinyltrimethoxysilane in treatment solutions No. 2 of Example 1 (b). As a result, the adhesive force was 1208 g/3 cm, which was almost the same as in the case of silane, and the cloth and silicone elastomer were firmly adhered.

Patent applicant: Toray Silicone Co., Ltd. 24-

Claims (1)

[Claims] (A) 100 parts by weight of silicone pressure-sensitive adhesive (B)
'Rn General formula Z-8i-X(3-n) (wherein, Z is an organic group having an aliphatic unsaturated group or a hydrogen atom, X is a hydrolyzable organic group, and R is an organic group having 1 to 5 carbon atoms. The fabric is treated with a treatment agent consisting of 1 to 10 parts by weight of silane represented by an alkyl group (n is 0.1 or 2) or its partially hydrolyzed filament; A method for producing a silicone elastomer-coated fabric, comprising coating and curing a silicone elastomer composition.