JPS58120880A - Durable water resistant, humidity permeable, air permeable and melt preventing processing of synthetic fiber knitted fabric - 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 involves coating a synthetic fiber knitted fabric with a mixed solution in which a vapor-permeable filler, a sublimable substance, a hardening agent, an adhesion promoter, and/or a pigment are dispersed or dissolved in Norikono rubber. and a durable water resistant material, which is characterized in that it undergoes a post-heat treatment to form a linconocomb layer having microscopic voids on the surface of the fabric.
Concerning moisture permeability, ventilation, and anti-melt processing methods.

Is the demand for synthetic fibers limited to clothing?Are they used in various industrial materials?Synthetic fibers such as polyamide and polyester generally have a melting point of 200 to 3000C, and for this reason, clothing and industrial material products made from these synthetic fibers are increasing. In the course of its use, it melts and opens pores due to heat compared to natural fiber materials, and encounters various problems caused by heat.

In other words, products made from synthetic fibers such as polyamide and polyester fibers may melt and open holes in the contact area due to contact with high-temperature objects such as cigarettes, torches, welding sparks, or sudden contact friction (3). Give the product a fatal defect.

In addition, general waterproof products such as coats and awnings do not allow rain to pass through, but they also allow air and water vapor to pass through, and there is a problem that they become stuffy when worn or used. For this reason, (1) a method in which a microporous 4-fluorinated ethylene film is laminated onto a fabric, or (2) a method in which a microporous film of 4-fluorinated ethylene is laminated onto a fabric, or (2) a method in which a resin solution mainly composed of polyurethane elastomer, which is generally called a wet method, is highly soluble in water or a special solvent. After mixing the filler and solvent and applying it on the fabric, it is passed through a special solvent tank and a washing tank (by passing it through a special solvent tank and a washing tank (1), the filler and solvent are eluted and a microporous resin film is formed. Moisture-permeable, waterproof fabrics have been produced.

However, the disadvantages of products produced by these methods are ■If you place emphasis on the performance of the film,
If we place emphasis on weak strength and peel strength, the adhesive will obstruct air permeability and moisture permeability, and the resulting product will become rough and hard.■
In general, the shape of the pores in the resin film that occurs when the filler solvent is eluted is vertically elongated, vertically cracked pores, etc. (4) It tends to form a columnar structure with respect to the film layer, which tends to cause defects in its waterproof performance. In addition, moisture-permeable and waterproof fabrics are manufactured using a so-called dry method using resins mainly composed of polyurethane elastomers that have moderate moisture absorption properties, and in order to maintain their performance, there is an upper limit to the thickness of the resin film. Naturally, this has the disadvantage of weakening the surface film.

Furthermore, when the above-mentioned processing method is applied to synthetic fiber fabrics, they do not have melt-proofing properties, and when they come into contact with cigarette sized objects, they melt and open holes, causing fatal defects in the product. Particularly in clothing made of horse hair, fluff may come out from the melted pores, which can be fatal to the product.

As a result of extensive research in order to solve the above problems, Fubenban et al. completed the present invention, which provides synthetic fiber knitted fabrics with a flexible texture and durability under simple and easy-to-manage conditions. This makes it possible to provide a water-resistant, moisture-permeable, breathable, and melt-proof processing method.

In melt-proof processing of synthetic fibers, there are methods to prevent or reduce damage caused by heat-induced melting or decomposition of fibers using physical or chemical methods. That is, by coating the surface of the fibers with a heat-resistant insoluble resin, the fibers are protected from heat, and even if the fibers are melted, flow is suppressed and the original shape of the fabric is maintained. Melt-proof resins commonly used in these melt-proofing processes include silicone resins, crosslinkable acrylic resins, mixtures of silicone resins and modified alkyd resins, and compositions in which acrylic resins are blended with metal salts such as zinc sulfate. However, all of them still have problems such as poor wash resistance and hardened texture after imparting anti-melt properties. Among these, the above-mentioned silicone resin is entirely crosslinked by steric bonding, so after the resin film is formed, the film is hardened strongly due to the steric crosslinking, resulting in a lack of flexibility in the processed fabric. Therefore, a linear combination type of two-component room-temperature-curing silicone rubber (hereinafter referred to as RTV-type silicone rubber) and a two-component-type low-temperature-curing silicone rubber (hereinafter referred to as LTV-type silicone rubber), which have properties very similar to those of silicone. We focused on the low intermolecular attraction caused by crosslinking properties, the good gas permeability and water vapor permeability based on the amorphous structure, and the heat resistance stability of the polymer (depending on the size of the siloxane bond).

In other words, two-component type T (
, TV, I, T ■ By utilizing Niconocom in fiber processing, the flexibility of the resin film due to its linear bonding and the heat resistance of the silicone resin itself give the processed fabric flexibility that is not found in conventional melt-proof processed fabrics. By adding texture, durability and anti-melt properties, and adding water vapor permeable fillers and sublimable substances, we succeeded in improving air permeability and permeability further north without reducing water resistance.

To explain the present invention item by item, 1) Silicon comb is R1'r v type, L T
V-type non-condensed rubber is preferred, and the main body is diorganopolynoroxane and the curing agent is acetoxin lano, oximune lano, noricordino, alkyl silica-1 - condensed type;
and Noriconcomb, which has a crosslinking type crosslinking mechanism in which the main body is a vinyl-containing silokanobolysiloxane and the curing agent is an Si-11-containing silokanobolysiloxano.

Nao, the present invention does not limit the use of silicone combs, fluorinated silicone rubbers, and phenylated silicone combs, which have a hynyl group, hydroxyl group, or hydrogen group in the side chain of noroxane. There are some problems with texture and heat resistance stability.

2) Vapor-permeable fillers are synthetic phosphor, silica, etc. made by the smoke method or wet method. It is a filler having hygroscopic and water-retaining functions such as quinruhinyl polymer, and those having a particle size in the range of 0.007 to 100 tt can be used.

The type and particle size of the filler have a large effect on the moisture permeability, air permeability, water control and anti-melt performance, texture, resin film surface quality and strength, and processing conditions such as uniform dispersion and application of the resin solution. Considering this, a filler having a particle size in the range of 0.007 to 30/l is preferable.

3) The sublimable substance has a boiling point of 60~aoo'c, preferably 1
00 to 250°C, such as α-1-'
) Oxane, DL-linochoic acid, maleinoic acid, dimethyl oxalate, valacyclolbenseno, oxalate (8) Acid, phthalic acid, naphthalene, benzoic acid, etc., which can be dissolved and dispersed in the resin. This substance has a larger molecular weight than the solvent in the resin, and is thought to form a random microporous shape in the resin film due to the difference in vaporization temperature during heat treatment.

4) Synthetic fiber knitted fabric is a well-known synthetic fiber knitted fabric composed of polyamide/polyester fibers, and is subjected to ordinary scouring,
It is a knitted fabric that has been dyed.

In addition, among polyamide, polyester fibers, cotton, rayon, Keepla, etc., polyamide,
It can also be applied to knitted fabrics containing 50% or more of polyester fibers.

5) The adhesion promoter is an organic functional group such as a vinyl group, an amino group, an epoxy group, or a mercapto group, and an organic metal salt such as butyl titanate or a peroxide such as benzoyl peroxide or platinum as a catalyst. For example, platinic acid is used.

6) The organic solvent may be any solvent as long as it can dissolve and disperse the resin, curing agent, adhesion promoter, filler, etc. used in the present invention.
Specifically, organic polar solvents such as i-lifluoroethylene, perchloroethylene, l-lueno, xyleno, hydrocarbon solvents, and alcohol solvents may be used.

7) The coating method may be essentially any method as long as it can coat the resin mixed solution of the present invention, but preferably an air knife coater, a floating knob knife coater, a knife over roll coater, a reverse roll coater, or a graphite coater. Heat coater and dip coater are suitable for working.

8) This product, for example, the film made from a mixed solution of silicone comb mainly composed of dimethylborinoxane, atomized resin, and a resin such as a hardening agent, is almost colorless and requires coloring to improve aesthetics. becomes. Heat-resistant and weather-resistant organic pigments such as quinacrid thread red, polyazo and monoazo red, disazo yellow, Noanino Green, Noanipple-1, etc. can be used to make this possible, but preferably, mainly inorganic pigments are used. In addition, pigments that take advantage of the properties of silicone rubber have excellent acid resistance, alkali resistance, chemical resistance, heat resistance, etc., such as titanium oxide (white), iron oxide (red, yellow, black), carhon frank (black), Made of aluminum powder (aluminum color), etc. with a particle size of 100μ or less, or moisture permeable.
Preferable in terms of ventilation, water resistance, etc.

Note that the purpose of coloring using these pigments is to improve aesthetics, and if coloring is not required, the pigments do not need to be mixed.

The processing method according to the present invention will be explained in detail below. 100 parts by weight of two-component RTV or L'T'V silicone rubber (
5 to 20 parts of a curing agent, 0.5 to 10 parts of a silane coupling agent containing a catalyst, 5 to IO parts of a hygroscopic and water-retaining filler, 10 to 40 parts of a sublimable substance, and an organic Alternatively, an organic solvent is added to a mixture of 0 to 30 parts of a coloring agent, which is an inorganic pigment, to adjust the viscosity and concentration as appropriate, and the mixture is stirred to prepare a resin solution in which additives are dispersed and mixed. Polyamide obtained by scouring and dyeing the resin liquid in a conventional manner,
Alternatively, it is evenly coated on the surface of the polyester knitted fabric by the coating method described above, such as the floating knob knife coating method, and dried. This is further heat-treated at 140-2000C for 30-120 seconds to harden the silicone comb and form a resin film on the fabric 3. In general, silicone combs and films have potential gas permeability and moisture permeability. However, in addition to this, in addition to the discontinuous arrangement of fillers with hygroscopic and water-retaining functions in the resin film, gradual and Due to the continuous vaporization action, microscopic pores of various shapes such as hammer-shaped, spherical, and elliptical shapes are formed in the silicone rubber film layer, and each of these pores is thought to have microscopic contact points. In addition, other factors include dehydrogenation and condensation reaction due to heat treatment.
One of the reasons for this is thought to be that continuous pores are formed in the film using the hydrogen scum generated by -ISi3-←35I-o-simi+H2↑ as a foaming agent.

The above fine pores have an average particle diameter of 100 to 500μ for drizzle or light rain.
and the average particle of water vapor is 0,0004 i
Since it is larger than t, it can exhibit water-resistant breathability (12) and moisture permeability functions.

The resulting product has a soft texture, excellent water resistance, air permeability, and does not easily melt and open holes even when exposed to a cigarette. This exhibits performance suitable for cold-resistant clothing and the like.

Examples of the present invention will be described below. Note that the comparative test characteristic values in the examples were measured and evaluated based on the following measurement method.

1) Evaluation method of melt-proofing performance: The time until the contact area melts and opens using the smoke-fire 75 degree method (
2) Water resistance, 11 S - L - 1092 (low water pressure method) units,...
120 3) Air permeability JTS-L-1006 Gurley method Unit: seconds/
Place the fabric in a moisture-permeable cup containing moisture-permeable calcium chloride (X 4) for about 8 minutes, and leave it in a constant temperature and humidity chamber at 40°C and 190%RH.
After 1 hour, it is taken out and its weight (W l) is measured. Further, it was left in a constant temperature and humidity chamber for 4 hours, taken out, and its weight (W2) was measured. Moisture permeability ■l) is calculated by the following formula.

However, S-moisture permeable area (m゛) 5) Washing resistance J I S-L -0217-+ No. 04 6) Dry cleaning resistance Petroleum-based solvents (Dry Sole) and chlorinated solvents (Perchlorethylene) Treat with a washliner at 30°C and a liquid ratio of 1:9 for 10 minutes, then dry in the wave air.

Example 1 Two-component RTV of vinyl-containing diorganopolysiloxane
Siliconcom (for example, product name [Lordsil RT V 1
47 A, 1 manufactured by Dai Nippon Ink Chemical Co., Ltd.) 100 copies, 5
i-H-containing dicappolysiloxane (e.g., trade name [
10 parts of an adhesion agent (e.g., trade name ['AP-21, manufactured by Shin-Etsu Chemical Co., Ltd.]), 10 parts of a vapor-permeable filler (e.g., product name [-Aerosil 200 J, manufactured by Nippon Aeronol Co., Ltd.) ), 10 parts of a sublimable substance (e.g. commercially available naphthalene), and 60 parts of toluene. longitude] 25 lines/inch, latitude 94EE/1 river 1
A film of 10 yen (dry weight) was applied uniformly onto one side of the fabric by the floatic knife coachic method, and after drying, it was heat-treated at 190°C for 30 seconds to obtain this product.

Example 2 Polyester taffeta (warp 50/24, weft 75/36, density warp 157 /
The fabric was coated uniformly on one side of the fabric with a dry weight of 12'/inch by the floatic knife coachic method, and after drying, it was heat-treated at 190°C for 60 seconds to obtain this product.

Comparative Example 1 100 parts of [Loadsil I (Tv) 47A], 8110 parts of [Loadsil 111F 14F], 2 parts of "AP-2", 1~
The resin solution prepared by dissolving in Part 3 of Le Technique was applied to one side of nylon taffeta (the same product as that used in Example 1) by the floatic knife coachic method in a dry weight of 10%.
'/m. After being uniformly coated and dried, the product was heat treated at 1900c for 30 seconds.

Comparative Example 2 Hygroscopic polyurethane elastomer (for example, trade name [Honey 1 to Nobu 8259 manufactured by El Honey Kasei Co., Ltd.) 10
0 parts, 10 parts of crosslinking agent (for example, trade name "Cryshon NXJ, manufactured by Dainippon Ink Chemical Co., Ltd.), I) A resin solution in which 30 parts of MF and 10 parts of ethyl acetate were dissolved was added to polyester taffeta (the one used in Example 2). 5v/m dry weight by knife-over-roll coach ink method on one side of the same product)
After applying it evenly and drying, apply a moisture-permeable polyurethane elastomer (for example, the product name [Honey Top 8252E]) on the same surface.
(manufactured by Honey Kasei Co., Ltd.) 100 parts, crosslinking agent (e.g. Crisphono NXj) 5 parts, ethyl acetate 30 parts, I) M F I
This product was obtained by coating a resin solution in which 0 part was dissolved in a resin solution with a dry weight of 72/cm by knife-over-roll coating method, and after drying, heat-treating at 190°C for 30 seconds.

Comparative Example 3 As a general soft coating agent, 100 parts of an acrylic resin (for example, trade name [Clinoh S 20 J manufactured by Dainippon Ink & Chemicals Co., Ltd.]) and a crosslinking agent (for example, trade name "Polyne 1") were used.
A resin solution prepared by dissolving 2 parts of J-70 (manufactured by Toyo Polymer Co., Ltd.) and 60 parts of toluene was applied uniformly to one side of nylon taffeta (the same product used in Example 1) at a dry weight of 10'/nr, and dried. This product was then heat treated at 180°C for 30 seconds.

Next, Example 1.2 according to this explanation and Comparative Example 1 which is a conventional product
．． The comparative test results of 2.3 are shown.

Procedural amendment (spontaneous) To the Commissioner of the Japan Patent Office, Patent Application No. 000765, filed on February 1, 1982, 2, title of the invention: ``Mis M Me's i Ding γ Types of Urine Collection, I Clan, Taku 3'' , Relationship with the case of the person making the amendment Patent applicant 4, lexical correction of the specification to be amended 5, Contents of the amendment, page 9, line 5, changing the shape of the pores to the shape of the pores, page 12, line 10 Millet Pores, in toad pores Page 12, line 16 Continuous pores are pores, continuous micro pores are °
〃 Page 12, line 18 - Correct - for the fine holes in F, and correct and cut out the fine holes as follows.

Applicant: Sokoseiren Co., Ltd.

Claims (1)

[Scope of Claims] 1) Silicone rubber with a vapor-permeable filler, a sublimable substance,
A mixed solution in which a curing agent, an adhesion promoter, and/or a pigment are dispersed or dissolved is applied to a synthetic fiber knitted fabric, and then heat-treated to form a porous silicone rubber layer on the surface of the fabric. Durable water-resistant, moisture-permeable, breathable, and moisture-proof processing method. 2) A patent in which the silicone comb is a room-temperature curing type or a low-temperature curing type rubber, and the main body of the crosslinking mechanism is diorganoporin loxane diol, hynyl-containing siorganopolysiloxano, hydrogen polysiloxane, or a copolymer thereof. The method according to claim 1. 3) Vapor-permeable filler made by fume method or wet method, such as synthetic silica, silica earth, quartz powder, siliceous sandstone, zirconium silicate, clay, etc., silicic acid (1) salt, calcium carbonate, or The method according to claim 1, which is a filler having hygroscopic and water-retaining functions such as carpoquinruhinyl polymer. 4) The sublimable substance has a boiling point of 60~aoo'c, preferably 10
Patent claims that are known sublimable substances having a temperature of 0 to 250°C, such as α-trioxane, DIF, -linchoic acid, maleic acid, dimethyl oxalate, valachlorherceno, oxalic acid, phthalic acid, naphthalene, benzoic acid, etc. How to describe paragraph 1 of the scope. 5) The method according to claim 1, wherein the synthetic fiber knitted fabric is composed of polyamide or polyester fibers. 6) The curing agent for Norikono rubber is a condensation type in which the curing agent is acetoquinolano, okinumuran, silicone comuno, alkyl silica-1, or an addition type in which a 5l-rr-containing silokanoporin loxane is used. The method described in Section 2. 7) The method according to claims 1, 2, and 3, wherein the tackifier is an tackifier (2) in which an organic functional group-containing oranocanopring agent is catalyzed by an organic metal. .