JPS60194183A - Durable coating 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 relates to a durable coated fabric in which the adhesiveness between the coating resin film and the base fabric is superior to 1.

In recent years, 0 comments regarding coated fabrics have been actively
It has been rapidly commercialized into raincoats, sports clothing, casual coats, mountain climbing equipment, etc.

In particular, fabrics obtained by laminating a neubril-like microporous film obtained by stretching a film of tetrafluoroethylene resin onto a knitted fabric with an adhesive, and wet-type fabrics using a dimethylborumamide solution of polyurethane. Regarding the film formation method,
Fabrics coated with microporous eyelids or fabrics obtained by special coating with silicone resin are common.

Since the pores of the film are connected, it has moisture permeability, and since there is only one small pore, it is the biggest factor in 1.1 that determines waterproofness.

However, fabrics laminated with tetrafluoroethylene resin films have low peeling strength between the film and the base fabric, and are prone to repeated kneading, abrasion, thickening, tension, and washing.
1.Dry cleaning causes the film and base fabric to peel off, which is a serious problem in practice.

In addition, coating fabric made using a wet polyurethane film formation method has low heat resistance and not only melts and opens holes when it comes into contact with a cigarette but also gets dirty easily, especially with oils. There is a problem in that the dirt that accumulates in the dry cleaning bath causes reverse contamination, resulting in six colors ranging from gray to black.

Furthermore, silicone resins are examples of resins that have recently attracted attention. As shown in JP-A No. 11ij58-120880, silicone rubber is coated with a mixed solution in which vapor-permeable fillers, sublimable substances, etc. are dispersed or dissolved, and then heat treated to form a porous silicone rubber layer on the base fabric. It is formed on top. This fabric also has high heat resistance.
There is no melting and opening caused by cigarettes, there is no problem of oil stains or back contamination during dry cleaning, and B! The fit is also flexible and good. However, unlike fabrics laminated with tetrafluoroethylene resin films, the peeling strength between the silicone layer and the base fabric is low, and they can be peeled off by repeated kneading, abrasion, friction, tension, washing 11, and dry cleaning. This poses a practical problem.

The present inventors found that among the above coating films, moisture permeability,
We focused on the silicone film that had poor waterproofness, heat resistance, reverse stain resistance, and texture, and determined that it would be possible to develop the product by improving the adhesion between the film and the base fabric.After careful consideration, we decided that the coating In order to prevent the resin liquid from penetrating into the base fabric, the fluorine-based water repellent that is normally applied to the base fabric before coating is replaced with a silicone-based water repellent, which improves the adhesion between the silicone film and the base fabric. The present invention was achieved by discovering that the water repellent decreases to a wider width.Furthermore, it was found that an even greater effect could be obtained by applying low-temperature plasma treatment1 before or after treating the silicone-based water repellent agent. .

However, the present invention consists of the following configuration.

(1) A durable coated fabric characterized in that a fibrous structure treated with a silicone water repellent agent is coated with a film made of silicone rubber.

(2) The durable coated fabric according to claim 1, which is subjected to low temperature plasma treatment before or after being treated with a silicone water repellent agent.

The present invention will be explained in detail below.

A silicone-based water repellent is generally a compound as shown in the following formula.
g! Alternatively, two or more types may be mixed and treated with the action of a catalyst depending on the case.

Z R' (in the formula, 1' is hydrogen, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an alkenyl group, an alicyclic group, or an amine, and Z is hydrogen or an organic group) , m represents O or an integer greater than or equal to 1. R'J3 and Z may be the same or different.

) These specific compounds, catalysts, and amounts used are described in detail in JP-A-57-154466.

Textile structure) cargo is not limited to 14, but includes nylon fiber,
These include woven, knitted, and nonwoven IT fabrics made of synthetic fibers such as polyester fibers, acrylic fibers, and modified fibers thereof, and natural fibers such as cotton, wool, and hemp.

Silicone rubber is a room-temperature curing type (R type V type). Synthetic reaction with mborisi U xane,
Addition reaction between diorganopolysiloxane and hydrogenoborisiloxane containing a nylon group, condensation reaction between diorganopolysiloxane and curing agent such as acetoxysilane, Aximesilane, silicone resin, argyl silica-1, etc. Although there are resins that can be obtained, the present invention is not particularly limited to these.

Also, O (in the defense, A/L, = in the side chain of siloquine → non)
It is also possible to use rubbers containing 1-l groups, 1'-oxy groups, hydrogen groups, aryl groups, alkoxy groups, alkoxycarbonyl groups, alkenyl groups, alicyclic groups, amines, fluorine, and the like.

Also, what about additives to silicone rubber? Synthetic silica, silica earth, quartz powder, siliceous sandstone, zirconium silicate, silica salts such as clay, calcium carbonate or carboxylic vinyl polymers with hygroscopic and water-retaining properties made by fog or wet methods. Fillers with or α-tos711-phosphorus, l) L-malic acid, maleic acid, dimethyl oxalate, paradichlorobenzene, ii!
M, R-based substances such as phthalic acid, naphthalene, and orthozoic acid, or adhesives having organic functional groups such as vinyl groups, amine groups, epoxy groups, and organic functional groups such as 47A ( For example, examples thereof include catalysts such as Ptylateditane-1~), peroxides (eg, penzoyl peroxide), and platinum compounds (eg, platinum M).

In addition, if necessary, pigments such as quinacrid red, polyazo and monononozo red, disazo yellow, cyanine green, cyanine blue, etc., and inorganic pigments such as titanium oxide, iron oxide, carbon black, and aluminum powder are added. A colored film can be obtained.

Combinations of a silicone water repellent, a fibrous structure, and a silicone rubber that are particularly preferred in the present invention include, but are not limited to, the following. Examples of silicone-based water repellent agents include methylhydrodi], polysiloxane, dimethylbolysiloxane diol, 1-helime 1-xysilane, and an organotin compound dissolved in mineral spirit 1-, and IJAIft structure. Taffeta is made of nylon 6, nylon 66 and polyester, and silicone rubber is made by dissolving vinyl-containing dimethylbolysiloxane, methylhydrodienebolysiloxane, platinic acid, synthetic silica obtained by atomization method, and naphthalene in toluene. Or there are other things like dispersed shinobi.

The thickness of the silicone film is not particularly limited, but for clothing, it is generally from 10 to 1000 microns.

Low-temperature pnosma treatment in the present invention! lj means that the fiber N or /iJ3 and the silicon tree 11Fj are subjected to plasma discharge generated by applying a high electric current L. There are various forms of such discharge, such as spark discharge, corona discharge, glow discharge, etc., but the discharge form does not matter as long as it does not damage the fibers, but if the discharge is uniform and has an activating effect. Tag[]-discharge is particularly preferred.

Glow discharge is less than 50 torr, roughly 2 Qt
orr or less, especially ri f tool I L < is 0.01 to 1
The reduction of 0 torr is generated by applying a high voltage in a gas atmosphere below, and the time period is selected depending on the type of fiber and processing equipment, but usually it takes from a few seconds to a few minutes. It is preferably about 1 second to 5 minutes.

Examples of the gas that provides the activation effect of the present invention include A
r, N2.1-1c, +12, N+-13, Co
;), Co, 02, CF4.1-120, air, etc., but especially Ar, l-1e, Go, CO2
, H2, N2, NH3, etc., and mixed gases thereof are preferable from the viewpoint of improving adhesiveness.

Note that the low-temperature plasma treatment is performed on the fibrous structure before being treated with the silicone water repellent, or on the fibrous structure after being treated with the silicone water repellent. Both treatments have the effect of improving the adhesion between the coated film and the base Tri, but the effect may be temporary. This is the case when an object is coated with a silicone rubber film after being subjected to low-temperature plasma treatment. Therefore, if low-temperature plasma treatment is applied after coating, there is no effect of improving adhesion and it is not included in the present invention.

The coating application method is not particularly limited, but generally includes a 70~teing knife coater, knife A-par roll]-ta, reverse L''-ru: 1-ta, roll doctor coater, and gradient rough 0-ru coater. , rod to evening,
A transfer coater, an air knife coater, a curtain coater, a roll coater, a nip roll coater, a coater, a spray method, etc. can be used.

Additionally, lamination methods, bonding methods, etc. can also be used.

The coated fabric obtained by the present invention not only has excellent adhesion between the film and the base fabric and is durable, but also has stain resistance and
It also has excellent reverse stain resistance, light resistance, low melting properties, moisture permeability, waterproof f11, and high commercial value.

Although the present invention will be described as an example, it is not limited to these in any way.

Example 1 Warp 70 denier 12 filaments, weft 70 denier 24 filaments, warp density 120/1 nch, I
After stringing nylon 6 taffeta with Q base thread 1WIlu90 wood 1nch in the usual way, pad with the following treatment bath a, and after drying,
Heat treatment was performed at 120°C for 5 minutes.

Processing bath a S l) -80001 Serious crime department (1--Les silicone (a) solvent type silicone water repellent) 1~Lichloroethylene 991ffi part Next] -
Apply the coating resin liquid evenly with a 70-inch knife coater, dry it, and then heat it at 180'Cr for 1 minute on an IH! did.

Coachingui H1177 liquid b Two-component type F<'l-V silicone rubber of vinyl-containing dimedylbolysiloxane (manufactured by Jinrohon Ink Chemical Co., Ltd., Rhodosil RT-V 147A) 100 parts by weight Methylhydrodiene polysiloxane (Dainippon Co., Ltd.) Manufactured by Kagaku Co., Ltd., Loadsil l<-1-V 14.71B>10
! J21j 1 part Nominal A 11j agent 2 parts (manufactured by Shin-Etsu Chemical Co., Ltd., AP-2) Filler 5 parts (manufactured by Nippon Aerosil Co., Ltd., Aerosil 200 > naphthalene ioi part tolu) 60 m part Example 2 In Example 1 , except that the nylon 6 tack was treated under the following low-temperature plasma condition C before covering the pad with treatment solution a.
All were processed in the same way.

Low temperature plasma condition C Gas knee carbon oxide 10cc/min reduction 1. Temperature: 0.2 torr [IJ applied voltage: 1.5 KV Processing speed: 1 m/min Example 3 After processing with processing solution a in Example 1, after processing nylon 6 taffeta under the above low temperature plasma condition C. , coded.

Comparative Example 1.2 In Example 1.2, the treatment with treatment liquid a was omitted.

Comparative Example 3 The same processing as in Example 1 was carried out except that the following treatment liquid d was padded instead of treatment liquid a.

Treatment liquid d Alihi Guard AG-7701 heavy foot part Asahi Glass Co., Ltd.
Fluorine-based water repellent) Coated fabrics containing 99 parts by weight or more of water were evaluated for BJI rlli properties, and the results shown in Table 1 were obtained. The thickness of each film was 30±2μ. Adhesive strength and contact strength after 10 washes were measured according to JIS-6328-11.

From this, it can be seen that the adhesiveness of the "-Ting fabric of the present invention is superior to that of non-fabric" even after washing. In particular, the adhesion is further improved by low-temperature plasma treatment Jp-d. I understand that.

In the table Strong adhesive crab ((] /cm) IB strong horns after 10 times of strong crab washing iM after washing.

The -j mark on the philtrum is unmarked due to peeling. means measurement.

Example 4 Warp ξ] 0 denier 24 filaments, weft 75 denier 36 filaments, warp density 118/in c
t+, a polyester tack with a weft density of 85 wood/1 nCh was dyed in a conventional manner, then the following treatment bath e was applied to a pad, and after drying, heat treatment was performed at 170° C. for 2 minutes.

Processing bath C 3l-1-824,02,0fffffiR1i(1-
- Emulsion type silicone water repellent manufactured by Le Silicone Co., Ltd.) Catalyst on St-1-22 0.2 mff! Bl+water 97
．． Next, coating resin liquid f below was applied uniformly to an 8 mm section using a reverse roll coater, and after drying, heat treatment was performed at 180° C. for 1 minute.

Coating resin liquid fSl) -8001100 parts by weight (1 to 1 silicone stock)! II silicone coating resin liquid, 30% torne solution) S [X-212 (catalyst) 0.5 parts by weight maleic acid
3 small parts toluene 10 parts Example 5 The same processing as in Example 4 was carried out except that the polyester taffeta was treated under the following low-temperature plasma condition q before being padded with the treatment liquid e.

Low-temperature plasma conditions Q Gas: Argon 1.4/472/min Depressurization degree + 0.33 torr Applied voltage: 10 KV Processing speed 20 m/min Example 6 In Example 4, treatment with treatment liquid e and the above-mentioned low-temperature plasma Polyvarnish delta lid was treated under condition q and then coated.

Comparative Examples 4 and 5 The same processing as in Example 4.5 was carried out except that the treatment in J3 and treatment bath C was changed to treatment in treatment bath d.

The surface properties of the above ]-ting fabrics were evaluated, and Table 2
I got the result.

The θ angle of the coatings was 40±2 μ in all cases, and IC6. This shows that the coated fabric of the present invention has very excellent adhesion. And especially, low temperature plasma treatment J
It can be seen that the adhesiveness is further improved by this.

Table 2 Patent applicant Higashi Shikikai Co., Ltd.

Claims (2)

[Claims] (1) Fiber ME treated with silicone water repellent 4
A durable coated fabric characterized by having an i4 structure coated with a film made of silicone rubber. (2) The durable coated fabric according to claim 1, which is subjected to low temperature plasma treatment before or after being treated with a silicone water repellent agent.