JPS60176755A - Resin coated fiber product - 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 resin-coated M & textile products laminated with a composition of rubbery chlorinated polyethylene obtained by chlorinating an ethylene/1-butene copolymer. Traditionally, resin-treated cloth (hereinafter referred to as treated cloth) has the waterproof, water-repellent, stain-resistant, weather-resistant, flame-resistant, abrasion-resistant, chemical-resistant, and oil-resistant properties of various woven fabrics. Cotton,
Natural fibers such as polyester, nylon, vinylon (trade name), glass, 1 synthetic fibers, recycled 1i11ffl, woven or non-woven fabrics of mineral fibers alone or in combination with these, natural rubber, synthetic rubber, chlorinated rubber, polyvinyl chloride, Coated with acrylic resin, urethane resin, ethylene-vinyl acetate resin, silicone resin, chlorosulfonated polyethylene resin, etc. It is processed and coated by methods such as depping processing, calendar processing, and lamination processing in the form of a film. These processed fabrics are usually in the form of rubberized 9-ply fabric, canvas, or tarpaulin fabric, and are processed and used to make sheets, covers, tents, container bags, etc. for vehicles, automobiles, ships, warehouses, and curing. has been done. Generally, a large amount of polyvinyl chloride-treated fabric is used because it provides processability and relatively stable physical properties, but polyvinyl chloride is originally a hard resin and does not have adhesive properties with fibers, so processed fabrics are not manufactured. In this case, it is necessary to provide fluidity of the resin and flexibility of the membrane, and also to coat the base fabric with fluff. For this reason, it is necessary to contain a large amount of plasticizer and process using the anchor effect of the base fabric. The polyvinyl chloride processed fabric produced in this way is soft and has a good texture, but on the other hand, because it contains a large amount of plasticizer, the plasticizer bleeds onto the surface of the processed fabric over time. When using an oil agent, the plasticizer is extracted and the coating layer hardens and deteriorates. In addition, processed fabrics coated with acrylic resin have good weather resistance, but are brittle and cold resistant when repeatedly bent. It has a drawback in corrosion resistance, and although ethylene-vinyl acetate resin is economically inexpensive and has good cold resistance, it has problems with oil resistance and abrasion resistance, which naturally limits its usage. The present inventors solved the above-mentioned problems by laminating a composition based on a specific chlorinated polyethylene, which has excellent low-temperature properties and rubber properties, on a fiber base material without using any plasticizer. The present invention was completed by finding a solution to the problem. That is, the present invention is a resin-coated IN product made by laminating a composition containing rubbery chlorinated polyethylene obtained by chlorinating an ethylene/1-butene copolymer or a vulcanized product thereof on a fiber N base material. Chlorinated polyethylene is weather and chemical resistant. It is a resin with excellent oil resistance, flammability, heat resistance, etc., and is used to modify polyvinyl chloride resin or blend it with flammable resins to impart flame retardancy. Ordinary chlorinated polyethylene is made from polyethylene with crystals, so the chlorinated product also retains plastic properties and has many drawbacks when used as an elastomer.For example, the hardness (JIS A) is 50. Higher and higher, 100%
It has relatively hard rubber-like properties, such as a high modulus and poor low-temperature properties. Processing such chlorinated polyethylene into a film requires high temperatures, and when laminated onto a fiber base material, the fluidity of the resin is poor, resulting in poor adhesion to the base material. In addition, the texture of the resulting processed cloth is hard and stiff, and in terms of cold resistance, it cannot withstand temperatures as low as -20°C, making it impractical. Further, in post-processing such as sewing, adhesive processing is performed using a high-frequency gluer, but such processed fabrics cannot be expected to have high adhesive strength because of their poor fluidity. For this reason, adding a plasticizer or blending with a fluid resin may be considered, but as mentioned above, the resulting processed fabric may have a sticky surface, bleed of plasticizer, and a decrease in corrosion resistance.
Moreover, the advantage of flame retardancy, which is the advantage of chlorinated polyethylene, cannot be effectively utilized. Ethylene, the raw material for the present invention
The 1-butene copolymer has a density of 0.88 to 0.94,
Ethylene content 1i 85-97% by weight, 1-1 tenene content 15
~3% by weight, preferably with a density of 0.915-0.930
, ethylene content 93-97% by weight, 1-butene content ml~
An at least partially crystalline linear ethylene copolymer having a DSC crystal melting point of 115° C. to 125° C. at 3% by weight is preferred. The rubbery chlorinated polyethylene used in the present invention is prepared by preparing such an ethylene/1-butene copolymer in an aqueous suspension at a temperature of about 100 to 130°C with a chlorine content of 20 to 55%.
It is suitable that it is obtained by chlorinating 25 to 35% by weight, preferably 25 to 35% by weight, and has a weight average molecular weight of 100.000 or more and a DSC crystal heat of fusion of 0.50allOr or less. If the chlorine content is smaller than the above range, the flexibility etc. will be insufficient, and if it is larger, the rubber elasticity will be weak and it is not suitable for the present invention. Such rubbery chlorinated polyethylene usually has 1 to 2 methylene groups per 100 carbon atoms, and has a 100% modulus of 10k (1/1) at room temperature.
Below cnr, the 25% modulus of 1 at -20℃ is 1
Low hardness (JISA) of 50 or less at 00k (J/cd or less) (Compared to conventional chlorinated polyethylene, it has excellent low temperature properties and rubbery properties, and has good fluidity during molding) It has the characteristic that it can be processed as a composition at relatively low temperatures without adding plasticizers or blending with other resins.Therefore, it can be easily formed into a film using a normal inflation or calendar molding machine, and its flow properties The result is a processed fabric that penetrates well into the fiber base material, exhibits high adhesion, has excellent flexibility at low temperatures, and has a unique texture not found in textile products coated with conventional chlorinated polyethylene 1. Fillers, pigments, processing aids, vulcanizing agents, acid acceptors, etc. can be optionally blended into the rubbery chlorinated polyethylene used in the present invention.As fillers, ordinary rubber compounding agents can be added. Calcium carbonate, talc, and clay used as fillers. Examples include alumina, magnesia, silica, barium sulfate, carbon, and metal powders such as aluminum, zinc, lead, and iron.
The appropriate amount to add is 5 to 300 parts by weight per 100 parts by weight of rubbery chlorinated polyethylene.
100 parts by weight is preferred. As pigments, both organic and inorganic pigments that are normally used in the processing of rubber and resin can be used, and if 0.3 to 20 parts by weight are added to 100 parts by weight of rubbery chlorinated polyethylene, coloring can be achieved freely. I can do it. Examples of processing aids include lubricants, stabilizers, ultraviolet absorbers, antistatic agents, and antiaging agents. Lubricants include metal soaps such as stearic acid, lauric acid, naphthenic acid, dibasic stearic acid, ricinoleic acid, and 2-ethylhexoic acid. Stabilizers include tin-based stabilizers that can generally be used for polyvinyl chloride. UV absorbers include benzophenone, benzotriazole,
Examples include salicylates. The amount of these processing aids used is 0 per 100 parts by weight of rubbery chlorinated polyethylene.
．． It is desirable to add 0.5 to 3 parts by weight. Such chlorinated polyethylene compositions can also be used in non-vulcanized systems, but their physical properties such as tensile strength and hardness are relatively low;
In addition, it is desirable to perform mild vulcanization to increase the softening temperature, and by this method, the physical properties of the material when covered with fibers can be improved, such as the tensile strength of C chlorinated polyethylene of 100 to 150 k (] /
d. A product with an elongation of 400 to 1000% can be obtained. Vulcanization also makes it possible to modify heat resistance and creep properties. Dicumyl peroxide is used as a vulcanizing agent. [-Peroxylides such as butyl cumyl peroxide, methyl iso-1 methyl ketone peroxide, mercaptotriazines, etc. are mentioned, and the amount added is 0.1 to 5 parts by weight per 100 parts by weight of rubbery chlorinated polyethylene,
Preferably L dimension n9. %-1! @m starvation sudden h number 41,
11 Add various amines, thiuram sulfides or dioxycarbamates along with azines at 0.1
~5 parts by weight may be used, preferably 0.2 to 1 part by weight. In this case, it is also possible to add a crosslinking agent such as a polyfunctional monomer such as styrene, diallyl phthalate, or triallyl cyanurate, or a prepolymer. The appropriate amount of the metal compound to be added as an acid acceptor is 0.2 to 10 parts by weight, preferably 0.2 to 10 parts by weight.
It is 2 to 5 parts by weight. This J: Sea urchin The reason why the amount of the vulcanizing agent used in the present invention is smaller than in the case of ordinary chlorinated polyethylene vulcanization is that the chlorinated polyethylene is hot-molded using a calender or the like to form fibers. This is because, when coating and bonding using a high-frequency welder in post-processing, if the vulcanized density of the chlorinated polyethylene is too high, the fluidity will deteriorate, causing poor adhesion. Processing of the composition according to the present invention involves mixing rubbery chlorinated polyethylene, fillers, pigments, and other additives in advance with a mixing roll, a Banbury mixer, various kneaders, etc.
The mixture is kneaded at 0 to 110°C for about 10 to 30 minutes and subjected to calender molding, or roughly pelletized when cooled and subjected to an inflation molding machine. There are various types of calender molding machines depending on the number and arrangement of rolls, but the composition according to the present invention can be molded at a molding temperature of 110 to 170°C with a temperature of 0.
Films with a thickness of 0.3 to several meters can be freely formed. In addition, processing using an inflation molding machine is performed at a temperature of 80 to 120°C for the closed type screw of the molding machine, and a temperature of 11°C for the tip of the eddy electric die.
By supplying the pellets at a temperature of 0 to 140°C and appropriately changing the amount of blowing air, it is possible to form a film with a thickness of 0.02 to 1000 io. The film formed in this way is pressed onto a fiber base material using a calendar roll and C-laminated (laminated) to obtain the resin-impregnated coating 11 of the present invention. Lamination is carried out at a calendering temperature of 110 to 170°C, but more preferably hot roll pressing is carried out at 150 to 110°C to ensure complete penetration of the resin composition into the I-fiber base material. To vulcanize the composition, add a vulcanizing agent as described above,
During calender molding, lamination and vulcanization can be carried out simultaneously by adjusting the temperature and speed of the calender, but it is preferable to carry out continuous vulcanization using press rolls, heating rolls, etc. that can be heated to 140 to 200°C. Economical and stable. Vulcanization conditions vary depending on the amount and type of vulcanizing agent, but a moderate crosslinking reaction will proceed at approximately 140°C to 180°C for 0.5 to 3 minutes. The fiber base material that can be used in the present invention is cotton. Natural fibers such as wool, silk, and linen, recycled fibers such as viscose, human silk, and acetate, and polyamide. Woven fabrics and non-woven fabrics made of synthetic fibers such as polyester, polynylidene chloride, polyacrylonitrile, polyvinyl chloride, polypropylene, and polyamino acids, and monoturbid systems of mineral fibers such as glass and asbestos, or blends of these. Examples include knitted fabrics, felt, and paper. A sheet made by coating a fiber substrate with a composition based on rubbery chlorinated polyethylene produced in this way has excellent tensile strength, tear strength, water resistance, abrasion resistance, chemical resistance, and oil resistance. It has sufficient physical properties such as strength and bending resistance, and -
This product has cold resistance of J3 from 20 to -30°C and is fully capable of high-frequency welder bonding. Furthermore, during processing, the rubbery chlorinated polyethylene composition used in the present invention requires heating at a high temperature of 80 to 120°C during kneading, whereas conventional chlorinated polyethylene compositions require high temperature heating of 120 to 150°C. It is possible to work in low humidity. Furthermore, in conventional vulcanization systems, during kneading, the temperature of the composition rises above the kneading temperature due to shear heat generation, so the vulcanization reaction progresses and the scorch phenomenon tends to occur, but the composition of the present invention Because of its good fluidity, this phenomenon rarely occurs. Furthermore, the product of the present invention is characterized by its flame retardancy due to the use of chlorinated polyethylene, but other flame retardants such as cresyl diphenyl phosphate, alkyl diallyl phosphate, and octyldiphenyl bosphate are also used. Triallyl phosphate, tributyl phosphate, triphenyl phosphate, 1-lis(dichloropropyl)bosphate, tris(2,3, dibromopropyl)
Go to Phosphe-1. Phosphate and phosphorus compounds such as ammonium phosphate,
Antioxidant, aluminum hydroxide. Flame retardancy can also be improved by adding about 2 to 10 parts by weight of dicyanamide or the like to 100 parts by weight of rubbery chlorinated polyethylene. Furthermore, the rubbery chlorinated polyethylene used in the present invention can be used in combination with conventional chlorinated polyethylene, but in this case, it has good calenderability and cold resistance below -20°C.
Molecular weight 10.00 considering high frequency welder adhesion etc.
It is preferable to use chlorinated polyethylene having a chlorine content of 0 to 200.000% and a chlorine content of 20 to 55% by weight, in an amount of 50% by weight or less. In addition, other rubbery substances, resins, etc. that can be processed in a compatible manner with the grains can be added in an amount of 30% by weight or less to maintain the physical properties of the composition according to the present invention. In this way, the resin-coated fiber products of the present invention are plasticizer-free, which was unthinkable when using conventional chlorinated polyethylene, and have excellent cold resistance, as well as a soft texture and bending resistance. It is a product with excellent wear resistance, corrosion resistance, oil resistance, and water resistance, especially resin coating #I that is made by vulcanization molding.
The A-fiber sheet has excellent high-frequency welding adhesion processability, so it is possible to obtain sewn products according to the purpose of use. Furthermore, since the rubbery chlorinated polyethylene used in the present invention has excellent film-forming performance, it is also possible to manufacture lightweight resin-coated products that are not available on the market. The present invention will be explained below with reference to Examples and Comparative Examples. Note that all of the net center, part, and % are based on heavy encircling standards. Example 1.2, Comparative Examples 1 and 2 Density 0.92, MIO, 8,1-butene content 4.
A rubbery chlorinated polyethylene with a molecular weight of t8o, ooo and a chlorine content of 28% was produced by chlorinating it in an aqueous suspension using an ethylene/1-butene copolymer with a DSC crystal melting point of 120°C as a raw material. Example 1). Similarly, a rubbery chlorinated polyethylene having a molecular weight of 210,000 and a chlorine content of 34% was obtained (Example 2). The above chlorinated polyethylene 1
00 parts, 10 parts of titanium oxide, 20 parts of barium sulfate
part, 0.8 part of methylpentamethylene dithiocarbamate pipericone, 2.5 parts of magnesium oxide, 0.5 part of stearic acid, 0.3 part of dibutyltin malate, 2(2'-
Add 0.3 parts of hydroxy-5'-methylphenyl) benzo 1 heliazole and mix in a kneader with a capacity of 80~
The mixture was kneaded at 100°C for 15 to 20 minutes. Next, transfer this to a mixing roll and use the vulcanizing agent trithiocyanuric? 11
0.4 parts were added, kneaded at 80° C. to 100° C. for about 1 to 5 minutes, and subjected to calender molding. The calender molding machine has 4 inverted rolls at a speed of 20 m/min and a temperature of 120 to 16 m/min.
It was formed into a sheet with a thickness of about 4 nm at 0°C. This sheet is made of polyester raw l1N (long lJA weihei woven fabric, 1oooo x
1oooo. After laminating on the front and back sides (16 x 17 pieces/1"), it was roll-pressed at 160°C with a hot roll/less and a linear pressure of 3kg/+a. Next, it was continuously crosslinked in a C hot air drying oven at 160°C for 2 minutes, and after cooling, A chlorinated polyethylene coated sheet with a winding thickness of 1111 was obtained.The physical properties of the rubbery chlorinated polyethylene 1-ethylene before and after vulcanization are shown in Table 1.For comparison, high-density polyethylene was used as the raw material. Chlorine content 4
Using two types of 5% and 35% chlorinated polyethylene (products of Osaka Soda Co., Ltd., product names Daisolak G245 and H135, hereinafter referred to as Examples 1 and 2), the same amount of the same chemicals as above were added, cross-wired, and vulcanized. and a similar fiber base material was laminated. Table 2 shows the processing conditions of Examples and Comparative Examples and the physical properties of the sheets after lamination. Table 1 Table 2 In Table 2 (the same applies to the following Examples and Comparative Examples), calendering property... ○ Good, △ Slightly poor fluidity, Adhesion to green mold... ○ Good, △ Slightly poor , Texture... Q Soft, △ Slightly hard, × Hard Bending fatigue resistance...O No abnormality, × Peeling from fiber braid, Measurement method in Table 2 (1) Tensile strength, elongation, tear strength, cold resistance The properties and waterproofness are based on JIS K-6328. (2) Flexural fatigue resistance was measured using a dematcher tester at a speed of 300.
Observe and measure the condition after bending 50,000 times per minute. (3) Texture is measured by tactile measurement of the hardness and softness of the sample. (4) Oil resistance and chemical resistance are measured using specified oils and chemicals in a constant temperature bath at 40℃ for 10 minutes. Measuring the appearance, feel, and dirt of the sample after immersion for one day (5) High-frequency welder adhesion was adhered using a machine manufactured by Sansui Vinita, and the shear peel strength (30 x 20., t) and peel strength (30, width) were measured. Example 3. Comparative Example 3 The same ethylene-butene-1 copolymer as in Example 1.2 was used as a raw material and subjected to eFA hydrogenation in an aqueous suspension state, with a chlorine content of 32%,
A rubbery chlorinated polyethylene having a molecular weight of 200,000 was obtained. To 100 parts of this chlorinated polyethylene, 1 part of phthalocyanine green, 15 parts of calcium carbonate, 2.5 parts of lineage, 0.5 part of triallyl isocyanurate, 3 parts of dibutyltin male-h, and 0.5 parts of lead stearate were added. Combined, 50! The mixture was kneaded for 15 to 20 minutes in a high capacity kneader. Next, 0.8 part of dicumyl peroxide was kneaded at 120° C. for 5 minutes using a mixing I call, and the mixture was calendered. Calendar molding was carried out in the same manner as in Examples 1 and 2.
Laminate the front and back sides of 0x20 pieces/1") and vulcanize in a hot air drying oven at 170℃ for 1 minute to a thickness of 0.6
．． , got a sheet of. Table 3 shows the physical properties of J3 before vulcanization and after vulcanization of the rubbery chlorinated polyethylene. For comparison, chlorine content 4 made from high-density polyethylene
Using 0% chlorinated polyethylene (manufactured by Osaka Soda Co., Ltd., trade name: Daisolac MR104) and adding the same amount of the same chemicals as above, kneading and vulcanization and lamination on the same 1itif base material were performed. Table 4 shows the processing conditions of Examples and Comparative Examples and the physical properties of the laminated sheets. Table 3 Table 4 Example 5 For 1σO part of rubbery chlorinated polyethylene (chlorine content 34%, molecular weight 220.000) in Example 2,
Phthalocyanine blue 1 part, titanium oxide 5 parts, calcium carbonate 20 parts, dipentamethylene diuram tetrasulfide 0.8 parts, magnesium hydroxide 3 parts, dibutyltin malate 0.4 parts, lubricant (SCHI LL&SE l)
Manufactured by mAGHER, trade name Structol WB-16
), 5 parts of antimony trioxide, and 1.5 parts of tricresyl phosphate, and heated at 100°C in a kneader.
After kneading for 15 minutes, 0.4 part of trithiocyanuric acid was added, kneading was carried out at 110° C. for 2 minutes, and calender molding was performed in the same manner as in Example 1.2. After molding, glass cloth (Kanebo Glass Fiber Co., Ltd. product, K
S 1600.200Q/M") and then vulcanized in a hot air drying oven at 160℃ for 90 seconds to a thickness of 0.4n.
I got a sheet of Table 5 shows the physical properties of this sheet according to JIS K-6772 and the results of the flame resistance test according to JIS K-6911 (!!, 24 IA method). Table 5 Example 6 Rubbery chlorinated polyethylene according to Example 3 (chlorine content 3
2%, molecular weight 200.000. Product A) and chlorinated polyethylene in Comparative Example 1 (chlorine content 45%, Osaka Soda Co., Ltd. product, trade name Daisolac G 245.8 product) were mixed in various proportions shown in Table 6, and the total 10
0 parts, 5 parts of carbon black, 30 parts of alumina,
1 part of dipentamethylenethiuram tetrasulfide, 0.5 part of calcium stearate, 2.5 parts of magnesium oxide
1 part, dibutyltin male-hO0 3 parts and kneader to 1 part.
After kneading at 10°C for 15 minutes, trithiocyanuric acid 0.5
The mixture was kneaded at 110°C for 2 minutes and subjected to calender molding. The calendering temperature was 140 to 160℃ Nylon raw 1 (long fiber plain woven fabric 420[) X420D
) was laminated to a total thickness of 0.5 nm on the front and back surfaces, pressed with a hot roll press at 160°C and a linear pressure of 2 kQ/II, and then vulcanized in a hot air dryer at 160°C for 1 minute to obtain Example 1. Physical properties were measured in the same manner as in 2. The results are shown in Table 6. Table 6 As shown in Table 6, when the proportion of conventional products is increased, there is a tendency for the practical cold resistance and high frequency welder adhesive strength to decrease. Applicant Osaka Sotatsu Co., Ltd. Agent Patent Attorney Toru Mayo

Claims (3)

[Claims] (1) Chlorinated ethylene/1-butene copolymer °C
A resin-coated fiber product obtained by laminating a composition containing the obtained rubbery chlorinated polyethylene or a vulcanized product thereof on a fiber base material. (2) The resin-coated m-string product according to claim 1, wherein the ethylene/1-butene copolymer has an ethylene content of 85 to 97% by weight and a 1-butene content of 15 to 3% by weight. (3) Rubber chlorinated polyethylene has a chlorine content of 20 to 55
Weight %, weight average molecular weight ioo, ooo or more, DSCS
The resin-coated fiber product according to claim 1 or 2, which has a heat of fusion of 0.5 cal/gr or less.