JP2010069816A - Rubber-coated fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber-coated fabric which is flexible, even when a phthalate ester-based plasticizer is not added to the rubber thin film and has a weak tackiness and free from the problem wherein the presence of a phthalate ester-based plasticizer in the rubber thin film increases the tackiness of the rubber-coated fabric causing the sticking of the rubber-coated fabrics with each other, and the difficulty in separating them and a poor handleability e.g. in unwinding the wound rubber-coated fabric. <P>SOLUTION: The rubber-coated fabric is composed of a base fabric and rubber thin films integrally laminated on both the sides of the base fabric. The rubber thin film includes an adipic acid diester-based plasticizer or a naphthene-based plasticizer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a rubberized cloth.

  A rubberized cloth formed by laminating and integrating rubber thin films on both surfaces of a base cloth is widely used as a material for rubber boats, rain clothes, mats and the like as described in Patent Document 1.

In addition, in order to impart flexibility to this type of rubberized cloth, a method of adding an inexpensive phthalate plasticizer to the rubber thin film is known.
Japanese Patent Laid-Open No. 05-338081

  However, if the phthalate ester plasticizer is contained in the rubber thin film, the adhesive force is likely to increase. For example, when unwinding the rubberized cloth wound in a roll shape, the rubberized cloths stick to each other and are not easily peeled off. There was a problem that workability was bad.

  Therefore, the present invention has an object of providing a rubberized cloth that can impart flexibility and further has a low adhesive strength even though a phthalate ester plasticizer is not added to the rubber thin film. .

  That is, the rubberized cloth of the present invention is a rubberized cloth comprising a base cloth and a rubber thin film laminated and integrated on both surfaces of the base cloth. In the rubber thin film, an adipic acid diester plasticizer or a naphthene plastic It contains an agent.

  The present invention can provide flexibility and provide a rubber-coated cloth with low adhesive strength even though a phthalate plasticizer is not added to the rubber thin film.

  As the base fabric in the rubberized fabric of the present invention, all those used as the base fabric of ordinary rubberized fabric can be used. Examples of such a base fabric include polyamide, polyester, polyurethane, polypropylene, vinylon, cotton, hemp, and the like.

  As a method for forming a rubber thin film in the present invention, a method of laminating and integrating a rubber thin film on a base fabric by a so-called calendar topping method that has been widely adopted, or applying or transferring liquid rubber directly on a base fabric A method of laminating by the above can be adopted. The thickness of the rubber thin film is preferably in the range of 0.3 to 1.5 mm.

  In the present invention, the rubber forming the rubber thin film may have any composition as long as it can be laminated and integrated with the base fabric. For example, as described in Japanese Examined Patent Publication No. 64-9941, it exhibits fluidity at room temperature, and crosslinks such as a carboxyl group, a hydroxyl group, a mercapto group, a halogen atom, an amino group, an aziridyl group, and an epoxy group at the molecular end. Reaction of polyisocyanates with telechelic liquid rubbers such as polybutadiene, polyisoprene, polychloroprene, butadiene-isoprene copolymer, acrylonitrile-butadiene copolymer, and styrene-butadiene copolymer having possible functional groups. Cross-linked rubber (hereinafter referred to as isocyanate cross-linked rubber) or the like can be used.

  In the present invention, the plasticizer contained in the rubber thin film is an adipic acid diester or a naphthenic compound. With these plasticizers, flexibility can be imparted and an increase in adhesiveness can be prevented. Further, other plasticizers may be added as long as they can provide flexibility and do not inhibit the increase in tackiness and are other than phthalate ester plasticizers.

  Various additives can be added to the rubber thin film of the rubberized cloth of the present invention to improve rubber physical properties. As the additive, all those added in the conventional rubberized cloth can be used, and examples thereof include a filler, a water absorbing agent, an anti-aging agent, a process oil, a colorant, an antistatic agent, and a solvent. .

  Examples of the filler include calcium carbonate, activated calcium carbonate, clay, talc, mica, white carbon, carbon black, aluminum hydroxide, zinc white, aluminum sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, rubber powder, and wood powder. And cork powder.

  As the water-absorbing agent, any agent that prevents the foaming phenomenon that occurs in the product due to the water absorption etc. of the above-mentioned filler may be used. For example, quicklime, silane coupling agent, titanate coupling agent, molecular sieve, anhydrous calcium sulfate, sulfuric acid Examples include magnesium, sodium sulfate, potassium carbonate, calcium oxide, magnesium oxide, activated alumina, and the like.

  As the anti-aging agent, general ultraviolet absorbers and antioxidants can be used. Examples include benzotriazoles, benzophenones, salicylic acid derivatives, monophenols, naphthylamines, phenylenediamines, polyphenols, carbamates, and the like. These are preferably added in an amount of 20 parts by weight or less, particularly 0.1 to 10 parts by weight per 100 parts by weight of rubber.

  Process oil is added as a softening agent, but trialkoxyalkyl phosphates and surfactants also serve as softening agents, so it is preferable to add as little as possible (general process oils are charged with It ’s better not to use it as it may reduce the prevention performance). However, what is called a conductivity-imparting softener or plasticizer such as dioctyl adipate can be used in combination.

  Either an organic pigment or an inorganic pigment can be used as the colorant.

  As the antistatic agent, trialkoxyalkyl phosphate is preferably used. For example, tributoxyethyl phosphate, triethoxyethyl phosphate, trimethoxyethyl phosphate, tributoxymethyl phosphate, triethoxymethyl phosphate, tributoxypropyl Phosphate, triethoxypropyl phosphate, tributoxybutyl phosphate, triethoxybutyl phosphate and the like can be used.

  Further, as the antistatic agent, a surfactant other than the trialkoxyalkyl phosphate may be used in combination.

  The addition amount of the antistatic agent is 5 to 35 parts by weight, preferably 20 to 30 parts by weight per 100 parts by weight of rubber.

  As the antistatic agent, the surfactant used in combination with the trialkoxyalkyl phosphate may be any surfactant as long as it has been conventionally used as an antistatic agent, but a nonionic surfactant is particularly preferable. Examples of nonionic surfactants include the following.

  That is, a) ether type nonionic surface activity such as polyoxyethylene (or propylene or ethylene / propylene block) alkyl ether, polyoxyethylene (or propylene or ethylene / propylene block) alkyl aryl ether, polyoxyethylene polyoxypropylene ether, etc. Agent, b) ester type nonionic surfactant such as polyoxyethylene (or propylene or ethylene / propylene block) alkyl ester, partial ester of polyhydric alcohol and fatty acid, c) polyoxyethylene (or propylene or ethylene / propylene block) ) Amino ether type nonionic surfactant such as alkylamine, d) Polyoxyethylene (or propylene or ethylene / propylene block) polyhydric alcohol fatty acid ester Ether ester type nonionic surfactants such as ether, and the like.

  Among the ester-type nonionic surfactants of b) above, specific examples of polyhydric alcohols and fatty acid partial esters include polyhydric alcohols such as sorbitan, sorbitol, mannitan, mannitol, glycerin, diglycerin, pentaerythritol and the like. And partial esters with fatty acids having 12 to 22 carbon atoms in the alkyl group.

  The ether ester type nonionic surfactant of d) is a polyoxy group having 1 to 20 moles of added alkylene oxide such as ethylene oxide and propylene oxide, and 12 to 22 carbon atoms in the fatty acid alkyl group. Ethylene (or propylene or ethylene / propylene block) sorbitan fatty acid ester, polyoxyethylene (or propylene or ethylene / propylene block) sorbitol fatty acid ester, polyoxyethylene (or propylene or ethylene / propylene block) mannitan fatty acid ester, polyoxyethylene ( Or propylene or ethylene / propylene block) glycerin fatty acid ester, polyoxyethylene (or propylene or ethylene / propylene block) propylene glycol Rumono fatty acid esters.

  The solvent is used to adjust the viscosity of the liquid rubber so as to improve the ease of handling and facilitate mixing with various additives. Examples of the solvent include hydrocarbon compounds such as butane, pentane, gasoline, petroleum spirit, and cyclohexane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; methyl chloride, methylene chloride, chloroform, carbon tetrachloride, and trichloroethane. Halogenated hydrocarbon compounds such as tetrachloroethane, trichloromonofluoromethane, dichlorodifluoromethane; halogenated aromatic hydrocarbon compounds such as chlorobenzene, chlorotoluene, bromobenzene; ethyl ether, isopropyl ether, dioxane, Ether compounds such as tetrahydrofuran; ketone compounds such as acetone, methyl acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, methyl acetate, isobutyl acetate, ethyl propionate , And ester compounds such as methyl propionate. Water, alcohols, etc. can also be used. The amount of these solvents added is 100 parts by weight or less, particularly preferably 1 to 10 parts by weight per 100 parts by weight of rubber.

  In the case of isocyanate cross-linked rubber, a reaction modifier, cross-linking agent, urethanization catalyst, blend polyol, etc. are added to the liquid rubber to accelerate or retard the urethanization reaction between the rubber and polyisocyanate. To do.

  Examples of the reaction regulator include acids such as sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid and maleic acid, and alkalis such as sodium hydroxide and potassium hydroxide. Two or more of these acids and alkalis can be used in combination, but a mixture of acids and alkalis cannot be used.

  The cross-linking agent serves as a cross-linking agent in the urethanization reaction between the rubber and polyisocyanate of the isocyanate cross-linked rubber. Examples of the cross-linking agent include 1,4-butanediol, 1,5-pentanediol, Bifunctional or higher functional low molecular weight hydroxyl compounds such as ethylene glycol, diethylene glycol, 1,6-hexanediol, glycerin, diethanolamine triethanolamine, and trimethylolpropane can be used.

  Examples of the urethanization catalyst that serves as a catalyst for the urethanization reaction include amines and organotins, and these can be used alone or in combination of two or more.

  The blend polyol may be any urethane polyol compatible with rubber, and any of polyester polyol and polyether polyol may be used.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example.

Example 1
The composition of the following surface layer composition is mixed with a mixer, and after kneading with a kneading roll, it is dispensed to a thickness of 0.5 mm with a calendar, topped on a base fabric (polyester fiber), vulcanized, and then the base fabric A surface layer (rubber layer) was formed thereon.

[Surface layer formulation]
-Acrylonitrile-butadiene rubber (rubber resin: NBR) 70 parts by weight-Polyvinyl chloride (PVC) 30 parts by weight-Sulfur (vulcanizing agent) 1.56 parts by weight-Zinc flower (vulcanizing aid) 2.5 parts by weight -Tetramethylthiuram disulfide (accelerator) 1.5 parts by weight-Tributoxyethyl phosphate (antistatic agent: TBXP) 10 parts by weight-Nonionic surfactant (antistatic agent) 10 parts by weight-Adipic acid ester (plastic) Agent) 0.24 parts by weight ・ Magnesium carbonate (filler) 90 parts by weight

  Next, the composition of the following back layer formulation was mixed with a mixer, and after kneading with a kneading roll, it was dispensed to a thickness of 1.0 mm with a calendar and topped on the side of the base fabric where the surface layer was not formed. And vulcanized to obtain a rubberized cloth of the present invention in which the base fabric was sandwiched between the front and back rubber layers.

[Back layer formulation]
-Styrene-butadiene rubber (rubber resin: SBR) 80 parts by weight-Acrylonitrile-butadiene rubber (rubber resin: NBR) 20 parts by weight-Sulfur (vulcanizing agent) 0.5 part by weight-Zinc flower (vulcanizing aid) 5 Parts by weight-tetramethylthiuram disulfide (accelerator) 1.25 parts by weight-tetrabutylthiuram disulfide (accelerator) 1 part by weight-sulfenamide type (accelerator) 1 part by weight-naphthenic type (plasticizer) 17 Weight parts ・ Carbon black SRF (Antistatic agent) 70 weight parts

  The resulting rubberized cloth was subjected to a stickiness evaluation test. As a result, the rubberized cloth of Example 1 was “good” because the adhesive strength was 1 N or less. The stickiness evaluation methods and evaluation criteria are as follows.

[Stickiness]
The obtained rubberized cloth was made into A4 size, and two sheets thereof were prepared. Thereafter, the back layers of the two rubberized cloths were attached to each other and a load of 5 kg was applied for 24 hours, and then the adhesive strength was measured by a method according to JIS-K-6404-5 to evaluate the stickiness. . The evaluation criteria were as follows.
○: Adhesive strength was 1 N or less.
X: Adhesive strength exceeded 1N.

Example 2
A rubberized cloth was obtained in the same manner as in Example 1 except that a naphthenic resin was used as the surface layer plasticizer. The obtained rubberized cloth was tested in the same manner as in Example 1. As a result, the rubberized cloth of Example 2 was “good” because the adhesive strength was 1 N or less.

Comparative Example 1
A rubberized cloth was obtained in the same manner as in Example 1 except that dioctyl phthalate (company name: DOP manufactured by CG Esther Co., Ltd.) was used as the plasticizer for the surface layer and the back layer. The obtained rubberized cloth was tested in the same manner as in Example 1. As a result, the rubberized cloth of Comparative Example 1 was x because the adhesive strength exceeded 1N.

  In Examples 1 and 2, since dioctyl phthalate was not used as a plasticizer, the stickiness was 1 N or less, and unwinding from a roll could be easily performed. On the other hand, in Comparative Example 1, since dioctyl phthalate was used as a plasticizer, the stickiness exceeded 1N, and unwinding from the roll was difficult.

Claims (1)

In a rubberized cloth comprising a base fabric and a rubber thin film laminated and integrated on both sides of the base fabric,
A rubberized cloth comprising an adipic acid diester plasticizer or a naphthenic plasticizer in a rubber thin film.