TW201835415A - Organic fiber treatment composition and method for treating organic fiber - Google Patents

Abstract

The purpose of the invention is to provide an organic fiber treatment composition and a method for treating organic fibers to achieve excellent adhesiveness between an ethylene propylene-based rubber and organic fibers. Disclosed is an organic fiber treatment composition comprising: a first treatment agent including a halohydrin compound or an epoxy compound, and a blocked isocyanate compound; and a second treatment agent including a resorcin-formalin resin, an ionomer resin, and a blocked isocyanate compound.

Description

 Organic fiber treatment composition and treatment method of organic fiber  

The present invention relates to an organic fiber treatment composition and a method of treating organic fibers.

Organic fibers such as polyester fibers are used as reinforcing materials for rubbers used in tires, various hoses, and various types of belts such as timing belts, conveyor belts, and V-belts. In particular, since the temperature of the engine room of the automobile is high, the hoses and the safety belts used as parts for automobiles and the like are gradually changed to those having excellent high-temperature characteristics in terms of rubber materials. One of the rubber materials excellent in such high-temperature characteristics is an ethylene propylene-based rubber. However, since the ethylene propylene-based rubber has a small number of double bonds in a chemical structure and lacks reactivity, it is difficult to sufficiently serve an organic fiber as a reinforcing material. The force proceeds next, and it is difficult to obtain satisfactory damage resistance characteristics and the like.

Patent Document 1 and Patent Document 2 disclose that an organic fiber treated with a first treating agent containing a polyepoxy compound is coated with a resorcinol-formaldehyde resin (RF), an ionic polymer resin, and a sealing agent. The film formed of the second treating agent of the terminal polyisocyanate compound improves the adhesion to the ethylene propylene-based rubber.

Prior technical literature

Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 07-310285

Patent Document 2: Japanese Patent Laid-Open No. Hei 10-110385

Even in order to reinforce the ethylene propylene-based rubber, the organic fiber treated by the conventional treatment composition and the treatment method is bonded to the ethylene propylene-based rubber, and it is particularly advantageous in terms of adhesion and further compatibility. The important index of the rubber adhesion to organic fibers is also insufficient. Accordingly, an object of the present invention is to provide an organic fiber treatment composition and a method for treating an organic fiber which are excellent in adhesion between an ethylene propylene rubber and an organic fiber.

The first invention of the present invention relates to an organic fiber treatment composition comprising a first treatment agent and a second treatment agent, wherein the first treatment agent contains a halogen alcohol compound or an epoxy compound, and a blocked isocyanate compound. The second treating agent contains a resorcinol-formaldehyde resin, an ionic polymer resin, and a blocked isocyanate compound.

A second invention of the present invention relates to an organic fiber treatment composition comprising a first treatment agent and a second treatment agent, wherein the first treatment agent contains a halogen alcohol compound or an epoxy compound, and a water-soluble curing agent. The second treating agent contains a resorcinol-formaldehyde resin, an ionic polymer resin, and a blocked isocyanate compound.

In the above organic fiber treatment composition, the organic fiber is preferably at least one selected from the group consisting of nylon fibers, ray fibers, polyester fibers and guanamine fibers.

A third invention of the present invention relates to a method for treating an organic fiber, comprising the steps of (1) and (2): (1) a step of treating the organic fiber with the first treating agent; and (2) using the above The second treatment agent is a step of treating the organic fiber treated with the first treatment agent.

In the method for treating an organic fiber, the organic fiber is preferably at least one selected from the group consisting of nylon fibers, ray fibers, polyester fibers, and guanamine fibers.

The fourth invention of the present invention relates to an organic fiber which has been treated by the above-described treatment method of the organic fiber.

A fifth invention of the present invention relates to a tire, a hose or a belt using an organic fiber treated by the above-described treatment method of an organic fiber.

The present invention provides an organic fiber treatment composition and an organic fiber treatment method for achieving excellent adhesion between an ethylene propylene-based rubber and an organic fiber.

Hereinafter, examples of preferred embodiments of the present invention will be specifically described. The first invention of the organic fiber treatment composition of the present invention comprises a first treatment agent containing a halogen alcohol compound, an epoxy compound, and a blocked isocyanate compound, and a second treatment agent, the second treatment The agent contains a resorcinol-formaldehyde resin, an ionic polymer resin, and a blocked isocyanate compound. Further, the second invention of the organic fiber treatment composition of the present invention comprises a first treatment agent and a second treatment agent, and the first treatment agent contains a halogen alcohol compound, an epoxy compound, and a water-soluble curing agent. 2 The treating agent contains a resorcinol-formaldehyde resin, an ionic polymer resin, and a blocked isocyanate compound.

[1st treatment agent]

The first aspect of the first treating agent is a halogenated alcohol compound or an epoxy compound, and a blocked isocyanate compound. Further, the second aspect of the first treating agent is a halogenated alcohol compound, an epoxy compound, and a water-soluble hardener.

(halo alcohol compound)

In the present invention, the term "halo alcohol compound" means a compound having a moiety in which a halogen and a hydroxyl group are bonded to an adjacent carbon.

The halogenated alcohol compound is, for example, a compound (halogen alcohol ether compound) obtained by reacting a polyol compound and an epihalohydrin under acidic conditions.

The term "polyol" refers to an alcohol having two or more hydroxyl groups in the molecule, and is not particularly limited, and examples thereof include glycols such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; erythritol and wood. Sugar alcohols such as sugar alcohol, sorbitol, maltitol; hydroxycarboxylic acids such as dimethylol butyric acid, tartaric acid, glyceric acid; glycerin, diglycerin, polyglycerol, trimethylolpropane, trimethylolethane , neopentyl alcohol and so on.

Further, examples of the epihalohydrin include epichlorohydrin and epibromohydrin.

The reaction of the polyol compound with the epihalohydrin can be carried out by adding an epihalohydrin to the polyol in the presence of a Lewis acid catalyst such as boron trifluoride diethyl ether complex, tin tetrachloride or aluminum chloride. And it is carried out in the temperature range of 50 ° C or more and 150 ° C or less.

Among these, a sugar alcohol such as sorbitol or a reaction product of a polyglycerol and an epihalohydrin is particularly preferred because it is polyfunctional and highly water-soluble.

(epoxy compound)

The epoxy compound used in the present invention is a compound having two or more epoxy groups in the molecule.

For example, ethylene glycol glycidyl ether, glycerol polyglycidyl ether, diglycerin polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol S Glycidyl ether such as diglycidyl ether, novolac glycidyl ether, brominated bisphenol A diglycidyl ether; glycidyl esters such as hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester; triglycidyl group Isocyanurate, intraglycolide glycidyl ester, tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, triglycidyl meta-aminophenol, diglycidyl aniline, two a glycidylamine such as glycidyltoluidine, diglycidyl metaxylylenediamine, diglycidyltribromoaniline, tetraglycidyl bisamine methylcyclohexane; or a carboxylic acid 3,4-epoxy ring An alicyclic or aliphatic epoxide such as hexylmethyl ester, epoxidized polybutadiene or epoxidized soybean oil. These may be used alone or in combination of two or more.

Among these, ethylene glycol glycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether are particularly preferred because of their high water solubility.

The first treating agent contains a halogenated alcohol compound or an epoxy compound, and may contain only one of a halogenated alcohol compound and an epoxy compound, and may contain both a halogenated alcohol compound and an epoxy compound.

The concentration of the halogenated alcohol compound or the epoxy compound in the first treatment agent is preferably 0.5% by weight or more and 10% by weight or less based on the total concentration of the halogenated alcohol compound and the epoxy compound, and more preferably 0.7% by weight or more and 5% by weight or less. This is to obtain a higher adhesion to the rubber containing the ethylene propylene rubber. On the other hand, if it is less than 0.5% by weight, the adhesion may be lowered. When the amount is more than 10% by weight, the amount of adhesion to the fibers may increase and the fibers may become too hard, which is not preferable.

(blocked isocyanate compound)

The blocked isocyanate compound is formed by the reaction of an isocyanate compound and a blocking agent, and the compound temporarily inactivated by the base derived from the blocking agent, if heated at a specific temperature, is derived from the base of the blocking agent. Will dissociate and form isocyanate groups.

As the isocyanate compound, those having two or more isocyanato groups in the molecule can be used. Examples of the diisocyanate having two isocyanato groups include hexamethylene diisocyanate, diphenylmethane diisocyanate, benzodimethyl diisocyanate, isophorone diisocyanate, and phenyl diisocyanate. Methyl phenyl diisocyanate, trimethyl hexamethylene diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, diphenylpropane diisocyanate, biphenyl diisocyanate and the isomers thereof , alkyl substituted compounds, halides, hydrides of p-benzene rings, and the like. Further, a triisocyanate having three isocyanato groups, a tetraisocyanate having four isocyanato groups, a polymethylene polyphenyl polyisocyanate or the like can be used. These isocyanate compounds may be used alone or in combination of two or more.

Among these, methylphenyl diisocyanate, meta-phenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and polymethylene polyphenyl polyisocyanate are industrially easy to obtain and have good heat resistance. good.

Examples of the terminal blocking agent include ε-caprolactam, δ-valeroguanamine, γ-butylide, β-propionamide, and the like; phenol, cresol, and resorcinol; Phenol such as xylenol; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Alcohols such as monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; methotrexate, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, acetophenone oxime, benzophenone oxime, cyclohexanone oxime, etc. Lanthanide; active methane such as dimethyl malonate, diethyl malonate, ethyl acetate, ethyl acetate, methyl acetate or the like. Among them, the mesamine-based, phenol-based, and guanidine-based blocking agents are preferred because they rapidly dissociate from the isocyanate compound at a relatively low temperature.

The content of the blocked isocyanate compound in the first treatment agent is preferably 50 parts by weight or more and 500 parts by weight or less, more preferably 200 parts by weight or more, based on 100 parts by weight of the total of the halogenated alcohol compound and the epoxy compound. 400 parts by weight or less. This is to obtain a higher adhesion to the rubber containing the ethylene propylene rubber. When the amount is less than 50 parts by weight, the reaction with the rubber containing the ethylene propylene-based rubber may be insufficient, and the strength may be lowered. If the amount exceeds 500 parts by weight, the fibers may become too hard or the solid components may be adhered to the treatment. The situation of the device is therefore not good.

(water soluble hardener)

The water-soluble curing agent contained in the first treatment agent is not particularly limited as long as it is water-soluble and promotes a curing reaction of a halogen alcohol compound or an epoxy compound. In the present invention, the water solubility is a standard of dissolving 1% by mass or more in water at normal temperature and normal pressure.

Examples of the water-soluble hardener include 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-phenylimidazolium triester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-all three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-all three Water-soluble imidazole compound; imidazoline such as 2-phenylimidazoline; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, p-hydroxybenzoic acid , an aromatic carboxylic acid such as dihydroxybenzoic acid, trihydroxybenzoic acid, benzoic acid, methyl salicylic acid, hydroxyphthalic acid, dihydroxyphthalic acid or hydroxyterephthalic acid; maleic acid, fumar Unsaturated carboxylic acids such as acid, itaconic acid, citraconic acid, mesaconic acid, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid; succinic acid, adipic acid, Carboxylic acids such as azelaic acid, sebacic acid, 1,2,3,4-butanetetracarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, adamantanedicarboxylic acid, dimethylolbutanoic acid, etc. Acids and chlorides of such carboxylic acids (carboxylated chlorine). These may be used alone or in combination of two or more.

As a water-soluble imidazole compound, selected from the group consisting of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methyl-imidazole, and 1-cyanoethyl- At least one of the groups consisting of 2-ethyl-4-methyl-imidazole is preferred because it has a high water solubility.

Carboxylic acid chloride is a chloride composed of a carboxylic acid and an alkali metal, an alkaline earth metal, an ammonium or an organic base. In the case of using carboxy ruthenium chloride, it may be a partial salt or a complete salt, or may be used by hydrolyzing an acid anhydride in a treatment bath. Further, the term "partial salt" refers to a salt obtained by neutralizing a partial carboxylic acid group of a carboxylic acid compound, and the term "complete salt" means neutralizing all the carboxylic acid groups of the carboxylic acid compound. The salt obtained.

As carboxymethyl chloride, m-xylylene chloride, terephthalic acid chloride, trimellitic acid chloride, pyromellitic chloride, p-hydroxybenzhydryl chloride, dihydroxybenzhydryl chloride, trihydroxybenzene Antimony chloride, benzamidine chloride, methyl salicylate chloride, hydroxyphthalic acid chloride, dihydroxyphthalic acid chloride, hydroxyterephthalic acid chloride due to the heat resistance of the obtained organic fiber treatment composition Good sex, so it is better. Further, in order to improve water solubility, a sodium salt or a potassium salt is preferred. These may be used alone or in combination of two or more.

The content of the water-soluble curing agent in the first treatment agent is preferably 1 part by weight or more and 300 parts by weight or less, more preferably 5 parts by weight or more, based on 100 parts by weight of the total of the halogenated alcohol compound and the epoxy compound. 100 parts by weight or less. This is to obtain a higher adhesion to the rubber containing the ethylene propylene rubber. The reason for this is that if the amount is less than 1 part by weight, the reaction with the rubber containing the ethylene propylene-based rubber may be insufficient, and the adhesion may be lowered. If the amount exceeds 300 parts by weight, the unreacted curing agent may remain. The situation of reduced force.

The concentration of all the solid content of the first treatment agent is preferably 1% by weight or more and 20% by weight or less, more preferably 2% by weight or more and 10% by weight or less. This is to obtain a higher adhesion to the rubber containing the ethylene propylene rubber. When it is less than 1% by weight, the amount of adhesion of the component of the first treating agent to the organic fiber is insufficient, and sufficient adhesion is not obtained. When it exceeds 20% by weight, the first treating agent is present. The amount of the component attached to the organic fiber becomes excessive and the fiber becomes too hard, or a gel is generated in the fiber or the processing apparatus.

[2nd treatment agent]

The second treatment agent includes a resorcinol-formaldehyde resin, an ionic polymer resin, and a blocked isocyanate compound.

(resorcinol-formaldehyde resin)

The resorcinol-formaldehyde resin is an initial condensate obtained by reacting resorcin with formaldehyde in an acidic catalyst such as hydrochloric acid or sulfuric acid, an alkali metal hydroxide such as sodium hydroxide, or ammonia in water.

Preferably, the resorcinol-formaldehyde resin is preferably resorcinol: formaldehyde = 1:0.1 to 1:8, more preferably 1:0.5 to 1:5, more preferably 1:1~1:4.

Further, the resorcinol-formaldehyde resin may contain resorcin, formaldehyde, a trace amount of a molecular weight modifier (for example, calcium chloride or the like), a solvent (for example, MEK (methyl ethyl ketone), etc.).

The content of the resorcinol-formaldehyde resin is preferably 2 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the ionic polymer resin (all solid content components) in the second treatment agent, more preferably 5 parts by weight or more and 50 parts by weight or less. This is to obtain a higher adhesion to the rubber containing the ethylene propylene rubber. The reason for this is that if the amount is less than 2 parts by weight, the adhesion may be lowered. When the amount is more than 100 parts by weight, the content of the ionic polymer resin in the second treatment agent may be lowered to lower the strength.

(ion polymer resin)

The ionic polymer resin is a copolymer of a monoolefin such as ethylene or propylene with an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, and a part of the carboxyl group between the polymer chains formed by the copolymer utilizes a monovalent or divalent metal ion. In the case of forming a salt, the polymer chain is chemically partially crosslinked via the metal ion. Typical examples of the metal include Ca, Zn, Mg, Na, and the like.

The ionic polymer resin is preferably used in the form of an aqueous dispersion, and the pH of the aqueous dispersion is preferably any of the conditions before the second treatment agent is adjusted and the second treatment agent is contained. It is 7.5 or more and 13 or less, more preferably 8 or more and 10 or less. The reason for this is that partial crosslinking of the ionic polymer resin can be maintained, and a uniform adhesive layer having a high cohesive force can be formed. When the pH of the aqueous dispersion of the ionic polymer resin is less than 7.5, the aqueous dispersion of the ionic polymer resin becomes unstable and becomes easily gelled. Further, the side chain carboxyl groups between the polymer chains of the ionic polymer resin are not neutralized, and are not partially chemically crosslinked. When the pH of the aqueous dispersion of the ionic polymer resin exceeds 13, the viscosity of the aqueous dispersion of the ionic polymer resin tends to fluctuate, and it is difficult to perform quality management of the adhesiveness.

The weight average molecular weight of the ionic polymer resin is not particularly limited, but is preferably 10,000 or more and 100,000 or less. The reason for this is that if it is less than 10,000, the cohesive force of the resin is lowered and the force is lowered. When the pressure exceeds 100,000, the obtained fiber becomes too hard and the fatigue resistance is lowered. Here, the weight average molecular weight means a weight average molecular weight in terms of styrene measured by gel permeation chromatography (GPC).

As the ionic polymer resin, for example, Chemipearl S300 (manufactured by Mitsui Chemicals, Inc.), Chemipearl S200 (manufactured by Mitsui Chemicals, Inc.), or the like can be used.

The concentration of the ionic polymer resin in the second treatment agent is preferably 5% by weight or more and 20% by weight or less. The reason for this is that if it is less than 5% by weight, it is difficult to exhibit a sufficient adhesion effect, and if it exceeds 20% by weight, the obtained fiber becomes too hard and the fatigue resistance is lowered.

(blocked isocyanate compound)

The blocked isocyanate compound used as the second treating agent can be used in any of the first treating agents.

The content of the blocked isocyanate compound in the second treatment agent is preferably 5 parts by weight or more and 30 parts by weight or less, and more preferably 10 parts by weight or more based on 100 parts by weight of the ionic polymer resin (all solid content). And 20 parts by weight or less. This is to obtain a higher adhesion to the rubber containing the ethylene propylene rubber. The reason for this is that if the amount is less than 5 parts by weight, the adhesion may be lowered. When the amount is more than 30 parts by weight, the obtained fiber may be too hard and the fatigue resistance may be lowered.

The concentration of all the solid content of the second treatment agent is preferably 5% by weight or more and 30% by weight or less, more preferably 10% by weight or more and 25% by weight or less. This is to obtain a higher adhesion to the rubber containing the ethylene propylene rubber. The reason for this is that if it is less than 5% by weight, the amount of adhesion of the second treatment agent-containing component to the organic fiber is small, and sufficient adhesion cannot be obtained. If it exceeds 30% by weight, the fiber obtained is obtained. Hard and bending fatigue strength and the like become lower.

[arbitrary ingredients]

The first treatment agent or the second treatment agent is preferably a water system, that is, a solvent containing water or water as a main component. In the first treating agent, water or a solvent containing water as a main component is used as a solvent for dissolving or dispersing a halogenated alcohol compound or an epoxy compound, a dispersion medium for blocking the isocyanate compound, and a halogen alcohol compound or epoxy. The compound and the blocked isocyanate compound or the water-soluble curing agent uniformly adhere to the solvent of the organic fiber to function. In the second treating agent, water or a solvent containing water as a main component is used as a dispersion medium of a resorcinol-formaldehyde resin, an ionic polymer resin, and a blocked isocyanate compound, and is used for uniformly adhering the organic fibers to the organic fiber. It functions as a solvent.

The organic fiber-treated composition of the present invention may contain any of the following optional components as needed within the range not impairing the object and effect of the present invention. Examples of the optional component in the first treatment agent include a resin which can be copolymerized with a halogenated alcohol compound or an epoxy compound, a curing agent other than a blocked isocyanate compound and a water-soluble curing agent, an organic tackifier, and an antioxidant. Light stabilizer, adhesion enhancer, reinforcing agent, softener, colorant, leveling agent, flame retardant, antistatic agent, surfactant, and the like. Examples of the second component of the second treatment agent include, in addition to the resorcinol-formaldehyde resin, the ionic polymer resin, and the blocked isocyanate compound, a vulcanization regulator, zinc white, an antioxidant, an antifoaming agent, and a wetting agent. , rubber latex, aqueous formaldehyde solution and other adhesion enhancers.

Examples of the resin which can be copolymerized with the above-mentioned halogen alcohol compound or epoxy compound include polyvinyl alcohol (PVA), aqueous acrylic resin, and aqueous polyurethane resin.

Examples of the curing agent other than the blocked isocyanate compound and the water-soluble curing agent include modified polyamine, polyamine resin, polythiol resin, polyether oxime resin, and carbodiimide.

[organic fiber]

The organic fiber treating agent composition of the present invention can be used for the treatment of various organic fibers. Examples of the various organic fibers include fibers which are generally used as reinforcing materials for tires, various hoses, timing belts, conveyor belts, belts such as V-belts, and the like. Further, examples of the type of the fiber include nylon fibers; ray fibers; vinylon fibers; polyester fibers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); Amidamide fiber; and polyurethane fiber.

Among these organic fibers, at least one selected from the group consisting of nylon fibers, ray fibers, polyester fibers, and guanamine fibers is preferably used because the fibers obtained are excellent in mechanical strength.

The organic fiber of the present invention may be in the form of a filament, a rope, a woven fabric, a woven fabric or the like.

As the nylon fiber, for example, two 940 dtex decitex multifilaments can be combined, and after 47 times/10 cm stranding, two of the lower reins are combined, and the same is performed in the opposite direction of the lower jaw. The number of times is above.

As the ruthenium fiber, for example, two 1840 dtex multifilaments can be combined, and after 47 times/10 cm of twisting, two of the lower reins are combined, and the same number of times are performed in the opposite direction of the lower jaw. The captain is the master.

As the polyester fiber, for example, polyethylene terephthalate having a yarn viscosity of 0.95 can be melt-spun and stretched, and the obtained 1,500 denier multifilaments obtained by combining two can be carried out 40 times/10 cm. After the twisting, the two lower reins are combined, and the same number of times is performed in the opposite direction of the lower jaw.

As the guanamine fiber, for example, two aromatic polyamine complexes (Kevlar manufactured by Dupon Co., Ltd.) having a fineness of 1,500 denier and 1,000 filaments may be combined and subjected to 35 times/10 cm stranding. Two of the lower reins are combined, and the same number of times is performed in the opposite direction of the lower jaw.

[Approach]

The method for treating an organic fiber according to the present invention includes the steps of: (1) treating the organic fiber with the first treating agent; and (2) performing the organic fiber treated with the first treating agent with the second treating agent. The steps of processing.

The treatment of the organic fiber by the first treating agent includes a treatment for adhering various components contained in the first treating agent to the organic fiber, and a subsequent heat treatment. As the adhesion method, for example, a coating by a roll, a spray by a nozzle, or a method of immersing in a bath (first treatment agent) can be used. In the heating method, the organic fiber to which the first treatment agent is applied is dried at 100° C. or higher and 250° C. or lower for 1 minute or longer and 5 minutes or shorter, and further, 150° C. or higher and 250° C. or lower for 1 minute or longer and 5 times. A method of heat treatment below a minute. The conditions of the heat treatment after the drying treatment are preferably heat treatment at 180 ° C or higher and 240 ° C or lower for 2 minutes or longer and 3 minutes or shorter. In particular, in the heat treatment after the drying treatment, if the temperature is too low, the adhesion to the ethylene propylene-based rubber may be insufficient. If the temperature is too high, the organic fibers may be deteriorated to lower the strength.

The amount of adhesion of the first treating agent to the organic fibers is preferably 0.1% by weight or more and 10% by weight or less on the basis of the solid content in order to obtain a sufficient adhesive force and the obtained fibers are not excessively hard. It is preferably 1% by weight or more and 7% by weight or less. Here, the unit of the adhesion amount [% by weight] is the weight of the solid content obtained when the weight of the organic fiber is 100.

The treatment of the organic fiber treated with the first treating agent by the second treating agent is performed by adhering the organic component treated with the first treating agent to the organic component treated with the first treating agent. Treatment and subsequent heat treatment. It can be carried out under the same means and conditions as those in the case of treating the organic fiber with the first treating agent. However, as a condition of the heat treatment, it is preferably heat-treated at 180 ° C or higher and 240 ° C or lower for 1 minute or longer and 2 minutes or shorter.

The amount of adhesion of the second treatment agent to the organic fibers is preferably 0.1% by weight or more and 10% by weight or less on the basis of the solid content in order to obtain sufficient adhesion and the obtained fibers are not excessively hard. It is preferably 0.5% by weight or more and 5% by weight or less. Here, the unit of the adhesion amount [% by weight] is the weight of the solid content obtained when the weight of the organic fiber is 100.

In order to adjust the amount of adhesion of the first treating agent or the second treating agent to the organic fibers, the step of treating the organic fibers with the first treating agent and the step of treating the organic fibers with the second treating agent are also performed. Further, it is possible to employ a pressing by a pressure roller, a scraping by a doctor blade or the like, a blowing by air blowing, suction, and a tapping by a stirrer.

[use]

The organic fiber or the like treated by the treatment method of the organic fiber of the present invention can be used for a tire, a hose or a belt. Specifically, for example, it can be used to reinforce tires, hoses, belts, and the like by a usual method such as providing a tire, a hose, or a belt, and more specifically, laminating the inside of the tire or the like. Reinforcing material.

Tires, hoses or belts can be formed from rubber, in particular, various tires, various hoses and belts, timing belts, conveyor belts, V-belts, which are used as parts for automobiles and the like that are easily exposed to high temperatures. It can be formed by using an ethylene propylene-based rubber excellent in high-temperature characteristics as a material.

It is difficult for the ethylene propylene-based rubber to cause the organic fibers to be adhered with a sufficient adhesive force by a usual treatment composition and a treatment method, and thus the fracture resistance characteristics are inferior. However, since the organic fiber treated with the organic fiber treatment composition of the present invention is excellent in adhesion to the ethylene propylene-based rubber, it is laminated on a tire, a hose or a belt formed of an ethylene propylene-based rubber. The usual method such as laminating the inner layer can be used as a reinforcing material for such tires, hoses, belts, and the like, and the damage resistance, fatigue resistance, and durability can be improved.

 Example  

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. In the following, "parts" or "%" means "parts by weight" or "% by weight" unless otherwise specified.

(Synthesis Example 1)

50 g of sorbitol was dispersed in 20 g of toluene, and 0.18 g of tin tetrachloride was added thereto, and 62 g of epichlorohydrin was added and reacted over 2 hours while stirring at a temperature of 95 ° C or more and 100 ° C or less. The disappearance of epichlorohydrin was confirmed by the titration method described in JIS K 7236, and toluene used as a solvent was removed by concentration under reduced pressure. The obtained concentrate was dissolved in 100 g of water to obtain an aqueous solution of sorbitol chlorohydrin compound (the total solid content concentration was 52.5%).

(Example 1)

4.8 g of EX-614B (manufactured by Nagase ChemteX Co., Ltd., sorbitol polyglycidyl ether) was added to 352 g of water while stirring, and then ε-caprolactone as a blocked isocyanate compound was added. A first treatment agent was prepared by subjecting an amine-terminated aqueous dispersion of diphenylmethane diisocyanate (having a total solid content of 54%) to 26.7 g.

As an ionic polymer resin, 69.7 g of Chemipearl S300 (manufactured by Mitsui Chemicals, Inc., total solid content concentration: 35%) was diluted with 74 g of water, and was added as resorcinol-formaldehyde (RF) to the diluted solution. Resin between the resin and the initial condensation dispersion of benzenediol-formaldehyde 67.3g (the molar ratio of resorcinol to formaldehyde is resorcinol: formaldehyde = 1:1.5, the concentration of all solids is 6.5%), and then add 37 A second treatment agent was prepared by adding 4.3 g of a % formaldehyde aqueous solution and 5.9 g of a ε-caprolactam-terminated diphenylmethane diisocyanate aqueous dispersion (all solid content concentration: 54%) as a blocked isocyanate compound.

As a polyester fiber, a polyester rope (a polyethylene terephthalate having a yarn viscosity of 0.95 was melt-spun and extended, and two 1,500 denier multifilaments obtained were combined and taken down at 40 times/10 cm.制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作The clock was then heat treated at 240 ° C for 130 seconds. Then, after immersing in the second treating agent, it was dried at 150 ° C for 130 seconds, and then heat-treated at 240 ° C for 70 seconds. The polyester fiber treated with the first treating agent and the second treating agent was subjected to the following methods to measure the adhesion force and the rubber adhesion. The results are shown in Table 1.

(Example 2)

4.8 g of an aqueous solution of sorbitol chloroethanol compound obtained in Synthesis Example 1 (all solid content concentration: 52.5%) was added to 315 g of water while stirring, and then ε-caprolactone as a blocked isocyanate compound was added. The first treating agent was prepared by dissolving 13.9 g of an amine-terminated aqueous dispersion of diphenylmethane diisocyanate (having a total solid content of 54%). The preparation of the second treatment agent and the treatment of the polyester fiber by the first treatment agent and the second treatment agent were carried out in the same manner as in Example 1. Moreover, the polyester fiber processed by the first treatment agent and the second treatment agent was used to measure the adhesion force and the adhesion of the rubber by the following method. The results are shown in Table 1.

(Comparative Example 1)

4.8 g of EX-614B (manufactured by Nagase ChemteX Co., Ltd., sorbitol polyglycidyl ether) was added to 352 g of water while stirring, and then ε-caprolactone as a blocked isocyanate compound was added. A first treatment agent was prepared by subjecting an amine-terminated aqueous dispersion of diphenylmethane diisocyanate (having a total solid content of 54%) to 26.7 g.

As a rubber latex, Nipol 2518FS (manufactured by Nippon Zeon Co., Ltd., vinyl pyridine-styrene-butadiene terpolymer water emulsion, all solid content concentration: 40.5%) 172 g and Nipol LX-112 ( Manufactured by Japan Reion Co., Ltd., styrene-butadiene copolymer 41% aqueous emulsion, total solid content concentration: 40.5%) 73 g diluted with 76 g of water, and added as resorcin to one side of the diluted solution -Formaldehyde resin benzenediol-formaldehyde initial condensation dispersion 270g (the molar ratio of resorcinol to formaldehyde is 1:1.5, the total solid content concentration is 6.5%) while slowly stirring to prepare RFL (between Hydroquinone-formaldehyde-latex) solution. The obtained RFL (resorcinol-formaldehyde-latex) solution was diluted with 591 g of water to prepare a second treating agent.

The treatment of the polyester fiber by the first treating agent and the second treating agent was carried out in the same manner as in Example 1. Moreover, the polyester fiber processed by the first treatment agent and the second treatment agent was used to measure the adhesion force and the adhesion of the rubber by the following method. The results are shown in Table 1.

(Comparative Example 2)

4.8 g of an aqueous solution of sorbitol chloroethanol compound obtained in Synthesis Example 1 (all solid content concentration: 52.5%) was added to 315 g of water while stirring, and then ε-caprolactone as a blocked isocyanate compound was added. The first treating agent was prepared by dissolving 13.9 g of an amine-terminated aqueous dispersion of diphenylmethane diisocyanate (having a total solid content of 54%). The preparation of the second treatment agent and the treatment of the polyester fiber by the first treatment agent and the second treatment agent were carried out in the same manner as in Comparative Example 1. Moreover, the polyester fiber processed by the first treatment agent and the second treatment agent was used to measure the adhesion force and the adhesion of the rubber by the following method. The results are shown in Table 1.

(Comparative Example 3)

10.0 g of EX-614B (manufactured by Nagase ChemteX Co., Ltd., sorbitol polyglycidyl ether) was added to 209 g of water while stirring, and then 1.0 g of boron trifluoride monoethylamine was added thereto. A first treatment agent was prepared. The preparation of the second treatment agent and the treatment of the polyester fiber by the first treatment agent and the second treatment agent were carried out in the same manner as in Example 1. Moreover, the polyester fiber processed by the first treatment agent and the second treatment agent was used to measure the adhesion force and the adhesion of the rubber by the following method. The results are shown in Table 1.

(Comparative Example 4)

As an epoxy compound, 10.0 g of EX-614B (manufactured by Nagase Chemte Co., Ltd., sorbitol polyglycidyl ether) was added to 190 g of water and stirred to prepare a first treating agent. The preparation of the second treatment agent and the treatment of the polyester fiber by the first treatment agent and the second treatment agent were carried out in the same manner as in Example 1. Moreover, the polyester fiber processed by the first treatment agent and the second treatment agent was used to measure the adhesion force and the adhesion of the rubber by the following method. The results are shown in Table 1.

<Measurement of force>

Five of the polyester fibers treated with the first treating agent and the second treating agent in each of Examples 1 and 2 and Comparative Examples 1 to 4 were prepared, and ethylene propylene-based unvulcanized rubber was placed on the five polyester fibers. The pressure was vulcanized at 160 ° C for 30 minutes, and then the force required to peel the polyester fiber from the rubber at a speed of 200 mm/min was measured for 5 polyester fibers. This force is expressed as a unit of force [N/5 roots]. The larger the value of the force, the more excellent the adhesion to the rubber.

<Evaluation of rubber adhesion>

The surface of the polyester fiber peeled off by the measurement of the adhesion force was visually observed, and the state of the adhered rubber was evaluated. The larger the value of the rubber adhesion rate, the more excellent the adhesion to the rubber.

○: The rubber adhesion rate of the adhesive surface of the polyester fiber and the rubber was 80% or more.

△: The rubber adhesion rate of the polyester fiber to the rubber back surface was 20% or more and less than 80%.

×: The rubber adhesion rate of the polyester fiber to the rubber back surface was less than 20%.

As is clear from Table 1, the organic fiber treated by the organic fiber treatment composition of the present invention has high adhesion and a high rubber adhesion rate, and therefore is excellent in adhesion to an ethylene propylene rubber.

Claims (7)

 An organic fiber treatment composition comprising a first treatment agent containing a halogen alcohol compound or an epoxy compound, and a blocked isocyanate compound, and a second treatment agent containing isophthalic acid Phenol-formaldehyde resin, ionic polymer resin and blocked isocyanate compound.    An organic fiber treatment composition comprising a first treatment agent containing a halogen alcohol compound or an epoxy compound, and a water-soluble curing agent, and a second treatment agent containing isophthalic acid Phenol-formaldehyde resin, ionic polymer resin and blocked isocyanate compound.    The organic fiber treatment composition according to claim 1 or 2, wherein the organic fiber is at least one selected from the group consisting of nylon fibers, ray fibers, polyester fibers, and guanamine fibers.    A method for treating organic fibers, comprising the steps of (1) and (2): (1) a step of treating an organic fiber with a first treating agent of claim 1 or 2; (2) applying for an application The second treating agent of the first or second aspect of the patent is a step of treating the organic fiber treated with the first treating agent of the first or second aspect of the patent application.    The method for treating an organic fiber according to the fourth aspect of the invention, wherein the organic fiber is at least one selected from the group consisting of nylon fiber, ray fiber, polyester fiber and guanamine fiber.    An organic fiber which has been treated by the treatment method of the organic fiber of claim 4 or 5.    A tire, hose or belt using the organic fiber of claim 6 of the patent application.