WO2018003570A1

WO2018003570A1 - Organic fiber treatment composition and method for treating organic fiber

Info

Publication number: WO2018003570A1
Application number: PCT/JP2017/022527
Authority: WO
Inventors: 細見　哲也; 將人伏木; 豊浩永野
Original assignee: ナガセケムテックス株式会社
Priority date: 2016-06-30
Filing date: 2017-06-19
Publication date: 2018-01-04
Also published as: KR20190037194A; CN109154130A; TW201835415A; JPWO2018003570A1

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 organic fiber treatment method

The present invention relates to an organic fiber treatment composition and an organic fiber treatment method.

Organic rubber such as polyester fiber is used as a reinforcing material for rubber used for tires, various hoses, and various belts such as timing belts, conveyor belts, and V-belts. In particular, hoses and belts used as parts for automobiles and the like are becoming more excellent in high temperature characteristics from the aspect of rubber materials because the temperature of the engine room of the automobile becomes high. One of such rubber materials having excellent high-temperature characteristics is ethylene propylene rubber, which is an organic fiber that is a reinforcing material because its chemical structure has few double bonds and poor reactivity. Is difficult to bond with sufficient adhesive strength, and it is difficult to obtain satisfactory fracture resistance.

In Patent Document 1 and Patent Document 2, an organic fiber treated with a first treating agent containing a polyepoxide compound is coated with a coating made of a second treating agent containing a resorcin / formalin resin (RF), an ionomer resin and a blocked polyisocyanate compound. Disclosing to improve adhesion to ethylene propylene rubber by coating is disclosed.

JP 07-310285 A Japanese Patent Laid-Open No. 10-110385

In order to reinforce the ethylene propylene rubber, even if the organic fiber treated by the conventional treatment composition and treatment method is bonded to the ethylene propylene rubber, its adhesiveness, and also from the viewpoint of practicality among its adhesiveness Rubber adhesion to organic fibers, which is an important indicator, was insufficient. Under such circumstances, an object of the present invention is to provide an organic fiber treatment composition and an organic fiber treatment method that realize excellent adhesion between ethylene propylene rubber and organic fiber.

The first of the present invention is an organic fiber treatment comprising a first treatment agent containing a halohydrin compound or an epoxy compound and a blocked isocyanate compound, and a second treatment agent containing a resorcin / formalin resin, an ionomer resin and a blocked isocyanate compound. Relates to the composition.

The second aspect of the present invention is an organic fiber comprising a first treatment agent containing a halohydrin compound or an epoxy compound and a water-soluble curing agent, and a second treatment agent containing a resorcin / formalin resin, an ionomer resin and a blocked isocyanate compound. It relates to a treatment composition.

In the organic fiber treatment composition, the organic fiber is preferably at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber and aramid fiber.

3rd of this invention is related with the processing method of an organic fiber including the process of (1) and (2) below.
(1) Process of processing organic fiber with said 1st processing agent (2) Process of processing organic fiber processed with said 1st processing agent with said 2nd processing agent

In the organic fiber treatment method, at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber and aramid fiber is preferable.

4th of this invention is related with the organic fiber processed by the processing method of the said organic fiber.

The fifth aspect of the present invention relates to a tire, a hose or a belt using an organic fiber processed by the organic fiber processing method.

The present invention provides an organic fiber treatment composition and an organic fiber treatment method that realize excellent adhesion between ethylene propylene rubber and organic fiber.

Hereinafter, an example of a preferred embodiment of the present invention will be specifically described. The first of the organic fiber treatment composition of the present invention is a first treatment agent containing a halohydrin compound or an epoxy compound and a blocked isocyanate compound, and a second treatment agent containing a resorcin / formalin resin, an ionomer resin and a blocked isocyanate compound. Consists of. The second of the organic fiber treatment composition of the present invention is a second treatment containing a halohydrin compound or an epoxy compound, a first treatment agent containing a water-soluble curing agent, a resorcin / formalin resin, an ionomer resin and a blocked isocyanate compound. It consists of a treatment agent.

[First treatment agent]
A 1st processing agent contains a halohydrin compound or an epoxy compound, and a block isocyanate compound as a 1st aspect. Moreover, a 1st processing agent contains a halohydrin compound or an epoxy compound, and a water-soluble hardening | curing agent as a 2nd aspect.

(Halohydrin compounds)
In the present invention, a halohydrin compound refers to a compound having a constituent part bonded to carbon in which a halogen and a hydroxy group are intermingled.

Examples of the halohydrin compound include a compound (halohydrin ether compound) obtained by reacting a polyhydric alcohol compound and epihalohydrin under acidic conditions.

The polyhydric alcohol refers to an alcohol having two or more hydroxyl groups in the molecule, and is not particularly limited. For example, glycols such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; erythritol, xylitol, sorbitol, Examples include sugar alcohols such as multirole; hydroxycarboxylic acids such as dimethylolbutanoic acid, tartaric acid, and glyceric acid; glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, and pentaerythritol.

In addition, examples of epihalohydrins include epichlorohydrin and epibromohydrin.

The reaction between the polyhydric alcohol compound and the epihalohydrin is, for example, by adding an epihalohydrin to the polyhydric alcohol in the presence of a Lewis acid catalyst such as boron trifluoride diethyl ether complex, tin tetrachloride, aluminum chloride, and the like at 50 ° C. or higher. It can be performed in a temperature range of 150 ° C. or lower.

Among these, sugar alcohols such as sorbitol and a reaction product of polyglycerin and epihalohydrins are preferable because they are multifunctional 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, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A di Glycidyl ethers such as glycidyl ether; glycidyl esters such as glycidyl hexahydrophthalate and glycidyl dimer; triglycidyl isocyanurate, glycidylhindantoin, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, di Glycidylaniline, diglycy Glycidylamines such as lutulidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisaminomethylcyclohexane; or alicyclic rings such as 3,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, epoxidized soybean oil And aliphatic epoxides. These can be used alone or in combination of two or more.

Among these, ethylene glycol glycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether are preferable because of their high water solubility.

The first treating agent contains a halohydrin compound or an epoxy compound, but may contain only one of the halohydrin compound or the epoxy compound, or may contain both the halohydrin compound and the epoxy compound.

The concentration of the halohydrin compound or the epoxy compound in the first treatment agent is such that the total concentration of the halohydrin compound and the epoxy compound is preferably 0.5% by weight or more and 10% by weight or less, and 0.7% by weight or more in the first treatment agent. 5% by weight or less is more preferable. This is because a higher adhesive force can be obtained for rubber containing ethylene propylene rubber. On the other hand, if it is less than 0.5% by weight, the adhesive strength may be lowered, and if it exceeds 10% by weight, the amount of adhesion to the fiber increases and the fiber may become too hard, which is not preferable.

(Block isocyanate compound)
A blocked isocyanate compound is a compound that is produced by a reaction between an isocyanate compound and a blocking agent and is temporarily inactivated by a group derived from the blocking agent. When heated at a predetermined temperature, the group derived from the blocking agent is dissociated. To generate isocyanate groups.

As the isocyanate compound, those having two or more isocyanate groups in the molecule can be used. Examples of diisocyanates having two isocyanate groups include hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, tolylene diisocyanate, trimethylhexamethylene diisocyanate, metaphenylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, Diphenylpropane diisocyanate, biphenyl diisocyanate, and their isomers, alkyl-substituted products, halides, hydrogenated products to the benzene ring, and the like can be used. Furthermore, triisocyanates having 3 isocyanate groups, tetraisocyanates having 4 isocyanate groups, polymethylene polyphenyl polyisocyanate, and the like can also be used. These isocyanate compounds can be used alone or in combination of two or more.

Among these, tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and polymethylene polyphenyl polyisocyanate are preferable because they are easily available industrially and have good heat resistance.

Blocking agents include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; phenols such as phenol, cresol, resorcinol, xylenol; methanol, ethanol, n-propyl alcohol, isopropyl Alcohols such as alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol; formamidoxime, acetoaldoxime, Acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexa Oxime such N'okishimu; dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and the like active methylene of acetylacetone. Of these, lactam-based, phenol-based, and oxime-based blocking agents are preferable because they rapidly deviate from the isocyanate compound at a relatively low temperature.

The content of the blocked isocyanate compound in the first treating agent is preferably 50 parts by weight or more and 500 parts by weight or less, and more preferably 200 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the total of the halohydrin compound and the epoxy compound. This is because a higher adhesive force can be obtained for rubber containing ethylene propylene rubber. If the amount is less than 50 parts by weight, the reaction with the rubber containing ethylene propylene-based rubber may be insufficient and the adhesive strength may be reduced. If the amount exceeds 500 parts by weight, the fiber may be too hard or the processing apparatus may have a solid content. Is not preferred because it may gum up.

(Water-soluble curing agent)
The water-soluble curing agent contained in the first treatment agent is not particularly limited as long as it has water solubility and can advance the curing reaction of the halohydrin compound or the epoxy compound. In the present invention, the term “water-soluble” means that 1% by mass or more dissolves in water at room temperature and normal pressure.

Examples of the water-soluble curing agent include 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 ' -Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, etc. Imidazole compounds; imidazolines such as 2-phenylimidazoline; phthalic acid, isophthalic acid Aromatic carboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, p-oxybenzoic acid, dioxybenzoic acid, trioxybenzoic acid, benzoic acid, methylsalicylic acid, oxyphthalic acid, dioxyphthalic acid, oxyterephthalic acid Unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid; succinic acid, adipic acid, sebacic acid, azelaic acid Saturated carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, adamantanedicarboxylic acid, dimethylolbutanoic acid, and the like; Compound). These can be used alone or in combination of two or more.

As the water-soluble imidazole compounds, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methyl-imidazole, and 1-cyanoethyl-2- have high water solubility. It is preferably at least one selected from the group consisting of ethyl-4-methyl-imidazole.

The carboxylate compound is a salt compound composed of a carboxylic acid and an alkali metal, alkaline earth metal, ammonium or organic base. When a carboxylate compound is used, it may be a partial salt or a complete salt, and an acid anhydride may be hydrolyzed in a treatment bath. In the carboxylate compound, the partial salt is a salt obtained by neutralizing a part of the carboxylic acid group of the carboxylic acid compound, and the complete salt is a salt obtained by neutralizing all the carboxylic acid groups of the carboxylic acid compound. It is.

As the carboxylate compound, since the heat resistance of the resulting organic fiber treatment composition is good, isophthalate compound, terephthalate compound, trimellitic acid salt compound, pyromellitic acid salt compound, p-oxybenzoate Compounds, dioxybenzoate compounds, trioxybenzoate compounds, benzoate compounds, methyl salicylate compounds, oxyphthalate compounds, dioxyphthalate compounds, and oxyterephthalate compounds are preferred. Moreover, in order to improve water solubility, a sodium salt and potassium salt are preferable. These can 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, and more preferably 5 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the total of the halohydrin compound and the epoxy compound. . This is because a higher adhesive force can be obtained for rubber containing ethylene propylene rubber. If it is less than 1 part by weight, the reaction with the rubber containing ethylene propylene-based rubber may be insufficient and the adhesive force may be reduced. If it exceeds 300 parts by weight, an unreacted curing agent remains and the adhesive force is reduced. It is because it may fall.

The total solid content concentration of the first treatment agent is preferably 1% by weight or more and 20% by weight or less, and more preferably 2% by weight or more and 10% by weight or less. This is because a higher adhesive force can be obtained for rubber containing ethylene propylene rubber. If it is less than 1% by weight, the amount of the component of the first treatment agent attached to the organic fiber is insufficient, and sufficient adhesive strength may not be obtained. If it exceeds 20% by weight, the component of the first treatment agent This is because the amount of the organic fibers adhering to the organic fiber becomes too large, the fiber becomes too hard, or a gel is formed in the fiber or the processing apparatus.

[Second treatment agent]
The second treating agent contains a resorcin / formalin resin, an ionomer resin and a blocked isocyanate compound.

(Resorcin / formalin resin)
The resorcin / formalin resin is an initial condensate obtained by reacting resorcin and formaldehyde in water in the presence of an acidic catalyst such as hydrochloric acid or sulfuric acid, an alkali metal hydroxide such as sodium hydroxide, or ammonia.

The molar ratio of resorcin to formaldehyde in the resorcin / formalin resin is preferably resorcin: formaldehyde = 1: 0.1 to 1: 8, more preferably 1: 0.5 to 1: 5, and 1: 1 to 1: 4. Further preferred.

The resorcin / formalin resin may contain resorcin, formaldehyde, a trace amount of a molecular weight regulator (for example, calcium chloride), a solvent (for example, MEK: methyl ethyl ketone), and the like.

The content of the resorcin / formalin resin is preferably 2 parts by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the ionomer resin (total solid content) in the second treatment agent. preferable. This is because a higher adhesive force can be obtained for rubber containing ethylene propylene rubber. This is because if it is less than 2 parts by weight, the adhesive strength may decrease, and if it exceeds 100 parts by weight, the content of the ionomer resin in the second treatment agent may decrease and the adhesive force may decrease.

(Ionomer resin)
The ionomer resin is a copolymer of a monoolefin such as ethylene or propylene and an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, and some carboxyl groups between the polymer chains formed by the copolymer. However, the monovalent or divalent metal ion forms a salt, and the polymer chain is chemically partially cross-linked through the metal ion. Typical metals include Ca, Zn, Mg, Na and the like.

The ionomer resin is preferably used as an aqueous dispersion, and the pH of the aqueous dispersion is 7.5 before both the preparation of the second treatment agent and when it is contained in the second treatment agent. It is preferably 13 or less and more preferably 8 or more and 10 or less. This is because partial crosslinking of the ionomer resin is maintained, and a uniform adhesive layer with high cohesive strength can be formed. When the pH of the aqueous dispersion of the ionomer resin is less than 7.5, the aqueous dispersion of the ionomer resin becomes unstable and easily gels. In addition, pendant carboxyl groups between the polymer chains of the ionomer resin are not neutralized, and partial chemical crosslinking is eliminated. When the pH of the aqueous dispersion of the ionomer resin exceeds 13, the viscosity of the aqueous dispersion of the ionomer resin tends to fluctuate, making it difficult to control the adhesive quality.

The weight average molecular weight of the ionomer resin is not particularly limited, but is preferably 10,000 or more and 100,000 or less. If it is less than 10,000, the cohesive strength of the resin may decrease and the adhesive force may decrease, and if it exceeds 100,000, the resulting fiber may become too hard and fatigue resistance may decrease. It is. Here, the weight average molecular weight refers to the weight average molecular weight in terms of styrene measured by gel permeation chromatography (GPC).

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

The concentration of the ionomer resin in the second treatment agent is preferably 5% by weight or more and 20% by weight or less. This is because if it is less than 5% by weight, a sufficient adhesion effect is hardly exhibited, and if it exceeds 20% by weight, the resulting fiber becomes too hard and the fatigue resistance may be lowered.

(Block isocyanate compound)
As the blocked isocyanate compound used for the second treating agent, any of those usable for the first treating agent can be used.

The content of the blocked isocyanate compound in the second treating 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 and 20 parts by weight or less with respect to 100 parts by weight of the ionomer resin (total solid content). This is because a higher adhesive force can be obtained for rubber containing ethylene propylene rubber. This is because if it is less than 5 parts by weight, the adhesive strength may be lowered, and if it exceeds 30 parts by weight, the resulting fiber becomes too hard and the fatigue resistance may be lowered.

The total solid concentration of the second treating agent is preferably 5% by weight or more and 30% by weight or less, and more preferably 10% by weight or more and 25% by weight or less. This is because a higher adhesive force can be obtained for rubber containing ethylene propylene rubber. If the amount is less than 5% by weight, the amount of the second treatment agent-containing component attached to the organic fiber is small, and sufficient adhesive strength may not be obtained. If the amount exceeds 30% by weight, the resulting fiber becomes hard, This is because the bending fatigue strength and the like may be lowered.

[Optional ingredients]
The first treatment agent or the second treatment agent is preferably aqueous, that is, contains water or a solvent containing water as a main component. In the first treating agent, water or a solvent containing water as a main component is a solvent that dissolves or disperses the halohydrin compound or the epoxy compound, a dispersion medium of the blocked isocyanate compound, and the halohydrin compound or the epoxy compound and the blocked isocyanate compound or water. It functions as a solvent for causing the adhesive curing agent to uniformly adhere to the organic fiber. In the second treatment agent, water or a solvent containing water as a main component functions as a dispersion medium for resorcin / formalin resin, ionomer resin and blocked isocyanate compound, and a solvent for uniformly attaching these to organic fibers.

The organic fiber treatment composition according to the present invention may contain the following optional components as necessary within a range that does not interfere with the object and effect of the present invention. Optional components in the first treating agent include resins that can be copolymerized with halohydrin compounds or epoxy compounds, hardeners other than blocked isocyanate compounds and water-soluble hardeners, organic thickeners, antioxidants, light stabilizers, and adhesiveness. Examples include improvers, reinforcing agents, softeners, colorants, leveling agents, flame retardants, antistatic agents, and surfactants. As optional components in the second treatment agent, in addition to resorcin / formalin resin, ionomer resin and blocked isocyanate compound, vulcanization regulator; zinc white; antioxidant; antifoaming agent; wetting agent; rubber latex, formaldehyde aqueous solution, etc. And an adhesion improver.

Examples of the resin copolymerizable with the halohydrin compound or epoxy compound include polyvinyl alcohol (PVA), aqueous acrylic resin, aqueous polyurethane resin, and the like.

Examples of the curing agent other than the blocked isocyanate compound and the water-soluble curing agent include modified polyamines, polyamide resins, polymercaptan resins, polysulfide resins, and carbodiimides.

[Organic fiber]
The organic fiber treating agent composition according to the present invention can be used for treating various organic fibers. Examples of various organic fibers include fibers that are usually used as reinforcing materials for tires, various hoses, belts such as timing belts, conveyor belts, and V belts. Examples of the fiber include nylon fiber; rayon fiber; vinylon fiber; polyester fiber such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); aramid fiber; and polyurethane fiber.

Among these organic fibers, it is particularly preferable to use at least one selected from the group consisting of nylon fibers, rayon fibers, polyester fibers, and aramid fibers because the resulting fibers have excellent mechanical strength. .

The organic fiber according to the present invention may be in the form of filament yarn, cord, woven fabric, woven fabric or the like.

As a nylon fiber, for example, two 940 decitex multifilaments are twisted 47 times / 10 cm in total, and then two lower twisted cords are combined to apply the same number of upper twists in the opposite direction to the lower twist. Multiplying can be used.

As a rayon fiber, for example, two 1840 dtex multifilaments are twisted 47 times / 10 cm each, and then two lower twisted cords are combined and the same number of upper twists in the opposite direction to the lower twist. Multiplying can be used.

Examples of polyester fibers include melt spinning of polyethylene terephthalate having a yarn viscosity of 0.95, stretching two 1,500 denier multifilaments, respectively, and twisting them 40 times / 10 cm, and then twisting them. A combination of two cords with the same number of upper twists in the opposite direction to the lower twist may be used.

As an aramid fiber, for example, after applying a twist of 35 times / 10 cm in combination of two aromatic polyamide multifilaments (Kevlar manufactured by DuPont) having a display fineness of 1,500 denier and 1,000 filaments, A combination of the two lower twist cords and applying the same number of upper twists in the opposite direction to the lower twist may be used.

[Processing method]
The organic fiber treatment method of the present invention includes (1) a step of treating organic fibers with a first treatment agent; and (2) a step of treating organic fibers treated with the first treatment agent with a second treatment agent. It is a waste.

Treating the organic fiber with the first treatment agent includes treatment performed for attaching various components contained in the first treatment agent to the organic fiber and subsequent heat treatment. As an attachment method, for example, any method such as application using a roller, spraying from a nozzle, immersion in a bath liquid (first treatment agent) can be used. As a heating method, the organic fiber to which the first treatment agent is attached is dried at 100 ° C. to 250 ° C. for 1 minute to 5 minutes and then further heat-treated at 150 ° C. to 250 ° C. for 1 minute to 5 minutes. The method of performing is mentioned. The heat treatment conditions after the drying treatment are preferably 180 ° C. or higher and 240 ° C. or lower and 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 adhesive force to the ethylene propylene rubber may be insufficient, and if it is too high, the organic fiber may be deteriorated and cause a decrease in strength.

The amount of the first treatment agent attached to the organic fiber is 0.1% by weight or more and 10% by weight or less based on the solid content in order to prevent the resulting fiber from becoming too hard while obtaining sufficient adhesive strength. 1 wt% or more and 7 wt% or less is more preferable. Here, the unit [wt%] of the adhesion amount is the weight of the solid content obtained by setting the organic fiber weight to 100.

Treating the organic fiber treated with the first treating agent with the second treating agent means that the various components contained in the second treating agent are attached to the organic fiber treated with the first treating agent and the subsequent treatments. Includes heat treatment. The same means and conditions as when treating organic fibers with the first treating agent can be used. However, the heat treatment condition is preferably 180 ° C. or higher and 240 ° C. or lower and 1 minute or longer and 2 minutes or shorter.

The amount of adhesion of the second treatment agent to the organic fiber is 0.1% by weight or more and 10% by weight or less based on the solid content in order to prevent the resulting fiber from becoming too hard while obtaining sufficient adhesive strength. Is preferable, and 0.5 wt% or more and 5 wt% or less is more preferable. Here, the unit [wt%] of the adhesion amount is the weight of the solid content obtained by setting the organic fiber weight to 100.

Both the step of treating organic fibers with the first treatment agent and the step of treating organic fibers with the second treatment agent are used to adjust the adhesion amount of the first treatment agent or the second treatment agent to the organic fibers. Means such as squeezing with a roller, scraping off with a scraper, blowing off with air blowing, suction, and hitting with a beater may be further employed.

[Usage]
The organic fiber processed by the organic fiber processing method of the present invention can be used for a tire, a hose, a belt, or the like. Specifically, for example, a reinforcing material that reinforces these tires, hoses, or belts by a general method such as providing them inside tires, hoses, or belts, and more specifically, laminating them inside them. Can be used as

The tires, hoses or belts can be formed from rubber. Among them, various tires, various hoses and belts, timing belts, conveyor belts, V-belts which are easily exposed to high temperature environments and used as parts for automobiles. Etc. can be formed using ethylene propylene rubber having excellent high temperature characteristics as a material.

Ethylene propylene-based rubber is inferior in fracture resistance and the like because it is difficult to bond organic fibers with sufficient adhesive force with a general processing composition and processing method. However, since the organic fiber treated with the organic fiber treatment composition of the present invention is also excellent in adhesiveness with ethylene propylene rubber, it is laminated on the inside of a tire, hose, belt or the like formed of ethylene propylene rubber. By using a general method such as these, reinforcing materials such as tires, hoses or belts can be obtained, and the fracture resistance, fatigue resistance and durability can be improved.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.

(Synthesis Example 1)
50 g of sorbitol was dispersed in 20 g of toluene, 0.18 g of tin tetrachloride was added, and 62 g of epichlorohydrin was added over 2 hours in the temperature range of 95 ° C. or more and 100 ° C. or less while stirring. The disappearance of epichlorohydrin was confirmed by a 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 (total solid content concentration 52.5%).

(Example 1)
As an epoxy compound, EX-614B (manufactured by Nagase ChemteX Corporation, sorbitol polyglycidyl ether) (4.8 g) was added to 352 g of water with stirring, and ε-caprolactam block diphenylmethane diisocyanate aqueous dispersion (all 26.7 g) (solid content concentration 54%) was added to prepare a first treatment agent.

As ionomer resin, 69.7 g of Chemipearl S300 (Mitsui Chemical Co., Ltd., total solid concentration 35%) was diluted with 74 g of water, and resorcin / formalin (RF) resin was used as the resorcin / formalin initial in this diluted solution. 67.3 g of condensed dispersion (molar ratio of resorcin to formaldehyde is resorcin: formaldehyde = 1: 1.5, total solid content concentration is 6.5%), and further, 4.3 g of 37% formaldehyde aqueous solution and blocked isocyanate As a compound, 5.9 g of an ε-caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid concentration: 54%) was added to prepare a second treating agent.

As polyester fibers, polyester cords (melt-spun polyethylene terephthalate having a yarn viscosity of 0.95, two stretched 1,500 denier multifilaments were combined and subjected to undertwisting 40 times / 10 cm to produce a lower twisted cord. Two lower twisted cords were combined and 40 twists / 10 cm in the direction opposite to the lower twist were immersed in the first treatment agent, dried at 150 ° C. for 130 seconds, and subsequently 240 ° C. For 130 seconds. Next, after being immersed in the second treatment agent, it was dried at 150 ° C. for 130 seconds, and subsequently heat-treated at 240 ° C. for 70 seconds. About the polyester fiber after a process by a 1st processing agent and a 2nd processing agent, the measurement of adhesive force and evaluation of rubber adhesion were performed by the below-mentioned method. The results are shown in Table 1.

(Example 2)
4.8 g of an aqueous solution (total solid concentration 52.5%) of the sorbitol chlorohydrin compound obtained in Synthesis Example 1 was added to 315 g of water with stirring, and ε-caprolactam blocked diphenylmethane diisocyanate water was added thereto as a blocked isocyanate compound. 13.9 g of a dispersion (total solid content concentration 54%) was added to prepare a first treatment agent. The preparation of the second treating agent and the treatment of the polyester fiber with the first treating agent and the second treating agent were carried out in the same manner as in Example 1. Moreover, about the polyester fiber after a process by a 1st processing agent and a 2nd processing agent, the measurement of the adhesive force and the evaluation of rubber adhesion were performed by the method mentioned later. The results are shown in Table 1.

(Comparative Example 1)
As an epoxy compound, EX-614B (manufactured by Nagase ChemteX Corporation, sorbitol polyglycidyl ether) (4.8 g) was added to 352 g of water with stirring, and ε-caprolactam block diphenylmethane diisocyanate aqueous dispersion (all 26.7 g) (solid content concentration 54%) was added to prepare a first treatment agent.

As rubber latex, 172 g of Nippon 2518FS (manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene / butadiene terpolymer aqueous emulsion, total solid concentration 40.5%) and NIPPOL LX-112 (manufactured by Nippon Zeon Co., Ltd., styrene / butadiene) A copolymer 41% aqueous emulsion (total solid content concentration 40.5%) 73 g was diluted with water 76 g, and resorcin-formalin initial condensation dispersion 270 g (resorcin-formaldehyde mol The ratio was 1: 1.5, and the total solid content concentration was 6.5%) while slowly stirring to prepare an RFL (resorcin / formalin / latex) solution. The obtained RFL (resorcin / formalin / latex) solution was diluted with 591 g of water to prepare a second treatment agent.

The treatment of the polyester fiber with the first treatment agent and the second treatment agent was carried out in the same manner as in Example 1. Moreover, about the polyester fiber after a process by a 1st processing agent and a 2nd processing agent, the measurement of the adhesive force and the evaluation of rubber adhesion were performed by the method mentioned later. The results are shown in Table 1.

(Comparative Example 2)
4.8 g of an aqueous solution (total solid concentration 52.5%) of the sorbitol chlorohydrin compound obtained in Synthesis Example 1 was added to 315 g of water with stirring, and ε-caprolactam blocked diphenylmethane diisocyanate water was added thereto as a blocked isocyanate compound. 13.9 g of a dispersion (total solid content concentration 54%) was added to prepare a first treatment agent. The preparation of the second treatment agent and the treatment of the polyester fiber with the first treatment agent and the second treatment agent were carried out in the same manner as in Comparative Example 1. Moreover, about the polyester fiber after a process by a 1st processing agent and a 2nd processing agent, the measurement of the adhesive force and the evaluation of rubber adhesion were performed by the method mentioned later. The results are shown in Table 1.

(Comparative Example 3)
As an epoxy compound, 10.0 g of EX-614B (manufactured by Nagase ChemteX Corporation, sorbitol polyglycidyl ether) is added to 209 g of water while stirring, and 1.0 g of boron trifluoride monoethylamine is added thereto, and the first treatment agent is added. Was prepared. The preparation of the second treating agent and the treatment of the polyester fiber with the first treating agent and the second treating agent were carried out in the same manner as in Example 1. Moreover, about the polyester fiber after a process by a 1st processing agent and a 2nd processing agent, the measurement of the adhesive force and the evaluation of rubber adhesion were performed by the method mentioned later. The results are shown in Table 1.

(Comparative Example 4)
As an epoxy compound, EX-614B (manufactured by Nagase ChemteX Corporation, sorbitol polyglycidyl ether) 10.0 g was added to 190 g of water with stirring to prepare a first treatment agent. The preparation of the second treating agent and the treatment of the polyester fiber with the first treating agent and the second treating agent were carried out in the same manner as in Example 1. Moreover, about the polyester fiber after a process by a 1st processing agent and a 2nd processing agent, the measurement of the adhesive force and the evaluation of rubber adhesion were performed by the method mentioned later. The results are shown in Table 1.

<Measurement of adhesive strength>
In Examples 1 and 2 and Comparative Examples 1 to 4, five polyester fibers treated with the first treating agent and the second treating agent were prepared, and ethylene propylene was formed on the five polyester fibers. The unvulcanized rubber was placed, press vulcanized at 160 ° C. for 30 minutes, and then the force required to peel the polyester fiber and rubber from the five polyester fibers at a rate of 200 mm / min was measured. The force is shown as a unit [N / 5] as an adhesive force. The larger the value of this force, the better the adhesion to rubber.

<Evaluation of rubber adhesion>
The surface of the polyester fiber after peeling by the measurement of adhesive force was visually observed to evaluate the state of rubber adhesion. The larger the value of the rubber adhesion rate, the better the adhesion to rubber.
○: The rubber adhesion rate on the adhesive surface of the polyester fiber with the rubber is 80% or more.
(Triangle | delta): The rubber adhesion rate in the adhesion surface with the rubber | gum of a polyester fiber is 20% or more and less than 80%.
X: The rubber adhesion rate on the adhesion surface of the polyester fiber to the rubber is less than 20%.

As is clear from Table 1, it can be seen that the organic fiber treated with the organic fiber treatment composition of the present invention has excellent adhesion to ethylene propylene rubber because of its high adhesion and high rubber adhesion.

Claims

An organic fiber treatment composition comprising a first treatment agent containing a halohydrin compound or an epoxy compound, and a blocked isocyanate compound, and a second treatment agent containing a resorcin / formalin resin, an ionomer resin and a blocked isocyanate compound.
An organic fiber treatment composition comprising a first treatment agent containing a halohydrin compound or an epoxy compound and a water-soluble curing agent, and a second treatment agent containing a resorcin / formalin resin, an ionomer resin and a 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 fiber, rayon fiber, polyester fiber, and aramid fiber.
The processing method of organic fiber including the process of (1) and (2) below.
(1) The process of processing organic fiber with the 1st processing agent of Claim 1 or 2 (2) The organic fiber processed with the 1st processing agent of Claim 1 or 2 is described in Claim 1 or 2 The process of processing with the 2nd processing agent of
The organic fiber processing method according to claim 4, wherein the organic fiber is at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber and aramid fiber.
Organic fiber processed by the organic fiber processing method according to claim 4 or 5.
A tire, hose or belt using the organic fiber according to claim 6.