JPH0812769A - Method for bonding thermoplastic elastomer to fibrous material - Google Patents

Abstract

PURPOSE:To bond a thermoplastic elastomer to a fibrous material firmly by a treatment performed without using any organic solvent by firmly fixing a specified resin composition on the fibrous material and thermocompression- bonding the material to the elastomer. CONSTITUTION:A water-based urethane resin composition is firmly fixed on a fibrous material, and the adherend is bonded to a thermoplastic elastomer by thermocompression. Desirable examples of the thermoplastic elastomers include a multiblock copolymer composed of crystalline hard segments and noncrystalline soft segments and a flexible vinyl chloride resin. Examples of the multiblock copolymers include polyurethane block polymers and thermoplastic polyester elastomers. Examples of the fibrous materials include nylons and polyesters which are used in the form of cords or canvasses. The water-base urethane resin composition is one prepared by adding a curing agent, etc., to a polyurethane resin dispersed, emulsified or solubilized in water. Desirable examples of the curing agents used include isocyanate and epoxy compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for adhering a thermoplastic elastomer and a fiber material.

[0002]

2. Description of the Related Art A thermoplastic elastomer has elasticity at room temperature, but is plasticized at a high temperature and easily molded by an ordinary molding machine for thermoplastic resins such as an extrusion molding machine, a blow molding machine, or a calendering machine. It has the characteristic that it can be processed. In particular, polyurethane-based elastomers, polyester-based elastomers and soft vinyl chloride resins are excellent in mechanical strength, bending fatigue resistance, wear resistance, molding processability, and are low in cost, so they are adhesive composites reinforced by different materials. As an article, it is expected to be used as an industrial product in various fields such as a transportation belt, a transmission belt, a hose, a tire, a tent, a tarpaulin, and a synthetic leather.

However, the above-mentioned thermoplastic elastomer has a problem that the adhesive property to the fiber material is originally low due to the small number of functional groups in the molecule, and the adhesive force is largely lowered in a high temperature environment.

In Japanese Patent Laid-Open No. 63-81186, a fiber material as an adherend is treated with a solvent-based adhesive composition containing an isocyanate compound or an epoxy compound in order to improve adhesiveness, and then, A method has been proposed in which, after treatment with a solution containing a saturated polyester resin, this is thermocompression-bonded to a polyester-based thermoplastic elastomer for adhesion. Since this method uses an organic solvent, not only there is a risk of fire and explosion, but there is a problem that it adversely affects the safety of human body and causes environmental pollution. Further, although the adhesive strength is improved to some extent by the above method, the adhesive strength is still insufficient when the adhesive composite is used in a high temperature environment where it is subjected to a dynamic external force such as bending, compression or extension. However, there is a problem that the product cannot maintain a long life.

Japanese Unexamined Patent Publication (Kokai) No. 2-151635 discloses a method for improving the adhesiveness between a polyester-based thermoplastic elastomer and a polyamide-based thermoplastic elastomer and an adherend. In this method, an adherend is treated in three steps: a first step of treating with an isocyanate compound or an epoxy compound, a second step of treating with a thermoplastic polyurethane and an epoxy compound, and a third step of applying a thermoplastic polyurethane. After that, it is brought into close contact with the thermoplastic elastomer. By this method, the adhesiveness was improved even in a polyamide thermoplastic elastomer having a surface activity inferior to that of the polyester thermoplastic elastomer, but the isocyanate compound and the epoxy compound are used by being dissolved in an organic solvent, and the use thereof is accompanied. The problem remained.

Japanese Unexamined Patent Publication (Kokai) No. 4-257374 discloses a treatment in which an aliphatic polyepoxy compound is blended with a spinning oil to give the epoxy compound to a polyester fiber (pretreatment),
Stretching and winding The fiber is made into a fabric with an appropriate basis weight, and after being subjected to a two-stage treatment of a treatment (post-treatment) of adding polyallylamine, a polyurethane resin, halogen-containing vinyl resin or ethylene -A method is disclosed in which a vinyl acetate resin is brought into close contact with the resin so as to have adhesiveness. This method has problems that it requires treatment at both the spinning stage and the fabric making stage, complicating the process, and that it cannot obtain sufficient adhesive strength with the vinyl chloride resin. It was

As a method for improving the adhesion between the polyester fiber and the vinyl chloride resin, an aqueous oil agent containing polyethyleneimine, a polyurethane resin and a leveling agent is used.
A method of applying the polyester fiber both in the spinning step and the stretching step or in the stretching step is disclosed in JP-A-5-25707. The above method is to improve the adhesiveness of the polyester fiber to the vinyl chloride resin by a method not using an organic solvent, but it is not a method for imparting adhesiveness to a fiber material that has already become a cloth, and It is not a method with a wide range of application that can improve the adhesiveness with thermoplastic elastomers other than vinyl chloride resins.

[0008]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide an adhesive method capable of firmly adhering a thermoplastic elastomer and a fiber material by a treatment method which does not use an organic solvent. To do.

[0009]

SUMMARY OF THE INVENTION The gist of the present invention resides in that after a water-based urethane resin composition is fixed to a fiber material, the adherend is thermocompression-bonded with a thermoplastic elastomer to bond them.

The thermoplastic elastomer used in the present invention is preferably a multi-block copolymer composed of a crystalline hard segment and an amorphous soft segment, and a soft vinyl chloride resin. Examples of the multi-block copolymer include, for example, a polyurethane-based thermoplastic elastomer in which the crystalline hard segment is made of polyurethane, a polyester-based thermoplastic elastomer in which the crystalline hard segment is made of polyester, and a polyamide-based thermoplastic elastomer in which the crystalline hard segment is made of nylon. Examples thereof include plastic elastomers.

The above-mentioned polyurethane-based thermoplastic elastomer is preferably one in which a polymer chain composed of a diisocyanate compound and a short chain diol constitutes a hard segment, and a polymer chain composed of a diisocyanate compound and a long chain polyol constitutes a soft segment. In such a case, the hardness and elastic modulus of the polymer can be adjusted by changing the ratio of the hard segment and the soft segment.

Examples of the diisocyanate compound include 4,4'-diphenylmethane diisocyanate,
1,6-hexamethylene diisocyanate, 2,4-toluene diisocyanate, 3-isocyanate methyl-
3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate and the like can be mentioned. Examples of the short-chain diol include ethylene glycol, propylene glycol, 1,
4-butanediol, bisphenol A, etc. are mentioned. Examples of the long-chain polyols include adipic ester-based ones such as polyethylene adipate and polybutylene adipate; and polycaprolactone-based polyester polyols.

Examples of the polyester-based thermoplastic elastomer include a condensate of 1,4-butanediol and terephthalic acid (PBT) as a hard segment, and polycondensation polymerization of polytetramethylene ether glycol and terephthalic acid (PTMEGT). Examples thereof include polyether / ester copolymers having a soft segment such as caprolactone polyol. These are multi-segment copolymers containing a plurality of each segment. In such a case, the hardness and elastic modulus of the polymer can be adjusted by changing the ratio of the hard segment and the soft segment.

Examples of the thermoplastic polyamide-based elastomer include copolymers having nylon 6, nylon 66, nylon 11 and nylon 12 as a hard segment and polyether or polyester as a soft segment. These polymers are multi-segment copolymers, and the hardness, elastic modulus, etc. of the polymers can be adjusted by changing the ratio of hard segment and soft segment.

If necessary, a plasticizer, a colorant, a filler, carbon black, an antiaging agent, an antistatic agent, etc. may be added to the thermoplastic elastomer to form a compound.

Examples of the fiber material used in the present invention include nylon and polyester, which are used in the form of cord or canvas.

In the bonding method of the present invention, as a first step, the water-based urethane resin composition is adhered to the above-mentioned fiber material in the form of a cord or canvas as an adherend. The adhesion method is not particularly limited, for example, a method of immersing the fiber material as an adherend in an aqueous urethane resin composition aqueous solution,
Examples of the method include coating. After that, the water-based urethane resin composition attached to the fiber material is heated and dried to be fixed on the adherend to obtain an adherend.

The above-mentioned water-based urethane resin composition is a polyurethane resin obtained by dispersing, emulsifying or solubilizing in water, and mixing a curing agent and the like.

The polyurethane resin can be prepared, for example, by chemically bonding the polyol (A), the isocyanate compound (B) and the chain extender (C). The polyol (A) is preferably a linear polyester diol and can be obtained by condensation of a polyol and a polycarboxylic acid. Examples of the polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol,
Examples include neopentyl glycol and polycaprolactone-based polyester polyols, and one or more of these are used. Examples of the polycarboxylic acid include succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, sebacic acid and the like, and one or more of these are used.

The molecular weight of the above linear polyester diol is preferably 1,000 to 10,000. If it is less than 1,000, the resulting polyurethane resin has a low crystallinity, so that the adhesive strength is small, and if it exceeds 10,000, the polyurethane resin has a high crystallinity and its softening point increases, and the processing temperature at the time of laminating the fiber material and the thermoplastic elastomer is high. Therefore, the adherend is thermally deteriorated. The chemical structure of the polyol (A) can be selected according to the adhesiveness of the water-based urethane resin composition to the fiber material.

Examples of the isocyanate compound (B) to be reacted with the polyol (A) include aromatic isocyanate compounds such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate; Aliphatic isocyanate compounds such as xylylene diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, etc. may be mentioned. 1 type (s) or 2 or more types are used. When it is necessary to avoid yellowing due to heat or light, it is preferable to use an aliphatic isocyanate compound.

As the chain extender (C), a short chain diol and a short chain diamine are used. Examples of the short-chain diol include ethylene glycol, propanediol, butanediol, hexanediol, neopentyl glycol and the like. Examples of the short-chain diamine include ethylenediamine, hexamethylenediamine, hydrazine, other ammonia, amino alcohol, water and the like.

The mixing ratio of the polyol (A), the isocyanate compound (B), and the chain extender (C) constituting the above polyurethane resin is such that the molar ratio of active hydrogen and isocyanate group is 100: 90 to 100: 120. It is preferable to do so.

The polyurethane resin used in the present invention is
The above-mentioned polyurethane resin is made water-based, and the types thereof include water dispersion type, self-emulsifying type and water solubilizing type.
Types. The water dispersion type is one in which a polyurethane resin is forcibly dispersed in water by using a surfactant. The self-emulsifying type is a surfactant such as by introducing a water-soluble polyol such as ethylene oxide into a polymer, and the water-solubilizing type is a surfactant by forming a salt in a polyurethane resin. It is emulsified or solubilized in water without using. The manufacturing method is not particularly limited.

Specifically, the water-solubilizing polyurethane resin is prepared by preparing a prepolymer having an NCO group terminal from a polyester diol and a diisocyanate, and adding the prepolymer and a diol or diamine containing a sulfonic acid group or a carboxylic acid group to a solution. Can be prepared by a method in which the reaction product is dispersed in water and then the solvent is distilled off.

The self-emulsifying polyurethane resin is
Specifically, for example, a urethane prepolymer having a terminal isocyanate group is prepared by reacting a linear polyester polyol with an excess amount of an isocyanate compound in an organic solvent such as acetone, and then a carboxylic acid group and a sulfone are included in the molecule. After reacting a compound having a hydrophilic group such as an acid group with a hydroxyl group, a compound having a reactive group such as an amino group, neutralized by a conventional method and emulsified in water,
Then, it can be prepared by increasing the molecular weight with a chain extender and removing the organic solvent.

Examples of the compound having a hydrophilic group such as carboxylic acid group and sulfonic acid group and the compound having reactive group such as hydroxyl group and amino group in the molecule include, for example, dimethylolpropionic acid, oxalic acid, 2, 4-diaminobenzol sulfonic acid, sodium taurine, etc. are mentioned.

As the polyurethane resin used in the present invention, the above self-emulsifying or water-solubilizing type polyurethane resin which does not use a surfactant is preferable from the viewpoint of adhesiveness and water resistance. Such polyurethane resin is commercially available, and for example, Dispercoll TP KA 8584 manufactured by Sumitomo Bayer Urethane Co.,
Dispercall TP KA 8481, Dispercall U53, Nogawa Chemical's Diabond DW8
43H, HYDRANHW series manufactured by Dainippon Ink and Chemicals, Inc., and the like.

The aqueous urethane resin composition used in the present invention is prepared by blending the above polyurethane resin with a curing agent and the like. Examples of the curing agent include isocyanate compounds, epoxy compounds, aziridine compounds, and melamine compounds, with isocyanate compounds and epoxy compounds being preferred. Of the above curing agents, those that are water-soluble and those that are insoluble in water need to be blended as an aqueous dispersion. The aqueous dispersion can be prepared according to a conventional method, for example, using a ball mill, a homogenizer or the like.

As the above-mentioned isocyanate compound, in consideration of reactivity with water, for example, 1,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'-
Aliphatic isocyanate such as diisocyanate can be used as it is or as an adduct with a compound having hydrophilicity. In addition, blocked isocyanates including those containing usual aromatic isocyanate compounds can also be used.

The above-mentioned epoxy compounds are usually epoxidized with, for example, phenol derivatives, glycols, organic acids, amines, etc., with epichlorohydrin, except those in which the double bond is epoxidized with peracetic acid. It is a thing. Phenol derivatives are preferred as the compound epoxidized by epichlorohydrin. Examples of the phenol derivative include dihydric phenols such as bisphenol A and bisphenol F; and polyhydric phenols such as phenol / novolak and orthocresol / novolak.

The above-mentioned polyurethane resin and curing agent are usually used in rubber latex blending, such as antioxidants, softeners, carbon black, fillers, tackifiers, dispersants,
Emulsifiers, stabilizers, thickeners and the like may be included and adjusted to provide desired coating, adhesion and other properties. Of the above-mentioned compounding agents, those which are insoluble in water need to be compounded as an aqueous dispersion. The aqueous dispersion can be prepared according to a conventional method, for example, using a ball mill, a homogenizer or the like.

A water-soluble thickener is preferred as the thickener. The water-soluble thickener is not limited to those commonly used as a thickener, as long as it increases the viscosity of the latex, for example, to increase the bulkiness of the particles by being adsorbed around the rubber particles. Examples include those that increase the viscosity of latex, those that enter the aqueous phase of latex to increase the viscosity of serum and those that increase latex viscosity, and those that increase the viscosity of latex by both the adsorption of rubber particles and the thickening of serum. be able to. Of these, those that are adsorbed around the rubber particles to increase the bulkiness of the particles to increase the viscosity, specifically, nonionic polyurethane thickeners are preferably used. The amount of the thickening agent added is preferably 0.5 to 3 parts by weight, more preferably 2 parts by weight, based on 100 parts by weight of the polyurethane resin.

In the method of the present invention, in the second step, the melted thermoplastic elastomer is brought into close contact with the adherend made of the fiber material to which the above-mentioned water-based urethane resin composition has been fixed, and the fiber material is cooled. And the thermoplastic elastomer are firmly bonded. The method for adhering the molten thermoplastic elastomer to the adherend is not limited in any way, and it is usually carried out by using a molding means used for the thermoplastic elastomer, for example, injection molding, extrusion molding, compression molding or the like. You can

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Preparation of Aqueous Urethane Resin Compositions Aqueous urethane resin compositions A to D were prepared at the compounding ratios shown in Table 1. In the table, Dispercall U53 (Dispe
rcoll U53) is a polyurethane resin manufactured by Sumitomo Bayer Urethane Co., Ltd., Voltigel L75 (Bolchige).
l L75) is a thickener made by Sumitomo Bayer Urethane Co., S
BU-isocyanate 0772 represents a water-dispersible isocyanate compound manufactured by Sumitomo Bayer Urethane Co., Ltd., and ADEKA BON TITER XW-2 represents a water-dispersible epoxy compound manufactured by Asahi Denka Co., Ltd. In Table 1, the unit of the blending amount is parts by weight.

[0037]

[Table 1]

Example 1 A canvas made of 1000 d / l polyester fiber (EE
M-50C (manufactured by Toray Industries, Inc.) was dip-treated with the water-based urethane resin composition A shown in Table 1 and dried at 150 ° C. After cooling, two sets of the laminated body of the sailcloth and the polyurethane-based thermoplastic elastomer, which have been subjected to the above-mentioned fixing treatment, are stacked, and the temperature is 150 ° C and 49k.
Pressed at Pa for 5 minutes. After cooling to about 60 ° C., it was taken out to obtain a canvas / thermoplastic elastomer / sailcloth / thermoplastic elastomer laminate (about 2 mm thick). The laminate was left for 7 days, cut into a width of 25 mm, and subjected to a peel test between the canvas and the thermoplastic elastomer at a tensile speed of 50 mm / min using a tensile tester. Table 2 shows the type of water-based urethane resin composition used, the type of thermoplastic elastomer,
The adhesive strength of the canvas / thermoplastic elastomer obtained in the above tensile test was shown. The type of thermoplastic elastomer is PU
Is a polyurethane-based thermoplastic elastomer (manufactured by Dainichiseika Kogyo KK), PVC is vinyl chloride resin (manufactured by Mitsubishi Kasei Vinyl Co., Ltd.), PE is a polyester-based thermoplastic elastomer (manufactured by Toyobo Co., Ltd.), and PP is a polypropylene-based thermoplastic elastomer ( Manufactured by Mitsubishi Petrochemical Co., Ltd.).

Examples 2 to 6 and Comparative Examples 1 to 3 A canvas / thermoplastic elastomer was prepared in the same manner as in Example 1 except that the types of the water-based urethane resin composition and the thermoplastic elastomer were changed as shown in Table 2. A laminate was obtained and a tensile test was conducted, and the results are shown in Table 2.

[0040]

[Table 2]

[0041]

According to the method of the present invention, since the adherend made of the fibrous material to which the water-based urethane resin composition is fixedly adhered is brought into close contact with the melted thermoplastic elastomer, the thermoplastic polyurethane elastomer and the thermoplastic polyester elastomer are used. It is possible to firmly bond the thermoplastic elastomer such as soft vinyl chloride resin and the fiber material by a safe manufacturing process without using an organic solvent.

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Claims (4)

[Claims] 1. A method for adhering a thermoplastic elastomer to a fiber material, which comprises fixing an aqueous urethane resin composition to the fiber material and then adhering the adherend by thermocompression bonding with the thermoplastic elastomer. 2. A water-based urethane resin composition dispersed in water,
The method for adhering a thermoplastic elastomer and a fiber material according to claim 1, which contains a polyurethane resin obtained by emulsification or solubilization and a curing agent. 3. The method for adhering a thermoplastic elastomer and a fiber material according to claim 2, wherein the curing agent comprises an isocyanate compound or an isocyanate compound and an epoxy compound. 4. The method for adhering a thermoplastic elastomer to a fiber material according to claim 1, wherein the thermoplastic elastomer is a polyurethane thermoplastic elastomer, a polyester thermoplastic elastomer or a soft vinyl chloride resin.