JPH1193079A - Improvement in adhesion of polyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester fiber improved in adhesion to rubber without using a toxic epoxy compound by applying an aqueous emulsion containing an ethyleneimine graft (co)polymer and a crosslinking agent to a yarn when producing the polyester fiber. SOLUTION: The treatment for applying an aqueous emulsion prepared by adding an ethyleneimine graft (co)polymer obtained by carrying out the graft copolymerization of ethyleneimine with a (co)polymer of acrylic monomers and a water-soluble or a water-dispersible blocked isocyanate or polycarbodiimide in an amount of 0.5-10 wt.% based on the (co)polymer thereto to a polyester fiber yarn is carried out in a step for cooling and solidifying the melt spun polyester fiber yarn and then applying a spinning oil agent thereto so as to apply the ethyleneimine graft copolymer in an amount of 0.05-1.0 wt.% based on the polyester fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for improving the adhesion of polyester fibers. More specifically, by treating a polyester fiber with a relatively low-toxic polyethyleneimine-grafted acrylic copolymer and a cross-linking agent, to express an effective adhesiveness particularly with rubber,
Provided is a method for producing a polyester fiber having improved adhesion.

[0002]

2. Description of the Related Art In recent years, polyester fibers have been used as a reinforcing material for rubber structures such as tires, belts, sheets, and hoses because of their excellent mechanical properties and thermal properties, and their cost advantages. It is becoming widely used. However, polyester has a molecular structure
There are few functional groups that are thought to induce adhesion,
The surface is inert, and the adhesion to rubber is insufficient compared to nylon or rayon.

Conventionally, when this polyester fiber is used, for example, as a tire cord, an epoxy compound, an isocyanate compound,
A method is known in which a surface is treated with polyethyleneimine or the like individually or in combination, a resorcin / formalin / latex adhesive (RFL adhesive) is applied, and a heat treatment is performed (Japanese Patent Publication No. 39-10514). JP-B-40-17131 and JP-A-3-82873. In this method, the treatment method is divided into two steps, and the operation becomes complicated, and it is necessary to use a highly toxic epoxy compound or isocyanate compound.

[0004] In recent years, in the process of producing polyester fibers, a treatment agent containing an epoxy compound having two or more epoxy groups in one molecule, a blocked isocyanate compound, and a silane coupling agent has been applied after heat drawing. A method for improving the adhesiveness by a one-stage adhesive treatment is also known (Japanese Patent Application Laid-Open No. H8-284025). In this method, since the yarn speed at the time of application is high, there is a concern that a highly toxic epoxy compound or silane coupling agent may be scattered to cause deterioration of the working environment.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel method for improving the adhesion of a polyester fiber using a combination of a treatment agent and a cross-linking agent having relatively low toxicity.

[0006]

Means for Solving the Problems In addition to the conventionally known methods for improving adhesiveness such as a method using an epoxy compound, the present inventors have investigated the adhesiveness of polyester fibers to rubber using a relatively low-toxicity agent. As a result of intensive studies on the method of improving the pretreatment, when producing a polyester fiber, by applying to the yarn a composition containing an ethyleneimine graft polymer and a composition containing a crosslinking agent, the polyester fiber Has been found to be able to improve the adhesion to rubber.

Hereinafter, the present invention will be described in detail.
The polyester in the present invention is a multifilament comprising polyethylene terephthalate, polyethylene naphthalate, and a polyester containing these as a main component, the presence or absence of an additive such as an end group sealing agent, the molecular weight of the polyester, the denier number, No limitation is imposed on the number of filaments, cross-sectional shape, surface structure, yarn properties, and the like.

[0008] The melt-spun polyester yarn is cooled and solidified, and then a spinning oil agent is applied thereto. The spinning oil is
The composition is not particularly limited, but generally includes components such as natural oil, synthetic oil, ester component, smoothing component, emulsifying / dispersing agent component, antistatic agent, antioxidant, and heat-resistant agent. It is preferably applied in an aqueous emulsion from an environmental point of view. A composition containing an ethyleneimine graft polymer and / or a composition containing a crosslinking agent can be blended with the spinning oil.

After the hot stretching, a treating agent can be applied. In this case, it is provided between the stretching step and the relaxation step or between the relaxation step and the winding step. The composition of the treating agent is not particularly limited, but generally contains components such as a smoothing agent and a softening agent, and is preferably applied in the form of an aqueous emulsion from the viewpoint of working environment. A composition containing an ethyleneimine graft polymer and / or a composition containing a crosslinking agent can be blended with the treating agent. Further, it is not necessary to use a treating agent. In that case, the composition containing the ethyleneimine graft polymer and / or the composition containing the crosslinking agent will be applied alone.

[0010] The composition containing the ethyleneimine graft polymer and / or the composition containing the cross-linking agent can be blended with one or both of the spinning oil and the treating agent, respectively. Typically,
The composition containing the ethyleneimine graft polymer,
It is preferably applied simultaneously with the composition containing the cross-linking agent or before the composition containing the cross-linking agent.

For the spinning oil and / or the treating agent,
When a composition containing an ethyleneimine graft polymer and / or a composition containing a crosslinking agent is blended and applied to a polyester filament, the blending ratio varies depending on the viscosity of the blending system and the amount applied to the yarn. be able to. Usually, 0.05 to 1.0% by weight of the ethyleneimine graft polymer is blended with the yarn, and 0.5 to 10% by weight of the water-dispersible polyethyleneimine graft acrylic copolymer is blended with the crosslinking agent. Is preferred. The applying method is generally performed by a usual roller-type oiling method or a nozzle-type oiling method, and the spinning oil and the treating agent are preferably used in the form of an aqueous emulsion.

As the ethyleneimine-grafted polymer, an ethyleneimine-grafted vinyl (co) polymer is preferable, and an ethyleneimine-grafted acryl (co) polymer is particularly preferably used. Acrylic (co) polymers
It refers to a (co) polymer obtained by polymerizing one or more types of monomers selected from the group consisting of acrylic acids, methacrylic acids, and acrylamides. Acrylic acids include alkyl acrylates such as acrylic acid and methyl acrylate, and methacrylic acids include alkyl acrylates such as methacrylic acid and methyl methacrylate. Examples of the vinyl (co) polymer include, in addition to the above-mentioned acrylic (co) polymer, styrenes such as styrene, halogenated styrene, alkylstyrene, alkoxystyrene, cyanostyrene, and nitrostyrene; acrylamide; Acrylamides such as amides, acrylonitrile, methacrylonitrile,
Butadiene, isobutylene, isoprene, chloroprene, vinylthiophene, vinyl chloride, vinylidene chloride,
One selected from the group consisting of allyl chloride, vinyl acetate, alkyl vinyl ketone, alkyl vinyl ether, alkyl vinyl sulfide, divinyl sulfide, triallyl isocyanurate, vinyl sulfonic acid, alkyl vinyl sulfonate, vinyl succinic acid, vinyl pyrrolidone, acrolein, etc. It refers to a (co) polymer obtained by polymerizing the above monomers.

The ethyleneimine graft polymer is preferably dispersed in water by using a dispersant or the like, or is preferably a water-soluble one. There is no particular limitation on the molecular weight. Commercial products include Polyment CK-200, NK-100PM, 20
0PM (Nippon Shokubai Co., Ltd.) or the like can be used.

Among the blocked isocyanate compounds used as a crosslinking agent, in particular, they are water-dispersible or water-soluble,
A low-temperature dissociation type is more preferably used. this is,
For example, Japanese Patent Application Laid-Open Nos.
No. -8060 and JP-B-55-39254, and commercially available products include Elastron BN-69, BN-44 and BN-0.
4, BN-08 (Daiichi Kogyo Seiyaku Co., Ltd.), Takenate WB-700, WB-770 (Takeda Pharmaceutical Co., Ltd.)
Etc. can be used.

[0015] Among the polycarbodiimides used as a crosslinking agent, a water-soluble polycarbodiimide resin is more preferably used. This is, for example,
-27450 and compounds according to the technology described in JP-A-7-330849, and commercially available products such as Carbodilite V-02, V-04, and V-06 (Nisshinbo Industries, Ltd.) can be used. .

When the composition containing the ethyleneimine graft polymer and the composition containing the cross-linking agent are applied together with the treating agent, it is more preferable to perform aging treatment after winding the yarn. See JP-B-51-39997). The aging treatment is usually performed at 50 ° C. to Tg + 30 ° C. (Tg
Is preferably performed at a temperature of the glass transition temperature (° C.) of the polyester fiber for 1 to 7 hours or more (JP-A-60-21970).
No.).

The adhesiveness-improved polyester filament (cord) obtained in the present invention is usually treated with an adhesive liquid containing resorcin / formalin polycondensate and latex (hereinafter referred to as RFL liquid) before bonding with rubber. You. The RFL liquid contains various known additives in addition to the above main components, but the composition thereof is not limited at all. Further, the applied amount is preferably 1 to 10% in terms of solid content with respect to the cord. After the application of the RFL solution, it is dried and heat-treated at a known temperature and time to be used for adhesion to rubber.

[0018]

EXAMPLES Next, specific examples of the present invention will be described below, but the present invention is not limited to these examples. Here, “parts” means parts by weight, and “%” means weight%. The adhesiveness improving agent of the present invention is characterized in that the composition containing an ethyleneimine graft polymer contains 0.3% of the ethyleneimine graft polymer as a pure component with respect to the yarn (polyester filament 1000de-192f).
For a composition containing a crosslinking agent, 5% of the ethyleneimine graft polymer was applied to the yarn with the crosslinking agent as a pure component. The obtained yarn was used as it is or after aging treatment at 50 ° C. for 3 hours to form a cord, and the adhesive strength was evaluated. The evaluation of the adhesive strength was performed by the following method.
Seven adhesive improving cords were placed on the carcass-containing unvulcanized rubber surface layer of a car tire for automobile tires, and 200k for 15 minutes at 160 ° C.
After vulcanizing under a pressure of g / cm ^2, the force required for peeling off the five cords at 20 cm / min is shown in Table 1 as a relative index with Comparative Example 1 being 100.

Examples 1 to 4 Polyment CK-200 which is a composition containing an ethyleneimine graft polymer as a main agent, and Elastron B which is a water-soluble blocked isocyanate as a crosslinking agent
An aqueous emulsion obtained by mixing N-04 (Examples 1 and 2), carbodilite V-02 (Example 3) and carbodilite V-04 (Example 4), which are water-soluble polycarbodiimides, respectively, as a spinning oil agent or a treating agent. As described above, the adhesiveness of the cord obtained by blending and applying was evaluated.

Examples 5 to 10 Polyment NK-100PM which is a composition containing an ethyleneimine graft polymer as a main component, Elastron BN-04 (Examples 5 and 6) as a crosslinking agent, and Carbodilite V-02 (Example 7) , 8, 9) and cord obtained by blending Carbodilite V-04 (Example 10) with a spinning oil or a treating agent, respectively, and evaluating the adhesiveness as described above.

COMPARATIVE EXAMPLE 1 A cord containing no composition containing an ethyleneimine graft polymer and no composition containing a crosslinking agent was evaluated in the same manner for cords obtained by applying only a spinning oil and a treatment agent.

Comparative Example 2 A treatment agent containing a composition containing an ethyleneimine graft polymer and containing only a spinning oil and a water-soluble polycarbodiimide carbodilite V-02 as a crosslinking agent was applied. The obtained cord was similarly evaluated.

Example 11 A cord obtained by aging the yarn obtained under the conditions of Example 1 at 50 ° C. for 3 hours was similarly evaluated.

Examples 12 to 14 The yarns obtained under the conditions of Examples 5, 7 and 10 were treated at 50 ° C.
The cord obtained by aging for 3 hours was similarly evaluated.

Comparative Examples 3 and 4 The yarns obtained under the conditions of Comparative Examples 1 and 2 were aged at 50 ° C. for 3 hours, and the cords were similarly evaluated.

[0026]

[Table 1]

[0027]

The production method of the present invention is a highly safe treatment in place of a highly toxic epoxy compound, and can produce a polyester fiber having improved adhesion to rubber.

Claims (4)

[Claims] 1. A method for producing a polyester fiber, comprising: applying a composition containing an ethyleneimine graft polymer and a composition containing a crosslinking agent to a yarn when producing the polyester fiber. 2. The method according to claim 1, wherein the crosslinking agent is a water-soluble or water-dispersible blocked isocyanate or polycarbodiimide. 3. The ethyleneimine-grafted acrylic (co) polymer obtained by grafting ethyleneimine onto a (co) polymer of acrylic monomers, wherein the ethyleneimine-grafted polymer is an ethyleneimine-grafted acrylic (co) polymer. The described method. 4. The method according to claim 1, wherein the composition containing the ethyleneimine graft polymer is applied before or simultaneously with the composition containing the crosslinking agent.