JPH08127966A - Aramid fiber for bonding resin - Google Patents

Abstract

PURPOSE: To obtain an aramid fiber excellent in yarn making property, yarn twisting property and processability in weaving, having good bonding property to a resin such as polyvinyl chloride or polyurethane as well as good yellowing resistance. CONSTITUTION: This aramid fiber for bonding a resin is obtained by attaching a treating agent containing 0.1-20wt.% of a molybdenum compound which is a catalyst for reacting an isocyanate group with a functional group having active hydrogen to an aramid fiber.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to aramid fibers for resin bonding. More specifically, it relates to a resin-bonding aramid fiber having excellent adhesiveness to a urethane resin.

[0002]

Conventionally, aramid fibers are generally used under severe conditions because they have excellent strength, elastic modulus, dimensional stability, heat resistance, fatigue resistance, cut resistance and the like. It has been widely used as a reinforcing fiber for rubber structures such as belts and hoses (hereinafter referred to as rubber bonding fiber).
In recent years, in addition to the purpose of bonding with these rubbers, it is expected to be used as a reinforcing fiber (hereinafter referred to as a resin bonding fiber) for a resin structure made of a vinyl chloride resin, a urethane resin or the like.

However, since the rubber-bonding fiber has been diverted as it is to the resin-bonding fiber, the adhesiveness with the resin is poor and the molded product has a short service life. This is because the type of adhesive used and the bonding method are different in rubber bonding applications, and in order to improve the adhesiveness, it is desired that the fiber be suitable for the type of the adhesive and the bonding method.

In order to solve such a problem, the amount of various treatment agents applied to the fiber surface in order to improve the post-processability of the aramid fiber such as the spinnability, twistability, and knitting and weaving properties. Although it is effective to reduce the amount of the treating agent, merely reducing the amount of the treating agent reduces the spinnability and the post-processability, and thus loses the practicality. Further, scouring for the purpose of reducing the treating agent on the fiber cloth after weaving and knitting is also effective for improving the adhesive performance, but it is not practical because the scouring process is increased.

In Japanese Patent Laid-Open No. 194076/1992, a fiber having a treatment agent containing an ester of an aliphatic alcohol and an aliphatic carboxylic acid as a main component and containing an amine component in an amount of 1 to 20% by weight is used before resin bonding. It is disclosed that the adhesive property is improved by volatilizing the treating agent component under the ordinary heat setting condition and by the presence of the amine component. However, such a fiber has a problem in that the quality of the obtained product deteriorates because the yellowing proceeds to a small extent when heat-set, and an improvement is desired.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and its object is to have excellent spinnability, twistability, processability during weaving, and adhesiveness with resins such as polyvinyl chloride and polyurethane. It is to provide an aramid fiber for resin adhesion, which has good properties and good yellowing resistance. As a result of intensive studies conducted by the present inventors to achieve the above object, a treating agent containing a molybdenum compound, which is a reaction catalyst of an isocyanate group and a functional group having active hydrogen, has a spinnability, a twistability, and a weaving property. It has been found that excellent adhesion performance can be obtained even if the adhesive treatment is performed without reducing the treatment agent and the treating agent is not removed during the adhesive treatment.

[0007]

That is, according to the present invention, "(Claim 1) A treatment agent containing 0.1 to 20% by weight of a molybdenum compound which is a reaction catalyst of an isocyanate group and a functional group having active hydrogen is attached. An aramid fiber for resin adhesion according to claim 2. (claim 2) The aramid fiber for resin adhesion according to claim 1, wherein the amount of the treatment agent attached is 0.3 to 3.0% by weight based on the weight of the fiber. .

The aramid fiber is a para-aromatic polyamide fiber, a meta-aromatic polyamide fiber, or a copolymer thereof. Examples of the aromatic ring include 1,4-
A phenylene group, a 1,3-phenylene group, a 4,4′-biphenylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, a 2,5-pyridylene group and the like can be mentioned, but preferably 1, It is a 4-phenylene group. Aromatic rings are, for example, halogen groups, (eg chlorine, bromine, fluorine),
A lower alkyl group (methyl group, ethyl group, isopropyl group, n-propyl group), lower alkoxy group (methoxy group, ethoxy group), cyano group, acetyl group, nitro group and the like may be contained as a substituent. Specific examples include polyparaphenylene terephthalamide (Kevlar manufactured by DuPont), polymetaphenylene isophthalamide (Conex manufactured by Teijin Ltd.), polyparaaminobenzamide, poly-3,4'oxydiphenylene terephthalamide / poly. It is a fiber composed of a para-phenylene terephthalamide copolymer (Technola manufactured by Teijin Limited), polyparaaminobenzhydrazide terephthalamide, and the like.

The molybdenum compound compounded in the treatment agent attached to the aramid fiber has a catalytic action for the reaction between the isocyanate group and the functional group having active hydrogen. For example, molybdenum dithiophosphate, molybdenum oxide ( Vl), molybdenum disulfide, molybdic acid, 1
2-molybdo (Vl) phosphoric acid, potassium molybdate,
Strontium molybdate, ammonium molybdate, barium molybdate, lead molybdate, sodium molybdate, calcium molybdate, molybdenum, molybdenum carbide, molybdenum carbonyl, molybdenum chloride, molybdenum oxide (IV), lithium molybdate, phosphomolybdic acid hydrate , Molybdenum acetylacetonate oxide, ammonium phosphomolybdate trihydrate, sodium phosphomolybdate hydrate, zinc molybdate, calcium zinc molybdate, chrome vermilion and the like are preferably used. Among them, molybdenum dithiophosphate is particularly preferable because it not only has high catalytic activity but also does not deteriorate the processability of yarn making, twisting, knitting and weaving.

The content of the molybdenum compound in the treating agent is 0.1 to 20% by weight in order to obtain the effects of the present invention.
It is preferably 0.5 to 10% by weight, particularly 1 to 5% by weight. When the content of the molybdenum compound is less than 0.1% by weight, the effect of improving the resin adhesion performance is hardly recognized. On the other hand, if it exceeds 20% by weight, the effect of improving the adhesive performance is lowered, and the stability of the treating agent tends to be lowered, and troubles such as yarn breakage occur in the yarn making process, the twisting process, the weaving process, etc. It is not preferable because it becomes easy.
The treatment agent to which the molybdenum compound is added is not particularly limited. Any of the conventionally used ordinary fiber treating agents can be used. Among them, a treating agent containing a polyether as a leveling agent component is preferable because the adhesiveness is improved because it is easily volatilized by a heat set applied before the adhesive treatment, and also has a functional group capable of reacting with an isocyanate group. Components, for example, ethylene oxide (EO) / propylene oxide (PO) copolymerized polyether as a smoothing agent component and EO-added alkyl ether as an emulsifier, are hardened by reacting with an isocyanate group in an adhesive and curing. It is preferable because excellent adhesion performance can be obtained.

The method of applying the treating agent to the aramid fiber is as follows:
There is no particular limitation. For example, it can be applied as a 1 to 25% aqueous emulsion liquid by any method such as a roller method, a dipping method, and a spray method at any stage such as spinning and drawing. The amount of the treatment agent applied is 0.1 to the fiber.
3.5% by weight, especially 0.5 to 1.5% by weight is preferred.

The aramid fiber of the present invention thus obtained generally has a total fineness of 500 to 1500 denier and a total number of filaments of 100 to 1000. For example, it is adhered to a resin as follows.

That is, first, in the twisting process, the number of twists (for example, 10 to 1) is smaller than that of rubber reinforcing fibers such as tires.
00 times / m) is applied (usually a ring type twisting machine is used). Next, in the weaving process, a shuttle type loom is usually used, and the above twisted yarn is used as the warp yarn, and the same twisted yarn or the twisted yarn having different total fineness and different twist number is used as the weft yarn depending on the purpose. Depending on the purpose, aramid fibers may be used for the warp, polyester fibers, polyamide fibers for the weft, or vice versa. The obtained woven fabric may be heat-set next, but usually, both ends of the woven fabric are grasped by pins and passed through a dryer in which hot air is circulated at a constant speed, and the temperature is 200 ° C or less. It is heat-treated for 1 to 5 minutes.

The woven fabric thus obtained is dipped or applied in an adhesive containing a one- or two-bath type isocyanate group dissolved in a solvent and a functional group having active hydrogen, and dried and heat-treated, usually for 1 to 3 days. After that, a urethane resin or a vinyl chloride resin (including paste) is pressure-bonded or applied to obtain a resin-bonded woven fabric.

[0015]

The reason why the aramid fiber of the present invention has excellent resin adhesiveness is not clear, but it is presumed as follows. That is, usually, the aramid fiber for resin adhesion is used as it is without being scoured, in the state of the woven fabric to which the treating agent for spinning and drawing is attached. Therefore, the fiber treating agent remains on the fibers constituting the cloth, and the remaining fiber treating agent is an adhesive containing an isocyanate group and a functional group having active hydrogen applied thereon. If it acts as a release agent for the agent, the resin-bonded woven fabric will easily undergo adhesive failure at the interface between the fiber cloth and the adhesive.

On the other hand, in the present invention, since the treatment agent contains a molybdenum compound which is a curing catalyst for the adhesive containing an isocyanate group and a functional group having active hydrogen, the curing reaction occurs near the fiber surface. It progresses faster, and a hardener film layer having a larger cohesive force is formed on the fiber surface. Therefore, as a result,
It is estimated that the adhesive strength between the fiber and the adhesive is improved.

[0017]

EFFECT OF THE INVENTION The aramid fiber of the present invention has no problem in the process passability from yarn production to weaving as described above, and has an isocyanate group and a functional group having active hydrogen even if it is adhered without scouring. It has high adhesiveness with urethane adhesives.

The present invention will be specifically described below with reference to examples. All% in the examples are% by weight. Also,
The adhesiveness was evaluated by the following method.

<Evaluation of Adhesiveness> A urethane adhesive having an isocyanate group (Pandex T-5205D-1 manufactured by Dainippon Ink and Chemicals Co.
Department, Dainippon Ink Co., Ltd. Burnock D-750 5
Part) (thickness: 0.05 mm) and dried at 150 ° C. for 2 minutes. After drying, it was stored at 20 ° C. and 65% for 24 hours, and then vinyl chloride plastisol (Zeon 121 manufactured by Nippon Zeon Co., Ltd.) was applied (220 g / m ² ) and 15 g / cm ²
Under a load of, heat treatment is performed at 190 ° C. for 30 minutes. Then, after standing for 24 hours, the peeling force between the vinyl chloride and the fabric was measured by a tensile tester. The adhesive strength is shown in kg / inch.

[0020]

Examples 1 to 8 and Comparative Examples 1 to 4 The adhesion amount of the treatment agent was 1.
0% aramid fiber (Technora; manufactured by Teijin Ltd.) is twisted to form a cord with a twist number of 10 T / 10 cm, and the cord is 60 warps / 5 cm, weft 56 warps / 5c
Weaving at a density of m, then 200 with a pin tenter
Heat set at 0 ° C. for 2 minutes. The resulting woven fabric was evaluated for adhesion. The results are shown in Table 1, Table 2, Table 3 and Table 4.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Embodiment 9] In Embodiment 2, the amount of the treatment agent attached is 2.
The same procedure as in Example 2 was performed except that the content was 0%. The result was a good adhesive force of 17.5 kg / inch.

Claims (2)

[Claims] 1. A molybdenum compound which is a reaction catalyst of an isocyanate group and a functional group having active hydrogen is added in an amount of 0.1 to 2.
An aramid fiber for resin bonding, characterized in that a treating agent of 0% by weight is attached. 2. The adhesion amount of the treating agent is 0.3 with respect to the weight of the fiber.
The aramid fiber for resin adhesion according to claim 1, which is ˜3.0 wt%.