JP3027264B2 - Bonding method between polyester synthetic fiber and polyester elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a method for bonding a synthetic polyester fiber and a polyester elastomer.

[0002]

2. Description of the Related Art It is well known that polyester synthetic fibers are used in all industrial fields. Polyester synthetic fibers are inexpensive and strong,
By combining this with a polyurethane resin, a halogen-containing vinyl resin, or an ethylene vinyl acetate resin as a reinforcing material, a sheet-like membrane structure such as a canvas, a tent, a tarpaulin, a curing sheet, a leather, a leather, a food belt,
It is used in a wide range of industrial materials such as hoses.

[0003] For example, a composite material with a polyurethane resin has been used for food belts and the like because of its excellent abrasion resistance. A composite material with a halogen-containing vinyl polymer is poor in heat resistance because a relatively large amount of a plasticizer and other components are added in order to improve its physical properties and processability. It is used for applications that make use of electrical insulation. A composite material with an ethylene vinyl acetate resin is used in a container application where non-toxicity is important. Above all, as a film material having flexibility, in the field of a film structure in which a base fabric made of polyester synthetic fiber is mainly coated with polyvinyl chloride resin, for example, various uses such as tents, containers, belts, and other hoses Have been deployed in large numbers.

However, halogenated vinyl polymers, when incinerated at the time of disposal, cause pollution problems that lead to air pollution such as generation of chlorine gas and dioxin. In addition, when a composite material with a polyurethane resin is incinerated, toxic gas such as cyan gas is generated when incinerated, and carbon dioxide gas which leads to global warming due to incineration of ethylene vinyl acetate resin is unavoidable. On the other hand, it is anticipated that the system will be sold in the future on the premise that the manufacturer / distributor assumes the burden of taking over disposal. The trend in each industry is to shift from the disposal and incineration method to the resource recycling method from the viewpoint of global environmental protection.

The inventors of the present invention have conducted intensive studies from the above viewpoints. As a result, polyester-based synthetic fibers and polyester-based elastomers from which used products can be re-synthesized by recovering monomer materials by ester hydrolysis and separation and purification. We devised a method of bonding that is effective for bonding to the surface. This allows the development of composite materials such as recyclable membrane structures, hoses and belts. On the other hand, polyester-based synthetic fiber materials that exhibit excellent physical reinforcement performance as a composite material, on the other hand, due to their chemical structure, have a surface that is inactive and difficult to adhere to polyester-based elastomers. At present, there is a need to further increase the level of adhesion because of concerns. As a means for overcoming this, generally, (1) a method of forming a resin film on both sides of the canvas by lowering the basis weight of the canvas, that is, a method of forming a bridge by heat-sealing through the gaps of the fabric,
(2) A method in which the fiber form of the canvas is fluffed as a spun yarn or the like to make the fabric fluffy and bulky, and the resin melted during processing is penetrated into the gaps between the single yarns to improve adhesion by an anchor effect. (3) Surface treatment by plasma treatment A method has been proposed exclusively to make the adhesive easy. In addition to the above physical methods, the following chemical methods, that is, (4) a method of incorporating a polyisocyanate into a coating resin, (5)
Proposals have been made such as a method of treating a cloth before coating with a resin with polyethylene imine.

[0006] However, even in products using the above-described method, the fibers and the resin are peeled off during long-term use due to insufficient adhesion between the fiber and the resin, causing various troubles. In the following, concretely, (1) voids or fluffs of a woven fabric are used for those utilizing a bridge effect or an anchor effect, but the effect can be exerted with a high-density woven fabric or a fabric having a small amount of fluff. Disappears.
Further, in the case of a canvas using filaments, even if the woven fabric is coarse and low in weight, the adhesion to the fibers is not good, so that a quality problem such as a peeling phenomenon between the fibers and the resin may become apparent. For example, in the case of a belt, a peeling phenomenon occurs due to repeated bending. In addition, woven fabrics with low basis weight and coarse texture, such as tarpaulin applications, exhibit the function as a composite material by forming bridges by resin fusion from both sides. Fatigue is caused by an external force received by use, and this causes troubles such as breakage of filament from the resin and damage to the canvas.

On the other hand, in the field where the adhesion to the polyester elastomer is required not only for the filament canvas but also for the spun canvas, in order to improve the interfacial adhesion besides the physical effect, the adhesive precoat or the polyester elastomer is used. In some cases, a polyisocyanate is added. Even in such a case, while the adhesiveness is improved, problems such as a hard feeling of the product itself and a significant decrease in tear strength often occur. On the other hand, if the proportion of the polyisocyanate in the polyester elastomer is reduced in order to increase the tear strength, the adhesive strength is significantly reduced. Further, a method has been proposed in which a polyester synthetic fiber is treated with a solution of a polyalkylenimine before coating with a polyester elastomer.
(Japanese Patent Publication No. 40-17131, Japanese Patent Publication No. 46-414)
No. 50, JP-A-49-7108, JP-A-49-7108
-4775, JP-A-49-11928, JP-A-55-36398, and JP-A-59-94640.
Gazette, Japanese Patent Publication No. 53-37473). However, when treated with polyalkyleneimine, the cloth made of polyester-based synthetic fibers is markedly colored, and this coloring usually takes on yellow or yellow-brown. This has an effect and becomes a practical problem.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to a polyester-based synthetic resin which is obtained from a polyester-based synthetic fiber and a polyester-based elastomer. It is an object of the present invention to provide an effective bonding method for bonding a fiber and a polyester elastomer.

That is, the present invention provides a polyester synthetic fiber represented by the following general formula:

[0010]

Embedded image

[0011] This is a method for bonding a polyester synthetic fiber and a polyester elastomer, which is characterized by treating with a agent containing a polyallylamine compound represented by the basic skeleton and then bonding with a polyester elastomer.

Here, the polyester synthetic fiber is a fiber made of a linear polyester containing an aromatic ring such as polyethylene terephthalate or polyethylene naphthalate, or a linear polyester containing a naphthalene ring, or one kind of glycol such as ethylene glycol or propylene glycol. Further, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, aromatic or aliphatic dicarboxylic acids such as adipic acid, or a fiber comprising a copolymerized polyester obtained by reacting with one or more derivatives thereof. is there. Fibers composed of flame-retardant linear polyesters containing a phosphorus element-containing compound such as carboxyphosphinic acid in the polymer molecule are also preferred. The fiber form may be any form such as filament form, yarn form, cord form, woven form or knitted form.

The polyester elastomer in the present invention is, for example, a crystalline hard polyester portion (hard segment) and an amorphous soft polyether (soft segment) or an amorphous soft polyester (soft segment) in the molecule. Is a block copolymerized polyester having Specific examples of the hard segment include polyethylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexyldimethylene terephthalate, poly-1,4-cyclohexyldimethylene-2,6-naphthalate, and polybutylene terephthalate. , Polybutylene-2,6-naphthalenedicarboxylate, 4,4 "-dihydroxy-p-terphenyl, 4,4""-dihydroxy-p-quarterphenyl,4,4""-di (2-hydroxy Ethoxy) -p-quarterphenyl and the like, and the soft segment is poly (oxy-1,2-propylene) glycol, a block of ethylene oxide and propylene oxide, or a random copolymer, a block of ethylene oxide and tetrahydrofuran. Or la Examples thereof include dam copolymers, aliphatic polyethers such as polytetramethylene glycol, and / or polyesters having a glass transition temperature of -10 ° C. Other components of the polyaliphatic diol include glycol and polyalkylene. The glycols include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,7-heptanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, etc., which are used alone Or two or more of them may be used in combination. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, and polyhexamethylene oxide. These may be used alone or in combination of two or more. If the number average molecular weight of the polyalkylene oxide is small, the ability to impart flexibility to the resulting polyester is reduced, and if it is too large, physical properties such as thermal stability of the obtained polyester are reduced. 2000
0 is preferable, and more preferably 500 to 5000. Heat resistance, weather resistance, oil resistance, fatigue resistance and flame retardancy can be imparted by further adding a new modifier or introducing a copolymer component to the basic skeleton. For example, there may be mentioned a flame-retardant linear polyester in which a phosphorus element-containing compound such as carboxyphosphinic acid is contained in a polymer molecule.

The polyallylamine compound in the present invention is an allylamine polymer having an amino group in a side chain and having a general formula:

[0015]

Embedded image

This is a polymer having a basic skeleton and a pendant group. The number average molecular weight (Mn) of the polyallylamine compound is preferably from 2000 to 100,000. More preferably, it is 2500 to 50,000. The synthesis method is as disclosed in JP-A-58-201811.
For example, an inorganic acid salt of a monoallylamine compound is polymerized in a polar solvent in the presence of a radical initiator containing an azo group and a group having a cationic nitrogen atom in a molecule. The polyallylamine compound is obtained by removing the inorganic acid from the polymerized inorganic salt of the polyallylamine compound through a strongly basic ion exchange resin, or dialyzing the solution with a neutralized salt aqueous solution formed with an alkali (eg, caustic soda). Since the polyallylamine compound is produced by a radical polymerization method, it is difficult to obtain a stable product in a low molecular weight region where Mn is less than 2,000. On the other hand, even when Mn exceeds 100,000, the adhesion between the fiber and the coating resin is improved,
The viscosity of the treating agent increases, and the handleability decreases.

The method for providing the polyallylamine compound is not particularly limited. Fibers can be treated with agents containing polyallylamine compounds having various degrees of polymerization as solutions of water or an organic solvent such as alcohol alone or as a mixed solvent solution. On the other hand, as the treatment liquid containing the polyallylamine compound, a polyallylamine compound alone, or an oil agent or a wetting improver for uniformly adhering the polyallylamine compound to the fibers can be used. For example, a nonionic surfactant such as a polyethylene oxide-added higher alcohol ether or the like can be appropriately used as needed as long as the purpose is not hindered.

In the polyester synthetic fiber of the present invention, a known oil agent may be used, if necessary, as long as the adhesion is not hindered. The oil agent is, for example, a spinning oil agent required at the time of drawing, an agent for imparting appropriate lubricity and bundling properties, for example, a mineral oil, a leveling agent such as esters,
Polyethylene oxide-added higher alcohol ethers,
A nonionic surfactant such as a polyethylene oxide-polypropylene oxide copolymer or an ionic surfactant can be appropriately used as needed as long as the adhesion is not inhibited.

Further, an aliphatic polyepoxy compound for further improving the adhesion level, and a component which is an emulsifying and dispersing agent for the polyepoxy compound and improves the uniform spreadability of the polyepoxy compound on the fiber yarn. Examples thereof include an alkyl sulfonate-based, alkyl sulfate-based, alkyl phosphate-based anionic surfactant or a polyalkylene oxide adduct thereof, and other alkyl ethers and alkyl esters.

The adhesion amount of the polyallylamine compound is 0.0
1-5.00% by weight is preferred. More preferably 0.1
~ 1.8% by weight. If the total adhesion amount is less than 0.01% by weight, the adhesion to the resin is insufficient. On the other hand, 5.0% by weight
When the ratio exceeds, the adhesive strength is exhibited, but the effect of improving the adhesive strength with the increase in the amount of adhesion cannot be expected so much, and other physical properties are deteriorated. The method of applying the treatment liquid containing the polyallylamine compound to the fibers may be appropriately selected, such as a method of applying the treatment liquid to the running yarn, a method of applying the treatment liquid at the stage of the twisting yarn, and a method of dipping into the woven or knitted fabric. After applying the agent containing the polyallylamine compound, heat treatment is performed. The heat treatment conditions are as follows: 110 ≦ T ≦ −34.5t + 283.5 T Atmospheric temperature (° C.) of the fiber t Heat treatment time (minute) However, it is preferable to perform the heat treatment under the condition represented by the following expression: 0.013 minute ≦ t. T
At <110 ° C., there is a problem in the process that drying is insufficient and sticky scum accumulates in guides. In addition, there is a quality problem that the agent cannot sufficiently exhibit the adhesiveness to the resin since the agent is not sufficiently absorbed into the fibers.

If T <−34.5t + 283.5, the primary and secondary amino groups of the polyallylamine compound are accelerated by thermal oxidative deterioration, and the adhesiveness to the resin cannot be sufficiently exhibited. By performing the heat treatment within the scope of the present invention, without causing oxidative deterioration of polyallylamine by heat, the polyallylamine compound is effectively sorbed at a high density on the fiber surface,
In addition, a material that satisfies high adhesiveness with resin can be obtained. or,
It is possible to obtain a fiber in which yellowing discoloration, which is inevitable with conventional amine compounds, is suppressed. Here, the primary and secondary amino groups of the polyallylamine compound can be confirmed by showing a positive ninhydrin color reaction.

After treating the polyester synthetic fiber with a treatment liquid containing a polyallylamine compound, coating, dipping or press-bonding the polyester elastomer film with a polyester elastomer solution is performed, followed by heat treatment.

[0023]

The composite material comprising the polyester elastomer and the polyester synthetic fiber obtained by the method of the present invention has high adhesiveness without impairing the tear strength of the product, and is therefore suitable for products such as canvas, tarpaulin and container. In groups, we can provide recyclable, earth-friendly products.

Next, the present invention will be described in detail with reference to examples.

[0025]

Examples 1-2, Comparative Examples 1-2 1000 denier / 1
A 7% aqueous solution of a polyallylamine compound was applied to a plain woven fabric (weight: 250 g / m 2) of polyethylene terephthalate fibers having 92 filaments, and dried at 150 ° C. for 1 minute. Table 1 shows the contents of the agent and the amount of adhesion. Next, polytetramethylene terephthalate 2 was added to the pre-treated fabric shown in Table 1.
Polyester 7 obtained from 5 parts of dimethyl isophthalate, dimethyl terephthalate, dimethyl sebacate (molar ratio 6: 1: 3) and hexamethylene glycol
The block polyester having a melting point of 175 ° C. extruded by a normal calendering method (the melting point of the endothermic peak measured at a heating rate of 20 ° C./min with a differential scanning calorimeter) and a thickness of 175 ° C. An unstretched film of a polyester elastomer produced by heating and extruding a 0.5 mm film was pressure-bonded and heated at 180 ° C. for 1 minute to obtain an adhesive cloth between the polyester fiber and the polyester elastomer. The adhesive force between the fiber and the polyester-based elastomer is determined according to JIS 6329-1968 (rubber-coated cloth).
It was measured according to the method of 3, 7 (peeling test -180 ° C). Table 1 shows the measurement results. The peeling force of the adhesive cloth was represented by an index conversion value with respect to the untreated cloth shown as a comparative example. Table 1 shows the contents of the agent and the amount of adhesion. As shown in Table 1, the polyester fiber treated by the method of the present invention can improve the adhesion without yellowing. The untreated cloth had a peeling force of 0.3.
kg / inch.

[0026]

[Table 1]

[0027]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-167371 (JP, A) JP-A-49-4775 (JP, A) JP-A-4-163371 (JP, A) (58) Investigation Field (Int.Cl. ⁷ , DB name) C08J 5/00-5/12 B32B 27/12 D06M 15/21-15/356

Claims (4)

(57) [Claims] 1. A polyester synthetic fiber represented by the following general formula: A method of bonding a polyester synthetic fiber and a polyester elastomer, wherein the method is treated with an agent containing a polyallylamine compound represented by the following basic skeleton and then bonded to a polyester elastomer. 2. The method according to claim 1, wherein the number average molecular weight of the polyallylamine compound is 2,000 to 100,000. 3. The method according to claim 1, wherein the adhesion amount of the polyallylamine compound is 0.
The method for bonding a polyester-based synthetic fiber to a polyester-based elastomer according to claim 1, wherein the amount is from 0.01 to 5.00% by weight. 4. The heating temperature for bonding is 1 at the substantial yarn surface temperature.
The method according to claim 1, wherein the temperature is 10 to 200 ° C.