JP2015183335A - Textile product for industrial belt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a textile product for an industrial belt using a polyoxamide fiber that is one of polyamide fibers having high toughness and, nevertheless, causes little change in the shape due to humidity.SOLUTION: There is provided an industrial belt obtained by coating a fiber structure with a resin such as rubber. The fiber structure is constituted of a fiber obtained from polyoxamide that comprises a dicarboxylic acid component comprising oxalic acid and a diamine component comprising aliphatic alkylene diamine.

Description

  The present invention relates to a textile product for industrial belts, which is a fiber structure using fibers obtained from polyoxamide and has high form stability against humidity.

  In some industrial belts, a fiber structure obtained by knitting and weaving synthetic fibers is covered with a resin such as rubber to improve and impart durability and grip properties. As the synthetic fiber mainly used, nylon 66 and nylon 6 are preferably used in view of high toughness of the fiber, high strength, and good compatibility with a resin such as rubber (for example, see Patent Document 1). .

  An industrial belt coated with a resin such as rubber can be used for a long period of time once installed. In that respect, a material having high form stability as well as the durability of the resin and the fiber structure can be used. It has been demanded. However, nylon 6 and nylon 66, which are widely used as fiber structures, expand and contract due to humidity, and may cause peeling, cracking, wrinkling, etc. from the resin.

JP 2009-242958 A

  In view of the above problems, an object of the present invention is to provide an industrial belt fiber product using a polyoxamide fiber that is one of polyamide fibers having high toughness and has a small form change due to humidity.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a fiber made of polyoxamide having a specific configuration, which is higher in strength than a conventional polyamide fiber, but less dependent on humidity. Therefore, the present inventors have found that a fiber structure excellent in form stability against humidity can be obtained by using the fiber, and have arrived at the present invention.

  That is, the present invention is an industrial belt fiber product obtained by coating a fiber structure with a resin, wherein the fiber structure is composed of oxalic acid as a dicarboxylic acid component and an aliphatic alkylenediamine as a diamine component. It is a textile product for industrial belts characterized by comprising fibers obtained from polyoxamide.

  In the textile product for industrial belt of the present invention, the aliphatic alkylenediamine is preferably composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an industrial belt fiber product using a polyoxamide fiber, which is one of polyamide fibers having high toughness but has a small form change due to humidity.

The present invention is described in detail below.
In the industrial belt fiber product of the present invention, it is important to use fibers obtained from polyoxamide in which the dicarboxylic acid component is composed of oxalic acid and the diamine component is composed of aliphatic alkylenediamine.

  The dicarboxylic acid component used for producing the polyoxamide in the present invention is composed of oxalic acid. As the oxalic acid source, oxalic acid diesters can be adopted, and these are not particularly limited as long as they have reactivity with amino groups. Dimethyl oxalate, diethyl oxalate, di-n-oxalate (or i- Fragrances such as oxalic acid diesters of aliphatic monohydric alcohols such as propyl, di-n- (or i-, or t-) butyl oxalate, oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate, and diphenyl oxalate Oxalic acid diesters of aliphatic alcohols. Among the oxalic acid diesters, oxalic acid diesters of aliphatic monohydric alcohols having more than 3 carbon atoms, alicyclic alcohol oxalic acid diesters, and aromatic alcohol oxalic acid diesters are preferred, among which dibutyl oxalate and oxalic acid Diphenyl is particularly preferred.

  On the other hand, the diamine component used for the production of the polyoxamide in the present invention comprises an aliphatic dialkylene diamine. The aliphatic alkylene diamine is not particularly limited as long as the effects of the present invention are not impaired. However, since the aliphatic alkylene diamine has high strength and excellent shape stability against humidity, 1,9-nonanediamine and 2-methyl-1 , 8-octanediamine is preferably used. The molar ratio of the 1,9-nonanediamine component to the 2-methyl-1,8-octanediamine component is preferably 1:99 to 99: 1, more preferably 5:95 to 95: 5, and even more preferably 5:95. -40: 60 or 60:40 to 95: 5, particularly preferably 5:95 to 30:70 or 70:30 to 90:10. By copolymerizing 1,9-nonanediamine and 2-methyl-1,8-octanediamine in the above specific amounts, in addition to performance such as high strength and shape stability, high molecular weight by melt polymerization while having low water absorption It is possible to obtain a polyoxamide having a wide moldable temperature range, excellent melt moldability, and excellent chemical resistance and hydrolysis resistance. In particular, when the molar ratio is 5:95 to 40:60, and further 5:95 to 30:70, the crystallinity is excellent, so that the low water absorption and mechanical properties are particularly excellent, and liquid and / or gas (for example, For example, the permeability of alcohol and the like is low, and the water absorption is lower than when the content of 1,9-nonanediamine is higher than the content of 2-methyl-1,8-octanediamine, for example. It also has the advantage of. On the other hand, when the molar ratio is 60:40 to 95: 5, further 70:30 to 95: 5, and further 70:30 to 90:10, the low water absorption and mechanical properties are particularly excellent and good. The advantage that transparency is imparted is obtained.

  When manufacturing the polyoxamide in this invention, you may mix another dicarboxylic acid component in the range which does not impair the effect of this invention. Examples of dicarboxylic acid components other than oxalic acid include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3 Aliphatic dicarboxylic acids such as 1,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and terephthalic acid Acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, di Benzoic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphe Rusuruhon-4,4'-dicarboxylic acid, 4,4'-biphenyl and the like alone aromatic dicarboxylic acids such as dicarboxylic acids, or may be added to any mixture thereof during the polycondensation reaction. Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as melt molding is possible. It is preferable that the usage-amount of another dicarboxylic acid component is 5 mol% or less of the whole dicarboxylic acid component.

  Similarly, you may mix another diamine component in the range which does not impair the effect of this invention. For example, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5- Aliphatic diamines such as pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, and cyclohexane Alicyclic diamines such as diamine, methylcyclohexanediamine, isophoronediamine, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenylsulfone, 4,4'-diaminodiphe And aromatic diamines such as ethers to be alone, or even the addition of any mixture thereof during the polycondensation reaction. It is preferable that the usage-amount of another diamine component is 5 mol% or less of the whole diamine component.

  In addition, the polyoxamide in the present invention may be one in which a part thereof is replaced with another polymer component as long as the effects of the present invention are not impaired. Examples of other polymer components include polyamides other than the species comprising the aliphatic dialkylenediamine of the present invention, polyamides such as aromatic polyamide, aliphatic polyamide, and alicyclic polyamide, and thermoplastic polymers other than polyamide. . The ratio of the polyoxamide composed of aliphatic dialkylenediamine used in the present invention is preferably 50% by mass or more, more preferably from the viewpoint of effectively imparting high-density fabrics performance such as high strength and shape stability. 70% by mass or more.

The molecular weight of the polyoxamide in the present invention is not particularly limited, but the relative viscosity η _r measured at 25 ° C. is 1.8 to 6.0 using a 96% concentrated sulfuric acid solution having a polyoxamide concentration of 1.0 g / dL. It is preferably within the range, more preferably 2.0 to 5.5, and particularly preferably 2.5 to 4.5. eta _r tends to decrease physical properties becomes brittle as low as molded than 1.8. On the other hand, if η _r is higher than 6.0, the melt viscosity becomes high and the moldability tends to be deteriorated.

  The polyoxamide used in the present invention can be produced using any method known as a method for producing a polyamide resin. For example, a polyoxamide resin can be obtained by performing a polycondensation reaction batchwise or continuously using the above-described oxalic acid diester and aliphatic dialkylenediamine.

  In addition, fibers obtained from the polyoxamide resin used in the present invention (hereinafter sometimes referred to as polyoxamide fibers) can be produced by any method known as a method for producing polyamide fibers. For example, a raw material composition containing a polyoxamide resin is melted with a melt extruder such as a single screw, and the melt is extruded from a spinneret through a gear pump or the like that quantitatively controls the discharge rate. The polyoxamide fiber of the present invention can be produced, for example, by drawing at a predetermined take-up speed while cooling. The fiber thus obtained may be further stretched at various magnifications depending on each application of the industrial material. Also, melt spinning and stretching may be performed simultaneously.

  The total fineness of the polyoxamide fiber used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but 200 to 800 dTex is preferable, for example, in terms of weaving property, high strength, airtightness, and thinness of the fabric, More preferably, it is 250-700 dTex, Most preferably, it is the range of 300-600 dTex. Further, the single yarn fineness is not particularly limited, but is preferably 2 to 8 dTex, more preferably 3 to 7 dTex, and particularly preferably 4 to 6 dTex from the viewpoint of weaving and airtightness.

  The tensile strength of the polyoxamide fiber used in the present invention is not particularly limited, but is preferably 3 to 11 cN / dTex. More preferably, it is 3.5-10 cN / dTex, Most preferably, it is 4-10 cN / dTex.

  It is important that the textile product for industrial belts of the present invention is woven using the polyoxamide fiber. Since the polyoxamide fiber has a small form change due to humidity (hygroscopic elongation described later), it is possible to realize a high-strength and excellent form-stabilized fabric by using the fiber for warp and / or weft. An industrial belt fiber product coated with a resin such as rubber, which requires long-term stability, can be obtained.

Further, the cover factor of the woven fabric used in the industrial belt textile product of the present invention is not particularly limited, but is preferably woven in the range of 1500 to 5000, more preferably 1800 to 4500, and particularly preferably. Is in the range of 2000-4000. Here, the cover factor (K) means the warp fineness DA (dTex), the warp density NA (main / 2.54 cm), the weft fineness DB (dTex), and the weft density NB (main / 2. 54 cm), it can be obtained from the following formula.
K = √ (DA) × NA + √ (DB) × NB

  The weaving method of the woven fabric used in the industrial belt fiber product of the present invention is not particularly limited, and a known method is used as long as the woven fabric is obtained from the polyoxamide fiber and satisfies the above-mentioned strength and thickness conditions. be able to. In addition, the raw machine obtained by weaving is arranged and processed, but the conditions are not particularly limited. For the purpose of removing excess oil agent and dirt of the obtained raw machine, washing with water or the like may be performed as appropriate.

  In the textile product for industrial belts of the present invention, it is important to coat the woven fabric with a resin. As the resin used for the coating layer, resins widely used for industrial belts can be used. Depending on the purpose of use, rubber resins, vinyl chloride resins, fluorine resins, silicone resins, urethane resins can be used. Polyolefin resins, acrylic resins, and the like can be used. Further, the coating method is not particularly limited, and a known method such as a calendar method or a knife coating method can be used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In addition, each measured value in an Example is a value measured with the following method.

[Fineness]
Measurement was performed in accordance with JIS L1013.

[Hygroscopic elongation]
After leaving the dough for more than 6 hours in an environment with a temperature of 15 ° C and a humidity of 60% RH, mark each 300mm interval in the direction of the dough. Then, after the fabric was allowed to stand for 6 hours or more in an environment of temperature 25 ° C. and humidity 90% RH, when the length between the marks was set to L, the hygroscopic elongation rate was determined by the following equation. The average value of three samples was taken as the measurement result.
Hygroscopic elongation (%) = {(L−300) / 300)} × 100

[Production method of polyoxamide resin]
In a pressure vessel having an internal volume of 150 L equipped with a stirrer, a thermometer, a torque meter, a pressure gauge, a raw material inlet port directly connected to a diaphragm pump, a nitrogen gas inlet port, a pressure release port, a pressure regulator and a polymer outlet port After charging 4 mol of dibutyl oxalate and pressurizing the inside of the pressure vessel to 0.5 MPa with 99.9999% purity nitrogen gas, the operation of releasing nitrogen gas to normal pressure was repeated 5 times to replace nitrogen. Then, the system was heated while stirring under a sealing pressure. After the temperature of dibutyl oxalate was brought to 100 ° C. over about 30 minutes, a mixture of 119.3 mol of 1,9-nonanediamine and 21.1 mol of 2-methyl-1,8-octanediamine was flowed at a flow rate of 1 with a diaphragm pump. The temperature was raised at the same time as feeding into the reaction vessel at 49 L / min over about 17 minutes. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 235 ° C. over 1 hour. Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 235 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. The temperature was raised from normal pressure while flowing nitrogen gas at 1.5 L / min, the temperature of the polycondensate was brought to 260 ° C. over about 1 hour, and the reaction was carried out at 260 ° C. for 4.5 hours. Thereafter, stirring was stopped, the inside of the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes, then released to an internal pressure of 0.5 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel. The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer. The resulting polymer was white and tough polyoxamide.

<Reference Example 1>
The polyoxamide resin obtained by the above production method is melt-extruded at a temperature of 330 ° C. using an extruder, discharged from a round hole nozzle of 0.25 mmφ × 72 holes, cooled with a cooling air of cross air, and 600 m / min. I wound up with. Next, a multifilament (tensile strength 8.0 cN / dTex) of polyoxamide fibers of 470 dTex 72 filaments was obtained by 4.0 times hot drawing using a 100 ° C. hot roller and a 180 ° C. hot plate.

<Example 1>
Polyoxamide fibers obtained in Reference Example 1 and 470dTex72 filaments were twisted twice at 180 times / 2.54 cm, weaved and dried in a water jet loom using the twisted yarn as a background, and using a pin setter And finished at a density of 70 warps / 2.54 cm and 45 wefts / 2.54 cm (cover factor is 3600). Subsequently, a rubber resin manufactured by Nippon Zeon Co., Ltd. was coated on the fabric by a calendar method to obtain a fabric for a textile product for an industrial belt. The hygroscopic elongation of the fabric was very good at 0.5%.

<Comparative Example 1>
Nylon 66 fiber, 470dTex68 filament (tensile strength 8.6cN / dTex) made by Sosei Co., Ltd. is twisted twice at 180 times / 2.54cm. And it heat-processed at 150 degreeC using the pin setter, and finished with the density of warp 70 / 2.54cm, 45 weft / 2.54cm (cover factor is 3600). Subsequently, a rubber resin manufactured by Nippon Zeon Co., Ltd. was coated on the fabric by a calendar method to obtain a fabric for a textile product for an industrial belt. However, the hygroscopic elongation rate of the fabric was 2.5%, lacking stability against humidity, and unsuitable for use as an industrial material.

Claims (2)

  An industrial belt fiber product obtained by coating a fiber structure with a resin, wherein the fiber structure is made of a fiber obtained from a polyoxamide in which a dicarboxylic acid component is composed of oxalic acid and a diamine component is composed of an aliphatic alkylenediamine. An industrial belt textile product characterized by comprising.   The textile product for an industrial belt according to claim 1, wherein the aliphatic alkylenediamine is composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine.