JPH0949121A - Polyester composition, monofilament and woven fabric for industrial use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a polyester fiber having excellent stain-proofing properties and hydrolytic resistance and a required and sufficient strength as various industrial woven fabrics, etc., and a composition therefor. SOLUTION: This polyester composition comprises a polymer component containing 99.9-70wt.% polyester having <=10 equiv./10<6> g terminal carboxyl group concentration and 0.1-30wt.% copolymer of propylene and vinylidene fluoride and further contains 0.005-1.5wt.% carbodiimide compound in an unreacted state therein. Furthermore, the polyester monofilament or multifilament yarn or industrial woven fabric such as a canvas for a papermaking dryer, a papermaking wire, a filter or a conveyor net used in a bonding process for heat bonding a nonwoven fabric using the monofilament is composed of the polyester composition comprising the polymer component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester composition, a polyester fiber, a polyester monofilament and an industry using the polyester monofilament, which has excellent antifouling property and further has excellent antifouling property and hydrolysis resistance. It relates to woven fabrics.

[0002]

BACKGROUND OF THE INVENTION Polyester has been widely used in various industrial parts, textile materials for clothing and industry, various woven fabrics, etc. because it has excellent tensile strength, acid resistance and dimensional stability. For example, it has been used as a monofilament for a paper making dryer canvas, a net conveyor for a thermal bonding process of a thermal bond non-woven fabric, a paper making wire, a filter, various brushes, a brush, a printing screen gauze and the like.

However, polyester products have problems that they are easily soiled and that they are prone to hydrolysis in a high temperature and high humidity atmosphere, and therefore various improvements have been conventionally made.

As an example of easily soiling, for example, polyester monofilament papermaking wire (woven fabric for pulp making process) and paper dryer canvas (woven fabric for paper drying process) were used for wood pitch and recovered waste paper. Paste, pulp, additives added to the papermaking stock solution,
Since dirt such as sizing agent, paper strengthening agent, and ink adheres and accumulates, it is unavoidable to wash these wires and canvas frequently. In addition, for example, in the net conveyor for the thermal bonding process of the thermal bond non-woven fabric, there is a problem that the fused polyethylene or the like adheres and accumulates on the belt fabric and adheres to another non-woven fabric product to deteriorate the product quality. Had. Further, when it is used for a filter, there is a problem that the peeling property of the cake is poor due to the adhesion of dirt and the filtration efficiency is lowered.

Therefore, in order to improve the drawback that the polyester is easily soiled, for example, a technique of post-treating the polyester fiber with a compound containing fluorine (Japanese Patent Laid-Open No. 52-5).
No. 400, JP-A-58-46123), a technique of adding a perfluoroalkyl sulfonate (monomer) to polyester (JP-A-59-66449), and a blend of ethylene and monochlorotrifluoroethylene with polyester. Technology (Japanese Patent Laid-Open No. 5-30221)
No. 2) is known.

On the other hand, as an example of easily hydrolyzing, for example, when polyester monofilament is used as a constituent material of a paper dryer canvas, the strength of the polyester monofilament decreases due to hydrolysis deterioration during use, so that it is used for a long period of time. Was difficult to withstand. Therefore, various proposals have been made to improve the hydrolysis resistance of this polyester monofilament.

As an example of means for improving the hydrolysis resistance of a polyester monofilament, a polyester monofilament in which a specific amount of polyethylene, polypropylene, polybutene, poly-4-methylpentene 1, polystyrene or the like is added (JP-A-51-136923). However, the filament obtained by this technique is not practical because it has low strength and a small effect of improving hydrolysis resistance.

A method is known in which an epoxy compound is added to improve the hydrolyzability of polyester.
For example, a method of adding glycidylphthalimide to polyester (Japanese Patent Publication No. 61-4843), a method of adding an epoxy compound to polyester in the presence of an alkali metal (Japanese Patent Publication No. 61-42728), and a method of adding oxazoline compound to polyester. (Japanese Patent Publication No. 63-8133, Japanese Patent Publication No. 61-48531, Japanese Patent Publication No. 61-5
No. 7182, Japanese Patent Publication No. 57-161122, Japanese Patent Publication No. 61-48532), a certain level of hydrolysis resistance improving effect can be obtained, but a high level of hydrolysis resistance currently required. You cannot be satisfied with your sex.

Also known is a method of improving the hydrolysis resistance of polyester by adding a carbodiimide compound. For example, a method in which a mono- or bis-carbodiimide compound is added and kneaded and spun in a short time to form a filament containing no unreacted carbodiimide (JP-A-50-95517), and having three or more carbodiimide groups in the molecule Method of adding polycarbodiimide compound (Japanese Examined Patent Publication No. 38-15220), carboxyl end group is capped by reaction with carbodiimide, free mono- and / or biscarbodiimide compound 30-200 ppm and free polycarbodiimide or still reactive Fibers and filaments containing at least 0.02% by weight of a reaction product containing a polycarbodiimide group having a hydroxyl group (JP-A-4-289221).
Has been proposed. Further, a method for producing an industrial polyester monofilament in which a specific carbodiimide compound is added to a polyester containing a specific amount of phosphorus (JP-A-57-57).
No. 205518) and a specific carbodiimide compound are left in a specific amount in an unreacted state, and polyester monofilament for papermaking canvas (Japanese Patent Laid-Open No. 58-2391).
Various improvements have been made such as the proposal of Japanese Patent No. 6).
Further, the inventors of the present application have found that the polymer component, which is one of the constituent requirements of the composition and monofilament of the present application, comprises a polyester having a terminal carboxyl group concentration of 10 equivalents / 10 ⁶ g or less, and a thermoplastic resin containing no fluorine atom. It is possible to provide a polyester composition and a polyester monofilament composed of a polymer, the polymer component containing a specific amount of a carbodiimide compound in an unreacted state, and to provide an extremely high level of hydrolysis-resistant polyester required in recent years. (Japanese Patent Laid-Open No. 7-258524). Further, as a technique for simultaneously exhibiting both excellent antifouling property and hydrolysis resistance in polyester, the terminal carboxyl group concentration is 10 equivalents / polyester 10 ⁶ g or less, and the carbodiimide compound in an unreacted state is 0. .005
-1.5 wt% and 0.01 to 30 wt% of a fluorine-based polymer such as an ethylene / tetrafluoroethylene copolymer available at the time of application is contained in the polyester monofilament (International Publication No. WO 92/07126). Issue) and has been widely used.

However, in recent years, from the viewpoint of resource protection, the spread of recycling of recovered recovered paper has increased the adherence of dirt from the recovered paper to the papermaking wire and the papermaking dryer canvas, and the dryer accompanying the increase in the papermaking speed for increasing the productivity of the paper. As the temperature has increased, there has been a strong demand for the provision of a polyester material having both antifouling properties and hydrolysis resistance superior to those of conventional products.

[0011]

In view of the above-mentioned requirements, the present invention has a polyester composition, a polyester fiber, and a polyester monofilament having a stain resistance more excellent than the conventional one and an extremely high level of hydrolysis resistance. The present invention also relates to various industrial fabrics and dryer canvases for papermaking using the polyester monofilament.

[0012]

SUMMARY OF THE INVENTION The above-mentioned objects of the present invention are as follows: 1. Polyester composition containing 99.9 to 70% by weight of polyester and 0.1 to 30% by weight of a copolymer mainly composed of ethylene tetrafluoride, propylene hexafluoride and vinylidene fluoride, a polyester fiber,
1. Polyester monofilament, industrial woven fabric, paper making dryer canvas, paper making wire, filter or net conveyor for thermal bonding non-woven fabric thermal bonding process or 2. The polyester composition has a terminal carboxyl group concentration of 10 equivalents / 10 ⁶ g or less, and the polyester composition contains 0.005 to 1.5% by weight of an unreacted carbodiimide compound, polyester fiber, 2. Polyester monofilament, industrial fabric, paper making dryer canvas, paper making wire, filter or net bond for thermal bonding non-woven fabric thermal bonding process or 3. The above polyester composition, wherein the polyester is polyethylene terephthalate, polyester fibers, polyester monofilaments, industrial fabrics,
Paper making dryer Canvas, paper making wire, filter or non-woven fabric for thermal bonding non-woven net conveyor for heat bonding process.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The polyester of the present invention is preferably one mainly composed of polyethylene terephthalate (hereinafter referred to as PET) and polybutylene terephthalate, and more preferably PET, but a part of its dicarboxylic acid component is isophthalic acid, 2,6- Naphthalene dicarboxylic acid, 1,4-
It may be replaced by cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dimer acid, sulfonic acid metal salt-substituted isophthalic acid, or the like, and a part of the glycol component may be diethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, 1,4- It may be replaced with cyclohexanedimethanol, polyalkylene glycol or the like. Further, a small amount of a chain branching agent such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, and boric acid can be used in combination.

In addition to the above polyesters, preferred examples of the polyester include polyethylene naphthalate and polycyclohexanedimethylene terephthalate. Some of the dicarboxylic acid components are isophthalic acid, 1,4-cyclohexanedicarboxylic acid, It may be replaced by adipic acid, sebacic acid, dimer acid, sulfonic acid metal salt-substituted isophthalic acid or the like, or part of the glycol component may be replaced by diethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, polyalkylene glycol or the like. Good. The polyester used in the present invention includes various inorganic particles such as titanium oxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin, zirconic acid, etc., crosslinked polymer particles, various metal particles and other particles. Other conventionally known antioxidants, sequestering agents, ion exchangers, anti-coloring agents, light stabilizers, flame retardants, clathrate compounds, antistatic agents, various colorants,
Waxes, silicone oils, various fluorosurfactants, various reinforcing fibers, etc. may be added.

The intrinsic viscosity of the polyester is usually 0.
It may be 6 or more, but is preferably 0.7 or more because the strength is excellent. Here, the intrinsic viscosity is the intrinsic viscosity obtained from the viscosity measured at 25 ° C. in an orthochlorophenol solution, and is represented by [η]. When the terminal carboxyl group concentration of the polyester is 10 equivalents / 10 ⁶ g or less, hydrolysis resistance becomes good, which is preferable. (The terminal carboxyl group concentration is according to Pohl, Anal. Chem., 24 161.
4 It is measured by the method described in (1954). ) The terminal carboxyl group concentration obtained 10 equivalents / 10 ⁶ g or less of the polyester compositions and polyester monofilaments, polyester terminal carboxyl group concentration is more than 10 equivalents / 10 ⁶ g By solid phase polymerization, the terminal carboxyl group The concentration may be 10 equivalents / 10 ⁶ g or less, and a polyester in a molten state may be mixed with a mono- or diepoxy compound, or a mono- or bisoxazoline compound,
Alternatively, a carbodiimide compound may be reacted in an appropriate amount, but the polyester composition of the present invention, polyester fiber,
When the polyester monofilament contains 0.005% by weight or more of unreacted carbodiimide compound, it is advantageous to use the carbodiimide compound.

The carbodiimide compound may be any compound as long as it has one or more carbodiimide groups in one molecule. For example, N, N '
-Di-o-triylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-dioctyldecylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide , N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-2,6-di-tert.-butylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N, N ' -Jip
-Nitrophenylcarbodiimide, N, N'-di-p-
Aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-cyclohexylcarbodiimide, N, N'-di-p-triylcarbodiimide, p-phenylene-bis-di-o- Examples thereof include triylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, hexamethylene-bis-dicyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, and aromatic polycarbodiimide represented by the following general formula.

[0017]

Embedded image (R in the formula represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 20) One or two or more compounds are arbitrarily selected from these carbodiimide compounds. Although it may be contained in the polyester, a compound having an aromatic skeleton tends to be advantageous in view of stability after addition to the polyester.
′ -Di-2,6-diisopropylphenylcarbodiimide, N, N′-di-2,6-di-tert.-butylphenylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N, N ′ -Di-o-triylcarbodiimide and the like tend to be advantageous, and particularly N, N′-
Di-2,6-diisopropylphenylcarbodiimide (hereinafter referred to as TIC) is preferable.

The polyester composition of the present invention, the polyester fiber or the polymer component of the polyester monofilament is used to prepare the carbodiimide compound in an unreacted state.
A content of 005% by weight or more and 1.5% by weight or less is preferable because the hydrolysis resistance becomes excellent. Further, it is more preferable that the content of the carbodiimide compound in the unreacted state is 0.01% by weight or more and 1.2% by weight or less. When the content of the carbodiimide compound in the unreacted state is less than 0.005% by weight, the effect of further improving the hydrolysis resistance is small, and the content is 1.5% by weight.
If it is more than that, the physical properties tend to deteriorate. Here, the content of the carbodiimide compound in the unreacted state in the present invention is the weight% of the proportion to the polymer component.

The content of the unreacted carbodiimide compound in the polyester composition, polyester fiber or polyester monofilament according to the present invention is measured by the following method. (1) Weigh about 200 mg of a sample in a 100 ml volumetric flask. (2) Add 2 ml of hexafluoroisopropanol / chloroform (volume ratio 1/1) to dissolve the sample. (3) When the sample is dissolved, add 8 ml of chloroform. (4) Acetonitrile / chloroform (volume ratio 9/1)
Is gradually added to make 100 ml while precipitating the polymer. (5) The sample solution is filtered through a 0.45 μm disk filter and quantitatively analyzed by HPLC. HPLC analysis conditions are as follows. Column: Inertsil ODS-2 4.6 mm
× 250 mm Mobile phase: acetonitrile / water (volume ratio 94/6) Flow rate: 1.5 ml / min. Sample amount: 20 μl Detector: UV (280 nm) To make the polyester contain the carbodiimide compound in an unreacted state of 0.005% by weight or more and 1.5% by weight or less, the terminal carboxyl group concentration of the raw material polyester and Depending on the reaction conditions, the unreacted residual carbodiimide compound in the polyester after the reaction is 0.0
The carbodiimide compound may be added to the polyester in an amount to achieve a concentration of from 05% by weight to 1.5% by weight and reacted. When the polyester composition, polyester fiber or polyester monofilament of the present invention contains the carbodiimide compound in an unreacted state of 0.005% by weight or more and 1.5% by weight or less, the effect of the present invention is obtained. For efficient expression, the phosphorus compound can be contained in the polyester in an amount of 50 ppm or less as a phosphorus atom and within the range of the following general formula. 5 × 10 ⁻³ ≦ P ≦ M + 8 × 10 ⁻³ (P in the formula is mol% of phosphorus atom with respect to dibasic acid constituting polyester, M is a metal in the polyester resin, Group II of the periodic table, It is the mol% of one or more metal atoms selected from Group VII and VIII and selected from the 3rd and 4th cycles with respect to the dibasic acid constituting the polyester, and even when M = 0. Good.)

The copolymer mainly composed of tetrafluoroethylene, propylene hexafluoride and vinylidene fluoride used in the present invention (hereinafter referred to as a fluorine-based terpolymer) is tetrafluoroethylene or propylene hexafluoride. If the three components of vinylidene fluoride and vinylidene fluoride are copolymerized, the copolymerization ratio of the three components may be any, but tetrafluoroethylene 5 to 80
A fluorine-based terpolymer composed of mol%, propylene hexafluoride 2 to 35 mol% and vinylidene fluoride 5 to 90 mol% is preferable, and tetrafluoroethylene 30 to 70 mol%,
A fluorinated terpolymer comprising 10 to 30 mol% of propylene hexafluoride and 10 to 50 mol% of vinylidene fluoride is more preferable. It may be a copolymer of other components in addition to the above three components. Examples of the other copolymerization component include α-olefins such as ethylene, trifluoromonochloroethylene and trifluoroperfluorooxyethylene. The melting point of the fluorine-based terpolymer is in the range of approximately 70 ° C to 200 ° C, but one having a melting point of 100 ° C to 190 ° C tends to be preferable.

The fluorine-based terpolymer can be produced by a known radical polymerization method such as an emulsion polymerization method, a suspension polymerization method and a solution polymerization method. Industrially, the emulsion polymerization method, The suspension polymerization method is preferred. Further, THV ^™ (a product of Sumitomo 3M Limited) is known as a commercially available product of the fluorine-based terpolymer.

The content of the fluorinated terpolymer contained in the polyester composition, the polyester fiber and the polyester monofilament of the present invention must be 0.1% by weight or more and 30% by weight or less. Weight% or more,
25% by weight or less is more preferable, 0.5% by weight or more, 1
It is more preferably 5% by weight or less. If it is less than 0.1% by weight, the antifouling property is insufficient, and if it is more than 30% by weight, the physical properties of the monofilament are impaired.

The polyester and the fluorinated terpolymer are mixed by adding the fluorinated terpolymer to the molten polyester immediately after the completion of the polycondensation reaction and kneading the fluorinated terpolymer to the polyester chips. It can be carried out by a method of adding and mixing the chips or powder of the copolymer and then kneading the mixture with a kneading can or an extruder. The polyester composition of the present invention can be prepared by kneading the polyester and the fluorinated terpolymer by the above-mentioned method and then molding the mixture into an arbitrary shape. When the polyester composition of the present invention, the polyester fiber, the monofilament and the like contain an unreacted carbodiimide compound, the carbodiimide compound and the polyester are added while adding a predetermined amount of the carbodiimide compound from the inlet or vent of the extruder. It can be carried out by kneading chips and a predetermined amount of a fluorinated terpolymer in an extruder and then molding them into an arbitrary shape. For example, in the case of polyester fibers and monofilaments, polyester, a fluorinated terpolymer and unreacted carbodiimide compound are preliminarily melt-kneaded to form pellets, which are spun by a known method.
Method such as stretching and heat setting, or after kneading the fluorinated terpolymer and unreacted carbodiimide compound in the extruder, spun from the spinneret provided at the tip of the extruder, and cooled and stretched under known conditions. -A method of manufacturing by a method of heat setting can be mentioned. It is also possible to combine and use streamline interchangers such as "static mixer" and "high mixer" before spinning.

The fluorinated terpolymer in the polyester composition of the present invention has a plurality of substantially fluorinated terpolymers in the polyester resin when the composition is a molded product without stretching. Existing in a dispersed state, and when it is stretched like fibers and monofilaments,
It exists in the polyester in the form of a plurality of finely chopped streaks in the stretching direction.

The polyester composition, polyester fiber and polyester monofilament of the present invention include
In addition to polyester, fluorine-based terpolymer, unreacted carbodiimide compound, epoxy resin, silicone resin,
It is also possible to blend various rubbers, polyurethanes and the like.

The polyester fibers of the present invention are multifilaments and monofilaments.

The monofilament of the present invention means 1
It is a continuous yarn consisting of a single yarn.

The shape of the cross section of the polyester fiber and the monofilament perpendicular to the fiber axis direction (hereinafter referred to as cross-sectional shape or cross section) is a circle, a flat shape, a square shape, a half-moon shape, a triangle, a polygon with five or more sides, a multilobal shape, It may have any cross-sectional shape such as a dog bone shape or a cocoon shape. When the monofilament of the present invention is used as a constituent material of an industrial fabric, the monofilament preferably has a circular or flat cross section. In particular, when the monofilament is a warp yarn of a papermaking dryer canvas, a monofilament having a flat cross section is preferably used from the viewpoint of effectively exhibiting antifouling property and flatness of the canvas. The flat in the present invention is an ellipse, a square or a rectangle, but in addition to a mathematically defined exact ellipse, a square or a rectangle, a shape generally similar to an ellipse, a square or a rectangle, for example, a square and a rectangle. It includes a shape with rounded corners. In the case of an ellipse, the length of the major axis (LD) and the length of the minor axis (SD) that intersect at a right angle at the center of the ellipse have a relationship satisfying the following expression, and in the case of a square or a rectangle, Long side length (LD) and short side length (SD) of the rectangle
It is preferable that and satisfy the following equation. 1.0 ≦ LD / SD ≦ 10 The length of the line segment passing through the center of gravity of the monofilament cross section can be appropriately selected depending on the application, but is preferably in the range of 0.05 to 2.5 mm. The required strength of the yarn varies depending on the application, but is preferably about 3.0 g / denier or more.

Further, the polyester fiber and the polyester monofilament of the present invention have, as a core component, a polyester containing no fluorine-based terpolymer, in addition to a single-structured yarn composed of polyester and a fluorine-based terpolymer. It may be a core-sheath composite structured yarn having a sheath component of polyester containing a fluorinated terpolymer.

The polyester composition, polyester fiber and polyester monofilament of the present invention may be in any shape such as non-woven fabric, staple fiber and fibrous form such as cotton, molded product such as connector and automobile wiper, bottle, film and sheet. Since it has excellent antifouling property and hydrolysis resistance, it can be preferably used for clothing and various industrial fabrics, electronic parts, automobile parts, bottles, films, sheets and the like.

Since the polyester fiber of the present invention has excellent antifouling properties or excellent antifouling properties and hydrolysis resistance, it is used for various sports such as ski wear, judo wear, training wear, soccer and volleyball. Sportswear such as uniforms and clean work clothes, work clothes for the food industry,
Aprons, table cloths, non-woven fabric filters, and medical clothes that are sterilized and disinfected in high temperature steam.
It can be suitably used for applications such as medical instruments.

The industrial woven fabric of the present invention means that the polyester monofilament of the present invention is used at least in part.
Papermaking wire (mesh for papermaking), papermaking dryer canvas, net conveyor for thermal bonding process of thermal bonding nonwoven fabric, various filters, etc. By using the polyester monofilament of the present invention as at least a part of the constituent material, It becomes an industrial woven fabric that is not easily soiled and is easily removed by washing and has excellent antifouling properties, or an industrial woven fabric in which hydrolysis deterioration when used in a hot and humid atmosphere is significantly suppressed.

Here, the papermaking wire refers to various woven fabrics such as a single woven fabric, a double woven fabric and a triple woven fabric, and is a fabric used in a paper making process and used as a Fourdrinier or a round net. . Further, the papermaking dryer canvas is a woven fabric such as a single woven fabric, a double woven fabric and a triple woven fabric, which is used for drying the paper in the dryer of the papermaking machine. Further, the thermal bonding process net conveyor for thermal bonding non-woven fabric is a woven fabric for passing the non-woven fabric into a furnace in order to fuse the heat-adhesive fibers such as low melting point polyethylene constituting the non-woven fabric, Textiles such as single weave and double weave.

[0034]

The present invention will be described in more detail with reference to the following examples. In the following examples, a monofilament, which is a preferred embodiment of the polyester composition of the present invention,
A paper dryer canvas, which is a preferable example of an industrial fabric, and taffeta, which is a preferable example of polyester fiber, will be specifically described. The characteristic values in the following examples are measured by the following methods unless otherwise specified.

1. Evaluation of Antifouling Property of Monofilament (1) Preparation of Contaminated Liquid Talc 1 part by weight Alkylketene dimer 0.5 part by weight Acrylamide 0.5 part by weight Water 98 parts by weight (2) While stirring the prepared contaminated solution at 300 rpm,
An operation of immersing the weighed monofilament in a bath ratio of 1: 5000 for 5 seconds and drying at 70 ° C. for 1 minute was repeated 10 times to obtain a stain-adhered sample. (3) The sample with stains was weighed to determine the amount of stains. (4) Contamination amount is P without fluorine-based terpolymer
The index was compared when the amount of adhered dirt on the ET monofilament was 100.

2. Taffeta contamination / cleanability evaluation (1) Contaminant A. Oily pollutant (a) Stearic acid 12.5% by weight (b) Oleic acid 12.5% by weight (c) Hardened oil 12.5% by weight (d) Olive oil 12.5% by weight (e) Cetyl alcohol 8.5 Wt% (f) solid paraffin 21.5 wt% (g) cholesterol 5.0 wt% (h) carbon black 15.0 wt% B. Dry pollutant (a) Clay 55.0 wt% (b) Portland cement 17.0 wt% (c) Silica gel 17.0 wt% (d) Ferric oxide 0.5 wt% (e) n-decane 8 .75 wt% (f) carbon black 1.75 wt% (2) Test procedure A. Take one test sample of about 45 cm x 45 cm ¹⁾ .

B. A 0.2% slightly alkaline synthetic detergent at 40 ± 2 ℃ in a washing tub of an automatic reversing spiral electric washing machine (JIS
Add 25 liters of K3371 weakly alkaline type 1 solution and adjust the total weight of the test sample and additional cloth ²⁾ to about 500 g, and then wash for 25 minutes under strong washing machine conditions.

C. Transfer the test sample and additional cloth to the centrifugal dehydrator ³⁾ attached to the washing machine, dehydrate for about 30 seconds, and then transfer to the washing tub ³⁾ filled with room temperature water again. Rinse for 10 minutes with water overflow. This operation is repeated twice.

D. The test sample is taken out without squeezing, the vertical direction is made vertical, one side is hung, and it is naturally dried.

E. 5 cm x 10 from the test sample after washing
Collect 5 cm test pieces. One of them is used as the standard test piece for contamination determination.

F. Launder meter type washing tester ⁴⁾ Contaminated liquid in the attached 450 ml test bottle ⁵⁾ 50 ml and diameter 6.4
Put 10 mm stainless steel balls and preheat to 40 ± 2 ° C.

G. Put 4 pieces of test piece moistened with water in a test bottle, seal it tightly and attach it to the tester.
Rotate for 20 minutes at 2 ° C.

H. Remove the test piece from the test bottle and
Rinse with 1 liter of room temperature water for 1 minute, and press the test piece with filter paper to remove excess dirt adhering to the surface. This operation is repeated once more, and left to stand for 24 hours or more in the horizontal state to naturally dry.

I. By comparing the color difference seen between the test piece after contamination and the standard test piece for contamination judgment of E, with the color difference seen between the color charts of the gray scale for contamination,
The degree of contamination is classified into grades, and the contamination property is represented by the average value of 4 sheets (1st grade (large pollution) to 5th grade (small pollution)).

J. Continuously, a 0.2% slightly alkaline synthetic detergent (JIS K3371 weakly alkaline, type 1) liquid 2 at 40 ± 2 ° C was added to the washing tub of the automatic inversion spiral electric washing machine.
Put 5 liters, put 2 pieces of test pieces after contamination and additional cloth ²⁾ into a cloth with a weight of 500g, and put it under the strong condition of the washing machine.
Wash for minutes.

K. The test sample and the additional cloth are transferred to a centrifugal dehydrator attached to a washing machine, dehydrated for about 30 seconds, and then transferred to a washing tub filled with room temperature water again. Rinse for 2 minutes with overflowing water. This operation is repeated twice.

L. Take out the test piece without squeezing it, lightly press it with a filter paper to remove water, and naturally dry in a horizontal state.

M. By comparing the color difference seen between the test piece after contamination and the standard test piece for contamination judgment of E, with the color difference seen between the color charts of the gray scale for contamination,
The degree of cleaning is classified into grades, and the cleaning property is represented by the average value of two sheets (1st class (large dirty) to 5th class (small dirty)).

Note 1) If the end thread is frayed during washing, prevent the end thread from fraying with an overedging machine.

2) Use an appropriate number of cloths of the same size as the test sample of about 45 cm × about 45 cm.

3) Wash thoroughly in advance so that no detergent remains in the washing tank and dehydration tank.

4) Those specified in JIS L0821.

5) Weakly alkaline synthetic detergent (JIS K33
71 Weakly alkaline (Type 1) and the following contaminants are weighed so that the weight ratio is 7: 3, mash the detergent in a mortar, add the contaminants and mix, then add a small amount of water. Dilute to a contaminated agent concentration of 0.075% by further adding and adding in batches. As the pollutant, a mixture of the above-mentioned oily pollutant and dry pollutant in a ratio of 3: 1 is used.

3. Water and oil repellency of monofilament The contact angle of a flat (substantially rectangular) cross section monofilament was measured by the following method. The larger the contact angle, the higher the water / oil repellency. (1) Using a goniometer type contact angle measuring device manufactured by Elma Optical Co., Ltd. (2) Water contact angle: distilled water, oil contact angle: using decalin (3) Droplet amount: 5 μl (4) Measuring temperature: 20 ° C.

4. Tensile test of monofilament The test was performed according to JIS L1013-1992. (1) Sample gripping interval 25 cm (2) Tensile speed 30 cm / min. (3) Test temperature 20 ℃

5. Hydrolysis resistance test of monofilament The monofilament was put into a 100 liter autoclave and kept in saturated steam at 121 ° C for 10 days, 12 days, and 1 day.
After treatment for 5 days, the tenacity of the monofilament after the treatment was obtained by the tensile test of the above monofilament, and the tenacity retention compared with the tenacity of the monofilament before the treatment was used as a measure of hydrolysis resistance (hereinafter, referred to as hydrolysis content). The strong retention rate after the solution). The higher the retention rate after hydrolysis is, the better the hydrolysis resistance is.

Example 1, Comparative Example 1 Intrinsic viscosity 0.93, terminal carboxyl group concentration 13 equivalents /
10 ⁶ g of PET dry chips were prepared (hereinafter referred to as PET
Called a chip). On the other hand, 4 as a fluorinated terpolymer
About 60 mol% of fluorinated ethylene and about 2 of propylene hexafluoride
Copolymer consisting of 0 mol% and about 20 mol% of vinylidene fluoride (THV ^™ 500G (Sumitomo 3M product), melting point of about 175 ° C, M at 265 ° C load of 5 kg)
FR (about 10 g / 10 minutes) (hereinafter referred to as THV500G) was prepared. As a typical example of the polyester composition of the present invention, a monofilament was produced and evaluated by the following method.

The PET chip and the THV500G chip were mixed at a weight ratio of PET / THV500G = 93/7 and supplied to the extruder. The molten polymer melt-kneaded at 280 ° C. for 3 minutes was spun from a spinneret for flat cross-section yarn through a gear pump, a filtration layer in a spinning pack and a streamline changer (“Static Mixer” manufactured by Chemix, USA). After the spun monofilament was cooled in a hot water bath at 80 ° C, it was stretched and heat-set to a total of 5.0 times according to the usual method, and the long side was 0.56 mm and the short side was 0.28 mm.
A monofilament having a substantially rectangular cross section (flat cross section) was obtained. Table 1 shows the strength, contact angle measurement results, and antifouling property evaluation results of this monofilament. THV50 for comparison
The results of the monofilament obtained in the same manner as in Example 1 except that 0 G is not used are also shown in Table 1 as Comparative Example 1.

Examples 2 to 9 and Comparative Examples 2 to 3 The same procedure as in Example 1 was carried out except that the compounding amounts of the PET chip and the THV500G chip in Example 1 were changed as shown in Table 1. The results of the monofilaments are also shown in Table 1.

Comparative Example 4 An ethylene / tetrafluoroethylene random copolymer (manufactured by Daikin Industries, Ltd., Neoflon ^TM EP-521, hereinafter referred to as EP-
The result of the monofilament obtained in the same manner as in Example 2 is also shown in Table 1.

Examples 10 to 11 The THV500G chip in Example 1 was prepared by adding about 50 mol% of tetrafluoroethylene and about 20 mol% of propylene hexafluoride.
And a copolymer of vinylidene fluoride of about 30 mol% (THV ^™ 400G (manufactured by Sumitomo 3M Limited), melting point of about 155 ° C., 265 ° C., MFR of about 1 at a load of 5 kg).
Table 1 also shows the results of monofilaments obtained in the same manner as in Example 1 except that the amount was changed to 0 g / 10 minutes) (hereinafter referred to as THV400G) (Example 10). Similarly, a copolymer consisting of about 40 mol% of tetrafluoroethylene, about 20 mol% of propylene hexafluoride and about 40 mol% of vinylidene fluoride (THV ^™ 200G (produced by Sumitomo 3M Limited), melting point about 120 ° C, MFR at 265 ° C load 5 kg, about 20 g / 10 minutes) (hereinafter, THV200
The result of the monofilament obtained in the same manner as in Example 1 except that it was changed to (G) (Example 10) is shown in Table 1.
It is shown together.

[0062]

[Table 1] From the above results, it is understood that the polyester monofilament of the present invention is excellent in water / oil repellency and antifouling property and has sufficient strength.

Examples 12 to 17 and Comparative Example 5 When the PET chip and the THV500G chip in Example 1 were supplied to the uniaxial extruder, the weight ratio of the liquid TIC shown in Table 2 at the inlet of the uniaxial extruder. A monofilament with a flat cross section was obtained in the same manner as in Example 1 except that the monofilament was fed while being metered so that The strength and elongation of this monofilament, the contact angle measurement result, the antifouling index, the content of unreacted carbodiimide compound (hereinafter referred to as unreacted TIC) in the monofilament, the COOH terminal group concentration, the strength retention after hydrolysis, etc. The characteristics are shown in Table 2. THV500G in Example 15 for comparison
Table 2 also shows the results of the monofilaments obtained in the same manner as in Example 15 except that PET chips equivalent to THV500G were added without adding chips.

[0064]

[Table 2] From the above results, when the monofilament, which is a preferred embodiment of the polyester composition of the present invention, contains 0.005 to 1.5% by weight of unreacted TIC, in addition to excellent antifouling property and sufficient strength and elongation, When the monofilament has excellent hydrolysis resistance and the unreacted TIC content of the monofilament is 0.01 to 1.2% by weight, antifouling property, hydrolysis resistance and strong elongation are obtained. It can be seen that the balance with the degree is even better.

Example 18, Comparative Example 6 In order to evaluate suitability as an industrial fabric, the monofilament obtained in Example 1 was used as a warp and a weft to prepare a plain fabric. A part of this plain woven fabric was cut out, immersed in the above-mentioned contaminated liquid, and then dried at 100 ° C. for 30 minutes, and the weight of the soiled plain woven fabric was measured. The soiled canvas was ultrasonically washed in water containing 0.5% by weight of a neutral surfactant for 3 minutes, washed with water and dried to measure the weight of the plain weave after washing. The amount of adhered dirt determined from the weight difference before and after cleaning is 0.7.
% By weight. (Example 18) For comparison, the amount of adhered stains when the same procedure as in Example 18 was performed except that the monofilament in Example 18 was changed to the monofilament obtained in Comparative Example 1.
It was 1% by weight. (Comparative Example 7) From these results, it can be seen that the industrial woven fabric using the monofilament of the present invention is excellent in antifouling property.

Example 19 A monofilament having a circular cross section with a diameter of 0.46 mm was produced by changing the flat section yarn spinneret used for spinning the monofilament in Example 15 to a circular cross section yarn spinneret.

This monofilament having a circular cross section was used as a weft, and the monofilament having a flat cross section obtained in Example 15 was used as a warp to prepare a twill canvas for a paper dryer (hereinafter referred to as canvas). The canvas was attached to a dryer of a neutral paper machine, used for drying the paper at 140 ° C. for 8 months, and then the canvas was removed.
The strength remaining ratio of the warp on the canvas after use to the strength of the warp on the canvas before use is 74%.
Met. Also, after cutting off a part of the canvas after this use, the weight is measured, ultrasonic cleaning is performed for 3 minutes in water containing 0.5% by weight of a neutral surfactant, and the plain fabric after cleaning is washed with water and dried. The stain adhesion rate determined by the method of measuring the weight of was 1.1% by weight.

Comparative Example 7 A monofilament having a circular cross section with a diameter of 0.46 mm was produced by changing the flat section yarn spinneret used for spinning the monofilament in Comparative Example 4 to a circular cross section yarn spinneret. Using this circular cross-section monofilament for weft,
A canvas was prepared by using the monofilament having the flat cross section obtained in Comparative Example 4 as the warp. This canvas was attached to a dryer of a neutral paper machine, used for drying the paper for 8 months at 140 ° C., and then the canvas was removed.
The strength remaining ratio of the warp on the canvas after use to the strength of the warp on the canvas before use is 70%.
Met. Also, after cutting off a part of the canvas after this use, the weight is measured, ultrasonic cleaning is performed for 3 minutes in water containing 0.5% by weight of a neutral surfactant, and the plain fabric after cleaning is washed with water and dried. The stain adhesion rate determined by the method of measuring the weight of was 3.5% by weight.

From the above results, it is understood that the papermaking dryer canvas of the present invention has both excellent hydrolysis resistance and antifouling property.

Examples 20 to 22 and Comparative Example 8 PET chips having an intrinsic viscosity of 0.65 were prepared. This PE
T-chip and THV500G chip, THV400G, T
HV200G was mixed with the weight ratio shown in Table 3 and supplied to an extruder type spinning machine, and at a polymer temperature of 290 ° C.,
It was spun out from a spinneret having 0.3 mmφ × 16 holes and wound at a speed of 800 m / min. Then a stretching temperature of 120 ° C.,
It was drawn at a draw ratio of 3.5 times to obtain a drawn yarn of 75D / 16 filament. This drawn yarn was used as a weft and woven into taffeta. Table 3 shows the results of evaluation of contamination / cleanability of this taffeta.

[0071]

[Table 3] From the above results, it can be seen that the multifilament of the present invention has excellent antifouling property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D21F 1/10 D21F 1/10 7/08 7/08 A // (C08L 67/02 27:12 (72) Inventor Kei Horii 4845 Mishima City, Shizuoka Prefecture, Toray Co., Ltd. Mishima Plant (72) Inventor Tadanori Iwama 1 Kawara, Showa-cho, Okazaki City, Aichi Toray Monofilament Co., Ltd.

Claims (8)

[Claims] 1. A polyester of 99.9 to 70% by weight,
A polyester composition comprising 0.1 to 30% by weight of a copolymer mainly composed of tetrafluoroethylene, propylene hexafluoride and vinylidene fluoride. 2. A carbodiimide compound in which the polyester has a terminal carboxyl group concentration of 10 equivalents / 10 ⁶ g or less and the polyester composition is in an unreacted state is 0.005.
The polyester composition according to claim 1, wherein the polyester composition is contained in an amount of about 1.5% by weight. 3. The polyester composition according to claim 1, wherein the polyester is polyethylene terephthalate. 4. A polyester fiber comprising the polyester composition according to claim 1. 5. A polyester monofilament comprising the polyester composition according to claim 1. 6. The polyester monofilament according to claim 5, wherein the cross section of the monofilament perpendicular to the fiber axis direction is circular or flat. 7. An industrial woven fabric using the polyester fiber according to any one of claims 4 to 6 in at least a part of a weft or a warp constituting the woven fabric. 8. The industrial woven fabric according to claim 7, wherein the industrial woven fabric is a papermaking dryer canvas, a papermaking wire, a filter or a net conveyor for a thermal bonding non-woven fabric thermal bonding process.