WO1990010100A1

WO1990010100A1 - Acrylic fiber of high thermal resistance, use of same and method of manufacturing same

Info

Publication number: WO1990010100A1
Application number: PCT/JP1990/000234
Authority: WO
Inventors: Toshihiro Yamamoto; Yasuaki Nakayama; Minoru Sasaki; Kenzi Arai; Yu Mihashi
Original assignee: Kanebo Ltd.
Priority date: 1989-03-03
Filing date: 1990-02-27
Publication date: 1990-09-07
Also published as: EP0423350A4; EP0423350A1

Abstract

This invention provides an acrylic fiber excellent in thermal resistance, creep resistance and transparency. The knit and union fabric produced from this fiber and, for example, an aromatic polyester fiber have clear color characteristics and soft hand inherent in the acrylic fiber. The acrylic fiber according to the present invention can be applied to electric blankets, electric carpets or waterproof cloths.

Description

'' Acryl fiber excellent in heat resistance, its use and production method thereof Industrial application field The present invention relates to an acrylic fiber excellent in heat resistance, an application utilizing its properties, and a production method thereof. Traditionally, acrylic fibers have been widely used in clothing, bedding, interiors, etc., taking advantage of their vivid color development and soft texture. However, because of the undesired heat resistance properties of high temperature treatment and large discoloration and discoloration, it could not be used for clothing such as anti-dyeing jerseys and hardly used for industrial materials. Conventionally, the following proposals have been made for the purpose of improving the heat resistance of acrylic fibers. Japanese Patent Application Laid-Open No. 51-73587 discloses itaconic acid, butyric acid, and the following formula:

-.

C H 2 = C-C

ROCH ₂ CH ₂ OH

Here, R is H or C i -C ₄ alkyl, and a compound represented by the following formula: ## STR1 ## in which 0.3 to 3 mol% of acrylonitrile is copolymerized. Acrylonitrile fibers or films having a structure are disclosed. Japanese Patent Application Laid-Open Publication No. Sho 53-12626 discloses a heterogeneous composition containing acrylonitrile as a main component and containing oxygen, sulfur or nitrogen atoms as heteroatoms.

A ring obtained by copolymerizing a 6-gen compound such as diaryl ether An arrowhead fiber of an acrylonitrile-based copolymer having a linear structure is disclosed. Also, Japanese Patent Application Laid-Open No. Sho 53-126263 discloses acrylonitrile having a cyclic structure, which is obtained by using a divinyl compound such as divinyl ether in place of the above-mentioned 1,6-diene compound. Disclosed are fibers of a system copolymer.

As described above, conventional heat-resistant acrylonitrile-based fibers have been designed to improve heat resistance by introducing a crosslinked structure or a ring structure.

On the other hand, JP-A-49-94921 discloses a copolymer containing 85% by weight or more of acrylonitrile and 0.5 to 15% by weight of 2-acrylamide-2-methylpropanesulfonic acid. A method for producing a hygroscopic acrylyl moth fiber by spinning a polymer is disclosed. Examples in the publication include 30 parts of a copolymer (master patch) obtained by copolymerizing 20 parts of 2-acrylamide-2-methylpropanesulfonic acid with 80 parts of acrylonitrile. 70 parts by weight of a copolymer of 91% by weight of acrylonitrile and 9% by weight of methyl acrylate were dissolved in dimethylacetamide, wet-spun, stretched, dried and ripened to give 20%. A specific example of producing a wet fiber having an equilibrium moisture content of 4.1% at 65 ° C. and 65% RH is disclosed.

Japanese Patent Application Laid-Open No. 54-34416 discloses that 70% by weight or more of acrylonitrile and 1 to 30% by weight of a copolymerizable compound having a sulfonic acid group or a salt thereof, Hollow fibers formed from copolymers comprising 0 to 29% by weight of monomers are disclosed. This publication discloses 2-acrylamide-2-methylpropanesulfonic acid as a copolymerizable compound having the sulfonic acid group or a salt thereof, and this compound has a sulfonic acid group. It is described that the resulting copolymer is provided with water absorption and anticoagulant properties. The hollow fibers in the publication are suitable for hemodialysis as pointed out in the publication.

Japanese Unexamined Patent Publication (Kokai) No. 56-1283133 discloses a side-by-side type self-contained composition of a non-hydrophilic acrylonitrile copolymer component and a hydrophilic acrylonitrile copolymer component. A crimpable bicomponent acrylic fiber is disclosed. The hydrophilic acrylonitrile copolymer contains 0.7 to 1.2 mol% of 2-acrylamide-2-methylpropanesulfonic acid or a salt thereof. The two-component acryl fiber disclosed in the publication is crimped by utilizing the fact that the hydrophilic acrylonitrile copolymer component has a relatively high hydrothermal swelling property. is there.

Also, Japanese Patent Application Laid-Open No. 61-119711 discloses a sulfonic acid group-containing compound selected from a number of specific sulfonic acids such as 2-acrylid-2-methylpropanesulfonic acid. A high-strength acrylic fiber containing 0.1 to 1.0 mol%, having an intrinsic viscosity of at least 2.0 and a tensile strength of 1 OgZd or more is disclosed. According to the description of the publication, this fiber not only has a high strength, but also has a strength retention after boiling water treatment of at least 70% or more, and a high elastic modulus. It is described in this publication that this fiber can be suitably used as a cement replacement material as an alternative to asbestos.

On the other hand, in the past, acrylic fiber has been taking advantage of its vivid coloration and flexible texture to make clothes such as knits and jerseys, interiors such as cars and curtains, and sleeping materials such as blankets and sheets. As mentioned above, it is widely used for garments, etc., but in the case of garments, when knitted or woven, dyeing after heating causes large settling due to heat, dimensional stability and texture. Will be defective Had to be done.

The following proposals have heretofore been made for the purpose of improving this drawback.

JP-A-47-43557 discloses that the content of the composite moth fibers contained in acryl-based synthetic fibers is 20 to 50% of the total amount, and that the polyester-based synthetic fibers Post-dyeing of acrylic synthetic fiber and polyester synthetic fiber with a content ratio of 25-60% and a shrinkage ratio of polyester synthetic fiber to acrylic synthetic fiber of 1: 1 to 4 It discloses a method of producing mixed spinning and knitting. Further, the publication discloses that a dyeing temperature of 98 ° C. to 105 ° C. is used by using a carrier that causes less cross-contamination. JP-A-49-18665 discloses an acryl-based spun yarn (A) composed of 30 to 70% of a composite moist fiber component and 70 to 30% of a non-composite fiber component. The mixing ratio of the polyester-based long fiber processed yarn (B) in the product is set to 20 to 55%, the shrinkage ratio between (B) and (A) is set to 1: 3 to 5, and (A) (B) is knitted into a knitted double knit and then dyed at a dyeing temperature of 96 ° C to 105 using a carrier with low cross-contamination. A method for producing a post-dyeed and knitted double knit composed of an acryl-based spun yarn and a polyester-based long-fiber processed yarn, which is sent and finished with an overfeed ratio of 18 to 25%, is disclosed.

As described above, the conventional blended, cross-knitted and cross-cut products of acryl fibers and polyester fibers that can be dyed are made by mixing a part of the acrylic fiber as a composite fiber and dyeing at low temperature using a carrier. Met.

On the other hand, Japanese Patent Application Laid-Open No. 58-13739 discloses a polyester arrowhead fiber and an acrylic fiber which are substantially composed of a homopolymer of polyethylene terephthalate and which can be dyed at normal pressure with a disperse dye. Interwoven fabrics and interwoven fabrics are disclosed, The above polyester fiber has an initial modulus at 30 ° C of 55 gZd or more, and a peak temperature (Tmax) of a mechanical loss tangent (tanS) at a measurement frequency i of 10 Hz; The peak value of tan δ [(tanS) max] is greater than 0.135, and the non-bulky fabric and / or the initial modulus at 30 ° C is 55 gZd or more. Tmax (° C) and bulk having a (tanS) max ^ (Tmax- 1 0 5) satisfies X 1 0- ² becomes formula and (Tans) max is 0.08 or more values between (Tans) max A highly processed fiber. Such an arrowhead fiber is spun at a high speed of, for example, 4.00 OmZ or more, and then matured by dry heat at a temperature of 220 ° C to 300 ° C and / or After being spun at a high speed of at least 1000 in / min, it is subjected to a heat treatment by dry heat at a temperature of 220 ° C to 300 ° C, and is then subjected to bulk processing by a conventional method. It is disclosed that there is. Japanese Patent Application Laid-Open No. 58-87340 discloses a polyester fiber having substantially the same properties as the polyester fiber disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 58-13739, atharyl moth fiber and a beast. The knitting and knitting with hair arrowheads are disclosed.

As mentioned above, polyester fiber used in knitting and knitting with acrylic fiber, which can be dyed at a low temperature without using a carrier, is spun at a high speed and then subjected to heat treatment after spinning. It was something.

In addition, conventionally, acrylic fiber has been used for household carpets that often walk on blankets or carpets, especially bare feet, taking advantage of its vivid coloration, soft and warm texture, and good heat retention. Has been widely used for On the other hand, electric blankets or electric power kits with heaters are also widely used, but conventional acrylic fibers have insufficient heat-fast dyeing fastness and stretch at high temperatures. Because of the high degree of When used as a surface material, there were defects such as discoloration or settling. As an electric blanket, it was necessary to mix it with polyester, wool, etc. to improve this. It is not used as a surface material for electric power.

As is well known, acrylic fiber has an excellent color-forming property, a feeling or a voluminous feeling. Therefore, if the above-mentioned disadvantages can be eliminated, acrylic textiles can take advantage of the above-mentioned excellent properties even when used alone as a blanket for electric blankets, and can be used as a surface material for electric power kits. It can be easily guessed that the material is no better or worse than polyester, polyamide, wool or the like currently used in practice. However, an acrylic fiber which has solved the above-mentioned disadvantages has not been developed nor known.

Polyester fiber, polyamide fiber, vinylon fiber, etc. have been used as the base fabric for waterproof fabrics such as tents, beach umbrellas, automobile power pars, port covers, etc. Although the fiber had excellent weather resistance and high strength retention, it was only slightly used in the above applications because of its poor cleave resistance and light fastness. Therefore, if the above-mentioned drawbacks can be eliminated, it is expected that ataryl fiber will be as good or better than the material of waterproofing cloth as compared with polyester fiber, polyamide moist fiber or vinylon fiber. Is done.

Disclosure of the invention

An object of the present invention is to provide a novel acryl fiber.

Another object of the present invention is to provide a novel acrylyl moth fiber having excellent heat resistance properties such as heat dimensional stability and heat dyeing fastness. An additional goal is to provide clear acrylic fiber.

Still another object of the present invention is to provide a novel acrylic fiber having excellent transparency.

Still another object of the present invention is to provide a novel acrylic fiber which can be dyed in a deep color and can be dyed in a dark color to a light color without using dyes and without dyeing.

Still another object of the present invention is to provide a novel acrylic fiber having moderate strength and relatively high elongation and excellent spinnability.

Still another object of the present invention is to provide a method for producing the novel acrylic fiber of the present invention.

Still another object of the present invention is to provide a cross-knitted / cross-woven fabric of an acrylic fiber and an aromatic polyester moth.

Still another object of the present invention is to provide a novel acrylic fiber material which can be post-dyed as an aromatic polyester fiber under ordinary dyeing conditions of aromatic polyester fibers as a cross-knit / cross cut product. is there.

Still another object of the present invention is to provide a novel knitted / cross-woven fabric of an acrylic fiber and an aromatic polyester fiber which is excellent in heat-resistant dimensional stability and has a soft feel.

It is another object of the present invention to provide a surface material for an electric carton and a raw cloth for an electric blanket containing an acrylic moth fiber which is excellent in heatfastness to dyeing and heat resistance.

Still another object of the present invention is to provide an acryl-based waterproofing cloth having excellent creep resistance and light fastness. Still other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention are:

(A), (a) The following equation (1)

-CH ₂ -CH-

C≡N · · · · (!) Polymerized unit and the following formula (2)

Wherein M is a hydrogen atom or an equivalent cation, consisting essentially of polymerized units represented by

(b) the polymerized unit (2) accounts for 0.4 to 1.5 mol% based on the total of the polymerized unit (1) and the polymerized unit (2), and

(c) the degree of polymerization is in the range of 600 to 1,500,

Consisting of an acrylonitrile copolymer,

(B) the tensile strength is in the range of 2-5 gZd, and

(C) 2'60 in relation to temperature and elongation measured at elevated temperature. This is achieved by the Acryl moth fiber, which is characterized in that the elongation in C is less than 10%. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the relationship between the temperature and the elongation of the acryl acrylic arrowhead fiber of the present invention and the conventional acryl fiber equivalent. FIG. 2 is a schematic diagram of the apparatus used to measure the relationship of FIG.

FIG. 3 is a schematic view of a sample support used in measuring the crystallinity of acryl fibers according to the present invention.

FIG. 4 shows the relationship between the temperature and the elongation of the acrylic fiber used in the cross-woven fabric of the present invention and the conventional equivalent of acrylic fiber.

FIG. 5 shows the relationship between the temperature and the elongation of the acryl fiber used in the electric carton surface material of the present invention and the conventional acryl fiber material.

FIG. 6 shows the relationship between temperature and elongation for Acryl moth fiber and conventional acryl fiber equivalents used in the electric blanket fabric of the present invention. FIG. 7 shows the relationship between the temperature and the elongation of the acryl fiber used in the waterproof cloth of the present invention and the conventional acryl fiber equivalent.

As described above, the acrylic moth fiber of the present invention has a requirement (A) for specifying a polymer forming the same, a requirement (B) for specifying its strength, and a requirement (C) for specifying its elongation at a low temperature. ).

Regarding the requirement (A), the polymer is a polymerized unit of the above formula (1) derived from acrylonitrile and the above formula (abbreviated as AMPS) or a salt thereof derived from 2-acrylyl-2-propanesulfonic acid (hereinafter abbreviated as AMPS). It consists essentially of the polymerized units of 2).

The ratio of the polymerized unit (1) to the polymerized unit (2) is 0.4 to 1.5 mol% based on the total of both polymerized units (polymerized unit (1) is 99.6 to 98. 5 mol%). Polymerized unit (2) is preferably 0.6 to 1.2 mol% based on the same standard (polymerized unit (1) is 99.4 to 98.8 mol%) Occupy. If the ratio of the polymerized unit (2) is less than 0.4 mol%, gelling in the polymerization process is apt to occur, and it becomes difficult to perform deep color dyeing due to insufficient dyeing seats. On the other hand, when the content exceeds 1.5 mol%, the heat resistance described later deteriorates.

Further, regarding the requirement (A), the above-mentioned polymer has a degree of polymerization in the range of 600 to 1,500. The preferred degree of polymerization is from 800 to 100.

If it is less than 600, the strength as ordinary acrylyl moth fiber cannot be obtained, and if it exceeds 1,500, gelation in the polymerization step is apt to occur, and the viscosity is too high for ordinary wet spinning.

Regarding requirement (B), the acrylic fiber of the present invention has a tensile strength of 2 to 5 gZd, that is, a tensile strength not so high but suitable as a so-called clothing fiber. The preferred tensile strength is 3 to 4 _gd . When the tensile strength is less than 2 g / d, normal spinning is apt to occur, and when the tensile strength exceeds 5 gZd, the strength becomes high and the tensile elongation described below is insufficient, and the elongation as a spun yarn is further reduced. Run short.

Further, regarding the acrylic fiber of the present invention, regarding the requirement (C), the elongation at 260 ° C. is 10% or less in relation to the temperature measured at elevated temperature and the elongation. The preferred elongation is 6% or less.

The acryl fiber of the present invention is superior in heat resistance and has a characteristic of less so-called set, as compared with the conventional acrylic molybdenum for clothing having the same tensile strength.

The acrylyl moth fiber of the present invention may or may not be crimped, and more preferably has the following properties.

The dry heat relaxation shrinkage at 210 ° C. is preferably 3% or less, and more preferably 1% or less. Regarding the heat resistance at the time of warming, the relaxation shrinkage after heating at 130 ° C. is preferably 3% or less, more preferably 1% or less.

As specified in the requirement (B), the acrylic fiber of the present invention has an appropriate strength as a normal garment fiber, and exhibits an elongation that gives good spinnability at such strength. it can. The preferred elongation is 35% or more, and the more preferred elongation is 35 to 60%.

The acrylic fiber of the present invention is preferable in that general acrylic fiber, particularly, acrylic fiber obtained by wet spinning using an organic solvent shows only poor transparency, but can show excellent transparency. The acrylic fibers of the present invention preferably exhibit a transparency of at least 80%, more preferably at least 90%, according to the measurement method described below.

§ click Lil fibers of the present invention are preferably Young's modulus of 400~ 70 OkgiZ negation ^2, further preferably from the this with the Young's modulus of 500 ~ 60 OkgfZmm ^2.

Further, the excellent heat resistance of the acrylic fiber of the present invention is that the heat resistance dyeing fastness (dry heat: 120 ° C. for 48 hours) is preferably at least 3 grade, more preferably at least 3.5 grade. They are also supported.

The acrylic fibers of the present invention preferably have a crystallinity of 20-40%, more preferably 25-35%.

As described in the requirement (A), the above-mentioned acrylic fiber of the present invention is obtained by adding the polymerized unit (2) to the polymerized unit (2) by 0.4 based on the sum of the polymerized unit (1) and the polymerized unit (2). It is contained at a ratio of ~ 1.5 mol%. According to the study of the present inventor, under the condition that the above-mentioned ratio of the polymerized unit (1) and the polymerized unit (2) is maintained, even if the polymerized unit (3) is further contained in a small amount, the above-mentioned object of the present invention and Profit It was found that the points could be retained.

Therefore, according to the present invention, second,

(AO (a ') a polymerized unit of the above formula (1), a polymerized unit of the above formula (2) and a polymerized unit different from the polymerized unit of the above formula (2) derived from a monomer copolymerizable with acrylonitrile (B) The polymerized unit (2) occupies 0.4 to 1.5 mol% based on the total of the polymerized unit (1) and the polymerized unit (2). (3) accounts for 5% by weight or less based on the polymerization unit (1),

(c) the degree of polymerization is in the range of 600 to 1,500,

Consisting of acrylonitrile copolymer,

(B) the tensile strength is in the range of 2-5 gZd, and

(C) 260 in relation to temperature and elongation measured at elevated temperature. The elongation in C is 10% or less,

An acryl fiber is provided.

As described above, the acrylic fiber of the present invention is specified by the requirements (A, (B) and (C). The requirements (B) and (C) are understood from the above description. Like.

Regarding requirement (要件 '), the ratio of the polymerized unit (1) and the polymerized unit (2) is 0.4 to 1.5 mol% based on the total of these both polymerized units (polymerized unit based on the same standard). (1) is 99.6 to 98.5 mol%), which is the same as the acryl fiber of the present invention described above.

Regarding requirement (Α '), in addition to the polymerized units (1) and (2), other polymerized units (3) different from the polymerized units (2) derived from monomers copolymerizable with atarilonitrile It is present in less than 5% by weight, based on polymerized units (1). polymerization Unit (3) is preferably present at 3% by weight or less, based on the same criteria. As the polymerized unit (3), preferably, for example, the following formula (3)

R

-CH ₂ -C)-.... (3)

Y where R is a hydrogen atom or a methyl group, and Y is a group represented by the formula CO 0 X, where X is a hydrogen atom, a sodium or methyl group, — OCO CH ₃ _{, - C ONH 2, - C} 6 H 5, is a group selected from a CH ₂ S 0 ₃ N a and the group consisting of one _{_{_{C 6 H 4 S 0 3 N}}} a,

Can be mentioned. Regarding the second acryl fiber of the present invention, it should be understood that the description of the first acryl fiber of the present invention is applied to the other points not described herein. According to the present invention, the acrylic fiber of the present invention can be produced from the acrylonitrile-based polymer specified in the above (A) or () ') by the following method. it can :

(1) extruding the spinning solution of the acrylonitrile-based copolymer specified in (Α) or (Α ') from the orifice of the spinneret to generate a trickle of the spinning solution; (2) It draws 5 to 10 times while solidifying to produce a drawn yarn,

(3) ripening the drawn yarn to shrink it by 3 to 25%, and

(4) A method for producing acryl fibers, wherein the obtained shrink yarn is subjected to a drying step. The acrylonitrile polymer used in the present invention is an acrylonitrile polymer. The ability to copolymerize trityl with 2-acrylamide-2-methylpropanesulfonic acid (AMPS) or a salt thereof, or other monomers capable of copolymerizing with acrylonitrile, AMPS and atalylonitrile. It can be produced by copolymerizing the monomer.

As the salt of AMP S can be, for example, (there you to hereinafter abbreviated as SAMP S) na Application Benefits Umushio, potassium salt, V ₂ calcium salt or Anmoniumu salts.

Other monomers copolymerizable with acrylonitrile include, for example, the following formula (3) ′

R

CH ₂ = C (3) '

Y Here, the definition of R and Y is the same as in the formula (3), and a compound represented by the following formula can be mentioned as a preferable example.

Examples of the compound of the formula (3) ′ include acrylic acid, methacrylic acid, their sodium salts, their methyl esters, vinyl nitrate, acrylamide, methacrylamide, styrene, sodium arylsulfonate, and methallylsulfonate. Sodium acid, sodium styrenesulfonate and the like can be mentioned. One or more of these other monomers copolymerizable with acrylonitrile can be used.

The polymerization method of the acrylonitrile polymer may be any known method such as aqueous polymerization, emulsion polymerization, and solution polymerization.

The spinning dope used in step (1) of the method of the present invention is thus obtained It goes without saying that the acrylonitrile yarn polymer can be prepared by dissolving it in a solvent, but it can also be a polymerization solution containing a polymer obtained as a result of polymerization. In the latter case, it is desirable to employ a polymerization reaction system which can be used as a spinning solution for wet spinning only by recovering unreacted monomers from the polymerization solution. The spinning method in the step (1) may be any known method such as wet spinning, dry-wet spinning, dry spinning, and semi-solid spinning. Particularly, wet spinning or dry spinning is preferred. These spinning methods are known per se. For example, for wet spinning, Japanese Patent Publication No. 57-167,410, JP-A-57-167,411, The method disclosed in Japanese Patent Application Laid-Open No. 57-210, 011, Japanese Patent Application Laid-Open No. 57-12410 or Japanese Patent Application Laid-Open No. 58-132107 is adopted. Details thereof are described in Examples 1 to 10 described later. For the dry method, for example, the method described in Japanese Patent Publication No. 499-1,665 or JP-A-59-21,711, and for the dry-wet method, refer to The method described in Japanese Patent Publication No. 1-92 3 16 is adopted. These methods are also described in detail in Examples 11 to 12 described later.

Regardless of which spinning method is adopted, the spinning stock solution is pressed from the spinneret in step (1) to form a fine stream of the spinning stock solution. In wet spinning, the trickle is extruded into the coagulating liquid, in dry spinning the trickle is discharged into a hot gas atmosphere, and in the dry-wetting method the trickle is extruded into a gaseous atmosphere and then guided into the coagulating liquid.

According to the present invention, in step (2), the trickle is stretched 5 to 10 times while undergoing solidification as described above. Stretching can be performed in one step or in multiple steps. The stretching ratio of each stage in multi-stage stretching is in the range where the total ratio is 5 to 10 times Is selected as appropriate. The preferred stretching ratio is 6 to 8 times. If the draw ratio is less than 5 times, the tensile strength of the fiber is insufficient, and if it exceeds 10 times, the single yarn breakage is liable to occur and the fiber is easily fibril.

The drawn yarn obtained in the step (2) is then subjected to a washing step (in the case of wet or dry-wet spinning) or oiled, if necessary, and then led to the heating step of the step (3).

In step (3), the drawn yarn is heated and contracted by 3 to 25%. If the shrinkage is less than 3%, the tensile elongation of the fiber is insufficient, and if it exceeds 25%, high temperature drying is required, which is not economical.

This shrinkage can be carried out using hot water or wet heat before the so-called pre-drying step before the drawn yarn is applied to the flimper, if the spinning in step (1) is performed by wet spinning, or It can also be performed in the process.

The obtained shrink yarn is then dried in step (4). When the shrinkage is performed in or before the so-called pre-drying step as described above, this step (4) corresponds to the so-called post-drying performed after crimping is performed as necessary. The acryl fiber of the present invention thus obtained is cut to a predetermined length by a cutter as necessary. The most significant feature of the method of the present invention is that, as understood from the above description, a specific acrylonitrile-based polymer is used and the drawn yarn is subjected to a heat shrinkage of 5 to 25% before being subjected to drying. Conventionally, the features of the method of the present invention have not been known.

According to the present invention, furthermore, in view of the fact that the acrylic fiber of the present invention has excellent heat resistance and low so-called settling under a high temperature environment, A cross-knitted / cross-woven fabric of the above-mentioned acrylic fiber and aromatic polyester fiber of the present invention is provided.

The cross-knitted / cross-woven fabric of the present invention can be dyed at the dyeing temperature of ordinary aromatic polyester fiber.

The aromatic polyester fiber used in the knitting / cross-woven fabric of the acryl fiber of the present invention and the aromatic polyester fiber is not particularly limited, but is preferably, for example, a polyethylene terephthalate whose main repeating unit is ethylene terephthalate. Polyhexamethylene terephthalate having hexamethylene terephthalate as the main repeating unit, polytetramethylene terephthalate having tetramethylene terephthalate as the main repeating unit, 1,4-dimethylcyclohexane Poly 1,4-dimethylcyclohexane terephthalate having hexane terephthalate as a main repeating unit and polybivalolactone having a ring-opened product of pivalolatatone as a main repeating unit can be given. These polyesters can be homo- or copolyesters. Examples of the copolyester include a copolymer in which the main repeating unit is ethylene terephthalate and the subordinate repeating unit (for example, 10% mol or less of all repeating units) is ethylenisophthalate. Can be. Examples of other copolyesters include polyethylene terephthalate containing 5% by mole or less of ethylene 5-sodium sulfisophthalate in all repeating units. More preferably, the aromatic polyester fiber is, for example, a homo- or copolyester of ethylene terephthalate having ethylene terephthalate as a main repeating unit. Conjugated fibers with the same or different aromatic polyester fibers or, for example, polyethylene It may be a conjugate moth with other materials such as mid moth. The polyester fiber may be either filament or stable.

The weaving of the knitted fabric of the present invention may be either double knit or single knit, and is not particularly limited. For example, double knits such as thread knitting, fleece knitting, smooth knitting, and knitting are preferred. The structure of the cross-woven fabric is also not particularly limited, but preferably includes plain weave, twill weave, and double weave.

The dyeing of the cross-knitted / cross-woven fabric of the acryl moth fiber and the aromatic polyester fiber of the present invention is performed, for example, when the aromatic polyester fiber is a homopolymer of ethylene terephthalate having ethylene terephthalate as a main repeating unit. The usual 120-130. The dyeing can be carried out in a single bath using, for example, a disperse dye and a cation dye (for Acryl moth fiber) under the temperature condition of C.

Further, according to the present invention, the electric power of the _c the MizunotoAkira electric carpets for surfacing Oyobi electric blankets dough is provided to Toku徵by containing acrylic fibers of the present invention one ^ ^ The surface material for cutting is special in that it contains the acryl fibers having the novel excellent performance described above. Such acrylyl moths are preferably used in the facing, at least 10% by weight, more preferably at least 30% by weight.

Surface materials containing at least 10% by weight of ataryl fibers are advantageous because they can make use of the sharp color development and warm taste of acrylic arrowheads. Examples of moth fibers mixed with acrylic fibers include, for example, fibers having good heat resistance such as wool, polyester and nylon. According to the present invention, the surface material of the present invention is used for the outermost surface or outer surface. Electrification power was provided as well. The structure of the surface material may be any known material such as a nonwoven fabric by needle punching or the like, a pile fabric by tufting or the like, or a knitted fabric in some cases.

The electric power unit of the present invention may be of a heater-integrated type, or may be of a separate type of a heater body and a cover cartridge.

The raw fabric for electric blanket of the present invention is special in that it contains the above-mentioned acrylic fiber having the novel excellent performance. Such acrylic fibers are preferably used in raw fabrics at least 50% by weight, more preferably at least 70% by weight.

A cloth containing at least 50% by weight of Acryl moth fiber is advantageous because it can make use of the vivid coloration and soft texture of acryl fibers. Examples of the fiber to be mixed with the acrylic fiber include polyester, wool, nylon, and other acrylic fibers.

According to the present invention, there is also provided an electric blanket using the above-described raw cloth of the present invention.

The structure of the raw cloth may be any known one such as a brushed cloth or a non-woven cloth.

Further, according to the present invention, it is possible to provide an unprecedented waterproof fabric base fabric which is excellent in creep resistance and light fastness by utilizing the original weather resistance of the novel Acryl moth fiber of the present invention. it can.

The base fabric of the waterproof fabric of the present invention is made of the above-mentioned acryl fabric. The fabric includes ordinary sheet-like structures such as woven fabric, knitted fabric, and non-woven fabric. These sheet-like structures can be produced by a method known per se. The waterproofing of the sheet-like structure is carried out according to a method known per se, using a waterproofing agent known per se.

As the waterproofing agent, in the case of a breathable waterproof cloth, for example, a fluorine resin or a silicone resin is preferable. In the case of a non-permeable waterproof cloth, for example, an acrylic resin or a vinyl chloride resin Etc. are preferably used.

Hereinafter, the present invention will be described in detail with reference to examples. Parts and% are parts by weight and% by weight unless otherwise specified. The analytical methods for various physical properties in the present invention and the following examples are described below.

[Polymer composition]

1) a polymerization unit formula (3) may not have an S 0 ₃ N a was by the following method.

i) The following formula (2) i CH ₂ CH

CO CH ₃

NH— C-CH ₂ -SO ₃ M

CH ₃

M: [% by weight], which is a ratio of a hydrogen atom or one equivalent of a cation to the polymer, was determined by the following measurement and calculation. First, polymer A [g] (about 1 g) was precisely weighed and dissolved in dimethylformamide (JIS special grade). Next, the mixture was mixed with a strong acid-type cation exchange resin {50-100 mesh, 3 (g)} for 1 hour and then stirred using a glass filter. The resin was identified. Further the port fluid potentiometric titrator - was titrated with N a OH of ^_1/50 N in (Hiranuma Sangyo COM 1 0 1 type). A blank test was performed under the same conditions to make corrections.

C

_{H (V 5.) Xf iX} (B 1 -C 1) [ml] xD 1 xl 0-3

[% By weight] = 2 x 100

A,

Y R c I I where; polymer amount [g],

BXV ₅ oN NaOH sample titer [ml] Ci; soN NaOH blank test titer [ml] D !: Molecular weight of polymerization unit formula (2) f! The titer of NasoH. Of VsoN ii) The following formula (3)

R: hydrogen atom or methyl group Y; C OOX, OCOCH ₃ ,

—C 0 NH ₂ , —C ₆ H ₅ X; The ratio of the hydrogen atom, sodium, or methyl group in the polymer i [% by weight] was determined by the following measurement and calculation. First, 0.5 g of the polymer was dissolved in dimethyl sulfoxide (JIS special grade) to prepare a 50 g Z1 solution. Infrared spectrophotometer (Shimadzu IR-4) using a liquid cell made of C a F ₂ and dimethyl sulfoxide as a control. The 2, 5 0 0 ~ l, 8 5 0 c ^m-1 and 1, 8 5 0-1, 5 0 0 infrared scan Bae-vector of c ^m-1 region were recorded at 3 0 type). Absorbance of polymer unit formula (3) obtained by baseline correction (If Y has one C0-, 1,500--1,800cm- ¹ C = 0 stretching vibration absorption band, the case having an _{_{C 6 H 5 1, 5 0}} 0~ 1, 7 0 0 cm- 1 of - C Ru using an H-plane outside deformation vibration absorption band) and the polymerization unit formula (1) The ratio of the absorbance of the 2,240 c π ^ ¹ absorption band to the absorbance determined by the above method was determined by mixing the polymer units (1) and (3) in various proportions in advance. The ratio was determined from a calibration curve.

Hi) The ratio [% by weight] of the polymerization unit formula (1) to the polymerization unit [% by weight] is at-100-(wherein, using these, the polymer composition [molar ratio] was calculated by the following formula.

r β α χ '= (Κ _χ 7 χ / 5 3.0 6) / Κ, β, / /

Κ _{ι α} x / D

However, a / and a, the ratio of the polymerized unit formula (1) in the polymer [mol%] and [wt%]

β ^ and! The ratio of the unit formula (3) in the polymer [mol%] and [wt%]

"And"; ratio of polymerized unit formula (2) in polymer [mol%] and [wt%]

Ex: Molecular weight of polymerization unit formula (3)

Ώ ₁ : molecular weight of polymerization unit formula (2)

Κ _ι; \ / {(7 _l / 53.0 6) + C ^ ₁ / E ₁ ) + (a ₁ / D ₁ )}-2) Y in the polymerization unit formula (3) is one CH ₂ S 0 ₃ N a or

— For C ₆ H ₅ S 0 ₃ Na, the following method was used. i) The ratio a ₂ [% by weight] of the polymer represented by the polymerization unit formula (2) to the polymer was determined by the following measurement and calculation.

The measurement and calculation were performed by the method of 1) and ii). However, the absorbance of the polymerization unit formula (2) is 1,666 cm- ^{1. Using an} absorption band, a single polymer of the polymerization unit formula (2) is used instead of the polymerization unit formula (3) to create a calibration curve. Was.

ii) The ratio S ₂ [% by weight] of the polymer represented by the polymerization unit formula (3) to the polymer was determined by the following measurement and calculation.

The measurement and calculation were performed by the method of i) in 1).

beta 2 _{[wt%] = [{(V 5} o) xf 2 X (B 2 - C 2) [ml] xE 2 1 0 one ^3} ZA _2] X

1 0 0

However, A ₂ ; polymer amount [g],

B ₂ ; V ₅₀ NN a OH Sample titer [m 1]

C ₂ ; VsoN NaOH blank test appropriate amount [ml]

E ₂ : molecular weight of polymerization unit formula (3)

f 2; titre of NaOH of VSQN

iii) The polymer composition [molar ratio] was calculated by the method of 1) iii). _{Ύ ζ '/ β 2' /} a 2 '= (Κ 2 7 2/5 3.0 6) / (K 2/5 2 / E 2) /

(K ₂ ₂ / D ₂ )

However § and § _2; the ratio of the polymerized unit formula occupying the polymer (1) [mol%] and [wt%]

β and β ₂ ; ratio of polymerized unit formula (3) in polymer [mol%] and [wt%]

<τ ₂ 'and "₂; ratio of polymerized unit formula (2) in polymer [mol%] and [wt%] E ₂ : molecular weight of polymerization unit formula (3)

D ₂ : molecular weight of polymerization unit formula (2)

K ₂ ; 1 {(α ₂ 5 3 .0 6) + C 3 ₂ E ₂ ) + ( _{ff 2} / D ₂ )}

[Degree of polymerization]

First, about 0.2 g of the polymer was dissolved in about 50 ml of dimethylformamide (special grade of JIS) to prepare a solution of C ′ [g / 1]. 30. The falling seconds A of the above solution and the falling seconds B of dimethylformaldehyde were measured using a Ostold viscometer in a thermostat kept at C.

The polymerization degree P was determined by the following calculation.

Relative viscosity 7 rel = AZB

Specific viscosity V sp = V rel- 1

Viscosity average molecular weight = (^ sp / C) /1.5 X 10 " ⁴

P = M v /

However, average polymerization unit molecular weight S = (53.0.06Χ7 + ΕΧ ^ + ϋΧα) / I 0 0 C [mol Zl] = C Vm

Where y is the ratio of the polymerization unit formula (1) in the polymer [mol%]

β: Ratio of polymerization unit formula (3) in polymer [mol%]

; Ratio of polymer unit formula (2) in polymer [mol%] E; Molecular weight of polymer unit formula (3)

D: molecular weight of polymerization unit formula (2)

[Relationship between temperature measured at elevated temperature and elongation]

The equipment used is shown in FIG. A loop of 80 mZm in length (40 mm, 2 in two folds) is made of a total of about 30 d of fiber, and this is held using a clip 3 in a ripening cylinder 1 that is open to the upper and lower atmosphere. , Wire ^ A load of 25 mg / d (approx. L, 500 mg, 4) was applied under the hot cylinder. Next, the temperature was raised from around 30 ° C by an average of 40 ° C, and the load position was tracked by the camera 5 and recorded together with the temperature. Figure 1 shows the relationship measured by this method for several acrylic fibers. The elongation percentage [%] was calculated by (load displacement [m no m] / 40 [m / m]) X 100.

[Relaxation shrinkage]

A fiber bundle of about 600 mZm was made from a total of about 900 d fibers, and a load of 0.1 g / d (about 900 g) was applied at room temperature to mark at 500 m / m intervals. . The unloaded fiber bundle was treated without applying tension at 210 ° C. for 30 minutes when dry, and at 130 ° C. for 10 minutes when wet heat. The fiber bundle cooled at room temperature was again subjected to a load of 900 g, and the mark interval A [m / m] was measured.

The relaxation contraction rate [o] was calculated from {(50 0 -A) / 500} × 100.

[Fastness to heat dyeing]

1) Ataryl fiber

The fiber reinforced to 30 to 150 m / m was degreased three times with hot water at a temperature of about 60 ° C and a bath ratio of 1: 200. Acetonitrile-sodium acetate adjusted the pH of the dye solution to about 4.5 (the dye brand, owf is shown in Table 1), and put the above fiber at a bath ratio of 1: 100 at about 60 ° C. ° C temperature rise (approximately 25 minutes) 1 85 ° C maintenance (approximately 10 minutes) 1 98. c Temperature rise (approx. 15 minutes)-Treatment was performed at 98 ° C (approximately 10 minutes).

Next, the above fibers are cooled to about 40 ° C, washed three times with normal temperature water and a bath ratio of 1: 200, and then centrifugally dehydrated to oiling (about 40 ° C, bath ratio of 1: 1). 200, the above moist fiber production process oil) ~ dehydration (the above oil owf 0.3%) ~ dry about 80 ° c for 3 hours. After cooling to room temperature, the moth fibers opened with the hand card were dried and heated 120. cX48 treatment for 8 hours. After cooling at room temperature, the discoloration was evaluated by the gray scale for discoloration (JISL0804) with the aid of the color scale for discoloration and fading, and indicated in the range of the best and worst.

Table 1

2) Raw blanket for electric blanket

The fresh cloth cut into a 20 cm square was dried and treated at i 20 ° C for 48 hours. Then, after cooling at room temperature, the discoloration was evaluated by the discoloration gray scale (JISL0804) with the aid of the discoloration color scale.

3) Surface material for electric car

A force cut into a square of 20 cm was treated with dry heat at 120 ° C. for 48 hours. Then, after cooling at room temperature, the discoloration was evaluated by the discoloration gray scale (JISL0804) with the aid of the discoloration color scale.

[Tension, strong elongation, Young's modulus]

The measurement was performed using a constant-speed extension-type testing machine (Toyo Poldwin UTM-II) based on JIS L1015.

[transparency]

Draw the fibers together with a hand card and cut to a length of 30m / m. 0.04 weighing A 2 Om / m square glass cell was placed together with anisol. The transmittance of light at a wavelength of 562 nm was measured with a spectrophotometer (U-1000, Hitachi, Ltd.), and the transmittance was compared with that of anisol 100%.

[Dyeability]

Approximately 1.5 kg of tow-like fiber is dyed under the following conditions using a high-temperature and high-pressure dyeing machine (Hisaka HU HF212 / 550 type) and dried at 95 ° C for 1 hour or more. After that, the stained state was visually evaluated.

A) Dye Aizer Cathilon Red T-BLH 0.015% owf

"Blue T-BLH 0.03% owf

"Yellow T-BLH 0-15¾owf

Acetic acid 1.0¾ owf

Mouth) temperature

60 ° C temperature rise (about 25 minutes) 198 ° C temperature rise (about 40 minutes) 198. Maintain C (approximately 10 minutes) — Cool at 75 ° C (approximately 25 minutes)

[Extensibility]

The degree of wrapping around a single moth fiber in the stretching bath to the take-up roller was visually evaluated.

[Spinnability]

The acryl fiber was cut to a fixed length of 51 m / m and subjected to the steps of carding, drawing and spinning. The occurrence of frying in each step was visually evaluated.

[Dry moisture content]

Fibers about 1 0-up of the stretching bath up centrifuge - and 3, 0 0 0 r _P mX 2 minutes deliquoring in (domestic centrifuge H 1 0 0 BC-type) and immediately weighed X [^.

Next, the above fibers are washed with warm water of about 60 ° C for 2 hours, and then dried at 95 ° C for 1 hour. After drying for more than an hour and cooling to room temperature, the weight x ₀ [^ was measured.

The dry carry-in moisture ratio [%〗] was determined by the following equation. X — X

X 1 0 0

X 0

[Crystallinity measurement method]

Both ends of the crimped moth fiber 75mgX75m / m length were fixed to the grooved support shown in Fig.3. First, using an X-ray measuring device (Rigaku Denki Geigerflex 2027 type), 2 <? = 5 to 40 by the sample rotation method. The average interference intensity curve was obtained, and this was corrected by air scattering. (This area is defined as T.) Next, each azimuth angle at 2 ° where the influence of crystalline interference is least? The lowest intensity among the five interference intensities was defined as an amorphous interference intensity curve, and this was corrected for air scattering.

The crystallinity [%] was calculated by the following equation. {(T−A) / Ύ} X 100 The X-ray source was filtered at 4 O Kv, 20 mA using a Cu counter cathode and a Ni filter.

[Light fastness]

5 A 2 m (2 inch) spinning of acryl fibers cut at a fixed length of 1 mZm was performed to obtain a spun yarn of 1 / 28th. A circular knitting was obtained using a 316 G circular knitting machine.

After the circular knitting was treated with a blue arc and a carbon arc fade meter (black panel temperature: 63 ° C), discoloration and discoloration were judged. (J I s L 0842)

[Example 1] Monomers AN / S AM PSxZy of various compositions shown in Table 2 Is dissolved in DMF and the catalyst azobisisobutyronitrile (hereinafter abbreviated as AIBN) is used. After polymerization for 17 hours at CX, unreacted monomers were removed by an evaporator to obtain a polymer solution. Table 2 shows the composition and degree of polymerization of the resulting polymer.

The above-mentioned polymer solution was adjusted to a polymer concentration of 26.5% by weight, and a spinning stock solution was fed from the orifice of a 50,000-hole spinneret having a circular cross section of 0.06 m / m in diameter into a coagulation bath DM FZ water-600. / 40 (weight ratio), extruded at 20 ° C, taken up with spinning draft 0.4,

- 3 0 / ^/ 70 (weight ratio), was stretched 8 times 8 5 ° C.

Subsequently, the oil was applied just before washing with water, followed by roller drying at 150 ° C. while giving 15% shrinkage. Furthermore, after the oil is added, the crimp is applied. The crimp set (warm 120 ° C) is subjected to the post-ripening and drying to obtain the 3d acrylic fiber. It had the characteristic values shown in Table 2.

Two

E xp. No. 1 2 3 4 5 Composition Raw material [% by weight] 98.9 / 1.1 97.6 / 2.4 96.9 / 3.1 96.3 / 3.7 93.4 / 6.6

AN / SAHPS polymer [mol%] 99.7 / 0.3 99-3 / 0.7 99.1 / 0.9 98.9 / 1.1 98.0 / 2.0 Degree of polymerization 800 770 820 870 790 Tensile strength [9 / d] (Gel during polymerization 3.5 3.3 3.2 3.0 [%] Chemical spinning is not possible) 3 4 6 12

One

Dry heat relaxation shrinkage * ² [¾] 2 2 3 4

_

Wet heat relaxation shrinkage * ³ [%] 2 2 3 5 Tensile elongation ί%] 1 43 47 48 50 Transparency [% 1 97 95 96 97 Young's modulus [kg f / mm ² ] 510 510 520 430 3-4 3-4 4-3-4 3-4 Staining spots ◎ 〇〇 X Crystallinity 28.2 28.7 27.5 26.0 Remarks Comparative example Example Example Example Example Comparative example

* 1 Elongation: The value at 260 ° C in relation to the temperature measured at elevated temperatures and the elongation.

Tree 2 Dry heat relaxation shrinkage; 2 10 ° C X 30 minutes treatment

* 3 Moisture relaxation contraction rate; 130 ° C x 10 minutes treatment

* 4 Fastness to heat dyeing; dry heat 1 20 ° C x 48 hours

The same applies to the following embodiments.

[Example 2]

AN / methyl acrylate (hereinafter abbreviated as MA) ZS AMP S = x / yX (100-x-y) (weight ratio) is dissolved in DMF, and the catalyst is heated to 68 ° CZ1 using AIBN. After polymerization for 7 hours, unreacted monomers were removed with an evaporator to obtain a polymer solution. Table 3 shows the origin and degree of polymerization of the produced polymer. However, for EXP. No. 9, sodium methallyl sulfonate (hereinafter abbreviated as SMAS) was used in place of SAMPS. Thereafter, the same treatment as in Example 1 was performed to obtain 3d acrylyl moth fiber.

The obtained Acryl moth fiber had the characteristic values shown in Table 3.

Three

* SMAS

[Example 3]

Polymers having the compositions and degrees of polymerization shown in Table 4 were prepared by the DMF solution polymerization method in the same manner as in Example 1. However, only Exp. No. 14 was prepared by dimethyl sulfoxide (hereinafter abbreviated as DMS 0) solution polymerization method.

The above polymer was dissolved in DMF to produce a spinning urine having the polymer concentration shown in Table 4, which was coagulated from the orifice of a 50,000-hole spinneret with a circular cross section of 0.06 m / m in diameter. Bath DMF / water = 60/40 (weight ratio), extruded at 20 ° C, taken up by spinning draft 0.4, DMFZ water = 30-70 (weight ratio), 85 ° C Stretched 8 times.

Next, after washing with water, it was shrunk by 10% at a wet heat of 120 ° C. Continue to apply oil before-roller drying (150 ° C)-apply oil after-clean crimp set (moist heat 120.C)-apply post-drying and apply the denier shown in Table 4 Acryl fiber was obtained.

The fibers obtained had the characteristic values shown in Table 4.

Cv5

CJ1 U1 Table 4

E xp. No. 1 0 1 1 1 2 1 3 1 4 Polymerization solvent DMF DMF DMF DMF DNS 0 Polymer crude AN / SAMPS [mol%] 98.7 / 1.3 98.9 / 1.1 99.0 / 1.0 99.2 / 0.8 99.3 / 0.7 Polymerization Degree 310 700 820 1,300 2,000 Density of polymer of spinning stock solution [wt%] 32.0 28.0 26.5 22.0 15.0 Denier [d] 3.2 2.8 2.7 2.2 1.5 Tensile strength / d] 2.5 3.2 3.5 4.2 4.8 Elongation] 12 6 4 2 2 Dry heat Relaxation shrinkage] 5 3 2 1 1 Wet heat relaxation shrinkage] 7 3 2 1 1 Stretching bath stretchability X 〇〇〇 X Tensile elongation [%] 35 40 42 37 30 Transparency] 70 92 93 90 90 Young's modulus [ kgf / mm ² ] 250 410 550 630 730 Fastness to heat dyeing 3 4 3 4 3 4

Crystallinity] 27.0 28.0 29.5

Remark Comparative example Example Example Example Example Comparative example

[Example 4]

A polymer solution having the composition and degree of polymerization of Exp. No. 3 of Example 1 was dissolved in DMF to adjust the polymer concentration to 26.5% by weight. Coagulation bath DMF / water = 60 ° 40 (weight ratio) from the hole spinneret orifice, extruded at 20 ° C, and taken up with spinning draft 0.4, then DMFZ water-30 / 7 0 (weight ratio), 85. The film was stretched in C at the magnification shown in Table 5.

Thereafter, the same treatment as in Example 3 was performed to obtain a 3d acrylic fiber. 'The resulting fibers had the characteristic values shown in Table 5.

Table 5

Ex-No-15 16 17 18 Stretching ratio 3 7 9 12 Base orifice 0.04 0.06 0.07 0.08 Diameter [m / m] Stretching bath stretchability ◎ ◎ 〇 X Dry carry-in moisture content (%) 210 140 120 Tensile strength [d] 1.9 3.2 3.5 Single yarn break multiple elongation [%] 6 4 4-Dry heat relaxation shrinkage [¾] 2 2 2-Wet heat relaxation shrinkage [%] 3 3 2-Tensile elongation [% ] 50 42 38-Transparency] 85 93 92-Yank rate Lkgf / ram ² ] 230 490 530 Heatfast dyeing fastness 3-4 3-4 Crystallinity 24.7 28.0 28.3 Remarks Comparative example Working example Working example Comparative example

[Example 5]

The spinning stock solution having the composition of EXP. No. 3 of Example 1 and the degree of polymerization of DMF dissolved in DMF to adjust the polymer concentration to 26.5% by weight has a circular cross section of 0.06 m // m in diameter. Coagulation bath DM FZ water = 60% 40% by weight) from the spinneret's orifice of 50,000 holes, extruded at 20 ° C, and taken out by the spinning draft shown in Table 6 / Water = 30/70 (weight ratio), 85. The film was stretched 8 times with C.

Next, after washing with water, it was shrunk at a heat of 120 ° C. at a rate shown in Table 6. However, only EXP. No. 19 was subjected to the following steps immediately after oil washing. Continue oil drying with one roller drying (150 ° C)-post oil applying crimp applying crimp set (moistened 120.C) After drying, 3d acryl fibers are removed. Obtained.

The fibers obtained had the characteristic values shown in Table 6.

Table 6

Exp. No. 19 20 21 22 Spinning draft 0-3 0.3 0.3 0.4 Shrinkage [%] 1 5 10 20 Tensile strength ^ / d] 4.4 3.8 3.4 3.0 Elongation [%] 4 4 4 5 Dry heat relaxation shrinkage [%] 2 2 2 2 Moisture heat relaxation shrinkage] 3 2 2 2 Tensile elongation] 30 37 44 50 Transparency] 94 92 92 90 Young's modulus [kgf / mm ² ] 640 590 530 410 Heat-resistant color fastness 3-4 3 ~ 4 3-4 3-4 Crystallinity [%] 28.0 28.5 28.3 28.0 Spinnability X 〇〇 ◎ Remarks Comparative example Working example Working example Working example

[Example 6]

A polymer having the composition and degree of polymerization of Exp. No. 3 of Example 1 was dissolved in DMSO to adjust the polymer concentration to 26% by weight, and the spinning stock solution having a circular cross section of 0.06 mZm in 20,000 holes was prepared. Coagulation bath DM S0 / water-60 / 40 (weight ratio) from the spinneret orifice at 22 ° C, after taking out with a spinning draft 0.4, hot water at 98 ° C And stretched 7 times.

Next, after washing with water, it was shrunk by 10% at a wet heat of 120 ° C. Apply oil before roll-drying (150 ° C) — Apply oil after — Apply crimp — Crimp set (moist heat 120 ° C) — Dry afterwards to obtain 3d acrylic fiber Was.

The obtained fiber has a tensile strength of 3.4 / d, an elongation of 5%, a dry heat relaxation / shrinkage rate of 2%, a wet heat relaxation / shrinkage rate of 3%, a tensile elongation of 40%, and a transparency of 88%. , Young's modulus; 500k fZ marauding ² , heat-resistant color fastness;

[Example 7]

A polymer solution having the composition and degree of polymerization of Exp. No. 3 of Example 1 was dissolved in dimethylacetamide (hereinafter abbreviated as DMAc) to adjust the polymer concentration to 22% by weight. The orifice of a 20,000-hole spinneret having a circular cross section of 0.08 m / m in diameter from the coagulation bath DM Ac water = 55/45 (weight ratio), 25. Extruded into C and taken up with spinning draft 0.5, 98. The film was stretched 9 times in hot water of C.

Thereafter, the same treatment as in Example 6 was performed to obtain 3d acryl fibers.

The obtained acryl fiber has a tensile strength of 3.7 Zd, an elongation of 4%, a dry heat relaxation shrinkage of 2%, a wet heat relaxation shrinkage of 2%, a tensile elongation of 40%, and a transparency of 89%. Young's modulus; 49 Ok ^ f / rara ² , fastness to heat-resistant dyeing; Indicated.

[Example 8]

A polymer having the composition and degree of polymerization of Exp. No. 3 of Example 1 was dissolved in 70% nitric acid, and the spinning stock solution adjusted to a polymer concentration i of 6% by weight was cut into a circular cross section having a diameter of 0.1 mZm. It was extruded from a 20,000 hole spinneret orifice into a coagulation bath of 35% nitric acid, 3.0, taken out with a spinning draft of 0.5, and then stretched 9 times in ripened water at 98 ° C.

Next, after washing with water, it was shrunk by 10% at a wet heat of 120 ° C. Subsequently, pre-oil application and roller drying (1i5.C) and post-oil application and crimp application—crimp set (wet heat 120.C) —post-drying were performed to obtain 3d acryl fibers.

The resulting acryl fiber has a tensile strength of 3.6 Zd, an elongation of 4%, a dry heat relaxation shrinkage of 2%, a wet heat relaxation shrinkage of 2%, a tensile elongation of 41% and a transparency of 93%. , Young's modulus; 4 8

Fastness to heat resistance;

[Example 9]

A spinning solution prepared by dissolving a polymer having the composition and degree of polymerization of Exp. No. 3 of Example 1 in sodium thiocyanate water = 50/50 (weight ratio) to adjust the polymer vagueness to 12% by weight The orifice of a 20,000-hole spinneret having a circular cross section of 0.08 mZm in diameter from the coagulation bath sodium thiocyanate / water-50-50 (weight ratio), —3. After being extruded into C and taken out by spinning drafts 0 and 3, it was stretched 9 times in hot water at 98 ° C.

Thereafter, the same treatment as in Example 8 was performed to obtain 3d acryl fibers.

The obtained acryl fiber has a tensile strength of 3.4 Zd, an elongation of 4%, and a dryness. Mature relaxation shrinkage; 2%, wet heat relaxation shrinkage; 3%, tensile elongation; 43%, transparency; 97%, Young's modulus; 46 Ok ^ f / mm ² , fastness to heat resistance; Class 4 was shown.

[Example 10]

A polymer having the composition and degree of polymerization of Exp. No. 3 of Example 1 was dissolved in zinc chloride Z calcium chloride Z water = 45/15/40 (weight ratio), and the polymer concentration was 10% by weight. % Of the spinning stock solution adjusted to 25% by weight from a 20,000 hole spinneret orifice having a circular cross section of 0.1 mZm in diameter and a coagulation bath zinc chloride water = 45/5 (weight ratio) at 25 ° C. After drawing at a draft of 0.3, it was stretched 9 times in hot water at 98 ° C.

The obtained acrylic fiber has a tensile strength of 3.4 d, an elongation of 6%, a dry relaxation shrinkage of 3%, a wet heat relaxation shrinkage of 3%, a tensile elongation of 44% and a transparency of 87. %, Young's modulus; 44 Ok f / mm ² , fastness to heat-resistant dyeing;

[Example 11]

The polymer having the composition and degree of polymerization of EXP. No. 3 of Example i was dissolved in DMF, the polymer concentration was adjusted to 30% by weight, and the spinning stock solution heated to 125 ° C was 0.2 mZm in diameter. It was extruded from the orifice of a spinneret having a circular cross section of 1,000 holes into hot air heated to 210 ° C, and was taken off at 300 m / min. The single moth fiber size was 14 denier.

Next, the film was stretched 6 times in hot water at 9.8 ° C, washed with water, and shrunk by 10% at 120 ° C with wet heat. Apply oil before pulling gun-Roller drying (115 ° C)-Apply oil after crimping-Crimp set (Moist heat 120.C) —After drying, 3d acrylic fiber was obtained.

The obtained acrylic fiber has a tensile strength of 2.9 ^ / d, an elongation of 6%, a dry heat relaxation shrinkage of 3%, a wet heat relaxation shrinkage of 3%, a tensile elongation of 50% and a transparency. 85%, Young's modulus; 410 k ^ f / mm \ Heat fastness;

[Example 12]

A polymer having the composition and degree of polymerization of Exp. No. 3 of Example 1 was dissolved in DMF, and the spinning dope adjusted to a polymer concentration of 30% by weight had a circular cross section with a diameter of 0.15 m / m. After being once extruded into the air from the orifice of the spinneret of the 00 hole, it was guided to a coagulation bath DMFZ water = 60 to 40 (weight ratio), 20 ° C, and taken out by the spinning draft 2.2. At this time, the distance between the spinneret surface and the coagulation bath surface was 5 mZm. Draw gun Stretched 9 times in hot water at 98 ° C. Thereafter, the same treatment as in Example 6 was performed to obtain 3d acryl fibers.

The resulting acryl fibers have a tensile strength of 3.7 d, an elongation of 4%, a dry heat relaxation shrinkage of 2%, a wet heat relaxation shrinkage of 2%, a tensile elongation of 37%, and a transparency of 93%. Young's modulus; 55 0 k Z醫^2, heat fastness, showed 3 to quaternary.

Examples 13 to 21 and Comparative Examples 1 to 6

(1) An acryl-based polymer having the composition and degree of polymerization shown in Table 7 was dissolved in dimethylformamide (hereinafter abbreviated as DMF) to obtain a spinning stock solution having a polymer concentration of 26.5% by weight. Coagulation bath DMF water = 60/40 (weight ratio), extruded from a 80,000-hole orifice with a circular cross section with a diameter of 0.055 mZm at 20 ° C, and taken out with a spinning draft of 0.4 Then, DMFZ water = 30 to 70 (weight ratio) and stretched 8 times at 85 ° C. After the washing and application of the pre-oil, the roller was dried at 150 with a shrinkage of 15%. Further, post-oil application-crimp application-crimp set (moistened 120.C)-post-drying was performed to obtain 2d acrylic fiber.

The obtained acrylic fiber had the characteristic values shown in Table 7. Fig. 4 shows the relationship between the elongation rate of Riml (curve ①), 2 (curve ②) and 5 (curve ③) measured at elevated temperatures.

Table 7

The meaning of each note in Table 7 above is as follows.

2-Acrylylamide-2-sodium methylpronosulfonate (s

AMP S)

* ² Abbreviation for methyl acrylate

* ³ The relationship between temperature and elongation measured at elevated temperature at 260 ° C Value,

* ⁴ Dry heat 2 1 0 ° c x 30 minutes treatment,

* ⁵ Sodium methallylsulfonate was used instead of SAMPS.

(2) Cut the acrylic fibers of Run Nos. 1 to 5 into a fixed length of 51 mm, and then spin 2-inch spinning to ¹ / ^ 2 count (Examples 19 to 21 and Comparative Example 5,

For 6 was obtained spun yarn of ^_2/52 cotton count).

Next, a woven fabric is produced with the structure, threading, and density shown in Table 8, and then the following fabrics are sequentially dyed by the following steps: refining, dyeing, reduction washing, sorbing, drying, finishing, and finishing. Obtained. O

For dyeing, disperse dyes (Dyanix, manufactured by Mitsubishi Kasei Corporation) and cationic dyes (Estol, manufactured by Sumitomo Chemical Co., Ltd.) were used as dyes, and Sun Salt CI-12 (as an auxiliary agent) was used. Nichika Chemical Co., Ltd.), Unisalt 5 M (Meisei Chemical Co., Ltd.) and sodium acetate Z 齚 O. In the dyeing bath, the temperature was raised from 60 to 130 ° C. at a rate of about I ° C., and the test was carried out at 130 ° C. for 15 minutes. Reduction washing was carried out in a bath containing hydrosulfite and caustic soda at 80. c for 15 minutes, and sorbing was carried out at 70 ° C. for 10 minutes in a bath containing Meisanol L-80 (manufactured by Meisei Chemical Co., Ltd.).

Table 9 shows the evaluations of the obtained mixed fabrics.

Table 9

Examples 22 to 27 and Comparative Examples 7 to 10

(1) An acryl-based polymer having the composition and the degree of polymerization shown in Table 10 was dissolved in dimethylformamide (hereinafter abbreviated as DMF), and the spinning dope was adjusted to a polymer solubility of 26.5% by weight. Coagulation bath DM FZ water = 60 / from the 90,000 hole spinneret orifice with a circular cross section of 0.05 mZm in diameter 40 (weight ratio), 20. After being extruded into c and taken out by a spinning draft of 0.4, it was stretched 8-fold at DMF / water-30Z70 (weight ratio) at 850 ° C. After pulling, washing and applying the oil before, the roller was dried at 150 ° C. while giving 15% shrinkage. Further, post-oil application-crimp application-crimp set (moist heat: 120 ° C) -post-drying was performed to obtain 1.5 d agrill fiber.

The obtained acrylic fiber had characteristic values as shown in Table 10.

Table 10

(2) After cutting the acrylic fiber of Run No. 6-10 into fixed length of 38 orchids, it was ¹ / _{18th by} open-end spinning method (Examples _{22 to} 24 and Comparative Examples 7 and 8). ) And ¹ / _26th count (Examples 25-27 and Comparative Examples 9, 10) were obtained.

Next, a knitted fabric was made with the structure and threading shown in Table 11, and then the following process steps were performed, followed by dyeing, reduction cleaning, soaking, drying, finishing, brushing, and shading. A cross-woven fabric was dyed after one ring and finish set. Table 11

Dyeing, reduction washing, and sorbing were performed in the same manner as in Example 13. Table 12 shows the evaluation of the obtained knitted fabric.

Table 12

Examples 28 to 30 and Comparative Examples 11 and 12

(1) An acryl-based polymer having the composition and degree of polymerization shown in Table 13 was dissolved in dimethylformamide (hereinafter abbreviated as DMF), and the spinning dope obtained by adjusting the polymer concentration to 26.5% by weight was used. 0.1 Extruded from a 10,000-hole spinneret orifice with a circular cross section of 1 mm into a coagulation bath (DMFZ water-60 / 40 (weight ratio)) at 20 ° C and taken up with a spinning draft of 0.4 , DMFZ water = 30-70 (weight ratio) 85. The film was stretched 8 times with C.

After the washing and the application of the pre-oil, the roller was dried at 150 ° C. while giving 15% shrinkage. Post-oiling crimping — crimp set (moist heat 120 ° C) — post-drying, single-filament 10d acrylyl moth I got a fiber.

After staining the brown (dark) showing 1 5 2 constant length cut was the fiber in Table 1, subjected to semi-worsted spinning, to obtain a spun yarn of ¹ eight fastest. Next, the backing of the fabric obtained was tufted (pile weight: 350 ^ / m ² ) on a base fabric made of polypropylene moth fiber (yarn density, 22 wefts per inch, warp: 15 per inch). solids 4 8% by weight of the latex (Borima component 1 2 wt%, calcium 35 wt carbonate%, anti-aging agent 1% by weight) after a 6 0 0 Roh m ² was applied, 1 4 0 C 1 5 minute dry did.

The obtained acryl fiber and electric power surface material had the characteristic values shown in Table 13.

Table 13

The meaning of each note in Table 13 above is as follows.

* 1 2—Acrylamide—2—Abbreviation for sodium methylpropanesulfonate

Abbreviation for methyl acrylate

* 3 The value at 260 ° C in the relationship between the temperature measured at elevated temperature and the elongation,

* 4 Dry heat 1 20 ° cx 4 8 hours treatment, * 5 Drying 2 1 0 ° cx 30 minutes treatment,

* 6 Sodium methallylsulfonate was used instead of SAMPS.

Examples 31 to 33 and Comparative Examples 13 and 1 4

(1) Chap .: An acryl polymer having the composition and the degree of polymerization shown in Table 4 was dissolved in dimethylformamide (hereinafter abbreviated as DMF), and the lysis degree of the polymer was adjusted to 26.5% by weight. From a 50,000 hole spinneret orifice with a circular cross section of 0.06 mm in diameter into a coagulation bath (DMF water-60 / 40 (weight ratio)) at 20 ° C. After picking up at 0.4, it was stretched 8 times at 85 ° C. in DMFZ water−30Z70 (weight ratio).

After pulling, washing and applying the pre-oil, the roller was dried at 150 ° C while applying 15% shrinkage. Further, the post-oil-applied crimp-applied crimp set (moist heat: 120 ° C.) and post-drying were carried out to obtain acryl fibers having a single yarn of 3 d.

The above fibers cut at a fixed length of 76 mm were dyed into the tea (dark color) shown in Table 1, and then woolen and spun to obtain a spun yarn of _5th .

A polyester spun yarn using the above acrylic spun yarn as the weft. ) Is used as a warp to make a double-woven fabric (density: 18 weft Z-inch, warp 32 / inch), brushed 5 times, sheared 2 times, electric blanket Was obtained. Next, an electric blanket was obtained at room temperature using the above-mentioned raw cloth. The obtained acrylic fiber and raw cloth for electric blanket had the characteristic values shown in Table 14. Table 14 Example 31 Example 32 Example 33 Comparative example 13 Comparative example 14

AN / SAMPS * ¹ QQ Q * JQ 1 qq i QQ 1 QQ Q polymer [mol%] / 0.9 / 0.9 / 0.9 / 0.9 / 0 ⁵ composition AN / MA * ² 100 100 100 100 100

/ 0 /1.0 /2.9 / 7-2 /9.4

820 820 815 800 815

C ³ 3 3 5 15 C240 ° c

[Cut in%]) Heat-resistant dyeing fastness 3-4 3-4 3-4 4 2-3-5 and 5-3 degrees * 4 [grade]

Relaxation contraction rate 9 0 0

o D 丄 ¾ [%] Young's ratio 51 Π on CA

4 U oDU [kgf / mm ² ] Tensile strength 3.5 QAQ o (\

· 0 ύ o-u * U [g / d] Tensile elongation 43 45 48 50 49

[%] Raw blanket for electric blanket

Fastness to heat dyeing 3 3 0

丄 * ϋ * ⁴ [Grade] Raw cloth for electric blanket 〇〇 △ ~ x X Het * ⁷ ◎

The meaning of each note in Table 14 above is as follows.

* 1 Abbreviation of 2- atarylamide-2-methylprononesulfonic acid,

* 2 Abbreviation for methyl acrylate

* 3 The value at 260 ° C in relation to the temperature and elongation measured at elevated temperature.

* 4 Dry heat 1 20 ° C X 48 hours treatment,

Dry heat 2 10 ° C x 30 minutes treatment,

* 6 Sodium methallylsulfonate was used instead of SAMPS.

* 7 The raw fabric surface condition after dry heat treatment at 210 ° C for 30 minutes was visually evaluated.

Example 34

A yellow pigment (Hoechst Green GG01) ground to an average particle size of about 1 was dispersed in dimethylformamide (hereinafter abbreviated as DMF).

An acryl polymer having the composition and the degree of polymerization shown in Table 15 was dissolved in DMF and added to and mixed with the above-mentioned pigment dispersion to obtain a polymer having a polymer content of 25% by weight and a pigment concentration of 2%. Was prepared.

The above spinning stock solution was extruded from a 80,000-hole spinneret orifice having a circular cross section of 0.055 mZni in diameter, at a coagulation bath DM FZ water = 60/40 (weight ratio), at 20 ° C, and taken up with a spinning draft of 0.4. DMFZ water = 30/70 (weight ratio), stretched 8 times at 85 ° C.

Subsequently, the oil was applied immediately before washing with water, followed by roller drying at 150 ° C. while giving 15% shrinkage. Crimping with oil after crimping (moist heat: 120 ° C)-After drying, 2d ataryl fiber is obtained. Was.

The obtained acryl fiber had the characteristic values shown in Table 15 and Table 15

The meaning of each note in Table 15 above is as follows.

* 1 2-Acrylamide 2 Abbreviation for sodium monomethylprononsulfonic acid

* 2 Abbreviation for methyl acrylate,

* 4 Dry heat 2 1 0 ° cx treatment for 30 minutes,

* 5 Sodium methallylsulfonate was used in place of S AMP S.

Example 3 5

Run No. 1 acryl fiber was cut to a fixed length of 51 niZm and spun for 2 mm to obtain a spun yarn of 2Z34 count. Next, using the above-mentioned spun yarn, a plain woven fabric having a density of 73 pieces of warp and 73 pieces of weft Z-inch was obtained.

5 parts by weight of Asahigard AG-710 (fluororesin waterproofing agent, made by Asahi Glass), 1 part by weight of High Softer K-10 (manufactured by Meisei Chemical), 2 parts by weight of isopropanol, 92 parts by weight of water After being immersed in a treatment bath consisting of a portion, the squeezing rate was reduced to 50%. Then 100. After drying in C 150. Heat treated in C.

Further, the above woven fabric was immersed in a treatment bath composed of 20 parts by weight of boron coat (a silicone resin-based waterproofing agent, manufactured by Shin-Etsu Chemical Co., Ltd.) and 80 parts by weight of trichloroethylene, and the squeezing ratio was reduced to 40%. Then 100. After drying in C 160. Heat treated with C.

The obtained waterproof cloth has a water content of 100 {JISL 1 092 spray Method, water resistance 25.8 cm {JISL1092A method (low water pressure method)}, light fastness class 4 or higher (JISL0842 third exposure method), elongation at dry heat of 140 ° C Vertical 1%, horizontal 0%. In addition, dry ripening 140. The elongation at C was measured by the following method. The upper end is fixed to the base. A grip of 50 mm width is sandwiched between the upper ends of a waterproof cloth cut to 25 mm width and 150 mm length. Next, the lower edge of the waterproof cloth was sandwiched between a 50 mm grip with a weight adjusted to 50 g in accordance with the weight of the clamp. The waterproof cloth was marked so as to have an interval of 100 mm. Next, the waterproof cloth suspended on the gantry was treated at a dry heat of 140 ° C. for 24 hours. After cooling to room temperature, the mark interval A [mm] was measured. The elongation was calculated by ((A-i 0 0) no 1 0 0) XI 0.0.

Claims

The scope of the claims

1. (A), (a) The following equation (i)

C H 2-C H-

C≡NCI)

A polymerized unit represented by 5 and

The following equation (2)

-C H 2-C H ^-

C 0 CH ₃ .

I I C2)

NH - C one CH ₂ - S0 ₃ M

CH ₃

10 where M is a hydrogen atom or an equivalent cation,

Consisting essentially of polymerized units represented by

(b) the polymerized unit (2) accounts for 0-4 to 1.5 mol% based on the total of the polymerized unit (1) and the polymerized unit (2), and

(c) the degree of polymerization is in the range of 600 to 1,500,

J5 Acrylonitrile copolymer,

(B) the tensile strength is in the range of 2-5 gZd, and

(C) The elongation at 260 ° C is not more than 10% in the relationship between the temperature and the elongation measured at elevated temperature.

Acryl fiber characterized by the fact that:

20 2. (AO (a) a polymerized unit of the above formula (1), a polymerized unit of the above formula (2) and a polymerized unit of the above formula (2) derived from a monomer copolymerizable with acrylonitrile; Consists essentially of polymerized units represented by different polymerized units (3),

(b) The polymerized unit (1) and the polymerized unit (2)

(2) accounts for 0.4 to 1.5 mol% and the polymerized unit (3) is the polymerized unit. Less than 5% by weight based on the position (1),

(c) the degree of polymerization is in the range of 600 to 500,

It is made of an attarilonitrile copolymer,

(B) the tensile strength is in the range of 2-5 g / d, and

(C) In the relationship between the temperature and the elongation measured at elevated temperature, the elongation at 260 ° C is 10% or less;

Acryl fiber, characterized in that:

3. Acryl fiber according to claims 1 or 2 attached with a crimp

4. The acryl fiber according to claim 1 or 2, having a dry heat relaxation shrinkage at 210 ° C of less than 3%.

5. The acryl fiber according to claim 1 or 2, wherein the ripening relaxation shrinkage at 130 ° C is less than 3%.

The acrylic fiber according to claim 1 or 2, wherein the elongation is in the range of 35 to 60%.

7. The acrylic fiber according to claim 1 or 2, which has a transparency of at least 80%.

8. Akuriru娥維to in 1 or 2 according to Young's modulus is in the range of 4 00~ 70 OkgZ discussions ^2.

9. The acryl fiber according to claim 1 or 2, wherein the fastness to heat dyeing (120 ° C x 48 hours) is at least grade 3.

10. The acryl fiber according to claim 1 or 2, having a crystallinity of 20 to 40%.

1 1. The polymerized unit (3) has the following formula R

-^ CH ₂ -C-C3)

Y where R is a hydrogen atom or a methyl group, and Y is a group represented by one COO X (where X is a hydrogen atom, a sodium or methyl group), one OCOCH ₃ , one C _3. The acryl fiber according to claim 2, which is a group selected from the group consisting of ONH ₂ , C ₆ H ₅ , —CH ₂ S 0 ₃ Na and C ₆ H ₄ SO ₃ Na.

1 2. (1) Extruding the spinning solution of the acrylonitrile copolymer specified in Claim 1 or Claim 2 from the orifice of the spinneret to generate a fine stream of the spinning solution.

(2) stretching the rivulet 5 to 10 times while coagulating to produce a drawn yarn,

(3) heating the drawn yarn to shrink it by 3 to 25%, and

(4) subjecting the obtained shrink yarn to a drying step,

A method for producing acryl fibers, characterized in that:

1 3. A cross-knitted / cross-woven fabric of an acrylic fiber and an aromatic polyester fiber, characterized by containing the acryl fiber of claim 1.

14. A mixed knitting according to claim 13, wherein the aromatic polyester of the aromatic polyester moth is a homo- or copolyester of ethylene terephthalate having ethylene terephthalate as a main repeating unit. ♦ Exchange

1 5. A cross-knitted / cross-woven fabric of acrylic fiber and aromatic polyester fiber, characterized by containing the acryl fiber of claim 2.

1 6. The aromatic polyester of the aromatic polyester fiber is a homopolymer of ethylene terephthalate whose main repeating unit is ethylene terephthalate. Or the cross-knitted / cross-woven fabric according to claim 15, which is a copolyester.

17. A surface material for an electric carpet, comprising the acrylic fiber according to claim 1.

18. A surface material for an electric carpet, characterized by containing the acryl fiber of claim 2.

1 9. An electric carton having the surface material of claim 17.

20. An electric carton having the surface material according to claim 18.

21. A raw fabric for electric blanket, comprising the acrylic fiber of claim i.

22. A raw fabric for electric blanket, characterized by containing the acrylic fiber of claim 2.

23. An electric blanket having the raw cloth according to claim 21.

24. An electric blanket having the raw cloth according to claim 22.

25-A waterproof cloth characterized in that the cloth comprising the acrylic fiber according to claim 1 is used as a base cloth.

26. A waterproof cloth, characterized by using a cloth made of the acryl fibers of claim 2 as a base cloth.

27. The waterproof cloth according to claim 25 or claim 26, wherein the acrylic fiber is undiluted.

28. A fabric comprising the acrylic fiber specified in claim 25 as a base fabric of the waterproof cloth in claim 25.

29. A fabric comprising the acrylic fiber specified in claim 26 as a base fabric of the waterproof cloth according to claim 26.