JPH08325869A - Special heterogeneously shrinkable blended polyester yarn - Google Patents

Abstract

PURPOSE: To obtain the special heterogeneously shrinkable blended yarn suitable for silky woven striped fabrics having good swelling, soft touch, drape, tension and dry touch by using low shrinkable fibers and high shrinkable fibers which comprise polyesters having specific compositions, respectively. CONSTITUTION: A polymer for low shrinkable fibers and polyethylene terephthalate copolymerized with 2,2-bis 4-(2hydroxyethoxyphenyl)propane and bis 4-(2hydroxyethoxyphenyl)sulfone in specific mol.% are melt-spun, respectively, and subsequently blended with each other to obtain the heterogeneously shrinkable blended yarn having a shrinkage difference of 5-25% between both the components. Therein, the polymer for the low shrinkable fibers is obtained by compounding polyethylene terephthalate with polyethylene glycol having a weight-average mol.wt. of 4000-50000 and alkyl(benzene) sulfonic acid alkali salts of formulas I and II (R,R<1> are a 8-20C alkyl; M,M<1> are Li, Na, K) in a ratio satisfying the following inequalities: 0.5 <=e P(a)<=5, 0.5<=P(b)+P(c)<=4, and 0<=P(c)<=1 [P(a), P(b) and P(c) are the weight (wt.%) of the polyethylene terephthalate, the weight of the compound of formula I and the weight of the compound of formula II].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester differential shrinkage mixed yarn. More specifically, the low shrinkage fiber is made of polyethylene terephthalate having a specific composition, and the high shrinkage fiber is made of copolymerized polyethylene terephthalate having a specific composition, which is usually required for a silky woven or knitted fabric by subjecting it to an alkali weight reduction treatment. The present invention relates to a polyester different shrinkage mixed yarn which gives a silky woven or knitted fabric having a unique dry touch and a feeling of kneading as well as a feeling such as swelling, softness, drape, elasticity and elasticity.

[0002]

2. Description of the Related Art Conventionally, woven and knitted fabrics using different shrinkage mixed fiber yarn are
It is known that swelling, softness, drape, elasticity, elasticity, etc., and rich silkiness are common methods for producing heterogeneous shrinkage mixed yarns, including a spinning mixed fiber method, a mixed fiber method during drawing, Examples include a post-mixing method of drawn yarn.

Among these, high shrinkage and low shrinkage
The spinning and blending method, in which various types of polyesters are spun using a complex spinning equipment, polyester blended undrawn yarns are obtained in the spinning step, and this is stretched, is the most excellent in terms of productivity. JP-B-51-30620 discloses a method of using a copolyester as the high shrinkable fiber and a polyester having no copolymerizable component as the low shrinkable fiber in the spinning mixed fiber method. Although a heterogeneous-shrink mixed yarn in which a yarn length difference is caused by a dry heat treatment at 200 ° C. is described without causing much length difference, a woven or knitted fabric having a sufficient bulge is obtained from the different-shrink mixed yarn. Not be
It is impossible to obtain a silky knitted fabric that is satisfactory in terms of texture.

Further, in JP-B-60-35450 and JP-A-55-57013, polyethylene terephthalate having no copolymerization component as a low shrinkage fiber component and 2,2-bis as a high shrinkage fiber component are disclosed. {4- (2-hydroxyethoxyphenyl)} propane (hereinafter, BAE
A mixed shrinkage yarn using BAEO copolymerized polyethylene terephthalate containing 5 to 15 mol% of (O)) based on the total glycol component and a woven fabric composed of the mixed yarn are proposed.

Similarly, Japanese Examined Patent Publication No. 61-13009 also has a difference in shrinkage rate of boiling water, and a low shrinkage fiber is a polyester such as polyethylene terephthalate and a high shrinkage fiber is a co-polyester. As a specific example of the copolymerized polyester, an example of BAEO copolymerized polyethylene terephthalate in which 10 mol% of BAEO is copolymerized is described in detail.

However, BAEO-copolymerized polyethylene terephthalate obtained by copolymerizing BAEO in the proportions described in these publications is characterized in that it is almost the same as the non-copolymerized polyethylene terephthalate in terms of the alkali weight loss rate. However, there is a problem in light fastness after dyeing and dry cleaning resistance, and the use is considerably limited.

Further, in JP-A-2-19528, JP-A-2-19539, JP-A-4-100932 and JP-A-4-119134, in order to improve light fastness after dyeing, An IPA / BAEO copolymer obtained by copolymerizing polyethylene terephthalate as a low shrinkage fiber component, isophthalic acid (hereinafter referred to as IPA) as a high shrinkage fiber component, and BAEO at 4.8 mol% or less or 4.6 mol% or less. There has been proposed a different shrinkage mixed yarn using polymerized polyethylene terephthalate or a woven fabric composed of these different shrinkage mixed yarn.

However, in order to impart a sufficient silky property to a woven or knitted product, the copolymerization ratio of BAEO must be made considerably low, so that it is necessary to increase the copolymerization ratio of IPA considerably. As a result, the alkali weight loss rate was almost the same as that of the non-copolymerized polyethylene terephthalate, and the light fastness and dry cleaning resistance after dyeing were considerably improved, but the melting point was considerably high. The problem of lowness arises and the application is quite limited.

In Japanese Patent Laid-Open No. 4-228634, polyethylene terephthalate is used as the low shrinkage fiber component and 2,2-bis {4- (2-hydroxyethoxyphenyl)} sulfone (hereinafter referred to as BSEO) as the high shrinkage fiber component. A different shrinkage mixed yarn using BSEO copolymerized polyethylene terephthalate in which 3) or more of 3) is copolymerized with respect to all glycol components has been proposed. However, as judged from the specification, in order to impart sufficient silkiness to a woven or knitted product, it is necessary to increase the copolymerization ratio of BSEO to about 7 mol%, and IPA is also copolymerized at the same time. If the BSEO copolymerization ratio is 4.5 mol%
As a result, although the light fastness after dyeing and the dry cleaning resistance are sufficiently improved, on the contrary, the alkali weight loss rate is significantly faster than that of polyethylene terephthalate which is not copolymerized. There are problems and the applications are quite limited.

In the above-mentioned different shrinkage mixed yarns or woven and knitted fabrics composed of these different shrinkage mixed yarns, all the low shrinkage fibers are polyesters such as polyethylene terephthalate having no special mixture or copolymerization component. By fibrillating the low-shrinkage fiber by alkali reduction treatment, or by expressing fine pores on the surface of the low-shrinkage fiber, swelling,
In addition to the soft feel, drape, firmness, and firmness, it is not intended to add a special texture such as dry touch, crease feeling, or downy hair touch at the same time.

In Japanese Unexamined Patent Publication (Kokai) No. 6-41836, a high shrinkage fiber having an alkali dissolution rate constant k is a specific value or less, and a difference from the low shrinkage fiber k is in a specific range. A technique for manufacturing a silky fabric having a downy touch by completely fibrillating low shrinkage fibers by subjecting a woven or knitted fabric composed of yarns to alkali reduction treatment is disclosed. As a specific example, polyethylene glycol having a molecular weight of 20,000 (hereinafter referred to as PE
Polyethylene terephthalate containing 0.8% by weight of G) and 0.4% by weight of an alkali metal salt of an alkylsulfonic acid having an average carbon number of 12 (hereinafter referred to as ASA) is used. Examples are given in which polyethylene terephthalate having no mixture or copolymer component is used.

Regarding a single yarn instead of a mixed yarn, a polyester containing a polyalkylene ether and an alkali metal salt of alkylbenzene sulfonic acid (hereinafter referred to as BSA) is treated in an alkali reduction treatment in Japanese Patent Publication No. 47-11280. Then, a method for obtaining a fiber having on its surface fine pores arranged in the fiber axis direction is described. further,
In JP-B-60-43858, a polyester containing an alkaline earth metal salt of ASA or an alkyl sulfonic acid is alkali-reduced to have fine pores which are evenly distributed in the fiber cross section and arranged in the fiber axial direction. A method for obtaining fibers is described.

[0013] As described above, by expressing the fine pores arranged in the fiber axis direction on the surface of the low-shrinkage fiber by the alkali weight reduction treatment, in addition to swelling, soft feeling, drape property, firmness, firmness, etc., dry touch, Different shrinkage mixed yarns for producing silky fabrics that also have a squeaky feeling have not been developed yet.

[0014]

SUMMARY OF THE INVENTION According to the present invention, a woven or knitted fabric is subjected to an alkali weight reduction treatment to develop micropores arranged in the fiber axis direction on the surface of the low shrinkage fiber.
An object of the present invention is to provide a polyester different shrinkage mixed filament yarn for producing a silky woven or knitted fabric which has dry touch and squeaky feeling at the same time as well as swelling, softness, drape, elasticity, stiffness and the like.

[0015]

The inventors of the present invention have arrived at the present invention as a result of intensive research to solve the above problems. The present invention relates to a polyester different shrinkage mixed yarn composed of two kinds of fiber groups having different heat shrinkage ratios of low shrinkage fiber and high shrinkage fiber, wherein the low shrinkage fiber is polyethylene glycol having a weight average molecular weight of 4,000 to 50,000,
An alkali metal salt of alkylbenzene sulfonic acid represented by the following formula (I) and an alkali metal salt of alkyl sulfonic acid represented by the following formula (II),

[0016]

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(However, in the above formula, R and R'have 8 to 8 carbon atoms.
20 alkyl groups, M and M'are Li, Na, K
Is one of. ) Made of polyethylene terephthalate compounded so as to satisfy all of the following formulas, 0.5 ≦ P (a) ≦ 5 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ P (B) + P (c) ≤ 4 ‥‥‥‥‥‥‥‥‥‥‥ 0 ≤ P (c) ≤1 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ (However, above Where P (a), P (b) and P (c) are
These are the weight percentages of polyethylene glycol, alkylbenzene sulfonic acid alkali metal salt and alkyl sulfonic acid alkali metal salt in polyethylene terephthalate, respectively. ) The high shrink fiber is isophthalic acid and 2,2-bis {4-
(2-hydroxyethoxyphenyl)} propane and 2,2-bis {4- (2-hydroxyethoxyphenyl)} sulfone are copolymerized in an amount that simultaneously satisfies the following formulas (1) to (5), which comprises the above-mentioned polyethylene. The difference in boiling water shrinkage between terephthalate and the copolymerized polyethylene terephthalate is 5 to 25.
%, And the boiling water shrinkage ratio of the heterogeneous-shrink mixed yarn is 15 to 30%.

0 ≤ Q (a) ≤ 8 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 6 ≦ 0.5 × Q (a) + Q (b) + Q (c) ≦ 12 (where, in the above formula, Q (a) is isophthalic acid based on all dicarboxylic acid components in the copolymerized polyethylene terephthalate) The mol% of the acid, Q (b) is 2,2-bis {4-based on the total glycol component in the copolymerized polyethylene terephthalate.
The mol% of (2-hydroxyethoxyphenyl)} propane and Q (c) are the mol% of 2,2-bis {4- (2-hydroxyethoxyphenyl)} sulfone with respect to the total glycol component in polyethylene terephthalate. ) Hereinafter, the present invention will be described in detail.

The low-shrinkage fiber constituting the different shrinkage mixed yarn of the present invention is PEG having a weight average molecular weight of 4,000 to 50,000,
It is necessary that the polyethylene terephthalate is a mixture of BSA and ASA in specific proportions. Even if any one of the three deviates from the specific range, the polyester different shrinkage mixed filament yarn with polyethylene terephthalate as the low shrinkage fiber is sufficient dry touch even if it is subjected to alkali weight reduction treatment after being woven or knitted. However, a high-quality silky woven or knitted fabric having a feeling of creaking cannot be obtained.

The low-shrinkage fiber constituting the heterogeneous-shrinkage mixed yarn of the present invention comprises PEG having a weight average molecular weight of 4,000 to 50,000 and the following formula: 0.5 ≦ P (a) ≦ 5 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ It must be made of polyethylene terephthalate that can be blended in an amount that satisfies the requirements. If the weight average molecular weight of PEG is less than 4000, the spinnability and stretchability will be poor, and if the weight average molecular weight is greater than 50,000, the fibers will be colored and the spinnability and stretchability will be poor. The weight average molecular weight is preferably 10,000 to 30,000. Further, when P (a) is less than 0.5, even if both BSA and ASA are blended in an amount satisfying the formula and the formula, polyethylene terephthalate obtained from them is used as a low-shrinkage fiber In the case of a woven or knitted product, a silky woven or knitted product having a sufficient dry touch and a squeaky feeling cannot be obtained even if alkali weight reduction is applied to the woven or knitted product. P (a) is preferably 1 to 4.
The PEG may be completely copolymerized, completely mixed, or partially copolymerized and partially mixed.

The low-shrinkage fibers constituting the different shrinkage mixed yarn of the present invention include the alkali metal salt of alkylbenzenesulfonic acid (BSA) represented by the following formula (I) and the following formula (I).
Regarding the compounding amount of the alkali metal salt of alkylsulfonic acid (ASA) represented by I),

[0022]

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[Wherein, R and R'in the above formula have 8 to 8 carbon atoms]
20 alkyl groups, M and M'are Li, Na, K
Is one of. ] The following formula and 0.5 ≦ P (b) + P (c) ≦ 4 ‥‥‥‥‥‥‥‥‥‥‥ 0 ≤ P (c) ≤1 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ It is necessary to satisfy. BSA corresponding to the above formula (I)
The alkyl group having 8 to 20 carbon atoms represented by R may be linear or may have a side chain. M is L
i, Na, or K. Specific examples of BSA include dodecylbenzenesulfonic acid sodium salt (hereinafter,
Examples thereof include DBS), dodecylbenzene sulfonic acid potassium salt, nonyl benzene sulfonic acid sodium salt, and the like, but are not limited thereto. Note that R may not be a single R, but may be a mixture of Rs different from each other. As BSA, R = 12, M =
Most preferred is DBS, which is Na. Similarly, the above formula (I
8 carbon atoms represented by R'in ASA corresponding to I)
The alkyl group of 20 may be linear or may have a side chain. M ′ is any one of Li, Na and K. Specific examples of ASA include dodecyl sulfonic acid sodium salt, octyl sulfonic acid sodium salt, and a mixture of alkyl sulfonic acid sodium salt having an average carbon number of 12 (hereinafter referred to as ASA12).
Of course, it is not limited to these. ASA12 is most preferred as ASA.

When the compounding amount P (c) of ASA is larger than 1, coloring of fibers and increase of pack pressure during spinning become remarkable. P
As (c), 0 to 0.7 is preferable. On the other hand, when the total amount P (b) + P (c) of BSA and ASA is less than 0.5, even if PEG is added in an amount satisfying the formula, the polyethylene terephthalate obtained from them has a low shrinkage fiber. From the shrinkage mixed yarn, a woven or knitted fabric having a sufficient dry touch and a feeling of creaking cannot be obtained even after the woven or knitted fabric is alkali-reduced. When it is more than 4, the mechanical properties of the fiber are deteriorated and the coloring is remarkable. Or the spinnability and stretchability may deteriorate. P (b) + P (c) is preferably 0.6 to 3.

Considering various characteristics, spinnability, cost, etc., the weight average molecular weight of PEG is 1000.
0-30000, DB as the BSA of the formula (I)
As S and ASA of the above formula (II), ASA12 is particularly preferable, and the ranges of the above formulas (1) to (5) are particularly preferably ranges that simultaneously satisfy the following formulas 'to'. 1 ≤ P (a) ≤ 4 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 0.6 ≤ P (b) + P (c) ≤ 3.0 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ ...... '0 ≤ P (c) ≤ 0.7 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ ‥ PEG, BSA and ASA are blended with polyethylene terephthalate by any method. That is, it may be carried out at any stage until the spinning is completed, for example, before the start of polycondensation of polyethylene terephthalate, during the polycondensation reaction, or at the end of the polycondensation reaction. Further, it may be mixed with a usual polyethylene terephthalate in an extruder before spinning or at the time of spinning. Among these, it is most preferable to mix PEG, BSA and ASA at the same time before the start of polycondensation or during the polycondensation reaction from the viewpoint of dispersibility and the like. In this case, of course, the entire amount of PEG is copolymerized and contained in the main chain of polyethylene terephthalate.

The polyethylene terephthalate prepared by blending PEG, BSA and ASA may contain diethylene glycol or the like in the main chain within the range of by-product in the production process, and the silky woven or knitted fabric which is the object of the present invention. Within the range where the manufacturing yarn can be manufactured, for example, BAEO, BSE
O, 1,3-propylene glycol, 1,4-butanediol and other diol compounds, IPA, adipic acid, sebacic acid and other dicarboxylic acid compounds, 4-hydroxybenzoic acid and other hydroxycarboxylic acid compounds, etc. as copolymerization components It may be included in the main chain.

On the other hand, the highly shrinkable fibers constituting the different shrinkage mixed yarn of the present invention must be made of polyethylene terephthalate obtained by copolymerizing IPA, BAEO and BSEO at a specific ratio. From any of the three types of heterogeneous shrinkage mixed yarns that have high shrinkage fibers of copolymerized polyethylene terephthalate that deviates from the specific range, it is possible to obtain a certain degree by subjecting the knitted fabric to alkali weight reduction treatment. Even if a woven or knitted fabric having a dry touch and a feeling of creaking is obtained, on the contrary, the texture usually required for a silky woven or knitted fabric,
That is, only a woven or knitted fabric having insufficient swelling, softness, drape, elasticity, stiffness, etc. can be obtained.

The high shrinkage fibers constituting the heterogeneous shrinkage mixed yarn of the present invention have the following formula with IPA as a copolymerization component: 0 ≦ Q (a) ≦ 8 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ It is necessary that the content of the copolymerized polyethylene terephthalate is in the range satisfying the following.

When Q (a) is larger than 8, BAEO and B
Even when both SEOs are copolymerized with the formula and the amount satisfying the formula, the melting point of the copolymerized polyethylene terephthalate is extremely lowered, and the melting point difference with the low shrinkage fiber becomes large. It is easy to do, many yarn breakages occur during spinning and drawing in the spinning mixed fiber method, and there are considerable restrictions on temperature conditions during manufacturing, post-processing, and use of woven or knitted materials. Q (a) is preferably 0 to 7.0.

The copolymerization amount of BAEO and BSEO is expressed by the following formula and 2 ≦ Q (b) + Q (c) ≦ 12 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ It is necessary to satisfy + Q (b) + Q (c) ≦ 12 at the same time. BAEO and BSE
When the total copolymerization amount of O, that is, Q (b) + Q (c), is less than 2, even if the amount of IPA satisfying the formula is copolymerized, the heterogeneous shrinkage mixture of the copolymerized polyethylene terephthalate as a highly shrinkable fiber is obtained. Only the woven or knitted fabric in which the feeling normally required for a silky woven or knitted fabric, that is, swelling, softness, drapability, firmness, stiffness, etc. is insufficient is obtained from the fine yarn. When Q (b) + Q (c) is greater than 12,
The same problem occurs when Q (a) is larger than 8 described above.

When 0.5 × Q (a) + Q (b) + Q (c) is smaller than 6, the heterogeneous shrinkage mixed yarn having the copolymerized polyethylene terephthalate as a highly shrinkable fiber usually gives a silky woven or knitted fabric. Only a woven or knitted fabric in which a part of the required feeling, that is, swelling, softness, drape, elasticity, elasticity, etc. is insufficient can be obtained. 0.5 x Q (a) + Q (b) + Q
When (c) is larger than 12, the same problem as in the case where Q (a) is larger than 8 described above occurs.

Note that Q (b) and Q (c) may be of any size, and one of them may be zero. However, Q (b)
Generally, the light fastness and dry cleaning resistance after dyeing tend to decrease, but the alkali weight loss rate hardly changes. On the other hand, as Q (c) increases, the alkali weight loss rate generally tends to increase, but the light fastness after dyeing and the dry cleaning resistance hardly change. In terms of cost, BAEO is BS
Generally cheaper than EO. Therefore, the values of Q (b) and Q (c) may be selected according to the end use of the different shrinkage mixed yarn of the present invention.

Considering various characteristics, yarn-forming property, cost and the like comprehensively, it is preferable that the ranges of the above formulas (1) to (4) simultaneously satisfy the following formulas (1) to (3). 0 ≤ Q (a) ≤ 7 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 3 ≤ Q (b) + Q (c) ≤ 11 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ "6.5 ≤ 0.5 x Q (a) + Q (b) + Q (c) ≤ 11 ..." Here, the copolymerized polyethylene terephthalate that constitutes the high shrinkage fiber is IPA, BAEO and BSEO in the main chain.
The above three have a structure in which they are randomly copolymerized in a specific range. This copolymerized polyethylene terephthalate may contain diethylene glycol or the like in the main chain within the range of being by-produced in the production process, and within the range in which the yarn for producing a silky woven or knitted fabric which is the object of the present invention can be produced. so,
For example, copolymerization components other than BAEO and BSEO, for example, diol compounds such as 1,3-propylene glycol and 1,4-butanediol, dicarboxylic acid compounds such as adipic acid and sebacic acid, and hydroxycarboxylic acids such as 4-hydroxybenzoic acid. The compound may be contained in the main chain.

The woven / knitted fabric composed of the different-shrinkage mixed yarn of the present invention, regardless of the presence / absence of the alkali weight reduction treatment, has a feeling normally required for a silky woven / knitted fabric, that is, swelling, softness, drapeability, In order to have sufficient firmness and elasticity, it is important that the heat-shrinkable property of the different shrinkage mixed yarn of the present invention is within a specific range. That is, the boiling water shrinkage ratio (hereinafter, referred to as BWS) of the entire different-shrink mixed fiber is 15 to 30%, and the difference between the low-shrink fiber BWS and the high-shrink fiber BWS (hereinafter, DW) is 5. It is necessary to be 25%. When the heat shrinkage property of the different shrinkage mixed yarn is in this range, a silky woven or knitted fabric excellent in swelling, softness, drapeability, firmness, elasticity and the like can be obtained.

If the BWS of the different shrinkage mixed yarn is less than 15%, a sufficient elasticity and elasticity cannot be obtained, and if it exceeds 30%, the thermal stability of the mixed yarn is poor and the yarn quality including BWS is poor. Change over time, and the resulting woven or knitted fabric has too strong a feeling of coarseness and hardness and has a low commercial value, which is a problem. BW
S is 17 to improve the softness and so on.
It is preferably -25%.

On the other hand, the difference between the BWS of the low shrinkage fibers and the BWS of the high shrinkage fibers constituting the different shrinkage mixed yarn, that is, DW is 5%.
If it is smaller, the resulting woven or knitted fabric becomes a paper-like one without sufficient bulge, and if it is more than 25%, the low shrinkage fibers buckle on the surface of the obtained woven or knitted product, making it difficult to make the surface appearance uniform. Become. This DW is preferably in the range of 7 to 15% in order to obtain a woven or knitted fabric with a higher bulge.

The heterogeneous-shrinkage mixed yarn of the present invention is excellent in swelling, softness, drapability, firmness, elasticity and the like even if it is subjected to ordinary relaxing scouring, dyeing, finishing set after weaving or knitting. Silky woven or knitted fabric, but when alkali weight reduction treatment is performed before dyeing, microscopic holes arranged in the fiber axis direction are developed on the surface of the low shrinkage fiber, so that the silky woven or knitted fabric also has sufficient dry touch Is the most important feature.

The blending composition of polyethylene terephthalate which constitutes the low shrinkage fiber and the copolymerization composition of copolymerized polyethylene terephthalate which constitutes the high shrinkage fiber, and the single yarn fineness and the number of filaments of the low shrinkage fiber and the single yarn fineness of the high shrinkage fiber, The relative alkali weight reduction rates of the low-shrinkage fiber and the high-shrinkage fiber differ depending on the number of filaments and the heat history until the alkali weight reduction treatment is performed using the mixed yarn as a woven or knitted fabric. In order to develop fine pores arranged on the surface in the fiber axis direction, it is necessary to reduce the amount of the low shrinkage fiber by 5 to 50% with alkali. When the alkali weight loss rate was 5% or less, the micropores arranged in the fiber axis direction on the surface of the low shrinkage fiber were not sufficiently developed, and when the alkali weight loss rate was 50% or more, the fine pores were arranged in the fiber axis direction on the surface. Although micropores are developed to some extent, a part of the surface of the low-shrinkage fiber is fibrillated, a large crack is generated in the entire low-shrinkage fiber, or the tear strength of the woven or knitted fabric is reduced, which is sufficient. It is not possible to obtain a high-quality silky woven or knitted fabric that has dry touch and a feeling of dryness at the same time. As an alkali weight loss ratio of low shrinkage fiber is 6 to 35
% Is preferable, and 7 to 25% is particularly preferable. The alkali weight reduction treatment is carried out, for example, in a 2 to 6% NaOH aqueous solution with 80 to 1
The treatment is carried out at 00 ° C. for 10 to 60 minutes, but it is necessary to set the conditions for the alkali weight loss treatment by trial and error so that the alkali weight loss rate of the low-shrinkage fiber falls within the above range.

By the way, in the different shrinkage mixed fiber of the present invention, the elongation of the whole different shrinkage mixed fiber is preferably 20 to 40%, more preferably 25 to 35%. Further, in one or both of the fiber groups constituting the different shrinkage mixed yarn of the present invention, a known matting agent, heat-resistant agent, to the extent that the effect of the present invention is not impaired,
Antioxidants, ultraviolet absorbers, flame retardants, fluorescent agents and the like may be added.

The cross-sectional shape of the fibers used in the fiber group constituting the different-shrinkage mixed filament yarn of the present invention may be appropriately selected from circle, triangle, flat, hexagon, Y-shape, T-shape and the like. Further, it is preferable that the highly shrinkable fibers constituting the heterogeneous shrinkage mixed yarn of the present invention have a single yarn fineness of 1 to 10 denier and the low shrinkage fibers have a single yarn fineness of 5 denier or less. The weight ratio of is preferably in the range of 3: 1 to 1: 3 from the viewpoint of the feel of the silky woven or knitted fabric, and the number of filaments of each can be arbitrarily selected as long as it is within these ranges.

The different-shrinkage mixed fiber of the present invention can be produced by a spun-mixing fiber system, a fiber-drawing fiber-mixing system, a post-fiber-blending system of a drawn fiber, and the like. The spinning mixed fiber method in which the copolymerized polyethylene terephthalate constituting the above is spun using a composite spinning facility, a mixed fiber unstretched yarn is obtained in the spinning step, and this is simultaneously stretched,
Most preferable in terms of productivity and workability. However, in order to produce a wide variety of different shrinkage mixed yarns, other mixed fiber methods are indispensable.

Further, in order to improve the process passability during weaving and knitting, it is preferable to perform fluid entanglement treatment within a range that does not impair the performance of the different shrinkage mixed yarn of the present invention. The degree of entanglement at this time is preferably 10 to 60 times / m. The different-shrinkage mixed filament yarn of the present invention is a false twist yarn having a twist number of 500 T / m or less, and can be most suitably applied to both warp and weft yarns, or to a woven or knitted fabric used for one of the warp yarn and the weft yarn, By subjecting this woven or knitted fabric to alkali reduction treatment, the texture normally required for silky woven or knitted fabrics, that is, swelling, softness, drape, firmness, stiffness, etc., as well as a unique dry touch and creaking feeling, are obtained. It is possible to obtain a silky knitted fabric having

[0043]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In addition,
Each evaluation item in the examples was measured by the following method. 1. Boiled water shrinkage (BWS) Load of 100 mg / d on the different shrinkage mixed fiber yarn, sample length L
After measuring ₀ , the sample is treated with boiling water for 30 minutes under no load, the load of 100 mg / d is applied again to measure the sample length L ₁ , and the BWS is calculated by the following formula.

BWS = {(L ₀ −L ₁ ) / L ₀ } × 100 (%) 2. Difference in boiling water shrinkage (DW) After the different shrinkage mixed fiber is divided into high shrinkage fiber and low shrinkage fiber,
The respective boiling water shrinkage rates W ₁ and W ₂ are obtained according to the method for measuring the boiling water shrinkage rate, and DW is calculated by the following formula.

DW = W ₁ -W ₂ (%) 3. Feeling The twill fabric described below is evaluated on a 9-point scale by sensory evaluation for swelling, softness, drapeability, firmness, stiffness, dry touch, and crease feeling. All grades 5 and above are acceptable.

[0046]

Reference Example 1 (Preparation of polyethylene terephthalate for low shrinkage fiber) After transesterification reaction using dimethyl terephthalate and ethylene glycol, PEG / ethylene glycol slurry, BSA / ethylene glycol slurry and ASA / ethylene glycol slurry solution Was added and polymerization was carried out according to a usual method, and the results are shown in Tables 1, 3, 5, 7, 9, and 1.
Chips of low shrinkage polyethylene terephthalate having various compositions shown in Nos. 1, 13 and 15 were obtained. The obtained chips all contain 0.04% by weight of titanium oxide (TiO ₂ ). The intrinsic viscosity of these chips is 0.58.
The range was ˜0.66.

[0047]

Reference Example 2 (Preparation of Copolyethylene Terephthalate for Highly Shrinkable Fiber) After transesterification reaction using dimethyl terephthalate, dimethyl isophthalate and ethylene glycol, BAEO / ethylene glycol solution and BSEO /
An ethylene glycol solution was added and polymerization was performed by a usual method to obtain chips of highly shrinkable copolymerized polyethylene terephthalate having various compositions shown in Tables 1, 3, 5, 7, 9, 11, 13, and 15. The obtained chips all contain 0.04% by weight of titanium oxide (TiO ₂ ).
The intrinsic viscosity of these chips is 0.60 to 0.65.
Was in the range.

[0048]

Examples 1 to 3 Chips of polyethylene terephthalate for low-shrink fiber (compounding composition shown in Table 1) obtained in Reference Example 1 and copolymerized polyethylene terephthalate for high-shrink fiber obtained in Reference Example 2 (co Polymerization composition described in Table 1) is used, and the spinning temperature is 290 ° C. by a composite spinning machine.
A mixed fiber undrawn yarn having a triangular cross section was spun at a spinning speed of 1500 m / min.

This mixed fiber undrawn yarn was drawn at a drawing speed of 800 m / min by hot roll (80 to 90 ° C.)-Hot plate (1
50-denier /
A different shrinkage mixed filament yarn of 24 filaments (25 denier / 12 filaments for both low shrinkage fiber and high shrinkage fiber) was produced. At the time of drawing, air entanglement was performed to give 20 entangles / m, and the draw ratio was adjusted so that the elongation of the drawn yarn was in the range of 25 to 35%.

Incidentally, when the mixed fiber of Example 1 was spun, the hot roll temperature was 87 ° C. and the hot plate temperature was 1.
At 28 ° C., the strength of the obtained mixed fiber was 4.5 g / d and the elongation was 31%. 30 to each of the obtained different shrinkage mixed yarns
After twisting 0 T / m, sizing (30 ° C.), drying (85 ° C.), warping, weaving, relaxing and scouring with hot water of 97 ° C., alkaline aqueous solution (6% NaOH solution) The mixture was boiled in a bath ratio of 1: 100 to reduce the amount of alkali, washed with water (30 ° C.), dried (85 ° C.), and finally set at 170 ° C. to prepare a twill fabric. In addition, at the time of the above-mentioned alkali weight loss, the alkali weight loss rate of the low shrinkage fiber is 10 to 20.
The alkali reduction treatment time was adjusted so that the value was in the range of%.

Table 2 shows the results of measuring the BWS and DW of the different shrinkage mixed yarn and the feel of the fabric (twill fabric).

[0052]

Examples 4 to 6 Chips of polyethylene terephthalate for low shrinkage fibers (compounding composition shown in Table 3) obtained in Reference Example 1 and copolymerized polyethylene terephthalate (copolymerization for high shrinkage fibers obtained in Reference Example 2 Polymerization composition is shown in Table 3), and the chips were spun on a conventional spinning machine at a spinning temperature of 290
A single undrawn yarn having a triangular cross section was spun at a spinning speed of 1500 m / min.

80% denier / 48 filaments (50 denier / 36 filaments for low shrinkage fiber and 30 denier / high shrinkage fiber) were drawn by aligning two types of single undrawn yarns and drawing in the same manner as in Examples 1-3. 12 filaments of different shrinkage mixed yarn was obtained, and then a twill fabric was prepared. Table 4 shows the results of measuring the BWS and DW of the different shrinkage mixed yarn and the feel of the fabric (twill fabric).

[0054]

[Examples 7 to 9] Chips of polyethylene terephthalate for low shrinkage fibers (compounding composition described in Table 5) obtained in Reference Example 1 and copolymerized polyethylene terephthalate for high shrinkage fibers (copolymerization composition described in Table 5). ) And the mixed fiber undrawn yarn having a triangular cross section is spun by a composite spinning machine in the same manner as in Examples 1 to 3, and further drawn to 50 denier / 2.
4 filaments (25 denier / 12 filaments for both low-shrink fiber and high-shrink fiber) of different shrinkage were obtained, and then a twill fabric was prepared.

Table 6 shows the results of measuring the BWS and DW of the different shrinkage mixed yarn and the feel of the cloth (twill fabric).

[0056]

Examples 10 to 12 Polyethylene terephthalate for low shrinkage fibers obtained in Reference Example 1 (compounding composition is shown in Table 7)
And a chip of the copolymerized polyethylene terephthalate for high-shrinkage fiber (copolymerization composition described in Table 7) obtained in Reference Example 2 at a spinning temperature of 290 ° C. and a spinning speed of 1500 m / min by an ordinary spinning machine. A single undrawn yarn of triangular cross section was spun.

80% denier / 48 filaments (50 denier / 36 filaments for low shrinkage fiber and 30 denier / high shrinkage fiber) were drawn by aligning two kinds of single undrawn yarns and drawn in the same manner as in Examples 1-3. 12 filaments of different shrinkage mixed yarn was obtained, and then a twill fabric was prepared. Table 8 shows the results of measuring the BWS, DW of the different shrinkage mixed yarn and the feel of the fabric (twill fabric).

[0058]

Examples 13 to 15 Polyethylene terephthalate for low shrinkage fibers obtained in Reference Example 1 (compounding composition is shown in Table 9)
And a tip of high-shrink fiber copolymerized polyethylene terephthalate (copolymerization composition is shown in Table 9) are used, and a mixed fiber undrawn yarn having a triangular cross section is obtained by a composite spinning machine in the same manner as in Examples 1 to 3. 50 denier / 24 filaments (both low shrinkage fiber and high shrinkage fiber
A different shrinkage mixed yarn of 5 denier / 12 filaments was obtained, and then a twill fabric was prepared.

Table 10 shows the results obtained by measuring the BWS, DW of the different shrinkage mixed yarn and the feel of the cloth (twill fabric).

[0060]

[Comparative Examples 1 and 2] Chips of polyethylene terephthalate for low shrinkage fibers (compounding composition shown in Table 11) obtained in Reference Example 1 and copolymerized polyethylene terephthalate for high shrinkage fibers obtained in Reference Example 2 (copolymer Each of the chips having a polymerization composition shown in Table 11) was spun into a single unstretched yarn having a triangular cross section at a spinning temperature of 290 ° C. and a spinning speed of 1500 m / min by a common spinning machine.

80% denier / 48 filaments (50 denier / 36 filaments for low shrinkage fiber and 30 denier / high shrinkage fiber) were drawn by aligning two types of single unstretched yarns and drawing in the same manner as in Examples 1-3. 12 filaments of different shrinkage mixed yarn was obtained, and then a twill fabric was prepared. Table 12 shows the results obtained by measuring the BWS and DW of the different shrinkage mixed yarn and the feel of the fabric (twill fabric).

[0062]

[Comparative Examples 3 to 4] Chips of polyethylene terephthalate for low-shrink fiber (compounding composition shown in Table 13) obtained in Reference Example 1 and copolymerized polyethylene terephthalate (co-polymer for high-shrink fiber obtained in Reference Example 2 Each of the chips having a polymerization composition shown in Table 13) was spun into a single unstretched yarn having a triangular cross section at a spinning temperature of 290 ° C. and a spinning speed of 1500 m / min by a common spinning machine.

80% denier / 48 filaments (50 denier / 36 filaments for low shrinkage fiber and 30 denier / high shrinkage fiber) were drawn by aligning two kinds of single undrawn yarns and drawing in the same manner as in Examples 1-3. 12 filaments of different shrinkage mixed yarn was obtained, and then a twill fabric was prepared. Table 14 shows the results of measuring the BWS and DW of the different shrinkage mixed yarn and the feel of the fabric (twill fabric).

[0064]

[Comparative Examples 5 to 12] Polyethylene terephthalate for low shrinkage fibers obtained in Reference Example 1 (compounding composition is shown in Table 15)
And a chip of the copolymerized polyethylene terephthalate for high-shrink fiber (copolymerization composition shown in Table 15) obtained in Reference Example 2 at a spinning temperature of 290 ° C. and a spinning speed of 1500 m / min by an ordinary spinning machine. A single undrawn yarn of triangular cross section was spun.

The individual undrawn yarns were used in Examples 1-3.
Stretched in the same manner as above, but the low shrinkage fiber is 50 denier / 3
6 filaments and a highly shrinkable fiber were 30 denier / 12 filaments, and a single drawn yarn was obtained. Since various problems as described in Table 16 occurred before the production of these single drawn yarns, the evaluation of the different shrinkage mixed fiber and the fabric was stopped.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

[Table 6]

[0072]

[Table 7]

[0073]

[Table 8]

[0074]

[Table 9]

[0075]

[Table 10]

[0076]

[Table 11]

[0077]

[Table 12]

[0078]

[Table 13]

[0079]

[Table 14]

[0080]

[Table 15]

[0081]

[Table 16]

[0082]

The polyester different shrinkage mixed yarn of the present invention is
The low-shrinkage fiber consists of polyethylene terephthalate with a specific composition, the high-shrinkage fiber consists of copolymerized polyethylene terephthalate with a specific composition, and after the woven or knitted fabric is subjected to alkali weight reduction treatment, the wind normally required for silky woven or knitted fabrics. In other words, swelling, softness, drape,
It is suitable as a yarn that constitutes a silky woven or knitted fabric that has a unique dry touch and peculiar feeling as well as a firmness and stiffness, and its industrial significance is extremely large.

Claims (1)

[Claims] 1. A polyester different shrinkage mixed yarn comprising two kinds of fiber groups of low shrinkage fiber and high shrinkage fiber having different heat shrinkage ratios, wherein the low shrinkage fiber has a weight average molecular weight of 4,000 to 4,000.
50,000 polyethylene glycol and the following formula (I)
And an alkali metal salt of an alkylbenzene sulfonic acid represented by the following formula and an alkali metal salt of an alkyl sulfonic acid represented by the following formula (II): (However, in the above formula, R and R ′ are an alkyl group having 8 to 20 carbon atoms, and M and M ′ are any one of Li, Na, and K.) Compounded so as to satisfy all of the following formulas 0.5 ≤ P (a) ≤ 5 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 0.5 ≤ P (b) + P (c) ≤ 4 ... ‥‥‥‥‥‥‥‥‥‥ 0 ≤ P (c) ≤ 1 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ (However, in the above equation, P (a), P (b ) And P (c) are
These are the weight percentages of polyethylene glycol, alkylbenzene sulfonic acid alkali metal salt and alkyl sulfonic acid alkali metal salt in polyethylene terephthalate, respectively. ) The high shrink fiber is isophthalic acid and 2,2-bis {4-
(2-hydroxyethoxyphenyl)} propane and 2,2-bis {4- (2-hydroxyethoxyphenyl)} sulfone are copolymerized in an amount that simultaneously satisfies the following formulas (1) to (5), which comprises the above-mentioned polyethylene. The difference in boiling water shrinkage between terephthalate and the copolymerized polyethylene terephthalate is 5 to 25.
%, And the boiling water shrinkage ratio of the heterogeneous shrinkage mixed yarn is 15 to 30%. 0 ≤ Q (a) ≤ 8 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 2 ≤ Q (b) + Q (c) ≤ 12 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ 6 ≦ 0.5 × Q (a) + Q (b) + Q (c) ≦ 12 (where, Q (a) is the mole of isophthalic acid based on all dicarboxylic acid components in the copolymerized polyethylene terephthalate. %, Q (b) is 2,2-bis {4- with respect to the total glycol component in the copolymerized polyethylene terephthalate.
The mol% of (2-hydroxyethoxyphenyl)} propane and Q (c) are the mol% of 2,2-bis {4- (2-hydroxyethoxyphenyl)} sulfone with respect to the total glycol component in polyethylene terephthalate. )