JP2001248018A - Elastic yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resilient material which is recyclable, can be incinerated without generating harmful substances, can be used for various members requiring elasticity, and has excellent returnability after elasticity. It is intended to provide a yarn (elastic monofilament). An elastic yarn comprising a polyetherester block copolymer obtained by copolymerizing the following components (a), (b) and (c). (A) a dicarboxylic acid component in which the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and its ester-forming derivative (b) a short-chain diol component in which the short-chain diol component is an aliphatic diol and its ester-forming derivative (c) The long-chain diol component is a polyether comprising a neopentylene oxide structural unit and a tetramethylene oxide structural unit, and both terminals are alcoholic hydroxyl groups,
Polyether glycol having a number average molecular weight of 400 to 6,000

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastic yarn, and more particularly to a member for clothing, a living article or a sanitary article, for example, a stretchable member (a member of a waist gather or a side gather) such as a disposable diaper or a napkin. It relates to an elastic yarn (elastic monofilament).

[0002]

2. Description of the Related Art Polyurethane foam is used as a member requiring elasticity, such as a member for clothes, household goods, gathers such as sanitary goods (for example, disposable diapers and napkins).
Synthetic rubber such as polyurethane film and styrene elastomer film, natural rubber, and the like are used.

[0003] However, polyurethane foams have problems such as low strength, high price, and cannot be thermally bonded to various nonwoven fabrics, and polyurethane films have problems such as poor hot-melt adhesion and thermal bonding. is there. Natural rubber, on the other hand, has an advantage in price, but has problems such as extremely poor hot melt adhesion, inability to heat adhere, and cause allergy. Further, common drawbacks of these elastic members are that they cannot be recycled and cannot be incinerated due to generation of harmful substances. Styrene-based elastomer films are recyclable, have low modulus and large elongation, and have properties close to those of natural rubber, but have poor heat resistance and have a problem of sagging at body temperature.

On the other hand, JP-A-11-222724 proposes an elastic member using a polyester elastomer composition using a polyetherester block copolymer. Although this composition is excellent in heat resistance and hard to block, it has a drawback that not only the tensile stress is large and it is difficult to elongate, but also the permanent elongation is large and the reversion property after expansion and contraction is poor.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to an elastic yarn which is recyclable, can be incinerated without generating harmful substances, and which can be used for various members requiring elasticity and which has excellent returnability after expansion and contraction. (Elastic monofilament).

[0006]

Means for Solving the Problems As a result of extensive studies, the present inventors have found that an elastic yarn made of a thermoplastic elastomer which is a polyetherester block copolymer having a special structure solves the above-mentioned problems. And completed the present invention.

That is, the present invention relates to an elastic yarn comprising a polyetherester block copolymer obtained by copolymerizing the following components (a), (b) and (c). (A) a dicarboxylic acid component in which the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and an ester-forming derivative thereof; and (b) a short-chain diol component in which the short-chain diol component is an aliphatic diol and an ester-forming derivative thereof. The long-chain diol component is composed of a neopentylene oxide structural unit represented by the following formula (1) (hereinafter abbreviated as N) and a tetramethylene oxide structural unit represented by the following formula (2) (hereinafter abbreviated as T)
A polyether having a ratio of N of 5 to 50 mol%, both ends having an alcoholic hydroxyl group, and having a number average molecular weight of 400 to 6,000.

[0008]

Embedded image

[0009]

Embedded image T: —CH ₂ CH ₂ CH ₂ CH ₂ O— (2)

Hereinafter, the present invention will be described in detail. Polyetherester block copolymer used in the present invention,
(A) a dicarboxylic acid component in which the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and an ester-forming derivative thereof,
(B) the short-chain diol component is an aliphatic diol and a short-chain diol component which is an ester-forming derivative thereof; and (c) the long-chain diol component is N represented by the following formula (1) and T represented by the following formula (2). A polyether having a ratio of N of 5 to 50 mol%, wherein both terminals are alcoholic hydroxyl groups,
It is a block copolymer obtained by copolymerizing a polyether glycol having a number average molecular weight of 400 to 6,000.

[0011]

Embedded image

[0012]

Embedded image T: —CH ₂ CH ₂ CH ₂ CH ₂ O— (2)

The component (a) used in the polymerization of the polyetherester block copolymer used in the present invention, that is, the aromatic dicarboxylic acid and its ester-forming derivative include terephthalic acid, isophthalic acid, phthalic acid and naphthalene- Examples include 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, and ester-forming derivatives thereof.

Also, alicyclic or aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanediic acid, dimer acid and the like and ester-forming derivatives thereof are used. You may. These may be used alone or in combination of two or more. Preferably, terephthalic acid, isophthalic acid, and naphthalene-2,6-dicarboxylic acid are used.

As the component (b), that is, an aliphatic diol and an ester-forming derivative thereof, a diol having a molecular weight of 300 or less is usually used. Examples include ethylene glycol, 1,3-propylene diol, 1,4-butane diol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, and ester-forming derivatives thereof.

Also, alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and tricyclodecanedimethanol, and ester-forming derivatives thereof; xylylene glycol, bis (p-hydroxy ) Diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4 (2-hydroxy) phenyl] sulfone, 1,1-bis [4-
(2-hydroxyethoxy) phenyl] cyclohexane, and the like, and ester-forming derivatives thereof.
Preferably, ethylene glycol, 1,4-butanediol and their ester-forming derivatives are mentioned.

The combination of the aromatic dicarboxylic acids and their ester-forming derivatives with the aliphatic diols and their ester-forming derivatives constitutes a hard segment of the polyetherester block copolymer, that is, a short-chain polyester. A preferred combination is a combination of terephthalic acid or terephthalic acid diester with ethylene glycol or 1,4-butanediol (polyethylene terephthalate, polybutylene terephthalate). More preferably, polybutylene terephthalate is preferably used for the hard segment.

The reason for this is that polybutylene terephthalate has a high crystallization rate and excellent moldability. Even when a polyetherester block copolymer is used, the balance of physical properties such as rubber elasticity, mechanical properties, heat resistance and chemical resistance is high. It depends on what is well equipped. Other dicarboxylic acids and their ester-forming derivatives up to 15 mol% in this combination,
Or other diols and their ester-forming derivatives
It can be used by adding up to 5 mol%.

The component (c) of the polyetherester block copolymer used in the present invention, that is, the polyether glycol constituting the long-chain polyester is composed of N and T, and the ratio of N is preferably 5 to 50 mol%, more preferably Is 10-30
Mole%, more preferably 15 to 25 mole%, both ends are alcoholic hydroxyl groups, and have a number average molecular weight of 400 to 6,000, preferably 8
00 to 3,000, more preferably 1,000 to 2,000
000.

The polyether glycol used for producing the polyetherester block copolymer used in the present invention is 3,3-dimethyloxetane (3,3-DM
O) cation polymerization, 3,3-DMO and neopentyl glycol (NPG) cation copolymerization, 3,3-
Cationic copolymerization of DMO and tetrahydrofuran (THF), cation terpolymerization of 3,3-DMO, NPG and THF, or neopentyl glycol and tetrahydrofuran as raw materials in the presence of a catalyst that is active in the presence of an alcoholic hydroxyl group And pure tetramethylene glycol under reaction conditions under which depolymerization proceeds.

In a copolymer composition in which N in the polyether glycol is less than 5 mol%, when this is made into a polyether ester block copolymer, in particular, permanent elongation and physical properties satisfactory for elastic recovery may not be obtained. It is not preferable because there is. Further, when N in the polyether glycol exceeds 50 mol%, the glass transition temperature of TPEE increases,
It is not preferable because permanent elongation is deteriorated.

The preferred method for producing a polyether glycol used for producing the polyetherester block copolymer used in the present invention is to prepare a large amount of neopentyl glycol in the presence of a catalyst which is active in the presence of an alcoholic hydroxyl group. The reaction is carried out at a high temperature at which the depolymerization of pure tetramethylene glycol proceeds and a low THF concentration, that is, a high polymer concentration. As a catalyst exhibiting activity in the presence of an alcoholic hydroxyl group, JP-A-60-203
Japanese Patent Application Laid-Open No. Sho 61-12083 discloses a heteropoly acid.
No. 0 describes salts of heteropolyacids, but these can be used. At this time, the requirement that the molar ratio of water or diol to the catalyst is 10 or less is unnecessary under the reaction conditions for providing the polyether glycol of the present invention.

The catalyst exhibiting activity in the presence of an alcoholic hydroxyl group is not particularly limited to a heteropolyacid, and benzenesulfonic acid, toluenesulfonic acid and the like may be used. The reason that the copolymerization ratio of neopentyl glycol can be increased in a special reaction condition method that gives a preferable polyether glycol used in the production of the polyetherester block copolymer used in the present invention is that a diol to a catalyst is used. This is because the polymerization can proceed even if the molar ratio of the compound is 30, so that a large amount of neopentyl glycol can be charged. Also, TH
The formation of a polymer molecular chain consisting only of F is suppressed because the polymerization proceeds under the depolymerization conditions of pure poly (tetramethyleneoxy) glycol.

The requirements for producing preferably the polyether glycol used for the polyetherester block copolymer used in the present invention are summarized as follows.
First, a catalyst that shows activity in the presence of an alcoholic hydroxyl group,
For example, the main reaction is to use a heteropoly acid or a sulfonic acid, etc., the second is to use a glycol which inhibits the propagation of depolymerization as a copolymerized glycol, that is, NPG, and the third is a polycondensation in which the copolymerization ratio is increased. For pure PTM
The reaction proceeds at a temperature and a polymer concentration at which the depolymerization of G proceeds.

In order to advance this polycondensation reaction at a preferable rate, the reaction temperature must be 70 ° C. or higher, preferably 75 ° C. or higher. However, if the reaction temperature is too high, the coloring of the reaction solution or the catalyst becomes strong, which is not preferable. For example, in the case where phosphotungstic acid is used as a catalyst, coloring usually becomes severe above 110 ° C.

Although the catalysts used in the present invention have been mentioned above, preferred catalysts among them are phosphotungstic acid which is commercially available, has good stability at high temperatures and high reaction activity. When a heteropolyacid such as tungstophosphoric acid is used as a catalyst, as the reaction proceeds, the reaction solution is composed of a catalyst layer having a high catalyst concentration and one catalyst.
%, And the reaction is carried out in a two-layer dispersed state. If the stirring is stopped at the end of the reaction and the mixture is allowed to stand, the heavy catalyst layer separates below and the light liquid layer separates above. The upper liquid layer is taken out, and THF, oligomers and dissolved catalyst are removed to obtain a target polymer. A new batch of NPG and THF is supplied to the catalyst layer left below, and a new batch reaction is started. In this way, a polyetherester block copolymer serving as a raw material of the present invention can be obtained while repeatedly using the catalyst.

When sulfonic acid is used as a catalyst, a catalyst that does not dissolve in the reaction solution, such as Nafion, is used.
Separation of the catalyst is simple and preferred. The amount of NPG to be used is preferably 2 to 10 moles of NPG per 1 equivalent of the catalyst with respect to the amount of the phosphotungstic acid or sulfonic acid used as the catalyst. If the amount of NPG is small, the amount of polymer to be collected at the end of the reaction will be small, and if the amount of NPG is large, the polycondensation reaction will be slow and it will take a long time to increase the degree of polymerization of the polymer.

The water produced by the polycondensation can be taken out and removed as gaseous water in the reaction system. The composition of the gas phase is mostly THF, and the water content of the gas phase is 0.4 to 2.0 wt.
% Is usually included. Therefore, when removing water, THF is taken out together, and it is necessary to replenish new THF by that much. Since it is necessary to take out the gas phase of the reaction system, the reaction solution is at the boiling temperature. In order to control the boiling temperature, that is, the reaction temperature, to a predetermined value, it is an easy method to control the THF concentration. As a specific operation, TH is adjusted so that the liquid temperature is maintained at a predetermined value.
If the replenishment rate of F was to be controlled, THF extracted together with vapor-phase moisture, a change in composition along with the progress of the reaction and consumption of THF due to polymerization, and a standard operation capable of coping with all these changes could be determined for THF. Will be.

The THF concentration in the reaction solution varies depending on the reaction pressure and the reaction temperature, ie, the boiling pressure and temperature. Therefore, THF
The concentration can be controlled by the reaction pressure given the reaction temperature. The concentration of water in the reaction solution is in dynamic equilibrium with the concentration of water in the gas phase of the reaction system. Therefore, the water concentration in the reaction solution is
It can be controlled by the water concentration in the gas phase of the reaction system.

The polyether glycol used for producing the polyether ester block copolymer used in the present invention has a number average molecular weight of 400 to 6,000. If it is less than 400, the average chain length of the short-chain polyester (hard segment) usually becomes small, depending on the hard / soft segment ratio of the final polyetherester block copolymer to be polymerized, and the melting point drops sharply, resulting in poor heat resistance. Inferior in both cases when used as a material as it is as a polyetherester block copolymer or when formed into a composition. On the other hand, if it exceeds 6,000, the terminal group concentration in the polyether glycol per unit weight becomes low, and it becomes difficult to polymerize.

The total amount of polyether glycol units (soft segments) in the polyetherester block copolymer is 20 to 90% by weight, preferably 30 to 90% by weight.
７０70% by weight, more preferably 40-60% by weight. This value must be in a range that satisfies the required hardness (20 to 70 in Shore D hardness) of the use of the present invention. In this case, the amount of the polyether glycol unit refers to the weight ratio of the soft segment, not the weight ratio of the charged polyether glycol in all monomers.

In general, the hard segment of the polyetherester block copolymer is a short-chain ester, and the soft segment is composed of a long-chain ester. It is connected to a segment. A unit including a unit constituting an ester bond at one end of the polyether portion was defined as a soft segment for convenience.

The ratio of this hard / soft segment is ¹
It can be accurately quantified by H-NMR. If the amount of the soft segment is less than 15% by weight, the flexibility is poor, which is not preferable. On the other hand, if this amount exceeds 50% by weight, it becomes too flexible, which is not preferable.

The polyetherester block copolymer of the present invention has a Shore D hardness of 20 to 70, preferably 25 to 70.
60, more preferably in the range of 30 to 50, and the soft segment amount is appropriately selected. If the Shore D hardness is less than 20, the strength and heat resistance of the obtained thermoplastic elastomer composition will be insufficient, which is not preferable. On the other hand, if the Shore D hardness exceeds 70, the flexibility and permanent elongation of the thermoplastic elastomer obtained are undesirably deteriorated.

The polyetherester block copolymer of the present invention can be produced by a known method. For example, a lower alcohol diester of a dicarboxylic acid, a transesterification reaction of an excessive amount of a low molecular weight glycol and a polyether glycol in the presence of a catalyst, followed by polycondensation of the resulting reaction product under reduced pressure, or a dicarboxylic acid and a glycol and A method in which polyether glycol is subjected to an esterification reaction in the presence of a catalyst, and then the resulting product is subjected to polycondensation. Alternatively, a short-chain polyester (for example, polybutylene terephthalate) is prepared in advance, and then another dicarboxylic acid, diol or Any method such as a method of adding ether glycol or adding another copolymerized polyester and performing randomization by transesterification may be employed.

As a catalyst common to the transesterification reaction or esterification reaction and the polycondensation reaction used for producing the polyetherester block copolymer, tetra (isopropoxy) titanate and tetra (n-butoxy) titanate are used. Representative tetraalkyl titanates, reaction products of these tetraalkyl titanates with alkylene glycols, partial hydrolysates of tetraalkyl titanates, metal salts of titanium hexaalkoxides, titanium carboxylate salts, titanium-based compounds such as titanyl compounds Catalysts are preferred. Also, mono-n-butyl monohydroxytin oxide, mono-n-butyltin triacetate, mono-n
Monoalkyltin compounds such as -butyltin monooctylate and mono-n-butyltin monoacetate, dialkyls such as di-n-butyltin oxide, di-n-butyltin diacetate, diphenyltin oxide, diphenyltin diacetate and di-n-butyltin dioctylate Alternatively, a diaryl) tin compound can be used.

In addition, catalysts such as metals such as Mg, Pb, Zr and Zn, metal oxides and metal salt catalysts are useful. These catalysts may be used alone or in combination of two or more.

The addition amount of the esterification or polycondensation catalyst is preferably from 0.005 to 0.5% by weight, more preferably from 0.03 to 0.2% by weight, based on the produced polymer. These catalysts may be added at the beginning of the transesterification or esterification reaction and may or may not be added again during the polycondensation reaction.

Further, as a part of dicarboxylic acid or glycol, polycarboxylic acid, other functional hydroxy compound, oxyacid or the like may be copolymerized. The other functional component effectively acts as a high viscosity component, and its copolymerizable range is 3 mol% or less. Those that can be used as such other functional components include trimellitic acid, trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid, butanetetracarboxylic acid, glycerin, pentaerythritol and their esters, acid anhydrides and the like. Can be.

Further, if necessary, the polyether glycol used in the present invention may be partially substituted with another polyether glycol. Examples of the polyether glycol used for such substitution include poly (ethyleneoxy) glycol, poly (propyleneoxy) glycol, poly (tetramethyleneoxy) glycol, poly (1,2-propyleneoxy) glycol, blocks of ethylene oxide and propylene oxide. Or a random copolymer, a random copolymer of THF and 3-methyl THF, a block or random copolymer of ethylene oxide and THF, poly (2-methyl-1,3-propyleneoxy) glycol, poly (propyleneoxy) diimidedi Acids and the like.

The preferred number average molecular weight of the polyether glycol used for these substitutions is from 400 to 6,000, particularly preferably from 1,000 to 3,000. Preferred substituted polyether glycols include poly (tetramethyleneoxy) glycol. When poly (tetramethyleneoxy) glycol is used for substitution, if the number average molecular weight (Mn) exceeds 1,800, the molecular weight distribution [Mv / Mn: Mn is the number average molecular weight determined from the terminal hydroxyl value, Mv is the formula Mv = Anti log (0.493 l
og η + 3.0646). However, η is the melt viscosity at a temperature of 40 ° C. expressed in poise.] Depending on the case, crystallization may occur to give an undesirable result in low-temperature performance.

When the value of the molecular weight distribution (Mv / Mn) is 1.
It is more preferable to use a material as narrow as 6 or less. More preferably, it is 1.5 or less. Preferably, however, the substituted polyether glycol is used in a range of not more than 90% by weight of the polyether glycol used in the present invention. If this value exceeds 90% by weight, depending on the content of the neopentyl oxide unit in the polyether glycol used in the present invention, in general, satisfactory results in physical properties such as water resistance and low temperature performance cannot be obtained. Therefore, selection according to the application is necessary.

The degree of polymerization of the polyetherester block copolymer thus polymerized is generally determined by the relative solution viscosity (η
rel), intrinsic viscosity ([η]) and melt flow rate (MFR). In the present invention, it is expressed by MFR. In the present invention, the MFR is preferably 0.1 to 50.
g / 10 minutes (load: 2.16 kg, 230 ° C.), more preferably 1 to 30 g / 10 minutes polyetherester block copolymer is used. If the MFR is more than 50, the molecular weight is not sufficiently increased, and particularly the mechanical properties (such as breaking strength and breaking elongation) and the permanent elongation are inferior, so that the use is limited. On the other hand, if the MFR is smaller than 0.1, the torque increases at the time of film formation, extreme melt fracture occurs, and the film formation stability deteriorates.

As additives used in the present invention, it is desirable to use at least an antioxidant, a light stabilizer and a heat stabilizer. The antioxidant can be added during or after the production of the polyetherester block copolymer, but especially when the polyether glycol is exposed to high temperatures, e.g., when it enters the polycondensation reaction. In order to prevent the oxidative deterioration of glycol, it is desirable to add an antioxidant which does not inhibit the polycondensation reaction and does not impair the function of the catalyst.

Examples of these antioxidants include aliphatic, aromatic or alkyl-substituted aromatic esters of phosphoric acid and phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl Pentaerythritol diphosphite,
Phosphorus compounds such as dialkylbisphenol A diphosphite; phenol derivatives, especially compounds containing sulfur such as hindered phenol compounds, thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, thiodipropionates; tinmalate, dibutyltin mono Tin compounds such as oxides can be used.

These may be used alone or in combination of two or more. The addition amount of these stabilizers is based on 100 parts by weight of the polyetherester block copolymer.
0.01 to 2 parts by weight is desirable. Generally, antioxidants can be divided into primary, secondary and tertiary antiaging agents. Particularly, as a hindered phenol compound as a primary anti-aging agent, Irganox 1010 (trade name: manufactured by Ciba Geigy), Irganox 1520 (trade name: manufactured by Ciba Geigy) and the like are preferable. PGA-36, PEP-24G and HP-10 (all trade names: manufactured by Asahi Denka Co., Ltd.) Irgafos 168 as a phosphorus-based compound as a secondary anti-aging agent.
(Trade name: Ciba-Geigy) is preferred. Further, as the sulfur compound as the tertiary aging inhibitor, thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP) are preferable.

If necessary, an ultraviolet absorber and a light stabilizer may be added in the same manner. Examples of these ultraviolet absorbers include benzotriazole-based compounds and benzophenone-based compounds. As the light stabilizer, a radical scavenging light stabilizer such as a hindered amine compound is suitably used.

Further, a plasticizer may be added to the polyetherester block copolymer of the present invention, if necessary. Examples of such plasticizers include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, diisononyl phthalate and the like:
Tricresyl phosphate, triethyl phosphate,
Phosphate esters such as tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, tris-dichloropropyl phosphate: octyl trimellitate, isodecyl trimellitate,
Fatty acids such as trimellitic acid esters, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl azelate, dioctyl azelate, dioctyl sebacate, di-2-ethylhexyl sebacate, methyl acetyl ricinocate, etc. Esters: Pyromellitic esters such as octyl pyromellitic acid: Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil and epoxidized fatty acid alkyl esters: Polyether plastics such as adipic ether esters and polyethers Agent: liquid rubber such as liquid NBR, liquid acrylic rubber, liquid polybutadiene, etc .;

These plasticizers can be used alone or in combination of two or more. The amount of the plasticizer to be added is appropriately selected depending on the required hardness and physical properties, but is preferably 1 to 100 parts by weight per 100 parts by weight of the polyetherester block copolymer.
50 parts by weight are preferred.

In addition, kaolin, as long as the physical properties are not impaired,
Silica, mica, titanium dioxide, alumina, calcium carbonate, calcium silicate, clay, kaolin, diatomaceous earth, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, carbon fiber, etc. Fillers and reinforcements: Lubricants or mold release agents such as zinc stearate and bis-amide amide: carbon black for coloring, ultramarine, titanium white, zinc white, zinc oxide,
Dyeing pigments such as navy blue, azo pigments, nitro pigments, lake pigments, phthalocyanine pigments, etc .: Flame retardants such as octabromodiphenyl, tetrabromobisphenol polycarbonate, etc.
Blowing agent: Thickener such as epoxy compound or isocyanate compound: Various known additives such as silicone oil and silicone resin can be used.

The polyetherester block copolymer of the present invention can be easily formed into pellets by melt-kneading and granulating with various extruders, Banbury mixers, kneaders, rolls, and combinations thereof. can get.

The present invention provides an elastic yarn (elastic monofilament) comprising the above polyetherester block copolymer.
It is. Although the thickness of the elastic yarn is not specified, it is usually 200 to
10,000 denier, preferably 500 to 8,000
Denier, more preferably 800 to 6000 denier. The elastic yarn made of the polyetherester block copolymer is formed by employing a normal spinning method.
Can be manufactured.

A typical method is to extrude the polyetherester block copolymer pellets by an extruder and spin a monofilament yarn from a spinning port. The cross-sectional shape of the elastic yarn is not particularly limited, and may be a circular, angular, or irregular cross-section, and is appropriately selected depending on the application. A circular shape is usually used as a substitute for a typical natural rubber string.

Further, the present invention is characterized by a stretchable elastic yarn obtained by further stretching the above elastic yarn. The stretching ratio of the elastic yarn is arbitrary, but is usually about 1.5 to 10 times, particularly preferably about 3 to 5 times. Stretching may be performed under heating.
After stretching, it is preferable to anneal at a temperature higher than the temperature at the time of stretching. By stretching the elastic yarn, stretchability and stretchability under low stress can be particularly improved. The above-mentioned elastic yarn, and furthermore, the above-mentioned stretchable elastic yarn can be used for various rubber cords and the like by utilizing its elasticity.

[0055]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. <Evaluation Method> First, physical property evaluation items used in Examples and Comparative Examples and evaluation methods thereof will be described below.

[Melt Flow Rate (MFR)] After about 5 g of pellets were vacuum-dried in a vacuum dryer at 70 ° C. for about 12 hours, immediately, the diameter was 2.090 mm and the length was 8 mm.
2.16 kg load, measured temperature 23
MFR was measured under the L condition of 0 ° C.

[Shore D Hardness] A sheet was prepared by injection molding at 25 ° C. and measured according to ASTM D-2240.

[Elastic yarn properties] <Spinning apparatus> Extruder: 30 mm diameter (L / D = 30) manufactured by Praco Co., Ltd. Extrusion temperature: 160-180-190-190 (die from hopper side) Spinner: 1 mm Diameter x 1 hole ・ Take-off speed 20m / min <Measurement method of physical properties of elastic yarn>
The measurement was carried out according to JIS L1096 with the following equipment and conditions. -Equipment used: Strograph W (manufactured by Toyo Seiki Co., Ltd.)-Sample size: 5,000 denier yarn x 200 mm-Chuck interval: 100 mm-Tensile speed: 300 mm / min-Measurement atmosphere: 23 ° C, 50% RH

Strength and elongation at break: JIS L1096
The measurement was performed under the same conditions as in the method of the strength at the time of extension, except that a device having a chuck interval of 50 mm was used. Permanent elongation: According to JIS K6301, the above yarn is 23
After elongating 100% at 50 ° C. and 50% RH and allowing to stand for 1 hour, the permanent elongation was measured.

[Polyetherester Block Copolymer] The following two types of polyoxyalkylene glycols were used as the polyoxyalkylene glycol used for the soft segment of the polyetherester block copolymer. (A) Neopentyl glycol copolymer poly (tetramethyleneoxy) glycol (copolymer of T and N, both ends of which are alcoholic hydroxyl groups): Asahi Kasei Corporation
Mn = 1480, Mv / Mn = 1.73, N content =
18.3 mol% (b) poly (tetramethyleneoxy) glycol: Hodogaya Chemical Co., Ltd., PTG-1,800, Mn = 182
8, Mv / Mn = 2.11

Example 1 1520 g of dimethyl terephthalate (manufactured by Mitsubishi Kasei Co., Ltd .; the same applies hereinafter) and 1,4-butanediol (Wako Pure Chemical Industries, Ltd.) were placed in a 15-liter conical reactor (VCR) manufactured by Mitsubishi Heavy Industries, Ltd. )), Reagent grade, same hereafter) 106
0 g of the polyoxyalkylene glycol of (a)
00g, Irganox 1010 (Ciba Geigy)
After charging 15 g and purging with nitrogen, 200 ° C. in a nitrogen atmosphere
Temperature. Then, 1.5 g of tetraisopropoxytitanate (Reagent 1st grade, manufactured by Tokyo Chemical Industry, same hereafter) was added. Then, after holding at 200 ° C. for 30 minutes, 230 ° C.
The ester exchange reaction was performed over 2 hours while stirring at 150 rpm. The amount of methanol distilled out was 94% of the theoretical amount. Then raise the temperature to 250
C., the pressure was reduced to 0.5 mmHg over 30 minutes while stirring at a rotation speed of 50 rpm, and then a condensation reaction was carried out for about 3 hours until no increase in torque occurred.

When the content of the reactor was extracted from the lower part, a polyetherester block copolymer was obtained as a transparent viscous polymer. Irganox 1 based on 100 parts by weight of the polyetherester block copolymer
010, 0.1 parts by weight of dilauryl thiopropionate (DLTP, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) and 0.15 parts by weight of TINUVIN327 (manufactured by Ciba Geigy).
A weight part was added, pelletized by extruder strand cutting at a temperature of 210 ° C., and vacuum dried at 70 ° C. for 12 hours. This polyetherester block copolymer had a Shore D hardness of 32 and an MFR of 23 g / 10 minutes. Using this pellet, a yarn is made by the above method,
Physical properties were measured. Table 1 shows an evaluation list.

Example 2 In Example 1, the charged dimethyl terephthalate 2070 was used.
g, 1440 g of 1,4-butanediol, and 2750 g of the polyoxyalkylene glycol of (a) were charged, and a transesterification reaction and a condensation reaction were carried out in the same manner.
The kind of the additive and the mixing ratio were similarly measured. The resulting polyetherester block copolymer had a Shore D hardness of 40 and an MFR of 21 g / 10 min. The obtained polyetherester block copolymer pellets were prepared in Example 1.
In the same manner as in the above, the yarn was measured for physical properties. Table 1 shows the result list.

Example 3 2490 g of dimethyl terephthalate charged in Example 1
The transesterification reaction and the condensation reaction were performed in the same manner except that 1,730 g of 1,4-butanediol and 2050 g of the polyoxyalkylene glycol of (a) were used. The kind of the additive and the mixing ratio were similarly measured. The obtained polyetherester block copolymer had a Shore D hardness of 56, MF
R was 21 g / 10 minutes. The obtained polyetherester block copolymer pellets were treated in the same manner as in Example 1,
The yarn was measured for physical properties. Table 1 shows the result list.

[0065]

[Table 1]

Comparative Example 1 A transesterification reaction and a condensation reaction were carried out in the same manner as in Example 1 except that the polyoxyalkylene glycol of (b) was replaced by 2500 g of the polyoxyalkylene glycol of (a). The kind of the additive and the mixing ratio were similarly measured. The resulting polyetherester block copolymer had a Shore D hardness of 45 and an MFR of 22 g / 10 min. Yarns were formed from the obtained polyetherester block copolymer pellets in the same manner as in Example 1, and the physical properties were measured. Table 2 shows the result list.

Comparative Example 2 Perprene® P-150U, a polyetherester block copolymer manufactured by Toyobo Co., Ltd. (soft segment: poly (tetramethyleneoxy) glycol)
, A yarn was prepared in the same manner as in Example 1, and the physical properties were measured. Table 2 shows the result list.

Comparative Example 3 LOMOD® B, a polyetherester block copolymer manufactured by GE (General Electric)
Using 0320 (soft segment: poly (propyleneoxy) glycol diimide diacid), a yarn was prepared in the same manner as in Example 1, and the physical properties were measured. Table 2 shows the result list.

[0069]

[Table 2]

Example 4 After preparing a monofilament raw yarn in the same manner as in Example 1,
After cooling in a water bath at 25 ° C., the film is stretched 4.5 times in hot water at 95 ° C., then annealed at 110 ° C., returned to the original state, and an elastic yarn (monofilament yarn) of 5,000 denier is obtained. Was. The physical properties of the obtained elastic yarn were measured in the same manner as in Example 1, and the results are shown in Table 3.

Comparative Example 4 An elastic yarn was obtained by stretching and annealing in the same manner as in Example 4 except that the polyetherester block copolymer used in Comparative Example 1 was used. The physical properties of the obtained elastic yarn were measured in Example 1.
The results were shown in Table 3.

[0072]

[Table 3]

[0073]

The elastic yarn of the present invention can be used for sanitary articles, such as gathers for disposable diapers and napkins with gathers.
Since it retains the physical properties required for members for stretchable compressive materials, clothing, etc., it can be suitably used for these applications. In addition, it can be used for daily necessities, for example, rubber bands, binding bands, and the like. Further, since the degree of blocking is small, the product can be stored for a long time under a constant environment. The film of the present invention is recyclable and can be incinerated without generating harmful substances.

Claims (2)

[Claims] 1. An elastic yarn comprising a polyetherester block copolymer obtained by copolymerizing the following components (a), (b) and (c). (A) a dicarboxylic acid component in which the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and an ester-forming derivative thereof; and (b) a short-chain diol component in which the short-chain diol component is an aliphatic diol and an ester-forming derivative thereof. The long-chain diol component is composed of a neopentylene oxide structural unit represented by the following formula (1) (hereinafter abbreviated as N) and a tetramethylene oxide structural unit represented by the following formula (2) (hereinafter abbreviated as T)
A polyether having an N ratio of 5 to 50 mol%, an alcoholic hydroxyl group at both terminals, and a number average molecular weight of 400 to 6,000. Embedded image T: —CH ₂ CH ₂ CH ₂ CH ₂ O— (2) 2. An elastic yarn obtained by stretching the elastic yarn according to claim 1.