CN101182661A - Polyoxymethylene fiber produced sewing thread - Google Patents

Abstract

The invention provides a sewing thread, in particular to a sewing thread including polyformaldehyde fibres, with the advantages of enough sewing intensity, excellent sewing property, repeat shrinking and distortion along with the fabric, being unable to be broken, and high tension recovery ability.

Description

Polyoxymethylene fiber produced sewing thread

Technical field

The present invention relates to contain polyoxymethylene resin fiber, have excellent elongation recovery, a seamability (Sew) etc. sewing thread.

Background technology

As hand suture (Shou Sew yarn), the machine line known in the past sewing threads that contains polyester, cotton, thin,tough silk, nylon etc. of sewing thread such as (ミ シ Application yarn), use to the various uses of industrial use in the dress material purposes.Above-mentioned sewing thread necessarily requires DIMENSIONAL STABILITY, seamability, intensity etc., and people have carried out a lot of improvement in order to meet the demands.

Recently, the situation that necessarily requires to have elongation recovery highly for sewing thread increases.For example in the violent motion dress material field of action or require in the material fields such as underwear of sense comfortable and easy to wear, adopt the lining that contains extendible cloth and silk mostly, in it is made, need to follow the sewing thread flexible, that can keep extending recovery of cloth.In the industrial sector purposes, sometimes cloth and silk being applied heavily stressed, cloth and silk has bigger elongation, must adopt the sewing thread with elongation recovery highly equally.Relative therewith, known in the past sewing thread can't be followed the flexible of cloth, when making, the problem of sewing thread broken string often takes place when stretching repeatedly, can not fully meet the demands.

For addressing the above problem, disclose in the TOHKEMY 2002-54047 communique that to contain poly terephthalic acid Sanya methyl esters be machine line polyester, elongation recovery excellence.

But, the essence of disclosed technology is to have certain above elongation recovery by being adjusted to too not high this sewing thread that makes of the broken string intensity that makes the machine line in the TOHKEMY 2002-54047 communique, be by sacrificing the technology that intensity obtains to extend recovery, therefore as the machine line, can't obtain enough intensity by making, its purposes is limited.

Summary of the invention

The present invention is that background is carried out with above-mentioned conventional art, and its purpose is to provide has enough intensity and excellent seamabilities made, can follow simultaneously cloth and silk dilatation repeatedly, can not break, have the sewing thread that highly extends recovery.

The inventor has carried out deep research for achieving the above object, found that: polyformaldehyde fibre satisfies above-mentioned performance fully, is the optimal material as sewing thread, thereby has finished the present invention.

That is, the present invention relates to contain the sewing thread of polyformaldehyde fibre.The present invention still is the purposes of polyformaldehyde fibre in sewing thread.

The fiber applications that will contain acetal resin in sewing thread and about polyformaldehyde fibre have enough make intensity, also have an elongation recovery of height simultaneously, this be in the past technology and known document in unknown fully.

The sewing thread (long filament (Off イ ラ メ Application ト yarn), staple fibre yarn (Spinning Performance yarn)) that contains polyformaldehyde fibre of the present invention has makes intensity and excellent seamability fully, simultaneously, have the dilatation repeatedly of following cloth and silk and the elongation recovery of the height that does not break, the utmost point is suitable as the sewing thread of material fields such as motion dress material field, underwear, industrial sector purposes.

The specific embodiment

Below describe the present invention in detail.The acetal resin that constitutes fiber is not particularly limited, and POM-H Acetal homopolymer, polyacetal copolymer (comprising terpolymer etc.) etc. all can be used.Its molecular structure also is not particularly limited, can use have linear chain structure, also can use and have side chain or cross-linked structure.Wherein, from preparation heat endurance or each characteristic such as the easiness of processing, the durability that fiber had during fiber and the processability equal angles consideration when forming sewing thread, preferably use polyacetal copolymer by fiber.

More particularly, preferably in the main polymer chain that repeats to form by formaldehyde unit, every 100mol formaldehyde unit contains the polyacetal copolymer (A) of the oxyalkylene units shown in the following general formula of 1.5～8.0mol (1).The more preferably ratio of the oxyalkylene units shown in the general formula (1) is that every 100mol formaldehyde unit is 1.8～5.0mol, and preferred especially every 100mol formaldehyde unit is 2.0～4.0mol.The ratio of oxyalkylene units is few shown in the general formula (1), and then the crystallization rate of polyacetal copolymer is accelerated, and not only the fracture of wire during spinning increases in the fiber manufacturing step, and because degree of crystallinity increases draftability the tendency of reduction is arranged also after the spinning.On the contrary, the ratio of oxyalkylene units is excessive, then the deficiencies such as intensity of fiber.

The acetal resin that uses among the present invention is preferably 1.0～120g/10 minute according to the melt index (MI) (MI) that ASTMD-1238 measures under 190 ℃, 2160g load, and more preferably 2.5～100g/10 minute, more preferably 5.0～90g/10 minute.

(MI) is excessive for melt index (MI), and then acetal resin is a low molecular weight, and therefore easy fracture of wire when spinning and stretching is made unstable.For the too small acetal resin of melt index (MI) (MI), owing to be high viscosity, so the load during spinning increases, difficulty in spinning, and tensile stress increases, and difficulty stretches.

Preparation method to the above-mentioned acetal resin that uses among the present invention is not particularly limited, when for example adopting polyacetal copolymer, usually can mainly use cationic polymerization catalyst, make three  alkane and obtain as the method that the cyclic ether compound or the cyclic formals compound of comonomer carries out bulk polymerization.Polyplant can use known any device such as batch (-type), continous mode.The importing ratio of the oxyalkylene units of above-mentioned general formula (1) expression can be regulated according to the amount of the comonomer of copolymerization, when melt index (MI) (MI) can be according to polymerization employed chain-transferring agent for example the addition of dimethoxym ethane etc. regulate.

The cyclic ether compound or the cyclic formals compound that use as comonomer have: oxirane, expoxy propane, epoxy butane, styrene oxide, oxetanes, oxolane, trioxepan (ト リ オ キ セ パ Application), 1,3-dioxolanes, propylene glycol formal, diethylene glycol (DEG) formal, triethylene glycol formal, 1,4-butanediol formal, 1,5-pentanediol formal, 1,6-hexylene glycol formal etc., optimization ethylene oxide, 1 wherein, 3-dioxolanes, diethylene glycol (DEG) formal, 1,4-butanediol formal.Polyacetal copolymer can have side chain or cross-linked structure.

The polyacetal copolymer that obtains by polymerization is after the washing of the removing of the inactivation treatment of having carried out catalyst, unreacted monomer, polymer, drying, unstable terminal stabilization processes etc., can carry out stabilization processes etc. by cooperating known various stabilizing agent, thereby supply in practical application.Representational stabilizing agent has: the hydroxide of hindered phenol based compound, nitrogen-containing compound, alkali or alkaline-earth metal, inorganic salts, carboxylate etc.

The acetal resin that uses among the present invention can be in the scope of not damaging purpose of the present invention, adds for example one or more of filler etc. of colouring agent such as dyestuff, pigment, lubricant, nucleator, releasing agent, antistatic additive, surfactant or high-molecular organic material, inorganic or organic fiber shape, tabular, powder shape of additive commonly used in the thermoplastic resin as required.

The fiber that uses among the present invention can use above-mentioned acetal resin to be prepared as follows, but is not limited to this.

Fiber preparation method can adopt conventional melt spinning method.Specifically, the acetal resin of fusion plastification (plasticization) is extruded, batched from the die head with required cross sectional shape hole, obtain undrawn yarn by single screw rod or double screw extruder.Then, the continuous or discontinuous heating on one side of this undrawn yarn is stretched on one side, obtain containing the fiber of acetal resin.In the stretching process, can carry out stretch process by room temperature to the temperature range of fusing point, also different according to different optimum temperatures such as draw speed, stretching ratio, heating means, therefore need suitably regulate.Consider that from the uniformity or the intensity angle of fibre diameter stretching ratio is preferably more than 3 times, considers then preferred 4 times～12 times of fibre strength and percentage elongation.

Below, the preparation method of the sewing thread that uses above-mentioned resulting polyoxymethylene filament is described.The following acquisition of sewing thread of the present invention: the multifilament doubling and the sth. made by twisting that will have above-mentioned rerum natura, have required fiber number, perhaps preparation will be somebody's turn to do and twisted filament doubling and twist with the fingers the compound and twisted filament obtain, then also twisted filament to make rolling density (rolling up I density) be 0.25～0.5g/cm ³The curled hair body.According to the state of target or twisted filament, to be replaced by the bobbin that suitably is provided with a plurality of liquid-through holes and to carry out hot water treatment more than 90 ℃, this stabilisation for twisting is an effective method.Here, the doubling radical of multifilament and twist with the fingers number of times and and twist with the fingers the sth. made by twisting produced and can suitably select according to the design specification of known sewing thread to, twisting count etc., can use that known doubler twister preparation such as Italianism twisting frame (イ リ same form Ran Shito Machine) contains regulation plying number (Block ラ イ) and twisted filament.This is also identical under the situation of staple fibre yarn.Sewing thread also has staple fibre yarn except with the long filament of continuous long filament as raw material, and sewing thread of the present invention can be a staple fibre yarn.Staple fibre yarn is that the long filament that will obtain by melt spinning etc. stretches, curls (Volume Shrink), be cut into about 50mm or lower, with this staple fibre as raw material, by acquisitions such as combing operation, mixing in doubling step, slubbing operation, spinning operations.

Preferred especially sewing thread is prepared as follows: twist with the fingers at the end that the multifilament that contains acetal resin is applied the S direction of 400～1000T/m, with three doublings, applies the retwist of the Z direction of 500～1500T/m, carries out and twist with the fingers.

Among the present invention, passing through to use specific polyacetal copolymer (A), the preparation sewing thread the constituent long filament time common spinning manufacturing process in, has the characteristic of easily carrying out molecularly oriented by low stress, make fiber have intensity, toughness owing to the degree of orientation is high, and texture, the mechanical properties of non-weaving cloth also had a significant impact.Therefore, sewing thread of the present invention uses preferably that to carry out the degree of orientation that the wide-angle x-ray diffraction measure to calculate be that fiber more than 70% is as the fiber of its constituent.When the degree of orientation was too small, the fiber characteristic of enbrittling lacked practical application.

Orientation order order parameter (orientation order パ ラ メ one one) is obtained by following formula, calculates as the degree of orientation with S.

$S\&equiv;\frac{1}{2}[3<{\cos }^2\mathrm{\&phi;}>-1]$

$<\mathrm{co}{s}^2\mathrm{\&phi;}>=\frac{{\&Integral;}_0^{\frac{\mathrm{\&pi;}}{2}}I\left(\mathrm{\&phi;}\right)\mathrm{co}{s}^2\mathrm{\&phi;}\sin \mathrm{\&phi;d\&phi;}}{{\&Integral;}_0^{\frac{\mathrm{\&pi;}}{2}}I\left(\mathrm{\&phi;}\right)\sin \mathrm{\&phi;d\&phi;}}$

φ: molecule chain rivet and fiber axis angulation

Embodiment

Specify the present invention by the following examples, but the present invention is not limited by it.

Assessment item and evaluation method in embodiment, the comparative example are as follows.

[melt index (MI) (MI) mensuration]

According to ASTMD-1238, under 190 ℃, the load of 2160g, measure.

[the polymer composition analysis of polyacetal copolymer]

The polyacetal copolymer that uses in estimating is dissolved among the hexafluoroisopropanol d2, carries out ¹H-NMR measures.Carry out quantitatively with the composition of the pairing peak area in each unit constituent.

[degree of orientation]

Use wide-angle x-ray diffraction instrument (motor of science is made Rint-1400), use carries out X ray (Cu-K α) the pin hole light beam of monochromatization by the Ni filter disc and the in-plane scatter figure of dull and stereotyped image plate (IP) shooting transmission beam method is measured.Calculate by following formula.

$S\&equiv;\frac{1}{2}[3<{\cos }^2\mathrm{\&phi;}>-1]$

$<\mathrm{co}{s}^2\mathrm{\&phi;}>=\frac{{\&Integral;}_0^{\frac{\mathrm{\&pi;}}{2}}I\left(\mathrm{\&phi;}\right)\mathrm{co}{s}^2\mathrm{\&phi;}\sin \mathrm{\&phi;d\&phi;}}{{\&Integral;}_0^{\frac{\mathrm{\&pi;}}{2}}I\left(\mathrm{\&phi;}\right)\sin \mathrm{\&phi;d\&phi;}}$

φ: molecule chain rivet and fiber axis angulation

[intensity]

Use cupping machine, under the condition apart from 20cm, draw speed 20cm/ minute between chuck, measure the intensity of sewing thread.

[10% elongation recovery]

Using cupping machine, clamp sewing thread with 20cm between chuck, apply stretcher strain with 20cm/ minute, reach after the percentage elongation of regulation, with identical speed it is replied, is L2 with the length after replying, and raw footage is L1, and the amount shown in the following formula of calculating is as response rate.

Response rate (%)=L2/L1 * 100

The preparation of＜polyacetal copolymer A-1～A-10 〉

The polyacetal copolymer that uses in embodiment 1～10 prepares by the following method.

Use the twin shaft continous mode polymerization machine of band heat transfer medium with sleeve pipe, when two rotating shafts that make the band paddle are respectively with the 150rpm rotation, supply with continuously three  alkane, as the cyclic ether or the cyclic formals (1 of comonomer, 3-dioxolanes (DO), 1,4-butanediol formal (BF), diethylene glycol (DEG) formal (DEGF)), simultaneously will be as the dimethoxym ethane of molecular weight regulator, supply with the polymerization machine continuously as the boron trifluoride 50ppm (with respect to whole monomers) of catalyst, carry out bulk polymerization, the polymer of the amount of comonomers shown in the preparation table 1.The amount of copolymerization units is regulated by employed amount of comonomers, and melt index (MI) (MI) passes through the amount of the dimethoxym ethane that added to be regulated.The heat transfer medium of the polymerization machine warm water that feeds 80 ℃ in the sleeve pipe.

Promptly cross disintegrating machine by the product that the polymerization machine is discharged, join the deactivation of carrying out catalyst in 60 ℃ the aqueous solution that contains 0.05 weight % triethylamine, separate again, washing, drying, obtain thick polyacetal copolymer.

Then, with respect to this thick polyacetal copolymer of 100 weight portions, add the aqueous solution that 4 weight portions contain 5 weight % triethylamines, [3-(3 for 0.3 weight portion four, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, with double screw extruder at 210 ℃ of following melting mixings, extrude, the unstable end portion of thick polyacetal copolymer is decomposed and removes thus, has obtained terminal stable polyacetal copolymer.

In the polyacetal copolymer that 100 weight portions obtain by said method, add 0.03 weight portion as stabilizing agent four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.15 weight portion melamine, at 210 ℃ of following melting mixings, obtain being used to supplying with the graininess polyacetal copolymer that the present invention estimates (A-1～A-10) with double screw extruder.

Embodiment 1～10

The polyacetal copolymer that use prepares as stated above (A-1～A-10), by the barrel design temperature is that 200 ℃ extruder carries out fusion plastification, with the molten resin gear pump weighing of plasticizing, carry out melt spinning with the die head in 225 ℃ of nozzle temperatures, 48 holes, obtain undrawn filament.Then, undrawn filament is passed in the hot-blast heater that temperature in the other step is set at 138 ℃, is stretched to 5～7 times, obtain 148dtex/48 threads (monofilament: polyoxymethylene filament about 3dtex).And twist with the fingers at the end that the gained multifilament is applied 650T/m on the S direction, with three doublings, applies the retwist of 950T/m along the Z direction, by and twist with the fingers and obtain sewing thread.

Evaluation result is as shown in table 1.

When using polyacetal copolymer A-7～A-9, fracture of wire often takes place in preparation section for preparing undrawn filament by melt spinning and stretching process thereof, stability, the productive rate of fiber process are low.In addition, when using polyacetal copolymer A-10, resin is a high viscosity, and therefore the load that when plastifying extruder screw is applied is big, and also difficult by the spinning of melt spinning die head in addition, stability, the productive rate of fiber process are low.When using the polyacetal copolymer of above-mentioned A-7～A-10, the evaluation result of table 1 is that the sewing thread than the long filament preparation that obtains under the stable state carries out in the short time to using, and its yield rate is extremely low.

Embodiment 11

Use POM-H Acetal homopolymer (manufacturing of デ ユ Port Application, デ Le リ Application 500P), with the barrel design temperature is that 210 ℃ extruder carries out fusion plastification, with the molten resin gear pump weighing of plasticizing, be that 225 ℃, the die head in 48 holes carry out melt spinning by nozzle temperature, obtain undrawn filament.Then, undrawn filament is passed in the hot-blast heater that in other step temperature is set at 140 ℃, is stretched to 5～7 times, obtain 148dtex/48 threads (monofilament: polyoxymethylene filament about 3dtex).All unstable in melt spinning operation and stretching process thereof, the fracture of wire that mostly occurs, processing stability, the productive rate of fiber are low.Use the short time than the elongate filaments that obtains under the stable state, twist with the fingers at the end that similarly applies 650T/m with the foregoing description on the S direction, with three doublings, applies the retwist of 950T/m along the Z direction, by and twist with the fingers and obtain sewing thread.Evaluation result is as shown in table 1.

Reference example 1-2

In commercially available industrial machine line, the long filament [525dtex (156dtex, 1 * 3)] of polyester, the long filament [175dtex (78dtex, 1 * 2)] of nylon system are estimated.

Sewing thread of the present invention and these commercially available sewing threads (machine line) are compared possibility and inappropriate, but sewing thread of the present invention as can be seen has enough intensity, have excellent elongation recovery.

Table 1

	The filament raw material polymer	Comonomer	Copolymerization units	With respect to 100mol formaldehyde (mol)	MI (g/ 10 minutes)	Constitute the degree of orientation of fiber	Intensity (GPa)	10% elongation recovery percentage (%)
									Embodiment 1	A-1	DO	(CH 2CH 2O)	2.3	5	0.94	0.70	93
Embodiment 2	A-2	DO	(CH 2CH 2O)	2.3	9	0.94	0.70	93
									Embodiment 3	A-3	DO	(CH 2CH 2O)	4.3	31	0.94	0.62	93
Embodiment 4	A-4	DO	(CH 2CH 2O)	5.7	45	0.94	0.60	93
									Embodiment 5	A-5	DEGF	(CH 2CH 2OCH 2CH 2O)	2.3	27	0.94	0.70	93
Embodiment 6	A-6	BF	(CH 2CH 2CH 2CH 2O)	2.3	27	0.94	0.70	93
									Embodiment 7	A-7	DO	(CH 2CH 2O)	0.48	9	0.85	0.59	93
Embodiment 8	A-8	DO	(CH 2CH 2O)	1.2	9	0.86	0.58	93
									Embodiment 9	A-9	DO	(CH 2CH 2O)	2.3	150	0.83	0.60	93
Embodiment 10	A-10	DO	(CH 2CH 2O)	2.3	1.0	0.80	0.58	93
									Embodiment 11	POM-H Acetal homopolymer	-	-	-	13	0.81	0.59	93
Reference example 1	Polyethylene terephthalate	-	-	-	-	-	0.54	69
									Reference example 2	Nylon	-	-	-	-	-	0.48	82

Claims (13)

1. sewing thread, it contains polyformaldehyde fibre.

2. the described sewing thread of claim 1, wherein, polyformaldehyde fibre is the polyacetal copolymer (A) that contains oxyalkylene units shown in the following general formula of 1.5～8.0mol (1) in every 100mol polyformaldehyde repetitive,

(in the formula, R ₁, R ₂Be selected from hydrogen, carbon number and be 1～8 alkyl, have organic group, phenyl that carbon number is 1～8 alkyl, have the organic group of phenyl, R ₁, R ₂Can be the same or different, m represents 2～6 integer).

3. the described sewing thread of claim 2, wherein, the every 100mol formaldehyde of polyacetal copolymer (A) repetitive contains the oxyalkylene units shown in the above-mentioned general formula of 1.8～5.0mol (1).

4. the described sewing thread of claim 2, wherein, the every 100mol formaldehyde of polyacetal copolymer (A) repetitive contains the oxyalkylene units shown in the above-mentioned general formula of 2.0～4.0mol (1).

5. each described sewing thread in the claim 2～4, wherein, polyacetal copolymer (A) has 1.0～120g/10 minute melt index (MI) (190 ℃, load 2160g).

6. each described sewing thread in the claim 2～4, wherein, polyacetal copolymer (A) has 2.5～100g/10 minute melt index (MI) (190 ℃, load 2160g).

7. each described sewing thread in the claim 2～4, wherein, polyacetal copolymer (A) has 5.0～90g/10 minute melt index (MI) (190 ℃, load 2160g).

8. each described sewing thread in the claim 2～4, wherein, polyacetal copolymer (A) has branch or cross-linked structure.

9. each described sewing thread in the claim 1～4, wherein, polyformaldehyde fibre is that to measure the axial degree of orientation of fiber that obtains by the wide-angle x-ray diffraction be polyformaldehyde fibre more than 70%.

10. each described sewing thread in the claim 1～4, wherein, sewing thread is that the end that the multifilament that contains acetal resin applies the S direction of 400～1000T/m is twisted with the fingers, and with three doublings, applies the retwist of the Z direction of 500～1500T/m, carries out and twists with the fingers gained.

11. each described sewing thread in the claim 1～4, wherein, sewing thread is the staple fibre yarn that contains the staple fibre of acetal resin.

12. each described sewing thread in the claim 1～4, wherein, 10% elongation recovery percentage is more than 90%.

13. the purposes of polyformaldehyde fibre in sewing thread.