JPS58180613A - Polyester type fiber containing dispersed fine particle and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain fibers containing dispersed fine particles without deteriorating the basic characteristics of the polyester type fibers and operability, by dispersing the fine particles in a polyester type polymer with a specific phosphorus compound as a dispersing medium. CONSTITUTION:Fine particles, e.g. TiO2, SiO2, polymer of tetrafluoroethylene, carbon black or a pigment, having <=5mum particle diameter are dispersed in a polyester type polymer with a phosphorus compound expressed by formula I (R1-R3 are 6-18C phenyl, biphenyl, naphthalene group or benzene nucleus having an alkyl or alkoxyl group; a is 0 or 1), and having 40-250 deg.C melting point as a dispersing medium. The contents of the phosphorus compound and fine particles are 0.5-12wt% and 0.05-5wt% respectively, and the content of the former is 2 times or more that of the latter. A compound expressed by formula II (n is 0 or 1) is preferably used as the phosphorus compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fine particle in which fine particles having a particle size of 5 microns (hereinafter sometimes abbreviated as μ) or less are dispersed in a polyester polymer using a phosphorus compound as a dispersion medium, and a method for producing the same. The object of the present invention is to easily modify polyester fines without impairing their operability or basic properties to obtain products with added value.

Polyester fibers have excellent physical and chemical properties and are widely used in clothing and industrial applications.

However, even though this polyester is delicate, (1) it has a silvery luster, (2) it has poor color development, (3) it is easily charged, (4) it melts and burns, and (5) it has poor wind resistance. There are also drawbacks such as the need for improvement in friction, and various research and development efforts have been made to improve this. for example,
For (1), add a matting agent such as Tie, or create an irregular cross-section; for (2), copolymerize with an ionic compound, or add finer surface dyeing by adding a roughening pigment such as smm; (For (branch) number ζ, add an antistatic agent or a conductive substance; for (4), add a flame retardant; for (5), make the cross section irregular and roughen the surface.

There are improvement techniques such as adding slippery substances, and it is often attempted to modify the fibers by adding fine particles of inorganic or organic compounds to polyester to reduce the size.

By the way, when the fine particles added as a modifier do not exhibit a melting point or have a melting point of 500°C or higher, the modification method is as follows:
Usually, scissor particles are dispersed and added to, for example, ethylene glycol before transesterification or polymerization, and the polyester is polymerized to obtain fibers with good particle dispersion. However, with this method, there are losses and contamination due to polymer switching.3. Problems such as ・ etc. are likely to occur, resulting in an increase in costs. Also, equity 56-4
A method of adding a pigment to a polymer using a dispersant as disclosed in Japanese Patent No. 7204 is also known, but at present no dispersant with good heat resistance and compatibility has been found.

On the other hand, as a method of adding a modifier and spinning after completing 1:& of polyester, for example, a method of injecting a flame retardant in the form of a melt into a spinning nozzle as seen in JP-A No. 49-2916, and a method of injecting a flame retardant into a spinning nozzle in the form of a melt, as described in JP-A No. 39-5214, No. Publication, Special Publication Showa 5b-4ass
The method of kneading or chip-blending the antistatic agent in the publication is attractive, but in both cases, the additive is mixed in the form of a solution with a melting point below the melting point of polyester, and unlike the present invention, the additive does not have a melting point or has a melting point of 500°. Fine particles that are incompatible with polyester fibers having a melting point of C or higher are added to polyester fibers.
There are no delicate or concentrated particles that were added after the spinning was completed and just before spinning, and were uniformly dispersed without deteriorating the physical properties of the polyester.

As a dispersion medium for polyester, there are many limitations as described below, and at present, a dispersion medium that is good for dispersing fine particles has not been found.

(υ Fine particles are uniformly dispersed and have good compatibility with polyester (solubility parameters are similar and melting point is 2.
50°C or higher) ■ Heat resistant (with little decomposition or weight loss even at 500°C) ■ Low viscosity change in the polymer during addition or after spinning (
(Polymer and inert) ■Those that do not produce color or odor ■Those that do not disintegrate or bleed out after addition (those that are solid at room temperature and have a large molecular weight) ■Those that do not reduce the properties or fastness of fibers υ) From the above background The present inventors have developed polyester polymerization for the purpose of obtaining polyester 4M fibers that have good passability through processes such as polymer spinning and drawing, are easy to change brands, have little contamination, and have high added value while taking advantage of conventional delicate physical properties. The present invention was arrived at as a result of extensive research on dispersion media and fine particles that uniformly disperse fine particles in a polymer immediately before spinning after completion of spinning, that is, the first invention of the present invention. is represented by the following general formula: A) Sai1 or -) Phosphorized particles with a melting point of 40 to 250℃ and fine particles that do not exhibit an FQIm point of less than 1 particle size or have a melting point of 500"C or more. has already been dispersed, and the phosphorus compound and W
Lifting platform L], 51mu11, where the heavy weight percent contained in one particle of the polyester polymer component is M and B, respectively.
0.05≦B45 and Mu22B, and the second invention relates to a fine particle-dispersed polyester-based fine particle that satisfies 0.05≦B45 and Mu22B. , lifting platform set as B, 0.5≦Mu≦12, 0.05
≦B≦5 and Mu 22B is satisfied, and the polyester-based fiber according to the present invention is characterized in that the polyester-based fiber is added after the completion of polymerization of the polyester-based polymer and immediately before spinning. Examples of fibers include terephthalic acid, isophthalic acid naphthalene 2.6 dicarboxylic acid,
Aromatic dicarboxylic acids such as phthalic acid and adipic acid,
Aliphatic dicarboxylic acids such as sepacic acid or their esters and ethylene glycol, diethylene glycol,
It is a polyester synthesized from a di-J compound such as 1,4 dibutanediol or un-4'-ethyl glycol, and especially J5 [means a polyester in which 80% or more of the structural units are polyethylene terephthalate]. .

As a dispersion medium, the general formula ji+ 0-P-OLs (R1
, "L2, Ls Fuchujima Tao is a phosphorus compound represented by a hydrocarbon residue containing one or more benzene nuclei of the same or different carbon number from 6 to 18) that satisfies the following conditions. Preferably, it means wood ends or those that do not have the ability to form esters.

ill 5 LI Ll', Polymer 1 has a heating loss of 10 vt% or less in Nl for <10 minutes, preferably 6 wt% or less, and has little color decomposition during the process up to polymer 1 & post-spinning (2) Polynisdel has similar solubility parameters to polyester. It has good compatibility with and has a melting point of 250'C.
(3) The viscosity of the polyester changes little during blending or after spinning, and preferably the terminal of the phosphorus compound is an organic group that does not have ester-forming ability, and Contains almost no moisture or impurities (4) From the viewpoint of bleed-out, in Fuzui, a phosphorus compound that is solid and has a large molecular weight, preferably a phosphorus compound with a melting point of 100 to 200'C and a molecular weight of 500 or more that satisfies the tea scoop. For example, 0 0 00
0 groups are mutually present (in the formula, 凰 is a C! ~ eta alkyl group or aJkoxy group, C6 ~ 'C) at least 1 benzene nucleus is present.
Hydrocarbon residues having more than 1,000,000 yen, -e, alkylene group, n, an integer of 0 or 1, etc., sulfates or phosphonates, especially those with high heat resistance and compatibility with polyester. Soluble phosphorus compounds are preferred. Although halogen-containing phosphorus compounds are excellent in terms of heat resistance, they are undesirable because they cause coloring of the polyester and a decrease in light resistance.

On the other hand, the fine particles that are uniformly dispersed in the dispersion rope are smaller than 5 μm.
Threads that aggregate and become coarse during spinning cannot be used because they tend to clog filters or break fluff during spinning. General wet or dry pulverizers such as ball mills, jet mills, and high-speed vibration mills can be used for micronization, and any method such as ultrasonic vibration 1 mechanical stirring may be used to mix the dispersion medium and the microparticles. .

In addition, the feature of the present invention is to obtain a high addition value 4i Q,) polynisple i axis by uniformly dispersing fine particles that are not compatible with polyester polymers, and the fine particles have no melting point or have a temperature of 500°C or higher. It must have a melting point and must not cause color decomposition during the spinning process. If the melting point of the fine particles is less than s o O'C, it is undesirable because they tend to melt and agglomerate when mixed with a polyester polymer, and their heat resistance also decreases.

Examples of cough particles include (1) TiO, which is well-known as a matting agent for synthetic delicate surfaces, and (2) titanium dioxide, which roughens and hardens delicate surfaces, as seen in JP-A-55-107512 and JP-A-56-125410. Sin used for coloring.

ALOs, C, Co3, etc., (3) conductive carbon black and 5nO1 type, (4) azo type, phthalocyanine type.

Organic pigments such as perylene-based pigments, inorganic pigments such as cobalt blue, titanium yellow, red iron oxide, and carbon black, (5) sulfonic group-containing compounds that can be dyed with cationic dyes as described in Japanese Patent Publication No. 11620/1983, etc. 6) Tetrafluoroethylene polymers and special N introduction 56- aimed at slipperiness
Mu J, O, -8i False 1 of Publication No. 1153j7 (711
1. Combustible IN additives include metal ta-rides such as antimony tin, mankan, cobalt, and zirconium, but the present invention is not limited thereto.

Dispersion medium 0) As a fine particle that can be uniformly dispersed in a phosphorus compound and exhibit its characteristics without problems in process passability or fiber properties.
', (J), SiO,, Tetrafluoroethylene l & stuff.

Pigments are particularly preferred, and one of the features of the present invention is that the fine particles are added and mixed after the completion of polymerization of the polyester polymer and immediately before spinning, thereby reducing side reactions and whitening (77,
The goal is to be able to eliminate problems such as loss, contamination, and rayon due to polymer switching.

Sub-)C In this defense, it is necessary to mix the dispersion medium and fine particles uniformly beforehand and then add them to the polymer, and in terms of dispersibility and secondary agglomeration of the fine particles, mixing of fine particles is difficult due to the storm of dispersion medium. It is 50% or more, preferably 60 liters or less, based on the seed. The dispersion medium and/or fine particles may have a size of 2 mm or more as long as there is no problem with dispersibility in the polyester polymer. When mixing both components, the fine particles are added to the molten dispersion medium by a conventional method such as mechanical stirring or ultrasonic vibration. In the Yoshiki invention, if the additives are mixed, there is no problem even if the mixed additive is used in a melted state or in a powdered state after being cooled to room temperature.

In order to reduce the viscosity of the polymer, decompose the J111 reaction 1 dispersion mechanism, and agglomerate the fine particles, the flAfr material of the dispersion medium and fine particles is made into a melt and injected into the polyester polymer just before spinning, and the percentage is uniformly mixed using a static mixer etc. & It is more preferable to disperse.

In addition, one of the requirements of the present invention is that when the weight percentages of the phosphorus compound and the fine particles contained in the dispersion medium relative to the polymer are M and B, respectively, &0.5≦A≦12, 0.05
．． S, Bmu 5?) It is necessary to satisfy A and 2B. As mentioned above, the fine particles are 0.1% by weight based on the phosphorus compound.
If the mixture exceeds the above, secondary agglomeration of fine particles is likely to occur, making it difficult to obtain a uniform dispersion state.Furthermore, in order to uniformly disperse Cough 1jj A&A in the polymer, the phosphorus compound must be present in an amount of 0.5% by weight or more. In addition, the fine particles are 0.
If the amount is less than 0.05% by weight, it is difficult to obtain the high value-added modified polyester resin according to the present invention. If the phosphorus compound is dispersed in the fiber in an amount exceeding 12% by weight, the spinning and drawing properties will be reduced. When C is contained in fibers in excess of 5% by weight, the value-adding effect is not much different from that in the case of 5% by weight, but on the contrary, there are strong negative factors such as increased cost, process passability, and poor delicate physical properties. Become.

From the above points, a particularly preferable content of phosphorus compounds is 2.
10% by weight, and 03% to 3% by weight for imitative particles.

# It is more preferable that the particles are [73011% or less] relative to the phosphorus compound.

The present invention has made it possible to easily obtain high value-added polyester fibers that have no problems in passing through processes such as polymer spinning and drawing, and are cost-effective in terms of brand switching and contamination.

The present invention will now be specifically explained using Examples.

Example 1 η1 = 0.65 dll'f (intrinsic viscosity measured using an isotropic mixed solvent of phenol and tetrachloroethane in a 6 o''C constant temperature bath using an Upperohde type viscosity needle is o, 6
5 dl/I) TiO, additive-free super bright polyethylene terephthalate chips were extruded using a 40φ extruder, and a mixed solution of the following dispersion medium and fine particles, which had been heated and mixed at 180°C in advance in the cough polymer stock solution tube, was added to the polymer. The mixture was injected to a concentration of 5 or 10% by weight, mixed with a static mixer, and spun from a nozzle. The spun yarn was stretched to 150 d using a roller plate method under normal conditions.
-9 out of 100 multifilaments of 48f were prepared.

A & liquid T10! The dispersibility is good and no coarse particles are observed.
Even when the mixed solution was added to the polymer, there was little change in the viscosity of the polymer, the number of fluff breakage during spinning and drawing was less than 1, and there was no coloration.

The Ti02 content of the obtained bipolar drawn yarn was 0.49% by weight and 0.97% by weight, and it was made by adding '11' and U at the early stage of electrolysis before the conventional ester reaction. There was no difference in dyeing spots and electron microscope observation from semi-dull yarn and full-dull yarn, and no tendency for fiber properties and color fastness to deteriorate was observed.

In addition, after carrying out this experiment, super bright polymer was discharged for 5 hours and the content was analyzed in the TL of the discharged thread, but TiO
It turned out that 2 was not detected and the brand could be changed easily.

In Comparative Examples 1 and 7, tristearyl phosphate (
The same test as in Example 1 was carried out using
) However, especially when 1% of 1031iJ was added, the dispersibility in polyester boll 7- and heat resistance were poor, resulting in large smoke generation and viscosity reduction during spinning, and frequent fluff breakage.

As Comparative Example 2, instead of TiO2 in Example 1, the particle size was 20
The fibers were spun using coarse calcium carbonate of μ or more, or the fibers had a lot of fluff and breakage, and only the fibers with a high undrawn yarn content were obtained.

Example 2 In advance,
Melt a dispersion medium called 2-1 Neil Posbonate, add finely powdered silica with a particle size of 1μ or less at a weight ratio of 5:1, mix it, cool it to room temperature, grind it to about 50μ with a bottle mill, and mix. A powder was created.

Next, 10% of the mixed powder was added to a polymer after completion of polymerization of polyethylene terephthalate containing 0.45% TjO.
After making semi-dull polyester chips with wt% addition [η) = OlA adl/fi, the chips were spun by a conventional method, concentrated into a tow of 400,000 dr, and stretched by a water bath drawing method.
．． 8 times grinding and mechanical crimp cutting to 1.5drX38■
Created a stable.

The obtained chips and fibers were observed with an electron microscope, but TiO
No aggregation of 2 or 8I02 was observed and they were uniformly dispersed.

Further, there was no fluff breakage during spinning and drawing, and no particular problems were observed in either fuming coloration or viscosity change. Furthermore, the results of differential heat and nuclear magnetic analysis by Shizuo showed that little diethylene glycol was produced and the melting point was 261°C, which was the same as that of ordinary polyester woven fabric.

The resulting stable was made into a 40-count cotton spun yarn and spun into a 2/2 twill fabric as warp and weft yarns, and then the fabric was reduced by 20% with hot caustic soda water #FIII and dyed black with a disperse dye. When dyed, a black fabric with unprecedented depth was obtained.

Furthermore, when the fiber surface of the dyed fabric was observed using an electron microscope, it was found that there were countless fine irregularities due to the elution effect of 81, which reduced diffuse reflection of light and appeared dark in color.

In addition, the phosphorus compound, which is a dispersion medium, is extracted by alkali treatment, and large irregularities are present in some places on the fiber surface.The a perspiration performance by wicking and Pyrex methods is 6 to 5 times that of conventional polyester, and the color fastness and fiber The result was that a fabric with high added value and low physical properties could be easily obtained.

Example 6 Di(biphenyl)phenylphosphonate was used as minute am and the decomposition starting point of 0.3 to 3μ was 3 as fine particles.
Using low polymerization degree tetrafluoroethylene at 20°C (803N, after pre-mixing both at 250°C in a ratio of 5:2).

Add 71j1 dyeing solution to one-on dyeable polyester polymer
% was added and spun to obtain a drawn yarn of 75d-52f.

When the drawn yarn was dyed with a cationic dye, there was no difference in dyeing amount, color fastness, etc. from the cationically dyeable polyester yarn with the addition of carcasses mixed liquid rice, and no dyeing spots were observed.

Furthermore, the massatu coefficient and 1/'1 of the drawn yarn obtained in the present invention
When the water repellency of the plain fabric was measured, it was found that it was easier to slip and had a higher water repellency than the control cationic dyeable yarn without additives, making it highly functional for outer clothing such as sportswear and raincoats. It has also been found that this functionality can also be used for film.

Dynamic mass coefficient Note 21 It water content is based on JIS-1079A method (spray method) Example 4 [ηJ-2(J, 68d]/f of polyethylene terephthalate polymer to one dispersion medium of tribiphenylphos/\- Cobalt blue is 9wt% and Is material is 0.9wt%.
% of the dispersion medium and the material so that the carbon black was added to 0.1 wt%. 'glIITi-('5Uudr-1
A 5Of solution-dyed multifilament was obtained. The filament was doubled to 1 million dr, stretched and crimped and cut to 8 drX.
After making a 76+W staple sol, I made a 6th grade wool spun yarn and used it as a carpet yarn to make a trial pile carpet.

The Ii material dispersibility of the additive mixture is good, and there is little fluff breakage during spinning and drawing, and there are no particular problems in passing through the spinning process.The navy blue pile car/cotton has no color unevenness and is bulky. The color fastness, compression recovery, light fastness, color fastness, and masaso color fastness are also the same as those obtained by the conventional method, and there is no discoloration.

In addition, as a brand change, after discharging polyethylene terephthalate containing no pigment for 5 hours, the fine particles were T10 as in Example 1! 0. 5% Svt% semi-dull yarn
Although the sample was collected for several days, there was no pigment contamination at all.

Patent applicant: Rishi Co., Ltd. Agent: Patent Attorney Ken Honda

Claims (1)

[Claims] (1) It is represented by the following general formula and has a melting point of 40 to 250°
The phosphorus compound of C and fine particles with a particle size of 5 microns or less and no melting point or a melting point of 500 ° C or more are dispersed, and the weight percentage of the phosphorus compound and fine particles relative to the polyester polymer component is determined respectively. Mu, B
If 0.5≦mu-12,0, L15≦Bmu5kamu and 2B, the fine particle dispersed polyester fiber is expressed by 0 or 1). Fine particle dispersed polyester fiber (3) according to claim 1, characterized in that the fine particles are any one of a polymer of Ti01, S, ox I tetrafluoroethylene, carbon black, or a pigment. Claim 4111
In a melt of a phosphorus compound represented by the fine-particle dispersed polyester wire ring described in Section 1 and having a melting point of 40 to 250°C, particles with a particle size of 5 microns or less do not show a melting point, or have a melting point of 300°C or more. A mixture in which fine particles are mixed and dispersed in an amount of 50% by weight or less is applied to the polymer between 0-5PA≧12 after completion of loading the polyester polymer and immediately before spinning.
, 0.052B≦5 and M≦2B (A and B are the addition weight percentages of the phosphorus compound and fine particles, respectively), mixed in a melt state, and then spun and produced by a conventional method. (6) A method for producing a polyester fiber dispersed in microparticles according to claim 114, characterized in that the method for producing a polyester fiber dispersed in microparticles is represented by 0 or 1). 70., 8102. 6 [Process for producing particle-dispersed polyester-based fine particles according to claim 4, characterized in that it is a polymer of tetrafluoroethylene, carbon black, or a pigment. (7) A patent characterized in that a mixture of a phosphorus compound and fine particles is made into a melt, injected into a polyester polymer just before spinning, and mixed in a stunner 24--Section 1!44 to 6 The method for producing the described fine particle dispersed polyester yarn - pongee