JPS5836280A - Polyester fiber structure with improved color - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a color-improved polyester fiber structure-Kl
Illll. More specifically, porous polyester fibers with special micropores are dyed, the surface of which is coated with a polymer having a lower refractive index than the porous polyester rut fibers, and #1 dyeing with improved color is produced. The present invention relates to a polyester fiber structure exhibiting sharpness and sharpness.

Polyester is widely used as a synthetic fiber because it has many excellent properties. However, compared to natural woven fibers such as wool and silk, cellulose fibers such as rayon and acetate, and acrylic fibers, polyester fibers have the disadvantage that they are inferior in color development and clarity because they are dyed in lIK and KR colors. There is.

In the past, attempts have been made to improve dyes and chemically modify polyester in order to overcome this drawback, but none of them have been sufficiently effective. In addition, a method for forming a transparent thin film on the surface of polynisder fibers and a method for forming a transparent thin film on the surface of polynisder fibers, and
A method has been proposed in which moldy unevenness is formed on the fiber surface by applying plasma irradiation at 500 mm.-.C/-.

However, even with these methods, the effect of improving the depth of color is opaque, and in addition, the transparent thin film formed on the fiber surface easily falls off when washed, etc., and its durability is also opaque. In the method of applying plasma irradiation, there is no unevenness on the surface of the fibers in the woven or knitted parts that will be in the shadow of the irradiated surface, so the smooth fiber surface will not appear on the surface due to the rolling of threads within the woven or knitted structure that occurs during wear. It has the disadvantage of causing color spots.

On the other hand, as a method of imparting irregularities to the surface of polyester fibers, I1m fibers made of polyester containing polyoxyethylene glycol or polyoxyethylene glycol and a sulfonic acid compound were treated with an alkaline aqueous solution to align them in the fiber axis direction. A method for producing hygroscopic fibers formed on the surface of microporous fibers, or zinc oxide.

A hygroscopic fiber that forms fine pores when treated with an alkaline aqueous solution to elute the inorganic fine particles from a polyester fiber prepared by adding fine particles of an inert inorganic substance such as magnesium phosphate into a polyester reaction system. Manufacturing methods have been proposed. However, the fibers obtained by these methods do not have the effect of improving color depth, and on the contrary, a decrease in visual density is observed. In other words, in these methods, if the treatment with the alkaline aqueous solution is not sufficient, no effect of improving the depth of color is observed, perhaps because unevenness occurs only on the very surface of the fiber, and if the treatment with the alkaline aqueous solution is not sufficient, the effect of improving the depth of color is not observed. However, rather than improving the depth of the color, the visual density decreases, perhaps due to the diffuse reflection of light by the micropores, and even if the color is darkened, it looks whitish, and the strength of the resulting clutter decreases. It is not suitable for practical use because it deteriorates significantly and easily becomes fibrillated.

In addition, fibers made of polyester containing inorganic fine particles such as silica having a particle size of less than S atμ are subjected to an alkali reduction treatment to provide irregular irregularities of α2 to α7μ on the fiber surface, and m0A-20 (A method has been proposed to improve the depth of color by making the fine irregularities of Jllp exist. However, even with this method, the effect of improving the depth of color is insufficient, and in addition, it is extremely complex. This may be due to the uneven shape.

There is a drawback that the unevenness is destroyed by external physical action such as abrasion, and the destroyed part becomes significantly discolored or has a difference in gloss compared to other undestructed parts.

In order to provide a polyester fiber structure which does not have the above-mentioned drawbacks and has excellent color depth and clarity, the present inventors have developed a method in which a one-porous polyester fiber is combined with at least a dicarboxylic acid, mainly terephthalic acid, or an ester-forming derivative thereof. A first stage reaction in which glycol ester of dicarboxylic acid and/or its low polymer is produced by reacting with one type of glycol, and a second R stage reaction in which the mosquito reaction product is polycondensed, and polyester is produced by K. In doing so, (a) α3 to 5 mol of orthophosphoric acid to the dicarboxylic acid component, and (
Gong Kai Sei Lin II! A polyester fiber obtained by melt-spinning a polynisdel obtained by adding Mn and/or Mg compounds in an amount of L2 to 2 times the mole of (without reacting with (b) in advance) is Treated with an aqueous solution of the compound to elute 2 to 50 weight of isthmus fibers.
proposed. However, when polyester fibers containing Mn and/or Mg compounds are treated with an aqueous solution of an alkali compound, the coloring of the polyester fibers is reduced, and K, which improves sharpness, is found to be inconvenient.

The present invention is the result of intensive studies aimed at providing a polyester fiber structure that does not have the above-mentioned drawbacks and has excellent color depth and clarity. When a polyester fiber obtained by melt-spinning a polyester synthesized by adding a specific amount of calcium acetate to a polyester reaction system without reacting in advance is treated with an alkali, it is possible to form a large number of special micropores. After dyeing the nine-pore polyester fiber obtained, the surface portion is coated with a polymer having a lower refractive index than that of the cough fiber, thereby creating a polyester that has excellent color depth and clarity and is sufficiently resistant to discoloration due to friction. It was discovered that a fiber structure can be obtained, and based on this knowledge, l! As a result of repeated studies, the present invention was completed.

That is, the present invention has micropores arranged in the fiber axis direction, and in the frequency distribution of the micropores, the value having the maximum s1 degree is +lLl~α with respect to the width in the cross-sectional direction perpendicular to the fiber axis.
It is within the range of 5μ, and the length in the fiber axis direction is α2~
A polyester characterized in that after dyeing a porous polyester fiber having a size in the range of 5 tones, the surface portion of the fiber is coated with a polymer having a refractive index lower than that of the porous polyester fiber. A first step in which a dicarboxylic acid, mainly terephthalic acid, or an ester-forming derivative thereof, which is a fibrous structure, is reacted with at least one type of glycol to produce a glycol ester of the dicarboxylic acid and/or a low polymer thereof. (a) at any stage until the synthesis of the polyester is completed.
(a) and (b) contain a pentavalent phosphorus compound of a5 to 3 moles relative to the acid component constituting the polyester, and a calclum compound (more than 1 time mole and less than L7 times the mole relative to the phosphorus compound). is added without reacting in advance, and then the synthesis of the polyester is completed, and the obtained polyester is melt-spun and then treated with an aqueous solution of an alkali compound to elute 2 weight or more of it. The micropores have micropores arranged in a frequency distribution, and the value having the maximum frequency in the cross-sectional direction perpendicular to the fiber axis is in the range αl - α5μ, and the length in the fiber axis direction is KIII. By doing so, it is possible to form a large number of micropores having a size in the range 11 of α2 to 5 tones,
After dyeing the resulting porous polyester fibers, the surface of the fibers is coated with a polymer having a lower refractive index than the fibers, resulting in superior color depth and clarity compared to K.

The polyester referred to in the present invention has terephthalic acid as the main acid component and at least one type of glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as the main glycol component. The main target is polyester.

It may also be a polyester in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/
Alternatively, it may be a polyester in which a part of the glycol component is replaced with the above-mentioned glycol other than the main component or another diol component.

The difunctional carboxylic acid other than terephthalic acid used here is, for example, in-7thalic acid.

Naphthalene dicarboxylic acid, diphenyl dicarmenic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, 5-sodium sulfoisophthal 11.7 dipine #, Sepacin II l 1
．． Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as 4-cyclohexanedicargenic acid. In addition, examples of diol compounds other than the above-mentioned glycols include cyclohexane-L4-dimetatool, neopentyl glycol, bisphenol, bisphenol S
Examples include aliphatic, alicyclic and aromatic diol compounds such as and polyoxyallic alcohols.

Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, usually terephthalic acid and ethylene glycol are directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol are transesterified, or terephthalic acid and ethylene glycol are transesterified. and ethylene oxide to produce a glycol ester of terephthalic acid and/or a low polymer thereof. It is produced by a step reaction and a second step reaction in which the reaction product of the first step is heated under reduced pressure and subjected to a polycondensation reaction until a desired degree of polymerization is achieved.

The pentavalent phosphorus compound used in the present invention is not particularly limited as long as it is pentavalent. For example, phosphoric acid triesters such as orthophosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, phosphoric acid mono- and diesters such as methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, Vilorin 112. Metalin 111. Types selected from condensed phosphoric acids such as polyphosphoric acid and their esters, pentavalent phosphorus compounds obtained by reacting these pentavalent phosphorus compounds with ethylene glycol and/or water, etc. The above phosphorus compounds can be used. Among these pentavalent phosphorus compounds, particularly preferred are phosphoric acid, phosphoric triesters, and phosphoric partial esters (
monoesters, diesters or mixtures thereof), etc.
The calcium compound used in the present invention is not particularly limited as long as it reacts with the pentavalent phosphorus compound described above to form a polyester Ki-soluble calcium salt. For example, calcium acetate, oxalate, benzoate, heptalate.

Organic calzenates such as stearates, borates, sulfates, silicates, carbonates, non-sulfuric salts such as monobicarbonate, chlorides such as chloride, ethylenediaminetetraacetic acid complex salts, etc. chelate compounds, pentahydroxides, oxides, methylates, ethylates), alcohols such as 13cholates)
IL7j-Nolato and the like can be mentioned. Organic carboxylic acid salts that are particularly soluble in ethylene glycol.

Halides, chelate compounds, and alcoholades are preferred, and organic carboxylates are particularly preferred.

Even if only one of the above calcium compounds is used alone,
An example of a polymer having a small refractive index as used in the present invention, which may be used in combination of two or more, is polytetrafluoroethylene.

Nato2 fluoroethylene-propylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer,
Tetrafluoroethylene? ) lafluoropropylene copolymer.

Polyfluorovinylidene, polypentadecafluorooctyl acrylate, polyfluorethyl acrylate,
Fluorine-containing polymers such as polytrifluoroisopropyl methacrylate and polytrifluoroethyl methacrylate, phoridimethylsilane, polymethyl hydrogen/
Examples include silicon-containing compounds such as silokinane and polydimethylsiloxane, ethylene-acetate picopolymers, acrylic esters such as polyethyl acrylate and polyethyl methacrylate, and polyurethane polymers.
It is not determined. Among these materials, the fiber substrate constituting the textile product may be appropriately selected from those having a small refractive index. In this case, it is desirable to select a material that has as large a difference in refractive index as possible with the substrate fiber.

The amount of the pentavalent phosphorus compound and calcium compound used in the present invention is the amount used as a catalyst or stabilizer during the production of ordinary polyester in order to give excellent color depth to the final polyester fiber. In order to impart transparency and lubricity to the polyester film, it is necessary to use a large excess amount far exceeding the amount used for forming internal precipitated particles. However, if a large excess of pentavalent phosphorus compounds and calcium compounds are added to the polyester reaction system, (a) the polycondensation reaction rate decreases)
Problems such as lowering of the softening point of polyester/1 @ generation of large agglomerated particles may occur, so it is necessary to avoid such problems and give the final polyester fiber excellent color depth and friction durability. In order to provide K, it is necessary to determine the amount of divalent phosphorus compound used and the ratio of the amount of calcium compound used to the amount of divalent phosphorus compound used. That is, if the amount of the pentavalent phosphorus compound used in the present invention is too small, the color depth of the final polyester fiber obtained will be insufficient, and as the amount is increased, the color depth will increase. However, when the amount of AtDK increases, the depth of color no longer shows any significant improvement, the abrasion resistance and durability deteriorate on the contrary, and it becomes difficult to obtain polynisdel with a sufficient degree of polymerization and softening point. This causes problems such as frequent cuts. For this reason, the amount of the pentavalent phosphorus compound to be added should be in the range α5 to 3 moles, particularly preferably in the range α6 to 2 moles, based on the acid component constituting the polyester. Furthermore, if the amount of calcium compound added is less than 1 mole of the amount of pentavalent phosphorus compound added, the color depth of the resulting polyester fiber will be insufficient, and the polycondensation rate will decrease, leading to high polymerization. It becomes difficult to obtain a polyester with a high temperature, and the softening point of the polynisder produced is significantly lowered. If a calcium compound is used in an amount exceeding 7 times the mole of a phosphorus compound with a reverse KS value, coarse particles of calcium salt of the polyester oligomer will be generated, and instead of improving the depth of color, it will actually deteriorate the visual appearance.
K becomes so that i* decreases. Therefore, the amount of calcium compound added to the pentavalent phosphorus compound should be in the range of more than 1 times the mole and less than 17 times the mole, and %
A range of KLI - 15 times the mole is preferred.

The calcium compound and the pentavalent phosphorus compound need to be added to the polyester reaction system without reacting in advance. By doing so, it becomes possible to produce uniform ultrafine particles in the insoluble particulate polyester.

If the calcium compound and the pentavalent phosphorus compound were reacted in advance to form a calcium salt of the phosphorus compound and then added to the polyester reaction system, the dispersibility of the insoluble particles in the polyester would be poor. Since coarse agglomerated particles are contained, the effect of improving the depth of color of the finally obtained polyester fiber is not observed, which is not preferable.

The above calcium compound and pentavalent phosphorus compound can be added in any order at any stage until the synthesis of the polyester is completed. However, if the pentavalent phosphorus compound is added at a stage where the first stage reaction has not yet completed, the completion of the first stage reaction may be inhibited, and such a large amount of calcium compound may be added to the first stage reaction. When this reaction is an esterification reaction, coarse particles are generated during this reaction.
During the transesterification reaction, the reaction may proceed abnormally quickly and cause a bumping phenomenon, so the timing of addition of at least 80% by weight of the calcium compound and the total amount of the pentavalent phosphorus compound should be set at the same time as the polyester. It is preferable that the reaction is carried out after the reaction in the first stage of synthesis has been substantially completed.

In addition, the timing of addition of the calcium compound and the hexavalent phosphorus compound should be determined when the second stage reaction has progressed too much, as particle aggregation and coarsening are unavoidable, and the color depth of the final polyester fiber becomes deeper. Because there is a tendency to yell insufficiently! The intrinsic viscosity of the reaction mixture in a step reaction is aS
Preferably before K is reached O The above calcium compound and pentavalent phosphorus compound may be added all at once at the above-mentioned addition time, added in two or more divided times, or continuously. May be added.

In the present invention, any catalyst can be used for the first stage reaction, but some of the calcium compounds mentioned above have the ability to catalyze the first stage reaction, particularly the transesterification reaction, and such compounds are used. When using this calcium compound, it is not necessary to use a separate catalyst.
It can be added before or during the reaction in the R stage to serve as a catalyst, but as mentioned above it may cause bumping, so the amount used is less than 20% by weight of the total amount of calcium compound to be added. It is preferable to keep it below -.

As explained above, a quantitative amount of the pentavalent phosphorus compound 041 and the calcium compound in a specific ratio to the phosphorus compound are added to the polyester reaction system without reacting in advance, and then the polyester is synthesized. By completing the process, it is possible to obtain a polyester that has a high degree of polymerization, a high softening point, and good passability through the spinning process, and can finally provide fibers with excellent color depth and friction durability. can. K, which is obtained by melt-spinning the polyester thus obtained into fibers, does not need to employ any special method, and any ordinary melt-spinning method for polyester fibers may be employed. The fibers spun here may be solid fibers without hollow portions or hollow fibers with hollow portions, but in the case of hollow fibers, even if micropores are formed, the depth of color It is preferable to use solid fibers because they tend to be slightly inferior to those of solid fibers. Further, the outer shape and the shape of the hollow portion in the cross section of the fiber to be spun may be circular or irregular. When spinning, a modified polyester to which the above-mentioned pentavalent phosphorus compound and calcium compound are added and an unmodified polyester to which no additives are added are used, and a core sheath having a modified polynisdel as a sheath component and an unmodified polyester as a core component is used. It may be made into a type conjugate fiber or a side-pie-side type conjugate fiber with two or more layers using modified polyester and unmodified polyester.

K, a part of which is removed from the polyester fiber thus obtained, can be removed by subjecting it to stretching heat treatment, false twisting, etc. as necessary, or by immersing it in an aqueous solution of an alkaline compound after making it into a fabric. Yong JIK can be done.

Examples of the alkali compounds used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, and the like.

Among these, sodium hydroxide and potassium hydroxide are particularly preferred.

The aqueous solution of the alkali compound varies depending on the type of alkali compound, processing conditions, etc., but is usually ao1 to
40 weight - is preferable, especially α! A range of ˜30 wt.

The treatment temperature is preferably in the range of room temperature to 10eC, and the treatment time is usually in the range of 1 minute to 4 hours. Further, the amount of alkaline compound to be eluted and removed by treatment with the aqueous solution should be in the range of 2 to 2 to 10% by weight based on the weight of the fiber. By treating with an aqueous solution of an alkaline compound in this way, the fiber has fine pores arranged in the axial direction, and the value having the maximum S degree in the frequency distribution of the pores is the width in the cross-sectional direction perpendicular to the fiber axis. It is possible to form a large number of micropores with a size in the range of αl-α5μ, and the length in the fiber axis direction is in the range of α2 to 5#, resulting in excellent color depth when dyed. K becomes like this.

In addition, polynisdel obtained by the method of the present invention includes:
Optional additives as necessary, such as catalyst 1 coloring fat-blocking agent,
A heat resistant agent, a flame retardant, a whitening agent, a matting agent, a coloring agent, non-mildew particles, etc. may be included.

As mentioned above, when the porous polyester fiber with a large number of micropores is dyed, it exhibits excellent color depth and clarity, and especially when dyed in a negative color, the effect is #9.
I got rejected for wearing S, but L! By coating the surface portion with a low refractive index polymer, even better color depth and clarity can be obtained.

The low refractive index polymer that coats the surface of porous polyester fibers is usually commercially available in the form of an organic solvent solution or an aqueous emulsion. The form is preferable.

The method of coating the surface of the porous polyester fiber with the low layer refractive index polymer emulsion Mly f is preferably a puffing method or a spraying method for a woven or knitted fabric formed from the porous polyester fiber.

Kiss simple method, knife coating method9. Any method such as adsorption in a bath is possible. However, the surface coating of the low refractive index polymer of 11 KsP is not possible.

All types of filament, yarn woven and knitted fabrics, plain woven fabrics, etc.
It can be applied to IO fiber crystal production.

Regarding the reason why extremely superior color depth and sharpness can be obtained when the surface of a porous polyester fiber with a large number of micropores is coated with a polymer having a refractive index lower than that of the porous polyester fiber. is explained as follows.

Except for objects that emit light from themselves, such as radiators, the color of an object is generally determined by the reflection and absorption of light, but in order to make the color look deep and vivid, it is necessary to reduce the reflection of light and increase the absorption of light. When it comes to light reflection, it is especially necessary to reduce surface reflected light.

This is because the surface reflected light hardly contributes to deepening and sharpening the color of the colored body since the light is reflected by the white light 11. This surface reflected light can be broadly divided into specular reflection and diffuse reflection, but if the specular reflection component is reduced by making the surface of the fiber porous as in the present invention, the deep coloring and sharpening effect can be achieved. It can be further increased.

[As a method for eliminating the amount of light reflected from the K surface, there is a technique known both theoretically and empirically to apply a substance with a lower refractive index to the surface of the object than the object constituting the substrate. There is. An example of this is lens coding technology. This is a technology that reduces the amount of light reflected from the sand surface by coating the lens surface with a transparent thin film that has a smaller refractive index than glass.

Therefore, when the surface of the fiber is made porous, the specular reflection component due to K decreases, and when the surface is coated with a low refractive index polymer, the amount of surface reflected light due to K decreases.The synergistic effect of JIK greatly increases the amount of absorbed light. , it is believed that excellent color effects as in the present invention can be obtained.

Further explanation will be given below with reference to Examples. The parts in the examples indicate parts by weight, and the depth of color, fibril resistance, and size of micropores when the resulting polyester fibers were dyed and coated were kept constant by the following method. In addition, the viscosity of chloroquinane indicates the viscosity of chloroquinane itself, and all measurements were taken at 25°C. (1) Deepness of color Bathochromicity (v8) is used as a measure to indicate the depth of color, and this value is calculated by comparing the spectral reflectance (6) of Nangle to Shimadzu Re-330.
It was measured using a self-recording spectrophotometer and determined from the following Kubelka-Munk equation. The larger this value is, the greater the deep color effect is.

R K is the absorption coefficient, and K is the scattering coefficient.

(il) Using a Gakushin type flat abrasion machine for fibril resistance friction fastness test, using a georgette made of polyethylene terephthalate took as the friction cloth, the test cloth was abraded a predetermined number of times under a load of 5oot. , Check the occurrence of discoloration on the sea bream.

G11l Size of micropores Unravel the fabric after alkali treatment and reduce the surface of the fibers by 50
Judgment was made with the naked eye based on an electron micrograph taken at a magnification of oo.

Example L <1') Production and dyeing of porous polyester fibers Transesterification of 100 parts of dimethyl 7-talate, 60 parts of ethylene glycol, and 06 parts of calcium acetate monohydrate α (aS 67 rues relative to dimethyl prephthalate) Pour into cans and heat from 140℃ to 10℃ of snow in a nitrogen gas atmosphere for 14 hours.
The temperature was raised at ★, and the transesterification reaction was carried out while the methanol produced was scavenged out of the system. Calcium acetate monohydrate assll (a·10 mole relative to dimethyl terephthalate) was added to the reaction product obtained. and then after 5 minutes amsg orthophosphoric acid (a69 for dimethyl prephthalate).
Add antimony trioxide a for another 5 minutes.
3.0 g was added and transferred to a polymerization can. Next, the pressure was reduced from 760°C to 120°C over 1 hour, and at the same time, the temperature was raised from ZSO°C to 285°C over 1 hour and 30 minutes.

Under reduced pressure of LwmH9 or less, the SO portion was polymerized for an additional 1 hour at a polymerization temperature of 285°C, for a total of 4 hours, until the intrinsic viscosity was α646. A polymer having a softening point of 262°C was obtained. After the reaction was completed, the polymer was made into chips according to a conventional method.

This chip was dried in a conventional manner and melt-spun in a conventional manner using a spinneret having 36 circular spinning holes with a hole diameter of aS to obtain an undrawn yarn of 328 denier/36 filaments.

Next, this undrawn yarn was stretched 4 times in accordance with a conventional method, and 7
A multifilament of 3 denier/36 filaments was obtained.

The obtained filament was woven into a strongly twisted plain fabric with a basis weight of 1 oof/m, and after scouring and presetting by a conventional method, it was woven with an aqueous sodium hydroxide solution of YuS- at boiling temperature so that the weight loss rate was to@yc. Processed.

Table 1 shows the size of the micropores resulting from this alkali treatment. The fabric of this treated piece was DiamlxBlack H (
)-78 (product of Mitsubishi Chemical Industries, Ltd.) After staining at 130°C for 6 minutes with tS% owf, dye at 70°C with an aqueous solution containing caustic soda-1f/L and hydronalphite lf/l.
The cloth was reduced and washed for 20 minutes to obtain an ink-dyed cloth. Table 1 shows the depth of color of the black cloth. Further, no discoloration was observed after wear z'oo.

(■) Manufacture of low refractive index polymer and surface coating of porous polyester fiber @ l 00 ocs dimethylpolysiloxane ma
r, tall fat containing basic oleic acid g@sr, ts
Weight - Ammonia water α5f.

Tori, ethanolamine α'16? , water 411L 75t
Don't homogenize! + Mixing to obtain a mixed solution.

Polymer solid content equivalent Sf obtained under the above conditions for ink-dyed cloth
, pick up an anionic emulsion blind treatment agent consisting of 5OOF of water by padding ys*), and after drying too much
Heat set for 1 minute with The depth of the obtained treated fabric is shown in 1st IIK.

Further, no discoloration was observed after 200 wears.

Example 2 The procedure was the same as in Example I, except that the amount of calcium acetate hydrate added after the end of the transesterification reaction was changed to a64 parts (αyos moles relative to dimethyl pre-7talate) K. I did it. The result is 11th! It was as shown.

Examples & Trimethyl phosphate αS moiety (a693 for dimethyl terephthalate)
The same procedure as in Example 1 was carried out except that mol.

The results were as shown in Table 1.

Number of works carried out (1) Manufacturing and dyeing of porous polyester fibers 1111
Trimethyl phosphate CLs moiety (for dimethyl terephthalate (L6
93 mol) and the ethylene glycol LS part in advance.
The same procedure as in Example 1 was carried out except that the reaction product obtained by reacting at 6 cK for 6 hours was added. There were nine results as shown in Table 1.

(1) Production of low refractive index polymer and surface coating of porous polyester In a 400cc stainless steel autoclave, nitrogen was maintained under 5tys of air and ionized water was heated to 20 liters.
Add ammonium acid LlF and am4nium perfluoro-n-octanoate α1lltf as an emulsifier, close the container, cool in a dry ice/acetone bath, and add l
Vacuum up to 40% and then add 40% detrafluoroethylene.
, introduce propylene 201, shake the container, and
The temperature of Q'cK was raised and polymerization was carried out for 8 hours. The reaction was then stopped, cooled to room temperature, and an extremely stable tetrafluoroethylene-propylene copolymer with a dry solid content of 20 bags was prepared. Obtained Luji Seal.

A black dyed cloth was padded with an emulsion treatment agent consisting of 3 grams of Na2-fluoroethylene-pcubylene copolymer obtained in the above reaction in terms of solid content and 5 ounces of water, then picked up for 80 minutes and dried at 160°C for 1 minute. Heat set.

The depth of color of the obtained treated fabrics is shown in the gt table.

Comparative Examples 1 to 1 The same procedure as in Example 1 was conducted except that the amounts of calcium acetate hydrate and orthophosphoric acid added after the transesterification reaction were changed to the amounts listed in Table 1. The results were as shown in Table 1.

Comparative number of bulky stirring dispersion Im (stirring blade outer diameter 28cm, outer diameter 11111I
Within % 2'h■, S G OO
RPM rotation speed has stopped falling / A mixed solution of 100 parts of s6 aqueous solution of acid, tso parts of ethylene glycol, and calcium acetate! A high-speed stirring dispersion treatment was carried out for 60 minutes with 352 parts of aqueous salt and 40% ethylene glycol solution. The final internal temperature reached at this time was 70° C., and a slurry was obtained in which most of the calcium salt of orthophosphoric acid was uniformly dispersed as fine particles of A3 or less. This slurry was left in a container for 72 hours to separate coarse agglomerated particles. Example 1 The same procedure as in Example 1 was carried out except that a corresponding amount of this slurry was added in place of calcium acetate monohydrate and orthophosphoric acid, which were added after the transesterification reaction. The results are shown in Table 1.

Claims (7)

[Claims] (1) It has micropores arranged in the fiber axis direction, and the value having the maximum frequency in the frequency distribution of the micropores is the width in the cross-sectional direction perpendicular to the fiber axis. After dyeing a porous polyester fiber having a size in the range of ~αsp and a length in the fiber axial direction in the range of α2 to 5 tones, the surface of the fiber is dyed with a refractive index lower than that of the porous polyester fiber. 1. A polyester fiber structure characterized by being coated with a polymer having a polyester fiber structure. (2) The porous polyester fiber reacts with a dicarboxylic acid mainly consisting of terephthalic acid or its ester-forming conductor and at least one type of glycol to produce a glycol ester of dicarboxylic acid and/or a low polymer thereof. During the first step of the reaction and the second step of polycondensation of the reaction product to produce a synthetic fiber made of the polyester synthesized by K, at any stage until the synthesis of the polyester is completed. (conversion) A phosphorus compound having a valency of αs-3 mol-05 with respect to the acid component constituting the polynisder and a calcium compound (more than 1 mole and less than L7 times the phosphorus compound) (a) and (b) are added without reacting in advance, and then the synthesis of polyester is completed and the cleared polyester is converted into a.
After im-spinning, part 2 is formed using an aqueous solution of an alkaline compound.
4111F11 The polyester fiber structure according to item 1, which is a porous polyester fiber obtained by eluating a weight of -4111F11 quintillion. (3) Claim 2 le@OII!, wherein the SSO phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphorus iron and its ester. Lyester fiber structure. (4) The polyester fiber structure according to claim 2 or 3, wherein the calcium compound is an organic carboxylate of calcium. (5) The polyester fiber structure according to any one of claims 2 to 4, wherein the amount of the calcium compound added is L1 to t5 times the mole of the pentavalent phosphorus compound. (6) The entire amount of the pentavalent phosphorus compound and at least 180% by weight of the calcium compound are added after the stage where the first stage reaction of the polyester synthesis is substantially completed and the second stage reaction is performed. The intrinsic viscosity of the reaction mixture at al
The polyester fiber structure according to any one of claims 2 to 5, wherein the polyester fiber structure is formed in any order before reaching K. (7) The polyester fiber structure according to any one of claims 2 to 6, wherein the glycol used as a raw material for the polyester is an alkylene glycol having 2 to 4 carbon atoms.