KR20040009762A - Manufa cturing method for polyester filament having improved light fastness - Google Patents

Abstract

PURPOSE: A method of preparing polyester fiber having improved light fastness by copolymerizing polyester and ester-forming monomers is provided. The fiber is suitable for automobile interior decoration, curtain and outdoor application and can keep fresh color without fading even when exposed to sunlight for a long period of time. CONSTITUTION: The method of polyester fiber comprises: copolymerizing, spinning and drawing dicarboxylic acid, a diol component and an ester-forming monomer having the formula:R2OOC-R1-COOR3, wherein the ester-forming monomer is present in an amount of 0.05% by mole, based on the total dicarboxylic acid components. In formula, R1 is a naphthalene ring, R2 and R3 are selected from H or C1-4 alkyl group, R2 is independent from R3, it can be the same or different with R3; the position of substitute group for the naphthalene ring on the ester-forming monomer can be:( -2,3-, -2,5-, -2,6-, -2,7-, -1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-), subjecting the formed copolyester component to a spinning and drawing process to obtain fiber having excellent light fastness after dyeing.

Description

Manufacturing method of polyester fiber with improved light fastness {MANUFA CTURING METHOD FOR POLYESTER FILAMENT HAVING IMPROVED LIGHT FASTNESS}

The present invention relates to a method for producing a polyester fiber with improved light fastness, and in detail, after co-polyester formed by adding an ester forming unit containing a naphthalene ring structure to the polyester copolymerized by spin-stretching and dyed to make fibers Therefore, it has extremely excellent light fastness and can prevent deterioration due to ultraviolet rays, and is suitable for the use of interior curtains and outer surfaces of automobiles.

It is about maintaining a fresh color and not fading even when exposed to daylight.

Since polyester has unique properties, it is widely used in various applications such as fibers, films, and industrial plastics. Among them, the fibers are used not only for medical purposes, but also for home decoration, automobile interiors, and industrial fibers.

However, when it comes to the interior of the car, the final product is directly exposed to sunlight, and the dye molecules in the fiber are easily decomposed, degraded and discolored due to the effects of high temperature or ultraviolet rays.

Several methods have already been proposed to improve the light fastness of polyester fibers. For example, U.S. Patent No. 4,789,382 discloses a method of dyeing by adding a benzophenone ultraviolet absorber at the time of dye bath to improve light fastness.

In addition, U.S. Patent No. 4,110,301 discloses a photo rearrangement compound that can improve the light fastness of a polyester fiber, and the photoelectric potential compound is added to a salt bath or a spinning step. Can also be added from

Japanese Patent Laid-Open No. Hei 2-41468 improves light fastness by dyeing by adding a benzotria zole ultraviolet absorber in a salt bath.

Japanese Patent Laid-Open No. 4-339885 improves light fastness by dyeing by simultaneously applying a benzotriazole-based and a benzophenone-based ultraviolet absorbent in a salt bath.

In addition, Japanese Patent Application Laid-Open No. 62-276018 improves the light fastness of polyester fibers by adding three components of a benzotriazole-based ultraviolet absorber, a tetramethyl piperidine compound, and an aliphatic polyester polyol in the spinning step. Doing.

In Japanese Laid-Open Patent Publication No. 4-240212 in the latter stage of polyester polymerization

Light fastness by adding acrylic copolymer containing 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone (acrylic copolymer) containing 2-hydroxy-4- (metacrylooxye oxy) enzophenone structure It discloses a method for improving the.

U.S. Patent No. 4,189,476 uses 10-23 mole% of 2,6-dioxy naphtalene aromatic polyester to melt high elongation and high modulus modulus. Polyester fiber is produced. The capacity of the ester forming units comprising the naphthalene ring structure of the 2,6-dioxynaphthalene units used is up to 10-23 mol% and is made of molten polyester fibers of high elongation and high modulus. However, none of the above methods can be said to be excellent in effect, and new improvements are needed.

In Japanese Patent Laid-Open No. 62-276018, a tetramethylpiperidine-based compound is blended with a benzotriazole-based ultraviolet absorbent and an aliphatic polyester ester polyol component is added to improve light fastness. However, the problem that the sublimation fastness of the benzotriazole-based ultraviolet absorbent is not improved is not improved, and since the added aliphatic polyester polyol component is a low molecular weight substance, it causes a drawback of lowering the fiber properties.

In Japanese Patent Laid-Open No. 4-240212, an ultraviolet absorber of an acrylate ester copolymer containing a 2-hydroxyl-4- (methacryloyloxyethoxy) benzophenone structure is added, but the compound has poor heat resistance and polymerization. In the late stages, when added to the polymer, the color turns yellow and yellows the fibers. In addition, adding a powdery ultraviolet absorber at the end of the polymerization is difficult in the production process operation.

In the method of adding a benzophenone UV absorber and a benzotriazole UV absorber in a salt bath, the sublimation fastness of the benzotriazole UV absorber is lowered and the affinity for the polyester fiber of the benzophenone UV absorber is not excellent and is not effectively absorbed. . In addition, the benzophenone ultraviolet absorbers and the benzotriazole ultraviolet absorbers used above are yellow powders, and the fibers produced are pale yellow, resulting in inferior colors.

In addition, since the added UV absorber is a small-molecular weight substance and does not bind to the polymer, it is transferred to the surface of the fiber during post-processing or use, causing contamination, or washing the water with water to reduce its effective component or exposure to sunlight in the long term. When it is gradually degraded, the effect has been inhibited.

In view of the above, the present invention does not cause a problem that the UV absorber migrates to the fiber surface to reduce the active ingredient or cause contamination, and the fabric produced is dyed to white and yellow by the UV absorber. The present invention provides a method for effectively improving the light fastness of fibers that do not discolor or transition after dyeing.

Another object of the present invention is to provide a polyester suitable for the use of interior and exterior surfaces of automobiles having excellent light fastness and maintaining permanence and having a bright color dyed in white.

In order to achieve the above object, the present inventors have studied and copolymerized an ester-forming unit having a structure of the following formula (1) with polyester, and the fiber produced from the copolymerized ester formed therefrom has extremely excellent light fastness. I found something.

[Formula 1] R2OOC-R1-COOR3 ......... (1)

(R1 is a naphthalene ring R2, R3 is selected from a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, R2 and R3 are independent of each other, may be the same or not the same,

The position of the substituent on the naphthalene ring of the ester-forming unit in the formula is -2, 3-, -2, 5-, -2, 6-, -2, 7-, -1, 2-, -1, 3-, -1, 4-, -1, 5-, -1, 6-, -1, 7-, -1, 8-)

The copolymerization method does not cause a problem of shifting to the fiber surface in order to bond in the polyester molecules and causing contamination or lowering the sublimation fastness. In addition, the fiber properties produced for forming the copolymer ester are extremely good, and the physical properties of the fibers usually caused by the low molecular material of the added aliphatic polyester polyol are not reduced. The obtained copolymer ester has excellent white color, and generally does not have a problem of yellowing by the ultraviolet absorber, and the fabric is dyed to a fresh color, and there is no drawback of changing the color tone by dyeing.

Specific examples of the ester-forming unit of formula (1) used in the present invention include 2,6-naphthalenedicarboxylic acid, 2,6-didimethylnaphthalenedicarboxylate, 2,6-diethylnaphthalenedicarboxylate, 2 , 6-dibrofilnaphthalenedicarboxylate, 2,6-dibutylnaphthalenedicarboxylate, 2,5-naphthalenedicarboxylic acid, 2,5-dimethylnaphthalenedicarboxylate, 2,5-diethylnaphthalenedicarboxylate And 2,5-dibronaphnaphthalene dicarboxylate, 2,5-dibutylnaphthalene carboxylate, and the like.

In this invention, the addition amount of the ester forming unit of Formula (1) is 0.05-100 mol% of the whole dicarboxylic acid component, and when the addition amount is 0.05 mol% or less, the produced polyester fiber will acquire the outstanding light fastness. It cannot meet the needs for automobiles.

If there is much addition amount, the effect will become more excellent by that much. Substantial addition amount is determined as needed, but the basic addition amount is not necessarily 0.05 mol% or more, sufficient effect cannot be obtained.

In addition, when the content of the ester-forming unit of formula (1) is 20 mol% or more and 80 mol% or less, the formed copolymer ester becomes amorphous, and crystal drying does not proceed smoothly.

Therefore, from the practical point of view, the content of the ester-forming unit of formula (1) is preferably 0.05 to 20 mol% and 80 to 100 mol%.

The addition method of the ester formation unit which has the said naphthalene ring structure can be performed using a well-known polyester manufacturing process. For example, a dicarboxylic acid unit having a naphthalene ring structure, a terephthalic acid and an ethylene glycolic acid are simultaneously esterified, followed by addition of a known antimony or germanium-based polymerization medium to carry out a polymerization reaction to obtain a copolyester. . Alternatively, esters of dicarboxylic acids having a naphthalene ring structure, dimethyl terephthalate, and ethylene glycol are simultaneously transesterified, followed by polymerization by adding a stabilizer, antimony or germanium-based polymerization catalyst to obtain a copolyester. In addition, when the esterification reaction is carried out in telephthalic acid and ethylene glycol and the esterification rate reaches 85% or more, esters of dicarboxylic acid having a naphthalene ring structure are added, followed by reaction until the esterification rate reaches 96% or more, and polymerization is carried out. The polymerization is carried out by adding the medium to obtain a copolyester of the present invention.

The polyester system in this invention is formed by making dicarboxylic acid or its ester react with dihydric alcohol. Specific examples of the dicarboxylic acid and its esters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 5-sulfonic acid sodium isophthalic acid, 5-sulfonic acid tetrabutylphosphine isophthalic acid and 5-sulfonic acid ethyl tributylphosphine isophthalic acid. And aliphatic dicarboxylic acids such as adipic acid, pimeline acid, subberic acid, azelaic acid and sebacic acid, aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and lower esters of the dicarboxylic acids.

Specific examples of the dihydric alcohol include aliphatic dihydric alcohols such as ethylene glycol, 1,2-propanediol, trimethylene glycol, 1,4-butylene glycol, pentanthylene glycol, 1,6-hexanediol, and isoamylene glycol, 1 Aliphatic dihydric alcohols such as, 4-cyclohexanediol, 1,4-cyclohexanedimethanol, parahydrooxybenzene, 2,2-bis (4-hydrooxyphenyl) propane, bis- (4-hydrooxyphenyl) naphthalene Aromatic dihydric alcohol, its ethylene oxide adduct, polyethyleneglycol, polypropylene glycol, polyethyleneglycol propanediol polymer, polybutanediol, polypolyhydric alcohol, etc. are mentioned.

The dicarboxylic acid and the dihydric alcohol may be selected from one kind, two kinds, or two or more kinds. Additives, such as a gloss remover, a fluorescent brightener, an antioxidant, an antibacterial agent, a deodorant, an antistatic agent, a flame retardant, and a far infrared ceramic powder, can also be added as needed of a use.

Next, an analysis method related to the present invention is briefly analyzed.

I V (intrinsic viscosity):

It measures at the temperature of 30 degreeC in a phenol and a 1,1,2,2- tetrachloroethane mixed solvent (weight ratio 3: 2).

Color:

L value and b value are measured with the color difference meter (model number TC-1800MK2) of TOKYO DENSHOKU of Japan.

Melting Point:

Measurement is performed at a temperature difference of 20 ° C./min using a Perkin Elmer DSC (differential scanning calorimeter).

Light fastness:

Based on Japanese Industrial Standard JISL-0842, carbon arc tablets are irradiated for 349 hours at a temperature of 83 ° C. Light fastness is judged using the gray scale of JISL-0804 standard.

EXAMPLE

The present invention will be described in detail with reference to the following Examples. However, the Example which shows this invention demonstrates this invention, The range of this invention is not limited to this.

Example 1

193.81 parts of dimethyl terephthalate, 0.244 parts of 2,6-dimethylnaphthalene dicarboxylate (0.1 mol% of the total acid component), 124 parts of ethylene glycol and 0.078 parts of manganese acetate were added to the reactor, and a transesterification reaction was carried out at 165 to 230 ° C. Do it.

When the distillate reaches the theoretical amount, trimethyl phosphate

0.0192 parts, antimony acetate 0.0864 parts, 0.4% by weight of a gloss remover (to all polyesters) are added, and the reaction system is subsequently heated to 280 ° C, and gradually reduced to 1 torr or less to carry out the polymerization reaction.

When the torsional force of the stirrer reaches a predetermined value, the reaction is stopped and the polymer is cooled by pressing it in water with nitrogen to cool it and cut into chips. An ester is obtained.

The copolyester was melted and spun in an extruder to obtain 125 deniers / 36 partially drawn yarns at a spinning temperature of 290 ° C. at a winding speed of 3200 m / min, followed by stretching to form 75 deniers / 36 flats. A flat yarn is produced.

When the flat lead is dyed with a plain woven fabric, the light fastness is measured to be third grade.

Dyeing condition

Dye SUMIKARON YELLOW SE-3GL 2% o. w. f.

Expense 1:50

Dyeing temperature 130 ℃

60 minutes dyeing time

Example 2

In addition to making the addition amount of 2, 6- dimethylnaphthalenedi carboxylate 0.5 mol% in Example 1 based on the step of Example 1, light fastness becomes a grade 3 grade.

Example 3

In addition to making 1.0 mol% the addition amount of 2, 6- dimethyl naphthalenedi carboxylate in Example 1, if it is performed based on the step of Example 1, light fastness will become 3-4 class.

[Comparative Example 1]

It is the same as that of Example 1 except not adding 2, 6- dimethyl naphthalene dicarboxylate and making the addition amount of a dimethyl telephthalate 194. L value of obtained polyester is 78, b value is 2.0, and light fastness becomes class 2.

Example 4

The same procedure as in Example 1 was carried out except that the addition amount of 2,6-dimethylnaphthalene carboxylate was 10.0 mol%, and the obtained copolyester of IV 0.615 had a melting point of 228 ° C, an L value of 78, and a b value of 3.0.

The copolyester 1 and 9 parts of unmodified polyester which does not contain 2,6-dimethylnaphthalenedicarboxylate are mixed evenly by a chip mixing method. (The final 2,6-dimethylnaphthalene carboxylate Content is 1.0 mol%). Subsequently, the steps of Example 1 were spun, stretched, woven and dyed. Light fastness of the polyester obtained becomes 3-4 class.

Example 5

A copolyester having a 2,6-dimethylnaphthalenedicarboxylate content of 10.0 mol% was prepared as in Example 4. The copolyester 1 and 1 part of unmodified polyester which does not contain 2,6-dimethylnaphthalenedicarboxylate are mixed evenly by a chip mixing method (final 2,6-dimethylnaphthalenedicarboxylate) Content is 5.0 mol%). When it is carried out in the same manner as in the other Example 4, the light fastness of the polyester obtained is quaternary.

Example 6

Except for directly spinning the copolyester having the content of 2,6-dimethylnaphthalenedicarboxylate of Example 4 in 10.0 mol%, the light fastness of the polyester obtained was 4 to 5 do.

Example 7

The acid component in Example 1 was changed to 2,6-dimethylnaphthalenedicarboxylate 244.21, that is, the same as in Example 1 except that the content of 2,6-dimethylnaphthalenedicarboxylate was 100 mol%.

IV 0.0485, melting point 265 ° C, L value 77, and b value 2.2 were obtained, and the light fastness of the obtained polyester was grade 5.

Example 8

The acid component in Example 7 was changed to 92 mol% of 2,6-dimethylnaphthalene carboxylate, and the same as in Example 7, except that the dimethyl terephthalate was 8 mol%.

It becomes IV 0.512, melting | fusing point 251 degreeC, L value 77, and b value 1.6, and the obtained light fastness of polyester becomes grade 5.

[Comparative Example 2]

When the added amount of 2,6-dimethylnaphthalenedicarboxylate in Example 6 is 21 mol%, the produced copolyester becomes amorphous, and crystals and drying are not easy to make into fibers.

[Comparative Example 3]

At the end of the synthesis of the polyester, 1.5% by weight of an ultraviolet absorber (BASF UVA635L) of an acrylic acid copolymer containing a 2-hydroxyl-4- (methacryloyloxyethoxy) benzophenone structure is added. It has a bright yellow color, its L value is 65, and its b value is 13.

Such a method of producing polyester fiber with improved light fastness has an extremely good light fastness, and is suitable for interior use, curtains and exterior surfaces of automobiles, and maintains fresh color even when exposed to sunlight for a long time, and does not fade. The effect is to provide a method for producing a polyester fiber with improved fastness.

Claims (3)

Light fastness, characterized in that the copolymer is formed by copolymerizing a dicarboxylic acid, a dihydric alcohol and an ester-forming unit composed of the formula (1) below 0.05 mole% of the entire acidic component, followed by spinning and stretching to form a fiber. Method for producing polyester fibers with improved The method for producing a polyester fiber having improved light fastness according to claim 1, wherein the content of the ester-forming unit having the electrical structure (1) is 0.05 to 20 mol% based on the total acid component. The method for producing polyester fiber having improved light fastness, characterized in that the content of the ester-forming unit of the structure (1) is 80 to 100 mol% based on the total acid component.