KR810001054B1 - Method for clear-coloring of linear aromatic polyester - Google Patents

Abstract

This invention relates to the method of linear aromatic polyester. Linear polyester was mixed with structure formula (I) or (II), and the mixture was heated at melting point of polyester. For example, a 99.5:0.5 mixt. of poly (ethylene terephthalate) and C. I. pigment Red 194 was dried at 180oC/0.01mmHg for 5hr. and spun at 300oC to give 3 deniers, reddish orange fiber showing no pigment particles under microscope.

Description

Linear Aromatic Polyester Transparent Coloring Method

The present invention relates to a coloring method, and more particularly to a transparent coloring method of linear aromatic polyester.

Linear aromatic polyesters are used in the manufacture of textile products, film products and other molded products. For example, tetraphthalate polyethylene is industrially used in the manufacture of fibers and films, and terephthalate polyethylene, terephthalate polypropylene and terephthalpolybutylene are industrially used in the manufacture of other molded articles.

The basic requirements for coloring of linear aromatic polyester using a pigment are: (1) The pigment should have good fixing properties. Pigments, for example, must be able to withstand high melting temperatures (up to 300 ° C), have good fixability to light and sublimation, and (2) pigment particles should be fine and homogeneous to polyester without agglomeration. Should be distributed. In recent years, audiences have been dissatisfied with pigmented opaque pastel shades alone, while tending to demand products with brilliant and transparent colors. In order to obtain a transparent colored linear aromatic polyester, a dope dyeing method has been proposed in which a dye is mixed with a polyester to melt the mixture. Japanese Patent Publication No. 68-26095 and US Patent No. 3,401,142 describe several anthraquinone dyes as suitable for use in the dope dyeing method.

The inventors have found that when a certain pigment is used in the linear aromatic polyester colorant instead of such a dye, a brilliant and transparent color appears.

Therefore, the present invention mixes at least one pigment selected from the pigment of the following structural formula (I) and the pigment of the following structural formula (II) with a linear aromatic ester, and then heats the mixture to the melting point of the polyester to The transparent coloring method of linear aromatic polyester characterized by dissolving or fully dissolving a pigment is produced.

In the above formula, X ₁ and X ₂ represent a hydrogen atom, a chlorine atom or a methyl group, and X ₃ represents a chlorine atom or a methyl group.

Among the pigments of the structural formula (II), those represented by the following structural formula (III) are preferred in the present invention.

X ₁ , X ₂ and X ₃ in formula (II) are as defined in formula (II).

Examples of particularly preferred pigments in the present invention are those of the following structural formula.

These pigments (1) to (6) are color index, 3rd edition, volume 3 (American Association of Textiles chemistry end colorists recognized by the Society of Diaries and Colorists (1) CI Pigment Red 194, (2) CI Pigment Red 87, (3) CI Pigment Red 88, (4) CI Pigment Red 198, (5) CI Pigment Violet 36 and (6) CI Pigment Violet, respectively. 38. They have a melting point of 300 ° C. or higher and are widely used as colorants for printing ink paints and rackers. It has been found that some of these pigments are used for cotton dyeing as vat dyes, and others are used for coloring polyolefins, rubbers, vinyl plastics and the like.

According to the researches of the present inventors, when the pigments of the above structural formulas are used for polypropylene coloring, these pigments are dispersed in polypropylene to produce a cloud red or cloud red color, and when used for 6-nylon coloring, these pigments are 6-nylon. It turns out that it discolors at the same time as melting. When these pigments are used for coloring linear aromatic polyesters having a melting point of 250 ° C. to 300 ° C., these pigments dissolve in the polyester during melting and there is no dispersion of the pigment particles, and the colored color is transparent and brilliant red or reddish purple. It has been surprisingly found that colored polyesters have excellent fixability for heat, light and sublimation applications.

Coloring method available linear aromatic polyesters of this invention is the structural formula of terephthalic acid or terephthalic acid dialkyl _{HO- (CH 2) n-OH} ( wherein, n is an integer from 2 to 10) writes Recliner flow or 1,4-a Linear terephthalate polyalkylene obtained by reacting with (hydroxymethyl) cyclohexane. These polyesters have long been known as fiber and film materials and their methods of preparation are described, for example, in US Pat. No. 2,465,319 and US Pat. No. 3,047,539.

Further, linear aromatic polyesters, ie, linear terephthalate polyalkylenes containing 2 to 10 alkylene groups as used herein, are meant to include copolyesters based on these polyesters. These copolyesters can be obtained by replacing the starting terephthalic acid component with some other dicarboxylic acid or hydroxycarboxylic acid and / or by replacing the starting glycol with some other glycol. Examples of other dicarboxylic acids or hydroxycarboxylic acids are isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, hydroxyethoxybenzoic acid, 1-hydroxybenzoic acid, adipic acid and sebacic acid. have.

Representative examples of linear aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and copolyesters obtained by replacing some of its component monomers with other monomers.

The linear aromatic polyester used in the present invention has an inherent viscosity of 0.4 to 1.2 measured at 25 ° C. in an equivalent mixture of tetrachloroethane and phenol.

The process of the invention mixes a pigment with a linear aromatic polyester, preferably with a finely divided pigment and a chip or granular linear aromatic polyester and blends the mixture with the melting point of the polyester, preferably Is achieved by heating to 250 ° C. to 300 ° C. to sufficiently dissolve the pigment in the polyester.

The amount of the pigment to be mixed with the linear aromatic polyester depends on the kind of the pigment used, but is usually up to 1% by weight based on the total weight of the polyester and the pigment. In consideration of the workability of the colored polyester in the spinning process and other weaving processes, the amount of the pigment is preferably 0.01 to 0.5% by weight.

Pigment particles are not detected in the colored linear aromatic polyester produced by the method of the present invention, and the color is brilliant and transparent. It also has excellent fixability to heat, light and sublimation.

If necessary, other pigments, fillers, reinforcing agents, stabilizers, etc. may be used simultaneously.

Detailed Description of the Invention The present invention will be described in detail by way of examples. Parts in the examples are parts by weight.

[Examples 1 and 2]

These pigments were dried at 180 ° C. and 0.01 mmHg for 5 hours while mixing 0.5 parts of the following pigments and 99.5 parts of polyethylene terephthalate having an intrinsic viscosity of 0.70. The mixture was melt spun at a conventional method at 300 ° C. for a residence time of 3 minutes to obtain 3 denier colored filament yarns. The characteristic of this colored filament yarn is as follows.

Note: (* 1) Ten milligrams of the colored filament yarn samples were melted. This was sandwiched between two thin layered glass plates at 290 ° C and observed under a microscope of 400x magnification.

(* 2) Measured on a blue scale according to JIS L0843-71 (xenon arc).

(* 3) The colored filaments obtained by spinning in the same manner as described above were compared with the gray scale for discoloration inspection except that the residence time was changed to 15 minutes.

(* 4) It measured on the gray scale according to JIS L0844-73 (70 degreeC +/- 2 degreeC, 45 minutes).

(* 5) It measured on the gray scale according to JIS L0860-74 (40 degreeC +/- 2 degreeC, 30 minutes).

(* 6) The sample of colored filament yarn was wrapped in a polyester cloth, left in a hot air dryer at 180 ° C. for 90 minutes, and the stain state of the polyester cloth was measured using a gray scale for discoloration inspection. .

(* 7) It measured according to JIS L0849-71 using the gray scale for discoloration test.

Example 3

0.2 parts of C. I. Pigment Violet 36, 0.3 parts of C. I. Pigment Red 194 and 99.5 parts of polyethylene terephthalate (0.68 intrinsic viscosity) were uniformly mixed and dried at 120 ° C. and 0.01 mmHg for 16 hours. This mixture was spun at 290 ° C. in a conventional manner to obtain brilliant red 6 denier filament yarns. When observed under a microscope of 400 times magnification, no pigment particles were detected.

This filament yarn had substantially fixing characteristics with the filament yarns obtained in Examples 1 and 2.

Example 4

0.3 parts of C. I. Pigment Red 198 and 99.7 parts of polyethylene terephthalate (intrinsic viscosity 1.0) were mixed and dried at 180 ° C. for 15 hours. This mixture was then fed to a Scruu extruder and molded at 290 ° C. to obtain a plate that was colored purple.

Example 5

2 parts of C. I. Pigment Red 87, 6 parts of C. I. Pigment Red 194, 2 parts of carbon black and 90 parts of polyethylene tetraphthalate (intrinsic viscosity 0.70) were mixed and dried at 180 ° C. and 0.01 mmHg for 5 hours. This mixture was extruded at 290 ° C. with a Scruu extruder to obtain a master batch with a pigment concentration of 10%. 5 parts of this masterbatch was mixed with 95 parts of polyethylene terephthalate, and the mixture was dried at 130 ° C. and 0.01 mmHg for 10 hours. The dried mixture was spun and softened at 290 ° C. in a conventional manner to obtain a brown 10 denier filament yarn. Ten milligrams of this colored filament yarn were melted and placed between two thin layered green plates at 290 ° C, and observed under a microscope with a magnification of 400 times. Only carbon black particles were observed. The resulting filament yarn had substantially the same fixing properties as the filaments obtained in Examples 1 and 2.

Example 6

0.3 parts of C. I. Pigment Red 194 and 99.7 parts of terephthalate polybutylene (containing a high viscosity of 0.7 and containing 30% by weight of glass fiber) were mixed and dried under reduced pressure at 120 ° C. This dry mixture was molded at 250 ° C. to obtain a reddish violet plate.

Example 7

0.2 parts of C. I. Pigment Violet 38 and 99.8 parts of terephthalic acid polybutylene (intrinsic viscosity 0.8) were mixed and dried. This mixture was molded at 250 ° C. to obtain a reddish violet plate. A coloring matter was prepared from this plate and observed under a microscope of 400 times magnification. Pigment particles were not observed and the color was transparent.

Claims (1)

At least one pigment selected from the pigment of formula (I) and the pigment of formula (II) is mixed with the linear aromatic polyester, and then the mixture is heated to the melting point of the polyester to A transparent coloring method of linear aromatic polyester, characterized by dissolving or sufficiently dissolving a pigment.

In the above formula, X ₁ and X ₂ represent a halogen atom, a chlorine atom or a methyl group, and X ₃ represents a chlorine atom or a methyl group.