JPH05230346A - Colorant for polyester spin dyeing and spin-dyed polyester fiber - Google Patents

Abstract

PURPOSE:To obtain the title colorant which is useful for the interior materials in automobiles because it has excellent ultraviolet absorptivity, light fastness, solubility, heat resistance and stability, by pigmenting the reaction product from a polyester which is liquid at room temperature and a specific cyclic imino-ester. CONSTITUTION:The objective colorant comprises a reaction product from a polyester which is liquid at room temperature and at least one selected from cyclic imino ester compound of formula I and II [X<1> is divalent aromatic residue; n is 1 to 3; R<1> is an n-valent hydrocarbon residue; R<2> is a monovalent hydrocarbon residue; X<2> is tetravalent aromatic residue; A is formula III (R<3> is a monovalent hydrocarbon residue) or the like], preferably in an amount of 0.1 to 1wt.% and a pigment or dye dispersed. The colorant is combined with a polyester to give spin-dyed fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester base dye and a polyester base fiber colored with the colorant. More specifically, the present invention relates to a colorant for use in polyester underwear, which has an effect of suppressing discoloration of a pigment or dye due to light, especially ultraviolet rays, and a polyester-dyed fiber having high light fastness using the colorant.

[0002]

2. Description of the Related Art Aromatic polyesters represented by polyethylene terephthalate are widely used for fibers, films, resins and the like because of their excellent heat resistance and light resistance. However, molded products of these polyesters have a serious drawback of poor dyeability, and as a method for improving this, a method of mixing and dispersing a pigment or dye in a polyester polymer, that is, a coloring method by dyeing is conventionally used. Various studies have been made. As typical examples thereof, a masterbatch method, a dry color method, and a method using a colorant in which a pigment or a dye is dispersed in a liquid colorant have been proposed.

Of these, the masterbatch method is because of the thermal history of the polyester resin used as the dispersion medium,
There is a drawback that the physical properties such as the tensile strength of the colored spun yarn are reduced, and in the dry color method, there is a problem with the scattering of the colorant during premixing and the dispersibility of the pigment or dye, and molding with sufficient quality It has the drawback that no product can be obtained. On the other hand, a coloring method using a liquid colorant having excellent characteristics that handling is easy and there is no contamination at the time of premixing and a time required for color change is a polyester fiber, a film, or another molding product at the time of molding. It has been widely used in recent years because it can be easily compounded, has excellent stability during the production of a molded article, and can produce a molded article with excellent quality uniformity.

However, depending on the kind and content of the pigment or dye used in the dyed fiber dyed with these liquid colorants, discoloration due to light, especially ultraviolet rays, is remarkable, and long-term use or strong light such as outdoors. There is a limit to its use in applications where it is subject to damage. As a means for preventing this, a method of previously mixing an ultraviolet absorber or a light stabilizer together with a pigment or a dye in a liquid colorant has been proposed, but it is possible to change the compatibility between the ultraviolet absorber or the light stabilizer and the polyester. May not obtain a certain light fastness due to localization due to aggregation of the ultraviolet absorber or the light stabilizer, and troubles during molding, for example, the concentration of the ultraviolet absorber or the light stabilizer is locally high. There arises a problem that a portion is generated to cause yarn breakage during spinning, or a thickness unevenness occurs in the length direction of the yarn. Therefore, even if the content of the ultraviolet absorber or the light stabilizer is increased, the trouble caused by the aggregation of the ultraviolet absorber and the light stabilizer is not only remarkable, but the light fastness is often not improved at all.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation as described above, and in order to obtain a polyester fiber having an excellent light fastness by uniformly dispersing an ultraviolet absorber in the polyester. The purpose of the present invention is to provide a suitable polyester undercoat colorant.

[0006]

The present invention achieves the above object and has the following structure.

That is, a pigment or dye is dispersed in a reaction product of a polyester which is in a liquid state at room temperature and at least one selected from the cyclic iminoester compounds represented by the following general formula (I) or (II). It is a colorant for polyester original wear.

[0008]

[Chemical 5]

[0009] [wherein, X ¹ is, X ¹ represented by the formula
Is a divalent aromatic residue in which the two bonds from are in the 1-position and 2-position relationship; n is 1, 2 or 3; R ¹
Is an n-valent hydrocarbon residue (which may further contain a hetero atom), or a direct bond when n = 2. ]

[0010]

[Chemical 6]

[Where A is the following formula (II) -a

[0012]

[Chemical 7]

A group represented by the following formula or
I) -b

[0014]

[Chemical 8]

R ² and R ³ are the same or different monovalent hydrocarbon residues; X ² is 4
A valent aromatic residue, which may further contain heteroatoms. The present invention will be described in detail below.

In the present invention, the medium in which the pigment or dye is dispersed is a liquid polyester at room temperature which has been previously reacted with a specific cyclic iminoester compound described below.

As the polyester used here,
It is not particularly limited as long as it is liquid at room temperature, for example, adipic acid, sebacic acid, aliphatic dicarboxylic acids such as azelaic acid, oleic acid, aliphatic saturated or unsaturated monocarboxylic acids such as lauric acid and phthalic acid, An aromatic carboxylic acid such as trimellitic acid is used as an acid component, and n-
Octyl alcohol, isooctyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol, n-
The alcohol component is a monohydric alcohol such as decyl alcohol, a polyhydric alcohol such as ethylene glycol, propylene glycol, tetramethylene glycol, pentaerythritol, dipentaerythritol, or sorbitol, and a liquid polyester at room temperature is preferable.

Such a liquid polyester is difficult to decompose and change even at a melt spinning temperature of a fiber-forming polyester resin typified by polyethylene terephthalate, and has a low viscosity so that it is fluid at room temperature even when a pigment or a dye is blended. In addition, since the compatibility with the polyester resin is also good, the dispersibility of the pigment or the dye in the polyester resin is good, and high concentration coloring is possible.

In the present invention, a cyclic iminoester type ultraviolet absorber having a specific structure is reacted and bonded to the liquid polyester. This reaction is, for example, a ring-opening addition reaction between the alcoholic terminal hydroxyl group of the liquid polyester and the cyclic iminoester represented by the following chemical reaction formula (III), and the iminoester compound is added to the molecular chain end of the liquid polyester. ..

[0020]

[Chemical 9]

It should be noted here that the cyclic iminoester-based UV absorber maintains its UV-stabilizing effect without being impaired even when it is reacted with the liquid polyester, and has a property as a dispersion medium of the liquid polyester. Is also not damaged. Therefore, it is possible to uniformly disperse the ultraviolet absorber without lowering the dispersibility of the pigment or dye in the polyester resin, and since there is a dispersion medium at a higher concentration around the pigment or dye, It has a feature that the effect of suppressing discoloration due to ultraviolet rays is further increased. Furthermore, since the ultraviolet absorber is chemically bonded to the liquid polyester, it does not evaporate even at the melt spinning temperature of the polyester, and thus can be spun very stably and without causing environmental pollution.

As the cyclic iminoester compound having a specific structure used for the above purpose, the compounds represented by the above formulas (I) and (II) are preferably used.

In the formula (I), X¹Is represented by formula (I)
X¹The two bonds from are in the 1st and 2nd positions.
A divalent aromatic residue; n is 1, 2 or 3
R; R ¹Is an n-valent hydrocarbon residue, which is a heteroatom
May contain a child, or R¹Is direct when n = 2
It can also be a tangential bond.

X ¹ is preferably 1,2-
Examples thereof include phenylene, 1,2-naphthylene and 2,3-naphthylene, and 1,2-phenylene is particularly preferable.

R ¹ may be an n-valent (wherein n is 1, 2 or 3) hydrocarbon residue, or may be a direct bond only when n is 2, and preferred examples are: , N = 1 is an aromatic residue having 6 to 12 carbon atoms (phenyl group, naphthyl group, biphenyl group), or

[0026]

[Chemical 10]

If n = 2, then p
-Phenylene, m-phenylene, 2,6-naphthylene,
p, p'-biphenylene can be mentioned, and n
= 3,

[0028]

[Chemical 11]

The following can be mentioned.

In the formula (II), X ² is a tetravalent aromatic hydrocarbon residue, for example,

[0031]

[Chemical 12]

(Here, R is --O--, --CO--, --S
-, -SO ₂ , -CH _2- , or -C (CH ₃ ) _2-
Can be given.

Specific examples of the cyclic iminoester compounds represented by the above formulas (I) and (II) that are preferably used include the following compounds.

When n = 1, the compound 2- (p-phthalimidophenyl) -3,1-benzoxazin-4-one, N-phenyl-4- (3,1-benzoxazin-4-one-2-one Yl) phthalimide,
2-phenyl-3,1-benzoxazin-4-one,
2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-
Benzoxazin-4-one, compound when n = 2 2,2'-bis (3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazine- 4-one), 2,2'-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 '
-(4,4'-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 '-(2,6- or 1,5-naphthalene) bis (3,1-benzoxazine-4) -One), 2,2 '-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), the compound when n = 3 1,3,5-tri (3,1) -Benzoxazin-4-one-2-yl) benzene, 1,3,5-tri (3,1-)
Benzoxazin-4-one-2-yl) naphthalene,
2,4,6-tri (3,1-benzoxazin-4-one-2-yl) naphthalene, compound of formula (II) 2,8-dimethyl-4H, 6H-benzo [1,2-d;
4,5-d '] bis- [1,3] -oxazine-4,6
-Dione, 2,7-dimethyl-4H, 9H-benzo [1,2-d; 4,5-d '] bis- [1,3] -oxazine-4,9-dione, 6,6'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,
6'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3,1-benzoxazine-
4-on), 6,6'-sulfonylbis (2-methyl-
4H, 3,1-benzoxazin-4-one).

Among the above-exemplified compounds, the compound of the above formula (I), more preferably the compound of the above formula (I) when n = 2, particularly preferably the following formula:

[0036]

[Chemical 13]

A compound represented by the formula (wherein R ⁴ is a divalent aromatic hydrocarbon residue or a direct bond) is preferably used.

Such compounds include, among others, 2,2'-p
-Phenylene bis (3,1-benzoxazin-4-one), 2,2'-bis (3,1-benzoxazin-4)
-ON) is preferred.

Next, the pigment or dye used in the present invention is not particularly limited, and examples thereof include azo, phthalocyanine, quinacridone, anthraquinone, dioxazine and perylene / perinone organic pigments. , Azo-based, anthraquinone-based, perylene-based, phthalocyanine-based, and heterocyclic-based dyes can be used, and they can of course be used in combination, and the above dispersion medium can be used for these organic pigments or dyes. The light stabilizing effect of is maximized. Naturally, titanium oxide, iron oxide, ultramarine, carbon black, etc., which have high fastness to light, are used as well as known pigments generally used for polyester, or antistatic agents, optical brighteners, matting agents, etc. It is also possible to mix functional additives and further add other ultraviolet absorbers and light stabilizers.

It is most preferable to add the polyester undercoat coloring agent described above in detail to the polyester whose main repeating unit is ethylene terephthalate, from the viewpoint of the mechanical properties of the obtained molded product, etc. It may be added to other polyesters such as butylene terephthalate. The term "mainly" as used herein means that a small amount (usually 20 mol% or less based on the terephthalic acid component) of a third component other than the terephthalic acid component and / or the ethylene glycol component may be copolymerized. ..
A small amount of other polymer (usually 1 for polyester)
It may be a mixed polyester.

The polyester-dyed fiber of the present invention can be obtained by melt-mixing the above liquid undercoating coloring agent with polyester, and then spinning, drawing and heat-treating according to a conventional method.
The amount of the colorant to be added here varies depending on the amount of the pigment or dye and the cyclic iminoester compound contained in the colorant, and the required degree of coloring, light fastness, etc., but the polyester obtained. Compounded so that the amount of cyclic iminoester compound (including ring-opened addition to liquid polyester) present in the fiber-dyed fiber is in the range of 0.05 to 5% by weight, preferably 0.1 to 1% by weight. It is desirable to do.

[0042]

The polyester-dyed fiber obtained by adding a liquid colorant prepared by mixing a pigment or a dye to the reaction product of the liquid polyester and the cyclic iminoester-based ultraviolet absorber of the present invention has not been heretofore available. Has lightfastness. The reason for this is presumed as follows, although it is still unclear.

Examples of the action of the ultraviolet absorber for improving the light fastness include an ultraviolet blocking action, a quenching action and a radical scavenging action, all of which contribute to stabilizing the pigment or dye against light. Conventionally, a method of adding an ultraviolet absorber and a light stabilizer having such an action to a molded article such as being contained in an undercoat coloring agent is widely used, but its effect on improving light fastness is not It was never enough. This is because the additive and polyester are not uniformly dispersed due to poor compatibility of the additive and localization of the additive due to aggregation, etc., and the light stabilizing effect originally possessed by the additive is not sufficiently exerted. It is thought to be because. On the other hand, since the colorant of the present invention has a light-stabilizing effect on the dispersion medium itself, which has excellent compatibility with polyester, the dispersion medium is dispersed evenly in the polyester, and at the same time the ultraviolet absorber is bonded. Is uniformly dispersed in the polyester, and the ultraviolet absorbers do not aggregate with each other, so that it is considered that a sufficient light stabilizing effect can be exhibited. Further, for the same reason, it is considered that troubles during manufacturing such as yarn breakage during spinning and uneven thickness in the length direction of the yarn can be eliminated.

[0044]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, the measurement and evaluation of the light fastness of the polyester fiber in the examples were performed by the following methods.

A polyester knitted fabric was used as a tube knitted fabric, and a carbon arc fade o meter FAL-3H type manufactured by Suga Test Instruments Co., Ltd. was used, and a black panel temperature was 83 ±.
Ultraviolet irradiation was performed at 3 ° C. for 200, 400, and 600 hours, and the degree of discoloration was evaluated on a gray scale (grade).

[0046]

Examples 1 and 2 Liquid polyester 10 comprising adipic acid and 1,3-butanediol and having an average molecular weight of about 2500.
10 parts by weight of a cyclic iminoester-based ultraviolet absorber having the following structure was reacted with 0 parts by weight to obtain a dispersion medium for a colorant. With respect to 100 parts by weight of this colorant dispersion medium, in Example 1, 8 parts by weight of phthalocyanine blue, 2 parts by weight of quinacridone red, and 0.2 parts by weight of carbon black, and in Example 2, 5 parts by weight of anthraquinone yellow. Parts, 3 parts each of 10 parts by weight of disazo yellow
The mixture was kneaded with this roll mill to obtain a colorant. 5 parts by weight of the obtained coloring agent was added to polyethylene terephthalate 10
0 parts by weight, spinning temperature 285 ° C., spinning speed 105
It was wound up at 0 m / min and then stretched at a ratio of 3.6 times at 80 ° C. to obtain a thread of 75 denier / 24 filament. Regardless of which colorant was used, the compatibility of the colorant during spinning and stretching and the tone of the manufacturing process were good, and uniformly colored yarn was obtained.

[0047]

[Chemical 14]

[0048]

Comparative Examples 1 and 2 In 100 parts by weight of liquid polyester (same as that in Example 1) as a dispersion medium, in Comparative Example 1 as a pigment, 8 parts by weight of phthalocyanine blue, 2 parts by weight of quinacridone-based red, and 0 of carbon black. 2 parts by weight, in Comparative Example 2, anthraquinone yellow 5
Parts by weight, 10 parts by weight of disazo yellow, 3 parts each
The mixture was kneaded with this roll mill to obtain a colorant. 5 parts by weight of the obtained coloring agent was added to polyethylene terephthalate 10
Add to 0 parts by weight, spin and stretch in the same manner as in Example 1, and
A yarn of 5 denier / 24 filament was obtained. Regardless of which colorant was used, the compatibility of the colorant during spinning and stretching and the tone of the manufacturing process were good, and uniformly colored yarn was obtained.

[0049]

[Comparative Examples 3 and 4] With respect to 100 parts by weight of the same liquid polyester as used in Example 1, Tinubin 320 manufactured by Ciba-Geigy Co., Ltd. as a commercially available benzotriazole-based ultraviolet absorber and Sanol LS944LD manufactured by Ciba-Geigy Co., Ltd. as a hindered amine-based light stabilizer are respectively used. 4 parts by weight were further added, and as a pigment, in Comparative Example 3, 8 parts by weight of phthalocyanine blue, 2 parts by weight of quinacridone red, 0.2 parts by weight of carbon black, and in Comparative Example 4, 5 parts by weight of anthraquinone yellow, 10 parts by weight of disazo yellow was kneaded with a three-roll mill to obtain a colorant. 5 parts by weight of the obtained colorant was added to 100 parts by weight of polyethylene terephthalate, respectively, to obtain Example 1
The yarn was spun and drawn in the same manner as in 1. to obtain a yarn of 75 denier / 24 filament. The compatibility of the colorants during spinning / stretching was good regardless of which colorant was used, but there was smoke generation during spinning, which is presumed to be caused by decomposition and evaporation of the ultraviolet absorber or light stabilizer, and stretching A considerable number of yarn breakages also occurred. The color of the yarn was good.

[0050]

Examples 3 and 4 Liquid polyester (same as Example 1)
100 parts by weight of the ultraviolet absorber having the structure of the following chemical formula was reacted with 10 parts by weight to obtain a dispersion medium for the colorant. 8 parts by weight of phthalocyanine blue, 2 parts by weight of quinacridone red and 0.2 parts by weight of carbon black are used in Example 3 and 5 parts by weight of anthraquinone type yellow in Example 4 per 100 parts by weight of the dispersion medium for the colorant. Parts and 10 parts by weight of disazo yellow were kneaded with a three-roll mill to obtain a colorant. 5 parts by weight of the obtained colorant was added to 100 parts by weight of polyethylene terephthalate, and the mixture was spun and stretched in the same manner as in Example 1 to obtain 75 denier /
A yarn of 24 filaments was obtained. Regardless of which colorant was used, the compatibility of the colorant during spinning and stretching and the tone of the manufacturing process were good, and uniformly colored yarn was obtained.

[0051]

[Chemical 15]

[0052]

Example 5 An ultraviolet absorber 1 having the structure shown in Chemical formula 14 with respect to 100 parts by weight of a liquid polyester composed of sebacic acid and 1,4-butanediol and having an average molecular weight of 4000.
0 part by weight was reacted to obtain a dispersion medium for a colorant. To 100 parts by weight of this colorant dispersion medium, 8 parts by weight of phthalocyanine blue, 2 parts by weight of quinacridone red and 0.2 parts by weight of carbon black were kneaded with a three-roll mill to obtain a colorant. 5 parts by weight of the obtained colorant was added to 100 parts by weight of polyethylene terephthalate and spun and stretched in the same manner as in Example 1 to obtain a yarn of 75 denier / 24 filament. The compatibility of the colorant during spinning and drawing and the tone of the manufacturing process were good, and a uniformly colored yarn was obtained.

The above results are summarized in Table 1. However,
The yarn breakage in the table indicates the percentage (%) at which the complete winding could not be completed due to the yarn breakage when the yarn was wound at 4.5 kg during spinning.

[0054]

[Table 1]

[0055]

As described in detail above, since the polyester primary wear colorant of the present invention uses a liquid polyester to which a specific compound having an ultraviolet absorbing ability is bonded as a dispersion medium, it is possible to use a conventional ultraviolet absorber. Since it does not cause a decrease in spinnability due to agglomeration of the polymer and smoke during spinning, and the solubility of the colorant in the polyester is good,
The coloring is also uniform. In addition, since the cyclic iminoester compound used in the present invention has good heat resistance and no deterioration in ultraviolet absorbing ability, it has a feature that polyester fibers excellent in light fastness can be obtained extremely stably.

Therefore, by making use of these characteristics, industrial data applications requiring high light resistance and high strength, such as seat belts as automobile interior materials, sling belts as outdoor reinforcing agents, container bags, ropes, etc. It can be developed as a colorant for polyester fibers used in.

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Claims (2)

[Claims] 1. A pigment or dye is dispersed in a reaction product of a polyester which is liquid at room temperature and at least one selected from the cyclic iminoester compounds represented by the following general formula (I) or (II). Naruto polyester original colorant. [Chemical 1] [Where X ¹ is a divalent aromatic residue in which the two bonds from X ¹ represented by the above formula have a positional relationship of 1-position and 2-position; n is 1, 2 or 3; R ¹ is an n-valent hydrocarbon residue (which may further contain a hetero atom),
Alternatively, when n = 2, it is a direct bond. ] [Chemical 2] [Where A is the following formula (II) -a: Or a group represented by the following formula (II) -b R ² and R ³ are the same or different monovalent hydrocarbon residues; X ² is a tetravalent aromatic residue, which may further contain a hetero atom. Good. ] 2. A polyester original-dyed fiber containing the polyester original-adhesion coloring agent according to claim 1.