JP2003277518A - Colorant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colorant composition which excels in the dispersibility of carbon black in coloring polyester based fibers, and obtains originally colored fibers exhibiting the so-called Japanese lacquer black color with bluish blackness. <P>SOLUTION: In the colorant composition comprising a thermoplastic resin and a plurality of types of carbon black having different primary particle diameters and having a total amount of the plurality of types of carbon black of 10-40 wt.%, when the carbon black having a fine primary particle diameter of smaller than 20 nm of the average of the primary particle diameter, that having an intermediate primary particle diameter of not smaller than 20 nm to smaller than 30 nm of the average of the primary particle diameter, and that having a coarse primary particle diameter of not smaller than 30 nm of the average of the primary particle diameter are taken as group A, group B, and group C, respectively, the colorant composition comprises, based on the entire types of carbon black, 40-80 wt.% carbon black of group A, 20-60 wt.% sum of carbon black of group B and carbon black of group C, and <60 wt.% carbon black of group C. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colorant composition, and more specifically, when coloring a polyester fiber, it is excellent in dispersibility of carbon black, has a bluish blackness, and is a so-called jet black original. The present invention relates to a colorant composition capable of obtaining a bonded fiber.

[0002]

2. Description of the Related Art The black hue of a carbon black original fiber is mainly influenced by the hue of the carbon black itself. That is, when carbon black having a fine primary particle diameter of less than 20 nm is used, the obtained primary dyed fiber has a blackness but a reddish hue. On the other hand, when carbon black having a primary particle diameter of 30 nm or more and a coarse primary particle diameter is used, a so-called gray tone having a bluish color but no blackness is obtained. It was not possible to obtain a primary dyed fiber having a jet black hue with a bluish color and blackness by conventional primary dyeing with carbon black.

A masterbatch in which carbon black is dispersed in the same resin is used for the primary deposition of PET fibers, but carbon black having a fine primary particle diameter of less than 20 nm is used as a masterbatch. Since it has a strong cohesiveness due to the fine primary particle size, it was difficult to produce a high-concentration masterbatch containing 20% or more of carbon black.

It is also desirable to use a carbon black having a fine primary particle diameter of less than 20 nm and to use a blue pigment or dye in order to eliminate the reddishness of the carbon black. It is not preferable in terms of cost and physical properties of the fiber, which is a negative direction.

Carbon black having an intermediate primary particle diameter of 20 nm or more and less than 30 nm has a current P value.
It is the most commonly used grade for ET wear. Many of them have good dispersibility in a masterbatch and have an appropriate degree of blackness, which is the most suitable as an underwear at the present time, but there is a defect that the jet black feeling originally required is not obtained.

Carbon black having a coarse primary particle diameter of 30 nm or more has a bluish color tone but is inferior in blackness, so that it is rarely used as a carbon black for black primary wear. However, this grade of carbon black is highly dispersible when it is processed into a masterbatch, and also has an advantageous property that a high concentration of 30% or more is possible.

[0007]

DISCLOSURE OF THE INVENTION In coloring the polyester fiber according to the present invention, it is possible to obtain a so-called jet black dyed fiber having excellent dispersibility of carbon black, bluish and blackness. An object is to provide an agent composition.

Another object of the present invention will be clarified by the following description.

[0009]

The above-mentioned problems can be solved by the following inventions.

(Claim 1) A colorant composition comprising a thermoplastic resin and a plurality of carbon blacks having different primary particle diameters, wherein the total amount of the plurality of carbon blacks is 10 to 40% by weight. Is a group A of carbon black having a fine primary particle size of less than 20 nm, a group B is a carbon black having an average primary particle size of 20 nm or more and less than 30 nm, and a coarse primary particle size average of 30 nm or more. When the carbon black having a primary particle size is defined as the C group, the carbon black of the A group is 40 to 80% by weight of the total amount of carbon black, and the total of the carbon blacks of the B group and the C group is 20% of the total carbon black amount.
The colorant composition is characterized in that it is blended so that the carbon black of the group C is less than 60 wt% of the total amount of carbon black.

(Claim 2) The blending coefficient (K) by blending the carbon blacks of the A, B and C groups is K = aα + b
The colorant composition according to claim 1, wherein β + cγ and 17 ≦ K ≦ 32. [In the formula, a represents the primary particle diameter (nm) of group A carbon black, and b
Represents the primary particle size (nm) of group B carbon black,
c represents the primary particle diameter (nm) of the C group carbon black, α represents the blending ratio of the A group carbon black, β represents the blending ratio of the B group carbon black, and γ represents the blending ratio of the C group carbon black. Represent However, α + β + γ =
1]

(Claim 3) The colorant composition according to claim 1 or 2, wherein the thermoplastic resin is a polyethylene terephthalate resin.

(Claim 4) Carbon black is DBP
Oil absorption of 40 to 180 CC / 100 g, coarse grain content of 50 pp
The colorant composition according to claim 1, 2 or 3, wherein the colorant composition is m or less.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The colorant composition according to the present invention comprises a thermoplastic resin and a plurality of carbon blacks having different primary particle diameters.

Examples of the thermoplastic resin used in the present invention include polyolefin resins and polyester resins. Among them, polyester resins are preferable, and polyethylene terephthalate resins (PET resins) are more preferable.

The PET resin used in the present invention is usually 90 mol% or more, preferably 9 mol% of the dicarboxylic acid component.
A crystalline thermoplastic resin in which 5 mol% or more is terephthalic acid and 80 mol% or more, preferably 90 mol% or more of the glycol component is ethylene glycol.

Other dicarboxylic acids include isophthalic acid and adipic acid, and other glycol components include propylene glycol and 1,4-butanediol.

The PET resin used in the present invention may be a copolymer or a mixture of PET and another polyester as long as terephthalic acid and ethylene glycol are in the above ranges.

The average primary particle size that characterizes the carbon black used in the present invention is a small spherical component (having a contour of fine crystals and not separable) constituting an aggregate of carbon black, measured and calculated on an electron micrograph. The diameter of a particle.

A plurality of carbon blacks having different primary particle diameters means a carbon black having a primary particle diameter of less than 20 nm and a fine primary particle diameter of A group, and a primary particle diameter of 20.
When the carbon black having an intermediate primary particle size of 30 nm or more and less than 30 nm is group B and the carbon black having a primary particle size of 30 nm or more and a coarse primary particle size is group C,
That is, it is a carbon black group of these A group, B group, and C group.

Examples of carbon black production methods include, but are not limited to, a furnace type incomplete combustion method, a contact type incomplete combustion method, and a thermal decomposition method.

The following carbon blacks are obtained by each production method. (1) Furnace type incomplete combustion carbon black: A furnace carbon black obtained by incompletely burning natural gas, oil, etc. in a furnace. (2) Contact-type incomplete combustion carbon black: Channel carbon black obtained by causing a flame to collide with an iron channel while incompletely combusting natural gas, oil and the like. (3) Pyrolytic carbon black: Thermal carbon black obtained by thermally decomposing natural gas, acetylene gas, etc. at high temperature.

As the carbon black used in the present invention, it is preferable to select carbon black containing few impurities rather than the difference in the production method.

The blending ratio of the carbon black in the present invention is the group A, the group B, and the group C. The carbon black of the group A is 40 to 80% by weight in the total amount of carbon black.
%, Preferably 45 to 60%, the total of the group B and C carbon black is 20 to 60%, preferably 40 to 55.
%, And the carbon black of group C is less than 60%, preferably less than 50%.

In the present invention, the average primary particle size is 20 n.
Carbon black having a fine primary particle diameter of less than m (Group A) is preferable because the blackness increases as the average primary particle diameter becomes smaller, but the hue becomes reddish, and the cohesive force of carbon black in masterbatch formation is high. Often increases and causes problems. Further, when the average primary particle size approaches 20 nm, the blackness decreases, making it difficult to achieve the object of the present invention. From the above, the group A carbon black is 13-18.
Those having an average primary particle diameter of nm are preferred.

Further, carbon black (group C) having a coarse primary particle diameter with an average primary particle diameter of 30 nm or more is preferable because the blueness increases as the average primary particle diameter increases.
On the contrary, since the blackness is extremely lowered, it is preferable that the average primary particle diameter of the carbon black of the group C is 35 to 120 nm.

In the present invention, the blending coefficient (K) by blending the carbon blacks of Groups A, B and C is K = aα
It is preferable that + bβ + cγ and 17 ≦ K ≦ 32. If the compounding coefficient is less than 17 or exceeds 32, the object of the present invention cannot be achieved. In the formula, a represents the primary particle diameter (nm) of group A carbon black, and b represents B
Represents the primary particle diameter (nm) of group carbon black, c represents the primary particle diameter (nm) of group C carbon black, and α
Represents the blending ratio of the group A carbon black, β represents the blending ratio of the group B carbon black, and γ represents the blending ratio of the group C carbon black. However, α + β + γ = 1.

The DBP oil absorption of carbon black is 30-
230CC / 100g is generally used, but one with a small oil absorption is advantageous for increasing the concentration of the masterbatch, but there are many impurities such as structure inhibitors mixed in the carbon black manufacturing process, and the dispersion surface Problem is easy to occur in. Further, those having a large oil absorption amount are not preferable because the structure of carbon black is overdeveloped and it is difficult to add a high concentration when forming a masterbatch. Therefore, the carbon black of the present invention preferably has a DBP oil absorption of 50 to 150 CC / 100 g. The DBP oil absorption can be obtained by measuring the DBP absorption per 100 grams when carbon black is added with DBP (dibutyl phthalate) by using an absorber meter (JIS K6217).

Further, the coarse particles of all carbon blacks used in the present invention have a content of 50 ppm or less selectively. The coarse particles include carbon grids and contaminants, but when the PET resin molded product is a fiber or film, the coarse particles greatly impair the molding operability. As a colorant for such applications, the coarse particle content is preferably 20 ppm or less. The method for measuring the coarse particles conforms to JIS K 5101 (pigment test method, sieve residue).

The colorant composition of the present invention can be obtained by a conventional method for producing a masterbatch in which, for example, a PET resin and carbon black are mixed, dried, and then kneaded and dispersed in a melt extruder. It is also possible to use agents together.

Further, this colorant composition can be widely used in various molding methods of polyester resin typified by PET and molded into fibers, films, bottles, etc., but is often used for fiber applications requiring jet black tone. it can.

[0032]

EFFECTS OF THE INVENTION The molded article colored according to the present invention, in particular, the dyed fiber exhibits a bluish and jet black color because two or more kinds of carbon black are finely dispersed in the colored product. In addition, it is considered that carbon blacks having different average primary particle diameters have a so-called synergistic effect in which the characteristics of blackness and hue which are characteristic of each other are increased. When coloring the polyester fiber, it is possible to obtain a so-called jet black fibrous fiber having excellent dispersibility of carbon black, bluish and blackness.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In addition, "part" in each example represents "part by weight" unless otherwise specified.

Example 1 As 80 parts of PET resin and carbon black of group A, average primary particle diameter was 16 nm, DBP oil absorption was 100 cc / 10.
0 g, 12 parts of carbon black having a coarse particle content of 10 ppm,
Average primary particle diameter 40n as carbon black of group C
m, DBP oil absorption 65cc / 100g, coarse particle content 8ppm
8 parts of carbon black, and after mixing them,
After vacuum drying at 0 ° C. for 5 hours, the resin temperature was 285 ° C. with a twin-screw extruder (screw diameter 45 mm, L / D35).
The mixture was kneaded and dispersed to obtain a masterbatch having a carbon black content of 20%.

10 parts of this masterbatch and PET resin 9
After mixing and drying 0 parts by a conventional method, an undrawn yarn was obtained by a 40 mm melt spinning machine set at a temperature of 285 ° C.
Dry draw 4 times at 0 ℃, 75 decitex / 24f
Of black long fibers. This is referred to as a "dyed yarn".

[Evaluation] Blending coefficient : calculated from K = aα + bβ + cγ a = primary particle size (nm) of group A carbon black b = primary particle size (nm) of group B carbon black c = primary particle size of group C carbon black (Nm) α = Group A carbon black blend ratio β = Group B carbon black blend ratio γ = C group carbon black blend ratio α + β + γ = 1 K = 16 × 0.6 + 40 × 0.4 = 25.6

The colorimetric values were measured for dyed yarn Dainichiseika Color & Chemicals Mfg. Co., Ltd., at Karakomu C type colorimeter.

Evaluation of Hue The values of L ^* , a ^* , and b ^* measured by colorimetry of the spun-dyed yarn were evaluated according to the following criteria. ^{〇: L *; <19, a} *; <- 2.0, b *; <0.9 ×: L *; ≧ 19, a *; ≧ -2.0, b *; ≧ 0.9

Spinning operability Whether or not spinning and drawing were performed well was evaluated by combining both the spinning step and the drawing step and evaluated according to the following criteria. (Evaluation Criteria) Good: Both the spinning process and the drawing process are good. Poor 1: The spinning process was successfully performed, but yarn breakage occurred in the drawing process, and there was a problem in drawability. Poor 2: There is thread breakage even in the spinning step, and further thread breakage occurs in the drawing step, causing problems in both the spinning and drawing steps.

[Evaluation Results] Table 1 shows the evaluation results.

Comparative Example 1-1 80 parts of PET and the same average primary particle diameter as in Example 1 16n
m, DBP oil absorption amount 100cc / 100g, coarse particle content 10p
After mixing 20 parts of pm carbon black, a master batch having a carbon black content of 20% was obtained under the same conditions as in Example 1. Under the same conditions as in Example 1, 10 parts of this masterbatch and 90 parts of PET resin were obtained as black long fibers of 75 decitex / 24f. This is designated as "dyed yarn-1".

[Evaluation and Evaluation Results] Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1. Regarding the spinning operability, the spinning process was successfully performed to obtain an undrawn yarn, but the yarn rupture frequently occurred in the drawing process, and there was a problem with the drawability, so the spinning operability was judged to be poor.

Comparative Example 1-2 80 parts of PET and the same carbon black as in Example 1 had an average primary particle diameter of 16 nm and a DBP oil absorption of 100 cc / 1.
00g, 4 parts of carbon black having a coarse particle content of 10 ppm,
Average primary particle diameter 40nm, DBP oil absorption 65cc / 10
After mixing 0 g and 16 parts of carbon black having a coarse particle content of 8 ppm, the carbon black content was 20% under the same conditions as in Example 1.
I got a master batch of. 10 parts of this masterbatch and 90 parts of PET resin were made into black long fibers of 75 decitex / 24f under the same conditions as in Example 1. This is the "dyed yarn-2"
And

[Evaluation and Evaluation Results] Evaluations were made in the same manner as in Example 1, and the results are shown in Table 1. Regarding the spinning operability, spinning and drawing were carried out satisfactorily, and the spinning operability was judged to be good as a result of evaluating both the spinning and drawing steps together.

Comparative Example 1-3 80 parts of PET and the same average primary particle diameter as in Example 1 40 n
m, DBP oil absorption 65cc / 100g, coarse particle content 8ppm
Carbon black (20 parts) was mixed and vacuum dried at 150 ° C. for 5 hours, and then a twin-screw extruder (screw diameter 45 mm,
L / D35) was kneaded and dispersed at a resin temperature of 285 ° C. to obtain a masterbatch having a carbon black content of 20%. After 10 parts of this masterbatch and 90 parts of PET resin were mixed and dried by a conventional method, black long fibers were obtained under the same conditions as in Example 1.
This is designated as "dyed yarn-3".

[Evaluation and Evaluation Results] Evaluations were made in the same manner as in Example 1, and the results are shown in Table 1. Regarding the spinning operability, spinning and drawing were carried out satisfactorily, and the spinning operability was judged to be good as a result of evaluating both the spinning and drawing steps together.

Example 2 80 parts of PET, 12 parts of carbon black having an average primary particle size of 15 nm, DBP oil absorption amount of 65 cc / 100 g and coarse particle content of 14 ppm, average primary particle size of 55 nm, DBP oil absorption amount of 140 cc / 100 g, coarse particle content Using 10 ppm of carbon black and 8 parts of the same conditions as in Example 1, a master batch having a carbon black content of 20% was obtained with a twin-screw extruder. After mixing and drying 10 parts of this masterbatch and 90 parts of PET resin by a conventional method, an unstretched yarn was obtained with a 40 mm melt spinning machine set at a temperature of 285 ° C., and further dry-stretched by 4 times at 120 ° C. A 150 decitex / 36 f long black fiber was used. This is referred to as a "dyed yarn".

[Evaluation and Evaluation Results] Evaluations were made in the same manner as in Example 1, and the results are shown in Table 1. Regarding the spinning operability, spinning and drawing were carried out satisfactorily, and the spinning operability was judged to be good as a result of evaluating both the spinning and drawing steps together.

Comparative Example 2-1 80 parts PET and the same average primary particle size as in Example 2 15n
m, DBP oil absorption 65cc / 100g, coarse particle content 14pp
After mixing 20 parts of carbon black of m, a masterbatch having a carbon black content of 20% was obtained with a twin-screw extruder under the same conditions as in Example 2. 10 parts of this masterbatch and PET
90 parts of the resin is 150 decitex / 3 in the same manner as in Example 2.
It was 6f black long fiber. This is designated as "dyed yarn-1".

[Evaluation and Evaluation Results] Evaluations were made in the same manner as in Example 1, and the results are shown in Table 1. Regarding the spinning operability, although there was some yarn breakage in the spinning process, undrawn yarn was obtained, the yarn breakage was severe in the drawing process, and it was judged that drawing was impossible on an industrial scale, so the spinning operability was poor. did.

Comparative Example 2-2 The same carbon black as in Example 2 with 80 parts of PET having an average primary particle diameter of 15 nm and a DBP oil absorption of 65 cc / 10
0 g, 4 parts of carbon black having a coarse particle content of 14 ppm, average primary particle diameter 55 nm, DBP oil absorption 140 cc / 10
After mixing 16 parts of 0 g of carbon black having a coarse particle content of 10 ppm, 20 parts of carbon black were added under the same conditions as in Example 2.
% Masterbatch was obtained. 10 parts of this masterbatch and 90 parts of PET resin were made into black long fibers of 150 decitex / 36f under the same conditions as in Example 1. This is designated as "dyed yarn-2".

[Evaluation and Evaluation Results] Evaluations were made in the same manner as in Example 1, and the results are shown in Table 1. Regarding the spinning operability, spinning and drawing were carried out satisfactorily, and the spinning operability was judged to be good as a result of evaluating both the spinning and drawing steps together.

Example 3 As 80 parts of PET and carbon black of group A, the average primary particle diameter was 16 nm, the DBP oil absorption was 105 cc / 100.
g, 12 parts of carbon black having a coarse particle content of 8 ppm, the average primary particle diameter of 25 nm as carbon black of group B,
DBP oil absorption of 75 cc / 100 g, 6 parts of carbon black having a coarse particle content of 3 ppm, carbon black of group C, average primary particle diameter of 85 nm, DBP oil absorption of 25 cc /
100 g of carbon black having a coarse particle content of 11 ppm was mixed at a ratio of 2 parts to obtain a masterbatch having a carbon black content of 20% by a twin-screw extruder under the same conditions as in Example 1. 10 parts of this masterbatch and 90 parts of PET resin were spun and stretched in the same manner as in Example 2 to obtain black long fibers of 150 decitex / 36f. This is referred to as a "dyed yarn".

[Evaluation and Evaluation Results] Evaluations were made in the same manner as in Example 1, and the results are shown in Table 1. Regarding the spinning operability, spinning and drawing were carried out satisfactorily, and the spinning operability was judged to be good as a result of evaluating both the spinning and drawing steps together.

Comparative Example 3-1 As 80 parts of PET and carbon black of group A, the average primary particle diameter was 16 nm, the DBP oil absorption was 105 cc / 100.
g, 12 parts of carbon black having a coarse particle content of 8 ppm, the average primary particle diameter of 85 nm as carbon black of group C,
A carbon black having a DBP oil absorption of 25 cc / 100 g and a coarse particle content of 11 ppm was mixed at a ratio of 8 parts to obtain a masterbatch having a carbon black content of 20% by a twin-screw extruder under the same conditions as in Example 1. 10 parts of the masterbatch and 90 parts of PET resin were spun and stretched in the same manner as in Example 3 to obtain black filaments of 150 decitex / 36f. This is the
1 ”.

[Evaluation and Evaluation Results] Evaluations were made in the same manner as in Example 1, and the results are shown in Table 1. Regarding the spinning operability, spinning and drawing were carried out satisfactorily, and the spinning operability was judged to be good as a result of evaluating both the spinning and drawing steps together.

[0057]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yukio Otake             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo               Dainichi Seika Kogyo Co., Ltd. (72) Inventor Yusuke Takahashi             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo               Dainichi Seika Kogyo Co., Ltd. F-term (reference) 4F070 AA12 AA47 AC04 AD04 AE04                       FA03 FB03                 4J002 AA011 BB011 CF061 DA036                       DA037 DA038 FA086 FA087                       FA088 FD096 FD097 FD098                       GK01

Claims (4)

[Claims] 1. A colorant composition comprising a thermoplastic resin and a plurality of carbon blacks having different primary particle sizes, wherein the total amount of the plurality of carbon blacks is 10 to 40% by weight, and the average primary particle size is less than 20 nm. Of carbon black having a small primary particle diameter of group A, carbon black having an average primary particle diameter of 20 nm or more and less than 30 nm having an average primary particle diameter of group B, and an average primary particle diameter of 30 n
Carbon black having a coarse primary particle size of m or more is C
When grouped, the carbon black of group A is 40 to 80% by weight of the total amount of carbon black, the total of carbon black of groups B and C is 20 to 60% by weight of the total amount of carbon black, and the carbon black of group C is carbon. A colorant composition characterized by being blended so as to be contained in an amount of less than 60% by weight based on the total amount of black. 2. The coloring according to claim 1, wherein the compounding coefficient (K) of the carbon black of the groups A, B and C is K = aα + bβ + cγ and 17 ≦ K ≦ 32. Agent composition. [In the formula, a represents the primary particle size (nm) of the group A carbon black, b represents the primary particle size (nm) of the group B carbon black, and c represents the primary particle size (nm) of the group C carbon black. Represents the blending ratio of the group A carbon black, β represents the blending ratio of the group B carbon black, and γ represents the blending ratio of the group C carbon black. However, α + β + γ = 1] 3. The colorant composition according to claim 1 or 2, wherein the thermoplastic resin is a polyethylene terephthalate resin. 4. A carbon black having a DBP oil absorption of 40 to 40.
The colorant composition according to claim 1, 2 or 3, which has a coarse particle content of 50 ppm or less at 180 CC / 100 g.