JPH06200207A - Coating composition and fishing line colored therewith - Google Patents

Abstract

PURPOSE:To obtain a coating composition which can clearly color a material without detriment to its soft handling, scarcely discolors, is safe for the human body, does not cause environmental pollution in the coloration of the material because it is of nonsolvent type, and is particularly desirable for the coloration of an ultrahigh-molecular-weight polyethylene fishing line. CONSTITUTION:This coating composition comprises an aqueous medium, a pigment, a (meth)acrylic acid polymer and an ethyleneimide derivative, and the amount of the (meth)acrylic acid polymer used is 8-12 times by weight as large as that of the pigment used, while that of the ethyleneimine derivative used is 0.3-2 times by weight as large as that of the pigment used. An ultrahigh- molecular-weight polyethylene fishing line is colored with this composition in such a manner that the fishing line has respective colors for its sections of a given length.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition and a fishing line colored with the coating composition, and more particularly, a coating which can be preferably used for coloring a fishing line made of ultra-high molecular weight polyethylene. The present invention relates to a composition and a fishing line colored with the coating composition.

[0002]

2. Description of the Related Art In the field of fishing line, various kinds of materials have been developed and used, but as the fishing method for fishing becomes more sophisticated, higher performance fishing line is required. Under such circumstances, the material that has begun to be widely used at present is ultra-high molecular weight polyethylene.

Since the fishing line made of ultra-high molecular weight polyethylene has high strength and low elongation, it can be accurately shelved even when it is long, when it is used as a road line in a striking device.
In addition, there is a feature that it is easy to get fish. Then, as a line thread for a body striking device, a fishing line in which ultra-high molecular weight polyethylene is produced in a braided shape and colored in multiple colors at a constant length is put on the market. The ultra high molecular weight polyethylene string is made for strengthening, and the fixed length coloring is done so that accurate shelving can be done at hand.

[0004]

By the way, a fishing line made of ultra-high molecular weight polyethylene has poor dyeability, and thus it is difficult to color it with a conventionally known dye, and an ultra-high molecular weight is used in a paint in which a pigment is dispersed in a binder. The adhesion between polyethylene and the binder is weak, and due to the bleeding of the paint, there is a drawback that stains on the angler's hands and clothes with pigments, and when the fishing line is repeatedly wound up on the reel, color transfer occurs due to the overlapping of the fishing line. . Moreover, since the above-mentioned paint is usually prepared by using an organic solvent, there is a problem in terms of manufacturing danger and environmental pollution due to waste water.

The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to maintain a supple texture of a material and to color it vividly, with almost no color fading.
Moreover, since it can be colored with a non-solvent system, it is safe for the human body during the coloring operation of the material and does not cause environmental pollution, and particularly to provide a coating composition suitable for coloring fishing line made of ultra-high molecular weight polyethylene. It is in. Another object of the present invention is to provide a fishing line made of ultra-high molecular weight polyethylene colored with such a coating composition.

[0006]

That is, the first aspect of the present invention
Of the present invention comprises a pigment, a (meth) acrylic acid-based polymer, and an ethyleneimine derivative in an aqueous medium.
The proportion of acrylic acid polymer is 8 to 12 times the weight of the pigment, and the proportion of ethyleneimine derivative is 0.3 to the pigment.
~ 2 times the weight of the coating composition,
The second gist is that the fishing line is made by braiding a large number of bundles of ultra-high molecular weight polyethylene filaments, and the fishing line is colored in multiple colors at a constant length, and the fishing line is colored with the above-mentioned coating composition. Exists in the fishing line to do.

The present invention will be described in detail below. First, the coating composition of the present invention will be described. The coating composition of the present invention comprises a pigment, a (meth) acrylic acid polymer and an ethyleneimine derivative in an aqueous medium.

In the present invention, as the pigment, an organic pigment is mainly used, but if necessary, a blended pigment obtained by blending an organic pigment with an inorganic pigment may be used in addition to the inorganic pigment. Organic pigments are classified from the viewpoint of chemical structure, and are shown as examples. Phthalocyanine, anthraquinone, quinacridone, azo, indigo, quinophthalone, isoindolinone, quinazoline, dioxazine, anthrone, perinone. There are various types such as system, perylene, and picoline.
In the present invention, the type of the organic pigment is not particularly limited as long as it can be dyed with a pigment, and an organic pigment having good light resistance can be appropriately selected and used according to a desired hue.

The pigments preferably used in the present invention are classified and shown from the viewpoint of hue as shown in Table 1 below.

[0010]

[Table 1] Yellow: Azo Yellow Orange: Azo Red / Azo Yellow Red: Azo Red Green: Copper Phthalocyanine Green Blue: Copper Phthalocyanine Green / Dioxane Black: Carbon

In the present invention, the (meth) acrylic acid type polymer acts as a binder (fixing agent) in pigment dyeing. The term (meth) acrylic acid means any one of acrylic acid and methacrylic acid or a mixture of both. Conventionally, various thermoplastic and thermosetting resins have been used as a binder in dyeing pigments, but in order to achieve the object of the present invention, a (meth) acrylic acid-based polymer is used as the binder. Need to use.

In the present invention, the (meth) acrylic acid-based polymer is not particularly limited as long as it is a polymer containing a (meth) acrylic acid unit, and it may be either a homopolymer or a copolymer. Good. Specific examples thereof include homopolymers of the monomers listed in Table 2 below and copolymers obtained by appropriately combining these monomers.

[0013]

Table 2 (1) (Meth) acrylic acid (2) Ester of (meth) acrylic acid and alkanolamine (3) Acid amide of (meth) acrylic acid and 5-aminobenzotriazole

In particular, the monomers (1) and (2) or (2)
A (meth) acrylic acid-based copolymer obtained by copolymerizing (3) with (3) is preferable. That is, since the copolymer composed of the monomers (1) and (2) is amphoteric, it is soluble in either acid or alkali, and it is necessary to use a surfactant during the production. There is no advantage, and (2)
The copolymer consisting of (3) and (3) is preferable because it has a substituted benzotriazole group having an ultraviolet absorbing ability and can prevent deterioration of the pigment.

Specific examples of the alkanolamine include dimethylethanolamine, diethylethanolamine, dipropylethanolamine, dibutylethanolamine, dimethylpropanolamine, dimethylbutanolamine and the like. Further, as the above-mentioned 5-aminobenzotriazole, specifically, various triazole compounds shown in the following Tables 3 to 6 can be mentioned.

[0016]

Table 3 2- (3'-methyl-2'-hydroxyphenyl) -5
-Aminobenzotriazole 2- (3 ', 5'-dimethyl-2'-hydroxyphenyl) -5-aminobenzotriazole 2- (3'-t-butyl-5'-methyl-2'-hydroxyphenyl) -5 -Aminobenzotriazole 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-aminobenzotriazole

[0017]

2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) -5-aminobenzotriazole 2- (3', 5'-di-t-octyl-2'-hydroxy Phenyl) -5-aminobenzotriazole 2- [3 ', 5'-di- (α, α-dimethylbenzyl)
-2'-hydroxyphenyl] -5-aminobenzotriazole 2- [3 '-(α, α-dimethylbenzyl) -5'-methyl-2'-hydroxyphenyl] -5-aminobenzotriazole

[0018]

Table 5 2- [3 '-(α, α-dimethylbenzyl) -5'-t
-Butyl-2'-hydroxyphenyl] -5-aminobenzotriazole 2- [3 '-(α, α-dimethylbenzyl) -5'-t
-Octyl-2'-hydroxyphenyl] -5-aminobenzotriazole 2- [3'-t-butyl-5 '-(α, α-dimethylbenzyl) -2'-hydroxyphenyl] -5-aminobenzotriazole 2 -[3'-t-octyl-5 '-(α, α-dimethylbenzyl) -2'-hydroxyphenyl] -5-aminobenzotriazole

[0019]

Table 6 2- [3 '-(α-methylbenzyl) -5'-t-octyl-2'-hydroxyphenyl] -5-aminobenzotriazole 2- (3'-benzyl-5'-t-butyl-2) '-Hydroxyphenyl) -5-aminobenzotriazole 2- (3'-N-phenylcarbamido-5'-t-butyl-2'-hydroxyphenyl) -5-aminobenzotriazole 2- (3'-t- Butyl-5'-methoxy-2'-hydroxyphenyl) -5-aminobenzotriazole

The respective monomers shown in Table 2 above are usually copolymerized in the following proportions. That is, the monomer (1)
And (2), the monomer (1) is in the range of 3 to 20 parts by weight per 100 parts by weight of the monomer (2), and the monomers (2) and (3) are the monomers. (2) The monomer (3) is in the range of 3 to 150 parts by weight per 100 parts by weight, and in the case of the monomers (1) and (3), the monomer (3) per 100 parts by weight of the monomer ( 1) is copolymerized in the range of 3 to 20 parts by weight.

The (meth) acrylic acid type copolymer obtained by copolymerizing the monomers (1) and (2) or (2) and (3) is disclosed in JP-A-62-283144. It is known and can be obtained according to the copolymerization methods described in these publications.

In the present invention, the molecular weight of the (meth) acrylic acid-based polymer is not particularly limited, but generally, the number average molecular weight is about 1,000 to 200,000, preferably about 50,000 to 150. About 1,000 is suitable. Further, the (meth) acrylic acid-based polymer is a third monomer such as styrene, (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, etc. in the range of less than 15% by weight in all monomers. The polymer may be copolymerized, and the monomers (1) and (2) may be in the form of various salts including a quaternary ammonium salt. And salt formation can also be performed after superposition | polymerization.

In the present invention, the ethyleneimine derivative acts as a crosslinking agent. As the ethyleneimine derivative, a substantially water-insoluble ethyleneurea compound obtained by reacting ethyleneimine with a urethane prepolymer having an isocyanate group at a terminal is particularly preferable.

The above-mentioned ethylene urea compound is known, for example, from Japanese Examined Patent Publication No. 55-21780. Therefore, according to the method described in the above-mentioned publication, the reaction is carried out by adding an organic polyisocyanate in excess to the terminal hydroxypolyol. To obtain a urethane prepolymer having an isocyanate group at the terminal, add ethyleneimine in an amount approximately equivalent to the terminal NCO%, and react at 40 to 70 ° C. for 2 to 4 hours.

In the preparation of the urethane prepolymer, various polyols obtained by reacting an alkylene diol with an aliphatic dicarboxylic acid and other polyol components may be used as the polyol component, and polyisocyanate may be used. As the component, an aliphatic diisocyanate such as hexamethylene diisocyanate or other polyisocyanate component can be used, and the reaction can be carried out by a conventional method.

The coating composition of the present invention is characterized in that an ethyleneimine derivative is used as a cross-linking agent and a (meth) acrylic acid polymer and an ethyleneimine derivative are used in a specific amount range. That is, in the coating composition of the present invention, from the viewpoint of coating film physical properties such as light resistance, abrasion resistance, and wash fastness, the (meth) acrylic acid-based polymer is 8 to 12 times by weight of the pigment and ethylene. The imine derivative is 0.3 to 2 times by weight, preferably 0.5 to 1.
It is important to use in the range of 5 parts by weight.

It is easy to handle each of the above raw material components in the form of a slurry using water as a medium.
For example, the above-mentioned pigments shown in Table 1 are usually prepared by using a nonionic surfactant as a dispersant and a suspension having a solid content concentration of 25 to 45% by weight and a pH of 7.5 to 9.5 as described above. The (meth) acrylic acid-based polymer usually has a solid content concentration of 30 to 4
0% by weight, as an anionic suspension of about PH7, the above-mentioned ethyleneimine derivative has a solid content concentration of 10 to 10.
It is preferable to prepare it as an anionic suspension containing 25% by weight and a pH of around 9.5.

And, in preparing the aqueous medium slurry of the ethylene urea compound, Japanese Patent Publication No. 55-2178.
A reaction product of a polyethylene oxide compound having a hydroxyl group at the terminal and an equimolar or more organic polyisocyanate compound as an emulsifier,
It is preferred to use compounds whose isocyanate groups at their ends are masked by masked compounds.

The above polyethylene oxide compound is
Alcohols such as ethylene glycol, amines, amino compounds as an initiator, obtained by addition reaction of alkylene oxide such as ethylene oxide,
Usually, those having a number average molecular weight of 1,000 to 20,000 are suitable. Then, as the organic polyisocyanate compound that is reacted with the above-mentioned polyethylene oxide compound, for example, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, etc. are used, and as the masked compound, a compound that is commonly used for isocyanate group masks. , For example, ε−
Examples thereof include caprolactam and phenol.

The aqueous medium slurry of the ethylene urea compound using the above emulsifier is 3 to 100 parts by weight, preferably 10 to 100 parts by weight of the ethylene urea compound.
80 parts by weight are blended, and this is mixed with a mixer at a temperature of 5 to 5.
Mix uniformly at 30 ° C., preferably 20-30 ° C., and add water 50 at a temperature of 5-20 ° C., preferably 15-20 ° C.
It is prepared by gradually dropping 0 to 800 parts by weight and emulsifying with a stirrer such as a homomixer. In the above aqueous medium, not only the ethylene urea compound but also the emulsifier itself undergoes a cross-linking reaction by the heat treatment, and therefore an operation such as soaping for removing the emulsifier is unnecessary.

In the coating composition of the present invention, the concentration of the pigment can be arbitrarily selected, but is usually in the range of 1 to 10% by weight. Therefore, when the above suspension is used as a raw material component, it is necessary to add water to the suspension to dilute it to a predetermined concentration. The ratio of the (meth) acrylic acid-based polymer and the ethyleneimine derivative to the pigment used in the coating composition of the present invention is as described above, but it is as follows in terms of the concentration in the aqueous medium. That is, when the pigment concentration is 3% by weight, the (meth) acrylic acid polymer is about 25 to 35% by weight, and the ethyleneimine derivative is about 1 to 5% by weight.

Next, the fishing line of the present invention will be described. The above-mentioned coating composition of the present invention is suitable for coloring fishing lines made of ultra-high molecular weight polyethylene, and specifically used for constant length coloring of road yarns made of ultra-high molecular weight polyethylene in a striking device. Can be done. As a result, according to the present invention, it is possible to obtain a fishing line made of ultra-high molecular weight polyethylene which is colored in multiple colors at regular intervals and has excellent performance.

Ultrahigh molecular weight polyethylene is a polyethylene having a weight average molecular weight of 500,000 or more, preferably 1,000,000 or more, and in the range of 5 mol% or less, propylene,
Butylene and the like may be copolymerized. Ultrahigh molecular weight polyethylene filaments are disclosed, for example, in JP-A-55-52.
28, JP-A-55-14245, JP-A-5
It is manufactured by the method described in JP-A 5-107506 and JP-A-59-130313, and has the characteristics of high strength and high elastic modulus.

The fineness of the above filament is 0.5 to 2
0 denier (d) is suitable, and 1 to 5 d is particularly preferable. The tensile strength of the filament is 15 g / d or more, preferably 20 g / d or more, and the knot strength is 10 g / d.
Or more, preferably 15 g / d or more, and an initial elastic modulus of 500
It is good to be g / d or more, preferably 800 g / d or more. The above filament has a total fineness of 50 to 35.
It is bundled so as to be 0d, and twisted or heat set if necessary. Then, 5 to 20 filament bundles are braided into a braid.

Coloring with the coating composition of the present invention is carried out by holding the fishing line made of ultra-high molecular weight polyethylene in the bath of the coating composition for 1 second or longer and then drying it at 80 to 130 ° C. for 90 seconds or longer. Can be done. Then, by a suitable means, the yarn can be colored in multiple colors at a fixed length to finish the yarn. The obtained yarn has a supple texture, a clear hue, almost no color loss, and has excellent quality as compared with commercially available products.

In the present invention, it is preferable to provide a coating layer of alcohol-soluble polyamide on the surface of the colored portion, which is colored in a multicolored manner at constant lengths as described above. Such a polyamide coating layer further improves the abrasion resistance and washing fastness of the colored portion.

Unlike conventional polyamides, alcohol-soluble polyamides are readily soluble in lower aliphatic alcohols such as methanol, ethanol and propanol. Alcohol-soluble polyamides are, for example, Japanese Patent Publication No. 63-37.
As described in publicly known documents such as No. 369, it is usually a cyclic polyamide synthesized from a diamine, an ω-amino acid, a lactam or a derivative thereof and a dibasic fatty acid by a known method.

And, typically, nylon 3, 4,
5, 6, 8, 11, 12, 13, 6, 6, 6, 10, 1
3.13 Polyamide from metaxylidenediamine and adipic acid, trimethylhexamethylenediamine or polyamide from isophoronediamine and adipic acid, ε
-Caprolactam / adipic acid / hexamethylenediamine / 4,4'-diaminodicyclohexylmethane, ε-
Copolyamides such as caprolactam / adipic acid / hexamethylene diamine / polyethylene glycol diamine, polyamides having basic tertiary nitrogen such as N, N′-di (7-aminopropyl) piperazine adipate / ε-caprolactam copolymer And polyamides to which a quaternizing agent capable of forming ammonium ions such as acrylic acid is added. These homopolymers may be used alone or in combination of two or more to form a copolymer,
It may be used as a block polymer or a mixture. In the present invention, for example, commercial products “CM4000”, “CM8000” and the like from Toray Industries, Inc. can be preferably used.

The coating of the colored portion with the alcohol-soluble polyamide is carried out by, for example, immersing the colored portion in an alcohol solution of the alcohol-soluble polyamide and then drying it. The polyamide concentration in the alcohol solution is
Usually, 1 to 10% by weight, the immersion time is 1 second or longer, and the drying is preferably performed at a temperature of 60 to 100 ° C. for 60 seconds or longer. In the present invention, an ultraviolet absorber may be added to the above alcohol solution, if necessary.

[0040]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

<Coating materials> (1) Pigment: Commercial products shown in the following Table 7 were used (all containing nonionic surfactants).

[0042]

[Table 7] ───────────────────────────────────── Hue Pigment component Solid content concentration (wt%) PH Yellow: Azo Yellow 30.0 9.2 Orange: Azo Red / Azo Yellow 29.5 9.2 Red: Azo Red 32.5 9.2 Green: Copper Phthalocyanine Green 39.0 8.2 Blue: Copper Phthalocyanine Green / Dioxane 26.0 8.8 Black: Carbon 43.5 7.5 ────────────────────────────── ──────

(2) Adhesive ((meth) acrylic acid type polymer): As the adhesive (A), a (meth) acrylic acid type polymer (methacrylic acid: dimethylaminoethyl methacrylate = 1: 24 weight ratio, number) Average molecular weight = about 100,000
0) suspension (solid concentration 35% by weight, PH 7.0 anionic suspension) was used.

As the adhesive (B), a (meth) acrylic acid type polymer (methacrylic acid: dibutylaminoethyl methacrylate = 1: 15 weight ratio, number average molecular weight = about 100,
000) suspension (solid concentration 35% by weight, PH 7.0)
Anionic suspension of) was used.

As the fixing agent (C), a (meth) acrylic acid type polymer (methacrylic acid: dimethylaminopropyl methacrylate = 1: 10 weight ratio, number average molecular weight = about 10).
50,000) suspension (solid concentration 35% by weight, PH
An anionic suspension of 7.0) was used.

As the fixing agent (D), a (meth) acrylic acid type polymer (methacrylic acid: dimethylaminobutyl methacrylate = 1: 7 weight ratio, number average molecular weight = about 100,0).
00) (an anionic suspension having a solid content concentration of 35% by weight and a pH of 7.0) was used.

As the fixing agent (E), a (meth) acrylic acid type polymer (dimethylaminoethyl methacrylate: 2-
[3 ', 5'-di- (α, α-dimethylbenzyl)-
2′-hydroxyphenyl] -5-methacryloylaminobenzotriazole = 1: 0.5 weight ratio, number average molecular weight = about 100,000) suspension (solid concentration 35% by weight, pH 7.0 anionic suspension). Suspension) was used.

As the fixing agent (F), a (meth) acrylic acid type polymer (diethylaminoethyl acrylate: 2-
(3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-acryloylaminobenzotriazole =
(1: 0.1 weight ratio, number average molecular weight = about 100,000)
Was used (an anionic suspension having a solid content concentration of 35% by weight and a pH of 7.0).

(3) Crosslinking agent (ethyleneimine derivative):
A suspension of an ethylene urea compound prepared according to the method described in Example 1 of JP-B-55-21780 (anionic suspension of solid content concentration 20% by weight, PH 9.5) was used. The above-mentioned suspension was prepared by mixing the following ethylene urea compound and an emulsifier at a temperature ratio of 30 ° C. in a weight ratio of 5: 1 and adding 1.5 parts by weight of water (20 ° C.) to the mixture for emulsification treatment. It was obtained.

(Ethylene urea compound) Terminal OH number 130
The ethylene urea compound obtained by reacting ethylene imine with a urethane prepolymer having a terminal NCO obtained from hydroxy adipate (using 1,6-hexanediol) and excess hexamethylene diisocyanate was used.

(Emulsifier) A urethane N-terminal urethane prepolymer obtained from mixed alkylene oxide having a number average molecular weight of 2000 (ethylene oxide / propylene oxide = 9/1 weight ratio) and xylylene diisocyanate has ε.
-The compound obtained by reacting caprolactam was used.

<Sample to be colored> Ultra high molecular weight polyethylene fiber (“Dyneema SK60” manufactured by Toyobo Co., Ltd., 15
0d: 1d x 150f) was used, and No. 6 yarn (1200d) prepared by striking 8 pieces with a commercially available stringing machine was used.

<Evaluation items and evaluation conditions> (1) Light resistance: using a fade meter, 48 hours, 1
An exposure test was performed for 50 hours and 300 hours, and evaluation was performed according to the following four-stage criteria shown in Table 8. The evaluation was carried out by a visual test using a monitor (10 persons) with a 50% gender ratio in random selection of age group (the same applies to the following abrasion resistance and washing fastness).

[0054]

[Table 8] ◎: Almost no color loss ○: Slight color loss Δ: Significant color loss X: Complete color loss

(2) Abrasion resistance: 100% cotton on a cylindrical jig
% Cloth is wound, the sample is brought into contact with the cloth, and a frictional motion is performed by applying a load of 2 kg (stroke: 100 mm, speed: 40 reciprocations / minute). Then, the frictional movement is performed in the following three states of the sample, that is, a dry state (A state), a state after being immersed in 25 ° C. water for 30 minutes (B state), and a state after being immersed in 90 ° C. water for 30 minutes. It carried out about (C state). Then, the degree of discoloration due to the frictional movement was evaluated according to the five-stage criteria shown in Table 9 below.

[0056]

[Table 9] 5: State without any color fading 4: State with almost no color fading 3: State with slight fading 2: State with considerable color fading 1: State of complete color fading

(3) Washing fastness: The sample was immersed in a test solution of 25 ° C. water, 90 ° C. water and 30 ° C. artificial seawater at a bath ratio of 1:50 and stirred with a stirrer for 30 minutes. To do. Then, the degree of discoloration after stirring was evaluated based on the five-stage criteria shown in Table 9 above.

(4) Texture: A blind test was carried out by the above-mentioned monitor, and evaluation was carried out according to the criteria of four stages shown in Table 10 below.

[0059]

[Table 10] ◎: Good ○: Fairly good △: Fairly poor ×: Bad

(5) Appearance: The presence or absence of surface roughness (pickup phenomenon) was examined by the above-mentioned monitor, and evaluated according to the following three-stage criteria shown in Table 11.

[0061]

[Table 11] ⊚: No roughness at all ∘: Slightly rough texture x: Marked roughness

Examples 1 to 12 The pigment suspension, the fixing agent suspension and the cross-linking agent suspension were weighed and mixed, water was added thereto, and various types shown in Tables 13 and 14 below were added. A coating composition was prepared. Then, using each of the above-mentioned coating compositions, a coloring test was performed on the ultrahigh molecular weight polyethylene fiber (No. 6 yarn) under the processing conditions shown in Table 12 below. That is, the yarn was colored in multiple colors at a constant length to finish the yarn.

[0063]

[Table 12] Staying time: 1 second or more Drying temperature: 110 to 130 ° C Drying time: 90 seconds or more

The above-mentioned evaluation items were tested for the above colored No. 6 yarn, and the obtained results are shown in Tables 13 and 14 below. The symbols in the table are the standards for creating the frequency distribution for each standard from the results of the monitor test and giving the maximum value (the same applies to the symbols in other tables).

[0065]

[Table 13] ───────────────────────────────────── Example 1 2 3 4 5 6 Pigment hue Yellow Yellow Yellow Yellow Yellow Yellow Pigment concentration 3.0 3.0 3.0 3.0 3.0 3.0 Adhesive type A B C D E F Adhesive concentration 30.0 30.0 30.0 30.0 30.0 30.0Crosslinker concentration 2.5 2.5 2.5 2.5 2.5 2.5 <Light resistance> 48 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ 150 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ 300 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ <Abrasion resistance> A state 4 4 4 4 4 B state 4 4 4 4 4 4 4 C State 4 4 4 4 4 4 <Washing fastness> 25 ° C water 4 4 4 4 4 4 90 ° C water 4 4 4 4 4 4 30 ° C artificial seawater 4 4 4 4 4 4 4 <texture> ◎ ◎ ◎ ◎ ◎ ◎ < Appearance ＞ ◎ ◎ ◎ ◎ ◎ ◎ ───────────────────────────────────── (Note) Concentration represents weight% in the aqueous medium, the balance is
Substantially water (also in the table below).

[0066]

[Table 14] ───────────────────────────────────── Example 7 8 9 10 11 12 Pigment hue Yellow Yellow Yellow Red Red Red Pigment concentration 3.0 3.0 1.0 3.0 3.0 1.0 Adhesive agent type A A A A A A A Adhesive agent concentration 25.0 35.0 10.0 25.0 35.0 10.0Crosslinker concentration 1.0 5.0 0.8 1.0 5.0 0.8 <Light resistance> 48 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ 150 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ 300 hours ◎ ◎ ◎ ○ ○ ○ ○ <Abrasion resistance> A state 4 4 4 4 4 B state 4 4 4 4 4 4 C State 4 4 4 4 4 4 <Washing fastness> 25 ° C water 4 4 3 4 4 4 90 ° C water 4 4 3 4 4 4 30 ° C artificial seawater 4 4 3 4 4 4 4 <texture> ◎ ◎ ◎ ◎ ◎ ○ < Appearance> ◎ ○ ○ ◎ ○ ○ ─────────────────────────────────────

Examples 13 to 18 Example 1 is different from Examples 1 to 6 except that a coating layer of alcohol-soluble polyamide is provided on the surface of the colored portion of each colored No. 6 yarn obtained in the same manner as in each Example. Polyamide-coated fishing line was obtained in the same manner as described above.

As the alcohol-soluble polyamide, a product "CM8000" manufactured by Toray Industries, Inc. was used, which was used as a solution containing 5% by weight of polyamide and 95% by weight of ethanol. Then, the colored part of each colored No. 6 yarn was immersed in an alcohol solution for 60 seconds and then dried at 80 ° C. for 60 seconds to form a polyamide coating layer. The obtained polyamide-coated fishing line was tested for each evaluation item in the same manner as in Example 1, and the obtained results are shown in Table 15 below.

[0069]

[Table 15] ───────────────────────────────────── Example 13 14 15 16 17 18 Pigment hue Yellow Yellow Yellow Yellow Yellow Yellow Pigment concentration 3.0 3.0 3.0 3.0 3.0 3.0 Adhesive type A B C D E F Adhesive concentration 30.0 30.0 30.0 30.0 30.0 30.0Crosslinker concentration 2.5 2.5 2.5 2.5 2.5 2.5 <Light resistance> 48 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ 150 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ 300 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ <Abrasion resistance> A state 5 5 5 5 5 B state 5 5 5 5 5 5 5 5 C State 5 5 5 5 5 5 5 <Washing fastness> 25 ° C water 5 5 5 5 5 5 5 90 ° C water 5 5 5 5 5 5 30 ° C artificial seawater 5 5 5 5 5 5 5 <texture> ◎ ◎ ◎ ◎ ◎ ◎ < Appearance ＞ ◎ ◎ ◎ ◎ ◎ ◎ ─────────────────────────────────────

Comparative Examples 1 to 5 Fishing lines were obtained in the same manner as in Example 1 except that the concentrations of the fixing agent and the cross-linking agent were changed as shown in Table 16 below. About the obtained fishing line, Example 1
Tests for each evaluation item were conducted in the same manner as in, and the results are shown in Table 1 below.
6 shows.

[0071]

[Table 16] ──────────────────────────────── Comparison Comparative Example 1 2 3 4 5 Pigment Hue Yellow Yellow Yellow Yellow Yellow Yellow pigment concentration 3.0 3.0 3.0 3.0 3.0 Adhesive type A A A A A Adhesive concentration 30.0 20.0 40.0 30.0 30.0 Crosslinker concentration 0 2.5 2.5 0.5 10.0 <Light resistance> 48 hours ◎ ◎ ◎ ◎ ◎ ◎ 150 hours ○ ○ ○ ○ ○ 300 hours ○ ○ ○ ○ ○ <Abrasion resistance> A state 2 4 3 3 3 B state 2 3 3 3 3 C state 2 3 3 3 3 <washing fastness> 25 ° C water 2 3 3 3 3 90 ° C water 2 2 3 2 3 3 30 ° C Artificial seawater 2 3 3 2 3 <Handle> ○ ○ × ○ × <Appearance> ◎ ○ × ○ × ───────────────────── ───────────

[0072]

According to the present invention described above, the material can be colored vividly while maintaining the supple texture.
Moreover, there is almost no color fading, and since it can be used in a non-solvent system, it is safe for the human body during coloring operation or use and there is no environmental pollution. Especially, it is suitable for coloring ultra-high molecular weight polyethylene fishing line. A coating composition is provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location D06M 15/263 (72) Inventor Shinya Mizuno 13-201 Higashisaki-cho, Tsuchiura-shi, Ibaraki Prefecture

Claims (7)

[Claims] 1. An aqueous medium containing a pigment, a (meth) acrylic acid-based polymer and an ethyleneimine derivative, wherein the ratio of the (meth) acrylic acid-based polymer is 8 to 12 relative to the pigment.
A coating composition, characterized in that the weight ratio of the ethyleneimine derivative is 0.3 to 2 times the weight of the pigment. 2. A (meth) acrylic acid-based polymer is an ester of (meth) acrylic acid and an alkanolamine and a copolymer derived from (meth) acrylic acid and / or (meth) acrylic acid and 5- The coating composition according to claim 1, which is a copolymer derived from an acid amide with aminobenzotriazole and an ester of (meth) acrylic acid with an alkanolamine. 3. The coating composition according to claim 1, wherein the ethyleneimine derivative is an ethyleneurea compound. 4. The coating composition according to claim 1, wherein the pigment concentration in the aqueous medium is 1 to 10% by weight. 5. The coating composition according to claim 1, which is used for coloring a fishing line made of ultra-high molecular weight polyethylene. 6. A coating composition according to any one of claims 1 to 4, which is a fishing line formed by braiding a large number of bundles of ultra-high molecular weight polyethylene filaments and colored in multiple colors at regular intervals. A fishing line characterized by being colored by objects. 7. The fishing line according to claim 6, wherein a coating layer of alcohol-soluble polyamide is provided on the surface of the colored portion.