JP3458660B2 - Chlorine-resistant aqueous colored resin composition and molded article thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored resin composition for molding a colored resin which is in direct contact with chlorine-containing water. More specifically, the present invention relates to a chlorine-resistant water-based colored resin composition capable of providing a molded product which does not cause punctiform protrusions or swelling on the surface of the molded product even when directly contacted with chlorine-containing water and has less color loss.

[0002]

2. Description of the Related Art In order to color-form polyolefin resins such as polyethylene and polybutene, inorganic pigments such as zinc oxide, titanium oxide, red iron oxide, ultramarine blue and cobalt blue,
Organic pigments such as azo, quinacridone, anthraquinone, perylene, isoindolinone, phthalocyanine, dioxazine, induslen, perinone, quinophthalone, carbon black, azo, anthraquinone, perylene , Perinone type, thioindigo type dyes are used.

When a molded product obtained by blending the above dyes and pigments with a polyolefin resin is brought into direct contact with chlorine-containing water, for example, when used in a water supply pipe, the surface of the molded product has punctiform protrusions or small diameter swelling ( (Hereinafter, referred to as swelling) occurs, and there is a problem that a part of the molded product is mixed into the clean water due to the separation of the swelling. This tendency was particularly remarkable in the case of water supply pipes to which organic pigments were added. In the case of a water supply pipe, strictness as specified in JIS K6762 is required for the occurrence of swelling due to the property that the water is supplied to food and drink.

[0004] Water supply pipes are pipes for introducing water from dams and rivers to water purification plants, pipes for water transmission from water purification plants to reservoir areas such as reservoirs and towers, and from reservoir areas to areas such as cities and municipalities. It is divided into water distribution pipes, water supply pipes from there to households and factories, and indoor water distribution pipes. Of these water supply pipes, high-density polyethylene is usually used for large-diameter pipes, and linear low-density polyethylene, polybutene or vinyl chloride is usually used for small-diameter pipes. Further, connecting parts such as joints are used to connect the pipes.

Of these water supply pipes, there is currently no particular color designation for connecting parts such as water-conducting pipes, water-supplying pipes, and joints for connecting the pipes, and various commonly used pigments are currently not specified. It is used. Water distribution pipes and their joints are generally colored in a bluish color, which is an image of water, in order to distinguish them from gas pipes colored in green and other pipes. For this blue coloring, blue pigments such as ultramarine blue, dark blue, kuresu, cobalt blue, cerulean blue, phthalocyanine-based, and indanthrene-based blue pigments are used, and among them, phthalocyanine-based, indanthrene-based, ultramarine blue, and cobalt-based blue pigments. Is preferably used. On the other hand, the water supply pipe is usually colored black using carbon black, aniline black, black titanium or the like. Indoor water distribution pipes are usually colored yellow by using azo, nitro, titanium yellow, ocher or the like.

In order to satisfy the strict conditions required for a water supply pipe, a two-layer structure in which a pigment-free layer is provided on the inner surface of the pipe that is in direct contact with chlorine-containing water and a pigment-containing layer is provided on the outer surface of the pipe Tubes have been proposed. However, such a double-layer pipe is more difficult to manufacture than a single-layer pipe,
There is also a problem that a special molding machine is required. Further, it is difficult to make the joint portion connecting the pipes into a two-layer structure because of the structure. Therefore, there is a demand for a colored resin composition that can provide a molded article having excellent chlorine-containing water resistance even in a single layer.

For the above-mentioned purpose, it has been considered that a pigment having a high acid value is used to coat the pigment to obtain a chlorine-containing water resistance to some extent. With the extension of the usage period, in recent years,
A colored resin composition having a higher level of chlorine-containing water content is desired.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a chlorine-containing water-based colored resin composition which solves the above-mentioned problems and can provide a molded product having excellent chlorine-containing water resistance and long-term durability. To do.

[0009]

A first aspect of the present invention relates to an organic pigment (2) obtained by treating an organic pigment (1) with a fatty acid metal salt (a), which has an α, β unsaturated double bond. A colorant (4) obtained by melt-kneading a copolymer resin (3) of a basic acid or its anhydride (b) and a monomer (c) having an α, β unsaturated double bond is mixed with a polyolefin resin (5). ) A chlorine-resistant water-based colored resin composition which is dispersed in

In a second aspect of the present invention, the coloring agent (4) contains 75 to 99.9% by weight of the organic pigment (1) as a fatty acid metal salt (a) of 0.
Chlorine-resistant according to the first invention, which is obtained by melt-kneading 100 parts by weight of an organic pigment (2) treated with 1 to 25% by weight with 1 to 500 parts by weight of a copolymer resin (3). The contained aqueous colored resin composition.

A third invention is the first invention or the second invention, wherein the fatty acid metal salt (a) is a metal salt of a fatty acid selected from the group consisting of caprylic acid, oleic acid and stearic acid.
The chlorine-resistant water-based colored resin composition according to the invention.

In a fourth aspect of the invention, the fatty acid metal salt (a) is a metal salt of a fatty acid containing at least one metal selected from the group consisting of lithium, calcium, magnesium and zinc. The chlorine-containing water-based colored resin composition according to any of the third inventions.

The fifth aspect of the invention is to add 0.005 to 10 parts of the organic pigment (2) to 100 parts by weight of the polyolefin resin (5).
The chlorine-resistant water-based colored resin composition according to any one of the first to fourth inventions, which is dispersed in a proportion of parts by weight.

A sixth invention is the first to fourth inventions, wherein the organic pigment (2) is dispersed in 100 parts by weight of the polyolefin resin (5) at a ratio of 0.05 to 10 parts by weight. The chlorine-containing aqueous colored resin composition according to any one of 1.

A seventh invention is the chlorine-resistant aqueous colored resin composition according to any one of the first to sixth inventions, wherein the organic pigment (1) is a phthalocyanine blue and / or an indanthrene blue. It is a thing.

An eighth invention is the chlorine-containing water-based colored resin as described in any one of the first invention to the seventh invention, wherein the monomer (c) having an α, β unsaturated double bond is an α-olefin. It is a composition.

A ninth invention is a chlorine-resistant water-based colored resin according to the eighth invention, wherein the copolymer resin (3) is a copolymer of an α-olefin having 6 to 30 carbon atoms and maleic anhydride. It is a composition.

In a tenth aspect of the invention, the copolymer resin (3) has an acid value of 200 to 600 mgKOH / g, and the acid value of 1 to 100 mgKOH together with the colorant (4).
/ G of the thermoplastic resin (3 ′) is dispersed in the polyolefin resin (5), which is the chlorine-resistant aqueous colored resin composition according to any one of the first to ninth inventions.

The eleventh invention is a copolymer resin (3) 10.
The chlorine-resistant aqueous colored resin composition according to the tenth invention, wherein 1 to 500 parts by weight of the thermoplastic resin (3 ′) is dispersed in 0 part by weight.

A twelfth invention is the ionomer resin, wherein the thermoplastic resin (3 ') is a metal salt of a copolymer of ethylene and an unsaturated carboxylic acid, and the twelfth invention is described in the tenth invention or the eleventh invention. It is a chlorine-resistant aqueous colored resin composition.

A thirteenth invention is the chlorine-resistant water-based colored resin composition according to the twelfth invention, wherein the unsaturated carboxylic acid is acrylic acid and / or methacrylic acid.

A fourteenth invention is a chlorine-resistant water-based colored resin composition according to any one of the first to thirteenth inventions, wherein the polyolefin resin (5) is a high-density polyethylene or a linear low-density polyethylene. It is a thing.

A fifteenth invention is the chlorine-resistant water-based colored resin composition according to any one of the first to fourteenth inventions, which is used for a water pipe.

The sixteenth invention is the fifteenth invention, wherein the water supply pipe is a water supply pipe or a joint of the water supply pipe.
The chlorine-resistant water-based colored resin composition according to the invention.

The seventeenth invention is the fifteenth invention or the sixteenth invention.
Is a pipe for water supply obtained by molding the chlorine-containing water-based colored resin composition according to the invention.

In this specification, the term "resin" means
It has a molecular weight of several hundred thousand and MFR according to JIS K7210.
(Melt flow rate, that is, melt viscosity), which is commonly referred to as "thermoplastic resin", is commonly referred to as "wax", and has a molecular weight of several thousand to tens of thousands according to JIS K7210. It is used in the sense of including both those for which conforming MFR measurement is not possible.

In the present invention, in order to provide a molded product obtained by molding the colored resin composition with a sufficient chlorine-containing water resistance, [1] the pigment particles are previously coated with a fatty acid metal salt, [2] Further, after melt-kneading the pigment particles with a thermoplastic resin having a high acid value, the pigment particles are dispersed in a polyolefin resin which is a base of the colored resin composition,
And two measures are taken.

Since the copolymer resin (3) having a high acid value has a high polarity, it has a high affinity for the pigment and wets the surface of the pigment well. Therefore, the resin (3) covers the surface of the pigment well. Furthermore, the resin (3) has a high antioxidant property. Due to the property of the copolymer resin (3) having such a high acid value, even if a chlorine water is directly contacted with a molded article produced by using the resin (3), the pigment particles existing in the molded article are There is no direct contact with chlorine water. Therefore, it is possible to suppress or prevent the occurrence of swelling, peeling, and color loss in the molded product.

However, when the pigment particles are directly coated with the copolymer resin having a high acid value as described above,
Organic pigments have a weaker surface polarity than inorganic pigments, and it tends to be difficult to obtain a sufficient pigment particle adsorption effect by the resin. In addition, when the pigment particles attract the hydrophobic portion of the copolymer resin, that is, the olefin portion, and as a result, the hydrophilic carboxyl group becomes oriented to the base resin, that is, the polyolefin resin (5) side, the pigment dispersibility and On the contrary, it will worsen the chlorinated water. As in the present invention, when the surface of the pigment particles is preliminarily treated with the fatty acid metal salt, the hydrophobic portion of the fatty acid metal salt, that is, the olefin portion is oriented to the pigment particle surface side to firmly coat the pigment particles, while the carboxyl group and The hydrophilic side forming the metal salt is oriented to the outside, so that adsorption with the resin becomes very easy. It is the portion having the carboxyl group of the copolymer resin molecule that easily forms the adsorption state with the fatty acid metal salt, and the copolymer resin molecule surrounding the pigment particles has the olefin portion facing outward and the colored resin composition It is considered that they will be easily dispersed in the polyolefin resin (5) which is the base of (3).

By using such a fatty acid metal salt and the copolymer resin in combination, the copolymer resin and the pigment are firmly bound to each other through the fatty acid metal salt, so that the copolymer resin having a high acid value is resistant to chlorine water. It is considered that since the effect is sufficiently exhibited, the chlorine water resistance of the molded product obtained by using the coloring composition of the present invention is improved.

Furthermore, in the present invention, in order to enhance the dispersibility of the copolymer resin (3) in the polyolefin resin (5), a colorant obtained by melt-kneading pigment particles with the copolymer resin (3). Instead of dispersing only (4) in the polyolefin resin, a thermoplastic resin (3 ′) having a lower acid value is dispersed in the polyolefin resin (5) together with the [3] colorant to obtain a colored resin composition. .

The polyolefin resin (5) having extremely low polarity and the copolymer resin (3) having a high acid value have poor compatibility due to the difference in polarity. Therefore, the high acid value copolymer resin (3) coated with the pigment (2) is replaced with the polyolefin resin (5).
If it is attempted to disperse it directly in the copolymer resin (3), the copolymer resins (3) are likely to aggregate with each other, and as a result, it is difficult to obtain a state in which the pigment is sufficiently dispersed in the resin. Therefore, coloring of the molded product is not uniform, or cracks or cracks occur in the molded product. Furthermore, by using the low acid value thermoplastic resin (3 ′), the dispersibility of the high acid value copolymer resin (3) in the polyolefin resin (5) is improved. As a result, the colored resin composition according to the present invention has a high chlorine-containing water resistance and very good dispersibility of the pigment in the resin.

That is, the thermoplastic resin (3 ') having a lower acid value with respect to the copolymer resin (3) having a higher acid value.
However, it works effectively to reduce the large polarity difference between the polyolefin resin (5) and the copolymer resin (3). Further, the polar group in the copolymer resin (3) not adsorbed on the pigment (2) is coated with the thermoplastic resin (3 ′). For this reason, the pigment (2) coated with the copolymer resin (3) and the thermoplastic resin (3 ′) is easily deflocculated and dispersed in the polyolefin resin (5) which is the base of the colored resin composition. It is thought to be easier.

The high acid value copolymer resin (3) and the low acid value thermoplastic resin (3 ') used in the present invention both have an acid value in the range of 1 to 900 mgKOH / g. It is necessary that the difference in acid value is at least 10 mgKOH / g or more. The difference in acid value is preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more. When the difference in acid value is less than 10 mgKOH / g, the dispersibility of the pigment (2) in the polyolefin resin (5) is hardly improved.

The acid value of the high acid value copolymer resin (3) is 7
It is preferably 0 to 900 mgKOH / g, and particularly preferably 200 to 600 mgKOH / g.
The acid value of the low acid value thermoplastic resin (3 ') is 1 to 100 m.
gKOH / g is preferred, especially 20-60 m
It is preferably gKOH / g.

The acid value of the copolymer resin (3) is 70 mgKO
If it is less than H / g, the affinity with the pigment (2) is small, it becomes difficult to coat the pigment, and the antioxidative property is also lowered, so that it tends to be difficult to suppress the occurrence of blistering and color loss. When the acid value of the copolymer resin (3) exceeds 900 mgKOH / g, the colored resin composition easily absorbs moisture and the adhesion to a metal becomes strong, so that the extrusion processability is likely to be adversely affected.

The acid value of the thermoplastic resin (3 ') is 1 mgKO
When it is less than H / g, the affinity for the copolymer resin (3) is low, the wettability with the copolymer resin (3) coated with the pigment (2) is poor, and the polyolefin resin (5) is nonpolar. The deflocculation of the pigment (2) in () becomes poor and, as a result, the dispersibility tends to decrease.

The acid value shown in this specification is JIS
It was obtained based on K0070 (1996).

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Copolymer resin (3), that is,
A dibasic acid having an α, β unsaturated double bond or its anhydride (b) and a monomer having an α, β unsaturated double bond (c)
As the copolymer resin (3) with, a resin having excellent coverage with the pigment particles (2) is used.

Α, which can be used in the present invention,
Examples of the monomer (c) having a β-unsaturated double bond include α-olefin, styrene, vinyl ether, diolefin, vinyl ester, vinyl sulfide, allyl monomer, (meth) acrylic acid ester monomer, and other copolymerizable compounds. Vinyl monomers or vinylidene monomers. Among these, carbon number 6-30
The above monomer is particularly preferable, and one kind or two or more kinds thereof can be used.

Specifically, as the α-olefin, ethylene, propylene, butylene, isobutylene, pentene, 1-hexene, 1-heptene, 1-octene, 1-
Nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-do Examples include triacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetracontene, and mixtures thereof. As commercially available products, dialen 10 (carbon number 10), dialen 124 (carbon number 12 to 14), dialen 208 (carbon number 20 to 28), dialen 30 (carbon number 30) (above, manufactured by Mitsubishi Chemical Corporation), Viper 260 (molecular weight 260
0), Viper 103 (molecular weight 2800) (above, Petrolite company make).

As the vinyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, nonyl vinyl ether,
Decyl vinyl ether, octadecyl vinyl ether,
Examples thereof include linear or branched aliphatic or alicyclic alkyl vinyl ethers such as 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, tetraethylene glycol monovinyl ether, trimethylolpropane trivinyl ether, p-dioxene, and mixtures thereof.

The diolefin is a polyene monomer having two or more conjugated or non-conjugated olefinic double bonds, such as butadiene, isoprene, neoprene,
Chloroprene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene,
2,4,6-octatriene, 1,5,9-decatriene, divinylbenzene, 1,3-cyclopentadiene,
1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, dicyclohexadiene, 5-ethylidene-2-norbornene, methylhydroindene, 2,
3-diisopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, and mixtures thereof.

As the allyl monomer, allyl acetate, isopropenyl acetate, allyl chloride, isopropenyl chloride,
Examples include trans-propenyl chloride and cis-propenyl chloride.

As the N-vinyl monomer, N-vinylcarbazole, N-vinyl-2-pyrrolidone, N-
Vinyl phthalimide may be mentioned.

Examples of vinyl sulfides include ethyl vinyl sulfide and phenyl vinyl sulfide.

Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
Examples thereof include acrylic acid esters and / or methacrylic acid esters of linear or branched aliphatic alcohols such as 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, lauryl acrylate and stearyl acrylate, and mixtures thereof. In the present specification, the (meth) acrylic acid ester monomer means an acrylic acid ester monomer and / or a methacrylic acid ester monomer.

Other copolymerizable vinyl monomers include vinyl ester, vinyl pyridine, vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, vinyl palmitate, vinyl n-decanoate, styrene and α. -Methylstyrene, β-methylstyrene, p-octylstyrene, p-nonylstyrene, acrylonitrile, methacrylonitrile, vinylidene chloride,
And its derivatives.

In the present invention, the monomer (c) having various α, β unsaturated double bonds described above can be copolymerized.
Examples of the dibasic acid having an α, β unsaturated double bond or its anhydride (b) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, crotonic acid, citraconic acid, and hymic acid. , Allylsuccinic acid, mesaconic acid, glutaconic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, hymic acid anhydride, allylsuccinic anhydride, glutaconic anhydride, anhydrous Examples include tetrahydrophthalic acid, methylhexahydrophthalic anhydride, and aconitic anhydride. One or more of these may be used, but maleic anhydride is particularly industrially advantageous.

Examples of the polymerization initiator that can be used in the copolymerization of the present invention include benzoyl peroxide, lauryl peroxide, cumene peroxide, diisopropyl peroxycarbonate, di-t-butyl peroxide and t-butyl peroxy. Peroxides such as benzoate, azobisisobutyronitrile, azobis-
Azo compounds such as 2,4-dimethylvaleronitrile may be mentioned.

The above-mentioned dibasic acid having an α, β unsaturated double bond or its anhydride (b) and the monomer (c) having an α, β unsaturated double bond are copolymerized to prepare the present invention. As the copolymer that can be used as the copolymer resin (3), ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / maleic anhydride copolymer,
Ethylene / ethyl acrylate / acrylic acid copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer,
Ethylene / methyl acrylate / maleic anhydride copolymer, ethylene / propylene / acrylic acid copolymer, ethylene / propylene / maleic anhydride copolymer, ethylene / butene / acrylic acid copolymer, ethylene / maleic anhydride copolymer Polymer, ethylene / α-olefin / maleic anhydride copolymer, ethylene / vinyl acetate / acrylic acid copolymer, ethylene / vinylidene chloride / maleic anhydride copolymer, propylene / acrylic acid copolymer, propylene /
Methacrylic acid copolymer, propylene / maleic anhydride copolymer, butene / acrylic acid copolymer, butene / maleic anhydride copolymer, propylene / butene / maleic anhydride copolymer, ethylene / propylene / butene / anhydrous Examples thereof include maleic acid copolymers, propylene / α-olefin / maleic anhydride copolymers, and the like. In particular, the copolymer resin (3) in the present invention is preferably a copolymer of an α-olefin having 6 to 30 carbon atoms and maleic anhydride.

As the thermoplastic resin (3 '), a resin having a good compatibility with the polyolefin resin (5) is used.

The thermoplastic resin (3 ') is used as the copolymer resin (3) and is variously listed above (R
1) It is preferable to use a copolymer resin of a dibasic acid having an α, β unsaturated double bond or an anhydride thereof and a monomer having an α, β unsaturated double bond, while appropriately adjusting the acid value. it can. The thermoplastic resin (R2) obtained by introducing a carboxyl group or an anhydride group thereof into the thermoplastic resin by graft modification, or (R3) may be the above-mentioned (R1).
Alternatively, various derivatives of (R2) can be used.

In the water distribution pipe and the liquid bleaching container, high density polyethylene, linear low density polyethylene,
Taking into consideration that polyolefin resins such as polypropylene are commonly used, thermoplastic resins (3 ')
As the above, it is desirable to use a polyolefin resin having a good affinity with the base resin of these molded products.

As the thermoplastic resin (R2) which can be used as the thermoplastic resin (3 ') of the present invention and which is obtained by introducing a carboxyl group or an anhydride group thereof into the thermoplastic resin by graft modification, polyolefin, Polymethylpentene, polystyrene, polyvinyl chloride, polyethylene terephthalate and polydiene-based polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM-
Various monobasic acids such as styrene (AES) resin, other acrylic resins, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, vinyl resin, amino resin, polyether, polyarylate, epoxy resin, polysulfone, phenol resin, etc. Examples of R1) include the dibasic acids having various unsaturated double bonds and the anhydrides thereof grafted as exemplified above.

For example, those grafted to a polyolefin resin include polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, propylene / Unmodified polyolefin resins such as butene copolymers, ethylene / vinyl acetate copolymers, ethylene / ethyl acrylate copolymers, ethylene / methyl acrylate copolymers, etc. can be added to monobasic acids or dibasic acids or A polyolefin resin grafted with the acid anhydride can be used.

(R3) is the above (R1) or (R
Esterification by reacting the carboxyl group or its anhydride group in the copolymer or graft product of 2) with a compound having at least one hydroxyl group in the molecule,
A compound obtained by reacting the carboxyl group or the like with a compound having at least one or more amino groups in the molecule to amidate or imidize, or by reacting the carboxyl group or the like with a metal compound for chelation. is there. By carrying out such modification, it becomes possible to appropriately control various physical properties of the thermoplastic resin (3 ') such as acid value and chlorine-containing water content.

The compound having a hydroxyl group used for the above esterification is not particularly limited as long as it has one or more hydroxyl groups in the molecule, and examples thereof include methanol, ethanol, propanol and isopropanol.
Butanol, sec-butanol, tert-butanol, pentanol, amyl alcohol, hexanol,
Heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, α-oxybutyric acid, 12-hydroxystearic acid, and the like. The mixture is used,
It is not particularly limited to these.

The amino compound used for amidation and imidation is not particularly limited as long as it has one or more amino groups in the molecule, and examples thereof include methylamine, ethylamine and propylamine. , Isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, aniline, o-toluidine, 2-ethylaniline,
2-fluoroaniline, o-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 5-aminoindane,
Examples thereof include aspartic acid, glutamic acid, γ-aminobutyric acid and the like, but not limited to these.

Examples of the metal compound used for chelation include acetates such as sodium, potassium, lithium, calcium, magnesium, aluminum, zinc, nickel, iron, cobalt, manganese and copper, acetylacetone salts and metal alkoxides. Typical examples include organic metal compounds and inorganic metal compounds represented by oxides and hydroxides, but the invention is not limited thereto.

As described above, as the thermoplastic resin (3 ') used in the present invention, the above-mentioned (R1) and (R
It may be either 2) or (R3). But especially
A maleated polyolefin is more preferable as the graft of (R2), and an ionomer resin which is a metal salt of a copolymer of ethylene and an unsaturated carboxylic acid is preferable as (R3).

The unsaturated carboxylic acid used for obtaining the ionomer resin is preferably acrylic acid and / or methacrylic acid, and the unsaturated carboxylic acid is 3 to 20 wt%.
It is preferable to copolymerize (1 to 8 mol%) with ethylene. In this case, the carboxyl group in the copolymer is neutralized with a metal ion to obtain an ionomer resin.
The ionomer resin is referred to as a metal salt of a copolymer as described above, as well as a neutralized product with a metal ion, a neutralized product with a metal, a metal ion adduct, a metal adduct, or a crosslinked product with a metal. be called. Examples of the metal ion used for neutralization include Ca, Li, Na, Zn, and the like, and examples of the metal ion source include metal oxides, hydroxides, carbonates, acetates, and the like.

The ionomer resin is generally prepared by melt-kneading the copolymer of ethylene and unsaturated carboxylic acid and the metal ion source using an extruder to neutralize the carboxyl groups in the copolymer. can get. It is preferable to neutralize 5 to 90 mol% of the carboxyl groups in the copolymer.

Examples of the polyolefin resin (5) used in the present invention include polyethylene, polypropylene and polybutene. Of these, polyethylene and polybutene are preferable. As for polyethylene,
High density (H), low density (L), linear low density (LL) and various other materials are mentioned, but in the case of water pipes, high diameter (H) polyethylene is used for large diameter pipes and small diameter For these, linear low density (LL) polyethylene is commonly used.

Further, a polyolefin resin having an MFR of 0.001 to 400 is preferable. When the MFR is 0.001 or less, the melt viscosity of the colored resin composition is too high, so that coloring failure occurs, color unevenness and flow marks occur. Occasionally, the chlorine-containing water content is reduced. On the other hand, MF
When R is 400 or more, bleeding from the molded product, weather resistance, heat resistance, mechanical properties, etc. may be adversely affected. Particularly, when using high density polyethylene for water pipes, MFR is preferably 0.005 to 10, and when using low density polyethylene, polypropylene or polybutene, MFR is preferably 0.005 to 100.

The shape of the polyolefin resin (5) used for producing the colored resin composition according to the present invention is not particularly limited, and a powdered one or a pelletized one may be used. Is also good.

Examples of the pigment (1) used in the present invention include azo type, quinacridone type, anthraquinone type, perylene type, isoindolinone type, phthalocyanine type, dioxazine type, induslen type, perinone type and quinophthalone type. Organic pigments are exemplified. For water pipes,
It is usually colored bluish to image water for identification. Therefore, a phthalocyanine-based or indanthrene-based blue pigment is used.

The form of the pigment may be any of dry powder pigment, pigment wet cake containing water before drying (also called an aqueous wet cake of pigment, filter cake, press cake) and a mixture thereof.

The phthalocyanine blue used in the present invention is represented by the following (formula 1), and the number of chlorine in one molecule is 0 to 8. In addition, M in (Equation 1) is a hydrogen atom or Cu, Zn, Ni, Fe, but in general, from the viewpoint of coloring power, in terms of hue to be obtained, and also in terms of price, Cu is Are suitable. The number of chlorine atoms is
From the viewpoint of heat resistance and hue, 2 to 4 are preferable. (Equation 1)

[Chemical 1] (Where M is a hydrogen atom or Cu, Zn, Ni, Fe
Indicates. X1 to X4 each represent a chlorine atom, and the number of chlorine atoms is 0 to 8) The indusrene blue used in the present invention is represented by the following (formula 2). (Formula 2)

[Chemical 2] The fatty acid metal salt (a), which is a treating agent for an organic pigment used in the present invention, has a high affinity with the pigment (1) and has a dibasic acid having an unsaturated double bond or an anhydride thereof and α, Copolymer resin with monomer having β-unsaturated double bond (3)
Both have a high affinity. As such, a metal salt of a fatty acid with caprylic acid, oleic acid or stearic acid and lithium, calcium, magnesium or zinc is desirable.

As described above, the polyolefin resin (5)
The colorant (4) dispersed in the organic pigment (1) 75-
100 parts by weight of an organic pigment (2) obtained by treating 99.9% by weight of a fatty acid metal salt (a) with 0.1 to 25% by weight of 1
It is desirable to melt-knead the copolymer resin (3) in an amount of up to 500 parts by weight. Further, the thermoplastic resin (3 ') is 1 part with respect to 100 parts by weight of the copolymer resin (3).
It is desirable to disperse it in the polyolefin resin (5) together with the colorant (4) in a proportion of ˜500 parts by weight.

The colored resin composition of the present invention may be in the form of pellets (hereinafter also referred to as colored pellets) to be directly used for molding, or may be pulverized into powder (hereinafter, It may be a dry color).
Alternatively, it may be a pellet-shaped colorant (hereinafter, also referred to as a masterbatch), which is a so-called masterbatch containing a pigment at a high concentration.

The molded article of the present invention is manufactured by molding colored pellets as it is, or by molding a master batch by diluting it with a thermoplastic resin. As the thermoplastic resin used for dilution, a resin having good compatibility and affinity with the polyolefin resin (5) used for obtaining the masterbatch is used, but in order to manufacture a pipe for waterworks and a container for liquid bleaching agent, Again, polyolefin resin is desirable.

When the colored resin composition of the present invention is a colored pellet, 0.002 parts by weight of the pigment (2) are added to 100 parts by weight of the polyolefin resin (5) in the colored resin composition.
It is desirable that the content is 5 to 10 parts by weight.
If the content of the pigment (2) is less than this range, only a light colored state is often obtained, and if it exceeds this range, the mechanical properties of the molded product are likely to be impaired. At this time, in order to sufficiently coat the pigment (2) with the copolymer resin (3) and the thermoplastic resin (3 ′), use of the copolymer resin (3) and the thermoplastic resin (3 ′) It is desirable that the amount is at least ½ weight of the pigment (2).

The above-mentioned numerical values define the desirable component ratio of each component in the colored pellet composition, but the contents of the copolymer resin (3) and the thermoplastic resin (3 ') are It doesn't matter if there is more or less. When the amount of the copolymer resin (3) is small, the chlorine-containing water resistance of the colored resin composition becomes poor. Further, when the amount of the thermoplastic resin (3 ') is small, the pigment dispersibility becomes poor. On the other hand, when the copolymer resin (3) and the thermoplastic resin (3 ′) are excessive, the compatibility with the base polyolefin resin (5) deteriorates and the mechanical properties of the molded product are likely to be impaired.

When the colored resin composition according to the present invention is a masterbatch, the pigment (2) is added in an amount of 0.05 to 100 parts by weight based on 100 parts by weight of the polyolefin resin (5) in the colored resin composition.
It is desirable that the content is 10 parts by weight. When the content of the pigment (2) is less than this range, only a light colored state is often obtained, and when it exceeds this range, the dispersibility of the pigment in the masterbatch tends to be insufficient. At this time, the copolymer resin (3) and the thermoplastic resin (3 ')
In order to sufficiently coat the pigment (2) with and, the amount of the copolymer resin (3) and the thermoplastic resin (3 ′) used should be at least half the weight of the pigment (2). desirable.

Each of the above numerical values defines a desirable component ratio of each component in the masterbatch composition, but the content of the copolymer resin (3) and the thermoplastic resin (3 ') is large. It is not good to be small or small. When the amount of the copolymer resin (3) or the thermoplastic resin (3 ′) is small, the chlorine-containing water resistance is deteriorated and the pigment dispersibility is also deteriorated. On the contrary, if the amount is large, granulation of the masterbatch becomes difficult.

The final molded product produced by diluting the masterbatch and manufacturing the polyolefin resin (5) 1 is the same as the molded product produced by directly molding the colored pellet.
0.005 to 1 parts of the organic pigment (2) with respect to 00 parts by weight.
It is desirable to contain 0 part by weight.

Comparing the masterbatch with the colored pellets, there is no great difference in the processing steps for obtaining them. However, since the masterbatch contains a high concentration of pigment, it is slightly more expensive than the colored pellet. However, in the case of a masterbatch, 1 part by weight of the masterbatch can be diluted with 0.5 to 800 parts by weight of an inexpensive thermoplastic resin to obtain a molded product. Therefore, the molded product manufactured from the masterbatch is cheaper and preferable than the molded product manufactured from the colored pellets.

The colored resin composition according to the present invention can be used as a film, a sheet, a plate, various containers, pipes, fibers, etc.
It can be formed into various shapes. However, from the viewpoint of excellent chlorine-containing water resistance, it is desirable to mold into water supply pipes, especially water supply pipes, bleaching agent containers and caps thereof. In the present specification, the pipe also refers to a pipe that is a pipe body and a component (for example, a joint) used for joining the pipe.

The colored resin composition according to the present invention contains other thermoplastic resins or waxes, their derivatives, metal soaps, antioxidants, etc. within a range that does not impair the effects of the present invention or causes no problem in hygiene. Various known additives for polymers, such as stabilizers such as agents, ultraviolet absorbers, lubricants, antistatic agents, and surfactants, can also be added.

[0081]

EXAMPLES The present invention will be described in more detail based on examples. In the following, "part" means "part by weight"
Shall mean.

[Pigment Preparation Example 1] A crude copper phthalocyanine (C.I. Pigme-n) was added to a 2000 liter kneader.
t Blue 15: 1) 100 parts and crushed sodium chloride 400 parts were charged and mixed uniformly, then 100 parts of diethylene glycol was gradually added, kept in a dough-like state, and ground at 100 to 110 ° C. for 5 hours. To do. Continuing,
The contents were put into 4000 parts of a 1% aqueous sulfuric acid solution, stirred at 80 ° C. for 1 hour, filtered and washed with water to obtain a wet cake.

[Pigment Preparation Example 2] The wet cake described in Pigment Preparation Example 1 was dried at 80 to 90 ° C and then pulverized to obtain a phthalocyanine blue pigment.

[Pigment Preparation Example 3] The wet cake of Pigment Preparation Example 1 (pigment content 100 parts by weight) was added to 200 parts by weight of water to reslurry, 2.5 parts of potassium hydroxide and 5 parts of oleic acid were added, After stirring at 70 ° C for 1 hour, 2.5 parts of anhydrous calcium chloride was added, and the mixture was stirred at 70 ° C for 1 hour. After allowing to cool, it was filtered, washed with water, the wet cake was dried at 80 to 90 ° C., and then pulverized to obtain a phthalocyanine blue pigment treated with 5% of calcium oleate.

[Pigment Preparation Example 4] 10 parts of potassium hydroxide
Part, oleic acid 20 parts, and anhydrous calcium chloride 10 parts, except that calcium oleate 20% -treated phthalocyanine blue pigment was obtained in the same manner as in Pigment Preparation Example 3.

[Pigment Preparation Example 5] Anhydrous calcium chloride 2.
A phthalocyanine blue pigment treated with 5% magnesium oleate was obtained in the same manner as in Pigment Preparation Example 3 except that 2.5 parts of anhydrous magnesium chloride was used instead of 5 parts.

[Pigment Preparation Example 6] A phthalocyanine blue pigment treated with 5% calcium stearate was obtained in the same manner as in Pigment Preparation Example 3 except that 5 parts of stearic acid was used instead of 5 parts of oleic acid.

Pigment Preparation Example 7 The crude copper phthalocyanine used in Pigment Preparation Example 1 (CI Pigment Blu) was used.
e 15: 1) in place of crude Induslen blue (CI Pigment Blue 60),
A wet cake of induslen blue was obtained, and a 5% calcium oleate-treated induslen blue pigment was obtained in the same manner as in Pigment Preparation Example 3 except that the wet cake of induslen blue was used.

[Example 1] Calcium oleate 5% surface-treated phthalocyanine blue (C.
I. Pigment Blue 15: 1) 50 parts,
Α-Olefin-maleic anhydride copolymer resin having 12 to 14 carbon atoms (weight average molecular weight 17,000, acid value 400 m
50 parts of gKOH / g and melt viscosity of 3000 poise / use of 160 ° C. flow tester) were melt-kneaded to obtain a pellet-like or powder-like colorant intermediate. After that, high-density polyethylene (MFR: 0.06g / 10min, density: 0.95
3.2 parts of the above colored intermediate was mixed with 100 parts of 2 g / cm ³ ) and melt-kneaded to obtain a pellet-shaped master batch.

Then, after mixing 100 parts of high-density polyethylene and 5 parts of the above masterbatch, a plate was prepared with an injection molding machine, and a chlorine-containing water test was conducted by a method according to JIS K6762 to swell the plate surface. The occurrence status / occurrence time and color loss were also evaluated. Further, about 2 mg of the sample cut out from the plate was hot-pressed between glass plates, and the dispersibility was evaluated by confirming the particle size of coarse particles and the dispersed particle size under an optical microscope of 100 times. The evaluation results are shown in Table 1.

[Test Conditions and Evaluation Criteria] ・ Chlorine-resistant water content test (Swelling Evaluation Criteria) The time required until the occurrence of swelling and the state of the plate surface after the immersion time are confirmed according to the following criteria. 1 ... Bulging occurred on the entire surface of the plate. 2 ... Bulging occurred on a part of the plate surface. 3 ... No swelling on the plate surface.

(Evaluation Criteria for Color Removal) The state of color loss on the plate surface after the immersion time is confirmed according to the following criteria. 1 ... Most of the color disappears and it becomes gray and it is impossible to confirm the color. 2 ... Some colors can be confirmed. 3 ... Almost no color loss.

[0093] ・ Dispersibility evaluation (Evaluation Criteria) 1 ... There are particles of 50 μm or more in a constant visual field.                 2 ... There are particles of 20 μm to 40 μm.                 3 ... There are particles of 10 μm to 20 μm.                 4: No particles, all less than 10 μm.

[Example 2] The procedure of Example 2 was repeated except that the calcium oleate 5% surface-treated phthalocyanine blue used in Example 1 was replaced by the magnesium oleate 5% surface-treated phthalocyanine blue obtained in Pigment Preparation Example 5. Example 1
A masterbatch was obtained in the same manner as. Further, using the obtained masterbatch, a chlorine-containing water resistance test was conducted in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 3] [0095] Instead of the calcium oleate 5% surface-treated phthalocyanine blue used in Example 1, the calcium stearate 5% surface-treated phthalocyanine blue obtained in Pigment Preparation Example 6 was used. 1
A masterbatch was obtained in the same manner as. Further, using the obtained masterbatch, a chlorine-containing water resistance test was conducted in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 4] The procedure of Example 4 was repeated except that the calcium oleate 5% surface-treated phthalocyanine blue used in Example 1 was replaced by the calcium oleate 20% surface-treated phthalocyanine blue obtained in Pigment Preparation Example 4. Example 1
A masterbatch was obtained in the same manner as. Further, using the obtained masterbatch, a chlorine-containing water resistance test was conducted in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 5] The carbon number used in Example 1 was 12
~ 14-α-olefin maleic anhydride copolymer resin instead of C 10 α-olefin maleic anhydride copolymer resin (weight average molecular weight 22000, acid value 460
mgKOH / g, melt viscosity 18,000 poise / 160 ° C
A masterbatch was obtained in the same manner as in Example 1 except that the flow tester was used). Further, using the obtained masterbatch, a chlorine-containing water resistance test was conducted in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Example 6 The carbon number used in Example 1 was 12
.About.14 .alpha.-olefin maleic anhydride copolymer resin in place of C.sub.20-28 .alpha.-olefin maleic anhydride copolymer resin (weight average molecule 5500, acid value 27
0 mgKOH / g, melt viscosity 1500 poise / 160 ° C
A masterbatch was obtained in the same manner as in Example 1 except that the flow tester was used). Further, using the obtained masterbatch, a chlorine-containing water resistance test was conducted in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Example 7 50 parts of the α-olefin maleic anhydride copolymer resin used in Example 1 and 50 parts of phthalocyanine blue (PigmentBlue 15: 1) surface-treated with 5% of calcium oleate were melted. The mixture was kneaded to obtain a pellet or powdery colorant intermediate.

Then, after mixing 3.2 parts of the above colored intermediate with 100 parts of high-density polyethylene and 5 parts of ionomer wax (Aklin 201A Allied Signal Co., acid value: 42 mgKOH / g) as a low acid value resin, Melt kneading was performed to obtain a pellet-shaped master batch.

Then, 100 parts of high-density polyethylene and 5 parts of the above masterbatch were mixed, and a plate was prepared by an injection molding machine. As in Example 1, the occurrence of swelling on the plate surface, discoloration and dispersibility Was evaluated. The results are shown in Table 1.

[Example 8] Instead of the ionomer wax (Aklin 201A Allied Signal, acid value: 42 mgKOH / g) as the low acid value resin in Example 7, an ionomer wax (Aklin 285A Allied Signal, acid value: A masterbatch was obtained in the same manner as in Example 7, except that 40 mgKOH / g) was used. Further, using the obtained masterbatch, a chlorine-resistant water content test was conducted in the same manner as in Example 7, and the evaluation results are shown in Table 1.

Example 9 Instead of the ionomer wax (Aklin 201A Allied Signal Co., acid value: 42 mgKOH / g) as the low acid value resin in Example 7, an ionomer wax (Petrolite C-400, Toyo Petrolite Co., Ltd.) was used. A masterbatch was obtained in the same manner as in Example 7, except that the product manufactured and the acid value: 14 mgKOH / g) was used. Further, using the obtained masterbatch, a chlorine-resistant water content test was conducted in the same manner as in Example 7, and the evaluation results are shown in Table 1.

[Example 10] The procedure of Example 10 was repeated except that the calcium oleate 5% surface-treated phthalocyanine blue used in Example 1 was replaced by the calcium oleate 5% surface-treated indanthrene blue obtained in Pigment Preparation Example 7. A masterbatch was obtained in the same manner as in Example 1. Further, using the obtained masterbatch, a chlorine-containing water resistance test was conducted in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[Example 11] The procedure of Example 11 was repeated except that the calcium oleate 5% surface-treated phthalocyanine blue used in Example 7 was replaced by the calcium oleate 5% surface-treated indanthrene blue obtained in Pigment Preparation Example 7. A masterbatch was obtained in the same manner as in Example 7. Further, using the obtained masterbatch, a chlorine-resistant water content test was conducted in the same manner as in Example 7, and the evaluation results are shown in Table 1.

Example 12 Carbon number 1 used in Example 7
Instead of 50 parts of 2 to 14 α-olefin maleic anhydride copolymer resin, a mixture of 25 parts of low molecular weight polyethylene and 25 parts of α-olefin maleic anhydride copolymer resin of 12 to 14 carbon atoms is used. A masterbatch was obtained in the same manner as in Example 7 except that the above was carried out. Further, using the obtained masterbatch, a chlorine-resistant water content test was conducted in the same manner as in Example 7, and the evaluation results are shown in Table 1.

[Example 13] Colored pellets were obtained in the same manner as in Example 1 except that 3.2 parts of the colorant intermediate described in Example 1 was used. Then, the colored pellets were supplied to an injection molding machine to prepare a plate. The obtained plate was subjected to a chlorine-resistant water content test in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Example 14 The ionomer wax (Aklin 20) used as the low acid value resin in Example 12
1A Allied Signal, acid value: 42mgKOH /
g) A masterbatch was obtained in the same manner as in Example 12, except that 1 part of this was used instead of 5 parts. Further, using the obtained masterbatch, a chlorine-resistant water content test was conducted in the same manner as in Example 12, and the evaluation results are shown in Table 1.

Example 15 The ionomer wax (Aklin 20) used as the low acid value resin in Example 12
1A Allied Signal, acid value: 42mgKOH /
g) A masterbatch was obtained in the same manner as in Example 12 except that 0.1 part was used instead of 5 parts. Further, using the obtained masterbatch, a chlorine-resistant water content test was conducted in the same manner as in Example 12, and the evaluation results are shown in Table 1.

[Comparative Example 1] Carbon number 12 used in Example 1
14-α-olefin maleic anhydride copolymer resin 5
A masterbatch was obtained in the same manner as in Example 1 except that 50 parts of low molecular weight polyethylene was used instead of 0 part.
Further, using the obtained masterbatch, a chlorine-containing water resistance test was conducted in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Comparative Example 2 The untreated phthalocyanine blue obtained in Pigment Preparation Example 2 was used in place of the phthalocyanine blue surface-treated with 5% of calcium oleate used in Example 1, except that A masterbatch was obtained in the same manner as in Example 1. Further, using the obtained masterbatch, a chlorine-containing water resistance test was conducted in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[0112]

[Table 1]

[0113]

By using the colored resin composition according to the present invention, it is possible to produce a molded product which is excellent in chlorine-containing water resistance and has excellent pigment dispersibility. Therefore, it is of course possible to achieve uniform coloring of the molded product, and even if the manufactured molded product is exposed to chlorine-containing water for a long period of time, the molded product does not lose color, swell, cracks or cracks. It can be used safely without deterioration for a long time.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Izumi Nakane 2-33 Kyobashi, Chuo-ku, Tokyo Toyo Ink Mfg. Co., Ltd. (72) Akiyoshi Iguchi 2-3-3 Kyobashi, Chuo-ku, Tokyo No. 3 Toyo Ink Mfg. Co., Ltd. (56) Reference JP-A-9-111057 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/00-23/24 E03C 1/02 F16L 9/12

Claims (17)

(57) [Claims] 1. An organic pigment (2) obtained by treating the organic pigment (1) with a fatty acid metal salt (a) is combined with a dibasic acid having an α, β unsaturated double bond or an anhydride thereof (b). Chlorine-resistant content obtained by dispersing a colorant (4) obtained by melt-kneading a copolymer resin (3) with a monomer (c) having an α, β unsaturated double bond into a polyolefin resin (5). Aqueous colored resin composition. 2. The coloring agent (4) is an organic pigment (1) 75-
100 parts by weight of an organic pigment (2) obtained by treating 99.9% by weight of a fatty acid metal salt (a) with 0.1 to 25% by weight of 1
The chlorine-resistant water-based colored resin composition according to claim 1, which is obtained by melt-kneading the copolymer resin (3) in an amount of ˜500 parts by weight. 3. The chlorine-resistant aqueous colored resin composition according to claim 1, wherein the fatty acid metal salt (a) is a metal salt of a fatty acid selected from the group consisting of caprylic acid, oleic acid, and stearic acid. object. 4. The fatty acid metal salt (a) is a metal salt of a fatty acid with at least one metal selected from the group consisting of lithium, calcium, magnesium, and zinc. The chlorine-containing water-based colored resin composition of. 5. The chlorine-containing material according to claim 1, wherein the organic pigment (2) is dispersed in 100 parts by weight of the polyolefin resin (5) in a proportion of 0.005 to 10 parts by weight. Aqueous colored resin composition. 6. The chlorine-resistant content according to claim 1, wherein the organic pigment (2) is dispersed in a proportion of 0.05 to 10 parts by weight in 100 parts by weight of the polyolefin resin (5). Aqueous colored resin composition. 7. The chlorine-resistant water-based colored resin composition according to claim 1, wherein the organic pigment (1) is phthalocyanine blue and / or indanthrene blue. 8. The chlorine-resistant aqueous colored resin composition according to claim 1, wherein the monomer (c) having an α, β unsaturated double bond is an α-olefin. 9. The chlorine-resistant water-based colored resin composition according to claim 8, wherein the copolymer resin (3) is a copolymer of an α-olefin having 6 to 30 carbon atoms and maleic anhydride. 10. The acid value of the copolymer resin (3) is from 200 to 200.
The thermoplastic resin (3 ') having an acid value of 1 to 100 mgKOH / g, which is 600 mgKOH / g and which has a colorant (4), is dispersed in the polyolefin resin (5). 9. The chlorine-resistant aqueous colored resin composition according to any one of 9 above. 11. The chlorine-resistant water-based colored resin composition according to claim 10, wherein 1 to 500 parts by weight of the thermoplastic resin (3 ′) is dispersed in 100 parts by weight of the copolymer resin (3). . 12. The chlorine-resistant water-based colored resin composition according to claim 10, wherein the thermoplastic resin (3 ′) is an ionomer resin which is a metal salt of a copolymer of ethylene and an unsaturated carboxylic acid. . 13. The chlorine-resistant water-based colored resin composition according to claim 12, wherein the unsaturated carboxylic acid is acrylic acid and / or methacrylic acid. 14. The chlorine-resistant aqueous colored resin composition according to claim 1, wherein the polyolefin resin (5) is high-density polyethylene or linear low-density polyethylene. 15. The chlorine-resistant water-based colored resin composition according to claim 1, which is used for water pipes. 16. The chlorine-resistant water-based colored resin composition according to claim 15, wherein the water pipe is a water pipe or a joint of the water pipe. 17. A water pipe obtained by molding the chlorine-resistant water-based colored resin composition according to claim 15 or 16.