JP3463509B2 - 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 use in a colored resin molded product which is in direct contact with chlorine-containing water. More specifically, even if the molded product is directly contacted with chlorine-containing water, it is possible to provide a molded product that does not cause dot projections or swelling on the surface and has less color loss. The present invention relates to a colored resin composition.

[0002]

2. Description of the Related Art Conventionally, for coloring and molding various thermoplastic resins, zinc oxide, zinc sulfide, lead sulfate, titanium oxide, molybdenum oxide, yellow lead, rouge, red lead, silver vermilion, ultramarine,
Indigo blue, Kuresu, chromium oxide, chromate, cadmium sulfide, silicate, cobalt blue, cerulean blue, aniline black, black titanium, inorganic pigments such as carbon black, or azo type, azomethine type, quinacridone type,
Anthraquinone-based, Benzidine-based, Perylene-based, Isoindolinone-based, Phthalocyanine-based, Dioxazine-based, Induslen-based, Perinone-based, Quinophthalone-based, Pyrozolone-based, Atine-based, Nitro-based, Nitroso-based organic pigments,
Alternatively, dyes of azo type, anthraquinone type, perylene type, perinone type, indigo type, thioindigo type and the like are used.

When a molded article produced from a thermoplastic resin containing the above dyes and pigments is used in applications such as direct contact with chlorine-containing water, such as liquid bleach containers and water supply pipes, Not only the color loss (discoloration) occurs in the molded product, but also dot-shaped projections and small-diameter swelling (hereinafter, swelling) occur on the surface of the molded product. Conventionally, due to such point-like projections and swelling that have occurred in the molded product, the strength of the molded product is reduced or the swelling is peeled off, and due to such strength reduction and peeling, a part of the molded product is There was a problem of mixing things and tap water in the pipe.

For example, a conventional container for liquid bleach made of high-density polyethylene and a container cap for liquid bleach made of polypropylene or polybutene are generally as described above for the purpose of protecting the contents and imparting a design to the container. It is colored with dyes and pigments. When hydrogen peroxide water or chlorine-containing water for bleaching clothes is contained in such a conventional container, the dye / pigment causes a chemical reaction with the hydrogen peroxide water or chlorine-containing water, and Chlorine-containing water is decomposed to generate oxygen gas. Conventionally, due to the reaction between such dyes and pigments and the contents of the container, the bleaching performance of the bleaching agent is significantly reduced, the container is deformed by the generated gas, and the container is further damaged. There were many.

Conventionally, a dye or pigment is not added to the inside of a container or cap that directly contacts the contents, and an uncolored resin layer is used on the inside to form a container or cap having a multilayer structure as described above. I was avoiding deterioration and damage to the container.
However, a multilayer container or cap has a problem that the manufacturing process is complicated and the manufacturing cost is high.

[0006] In addition, from the viewpoint that drinking water is used for drinking and drinking, water supply pipes are required to have strict performance stipulated in JIS K6762 against deterioration such as swelling occurring in the pipes.

[0007] Water supply pipes are pipes for introducing water from dams and rivers to water treatment plants, pipes for water transmission from water treatment plants to reservoir areas such as reservoirs and water 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.

[0008] Of these water supply pipes, there is currently no particular color designation for connecting parts such as water-conducting pipes, water-conveying pipes, and joints for connecting 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 prevent color fading (bleaching) and swelling of water supply pipes colored with various pigments to obtain distinctiveness, in the past, the inner surface of the pipe that is in direct contact with chlorine-containing water has been conventionally used. There has been proposed a water supply pipe comprising a two-layer pipe provided with a layer containing no pigment and a layer containing the pigment on the outer surface of the pipe.

However, such a two-layer pipe is difficult to manufacture as compared with a single-layer pipe, and a special molding machine is required for its manufacture, which is a manufacturing problem. In particular, it has been difficult to make the joint portion connecting the pipes into a two-layer structure because of the structure.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides a colored resin composition which solves the above-mentioned various problems and is capable of producing a molded article excellent in chlorine-containing water resistance even with a single layer. The purpose is to do.

[0012]

In order to achieve the above object of the present invention, in the present invention, a thermoplastic resin (a) having substantially no acid value and an acid value of 1 to 900 mgKOH /
In a colored resin composition containing a thermoplastic resin (b) composed of two or more thermoplastic resins of g and a pigment (c), at least one kind (b1) of the thermoplastic resins (b). Acid value difference between the other and 1 kind (b2) is 10mgK
A chlorine-resistant water-based colored resin composition is produced so as to have an OH / g or more.

In the present invention, the thermoplastic resin (b
The acid value of 1) is 70 to 900 mgKOH / g, and the acid value of the thermoplastic resin (b2) is 1 to 70 mgK.
It is preferably OH / g.

The chlorine-containing aqueous coloring resin composition according to the present invention comprises 100 parts by weight of the thermoplastic resin (a), the pigment (c).
0.01 to 60 parts by weight, and the thermoplastic resin (b1) to 0.
005 to 30 parts by weight, 0.00 of thermoplastic resin (b2)
It is desirable that the content is 05 to 30 parts by weight.

Alternatively, the chlorine-resistant aqueous colored resin composition according to the present invention comprises 100 parts by weight of the thermoplastic resin (a), 0.1 to 200 parts by weight of the pigment (c), and the thermoplastic resin (b1). It is desirable to contain 0.005-200 parts by weight and 0.005-200 parts by weight of the thermoplastic resin (b2).

The thermoplastic resin (b1) is preferably a polyolefin resin having a carboxyl group. The thermoplastic resin (b1) is also preferably a copolymer resin of a monomer having an α, β unsaturated double bond and a dibasic acid having an unsaturated double bond or an anhydride thereof.
Further, the monomer having an α, β unsaturated double bond is more preferably at least one monomer selected from α-olefin, styrene, vinyl ether, vinyl ester, and derivatives thereof. Furthermore, the dibasic acid having an unsaturated double bond or its anhydride is more preferably maleic acid or its anhydride .

The thermoplastic resin (b1) has 6 carbon atoms.
It is desirable that it is a copolymer of α-olefin of 30 to maleic anhydride, and the thermoplastic resin (b2) is a polyolefin resin having a carboxyl group. Further, the thermoplastic resin (b2) is also preferably an ionomer resin which is a metal salt of a copolymer of ethylene and an unsaturated carboxylic acid, and the unsaturated carboxylic acid is acrylic acid and / or methacrylic acid. Is especially desirable. Further, the thermoplastic resin (b2) is preferably a maleinized polyolefin. further,
It is particularly desirable that the maleated polyolefin is obtained by graft-polymerizing maleic anhydride onto a polyolefin resin.

In the present specification, the term "polyolefin resin" means a resin composed of an olefin homopolymer, or a copolymer of an olefin and another monomer, the olefin being the main component of the copolymer. It is used to mean a resin made up of.

When the pigment (c) is a blue pigment and an organic pigment, the organic pigment is preferably phthalocyanine blue or indanthrene blue. When the pigment (c) is a blue pigment and an inorganic pigment, the inorganic pigment is preferably ultramarine blue or cobalt blue.

Further, the thermoplastic resin (a) is preferably a polyolefin resin or a vinyl chloride resin,
The polyolefin resin is preferably polyethylene, polypropylene, or polybutene. Furthermore, it is particularly desirable that the polyethylene is high density polyethylene or linear low density polyethylene.

The colored resin composition according to the present invention is particularly preferably used for a bleaching agent container or a cap for the bleaching agent, and is also preferably used for a water pipe. At this time, the water pipe is for water supply. It can be a pipe or fitting.

In the chlorine-containing aqueous colored resin composition according to the present invention (hereinafter referred to as a colored resin composition), a thermoplastic resin (a) having substantially no acid value (hereinafter referred to as a resin (a)) And an acid value of 1 to 900 mgKOH / g and a difference in acid value of at least 10 mgKOH / g.
g or more, at least two types of thermoplastic resin (b
It is important to include 1) and (b2). Less than,
The thermoplastic resin (b1) is a high acid value resin, a thermoplastic resin (b
2) will be called a low acid value resin.

In the present specification, "thermoplastic resin"
Or simply the term “resin” means that the molecular weight is several hundred thousand and JIS K
MFR (melt viscosity) can be measured according to 7210, which is generally called "thermoplastic resin" and generally "wax", and has a molecular weight of several thousand to
MFR (melt viscosity) according to JIS K7210 for tens of thousands
It is used to include both those that cannot be measured.

Since the high acid value resin (b1) has a high polarity, it has a high affinity for the pigment and wets the surface of the pigment well.
Therefore, the resin (b1) covers the surface of the pigment well.
Further, the resin (b1) has a high antioxidant property. Due to the property of the high acid value resin (b1), even when chlorine water is directly contacted with a molded article produced using the resin (b1), the chlorine water directly contacts the pigment particles present in the molded article. There is no contact. Therefore, it is possible to suppress or prevent the occurrence of swelling, peeling, and color loss in the molded product.

However, a thermoplastic resin having an extremely low polarity,
That is, the thermoplastic resin (a) having substantially no acid value and the high acid value resin (b1) have poor compatibility due to the difference in polarity. Therefore, the high acid value resin (b) coated with the pigment (c)
When 1) is directly dispersed in the thermoplastic resin (a), the high acid value resins (b1) are likely to aggregate with each other, and as a result, a state in which the pigment is sufficiently dispersed in the resin cannot be obtained. Therefore, coloring of the molded product is not uniform, or cracks or cracks occur in the molded product.

The present invention can further improve the dispersibility of the high acid value resin (b1) in the thermoplastic resin (a) by using the low acid value resin (b2). 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, for the high acid value resin (b1),
The low acid value resin (b2) having an acid value difference of at least 10 mgKOH is the thermoplastic resin (a) and the high acid value resin (b).
It works effectively to alleviate a large polarity difference with 1). Further, the low acid value resin (b2) covers the polar group in the high acid value resin (b1) which is not adsorbed on the pigment. Therefore, it is considered that the pigment (c) coated with the high acid value resin (b1) and the low acid value resin (b2) is likely to be deflocculated and dispersed in the thermoplastic resin (a).

In order to obtain the colored resin composition according to the present invention, there is no particular limitation on the order of mixing the raw materials. However, after the pigment (c) and the high acid value resin (b1) are melt-kneaded and dispersed in advance, the low acid value resin (b2) and the thermoplastic resin (a) are added thereto, and further melt-kneaded and dispersed. Such a procedure is preferable from the viewpoint of pigment dispersibility.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The high acid value resin (b1) and the low acid value resin (b2) used in the present invention have an acid value of 1 to 1, respectively.
Within the range of 900 mgKOH, it is necessary that the difference in acid value is at least 10 mgKOH or more. The difference in acid value is preferably 20 mgKOH or more, 50
More preferably, it is at least mgKOH. When the difference in acid value is less than 10 mgKOH, the dispersibility of the pigment (c) in the thermoplastic resin (a) is hardly improved, or
As a result, the chlorine-containing water resistance of the obtained colored resin composition is inferior.

The acid value of the high acid value resin (b1) is 70 to 90.
It is preferably 0 mgKOH, particularly 100 to 60
It is preferably 0 mg KOH. On the other hand, the acid value of the low acid value resin (b2) is preferably 1 to 70 mgKOH, and particularly preferably 20 to 60 mgKOH.

The acid value of the high acid value resin (b1) is 70 mgKO
When it is less than H, the affinity with the pigment (c) is small, it becomes difficult to coat the pigment, and the antioxidative property is also lowered, so that the occurrence of blistering and color loss tends to be difficult to suppress. On the other hand, when the acid value of the high acid value resin (b1) exceeds 900 mgKOH / g,
Since the colored resin composition easily absorbs moisture and also has strong adhesiveness to a metal, it tends to adversely affect extrusion processability.

The acid value of the low acid value resin (b2) is 1 mgKOH
When it is less than, the affinity with the high acid value resin (b1) is low, the wettability with the high acid value resin (b1) coated with the pigment (c) becomes poor, and the non-polar thermoplastic resin (a) is contained. The deflocculation of the pigment (C) and the like on the surface becomes poor, and as a result, the dispersibility tends to decrease.

The acid values shown in this specification are in accordance with JIS.
It was obtained based on K0070 (1996).

The high acid value resin (b1) and the low acid value resin (b2) used in the present invention will be described below.

The high acid value resin (b1) used in the present invention,
The low acid value resin (b2) is (R1) a copolymer resin of a monomer having an α, β unsaturated double bond and a dibasic acid having an unsaturated double bond or an anhydride thereof, (R2) Examples thereof include those obtained by introducing a carboxyl group or its anhydride group into a thermoplastic resin by graft modification, or (R3) various derivatives of (R1) or (R2) above. The high acid value resin (b1) is a resin having a good affinity with the pigment (C) described later, and the low acid value resin (b2) is a resin having a good compatibility with the thermoplastic resin (a) described later. Any of the above (R1), (R2) and (R3) can be used.

However, from the viewpoint that the resin is excellent in coating property for pigment particles, it is particularly preferable to use the above (R1) as the high acid value resin (b1). In addition, polyolefin resins such as high-density polyethylene (hereinafter referred to as HDPE), linear low-density polyethylene (hereinafter referred to as LLDPE), and polypropylene are generally used in water distribution pipes and containers for liquid bleaching agents. Considering this, it is preferable to use a polyolefin resin as the low acid value resin (b2), and it is preferable to use the above (R2) or (R3).

A copolymer resin of (R1) a monomer having an α, β unsaturated double bond and a dibasic acid having an unsaturated double bond or an anhydride thereof will be described below.

Α, which can be used in the present invention,
Examples of the monomer having a β unsaturated double bond include α
-Olefins, styrenes, vinyl ethers, diolefins, vinyl esters, vinyl sulfides, allyl monomers, (meth) acrylic acid ester monomers, other copolymerizable vinyl monomers or vinylidene monomers. Among these, a monomer having 6 to 30 carbon atoms is particularly preferable, and one kind or two or more kinds of these 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 the vinyl sulfide include ethyl vinyl sulfide and phenyl vinyl sulfide.

As the (meth) acrylic acid ester monomer, 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 dibasic acid having an unsaturated double bond or its anhydride copolymerizable with the above-mentioned various monomers having an α, β unsaturated double bond is acrylic acid or methacrylic acid. , Maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, crotonic acid, citraconic acid, hymic acid, allylsuccinic acid, mesaconic acid, glutaconic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, aconitic acid, maleic anhydride , Itaconic anhydride, citraconic anhydride, hymic acid anhydride, allyl succinic anhydride, glutaconic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, 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.

(R1) As a copolymer of a monomer having an α, β unsaturated double bond and a dibasic acid having an unsaturated double bond or its anhydride, an 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, 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-maleic anhydride copolymer, propylene Examples include α-olefin / maleic anhydride copolymers. Particularly, as the high acid value resin (b1) in the present invention, a copolymer of an α-olefin having 6 to 30 carbon atoms and maleic anhydride is preferable.

Next, the (R2) thermoplastic resin having a carboxyl group or its anhydride group introduced by graft modification will be described.

(R2) In which a carboxyl group or an anhydride group thereof is introduced into a thermoplastic resin by graft modification, polyolefin, polymethylpentene, polystyrene, polyvinyl chloride, polyethylene terephthalate or polydiene-based polybutylene terephthalate, Acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM-styrene (AES)
Examples of various monobasic acids and (R1) for resins, other acrylic resins, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, vinyl resin, amino resin, polyether, polyarylate, epoxy resin, polysulfone, phenol resin, etc. The dibasic acid having various unsaturated double bonds or the one obtained by grafting the anhydride thereof can be mentioned.

For example, those grafted on a polyolefin resin include polyethylene, polypropylene,
Polybutene, ethylene / propylene copolymer, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, propylene / butene copolymer, ethylene /
A polyolefin obtained by grafting a monobasic acid or the dibasic acid or its acid anhydride onto an unmodified polyolefin resin such as a vinyl acetate copolymer, an ethylene / ethyl acrylate copolymer, or an ethylene / methyl acrylate copolymer. Examples include resin of the system.

Further, (R3) will be described. (R3)
Is esterified by reacting the carboxyl group or its anhydride group in the copolymer or graft of (R1) or (R2) with a compound having at least one hydroxyl group in the molecule, or It is obtained by reacting a carboxyl group or the like with a compound having at least one amino group in the molecule to amidate or imidize, or by reacting the carboxyl group or the like with a metal compound for chelation. .

By carrying out such modification, it becomes possible to appropriately control various physical properties such as the acid value of the high acid value resin (b1) and the low acid value resin (b2) and the chlorine-containing water.

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.

The low acid value resin (b2) used in the present invention may be any of the above (R1), (R2) and (R3). However, as the low acid value resin (b2), maleated polyolefin is more preferable as the graft body of (R2), and as (R3), a metal salt of a copolymer of ethylene and an unsaturated carboxylic acid. Ionomer resins are preferred.

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.

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.

The metal ions used for neutralization include C
Examples of the metal ion source include metal oxides, hydroxides, carbonates, and acetates.

The ionomer resin is generally prepared by melt-kneading the ethylene / unsaturated carboxylic acid copolymer 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.

Next, the thermoplastic resin (a) in the present invention
Will be described.

The thermoplastic resin (a) in the present invention has a melt flow rate (hereinafter referred to as MFR) of 0.
001 to 400 resins are preferable, and MFR is 0.001
In the following, since the melt viscosity of the colored resin composition is too high, coloring defects may occur, and color unevenness and flow marks may occur, which lowers the chlorine-containing water content. On the other hand, when the MFR is 400 or more, bleeding from the molded product, weather resistance, heat resistance, mechanical properties, etc. may be adversely affected.

Among the thermoplastic resins (a) of the present invention, examples of the polyolefin resin include crystalline or amorphous polypropylene, high density, low density or linear low density polyethylene, polybutene, and random ethylene / propylene. , Block or graft copolymers, 1-butene ethylene and propylene copolymers, α-olefin and ethylene or propylene copolymers, ethylene / vinyl acetate copolymers, ethylene / methyl acrylate copolymers, ethylene -Ethyl acrylate copolymer etc. are mentioned, and these 1 type (s) or 2 or more types are used.

As the thermoplastic resin other than polyolefin, polyesters such as polymethylpentene, polystyrene, polyethylene terephthalate and polydiene polybutylene terephthalate, acrylonitrile-
Heat of butadiene-styrene (ABS) resin, acrylonitrile-EPDM-styrene (AES) resin, other acrylic resins, polybutadiene, polyamide, polycarbonate, polyacetal, polyarylate, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyurethane, etc. A plastic resin may be used, and one or more of these may be used, but a polyolefin resin is more preferable.

Among them, polyolefin resins such as high density polyethylene (hereinafter abbreviated as HDPE), linear low density polyethylene (hereinafter abbreviated as LLDPE) and polypropylene are used for the bleaching agent container as the bleaching agent container. Polypropylene or polybutene is preferred for the cap.

Of the water pipes, HDPE is used for large diameter pipes, and LLDPE, polybutene or vinyl chloride is used for small pipe diameters.

MFR for water pipe of HDPE
0.005-10, MFR 0.005-10 for containers
0 is preferable, and in the case of LLDPE, polypropylene, polybutene, and vinyl chloride, MFR 0.005 to 100 is preferable for both water pipes and containers.

The shape of the thermoplastic resin (a) is not particularly limited and may be powder or pellet.

As the pigment (c) used in the present invention, known organic pigments and inorganic pigments conventionally used for coloring printing inks, paints or thermoplastic resins can be used without particular limitation.

Examples of organic pigments include azo, azomethine, quinacridone, anthraquinone, benzidine, perylene, isoindolinone, phthalocyanine, dioxazine, dioxane, induslen,
Examples thereof include perinone-based pigments, quinophthalone-based pigments, pyrazolone-based pigments, atine-based pigments, nitro-based pigments, and the like.

As the inorganic pigment, zinc oxide, zinc sulfide,
Lead sulfate, titanium oxide, iron oxide, molybdenum oxide, yellow lead,
Benji, red lead, silver vermilion, ultramarine, navy blue, gosu, chromium oxide, chromate, cadmium sulfide, cadmium selenide, silicate, cobalt blue, cerulean blue, aniline black, black titanium, carbon black, etc. One or more of these pigments are used.

As described above, the water distribution pipes and their joints from the water storage area to the area of each city, municipality, etc. are usually colored blue, because of this.
Ultramarine blue, dark blue, Kuresu, cobalt blue, cerulean blue, phthalocyanine-based, and indanthrene-based blue pigments are used, and among them, phthalocyanine-based, induslen-based, ultramarine blue, and cobalt-based blue pigments are preferably used.

Similarly, carbon black, aniline black and black titanium are used for the water supply pipe, which is usually colored black, and carbon black is preferably used. Similarly, indoor water distribution pipes are usually colored yellow,
Azo-based, nitro-based, titanium yellow and ocher are used, but azo-based is preferably used.

The pigment may be in the form of dry powder pigment, pigment wet cake containing water (also referred to as an aqueous wet cake of pigment, filter cake, press cake) or a mixture thereof.

The phthalocyanine blue used in the present invention is represented by the following formula (Formula 1) and has 0 to 8 chlorine atoms in one molecule. In (Equation 1), M is a hydrogen atom, Cu, Zn, Ni, or Fe, but in general, Cu is preferable from the viewpoint of hue as a coloring material and manufacturing cost, and also from the viewpoint of coloring power. Cu is preferred. (Equation 1)

[Chemical 1] X1 to X4 represent chlorine atoms, and the number of chlorine atoms is 0 to 8
However, it is preferably 2 to 4 in terms of heat resistance and hue.

The indacerene-based blue used in the present invention is represented by the following formula (formula 2). (Formula 2)

[Chemical 2] The ultramarine used in the present invention is the following (formula 3) or (formula 4),
The cobalt-based blue is represented by the following (formula 5) to (formula 7). That is, ultramarine is 3NaAl ・ SiO ₄・ Na ₂
S ₂ (formula 3) or 2 (Na ₂ O · Al ₂ O ₃ · 2S
_{iO 2) · Na 2 S 2} ( Equation 4), cobalt blue, C
oO · nAl ₂ O ₃ (Formula 5), Cerulean Blue is C
oO · nSnO ₂ · mMgO (formula 6), Kuresu Co ₃
O ₄ + SiO ₂ + Al ₂ O ₃ + FeO ₃ + NiO + Mn
O (equation 7).

In the formula (5), n is preferably 2-3.
In Formula 6, n is preferably 1.5 to 3.5 and m is preferably 2 to 6. Further, in (Equation 7), the main component is Co ₃ O ₄ , SiO ₂ , Al ₂ O ₃ , FeO ₃ , NiO, M
Although it contains nO, its composition ratio is not constant because it is a natural product.

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.

When the colored resin composition according to the present invention is a colored pellet, the colored resin composition contains 100 parts by weight of the thermoplastic resin (a) and 0.00 parts by weight of the high acid value resin (b1).
5 to 30 parts by weight, low acid value resin (b2) 0.0005 to
It is preferable to contain 30 parts by weight and 0.01 to 60 parts by weight of the pigment (c). If the amount of the pigment (c) is less than 0.01 part by weight, only a very light colored state can be obtained, and if it exceeds 60 parts by weight, the mechanical properties of the molded product are likely to be impaired. When the high acid value resin (b1) is less than 0.0005 parts by weight, the chlorine-containing water resistance of the colored resin composition is deteriorated. When the low acid value resin (b2) is less than 0.0005 parts by weight, the pigment dispersibility becomes poor. On the other hand, when the amount of the high acid value resin (b1) or the low acid value resin (b2) exceeds 30 parts by weight, the compatibility with the thermoplastic resin deteriorates and the mechanical properties of the molded product are likely to be impaired.
Further, in order to sufficiently coat the pigment (c) with the high acid value resin (b1) and the low acid value resin (b2), the high acid value resin (b1) and the low acid value resin (b2) are respectively pigments. It is desirable that it is at least one-half of the weight.

When the colored resin composition according to the present invention is a masterbatch, the colored resin composition contains 100 parts by weight of the thermoplastic resin (a) and 0.00 parts by weight of the high acid value resin (b1).
5 to 200 parts by weight, 0.005 to the low acid value resin (b2)
It is preferable to contain 200 parts by weight and 0.1 to 200 parts by weight of the pigment (c). If the amount of the pigment (c) is less than 0.1 part by weight, only a very light colored state can be obtained, and 200
If it exceeds the weight part, the dispersibility of the pigment in the masterbatch tends to be insufficient. When the high acid value resin (b1) or the low acid value resin (b2) is less than 0.005 parts by weight, the chlorine-containing water resistance is deteriorated and the pigment dispersibility is also deteriorated. On the other hand, 20
If it exceeds 0 parts by weight, granulation of the masterbatch becomes difficult. Further, in order to sufficiently coat the pigment (c) with the high acid value resin (b1) and the low acid value resin (b2), the high acid value resin (b1) and the low acid value resin (b2) are respectively pigments. It is desirable that the weight is at least one half of (c).

The molded product of the present invention is manufactured by molding the colored pellet as it is, or by diluting the masterbatch with a thermoplastic resin and molding. As the thermoplastic resin used for dilution, the same resin as the thermoplastic resin (a) used in obtaining the masterbatch can be used, and for producing a pipe for water supply and a container for liquid bleaching agent, A polyolefin resin is more preferable.

The final molded product produced by diluting the masterbatch and manufacturing the same is also the same as the molded product produced by directly molding the colored pellets, with 100 parts by weight of the thermoplastic resin (a) and a high acid value resin. 0.005 to 30 parts by weight of (b1),
It is desirable to contain 0.0005 to 30 parts by weight of the low acid value resin (b2) and 0.01 to 60 parts by weight of the pigment (c).

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 for films, sheets, plates, 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 pipes, especially water pipes, bleach containers and caps. 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 or derivatives thereof, metal soaps, and oxidants so long as the effects of the present invention are not impaired or there is no problem in hygiene. Inhibitors, ultraviolet absorbers, lubricants Stabilizers such as antistatic agents, and various known additives for polymers such as surfactants can be added.

[0088]

EXAMPLES Next, examples of the present invention will be shown. In the following, "part" means "part by weight" and "%" means "% by weight".
Shall mean.

[Production Example 1] 650 g of an α-olefin having 12 to 14 carbon atoms and 4.4 g of di-t-butyl peroxide as a polymerization initiator were charged in a flask, and the atmosphere was replaced with nitrogen, followed by heating at 150 ° C. with stirring. A total of 350 g of maleic anhydride was added every 2 minutes in an amount of 11.7 g, and a total of 4.4 g of di-t-butyl peroxide was added in an amount of 1.1 g every 20 minutes. After the addition was completed, 1.1 g of di-t-butyl peroxide was further added, the system temperature was kept at 180 ° C., and the reaction was further advanced. After 1 hour and 3 hours, 1.2 g of t-butyl peroxide was added, and the mixture was reacted for 3 hours. Then, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to complete the reaction. Take out the contents when it is hot, cool, solidify,
A copolymer resin having an acid value of 420 mgKOH / g was obtained.

[Production Example 2] 788 g of the copolymer resin obtained in Production Example 1, 212 g of ethylene glycol monomethyl ether (molecular weight: 750) as a modifier and 0.79 g of sodium paratoluene sulfonate were charged in a flask and stirred. It was melted in a nitrogen stream and dehydrated at a reaction temperature of 180 ° C. for 6 hours. After the reaction was completed, the contents were taken out while being hot, cooled and solidified to obtain a resin having an acid value of 240 mgKOH / g.

[Production Example 3] 787 g of the copolymer resin obtained in Production Example 1 and 213 g of stearylamine as a modifier were charged into a flask and melted in a nitrogen stream with stirring, and the reaction was carried out at a reaction temperature of 180 ° C. for 6 hours. went. After the reaction was completed, the contents were taken out while heating, cooled and solidified to give an acid value of 290.
A resin of mg KOH / g was obtained.

[Production Example 4] 300 g of the copolymer resin obtained in Production Example 1 and 22.1 g of potassium acetate as a modifier were placed in a flask and melted in a nitrogen stream with stirring, and the reaction temperature was 180 ° C. for 6 hours. Deacetic acid reaction was performed. Then, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to complete the reaction. When the contents are taken out when heated, cooled and solidified, acid value 350mgKOH / g
Was obtained.

[Production Example 5] Styrene 208 g, carbon number 1
0 g of α-olefin (144 g) and di-t-butyl peroxide (2.7 g) were charged in a flask, and the atmosphere was replaced with nitrogen.
Maleic anhydride meter 29 with heating and stirring at 50 ° C
4.2 g of tert-butyl peroxide was added in an amount of 9.8 g every 2 minutes, and 0.7 g of di-t-butyl peroxide was added in an amount of 0.7 g every 20 minutes. After the addition was completed, the system temperature was kept at 160 ° C. and the reaction was carried out for 3 hours. Then, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to complete the reaction. Take out the contents when it is hot, cool, solidify,
A copolymer resin having an acid value of 520 mgKOH / g was obtained.

Production Example 6 638 g of α-olefin having 20 to 28 carbon atoms, 650 g of stearyl methacrylate,
120 g of maleic anhydride, 3.6 g of di-t-butyl peroxide and 400 g of ethyl acetate were charged into an autoclave, and after nitrogen substitution, the system temperature was maintained at 160 ° C. while stirring and pressurizing to 3 kg / m ^2. The reaction was carried out for 6 hours. Then, the temperature of the system was kept at 200 ° C., unreacted monomers were removed under reduced pressure, and the reaction was terminated. When the contents are taken out when heated, cooled and solidified, acid value 230mg
A KOH / g copolymer resin was obtained.

[Production Example 7] 624 g of 2-ethylhexyl vinyl ether and 0.6 g of di-t-butyl peroxide
Was charged into a flask and, after purging with nitrogen, while heating and stirring at 150 ° C., a total of 412 g of maleic anhydride was added at 13.7 g every 2 minutes, and 1.2 g of di-t-butyl peroxide was added at every 20 minutes. 0.6 g each was added. After the addition was completed, 0.6 g of di-t-butyl peroxide was further added to maintain the system temperature at 180 ° C., and the reaction was further advanced.
After 1 hour and 3 hours, 1.2 g of t-butyl peroxide was added, and the mixture was reacted for 3 hours. Then, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to complete the reaction. When the contents are hot, it is taken out, cooled and solidified to give an acid value of 432 mgK.
An OH / g copolymer resin was obtained.

[Production Example 8] Vinyl stearate 620
g, 2.7 g of di-t-butyl peroxide was charged into a flask, and after nitrogen substitution, while heating and stirring at 150 ° C., 206 g of maleic anhydride meter was added in an amount of 6.9 g every 2 minutes, and di-t-butyl peroxide. 20 g of 2.1 g of peroxide
0.7 g was added every minute. After the addition was completed, the temperature of the system was kept at 160 ° C. and the reaction was continued for 3 hours. Then, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to complete the reaction. The contents are taken out when heated, cooled and solidified to give an acid value of 275 mgKOH /
g of copolymer resin was obtained.

[Production Example 9] 362 g of α-olefin having 12 to 14 carbon atoms, 328 g of cyclohexanedimethanol monovinyl ether, 452 g of vinyl laurate and dit.
Charge 0.6 g of butyl peroxide into the flask,
After purging with nitrogen, while heating at 150 ° C. and stirring, 206 g of maleic anhydride meter was added every 6.9 g every 2 minutes, and 1.2 g of di-t-butyl peroxide was added every 0.6 minutes every 0.6 g.
g was added. After the addition was completed, 0.6 g of di-t-butyl peroxide was further added, the system temperature was maintained at 180 ° C., and the reaction was further advanced. After 1 hour and 3 hours, 1.2 g of t-butyl peroxide was added,
The reaction was carried out for 3 hours. Then, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to complete the reaction. The contents were taken out while hot, cooled and solidified to obtain a copolymer resin having an acid value of 390 mgKOH / g.

[Production Example 10] Ethylene / methacrylic acid copolymer resin "Nucrel N2060" (Mitsui DuPont Polychemical Co., Ltd., MFR: 60, acid value: 132) 4
00 parts, 330 parts of uniline alcohol 700 (manufactured by Petrolite, average molecular weight 700) as a modifier are charged into a reaction kettle, heated to 180 ° C. under a nitrogen stream, and 0.4 part of sodium paratoluenesulfonate is added. did. Then, the reaction was carried out for 5 hours under reduced pressure by a vacuum pump, and an acid value of 34 mgKOH in which 50% of the carboxyl groups were modified
/ G of higher alcohol-modified resin was obtained.

Example 1 50 parts of the high acid value resin (b1) obtained in Production Example 1 and phthalocyanine blue (CI Pigment
Blue 15: 1) Mix with 50 parts by melt-kneading and dispersing,
A masterbatch intermediate was obtained.

Next, with respect to 100 parts of high-density polyethylene "SHOREX 2002E" (manufactured by Showa Denko KK, MFR: 0.2) used as the thermoplastic resin (a), 3.5 parts of the above masterbatch intermediate, and Low acid value resin (b
2) Ionomer wax used as “Akulin 20”
5 parts of "1A" (manufactured by Allied Signal Co., acid value: 42) were mixed with a Henschel mixer, and then extruded at 220 ° C with a single-screw extruder, stranded, cooled and pelletized to obtain a masterbatch.

Examples 2 to 18 Master batches were obtained by the same method as in Example 1 except that 50 parts of various high acid value resins (b1) shown in Table 1 were used.

[Examples 19 to 24] Examples 19 to 24, except that the various pigments (c) shown in Table 2 and the high acid value resin (b1) of Production Example 1 were used in the amounts shown in Table 2. A masterbatch was obtained by the same method.

[Examples 25 to 28] Instead of using 100 parts of the high-density polyethylene (a) used in Example 1, 100 parts of various thermoplastic resins (a) shown in Table 3 were used.
A masterbatch was obtained by the same method as in Example 1.

Example 29 Instead of 100 parts of the high-density polyethylene (a) used in Example 1, polybutene “M0” was used.
200 "(manufactured by Mitsui Petrochemical Industry Co., Ltd.) (a) 100
Part, the high acid value resin (b1) 5 of Production Example 1 used in Example 1
Instead of 0 part, a butadiene / maleic anhydride copolymer “BN-1010” (manufactured by Nippon Soda Co., Ltd.) (b1) 50
A masterbatch was obtained in the same manner as in Example 1 except that parts were used.

Example 30 Instead of 100 parts of the high-density polyethylene (a) used in Example 1, polyvinyl chloride “ZEST 1000Z” (manufactured by Nippon Zeon Co., Ltd.)
(A) 100 parts, 50 parts of the high acid value resin (b1) of Production Example 1 used in Example 1 was replaced with styrene / maleic anhydride copolymer "GSM1001" (manufactured by Gifu Serratsk Manufacturing Co., Ltd.) (b1). ) A masterbatch was obtained by the same method as in Example 1 except that 50 parts were used.

Example 31 15 parts of the high acid value resin (b1) obtained in Production Example 1, quinacridone red (CI Pigment R
ed 122) 30 parts, titanium oxide (CI Pigment White 6)
5 parts and polypropylene "Mitsui High Pole J900"
50 parts of "P" (MFR, 40, manufactured by Mitsui Petrochemical Co., Ltd.) was premixed with a Henschel mixer. Then, this mixture was fed to a screw extruder having a screw diameter of 30 mm and an L / D value of 42, the rotation speed was 350 rpm, and the set temperature was 1
The mixture was kneaded under the conditions of 63 ° C., extruded, and cut with a pelletizer to obtain a masterbatch intermediate.

Next, polypropylene "Mitsui Highpol J400" (Mitsui Petrochemical Industry Co., Ltd., MFR: 3) 10
0 part, 5 parts of maleated PP wax "NP0555A" (Mitsui Petrochemical Co., Ltd., acid value: 45) as a low acid value resin (b2), and 5 parts of the above masterbatch intermediate were mixed with a Henschel mixer. . Then, this mixture was extruded by a single-screw extruder at 220 ° C., formed into a strand, cooled, and pelletized to obtain a masterbatch.

Example 32 5 parts of the high acid value resin (b1) obtained in Production Example 1 and titanium oxide (CI Pigment White 6) 5
5 parts, Benji (CI Pigment Red 101) 5 parts, polypropylene "Mitsui Hypol J900P" (Mitsui Petrochemical Co., Ltd., MFR: 40) 30 parts, and low acid value resin (b2)
Using 5 parts of maleated PP "Polytac H1000P" (manufactured by Idemitsu Petrochemical Co., Ltd., MFR: 200, acid value: 54) as the above, a masterbatch intermediate was obtained by the same method as in Example 31.

Next, polypropylene "Mitsui Highpol J800" (Mitsui Petrochemical Industry Co., Ltd., MFR: 22) 1
00 parts and 3.5 parts of the masterbatch intermediate were mixed with a Henschel mixer. Then, this mixture was extruded by a single-screw extruder at 220 ° C., formed into a strand, cooled, and pelletized to obtain a masterbatch.

[Examples 33 to 46] Masterbatches were obtained in the same manner as in Example 1 except that 5 parts of various low acid value resins (b2) shown in Table 4 were used.

Comparative Examples 1 to 7 50 parts of various resins (b1 ′) shown in Table 5 were used in place of the high acid value resin (b1),
A masterbatch was obtained by the same method as in Example 1 except that 5 parts of various resins (b2 ′) shown in Table 5 were used instead of the low acid value resin (b2).

[Evaluation of Dispersibility] In order to evaluate the dispersibility of the colored resin composition according to the present invention, first, 10 parts of the masterbatch obtained in each example is shown below in each thermoplastic resin 10.
Mixed with 0 parts.

That is, Examples 1 to 24 and Example 33 to
46 and Comparative Examples 1 to 3, high-density polyethylene "HIZEX 6300M" (manufactured by Mitsui Petrochemical Industries,
Mix with 100 parts of MFR: 0.11). Example 25,
In the case of 31, 32 and Comparative Example 4, polypropylene “U
BE polypro ZS633 "(manufactured by Ube Industries, MFR:
0.35) mixed with 100 parts. In the case of Example 26 and Comparative Example 5, a linear low-density polyethylene "Neozex 2015M" (Mitsui Petrochemical Co., Ltd., MFR: 1.
3) Mix with 100 parts. In the case of Examples 27 and 29 and Comparative Example 6, 100 parts of polybutene "Polybutene M-801" (Mitsui Petrochemical Co., Ltd., MFR: 0.03) was mixed. In the case of Examples 28 and 30 and Comparative Example 7, polyvinyl chloride "ZEST1000Z" (manufactured by Zeon Corporation,
Mixed with 100 parts of MFR: 0.1).

3 kg of each mixture was extruded by a single-screw extruder with a screw diameter of 30 mm equipped with a 500-mesh wire mesh at the tip, and the pressure rise value of each mixture at the tip at this time ( 3 kg
The difference from the pressure at the end of extrusion was measured. Such a value is called a clogging value (Kg / cm ² ), and the pigment dispersibility was evaluated based on the magnitude of this clogging value. The smaller the clogging value, the better the pigment dispersibility in the resin. The results are shown in Table 6.
Shown in.

[Evaluation of Chlorine Water Resistance] In order to evaluate the chlorine water resistance of the colored resin composition according to the present invention, 5 parts of each masterbatch obtained in each Example is the same as the pigment dispersibility evaluation. Were mixed with 100 parts of each of the thermoplastic resins. Each mixture was introduced into an injection molding machine, molded into a plate, and subjected to a chlorine water resistance test under the following conditions according to JIS K6762. Chlorine water resistance is evaluated by immersing the plate-shaped molded product in chlorine-containing water at a constant temperature for a certain period of time, and then visually observing whether swelling or color loss has occurred on the plate surface after immersion. It was The results are shown in Table 6.

Test conditions Chlorine concentration: 2000 ± 100 ppm Temperature: 60 ° C. pH: 6.5 ± 0.5 Immersion time: 168 hours Evaluation criteria blister generation 1: Diameter 0.4 mm over the entire plate surface There are the above-mentioned protrusions or small-diameter bulges.

2: Within 1 cm ^{2 of the} plate surface, a diameter of 0.
There are 10 or more protrusions of 4 mm or more or small-diameter bulges.

3: Within 1 cm ^{2 of the} plate surface, a diameter of 0.
There are 4 to 9 protrusions of 4 mm or more or small-diameter bulges.

4: Within 1 cm ^{2 of the} plate surface, a diameter of 0.
There are 2 to 3 protrusions of 4 mm or more or small-diameter bulges.

[0120] 5: 1cm ² of the plate surface, the diameter 0.
There is one or less protrusion of 4 mm or more or small-diameter bulge.

Occurrence of color loss A: Almost no color loss occurs.

[0122] B: Some color remains.

[0123] C: Most of the color is lost.

[0124]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[0125]

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 directly contacts the chlorine-containing water,
The molded product can be used safely without causing color loss, swelling, cracking or cracking, without deterioration for a long period of time.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08L 31/04 C08L 31/04 C 33/02 33/02 35/00 35/00 (72) Inventor Akiyoshi Iguchi Chuo-ku, Tokyo Kyobashi 2-chome No. 3-13 Toyo Ink Mfg. Co., Ltd. (56) Reference JP-A-57-174327 (JP, A) JP-A-10-60182 (JP, A) JP-A-10-265621 (JP , A) JP 9-111057 (JP, A) JP 10-338772 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L

Claims (27)

(57) [Claims] 1. A thermoplastic resin (a) having substantially no acid value, a thermoplastic resin (b) comprising two or more thermoplastic resins having an acid value of 1 to 900 mgKOH / g, and a pigment. In the colored resin composition containing (c), the difference in acid value between at least one kind (b1) and another kind (b2) of the thermoplastic resin (b) is 10 mgKOH / g or more. And the thermoplastic resin (a) is a polyolefin
A chlorine-resistant water-based colored resin composition which is a resin or a vinyl chloride resin . 2. The acid value of the thermoplastic resin (b1) is 70.
The chlorine-resistant water-based colored resin composition according to claim 1, wherein the thermoplastic resin (b2) has an acid value of 1 to 70 mgKOH / g. 3. A thermoplastic resin (a) of 100 parts by weight, a pigment (c) of 0.01 to 60 parts by weight, and a thermoplastic resin (b).
0.005 to 30 parts by weight of 1), a thermoplastic resin (b2)
The chlorine-resistant water-based colored resin composition according to claim 1 , which contains 0.0005 to 30 parts by weight. 4. A thermoplastic resin (a) of 100 parts by weight, a pigment (c) of 0.1 to 200 parts by weight, and a thermoplastic resin (b).
1) 0.005 to 200 parts by weight, a thermoplastic resin (b
2) containing 0.005 to 200 parts by weight, claim 1 Symbol
Salt-containing aqueous colored resin composition of the mounting. 5. The thermoplastic resin (b1) is a polyolefin resin having a carboxyl group, according to claim 1 to 4
The chlorine-containing water-based colored resin composition according to any one of the above. 6. The thermoplastic resin (b1) is, alpha, which is a copolymer resin of a monomer having a β-unsaturated double bond, a dibasic acid or its anhydride having an unsaturated double bond, wherein
Item 5. A chlorine-resistant aqueous colored resin composition according to any one of items 1 to 5 . 7. The monomer having an α, β unsaturated double bond is α-olefin, styrene, vinyl ether,
The chlorine-resistant water-based colored resin composition according to claim 6, which is at least one kind of monomer selected from vinyl ester and derivatives thereof. Wherein said unsaturated dibasic acid or anhydride thereof having a double bond is between maleic acid or anhydride, according to claim 6 or 7 salt-containing aqueous colored resin composition according to any one of. 9. The thermoplastic resin (b1) has 6 to 3 carbon atoms.
The chlorine-resistant water-based colored resin composition according to any one of claims 1 to 8 , which is a copolymer of 0-α-olefin and maleic anhydride. 10. A thermoplastic resin (b2) is a polyolefin resin having a carboxyl group, to claim 1
9. The chlorine-resistant water-based colored resin composition according to any one of 9 above. 11. The thermoplastic resin (b2) is an ethylene ionomer resin which is a copolymer of a metal salt of an unsaturated carboxylic acid, salt-containing aqueous colored resin composition according to any one of claims 1 to 9 object. 12. The chlorine-resistant water-based colored resin composition according to claim 11, wherein the unsaturated carboxylic acid is acrylic acid and / or methacrylic acid. 13. The chlorine-resistant water-based colored resin composition according to claim 10 , wherein the thermoplastic resin (b2) is a maleinized polyolefin. 14. The chlorine-resistant water-based colored resin composition according to claim 13, wherein the maleated polyolefin is obtained by graft-polymerizing maleic anhydride onto a polyolefin resin. 15. The chlorine-resistant aqueous colored resin composition according to claim 1, wherein the pigment (c) is a blue pigment. 16. The chlorine-resistant water-based colored resin composition according to claim 15, wherein the blue pigment is an organic pigment. 17. The chlorine-resistant water-based colored resin composition according to claim 16, wherein the organic pigment is phthalocyanine blue or indathrene blue. 18. The chlorine-resistant water-based colored resin composition according to claim 15, wherein the blue pigment is an inorganic pigment. 19. The chlorine-resistant aqueous colored resin composition according to claim 18, wherein the inorganic pigment is ultramarine blue or cobalt blue. 20. The thermoplastic resin (b2) comprises α, β
Have a monomer and an unsaturated double bond to have a unsaturated double bond
Copolymer with dibasic acid or its anhydride, thermoplastic resin
Carboxyl group or its anhydride by graft modification on fat
Consists of a substance group introduced and derivatives thereof
Salt resistant according to claim 1, consisting of a substance selected from the group
A base-containing aqueous colored resin composition. 21. The polyolefin resin is polyethylene, polypropylene, or polybutene, claim
1. The chlorine-containing water-based colored resin composition according to 1. 22. The chlorine-resistant water-based colored resin composition according to claim 21, wherein the polyethylene is high-density polyethylene or linear low-density polyethylene. 23. The chlorine-resistant water-based colored resin composition according to claim 1, which is used in a bleaching agent container or a cap of the container. 24. The method according to claim 1, which is used for a water pipe.
22. A chlorine-resistant water-based colored resin composition according to any one of items 22 to 22. 25. The chlorine-containing water-based colored resin composition according to claim 24, wherein the water pipe is a water pipe or a joint. 26. A container for a bleaching agent obtained by molding the chlorine-containing aqueous colored resin composition according to claim 23, or a cap for the container. 27. A pipe for a water supply obtained by molding the chlorine-resistant water-based colored resin composition according to claim 24 or 25.