JP3428367B2 - Colored resin composition for water pipe and colored resin water pipe using the composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored resin composition for water pipes, and more particularly to a colored resin composition for water pipes excellent in color fastness of a coloring component to chlorine-containing water and a colored resin water pipe using the same. .

[0002]

2. Description of the Related Art Conventionally, pipes for water supply distribution pipes in Japan have been made of materials such as steel pipes, ductile cast iron pipes and vinyl chloride pipes. However, after the Great Hanshin-Awaji Earthquake, it was confirmed that water pipes made of such materials suffered from cracks, cracks, etc. due to the earthquake and were weak in earthquake resistance. On the other hand, polyethylene pipes used for gas pipes and water pipes are subject to recent major earthquakes, such as the Hokkaido Kushiro-oki Earthquake in January 1993 (M: 7.8) and the Hokkaido Nansei-oki Earthquake in July 1993 ( M: 7.8) and the Great Hanshin-Awaji Earthquake (January 1995) (M: 7.2), etc., it has been found that there is almost no damage such as cracks and cracks, and it has excellent earthquake resistance. For water supply pipes made of polyethylene, LD polyethylene, LLD polyethylene, etc. are usually used as a raw material resin, and a single-layer pipe colored with carbon black and an uncolored polyethylene pipe inside the polyethylene pipe colored with carbon black are used. The constructed two-layer pipe is put to practical use. However, water supply pipes are mainly composed of single-layer pipes colored with a blue pigment in European and American countries, and research and development are being conducted in Japan on the premise that the pipes will be single-layer pipes. The water distribution pipe here means a main water pipe from a water distribution tower (pond) to each household, and the water supply pipe means a water pipe from the water distribution pipe to each household. Generally, copper phthalocyanine blue pigment with excellent weather resistance is used as a pigment for coloring polyethylene in blue, but in the case of water pipe coloring, tap water is sterilized with chlorine, so the pigment used was subjected to a chlorine water resistance test. In that case, it is an essential requirement that there be little discoloration. The unsubstituted copper phthalocyanine blue pigment was weak against an oxidant, and was significantly discolored in a chlorine water resistance test to become almost white.

[0003]

Accordingly, an object of the present invention is to provide a polyolefin water supply pipe using a specific phthalocyanine blue pigment as a coloring component, which is excellent in color fastness of the coloring component by chlorine water for sterilization. Disclosed is a chlorine-resistant water-based colored resin composition for water distribution pipes, and a colored resin water distribution pipe using the same.

[0004]

Means for Solving the Problems As a result of research to overcome such a situation, the inventors have used a bromine-substituted phthalocyanine blue pigment as a blue pigment for coloring a polyolefin resin. As a result, the present invention has been completed based on the finding that a colored polyolefin resin composition with less discoloration can be obtained by chlorine water for sterilization of water. That is, the present invention provides: (1) A water-dispersed colored resin composition comprising a resin containing a polyolefin resin as a main component and a blue pigment, wherein a bromine-substituted phthalocyanine blue pigment is used as the blue pigment. A colored resin composition for pipes is provided. In a preferred embodiment of the present invention, (2) the bromine-substituted phthalocyanine blue pigment has a bromine number of 2
The colored resin composition for water pipes according to the above (1), which comprises 8 to 8 bromine-substituted phthalocyanine blue pigments. (3) The colored resin composition for water pipes according to the above (1), wherein the polyolefin resin is a polyethylene resin. (4) The colored resin composition for a water pipe according to (1) above, wherein the bromine-substituted phthalocyanine blue pigment is coated with a synthetic resin or an inorganic compound. (5) Furthermore, the present invention provides a colored resin water pipe containing the colored resin composition for a water pipe described in (1) to (4) above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The resin containing a polyolefin resin as a main component used in the present invention is a conventionally known polyolefin resin used in extrusion molding, injection molding and the like, and specifically has a density of 0.910 to 0. 0.980 g / cm ³ , preferably 0.940 to 0.960 g / cm ³ , MFR 0.01-1
0.0 g / 10 min, preferably 0.05-1.0 g / 10
min polyethylene homopolymer, ethylene content 1-5
An ethylene / propylene-block copolymer having 0% by weight and a propylene content of 99 to 50% by weight can be mentioned. The block copolymer in the present invention may be used even if a part of the above ethylene or propylene is replaced with an olefin having 4 to 6 carbon atoms.

The bromine-substituted phthalocyanine blue pigment used in the present invention is a bromine-substituted phthalocyanine blue pigment having a bromine number of 2 to 8, preferably 3 to 6. Bromine number is 2
If it is less than the number, discoloration due to chlorine-containing water occurs, which is not preferable. Further, when the number of bromine is 8 or more, the color tone changes from blue to green and the water distribution pipe does not become blue, which is not preferable. The bromine-substituted phthalocyanine blue pigment used in the present invention is produced by a known method for producing a usual bromine-substituted phthalocyanine blue pigment. That is, using bromine-substituted phthalic anhydride or a derivative thereof or bromine-substituted phthalodinitrile as a starting material, the bromine-substituted phthalic acid and urea and a metal compound such as copper, cobalt, or nickel are mixed with ammonium molybdate, phosphomolybdic acid, or the like. The reaction is carried out in the presence or absence of a catalyst such as ammonium or titanium tetrachloride in an organic solvent such as alkylbenzene, trichlorobenzene, dichlorobenzene or nitrobenzene at 150 to 230 ° C. for 2 to 10 hours under normal pressure or pressure. In this case, as the bromine-substituted phthalic acid used as the starting material, a single kind may be used, or two kinds of bromine-substituted phthalic acids having 0 to 4 substitutions depending on the number of bromine substitutions of the desired bromine-substituted cyanine blue pigment. The above may be mixed and used. Further, using an unsubstituted phthalocyanine-based blue pigment or a crude material as a starting material, suspending or dissolving these in an organic solvent, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like at 20 to 100 ° C., and adding a predetermined amount of bromine. A bromine-substituted phthalocyanine blue pigment can also be obtained by a method of bromination with bromine. The bromine-substituted phthalocyanine blue crude pigment obtained by the above method has large particles of a few microns, so that the pigment properties such as coloring power as a colorant, dispersibility and clarity are not sufficient. If necessary, it is preferably further pigmented. For example, a crude bromine-substituted phthalocyanine blue pigment is ground with an attritor, a ball mill, a vibration mill, a double-arm kneader, or the like in the presence or absence of a grinding aid, or with a binder such as polyethylene glycol. A method of milling in the presence of a grinding aid to make it finer. Further, as another method, a crude bromine-substituted phthalocyanine blue pigment is dissolved in concentrated sulfuric acid or fuming sulfuric acid or the like, and pigmented by a known method such as an acid paste method in which it is precipitated in water or ice water. It is also a preferable method to coat the surface of the bromine-substituted phthalocyanine blue pigment with a coating material such as an inorganic compound or a synthetic resin before use. The surface treatment with an inorganic compound such as hydrated amorphous silica, anhydrous amorphous silica, or a mixture thereof is performed by a conventionally known method for forming silicas. For example, the above-mentioned bromine-substituted phthalocyanine blue pigment is treated with a silane coupling agent or the like, if necessary, and finely dispersed in water, and an aqueous solution of sodium silicate, potassium silicate or the like and a dilute sulfuric acid aqueous solution are not dropped at the same time. Add by flowing down and stirring, or by finely dispersing these pigments in a solvent such as hydrous ethanol, adding tetraethyl orthosilicate or tetramethyl orthosilicate, etc., by a method of hydrolysis reaction and condensation reaction. can get. The coating treatment with synthetic resins is, for example, a coating treatment with a cured polymer, a polymer which is substantially insoluble in a medium, or the like, and is performed by a conventionally known method for forming these synthetic resins. A conventionally known cured resin is used as the cured polymer, and examples thereof include cured amino resin, cured epoxy resin, cured phenol resin, cured urethane resin, cross-linked unsaturated polyester resin,
Examples thereof include crosslinked poly (meth) acrylate resins.
Also, a non-curable polymer can be used as long as it is substantially insoluble in the polyolefin resin or has a melting point higher than the processing temperature of the resin. For example, a polyamide resin, a polyimide resin, a polyamide-imide resin, etc. may be mentioned. In the case of a curable resin, as is conventionally known, each monomer, a suitable crosslinking agent in a soluble state such as an initial condensate, if necessary,
It is used with curing agents, catalysts, polymerization initiators, etc. In the case of a non-curable polymer, it is dissolved in a soluble solvent before use. If necessary, the bromine-substituted phthalocyanine blue pigment is treated with a silane coupling agent or the like, finely dispersed in water or a solvent, and, under stirring, the above-mentioned organic compounds are respectively added thereto according to a conventional method for forming a coating, for example. , A solution such as an aqueous solution, an emulsion, or a solvent solution, which is added by dropping or flowing down, followed by heating as necessary, and a coating treatment by adding a curing agent such as amine or a curing catalyst such as acid or alkali, a polymerization initiator, etc. Done. In the produced surface-treated bromine-substituted phthalocyanine blue pigment, the treatment amount of these inorganic compounds or synthetic resins needs to be an amount such that the surface of the pigment is coated, and is 3 to 3000 parts by weight, preferably 100 parts by weight per 100 parts of the pigment.
~ 2000 parts by weight are treated.

In the present invention, for the purpose of color matching (toning), other pigments may be blended with the above bromine-substituted phthalocyanine blue pigment. Other pigments include, for example, phthalocyanine pigments, azo pigments, isoindolinone pigments, quinacridone pigments, anthraquinone pigments, organic pigments such as dioxazine pigments and perylene pigments, complex oxide pigments (for example, C. I. Pigment Yellow 157, C. I. Pigment Yellow 53, C.I.
I. Pigment Yellow 119, C.I. I. Pigment Brown 24, C.I. I. Pigment Brown 33, C.I.
I. Pigment Brown 34, C.I. I. Pigment Green 26, C.I. I. Pigment Green 50, C.I. I.
Pigment Blue 28, C.I. I. Pigment Blue 3
6, C.I. I. Pigment Black 26, C.I. I. Pigment Black 27, C.I. I. Pigment Black 28
Etc.), titanium oxide pigments, carbon black, ultramarine blue, red iron oxide, and other inorganic pigments. The blending amount of the bromine-substituted phthalocyanine blue pigment is 0.001 to 10 with respect to 100 parts by weight of a resin containing a polyolefin resin as a main component.
Parts by weight, preferably 0.01 to 2.0 parts by weight. The white or colored pigments can be used alone or in combination of two or more.

In the colored resin composition of the present invention, a dispersant such as metallic soap or polyethylene wax is used in order to improve the dispersion of the pigment. For metal soap,
Examples thereof include magnesium palmitate, calcium oleate, copper oleate, lithium stearate, magnesium stearate, zinc stearate, calcium stearate and the like. As the polyethylene wax, various polyethylene waxes such as general polymerization type, decomposition type and modified type are used.

The colored resin composition for water pipes of the present invention contains, in addition to the above-mentioned components, an antioxidant, a UV inhibitor, an antistatic agent, an antibacterial agent, a stabilizer, a crosslinking agent, talc, if necessary. Inorganic fillers such as clay, silica and alumina are blended.

As an example of preparing the colored resin composition for water pipes of the present invention, a resin containing a polyolefin resin as a main component, a bromine-substituted phthalocyanine blue pigment and a dispersant are mixed, and if necessary, the above-mentioned other components are added. Add the additives and put them in a mixer [trade name: Henschel Mixer Mitsui Miike Seisakusho], mix at room temperature or by heating, knead the kneaded product with a heated two-roll mill, cool it, and then grind it with a grinder. Or pelletized or subjected to an extrusion molding machine and extrusion-molded to form beads or columns.

The colored resin water distribution pipe of the present invention is prepared by mixing the above-mentioned colored resin composition for water distribution pipe with a polyolefin resin together with other additives as required according to a known method, and then subjecting the mixture to an extrusion molding machine to obtain a predetermined composition. Molded into a water distribution pipe of the size.

[0012]

EXAMPLES Next, the present invention will be specifically described with reference to examples. Synthesis Example 1 Synthesis of brominated copper phthalocyanine blue pigment 4-bromophthalic anhydride 45.4 parts by weight, urea 60.0
Parts by weight, cupric chloride 7.0 parts by weight, titanium tetrachloride 4.5
Parts by weight and 52.3 parts by weight of an alkylbenzene-based solvent [trade name: Hysol P Nippon Oil Co., Ltd. product] are placed in a glass-lined reaction vessel and stirred at 170 to 20.
The temperature is raised to 0 ° C. and the reaction is performed for 4 hours. After the reaction is completed, the solvent is removed by distillation under reduced pressure, and the mixture is heated (80 to 100 ° C.) with a dilute acid solution and a dilute aqueous alkali solution to separate impurities (unreacted substances, by-products) by filtration, and the precipitate is washed with water. Dry (8
(0 ° C.) to obtain blue crude tetrabromo copper phthalocyanine. Then, the above-mentioned crude tetrabromo copper phthalocyanine is put into a double-arm kneader, 300 parts by weight of anhydrous sodium sulfate and 40 parts by weight of polyethylene glycol (molecular weight 400) are added thereto, and the mixture is kneaded for 5 hours to form a pigment. This kneaded product was added to a dilute aqueous acid solution, subjected to heat treatment, filtered, washed with water, and dried at 80 ° C. to obtain 41.0 parts by weight of a tetrabromo copper phthalocyanine pigment having a clear color tone (yield 91.8%). Obtained. As a result of elemental analysis of this pigment, the average number of bromine substitutions was 4. Synthesis Example 2 Surface coating treatment of bromine-substituted phthalocyanine blue pigment 10 parts by weight of bromine-substituted phthalocyanine blue pigment obtained in Synthesis Example 1 and ethylene oxide-modified bisphenol A
40 parts by weight of diacrylate, 30 parts by weight of trimethylolpropane triacrylate and 20 parts by weight of stearyl methacrylate were blended and uniformly dispersed and mixed by a roll mill. 0.8 parts by weight of azoisobutyronitrile as a polymerization initiator was added thereto and mixed, and the mixture was added to an aqueous polyvinyl alcohol solution which was stirred by a high speed stirrer to prepare a suspension having an average particle size of about 3μ. did. The obtained suspension was charged into a suspension polymerization apparatus and polymerized at 65 to 75 ° C while stirring. The polymerized suspension slurry is filtered, washed with water and dried,
A surface-coated product of a bromine-substituted phthalocyanine blue pigment was obtained. The pigment content was 10% and the average particle size was about 3μ. Example 1 High-density polyethylene (density: 0.949 g / cm ³ , M
FR: 0.10 g / 10 min. ) 100 parts by weight, 0.05 part by weight of bromine-substituted phthalocyanine blue obtained in Synthesis Example 1, polyethylene wax [trade name: sun wax 15
1P Sanyo Chemical Industry Co., Ltd.] 0.06 part by weight was kneaded with a two-roll mill at 185 ° C. for 2 minutes to obtain a colored resin composition for water pipes. Then, the above kneaded product was hot pressed to prepare a press sheet having a thickness of 2 mm. The press sheet is prepared under the conditions of 230 ° C and 2 minutes of preheating (20 kg / c
m ² ), pressurization 2 minutes (200 kg / cm ² ) cooling temperature 2
It was performed at 0 ° C. for 5 minutes. 20m from the obtained press sheet
A test piece of m × 120 mm was prepared. The test piece was used for the evaluation of discoloration in the chlorine resistance test. As a result, almost no fading occurred, and excellent color fastness was exhibited. Example 2 A colored resin composition for water pipes was obtained in the same manner as in Example 1 except that 0.06 parts by weight of calcium stearate was used instead of the polyethylene wax of Example 1. Test pieces were prepared from this colored resin composition for water pipes in the same manner as in Example 1 and evaluated for discoloration in a chlorine water resistance test. As a result, it showed almost no color fading and showed excellent color fastness. Example 3 High-density polyethylene (density: 0.949 g / cm ³ , M
FR: 0.10 g / 10 min. ) 100 parts by weight, 0.05 part by weight of bromine-substituted phthalocyanine blue obtained in Synthesis Example 1, titanium dioxide [trade name: Taipek CR90 Ishihara Sangyo Co., Ltd. product] 0.02 part by weight, polyethylene wax [trade name: sun wax] 151P] 0.07 part by weight was kneaded with a two-roll mill at 185 ° C. for 2 minutes to obtain a colored resin composition for a water pipe. Then, the above kneaded product was hot pressed to prepare a press sheet having a thickness of 2 mm. The press sheet is prepared under the conditions of 230 ° C and 2 minutes of preheating (20 kg / c
m ² ), pressurization 2 minutes (200 kg / cm ² ) cooling temperature 2
It was performed at 0 ° C. for 5 minutes. 20m from the obtained press sheet
A test piece of m × 120 mm was prepared. In the same manner as in Example 1, this test piece was used to evaluate discoloration in a chlorine water resistance test. As a result, almost no fading occurred, and excellent color fastness was exhibited. Example 4 High-density polyethylene (density: 0.949 g / cm ³ , M
FR: 0.10 g / 10 min. ) 100 parts by weight, 0.5 part by weight of the bromine-substituted phthalocyanine blue-coated pigment obtained in Synthesis Example 2, copper phthalocyanine green pigment 0.00 part
1 part by weight of polyethylene wax [trade name: Sun Wax 151P] 0.07 part by weight of 185
The mixture was kneaded at ℃ for 2 minutes to obtain a colored resin composition for water pipe. Then, the above kneaded product was hot pressed to prepare a press sheet having a thickness of 2 mm. The press sheet creation condition is 230
2 minutes (20kg / cm ² ) preheating at ℃, 2 minutes pressurization (2
00kg / cm ²⁾ was carried out cooling temperature 20 ° C. for 5 minutes. A 20 mm × 120 mm test piece was prepared from the obtained press sheet. In the same manner as in Example 1, this test piece was used to evaluate discoloration in a chlorine water resistance test. As a result, almost no fading occurred, and excellent color fastness was exhibited. Example 5 The colored resin composition for water pipes obtained in Example 1 was charged into the hopper of an extrusion molding machine, and the set temperature of the cylinder and the die was set to 18.
The colored resin composition was melt-kneaded at 0 to 200 ° C. to obtain a blue water pipe having an inner diameter of 26 m / mφ and an outer diameter of 34 m / mφ.
A part of this water distribution pipe was cut out to form a test piece, and the discoloration evaluation of the chlorine water resistance test was performed in the same manner as in Example 1. As a result, almost no fading occurred, and excellent color fastness was exhibited. Comparative Example 1 High-density polyethylene (density: 0.949 g / cm ³ , M
FR: 0.10 g / 10 min. ) 100 parts by weight, monochloro copper phthalocyanine blue (chlorine substitution number 1) 0.
05 parts by weight, 0.06 parts by weight of polyethylene wax [trade name: Sun Wax 151P] are formed by a double roll 18
The mixture was kneaded at 5 ° C. for 2 minutes to obtain a colored resin composition for comparison. Then, the above kneaded product was hot pressed to prepare a press sheet having a thickness of 2 mm. The press sheet creation condition is 230
2 minutes (20kg / cm ² ) preheating at ℃, 2 minutes pressurization (2
00kg / cm ²⁾ was carried out cooling temperature 20 ° C. for 5 minutes. A 20 mm × 120 mm test piece was prepared from the obtained press sheet. The test piece was used for the evaluation of discoloration in the chlorine resistance test. As a result, it was considerably discolored and was unsuitable as a blue colorant. Comparative Example 2 A colored resin composition for comparison was obtained in the same manner as in Comparative Example 1 except that 0.06 parts by weight of calcium stearate was used instead of the polyethylene wax of Comparative Example 1. Test pieces were prepared from this colored resin composition in the same manner as in Comparative Example 1 and evaluated for discoloration in a chlorine water resistance test. As a result, it shows a considerable fading,
It was unsuitable as a blue colorant. Comparative Example 3 High-density polyethylene (density: 0.949 g / cm ³ , M
FR: 0.10 g / 10 min. ) 100 parts by weight, unsubstituted copper phthalocyanine blue 0.05 parts by weight, polyethylene wax [trade name: Sunwax 151P] 0.06
A part by weight was kneaded with a two-roll mill at 185 ° C. for 2 minutes to obtain a colored resin composition for comparison. Then, the above kneaded product was hot pressed to prepare a press sheet having a thickness of 2 mm. The conditions for creating the press sheet are 230 ° C and 2 minutes of preheating (20 kg
/ Cm ² ) and pressurization for 2 minutes (200 kg / cm ² ) at a cooling temperature of 20 ° C. for 5 minutes. 2 from the obtained press sheet
A 0 mm × 120 mm test piece was prepared. In the same manner as in Comparative Example 1, this test piece was used for evaluation of discoloration in a chlorine water resistance test. As a result, it showed complete fading and was unsuitable as a blue colorant. Comparative Example 4 A colored resin composition for comparison was obtained in the same manner as in Comparative Example 3 except that 0.06 parts by weight of calcium stearate was used instead of the polyethylene wax of Comparative Example 3. A test piece was prepared from this colored resin composition in the same manner as in Comparative Example 3 and was evaluated for discoloration in a chlorine water resistance test. Comparative Example 5 The colored resin composition for water pipes obtained in Comparative Example 1 was charged into the hopper of an extrusion molding machine, and the set temperature of the cylinder and the die was set to 18.
The colored resin composition was melt-kneaded at 0 to 200 ° C. to obtain a blue water pipe having an inner diameter of 26 m / mφ and an outer diameter of 34 m / mφ.
A part of this water distribution pipe was cut out to obtain a test piece, and in the same manner as in Comparative Example 1, the discoloration evaluation of the chlorine resistance test was performed. As a result, it was considerably discolored and was unsuitable as a blue colorant.

The chlorine water resistance test in Examples and Comparative Examples was conducted as follows. Chlorine water concentration: 2000 ± 100ppm Chlorine water temperature: 60 ± 1 ℃ Test time: 168 hours

[0014]

EFFECTS OF THE INVENTION The colored resin composition for water pipes of the present invention is excellent in color fastness to chlorine-containing water. Therefore, a water pipe for water supply molded using the colored resin composition for water pipes can be used for a long period of time. Stable color tone and physical properties can be maintained even during use and sterilization of water supply.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasutaka Momoi 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Within Dainichi Seika Chemicals Co., Ltd. (72) Atsushi Nogami 1-7-chome Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 6 Within Dainichi Seika Industry Co., Ltd. (72) Inventor Yoshitake Gun 1-chome, Nihombashi Bakuro-cho, Chuo-ku, Tokyo No. 6 Within Dainichi Seika Industry Co., Ltd. (72) Inventor Yoshio Abe 1-chome, Nihonbashi Bakuro-cho, Chuo-ku, Tokyo 7-6 Dainichi Seika Kogyo Co., Ltd. (72) Inventor Michie Nakamura 1-7-6 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3/00-13/08 E03C 1/02

Claims (5)

(57) [Claims] 1. A colored resin composition for water pipes, wherein a bromine-substituted phthalocyanine blue pigment is used as the blue pigment in a colored resin composition for water pipes, which comprises a resin containing a polyolefin resin as a main component and a blue pigment. object. 2. The colored resin composition for water pipes according to claim 1, which is a bromine-substituted phthalocyanine blue pigment having a bromine number of 2 to 8. 3. The colored resin composition for water pipe according to claim 1, wherein the polyolefin resin is a polyethylene resin. 4. The colored resin composition for water pipe according to claim 1, wherein the bromine-substituted phthalocyanine blue pigment is coated with a synthetic resin or an inorganic compound. 5. A colored resin water pipe containing the colored resin composition for water pipe according to any one of claims 1 to 4.