JPH01288425A - Hot water supply and drain transfer pipe - Google Patents

Abstract

PURPOSE:To prevent blister, layer separation and cracks or the like by forming a product with a bridged polyolefin resin compounded with at least a kind of coloring agent selected from an organic pigment and inorganic pigment such as azo, phthalocyanine and the like having a specified wt.%, and at least a kind of a stabilizer selected from an antioxidant and light stabilizer. CONSTITUTION:A hot water supply and drain transfer pipe is made up of a bridged polyolefin resin compounded with at least a kind of a coloring agent of 0.02-7wt.% selected from an organic pigment of azo, phthalocyanine, threne, coloring lake, quinaklydon, dioxazine, isoindolinon, and an inorganic pigment of metallic oxide, chromic acid molybdic acid, sulfide selenide, ferrocyanide, aluminium silicate, and at least a kind of stabilizer of 0.005-2wt.% selected from an antioxidant and light stabilizer. The polyolefin resin is mixed with a coloring agent and stabilizer directly, or as a master batch, and mixed with a dispersing agent, neutralizer, lubricant, antistatic additives and the like, as required, and the melt-kneaded and extruded into a tubular by means of an extruder, furthermore, given a bridging treatment.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a wandering hot water supply transfer pipe used for supplying and discharging hot water, etc.
More specifically, the present invention relates to a hot water supply/discharge pipe made of a crosslinked polyolefin resin that has weather resistance and prevents the occurrence of blisters, delamination, cracks, etc. due to contact with halogen-containing water.

[Conventional technology]

Traditionally, pipes made of cross-linked polyolefin such as polyethylene, which has been cross-linked to provide heat resistance, have been used as hot water supply/discharge pipes, and especially when the pipes are exposed pipes,
Additionally, carbon black is added to impart weather resistance.

However, in water supply and drainage pipes made of cross-linked polyolefin resin containing carbon black, halogen (mostly chlorine) is added to the tap water for the purpose of sterilization, so if used for a long period of time, blisters may form on the contact surface with high-temperature water. occur, 30
Examples were found where delamination occurred with a thickness of ~70 μm.

[Problem to be solved by the invention]

Although conventional hot water supply/discharge pipes made of crosslinked polyolefin resin containing carbon blank have weather resistance, they have problems such as blisters and delamination due to contact with halogen-containing water. According to experiments conducted by the present inventors, it has been found that even in the case of a transfer pipe that does not contain halogen-containing water, it deteriorates due to halogen-containing water and minute cracks occur inside the pipe after long-term use.

The present invention has been made to solve these problems in the supply/drainage channel transfer pipe. Therefore, the present invention has weather resistance and is free from blisters, delamination, cracks, etc. due to contact with halogen-containing water. It is an object of the present invention to provide a supply/discharge groove transfer pipe that prevents the occurrence of.

[Means to solve the problem]

The supply/discharge groove transfer pipe of the present invention is based on ab-based, phthalocyanine-based,
Thread-based, dye lake, quinacridone-based, dioxazine-based, isoisodorinone-based organic pigments, as well as metal oxide-based, chromic acid molybdic acid-based, sulfide-selenide-based pigments,
0.02 to 7% by weight of at least one colorant selected from ferrocyanide-based and aluminum silicate-based inorganic pigments, and at least one stabilizer selected from antioxidants and light stabilizers 0°005 2% by weight of crosslinked polyolefin resin.

Here, the polyolefin resin refers to low-density polyethylene, medium-high density polyethylene, ethylene, and α-olefin having about 3 to 20 carbon atoms, preferably butene-11 pentene-1, which are obtained by polymerization by a high pressure method or a medium-low pressure method. , hexene-1,4-methylpentene-1, octene-1, and ethylene-α-olefin copolymer ( Its α-olefin content is usually 0.5
~15% by weight), polypropylene obtained by polymerization by a gas phase method, a solution method, a slurry method, etc., and propylene and an α-olefin having about 2 to 10 carbon atoms, preferably ethylene, butene-1, pentene-1, etc. Typical examples include propylene-α-olefin copolymers obtained by copolymerizing 1 and hexene-1 by a gas phase method, a solution method, a slurry method, etc.

The cross-linked polyolefin resin in the present invention refers to the so-called radiation cross-linking method in which the polyolefin resin is irradiated with electron beams, T-rays, etc., mixed with organic peroxide, etc., and exposed to high temperatures.
It refers to a product that is crosslinked to a gel fraction of 40% or more by a known crosslinking method such as a so-called chemical crosslinking method or a so-called water crosslinking method in which an unsaturated silane compound is copolymerized and exposed to water.

Moreover, as a coloring agent, specifically, for example, as an azo type organic pigment, Permanent Red 2B is used.

Permanent yellow HR, permanent yellow n1
OC, Brilliant Carmino 6B, Pigment Scarlet 3B, Pyrazolone Red, Polyazole Red, Monoazoleft, Polyazo Yellow, Naphthol Red, Benzidine Yellow, etc. Phthalocyanine-based products include Phthalocyanine Blue, Phthalocyanine Green, etc. Threne-based products include Anthra Quinone yellow, flavanthrone yellow, anthrapyrimidine, indanthrembule,
Perylene red, thioindigo, etc.; examples of dyeing lakes include rhodamine lake; examples of quinacridones include quinacridone; examples of dioxazine types include dioxazine violet; examples of isoisodriones include isoisodorinone yellow; Preferred are phthalocyanine blue, phthalocyanine green, anthrapyrimidine, indanthrene blue, perylene red, quinacridone, dioxazine violet, and isoisodorinone yellow, with phthalocyanine blue and perylene red being particularly preferred. In addition, examples of metal oxide inorganic pigments include titanium white (rutile) and titanium white (rutile).
Anatase), titanium yellow, iron black, Bengara, yellow iron oxide, chromium oxide green, cobalt blue, etc. Chromic acid molybdate type includes yellow lead, molybdenum red, etc.
Examples of sulfide and selenide types include cadmium red, cadmium yellow, and lithopone; ferrocyanide types include navy blue; examples of aluminum silicate types include ultramarine; among them, titanium white (rutile) and titanium yellow. , Bengara, yellow iron oxide, chromium oxide green, cobalt blue, cadmium red, and cadmium yellow are preferred, and titanium white (rutile), titanium yellow, yellow iron oxide, and cobalt blue are particularly preferred.

In addition, as a stabilizer, specifically, for example, as an antioxidant, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-β-(3,5-di-t-butyl- 4-Hydroxyphenyl)propionate, 414
'-thio-bis(3-methyl-6-t-butylphenol), 1.3.5-trimethyl-2,4,6-)lis(3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis [methylene-3-(3', 5'-
Di-t-butyl-4'-hydroxyphenyl)propionate comethane, 1.3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 3,5-di- tert-butyl-4-hydroxyhydrocinnamic acid and 1.3.5-)lis(2-
hydroxyethyl)-3-) riazine-2,4,6(I
Triester of H,3H,5H)-)ion, 2-t-
Butyl-4-methyl-6-(2'-hydroxy-3'-
Phenolic compounds such as 1-butyl-5'-methylbenzyl) phenyl acrylate, dilauryl-3,3'-
Sulfur-based compounds such as thiodipropionate, similystyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythritol-tetra (β-lauryl-thiopropionate) , tris (mixed, mono and dinonylphenyl) phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, 4,4'-butylidene-bis(3- Phosphorous compounds such as methyl-6-t-butylphenyl-di-tridecyl) phosphite and tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphite are used as light stabilizers. , dimethyl succinate-1-
(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine polycondensate, poly(
(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-)riazine-2,4-diyl)((2,
2,6,6-tetramethyl-4-piperidyl)imino)
Hexamethylene ((2,2,6,6-tetramethyl-4
-piperidyl)imino)], bis(2,2゜6.6-tetramethyl-4-piperidyl)sebacate, tris(1
,2,2,6,6-bentamethyl-4-piperidyl)-
Hindered amine compounds such as dodecyl-1,2,3,4-butanetetracarboxylate, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-
5-chlorobenzotriazole, benzotriazole compounds such as 2-(2'-hydroxy-3', 5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-hydroxy-4-octadecyloxybenzophenone, Benzophenone compounds such as 2.2'-dihydroxy-4-methoxybenzophenone, 2.4-di-t-
Benzoate compounds such as butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, ethyl-
Cyanoacrylate compounds such as 2-cyano-3,5-diphenylacrylate, (2,2'-thio-bis(4
Examples include nickel-based compounds such as -t-octylphenol))-n-butylamine nickel, and formamidine-based compounds such as N-(4-ethoxycarbonylphenyl)-N'-ethyl-N'-phenylformamidine.

In the hot water supply/discharge pipe of the present invention, at least one of the colorants is 0.02 to 7% by weight, preferably 0.1 to 3% by weight, based on the total amount of the formulation, and at least one of the stabilizers is One type is the same < o, o o s ~ 2% by weight, preferably 0.01
It consists of the above-mentioned crosslinked polyolefin resin blended in an amount of ~1% by weight. In other words, it is essential that both the colorant and the stabilizer be blended, and in the case of blended ingredients other than these, and even if the colorant and stabilizer are blended, the blended amount must be below the lower limit. In this case, the effects of the present invention cannot be obtained. Furthermore, even if the amount added exceeds the upper limit, no further improvement in the desired properties is observed.

The hot water supply/discharge transfer pipe of the present invention is manufactured by adding the colorant and stabilizer to the polyolefin resin either directly or as a master bunch, and if necessary, adding a dispersant and a medium. This is done by adding a Japanese additive, a lubricant, an antistatic agent, etc., melting and kneading the mixture in an extruder, extruding it into a tube, and subjecting it to crosslinking.

[Effect]

The feeding groove transfer pipe of the present invention is made of cross-linked polyolefin resin and contains specific amounts of a specific colorant and stabilizer, so it has weather resistance and is free from blistering caused by contact with halogen-containing water. This prevents delamination and the appearance of cracks.

Polyethylene HE30J, density 0.920 g/cm'
.

MFRo, 3 g/10 min) and tetrakis[methylene-3-(3',5'-di-t-butyl-4') as a stabilizer.
-Hydroxyphenyl)propionate cometaf 0.1
% by weight was added and granulated into pellets using an extruder with a diameter of 40 mm. On the other hand, an ethylene-butene-1 copolymer resin,
Titanium white (rutile) as a coloring agent was kneaded with a roll to prepare a master bunch with a colorant concentration of 20% by weight, and this was mixed with 1/7 of the above batch to a final concentration of 1.0% by weight. After mixing with JIS K 676i
A cross-linked polyolefin resin hot water supply/discharge transfer pipe was manufactured by extrusion molding a polyethylene pipe with a nominal diameter of 13 defined by the formula and irradiating the liquid pipe with an electron beam so that the gel fraction was approximately 80%.

A short pipe with a length of 50 (2) was cut from the obtained pipe, and after passing chlorine water at 80°C with a chlorine concentration of 1100 pp for 30 days at a flow rate of 101/min, the short pipe was cut into rounds of 20 m in length. Fig. 4 of ASTIID 714-56.
Evaluation was made based on (11 levels: 0 points; no abnormality - 8 points; severe occurrence on the entire surface - 10 points; peeling).

Next, this sample was placed on a fixed plate and compressed to 70% of its diameter using a parallel plate, and in this state, the parallel plate was moved and rotated while the entire outer circumference of the sample was in contact with the fixed plate for 20 minutes. After repeating the test several times, the state of delamination and cracking on the inner surface of the sample was observed and evaluated based on the following criteria.

Layered @ peeling ○; No peeling force ×; Peeling occurred on the entire surface Cracks 0; No cracks were observed △; Cracks occurred in some areas X; Cracks occurred on the entire surface After irradiating for 2000 hours at a blank panel temperature of 83℃, 12 minutes/60 minutes of rain and 48 minutes/60 minutes of no rain, the dumbbells were cut out and the tensile elongation was measured, and the retention rate for the tensile elongation before irradiation was calculated. Weather resistance was evaluated by culturing.

The evaluation results are shown in the table.

Example 2 High-density polyethylene (manufactured by Mitsubishi Yuka Co., Ltd. [Mitsubishi Polyethylene EY
40HJ, density 0.952 g/cm3, MFRl, 5
g/10 min) and tetrakis[methylene-
13772.0% by weight of 1-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, % of dibutyltin dilaurate lfi as a condensation catalyst, and titanium white (rutile) as a coloring agent were mixed by roll. A masterbatch with a colorant concentration of 20% by weight is prepared by kneading, and this is mixed with crosslinkable polyethylene resin (manufactured by Mitsubishi Yuka Co., Ltd. [Linkron H] so that the final colorant concentration is 1.0% by weight.
E707NJ, density 0.945g/α', MFRo, 4
g/10 minutes), extrusion molded a polyethylene pipe with a nominal diameter of 13 as specified in JIS K 6761, and immersed the cough pipe in warm water at 80°C for 10 hours, resulting in a gel fraction of 72%. A cross-linked polyolefin resin feed groove transfer pipe was manufactured and its various properties were evaluated.

Example 3 Ethylene-butene-1 copolymer resin (Mitsubishi Poly J, Chi LL M 4 manufactured by Mitsubishi Yuka Co., Ltd.) was used as a polyolefin resin.
0FJ, butene-1 content 7.5% by weight, density 0.92
2 g/cm3, MFRo, 7 g/10 min) and blended with dicumyl peroxide to achieve a gel fraction of approximately 80%.
A crosslinked polyolefin hot water supply/discharge transfer pipe was produced in the same manner as in Example 1, except that it was crosslinked so that the following properties were evaluated.

Example 4 Same as Example 1 except that the colorant was changed to phthalocyanine blue.
A hot water supply/discharge transfer pipe was manufactured in the same manner as above, and its characteristics were evaluated.

Example 5 Stabilizer was added to poly((6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl)((2,2,6,6- Tetramethyl-4-piperidyl)imino)hexamethylene ((2,2,6,6
-tetramethyl-4-piperidyl)imino)] A hot water supply/discharge transfer pipe was manufactured in the same manner as in Example 1, and its properties were evaluated.

Example 6 A hot water supply/discharge transfer pipe was manufactured in the same manner as in Example 1, except that the stabilizer was similystyl-3,3'-thiodipropionate and the blending amount was changed to 0.022 times. The characteristics of the fibers were evaluated.

Example 7 Stabilizer 4,4'-thio-bis(3-methyl-6-t-
butylphenol) and its blending amount is 0.02% by weight.
A hot water supply/discharge transfer pipe was manufactured in the same manner as in Example 1, except that the material was changed to , and the pipe characteristics were evaluated.

Example 8 Poly((6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-)riazine=2.
4-diyl) ((2,2,6,6-tetramethyl-
4-piperidyl)imino)hexamethylene ((2,2゜6.6-tetramethyl-4-piperidyl)imino)〕0
A hot water supply/discharge transfer pipe was manufactured in the same manner as in Example 1 except that 1% by weight of 1% by weight was used, and the pipe characteristics were evaluated.

Comparative Example 1 The same procedure as Example 1 was carried out except that the colorant was changed to 2.2% by weight of carbon black (furnace black, particle size 20 mμ).

Comparative example 2 The procedure was the same as in Example 1 except that no colorant was blended.

Comparative example 3 The procedure was the same as in Example 3 except that no colorant was added.

Comparative example 4 The procedure was the same as in Example 1 except that no stabilizer was blended.

Claims (1)

[Claims] Azo-based, phthalocyanine-based, threne-based, dyeing lake, quinacridone-based, dioxazine-based, isoisodorinone-based organic pigments, as well as metal oxide-based, chromic acid-molybdic acid-based, sulfide-selenide-based, ferrocyanide-based pigments, 0.02 to 7% by weight of at least one colorant selected from aluminum silicate-based inorganic pigments, and 0.005 to 2% by weight of at least one stabilizer selected from antioxidants and light stabilizers. A hot water supply/discharge pipe characterized by being made of a crosslinked polyolefin resin blended with.