JPS63213543A - Water-hot water supply pipe consisting of poly-1-butene resin - Google Patents

Abstract

PURPOSE:To obtain a water.hot water supply pipe having excellent pressure- resistant strength and chlorine water resistance, by blending poly-1-butene with a specific amount of a specified hindered phenol and molding the resultant blend. CONSTITUTION:100pts.wt. poly-1-butene having 0.1-50g/10min melt flow rate is blended with 0.1-1pt.wt., preferably 0.2-0.5pt.wt. one or more compounds selected from 9 hindered phenols, such as 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert- butyl-4-hydroxybenzyl)benzene and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl- phenyl) isocyanurate, and the resultant blend is molded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention relates to a vibrator for water supply and hot water supply made of poly-1-butene resin having excellent pressure resistance and chlorine water resistance.

(Conventional technology and its problems) Conventionally, galvanized steel pipes,
Metal pipes such as steel pipes and lead pipes are used, but steel pipes have drawbacks such as the formation of red water or black water due to rust, and the formation of pinholes or blue water due to electrolytic corrosion. Materials are needed. In some cases, synthetic resin pipes such as polyvinyl chloride, polyethylene, and poly-1-butene, which do not generate pinholes due to rust or electrolytic corrosion, are already being used. Among them, poly-1-butene is the most suitable resin as a material for vibrators for water supply and hot water supply because it has excellent pressure resistance, internal pressure creep durability at high temperatures, high and low temperature characteristics, abrasion resistance, etc., and is also excellent in flexibility. one of.

However, like other synthetic resins, poly-1-butene, which has these characteristics, undergoes chemical deterioration due to the action of sterilizing chlorine added to tap water, so its original high performance is lost. This effect tends to be particularly large in piping for hot water supply equipment that is subjected to high temperature and high pressure loads.

(Means for Solving the Problems) In view of the current situation, the inventors of the present invention have conducted extensive research to find a vibrator for water supply and hot water supply made of poly-1-butene resin that has excellent resistance to chlorine water. As a result, when a chlorine water resistance test was conducted by adding resin additives conventionally known as antioxidants and stabilizers to poly-1-butene, it was found that certain compounds among hindered phenols were mixed with poly-1-butene. It has been discovered that a vibrator molded by blending with chlorine has excellent chlorine water resistance, and the present invention has been achieved.

That is, according to the present invention, 0.1 to 1.0 parts by weight of at least one compound selected from the following group of hindered phenols is added to 100 parts by weight of poly-1-butene, (a) 1, 3.5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)
Benzene (b) 1,3.5-)-lith(4-tert-butyl-3-
Hydroxy-2,6-dimethylphenyl)isocyanurate (c) Tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate (d) n-octadecyl-3(3,5-di-tert. Butyl-4-hydroxyphenyl) propionate (e) Nickel salt of bis(3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid) monoethyl ester (f) 2,2°-dihydroxy-3,3° -di(α-
methylcyclohexyl)-5,5°-dimethyl-diphenylmethane (g) 4,4-thio-bis(3-methyl-6-tert-butyl-phenol) (h) 1,1,3-tris(2-methyl- 4-Hydroxy-5-tert-butyl-phenyl)butane (i) Tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] A water supply product made by blending and molding comethane. A vibrator for hot water supply is provided.

(Function) The hindered phenols listed above have a small decrease in [η] over time, and the initial [η] at the time of blending is relatively high, so they prevent the entire poly-1-butene from deteriorating due to chlorine water. It is thought that this shows the effect.

(Description of preferred embodiments) Poly-1-butene in the present invention refers to a homopolymer of 1-butene or 1-butene and 10 mol% or less of other α
- copolymers with olefins, such as ethylene and/or propylene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc. and/or mixtures with up to 50% by weight of other α-olefin polymers; The melt fluorate (hereinafter referred to as VFR) is usually 0.1 to 50 g/1.
10 m1n (AST D 1238N).

Furthermore, the hindered phenols used in the present invention are known by the following trade names.

(a) Irganox 1330, (b) 5yan
ox 1790, (c) Goodr i te311
4, (d) Irganox 1076, (e) Ir
gustab 2002, (f) Nonox WSP,
(g) Antage RC, (h) Topanol
CA, (i) Irganox 1010, these are 0.
1 to 1.0 parts by weight, particularly preferably 0.2 to 0.0 parts by weight.
Add 5 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving chlorine aqueous resistance will be small, and if it exceeds 1.0 parts by weight, the tensile yield stress will decrease and the hydraulic rupture strength of the poly-1-butene vibe will decrease.

The above compounds can improve the chlorine water resistance of poly-1-butene, whether used alone or in combination of two or more.

The compound can be blended with poly-1-butene by various known methods, such as mixing each component with a ribbon blender or Henschel mixer and then granulating it with an extruder, or directly using a Pan Bali mixer or kneader. Examples include a method of melt-mixing with a roll or the like and then granulating with an extruder.

Further, during molding, other ultraviolet absorbers, fungicides, rust inhibitors, lubricants, fillers, pigments, dyes, heat stabilizers, etc. may be added as necessary. Among these, rust inhibitors include metal salts of higher fatty acids and compounds with the general formula % (where M is Mg, Ca or Zn, A is an anion other than a hydroxyl group, X% y and 2 are positive numbers, and a is It is preferable to use a composite compound or the like represented by 0 or a positive number because rusting of the melt processing machine caused by catalyst residue can be prevented.

As a method for molding the water/hot water supply vibrator made of the poly-1-butene resin of the present invention, for example, poly-1-butene mixed with the various stabilizers described above is melted at a temperature of 150 to 300°C using an extruder. For example, the material may be extruded through a die, sized, cooled with a layer of cooling water at a temperature of 5 to 50.degree. C., and cut or wound through a take-up machine. As an extruder, a single metal ring type screw can generally be used. Examples of the die include a straight head type, a cross head type, and an offset type. Sizing methods include a sizing plate method, an outside mandrel method, a sizing box method, and an inside mandrel method. Further, the joint pipe or the hot water storage tank is molded using a combination of an ordinary injection molding machine or a blow molding machine and a mold.

(Effects of the Invention) According to the present invention, poly-1-butene contains 0.1 to 1.
By blending a small amount of the above-mentioned specific hindered phenol (0 parts by weight) and molding it, a vibrator for water supply and hot water supply having excellent chlorine water resistance can be obtained. It also has high pressure resistance, internal pressure creep durability at high temperatures, high and low temperature characteristics, and wear resistance, so it can be widely used in piping for water supply equipment and hot water supply equipment.

(Example) Examples 1 to 9 Differences in chlorine water resistance mechanism of the above compounds were tested by the following method, and the results are shown in Table 1.

In this example, poly-1-butene manufactured by Mitsui Petrochemical Industries, Ltd. (MFR 0.8 g/10 m1n: ASTM D 1
0.15 parts by weight of calcium stearate and synthetic hydrotalcite (trade name D) per 100 parts by weight of 238N)
After blending 0.05 parts by weight of HT-4A) and further blending 0.4 parts by weight of the compounds shown in Table 1, the mixture was mixed with a Henschel mixer and granulated with an extruder of 20 mmφ. The specific test method was to melt the pellets in a hot press at a temperature of 200°C for 10 minutes, and then pressurize them in a cooling press at a temperature of 30°C for 3 minutes to produce a press sheet with a thickness of 1 mm.
A test piece of 10 mm x 150 mm was cut out, the test piece was attached to a holder, and the effective chlorine concentration was 1100 pp and the temperature was 9.
Gloss (incident light 45°) and [η] (decalin at 135°C) were measured over time by immersing the sample in a container into which chlorine-containing water at 0°C was being poured at a rate of 1 per hour.

All glosses immediately after molding were within the range of 90 to 95%.

Table 1 (Note) A: 1,3,5-trimethyl-2,4,6-tris (
3,5-di-tert-butyl-4-hydroxybenzyl)benzene (Irganox 1330) Mouth: 1.3.5
-Tris(4-tert-butyl-3-hydroxy-2,6-
dimethylphenyl) isocyanurate (Syanox
1790) Ha: Tris(3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate (Goodrite 3114) 2: n-year-old tadecyl-3(3,5-di-tert-butyl-
4-Hydroxyphenyl)propionate (Irgan
ox 1078) Ho: To the nickel salt of bis(3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid) monoethyl ester (Irgastab 2002): 2,2'-dihydroxy-3,3°-di( α-methylcyclohexyl)
-5,So-dimethyl-diphenylmethane (Nono
x WSP) H: 4,4-thiobis(3-methyl-6-tert-butyl-phenol) (Antage RC) H: 1,1
．． 3-tris(2-methyl-4-hydroxy-5-tertiary
Butyl-phenyl)butane (Topanol C^) Su:tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate comethane (Irganox 1010) Comparative Examples 1 to 5 Table 1 Tests similar to those in Examples were conducted using the compounded compounds shown in Table 2 instead of the compounded compounds shown. Second result
Shown in the table.

Table 2 (note) Nu: 2(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (Tlnu
Sanol LS
-770)

Claims (1)

[Claims] (1) 0.1 to 1.0 parts by weight of at least one compound selected from the group of the following hindered phenols per 100 parts by weight of poly-1-butene, (a) 1, 3, 5
-trimethyl-2,4,6-tris(3,5-di-tertiary
Butyl-4-hydroxybenzyl)benzene (b) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)isocyanurate (c) Tris(3,5-di-tert) 3-butyl-4-hydroxyphenyl)isocyanurate (d) n-octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e) Bis(3,5-di-tert-butyl- Nickel salt of 4-hydroxybenzoylphosphonic acid) monoethyl ester (f) 2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyl-diphenylmethane (g) 4,4 -thio-bis(3-methyl-6-tert-butyl-phenol) (h) 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)butane (i) Tetrakis [ A water supply/hot water supply pipe formed by blending methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane.