JPS63213542A - Poly-1-butene resin composition for water-hot water supply pipe - Google Patents

Abstract

PURPOSE:To obtain the titled composition, having improved chlorine water resistance and excellent pressure-resistant strength and internal pressure creep durability at high temperatures and suitable as pipes of water supply and hot water supply equipment, by blending a specific amount of one or more compounds of the group of specific hindered phenols. CONSTITUTION:A composition obtained by blending 100pts.wt. poly-1-butene having 0.1-50g/10min melt flow rate with (A) 0.1-1pt.wt., preferably 0.2-0.5pt.wt. one or more kinds of compounds selected from the groups of hindered phenols such as (A1) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydro- xybenzyl)benz ene and (A2) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl) isocyanurate, and (B) 0.01-1pt.wt., preferably 0.05-0.5pt.wt. one or more selected from compounds such as (B1) 2,6-di-tert-butyl-p-cresol.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a poly-1-butene resin composition for water supply and hot water supply piping, which has 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 one of the most suitable resins for water supply and hot water supply pipes because it has excellent pressure resistance, internal pressure creep durability at high temperatures, high and low temperature characteristics, abrasion resistance, and excellent flexibility. It is.

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 present inventors have conducted extensive research to find a poly-1-butene resin composition for water supply and hot water supply that has excellent chlorine water resistance. The results of a chlorine water resistance test of poly-1-butene mixed with resin additives conventionally known as antioxidants and stabilizers revealed that the mechanisms of chlorine water deterioration and the effects of addition varied widely. However, it was discovered that only poly-1-butene blended with a specific compound showed sufficient chlorine water resistance, and the present invention was achieved.

That is, according to the present invention, with respect to 100 parts by weight of poly-1-butene, - (^) 0.1 to 1.01 parts by weight of at least one compound selected from the group of the following hindered phenols, ( a) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)
Benzene (b) 1,3,5-tris(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) Bis(3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid) Nickel salt of 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 comethane, and (B) selected from the group of At least one compound that
．． 01 to 1.0! Parts by weight, (j) 2.8-di-tert-butyl-p-cresol (k
) 4,4°-methylene-bis(2,6-di-tert-butyl-phenol) (1) Tris(2,4-di-tert-butyl-phenyl) phosphite (m) containing vitamin E A poly-1-butene resin composition for water supply/hot water supply piping is provided.

(Function) The compounds (A) and CB) added to poly-1-butene are thought to have different mechanisms of imparting chlorine water resistance, although the reason is unknown.

Table 1 shows test examples for examining the differences in the chlorine water resistance mechanisms of (A) and (B). This test example uses poly-1-butene (MFR 0.8g) manufactured by Mitsui Petrochemical Industries, Ltd.
/10m1n:^STM D 1238N) 100
0.15 parts by weight of calcium stearate and synthetic hydrotalcite (trade name D) IT-4A) per mm part
0.05 parts by weight was blended, and further 0.05 parts by weight of the compounds shown in Table 1 were added.
．． After blending 4 parts by weight, they were mixed in a Henschel mixer and granulated in an extruder of 20 mm diameter.

A 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.
Cut out a test piece of mm x 150 mm, attach the test piece to a holder, and store it at an effective chlorine concentration of 1100 pp and a temperature of 90°C.
of chlorine-containing water was immersed in a container through which water was flowing at Ik per hour, and the gloss (incident light 45°) and [
ηJ (135°C decalin) was measured.

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

Table 1 (Note) A: 1,3,5-trimethyl-2,4,8-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) Honeytris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate (Goodrite 3114) 2:n-octadecyl-3(3,5-di-tert-butyl-
4-Hydroxyphenyl)propione-)-(Irga
nox 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)
-5,5°-dimethyl-diphenylmethane (Nonox
WSP) t:4,4-thio-bis(3-methyl-6-tert-butyl-phenol) (Antage I(c) t: 1,
1.3-Tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)butane (Topanol CA) Tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate comethane (Irganox 1010): 2,6-di-tert-butyl-p-cresol (BIT): 4,4'-methylene-bis(2,6-di-tert-butyl-phenol) (Ionox 220) Onitris (2,4-di-tert-butyl-phenyl) phosphite (Irgaphos 168): As for vitamin E (A), as seen in Table 1, the gloss decreases markedly over time, but [η ] is small over time, and the initial [η] at the time of blending is relatively high, so it is thought that poly-1-butene acts to prevent chlorine water deterioration throughout the entire poly-1-butene. (8) showing such an effect is the above-mentioned (a
) to (i), each with the product name Irgan.
ox1330.5yanox1790, Goodr
ite 3114, Irganox 1076, Irg
astab2002, Nonox WSP, ^n
tage R (:, Topanol CA.

It is known as Irganox 1010.

These amounts are 0.0% per 100 parts by weight of poly-1-butene.
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 part by weight, the tensile yield stress will decrease, and for example, the hydraulic fracture strength of poly-1-butene pipes will decrease. .

As shown in Table 1, for (B), both the gloss and [η] tend to decrease significantly over time;
η] is high. In general, resins partially deteriorate under the conditions during molding, that is, in the presence of oxygen and in a high-temperature atmosphere [η]
However, (B) shows that poly-1 under such conditions
- It is thought that the initial [η] during molding is at a high level because it has the effect of preventing the deterioration of butene. (B) exhibiting such an effect is selected from the above-mentioned (j) to (m), each of which is named BIT or Ion.

x 22Q, Irgaphos 16B, x, -
It is known as zyvitamin E. these are,
Poly-1-butene 100! It is blended in an amount of 0.01 to 0.1 part by weight, particularly preferably 0.05 to 0.5 part by weight. If the blending amount is less than 0.0111 parts by weight, the above-mentioned effect will be small, and if it exceeds 1.0 parts by weight, the above-mentioned (A
), the tensile yield stress decreases.

The compound selected from (A) can improve chlorine water resistance even when used alone, but it is more preferable to use at least one compound selected from each group (A) and (B), especially The combined use of two or more compounds selected from the group (^) can reduce deterioration due to molding, improve the chlorine water resistance of the surface portion, and improve the chlorine water resistance of the entire poly-1-butene. This is particularly preferable because it can be done.

(Description of preferred embodiments) Poly-1-butene in the present invention is a 1-butene homopolymer or a 1-butene homopolymer. -butene and up to 10 mol% of other α-olefins, such as ethylene and/or propylene, 4-methyl-1-pentene, 1-hexene, 1-
It is a copolymer with octene etc. and/or a mixture with 50% by weight or less of other α-olefin polymers, and the melt fluorate (hereinafter referred to as MFR) is usually 0.1 to 50g7
10 min (ASTM D 12311N).

Various known methods can be used to blend (A) and (B) into poly-1-butene. For example, each component may be mixed in a ribbon blender or Henschel mixer and then granulated in an extruder, or directly. Pan Bali mixer, kneader 12
Examples include a method of melt-mixing with a wooden roll or the like and then granulating with an extruder.

The poly-1-butene composition of the present invention may also contain other ultraviolet absorbers, fungicides, rust inhibitors, lubricants, fillers, pigments, dyes, heat stabilizers, etc., as necessary. Good too. Among these, rust inhibitors include metal salts of higher fatty acids and the general formula % (where M is Mg, Ca or Zn, A is an anion other than a hydroxyl group, X% 3' and 2 are positive numbers, a It is preferable to use a composite compound or the like represented by 0 or a positive number, since it is possible to prevent rusting of the molten soil application machine due to catalyst residue.

As a method for molding water supply/hot water supply piping, etc. using the poly-1-butene resin composition for water supply/hot water supply piping of the present invention, for example, a poly-1-butene resin composition containing the various stabilizers described above may be used using an extruder.
An example of a method is to melt butene at a temperature of 150 to 300°C, extrude it through a die, perform sizing, cool it in a cooling water layer with a water temperature of 5 to 50°C, and cut or wind it through a drawing machine. The extruder is generally an axle-type metalinget type screw. 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) The poly-1-butene resin composition of the present invention has improved chlorine water resistance, as well as the inherent compressive strength of poly-1-butene, internal pressure creep durability at high temperatures, high and low temperature characteristics, and Because it also has abrasive properties, it can be widely used for piping in water supply equipment and hot water supply equipment.

(Example) Comparative Examples 1 to 5 Tests similar to those in the Test Examples were conducted using the compounded compounds shown in Table 2 instead of the compounded compounds shown in Table 1. Second result
Shown in the table.

Table 2 (note): 2(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (Tinu
vin 326) Yo:bis(2,2,6,6-tetramethyl-4-piperisily) sebacate (Sanol LS
-770) Ri: Distearylthiodipropionate (DSTDP)
1,3.5-trimethyl-2,4,8-tris(3, 5-di-tert-butyl-
4-hydroxybenzyl)benzene and 4,4'-methylene-bis(2,6-di-tert-butyl-phenol),
The same procedure as in the test example was conducted except that 0.231 parts of each were added.

Gross ratio of the obtained composition) and [η] (dJZ/g
) was as follows.

Claims (1)

[Claims] (1) For 100 parts by weight of poly-1-butene, (A)
0.1 to 1.0 parts by weight of at least one compound selected from the following group of hindered phenols, (a) 1,3,5-trimethyl-2,4,6-tris (
3,5-di-tert-butyl-4-hydroxybenzyl)benzene (b) 1,3,5-tris(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) bis(3, Nickel salt of 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]methane, and (B) at least one compound selected from the following group.
．． 01 to 1.0 parts by weight, (j) 2,6-di-tert-butyl-p-cresol (k)
4,4'-methylene-bis(2,6-di-tert-butyl-
A poly-1-butene resin composition for water supply/hot water supply piping, characterized in that it is blended with (l) tris(2,4-di-tert-butyl-phenyl) phosphite (m) vitamin E.