JPS6342932B2 - - Google Patents

Description

[Detailed description of the invention]

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. Conventionally, metal pipes such as galvanized steel pipes, copper pipes, and lead pipes have been used as piping materials for water supply and hot water supply, but steel pipes may produce red water or black water due to rust, and copper pipes may cause electrolytic corrosion. There are drawbacks such as the generation of pinholes and blue water, and new piping materials are required. 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, etc., and is also excellent in flexibility. 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. In view of the current situation, the present inventors have conducted intensive research to find a poly-1-butene resin composition for water supply and hot water supply piping that has excellent resistance to chlorine water. The results of a chlorine water resistance test by blending known resin additives into poly-1-butene revealed that although the mechanisms of chlorine water deterioration and the effects of addition vary widely, It was discovered that only -1-butene exhibits sufficient chlorine water resistance, and the present invention was achieved. That is, the gist of the present invention is mainly a poly-1-butene resin composition blended with a specific phenolic antioxidant.
For 100 parts by weight of butene, (A) general formula, (In the formula, R is an alkyl group having 1 to 18 carbon atoms or an arylalkyl group) and (B) 0.05 to 1.0 parts by weight of at least one compound represented by the following group of hindered phenols: 0.1 to 1.0 parts by weight of at least one selected compound, (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) Nickel salt of bis(3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid) monoethyl ester (f) 2,2'-dihydroxy-3,3 ′-ji(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-
Tertiary-butyl-4-hydroxyphenyl) propionate] A poly-1-butene resin composition for water supply and hot water supply piping, which is characterized by containing methane, and based on 100 parts by weight of poly-1-butene. , (A) general formula, (In the formula, R is an alkyl group having 1 to 18 carbon atoms or an arylalkyl group.) 0.05 to 1.0 parts by weight of at least one compound represented by (B) selected from the group of hindered phenols shown below. (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) a nickel salt of bis(3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid) monoethyl ester, and (C) at least one member selected from the following group: 0.01 to 1.0 parts by weight of the seed compound, (j) 2,6-di-tert-butyl-p-cresol (k) 4,4'-methylene-bis(2,6-tert-butyl-phenol) (l) ) Tris (2,4-di-tert-butyl-phenyl) phosphite (m) Vitamin E is a poly-1-butene resin composition for water supply and hot water supply piping. In the present invention, poly-1-butene refers to a homopolymer of 1-butene or 10 mol% of 1-butene.
Copolymers with the following other α-olefins, such as ethylene and/or propylene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc. and/or copolymers of other α-olefins of up to 50% by weight. Melt fluorate (MFR) is usually 0.1 to 50g/10min.
(ASTM D 1238N). (A), (B), and (C) added to poly-1-butene are thought to have different mechanisms of chlorine water resistance, although the reason is unknown. Next, Table 1 shows test examples to see the differences in the chlorine water resistance mechanisms of (A), (B), and (C). This test example uses poly-1-butene (MFR0.8g/10min: ASTM D 1238N) manufactured by Mitsui Petrochemical Industries, Ltd.
Calcium stearate 0.15 per 100 parts by weight
Weight parts and synthetic hydrotalcite (product name DHT)
-4A) 0.05 parts by weight was blended, and 0.4 parts by weight of the compounds shown in Table 1 were blended, mixed in a Henschel mixer and granulated in a 20 mmφ extruder. The specific test method involves testing the pellets at
After melting with a hot press at 200℃ for 10 minutes, pressurize with a cooling press at 30℃ for 3 minutes to make a 1mm thick press sheet, and cut out a 10mm x 150mm test piece.
Attach the test piece to the holder and check the effective chlorine concentration.
Gloss (incident light 45°) and [η] (decalin at 135°C) were measured over time by immersing the sample in a container in which chlorine-containing water of 100 ppm and a temperature of 90°C was passed through once per hour. In addition, all glosses immediately after molding are in the range of 90 to 95%.

【table】

[Table] It was hot inside. When (A) is blended with poly-1-butene, as shown in Table 1, even when immersed in chlorine water, the poly-1-butene
- There is little deterioration at the interface between butene and chlorine water, and the degree of decrease in gloss (hereinafter referred to as gloss) is small.
However, since the intrinsic viscosity (hereinafter referred to as [η]) was greatly reduced, it is thought that (A) has the effect of improving the chlorine water resistance of the surface portion of poly-1-butene. Compound (A) exhibiting such an action has the general formula (wherein R is an alkyl group having 1 to 18 carbon atoms or an arylalkyl group), specifically 2,6-
Di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoate and trade name
Examples include n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate known as CyasorbUV-2908. The blending amount of (A) is 0.05 to 1.0 per 100 parts by weight of poly-1-butene.
Parts by weight, particularly preferably 0.1 to 0.5 parts by weight. If the amount is less than 0.05 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), the gloss decreases significantly over time, but the decrease in [η] over time is small, and the initial [η] at the time of blending is also relatively high. It is thought to have the effect of preventing chlorine water deterioration throughout the butene. (B) exhibiting such an effect was selected from the above-mentioned (a) to (i), and the product names were Irganox1330, Syanox1790, and Syanox1790, respectively.
Goodrite3114, Irganox1076, Irgastab2002,
NonoxWSP, AntageRC, TopanolCA,
It is known as Irganox1010. These are added in an amount of 0.1 to 1.0 parts by weight, particularly preferably 0.2 to 0.5 parts by weight, per 100 parts by weight of poly-1-butene. 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. (C) is the gross, [η] as seen in Table 1.
Although many of them show a significant decrease over time, [η] is high at the initial stage of blending. Generally, resins partially deteriorate under conditions during molding, such as the presence of oxygen and a high temperature atmosphere, leading to a decrease in [η], but (C) shows that poly-1-butene deteriorates under these conditions. It is thought that the initial [η] during molding is at a high level because it has the effect of preventing this. Showing this kind of effect (C)
is selected from (j) to (m) mentioned above,
These are BHT or product names respectively.
These are known as Ionox220, Irgaphos168, and Eisai Vitamin E. These are poly-1-
0.01 to 1.0 parts by weight per 100 parts by weight of butene,
Particularly preferred is 0.05 to 0.5 parts by weight.
If the amount is less than 0.01 part by weight, the above-mentioned effect will be small, and if it exceeds 1.0 part by weight, the tensile yield stress will decrease as in the cases of (A) and (B) above. Compounds selected from (A) and (B) can improve chlorine water resistance even when used alone, but (A), (B),
It is more preferable to use two or three compounds selected from each group (C) in combination. In particular, it is particularly preferable to use the three in combination because it 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. Poly-1-butene (A) and (B), or (A), (B)
Various known methods can be used to incorporate and (C). Examples include a method in which each component is mixed in a ribbon blender or a Henschel mixer and then granulated in an extruder, or a method in which the components are directly melt-mixed in a Banbury mixer, kneader, two rolls, etc. and then granulated in 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, metal salts of higher fatty acids and the general formula MxAly(OH) _2x+3y-2z (A) _z・aH ₂ O (where M is Mg, Ca or Zn, and A is other than hydroxyl) are used as rust inhibitors. It is preferable to use a composite compound represented by an anion of , x, y, and z are positive numbers, and a is 0 or a positive number, since rusting of the melt processing machine caused by catalyst residue can be prevented. As a method for molding water supply/hot water supply pipes, etc. using the poly-1-butene resin composition for water supply/hot water supply piping of the present invention, for example, poly-1-butene mixed with the various stabilizers described above is mixed with 150% by extruder. An example is a method in which the material is melted at a temperature of 300° C. to 300° C., extruded through a die, sized, cooled with a layer of cooling water at a temperature of 5° C. to 50° C., and cut or wound through a take-up machine. As the extruder, a single-screw metering type screw can generally be used. Examples of the die include a straight head type, a crosshead type, and an offset type. The sizing method may be a sizing plate method, an outside mandrel method, a sizing box method, or 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. The poly-1-butene resin composition of the present invention has improved chlorine water resistance, and also has the inherent compressive strength of poly-1-butene, internal pressure creep durability at high temperatures, high and low temperature characteristics, abrasion resistance, etc. Therefore, it can be widely used in water supply equipment, hot water supply equipment, etc. Comparative Examples 1 to 5 Tests similar to those in the Test Examples were conducted using the compound compounds shown in Table 2 instead of the compound compounds shown in Table 1. The results are shown in Table 2.

[Table] Examples 1 to 6 Tests were conducted in the same manner as in the test examples, except that 0.2 parts by weight of each of the compounds shown in Table 3 were added instead of the compounds shown in Table 1. The results are shown in Table 3.

[Table] (Note) The symbols of the compounded compounds are the same as those in Table 1. Examples 7 to 15 Same as the test examples except that 0.2 parts by weight of each of the compounds shown in Table 4 was added instead of the compounded compounds shown in Table 1. I went in the same way. The results are shown in Table 4.

[Table] (Note) Symbols of compound compounds are the same as in Table 1.

Claims (1)

[Claims] 1. For 100 parts by weight of poly-1-butene, (A) general formula, (wherein R is an alkyl group having 1 to 18 carbon atoms or an arylalkyl group) and (B) the following hindered phenol group: 0.1 to 1.0 parts by weight of at least one compound selected from (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) Nickel salt of bis(3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid) monoethyl ester (f) 2,2'-dihydroxy-3,3 ′-ji(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-
A poly-1-butene resin composition for water supply and hot water supply piping, characterized in that it contains tert-butyl-4-hydroxyphenyl) propionate (methane). 2 For 100 parts by weight of poly-1-butene, (A) general formula, (In the formula, R is an alkyl group having 1 to 18 carbon atoms or an arylalkyl group.) 0.05 to 1.0 parts by weight of at least one compound represented by (B) selected from the group of hindered phenols shown below. (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) Nickel salt of bis(3,5-di-tert-butyl-4-hydroxybenzoylphosphonic acid) monoethyl ester (f) 2,2'-dihydroxy-3,3 ′-ji(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 (C) 0.01 to 1.0 parts by weight of at least one compound selected from the following group, (j) 2,6-di-tert-butyl-p -Cresol (k) 4,4'-methylene-bis(2,6-di-tert-butyl-phenol) (l) Tris(2,4-di-tert-butyl-phenyl) phosphite (m) Vitamin E A poly-1-butene resin composition for water supply and hot water supply piping, characterized in that it is a poly-1-butene resin composition.