JP2000219785A - Host for feedwater and feed hot water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hose for feedwater and feed hot water being excellent in crosslinking characteristics, mechanical strengths, heat distortion resistance, flexibility, hygienic qualities, resistance to an aqueous chlorine solution and productivity as well as being excellent in extrusion moldabitity. SOLUTION: A hose for feedwater and feed hot water comprises forming a resin composition consisting of (i) a base polymer of a substantially linear olefin copolymer consisting of ethylene and at least one member of a 4-12C α-olefin, the compolymer having density of 0.85-0.92 g/cm3, melt index of 0.3-20 g/10 min and the extent of molecular weight distribution of not more than 3, and (ii) a substantially water free carrier polymer A containing an organic unsaturated silane and a free radical generator that a decomposition temperature in order to obtain a half-life period of one min is at least 170 deg.C and not more than 250 deg.C, and an active oxygen content is at least 8%, and (iii) a carrier polymer B containing a silanol condensation catalyst and an antioxidant, melting and mixing the composition at a higher temperature than a crystalline melting point of the base polymer to mold the resulted product, and then bringing the molding into contact with water to crosslink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hose having good heat deformation resistance and excellent workability, hygiene, chlorine water resistance and productivity. Used for piping for hot and cold water supply to water heaters, etc.
The present invention relates to a flexible hose that replaces a hard plastic tube or the like.

[0002]

2. Description of the Related Art Generally, metal pipes such as iron pipes and copper pipes and hard plastic pipes are used for water supply and hot water supply pipes. However, these pipes are hard and require a bending process according to the situation of construction. And In order to reduce the bending process, an ethylene / propylene rubber (EPDM) rubber hose having excellent flexibility and heat resistance is used. However, the work efficiency is poor because vulcanization is required after molding, and the rubber is inferior in colorability, and it is not possible to color light colorful colors in particular. There was a disadvantage of discoloration. In addition, since tap water used for tap water and hot water supply pipes contains free chlorine, the free chlorine causes ethylene propylene rubber (EPDM) to deteriorate and become brittle. As a result, cracks were likely to occur, and there were cases where durability for long-term use was considered to be insufficient. In general, it is known to crosslink a polyolefin with silane in order to improve the durability of the polyolefin against free chlorine water, that is, the resistance to chlorine water and heat deformation. However, silane-crosslinked ethylene / propylene rubber (EPDM) is excellent in chlorine water resistance, but has an odor in contact with water, and has a problem in hygiene. On the other hand, as a conventional simple method of crosslinking a polyolefin, the polyolefin is subjected to a graft reaction with an organic unsaturated silane in the presence of a free radical generator, followed by silane grafting, and then the silane graftomer is reacted in the presence of a silanol condensation catalyst. A so-called silane cross-linking method for cross-linking by contacting with water is generally known. For example,
No. 1711, JP-A-57-49109 and the like. However, this method involves at least two steps. That is, a silane grafting reaction step and a silanol condensation reaction step. Therefore, at least two extrusion steps are required, and an economic problem as an end product cannot be avoided. As a one-step process, there is a mono-seal method. However, this method requires a liquid addition device for injecting the organic unsaturated silane in a liquid state into the extruder, but has problems of slippage and poor measurement. Extruders also require expensive and special types with large L / D to uniformly disperse small amounts of additives.
Economic problems are inevitable. In addition, very high technology is required for extrusion. Further, as a one-step process, a silane crosslinking method in which silane is introduced into a solid carrier polymer is disclosed in JP-A-3-167229. However, in this method, the solid carrier polymer is a porous polymer or EVA, and additives such as a silanol condensation catalyst and an antioxidant are introduced into the solid carrier polymer in addition to the silane and the free radical generator. For this reason, there has been a problem that crosslinking efficiency and storage stability are inferior due to oligomerization by silane condensation or crosslinking inhibition by radical scavenging.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve these problems, and is intended to provide a carrier containing a high concentration of an organic unsaturated silane or the like in a silane crosslink of a polyolefin having excellent flexibility and processability and low odor. A silane-crosslinked polyolefin-based resin composition was formed in one step by using a polymer A and a carrier polymer B containing a silanol condensation catalyst, etc., and was subjected to bending workability, heat deformation resistance, colorability, chlorine water resistance, sanitation, and moldability. Another object of the present invention is to provide a hose for water supply and hot / cold water supply piping having excellent productivity.

[0004]

[Means for Solving the Problems]

According to the present invention, (i) the density is from 0.85 to 0.92
g / cm ³ , melt index (190 ° C., 2.16
kgf) having a molecular weight distribution of 0.3 to 20 g / 10 min and a molecular weight distribution (Mw / Mn) of less than 3, which is substantially linear composed of ethylene and at least one α-olefin having 4 to 12 carbon atoms. A base polymer of an olefin copolymer, and (ii) a general formula RR′SiY ₂ (R is a monovalent olefinically unsaturated hydrocarbon group, Y is a hydrolyzable organic group,
R 'is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon or the same as Y), and the amount of addition is 0.1 to 5% by weight based on the total weight of the polymer. Decomposition temperature to obtain silane and half-life of 1 minute is 170
℃ to 250 ℃, and the amount of active oxygen is 8% or more,
The amount added is 0.01 to 0.5 based on the total weight of the polymer.
A substantially free water-free carrier polymer A containing a free radical generator in an amount of 0.01 to 0.2% by weight, based on the total weight of the polymer; A silane characterized in that a resin composition comprising a carrier polymer B containing a condensation catalyst and an antioxidant is melt-mixed at a temperature higher than the crystal melting point of the base polymer, molded and then contacted with moisture to form a silane. It is a water / hot water supply hose made of cross-linked polyolefin. Preferably, the substantially linear olefin copolymer of the base polymer is produced using a metallocene-based catalyst, and at least one of the α-olefins in the substantially linear olefin copolymer of the base polymer is produced. One is 1
Octene, wherein the carrier polymer A is an ethylene-ethyl acrylate copolymer (EE
A), ethylene-methyl methacrylate copolymer (EM
MA) a hydrogenated block obtained by hydrogenating a block copolymer consisting of at least one polymer block mainly composed of a vinyl aromatic compound and at least one polymer block mainly composed of a conjugated diene compound A carrier selected from the group consisting of copolymers and mixtures thereof, wherein the carrier polymer B is a polymer selected from the group consisting of polyethylene, polypropylene, copolymers of ethylene and α-olefins, and mixtures thereof. A water / hot water supply hose wherein the total amount of the carrier polymer A and the carrier polymer B is 3 to 15% by weight. Further, the water supply and hot water supply hose is JIS C 3200
-7 (water supply equipment-leaching performance test method), in the equipment test at the maximum operating temperature of 95 ° C of the “water supply pipe intended to pass heated water”, the consumption of potassium permanganate was It is a water / hot water supply hose characterized by being at most 10 ppm.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The substantially linear olefin copolymer of the base polymer of the present invention is a copolymer composed of ethylene and at least one or more α-olefins having 4 to 12 carbon atoms, having a specific density and a melt index. And a specific molecular weight distribution. The substantially linear olefin copolymer used in the present invention can be produced by a known metallocene catalyst.
The substantially linear olefin copolymer used in the present invention has a different polymerization catalyst as compared to the conventional one using a Ziegler catalyst or the like, and the properties of the obtained polymer are also compared to those of the conventional one. And it is very different. The characteristics of the substantially linear olefin polymer using the metallocene polymerization catalyst are listed below. Since the polymerization catalyst is super-active, the comonomer α-
The composition of the olefin can be greatly increased as compared with the conventional art, and an elastomeric polymer having high flexibility can be obtained even without a plasticizer. 2. Uniform distribution of comonomer compared to Ziegler-based polymers. 3. Extremely sharp molecular weight distribution compared to Ziegler polymers, extremely low molecular weight components, excellent odor, chlorine water resistance, easy crosslinking, abrasion resistance, mechanical strength, and processability, high quality It is. 4. Despite the sharp molecular weight distribution, when a long-chain branch is introduced, the melt index (I ₁₀ ) at 190 ° C./10 kgf specified by ASTM D1238 and the melt index (I ₂ ) at 190 ° C./2.16 kgf ) And the ratio (I ₁₀ / I ₂ ) is large, and the workability is excellent. 5. Excellent in weather resistance. And so on.

As the α-olefin having 4 to 12 carbon atoms, for example, butene-1, pentene-1, hexene-
1,4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, and the like. As an α-olefin,
1-octene is more preferred. In this case, further improvement in mechanical strength is expected. What is a metallocene catalyst?
It is composed of a cyclopentadienyl derivative of a group metal such as titanium or zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst, but also has a higher molecular weight than a conventional catalyst, for example, a Ziegler catalyst. The distribution is narrow, the distribution of α-olefins having 4 to 12 carbon atoms, which is a comonomer in the copolymer, is uniform, and the catalyst species are uniform. In addition, in the case of an olefin polymer which is a copolymer of ethylene and an α-olefin using a Ziegler catalyst, the above-mentioned melt index ratio (I ₁₀ / I ₂ ) and the molecular weight distribution show a substantially linear proportional relationship. The molecular weight distribution tends to increase as the ratio increases. The molecular weight distribution is about 3 to 10. On the other hand, the molecular weight distribution of the olefin polymer with the metallocene catalyst is 3.0 regardless of the value of the melt index ratio.
And a low molecular weight component is extremely small. Accordingly, the substantially linear olefin copolymer of the base polymer of the water / hot water supply hose of the present invention has low odor, chlorine water resistance, easy crosslinking, mechanical strength, abrasion resistance and workability. Is very good. Measurement of the molecular weight distribution of the linear or substantially linear olefin copolymer: The measurement of the molecular weight distribution of the linear or substantially linear olefin copolymer of the present invention is performed by gel permeation. It is calculated by chromatography (hereinafter GPC). The GPC apparatus and the measuring method are not particularly limited, but the present inventors used the following apparatus and measuring method. 1. Equipment Waters 150C high temperature chromatography Column Laboratories 103, 10
4, 105, and 106 Solvent 1,2,4-trichlorobenzene 4. Measurement temperature 140 ° C 5. Standard Materials Polystyrene Substantially Linear Olefinic Copolymer: A “substantially linear” olefinic copolymer of the base polymer of the present invention is defined as a polymer whose backbone is 100 carbon atoms.
This means that 0.01 long-chain branch per 0 is substituted with 3 long-chain branches per 1000 carbons, and the above melt index ratio (I ₁₀ / I ₂ ) is 5 or more. Large, giving good moldability. As used herein, long chain branching is defined as a chain length of at least about 6 carbons, long chain branching is measured using 13 C nuclear magnetic resonance (NMR) spectroscopy, and the method of Randall (Rev.
Macromol. Chem. Phys. , C29 (2
& 3), and quantify it using 285-297. In contrast, the term "linear" olefin-based copolymer means that the olefin copolymer does not contain long-chain branches. In addition, the substantially linear olefin-based copolymer of the base polymer of the present invention may be used during polymerization in an appropriate constrained geometry catalyst (co-polymer) among metallocene-based catalysts.
nstrainedgeometrycatalyst
s). US Patent 5,026,798
The olefin polymerization catalyst of the monocyclopentadienyl transition metal taught in US Pat. Suitable for use in making certain olefin copolymers. Suitable cocatalysts for use in preparing the substantially linear olefin copolymer of the base polymer of the present invention include, but are not limited to, polymeric or oligomeric aluminoxanes, especially methylaluminoxane , As well as inert,
Includes compounds that show compatibility, do not coordinate, and generate ions. Suitable cocatalysts are non-coordinating inert boron compounds. Polymerization of substantially linear olefin copolymer The polymerization conditions suitable for producing the substantially linear olefin copolymer of the base polymer of the present invention are generally effective in a solution polymerization method. However, the application of the present invention is not limited thereto. Slurry and gas phase polymerization methods are also effective provided appropriate catalysts and polymerization conditions are used. In the preparation of substantially linear olefinic copolymers of the base polymer of the present invention, multiple reactor polymerization methods, such as US Pat. No. 3,914,342
It is also possible to use the polymerization method disclosed in the above document. The reactors can be operated in series or in parallel using at least one constrained geometry catalyst in one of the multiple reactors.

The density of the substantially linear olefin polymer used in the present invention is 0.85 to 0.92 g / cm.
The range is ³ . Those with less than 0.85 g / cm ³ are difficult to produce industrially. If it exceeds 0.92 g / cm ³ , desired flexibility cannot be obtained. The melt index (I ₂ ) of the substantially linear olefin polymer used in the present invention is 0.3 to 20 g / 10 min (190 ° C. /
2.16 kg load). 0.3g / 10mi
If it is less than n, the extrudability will be poor, and if it exceeds 20 g / 10 min, the degree of crosslinking will decrease. In an embodiment of the present invention, another ethylene polymer may be blended with the substantially linear olefin copolymer of the base resin of the present invention. In this case, the ethylene copolymer to be blended may be, for example, a high pressure polymerization method. Low density polyethylene (LDPE), medium density polyethylene (MDPE),
Very Low Density Polyethylene (VLDPE), Linear Low Density Polyethylene (LLDP) Polymerized with Multisite Catalyst
E), a homopolymer type such as high-density polyethylene (HDPE), or one or two of ethylene copolymers obtained by copolymerizing propylene, vinyl acetate, ethyl acrylate and other comonomers with the majority of ethylene.
More than seeds are used.

[0009] The organic unsaturated silane of the present invention is grafted to the base resin so as to be a cross-linking point between the base resins. The organic unsaturated silane used in the present invention is represented by the general formula RR'SiY ₂ (R is a monovalent olefinically unsaturated hydrocarbon group, Y is a hydrolyzable organic group, and R 'is an aliphatic unsaturated hydrocarbon group. Monovalent hydrocarbon groups other than hydrogen or
The same compound as used for Y) is used. It is desirable to use an organic unsaturated silane represented by the general formula RSiY _{3 in} which R ′ is the same as Y, for example, vinyltrimethoxysilane,
Vinyl triethoxy silane, vinyl tributoxy silane, allyl trimethoxy silane, allyl triethoxy silane and the like can be mentioned. The amount of these additives is from 0.1 to 5% by weight, preferably from 0.7 to 3% by weight, based on the total weight of the polymer. If the amount is less than 0.1% by weight, sufficient grafting does not occur, and if the amount exceeds 5% by weight, molding failure occurs and it is not economical.

[0010] The free radical generator of the present invention acts as an initiator of the silane grafting reaction. The free radical generator used in the present invention has a decomposition initiation temperature of 170 ° C. or more and 250 ° C. or less and an active oxygen content of 8% or more for obtaining a half-life of 1 minute. Various organic peroxides whose substances do not generate odor are used.
These organic peroxides include 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane, α, α'-
One or more organic peroxides selected from bis (t-butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, di-t-butylperoxyisophthalate and the like are used. Is done. If the decomposition temperature for obtaining a half-life of 1 minute is less than 170 ° C., the reaction becomes violent and the control becomes difficult. If it exceeds 250 ° C., the reaction does not occur under appropriate conditions. If the amount of active oxygen is less than 8%,
Compared with the same addition amount, the degree of crosslinking is reduced. The amount of these additives is 0.01% based on the total weight of the polymer.
0.5% by weight, preferably 0.015% to 0.2% by weight
It is. If the amount is less than 0.01% by weight, the silane grafting reaction does not proceed sufficiently. If the amount exceeds 0.5% by weight, the extrudability decreases and the molding surface deteriorates.

The carrier polymer A of the present invention can be added by swelling a liquid mixture in which a free radical generator is dissolved in a silane with the liquid mixture of the silane. At this time, in order to add silane at a high concentration, preheating of the carrier polymer A is necessary, but the temperature must be lower than the crystal melting point so that the polymer does not melt. Also, the carrier polymer A must be in solid form and be solid and compatible with the crosslinkable base polymer and silane. Compatible means that the carrier polymer A must not readily react with the silane and must be dispersible or soluble in the base polymer. Suitable carrier polymers A are non-hygroscopic. That is, it is preferred that the water absorption be relatively slow to minimize the potential for premature hydrolysis and condensation of the silane. In any case, the carrier polymer A should be substantially free of water. The carrier polymer A of the present invention comprises granules,
Alternatively, granules are usually in the form of pellets, the preferred form being pellets. Examples of the carrier polymer A used in the present invention include an ethylene-ethyl acrylate copolymer (EEA), an ethylene-methyl methacrylate copolymer (EMMA), and a polymer block mainly composed of at least one vinyl aromatic compound. When,
A hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block mainly composed of at least one conjugated diene compound, for example, a hydrogenated styrene-isoprene block copolymer (SEPS), Styrene-
Butadiene block copolymer (SEBS), and mixtures thereof.

The carrier polymer B of the present invention can be added by kneading and granulating a silanol condensation catalyst, an antioxidant and the like. Also, the carrier polymer B must be in particulate form and a solid compatible with the base polymer to be crosslinked. The carrier polymer B of the present invention is usually in the form of granules or granules in the form of pellets, the preferred form being pellets. Examples of the carrier polymer B used in the present invention include polyethylene, polypropylene, a copolymer of ethylene and an α-olefin, and examples of the α-olefin include C3 to C12.
For example, propylene, butene-1, pentene-1, octene-1, 4-methylpentene-1, 4-methylhexene-1, 4,4-dimethylpentene-1, nonene-1,
Decene-1, undecene-1, dodecene-1, etc.
And mixtures thereof.

The silanol condensation catalyst of the present invention includes dibutyltin dilaurate, dioctyltin dilaurate, stannous acetate, dibutyltin diacetate, dibutyltin dioctoate, lead naphthenate, zinc caprylate, cobalt naphthenate, and tetrabutyl titanate. Examples include organic metal compounds such as esters, lead stearate, zinc stearate, cadmium stearate, barium stearate, and calcium stearate. The amount of these additives is 0.01 to 0.2% by weight based on the total weight of the polymer,
Preferably it is 0.02 to 0.1% by weight. If it is less than 0.01% by weight, a sufficient crosslinking reaction does not proceed, and 0.2% by weight
If it exceeds 300, the crosslinking is locally advanced in the extruder at the time of extrusion, and the appearance is significantly deteriorated. Also, a silanol condensation catalyst must be added to the carrier polymer B. This is because the addition to the carrier polymer A promotes oligomerization by condensation of silane and causes deterioration in appearance.

The antioxidant of the present invention is generally used when processing a polyolefin and is not particularly limited, but must be added to the carrier polymer B. This is because the addition to the carrier polymer A inhibits crosslinking by scavenging radicals. Even when other additives are added, additives that may inhibit crosslinking must be added to the carrier polymer B.

The added amount of the carrier polymer is such that the total amount of the carrier polymer A and the carrier polymer B is in the range of 2 to 15% by weight. If it is less than 2% by weight, sufficient grafting does not occur, and if it exceeds 15% by weight, molding failure occurs and it becomes uneconomical.

As other additives, if desired, commonly used additives such as neutralizers, ultraviolet absorbers, antistatic agents, pigments, dispersants, thickeners, metal deterioration inhibitors, fungicides, A flow regulator, other inorganic fillers, or the like, or other synthetic resins can also be contained.

The water supply hot water supply hose of the present invention is JIS C
Potassium permanganate consumption in an appliance test at a maximum operating temperature of 95 ° C for a "water supply pipe intended to allow heated water to pass through" specified in 3200-7 (Utility equipment-Test method for leaching performance) Is preferably 10 ppm or less. If it exceeds 10 ppm, it cannot be used as a water supply hot water supply hose.

[0018]

Embodiments will be described below with reference to embodiments. << Production of Carrier Polymer A >> According to the compounding ratio as shown in Table 1, first, the carrier polymer A is charged into a super mixer, stirred and mixed, and preheated to 80 ° C. Next, a liquid mixture in which a free radical generator was dissolved in an unsaturated silane was charged into a supermixer and impregnated with the carrier polymer A for 10 minutes while stirring. << Production of Carrier Polymer B >> The carrier polymer B, a silanol condensation catalyst, an antioxidant, and the like were kneaded and granulated according to the compounding ratio shown in Table 2 using a pressure kneader.

* Raw materials used (1) EEA: ethylene-ethyl acrylate copolymer (E
(A content: 23% by weight) (2) SEPS: hydrogenated styrene-isoprene block copolymer (styrene content: 30% by weight) (3) L-LDPE (1): linear low-density polyethylene (density: 0.924 g) (4) VTMOS: vinyltrimethoxysilane (5) Organic peroxide (1): α, α'-bis (t-butylperoxy-m-isopropyl) benzene (1) Decomposition temperature to obtain a half-life of 1 minute; 175.4 ° C, active oxygen content; 9.4
(6) Organic peroxide (2): 2,5-dimethyl-2,5-
Di (t-butylperoxy) hexane (decomposition temperature for obtaining a half-life of 1 minute; 179.8 ° C., amount of active oxygen; 11.02
%) (7) Organic peroxide (3): dicumyl peroxide (1
Decomposition temperature for obtaining a half-life of 1 minute; 175.2 ° C, active oxygen content: 5.92%) (8) LDPE (1): low-density polyethylene (density; 0.925)
g / cm3, MI; 1.5 g / 10 min) (9) PP: polypropylene (homopolymer, MI (230 ゜)
(C); 2.0 g / 10 min) (10) DOTDL: dioctyltin dilaurate (11) Antioxidant: phenolic antioxidant / Irganox 1010 (manufactured by Ciba Geigy) (12) Lubricant: low molecular weight polyethylene / sun wax 171
P (manufactured by Sanyo Chemical Industries, Ltd.) (13) Ethylene / 1-octene copolymer (1): a substantially linear ethylene / 1-octene copolymer (density) produced by a continuous polymerization method using a constrained geometric catalyst ; 0.910 g / c
^{m 3, MI; 3.5g / 10min} , Mw / Mn; about 2) (14) Ethylene / 1-octene copolymer (2): ethylene substantially linear prepared in a continuous polymerization process using a constrained geometry catalyst / 1-octene copolymer (density; 0.868 g / c
m ³ , MI; 0.5 g / 10 min, Mw / Mn; about 2) (15) Ethylene / 1-octene copolymer (3): substantially linear ethylene produced by a continuous polymerization method using a constrained geometric catalyst. / 1-octene copolymer (density; 0.880 g / c
m ³ , MI; 18 g / 10 min, Mw / Mn; about 2) (16) LDPE (2): low-density polyethylene (density; 0.91
(9 g / cm3, MI; 2.0 g / 10 min) (17) Ethylene / 1-octene copolymer (4): A substantially linear ethylene / 1-octene copolymer produced by a continuous polymerization method using a constrained geometric catalyst ( Density: 0.935g / c
^{m 3, MI; 2.5g / 10min} , Mw / Mn; about 2) (18) Ethylene / 1-octene copolymer (5): ethylene substantially linear prepared in a continuous polymerization process using a constrained geometry catalyst / 1-octene copolymer (density; 0.868 g / c
m ³ , MI; 0.2 g / 10 min, Mw / Mn; about 2) (19) Ethylene / 1-octene copolymer (6): substantially linear ethylene produced by a continuous polymerization method using a constrained geometric catalyst. / 1-octene copolymer (density; 0.885 g / c
^{m 3, MI; 30g / 10min} , Mw / Mn; about 2) (20) Ethylene / propene elastomer (1): linear ethylene / propene elastomer (density; 0.867g / cm ^3, M
I; 0.4 g / 10 min, Mw / Mn; about 2)

* Evaluation method (21) Impregnation of silane: The impregnation when the VTMOS / DCP liquid mixture was heated and stirred with a super mixer was evaluated. ○: good impregnation, ×: impregnable (22) Tape extrusion appearance: 50mmφ extruder 120-150-170-180-170 ℃ L / D: 20 Compression ratio 3.5 Tape die: width 100mm Rip interval 1mmt Evaluation: ○> The order of △> × was set, and the level of ○ was judged as acceptable. (23) Gel fraction (%): 120 ° C., 20 hours, xylene immersion method (24) Tensile strength (MPa) and elongation (%): JIS K 6760
by. (25) Heat deformation ratio (%): According to JIS K 6723. (26) Shore D hardness (-): According to ASTM D-2240. (27) Tube extrusion appearance: 50mmφ extruder 120-150-170-180-170 ℃ L / D: 20 Compression ratio 3.5 Tube die: Outer diameter 15mm Inner diameter 1
2mm Evaluation: ○>△> ×, and the level of ○ was accepted. (28) Odor and taste (-): JIS K 3200-7 Water pipe for passing heated water (maximum operating temperature 95 ° C)
According to the instrument test. (29) Potassium permanganate consumption (mg / l): JIS K
3200-7 Apparatus test for water supply pipes (maximum operating temperature 95 ° C) for passing heated water. (30) Chlorine resistance (-): The extruded tube was immersed in a test solution containing 200 ppm of free chlorine at 80 ° C for 4 days according to JIS K 6258, and abnormalities such as cracks occurred on the inner surface of the extruded tube. Check for any. The polyolefin base polymer and the obtained carrier polymers A and B were mixed in the ratios in Tables 3 to 7, and the tape and the tube were extruded using an extruder,
Further, a cross-linking treatment was performed by immersion in warm water.
The extruded tape was used to evaluate the gel fraction, tensile strength, elongation, heat deformation rate and Shore D hardness. Using this extruded tube, the odor and taste, the dissolution of potassium permanganate consumption and the chlorine resistance were evaluated. An aqueous evaluation was performed.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

As is clear from the table, Examples 1, 2 and
The materials shown in Nos. 3 and 4 have good extrusion processability and show very excellent crosslinking properties, mechanical strength, heat deformation resistance, flexibility, hygiene, and chlorine water resistance. On the other hand, all of the comparative examples do not have the balance of extrudability, cross-linking properties, mechanical strength, heat deformation resistance, flexibility, hygiene, and chlorine water resistance.

[0029]

According to the present invention, excellent extrudability, cross-linking properties, mechanical strength, heat deformation resistance, flexibility, hygiene,
A water / hot water supply hose excellent in chlorine water resistance and productivity can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/14 C08K 5/14 5/5425 C08L 23/06 C08L 23/06 23/12 23/12 53 / 02 53/02 F16L 11/04 F16L 11/04 C08K 5/54 D // B29K 23:00 105: 24 B29L 23:00 (72) Inventor Kenji Kasai 29 Higashigawara, Awa-cho, Awa-gun, Awa-gun, Tokushima Pref. F-term in rubber Tokushima Awa factory (reference) AA08 AA10 AA11 AA13E AB03 AG08 AH01 AH49 AH51 KA01 KA17 KF01 KF02 KK01 4J002 BB03Y BB035 BB05W BB05Y BB055 BB065 BB07X BB075 BB12Y BB15Y BB155 BP01X EG0237 EX016 EX036 EZ048 FD010 FD050 FD079 FD090 FD100 FD180 FD200 FD330 GM00

Claims (7)

[Claims] (I) a density of 0.85 to 0.92 g / c;
m ³ , melt index (190 ° C., 2.16 kg
f) is 0.3 to 20 g / 10 min, and the molecular weight distribution (Mw
/ Mn) is less than 3, a substantially linear olefin copolymer base polymer comprising ethylene and at least one α-olefin having 4 to 12 carbon atoms;
(ii) Formula RR′SiY ₂ (R is a monovalent olefinically unsaturated hydrocarbon group, Y is a hydrolyzable organic group, R ′ is a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon, or Y
The organic unsaturated silane having an addition amount of 0.1 to 5% by weight based on the total weight of the polymer, and a decomposition temperature of 170 ° C. or higher for obtaining a half life of 1 minute 2
Presence of substantially water containing a free radical generator at a temperature of 50 ° C. or less, an amount of active oxygen of 8% or more, and an addition amount of 0.01 to 0.5% by weight based on the total weight of the polymer. A resin composition comprising a carrier polymer A not containing, and (iii) a carrier polymer B containing a silanol condensation catalyst having an addition amount of 0.01 to 0.2% by weight based on the total weight of the polymer and an antioxidant. Is melt-mixed at a temperature higher than the crystal melting point of the base polymer, molded, and then brought into contact with moisture to crosslink the silane-crosslinked polyolefin water / hot water supply hose. 2. The hot and cold water supply hose according to claim 1, wherein the substantially linear olefin copolymer of the base polymer is produced by using a metallocene catalyst. 3. The hose for hot and cold water supply according to claim 1, wherein at least one of the α-olefins in the substantially linear olefin copolymer of the base polymer is 1-octene. 4. A polymer block mainly comprising an ethylene-ethyl acrylate copolymer (EEA), an ethylene-methyl methacrylate copolymer (EMMA), at least one vinyl aromatic compound, and at least one polymer block. 4. The water supply according to claim 1, wherein the water is selected from the group consisting of a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block mainly composed of two conjugated diene compounds and a mixture thereof. Hot water supply hose. 5. The method according to claim 1, wherein the carrier polymer B is selected from the group consisting of polyethylene, polypropylene, a copolymer of ethylene and α-olefin, and a mixture thereof.
Or the hose for hot and cold water supply described in 4. 6. The method according to claim 1, wherein the total amount of the carrier polymer A and the carrier polymer B is 3 to 15% by weight.
4. The water supply and hot water supply hose according to 4 or 5. 7. The water supply / hot water supply hose according to claim 1, which has a potassium permanganate consumption of 10 ppm in an appliance test at a maximum operating temperature of 95 ° C. according to JIS C 3200-7. A water / hot water supply hose characterized by the following.