JP2007031699A - Highly chlorine water-resistant polyolefin resin and hose for supplying water and hot-water - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly chlorine water-resistant polyolefin resin which can give a hose for suppling water and hot water being remarkably excellent in the chlorine water resistance, excellent in flexibility, durability, bending properties, and anti-kinking property, and a hose for supplying water and hot water having a long life and excellent in processability using the highly chlorine water-resistant polyolefin resin in the innermost layer. <P>SOLUTION: This highly chlorine water-resistant polyolefin resin is prepared by compounding 1-10 wt.% hindered phenol antioxidant into a poly-1-butene resin or a crosslinked polyethylene. This hose for supplying water and hot water has an innermost layer made of the highly chlorine water-resistant polyolefin resin. The chlorine water resistance is remarkably improved by compounding the hindered phenol antioxidant at a high concentration to the poly-1-butene resin or the crosslinked polyethylene. With the hose supplying water and hot water applying the highly chlorine water-resistant polyolefin resin to its innermost layer, sufficient chlorine water resistance and a long life can be obtained even with a relatively thin innermost layer to secure sufficient flexibility, and a hose supplying water and hot water excellent in bending property, anti-kinking property, and processability, and high in product value can be provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a highly chlorinated water-resistant polyolefin resin suitable as a constituent material of the innermost layer of a water and hot water supply hose, and to a water and hot water supply hose having an innermost layer made of the highly chlorinated water-resistant polyolefin resin. Specifically, it has sufficient flexibility as the innermost layer of the hot water supply hot water hose and has excellent chlorine water resistance, so it can provide a hot water hot water supply hose with excellent flexibility, kink resistance, and durability. The present invention relates to a long-life water supply and hot water supply hose provided with a chlorine-based polyolefin resin and an innermost layer made of this highly chlorine-resistant aqueous polyolefin resin.

  Conventionally, as the hot water supply / water supply hose used in system kitchens, vanity tables, toilet storage tanks, heating storage tanks, and other water / hot water supply facilities, the innermost layer (water contact layer) is made of thermoplastic elastomer (TPE). A structure in which a reinforcing layer made of braided organic fibers such as stainless wire, nylon, and polyester is provided thereon, and this reinforcing layer is coated with an outermost layer made of TPE has been widely used. However, TPE has insufficient chlorine water resistance, and due to deterioration due to chlorine water, the market life of such a water supply hot water supply hose has been generally said to be about 5 years.

  Therefore, in recent years, an innermost layer made of a polybutene resin or a crosslinked polyethylene resin having excellent chlorine water resistance is provided, and a polybutene resin layer as an innermost layer, a TPE layer, an organic fiber reinforcing layer, a stainless wire reinforcing layer, and a TPE as an outermost layer. A hot and cold water supply hose having a layered structure has been generally used (Japanese Patent Laid-Open No. 2003-343773).

In addition to such an innermost layer of chlorine-resistant water, the hot water supply hot water hose is required to have flexibility so that it can be easily constructed even in a narrow space and a small minimum bending radius. In other words, when the water supply hot water supply hose is forcibly bent during construction, or when an external force is applied by contact with surrounding members, the hose bends and a kink that flattenes the portion occurs. Sometimes. If kinks occur, the water passage will be blocked, reducing the amount of water flow, and in extreme cases, water flow itself will not be possible. Therefore, it is required to be easy to bend even with a small radius and to be free of kinks so that it can be easily constructed even in a narrow space.
JP 2003-343773 A

  By providing the innermost layer of polybutene resin and cross-linked polyethylene resin, especially polybutene resin, the life could be extended about 3-4 times compared to the one with the TPE layer as the innermost layer. The life of about 20 years cannot be said to be sufficient, and preferably a life equivalent to that of the faucet device body is required.

  As one means for extending the life of the conventional hot water / hot water supply hose, it is conceivable to increase the thickness of the innermost polybutene resin layer or the crosslinked polyethylene resin layer. That is, for example, the thickness of the innermost polybutene resin layer of the conventional water and hot water supply hose is about 0.25 mm. By increasing the thickness of the polybutene resin layer, the polybutene resin layer is completely deteriorated. By earning this time, the life is extended accordingly.

  However, since the polybutene resin and the crosslinked polyethylene resin are harder than other materials constituting the water and hot water supply hose, the flexibility is greatly impaired by increasing the thickness of the polybutene resin layer or the crosslinked polyethylene resin layer. There is. On the other hand, if the polybutene resin layer or the cross-linked polyethylene resin layer is thick, the hose is kinked, the bending radius becomes a large value, and workability is impaired. For this reason, it is the present condition that the lifetime extension by the thickening of a polybutene resin layer or a crosslinked polyethylene resin layer cannot be expected.

  The present invention has been made in view of the above-described conventional circumstances, and has a water supply / hot water hose having extremely excellent chlorine water resistance, excellent flexibility, durability, flexibility, and kink resistance. An object of the present invention is to provide a high chlorine-resistant water-soluble polyolefin resin that can be provided and a long-life water-supplying hot-water supply hose that is provided with the high-chlorine-resistant water-based polyolefin resin in the innermost layer and has excellent workability.

  As a result of intensive studies to solve the above problems, the present inventor has focused on a hindered phenol-based oxidative degradation inhibitor effective for improving the chlorine-resistant water resistance of poly-1-butene resin, and prevented hindered phenol-based oxidative degradation. It was found that the chlorine-resistant water resistance of the poly-1-butene resin or the cross-linked polyethylene resin can be remarkably improved by prescribing the agent at a high concentration, and a long life until water leakage can be achieved.

  The present invention has been achieved based on such knowledge, and the gist thereof is as follows.

[1] A highly chlorinated water-resistant polyolefin resin comprising 1 to 10% by weight of a hindered phenol oxidative degradation inhibitor in a poly-1-butene resin or a crosslinked polyethylene resin.

[2] A highly chlorine-resistant aqueous polyolefin resin according to [1], comprising two or more hindered phenol oxidative degradation inhibitors having different melting points.

[3] In [2], a hindered phenol oxidative degradation inhibitor having a melting point of 100 ° C. or less, a hindered phenol oxidative degradation inhibitor having a melting point of more than 100 ° C. and 200 ° C. or less, and a melting point of more than 200 ° C. A high chlorine-resistant aqueous polyolefin resin comprising a hindered phenol-based oxidative degradation inhibitor at 300 ° C. or lower.

[4] A highly chlorinated water-resistant polyolefin resin according to [1] to [3], which is a polyolefin-based composite resin further containing an elastomer.

[5] A water / hot water supply hose comprising an innermost layer made of the high chlorine-resistant water-based polyolefin resin according to [1] to [4].

[6] In the water supply hot water supply hose according to [5], the innermost layer has a thickness of 0.25 to 4.0 mm.

  According to the present invention, chlorine water resistance can be remarkably improved by blending a hindered phenol-based oxidative degradation inhibitor at a high concentration with poly-1-butene resin or crosslinked polyethylene resin. Therefore, according to the hot water supply hot water hose in which such a high chlorine-resistant water-based polyolefin resin or cross-linked polyethylene resin of the present invention is applied to the innermost layer, the innermost layer having a relatively thin thickness that can ensure sufficient flexibility. Provided is a hot water supply / water supply hose with a high commercial value, which has a sufficient chlorine resistance and a long life, and is excellent in flexibility, kink resistance and workability.

  Hereinafter, embodiments of the highly chlorine-resistant water-based polyolefin resin and the water / hot water supply hose of the present invention will be described in detail.

  First, the highly chlorine-resistant aqueous polyolefin resin of the present invention will be described.

  The high chlorine-resistant water-borne polyolefin resin of the present invention is a poly-1-butene resin or a crosslinked polyethylene resin blended with a hindered phenol-based oxidative degradation inhibitor.

  Examples of the poly-1-butene resin include 1-butene homopolymer, or 1-butene and other α-olefins of 10 mol% or less such as ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1 -Copolymers with at least one monomer such as octene. The poly-1-butene resin is also composed of such 1-butene homopolymer and / or 1-butene / α-olefin copolymer and other α-olefin copolymer and / or copolymer. It may be a mixture. The content of the other α-olefin (co) polymer in this mixture is preferably 50% by weight or less.

  Crosslinked polyethylene resins are those in which active silane groups in the polymer react with water and crosslink to form polyethylene as a fine polymer. As the polyethylene resin, ethylene homopolymer or ethylene and other polymers are used. Examples include α-olefins such as copolymers with at least one monomer such as propylene, 1-butene, 1-hexene and 1-octene. The polyethylene resin may also be a mixture of such an ethylene homopolymer and / or ethylene / α-olefin copolymer and another α-olefin copolymer and / or copolymer. The content of the other α-olefin (co) polymer in this mixture is preferably 50% by weight or less.

  Examples of hindered phenol-based oxidative degradation inhibitors include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t. -Butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,6-hexanediol- Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t- Butylanilino) -1,3,5-triazine, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate And it can be exemplified compounds contain other heating hindered phenol group. As the molecular weight of this compound, those having a number average molecular weight of 500 or more are preferred from the viewpoint of compatibility with the resin.

  The amount of hindered phenol-based oxidative degradation inhibitor is preferably as high as possible from the viewpoint of chlorine water resistance, but basically the oxidative degradation inhibitor can only enter the non-crystalline part of the resin. For this reason, when the amount exceeds the allowable amount, a bloom phenomenon that precipitates on the resin surface occurs. Therefore, the blending amount of the hindered phenol-based oxidative degradation inhibitor is 1 to 10% by weight, preferably 1.0 to 8.0% by weight, based on the poly-1-butene resin or the crosslinked polyethylene resin. If the amount of the hindered phenol-based oxidative degradation inhibitor is less than 1% by weight, the effect of improving the chlorine water resistance is low, and if it exceeds 10% by weight, not only the appearance is impaired due to the occurrence of bloom, but also specified in food standards. May exceed maximum acceptable elution criteria.

  One kind of hindered phenol-based antioxidant may be used alone, or two or more kinds may be used in combination. Since the temperature range that the resin receives, such as the thermal history at the time and the thermal history at the time of blending the oxidation degradation inhibitor, is diverse, it is particularly preferable to use two or more types of hindered phenolic oxidation degradation inhibitors having different melting points. It is preferable to use a mixture of an oxidation deterioration preventing agent having a melting point of 100 ° C. or less, an oxidation deterioration preventing agent having a melting point of more than 100 ° C. and not more than 200 ° C., and an oxidation deterioration preventing agent having a melting point of more than 200 ° C. and not more than 300 ° C. .

  Thus, when using 2 or more types of hindered phenolic oxidative degradation inhibitors, the total blending amount is 1 to 10% by weight based on the poly-1-butene resin or the crosslinked polyethylene resin. What is necessary is just to adjust the compounding quantity of each hindered phenol-type oxidation degradation inhibitor according to the heat | fever history anticipated to the said water supply hot-water supply hose. In general, an oxidation degradation inhibitor having a melting point of 100 ° C. or lower is 0.2 to 4.0% by weight based on the poly-1-butene resin or the crosslinked polyethylene resin, and an oxidation temperature of 100 ° C. or higher and 200 ° C. or lower. The deterioration inhibitor is 0.3 to 4.0% by weight based on the poly-1-butene resin or cross-linked polyethylene resin, and the oxidative deterioration inhibitor having a melting point of more than 200 ° C. and 300 ° C. or less is poly-1-butene resin or cross-linked. It is preferable to mix | blend so that it may become 0.3 to 4.0 weight% with respect to polyethylene resin, and becomes 1 to 10 weight% in total.

  By the way, as described above, as one means for extending the life of the water / hot water supply hose, an increase in the thickness of the innermost polybutene resin layer or the crosslinked polyethylene resin layer can be considered. That is, for example, by increasing the thickness of the polybutene resin layer, it is possible to earn time until the polybutene resin layer is completely deteriorated, thereby extending the life accordingly. However, since the polybutene resin or the crosslinked polyethylene resin is harder than other materials constituting the water supply hot water supply hose, increasing the thickness of the polybutene resin layer or the crosslinked polyethylene resin layer increases the rigidity of the water supply hot water supply hose. There is a drawback that flexibility is greatly impaired. On the other hand, if the polybutene resin layer or the cross-linked polyethylene resin layer is thick, the hose is kinked, the bending radius becomes a large value, and workability is impaired.

  However, by adding an elastomer as a flexibility-imparting agent to a poly-1-butene resin or a crosslinked polyethylene resin to form a polymer alloy, the flexibility can be remarkably improved while suppressing a decrease in chlorine-resistant water resistance, As a result, even if the innermost layer of the water / hot water supply hose is thickened, the flexibility and kink resistance are not impaired, and a long-life water / water supply hose can be provided.

  As the elastomer, ethylene / butene copolymer, EEA (ethylene-vinyl acetate copolymer), EPR (ethylene-propylene copolymer), EPDM (ethylene-propylene-diene terpolymer), ionomer, α- Examples include olefin copolymers, SEBS (styrene-ethylene-butylene-styrene copolymers), halogenated isobutylene-paramethylstyrene copolymers, ethylene-ethyl acrylate copolymers, and mixtures containing these as main components. . These may be used alone or in combination of two or more.

  As the elastomer added to the polybutene resin, in particular, those containing butene as a copolymerization component are excellent in compatibility with the poly-1-butene resin and have a fine alloy structure based on the poly-1-butene resin. Is preferable.

  In addition, as an elastomer to be added to the crosslinked polyethylene resin, in particular, those containing ethylene as a copolymer component are excellent in compatibility with the crosslinked polyethylene resin and obtain a fine alloy structure having the crosslinked polyethylene resin as a base polymer. This is preferable.

  When an elastomer is blended with a poly-1-butene resin or a crosslinked polyethylene resin to form a composite resin, if the elastomer content in the composite resin is too small, the effect of improving flexibility due to the blending of the elastomer can be sufficiently obtained. If the amount of the elastomer is too large, the general elastomer is inferior in chlorine water resistance compared to the poly-1-butene resin or the crosslinked polyethylene resin, so that the chlorine water resistance is impaired. For this reason, it is preferable that the content rate of the elastomer in a composite resin is 20 to 49 weight%, especially 25 to 35 weight%.

  Even when blending a hindered phenol-based oxidative degradation inhibitor with a poly-1-butene resin or a crosslinked polyethylene resin, or when blending an elastomer, a poly-1-butene resin or a crosslinked polyethylene resin and a hindered phenol-based resin are used. In order to mix the oxidative degradation inhibitor uniformly, the poly-1-butene resin or cross-linked polyethylene resin and the elastomer are sufficiently uniform and fine with the poly-1-butene resin or cross-linked polyethylene resin as the base polymer. In order to obtain an alloy structure, the temperature is about 10 to 50 ° C. higher than the melting point of the poly-1-butene resin or cross-linked polyethylene resin using a twin-screw kneading extruder or the like, for example, 210 to 230 for polybutene resin. It is preferable to knead sufficiently uniformly at a temperature of about ° C.

  Other additives may be added to the highly chlorine-resistant water-based polyolefin resin of the present invention as necessary.

  Next, the water / hot water supply hose of the present invention having the innermost layer made of the highly chlorine-resistant water-based polyolefin resin of the present invention will be described with reference to the drawings.

  1 (a) and 1 (b) are perspective views showing an embodiment of a water and hot water supply hose of the present invention.

  1A and 1B includes an inner surface layer 1, a reinforcing layer 2 provided on the inner surface layer 1, and an outer surface layer 3 covering the reinforcing layer 2.

  The inner surface layer 1 has an innermost layer 1A and an outer layer 1B provided on the innermost layer 1A. In the present invention, the innermost layer 1A is formed of the high chlorine resistant water-based polyolefin resin of the present invention.

  If the thickness of the innermost layer 1A is too thin, the chlorine-resistant water resistance is insufficient, and if it is too thick, the flexibility is impaired. Therefore, it is usually preferable to set the thickness to about 0.25 to 4.0 mm.

  The outer layer 1B is usually formed of TPE, preferably olefinic TPE, and has a thickness of about 0.5 to 2.0 mm.

  Although the total thickness of the inner surface layer 1 having a two-layer structure of the innermost layer 1A and the outer layer 1B is appropriately determined according to the purpose of use of the hot water supply / hot water hose, it is generally about 1.0 to 4.5 mm.

  There is no restriction | limiting in particular as a method of forming the inner surface layer 1, A well-known method can be employ | adopted, for example, a two-layer extrusion molding of the inner wall layer of desired thickness to the mandrel as a mandrel using an extrusion molding machine etc. And the like.

  There is no restriction | limiting in particular as a constituent material of the reinforcement layer 2, Although it can select suitably according to the objective, For example, metal hard wires, such as single metals, such as iron, copper, and aluminum, alloys, such as stainless steel, polyethylene Reinforcing yarns made of organic fibers such as terephthalate (PET) fibers, polyethylene naphthalate (PEN) fibers, nylon fibers, and aramid fibers can be used. The reinforcing layer 2 is formed by braiding or spirally winding one of these alone or in combination of two or more to form a braided layer or a spiral layer wound in a pairing direction.

  Although there is no restriction | limiting in particular as the diameter of the metal hard wire which comprises a reinforcement layer, and the fineness of a reinforcement thread | yarn, It is preferable that the wire diameter of a metal hard wire is 0.1-0.5 mm. If the wire diameter of the metal hard wire is less than 0.1 mm, the metal hard wire is likely to bite into the inner surface layer, and the metal hard wire may be broken. On the other hand, if the wire diameter of the metal hard wire exceeds 0.5 mm, it is too thick to form a reinforcing layer.

  The fineness of the organic fiber reinforcing yarn is preferably 1100 to 3300 dtex. When the fineness of the reinforcing yarn is less than 1100 dtex, the strength and durability are insufficient, and when it exceeds 3300 dtex, the appearance may deteriorate due to being too thick.

  As shown in FIG. 1 (a), the reinforcing layer 2 according to the present invention may be composed of one layer of a metal hard wire or a braided layer 2A of reinforcing yarn, but as shown in FIG. 1 (b). Thus, a two-layer structure of an organic fiber reinforcing layer 2B made of a braided layer of organic fiber reinforcing yarn and a metal hard wire reinforcing layer 2C made of a braided layer of metal hard wire is preferable, and in particular, 1100 to 3300 dtex, twisted A reinforcing layer 2 having an organic fiber reinforcing layer 2B braided with reinforcing yarns of several 6 to 15 times / 10 cm, and a metal hard wire reinforcing layer 2C braided with a metal hard wire having a wire diameter of 0.1 to 0.5 mm, Alternatively, a metal wire braided with an organic fiber reinforcing layer 2B in which reinforcing yarns of 1100 to 3300 dtex and 0 to 10 twists / 10 cm are wound spirally and a metal hard wire having a wire diameter of 0.1 to 0.5 mm Preferably, the reinforcing layer 2 has the reinforcing layer 2C. If the reinforcing layer of 2-layer structure, it is possible to obtain sufficient pressure resistance, durability.

  In the case of a two-layer structure, it is preferable in terms of manufacturing and appearance that the organic fiber reinforcing layer 2B is on the inner layer side and the hard metal wire reinforcing layer 2C is on the outer layer side.

  In forming the reinforcing layer 2, an adhesive layer may be interposed as necessary. By providing the adhesive layer, it is possible to prevent the displacement of the reinforcing layer 2 and improve the quality stability of the hose.

  The outer surface layer 3 is usually formed of TPE such as styrene TPE.

  There is no restriction | limiting in particular as a method of forming this outer surface layer 3, A well-known method is employable. For example, the coating can be formed on the reinforcing layer 2 using a known extruder.

  There is no restriction | limiting in particular as thickness of the outer surface layer 3, Although it can select suitably according to the objective, Usually, it is 0.1-2.0 mm, Preferably it is 0.3-1.5 mm.

  Such a water supply hot water supply hose of the present invention is excellent in workability and durability, and is useful as a water supply hot water supply hose for a system kitchen, a bathroom vanity, a toilet, a cleaning toilet seat, a water storage tank for heating, and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Examples 1 and 2 and Comparative Example 1
In a conventional method, a metal layer is braided into a blade structure on the outer peripheral surface of the inner surface layer consisting of the innermost layer and outer layer, and a reinforcing layer is formed. A hose (inner diameter 9 mm) was produced.

The material and dimensions of each part of the hot and cold water supply hose are as follows.
Material of innermost layer: As shown in Table 1. Poly-1-butene resin and hindered pheno
Is a kneading at 220 ° C using a twin screw kneading extruder.
And made into pellets.
Innermost layer thickness: 0.25mm
Outer layer material: Olefinic TPE
Outer layer thickness: 1.0 mm
Reinforcing layer metal hard wire: stainless steel wire (wire diameter 0.29mm)
Material of outer layer: Styrene TPE
External layer thickness: 0.8mm

The obtained water / hot water supply hose was evaluated for chlorine water resistance and flexibility by the following method, and the results are shown in Table 1.
Chlorine resistance: A hose is attached to a chlorine water circulation tester, chlorine concentration is 50 pphm, temperature is 8
Time (day) until the hose leaks at 0 ℃ and flow rate 0.3L / min
Number).
Flexibility: Three-point bending test with 200mm span between rollers at the center of the load cell
Indentation was performed at 500 mm / min, the indentation load was measured, and the value of Comparative Example 1 was 1
Expressed as an index with a value of 00. The smaller this value, the better the flexibility.
To express.

  As is clear from Table 1, the highly chlorine-resistant water-based polyolefin resin of the present invention is remarkably excellent in chlorine-water-resistant water. Therefore, according to the hot-water supply hot water hose using this high-chlorine-resistant water-soluble polyolefin resin as the innermost layer, its life is extended. Can be achieved.

It is a perspective view which shows an example of embodiment of the water supply hot-water supply hose of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Inner surface layer 1A Innermost layer 1B Outer layer 2 Reinforcement layer 2B Organic fiber reinforcement layer 2C Metal hard wire reinforcement layer 3 Outer surface layer

Claims (6)

  A high chlorine-resistant water-based polyolefin resin comprising 1 to 10% by weight of a hindered phenol oxidative degradation inhibitor in a poly-1-butene resin or a crosslinked polyethylene resin.   The high chlorine-resistant water-based polyolefin resin according to claim 1, comprising two or more hindered phenolic oxidative degradation inhibitors having different melting points.   3. The hindered phenol oxidative degradation inhibitor having a melting point of 100 ° C. or lower, a hindered phenol oxidative degradation inhibitor having a melting point of more than 100 ° C. and 200 ° C. or lower, and a melting point of more than 200 ° C. and 300 ° C. or lower. And a hindered phenol-based oxidative degradation inhibitor.   4. The high chlorine-resistant water-based polyolefin resin according to claim 1, which is a polyolefin-based composite resin further containing an elastomer.   A water / hot water supply hose comprising an innermost layer made of the highly chlorine-resistant water-based polyolefin resin according to claim 1.   6. The hot water and hot water supply hose according to claim 5, wherein the innermost layer has a thickness of 0.25 to 4.0 mm.

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