JP2006348243A - Flexible polybutene-based composite resin and hose for feeding hot/cold water - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flexible polybutene composite resin capable of providing a hose for feeding hot/cold water having an utmost inner layer which is excellent in bending properies and the resistance to kinking even when the layer is thick, in addition to its enough resistance against chlorine water as the utmost inner layer of a hose for feeding hot/cold water and also to provide a hose for feeding hot/cold water comprising the flexible polybutene composite resin equipped with the utmost inner layer, which is excellent in life and processability. <P>SOLUTION: The flexible polybutene-based composite resin comprises a poly-1-butene resin and an elastomer. The hose for feeding hot/cold water comprises the utmost inner layer composed of the flexible polybutene composite resin. The flexible polybutene-based composite resin excellent in the resistance against chlorine water and flexibility can be obtained by adding an elastomer as an agent for giving flexibility to the poly-1-butene resin, to thereby form a polymer alloy. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a flexible polybutene-based composite resin suitable as a constituent material of the innermost layer of a water supply / hot water supply hose, and a water supply / hot water supply hose having an innermost layer made of the flexible polybutene-based composite resin. Specifically, it has sufficient chlorine water resistance as the innermost layer of the hot water supply hot water hose and has excellent flexibility, so that it can provide a hot water hot water supply hose excellent in flexibility and kink resistance even when it is thickened. The present invention relates to a long-life water supply and hot water supply hose provided with a conductive polybutene-based composite resin and an innermost layer made of the flexible polybutene-based composite 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. That is, when the water supply hot water supply hose is forcibly bent at the time of construction, or when an external force is applied to the surrounding members, the hose bends and a kink that flattenes the part occurs. There is. 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, the life could be extended by about 3 to 4 times compared to the one having the TPE layer as the innermost layer. It is not sufficient, and preferably a life equivalent to that of the faucet body is required.

  As one means for extending the life of the conventional hot water / hot water supply hose, an increase in the thickness of the innermost polybutene resin layer can be considered. That is, the thickness of the innermost polybutene resin layer of the conventional water and hot water supply hose is about 0.25 cm. By increasing the thickness of this polybutene resin layer, the oxidation degradation inhibitor contained in the polybutene resin layer is increased. The total amount will increase, and the life until the polybutene resin layer will be completely deteriorated can be increased.

  However, since polybutene resin is harder than other materials that make up the water and hot water supply hose, increasing the wall thickness of the polybutene resin layer increases the rigidity of the water and hot water supply hose, and the flexibility is greatly impaired. There is. Further, if the polybutene resin layer is thick, the hose is kinked, and the bending radius becomes a large value. From this point as well, the commercial value is impaired. For this reason, it is the present condition that the lifetime extension by the thickening of the polybutene resin layer cannot be expected.

  The present invention has been made in view of the above-described conventional circumstances, and has sufficient chlorine water resistance as the innermost layer of a water supply hot water supply hose and the like, and also has flexibility even if it is thickened in order to have excellent flexibility. A flexible polybutene composite resin that can provide a water supply and hot water hose with excellent kink resistance, and a long-life and excellent workability hot water supply hose that has this flexible polybutene composite resin placed in the innermost layer For the purpose.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has made the poly-1-butene resin flexible, and in particular, the flexibility of the poly-1-butene resin while minimizing the deterioration in chlorine water resistance. By adding an elastomer as a flexibility-imparting agent to a poly-1-butene resin to make a polymer alloy, the flexibility can be remarkably improved while suppressing a decrease in chlorine-resistant water resistance, As a result, it has been found that even when the innermost layer of the water supply hot water supply hose is thickened, the flexibility and kink resistance are not impaired, and a long-life water supply hot water supply hose can be provided.

The present invention has been achieved based on such knowledge, and the gist thereof is as follows.
[1] A flexible polybutene-based composite resin comprising a poly-1-butene resin and an elastomer.
[2] The flexible polybutene composite resin according to [1], wherein the elastomer content is 49% by weight or less.
[3] The flexible polybutene composite resin according to [2], wherein the elastomer content is 20 to 49% by weight.
[4] A flexible polybutene composite resin according to [3], wherein the elastomer contains butene as a copolymerization component.
[5] A water / hot water supply hose comprising an innermost layer made of the flexible polybutene composite resin according to any one of [1] to [4].
[6] In the water supply hot water supply hose according to [5], the innermost layer has a thickness of 1.0 to 6.0 mm.

  According to the present invention, a flexible polybutene-based composite resin excellent in chlorine water resistance and flexibility is realized by adding an elastomer as a flexibility-imparting agent to a poly-1-butene resin to form a polymer alloy. . Therefore, according to the hot water supply hot water hose in which the flexible polybutene-based composite resin of the present invention is applied to the innermost layer, the innermost layer is made thicker to increase the life, and the flexibility, kink resistance, A water supply hot water supply hose with excellent workability and high commercial value is provided.

  Hereinafter, embodiments of the flexible polybutene-based composite resin and the water / hot water supply hose of the present invention will be described in detail.

  First, the flexible polybutene composite resin of the present invention will be described.

  The flexible polybutene-based composite resin of the present invention is a polymer alloy obtained by adding an elastomer as a flexibility-imparting agent to a poly-1-butene resin.

  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.

  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 an elastomer, in particular, those containing butene as a copolymer component are excellent in compatibility with poly-1-butene resin, and a fine alloy structure based on poly-1-butene resin can be obtained. ,preferable.

  If the elastomer content in the flexible polybutene-based composite resin of the present invention is too small, the effect of improving the flexibility due to the blending of the elastomer cannot be sufficiently obtained. Since it is inferior in chlorine water resistance compared to 1-butene resin, the chlorine water resistance of the flexible polybutene composite resin is impaired. Therefore, the content in the flexible polybutene composite resin is 20 to 49% by weight, particularly 25%. It is preferably ~ 35% by weight.

  Thus, by mix | blending an elastomer with poly-1-butene resin, although a softness | flexibility is improved, the fall of chlorine-resistant water resistance is inevitable. However, by taking a fine alloy structure of the poly-1-butene resin and the elastomer, the island phase of the elastomer is dispersed in the sea phase of the poly-1-butene resin. A dispersion structure of ˜1.0 μm is preferable because it can suppress a decrease in chlorine water resistance due to the blending of the elastomer.

  The poly-1-butene resin and the elastomer are prepared by using a biaxial kneading extruder or the like in order to obtain a sufficiently uniform and fine alloy structure using the poly-1-butene resin as a base polymer. It is preferable to knead sufficiently uniformly at a temperature 10 to 30 ° C. higher than the melting point of the resin, for example, a temperature of about 210 to 230 ° C.

  To such a flexible polybutene-based composite resin of the present invention, additives such as an anti-aging agent and an oxidative deterioration agent may be added as necessary.

  Next, the water / hot water supply hose of the present invention having the innermost layer made of the flexible polybutene composite 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 thereon. In the present invention, the innermost layer 1A is formed of the flexible polybutene composite resin of the present invention.

  The thickness of the innermost layer 1A has conventionally been about 1.5 to 2.5 mm, but according to the present invention, this innermost layer 1A can be obtained by using the flexible polybutene composite resin of the present invention that is excellent in flexibility. The inner layer is a thick layer having a thickness of about 1.0 to 6.0 mm, and the life can be extended. The preferred innermost layer thickness varies depending on the elastomer content of the flexible polybutene composite resin used in the innermost layer, and the elastomer content is relatively large. The flexible polybutene composite resin having a thickness of about 30 to 45% by weight In that case, the chlorine resistance water is reduced by that amount, but the flexibility is good. Therefore, the thickness is increased to about 4.0 to 6.0 mm to ensure the chlorine water resistance, and the elastomer content is relatively small. In the case of a flexible polybutene-based composite resin of about 10 to 30% by weight, the chlorine water resistance is good, but the flexibility is slightly inferior, so the thickness is reduced to about 2.5 to 4.0 mm. Is preferably ensured.

  The outer layer 1B is usually formed of TPE, preferably olefinic TPE, and has a thickness of about 1.0 to 2.0 mm.

  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, but is usually about 2.0 to 7.0 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, it is easy 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 1-4, 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 elastomer are two
Uniform polymer alloy by kneading at 215 ° C using a shaft kneading extruder.
Used as pellets.
Innermost layer thickness: as shown in Table 1 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 resistant water: 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: 3-point bend test with 200mm span between rollers at center with 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 apparent from Table 1, the hot water / hot water hose using the flexible polybutene-based composite resin of the present invention as the innermost layer is improved in flexibility without greatly impairing the chlorine water resistance, and due to its excellent flexibility, Even if the thickness of the innermost layer is increased, the flexibility is not significantly impaired as compared with the conventional product. Therefore, the life can be extended by increasing the thickness of the innermost layer.

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 flexible polybutene-based composite resin comprising a poly-1-butene resin and an elastomer.   The flexible polybutene composite resin according to claim 1, wherein the elastomer content is 49% by weight or less.   The flexible polybutene composite resin according to claim 2, wherein the elastomer content is 20 to 49% by weight.   4. The flexible polybutene composite resin according to claim 3, wherein the elastomer contains butene as a copolymerization component.   A water supply and hot water supply hose comprising an innermost layer made of the flexible polybutene-based composite resin according to any one of claims 1 to 4.   6. The hot water and hot water supply hose according to claim 5, wherein the innermost layer has a thickness of 1.0 to 6.0 mm.

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