WO2017078124A1

WO2017078124A1 - Fiber composite hose

Info

Publication number: WO2017078124A1
Application number: PCT/JP2016/082758
Authority: WO
Inventors: 直也木村; 智至長谷川; 博朗藤田
Original assignee: クラレプラスチックス株式会社
Priority date: 2015-11-05
Filing date: 2016-11-04
Publication date: 2017-05-11
Also published as: JPWO2017078124A1; JP6724284B2

Abstract

[Problem] To decrease fluid pressure loss and decrease reduction of fluid flow by the hose inner surface having specific shapes of protrusions and recesses. Also, for weight reduction, to make the specific gravity of the thermoplastic resin configuring the hose to be 1.0 or less. To make the hose to have pressure resistance performance, abrasion resistance and durability. [Solution] A fiber composite hose that is obtained, in order from the hose inner circumferential surface, from a soft resin layer (A)/reinforcing fiber layer (B)/outer surface resin layer (C)/reinforcing hard core (D), and that satisfies all of conditions (1)-(3) below. (1) When expanded in the longitudinal direction of the hose, 5 mm ≤ X ≤ 25 mm when the repeating unit of the apices of the inner protrusions is X (mm). (2) When the depth of the depressions between the hose inner protrusions is Z (mm) and the hose internal diameter is ID (mm), 0.003 ≤ Z/ID ≤ 0.05. (3) The specific gravity of the thermoplastic resins forming the soft resin layer (A) and the outer surface resin layer (C) is 1.0 or less.

Description

Fiber composite hose

The present invention relates to a lightweight fiber composite hose having a specific uneven shape on the inner surface.
Since the fiber composite hose of the present invention has a small fluid pressure loss, the fluid composite hose has a feature that there is little decrease in fluid flow rate. That is, when the fiber composite hose of the present invention is used by being connected to a pump, for example, it is not necessary to waste energy and costs such as increasing the source pressure of the pump or increasing the capacity of the pump itself. There are advantages.

Fiber composite hoses have many features such as excellent pressure resistance, wear resistance, and durability, so they are widely used in civil engineering, construction, agriculture, etc. As a hose for supplying and discharging fluids such as these, techniques for further improving wear resistance and durability have been studied.
In particular, in the fields of civil engineering, construction work, and agriculture, transportation by suction of fluids using a high-pressure pump is common, which reduces energy consumption during use and reduces the size and specifications of equipment such as pumps. There is a strong demand. At the same time, in order to reduce the construction days and labor costs, it is required that the hose is lighter and has better operability.
For example, Patent Document 1 discloses a wear-resistant composite hose using a specific rubber material on its inner surface as a hose used for applications requiring pressure resistance and wear resistance, such as for civil engineering. When the hose is connected to a high-pressure pump, it is not satisfactory in terms of fluid pressure loss, and a material having a specific gravity greater than 1 such as polyvinyl chloride is used for the soft resin layer constituting the hose. Therefore, there is a problem that the weight of the hose increases and the operability of the hose is inferior.
Patent Document 2 discloses a flexible pressure-resistant / wear-resistant hose that uses a wear-resistant thermoplastic elastomer on the inner surface of the hose, and the inner surface is substantially flat. Furthermore, Patent Document 3 discloses that a thermoplastic polymer composition having wear resistance comparable to that of a polyurethane-based thermoplastic elastomer or a polyester-based thermoplastic elastomer is obtained, and molding processing is performed from this thermoplastic polymer composition by extrusion molding or the like. The technology to do is disclosed.
However, these hoses can achieve weight reduction by using a thermoplastic elastomer as a tube material, but when the hose is connected to a high pressure pump, the pressure loss of the fluid reaches a desired level. There is room for improvement.
Furthermore, Patent Document 4 is mainly related to a duct hose for air conditioning. Like Patent Document 2, the presence of an uneven state in the pipe is an undesirable element from the viewpoint of pressure loss. Discloses a technique of a flexible tube material in which there is almost no unevenness.
However, even if the duct hose technology for air conditioning where the inside of the pipe is almost flat and there is almost no unevenness in the pipe is applied to the fiber composite hose, the fluid is not used when the hose is connected to a high-pressure pump. This is not satisfactory in terms of pressure loss, and there is room for improvement.

Japanese Patent No. 3104962 JP 2010-144808 A Japanese Patent No. 5736529 JP 2014-129838 A

The object of the present invention is to effectively reduce the pressure loss of the fluid without losing the excellent characteristics inherent to the fiber composite hose, in particular, pressure resistance performance, wear resistance, durability, and light weight. It is to provide a fiber composite hose excellent in workability.

As a result of intensive studies to achieve the above object, the present inventors, in order, from the inner peripheral surface of the hose, the soft resin layer (A) / the reinforcing fiber layer (B) / the outer surface resin layer (C) / the reinforced hard core material ( It was found that a fiber composite hose consisting of D) and satisfying a specific structure can reduce the pressure loss of the fluid, thereby completing the present invention.
Furthermore, the required weight reduction of the fiber composite hose was achieved by making specific gravity of the thermoplastic resin which forms a soft resin layer (A) and an outer surface resin layer (C) into 1.0 or less.

That is, the present invention comprises, in order from the inner peripheral surface of the hose, a soft resin layer (A) / reinforcing fiber layer (B) / outer surface resin layer (C) / reinforced hard core material (D). It is a fiber composite hose that satisfies all the conditions of 3).
(1) When deployed in the length direction of the hose, when X (mm) is the repeating unit of the convex portion on the inner side, 5 mm ≦ X ≦ 25 mm,
(2) When the depth of the recess between the convex portions inside the hose is Z (mm) and the inner diameter of the hose is ID (mm), 0.003 ≦ Z / ID ≦ 0.05,
(3) The specific gravity of each thermoplastic resin forming the soft resin layer (A) and the outer resin layer (C) is 1.0 or less.

In the present invention, the soft resin layer (A) is preferably an addition polymer (P) having an aromatic vinyl polymer block and a (hydrogenated) conjugated diene polymer block, an olefinic thermoplastic resin and / or an acrylic. It is said fiber composite hose characterized by containing a type | system | group polymer (Q) and a softening agent (R) in the following weight ranges.
20 ≦ (P) ≦ 80
0 ≦ (Q) ≦ 50
0 ≦ (R) ≦ 50
And (P) + (Q) + (R) = 100

Furthermore, this invention contains said fiber composite hose which is a laminated structure which consists of an above-mentioned soft resin layer (A) and another thermoplastic resin layer (A ') in order from the internal peripheral surface of a hose as a preferable form. .

More preferably, the reinforcing hard core material (D) is made of polypropylene resin or polyethylene resin, and when the length between the reinforcing hard core materials (D) is Y (mm), the repeating unit X ( mm), the above fiber composite hose satisfying 0.90 ≦ X / Y ≦ 1.10.

Since the fiber composite hose of the present invention has a specific uneven shape on the inner surface, the pressure loss of the fluid can be reduced and the decrease in the flow rate of the fluid can be reduced. It is possible to eliminate the need to waste energy and costs, such as increasing the source pressure of the pump or increasing the capacity of the pump itself. At the same time, the conventional inner surface layer is a mixture containing a hydrogenated polystyrene-based thermoplastic elastomer and a polyolefin-based resin, a wear-resistant thermoplastic elastomer such as a polyurethane-based thermoplastic elastomer, a polyamide-based elastomer, or an acrylonitrile butadiene rubber copolymer. It is possible to achieve both wear resistance, durability and light weight as compared with a hose made of a rubber material.

FIG. 1 shows an overall view and a partial schematic sectional view of a fiber composite hose representing an embodiment of the present invention. As shown in FIG. 1 (enlarged sectional view 2), the fiber composite hose of the present invention has a soft resin layer (A), a reinforcing fiber layer (B), an outer surface resin layer (C), and a reinforced hard core material in order from the inner peripheral surface. It is a laminated molded body made of (D). Hereinafter, the soft resin layer (A) to the reinforced hard core material (D) and the uneven shape inside the hose will be described in detail.

[Uneven shape inside hose]
The fiber composite hose of the present invention satisfies the following conditions (1) and (2) when deployed in the length direction.
(1) When deployed in the length direction of the hose, when X (mm) is the repeating unit of the convex portion on the inner side, 5 mm ≦ X ≦ 25 mm.
(2) When the depth of the depression between the convex portions inside the hose is Z (mm) and the inner diameter of the hose is ID (mm), 0.003 ≦ Z / ID ≦ 0.05.

It is important that the repeating unit X (mm) of the inner convex portion apex is configured at equal intervals of 5 mm ≦ X ≦ 25 mm. And the repeating unit X (mm) of the convex portion apex on the inner side can take an appropriate value in the above-described range depending on the size of the hose inner diameter ID (mm). For example, when the hose inner diameter ID (mm) is 25 mm, the repeat unit X (mm) is preferably in the range of 5 to 8 mm, and when 50 h, the repeat unit X (mm) is preferably in the range of 9 to 12 mm, and 75 mm. Then, the repeating unit X (mm) is preferably in the range of 11 to 14 mm, the repeating unit X (mm) is preferably 14 to 18 mm if it is 100 mm, and the repeating unit X (mm) is 22 to 25 mm if it is 200 mm. Is preferred.
Further, when the repeating unit X (mm) at the apex of the inner convex portion is less than 5 mm or exceeds 25 mm, the pressure loss of the fluid increases.

The repeating unit X (mm) of the convex part on the inside is the cross-sectional shape of the hose deployed in the length direction, observed with a microscope with a magnification of 8 times or more or a magnifying loupe, and the distance between the convex vertices It can be obtained by a measuring method.

Next, the depth Z (mm) of the recess between the convex portions on the inner side of the hose is in the range of 0.003 ≦ Z / ID ≦ 0.05 when the inner diameter of the hose is ID (mm).
In the fiber composite hose in which the depth Z (mm) of the depression between the convex portions inside the hose is in this range, the pressure loss of the fluid becomes small.
However, if the relationship between the depth Z (mm) of the dent and the hose inner diameter ID (mm) is less than 0.003, the inner surface is almost flat even when touched and observed inside the tube with a fingertip. Is not suitable because the pressure loss of the fluid increases and the resistance when flowing the fluid increases. In addition, when the relationship between the depth Z (mm) of the dent and the hose inner diameter ID (mm) is greater than 0.05, the pressure loss of the fluid increases, and the resistance when flowing the fluid increases. Not.
The relationship Z / ID between the recess depth Z (mm) and the hose inner diameter ID (mm) is preferably in the range of 0.003 to 0.03, and more preferably in the range of 0.005 to 0.03. Is more preferred.

The depth Z (mm) of the recess between the convex portions on the inner side of the hose was obtained by observing the cross-sectional shape of the hose developed in the length direction with a microscope having a magnification of 10 times and connecting the apexes of three or more convex portions. It can be determined by measuring the distance between the line and the line connecting the deepest points of two or more recesses.
In addition, the inner diameter ID (mm) of the hose is a value obtained by inserting a taper gauge having a minimum graduation of 0.1 mm into the hose (the distance between the convex portions facing each other on the inner surface of the hose), and the depth Z ( mm) and adding a value twice as large.

[Specific gravity of thermoplastic resin]
The thermoplastic resin forming the soft resin layer (A) and the outer resin layer (C) constituting the fiber composite hose of the present invention has a specific gravity of 1.0 or less.

The specific gravity of the thermoplastic resin can be determined in accordance with Method A (water displacement method) of JIS K7112 (“Plastics—Method for Measuring Density and Specific Gravity of Non-foamed Plastic”).

The relationship between the repeating unit X (mm) at the apex of the inner convex portion and the length Y (mm) between the reinforcing hard core material (D) is preferably in the range of 0.90 ≦ X / Y ≦ 1.10. . The value of X / Y is more preferably in the range of 0.93 to 1.07, and more preferably in the range of 0.95 to 1.05 from the viewpoints of flexibility, radial strength, pressure resistance, etc. of the hose. Most preferably. If the value of X / Y is less than 0.90 or exceeds 1.10, the pressure loss of the fluid increases, and the resistance when flowing the fluid increases.
The length Y (mm) between the reinforced hard core materials (D) was measured with calipers having a minimum scale of 0.05 mm, and the value of the length of 10 reinforced hard core materials continuous on the outer surface of the hose. It can be obtained by dividing by the number of 10.

[Soft resin layer (A)]
The soft resin layer (A) of the present invention has a Shore A hardness of 40 to 90 in accordance with JIS K6253 (“Method of testing hardness of vulcanized rubber and thermoplastic rubber”) from the viewpoint of operability of the hose. Some are preferred, and the range of 55 to 70 is more preferred. If the Shore A hardness is less than 40, there is a problem such as kink (breaking or crushing) of the hose. On the other hand, if the Shore A hardness is more than 90, there is a problem such as deterioration of the hose operability.

The soft resin layer (A) of the present invention has an aromatic vinyl polymer block and a (hydrogenated) conjugated diene polymer block from the viewpoint of having a specific gravity of 1.0 or less and reducing the pressure loss of the fluid. Addition polymer (P), olefinic thermoplastic resin and / or acrylic polymer (Q), softener (R), 20 ≦ (P) ≦ 80, 0 ≦ (Q) ≦ 50, 0 ≦ (R ) ≦ 50 and (P) + (Q) + (R) = 100 is preferable. More preferably, 45 ≦ (P) ≦ 75, 25 ≦ (Q) ≦ 35, 0 ≦ (R) ≦ 20 and (P) + (Q) + (R) = 100.

As the aromatic vinyl compound forming the aromatic vinyl polymer block in the addition polymer (P) having the aromatic vinyl polymer block and the (hydrogenated) conjugated diene polymer block used in the present invention, for example, styrene , Α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, 4-propylstyrene, t-butyl Styrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, vinylanthracene, indene, acetonaphthylene, monofluorostyrene, difluorostyrene, monochloro Such as styrene, methoxystyrene, etc. An aromatic vinyl compound can be mentioned, and the aromatic vinyl polymer block can be formed of one or more of these. Among them, the aromatic vinyl polymer block is preferably mainly composed of α-methylstyrene and / or a structural unit derived from styrene, and is derived from α-methylstyrene from the viewpoint of reducing the pressure loss of the fluid. It is more preferable that the main unit is a structural unit.

The conjugated diene compound that forms the (hydrogenated) conjugated diene polymer block in the addition polymer (P) having an aromatic vinyl polymer block and a (hydrogenated) conjugated diene polymer block includes 1,3-butadiene, -Methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. (hydrogenated) conjugated diene polymer The block may be formed from one or more of the conjugated diene compounds described above. (Hydrogenated) When the conjugated diene polymer block contains structural units derived from two or more conjugated diene compounds, their bonding form may be random, tapered or partially blocky. Furthermore, they may be mixed.
The (hydrogenated) conjugated diene polymer block has a structure unit derived from the conjugated diene compound which may be hydrogenated or non-hydrogenated. % Or more, more preferably 60 mol% or more, and particularly preferably 80 mol% or more are hydrogenated.

The (hydrogenated) conjugated diene in the addition polymer (P) having an aromatic vinyl polymer block and a (hydrogenated) conjugated diene polymer block from the viewpoint of easy formation of the irregular shape on the inner surface of the fiber composite hose of the present invention. The polymer block is at least one selected from an isoprene polymer block that may be hydrogenated, a butadiene polymer block that may be hydrogenated, and a copolymer block of isoprene and butadiene that may be hydrogenated. A seed polymer block is preferred.
The bonding form of the aromatic vinyl polymer block and the (hydrogenated) conjugated diene polymer block in the addition polymer (P) having the aromatic vinyl polymer block and the (hydrogenated) conjugated diene polymer block is not particularly limited. , Linear, branched, radial, or a combination form in which they are combined, and among them, a linear combination form is preferable.
When the addition polymer (P) having an aromatic vinyl polymer block and a (hydrogenated) conjugated diene polymer block is composed of a linear block copolymer, the aromatic vinyl polymer block is represented by S, ( (Hydrogenated) When the conjugated diene polymer block is represented by J, the formula: (SJ) _m -S, (SJ) _n , J- (SJ) _P [wherein m, n and p Each represents an integer of 1 or more] and the like. Among them, the addition polymer (P) having an aromatic vinyl polymer block and a (hydrogenated) conjugated diene polymer block has two or more aromatic vinyl polymer blocks and one or more (hydrogenated) conjugated diene. A block copolymer in which a polymer block) is bonded in a straight chain, particularly a triblock copolymer represented by the formula: SJS, ensures the uneven shape on the inner surface of the fiber composite hose of the present invention. It is preferable from the viewpoint that the pressure loss of the fluid can be effectively reduced.

The acrylic polymer (Q) used as necessary in the soft resin layer (A) of the present invention is a homopolymer of methyl methacrylate or a single copolymer having other copolymerizability mainly composed of methyl methacrylate. It is a copolymer obtained by copolymerizing a monomer. Examples of other copolymerizable monomers include acrylic acid or a metal salt thereof; methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate, t-butyl acrylate, acrylic acid 2 Acrylic esters such as ethylhexyl; methacrylic acid or metal salts thereof; ethyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid Methacrylic acid esters such as cyclohexyl; Vinyl acetate; Aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; Maleic anhydride; Maleimides such as N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide Compounds etc. It is below.
When these are copolymerized with methyl methacrylate, one type may be used alone, or two or more types of compounds may be used in combination. In a copolymer obtained by copolymerizing methacrylic acid and another copolymerizable monomer, the ratio of the other copolymerizable monomer is a ratio that does not greatly change the properties of the acrylic polymer. It is preferable that it is 30% by weight or less.

The acrylic polymer (Q) can be produced by a general polymerization technique such as solution polymerization, emulsion polymerization or suspension polymerization, and the production method is not particularly limited. Moreover, in this invention, a well-known thing can also be used without a restriction | limiting especially as an acrylic polymer (Q). For example, “ACRYPET” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “DELPET” (trade name) manufactured by Asahi Kasei Co., Ltd., “Sumipex” manufactured by Sumitomo Chemical Co., Ltd. (SUMIPEX) "(trade name)," PARAPET "(trade name) manufactured by Kuraray Co., Ltd., and the like.

On the other hand, as the olefinic thermoplastic resin (Q) used as necessary in the soft resin layer (A) of the present invention, a so-called polypropylene resin, that is, a homopolymer made of propylene, a copolymer of propylene and ethylene, etc. is preferably used. Although it can be used, polyethylene resins such as low density polyethylene, high density polyethylene, and linear low density polyethylene can also be used.

Examples of the softening agent (R) used as necessary in the soft resin layer (A) of the present invention include hydrocarbon oils such as paraffinic, naphthenic, and aromatic; vegetable oils such as peanut oil and rosin; Low molecular weight polyethylene glycol; liquid paraffin; low molecular weight polyethylene, ethylene-α-olefin copolymer oligomer, liquid polybutene, liquid polyisoprene or hydrogenated product thereof, hydrocarbon synthesis such as liquid polybutadiene or hydrogenated product thereof Known softening agents such as oil can be used. These may be used alone or in combination of two or more. Among these, in the present invention, hydrocarbon-based synthetic oils such as paraffin-based hydrocarbon oils and ethylene-α-olefin copolymer oligomers are preferably used as the softening agent (R).

The thickness of the soft resin layer (A) forming the fiber composite hose of the present invention is the thickness of the entire soft portion of the hose [thickness of the soft resin layer (A) and the outer surface resin layer from the viewpoint that the hose is lightweight and durable. 10 to 70% of the sum of (C) thickness]. When the thickness of the soft resin layer (A) is less than 10% or more than 70% with respect to the thickness of the entire soft portion of the hose, there is a problem such as impaired durability, which is not preferable. More preferably, it is 33 to 60%.

And the soft resin layer (A) which forms the fiber composite hose of this invention is a laminated structure which consists of an above-described soft resin layer (A) and another thermoplastic resin layer (A ') in order from the inner peripheral surface of a hose. It may be a body.
When the soft resin layer (A) includes a part of the other thermoplastic resin layer (A ′), each thickness is (A) :( A ′) = 3 to 10: 7 to 0 It is preferable that it exists in the range. When the thickness of the soft resin layer (A) is less than the above range, the durability of the hose tends to decrease.

The thermoplastic resin constituting the other thermoplastic resin layer (A ′) has a polarity similar to that of the soft resin layer (A) from the viewpoint of excellent adhesiveness or heat-fusibility with the soft resin layer (A). Of these, olefinic thermoplastic elastomers and / or styrenic thermoplastic elastomers are preferable, and heat-fusibility with a reinforced hard core material (D), which is described later, and elongation at break are preferred. Styrenic thermoplastic elastomers are more preferred from the standpoint of degree.
Examples of olefinic thermoplastic elastomers include general olefinic thermoplastic elastomers in which ethylene-propylene rubber (EPDM, EPM, etc.) is finely dispersed in an olefinic resin matrix, and styrene thermoplastic elastomers. Examples thereof include, but are not particularly limited to, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or a hydrogenated product thereof.

The other thermoplastic resin layer (A ′) has a Shore A hardness of 40 to 75 in accordance with JIS K6253 (“Method for testing hardness of vulcanized rubber and thermoplastic rubber”) from the viewpoint of operability of the hose. It is preferable that If the Shore A hardness is less than 40, there is a problem such as kinking (breaking or crushing) of the hose, and if it is greater than 75, the operability of the hose is deteriorated. More preferably, the Shore A hardness is in the range of 55 to 70.

[Reinforcing fiber layer (B)]
Reinforcing fibers constituting the reinforcing fiber layer (B) of the present invention are formed by reinforcing a monofilament or multifilament braided into a net and a monofilament or multifilament spirally wound along the reinforcing hard core (D). It consists of two types of reinforcing fibers. Examples of these reinforcing fibers include polyarylate fibers and polyaramide fibers monofilaments or multifilaments made of thermoplastic liquid crystal polymers such as wholly aromatic polyesters, polyester filament monofilaments or multifilaments, polyvinyl alcohol fibers monofilaments or multifilaments, and the like. Among them, polyarylate fibers and polyaramid fibers are preferable in terms of high strength and low elongation. From the viewpoint of pressure resistance of the fiber composite hose, the fiber strength is preferably 10 cN / dtex or more.

In the present invention, a reinforced hard core material (D) includes reinforcing fibers braided in a net shape using multifilaments having a fiber fineness in the range of 1,000 to 30,000 dtex, and monofilaments having a fiber fineness of 1,000 to 30,000 dtex. It is preferable that the reinforcing fiber layer is composed of two types of reinforcing fibers that are spirally wound along the surface. Reinforcing fibers braided in a net shape preferably have a knitting angle (angle formed by a horizontal line drawn in the length direction of the hose and the reinforcing fiber) of 25 to 80 degrees, and from the viewpoint of pressure resistance, it is 30 to 60 degrees. More preferably.

It is desirable to knit 8 to 96 reinforcing fibers braided in a net shape, but the number of braids may be appropriately set depending on the pressure resistance required for the hose and the size of the inner diameter. For example, the inner diameter ID (mm) is 50 mm. The number of braids of the fiber composite hose is preferably about 64.
Reinforcing fibers spirally braided along the reinforcing hard core material (D) are arranged at regular intervals within a range of 5 to 40 mm so that one thread is along the reinforcing hard core material (D) of the hose. Although it is wound, the interval between the reinforcing fibers may be appropriately set depending on the length between the reinforcing hard core materials (D). For example, the interval between the fiber composite hoses having an inner diameter ID (mm) of 50 mm is preferably about 10 mm. .

[Outer surface resin layer (C)]
The thickness of the outer surface resin layer (C) of the present invention is the thickness of the entire hose soft part [thickness of the soft resin layer (A) and the thickness of the outer surface resin layer (C) from the viewpoint that the hose is light and durable. 30 to 90%, and more preferably 40 to 67%. When the thickness of the outer surface resin layer (C) is less than 30% or more than 90% with respect to the entire thickness of the hose soft part, there is a problem that durability of the hose is impaired, which is not preferable.

The thermoplastic resin constituting the outer surface resin layer (C) of the present invention is excellent in adhesion or thermal fusion with the above-described soft resin layer (A) or other thermoplastic resin layer (A ′), A thermoplastic elastomer having a polarity similar to that of the soft resin layer (A) or other thermoplastic resin (A ′) is preferable, and among them, an olefin-based thermoplastic elastomer and / or a styrene-based thermoplastic elastomer is preferable. Styrenic thermoplastic elastomers are more preferable from the viewpoints of heat-fusability with the reinforcing hard core material (D), which will be described later, and elongation at break.
Examples of olefinic thermoplastic elastomers include general olefinic thermoplastic elastomers in which ethylene-propylene rubber (EPDM, EPM, etc.) is finely dispersed in an olefinic resin matrix, and styrene thermoplastic elastomers. Examples thereof include, but are not particularly limited to, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or a hydrogenated product thereof.

The outer surface resin layer (C) has a Shore A hardness in the range of 40 to 75 in accordance with JIS K6253 (“Hardness test method of vulcanized rubber and thermoplastic rubber”) from the viewpoint of operability of the hose. preferable. If the Shore A hardness is less than 40, there is a problem such as kinking (breaking or crushing) of the hose, and if it is greater than 75, the operability of the hose is deteriorated. More preferably, the Shore A hardness is in the range of 55 to 70.

[Reinforced hard core material (D)]
The resin constituting the reinforced hard core material (D) in the present invention is a hard olefin resin. Reinforced hard core material (D) is formed by spiral winding so that it is embedded in the outer resin layer (C) (FIGS. 4 to 6) or exposed outside the outer resin layer (C) (FIGS. 1-3). However, it is preferable that it is exposed to the outside of the reinforcing hard core material (D) from the viewpoint of the operability of the hose, the bendability and the like. The hard olefin resin is not particularly limited, and examples thereof include polyethylene resins such as high density polyethylene (HDPE), medium density polyethylene, and low density polyethylene (LDPE), and polypropylene resins such as homopolypropylene, random polypropylene, and block polypropylene. However, block polypropylene is preferable from the viewpoints of heat-fusability with the outer surface resin layer (C), break strength, extrusion processability, versatility, and the like. The hardness of the hard olefin resin is preferably in the range of 70 to 130 on the R scale according to JIS K7202 (“Rockwell hardness measurement test”) from the viewpoint of hose strength.

[Production method of fiber composite hose]
As a method for producing the fiber composite hose of the present invention, for example, the following molding performed on a pipe-making machine comprising a cylindrical tube and a spring-like rotating rod positioned to be inclined with respect to the tube length direction along the tube surface. Although a method is mentioned, it is not specifically limited.
Step (1): The thermoplastic resin constituting the soft resin layer (A) is extruded into a thin tape shape, wound on a pipe making machine in a spiral shape, and the adjacent side edges are fused together to form a soft material. A tubular molded product of the resin layer (A) is formed.
Step (2): Further, in the case of constituting another thermoplastic resin layer (A ′) in addition to the soft resin layer (A), the thermoplastic resin constituting the other thermoplastic resin layer (A ′) is a step ( Other thermoplastic resin layers (A ′) are laminated on the outside of the soft resin layer (A) by extruding into a tape shape in the same manner as in 1) and winding so as to cover the soft resin layer (A). The formed tubular molded product is molded. The soft resin layer (A) and the other thermoplastic resin layers (A ′) are arranged inside and outside the pipe making machine so that the surface temperature immediately before the reinforcing fiber layer (B) is braided is 80 ° C. to 150 ° C. Cooling process by air cooling etc. is performed.
Step (3): On the same pipe making machine as in step (1) and step (2), the reinforcing fiber is replaced with the soft resin layer (A) or other thermoplastic resin layer (A ′) [soft resin layer (A). When the other thermoplastic resin layer (A ′) is formed in addition to the above], the reinforcing fibers are spirally wound at regular intervals equal to the repeating unit length of the tubular molded product. A layer (B) is formed.
Step (4): Immediately after braiding the reinforcing fiber layer (B), the thermoplastic resin and the reinforcing hard core material (D) constituting the outer resin layer (C) are exposed or covered from the outer resin layer (C). A hose-like molded body is formed by coextrusion into a tape shape and winding so as to cover the reinforcing fiber layer (B).
In these steps, the soft resin layer (A) extruded from the extruder and cooled on the pipe making machine, other thermoplastic resin layers (A ′) [other thermoplastic resins in addition to the soft resin layer (A) When the resin layer (A ′) is configured], by controlling the cooling rate of the outer surface resin layer (C) and the reinforced hard core material (D), the uneven shape of the inner surface of the fiber composite hose can be formed. For example, when winding the outer surface resin layer (C) and the reinforced hard core material (D) in the above step (4) to a pipe making machine, factors such as the temperature, flow rate, and cooling time of the cooling water of the hose-shaped molded product The value of Z / ID representing the relationship between the depth Z (mm) of the depression between the convex portions inside the hose and the hose inner diameter ID (mm) can be controlled within a preferable range. Specifically, the temperature after cooling of the hose-shaped molded product after the outer surface resin layer (C) and the reinforced hard core material (D) are wound is in the range of 70 to 100 ° C. on the pipe making machine. It is preferable.

The fiber composite hose of the present invention is not only small in pressure loss of fluid, but also excellent in pressure resistance, wear resistance, durability and light weight. For example, civil engineering work, building work, agriculture, fishery, or nuclear power It can be used for transporting not only water but also powder or mixed water of powder at a power plant or the like.

Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to the description.
In the following examples and comparative examples, various physical properties were measured and evaluated as follows.

<Pressure loss: Measurement of friction loss coefficient (λ) for straight pipe>
A 3m long hose is installed in a straight tube, and an air blower ("SJF-250-2" manufactured by Suiden Co., Ltd.) is attached to one end of the hose, and 0.5m inside from both ends of the hose. Make a hole of φ8mm and attach a differential pressure gauge. Next, the air volume generated from the air blower is changed stepwise, and the pressure difference ΔP (Pa) and the corresponding flow velocity V (m / sec) at that time are measured.
Using the equivalent flow velocity V (m / sec) measured by the method (1) and the cross-sectional area A (m ² ) of the hose, the value of the air flow rate Q (m ³ / hour) is calculated according to the formula (1). To do.
Formula (1) Ventilation amount Q = 3,600 × V × A
From the value of the air flow rate Q (m ³ / hour) calculated in the above (2) and the pressure difference ΔP (Pa), the value of the air permeability a (m ³ / hour / Pa ^1/2 ) ).
Formula (2) Air permeability a = ΔP ^1/2 / Q
The pressure loss coefficient ζ is calculated according to the equation (3) using the value of the air permeability a (m ³ / hour / Pa ^1/2 ) calculated in the above (3).
Formula (3) Pressure loss coefficient ζ = 2 / [ρ (a / 3,600) ² ]
Note that ρ represents the air density (kg / m ³ ).
Using the pressure loss coefficient ζ calculated in the above (4), the friction loss coefficient λ in the straight pipe is calculated according to the equation (4).
Formula (4) Friction loss coefficient λ = (ID × ζ) / L
ID represents the hose inner diameter (m), and L represents the hose length (m).
(6) The friction loss coefficient λ in the straight pipe was evaluated according to the following criteria.
A: 0.020 <λ ≦ 0.045 (the friction between the fluid and the inner pipe surface is small, and there is almost no fluid pressure loss)
○: 0.045 <λ ≦ 0.060 (Although there is some friction between the fluid and the inner tube surface, there is no problem with fluid pressure loss when using a hose)
Δ: 0.060 <λ ≦ 0.080 (there is friction between the fluid and the inner tube surface, and a decrease in flow rate due to fluid pressure loss is observed when using a hose)
×: 0.080 <λ (Since the friction between the fluid and the inner pipe surface is large, the pressure loss of the fluid increases when using the hose, which is not suitable for using the hose)

<Lightweight: Specific gravity measurement>
(1) The specific gravity of the thermoplastic resin constituting the soft resin layer (A) and the outer resin layer (C) is JIS K7112 (“Plastics—Method for Measuring Density and Specific Density of Non-foamed Plastic”) Method A (substitution on water) Law) and measure.
(2) The specific gravity was evaluated according to the following criteria.
○: Specific gravity is 1.0 or less.
X: Specific gravity exceeds 1.0.

<Pressure resistance: Hose burst pressure measurement test>
(1) Clamping using an S-colored bamboo shoot fitting (S1 cap manufactured by Sanko Seisakusho Co., Ltd.) suitable for the inner diameter of the hose and an aluminum cylindrical outer cylinder at both ends of an approximately 1 m hose. Is sealed with a stopper fitting, and the terminal on the opposite side is connected to a pressure pump (manufactured by Aritsu Kogyo Co., Ltd.).
(2) Pressurize the hose at 23 ° C.
(3) The pressure immediately before the pressure (MPa) inside the hose significantly decreases due to the occurrence of a hole or crack in the hose in the hose, and the burst pressure (MPa).
The pressure resistance performance was evaluated according to the following criteria.
○: Burst pressure is 4.5 MPa or more ×: Burst pressure is less than 4.5 MPa

<Unit weight of hose; unit weight measurement>
(1) The length L (m) of the hose is measured with a precision of a minimum of 1 mm using a meter scale.
(2) The weight m (g) of this hose is measured with an electronic balance with a minimum accuracy of 1 g.
(3) The unit weight W (g / m) of the hose is calculated by W = m / L (g / m), and the lightness is compared with a hose molded body having an inner diameter ID = 50 mm (Examples 3 to 6, Comparative Examples 5-7).

<Abrasion resistance: Sandblaster built-in continuous wear test>
(1) A hose with an inner diameter ID of 50 mm is attached to a wear test device (“Pneuma Blaster SDO-F1-F” manufactured by Fuji Seisakusho Co., Ltd.) so that the bending radius of the hose is 400 mm. (Fuji Random A36) manufactured by Fuji Seisakusho Co., Ltd. is circulated at a pressure of 0.45 MPa.
(2) The hose weight loss Δm (g / 10 minutes) every 10 minutes is continuously measured 6 times.
(3) An average weight loss Δm (g / 10 minutes) of the hose for 10 minutes was calculated and used as an index of wear resistance.

Abbreviations and contents relating to materials such as thermoplastic resins used in Examples and Comparative Examples are shown below.
≪Thermoplastic resin constituting the soft resin layer (A) and the outer resin layer (C) ≫
A-1:
Thermoplastic resin containing 50% by weight of SEBS, 32% by weight of AC and 18% by weight of PW [Shore A hardness = 60A, specific gravity = 0.98]
・ SEBS:
Poly (α-methylstyrene) block-polybutadiene block-poly (α-methylstyrene) block type hydrogenated triblock copolymer [number average molecular weight = 78,700, styrene content = 33 wt%, polybutadiene block Hydrogenation rate in water = 98 mol%, 1,4-bond amount in polybutadiene block = 60 mol% (produced using α-methylstyrene and butadiene as raw materials according to the method described in Polymerization Example 1 of Japanese Patent No. 3839773) ]
・ AC:
Acrylic polymer [“Parapet LW-1000P” manufactured by Kuraray Co., Ltd.]
・ PW:
Paraffin oil [“Diana Process PW-380” manufactured by Idemitsu Kosan Co., Ltd.]
A-2:
Thermoplastic resin containing 70% by weight of the following HVSIS and 30% by weight of PP [Shore A hardness = 75A, specific gravity = 0.89]
・ HVSIS:
Hydrogenated product of polystyrene block-polyisoprene block-polystyrene block type triblock copolymer [number average molecular weight = 63,000, styrene content = 30% by weight, hydrogenation rate in polyisoprene block = 90 mol%, poly 1,4-bond amount in isoprene block = 45 mol%, total amount of 1,2-bond and 3,4-bond amount = 55 mol%]
PP-1:
Random polypropylene [“Novatec PP FL02C” manufactured by Nippon Polypro Co., Ltd.]
A-3:
Olefin-based thermoplastic elastomer [RQR7167R manufactured by Riken Technos Co., Ltd. (specific gravity = 0.87, Shore A hardness = 67)]
A-4:
-Soft vinyl chloride resin [“T-871” manufactured by Showa Kasei Kogyo Co., Ltd. (specific gravity = 1.2, Shore A hardness = 72)]
A-5:
・ Soft vinyl chloride resin [“TC2190-4” manufactured by Showa Kasei Kogyo Co., Ltd. (specific gravity = 1.2, Shore A hardness = 66)]
≪Reinforcing fiber used for reinforcing fiber layer (B) ≫
B-1: Multifilament of polyarylate fiber [“Vectran HT” manufactured by Kuraray Co., Ltd. (fiber fineness = 1,670 dtex)]
B-2: Multifilament of polyarylate fiber [“Vectran HT” manufactured by Kuraray Co., Ltd. (fiber fineness = 5,000 dtex)]
B-3: Multifilament of polyester fiber [“Polyester 1,670T / 1” manufactured by Toray Industries, Inc. (fiber fineness = 1,670 dtex)]
≪Resin used for reinforced hard core material (D) ≫
D-1: Block polypropylene [“Novatec PP EA9HD” (R scale hardness = 100) manufactured by Nippon Polypro Co., Ltd.]
D-2: High density polyethylene [Nippon Polyethylene Co., Ltd. “Novatech HD HY-540” (R scale hardness = 70)]
D-3: Hard vinyl chloride resin [“PLUS 439 Y-1” (R scale hardness = 90) manufactured by Plus Tech Co., Ltd.]

<Example 1>
The thermoplastic resin A-1 is extruded into a 15 mm wide tape using a single screw extruder (40 mmφ, cylinder temperature = 160 to 170 ° C., die temperature = 210 ° C.), and on a pipe making machine having an outer diameter of 25 mm. A tubular molded product having a thickness of 0.5 mm was formed by spirally winding the adjacent side edges together at a temperature of 170 ° C.
(2) Subsequently, on the same pipe making machine as in (1) above, using a braiding device (Kyoritsu Co., Ltd. horizontal yarn spiral winder) braided 24 reinforcing fibers B-1 on a tubular molded product. Braided, and one reinforcing fiber B-1 was wound spirally at an interval of 7 mm from the upper surface to form a reinforcing fiber layer.
(3) Immediately after braiding the reinforcing fiber layer, the thermoplastic resin A-2 and the resin D-1 are exposed from the upper surface of the thermoplastic resin A-2 in a circular shape having a diameter of 3 mm. Two single screw extruders joined by a cross die (for thermoplastic resin A-2; 65 mmφ, cylinder temperature = 180 to 190 ° C., die temperature = 230 ° C., for resin D-1; 65 mmφ, cylinder temperature = 200 to 220) The inner diameter ID is 25 mm and the length Y between the reinforced hard core materials (D) is 7 mm by coextruding into a tape shape using a ℃, die temperature = 230 ° C. and wound so as to cover the reinforcing fiber layer. A hose-shaped molded article having a total thickness of the soft part of 1.0 mm was obtained.
(4) In the step of obtaining the hose-shaped molded product, the inside of the pipe making machine is set so that the temperature of the thermoplastic resin immediately before braiding the fiber reinforcing layer on the tubular molded product made of the thermoplastic resin A-1 is 120 ° C. To 12 ° C. cold air. Moreover, after applying the chiller water of 7 ° C from the outside of the pipe making machine to 80 ° C, the hose-like molded product on the pipe making machine is removed from the pipe making machine and further cooled, so that the top of the inner convex portion is repeated. The unit X (mm) was 7 mm, and the relationship Z / ID between the depression depth Z (mm) between the convex portions inside the hose and the hose inner diameter ID (mm) was 0.026.
The performance evaluation is shown in Table 1.

<Example 2>
(1) The thermoplastic resin A-1 is extruded into a 40 mm wide tape using the single screw extruder used in <Example 1> and wound on a pipe making machine having an outer diameter of 200 mm. Thus, a soft resin layer (A) having a thickness of 2.0 mm was formed.
(2) Subsequently, the thermoplastic resin A-2 was extruded into a 40 mm width tape using a single screw extruder (50 mmφ, cylinder temperature = 180 to 190 ° C., die temperature = 230 ° C.), and soft. Another thermoplastic resin layer (A ′) having a thickness of 2.5 mm was formed so as to cover the resin layer (A).
(3) Then, the reinforcing fiber layer (B), the outer resin layer (C), and the reinforcing hard core material (D) are molded through the same steps as (2) and (3) in <Example 1>. . The reinforcing fiber layer (B) was formed by braiding 96 reinforcing fibers B-2 and winding one reinforcing fiber B-2 in a spiral shape. The reinforcing hard core material (D) was made of resin D-2 in a circular shape with a cross-sectional shape of 9 mm in diameter. Finally, a hose-shaped molded article having an inner diameter ID of 200 mm, a length Y between the reinforced hard core materials (D) of 25 mm, and a total thickness of the soft part of 9.0 mm was obtained.
(4) The cooling condition in the step of obtaining the hose-shaped molded product is the same as in <Example 1>, and the thermoplastic resin layer just before braiding the fiber reinforcing layer on the tubular molded product made of the thermoplastic resin A-1 Was 129 ° C., and the temperature of the hose-shaped molded product on the pipe making machine was 88 ° C. The repeating unit X (mm) of the convex part on the inner side of the hose-shaped molded product is 25 mm, and the relationship between the depth Z (mm) of the concave part between the convex parts on the inner side of the hose and the inner diameter ID (mm) of the hose Z / ID Was 0.020. The performance evaluation is shown in Table 2.

<Example 3>
A hose-shaped molded product was obtained through the same steps as in Example 2. Note that, using a pipe making machine having an outer diameter of 50 mm, the thermoplastic resin A-1 for forming the soft resin layer (A) and the thermoplastic resin A-2 for forming the other thermoplastic resin layer (A ′) are: The film was extruded into a 30 mm width tape, and the thickness of the flexible resin layer (A) and the other thermoplastic resin layer (A ′) of the tubular molded product was 1.0 mm. Further, the subsequent reinforcing fiber layer (B), outer surface resin layer (C), and reinforcing hard core material (D) are molded and reinforced by the same steps as (2) and (3) in <Example 1>. The fiber layer (B) is formed by winding 64 reinforcing fibers B-2 and one reinforcing fiber B-2 in a spiral manner, and the reinforcing hard core material (D) is made of resin D-1. The cross-sectional shape was a circle having a diameter of 5 mm. Finally, a hose-shaped molded product having an inner diameter ID of 50 mm, a length Y between the reinforced hard core materials (D) of 10 mm, and a total thickness of the soft part of 3.5 mm was obtained.
The cooling conditions in the step of obtaining the hose-shaped molded product are the same as those in <Example 1>, and a fiber-reinforced layer is formed on a tubular molded product made of a laminate of the thermoplastic resin A-1 and the other thermoplastic resin A-2. The temperature of the above-mentioned laminate immediately before braiding was 120 ° C., and the temperature of the hose-shaped molded product on the pipe making machine was 80 ° C.
The repeating unit X (mm) of the convex part on the inner side of the obtained hose-shaped molded product is 10 mm, and the relationship between the depth Z (mm) of the concave part between the convex parts on the inner side of the hose and the inner diameter ID (mm) of the hose Z / ID Was 0.008. Table 3 shows the performance evaluation.

<Example 4>
Molding is performed through the same steps as in <Example 3>. The other thermoplastic resin layer (A ′) and the outer resin layer (C) were made of thermoplastic resin A-3, respectively. At this time, after setting the temperature of the hose-shaped molded product on the pipe making machine to 70 ° C., it was removed from the pipe making machine and further cooled.
The repeating unit X (mm) of the convex part on the inner side of the obtained hose-shaped molded product is 10 mm, and the relationship between the depth Z (mm) of the concave part between the convex parts on the inner side of the hose and the inner diameter ID (mm) of the hose Z / ID Was 0.003. Table 3 shows the performance evaluation.

<Example 5>
Molding is performed through the same steps as in <Example 3>. The soft resin layer (A) was made of thermoplastic resin A-2 and had a thickness of 2.0 mm. In addition, the other thermoplastic resin layer (A ') was not laminated | stacked. Further, the reinforcing fiber layer (B) was formed by braiding 64 reinforcing fibers B-3 and winding one reinforcing fiber B-3 in a spiral shape.
The cooling conditions in the process of obtaining the hose-shaped molded product are as follows: the temperature of the cooling water from the outside of the pipe making machine is 21 ° C., and the hose-like molded product on the pipe making machine is set to 100 ° C. And then cooled further. The repeating unit X (mm) of the convex part on the inner side of the obtained hose-shaped molded product is 10 mm, and the relationship between the depth Z (mm) of the concave part between the convex parts on the inner side of the hose and the inner diameter ID (mm) of the hose Z / ID Was 0.050. Table 3 shows the performance evaluation.

<Example 6>
Molding is performed through the same steps as in <Example 3>. The soft resin layer (A) was made of thermoplastic resin A-2 and had a thickness of 2.0 mm. The other thermoplastic resin layer (A ′) was not laminated. Further, the resin D-1 was coextruded into a tape shape so as to be embedded in the thermoplastic resin A-2 with a circular shape having a cross section of 3 mm in diameter, and was wound so as to cover the reinforcing fiber layer (B). Finally, a hose-shaped molded article having an inner diameter ID of 50 mm, a length Y between the reinforced hard core materials (D) of 10 mm, and a total thickness of the soft part of 7.0 mm was obtained. The cooling conditions for the hose-shaped molded product were the same as those in <Example 3>.
The repeating unit X (mm) of the convex part on the inner side of the obtained hose-shaped molded product is 10 mm, and the relationship between the depth Z (mm) of the concave part between the convex parts on the inner side of the hose and the inner diameter ID (mm) of the hose Z / ID Was 0.020. Table 3 shows the performance evaluation.

<Comparative Example 1>
It is molded through the same thermoplastic resin, reinforcing fiber, resin and steps as in <Example 1>. At this time, the length Y between the reinforcing hard cores (D) was set to 4 mm by loosening the twist angle of the spring-like rotating rod of the pipe making machine. The cooling conditions for the hose-shaped molded product were the same as those in <Example 1>.
Finally, a hose-shaped molded product having an inner diameter ID of 25 mm, a length Y between the reinforced hard core materials (D) of 4 mm, and a total thickness of the soft part of 1.0 mm was obtained. The repeating unit X (mm) of the convex part on the inner side of the obtained hose-shaped molded product is 4 mm, and the relationship between the depth Z (mm) of the concave part between the convex parts on the inner side of the hose and the inner diameter ID (mm) of the hose Z / ID Was 0.027. The performance evaluation is shown in Table 1.

<Comparative Example 2>
It is molded through the same thermoplastic resin, reinforcing fiber, resin and process as in Example 2. At this time, the length Y between the reinforcing hard cores (D) was set to 30 mm by increasing the twist angle of the spring-like rotating rod of the pipe making machine. The cooling conditions for the hose-shaped molded product were the same as those in <Example 2>.
Finally, a hose-shaped molded product having an inner diameter ID of 200 mm, a length Y between the reinforced hard core materials (D) of 30 mm, and a total thickness of the soft part of 8.7 mm was obtained. The repeating unit X (mm) of the convex portion apex inside the hose-shaped molded product is 30 mm, and the relationship Z / ID between the concave depth Z (mm) between the convex portions inside the hose and the hose inner diameter ID (mm) is 0. 014. The performance evaluation is shown in Table 2.

<Comparative Example 3>
It is molded through the same thermoplastic resin, reinforcing fiber, resin and process as in Example 3. At this time, the cooling condition of the hose-shaped molded article is that the temperature of the chiller water from the outside of the pipe making machine is 6 ° C., the temperature of the hose shaped molded article on the pipe making machine is 60 ° C., and then removed from the pipe making machine. And further cooled. The repeating unit X (mm) of the convex part on the inner side of the obtained hose-shaped molded product is 10 mm, and the relationship between the depth Z (mm) of the concave part between the convex parts on the inner side of the hose and the inner diameter ID (mm) of the hose Z / ID Was 0.002. Table 3 shows the performance evaluation.

<Comparative Example 4>
It is molded through the same thermoplastic resin, reinforcing fiber, resin and process as in Example 5. At this time, the temperature of the cooling water from the outside of the pipe making machine was set to 21 ° C. factory water, and the hose-shaped molded product on the pipe making machine was set to 110 ° C. and then removed from the pipe making machine and further cooled. The repeating unit X (mm) of the convex part on the inner side of the obtained hose-shaped molded product is 10 mm, and the relationship between the depth Z (mm) of the concave part between the convex parts on the inner side of the hose and the inner diameter ID (mm) of the hose Z / ID Was 0.070. Table 3 shows the performance evaluation.

<Comparative Example 5>
Molding is performed through the same steps as in <Example 3>. The soft resin layer (A) was obtained by extruding the thermoplastic resin A-4 into a tape having a width of 30 mm (single screw extruder 40 mmφ, cylinder temperature = 160 to 170 ° C., die temperature = 200 ° C.) and having a thickness. 2.0 mm. The reinforced hard core material (D) is a resin D-3 having an elliptical shape with a cross section of 3 mm in length and 4 mm in width, and coextruded in a tape shape so as to be embedded in the thermoplastic resin A-5, and a reinforcing fiber layer ( B) was wound to cover. Finally, a hose-shaped molded product having an inner diameter ID of 50 mm, a length Y between the reinforced hard core materials (D) of 10 mm, and a total thickness of the hose soft part of 7.0 mm was obtained. The cooling conditions for the hose-shaped molded product were the same as those in <Example 3>.
The repeating unit X (mm) of the convex portion inside the obtained hose-shaped molded product is 11 mm, and the relationship between the concave depth Z (mm) between the convex portions inside the hose and the hose inner diameter ID (mm) Z / ID Was 0.007. Table 3 shows the performance evaluation.

<Comparative Example 6>
Molding is performed through the same steps as in <Comparative Example 5>. The reinforcing hard core material (D) was made of resin D-1, and the outer surface resin layer (C) was made of thermoplastic resin A-2. The structure of the hose-shaped molded product was the same size as in <Example 3>. Finally, there is a problem that the thermoplastic resin A-4 and the thermoplastic resin A-2 easily peel off, but the inner diameter ID is 50 mm, the length Y between the reinforced hard core materials (D) is 11 mm, and the hose softness A hose-shaped molded product having a total wall thickness of 3.5 mm was obtained. The cooling conditions for the hose-shaped molded product were the same as those in <Example 3>.
The repeating unit X (mm) of the convex portion inside the obtained hose-shaped molded product is 11 mm, and the relationship between the concave depth Z (mm) between the convex portions inside the hose and the hose inner diameter ID (mm) Z / ID Was 0.007. Table 3 shows the performance evaluation.

<Comparative Example 7>
It is molded through the same steps as in <Comparative Example 5>. For the soft resin layer (A), a thermoplastic resin A-2 was used. The structure of the hose-shaped molded product was the same as that of Comparative Example 5. Finally, there is a problem that the thermoplastic resin A-2 and the thermoplastic resin A-5 are easily peeled, but the inner diameter ID is 50 mm, the length Y between the reinforced hard core materials (D) is 11 mm, and the hose is soft. A hose-shaped molded product having a total wall thickness of 7.0 mm was obtained. The cooling conditions for the hose-shaped molded product were the same as those in <Example 3>.
The repeating unit X (mm) of the convex portion inside the obtained hose-shaped molded product is 11 mm, and the relationship between the concave depth Z (mm) between the convex portions inside the hose and the hose inner diameter ID (mm) Z / ID Was 0.007. Table 3 shows the performance evaluation.

As is apparent from the results of Table 1, Table 2, and Table 3, the repeating unit of the convex vertices on the inner side of Comparative Examples 1 to 4 is the case where X (mm) is X <5 mm or 25 mm <X or the hose inner side When the depth of the recess between the protrusions of Z is the hose inner diameter ID (mm), the fiber composite hose with Z / ID <0.003 or 0.05 <Z / ID The friction loss coefficient λ is 0.060 <λ, which is not possible because the pressure loss increases. Further, regarding Comparative Examples 5 to 7 in Table 3, when the specific gravity of the thermoplastic resin forming the soft resin layer (A) and / or the outer resin layer (C) exceeds 1.0, the unit weight of the hose increases. The operability is inferior and cannot be used.

Since the fiber composite hose of the present invention is a lightweight hose that has a small fluid pressure loss and is excellent in pressure resistance, wear resistance, and durability, for example, civil engineering work, building work, agriculture, fishery, nuclear power plant, etc. In addition to water, it can be beneficially used for transporting powder or powder mixed water.

The whole figure of the structure where the reinforcement hard core material (D) which exposes an example of the fiber composite hose of this invention is exposed from the outer surface resin layer (C), and the schematic diagram of a partial cross section. The schematic diagram which expanded the cross section of FIG. The schematic diagram which expanded the cross section which the fiber composite hose of FIG. 1 consists of a soft resin layer (A) and another thermoplastic resin layer (A '). The whole figure and partial schematic diagram of the structure where the reinforcement hard core material (D) showing an example of the fiber composite hose of this invention is embedded in the outer surface resin layer (C). The schematic diagram which expanded the cross section of FIG. The schematic diagram which expanded the cross section which the fiber composite hose of FIG. 4 consists of a soft resin layer (A) and another thermoplastic resin (A ').

A Soft resin layer A ′ Other thermoplastic resin layer B Reinforcing fiber layer C Outer surface resin layer D Reinforced hard core material X Repeating unit of convex apex inside hose (mm)
Y Length between reinforced hard core (D) (mm)
Z Depth of recess between convex parts inside hose (mm)
ID hose inner diameter (mm)

Claims

In order from the inner peripheral surface of the hose, it consists of a soft resin layer (A) / reinforcing fiber layer (B) / outer surface resin layer (C) / reinforced hard core material (D), and all the following conditions (1) to (3) are satisfied. Filling fiber composite hose.
(1) When deployed in the length direction of the hose, when X (mm) is the repeating unit of the convex portion on the inner side, 5 mm ≦ X ≦ 25 mm,
(2) When the depth of the recess between the convex portions inside the hose is Z (mm) and the inner diameter of the hose is ID (mm), 0.003 ≦ Z / ID ≦ 0.05,
(3) The specific gravity of each thermoplastic resin forming the soft resin layer (A) and the outer resin layer (C) is 1.0 or less.
The soft resin layer (A) is an addition polymer (P) having an aromatic vinyl polymer block and a (hydrogenated) conjugated diene polymer block, an olefin thermoplastic resin and / or an acrylic polymer (Q), softening The fiber composite hose according to claim 1, wherein the agent (R) is contained in the following weight range.
20 ≦ (P) ≦ 80
0 ≦ (Q) ≦ 50
0 ≦ (R) ≦ 50
And (P) + (Q) + (R) = 100
The fiber composite hose according to claim 1 or 2, which is a laminated structure comprising a soft resin layer (A) and another thermoplastic resin layer (A ') in order from the inner peripheral surface of the hose.
The fiber composite hose according to any one of claims 1 to 3, wherein the reinforcing hard core material (D) is made of polypropylene resin and / or polyethylene resin.
When the length between the reinforced hard core materials (D) is Y (mm), the relationship with the repeating unit X (mm) of the inner convex portion vertex is 0.90 ≦ X / Y ≦ 1.10. The fiber composite hose according to any one of claims 1 to 4, which is satisfactory.