JPH11159667A - Hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance fluid cutoff performance, and to improve vibration absorptivity and durability by constituting a hose of organized clay and a polymer, and orienting the organized clay in parallel to the surface direction of the hose. SOLUTION: While a polymer is generally hydrophobic, clay is hydrophilic. Therefore, both are hot uniformly mixed together only by the polymer and the clay. However, mutual layers of organized clay 1 swell to a certain degree by forming the organized clay 1 by organizing the clay, and the polymer 2 enters between the layers. Therefore, the flow of fluid 9 such as air and liquid trying to pass through into a hose is cut off by the organized clay 1. Since the passage of the fluid 9 trying to flow in the polymer 2 is formed so as to meander through the mutual layers of the organized clay 1 oriented in the surface direction of the hose 61, the organized clay 1 is desirably oriented in parallel to the surface direction of the hose.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hose used for transporting a refrigerant.

[0002]

2. Description of the Related Art As hoses for transporting refrigerant of air conditioners,
Conventionally, for example, there is one using a polyamide resin (JP-A-5-52280). This hose has a significantly higher refrigerant (such as Freon gas) blocking property than a rubber hose having no resin layer, and can efficiently prevent refrigerant leakage.

[0003]

However, the above-described conventional hose for transporting refrigerant has a problem in that it has low vibration absorption and durability under severe vibration. In recent years, an air conditioner using a refrigerant other than chlorofluorocarbon, such as carbon dioxide, has been constructed. In this case, however, there is a problem that even a hose having a resin layer greatly deteriorates the refrigerant blocking property.

The present invention has been made in view of the above-mentioned conventional problems, and has as its object to provide a rubber hose having a high fluid-blocking property, excellent vibration absorption and durability, and a resin hose having a further enhanced fluid-blocking property.

[0005]

According to a first aspect of the present invention, there is provided a hose comprising an organic clay and a polymer.

The operation and effect of the present invention will be described.
The hose of the present invention is obtained by mixing an organic clay with a polymer. As described in claim 6, the organized clay is:
Clay (clay mineral) is formed by ion bonding organic onium ions. Therefore, the originally hydrophilic clay surface is hydrophobized to some extent by organic onium ions,
The affinity with the hydrophobic polymer is increased. Therefore, the organized clay can be uniformly dispersed in the matrix composed of the polymer. In addition, it is possible to prevent the permeation of fluids such as gas and liquid, improve the fluid blocking performance, and also has high vibration absorption and excellent durability. The reason will be described with reference to FIGS.

[0007] Clays are hydrophilic, whereas polymers are generally hydrophobic. Therefore, only the polymer and the clay do not mix uniformly. However,
As shown in FIG.
By this, the layers of the organized clay 1 swell to some extent, and the polymer 2 enters between the layers. For this reason, the flow of the fluid 9 such as air or liquid that is going to pass through the hose is blocked by the organized clay 1. Therefore, it is considered that the hose of the present invention is excellent in fluid blocking properties. In addition, the behavior of the polymer 2 is restricted by the presence of the organized clay 1, and the mechanical strength of the hose is improved.
Vibration absorption and durability are also increased.

As shown in FIG. 2, the characteristics of such a hose are improved as the dispersibility of the organic clay 1 in the polymer 2 becomes higher. That is, by making the organically-organized clay 1 finely dispersed in the polymer 2 so as to be in an infinitely swollen state, the bypass effect of the fluid is further enhanced, and the fluid blocking property is enhanced. In addition, vibration absorption and durability are increased.

Preferably, the organic clay is oriented parallel to the surface direction of the hose. As a result, as shown in FIG. 3, the flow path of the fluid 9 to flow in the polymer is formed by sewing between the layers of the organized clay 1 oriented in the plane direction of the hose 61. The length is much longer than in the case of the non-organized clay shown in (1). Therefore, the detour effect of the fluid is further enhanced, and the fluid blocking performance of the hose is further enhanced.

Next, the details of the present invention will be described. (Organized clay) Organized clay is obtained by ion-bonding an organic onium ion to clay as described above. It is preferable to use a clay having a large contact area with the polymer. Thereby, the interlayer between the clays can be largely swollen. Specifically, as set forth in claim 7, the cation exchange capacity of the clay is 50.
Preferably, it is -200 milliequivalents / 100 g. 5
If the amount is less than 0 milliequivalents / 100 g, onium ions may not be sufficiently exchanged, and it may be difficult to swell the interlayer between clays. On the other hand, 200 milliequivalents / 100
If it exceeds g, the bonding force between the clay layers becomes strong, and it may be difficult to swell the clay layers.

The clay includes, for example, smectite clay such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and mica. It may be natural or synthetic.

The organic onium ion preferably has 6 or more carbon atoms. If the number of carbon atoms is less than 6, the hydrophilicity of the organic onium ion may be increased, and the compatibility with the modified polymer may be reduced. Examples of the organic onium ion include hexyl ammonium ion, octyl ammonium ion, 2-ethylhexylammonium ion, dodecylammonium ion,
Lauryl ammonium ion, octadecyl ammonium ion, stearyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion, distearyl dimethyl ammonium ion,
Alternatively, ammonium laurate ions or the like can be used.

As described below, when the polymer is a vinyl alcohol copolymer, the organic onium ion is 1
It preferably has 0 to 80 mol% of hydroxyl groups. The hydroxyl group of the organic onium ion has a high affinity with the vinyl group of the vinyl alcohol copolymer. For this reason, the vinyl alcohol copolymer enters between the layers of the organized clay and can cause interlayer swelling.

It is preferable that the organic onium ion is used in an amount of 0.3 to 3 equivalents of the ion exchange capacity of the clay. 0.3
If it is less than the equivalent, it may be difficult to swell between the clay layers, and if it exceeds 3 equivalents, it may cause deterioration of the polymer and cause coloring of the hose. More preferably, the organic onium ion is used in an amount of 0.5 to 2 equivalents of the ion exchange capacity of the clay. Thereby, the clay layer can be further swollen, and the deterioration and discoloration of the hose can be further prevented.

According to the present invention, the amount of the organic clay is 0.01 to 2 parts by weight based on 100 parts by weight of the polymer.
It is preferably 00 parts by weight. Thereby, the mechanical strength of the hose is improved. On the other hand, when the amount is less than 0.01 part by weight, there is a possibility that the mechanical strength is not improved by the addition of the organized clay. If the amount exceeds 200 parts by weight, the formability of the hose may be reduced.

Further, it is preferably 0.1 to 100 parts by weight. As a result, a hose having a good balance between mechanical properties and moldability can be obtained. In particular, it is preferably 0.1 to 30 parts by weight.

It is preferable that the organized clay is dispersed in the polymer in a size of 1 μm or less. Thereby, the mechanical properties of the hose are improved.

(Polymer) The polymer is, for example, a resin and / or a rubber.

(When the polymer is a resin) As the resin,
For example, polyethylene, polypropylene, polybutene,
Polypentene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, ethylene-propylene-diene copolymer, ethylene-butene
Diene copolymer, butyl rubber, polystyrene, styrene-butadiene copolymer, styrene-hydrogenated butadiene copolymer, polyamide, polycarbonate, polyacetal, polyester, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyether ketone, polyarylate , Polymethylpentene, polyphthalamide, polyethernitrile, polyethersulfone, polybenzimidazole, polycarbodiimide, polytetrafluoroethylene, fluororesin, polyamideimide, polyetherimide, liquid crystal polymer, epoxy resin, melamine resin, Urea resin, diallyl phthalate resin, phenol resin, polysilane, polysiloxane,
Polymers such as silicone resins and urethane resins can be used.

Further, a vinyl alcohol copolymer can be used as the resin. In this case, the vinyl alcohol copolymer preferably contains a vinyl alcohol skeleton in an amount of 10 mol% or more. This further enhances the affinity with the organized clay. In this case, it is preferable to add water. Thereby, the organic clay can be finely dispersed in the vinyl alcohol copolymer.
The amount of water to be added is preferably 10 to 200 parts by weight based on 100 parts by weight of the clay in the organized clay.
Thereby, the organic clay can be finely dispersed without leaving water in the mixture.

As a polymer, -Si is contained in the main chain.
Polysiloxane having —O—, or —C in the main chain
Polyoxyalkylene having -O- can also be used.

Further, an ionomer resin can be used as the polymer. The ionomer resin is a polymer in which an ionic group (for example, a COOH ⁻ group and a metal ion (M ⁺ )) is bonded to a side chain or a main chain of a polymer. In ionomer resins, the ionic groups aggregate to form ionic crosslinks. The ionic cross-linking point has high affinity with the clay surface of the organized clay. As a result, the ionomer resin intervenes between the layers of the organic clay, and the dispersibility of the organic clay increases,
The hose has a high fluid blocking property.

The ionomer resin is an ion-containing polymer having an ion in a side chain or a main chain of the polymer. The ionomer resin is a side chain type in which a side chain ionic group (eg, COO ⁻ M ⁺ ) partially exists in the main chain of a polymer, and a polymer or an oligomer having an anionic group (eg, a carboxylic acid group) at both ends. In addition, cations (for example, metal ions M ²⁺ ) intervene and neutralize, resulting in a polymerized telechelic type,
Examples include ionene in which an anion X ^- is bonded to a polymer having a cation N ^{+ in the} main chain. Ionomer resin is a combination of polymer and its counter ion.
There are various things.

The number average molecular weight of the polymer is from 5,000 to
Preferably it is 10,000,000. 5,000
If it is less than 0, the mechanical properties of the hose may be reduced. If it exceeds 10,000,000, a problem may occur in the workability of the hose. In this case, however, it is possible to achieve both moldability and mechanical properties by increasing the molecular weight by adding a crosslinking agent or crosslinking by electron beam irradiation or the like after or simultaneously with the molding.

More preferably, for the same reason as above, the number average molecular weight of the polymer is from 10,000 to 1,0.
00,000. Particularly preferably, the number average molecular weight of the polymer is between 100,000 and 1,000,000. Thereby, the mechanical properties and workability of the hose can be further improved.

As described in claim 4, the polymer is:
It preferably has a polar group. This further enhances the dispersibility of the organized clay in the polymer. The above-mentioned polar group refers to a substance in which electrons are localized in a molecule and a charge is biased, and does not include a completely polarized ionic functional group. Therefore, onium ions are not included in the polar groups.

The polymer having a polar group is, for example,
It is a modified polymer in which a functional group is introduced by modifying the polymer, and a copolymer having a functional group.

The functional group introduced by the modification may be any functional group capable of intercalating between the clay layers. In order to determine whether or not intercalation can be performed between the clay layers, a compound having the functional group is mixed with the organized clay, and the interlayer distance between the organized clays may be measured by X-ray diffraction. When intercalated, the interlayer distance of the organized clay increases.

The functional groups include, for example, acid anhydride groups, carboxylic acid groups, hydroxyl groups, thiol groups, epoxy groups,
Halogen group, ester group, amide group, urea group, urethane group, ether group, thioether group, sulfonic acid group, phosphonic acid group, nitro group, amino group, oxazoline group and other functional groups, or benzene ring, pyridine ring, pyrrole It is preferable to use an aromatic ring such as a ring, a furan ring or a thiophene ring, but the present invention is not limited thereto. This further improves the dispersibility of the organized clay in the modified polymer. In the case of a polymer having a functional group such as polystyrene, it is preferable to use a functional group having a larger interaction with the clay layer as the functional group introduced by modification.

The amount of the functional group introduced into the polymer is 0.0
It is preferably from 0.01 to 1 mmol / g (equivalent to 0.01 to 10% by weight when the functional group is converted to maleic anhydride). This makes it possible to finely disperse the organized clay while maintaining the physical properties of the polymer. on the other hand,
If the amount is less than 0.001 mmol / g, the polymer cannot intervene between the clay layers, and the organic clay may not be finely dispersed. If it exceeds 1 mmol / g,
When the polymer is modified, the polymer chain may be cut or cross-linked, so that the physical properties of the polymer may not be maintained. More preferably, for the same reason as above, the amount of the functional group introduced into the polymer is 0.005 to 0.5 mmol / g (0.05 to 5% by weight when the functional group is converted to maleic anhydride). Equivalent).

Copolymer The form of the copolymer is not particularly limited as to the form of distribution of the functional group monomer in the copolymer. Even in an alternating copolymer in which a functional monomer and a copolymerizable monomer are alternately bonded, the functional monomer is irregular in the copolymer (random)
May be distributed, or a plurality of functional group monomers may be continuously distributed. Generally, as the amount of the functional group monomer in the copolymer increases, the blocking property necessarily increases. Further, the copolymer may have a branched structure due to the presence of a monomer having two or more polymerizable groups.

The functional group may be any functional group capable of intercalating between the clay layers. In order to determine whether intercalation can be performed between the clay layers, the functional group monomer and the organic clay are mixed, and the interlayer distance between the organic clays may be measured by X-ray diffraction. When intercalated, the interlayer distance of the organized clay increases. For example, functional groups that can be intercalated include acid anhydride groups, carboxylic acid groups, hydroxyl groups, thiol groups, epoxy groups,
Halogen group, ester group, amide group, urea group, urethane group, ether group, thioether group, sulfonic acid group, phosphonic acid group, nitro group, amino group, urea group, ether group, thioether group, sulfonic acid group, phosphonic acid Functional groups such as a nitro group, a nitro group, an amino group, an oxazoline group, and an imide group; or an aromatic ring such as a benzene ring, a pyridine ring, a pyrrole ring, a furan ring, and a thiophene ring, but are not limited thereto. .

The functional group monomer is not particularly limited as long as it is a polymerizable monomer having the above functional group. The functional group is
One or more are present in the monomer. When two or more are present, the functional groups may be the same,
It may be different. For example, monomers having such a functional group include acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate, acrylic (meth) amide, methyl (meth) amide, and ethyl (meth) amide. Compounds having unsaturated carbon such as acrylamide, (meth) acrylic acid, maleic anhydride, maleimide, etc .; aromatic rings such as benzene, pyridine, thiophene, etc. such as styrene, vinylpyridine, vinylthiophene, etc. And the like. Further, the functional group monomer may be a monomer having two or more polymerizable groups (for example, vinyl group) in one molecule.

The content of the functional group monomer is preferably 0.01 to 50 mol% in the copolymer. Thereby, the organized clay can be finely dispersed in the copolymer. When the amount is less than 0.01 mol%, the organic clay may not be finely dispersed. In addition, 50mol%
If it exceeds 3, the organic clay may not be finely dispersed.

More preferably, the content of the functional group monomer is 0.05 to 50 mol% in the copolymer.
Particularly preferably, it is 0.05 to 40 mol%, particularly preferably 0.05 to 30 mol%. Thereby, the organic clay can be more finely dispersed.

The monomer copolymerizable with the functional group is, for example, a hydrocarbon compound having a double bond such as ethylene, propylene, butene or pentene, a hydrocarbon compound having a triple bond such as acetylene or propylene, or butadiene or isoprene. And the like, and may have a branched structure or a cyclic structure in their carbon chains.

The above monomers may be combined with a functional group monomer to form an acrylic monomer such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, acryl (meth) amide, or methyl (meth) amide. , Acrylamide such as ethyl (meth) amide, or a monomer having an aromatic ring such as styrene or methylstyrene. In this case, an aromatic ring such as methylstyrene may contain a substituent. Further, it may be a monomer having two or more polymerizable groups in one molecule.

As a combination of monomers, a monomer having a larger interaction with the clay layer is defined as a functional group monomer. For example, in the case of an ethylene-styrene copolymer, styrene having a large interaction with the clay layer is the functional group monomer. In the case of a styrene-vinyl oxazoline copolymer, vinyl oxazoline having a larger interaction is the functional group monomer.

The polymer may be used in combination of two or more kinds. In this case, two or more polymers are compatible or incompatible, and in the latter case, the functional group is formed on either the polymer constituting the matrix or the polymer constituting the micelle. This changes the dispersed state (morphology) of the organized clay. Therefore, such a difference in the dispersion state greatly affects the physical properties of the hose.

(When the polymer is rubber) Next, when rubber is used as the polymer, elasticity can be imparted to the hose by vulcanization of the unvulcanized rubber, and the vibration absorption is enhanced. Examples of the rubber include polymers used as synthetic rubbers, such as styrene butadiene copolymer, polybutadiene, polybutadiene, polyisoprene, polyacrylonitrile butadiene copolymer, polychloroprene,
Polyethylene propylene copolymer Rubber oligomers such as butylene, polyacryl, silicone, polyvinylidene fluoride, polyurethane, and natural rubber can be used. Further, the molecular chain of the rubber oligomer may be linear or branched.

As the rubber, besides the above rubber oligomer, natural rubber, isoprene rubber, chloroprene rubber, styrene rubber, nitrile rubber, ethylene-propylene rubber, butadiene rubber, styrene-butadiene rubber,
Butyl rubber, epichlorohydrin rubber, acrylic rubber,
Urethane rubber, fluorine rubber, silicone rubber and the like can also be used.

The molecular weight of the unvulcanized rubber oligomer is from several hundreds to
It is preferable that the number is about tens of thousands. As a result, the elastic modulus of the crosslinked vulcanized rubber oligomer increases, and the Mooney viscosity can be reduced. On the other hand, when the molecular weight of the unvulcanized rubber oligomer is less than several hundreds, the elastic modulus of the oligomer crosslinked product is lowered, which may not be practical. On the other hand, when it exceeds about tens of thousands, the Mooney viscosity increases, and the moldability may be reduced. Among them, the practical rubber oligomer has a molecular weight range of about 3,000 to 10,000 due to the combination of elastic modulus and Mooney viscosity. However, it is not limited to this.

When the polymer is a rubber oligomer molecule, the polymer preferably has a polar group. Among the polar groups, it is particularly preferable to have a hydrogen bonding functional group. Examples of the hydrogen bonding functional group include a hydroxyl group, a carboxyl group, an amide group, an imide group, an acid anhydride, an amino group, an imino group, a sulfonyl group,
Examples include a phosphoryl group and a thiol group. The functional group may be bonded to the end of the unvulcanized oligomer molecule or to any position in the molecular chain.

Examples of the rubber oligomer include polymers used as synthetic rubbers, for example, polybutadiene oligomers having hydroxyl groups at both ends, hydrogenated polybutadiene oligomers having hydroxyl groups at both ends, and hydroxyl groups at both ends. Polyisoprene oligomers, hydrogenated polyisoprene oligomers containing hydroxyl groups at both ends, polyisoprene oligomers containing hydroxyl groups in side chains, polyester oligomers containing hydroxyl groups, and polyether oligomers containing hydroxyl groups can be used.

When rubber is used as the polymer, it is preferable to mix it with a process oil for rubber or / and a plasticizer. As a result, the permeability of rubber molecules between the layers of the organized clay is increased, and the organized clay can be uniformly dispersed.

(Addition of Guest Molecule) Further, as described in claim 5, the hose has, in addition to the polymer and the organized clay, a guest molecule having a higher affinity for the organized clay than the polymer. Is preferred. Thus, even if the polymer has a low affinity for the organized clay, the organized clay can be dispersed in the polymer with the help of the guest molecule having a high affinity, and the fluid barrier property can be further enhanced.

The guest molecules having a high affinity for the organized clay are as follows. A first guest molecule having a molecular length equal to or smaller than that of the organic onium ion and having a polar group capable of forming a hydrogen bond with clay in the molecule; Second without polar group
Composite guest molecule A consisting of guest molecule

A guest molecule B having a molecular length equal to or larger than that of the organic onium ion and having a polar group capable of forming a hydrogen bond with clay in the molecule has a polar group in the molecule, and has a molecular length of organic onium ion A guest molecule having an unsaturated carbon chain which is the same as or larger than the ion and which can form a cross-link with the unsaturated carbon chain in the organic onium ion, comprising a polyolefin oligomer having a C 2 functional group Guest molecule D Hereinafter, these will be described in detail.

Guest complex molecule A The guest complex molecule A is composed of a first guest molecule and a second guest molecule. The first guest molecule is one or two in the molecule.
It has one or more polar groups. The polar group is bonded to at least one of the main chain, side chain, or terminal of the first guest molecule. Among them, the polar group is preferably bonded to the terminal of the first guest molecule. This allows the clay layers to swell more greatly.

In the present invention, a polar group refers to a group in which electrons are localized in a molecule and a charge is biased, and does not include a completely polarized ion. Therefore, onium ions are not included in the polar groups. The polar group of the first guest molecule is, for example, a hydroxyl group (OH), a halogen group (F, Cl, Br, I), a carboxyl group (COO).
H), one or two selected from the group consisting of a carboxylic anhydride group, a thiol group (SH), an epoxy group, and an amino group
More than a species. The amino group is a primary, secondary, or tertiary amine (NH ₂ , NH, N).

Incidentally, groups having a relatively strong degree of polarization, such as imino group, phosphonyl group, and sulfonyl group, fall under the above definition of the "polar group", but these groups are more preferable in the present invention. Absent. This is because the first guest molecule containing these groups has low solubility in a solvent and lacks high-temperature stability for melting.

The molecular length of the first guest molecule is equal to or smaller than that of the organic onium ion. If the molecular length is longer than the organic onium ion, it may be difficult to obtain the first guest molecule, and the type of the first guest molecule that is compatible with the low-polarity polymer is limited. There is.

The first guest molecule is, for example, an olefin or paraffin having a linear or branched structure, or a linear or branched structure having an aromatic ring in a main chain and / or a side chain. Olefin or paraffin. That is, the first guest molecule has, for example, one or more polar groups and a saturated or unsaturated linear or branched structure. Further, the main chain and / or the side chain may contain an aromatic ring.

The first guest molecule having a polar group is, for example, lauryl alcohol (12 carbon atoms), stearyl alcohol (18 carbon atoms), stearic acid (18 carbon atoms), or stearyl chloride (18 carbon atoms).
Can be used. OH, COO at both ends
Polyethylene, polypropylene, polyisoprene, polybutadiene having a polar group such as H, Cl, or an epoxy group, or a hydrogenated product or copolymer thereof may be used. These first guest molecules are selected and used so as to be substantially equal to or less than the molecular length of the organic onium ion. The first guest molecule preferably has 6 or more carbon atoms.

The first guest molecules tend to expand widely between clay layers as the mixing ratio increases. The mixing ratio of the first guest molecule is preferably at least 0.1 part by weight based on 1 part by weight of the organized clay. If the amount is less than 0.1 part by weight, swelling between layers may be insufficient.

Next, the second guest molecule is a non-polar or low-polarity oligomer or polymer having no polar group. The second guest molecule has a linear or branched structure, is saturated or unsaturated, and
It may or may not contain an aromatic ring. The molecular length of the second guest molecule is larger than that of the organic onium ion. When the molecular length is equal to or smaller than the molecular length of the organic onium ion, there is a problem that swelling between the layers of the clay becomes insufficient.

The second guest molecule has a molecular weight of 1,000.
Preferably it is a non-polar or less polar oligomer or polymer of up to 500,000. If it is less than 1,000, swelling between layers of the clay may be insufficient. On the other hand, if it exceeds 500,000, it may be hardly soluble in a solvent, or its softening point or melting point may be higher than the decomposition point of clay. It is more preferable that the second guest molecule has a molecular length of about 3 to 4 times or more of the organic onium ion. As the second guest molecule, for example, liquid polybutadiene, liquid polyisoprene, and liquid butyl rubber can be used.

The second guest molecules tend to swell between the layers of the clay as the mixing ratio increases. The mixing ratio of the second guest molecule is preferably 0.1 part by weight or more based on 1 part by weight of the organized clay. If the amount is less than 0.1 parts by weight, the swelling between the layers of the clay may be insufficient. The second guest molecule is
At least part of the clay enters between the clay layers. Not all of the second guest molecules need be involved.

Guest molecule B The molecular length of the guest molecule B is equal to or larger than that of the organic onium ion. When the molecular length is smaller than the molecular length of the organic onium ion, the guest molecule B does not protrude outside the region where the organic onium ion exists at the clay interface, so that the clay is not easily dispersed in the polymer.

The guest molecule B is, for example, an olefin or paraffin having a linear or branched structure, or
An olefin or paraffin having a linear or branched structure and having an aromatic ring in the main chain and / or side chain. That is, the guest molecule B has, for example, one or more polar groups and a saturated or unsaturated linear or branched structure. The main chain and / or side chain may contain an aromatic ring.

As the guest molecule B, for example, lauryl alcohol (C12), stearyl alcohol (C18), stearic acid (C18), stearyl chloride (C18) and the like are particularly preferable. In addition, polyethylene, polypropylene, polyisoprene, polybutadiene having polar groups such as OH, COOH, Cl, and epoxy groups at both terminals may be used, or a hydrogenated product or copolymer thereof. These guest molecules B are selected and used so as to be equal to or longer than the molecular length of the organic onium ion.

As for the guest molecules B, as the mixing ratio increases, the interlayer between the clays tends to expand widely. The mixing ratio of the guest molecules is preferably 0.5 part by weight or more with respect to 1 part by weight of the organized clay.
If the amount is less than 0.5 part by weight, the swelling between layers of the clay may be insufficient.

The molecular weight of the guest molecule B is 500 to
It is preferably 100,000. If it is less than 500, the interlayer swelling of the clay may be insufficient. On the other hand, if it exceeds 100,000, it may be insoluble in a solvent or its softening point or melting point may be higher than the decomposition point of clay. The guest molecule B may have a molecular length of about 3 to 4 times or more of the organic onium ion,
More preferred.

Guest molecule C The guest molecule C has a polar group in the molecule. The polar group is a group in which electrons are localized in the molecule of the guest molecule C and a charge is biased, and does not include a completely polarized ion. Therefore, onium ions are not included in the polar groups.

The polar group of the guest molecule C is a hydroxyl group (O
H), halogen groups (F, Cl, Br, I), carboxyl groups (COOH), and carboxyl anhydride groups (—COO—C
O-), a thiol group (SH), an epoxy group, and an amino group (NH ₂ ).

The guest molecule C has a molecular length equal to or larger than that of the organic onium ion. Guest molecule C
When the molecular length of is smaller than the molecular length of the organic onium ion, the guest molecule C may not protrude outside the region where the organic onium ion exists at the clay interface. Therefore, the clay may be difficult to disperse in a matrix such as a rubber material.

The guest molecule C has an unsaturated carbon chain having an unsaturated bond in the molecule. The unsaturated bond is highly reactive and forms a cross-link with the unsaturated bond of the organic onium ion in the presence of the cross-linking agent.

The guest molecule C has a molecular weight of 1,000.
Preferably, it is an oligomer or polymer of 100,000. If the molecular weight is less than 1,000, the swelling between the layers of the clay may be insufficient. On the other hand, when the molecular weight exceeds 100,000, the guest molecule C may become insoluble in the solvent, or the softening point or melting point may be higher than the decomposition point of the clay.

Guest molecule D The guest molecule D is made of a polyolefin oligomer having a functional group. The functional group is a chemically modified group having a relatively polar chemical structure, which is covalently bonded to a polyolefin-based oligomer. Examples thereof include a maleic anhydride group, a hydroxyl group, a carboxyl group, an amide group, an amino group, a urethane group, an ester group, an imide group, a maleimide group, a halogen group, an ether group, a thiol group, and an epoxy group. The site where the functional group is covalently bonded to the polyolefin oligomer may be at the end of the oligomer molecule or may be bonded as a side chain in the middle of the molecular chain.

Among the above-mentioned various functional groups, a maleic anhydride group which can impart high intercalation ability to the polyolefin oligomer is particularly preferable. Particularly preferred are a hydroxyl group, a carboxyl group, an amide group, a urethane group, an imide group, a maleimide group, and a thiol group, which are functional groups having hydrogen bondability and high polar interaction.

The polyolefin-based oligomer refers to a chain (straight-chain or branched) polymer consisting essentially of a combination of atoms of only carbon and hydrogen and containing no aromatic chemical group. For example, polyethylene, polypropylene (hereinafter, also simply referred to as “PP”), ethylene-propylene copolymer, polybutadiene, polyisoprene, or a hydrogenated product or copolymer of polybutadiene or polyisoprene can be exemplified. No.

Here, the oligomer is defined as having a molecular weight of 500 to 500.
It means a polymer of about 1,000,000. Particularly preferred molecular weight is about 1,000 to 500,000. Oligomers that deviate from the above range of molecular weight may lower the physical properties of the clay composite material on the low molecular weight side or may cause insufficient swelling between layers of the layered clay, and on the high molecular weight side, the melt viscosity of the oligomer May be too high to intercalate into layered clay.

The polyolefin-based oligomer of the present invention has the above-mentioned functional groups covalently bonded thereto. The amount of the bonded functional groups is 0.001 mmol / mol of the polyolefin-based oligomer for the reason described in the above description of the operation. g or more and 0.45 mmol / g or less.

As described in claim 9, the total content of the organized clay and the polymer in the hose is preferably at least 60% by weight or more. 60% by weight
If it is less than the above, there is a possibility that the effect of the present invention may not be sufficiently exerted.

Further, it is preferable that the hose is used for transporting a refrigerant of an automobile air conditioner. Thereby, the effect of the hose of the present invention can be maximized.

[0076]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 A hose according to an embodiment of the present invention will be described with reference to FIGS. As shown in FIG. 4, the hose of this example is a refrigerant transport hose 6 of an air conditioner for an automobile.
In the innermost layer. The hose 61 is formed in a tubular shape, and its surface is covered with a reinforcing thread 62 and an outer rubber 63. The hose 61 is composed of the organized clay 1 and the polymer 2 as shown in FIG. Organized clay 1, as shown in FIG.
It is finely dispersed in the polymer 2 and oriented parallel to the surface direction of the hose 61.

As shown in FIG. 5, the organized clay 1 refers to clay that has been organically formed by ionic bonding of an organic onium ion 12 to the clay 11. Polymer 2 is
A cross-link 20 such as a sulfur bond is formed with the other polymer 2 in the middle of the molecular chain. In addition, the hose 61 contains the guest molecules 3 for improving the dispersibility of the organic clay 1. The guest molecule 3 has a polar group 30 having a high affinity for the clay 11.

Table 1 shows details of the composition of the hose. Table 1
As shown in the figure, the hose consists of 15 parts by weight of organic clay,
100 parts by weight of polymer. The polymer is rubber 5
0 to 85 parts by weight and guest molecules 50 to 15 parts by weight. Butyl rubber is used as the rubber, and modified butyl rubber having an anhydrous carboxyl group is used as the guest molecule. In addition, the hose contained 1 part by weight of stearic acid, 3 parts by weight of zinc oxide, 1.75 parts by weight of sulfur, 3 parts by weight of a vulcanization accelerator, and 10 to 50 parts by weight of carbon black based on 100 parts by weight of the polymer. Contains. The hose is obtained by mixing raw materials composed of these components, extruding into a tube, and vulcanizing by heating.

[0079]

[Table 1]

As shown in FIG. 6, the refrigerant transport hose 6 is used to transport the refrigerant of the air conditioner 7 for an automobile. That is, the automotive air conditioner 7 is provided with a compressor 7 for compressing a gaseous refrigerant.
1 and a condenser 72 for liquefying the compressed refrigerant
, A receiver 73 for temporarily storing the refrigerant, an expansion valve 74 for depressurizing and spraying the refrigerant, and an evaporator 75 for evaporating the refrigerant and cooling the air with the heat of vaporization thereof. ing.
The compressor 71 is operated by the power of the engine 8 of the automobile.

Next, the operation and effect of this embodiment will be described. In the hose 61 of this example, as shown in FIG. 3, the organized clay 1 is finely dispersed in the polymer 2, and the organized clay 1 is oriented in the plane direction of the hose 61. Therefore, the detour effect of the fluid such as the refrigerant and the air is high, and the fluid blocking property is extremely high. Therefore, leakage of the refrigerant can be prevented in the refrigerant circulation system of the air conditioner shown in FIG.

Further, it is preferable that the hose for transporting refrigerant of this embodiment is mounted on a refrigerant transport system near the compressor. The reason is that the compressor, together with the other refrigerant circulation systems, is mounted on the body of the automobile, which is a separate member from the engine. For this reason, the vibration characteristics of the refrigerant circulation system and the engine are different, and a large vibration difference occurs particularly in the refrigerant transportation system near the compressor. For this reason, it is significant to use a hose having excellent vibration absorption properties as in this example in the refrigerant transport system near the compressor.

Embodiment 2 In this embodiment, as shown in FIG. 7, hoses 611 and 612 containing resin and rubber, respectively, are used as a refrigerant transport hose 6 of an air conditioner for an automobile. The inner layer side hose 611 is composed of 100 parts by weight of the resin and 0.5 to 30 parts by weight of the organized clay. As the resin, polyamide such as nylon is used. Specific examples of nylon include nylon 6, nylon 66, nylon 6-12, and nylon 1.
2 nylon, 46 nylon, aromatic nylon, 6-10
Nylon, modified nylon (mixed with a rubber component to improve impact) may be used alone or as a mixture of two or more. As the organized clay, the same clay as that used in the first embodiment was used. The outer layer side hose 612 contains butyl rubber as rubber. The component composition of the hose 612 is the same as that of the hose of the first embodiment. The hose of this example also exhibited excellent fluid blocking properties, vibration absorbing properties, and mechanical strength as in the first embodiment.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory view showing a fluid blocking property of a hose in which an organized clay is dispersed in a finite swelling state in a polymer according to the present invention.

FIG. 2 is an explanatory view showing a fluid blocking property of a hose in which an organized clay is dispersed in an infinite swelling state in a polymer according to the present invention.

FIG. 3 is an explanatory view showing a fluid blocking property of a hose in which an organized clay is dispersed in a polymer while being oriented in a plane direction of the hose in the present invention.

FIG. 4 is a perspective view of a refrigerant transport hose according to the first embodiment.

FIG. 5 is an explanatory diagram showing the interrelationship between the organized clay and the polymer in the first embodiment.

FIG. 6 is a diagram illustrating the principle of an automotive air conditioner according to the first embodiment.

FIG. 7 is a perspective view of a refrigerant transport hose according to a second embodiment.

[Explanation of symbols]

 1. . . 1. Organized clay, . . 2. host molecule, . . Guest molecule, 6. . . Hose for transporting refrigerant, 61. . . Hose, 7. . . Automotive air conditioner, 71. . . Compressor, 72. . . Capacitor, 73. . . Receiver, 74. . . Expansion valve, 75. . . Evaporator, 8. . . Engine, 9. . . fluid,

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B29K 501: 12 (72) Inventor Fumio Kato 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside DENSO CORPORATION (72) Inventor Wakabayashi Hiroyuki 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside DENSO Corporation (72) Inventor Keiichi Kitamura 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside DENSO Corporation (72) Inventor Yumi Usuki Aichi-gun, Aichi Prefecture 41 Toyota Chuo R & D Co., Ltd. (72) Inventor Makoto Kato 41 Toyota Chuo R & D Co., Ltd.

Claims (10)

[Claims] 1. A hose comprising an organized clay and a polymer. 2. The hose according to claim 1, wherein the organized clay is oriented parallel to a surface direction of the hose. 3. The hose according to claim 1, wherein the polymer is a resin and / or rubber. 4. The method according to claim 1, wherein:
A hose, wherein the polymer has a polar group. 5. The method according to claim 1, wherein:
The hose according to claim 1, wherein the hose has, in addition to the polymer and the organized clay, a guest molecule having a higher affinity for the organized clay than the polymer. 6. The method according to claim 1, wherein:
The above-mentioned organically modified clay is characterized in that an organic onium ion is ion-bonded to the clay. 7. The hose according to claim 6, wherein the clay has a cation exchange capacity of 50 to 200 meq / 100 g. 8. The method according to claim 1, wherein:
The hose according to claim 1, wherein the amount of the organic clay is 0.01 to 200 parts by weight based on 100 parts by weight of the polymer. 9. The method according to claim 1, wherein:
The hose according to claim 1, wherein a total content of the organized clay and the polymer is at least 60% by weight or more. 10. The hose according to claim 1, wherein the hose is used for transporting a refrigerant of an automobile air conditioner.