JP2002080645A - Elastomer molding - Google Patents

Abstract

(57) Abstract: An elastomer molded article having excellent gas barrier properties without impairing flexibility as an elastomer. [1] An elastomer molded article comprising an elastomer and a liquid crystal polymer. [2] The molded article according to the above [1], wherein the liquid crystal polymer is laminated between two layers made of an elastomer. [3] The molded article according to the above [1] or [2], wherein the liquid crystal polymer is in the form of a film. [4] The molded article according to the above [1] or [2], wherein the liquid crystal polymer is in the form of a flat flake. [5] having a plate-like shape substantially without branching,
A flat flake liquid crystal polymer characterized in that the length, width and length are greater than the thickness in the thickness, length and width.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an elastomer molded article. More specifically, the present invention relates to an elastomer molded article comprising an elastomer and a liquid crystal polymer.

[0002]

2. Description of the Related Art Elastomer molded articles generally have elasticity (deformation recovery), elongation, flexibility and the like as their properties and are used in a wide range of fields. For example, seats, tubes, balls, tires, balloons, and the like require elasticity, elongation, and flexibility as their characteristics, and elastomers are used as their materials. As the elastomer as a material, for example, a conventionally known chemically crosslinked elastomer of natural rubber or synthetic rubber such as chloroprene, and a thermoplastic elastomer which is easy to mold in recent years are used.

[0003] However, elastomers do not have sufficient gas barrier properties, so that, for example, balloons, balls, and the like have a problem in that they become smaller or less resilient over time. There is also a problem that it is necessary to periodically inflate tires. Conventionally, in order to improve the gas barrier property of an elastomer, an attempt has been made to improve the gas barrier property by increasing the thickness of the elastomer or curing the elastomer by a special method. However, these methods are not always satisfactory in performance, and when the thickness is increased, the method becomes heavy, and when cured, the flexibility may be impaired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an elastomer molded article having excellent gas barrier properties while maintaining flexibility as an elastomer.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an elastomer molded article made of an elastomer and a specific polymer, a liquid crystal polymer exhibiting optical anisotropy when melted, can solve the above-mentioned problems. As a result, the present invention has been completed. That is, the present invention provides an elastomer molded article comprising an elastomer and a liquid crystal polymer. Further, the present invention provides
Another object of the present invention is to provide a flat flake liquid crystal polymer used as a raw material of the elastomer molded article and a method for producing the same.

[0006]

Next, the present invention will be described in more detail. The elastomer molded article of the present invention is characterized by comprising an elastomer and a liquid crystal polymer.
The liquid crystal polymer may be present as a layer or may be dispersed in the elastomer. In the former case, the liquid crystal polymer may be in the form of a film or a flat flake,
In the latter case, it is preferably in the form of a flat flake.

In the former case, a layer containing a liquid crystal polymer,
It is preferable that a layer composed of an elastomer is laminated, and it is more preferable that the liquid crystal polymer is laminated between two layers composed of the elastomer. In these cases, when the liquid crystal polymer is in the form of a film, the film may be thermocompression-bonded to the surface of the elastomer, or may be bonded with an adhesive. When it is in the form of a flat flake, it can be laminated by dispersing it in a pressure-sensitive adhesive, an adhesive or a solution thereof and applying it to the surface of the elastomer. On the other hand, in the latter case, for example, the elastomer and the flat flake liquid crystal polymer can be dispersed by kneading.

Next, the liquid crystal polymer used in the present invention will be described. As the liquid crystal polymer used in the present invention, a so-called thermotropic liquid crystal polymer which exhibits optical anisotropy when melted is preferably used. As the liquid crystal polymer, for example, a wholly aromatic or semi-aromatic, polyester,
Examples thereof include polyesterimide, polyesteramide, and the like, and a resin composition containing them. In the present invention, as such a liquid crystal polymer, a composition or a liquid crystal polyester using a liquid crystal polyester as one component is preferably used.From the viewpoint of moldability and performance of a film to be obtained, in the present invention, It is more preferable to use a liquid crystal polyester resin composition having (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase.

The liquid crystal polyester referred to herein is, specifically, (1) a polyester obtained by reacting an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid;
(2) a product obtained by reacting a combination of different kinds of aromatic hydroxycarboxylic acids, (3) a product obtained by reacting an aromatic dicarboxylic acid with an aromatic diol, and (4) a polyester such as polyethylene terephthalate. Examples thereof include those obtained by reacting an aromatic hydroxycarboxylic acid, and those which form an anisotropic melt at a temperature of 400 ° C. or lower are preferable. In addition, instead of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, their ester derivatives may be used. Furthermore, as these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, those in which the aromatic portion is substituted with a halogen atom, an alkyl group, an aryl group, or the like may be used.

The repeating structural units of the liquid crystal polyester include the following repeating structural units derived from an aromatic dicarboxylic acid, the following repeating structural units derived from an aromatic diol,
Examples of the repeating structural unit derived from an aromatic hydroxycarboxylic acid include, but are not limited to, these.

A repeating structural unit derived from an aromatic dicarboxylic acid:

The aromatic ring in each of these structural units may be substituted with a halogen atom, an alkyl group, an aryl group, or the like.

A repeating structural unit derived from an aromatic diol:

The aromatic ring in each of these structural units may be substituted with a halogen atom, an alkyl group, an aryl group, or the like.

A repeating structural unit derived from an aromatic hydroxycarboxylic acid: The aromatic ring in each of these structural units is a halogen atom,
It may be substituted with an alkyl group, an aryl group or the like.

A liquid crystal polyester which is particularly preferred from the balance of heat resistance, mechanical properties and workability is And more preferably such repeating structural units at least 3 times in total.
It contains 0 mol% or more. Specifically, the combination of repeating structural units is preferably any one of the following (I) to (VI). Further, from the viewpoint of moisture resistance, a wholly aromatic polyester type other than (IV) is more preferable.

(I)

(II)

(III)

(IV)

(V)

(VI)

The liquid crystal polyesters of the above combinations (I) to (VI) are described, for example, in JP-B-47-47870, JP-B-63-3888, and JP-B-63-389.
No. 1, JP-B-56-18016, JP-A-2-
It can be produced according to the method described in, for example, Japanese Patent No. 51523. Among these, preferred combinations are (I) and (I
I) or (IV), more preferably (I) or (I
I).

In the present invention, in the field where high heat resistance is required, the following repeating unit (a ') is 30 to 80 mol%, the repeating unit (b') is 0 to 10 mol%, and the repeating unit (c) Liquid crystal polyesters comprising ') of 10 to 25 mol% and repeating units (d') of 10 to 35 mol% are preferably used.

[0025] (In the formula, Ar represents a divalent aromatic group.) The divalent aromatic group in the repeating unit (d ′) is preferably a divalent aromatic group in the above-described aromatic diol,
In particular, a wholly aromatic diol is preferred for applications requiring high heat resistance.

In the elastomer molded article of the present invention, from the viewpoint of environmental problems, etc., the fields in which easy disposal such as incineration after use is required are included in the preferred combinations of the fields required in each of the above. In particular, a liquid crystal polyester obtained by combining only carbon, hydrogen and oxygen is particularly preferably used.

When a film is used for the elastomer molded article of the present invention, (A) a liquid crystalline polyester is used as a continuous phase (B) from the viewpoint of processability in molding a liquid crystal polymer.
It is more preferable to use a liquid crystal polyester resin composition containing a copolymer having a functional group reactive with liquid crystal polyester as a dispersed phase. The component (B) used in the liquid crystal polyester resin composition is a copolymer having a functional group reactive with the liquid crystal polyester. Such a functional group having reactivity with the liquid crystal polyester may be anything as long as it has reactivity with the liquid crystal polyester,
Specific examples include an oxazolyl group, an epoxy group, and an amino group. Preferably, it is an epoxy group. Epoxy groups etc. may be present as part of other functional groups,
Such an example includes, for example, a glycidyl group.

In the copolymer (B), the method for introducing such a functional group into the copolymer is not particularly limited, and it can be carried out by a known method. For example, at the stage of synthesizing the copolymer, it is possible to introduce the monomer having the functional group by copolymerization, or it is also possible to graft copolymerize the monomer having the functional group to the copolymer. It is.

A monomer having a functional group reactive with the liquid crystal polyester, particularly a monomer containing a glycidyl group, is preferably used. As the monomer containing a glycidyl group, for example, the following general formula (Wherein, R represents a carbon number 2 having an ethylenically unsaturated bond)
X represents -C (O) O-, -C
H ₂ —O— or Represents The unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl ether represented by the formula (1) is preferably used.

The unsaturated carboxylic acid glycidyl ester includes, for example, glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, and p-glycidyl ester.
Glycidyl styrene carboxylate;

Examples of the unsaturated glycidyl ether include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, methacryl glycidyl ether, and styrene-p-glycidyl ether.

The copolymer (B) having a functional group reactive with the liquid crystal polyester preferably contains 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. It is a copolymer containing.

Preferably, the copolymer (B) having a functional group reactive with the liquid crystal polyester is a copolymer having a heat of fusion of crystal of less than 3 J / g. The copolymer (B) preferably has a Mooney viscosity of 3 to 70, more preferably 3 to 30, and particularly preferably 4 to 25. The Mooney viscosity referred to here is JI
A value measured using a large rotor at 100 ° C. according to SK6300. Outside these ranges, the thermal stability and flexibility of the composition may be undesirably reduced.

The copolymer (B) having a functional group reactive with the liquid crystal polyester may be a thermoplastic resin or a rubber, or a mixture of a thermoplastic resin and a rubber. You may. A rubber having excellent thermal stability and flexibility of a molded product such as a film or sheet obtained by using the liquid crystal polyester resin composition is more preferable.

The method for introducing a functional group reactive with the liquid crystal polyester into the rubber is not particularly limited, and it can be carried out by a known method. For example, it is possible to introduce the monomer having the functional group by copolymerization at the stage of synthesizing the rubber, or it is also possible to graft copolymerize the monomer having the functional group to the rubber.

Examples of the rubber having an epoxy group as a specific example of the copolymer (B) having a functional group reactive with the liquid crystal polyester include (meth) acrylate-ethylene- (unsaturated glycidyl carboxylate and And / or unsaturated glycidyl ether) copolymer rubber.

Here, the (meth) acrylate is
An ester obtained from acrylic acid or methacrylic acid and an alcohol. Alcohols have 1 carbon atom
~ 8 alcohols are preferred. Specific examples of (meth) acrylates include methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, ter
Examples thereof include t-butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. As the (meth) acrylic acid ester, one kind thereof may be used alone, or two or more kinds may be used in combination.

In the copolymer rubber of the present invention,
(Meth) acrylate unit is preferably more than 40% by weight and less than 97% by weight, more preferably 45 to 70%.
% By weight, preferably 3% by weight or more and less than 50% by weight, more preferably 10-49% by weight, more preferably 0.1-30% by weight of unsaturated carboxylic acid glycidyl ether unit and / or unsaturated glycidyl ether unit. %, More preferably 0.5 to 20% by weight. If the ratio is outside the above range, the resulting molded product such as a film or sheet may have insufficient thermal stability and mechanical properties, which is not preferable.

The copolymer rubber can be produced by a usual method, for example, bulk polymerization, emulsion polymerization, solution polymerization or the like using a free radical initiator. Typical polymerization methods are described in JP-A-48-11388,
1-1127709, etc.,
Pressure of 5 in the presence of a free radical generating polymerization initiator
It can be manufactured under the conditions of at least 00 kg / cm ² and a temperature of 40 to 300 ° C.

Other examples of the rubber that can be used for the copolymer (B) include an acrylic rubber having a functional group reactive with the liquid crystal polyester and a vinyl aromatic hydrocarbon compound having a functional group reactive with the liquid crystal polyester -Conjugated diene compound block copolymer rubber can also be exemplified.

The acrylic rubber mentioned here is preferably of the general formulas (1) to (3): CH ₂ CH—C (O) —OR ¹ (1) CH ₂ ＣＨCH—C (O) —OR ² OR ³ (2) CH ₂ ＣＲCR ⁴ H—C (O) —O (R ⁵ (C (O) O) n R ⁶ (3) (wherein, R ¹ is an alkyl group having 1 to 18 carbon atoms or cyanoalkyl R ² represents an alkylene group having 1 to 12 carbon atoms, R ³ represents an alkyl group having 1 to 12 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a carbon atom having 3 carbon atoms. 30 alkylene group, R ⁶ is 1 to carbon atoms
20 alkyl groups or derivatives thereof, and n represents an integer of 1 to 20. )) At least one monomer selected from the compounds represented by the formula (1).

Specific examples of the alkyl acrylate represented by the general formula (1) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Examples thereof include butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, and cyanoethyl acrylate.

The alkoxyalkyl acrylate represented by the general formula (2) includes, for example, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate and the like. One or more of these can be used as the main component of the acrylic rubber.

As a constituent component of such an acrylic rubber, an unsaturated monomer copolymerizable with at least one monomer selected from the compounds represented by the above general formulas (1) to (3), if necessary. A dimer can be used. Examples of such unsaturated monomers include styrene, α-methylstyrene, acrylonitrile, halogenated styrene, methacrylonitrile, acrylamide, methacrylamide, vinylnaphthalene, N-methylolacrylamide, vinyl acetate, vinyl chloride, chloride Vinylidene, benzyl acrylate, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.

The preferred component ratio of the acrylic rubber having a functional group reactive with the liquid crystal polyester is at least one monomer selected from the compounds represented by the above general formulas (1) to (3). 0 to 99.9% by weight, 0.1 to 30.0% by weight of unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether, selected from the compounds represented by the above general formulas (1) to (3). Unsaturated monomer copolymerizable with at least one monomer 0.0
３30.0% by weight. When the constituent ratio of the acrylic rubber is within the above range, heat resistance and impact resistance of the composition,
The molding processability is good and preferable.

The method for producing the acrylic rubber is not particularly limited. For example, JP-A-59-113010, JP-A-62-64809, and JP-A-3-160008.
Or a well-known polymerization method described in WO95 / 04764 or the like, and can be produced by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization in the presence of a radical initiator. .

The vinyl aromatic hydrocarbon compound / conjugated diene compound block copolymer rubber having a functional group reactive with the liquid crystal polyester includes, for example, (a) a sequence mainly composed of a vinyl aromatic hydrocarbon compound; b) Rubber obtained by epoxidizing a block copolymer composed of a sequence mainly composed of a conjugated diene compound, and rubber obtained by epoxidizing a hydrogenated product of the block copolymer.

Here, as the vinyl aromatic hydrocarbon compound, for example, styrene, vinyltoluene, divinylbenzene, α-methylstyrene, p-methylstyrene, vinylnaphthalene and the like can be mentioned, among which styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 3-butyl-1,3-octadiene and the like, butadiene or isoprene is preferred.

Such a vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer or a hydrogenated product thereof can be produced by a well-known method.
No. 23798, JP-A-59-133203 and the like.

The rubber used as the copolymer (B) is preferably (meth) acrylate-ethylene-
(Unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is used.

The rubber used as the copolymer (B) may be vulcanized as required, and used as a vulcanized rubber. The above (meth) acrylic acid ester-ethylene-
Vulcanization of the (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is achieved by using a polyfunctional organic acid, a polyfunctional amine compound, an imidazole compound, and the like. It is not limited.

On the other hand, the thermoplastic resin having an epoxy group as a specific example of the copolymer (B) having a functional group reactive with the liquid crystal polyester includes (a) 50 to 99% by weight of ethylene units, b) 0.1 to 30% by weight, preferably 0.5 to 2% by weight of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units.
0% by weight and (c) an epoxy group-containing ethylene copolymer in which the ethylenically unsaturated ester compound unit is 0 to 50% by weight.

Examples of the ethylenically unsaturated ester compound (c) include vinyl carboxylate such as vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. Esters, α, β-unsaturated carboxylic acid alkyl esters, and the like. Particularly, vinyl acetate, methyl acrylate and ethyl acrylate are preferred.

Specific examples of the epoxy group-containing ethylene copolymer include, for example, a copolymer composed of ethylene units and glycidyl methacrylate units, a copolymer composed of ethylene units and glycidyl methacrylate units, and methyl acrylate units. Copolymers composed of glycidyl methacrylate units and ethyl acrylate units, and copolymers composed of ethylene units, glycidyl methacrylate units and vinyl acetate units are exemplified.

The melt index of the epoxy group-containing ethylene copolymer (hereinafter sometimes referred to as MFR. JI
SK6760, 190 ° C, 2.16 kg load) is preferably 0.5 to 100 g / 10 min, more preferably 2 to 50 g / 10 min. The melt index may be outside this range, but the melt index is 100
If it exceeds g / 10 minutes, it is not preferable in view of the mechanical properties of the composition, and if it is less than 0.5 g / 10 minutes, the component (A)
Is inferior in compatibility with the liquid crystal polyester.

[0056] Also, the epoxy group-containing ethylene copolymer is preferably in the range stiffness modulus of 10~1300kg / cm ^2, further preferably from 20~1100kg / cm ^2. If the flexural rigidity is outside this range, the moldability and mechanical properties of the composition may be insufficient.

The epoxy group-containing ethylene copolymer is usually prepared by reacting an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a high-pressure radical polymerization method in which copolymerization is carried out in the presence. Further, it can also be produced by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt-grafted and copolymerized in an extruder.

In the liquid crystal polyester resin composition of the present invention, the above-mentioned (A) liquid crystal polyester is used as a continuous phase and the above-mentioned (B) copolymer having a functional group reactive with the liquid crystal polyester is dispersed. The resin composition is preferably a phase. When the liquid crystal polyester is not in the continuous phase, the gas barrier properties, heat resistance, and the like of the film made of the liquid crystal polyester resin composition may be significantly reduced.

The details of the mechanism of such a resin composition of a copolymer having a functional group and a liquid crystal polyester are not clear, but the resin composition between the component (A) and the component (B) of the composition is not clear. It is considered that a reaction occurs, and the component (A) forms a continuous phase, and the component (B) is finely dispersed, thereby improving the moldability of the composition.

One embodiment of the above liquid crystal polyester resin composition for suitably obtaining a liquid crystal polymer film is as follows:
(A) 56.0 to 99.9% by weight, preferably 65.0 to 99.9% by weight, more preferably 70 to 98% by weight of the liquid crystal polyester, and (B) a functional group reactive with the liquid crystal polyester. Having a copolymer of 44.0 to 0.1
%, Preferably 35.0 to 0.1% by weight, more preferably 30 to 2% by weight.
If the content of the component (A) is less than 56.0% by weight, the water vapor barrier property and heat resistance of a film obtained from the composition may be reduced. When the amount of the component (A) is more than 99.9% by weight, the molding processability of the composition may be reduced, and the composition is expensive. Further, in the method for producing a flat flake liquid crystal polymer used in the present invention described later, one embodiment in which the flake liquid crystal polymer is obtained by beating a film includes (A) liquid crystal polyester 7
0.0 to 95.0% by weight, and (B) a copolymer having a functional group reactive with the liquid crystal polyester.
5.0% by weight is preferred. 70.0% by weight of component (A)
If less than this, the film obtained from the composition may not be formed into a flat plate when the liquid crystal polymer flakes are beaten, and furthermore, the elastic modulus is lowered and the flat plate shape cannot be maintained when blended into the elastomer. It is not preferable because it may occur. On the other hand, if the content of the component (A) exceeds 95.0% by weight, the film obtained from the composition may be unduly excessively branched when the film is beaten, so that the flat form cannot be maintained.

As a method for producing such a liquid crystal polyester resin composition, a known method can be used. For example, a method of mixing each component in a solution state and evaporating the solvent, or a method of precipitating in the solvent may be mentioned. From an industrial point of view, a method of kneading each component of the above composition in a molten state is preferred. For the melt kneading, kneading apparatuses such as a single-screw or twin-screw extruder and various kneaders which are generally used can be used. In particular, a biaxial high kneader is preferred. At the time of melt-kneading, the cylinder set temperature of the kneading device is preferably in the range of 200 to 360 ° C, more preferably 230 to 350 ° C.

At the time of kneading, each component may be previously mixed uniformly with a device such as a tumbler or a Henschel mixer, or the mixing may be omitted if necessary.
It is also possible to use a method of separately supplying a fixed amount to the kneading device.

The liquid crystal polymer used in the present invention may further contain, if necessary, an organic filler, an antioxidant, a heat stabilizer,
Light stabilizer, flame retardant, lubricant, antistatic agent, inorganic or organic colorant, rust inhibitor, cross-linking agent, foaming agent, fluorescent agent, surface smoothing agent, surface gloss improving agent, release improver such as fluororesin And various additives can be added during the manufacturing process or in a subsequent processing step.

In the present invention, the film-like liquid crystal polymer is preferably formed by inflation film formation which can be simultaneously biaxially stretched. That is, the liquid crystal polyester resin composition obtained by the above method is supplied to a melt kneading extruder equipped with an annular slit die, and the cylinder set temperature is preferably 200 to 360 ° C, more preferably 23 ° C.
It is melt-kneaded at 0 to 350 ° C. Next, the molten resin is extruded upward or downward from the annular slit of the extruder to form a cylindrical film (this direction is the MD direction). The annular slit interval is usually 0.1 to 5 mm, preferably 0.5
~ 2mm, the diameter of the annular slit is usually 20 ~ 1000
mm, preferably 50 to 300 mm.

In inflation molding (film formation),
The preferred blow ratio is 1.5 to 10, and the preferred MD draw ratio is 1.5 to 40. If the setting conditions during the inflation film formation are outside the above range, it may be difficult to obtain a high-strength film having a uniform thickness and no wrinkles. When a flat flake liquid crystal polymer is obtained by beating a film formed by inflation molding, a preferable blow ratio for obtaining the film is 2.0 to 10.
If the ratio is less than 2.0, the obtained flakes may be undesirably branched.

The expanded film is air-cooled or water-cooled on its circumference, and then passed through a nip roll to be taken out.

In the case of inflation film formation, conditions can be selected according to the properties of the composition so that the cylindrical molten film expands to a uniform thickness and a smooth surface.

If the method is other than the inflation film forming method, the film may not be biaxially stretched to obtain a necessary minimum strength, or even if the film is biaxially stretched successively by another method, the production method may be too costly. is there.

In the present invention, the surface free energy of the film-like liquid crystal polymer exhibiting optical anisotropy upon melting is 3
It is preferably at least 5 dyne / cm. If it is less than this, the adhesion between the elastomer and the liquid crystal polymer may be insufficient. When the surface free energy of the obtained liquid crystal polymer film is less than 35 dyne / cm, surface treatment such as corona treatment may be performed.

The preferred thickness of the film-like liquid crystal polymer used in the present invention is 0.5 μm or more and 500 μm or less.
If it is less than 0.5 μm, the handling properties are significantly impaired, and if it exceeds 500 μm, the suppleness may be impaired, which is not preferable.

The flake liquid crystal polymer of the present invention has a flat plate shape having substantially no branching, and the thickness, length and width of the polymer are larger than the thickness. The horizontal length is more preferably at least 5 times the thickness, even more preferably at least 10 times the thickness.
Further, in each case, it is preferable that one length in the vertical and horizontal directions is larger than the other length, and the longer one is more preferably twice or more the shorter one, more preferably four times or more. By having such a substantially flat shape, when mixed and dispersed in an elastomer to form a composite, the liquid crystal polymer flakes are positioned so as to overlap in the plane direction, and the gas barrier properties of the molded body are improved, The effect of improving rigidity is easily obtained. Further, when dispersed in an adhesive and / or a pressure-sensitive adhesive or a paint, the surface of the liquid crystal polymer in the form of a flat filler is arranged in parallel with the application surface, and the effect of improving the gas barrier properties of the applied elastomer is easily obtained. Become.

The average thickness of the plate-like flake having substantially no branch is preferably 0.5 μm or more and 500 μm or less, more preferably 3 μm or more and 200 μm or less.
μm or less, more preferably 5 μm or more and 100 μm or less. When the thickness is 0.5 μm or less, the properties as a liquid crystal polymer are hardly exhibited, and when the thickness is 500 μm or more, dispersion failure may occur when compounding with another resin or the like, which is not preferable. Although there is no particular limitation on the method of molding and processing the filler-like liquid crystal polymer of the present invention, it is preferable to manufacture the film by using a film made of a liquid crystal polymer exhibiting optical anisotropy when molten as a raw material and performing processing such as cutting and grinding. . Thereby, a flat shape can be easily and uniformly obtained, and a filler having an average uniform thickness can be obtained. In the method of molding and processing a filler-like liquid crystal polymer according to the present invention, cutting of a film-shaped material usually requires 2
A general paper or film cutting method using a single blade or a rotating blade and a fixed blade is used.

As a processing method for converting a film-shaped product into a flake liquid crystal polymer, various grinders, mills, beaters, jordans, refiners and the like are effectively used as examples of mechanical beating operation. When the beating operation is performed in a wet state, water or an oil agent or a surfactant may be used for the purpose of preventing fusion of the raw material resin. Addition of alcohols such as isopropanol, ethanol and ethylene glycol to increase the wettability of the surface,
The beating can be facilitated. Most preferably, it is obtained by obtaining a biaxially stretched film by inflation from the liquid crystal polyester composition and wet-beating it with a beater.

In the present invention, as a pulverizing film for obtaining a flaky liquid crystal polymer, for example, a film obtained using the above liquid crystal polymer can be employed.
Such a film is obtained by, for example, a T-die method of extruding and winding a molten resin from a T-die, or an inflation film forming method of extruding a molten resin into a cylindrical shape from an extruder provided with an annular die, cooling and winding the same. Use of a film or sheet, a film or sheet obtained by a hot press method or a solvent casting method, or a film or sheet obtained by further uniaxially or biaxially stretching a sheet obtained by an injection molding method or an extrusion method. However, in order to obtain a filler having no branching after pulverization, a biaxially stretched film is preferable, and more preferably, the stretching ratio in the TD direction is 2 times or more. If it is less than twice, branching may occur, which is not preferable. When pulverizing a film-shaped material,
Set the length of either D or TD to 0.5 mm to 50 in advance.
mm, more preferably about 0.1 mm to 20 mm, the pulverization proceeds easily.

The elastomer used in the present invention generally contains the rubber described above, that is, has a rubber elasticity at room temperature according to a new edition of Polymer Dictionary (published by The Society of Polymer Science, 1988, published by Asakura Shoten). And specific examples thereof include natural rubber, butadiene polymer, butadiene-styrene copolymer (random copolymer, block copolymer (including SEBS rubber or SBS rubber, etc.)) , Including graft copolymers)
Or its hydrogenated product, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer rubber, isobutylene-isoprene copolymer, acrylate-ethylene copolymer Rubber, ethylene-
α-olefin copolymer rubber (for example, ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, etc.), ethylene-propylene-styrene copolymer rubber,
Styrene-isoprene copolymer rubber, styrene-butylene copolymer, styrene-ethylene-propylene copolymer rubber, perfluoro rubber, fluoro rubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-α-olefin-non-conjugated diene copolymer Polymer rubber (eg, ethylene-
Propylene-non-conjugated diene copolymer rubber), thiol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (for example, polypropylene oxide), epichlorohydrin rubber, polyester elastomer, polyamide elastomer and the like. Among them, natural rubber, chemically crosslinked elastomers such as chloroprene rubber, butadiene-
A hydrogenated acrylonitrile copolymer and an ethylene-propylene-nonconjugated diene copolymer rubber are preferably used. These rubbers can be produced by any production method (eg, emulsion polymerization method, solution polymerization method, etc.), any catalyst (eg, peroxide, trialkylaluminum, lithium halide,
Nickel-based catalyst, titanium-based catalyst, vanadium-based catalyst, metallocene-based catalyst, etc.).

A specific configuration example of the elastomer molded article of the present invention will be described. The elastomer molded article of the present invention is obtained, for example, by laminating and laminating a layer containing a liquid crystal polymer and a layer made of an elastomer. When laminating and bonding, it is preferable to bond via an adhesive layer. Specifically, there is a case where a liquid crystal polymer film is bonded to an elastomer sheet via an adhesive.
Further, as the elastomer molded article of the present invention, an elastomer molded article obtained by disposing a flat flake made of a liquid crystal polymer on the surface of an elastomer is exemplified. Specifically, as a method for forming a layer containing the flat flakes from the adhesive and / or the flat flakes from the liquid crystal polymer, the flat flakes from the liquid crystal polymer are dispersed in the adhesive. The adhesive composition is applied to a layer made of an elastomer to form a layer containing flat flakes made of the liquid crystal polymer.

In the present invention, the adhesive used for the adhesive layer and the adhesive used for coating are not particularly limited, but include urethane adhesives, epoxy adhesives, and the like.
A thermoplastic elastomer adhesive is preferably used, and in particular, a thermoplastic elastomer adhesive, an adhesive based on an aqueous emulsion of an epoxy group-containing ethylene copolymer, and the like are more preferably used.

As the thermoplastic elastomer-based adhesive,
(Meth) acrylic ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer having an epoxy group, and further vinyl alcohol-ethylene- (unsaturated carboxylic acid glycidyl ester and / or Unsaturated glycidyl ether) copolymer.

The epoxy group-containing ethylene copolymer includes an ethylene- (unsaturated glycidyl carboxylate and / or unsaturated glycidyl ether) copolymer.

The method for producing the elastomer molded article is not particularly limited. The adhesive is applied to a liquid crystal polymer film having optical anisotropy at the time of melting and bonded to an elastomer sheet to form a sheet-shaped elastomer molded article. And further processing the sheet to obtain a balloon-shaped or hollow spherical molded body. In addition, the above adhesive is coated, and the longitudinal direction of the liquid crystal polymer film having optical anisotropy at the time of melting is wound along the circumference of the elastomer molded into a cylindrical shape. A method of performing a treatment to obtain a tube-shaped molded body is preferably used. In addition, for the tubular molded body, a liquid crystal polymer film having optical anisotropy when applied with an adhesive is wound around a cylindrical core material, and an elastomer layer is provided on the outside. Can also be extracted and obtained.

Further, the elastomer molded article of the present invention can be obtained by dispersing flat flakes made of a liquid crystal polymer exhibiting optical anisotropy when melted inside the elastomer. Specifically, a flat flake made of a liquid crystal polymer that exhibits optical anisotropy when melted is blended with the elastomer before the crosslinking treatment, and kneaded with a Banbury mixer to form an elastomer composition. A method of forming a body, a tire, a balloon, a tube, or the like into a predetermined shape and then performing a crosslinking treatment.

Further, the elastomer molded article of the present invention
It can also be obtained by applying a flat flake made of a liquid crystal polymer to the surface of the elastomer. Specifically, a flake made of a liquid crystal polymer exhibiting optical anisotropy when melted is dispersed in an adhesive or pressure-sensitive adhesive diluted with a solvent on an elastomer molded body such as a sheet, a balloon, a tube, or a donut. It can be obtained by applying a state filler and drying the solvent. As the adhesive, the above-mentioned adhesive can be used, and as the adhesive, a silicone-based, acrylic-based, or rubber-based adhesive is preferably used.

[0083]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but these are merely examples, and the present invention is not limited thereto. (1) Liquid crystal polyester of component (A) (i) 8.3 kg (60 mol) of p-acetoxybenzoic acid, 2.49 kg (15 mol) of terephthalic acid, 0.83 kg (5 mol) of isophthalic acid and 4,4 ′ 5.45 kg (20.2 mol) of diacetoxydiphenyl was charged into a polymerization tank having a comb-shaped stirring blade, and the temperature was increased while stirring under a nitrogen gas atmosphere to carry out polymerization at 330 ° C. for 1 hour. The acetic acid gas produced as a by-product during this period was polymerized under strong stirring while being liquefied and collected and removed by a cooling tube. Thereafter, the system was gradually cooled, and the polymer obtained at 200 ° C. was taken out of the system.
The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less. This is further heated at 280 ° C. in a rotary kiln under a nitrogen gas atmosphere.
For 3 hours, the flow start temperature becomes 324.
A wholly aromatic polyester composed of the following repeating structural units in the form of particles at a temperature of ° C was obtained. Here, the flow start temperature is defined as 4 using a Shimadzu Flow Tester Model CFT-500 manufactured by Shimadzu Corporation.
The resin heated and melted at a heating rate of
When extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under kgf / cm ² , this refers to a temperature (° C.) at which the melt viscosity shows 48,000 poise. Hereinafter, the liquid crystal polyester is abbreviated as A-1. The polymer is compressed under pressure to 34
Optical anisotropy was exhibited at 0 ° C. or higher. Liquid crystal polyester A-
One repeating structural unit is as follows.

[0084]

(Ii) p-hydroxybenzoic acid 16.6k
g (12.1 mol), 8.4 kg (4.5 mol) of 6-hydroxy-2-naphthoic acid and 18.6 kg of acetic anhydride
(18.2 mol) was charged into a polymerization tank equipped with a comb-shaped stirring blade,
The temperature was increased while stirring in a nitrogen gas atmosphere.
Time, and then 320 ° C. under a reduced pressure of 2.0 torr
For 1 hour. During this time, acetic acid produced as a by-product was continuously distilled out of the system. Thereafter, the system was gradually cooled, and the polymer obtained at 180 ° C. was taken out of the system. The obtained polymer is pulverized in the same manner as in the above (A-1), and then treated in a rotary kiln under a nitrogen gas atmosphere at 240 ° C. for 5 hours to obtain a particulate material having a flow start temperature of 270 ° C. A unitary aromatic polyester was obtained. Hereinafter, the liquid crystal polyester is abbreviated as A-2. This polymer showed optical anisotropy at 280 ° C. or more under pressure. The ratio of the repeating structural units of the liquid crystal polyester A-2 is as follows.

[0086]

(2) Rubber of Component (B) (i) Methyl acrylate / ethylene / glycidyl methacrylate = 59.0 / 38. According to the method described in Example 5 of JP-A-61-127709. 7 / 2.3
(Weight ratio), a rubber having a Mooney viscosity of 15 was obtained. Hereinafter, the rubber may be abbreviated as B-1. Here, the Mooney viscosity is a value measured using a large rotor at 100 ° C. according to JIS K6300.

(3) Using a TEX-30 type twin screw extruder manufactured by Nippon Steel Co., Ltd. in a mixing ratio of 80 parts by weight of the flat flake liquid crystal polymer A-1 and 20 parts by weight of B-1. Set temperature 350 ° C, screw rotation 2
The composition was obtained by melt-kneading at 50 rpm. The composition pellets exhibited optical anisotropy at 340 ° C. or higher under pressure. The resulting composition may be referred to as D-1. D
-1, using a 60 mmφ single screw extruder equipped with a cylindrical die, at a cylinder set temperature of 350 ° C. and a screw rotation speed of 6
The resin is melt-extruded at 0 rpm, the molten resin is extruded upward from a cylindrical die having a diameter of 50 mm, a lip interval of 1.0 mm, and a die setting temperature of 348 ° C., and dry air is pressed into the hollow portion of the obtained tubular film to expand it. After cooling, the film was passed through a nip roll to obtain a film. The blow ratio was 2.3, the drawdown ratio was 15.4, and the measured average thickness of the film was 30 μm. The tensile properties were measured in accordance with JIS C2318, and were 30 kg / mm ² , elongation at break of 1.6%, and elastic modulus of 2200 kg / mm ² in the longitudinal direction.
The oxygen permeability of the film is 3.5 (cc / m ² · 24
h · 1 atm), water vapor permeability is 0.6 (g / m ² · 2)
4 h · 1 atm), which was good. This film is sometimes called F-1.

F-1 100 g with scissors approximately 1 cm ×
It was cut into a size of 3 cm, and it was cut with 2,000 g of water and the distance between the discs was previously measured with a distance meter to 0.1.
Once beaten with a KRK high-concentration disc refiner manufactured by Kumagai Riki Kogyo Co., Ltd. adjusted to 0 mm, width 0.5 mm to 1 m
m, and a flaky filler having a length of 1 mm to 2 mm was obtained. This flaky filler is sometimes referred to as R-1. Further, R
The distance between the disks is set to 0 in advance by reading a distance meter.
After further beating 10 times with a KRK high-concentration disc refiner manufactured by Kumagai Riki Kogyo Co., Ltd. adjusted to 01 mm and dispersing in water, a portion passing through a wire mesh of 80 mesh and not passing through a wire mesh of 140 mesh was used. After drying, a plate-like flake R-2 was obtained. The composition ratio of A-1 was 9
The average actually measured thickness was 3 in the same manner as described above except that 5.5 wt%, B-1 was 4.5 wt%, and the stretching conditions during inflation molding were a blow ratio of 1.2 and a drawdown ratio of 29.1.
When a film having a thickness of 0 μm was obtained and beaten once by the above method, a plate-like flake having many branches and having substantially no branch was not obtained.

(4) Liquid crystal polymer film A-2: 95 parts by weight, B-1: 5 parts by weight, using a TEX-30 twin screw extruder manufactured by Nippon Steel Co., Ltd. 290 ° C, screw rotation speed 4
The composition was obtained by melt-kneading at 00 rpm. The composition pellets exhibited optical anisotropy at 283 ° C. or higher under pressure. The resulting composition may be referred to as D-2. D
-2, using a 60 mmφ single-screw extruder equipped with a cylindrical die, a cylinder set temperature of 305 ° C. and a screw rotation speed of 7
The resin is melt-extruded at 0 rpm, the molten resin is extruded upward from a cylindrical die having a diameter of 70 mm, a lip interval of 1.0 mm, and a die setting temperature of 300 ° C., and dry air is pressed into the hollow portion of the obtained tubular film, and expanded, After cooling, the film was passed through a nip roll to obtain a film. The blow ratio was 2.6, the drawdown ratio was 38.5, and the measured average thickness of the film was 12 μm. The tensile properties were measured in accordance with JIS C2318, and were 34 kg / mm ² and elongation at break of 2.3% in the longitudinal direction. The oxygen permeability of the film is
0.9 (cc / m ² · 24 h · 1 atm) and water vapor permeability of 0.3 (g / m ² · 24 h) were favorable. This film may be called F-2.

(5) Adhesive According to the method described in JP-A-61-127709,
Vinyl alcohol / ethylene / glycidyl methacrylate = 5.0 / 83.0 / 12.0 (weight ratio), MFR
(190 ° C.) 7 g of a copolymer was obtained. This copolymer is
It was hot-pressed at 80 ° C. to obtain a sheet-shaped molded body of about 60 μm. Hereinafter, this sheet may be referred to as S-1.

(6) Elastomer (Production of vulcanizable rubber composition) Ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber (manufactured by Sumitomo Chemical Co., Ltd., trade name "Esprene E-582F", ethylene) / Mole ratio of propylene =
90/10, iodine value = 14) 50 parts by weight, ethylene-
Propylene-5-ethylidene-2-norbornene copolymer rubber (trade name "Esprene E-5" manufactured by Sumitomo Chemical Co., Ltd.)
12F ", ethylene / propylene molar ratio = 78/2
2, Iodine value = 12) 50 parts by weight, stearic acid 1 part by weight, zinc white (# 1) 5 parts by weight, carbon black (trade name “SEIST 116” manufactured by Tokai Carbon Co., Ltd.) 70 parts by weight, magnesium silicate ( 70 parts by weight, manufactured by Takehara Chemical Co., Ltd., trade name "Hytron"; 45 parts by weight of process oil (manufactured by Idemitsu Kosan Co., Ltd., trade name: "Diana PW380");
A compound was obtained by kneading 5 parts by weight and 5 parts by weight of an aliphatic hydrocarbon resin (trade name “Escolets 1102B” manufactured by Exxon Chemical Co., Ltd.) using a Banbury mixer. Next, a rubber composition which can be vulcanized by adding 1.0 part by weight of sulfur, 1.5 parts by weight of TT for vulcanization and 0.5 parts by weight of M for vulcanization to the compound and kneading using an open roll. I got The vulcanizable rubber composition may be referred to as E-1.

(7) (Oxygen Permeability Measurement) According to JIS K7126 (isobaric method), an oxygen permeability measuring device (OX-TRAN10 / 50A, manufactured by MOCON) was used. The test gas was 99.99% oxygen, and the carrier gas was Is 98% nitrogen, 2% hydrogen, temperature 23 ° C, relative humidity on test gas side and relative humidity on carrier gas side are both 60%
Was measured. The unit of the obtained oxygen permeability is cc / m ^2.
The value is 1 atm.24 hr, the thickness is not converted, and the value is based on the film thickness used.

(8) Measurement of Water Vapor Permeability A temperature of 23 was measured in accordance with JIS Z0208 (cup method).
The measurement was performed under the conditions of ° C and 90% relative humidity. The unit is g / m ²
・ 24 hours. It should be noted that the thickness is not converted, but is a value based on the film thickness used.

Example 1 A sheet (15 cm × 15 cm × 1 mm (thickness)) was prepared using the elastomer (vulcanizable rubber composition) obtained above. S-1 / F-2 is placed on the sheet from the sheet side.
The adhesive layer (S-1) and the liquid crystal polymer film (F-2) are stacked so as to be in the order of, and vulcanization and adhesion are performed using a hand press at 160 ° C. for 30 minutes using a 1.2 mm spacer, An elastomer laminate was obtained. The feel when bending was not much different from the sheet of Comparative Example 1. The oxygen permeability and water vapor permeability of the test piece were measured. Oxygen permeability: 0.9 cc / m ² · 24 hr · 1 atm, Water vapor permeability: 0.2 to 0.3 g / m ² · 24 hr Very good.

Example 2 A commercially available vulcanized natural rubber 0.5 mm sheet was coated with S-1 / F-
Then, the adhesive layer (S-1) and the liquid crystal polymer film (F-2) are superimposed on each other to obtain a sheet-like elastomer molded body at 140 ° C. for 10 minutes using a 0.5 mm spacer and a hand press. When the oxygen permeability was measured, the oxygen permeability was 0.9 cc / m ² · 24 hr · 1 atm, which was very good.

Example 3 E-1 (75% by weight), R-1 (25% by weight) were kneaded with a Banbury mixer for 3 minutes, passed through a calender roll having a gap of 0.9 mm, and formed into a sheet (1 mm (thickness)). It was created. Vulcanization and bonding were carried out using a 1.0 mm spacer at 160 ° C. for 30 minutes using a hand press to obtain a flexible elastomer molded article. When the oxygen permeability and the water vapor permeability of the test piece were measured, the oxygen permeability: 65 cc / m ² · 24 hr · 1 atm, and the water vapor permeability: 3 to 4 g / m ² · 24 hr were relatively good.

Example 4 Two sheets (15 cm × 15 cm × 1 mm (thickness)) were prepared using the elastomer (vulcanizable rubber composition) obtained above. A liquid crystal polymer film (F-2) was sandwiched between the sheets, and vulcanization and bonding were performed using a hand press at 160 ° C. for 30 minutes using a 2.1 mm spacer to obtain a laminate. The oxygen permeability and water vapor permeability of the test piece were measured. Oxygen permeability: 0.9 cc / m ² · 24 hr · 1 atm, Water vapor permeability: 0.2 to 0.3 g / m ² · 24 hr Very good.

Example 5 E-1, 80% by weight, R-1, 20% by weight were kneaded with a Banbury mixer for 3 minutes, passed through a calender roll having a gap of 0.9 mm, and sheeted (1 mm (thickness)). It was created. Vulcanization and bonding were carried out using a 1.0 mm spacer at 160 ° C. for 30 minutes using a hand press to obtain a flexible elastomer molded article. When the oxygen permeability and the water vapor permeability of the test piece were measured, the oxygen permeability: 28 cc / m ² · 24 hr · 1 atm, and the water vapor permeability: 2 g / m ² · 24 hr were good.

Example 6 10 g of R-2 was added to a 50% chloroform solution 50c of B-1.
c, and applied to one surface of a commercially available 0.5 mm sheet of vulcanized natural rubber and dried. The oxygen permeability of the film was 130 cc / m ² · 24 hr · 1 atm.

Comparative Example 1 A sheet (15 cm × 15 cm × 1.0 mm (thickness)) was prepared using the elastomer (vulcanizable rubber composition) obtained above, and the adhesive layer and the liquid crystal polymer layer were laminated. Except for this, one sheet was vulcanized under the same conditions as in Example 1 and the oxygen permeability and water vapor permeability were measured. The oxygen permeability: 680 cc / m ² · 24 hr · 1 atm, water vapor permeability Degree: 9 to 11 g / m ² · 24 hr.

Comparative Example 2 The oxygen permeability of a commercially available 0.5 mm sheet made of vulcanized natural rubber was measured and found to be 2000 cc / m ² · 24 hr.
-A value of 1 atm was obtained.

[0103]

Industrial Applicability The elastomer molded article of the present invention is excellent in gas barrier properties without impairing flexibility as an elastomer, and therefore has great industrial value.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 67/00 C08L 67/00 101/12 101/12 // B29K 86:00 B29K 86:00 B29L 23: 00 B29L 23:00 (72) Inventor Hiroaki Kumada 6 Kitahara, Tsukuba-shi, Ibaraki F-term (reference) in the company Sumitomo Chemical Co., Ltd. AA33X AA34X AA43 AA43X AA51 AA51X AA53 AA54 AA54X AA56 AA56X AA57 AA57X AA60X AA61X AA67X AA75X AA76X AA77X AD05 AF07 AH08 BB06 BC01 BC04 BC05 4F100 AK41B AL09A AL09C AN01A AN01C AN02A AN02C AS00B BA03 BA06 DA11 DD23 DE02B EJ05A EJ05C GB15 GB87 JB16B JD02 4F210 AA27 AG08 AH20 AH32 AR06 AR12 QA01 QC07 QG02 QG18 QK01 4J002 AA01W AA02W AC01X AC02W AC03W AC07W AC08W AC09W BB05W B B07W BB10W BB15W BB18W BC02W BC05W BD14W BG043 BN15W BP01W CD193 CF001 CF162 CH021 CH041 CK02W CL001 CL082 CM042 CN01W CP02W GF00 GN01

Claims (26)

[Claims] 1. An elastomer molded article comprising an elastomer and a liquid crystal polymer. 2. A liquid crystal polymer comprising an elastomer.
The molded article according to claim 1, wherein the molded article is laminated between two layers. 3. The molded article according to claim 1, wherein the liquid crystal polymer is in the form of a film. 4. The molded article according to claim 1, wherein the liquid crystal polymer and the elastomer in the form of a film are laminated via an adhesive layer. 5. The molded article according to claim 1, wherein the liquid crystal polymer is in the form of a flat flake. 6. The molded article according to claim 2, wherein the laminated liquid crystal polymer is formed by applying a solution containing a flat flake liquid crystal polymer. 7. The molded article according to claim 5, wherein the flat flake liquid crystal polymer is dispersed in the elastomer. 8. The molded article according to claim 7, wherein the amount of the flat flake liquid crystal polymer is 5 to 100 parts by weight based on 100 parts by weight of the elastomer. 9. The molded article according to claim 1, wherein the liquid crystal polymer is a liquid crystal polyester. 10. A liquid crystal polyester resin composition comprising (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase. The molded article according to any one of claims 1 to 8, wherein 11. A copolymer comprising (A) 56.0 to 99.9% by weight of a liquid crystal polyester and (B) a copolymer having a functional group reactive with the liquid crystal polyester.
The molded article according to any one of claims 1 to 9, which is a composition obtained by melt-kneading 0 to 0.1% by weight. 12. The molded article according to claim 10, wherein the functional group reactive with the liquid crystal polyester is an epoxy group, an oxazolyl group or an amino group. 13. The copolymer (B) having a functional group reactive with a liquid crystal polyester, wherein the copolymer (B) contains 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. The molded article according to any one of claims 10 to 12, which is a polymer. 14. The molded article according to claim 10, wherein the copolymer (B) having a functional group reactive with the liquid crystal polyester is a rubber having an epoxy group. 15. The copolymer (B) having a functional group reactive with the liquid crystal polyester is a thermoplastic resin having an epoxy group.
The molded article according to the above. 16. The molded article according to claim 1, wherein the elastomer has thermoplasticity. 17. The method according to claim 1, wherein the elastomer is a crosslinked natural rubber or a crosslinked synthetic rubber.
5. The molded article according to any one of 5. 18. The molded article according to claim 3, wherein the film made of a liquid crystal polymer is a film obtained by an inflation film forming method. 19. The molded article according to claim 5, wherein the flat flake liquid crystal polymer is obtained by crushing a film. 20. The molded article according to claim 1, wherein the elastomer molded article is in the form of a sheet, a tube, a hollow sphere, a donut or a balloon. 21. A flat plate flake having a flat plate shape having substantially no branching and having a thickness, a vertical length and a horizontal length larger than the thickness. Liquid crystal polymer. 22. The thickness is not less than 0.5 μm and not more than 500 μm.
22. The flat flake liquid crystal polymer according to claim 21, wherein: 23. A method for producing a flat flake liquid crystal polymer, comprising pulverizing a film by thermoforming. 24. The method according to claim 23, wherein the thermoforming method is an inflation film forming method. 25. The method according to claim 24, wherein the blow ratio in the inflation film forming method is in a range of 2.0 or more and less than 15.0. 26. The method according to claim 23, wherein the pulverization of the film is beating using a beating machine.