JP2001302917A - Resin structure and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin structure having properties which have inhibited lowering in properties such as toughness and molding processability as the essential characteristic features of polyolefin resins and has specifically improved chemical and gas permeation resistances, a laminated structure which gives a plastic container and a tubular body having excellent barrier properties, strength, durability, and molding processability as well, and also provide its use. SOLUTION: The thermoplastic resin structure is composed substantially of a resin composition comprising (a) 5-80 vol.% polyolefin resin and (b) 95-20 vol.% polyphenylene sulfide resin and, at the same time, forms a phase structure such that the polyphenylene sulfide resin (b) comes to a matrix phase (a continuous phase) and the polyolefin resin (a) comes to a dispersion phase in the resin phase separation structure to be observed by an electron microscope.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin structure having excellent resistance to gas and / or liquid permeation and its use. Particularly, application to gas and / or liquid barrier parts having specific permeation resistance and moldability, which are obtained by forming a polyolefin resin and a polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) into a specific phase structure. Resin moldings and oils suitable for
The present invention relates to a resin structure suitable for application to containers for storing and transporting chemicals such as gasoline, piping, foodstuffs, medical packaging materials and containers, and uses thereof.

[0002]

2. Description of the Related Art Polyolefin resins such as polyethylene and polypropylene are widely used as general plastics in daily necessities, toys, mechanical parts, electric / electronic parts, automobile parts and the like. However, in recent years, resin products that require gas barrier properties (permeation resistance) for the purpose of preventing leakage of contents and preventing intrusion of outside air in order to ensure safety, storage stability, and environmental pollution prevention properties have been developed. Although the number of polyolefin resins has been increasing, the range of use of polyolefin resins is often limited due to insufficient permeation resistance to chemicals and gases, and improvement thereof is desired.

[0003] In order to supplement the physical properties of such polyolefin resins, resin compositions and molded articles in combination with polyamide resins having excellent permeation resistance have been proposed. However, although these methods certainly improve permeation resistance as compared with a polyolefin resin alone, they are not always satisfactory, and a technique for further improving permeation resistance is desired.

[0004] Also, in the case of containers such as fuel tanks and oil tanks for automobiles, the conversion from metal containers to plastic containers is active in terms of lightness, ease of molding, freedom of design and ease of handling. Is being considered.
In the case of such a container, it is important to prevent the leakage of contents and the intrusion of outside air in order to ensure safety, storage stability, and environmental pollution prevention. Polyethylene, polypropylene and other polyolefin containers are the most common plastic containers, but because of insufficient barrier properties against gasoline and specific oils, it is difficult to use them as they are as fuel tanks and oil tanks for automobiles. Usually, it is used in the form of a laminated structure in which barrier layers made of a resin having high barrier properties are laminated.

A resin forming such a barrier layer is a polyamide resin (for example, Japanese Patent Application Laid-Open No. 58-220938).
Publication) can be cited as a representative example. But,
Recently, the use of a mixture of gasoline and alcohols, that is, a so-called gas hole, as an automobile fuel has been increasing. In such a case, the plastic container obtained by the above-mentioned prior art has insufficient barrier properties. Therefore, a technique for further improving barrier properties is desired.

On the other hand, PPS resins are known to exhibit extremely high barrier properties against chemicals such as gasoline and automobile oil, water, and carbon dioxide.
Molded hollow containers and tubular bodies (for example, Japanese Patent Application Laid-Open No. 62-9021)
No. 6, Japanese Patent Application Laid-Open No. 61-255832, Japanese Patent Application Laid-Open
JP-A-32816) and specific copolymerized PP
Laminate having barrier layer composed of S resin and modified polyolefin (for example, JP-A-6-190980)
And so on. However, the PPS resin has insufficient interlayer adhesion with other resins, so that it is difficult to co-extrude or laminate with other resin materials such as polyolefin materials such as polyethylene and polypropylene, or it is expensive. There is a problem that the application range is limited because a special PPS resin must be used as a main component.

[0007]

An object of the present invention is to improve the permeation resistance of a polyolefin resin, and further suppress the deterioration of properties such as toughness and moldability which are essential characteristics of the polyolefin resin, and -PPS suitable for application to a resin structure, and particularly to gas and / or liquid barrier parts, which has specifically improved gas permeation resistance
Resin structure and barrier properties, moldability, interlayer adhesion,
It is an object of the present invention to provide a laminated structure which is excellent in toughness, is suitable for making a plastic container excellent in production stability and economical efficiency, and its use.

[0008]

The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, a polyolefin resin and a PPS resin are blended in a specific amount, and if necessary, an inorganic filler is blended. In the resin composition, the above problem is solved by controlling the dispersion structure such that the PPS resin phase forms a continuous phase or a band (layer) -like phase in the structure in the resin phase separation structure. The present invention has been reached.

That is, the present invention provides a resin composition consisting essentially of (1) 5 to 80% by volume of a polyolefin resin and (b) 95 to 20% by volume of a polyphenylene sulfide resin. In the observed resin phase separation structure, (b) a thermoplastic resin structure characterized by forming a phase structure in which a polyphenylene sulfide resin forms a matrix phase (continuous phase) and (a) a polyolefin resin forms a dispersed phase, (2) The thermoplastic resin structure according to (1), wherein the mixing ratio of (a) the polyolefin resin and (b) the polyphenylene sulfide resin is 55 to 80% by volume and 45 to 20% by volume, respectively.
(3) The thermoplastic resin structure according to (1), wherein the mixing ratio of (a) the polyolefin resin and (b) the polyphenylene sulfide resin is 60 to 75% by volume and 40 to 25% by volume, respectively. (4) In a resin phase separation structure which is composed of a resin composition comprising (a) 15 to 85% by volume of a polyolefin resin and (b) 85 to 15% by volume of a polyphenylene sulfide resin and is observed by an electron microscope, (b) (5) (a) a polyolefin resin 55, wherein both the phase composed of polyphenylene sulfide resin and (a) the phase composed of polyolefin resin form a phase structure that is a substantially continuous phase. 95% by volume and (b) 45 to 5% by volume of a polyphenylene sulfide resin. In the resin phase separation structure to be (a) a continuous phase comprising a polyolefin resin (b)
A thermoplastic resin structure characterized by forming a phase structure composed of a band-shaped dispersed phase composed of polyphenylene sulfide resin, (6) (a) the polyolefin resin is polyethylene, polypropylene, ethylene / α-olefin copolymer, [Copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)], [(ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid) (1.) The thermoplastic resin structure according to any one of (1) to (5), wherein at least one of the carboxyl groups of the acid ester) is metal chlorided. (7) A total of 1 of the polyolefin resin (a) and the polyphenylene sulfide resin (b)
(C) The thermoplastic resin structure according to any one of (1) to (6), wherein the thermoplastic resin structure contains 0.5 to 200 parts by weight of an inorganic filler with respect to 00 parts by weight. Molding,
The thermoplastic resin structure according to any one of (1) to (7), which is molded by at least one method selected from injection compression molding and compression molding, (9) any one of (1) to (8). A container for transporting or storing a chemical solution or gas obtained by processing the thermoplastic resin structure according to the above. (10)
(1) Attached parts of a container for transporting or storing a chemical solution or gas obtained by processing the thermoplastic resin structure according to any one of (1) to (8). (11) A laminated structure wherein the thermoplastic resin structure according to any one of (1) to (7) forms a barrier layer, (12) an adjacent layer on one side or both sides of the barrier layer Wherein the resin layer constituting the adjacent layer is formed of a thermoplastic resin layer different from the thermoplastic resin structure constituting the barrier layer (11).
(13) The thermoplastic resin constituting the adjacent layer is a polyolefin resin, a thermoplastic polyester resin, a polyamide resin, a polycarbonate resin, AB
(14) The laminated structure according to (12), wherein the thermoplastic resin constituting the adjacent layer is a polyolefin resin,
It is characterized by being at least one resin selected from thermoplastic polyester resin and polyamide resin (1.
(15) The thermoplastic resin constituting the adjacent layer has a melt flow rate of 0.01 to 30.
g / 10 minutes, and the density is 0.90 to 0.97 g /
(12) an adhesive layer between the barrier layer and the adjacent layer, wherein the laminate structure is an ethylene homopolymer and / or an ethylene / α-olefin copolymer having a cm ^3. (1)
The laminated structure according to 2), (17) the adhesive layer is a modified polyolefin having a crystallinity of 50% or less and containing 0.01 to 10% by weight of a grafted unsaturated carboxylic acid or a derivative thereof. (18) The laminated structure according to (16), wherein the adhesive layer has a crystallinity of 50%.
The following are 99 to 60 parts by weight of a modified polyolefin containing 0.01 to 10% by weight of an unsaturated carboxylic acid or a derivative thereof by a grafting treatment, and tackifiers 1 to 4
(17) The laminated structure according to any one of (11) to (18), wherein the laminated structure comprises 0 parts by weight, and (19) the laminated structure formed by a coextrusion molding method. (20) The laminated structure according to any one of (11) to (19), which is formed into a multilayer tube or a multilayer blow-molded body using a coextrusion molding method.
Is provided.

[0010]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The polyolefin resin (a) used in the present invention is a thermoplastic resin obtained by polymerizing or copolymerizing olefins such as ethylene, propylene, butene, isoprene and pentene. Specific examples include polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, poly 1-
Homopolymers such as butene, poly-1-pentene and polymethylpentene, ethylene / α-olefin copolymers, vinyl alcohol ester homopolymers, and polymers obtained by hydrolyzing at least a part of vinyl alcohol ester homopolymers A polymer obtained by hydrolyzing at least a part of a copolymer of ((ethylene and / or propylene) and a vinyl alcohol ester), [(ethylene and / or
Or propylene) and (copolymer of (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)), [(ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) Copolymer in which at least a part of the carboxyl group of the copolymer is metallized], a block copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, and a hydride of the block copolymer.

Among them, polyethylene, polypropylene, ethylene / α-olefin copolymer, [copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)], [ (Ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) are preferred. And high-density polyethylene, polypropylene, and ethylene / α-olefin copolymer are preferred.

[0013] Such polypropylene is not particularly limited, and any of isotactic, atactic, syndiotactic and the like can be used. In addition to the homopolymer, a block with another olefin component containing 70% by weight or more of a propylene component or a random copolymer can also be used.

The ethylene / α-olefin copolymer referred to herein is a copolymer of ethylene and at least one α-olefin having 3 to 20 carbon atoms. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene,
3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1- Pentene, 4-ethyl-1-hexene, 3-
Ethyl-1-hexene, 9-methyl-1-decene, 11
-Methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof. These α
-Among olefins, copolymers using α-olefins having 3 to 12 carbon atoms are preferred from the viewpoint of improving mechanical strength. This ethylene / α-olefin copolymer is α-
The olefin content is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and still more preferably 3 to 20 mol%.

Further, non-emulsions such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene and 5- (1'-propenyl) -2-norbornene At least one of the conjugated dienes may be copolymerized.

The unsaturated carboxylic acid used in [copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)] may be any of acrylic acid and methacrylic acid. Or a mixture thereof, and examples of the unsaturated carboxylic acid ester include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, and decyl ester of these unsaturated carboxylic acids. ,
Alternatively, a mixture thereof may be mentioned, but a copolymer of ethylene and methacrylic acid, and a copolymer of ethylene, methacrylic acid and acrylate are particularly preferable.

The melt flow rate of the polyolefin resin (a) of the present invention (hereinafter abbreviated as MFR: ASTM D 1)
238) is preferably 0.01 to 70 g / 10 min, more preferably 0.03 to 60 g / 10 min. When the MFR is less than 0.01 g / 10 min, the fluidity is poor, and when it exceeds 70 g / 10 min, the impact strength is lowered, which is not preferable. The polyolefin resin preferably having the above MFR may be prepared by thermally decomposing a polymerized polyolefin resin together with an organic peroxide.

The method for producing the polyolefin resin (a) used in the present invention is not particularly limited, and may be any of radical polymerization, coordination polymerization using a Ziegler-Natta catalyst, anionic polymerization, and coordination polymerization using a metallocene catalyst. Can also be used.

In the present invention, it is preferable that the polyolefin resin (a) is used after being modified with at least one compound selected from unsaturated carboxylic acids and derivatives thereof. When using a modified polyolefin resin,
This is one of the preferred embodiments, showing a feature that the compatibility is improved, the controllability of the phase separation structure of the obtained resin composition is improved, and as a result, excellent permeation resistance is exhibited.

Examples of the unsaturated carboxylic acids or derivatives thereof used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid,
Citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, methyl methacrylate, Methacrylic acid 2
-Ethylhexyl, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5
Heptene-2,3-dicarboxylic acid, endobicyclo-
(2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, Glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferred, and maleic acid and maleic anhydride are particularly preferred.

The method of introducing the unsaturated carboxylic acid or its derivative component into the polyolefin resin is not particularly limited, and the olefin compound as the main component and the unsaturated carboxylic acid or its derivative compound may be previously copolymerized, or an unmodified polyolefin resin may be used. A method of introducing an unsaturated carboxylic acid or a derivative compound thereof into the resin by performing a grafting treatment using a radical initiator or the like can be used. The amount of the unsaturated carboxylic acid or its derivative component to be introduced is preferably 0.001 to 40 mol%, more preferably 0.01 to 40 mol%, based on the whole olefin monomer in the modified polyolefin.
Suitably, it is in the range of ~ 35 mol%.

The (b) PPS resin used in the present invention comprises:
A polymer having a repeating unit represented by the following structural formula (I),

[0023]

Embedded image From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more, of the polymer containing the repeating unit represented by the above structural formula is preferable. In the PPS resin, less than about 30 mol% of the repeating unit may be composed of a repeating unit having the following structure.

[0024]

Embedded image Since the melting point of the PPS polymer partially having such a structure is low, when the melting point of the thermoplastic resin used in the laminated structure of the present invention other than the barrier layer is low, it is advantageous in terms of moldability.

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible.
0 to 20000 poise (320 ° C., shear rate 100
0 sec ^-1 ) is used, and 100 to 5000 po
The range of is is more preferable.

Such a PPS resin can be prepared by a generally known method, that is, a method of obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, JP-B-52-12240, and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the gazette. In the present invention, the PPS resin obtained as described above is crosslinked / high molecular weight by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, an acid aqueous solution or the like, Of course, it is also possible to use after performing various treatments such as activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, and a functional group-containing disulfide compound.

As a specific method for crosslinking / high molecular weight of the PPS resin by heating, the method may be carried out in an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method in which heating is performed in a heating vessel at a predetermined temperature under an atmosphere until a desired melt viscosity is obtained. The heat treatment temperature is usually
170-280 ° C is selected, preferably 200-27 ° C.
0 ° C. The heating time is usually 0.5 to 100.
The time is selected, preferably 2 to 50 hours, but by controlling both, the target viscosity level can be obtained. The heating device may be an ordinary hot air dryer or a heating device with a rotary or stirring blade, but for efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. Is more preferred.

When the PPS resin is heat-treated in an inert gas atmosphere such as nitrogen or under reduced pressure, a specific method is as follows.
Heat treatment temperature 150 to 280 ° C, preferably 200 to 2
70 ° C., heating time is 0.5 to 100 hours, preferably 2 hours
A method of performing heat treatment for up to 50 hours can be exemplified. The heating device may be an ordinary hot-air dryer or a rotary or heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary or stirring blade is required. More preferably, it is used.

The PPS resin used in the present invention is preferably a deionized PPS resin. Specific examples of such deionization treatment include acid aqueous solution washing treatment, hot water washing treatment, organic solvent washing treatment, and the like, and these treatments may be used in combination of two or more kinds of methods.

As a specific method for washing the PPS resin with an organic solvent, the following method can be exemplified. That is,
The organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethylsulfoxide, dimethyl Sulfoxides such as sulfone, sulfone solvents, acetone, methyl ethyl ketone, diethyl ketone, ketone solvents such as acetophenone, dimethyl ether, dipropyl ether, ether solvents such as tetrahydrofuran, chloroform, methylene chloride,
Halogen solvents such as trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, and chlorobenzene; alcohols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, and polyethylene glycol; phenol solvents And aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferred. These organic solvents are used alone or in combination of two or more. As a method for washing with an organic solvent, there is a method such as immersing a PPS resin in an organic solvent, and it is also possible to appropriately stir or heat as necessary. The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and an arbitrary temperature from ordinary temperature to about 300 ° C. can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect can usually be obtained at a cleaning temperature of normal temperature to 150 ° C. Further, the PPS resin subjected to the organic solvent washing is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

The following method can be exemplified as a specific method for washing the PPS resin with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a favorable effect of chemical modification of the PPS resin by washing with hot water. The operation of the hot water treatment is usually performed by charging a predetermined amount of PPS resin into a predetermined amount of water, and heating and stirring the mixture at normal pressure or in a pressure vessel. PPS
The proportion of the resin and water is preferably as high as possible. Usually, a bath ratio of 200 g or less of the PPS resin to 1 liter of water is selected.

The following method can be exemplified as a specific method for treating the PPS resin with an acid. That is, there is a method of immersing the PPS resin in an acid or an aqueous solution of an acid, or the like, and if necessary, stirring or heating can be performed. The acid to be used is not particularly limited as long as it does not have a function of decomposing the PPS resin, and aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic acids such as chloroacetic acid and dichloroacetic acid are used. Saturated carboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, and sulfuric acid And inorganic acidic compounds such as phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Among them, acetic acid and hydrochloric acid are more preferably used. The PPS resin subjected to the acid treatment is preferably washed several times with water or hot water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

In the present invention, a conventionally known compatibilizer may be blended for the purpose of improving the compatibility between the polyolefin resin (a) and the PPS resin (b). Specific examples of these compatibilizers include an epoxy silane, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, an organosilane compound such as an alkoxysilane having at least one functional group selected from ureido groups,
Α-olefins, such as ethylene and propylene, and α, such as acrylic acid, methacrylic acid, maleic acid, crotonic acid, etc.
random, block, graft copolymers with at least one compound selected from derivatives such as salts with β-unsaturated carboxylic acids, their esters, anhydrides, halides, sodium, potassium, magnesium, zinc, etc. Modified polyolefins such as α-olefin and α,
Epoxy group-containing olefin-based copolymers such as olefin-based copolymers having a glycidyl ester of β-unsaturated acid as a main component and polyfunctional epoxy compounds, and the like can be used. Two or more of these can be used simultaneously. .

The thermoplastic resin structure referred to in the present invention is:
(1) a phase structure (for example, a sea-island structure) in which the PPS resin component forms a continuous phase (matrix phase) and the polyolefin resin component forms a dispersed phase, and (2) both the PPS resin component and the polyolefin resin component are substantially continuous. A phase structure (for example, a sea-sea structure) that forms a phase, or (3) a polyolefin resin component forms a continuous phase, and a PPS resin component forms a dispersed phase as a number of thin two-dimensionally overlapped bands (layers). Is a structure having a phase structure (laminar structure) in a part or the whole thereof. There is no particular limitation on the shape of the structure.
Further, the phase structures (1) and (2) may be used at various places in the structure.
Or (3) may coexist or appear more than once. This phase structure (1), (2) or (3) is observed and confirmed using a scanning electron microscope and a transmission electron microscope.

In the thermoplastic resin structure of the present invention, the polyolefin resin of the component (a) and the polyolefin resin of the component (b)
In the case of a phase structure in which the PPS resin component forms a continuous phase (matrix phase) and the polyolefin resin component forms a dispersed phase (for example, a sea-island structure, FIG. 1), the mixing ratio of the PS resin is 5 to 80%. % By volume, PPS resin 9
5 to 20% by volume. Preferably, it is 55 to 80% by volume of the polyolefin resin and 45 to 20% by volume of the PPS resin. When such a PPS resin component is a small component,
For example, by appropriately controlling the melt viscosity ratio of the polyolefin resin / PPS resin, a phase structure in which the PPS resin takes a continuous phase can be formed. The molded product having this phase structure is excellent in balance between the properties at the time of water absorption and permeation resistance, and the barrier layer of the laminated structure is excellent in balance between toughness, interlayer adhesion, barrier properties, and economic efficiency, and is particularly preferable. . Furthermore, the compounding ratio of both components is polyolefin resin 60 ~
Preferably, it is 75% by volume and 40 to 25% by volume of the PPS resin. When the content of the polyolefin resin (a) exceeds 80% by volume, PPS which is a feature of the resin molded article of the present invention is used.
It becomes difficult for the resin component to form a continuous phase, and the object of the present invention cannot be achieved. Further, if the content of the polyolefin resin (a) is less than 5% by volume, the toughness of the resin molded article and the interlayer adhesion of the laminated structure are undesirably reduced.

When obtaining a phase structure (for example, a sea-sea structure, FIG. 2) in which the PPS resin component and the polyolefin resin component together form a substantially continuous phase (matrix phase), the polyolefin resin is 15 to 85% by volume, the PPS resin In the composition range of 85 to 15% by volume, the polyolefin resin and P
It is important to control the melt viscosity and compatibility of the PS resin. For realizing this phase separation structure, the composition of the polyolefin resin is preferably 30 to 70% by volume and the PPS resin is 70 to 30% by volume, more preferably 35 to 65% by volume of the polyolefin resin and 65 to 35% by volume of the PPS resin.
When the content of the polyolefin resin (a) exceeds 85% by volume, it becomes difficult for the PPS resin component to form a substantially continuous phase, and a structure that achieves the object of the present invention cannot be obtained.

Next, the polyolefin resin component forms a continuous phase (matrix phase), and the PPS resin component forms a dispersed phase (laminar structure, FIG. 3) as a number of thin two-dimensionally overlapped bands (layers). To obtain a phase structure of 55 to 95% by volume of a polyolefin resin and 45 to 95% by volume of a PPS resin.
5% by volume. Preferably polyolefin resin 60 ~
90% by volume, 40 to 10% by volume of the PPS resin, more preferably 65 to 85% by volume of the polyolefin resin, and 35 to 15% by volume of the PPS resin. When the content of the polyolefin resin of the component (a) exceeds 95% by volume, it is difficult to make the band-shaped dispersed phase of the PPS resin component a sufficient length and amount, and the object of the present invention cannot be achieved. If the content of the polyolefin resin (a) is less than 55% by volume, it becomes difficult for the PPS resin component to form a band-shaped dispersed phase.

L of the PPS resin component forming the band-shaped dispersed phase
/ T (length / thickness) is preferably 30 or more. More preferably, L / T is 100 or more, and particularly preferably, L / T is 150 or more. When L / T is 30 or less, it is not possible to obtain a structure that achieves a desired barrier property. The upper limit of L / T is not particularly limited, but is practically 1 × 10 ⁶ or less.

The inorganic filler (c) used in the present invention is not particularly limited, but fibrous, plate-like, powdery, granular fillers and the like can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber,
Gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber,
Fibrous forms such as silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker,
Whisker-like filler, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes,
Glass microballoon, clay, molybdenum disulfide,
Examples include powdery, granular or plate-like fillers such as wollastenite, titanium oxide, zinc oxide, calcium polyphosphate, and graphite. Among the above fillers, glass fibers and PAN-based carbon fibers are preferably used when conductivity is required. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or a short fiber type chopped strand, a milled fiber or the like can be used. The above fillers can be used in combination of two or more kinds. The filler used in the present invention can be used after its surface is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, or the like) or another surface treatment agent. , Glass fiber is ethylene /
It may be coated or bundled with a thermoplastic resin such as a vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

The content of the above-mentioned inorganic filler is 100% in total of (a) the polyolefin resin and (b) the PPS resin.
It is preferably 0.5 to 200 parts by weight based on parts by weight. More preferably, it is 5 to 200 parts by weight, particularly preferably 10 to 150 parts by weight.

The laminated structure referred to in the present invention is a structure in which a plurality of kinds of resins are laminated, and at least one thermoplastic resin structure having the above-mentioned specific phase structure (hereinafter referred to as (a) barrier layer). And the thermoplastic resin structure of the present invention having another composition or phase structure (the layer is also a barrier layer) or a resin layer different from the barrier layer on at least one surface side of the barrier layer ( (Hereinafter referred to as (b) adjacent layer)
Is a structure constituted. Further, in a preferred embodiment of the laminated structure of the present invention, in order to improve the adhesive force between (a) the barrier layer and (b) the adjacent layer, the laminated structure has adhesion between the two layers. And a laminate in which a resin layer having co-extrusion properties (hereinafter referred to as (c) an adhesive layer) is appropriately configured.
Specifically, for example, a two-type two-layer structure of (a) layer / (b) layer, a two-type three-layer structure of (b) layer / (a) layer / (b) layer,
(B) layer / (c) layer / (a) layer three-layer structure, (b)
Layer / (c) layer / (b) layer / (b) layer;
A laminated structure such as a three-layered five-layer structure of (ii) layer / (iii) layer / (ii) layer / (iii) layer / (ii) layer may be mentioned, but is not limited thereto.

In the present invention, (b) the resin constituting the adjacent layer is made of a thermoplastic resin having a phase structure or composition different from the requirements of the present invention. The type of the thermoplastic resin is not particularly limited, and can be appropriately selected depending on the intended use of the laminated structure. Specific examples thereof include a saturated polyester resin, a polysulfone resin, a polyethylene tetrafluoride resin, a polyetherimide resin, a polyamideimide resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polyethersulfone resin, a polyetherketone resin, and a polythioetherketone. Examples thereof include resins, polyetheretherketone resins, thermoplastic polyurethane resins, polyolefin resins, ABS resins, polyamide elastomers, polyester elastomers, and the like, and these may be used as a mixture of two or more. Among them, polyolefin resins, thermoplastic polyester resins, polyamide resins, polycarbonate resins and ABS resins are more preferably used.

Preferred polyolefin resins are, for example, the same as the aforementioned polyolefin resins as the component (a). Among them, low, medium and high density polyethylenes, polypropylenes, ethylene / α-olefin copolymers, poly-4- Preferred are methylpentene-1, chlorinated polyethylene and chlorinated polypropylene, etc., and an ethylene homopolymer having a melt flow rate of 0.01 to 30 g / 10 min and a density of 0.90 to 0.97 g / cm3; And / or ethylene / α-olefin copolymer is particularly preferably used.

Preferred thermoplastic polyesters include:
For example, it refers to a polyester obtained from a dicarboxylic acid such as terephthalic acid and an aliphatic diol. Examples of dicarboxylic acids other than terephthalic acid include azelaic acid, sebacic acid, adipic acid, and C2-C2 such as decanedicarboxylic acid.
20 aliphatic dicarboxylic acids, such as aromatic dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These may be used alone or as a mixture. As the aliphatic diol, ethylene glycol,
Examples thereof include 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, trimethylene glycol, 1,4-cyclohexanedimethanol, and hexamethylene glycol. Specifically, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene naphthalate, and the like, among which polybutylene terephthalate having appropriate mechanical strength, or terephthalate Copolyesters comprising a dicarboxylic acid component containing 60% by mole or more, preferably 70% by mole or more of an acid, dodecanedicarboxylic acid and / or isophthalic acid, and 1,4-butanediol component are particularly preferably used.

Although the degree of polymerization of these thermoplastic polyester resins is not particularly limited, in the case of polybutylene terephthalate and copolyester which are preferably used, the degree of polymerization is preferably 0.1%.
A 5% orthochlorophenol solution having an intrinsic viscosity measured at 25 ° C. of 0.5 to 2.5, particularly preferably 0.8 to 2.0 is preferred. In the case of polyethylene terephthalate, a 0.5% orthochlorophenol solution is used for 2 hours.
Those having an intrinsic viscosity measured at 5 ° C. in the range of 0.54 to 1.5, particularly 0.6 to 1.2 are preferred.

Preferred polyamide resins are, for example, polyamides containing amino acids, lactams or diamines and dicarboxylic acids as main components. Representative examples of the main components include 6-aminocaproic acid and 11-aminocaproic acid.
Amino acids such as aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, Decamethylenediamine, dodecamethylenediamine, 2,2
4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl ) Cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-
Aminocyclohexyl) methane, bis (3-methyl-4)
-Aminocyclohexyl) methane, 2,2-bis (4-
Aliphatic, alicyclic, aromatic diamines such as aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid;
Aliphatic, alicyclic, aromatic, such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

Particularly useful polyamide resins are polyamide resins having a melting point of 150 ° C. or higher and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6) and polyundecaneamide (nylon 11). , Polydodecaneamide (nylon 12), polyhexamethylene adipamide (nylon 66), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/6
6), polytetramethylene adipamide (nylon 4
6), polyhexamethylene sebacamide (nylon 61
0), polyhexamethylene dodecamide (nylon 61
2), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene Isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (Nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecaneamide copolymer (nylon 6T / 12), polyhexamethylene terephthalamide / poly (2-meth Le pentamethylene) terephthalamide copolymer (nylon 6T / M5T), polyxylylene adipamide (nylon XD6), poly nonamethylene terephthalamide (nylon 9T), and mixtures thereof or copolymers, and the like.

Particularly preferred are nylon 6, nylon 66, nylon 12, nylon 11, nylon 6/66 copolymer, nylon 610, and nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T / 6 copolymer and the like. Copolymers having hexamethylene terephthalamide units can be mentioned, and it is also practically preferable to use these polyamide resins as a mixture depending on required properties such as moldability, heat resistance and barrier properties.

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is 2.0 to 2.0.
Those having a range of 7.0 are preferable, and those having a range of 2.5 to 6.0 are particularly preferable.

The thermoplastic resin constituting the (b) adjacent layer may contain additives such as a plasticizer, an antioxidant, a nucleating agent, and a coloring agent suitable for each resin.

The (a) barrier layer composed of the thermoplastic resin structure having the phase separation structure specified in the present invention, and (b) the laminated structure composed of the adjacent phase on one side or both sides thereof, Although it can be produced by a color injection molding method or the like, when it is to be obtained in the form of a film or a sheet, the composition for forming each layer is melted by a separate extruder, and then supplied to a die having a multilayer structure. It can be manufactured by an extrusion molding method, a so-called laminate molding method in which an adjacent layer is formed in advance, and then the barrier layer is melt-extruded. In addition, the shape of the laminated structure is hollow containers such as bottles, barrels, tanks, pipes,
In the case of a tubular body such as a tube, a common co-extrusion molding method can be employed. For example, a two-layer hollow molded body in which an inner layer is formed of a barrier layer having a specific phase separation structure and an outer layer is formed of an adjacent layer In the case of the above, the resin composition for the barrier layer and the resin composition for the adjacent layer are separately supplied to two extruders.
After supplying the kind of molten resin into the common die under pressure to form an annular flow, the barrier layer is joined to the inner layer side and the adjacent layer is joined to the outer layer side, and then co-extruded out of the die Then, a two-layer hollow molded body can be obtained by performing a generally known tube molding method, blow molding method, or the like. In the case of a three-layer hollow molded body, a three-layer structure is formed in the same manner as described above using three extruders, or a two-layer three-layer hollow is formed using two extruders. It is also possible to obtain molded articles. Among these methods, it is preferable to mold using a co-extrusion molding method in view of interlayer adhesion.

In the laminated structure of the present invention, for the purpose of further improving the impact resistance and moldability of the molded article and the adhesive strength between the layers, (a) a layer between the barrier layer and (b) the adjacent layer. It is preferable that the adhesive layer is appropriately formed. The structure of the resin constituting the adhesive layer is not particularly limited as long as it exhibits adhesiveness to the (a) barrier layer and (b) the adjacent layer and can be co-extruded therewith. Specific examples include α-olefins such as ethylene and propylene, and α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, crotonic acid, esters, anhydrides, halides, and sodium salts thereof. , Potassium, magnesium, modified polyolefins such as random, block, graft copolymers with at least one compound selected from derivatives such as salts with zinc, ethylene,
Α-olefin such as propylene and at least one selected from vinyl acetate, vinyl alcohol and styrenes
Examples include random, block, graft copolymers, copolyamide-based adhesives, and copolyester-based adhesives with various kinds of compounds. Among these adhesive layers, the crystallinity measured by the X-ray diffraction method is 50% or less,
The modified polyolefin is preferably 40 to 0% and contains 0.01 to 10% by weight, preferably 0.05 to 3% by weight of a grafted unsaturated carboxylic acid or a derivative thereof. When the amount of the acid or its derivative and the degree of crystallinity are in the above ranges, a laminated structure having particularly excellent adhesion to the barrier layer can be obtained. Examples of preferable unsaturated carboxylic acids or derivatives thereof used herein include a series of compounds exemplified as the modifier for the polyolefin component of the component (a). Among them, unsaturated compounds such as acrylic acid and methacrylic acid are exemplified. Preferred are dicarboxylic anhydrides such as dicarboxylic acid, maleic anhydride and itaconic anhydride, and glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate.

The modified polyolefins may be used alone or as a mixture of two or more. 2
In the case of a mixture of more than one species, the degree of crystallinity and the amount of graft as a mixture may be within the above-mentioned range, and a graft-modified polyolefin having a degree of crystallinity and / or a graft amount outside the above-mentioned range, and / or not graft-modified A polyolefin may be included.

Preferable examples of the polyolefin before or without graft modification include homopolymers or copolymers of two or more α-olefins having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, and 1-octadecene. The polyolefin may be copolymerized with a small amount of a monomer other than the α-olefin, for example, 10 mol% or less.

Particularly preferred polyolefins include ethylene homopolymers and ethylene / α-olefin random copolymers. Specific examples include linear low-density polyethylene (L-LDPE), ethylene / propylene copolymer, ethylene / butene copolymer, and the like. Among them, the MFR is particularly 0.1 to 50 g.
/ 10 min, preferably 0.2 to 20 g / 10 mi
n, a density of 0.850 to 0.940 g / cm ³ , preferably 0.855 to 0.920 g / cm ³ , and an ethylene content of 30 to 95 mol%, preferably 40 to 92 mol%,
It is desirable that the crystallinity measured by the X-ray diffraction method is 50% or less, preferably 40% or less.

The modified polyolefin used as the adhesive layer can contain a tackifier. Specifically, for example, an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin obtained by hydrogenating an aromatic hydrocarbon resin, an α-pinene resin, a terpene resin, a rosin, a modified rosin, a mixture thereof, and the like. Conventionally, a solid amorphous polymer which has been used as an adhesive or an adhesive in the fields of adhesive tapes, paints and hot melt adhesives has been used as a tackifier resin. Above all, the softening point (ring and ball method) is 105 to 150 ° C, preferably 110 to 140 ° C.
And an alicyclic hydrocarbon having a hydrogenation rate of at least 80%, preferably at least 85%, to the aromatic nucleus is particularly preferred.
Commercial products can also be used as the adhesion-imparting agent. For example, Alcon P-125 manufactured by Arakawa Chemical Industry Co., Ltd. may be mentioned.

The mixing ratio of the modified polyolefin and the tackifier is 99 to 60% by weight, preferably 95 to 80% by weight, and the tackifier is 1 to 40% by weight, preferably 5 to 20% by weight.

In the thermoplastic resin structure of the present invention, a conductive filler and / or a conductive polymer can be used to impart conductivity, and the material is not particularly limited. As the conductive filler, there is no particular limitation as long as it is a conductive filler that is usually used for making the resin conductive, and specific examples thereof include metal powder, metal flake,
Metal ribbon, metal fiber, metal oxide, inorganic filler coated with conductive material, carbon powder, graphite, carbon fiber,
Examples include carbon flake and flaky carbon.

Specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

Specific examples of the metal species of the metal fiber include iron,
Examples thereof include copper, stainless steel, aluminum, and brass.

The metal powder, metal flake, metal ribbon and metal fiber may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum or silane.

Specific examples of the metal oxide include SnO ₂ (antimony doped), In ₂ O ₃ (antimony doped), Z
Examples thereof include nO (aluminum dope), which may be surface-treated with a surface treatment agent such as a titanate-based, aluminum-based, or silane-based coupling agent.

The inorganic filler coated with the conductive substance
Aluminum, nickel, etc.
, Silver, carbon, SnO_Two(Antimony dope), I
n_TwoO _Three(Antimony dope) and the like. In addition,
Mica, glass bee
Size, glass fiber, carbon fiber, potassium titanate whisker
ー, barium sulfate, zinc oxide, titanium oxide, aluminum borate
Minium whisker, zinc oxide whisker, titanium oxide
Acid whisker, silicon carbide whisker, etc.
You. As a coating method, a vacuum deposition method, a sputtering method,
Examples include an electroless plating method and a baking method. Again
These are titanate, aluminum and silane couplings
Surface treatment with a surface treatment agent such as an agent.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disk black and the like according to the raw material and the production method. The raw material and the production method of the carbon powder that can be used in the present invention are not particularly limited, but acetylene black and furnace black are particularly preferably used. Various carbon powders having different properties such as particle diameter, surface area, DBP oil absorption, and ash content are produced. The carbon powder that can be used in the present invention is not particularly limited in these properties, but from the viewpoint of strength and electrical conductivity, the average particle size is 500 nm or less, particularly 5 to 100 nm,
Further, the thickness is preferably 10 to 70 nm. The specific surface area (BE
(T method) is preferably at least 10 m2 / g, more preferably at least 30 m2 / g. The DBP lubrication amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. The ash content is preferably 0.5% by weight or less, particularly preferably 0.3% by weight or less.

The carbon powder may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum, or silane. It is also possible to use those granulated for improving the workability of the melt-kneading.

A molded article obtained by processing the thermoplastic resin composition composition of the present invention is often required to have a smooth surface. From this viewpoint, the conductive filler used in the present invention is more powdery than the fibrous filler having a high aspect ratio, like the inorganic filler (c) used in the present invention.
It is preferably in any form of granule, plate, scale, or fibrous having a length / diameter ratio of 200 or less in the resin composition.

Specific examples of the conductive polymer include polyaniline, polypyrrole, polyacetylene, poly (paraphenylene), polythiophene, and polyphenylenevinylene.

The above-mentioned conductive filler and / or conductive polymer may be used in combination of two or more kinds. Among these conductive fillers and conductive polymers, carbon black is particularly preferably used in terms of strength and economy.

The conductive filler used in the present invention and / or
Alternatively, since the content of the conductive polymer varies depending on the type of the conductive filler and / or the conductive polymer used, it cannot be unconditionally specified. However, from the viewpoint of the balance between conductivity, fluidity, mechanical strength, and the like, ( The range of 1 to 250 parts by weight, preferably 3 to 100 parts by weight, is preferably selected with respect to 100 parts by weight of the total of the components (a) and (b) and the component (c). Further, more preferably, the range of 3 to 100 parts by weight is preferably selected for imparting a conductive function to the total of 100 parts by weight of the components (a) and (b).

When conductivity is imparted, the volume specific resistance is 10 ¹⁰ Ω · c in order to obtain sufficient antistatic performance.
m or less. However, the blending of the above-mentioned conductive filler and conductive polymer generally tends to cause deterioration in strength and fluidity. Therefore, if a target conductivity level can be obtained, it is desirable that the amount of the conductive filler and conductive polymer is as small as possible. The target conductivity level depends on the application, but usually the volume resistivity is 100Ω
· It is more than ¹⁰ cm and not more than 10 ¹⁰ Ω · cm.

In the composition of the present invention, other components such as antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites and substituted products thereof, etc.) as long as the effects of the present invention are not impaired. ), Weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide, various bisamides) , Bisurea, polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate) , N-butylbenzenesulfonamide, etc.) Antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), difficult Flame retardants (for example, hydroxides such as red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, etc., ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin and brominated epoxy resins thereof) Combination of flame retardant and antimony trioxide),
Other polymers can be added.

The method for obtaining the resin structure of the present invention includes:
There is no particular limitation as long as the phase structure required by the present invention is obtained, but in melt kneading, in order to realize a preferable phase structure, for example, when melt kneading with a twin screw extruder, the polyolefin resin is mixed with the polyolefin resin from the main feeder. A method of supplying a PPS resin and supplying an inorganic filler from a side feeder at a tip portion of an extruder, or a method in which a polyolefin resin and a PP are used in advance.
After melting and kneading the S resin, a method of melting and kneading with the inorganic filler may be used.

The thermoplastic resin structure and the laminated structure of the present invention can be shaped by a known method, and the molding method is not limited, and injection molding, extrusion molding, blow molding, press molding and the like can be used. . Among them, it is preferable to employ one method selected from injection molding, injection compression molding, and compression molding in terms of excellent productivity and industrially implementing the present invention. The molding temperature is usually selected from a temperature range 5 to 50 ° C. higher than the melting point of the PPS resin, and is generally a single layer, but may be a multilayer by a two-color molding method.

The arrangement of each layer in the resin structure of the present invention is not particularly limited, and all the layers may be constituted by the thermoplastic resin structure of the present invention, or other layers may be formed of another thermoplastic resin. You may comprise using it. In the case of two layers, the layer made of the thermoplastic resin structure of the present invention is preferably the innermost layer in order to sufficiently exhibit the permeation resistance effect.
The obtained molded articles may be bonded or welded to each other or to other molded articles. The method is not particularly limited, and a known technique can be used.

The thermoplastic resin structure and the laminated structure of the present invention make use of their excellent gas barrier properties, durability and processability, and can be used for a container for transporting and / or storing a chemical solution or gas and / or its auxiliary parts and coextrusion molding method. It can be preferably used as a multilayer tube or a multilayer blow-molded hollow article molded by using the same. As the chemical solution or gas, for example, Freon-11, Freon-12, Freon-21, Freon-2
2, Freon-113, Freon-114, Freon-11
5, Freon-134a, Freon-32, Freon-12
3, Freon-124, Freon-125, Freon-143
a, CFC-141b, CFC-142b, CFC-2
25, Freon-C318, R-502, 1,1,1-trichloroethane, methyl chloride, methylene chloride, ethyl chloride, methyl chloroform, propane, isobutane, n-
Butane, dimethyl ether, castor oil based brake fluid, glycol ether based brake fluid, borate ester based brake fluid, brake fluid for extreme cold, silicone oil based brake fluid, mineral oil based brake fluid, power steering oil, window washer fluid, gasoline, Methanol, ethanol, isoptanol, butanol, nitrogen, oxygen,
Gases and / or liquids such as hydrogen, carbon dioxide, methane, propane, natural gas, argon, helium, xenon, pharmaceutical agents and the like, and excellent permeation resistance to vaporized gases and the like, for example, the above-mentioned gases and / or liquids , Shampoo, rinse, liquid soap, detergent, etc., various chemical bottles, chemical liquid storage tank, gas storage tank, cooling liquid tank, oil transfer tank, disinfectant liquid Tanks, transfusion pump tanks, fuel tanks, canisters, washer fluid tanks, oil reservoir tanks, and other automotive parts, medical equipment parts, and general living equipment parts tanks, bottle-shaped molded articles or attached to these tanks and bottles Valves and fittings such as cut-off valves, gauges for attached pumps, cases, etc. Products, fuel filler underpipe, ORVR hose, reserve hose, vent hose, etc. various fuel tubes and connecting parts (connectors, etc.), oil tubes and connecting parts, brake hoses and connecting parts, nozzles and hoses for window washer fluid, cooling water , Refrigerant hoses and connecting parts, air conditioner refrigerant tubes and connecting parts, floor heating pipes and connecting parts, fire extinguishers and fire extinguishing equipment hoses, medical cooling equipment tubes and connecting parts and valves, etc. Tubes for transporting chemicals and gas, applications requiring chemical solution and gas permeation resistance such as containers for storing chemicals, automotive parts, internal combustion engines, mechanical parts such as power tool housings, electric and electronic parts, Medical, food, household / office supplies, building materials-related parts, Various applications and the like component ingredients.

[0076]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the gist of the present invention is not limited to the following Examples. (1) Alcohol gasoline permeability A die for forming a tube at the tip of an extruder having a diameter of 40 mm, a sizing die for cooling and controlling the size of the tube,
A tube having an outer diameter of 8 mm and an inner diameter of 6 mm was formed using a take-up machine. The tube is 20c
The tube was cut into a length of m, the tube was sealed at one end, 6 g of an alcohol gasoline mixture obtained by mixing a commercial regular gasoline and ethanol at a weight ratio of 75 to 25 was precisely weighed and charged inside, and the other end was also sealed. Thereafter, the entire weight was measured, and the test tube was placed in an explosion-proof oven at 60 ° C., treated for 500 hours, and the reduced weight was measured. (2) Oxygen permeability GTR- according to JIS K7126 A method (differential pressure method)
10 (manufactured by Yanako Kagaku Kogyo). (3) Material strength Measured according to the following standard method. Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Izod impact strength: ASTM D256 (4) Observation of phase separation structure The cross section (barrier layer) of the tube molded product was observed using an electron microscope (TEM, SEM). . (5) Physical properties of the laminated structure (A) Gas hole barrier property: One end of a tube cut into a size of 30 cm is sealed, and 85:15 (weight ratio) of commercially available regular gasoline and methyl alcohol is contained therein.
And the remaining end was sealed. Thereafter, the entire weight was measured, and the test tube was placed in an explosion-proof oven at 40 ° C., and the alcohol gasoline permeability was evaluated based on the change in weight. (B) Adhesive strength between molded product layers: Tube is 10 mm wide
By cutting the strip into a strip shape and pulling the inner and outer layers sandwiching the adhesive layer (the adhesive layer adheres to the adjacent layer side made of the thermoplastic resin composition) in the direction of 180 ° to each other, thereby increasing the adhesive strength per unit length. It was measured. Reference Example 1 (Production of Copolymerized PPS) In an autoclave equipped with a stirrer, 3.26 kg of sodium sulfide (25 mol, containing 40% of water of crystallization), 4 g of sodium hydroxide, 1.36 kg of sodium acetate trihydrate (about 10 kg) were added. Mol) and N-
7.9 kg of methylpyrrolidone was charged, and the temperature was gradually raised to 205 ° C. while stirring to remove about 1.5 liter of distillate water containing 1.36 kg of water. 3.38 kg (23.0 mol) of 1,4-dichlorobenzene, 1,3
-0.37 kg (2.5 mol) of dichlorobenzene and 2 kg of NMP were added and heated at 265 ° C for 5 hours. The reaction product was washed three times with warm water at 70 ° C., then washed with an aqueous acetic acid solution at pH = 4 at 60 ° C., further washed four times with warm water at 70 ° C., and dried under reduced pressure at 80 ° C. for 24 hours. 255
About 2 kg of a copolymerized PPS resin having a MFR of 800 g / 10 minutes (315 ° C., 5000 g load) was obtained.

The polyolefin resins and PPS used in Examples and Comparative Examples are as follows. Unless otherwise specified, polymerization was carried out in accordance with a conventional method. <Polyolefin resin> (PO-1): High-density polyethylene having MFR14 and a density of 0.96. (PO-2): MFR32, high density polyethylene having a density of 0.96. (PO-3): MFR10, density 0.89 polypropylene. (PO-4): High-density polyethylene having an MFR of 0.3 and a density of 0.95. (PO-5): High-density polyethylene having an MFR of 6.0 and a density of 0.96. (PO-6): a low-density polyethylene having an MFR of 1.0 and a density of 0.92. (PO-7): polypropylene having an MFR of 0.5 and a density of 0.89. (PO-8): an ethylene-ethyl acrylate copolymer having an MFR of 1.5 and a density of 0.93. (PO-9): an ethylene-propylene copolymer having an MFR of 0.6 and a density of 0.88. <PPS resin> (PPS-1): melting point 280 ° C., MFR 1000 g / 1
A PPS resin having a weight average molecular weight (Mw) of 30,000 for 0 minute (315 ° C., 5000 g load). (PPS-2): melting point 280 ° C., MFR 300 g / 10
Min, Mw: 49000, 700 poise PPS resin. (PPS-3): melting point 280 ° C., MFR 100 g / 10
Min, Mw: 70000, 1700 poise PPS resin (PPS-4): melting point 280 ° C., MFR 600 g / 10
Min, Mw: 38000, 450 poise PPS resin. (PPS-5): melting point 255 obtained in Reference Example 1 above
CPS, copolymerized PPS resin with MFR of 800 g / 10 min. <Thermoplastic resin layer other than the resin composition forming the barrier layer (adjacent layer)> (b-1): High density polyethylene having an MFR of 0.3 g / 10 min and a density of 0.94. (B-2): Polybutylene terephthalate (manufactured by Toray Industries, Inc.)
Lumicon "5201X11" (b-3): Nylon 11 ("Rilsan" BE manufactured by Toray Industries, Inc.)
SN O P40TL). (B-4): An ethylene / 1-hexene copolymer having a MFR of 4 g / 10 min and a density of 0.92. <Adhesive layer> (C-1): ethylene / glycidyl methacrylate = 9
0/10 (wt%) copolymer. (C-2): Ethylene / methyl acrylate / glycidyl methacrylate = 64/30/6 (% by weight) copolymer. (C-3): Maleic anhydride-modified ethylene / 1-butene copolymer (density 0.88, crystallinity = 15%, maleic anhydride graft amount = 0.4% by weight) (C-4): Anhydrous Maleic acid-modified ethylene / 1-octene copolymer (density 0.86, crystallinity = 5% or less, maleic anhydride graft amount = 0.8% by weight) (C-5): maleic anhydride-modified ethylene / 1 -Butene copolymer (density 0.88, crystallinity = 15%, maleic anhydride graft amount = 0.4% by weight) // maleic anhydride-modified polyethylene (density 0.96, maleic anhydride graft amount = 2) 0.0% by weight) // tackifier ("Alcon" P-125 manufactured by Arakawa Chemical Industry Co., Ltd.) = 85 // 5 // 10 parts by weight and a cylinder temperature of 20 using a twin-screw extruder.
An adhesive layer composition obtained by melt-kneading at 0 ° C.

Examples 1 to 15 and Comparative Examples 1 to 4 As shown in Tables 1 and 2, a PPS resin melt-kneaded in advance and a compatibilizer (ethylene / glycidyl methacrylate = 90)
/ 10 (weight%) copolymer) and a polyolefin resin are supplied from the main feeder of a TEX30 type twin screw extruder manufactured by Nippon Steel Works Co., Ltd., and when an inorganic filler is supplied, a side feeder in the middle of the cylinder is used. The melt-kneading was carried out at a kneading temperature of 300 ° C. and a screw rotation speed of 200 rpm by a method of supplying the mixture. After the obtained pellet was dried, a test piece was prepared by injection molding (IS100FA manufactured by Toshiba Machine Co., mold temperature 80 ° C.). Further, a tube for evaluating alcohol gasoline permeability was prepared by the above method. Tables 1 and 2 show the results of measuring the permeation resistance and material strength of each sample. In addition, electron micrographs of the phase separation structure are shown in FIGS. 4 (Example 8) and 5 (Comparative Example 2).
Shown in

In the table, GF is glass fiber (fiber diameter: 10 μm, 3 mm chopped strand, manufactured by NEC Corporation), and MF is milled fiber (average fiber length: 1).
40 μm, average fiber diameter 9 μm, manufactured by NEC Corporation).

[0080]

[Table 1]

[0081]

[Table 2] The resin molded product of the present invention in which a specific phase separation structure is defined from Examples 1 to 15 and Comparative Examples 1 to 4 has high practical value in that characteristics excellent in permeation resistance can be obtained. Also, the test pieces prepared by injection molding had excellent permeation resistance and high practical value. Examples 16 to 32 and Comparative Examples 5 to 8 As shown in Tables 3 to 5, a PPS resin and a compatibilizer (ethylene / glycidyl methacrylate = 90/10 (wt%) copolymer) were mixed, and Steelworks TEX30 type 2
Melt kneading was performed at a kneading temperature of 270 to 300 ° C. and a screw rotation speed of 200 rpm by a method of supplying the polyolefin resin from the main feeder of the screw extruder and using a side feeder in the middle of the cylinder. After the obtained pellets were dried, they were subjected to tube molding.

(A) Barrier layer 1 comprising the obtained composition
A three-layer, three-layer tube consisting of two layers, a thermoplastic resin, (b) one adjacent layer, and (c) one adhesive layer interposed between the barrier layer and the adjacent layer was molded (there is no adhesive layer). Sometimes, two types and two layers). The molding apparatus has three extruders, a die for collecting the resin discharged from the three extruders by an adapter and forming the same into a tube, a sizing die for cooling and controlling the size of the tube, and a take-off machine. Was used.

The obtained three-layer tube had an outer diameter of 8 mm,
Inner diameter: 6 mm, outer layer (thermoplastic resin layer) thickness: 0.7
0 mm (0.80 mm for a two-layer tube), adhesive layer thickness 0.10 mm, inner layer (barrier layer) thickness: 0.20 mm
Met. Tables 3, 4, and 5 show the evaluation results of this multilayer tube.
Shown in

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5] The laminated structure having a phase separation structure of the present invention obtained by Examples 16 to 32 has high gas hole barrier properties,
It was excellent in interlayer adhesion and of high practical value. Similarly, when the material obtained in the example was processed into a multilayer blow-molded body, it had good properties.

[0087]

Industrial Applicability The thermoplastic resin structure of the present invention has good gas and / or liquid barrier properties and can be applied to various uses, for example, electric / electronic related equipment, precision machine related equipment, office equipment. It is suitable for automobile / vehicle related parts, building materials, packaging materials, furniture, daily necessities, etc. Further, the laminated structure of the present invention has a high barrier property against gas holes and the like, and provides a plastic container and a tubular body having excellent strength, durability and moldability. Tanks, containers for transporting and storing chemicals, piping,
It is suitable for application to food and medical packaging materials and containers.

[Brief description of the drawings]

FIG. 1 is a phase structure model diagram in which a PPS resin component (PPS) forms a continuous phase and a polyolefin resin component (PO) forms a dispersed phase.

FIG. 2 is a model diagram of a phase structure example in which a PPS resin component and a polyolefin resin component together form a substantially continuous phase.

FIG. 3 shows that a polyolefin resin component forms a continuous phase,
FIG. 4 is a phase structure model diagram in which a dispersed phase is formed as a plurality of thin two-dimensionally overlapped belts (layers) in which a PPS resin component is formed.

FIG. 4 is an electron micrograph showing the phase structure of the resin structure obtained in Example 8, in which a portion dyed black is a polyolefin resin component.

FIG. 5 is an electron micrograph showing the phase structure of the resin structure obtained in Comparative Example 1, in which a portion stained black is a polyolefin resin component.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/32 B32B 27/32 D B65D 1/09 C08J 5/00 CES C08J 5/00 CES CEZ CEZ C08K 3 / 00 C08K 3/00 C08L 23/00 C08L 23/00 B65D 1/00 A (31) Priority claim number Japanese Patent Application No. 2000-39191 (P2000-39191) (32) Priority date February 17, 2000 (2000) 2.17) (33) Priority Country Japan (JP) (72) Inventor Mitsushige Hamaguchi 9-9 Oe-cho, Minato-ku, Nagoya-shi, Aichi, Japan Toray Industries, Inc. Nagoya Office (72) Inventor Kobayashi Kazuhiko 1 Nagoya Office, 9-9 Oe-cho, Minato-ku, Nagoya-shi, Aichi Prefecture (72) Inventor Akira Todo 61-2-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Chemicals, Inc. Iwakuni Univ. Inside the bamboo plant (72) Inventor Taku Kanda 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture F-term in the Iwakuni-Ohtake Plant Mitsui Chemicals Co., Ltd. 3E033 AA20 BA13 BA14 BA17 BA21 BA26 BB01 BB04 BB08 CA03 CA16 FA02 FA03 GA02 4F071 AA14 AA15 AA15X AA20 AA20X AA21X AA32X AA33X AA62 AA78 AB03 AB28 AD01 AE17 AH03 AH05 AH07 AH12 AH17 AH19 4F100 AA01A AK01B AK03A AK03B AK03G AK04A AK07A AK41B AK45B AK46B AK54A AK62A AK70A AK74B AL06G BA02 BA03 CA23A CB00 EH20 GB16 JA06B JA13B JB16B JD01A YY00A YY00B 4J002 BB00W BB03W BB05W BB07W BB08W BB12W BB14W BB15W BB17W BB23W BC03W BG04W BG05W BP01W CL06Y CN01X DA016 DA026 DA096 DC006 DE096 DE136 DE146 DE166 DE186 DE236 DG026 DG056 DH046 DJ006 DJ016 DJ026 DJ036 DJ046 DJ056 DK006 DL006 FA016 FA04Y FA046 FA066 FA086 FA106 FD01Y FD016 GB01 GC00 GF00 GG01 GM00 GN00 GQ00

Claims (20)

[Claims] (1) substantially (a) a polyolefin resin
80% by volume and (b) polyphenylene sulfide resin 9
A resin composition comprising 5 to 20% by volume, and
In the resin phase separation structure observed with an electron microscope (b)
A thermoplastic resin structure, wherein the polyphenylene sulfide resin forms a matrix structure (continuous phase), and (a) the polyolefin resin forms a dispersed phase. 2. The mixing ratio of (a) the polyolefin resin and (b) the polyphenylene sulfide resin is 55 to 8 respectively.
The thermoplastic resin structure according to claim 1, wherein the content is 0% by volume and 45 to 20% by volume. 3. The mixing ratio of (a) the polyolefin resin and (b) the polyphenylene sulfide resin is 60 to 7 respectively.
The thermoplastic resin structure according to claim 1, wherein the content is 5% by volume and 40 to 25% by volume. 4. A polyolefin resin of 15 to 85% by volume and (b) a polyphenylene sulfide resin 85-1.
In the resin phase separation structure observed by an electron microscope, both the (b) phase composed of the polyphenylene sulfide resin and the (a) substantially the same phase composed of the polyolefin resin are substantially continuous phases. A thermoplastic resin structure characterized by forming a phase structure as follows: 5. A polyolefin resin having 55 to 95% by volume (a) and a polyphenylene sulfide resin 45 to 5%.
% By volume, and in a resin phase separation structure observed by an electron microscope, a phase structure comprising (a) a continuous phase composed of a polyolefin resin and (b) a strip-shaped dispersed phase composed of a polyphenylene sulfide resin. The thermoplastic resin structure characterized by forming. 6. The polyolefin resin according to claim 1, wherein the polyolefin resin is polyethylene, polypropylene, ethylene / α-olefin copolymer, [(ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) At least one selected from the group consisting of (copolymer), [(ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) a metal salt of at least a part of the carboxyl group] The thermoplastic resin structure according to any one of claims 1 to 5, wherein 7. A total of 10 parts of the polyolefin resin (a) and the polyphenylene sulfide resin (b).
The thermoplastic resin structure according to any one of claims 1 to 6, further comprising (c) 0.5 to 200 parts by weight of an inorganic filler with respect to 0 parts by weight. 8. The thermoplastic resin structure according to claim 1, which is formed by at least one method selected from injection molding, injection compression molding, and compression molding. 9. A container for transporting or storing a chemical solution or gas obtained by processing the thermoplastic resin structure according to claim 1. 10. An accessory part for a container for transporting or storing a chemical solution or gas obtained by processing the thermoplastic resin structure according to claim 1. 11. A laminated structure, wherein the thermoplastic resin structure according to claim 1 constitutes a barrier layer. 12. An adjacent layer is formed on one side or both sides of the barrier layer, and the resin layer forming the adjacent layer is formed of a thermoplastic resin layer different from the thermoplastic resin structure forming the barrier layer. The laminated structure according to claim 11, characterized in that: 13. The method according to claim 12, wherein the thermoplastic resin constituting the adjacent layer is at least one resin selected from a polyolefin resin, a thermoplastic polyester resin, a polyamide resin, a polycarbonate resin, and an ABS resin. The laminated structure according to the above. 14. The laminated structure according to claim 12, wherein the thermoplastic resin forming the adjacent layer is at least one resin selected from a polyolefin resin, a thermoplastic polyester resin, and a polyamide resin. 15. The thermoplastic resin constituting the adjacent layer has a melt flow rate of 0.01 to 30 g / 10 minutes,
The laminated structure according to claim 12, which is an ethylene homopolymer and / or an ethylene / α-olefin copolymer having a density of 0.90 to 0.97 g / cm ³ . 16. The laminated structure according to claim 12, wherein an adhesive layer is formed between the barrier layer and the adjacent layer. 17. The modified polyolefin as claimed in claim 17, wherein the adhesive layer has a crystallinity of 50% or less and contains 0.01 to 10% by weight of a grafted unsaturated carboxylic acid or a derivative thereof. 17. The laminated structure according to 16. 18. The adhesive layer has a crystallinity of 50% or less, 99 to 60 parts by weight of a modified polyolefin containing 0.01 to 10% by weight of an unsaturated carboxylic acid or a derivative thereof by grafting, and an adhesive layer. The laminated structure according to claim 17, comprising 1 to 40 parts by weight of an imparting agent. 19. The laminated structure according to claim 11, wherein the laminated structure is formed by a coextrusion molding method. 20. The laminated structure according to claim 11, wherein the laminated structure is formed into a multilayer tube or a multilayer blow-molded body by a coextrusion molding method.