JPH09249783A - Novel nitrile resin composition and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nitrile resin composition having markedly improved adhesion to a modified polyolefin having functional groups and having improved barrier properties by mixing specified hydroxylated nitrile resin with an ethylene/vinyl acetate copolymer saponificate. SOLUTION: This composition comprises a nitrile resin (A) comprising 50-99wt.% unsaturated nitrile monomer component, 0.05-10wt.% polyrherizable hydroxy monomer component and 0.5-49.95wt.% monomer component comprising at least one member selected from among compounds copolymerizable with the unsaturated nitrile and an ethylene/vinyl acetate copolymer saponificate (B) in an A/B weight ratio of 99.5/0.5 to 50/50. It is desirable that methacrylonitrile constitutes at least 50wt.% of the total unsaturated nitrile monomer component, because the heat stability of the composition can be improved, and its gelation can be prevented.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent adhesiveness with a modified polyolefin containing an acid anhydride group, an unsaturated carboxylic acid group, an epoxy group or the like, and containing oxygen, carbon dioxide, water, The present invention relates to a novel nitrile resin composition suitable as a barrier resin because it has a low permeation amount of hydrocarbons, gasoline, alcohol-containing gasoline and the like. Further, by using methacrylonitrile, a novel nitrile resin composition which is excellent in thermal stability and is hard to gel is provided. Furthermore, the present invention relates to a laminate utilizing the fact that the nitrile resin composition of the present invention has excellent adhesiveness to a modified polyolefin. This laminate is suitable for container materials and packaging materials, and is useful as multilayer container materials and multilayer packaging materials for foods, drugs, organic solvents and the like.

[0002]

2. Description of the Related Art Nitrile resins are used in container materials and packaging materials because of their excellent chemical resistance and gas barrier properties. For example, they are disclosed in JP-A-62-235078 and JP-A-62-235079. Publication, JP-A-63-3
It is disclosed in Japanese Patent Publication No. 07078. In addition, Japanese Unexamined Patent Publication
As disclosed in Japanese Patent No. 366636, a material obtained by laminating a nitrile resin on a polyolefin is used as a container material or a packaging material. As a nitrile resin generally used so far, Japanese Examined Patent Publication No. 46-25005
Most of them are nitrile resins obtained by polymerizing acrylonitrile and an unsaturated ester monomer as disclosed in Japanese Patent Laid-Open Publications.

[0003]

However, it is known that these nitrile resins containing acrylonitrile and an unsaturated ester monomer as main components have poor adhesion to polyolefin. Therefore, JP-A-5-138837
As disclosed in the publication, it has been proposed to introduce a functional group such as an epoxy group, a hydroxyl group, an amino group and an amide group into a nitrile resin. However, although the introduction of these functional groups improves the adhesiveness, further improvement of the adhesiveness is required. Further, there is a problem that the introduction of an epoxy group or the like lowers the thermal stability of the nitrile resin and promotes gelation.

[0004]

Means for Solving the Problems As a result of earnest studies to overcome these problems, the present inventor has found that the nitrile resin contains a hydroxyl group and is functionalized by blending a saponified ethylene-vinyl acetate copolymer. It was found that not only the adhesiveness with the modified polyolefin having a group can be significantly improved, but also the barrier property is improved as compared with the base resin. Further, they have found that the use of a nitrile resin containing methacrylonitrile as a main component makes it difficult to cause gelation, and completed the present invention. That is, the present invention is an unsaturated nitrile monomer component 50 to 99 wt%, a polymerizable monomer component having a hydroxyl group 0.05 to 10 wt%,
Monomer component 0.5 to 4 consisting of one or more selected from compounds copolymerizable with unsaturated nitrile monomer
A resin composition composed of a nitrile resin (A) composed of 9.95% by weight and a saponified product of ethylene-vinyl acetate copolymer (B) having a ratio of (A) / (B) of 99.5 / 0. .5-
A novel nitrile resin composition having a weight ratio of 50/50,
And a laminate having a structure in which a layer made of this nitrile resin composition and a layer made of modified polyolefin are stacked. Furthermore, the nitrile resin composition becomes a resin composition having impact resistance at low temperature by containing a rubbery polymer, and when methacrylonitrile is used as the unsaturated nitrile monomer, thermal stability is improved. A resin composition that does not easily gel even when heated is obtained. Furthermore, by laminating the above-mentioned laminated body with a non-modified polyolefin, it is possible to obtain a hygienic preferable laminated body. Hereinafter, the present invention will be described in detail.

The nitrile resin in the present invention is a resin containing an unsaturated nitrile monomer component as a main component, and it is necessary that the nitrile resin contains 50 to 99% by weight of the unsaturated nitrile monomer component. If the amount of the unsaturated nitrile monomer component is less than 50% by weight, only those having low chemical resistance and gas barrier properties, which are characteristic of nitrile resin, can be obtained. If the unsaturated nitrile monomer component exceeds 99% by weight, practical fluidity cannot be obtained and the resin becomes difficult to thermoform. Preferred is a nitrile resin containing 60 to 95% by weight of an unsaturated nitrile monomer component. More preferably, it is a nitrile resin containing 70 to 90% by weight of an unsaturated nitrile monomer component.

Examples of the unsaturated nitrile monomer component include acrylonitrile, methacrylonitrile, vinylidene cyanide and the like. Preferably, acrylonitrile and methacrylonitrile are each polymerized, or both are copolymerized, and more preferably, methacrylonitrile is 50% by weight or more of the unsaturated nitrile monomer component, This improves thermal stability and prevents gelation.

Examples of the polymerizable monomer component having a hydroxyl group include vinyl alcohol and acrylic acid or methacrylic acid derivatives. Preferred is a derivative of acrylic acid or methacrylic acid. Specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 1,4-butanediol acrylate,
1,6-hexanediol acrylate, pentaerythritol acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 1,
4-butanediol methacrylate, 1,6-hexanediol methacrylate, pentaerythritol methacrylate and the like can be mentioned. Most preferably, it is 2-hydroxyethyl methacrylate. The content of the polymerizable monomer component having a hydroxyl group in the nitrile resin is 0.05.
It is necessary to be 10% by weight. 0.05% by weight
If the amount is smaller, the adhesion with the modified polyolefin will not be improved. On the other hand, if it exceeds 10% by weight, the polymerization rate is difficult to increase and the productivity is lowered. The content of the polymerizable monomer component having a hydroxyl group is preferably 0.5 to 7% by weight. More preferably, the content is 1 to 5% by weight.

Examples of the compound copolymerizable with the unsaturated nitrile monomer include aromatic vinyl compounds, (meth) acrylic acid esters, maleimide compounds and the like. Each will be specifically described below. Examples of the aromatic vinyl compound include styrene, α-alkylstyrene such as α-methylstyrene, nuclear-substituted alkylstyrene such as p-methylstyrene, halogenated styrene, and vinyl-substituted naphthalene. These may be one kind or a mixture of two or more kinds. Preferred are styrene, α-methylstyrene, and a mixture of styrene and α-methylstyrene.

As the (meth) acrylic acid ester, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2- Examples include ethylhexyl methacrylate and the like. Examples of the maleimide compound include N-phenylmaleimide, N-o-methylphenylmaleimide, N-cyclohexylmaleimide, Nt-butylmaleimide and the like.

Aromatic vinyl compounds, (meth) acrylic acid esters, maleimide compounds and the like may be used alone or in combination with a polymerizable compound having an unsaturated nitrile monomer and a hydroxyl group, but they may be copolymerized using two or more kinds. I don't mind. Most preferably, styrene, methyl acrylate,
n-butyl acrylate, methyl methacrylate, N-
It is a monomer selected from phenylmaleimide. The sum of the monomer components selected from the compounds copolymerizable with these unsaturated nitrile monomers in the nitrile resin is 0.5 to
It must be 49.95% by weight. When the amount is less than 0.5% by weight, the nitrile resin has poor practical fluidity, and when the amount is more than 49.95% by weight, the barrier property is insufficient or the thermal stability is deteriorated.

As the method for producing the nitrile resin in the present invention, known emulsion polymerization method, suspension polymerization method and solution polymerization method are used. A typical production method is an emulsion polymerization method, which is an unsaturated nitrile monomer in water in which a surfactant is dispersed, or water in which a rubbery polymer and a surfactant are dispersed, and a polymerizable monomer having a hydroxyl group. Body, one or more monomers selected from compounds capable of polymerizing with unsaturated nitrile monomers,
Polymerization is performed using an initiator, a chain transfer agent, a pH adjuster, etc. to obtain a nitrile resin latex. A nitrile resin is obtained by salting out the obtained latex with an electrolyte aqueous solution or the like by a known method, further dehydrating and drying.

The saponification product of the ethylene-vinyl acetate copolymer used in the present invention will be described. This resin is generally called an ethylene-vinyl alcohol copolymer. Vinyl is polymerized in the presence of a solvent, an initiator, etc., and saponified with an alkali metal such as sodium hydroxide, and then separated,
It can be obtained by washing and drying. In the present invention, the ethylene content is 10 to 50 mol% and the saponification degree is 90%.
The above saponified ethylene-vinyl acetate copolymer is used. When the ethylene content is less than 10 mol%, the melt moldability is deteriorated, and when the ethylene content is more than 50 mol%, the barrier property is deteriorated. Further, even if the degree of saponification is less than 90%, the barrier property is lowered.

In the present invention, the blending ratio of the nitrile resin and the saponified product of the ethylene-vinyl acetate copolymer is 99.
It is necessary to be 5 / 0.5 to 50/50 (weight ratio). Outside this range, the adhesiveness to the modified polyolefin is poor, or the barrier properties against water vapor and alcohol-containing substances are reduced. The method for blending the nitrile resin and the saponified product of the ethylene-vinyl acetate copolymer is not particularly limited, but it is preferable to heat and knead using an extruder, a kneader, a roll mixer, a Banbury mixer, a Brabender or the like.

The nitrile resin composition has improved impact resistance at low temperatures by containing a rubbery polymer.
The rubbery polymer is a rubbery polymer having a glass transition point of 0 ° C or lower, preferably -20 ° C or lower. Specifically, polybutadiene, styrene-butadiene copolymer rubber, diene rubber such as acrylonitrile-butadiene copolymer rubber, acrylic rubber such as polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyisoprene, poly Chloroprene, ethylene-propylene rubber, ethylene-propylene-diene terpolymer rubber,
Styrene-butadiene block copolymer rubber, styrene-
Block copolymers such as isoprene copolymer rubbers and hydrogenated products thereof can be used. Preferred are acrylonitrile-butadiene copolymer rubber, polybutadiene, and styrene-butadiene copolymer rubber. The amount of the rubbery polymer is a single monomer selected from an unsaturated nitrile monomer component, a polymerizable monomer component having a hydroxyl group, and a compound copolymerizable with the unsaturated nitrile monomer, or a single monomer selected from two or more compounds. It is preferable to contain 0.5 to 19.9 parts by weight with respect to 100 parts by weight of a resin composition composed of a nitrile resin composed of a monomer component and a saponified ethylene-vinyl acetate copolymer. If it is less than 0.5 part by weight, impact resistance cannot be obtained.
When it is more than 19.9 parts by weight, the gas barrier property which is a characteristic of the nitrile resin is deteriorated. The amount is preferably 2 to 18 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts by weight of the resin composition comprising the nitrile resin and the saponified ethylene-vinyl acetate copolymer.

As a method of incorporating the rubbery polymer into the nitrile resin composition, the nitrile resin composition and the rubbery polymer are heated and kneaded by using an extruder, a kneader, a roll mixer, a Banbury mixer, a Brabender or the like. Method, a nitrile resin, a method in which a rubbery polymer is dispersed in a suitable solvent and solution blending, a method in which a nitrile resin latex and a rubbery polymer latex are blended and simultaneously salted out, in the presence of a rubbery polymer Examples thereof include a method of polymerizing a nitrile resin.

If necessary, additives such as antioxidants and ultraviolet absorbers can be added during the polymerization process, salting-out process, kneading process, etc. within a range that does not impair the intended features of the present invention. Further, in the resin composition, within a range that does not impair the intended features of the present invention, an antistatic agent, a flame retardant, a pigment, a dye,
Additives such as lubricants and bleaching agents, and reinforcing agents such as glass fibers, carbon fibers and fillers can be added. The method of mixing these is not particularly limited. It can be obtained by a conventional method, for example, kneading using a device such as an extruder, a kneader, a roll mixer, a Banbury mixer, and a Brebender.

The modified polyolefin used in the present invention is
A polymer having a structure represented by the following general formula (1), further comprising a carboxyl group, an epoxy group, an acid anhydride, an ester group, a ketone group, a hydroxyl group, a halogen, a carboxylic acid halide, and a sulfonic acid halogen. It is a polymer having any of functional groups and structures such as compounds, nitrile groups, phenyl groups and unsaturated bonds.

[0018]

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For example, those obtained by introducing functional groups into polyolefin by a graft reaction, those obtained by introducing functional groups into polyolefin by a copolymerization reaction, those obtained by substituting hydrogen in the polyolefin with functional groups, elastomers, etc. It corresponds to the modified polyolefin of the present invention. The modified polyolefin will be specifically described below.

As a method of introducing functional groups by a graft reaction, polyolefin and an unsaturated compound having a functional group are heated and mixed with a radical initiator in an organic solvent to react, or kneading with an extruder, a kneader or the like. There is a method in which an unsaturated compound having a functional group and a radical initiator such as polyolefin and organic peroxide are mixed and reacted in a molten state using a machine. The latter is the preferred method because the process is simple and economical. The polyolefin used for producing the modified polyolefin by the graft reaction is specifically an ethylene homopolymer, ethylene and propylene, 1-butene, 1-hexene, 1-
Copolymers of α-olefins such as octene and 4-methyl-1-pentene with one or more comonomers, homopolymers of propylene, binary or ternary copolymers of propylene and ethylene, 1-butene. Examples thereof include polymers and butylene homopolymers. The average molecular weight of these polyolefins is generally 10,000 to 1,000,000, preferably 20,000 to 500,000. The shape of the polyolefin may be either powder or pellets, but from the viewpoint of enhancing the dispersibility and the efficiency of modification, a shape having a large surface area, that is, powder is preferable. The polyolefin used as the raw material of the modified polyolefin is a catalyst system (Ziegler catalyst) obtained from a transition metal compound and an organoaluminum compound, or a Ziegler catalyst supported on silica or magnesium, or a chromium compound (eg silica) on a carrier (eg silica). (Chromium oxide) -supported catalyst system (Phillips catalyst) or radical initiator (eg organic peroxide), or catalyst system consisting of metallocene and co-catalyst (methylalumoxane (MAO) or cation generator) Is obtained by homopolymerizing or copolymerizing an olefin.

Further, the unsaturated compound having a functional group used for producing a modified polyolefin by a graft reaction is
Having at least one or more double bonds and at least one
It is a compound having the above carboxyl group, epoxy group, and acid anhydride. Specifically, (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, glycidyl (meth) acrylate, allyl glycidyl ether, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be mentioned. Preferred are (meth) acrylic acid, glycidyl (meth) acrylic acid, and maleic anhydride. These unsaturated compounds may be used alone or in combination of two or more kinds. Typical examples of the organic peroxide used in the production of the modified polyolefin by the graft reaction include t-butylperoxybenzoate, 2,5-dimethyl-2,
Examples thereof include 5-di (t-butylperoxy) hexane and di-t-butylperoxide. The organic peroxides may be used alone or in combination of two or more.

The amount of the unsaturated compound having a functional group is 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, based on 100 parts by weight of the polyolefin when the modified polyolefin is produced by the graft reaction. , And more preferably 0.05 to 5 parts by weight. If it is less than 0.01 part by weight, the adhesiveness between the modified polyolefin and the nitrile resin is poor, and if it exceeds 10 parts by weight, the graft reaction rate decreases, so that the unreacted unsaturated compound or the unsaturated compound as a by-product is Not only does the adhesion decrease because the homopolymer remains considerably in the modified polyolefin,
The physical properties originally possessed by polyolefin will be impaired. Further, the blending amount of the organic peroxide is polyolefin 10
It is 0.001 to 15 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.0 to 0 parts by weight.
It is preferable to add 2 to 5 parts by weight. If it is less than 0.001 part by weight, the adhesion between the modified polyolefin and the nitrile resin is poor. On the other hand, if the amount exceeds 15 parts by weight, not only the physical properties originally possessed by the polyolefin are impaired, but also the graft reaction efficiency decreases, so that homopolymerization of an unreacted unsaturated compound or an unsaturated compound which is a by-product. Since the material remains in the modified polyolefin, the adhesiveness decreases.

The method for producing a modified polyolefin by a graft reaction can be obtained by carrying out modification while melt-kneading using an extruder used in the field of general synthetic resins. At this time, the extruder used may be either a non-vent type or a vent type, but from the viewpoint of removing unreacted or by-product unsaturated compound homopolymers or decomposed products of organic peroxides. A vented extruder is desirable. Further, the kneading temperature is 140 to 280 ° C, and it is preferably 180 to 230 ° C, though it depends on the kinds of the polyolefin and the organic peroxide used. Kneading temperature is 1
If the temperature is lower than 40 ° C, the denaturation will not be performed well. Meanwhile, 280
If the temperature exceeds ℃, a part of the polyolefin is deteriorated. The residence time in the extruder is 60 seconds or more,
0 second or more is suitable. If the residence time in the extruder is less than 60 seconds, satisfactory modification will not occur. Further, a stabilizer against oxygen and heat generally used in the field of polyolefin during melt modification, a filler (for example, mica, talc, glass, organic fiber, wood powder, etc.), a lubricant and a flame retardant are added, It may be used as a composite material.

Next, the method of introducing functional groups by a copolymerization reaction will be described. As a general method, a suspension polymerization method, a high pressure radical polymerization method, a solution polymerization method, a bulk polymerization method, an emulsion polymerization method or the like is used. It is preferable to copolymerize a monomer having a functional group with an olefin. Examples of the monomer having a functional group include vinyl chloride, vinyl acetate, maleic acid, fumaric acid, maleic anhydride, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and the like. You may use 1 type or 2 or more types. As the olefin, ethylene alone, propylene alone, butylene alone, ethylene and propylene, 1-butene, 1-hexene, 1-octene, α-, such as 4-methyl-1-pentene
Examples thereof include one kind or a mixture of two or more kinds of olefins. Further, modified polyolefins are also those in which the functional groups are changed to other functional groups by post-reaction such as hydrolysis. Examples of the modified polyolefin having functional groups introduced by a copolymerization reaction include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene-acrylic rubber and the like. Examples of the post-reacted products include ethylene-vinyl alcohol-vinyl acetate copolymers and ethylene-vinyl alcohol copolymers.

The method of substituting the hydrogen groups contained in the polyolefin with the functional groups will be described. As a general method, a method of contacting the polyolefin and the substituting gas in a solvent in the presence of a catalyst or the like is used. Examples include a method of contacting a polyolefin and a replacement gas in the presence of a catalyst or the like in an aqueous solution suspension, a method of contacting a molten polyolefin with a replacement gas in the presence of a catalyst, and the like. Specific examples of the polyolefin here include ethylene homopolymers, ethylene and propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, and the like α-.
Unmodified polyolefins such as copolymers of olefins with one or more comonomers, propylene homopolymers, propylene and ethylene, binary or terpolymers of 1-butene, butylene homopolymers, etc. And modified polyolefins having functional groups introduced by copolymerization. Examples of the replacement gas include chlorine and sulfur dioxide. Examples include chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene rubber and the like.

As the elastomer, hydrogenated nitrile rubber, hydrogenated styrene-butadiene block copolymer,
Examples thereof include hydrogenated styrene-isoprene block copolymers, chloroprene rubber, ethylene-propylene-diene copolymers and the like, and those having a functional group grafted thereto or a functional group introduced by copolymerization may be used. Absent. A laminate comprising a layer made of the modified polyolefin as described above (hereinafter referred to as “MPO layer”) and a layer made of the nitrile resin composition shown above (hereinafter referred to as “N layer”). The laminate of the present invention has a structure in which layers and MPO layers are stacked. Further, a laminated body in which the N layer is sandwiched between MPO layers, that is, the cross section of the laminated body is MPO layer-N layer-MPO.
Laminates that overlap the layers are also included in the invention. N layer and M
The PO layers are bonded together by a method such as hot pressing.

Unsaturated compounds and oligomers of unsaturated compounds remaining in the modified polyolefin, monomers used for modification and unreacted products of the substitution gas, etc. may affect the taste and flavor of foods. Conceivable. In order to prevent these influences, the polyolefin layer which has not been modified (hereinafter referred to as "PO layer") is formed on the laminate in which the N layer and the MPO layer are stacked.
It is effective to stack the. The PO layer is a laminated MPO
It is effective to stack on the layer side. For the laminated body in which the N layer is sandwiched by the MPO layers, one side or both sides of the laminated body may be used. That is, in the case of a single-area layer of the PO layer, the cross section of the laminate is laminated with PO layer-MPO layer-N layer-MPO layer (or vice versa). In the case of laminating both sides of the PO layer, the cross section of the laminated body is PO layer-MPO layer-N layer-MP.
It becomes an O layer-PO layer. Further, the PO layer may be two or more polyolefin layers made of different polyolefins. Moreover, you may laminate using the resin which consists of 2 or more types of polyolefins. Furthermore, it is also possible to stack the MPO layer-N layer-MPO layer-PO layer on the PO layer.

The unmodified polyolefin used as the PO layer is specifically an ethylene homopolymer, ethylene and propylene, 1-butene, 1-hexene, 1-
Copolymers of α-olefins such as octene and 4-methyl-1-pentene with one or more comonomers, homopolymers of propylene, binary or ternary copolymers of propylene and ethylene, 1-butene. Examples thereof include polymers and butylene homopolymers. The average molecular weight of these polyolefins is generally 10,000 to 1,000,000, preferably 20,000 to 500,000. The shape of the polyolefin may be either powder or pellets. These polyolefins are a catalyst system (Ziegler catalyst) obtained from a transition metal compound and an organoaluminum compound, or a Ziegler catalyst supported on silica or magnesium,
Alternatively, a catalyst system (Phillips catalyst) obtained by supporting a chromium compound (for example, chromium oxide) on a carrier (for example, silica), a radical initiator (for example, organic peroxide), or a metallocene and a cocatalyst (methylalmo). Obtained by homopolymerizing or copolymerizing olefins using a catalyst system consisting of xanthane (MAO) or a cation generator).

In addition, stabilizers, fillers (for example, mica, talc, glass, organic fibers, wood powder, etc.) to oxygen and heat, which are generally used in the field of synthetic resins, are added to this polyolefin, lubricants and flame retardants. May be added and used as a composite material. In order to manufacture the laminate of the present invention, a molding method such as that practiced in the field of general synthetic resins, for example, hollow molding, film molding, sheet molding, stamping molding or the like may be applied. As a typical example of this molding method, the MPO layer, the N layer, and the PO layer are separately melt-extruded, each thin material (sheet, film, etc.) is molded, and then these are adhered to each other to produce a laminate. Then, a method for producing a container by a vacuum forming method, a pressure forming method, a press forming method, or MPO.
Layer, N layer, and PO layer are co-extruded with a T-die (multilayer sheet molding), MPO layer, N layer, and PO layer are coextruded, and then a container is manufactured by a hollow molding method (multilayer hollow). Molding method) and the like.

[0030]

EXAMPLES The following examples and comparative examples are for more specifically explaining the present invention, and the present invention is not limited to these examples. (Hereinafter, “part” means “part by weight”.) (A) Nitrile resin composition used in Examples and the like below,
The (B) modified polyolefin, (C) polyolefin, (D) nitrile resin composition test method, (E) laminate manufacturing method, (F) peel strength test method, and (G) barrier property test method will be described. .

(A) Nitrile Resin Composition [Manufacture of Nitrile Resin (A-1)] Alkenyl succinate (manufactured by Kao Corporation, Latemur AS) in 100 parts of deionized water.
K) 2.0 parts was added, the gas phase was replaced with nitrogen, and then 70 ° C.
The temperature rose. Subsequently, 90 parts of methacrylonitrile, 6 parts of styrene, 4 parts of 2-hydroxyethyl methacrylate,
A monomer mixture consisting of 0.4 parts of tertiary decyl mercaptan and 0.5 part of cumene hydroperoxide, 50 parts of deionized water, 0.5 parts of sodium formaldehyde sulfoxylate, and 0.025 parts of ferrous sulfate. An aqueous solution prepared by dissolving 0.15 parts of ethylenediaminetetraacetic acid disodium salt was added over 8 hours and polymerized at a temperature of 70 ° C. to obtain a nitrile resin latex.

Freezing and salting out this nitrile resin latex,
The reduced viscosity of the resin obtained by filtration and drying (measured with a solution of 0.5 g per 100 ml of methyl ethyl ketone at 30 ° C.) was 0.41. The methacrylonitrile component content in the nitrile resin calculated from the monomers remaining without reaction was 89% by weight, the styrene component content was 7% by weight, and the 2-hydroxyethylmethacrylate component content was 4% by weight. . 70% of this nitrile resin latex
The mixture was heated to 0 ° C., and an aqueous solution of aluminum sulfate was added with stirring so that the amount of aluminum sulfate was 0.8 parts with respect to 100 parts of the resin, to obtain a nitrile resin aggregate. This was dehydrated with a centrifuge and then dried in a dryer at 100 ° C. for 1 hour to obtain a nitrile resin (A-1).

[Manufacture of Nitrile Resin (A-2)] 70 parts of methacrylonitrile, 20 parts of acrylonitrile, 8 parts of styrene, 2 parts of 2-hydroxyethyl methacrylate, 1.5 parts of tert-lead decyl mercaptan were mixed with the monomer mixture.
Parts and cumene hydroperoxide, except that the amount was 0.35 part, the same nitrile resin (A-1) as the polymerization method, salting-out method, dehydration and drying were carried out to obtain a nitrile resin (A-2). Reduced viscosity of this nitrile resin (A-2) (30 ° C
(Measured with a solution of 0.5 g based on 100 ml of N, N-dimethylformamide) was 0.64.
The methacrylonitrile component content in the nitrile resin calculated from the monomers remaining without reaction was 68% by weight, the acrylonitrile component content was 21% by weight, the styrene component content was 9% by weight, and the 2-hydroxyethylmethacrylate component was The content was 2% by weight.

[Production of Nitrile Resin (A-3)] Acrylonitrile-butadiene copolymer rubber latex (weight average particle diameter 0.2 μm) 10 parts (solid content conversion), deionized water 100 parts, alkenyl succinate 2 .0 parts,
After substituting the gas phase with nitrogen, the temperature was raised to 70 ° C. continue,
A monomer mixture liquid consisting of 81 parts of methacrylonitrile, 5.4 parts of styrene, 3.6 parts of 2-hydroxyethyl methacrylate, 0.7 part of cumene hydroperoxide, 0.4 part of tertiary reed decyl mercaptan, and deionized. An aqueous solution prepared by dissolving 0.7 part of sodium formaldehyde sulfoxylate, 0.035 part of ferrous sulfate and 0.21 part of ethylenediaminetetraacetic acid disodium salt in 50 parts of water was added over 7 hours, and polymerization was performed at 70 ° C. The reaction was carried out at a temperature to obtain a nitrile resin latex. This nitrile resin latex was salted out with aluminum sulfate in the same manner as the nitrile resin (A-1), dehydrated and dried to obtain a nitrile resin composition (A-3). The rubber polymer of the nitrile resin composition (A-3) and the resin grafted to the rubber polymer were separated with acetone, and the nitrile resin dissolved in acetone was dried to obtain a reduced viscosity (at 30 ° C.). It was 0.40 when the measurement (measurement with a solution of 0.5 g per 100 ml of methyl ethyl ketone) was measured. The methacrylonitrile component content in the nitrile resin calculated from the monomers remaining without reaction was 89% by weight, the styrene component content was 7% by weight, and the 2-hydroxyethylmethacrylate component content was 4% by weight. Nitrile resin 10
The amount of rubbery polymer relative to 0 part was 11 parts.

[Production of Nitrile Resin (A-4)] Except for using 90 parts of methacrylonitrile, 6 parts of methyl acrylate, 4 parts of 2-hydroxyethyl methacrylate, and 0.5 parts of tertiary decyl mercaptan as the monomer mixture. Was subjected to the same polymerization method, salting out method, dehydration and drying as those of the nitrile resin (A-1) to obtain a nitrile resin (A-4).
The reduced viscosity of this nitrile resin (A-4) (measured with a solution of 0.5 g per 100 ml of methyl ethyl ketone at 30 ° C.) was 0.44. The content of methacrylonitrile component in the nitrile resin calculated from the monomers remaining without reaction was 89% by weight, the content of methyl acrylate component was 7% by weight, and the content of 2-hydroxyethyl methacrylate component was 4% by weight. It was

[Production of Nitrile Resin (B-1)] Nitrile resin (A-) except that the monomer mixture liquid was changed to 40 parts of methacrylonitrile, 5 parts of acrylonitrile, 50 parts of styrene and 5 parts of 2-hydroxyethyl methacrylate. Polymerization method and salting-out method, dehydration and drying similar to those in 1) were performed to obtain a nitrile resin (B-1). Reduced viscosity of this nitrile resin (B-1) (methyl ethyl ketone 100 m at 30 ° C.
(measured with 0.5 g of solution per liter) was 0.42. The content of methacrylonitrile component in the nitrile resin calculated from the monomers remaining without reaction is 39% by weight,
The acrylonitrile component content was 5% by weight, the styrene component content was 51% by weight, and the 2-hydroxyethylmethacrylate component content was 5% by weight.

[Production of Nitrile Resin (B-2)] Nitrile resin (A) except that the monomer mixture liquid was changed to 70 parts of methacrylonitrile, 20 parts of acrylonitrile and 10 parts of styrene.
-2), the same polymerization method, salting-out method, dehydration and drying were carried out to obtain a nitrile resin (B-2). The reduced viscosity of this nitrile resin (B-2) (measured with a solution of 0.5 g per 100 ml of N, N-dimethylformamide at 30 ° C.) was 0.59. The content of methacrylonitrile component in the nitrile resin calculated from the monomers remaining without reaction was 68% by weight, the content of acrylonitrile component was 21% by weight, and the content of styrene component was 11% by weight.

[Production of Nitrile Resin (B-3)] 70 parts of methacrylonitrile, 10 parts of styrene,
A nitrile resin (B-3) was obtained by performing the same polymerization method, salting out method, dehydration and drying as those of the nitrile resin (A-1) except that 20 parts of 2-hydroxyethyl methacrylate was used. The reduced viscosity (measured with a 0.5 wt% solution of methyl ethyl ketone at 30 ° C.) of this nitrile resin (B-3) was 0.37. The reaction rate was as low as 50%.
Further, the content of methacrylonitrile component in the nitrile resin calculated from the monomers remaining without reaction was 69% by weight, the content of styrene was 11% by weight of the component, and the content of 2-hydroxyethylmethacrylate component was 20% by weight. It was

85 parts of nitrile resin (A-2) and saponified ethylene-vinyl acetate copolymer (Kuraray Co., Ltd., grade: EVAL EP-L101B (ethylene content 2
7 mol%) was used. same as below. ) 15 copies for 200
A nitrile resin composition (N1) melt-kneaded by a twin-screw extruder set to ° C was obtained. Nitrile resin (A-2) 90
2 parts of saponified ethylene-vinyl acetate copolymer
Melt kneading was performed with a twin-screw extruder set at 00 ° C. to obtain a nitrile resin composition (N2). Nitrile resin (A-3)
A nitrile resin composition (N3) was obtained by melt-kneading 85 parts and 15 parts of an ethylene-vinyl acetate copolymer saponification product with a twin-screw extruder set at 200 ° C. Nitrile resin (B-
2) 85 parts and saponified product of ethylene-vinyl acetate copolymer 1
A nitrile resin composition (N4) was obtained by melt-kneading 5 parts by an extruder set at 200 ° C.

(B) Modified Polyolefin and Elastomer As the modified polyolefin, maleic anhydride-modified high density polyethylene (manufactured by Showa Denko KK, grade: ADTEX ER) (hereinafter referred to as "GPE") was used. Melt flow rate 2.0 g / 10 minutes (ASTM-D-1
Compliant with 238. 230 ° C., weighted 2.16 Kg) 100 parts hydrogenated styrene-butadiene block copolymer, 0.5 part maleic anhydride, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane 0.01
Parts were mixed in advance with a Henschel mixer, and this mixture was mixed with 4
A 0 mmφ single screw extruder was used to melt-knead at a resin temperature of 260 ° C. to obtain a hydrogenated styrene-butadiene block copolymer (hereinafter referred to as “GSB”) grafted with maleic anhydride.

(C) Polyolefin A linear high-density polyethylene (Showlex Super: 4551H, manufactured by Showa Denko KK) was used. (D) Test Method of Nitrile Resin Composition Adhesiveness A film of the maleic anhydride-modified high-density polyethylene and the nitrile resin composition described in (B) is hot-pressed (200
The adhesiveness was confirmed by carrying out the heating at 3 ° C. for 3 minutes at 10 kg / cm ² . Those with strong adhesion were evaluated as ⊚, those with adhesion were evaluated as ○, and those without adhesion were evaluated as ×.

Alcohol-containing gasoline (gasohol)
Chemical resistance to nitrile resin composition as a flat plate with a thickness of 1 mm, gasohol (toluene: isooctane: methanol = 42.5: 4)
It was dipped in a mixed solution of 2.5: 15 (weight ratio) for 3 days, and the swelling amount was examined. Swelling amount is 1% of initial sample weight
The following is ◎, 1-3% is ○, 3-5% is △,
When it exceeded 5%, it was evaluated as x. Thermal stability To confirm thermal stability, hold at 250 ° C for 30 minutes and
The melt flow rate (MFR) at 0 kg load was measured.

Gas Barrier Property to Gasohol The nitrile resin composition was formed into a film having a thickness of 200 μm, and the gas permeability at 40 ° C. was measured by the cup method (JIS-Z-0208). (E) Method for producing laminated body Nitrile resin composition (N1, N2, N3 and N4),
Each of the modified polyolefin (GPE and GSB) and polyolefin (4551H) single-layer sheets was heated at 190 ° C. for 300 seconds under heating at a pressure of 60 kg / c.
It was prepared under the condition of m ² . After that, N layer, GPE layer, P
Each of the single-layer sheets obtained by stacking the O layers so as to form a desired laminate is heated at 190 ° C. using a heat press molding machine and heated to 300
Second, a laminate was formed under the condition of a pressure of 60 kg / cm ² .

(F) Peel strength test method A test piece having a width of 10 mm was cut from the above-mentioned laminate, and the peel strength of the interface (GPE layer) adjacent to the nitrile resin layer (N layer) was measured. The peel strength was measured by a T-type peel test using a tensile tester on the laminated test piece having a width of 10 mm at a speed of 50 mm / min. (G) Barrier property test As a barrier property test, the transmission coefficient was measured according to JIS-Z-0280. The test method was as follows: An aluminum container having an inner diameter of 60 mm was filled with 30 ml of the test solvent, a laminated sheet cut on a circle having a diameter of 70 mm was fixed to the lid part, and the container was sealed, and the container was placed in an oven under an atmosphere of 40 ° C. The sample was allowed to stand still and the permeation coefficient per unit area and unit thickness was calculated from the change in weight with time. The test solvent was (a) a mixed solvent of 50% by weight of toluene and 50% by weight of isooctane,
(B) Gasohol, two types were used.

(Example 1) Nitrile resin (A-1) 80
20 parts of ethylene-vinyl acetate copolymer saponified product
The test (D) was conducted on the nitrile resin composition melt-kneaded by an extruder set at 00 ° C. (Example 2) A test of (D) was conducted on a nitrile resin composition obtained by melt-kneading 80 parts of a nitrile resin (A-2) and 20 parts of a saponified ethylene-vinyl acetate copolymer with an extruder set at 200 ° C. It was

(Example 3) Nitrile resin (A-3) 80
20 parts of ethylene-vinyl acetate copolymer saponified product
The test (D) was conducted on the nitrile resin composition melt-kneaded by an extruder set at 00 ° C.

(Example 4) Nitrile resin (A-4) 80
20 parts of ethylene-vinyl acetate copolymer saponified product
The test (D) was conducted on the nitrile resin composition melt-kneaded by an extruder set at 00 ° C. (Comparative Example 1) A nitrile resin composition obtained by melt-kneading 80 parts of a nitrile resin (B-1) and 20 parts of a saponified product of an ethylene-vinyl acetate copolymer with an extruder set at 200 ° C was subjected to the test (D). It was

(Comparative Example 2) Nitrile resin (B-2) 80
20 parts of ethylene-vinyl acetate copolymer saponified product
The test (D) was conducted on the nitrile resin composition melt-kneaded by an extruder set at 00 ° C. (Comparative Example 3) A test of (D) was conducted on a nitrile resin composition obtained by melt-kneading 80 parts of a nitrile resin (B-3) and 20 parts of a saponified ethylene-vinyl acetate copolymer with an extruder set at 200 ° C. It was

(Comparative Example 4) A test (D) was conducted on a resin obtained by melt-kneading only the nitrile resin (B-2) with an extruder set at 200 ° C. (Comparative Example 5) The saponified ethylene-vinyl acetate copolymer was evaluated (D). Table 1 shows the evaluation results.

[0050]

[Table 1]

As shown in Table 1, it is understood that those satisfying the conditions specified in the present invention are nitrile resin compositions having high adhesiveness to the modified polyolefin, chemical resistance and barrier properties superior to those of the base resin. That is, one selected from a compound which is copolymerizable with an unsaturated nitrile monomer component of 50 to 99% by weight, a hydroxyl group-containing polymerizable monomer component of 0.05 to 10% by weight, and an unsaturated nitrile monomer. Alternatively, a resin composition comprising a nitrile resin (A) obtained by polymerizing 0.5 to 49.95% by weight of a monomer component consisting of two or more kinds and a saponified ethylene-vinyl acetate copolymer (B). , (A)
It can be seen that the nitrile resin composition having a ratio of / (B) of 99.5 / 0.5 to 50/50 (weight ratio) is a resin composition that solves the conventional problems.

(Example 5) A laminate having a cross-section of the laminate having a structure of GPE-N1-GPE was prepared by the manufacturing method of (E). (Example 6) Using the manufacturing method of (E),
A laminated body having a structure of 4551H-GPE-N1-GPE-4551H was prepared, and tests (F) and (G) were performed. (Embodiment 7) The cross section of the laminate is 4 by the manufacturing method of (E).
A laminate having a structure of 551H-GPE-N2-GPE-4551H was prepared, and tests (F) and (G) were performed.

(Embodiment 8) According to the manufacturing method of (E), the laminated body has a cross section of 4551H-GSB-N2-GSB-455.
A laminated body having a structure of 1H was prepared, and tests (F) and (G) were conducted. (Example 9) The cross-section of the laminate was 4 by the manufacturing method of (E).
A laminate having a structure of 551H-GPE-N3-GPE-4551H was prepared, and tests (F) and (G) were performed. (Comparative Example 6) For comparison, a laminated body obtained by removing the GPE layer from Example 5 has a laminated body cross section of 4551H-N1-4551.
A laminate having a structure of H was created by the manufacturing method of (E), and the tests of (F) and (G) were performed.

(Comparative Example 7) A laminate having a structure having a cross section of 4551H-GPE-4551H without a nitrile resin composition layer was prepared by the production method (E),
The tests (F) and (G) were performed. (Comparative Example 8) According to the manufacturing method of (E), the laminated body has a cross section of G
Create a laminate with the structure PE-N4-GPE,
The tests (F) and (G) were performed.

(Comparative Example 9) Instead of the nitrile resin composition layer, a saponified product of ethylene-vinyl acetate copolymer (EVO) was used.
H) is laminated with a GPE layer, and the cross section of the laminated body is GPE-
A laminate having a structure of EVOH-GPE was prepared by the manufacturing method (E), and the tests (F) and (G) were performed. (Comparative Example 10) Ethylene as a nitrile resin composition layer
The cross-section of the laminate using the nitrile resin (A-3) containing no saponified vinyl acetate copolymer is GPE- (A-
3) A laminated body having a structure of -GPE was prepared by the manufacturing method of (E), and the tests of (F) and (G) were conducted. Table 2 shows the evaluation results of the laminate produced as described above.

[0056]

[Table 2]

As shown in Table 2, since the nitrile resin composition satisfying the conditions specified in the present invention has a high adhesiveness with the modified polyolefin, it can be seen that the laminate has an excellent barrier property. That is, one selected from a compound which is copolymerizable with an unsaturated nitrile monomer component of 50 to 99% by weight, a hydroxyl group-containing polymerizable monomer component of 0.05 to 10% by weight, and an unsaturated nitrile monomer. Alternatively, a resin composition comprising a nitrile resin (A) obtained by polymerizing 0.5 to 49.95% by weight of a monomer component consisting of two or more kinds and a saponified ethylene-vinyl acetate copolymer (B). , (A) / (B)
A laminate having a structure in which a layer made of a nitrile resin composition having a ratio of 99.5 / 0.5 to 50/50 (weight ratio) and a modified polyolefin layer are laminated solves the conventional problems. I understand. Also, by laminating a polyolefin on these laminated bodies, a laminated body which is preferable in terms of hygiene is obtained.

[0058]

INDUSTRIAL APPLICABILITY According to the present invention, a nitrile resin composition having an extremely high adhesiveness with a modified polyolefin and an excellent barrier property can be obtained. The nitrile resin composition, the modified polyolefin and an unmodified polyolefin are obtained. With a laminated body consisting of oxygen, carbon dioxide, gas such as nitrogen, water,
A laminate having a high barrier property against liquids such as hydrocarbons, gasoline and alcohol-containing gasoline, and useful as a multilayer container material and a multilayer packaging material for foods, chemicals, organic solvents and the like can be obtained.

Claims (7)

[Claims] 1. An unsaturated nitrile monomer component 50 to 99% by weight, a hydroxyl group-containing polymerizable monomer component 0.05 to 10
%, A monomer component consisting of one or more selected from compounds copolymerizable with the unsaturated nitrile monomer.
Nitrile resin (A) consisting of 5 to 49.95% by weight
And a saponified ethylene-vinyl acetate copolymer (B), wherein the ratio of (A) / (B) is 99.5.
/0.5 to 50/50 (weight ratio), the nitrile resin composition. 2. A rubbery polymer (C) is added to 0.5 parts by weight with respect to 100 parts by weight of a resin composition comprising the nitrile resin (A) according to claim 1 and a saponified ethylene-vinyl acetate copolymer (B). A nitrile resin composition containing 19.9 parts by weight. 3. In the unsaturated nitrile monomer component, methacrylonitrile is 50% of the total unsaturated nitrile monomer component.
The nitrile resin composition according to claim 1 or 2, wherein the nitrile resin composition is at least wt%. 4. A laminate comprising a layer comprising the resin composition according to claim 1 and a layer comprising a modified polyolefin. 5. A laminate comprising a layer comprising the resin composition according to claim 2 and a layer comprising a modified polyolefin. 6. A laminate comprising a layer comprising the resin composition according to claim 3 and a layer comprising a modified polyolefin. 7. A structure in which a layer containing a polyolefin as a main component is laminated on a modified polyolefin layer,
The laminated body according to 5 or 6.