JPH05138837A - Laminate - Google Patents

Abstract

PURPOSE:To provide a laminate with a good permeation preventive ability (a barrier property) for hydrocarbon such as gasoline and a mixture of an oxygen-contained organic compound and hydrocabon, for example, alcohol- contained gasoline. CONSTITUTION:The laminate is made such that two layers are bonded wherein one layer consists of (a) high nitrile resin leaving a content, of 50-99wt.% unsaturated nitrile monomer and 0.01-50wt.% ethylene monomer including an epoxy group or hydroxyl group or amide group, and the other layer consists of (b) polyolefin in which unsaturated carboxylic acid or at least one kind of a monomer selected from the derivative thereof is grafted or copolymerized. Herein, in the range of composition, the high nitrile resin (a) may contain one kind of a 49.9wt.% or less unsaturated compound selected from unsaturated carboxylic acid ester, vinyl ester, vinyl ether, vinylidene compound, and aromatic vinyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate, and more specifically, to a laminate excellent in permeation-preventing ability (barrier property) for hydrocarbons such as gasoline and mixtures of oxygen-containing organic compounds and hydrocarbons such as alcohol-containing gasoline. Regarding the body

[0002]

2. Description of the Related Art As described in JP-B-55-49989, conventionally, a laminate of polyolefin and nylon is used as a liquid hydrocarbon container such as a gasoline tank for automobiles. It has been found to have excellent anti-permeability. Further, a laminated body using a polyolefin and a high nitrile resin is disclosed in Japanese Patent Publication No. 54-41634 and Japanese Unexamined Patent Publication No. 62-22043.
It is written in.

[0003]

However, from the viewpoint of environmental pollution and depletion of petroleum resources, the use of gasoline containing oxygen-containing organic compounds such as alcohol has recently become obligatory. However, when a laminated body of polyolefin and nylon is used in a container of alcohol-containing gasoline, nylon swells with alcohol, and the permeation-preventing ability is significantly lowered, which is a fatal defect. Also, in the case of a laminate of polyolefin and high nitrile resin, 2
Due to poor adhesion between layers, the ability to prevent permeation of gasoline and alcohol-containing gasoline is insufficient. Therefore, the present inventor has conducted earnest research with the object of obtaining a material having excellent barrier properties against hydrocarbons such as gasoline and a mixture of an oxygen-containing organic compound and a hydrocarbon.

[0004]

As a result, it has been found that the above object can be achieved by laminating a layer of a specific high nitrile resin and a modified polyolefin layer. The present invention has been completed based on such findings. That is, the present invention has an unsaturated nitrile monomer content of 50 to 99.99.
0.01 to 5% by weight of ethylene-based monomer containing epoxy group or hydroxyl group, amino group or amide group
A layer of 0% by weight of a high nitrile resin (a) and a layer of a polyolefin (b) obtained by grafting or copolymerizing at least one monomer selected from unsaturated carboxylic acids or their derivatives. The high nitrile resin (a) has at least one unsaturated compound selected from unsaturated carboxylic acid ester, vinyl ester, vinyl ether, vinylidene compound and aromatic vinyl in the above composition range. It may be contained in an amount of not more than 99% by weight. Hereinafter, the present invention will be described in detail.

Unsaturated nitrile monomer content is 50-9
High nitrile resin (a) of 9.5 wt% The high nitrile resin (a) used in the laminate of the present invention contains 50 to 99.9 wt% of an unsaturated nitrile monomer, an epoxy group or a hydroxyl group or an amino group. Or a high nitrile resin having an amide group-containing ethylene monomer in an amount of 0.01 to 50% by weight, and in the above composition range, an unsaturated carboxylic acid ester, a vinyl ester, for facilitating melt molding, It may contain 49.9% by weight or less of at least one unsaturated compound selected from vinyl ether, vinylidene compound and aromatic vinyl. The unsaturated nitrile monomer is represented by the following structural formula.

[Chemical 1] However, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or halogen, and specifically, acrylonitrile,
Methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, and the like. When the composition ratio of the unsaturated nitrile monomer is less than 50% by weight, the barrier property of the laminate is insufficient, and 99.
If it exceeds 9% by weight, the thermal decomposition temperature and the melting temperature of the high nitrile resin are close to each other, which makes molding difficult.
It must be in the range of wt%, preferably 55-75
% By weight.

Further, the ethylene-based monomer having an epoxy group or a hydroxyl group or an amino group or an amide group imparts adhesiveness to the polyolefin (b) obtained by grafting or copolymerizing an unsaturated carboxylic acid or its derivative. Is a comonomer copolymerized with. Specifically, glycidyl (meth) acrylate, hydroxyethyl (meth)
Acrylate, acrylamide, etc. If the ethylene-based monomer is less than 0.01% by weight, the adhesion with (b) will be insufficient, and if it exceeds 50% by weight, the barrier property of the laminate will be insufficient. It should be in the range of 0.01 to 50% by weight, preferably 3 to 8% by weight.

To facilitate melt molding, at least one unsaturated compound selected from unsaturated carboxylic acid ester, vinylidene compound, vinyl ether, vinyl ester and aromatic vinyl can be copolymerized. The unsaturated carboxylic acid ester is a monomer represented by the structural formula below.

[Chemical 2] However, R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or halogen, and R ₂ is an alkyl group having 1 to 30 carbon atoms. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
Amyl acrylate, hexyl acrylate, methyl-
Examples include α-chloroacrylate and ethyl-α-chloroacrylate.

The vinylidene compound is a monomer represented by the structural formula below.

[Chemical 3] However, R ₃ and R ₄ are alkyl groups having 1 to 7 carbon atoms, and specifically, isobutylene, 2-methylbutene-1, 2-
Methylpentene-1,2-methylhexene-1,2-methylheptene-1,2-methyloctene-1,2-ethylbutene-1,2-propylpentene-1,2,4,4
-Trimethylpentene-1 and the like, and a mixture thereof, among which isobutylene is preferable.

Vinyl ether includes methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether,
There are butyl vinyl ether, methyl isopropenyl ether, ethyl isopropenyl ether and the like. Among them, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether are preferable.

Vinyl ester includes vinyl acetate,
Vinyl propionate, vinyl butyrate, etc.
Of these, vinyl acetate is preferred. Aromatic vinyl includes styrene, α-methylstyrene, vinyltoluene,
There are vinyl xylene, indene and the like, and among them, styrene is preferable. The composition ratio of this unsaturated compound is 49.9.
If it exceeds 5% by weight, the barrier property of the laminate is insufficient, preferably 25 to 35% by weight. When these unsaturated compounds are copolymerized with unsaturated nitrile monomers,
You may use individually or in mixture of 2 or more types.

Further, the copolymerization of the unsaturated nitrile monomer with the ethylene group monomer having an epoxy group, a hydroxyl group, an amino group or an amide group is carried out by the presence of a rubber such as a homopolymer or a copolymer of a conjugated diene. It may be polymerized below. This improves impact resistance. The conjugated diene monomer includes
1,3-butadiene, isoprene, chloroprene, bromoprene, cyanoprene, 2,3-dimethyl-1,3-
Butadiene, 2-ethyl 1,3-butadiene, 2,3-
Diethyl-1,3-butadiene, etc., among which 1,
3-Butadiene and isoprene are preferred. The comonomers copolymerized with the conjugated diene include the following.

[Chemical 4] R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or halogen, and R ₂ is an alkyl group having 1 to 30 carbon atoms.

[Chemical 5] R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or halogen, and R ₂ is an alkyl group having 1 to 30 carbon atoms.

[Chemical 6] R ₃ and R ₄ are alkyl groups having 1 to 7 carbon atoms. Also,
There are also vinyl ether and vinyl ester. The conjugated diene content is 50-100% by weight. Specific examples thereof include a butadiene-acrylonitrile copolymer, an isoprene-acrylonitrile copolymer, and polybutadiene.

Polyolefin (b) grafted or copolymerized with an unsaturated carboxylic acid or its derivative (b) Grafting or copolymerizing at least one monomer selected from unsaturated carboxylic acid or its derivative having excellent adhesion with (a). The polymerized polyolefin (b) has excellent adhesiveness with (a), and is specifically obtained by a graft reaction and a copolymerization reaction.

As the polyolefin used in the graft reaction, various types can be used. For example, a homopolymer of an olefin monomer having 2 to 8 carbon atoms such as polyethylene, polypropylene and polybutylene, and 2 of these olefins can be used. One or more or other comonomers such as vinyl acetate, a copolymer with maleic anhydride, etc. are included. In particular, ethylene homopolymers or copolymers with ethylene-containing α-olefins such as butene-1, hexene-1, and propylene are preferable. Specific examples include high-, medium- and low-density polyethylene, propylene homopolymer, and impact resistant polypropylene. Further, an elastomer such as an ethylene-propylene copolymer or an ethylene-propylene-diene copolymer can be mixed with the polyolefin-based polymer. Generally, the elastomer content is preferably 25% by weight or less. The graft reaction is obtained by graft-polymerizing an unsaturated carboxylic acid or its derivative on the polyolefin skeleton. As a method of the graft reaction,
Xylene, aromatic hydrocarbon compound such as toluene, hexane, polyolefin in a solvent such as aliphatic hydrocarbon compound such as heptane, a method of producing by heating and mixing an unsaturated carboxylic acid or its derivative and a radical initiator,
In addition, a polyolefin, an unsaturated carboxylic acid or its derivative and a radical initiator are mixed in advance under conditions that do not essentially crosslink, and the resulting mixture is kneaded generally in the field of synthetic resins such as extruders, Banbury mixers and kneaders. A production method by melting and mixing using a machine can be mentioned, but the latter method is preferably adopted from the viewpoint of operability and economy.

When graft-modified with a kneader,
The grafting condition is appropriately selected in consideration of the deterioration of the polyolefin, the decomposition of the unsaturated carboxylic acid or its derivative, the decomposition temperature of the radical initiator, etc., but is generally 100 to 350 ° C, and 150 to 300 ° C. Is preferred.

The unsaturated carboxylic acids used in the graft reaction are roughly classified into monobasic unsaturated carboxylic acids and dibasic unsaturated carboxylic acids. The carbon number of the monobasic unsaturated carboxylic acid is usually at most 20, preferably 15 or less, and representative examples thereof include acrylic acid and methacrylic acid. The carbon number of the dibasic unsaturated carboxylic acid is generally at most 40, preferably 3
The number is 0 or less, and typical examples thereof include maleic acid, itaconic acid, nadic acid and fumaric acid.
Further, the derivatives include metal salts of these monobasic unsaturated carboxylic acids and dibasic unsaturated carboxylic acids, and acid anhydrides. Among these derivatives, the metal of the metal salt generally includes an alkali metal and a metal of Group 2 of the periodic table, and typical examples thereof include sodium, potassium, zinc, magnesium and calcium. Representative examples of these derivatives include sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.

As the radical initiator used in the graft reaction, the one-minute half-life temperature of the radical initiator is usually 100 ° C. or higher, preferably 105 ° C. or higher, and particularly 1
A temperature of 20 ° C. or higher is suitable. Typical examples of the radical initiator include dicumyl peroxide, benzoyl peroxide, di-tertiary-butyl peroxide, 2,
Organic peroxides such as 5-dimethyl-2,5-di (tertiary-butyl-peroxy) hexane are mentioned.

The ratio of the unsaturated carboxylic acid or its derivative and the radical initiator to 100 parts by weight of the polyolefin is usually as follows.

The unsaturated carboxylic acid or its derivative is generally 0.01 to 5.0 parts by weight, preferably 0.05 to 3.0 parts by weight, particularly preferably 0.1 to 2.0 parts by weight. If the unsaturated carboxylic acid or its derivative is less than 0.01 parts by weight, the adhesiveness will be insufficient. On the other hand, when the amount is more than 5.0 parts by weight, decomposition or cross-linking reaction occurs at the same time during the grafting reaction, which not only makes the production difficult but also lowers the adhesiveness.

The radical initiator is generally 0.001 to
It is 1.0 part by weight, preferably 0.01 to 1.0 part by weight, and particularly preferably 0.01 to 0.5. When the proportion of the radical initiator used is less than 0.001 part by weight, the graft reaction is not sufficient, while when it exceeds 1.0 part by weight, decomposition and crosslinking reactions occur, which is not preferable. Further, in the present invention, (b) may be mixed with an unmodified polyolefin.

The copolymerization reaction can be obtained by using a high-pressure process low-density polyethylene production facility. The unsaturated carboxylic acid or its derivative used in the copolymerization reaction is the same compound as in the graft reaction, and is preferably used in an amount of 0.2 to 20 mol%, particularly 0.5 to 15 mol%. If the copolymerization ratio of the unsaturated carboxylic acid or its derivative is less than 0.2 mol%, sufficient adhesion with the high nitrile resin cannot be obtained, while if it exceeds 20 mol%, it has adhesive strength but is difficult to produce. Financially difficult. It is also possible to copolymerize a polyolefin obtained by copolymerizing an unsaturated carboxylic acid or its derivative with another comonomer.
The comonomers include unsaturated carboxylic acid esters and vinyl esters.

Examples of the unsaturated carboxylic acid ester include alkyl (meth) acrylate and alkoxy (meth) acrylate. Of these, alkyl (meth) acrylates generally have 4 to 3 carbon atoms.
It is 0, and particularly preferably 4 to 20. Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. Alkoxyalkyl (meth) acrylates generally have 4 to 35 carbon atoms, and particularly preferably 4 to 20 carbon atoms.
For example, methoxy acrylate, ethoxy acrylate, butoxy acrylate, methoxy methacrylate, etc. may be mentioned.

The vinyl ester preferably has at most 20 and 4 to 16 carbon atoms, and examples thereof include vinyl acetate, vinyl propionate and vinyl butyrate, with vinyl acetate being particularly preferred.

The laminate of the present invention is basically composed of at least the layer consisting of (a) and the layer consisting of (b), but other than the above, a polyolefin layer, a regrind layer, nylon, EVOH and the like are also included. A barrier layer may be added. And each thickness is not particularly limited.

In order to produce the laminate of the present invention, a molding method such as T-die molding, inflation molding, blow molding, injection molding, stamping molding, etc., which is practiced in the field of general polyolefins, may be applied. Good. As a typical example of this molding method, each thin material (film, sheet) of the inner and outer layers and the adhesive layer is separately melt-extruded by using a molding machine used in these fields, and each thin material in a die. The method of manufacturing a laminated body by making it adhere | attach by. Then, the sheet can be manufactured into a container by a vacuum forming method, a pressure forming method, or a press forming method. By molding the resin forming the inner and outer layers and the adhesive layer by a coextrusion molding method,
You may manufacture the said laminated body.

This laminate has excellent resistance to hydrocarbons such as gasoline and mixtures of oxygen-containing organic compounds and hydrocarbons, especially alcohol-containing gasoline, and also has excellent permeation-preventing ability, so that the container of this laminate is excellent. Are useful as containers for gasoline and alcohol-containing gasoline (eg, fuel tanks for automobiles).

[0026]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The polyolefins obtained by grafting or copolymerizing the high nitrile resin, unsaturated carboxylic acid or its derivative used are shown below.

(A) High nitrile resin (a-1) Emulsion polymerization of a mixture of 70 parts by weight of acrylonitrile, 15 parts by weight of methyl acrylate and 5 parts by weight of glycidyl methacrylate in the presence of 10 parts by weight of acrylonitrile-butadiene rubber. High nitrile resin with acrylonitrile content of about 70% by weight. However, MFR: 0.
18g / 10min (JISK6760 compliant. The load is 2.
16 kg). (A-2) Acrylonitrile-butadiene rubber in the presence of 10 parts by weight, acrylonitrile content of about 70% by weight obtained by emulsion polymerization of a mixture of 70 parts by weight of acrylonitrile, 15 parts by weight of methyl acrylate, and 5 parts by weight of hydroxyethyl methacrylate. High nitrile resin. However, MF
R: 0.18 g / 10 min (based on JIS K6760. The load is 2.16 kg). (A-3) High nitrile having an acrylonitrile content of about 70% by weight obtained by emulsion polymerization of a mixture of 70 parts by weight of acrylonitrile, 15 parts by weight of methyl acrylate and 5 parts by weight of acrylamide in the presence of 10 parts by weight of acrylonitrile-butadiene rubber. resin. However, MFR: 0.18g / 10
min (according to JIS K6760. The load is 2.16 kg). (A-4) A high nitrile resin having an acrylonitrile content of about 70% by weight obtained by emulsion polymerization of a mixture of 70 parts by weight of acrylonitrile and 20 parts by weight of methyl acrylate in the presence of 10 parts by weight of acrylonitrile-butadiene rubber. However, MFR: 0.18g / 10min (based on JIS K6760.
The load is 2.16 kg).

(B) Polyolefin grafted or copolymerized with unsaturated carboxylic acid or its derivative (b-1) Polyolefin grafted with unsaturated carboxylic acid or its derivative 100 parts by weight of high density polyethylene having MFR of 5.0 g / 10 min 0.3 parts by weight of maleic anhydride and 0.02 parts by weight of Perhexa 25B (manufactured by NOF CORPORATION) were mixed in advance with a Henschel mixer. A polyolefin grafted with maleic anhydride obtained by melt-kneading the obtained mixture at a resin temperature of 260 ° C. using a 40 mmφ single screw extruder. (B-2) ET composed of ethylene (ET), maleic anhydride (MAH), and methyl methacrylate (MMA) produced by using a facility for producing a high-pressure low-density polyethylene polyolefin by copolymerizing an unsaturated carboxylic acid or a derivative thereof /MAH/MMA=93.3/3.0/3.7 (mol%), MFR = 2.5 g / 10 min, terpolymer.

(C) Other Resins (c-1) High Density Polyethylene Density: 0.945g / cm ³ (according to JIS K6760) HLMFR: 5.0g / 10min (according to JIS K6760,
The load is 21.6 kg. (C-2) Acrylonitrile content obtained by emulsion-polymerizing a mixture of 15 parts by weight of acrylonitrile, 70 parts by weight of methyl acrylate and 5 parts by weight of acrylamide in the presence of 10 parts by weight of acrylonitrile-butadiene rubber. 15% by weight of nitrile resin. However, MFR: 7.0g / 10min
. (C-3) Polyamide 6 Melt viscosity (250 ° C.): 1.78 × 104 (poise)

The laminates used in the following examples and comparative examples are multi-layer sheets having a thickness of 1 mm formed by using a coextrusion sheet forming machine consisting of four extruders having an inner diameter of 40 mm.

A barrier test for gasoline and gasoline containing alcohol was carried out in a cup 6 cm in diameter and 2.5 cm in depth, each containing 30 cc of toluene / isooctane = 50.
/ 50 (volume%) mixed solution and toluene / isooctane / methanol = 45/45/10 (volume%) mixed solution were put, and the molded sheet was attached so as not to leak completely,
The cup is placed upside down in an oven at 40 ° C., and its weight change with time is measured to obtain a unit thickness (1 mm), a unit surface area (1 m ² ), and a transmission coefficient (P) which is a weight change for 24 hours. It was

Example 1 (a-1) A high nitrile resin, (b-1) a polyolefin grafted with an unsaturated carboxylic acid or a derivative thereof, and (c-1) a high-density polyethylene were used as an outer layer / adhesive layer / inner layer = ( c-1) / (b-1) / (a-1) = 94/3/3
A coextrusion sheet having a thickness of 1 mm and having a composition of (thickness ratio) was prepared, and a barrier property test of the sheet was performed. The results are shown in Table 1.
Shown in.

Example 2 (a-1) High nitrile resin and (b-2) Ethylene-
A maleic anhydride-methyl methacrylate terpolymer and (c-1) high-density polyethylene were formed into a 1 mm sheet in the same manner as in Example 1, and a barrier property test of the sheet was performed. The results are shown in Table 1.

Example 3 A sheet was prepared in the same manner as in Example 1 except that the above-mentioned (a-2) was used as the high nitrile resin, and the sheet was subjected to a barrier property test. The results are shown in Table 1.

Example 4 A sheet was prepared in the same manner as in Example 1 except that the above-mentioned (a-3) was used as the high nitrile resin, and the barrier property test of the sheet was conducted. The results are shown in Table 1.

Example 5 (a-1) A high nitrile resin, (b-1) a polyolefin grafted with an unsaturated carboxylic acid or a derivative thereof, and (c-1) high density polyethylene were used as the outermost layer / adhesive layer / intermediate layer. / Adhesive layer / Innermost layer = (c-1) / (b-1) / (a
-1) / (b-1) / (c-1) = 94 / 1.5 / 3 /
A coextruded sheet having a thickness of 1/3 and having a composition of 1.5 / 3 (thickness ratio) was prepared, and a barrier property test of the sheet was conducted.
The results are shown in Table 1.

Comparative Example 1 (c-1) A 1 mm sheet of high density polyethylene was prepared and subjected to a barrier test. The results showed extremely low barrier properties as shown in Table 1.

Comparative Example 2 A sheet was prepared in the same manner as in Example 1 except that the above-mentioned (c-2) was used as the nitrile resin. The results of the barrier property test showed that the performance was low as shown in Table 1. showed that.

COMPARATIVE EXAMPLE 3 Instead of the (b) polyolefin grafted or copolymerized with the unsaturated carboxylic acid or its derivative of the present invention, an isoprene-styrene block copolymer used in JP-A-62-220436 is used. A sheet similar to that of Example 1 was prepared except that PR-1111 ″ was used. The barrier property showed low performance.

Comparative Example 4 A sheet was prepared in the same manner as in Example 1 except that (c-3) Polyamide 6 was used in place of the high nitrile resin (a) of the present invention. The barrier property against toluene / isooctane, 50/50 mixed liquid corresponding to gasoline was as high as that of Example 1, but against alcohol-containing gasoline,
Toluene / isooctane / methanol, 45/45/1
The barrier property to the 0 mixture showed low performance.

Comparative Example 5 A sheet was prepared in the same manner as in Example 1 except that the high nitrile resin (a-4) used in Japanese Patent Publication No. 54-41634 was used. The results showed that the performance was low as shown in Table 1.

[0042]

[Table 1]

[0043]

As described above, the laminate of the present invention is excellent in permeation-preventing ability (barrier property) for hydrocarbons and mixtures of hydrocarbons and oxygen-containing organic compounds, especially alcohol-containing gasoline. is there. Therefore, the laminate of the present invention can be used as molded articles such as various sheets, films, pipes, pipes, containers, etc., but as a material for fuel tanks for automobiles using alcohol-containing gasoline as a fuel as described above. It can be used effectively.

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[Procedure amendment]

[Submission date] December 20, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction content]

Unsaturated nitrile monomer content is 50-9
High nitrile resin (a) of 9.99% by weight The high nitrile resin (a) used in the laminate of the present invention contains 50 to 99.99% by weight of an unsaturated nitrile monomer, an epoxy group or a hydroxyl group or an amino group. Or a high nitrile resin in which the amide group-containing ethylene monomer is 0.01 to 50% by weight, and in the above composition range,
At least one unsaturated compound selected from unsaturated carboxylic acid esters, vinyl esters, vinyl ethers, vinylidene compounds, and aromatic vinyl may be contained in an amount of 49.99% by weight or less. The unsaturated nitrile monomer is represented by the following structural formula.

[Chemical 1] However, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or halogen, and specifically, acrylonitrile,
Methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, and the like. When the composition ratio of the unsaturated nitrile monomer is less than 50% by weight, the barrier property of the laminate is insufficient, and 99.
If it exceeds 99% by weight, the thermal decomposition temperature and the melting temperature of the high nitrile resin are close to each other, which makes molding difficult.
It should be in the range of 99% by weight, and preferably 55 to
It is 75% by weight.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

Vinyl ester includes vinyl acetate,
Vinyl propionate, vinyl butyrate, etc.
Of these, vinyl acetate is preferred. Aromatic vinyl includes styrene, α-methylstyrene, vinyltoluene,
There are vinyl xylene, indene and the like, and among them, styrene is preferable. The composition ratio of this unsaturated compound is 49.9.
If it exceeds 9% by weight, the barrier property of the laminate is insufficient, and preferably 25 to 35% by weight. When these unsaturated compounds are copolymerized with unsaturated nitrile monomers,
You may use individually or in mixture of 2 or more types.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

Further, the copolymerization of the unsaturated nitrile monomer with the ethylene group monomer having an epoxy group, a hydroxyl group, an amino group or an amide group is carried out by the presence of a rubber such as a homopolymer or a copolymer of a conjugated diene. It may be polymerized below. This improves impact resistance. The conjugated diene monomer includes
1,3-butadiene, isoprene, chloroprene, bromoprene, cyanoprene, 2,3-dimethyl-1,3-
Butadiene, 2-ethyl 1,3-butadiene, 2,3-
Diethyl-1,3-butadiene, etc., among which 1,
3-Butadiene and isoprene are preferred. The comonomers copolymerized with the conjugated diene include the following.

[Chemical 4] R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or halogen.

[Chemical 5] R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or halogen, and R ₂ is an alkyl group having 1 to 30 carbon atoms.

[Chemical 6] R ₃ and R ₄ are alkyl groups having 1 to 7 carbon atoms. Also,
There are also vinyl ether and vinyl ester. The conjugated diene content is 50-100% by weight. Specific examples thereof include a butadiene-acrylonitrile copolymer, an isoprene-acrylonitrile copolymer, and polybutadiene.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

Polyolefin (b) grafted or copolymerized with an unsaturated carboxylic acid or its derivative (b) Grafted or copolymerized with at least one monomer selected from unsaturated carboxylic acid or its derivative having excellent reactivity with (a). The polymerized polyolefin (b) has excellent adhesiveness with (a), and is specifically obtained by a graft reaction and a copolymerization reaction.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

(C) Other Resins (c-1) High Density Polyethylene Density: 0.945g / cm ³ (according to JIS K6760) HLMFR: 5.0g / 10min (according to JIS K6760,
The load is 21.6 kg. (C-2) Acrylonitrile content obtained by emulsion-polymerizing a mixture of 15 parts by weight of acrylonitrile, 70 parts by weight of methyl acrylate and 5 parts by weight of acrylamide in the presence of 10 parts by weight of acrylonitrile-butadiene rubber. 15% by weight of nitrile resin. However, MFR: 7.0 g / 10 min (c-3) Polyamide 6 Melt viscosity (250 ° C.): 1.78 × 10 ⁴ (poise)

Claims (2)

[Claims] 1. An unsaturated nitrile monomer content of 50 to 9
9.99% by weight, 0.0% ethylene-based monomer containing epoxy group or hydroxyl group or amino group or amide group
Adhesion of a layer consisting of 1 to 50% by weight of a high nitrile resin (a) and a layer consisting of a polyolefin (b) grafted or copolymerized with at least one monomer selected from unsaturated carboxylic acids or their derivatives. Characteristic laminate. 2. The unsaturated nitrile monomer content is 50-9.
9.99% by weight, 0.0% ethylene-based monomer containing epoxy group or hydroxyl group or amino group or amide group
1 to 50% by weight, unsaturated carboxylic acid ester,
Vinyl ester, vinyl ether, vinylidene compound,
High nitrile resin (a) containing 49.99% by weight or less of at least one unsaturated compound selected from aromatic vinyl
A layered product comprising a layer composed of (b) and a layer composed of a polyolefin (b) obtained by grafting or copolymerizing at least one monomer selected from unsaturated carboxylic acids or their derivatives.