JPH04246446A - Adhesive resin composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive resin composition which is inexpensive and lowly odorous, has a low content of a gel and excellent moldability, etc., and is suited for the production of a laminate by mixing a radical-polymerizable acid anhydride/ethylene copolymer with a specified compound containing a metallic element in a specified ratio. CONSTITUTION:Ethylene is random-copolymerized with a radical-polymerizable acid anhydride copolymer containing 0.1-20wt.% radical-polymerizable acid anhydride. This copolymer is mixed with a compound prepared by partially or fully neutralizing an ethylene/unsaturated carboxylic acid (derivative) copolymer with a metallic compound or/and a metal salt of a higher fatty acid in such an amount that the ratio of the units of the metallic atoms to the units derived from the radical-polymerizable acid anhydride in the composition is in a range of 2-0.05 to produce a polyethylene resin composition. This composition can desirably be used for the production of a laminate of a thermoplastic resin, metal, paper or wood.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyethylene and polyolefin resin compositions having excellent adhesive properties and laminates using the compositions.

0002

BACKGROUND OF THE INVENTION Polyolefin resins are used in various packaging materials and structural materials from the viewpoints of mechanical strength, hygiene, cost, moldability, etc. However, as is known from the past, polyolefin resins have poor oil permeability, gas barrier properties, adhesion, printability, etc., and are used alone as high-performance materials required in the fields of packaging materials and structural materials. It has become insufficient in its functionality.

[0003] Various proposals have been made to improve these drawbacks of polyolefin resins, but they have limitations such as complicating the manufacturing process, increasing costs, and limiting the application design. Therefore, satisfactory performance cannot be obtained as a single material.

One solution to this problem is to use polyesters, polyamides, saponified products of ethylene-vinyl acetate copolymers, metals such as aluminum, glass, metals, etc., which have properties that compensate for the drawbacks of the above-mentioned polyolefin resins. Lamination or composites are performed with vapor-deposited materials, cloth, nonwoven fabric, paper, etc. However, polyolefins have poor affinity with the above-mentioned resins due to their chemical structure, making it difficult to laminate them.

[0005] As a solution to this problem, there is a proposal to provide another layer for adhesion between these layers, but this requires a new process of applying adhesive, which has the disadvantage of complicating the manufacturing process. there were.

It is well known that polyolefin resins graft-modified with unsaturated carboxylic acids or acid anhydrides are used as adhesive resins for lamination; however, crosslinking reactions and decomposition reactions that occur during graft modification , other side reactions, etc. may cause coloring, which is often unfavorable in terms of appearance.

[0007] In order to suppress these side reactions, it may be considered to reduce the amount of grafting for modification, but as a result, sufficient adhesion cannot be obtained and delamination of the laminates is often observed. Furthermore, since a modification step is required once the polymer has been produced, there is a problem in that the production cost increases.

[0008]

[Problems to be Solved by the Invention] Taking the above problems into consideration, the present invention not only has higher adhesive strength to polyolefin resins than conventional materials, but also has a high adhesion strength to polyolefin resins as well as packaging materials for food and industrial materials, and automobiles. The present invention provides an adhesive resin composition having the advantage of low cost in the field of parts materials, and a laminate in which the resin composition is firmly bonded to a base material such as a thermoplastic resin layer or aluminum foil without an adhesive. be.

[0009]

[Means for Solving the Problems] In order to solve the above problems, the inventors have conducted intensive research and have developed an ethylene copolymer containing at least 0.1 to 20% by weight of a radically polymerizable acid anhydride. and (a) a compound formed by partially or completely neutralizing a copolymer consisting of ethylene and at least an unsaturated carboxylic acid or a derivative thereof with a metal compound (hereinafter referred to as
It's called an ionomer. ), (b) metal salt of higher fatty acid,
In the composition, the ratio of the metal atom units to the units derived from the acid anhydride in the composition is 0.005 to
It has been found that the above-mentioned problems can be solved by using a polyethylene resin composition characterized in that the polyethylene resin composition is in the range of 2.

[0010] A polyethylene resin composition (hereinafter referred to as a polyethylene resin blend) obtained by blending an ethylene copolymer containing at least 0.1 to 30% by weight of a radically polymerizable unsaturated acid with the above polyethylene resin composition. I will provide a.

Another object of the present invention is to provide a polyolefin resin composition in which a polyolefin resin is further blended with the above polyethylene resin composition or polyethylene resin blend (both are referred to as a polyethylene resin composition, etc.).

Furthermore, the present invention provides an adhesive resin composition suitable for producing a laminate of the above resin composition with a thermoplastic resin, metal, paper, or wood.

The ethylene copolymer used in the present invention is
It is a random copolymer of at least ethylene and a radically polymerizable acid anhydride, and may be a multicomponent copolymer containing another radically polymerizable comonomer (hereinafter referred to as a third comonomer) component as necessary.

The radically polymerizable acid anhydrides used in the present invention include maleic anhydride, itaconic anhydride, endic anhydride, citraconic anhydride, 1-butene-3,4-
Examples include dicarboxylic acid anhydrides, alkenyl succinic anhydrides having a terminal double bond having at most 18 carbon atoms, and alkadienyl succinic anhydrides having a terminal double bond having at most 18 carbon atoms. Two or more of these may be used in combination. Among these, maleic anhydride,
Itaconic anhydride is particularly preferred.

The ethylene copolymer of the present invention contains 0.1 to 20% by weight of units derived from radically polymerizable acid anhydrides.
Must contain. If the number of units derived from the acid anhydride is less than 0.1, the adhesive strength, which is the object of the present invention, will be insufficient, and peeling will occur between the layers when used as a laminate. Furthermore, if the amount exceeds 20% by weight, the properties such as flexibility and moisture stability inherent to the polyethylene resin that are expected of the ethylene copolymer of the present invention will be impaired. It is also difficult to produce commercially. Even if it were possible to produce it, it would be of no practical use and would only lead to a decline in economic efficiency and moldability.

Examples of the third comonomer that can be used in combination with the radically polymerizable acid anhydride include ester compounds, amide compounds, acid compounds, ether compounds, and hydrocarbon compounds. Specifically, the ester compounds include vinyl acetate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, benzyl acrylate,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, fumaric acid diethyl,
Examples include dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, and dibutyl maleate. Amide compounds include acrylamide, methacrylamide, N-methylacrylamide,
N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-hexylacrylamide, N-octylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide,
Examples include N,N-dimethylmethacrylamide and N,N-diethylmethacrylamide. Examples of acid compounds include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. Examples of the ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether, and phenyl vinyl ether. Examples of hydrocarbon compounds and other compounds include styrene, norbornene, butadiene, acrylonitrile, methacrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, vinyl chloride, vinylidene chloride, and the like. Among these, particularly preferred compounds include acrylic esters,
Examples include methacrylic esters, maleic esters, fumaric esters, acrylic acid, and methacrylic acid. If necessary, two or more of these third comonomers may be used in combination.

When the third comonomer is used in combination, the content of the third comonomer in the ethylene copolymer is preferably at most 40% by weight. When it exceeds 40% by weight, moldability is significantly reduced and a composition that meets the objectives of the present invention cannot be obtained.

MFR (JIS
K-7210 190℃) is 0.1-1000g/
It is in the range of 10 minutes. Outside this range, the moldability during the production of a laminate will be significantly reduced and the compatibility will be insufficient when mixed with an ionomer or a metal salt of a higher fatty acid, making it impossible to produce a preferred laminate.

In addition, the present ethylene copolymer has corrosivity and hygiene problems when unreacted monomers are present, and
Since this may cause a decrease in adhesive properties, a step is performed to separate unreacted radically polymerizable acid anhydride and unreacted third comonomer from the polymer.

The ethylene copolymer used in the present invention is manufactured by polymerization processes such as bulk, solution, suspension, or emulsion, but the manufacturing process basically uses conventional low-density polyethylene manufacturing equipment and technology. can be used.

The most common method is the bulk copolymerization method, which is produced by radical polymerization at a temperature of 100 to 300° C. under a pressure of 700 to 3,000 atmospheres. Preferred pressure and temperature ranges are 1,000 to 2,500 atmospheres, and the average temperature in the reactor is 150 to 270°C.

[0022] If the pressure is below 700 atm, the molecular weight of the polymer cannot be sufficiently increased, resulting in deterioration of moldability and resin properties of the composition. Pressures above 3000 atmospheres are practically meaningless and only increase production costs.

[0023] If the average polymerization temperature is below 100°C, the polymerization reaction will not be stable and the conversion rate to the copolymer will decrease, causing economic problems. Furthermore, if the temperature exceeds 300°C, the molecular weight of the copolymer cannot be increased and there is a risk of runaway reaction.

It is desirable to use a vessel type reactor as the manufacturing apparatus. In particular, since radically polymerizable acid anhydrides have poor polymerization stability, a high degree of uniformity within the reactor is required.

[0025] Furthermore, if necessary, a plurality of reactors can be connected in series or in parallel to carry out multistage polymerization. Furthermore, by partitioning the inside of the reactor into multiple zones, it is also possible to create a temperature distribution and to perform more precise temperature control.

The ethylene copolymer used in the present invention is produced under the above reaction conditions in the presence of at least one free radical initiator. Examples of the free radical initiator include oxygen; di-t-butyl peroxide;
Dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide; acetyl peroxide,
Diacyl peroxides such as i-butyl peroxide and octanoyl peroxide; peroxydicarbonates such as di-i-propyl peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate; t-butyl peroxypivalate, Peroxy esters such as t-butyl peroxylaurate; Ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis-t-butylperoxycyclohexane, 2,2-bis-t-butylperoxy Examples include peroxyketals such as octane; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; and azo compounds such as 2,2-azo-i-butyronitrile.

[0027] Furthermore, various chain transfer agents can be used as molecular weight regulators during polymerization. Examples of chain transfer agents include olefins such as propylene, butene, and hexene, paraffins such as ethane, propane, and butane, carbonyl compounds such as acetone, methyl ethyl ketone, and methyl acetate, and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. There are many examples of this.

The copolymer obtained by polymerization by the method described above is discharged from the reactor together with unreacted monomers, and passes through a high-pressure separator, optionally a medium-pressure separator, and a low-pressure separator to form a polymer. After separating the monomer or low molecular weight polymer, it is pelletized through an extruder, and unreacted monomers are recycled and reused after removing the low molecular weight polymer with a filter. Various additives as described later can also be added during pelletization.

[0029] The copolymer of ethylene and unsaturated carboxylic acid or its derivative used in the present invention, partially or completely neutralized with a metal compound, is generally called an ionomer resin. .

Examples of unsaturated carboxylic acids or derivatives thereof that copolymerize with ethylene include acrylic acid, methacrylic acid, maleic acid, fumaric acid, monomethyl maleate,
Examples include monomethyl fumarate, monoethyl maleate, monoethyl fumarate, monobutyl maleate, and monobutyl fumarate.

Examples of metal compounds used for neutralization include:
Group I of the periodic table, such as Na, K, Ca, Mg, Zn, Al, etc.
Compounds of Group I and Group III can be mentioned. Particularly preferred is a copolymer formed by partially neutralizing a copolymer of ethylene and acrylic acid or methacrylic acid using a compound of Mg, Zn or Na. The neutralization rate of the carboxylic acid in the copolymer is preferably 10% or more; if it is less than 10%, the addition rate of the copolymer becomes too large, resulting in insufficient adhesion of the laminate.

[0032] As the metal salt of higher fatty acid used in the present invention, salts of metals of Groups I, II, and III of the periodic table are preferred. Examples include metal salts of higher fatty acids having 12 or more carbon atoms, preferably metal salts of palmitic acid, stearic acid, and oleic acid, salts of organic acids such as sodium stearate, calcium stearate, zinc stearate, and sodium oleyl sulfate. can be mentioned.

The compound (ionomer) obtained by partially or completely neutralizing a copolymer of ethylene and at least an unsaturated carboxylic acid or a derivative thereof with a metal compound and the metal salt of higher fatty acid used in the present invention are as follows: It has superior solubility in resins compared to inorganic acid salts and lower fatty acid salts, and therefore interacts easily with the acid anhydride group in the ethylene copolymer, resulting in a great adhesive effect. We estimate that this will be the case.

In particular, the ionomer contains at least 0 radically polymerizable acid anhydride, which is the raw material resin of the resin composition of the present invention.
．． It has excellent compatibility with ethylene copolymers containing 1 to 20% by weight, ethylene copolymers containing 0.1 to 30% by weight of radically polymerizable unsaturated acids, and polyolefin resins, making it the easiest to use. It is something.

In addition, in the case of a resin composition consisting of an ethylene copolymer and an ethylene copolymer containing an unsaturated acid, ion exchange between the unsaturated acid and metal ions occurs,
It is estimated that this increases compatibility with the ethylene copolymer and facilitates interaction, thereby increasing the adhesive effect.

In the polyethylene resin composition of the present invention, the compound containing a specific metal element to be added to the ethylene copolymer containing at least a radically polymerizable acid anhydride is
By reacting or strongly interacting with the acid anhydride in the ethylene copolymer, which is effective for adhesion, the acid anhydride group activates the interaction with the substrate surface, increasing the melt tension of the copolymer and improving adhesion. It is considered to be effective. Therefore, the ethylene copolymer composition has excellent moldability and adhesive properties.

[0037] The ratio of units of metal atoms contained in the ionomer or metal salt of higher fatty acid to units derived from acid anhydride groups in the polyethylene resin composition is 0.00.
It is in the range of 5 to 2.0, preferably 0.05 to 0.5. If this ratio is less than 0.005, improvements in adhesion and moldability will not be sufficient, making it difficult to efficiently produce a laminate. If this ratio exceeds 2.0, the reaction or interaction will proceed too much and the number of effective acid anhydride groups will decrease, resulting in a decrease in adhesion, as well as a decrease in the melt flowability of the resin and a decrease in moldability. . In addition, gel is generated and the appearance of the laminate is deteriorated.

[0038] In the present invention, the composition consisting of an ethylene copolymer and an ionomer or a metal salt of a higher fatty acid is a composition with excellent adhesive properties by itself, but when blended with a polyolefin resin, adhesive properties were maintained. It has been discovered that this can result in an excellent polyethylene resin compound that can dramatically improve processability and achieve significant cost reductions.

The polyolefin resins used in this polyethylene resin composition include polyethylene, polypropylene, polyisoprene, polybutene, poly3-methylbutene-1, poly4-methylpentene-1, polybutadiene, polystyrene, and the above resins. Copolymers of structural units, such as ethylene-propylene copolymers, linear low-density polyethylene with comonomers such as 1-butene, 1-4-methylpentene, 1-hexene, and 1-octene, and propylene-ethylene blocks. Examples include copolymers, styrene-butadiene copolymers, mixtures of these resins, graft polymers, crosslinked products, block copolymers, and ethylene-vinyl acetate copolymers. Among these, polyolefin resins containing at least 60% by weight of units based on ethylene are preferred.

This is related to the compatibility with the polyolefin resin when blended with an ethylene copolymer to form a compound, and the polyolefin resin compound produced when the ethylene-based unit is less than 60% by weight. This is because the strength of

In order to improve this, 1 to 10% by weight of a modified resin obtained by graft-modifying the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride of the polyolefin resin to be used is blended with the polyolefin resin. This can be solved by

MFR (190
C) of 0.1 to 1000 can be used. The above midfielder
When the R value is less than 0.1, it is generally difficult to form a composition with the ethylene copolymer of the present invention, and the moldability also decreases, making it difficult to mold a laminate. Also M
When the FR value exceeds 1000, it becomes difficult to mix the resins together, and when the amount of the polyolefin resin increases, the strength of the resulting composition becomes extremely low.

The polyolefin resin composition of the present invention is a blend of the above-described ethylene copolymer and an ionomer or a metal salt of a higher fatty acid, or an ethylene copolymer containing the same and a radically polymerizable unsaturated acid, and a polyolefin resin composition. It is a composition consisting of a resin, and must contain 0.05 to 15% by weight of units derived from acid anhydride, preferably 0.1 to 5% by weight. especially,
The amount of units derived from the radically polymerizable acid anhydride is 0.
If the amount is less than 0.05% by weight, the adhesion between the layers of the laminate of the present invention will be insufficient. Moreover, it is not necessary that the amount of units derived from the radically polymerizable acid anhydride is substantially 15% by weight or more. Furthermore, taking economic efficiency into consideration, the above-mentioned amount required to achieve the practical performance of the laminate of the present invention is smaller than expected, and is 0.
05 to 3% by weight. If further limited, the performance will be achieved at 0.1 to 0.5% by weight.

[0044] The polyolefin resin composition can be produced by any of the commonly known methods of mixing various resins. Specific methods include a method in which a polyethylene resin composition and a polyolefin resin are dissolved in a good solvent for each resin component such as high-temperature toluene and reprecipitated, a method in which both resin components are mixed in a molten state, i.e. Commonly used pressure kneaders, rolls, Banbury mixers,
This can be carried out using a static mixer, screw extruder, or the like.

[0045] Furthermore, when manufacturing a laminate using the adhesive resin composition of the present invention comprising the above-mentioned polyolefin resin composition, the resins of each component may be mixed in the form of powder or pellets (dry blend). It is also possible to perform melt mixing using the laminate production stage. Alternatively, when producing the polyolefin resin composition, the constituent components may be mixed at once, or the polyolefin resin may be mixed after producing the polyethylene resin composition.

Lamination using the resin composition obtained by the above method can be carried out by a conventionally known method. That is, extrusion lamination method (including single method, tandem method, coextrusion method, and sandwich lamination method), adhesive lamination method (including dry lamination method, wet lamination method, and solution coating method). , hot melt method.)
Various coextrusion methods (coextrusion film, coextrusion sheet, coextrusion blowing, etc.) and thermal bonding methods can be mentioned.

As the base material for the laminate of the present invention, thermoplastic resin sheets or films, metal foils, paper, wood, etc. can be used. Specifically, the adjacent layer or base material to be laminated with the resin composition of the present invention includes polyethylene, polypropylene, polystyrene, nylon, polyester, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, etc. Thermoplastic resins, non-woven fabrics and other fabrics made using thermoplastic resins, phenolic resins,
Examples include thermosetting resins such as melamine resins, unsaturated polyester resins, and epoxy resins, metal foils such as iron and aluminum, papers such as Kent paper and coated paper, and wood such as wooden plywood.

[0048] Various additives and compounding agents may be used in the ethylene copolymer, etc. and the composition of the copolymer, etc. and polyolefin resin according to the present invention, within the range that does not impair the characteristics of the composition. Is possible. Examples of additives and compounding agents include antioxidants (heat stabilizers), ultraviolet absorbers (
light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), inorganic and organic fillers, reinforcing materials, coloring agents (dyes, pigments), blowing agents, crosslinking agents,
Examples include fragrances and the like.

The laminate obtained by the above method has strong interlayer adhesion and is excellent in appearance, odor, etc., and therefore can be used for various purposes as packaging materials and containers.

Specifically, packaging container materials such as blow molds, tubes, films, and sheets that require oxygen barrier properties;
Packaging container materials whose innermost layer is laminated with ethylene-vinyl alcohol copolymer, etc. for the purpose of preventing the adsorption of aromatic components of foods; containers that require oil permeation resistance, such as gasoline tanks; and containers that require water resistance. It can be used in a wide variety of applications, including paper packs, release paper for cross-linking and laminating silicone resin, and vapor-deposited paper. Furthermore, the polyethylene resin composition and polyolefin resin composition obtained in the present invention can be used not only as a laminate but also as a blend material. Specifically, it can be used as a compatibilizing agent such as a polymer alloy, an impact imparting agent such as an engineering plastic, and a material for composite fibers such as a nonwoven fabric.

[0051] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples and can take various forms.

Examples (Example 1) A copolymer of ethylene and maleic anhydride was produced using a high-pressure polyethylene production facility equipped with a tank reactor. The obtained ethylene copolymer (
A) had an MFR (190° C.) of 12.3 and a unit derived from maleic anhydride of 2.1% by weight. The copolymer 20
Weight%, MFR (190°C) 6.0, density 0.9165
g/cc low density polyethylene 75% by weight, MFR
(190°C) 3.0, density 0.94 ionomer (a: methacrylic acid content 18 wt%, copolymer <sodium salt> in which about 10% of the methacrylic acid is neutralized)
5% by weight was mixed. For mixing, the three components were dry blended in a tumbler, and then melted and kneaded at 190° C. using a 50 mmφ single screw extruder to form pellets. The MFR (190°C) of the mixture was 5.22, and the unit derived from maleic anhydride was 0.41% by weight. Note that the polymer composition was determined by infrared absorption spectrum. A laminate of 3 types and 5 layers consisting of polyethylene layers as both outer layers, an EVOH layer in the middle, and the above composition between both layers was produced by coextrusion molding under the following conditions. Molding is done using 3 65φ extruders, 130
A laminate with a total thickness of 50 μm was produced using a coextrusion multilayer film molding machine having a T-die with a width of 0 mm at a resin temperature of 180° C. and a take-up speed of 30 m/min.

[0052] Molding was carried out without any particular problems. The obtained laminate had good appearance and transparency. The obtained laminate was conditioned for 24 hours at 23° C. and 50% relative humidity, then cut into strips with a width of 15 mm, and the 180 degree peel strength between the layers was measured at a speed of 300 mm/min. 580g/1
It showed an adhesive strength of 5 mm, indicating that it had excellent interlayer adhesive strength. Further, an attempt was made to heat-seal only the outermost layer and peel it off, but the outermost layer of polyethylene was only destroyed and the layers could not be peeled off. the result,
It was confirmed that the laminate had sufficient interlaminar strength. Furthermore, when nylon was used instead of EVOH, the 180 degree peel strength was 470 g/15 mm. Separately, the polyethylene resin composition produced above was laminated onto a 30 μm thick aluminum foil using a laminate molding machine with an extruder of 90 mmφ and a die width of 750 mm. The extrusion temperature is 25
The temperature was 0° C., the extruder screw rotation speed was 60 rpm, the take-up speed was 80 m/min, and the total thickness of the obtained laminate was 60 μm. Molding was carried out without any particular problems. The obtained laminate was conditioned for 24 hours at 23° C. and 50% relative humidity, then cut into strips with a width of 15 mm, and the 180 degree peel strength between the layers was measured at a speed of 300 mm/min. It was found that it exhibited a strength of 480 g/15 mm and had excellent interlayer adhesion. When polyethylene terephthalate film was used instead of aluminum foil, the peel strength was 350 g/15 mm. From the above results, it can be seen that the laminate obtained by the manufacturing method according to the present invention is a good laminate that can be used for various purposes.

(Examples 2 to 10, Comparative Examples 1 to 6) Ethylene copolymer (A) or (B) was prepared in the same manner as in Example 1.
A polyethylene resin composition was produced using the metal compounds shown in Table 1, and a laminate with a thermoplastic resin and aluminum foil was separately produced. The performance is shown in Tables 1 to 3.

[0054]

[Table 1]

1) LDPE: Low density polyethylene (MF
R6.0, density 0.917) 2) LLDPE: Linear low density polyethylene (MFR5
．． 5, density 0.921) 3) EVA: ethylene-vinyl acetate copolymer 4) EPR
: Ethylene-propylene copolymer rubber 5) EAA: Ethylene-acrylic acid copolymer 6) Ionomer (a): Methacrylic acid (18 wt%), Na (10 wt% to methacrylic acid), MFR (190°C) 3.0 7) Ionomer (b): Methacrylic acid (10wt%
), Zn (10% by weight based on methacrylic acid), MFR
(190℃) 4.0

[0056]

[0057]

[0058]

[Effects of the invention] Lamination of polyolefin resins with poor adhesiveness, gas barrier properties, printability, etc. and gas barrier resins such as ethylene-vinyl alcohol copolymers, nylon, polyester, vinylidene chloride, etc., or thermal adhesive properties and rigidity. Adhesive resins between polyolefin resins and various synthetic resins have been developed to improve the performance of polyolefin resins, such as laminates of polyethylene, polypropylene, etc. and other thermoplastic resins for the purpose of imparting There were no adhesive resins that were inexpensive and suitable for coextrusion.

[0059] For this reason, either a dry lamination method is used, an expensive adhesive resin such as a modified polyolefin obtained by graft polymerization of maleic anhydride is used, or a laminate with insufficient peel strength is unavoidably produced.

The polyolefin resin composition of the present invention is prepared by mixing an ethylene copolymer, which is a copolymer of a radically polymerizable acid anhydride and ethylene, with a compound containing a metal element, or by mixing the ethylene resin composition. By further blending it with a polyolefin resin, it is inexpensive, has a lower gel content compared to graft-modified polyolefins, has an excellent appearance when commercialized, and has excellent moldability equivalent to ordinary low-density polyethylene. Therefore, the polyethylene resin composition and polyolefin resin composition are suitable for obtaining a laminate with sufficiently high adhesive strength even by a highly productive coextrusion method, and a laminate using them has also been developed.

The resin composition of the present invention has only the same odor as ordinary high-density polyethylene, and its adhesive strength does not decrease even when diluted, and it is particularly suitable for coextrusion molding with ethylene-vinyl alcohol copolymers, nylon, etc. It also shows excellent performance in lamination molding with aluminum foil and polyester film, and is a laminated material that is cheaper and has superior peel strength than graft copolymers of polymeric acid anhydrides currently on the market as adhesive resins. It is something that gives something.

Claims (4)

[Claims] Claim 1: An ethylene copolymer containing at least 0.1 to 20% by weight of a radically polymerizable acid anhydride;
) a compound formed by partially or completely neutralizing a copolymer of ethylene and at least an unsaturated carboxylic acid or a derivative thereof with a metal compound; and (b) a composition containing at least one of metal salts of higher fatty acids. In the composition, the ratio of units of metal atoms to units derived from radically polymerizable acid anhydride in the composition is 0.0.
A polyethylene resin composition characterized in that the polyethylene resin composition has a molecular weight in the range of 05 to 2. 2. An ethylene copolymer containing 99.9 to 40% by weight of the polyethylene resin composition according to claim 1 and 0.1 to 60% by weight of at least a radically polymerizable unsaturated acid. A polyethylene resin composition consisting of % by weight. 3. A polyolefin resin comprising the polyethylene resin composition according to claim 1 or 2 and a polyolefin resin, wherein the content of acid anhydride in the composition is 0.05 to 15% by weight. Composition. 4. An adhesive resin composition for laminating synthetic resins, metals, paper, wood, etc., comprising the polyethylene resin composition or polyolefin resin composition according to claim 1, 2 or 3.