JPH03255150A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare a cheap, odorless resin compsn. excellent in the adhesion to a polyester, flexibility, etc., by mixing an ethylene/radical-polymerizable acid anhydride copolymer and an ethylene/radical-polymerizable ester copolymer in a specified wt. ratio. CONSTITUTION:Ethylene is copolymerized with a radical-polymerizable acid anhydride (e.g. maleic anhydride) to give a copolymer A. Separately, ethylene is copolymerized with a radical-polymerizable ester monomer (e.g. vinyl acetate or methyl acrylate) to give a copolymer B. 20-80 pts.wt. copolymer A and 80-20 pts.wt. copolymer B are mixed to give a resin compsn., which is suitably used for laminating with paper, aluminum, nylon, polyester, saponified ethylene/vinyl acetate copolymer etc., giving a food packaging material, etc.

Description

[Detailed description of the invention] [Not for industrial use? F] The present invention relates to an ethylene thread copolymer composition, which is used as a food packaging material, an industrial packaging material, a resin modification material in the food, packaging, automobile industries, etc.6. In particular, it relates to materials such as metallurgical paper, cloth, polyester, polyamide, and saponified products of ethylene-vinyl acetate copolymers (compositions having poor adhesion).

[Conventional technology] For packaging materials for food and industrial materials, as well as automobile materials, no single material has been able to meet all performance requirements, and it has become almost impossible for Germany to use such materials. Therefore, much effort has been wasted to provide materials that meet the increasingly sophisticated requirements due to material composites, alloys, etc. Lamination of materials is one of the ways to achieve this, but there are 1. (The main reason for this is that lamination requires different performance between each material, which often results in a combination of contradictory properties, making it difficult to connect the materials together.) For this reason, various types of adhesive resins have been proposed, but they are not necessarily able to fully meet the increasingly sophisticated demands.

On the other hand, polyolefins are used in a wide range of applications because they have well-balanced performance such as low cost, long mechanical strength, hygiene, and moldability. However, since polyolefin alone has poor oil resistance and gas barrier properties, when used as containers for foods such as mayonnaise and soy sauce, it is impossible to preserve these foods for a long period of time. Furthermore, when used as a gasoline container, there are drawbacks such as a large amount of Karin being lost, and the container swelling and deforming.

Various proposals have been made to improve the thermal power of polyolefins, but the results have not been satisfactory due to constraints such as complicated manufacturing processes, increased costs, and limited application designs. was not obtained.

One of the solutions is lamination with polynisder, polyamide, saponified ethylene-vinyl acetate copolymer, aluminum foil, glass, etc., which have properties that compensate for the disadvantages of polyolefins, metal or non-metallic vapor deposition. However, considering the chemical structure of polyolefin C, it is difficult to form an St layer due to its poor affinity with the resins mentioned above. Therefore, it has been proposed to provide another adhesive layer having affinity for both layers between the two layers, but this requires a step of applying an adhesive, which has the disadvantage of complicating the manufacturing process.

In addition, it is well known that a polyolefin modified with Kraft anhydride, which is similar to an unsaturated carboxylic acid, is used as an adhesive resin that can be directly bonded to the above-mentioned resins for the M layer, but its performance is sufficient. However, delamination of the layers of the shell is often observed. This type of adhesive resin has the drawback of high manufacturing cost because it requires a craft modification process in addition to polymerization. Furthermore, in order to reduce costs, a proposal has been made to use a copolymer obtained by general high-pressure radical copolymerization of ethylene, a radically polymerizable acid anhydride, and a radically polymerizable ester monomer (see Japanese Patent Application Publication No. 2003-100000). 57-187246, 1986-13
678. 1986-21.93361゜[Problem to be solved by the research] A copolymer that can be obtained by high-pressure radical copolymerization of conventional ethylene, a radically polymerizable acid anhydride, and a radically polymerizable ester monomer. Although it has the advantages of adhesiveness and low cost, it is difficult to use in the food field because it has an odor based on the radically polymerizable ester monomer.

In order to reduce the odor caused by radically polymerizable ester monomers, which is such a major drawback, the present inventors discovered a copolymer consisting of Niegren and radically polymerizable FIig hydrate, which does not contain radically polymerizable ester monomers.
A patent application has been filed.

However, because this copolymer does not contain radically polymerizable ester monomers, it has insufficient adhesion, which may be due to the copolymer's high melting point, stiffness, and low polarity. This has hindered its use in fields that require the opposite performance.

The present invention is low cost, has adhesive properties, has excellent contact with polynisder, polyamide, saponified ethylene-vinyl acetate symbiotic union, aluminum foil, etc., and has low odor, and can be used in the food packaging field. The purpose is to develop resin compositions.

1. Means for Solving the Problem J The present inventors have conducted extensive studies in order to reduce the odor caused by the radically polymerizable ester monomer, which is such a major drawback. The present invention has been achieved by discovering a resin composition characterized by comprising 1 part by weight of a copolymer of 20 to 80''ffi ff and 80 to 20 parts by weight of a copolymer comprising at least ethylene and a radically heavy Nisder monomer.

In the present invention, the copolymer consisting of ethylene and a radically bonded FF acid anhydride (hereinafter referred to as copolymer) is a radical copolymer of ethylene and the acid anhydride,
It does not include so-called graft copolymers, such as polyethylene radically modified with an acid anhydride.

A radically polymerizable pyrohydride is a compound that has one or more radically polymerizable unsaturated bonds and one or more acid anhydride groups in its molecule, and the acid anhydride group can be introduced into the polymer through polymerization. It is. The acid anhydride is preferably a cyclic one, and specific examples of the compound include maleic anhydride, itaconic anhydride, citraconic anhydride, endic anhydride, dodecenyl succinic anhydride, etc. Maleic anhydride and itaconic anhydride are particularly preferred, and in some cases two or more of these may be used in combination.

The content of units derived from radically polymerizable acid anhydride in the copolymer must be in the range of 0.1 to 10% by weight. If the content is less than 0.1% by weight, the adhesion to the base material is low, and if the content is 10% by weight or more: i In addition, it is very difficult to produce the copolymer.

When mixed with a copolymer consisting of at least 6 ethylene and a radically polymerizable ester monomer (hereinafter referred to as copolymer II), the compatibility with the partner resin deteriorates, making it difficult to obtain a good composition. To become.

MFR of Copolymer I (JIS-7210,1
Although there is no particular restriction on the MFR (at 190°C) of the resin composition of the present invention, it should be within the range of 0.5 to 100g/710 min. The MFR of the composition (19
0°C) is less than 0.5 g/10 minutes, it is difficult to mold the composition of the present invention, and a good laminate cannot be obtained.
If F R1!90''C) exceeds 100 g/10 minutes, moldability will deteriorate due to insufficient melt tension in applications such as laminates, which are mainly used.

In producing the copolymer I (7) according to the invention, it is appropriate to use a high-pressure I-removed low-density polyethylene 'A production facility. That is, using a front-type reactive group or a waste-type reactive group, ethylene compressed to 1000 atmospheres or more and a radically polymerized FF acid anhydride were injected into the reactive group, and at the same time, the 4-1 machine was injected into the base circle using a separate pipe. Polymerization is performed using a radical polymerization initiator represented by an oxide to obtain a copolymer. The copolymer is pelletized using an extruder after separating unreacted monomers using a plurality of separators.The polymerization initiator used in the present invention is a compound that generates a free M group, mainly a peroxide. use. For example, dibutyl peroxide, dicumyl peroxide, t
- dialkyl peroxide such as butylcumyl peroxide, acetyl peroxide, i-butyl peroxide,
diacyl peroxides such as octanoyl peroxide,
G-i-Brovyl peroxydicarbonate, G-2-
Peroxy dicarbonates such as ethylhexyl oxydicarbonate-1-, peroxy esters such as [-butyl peroxy biparate and t-butyl peroxy laurate, methyl edyl getone peroxide, cyclohexanone peroxide, etc. Ketone peroxide, peroxy ketals such as 1,1-bis-L-butyl peroxycyclohexane, 2,2-bis-t-butyl peroxyoctane, hydroperoxides such as [-butyl hydroperoxide, cumene hydroperoxide, etc. , 2,2-azobisisobutyronitrile and other azo compounds, and oxygen.

Specifically, the above copolymer I is a copolymer obtained when the polymerization pressure is preferably lower than 1700 atm and the average polymerization temperature is 180 to 230°C. The molecular weight of the coalescence does not increase and the amount of polymerization catalyst consumed increases significantly! 8j is shown. The polymer obtained when the polymerization pressure exceeds 3,000 atmospheres does not have any disadvantages, but the polymerization equipment becomes expensive and there is a lot of waste in terms of energy for one polymerization. Also, the polymerization temperature is 1
If the tripolymerization temperature is lower than 80°C, the polymerization reaction will become unstable, making it difficult to obtain a stable copolymer, and may also induce 5A chemotactic reaction.
There is a risk that the molecular weight of the copolymer to be tl will not increase and that a runaway reaction will be induced.

The three radically polymerizable ester monomers in copolymer 11 of the present invention include vinyl acetate, megyl acrylate, acrylic acid, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and lauryl acrylate. , benzyl acrylate, allyl acrylate, 2-hydroxydiyl acrylate, 2-acrylate
Hydroxypropyl, N-dimethylaminoethyl acrylate, aminoethyl acrylate, butanediol diacrylate, hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glyfur diacrylate, methyl methacrylate , ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate,
lauryl methacrylate, benzyl methacrylate,
2-Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-dimethylaminoedyl methacrylate, aminoethyl methacrylate, allyl methacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, tri- Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, dimedyl fumarate, diethyl fumarate, dipropyl fumarate, dibdel fumarate.

Examples include dimethyl maleate, diethyl maleate, dipropyl maleate, and dibutyl maleate.

Because in the copolymer of the radically polymerizable ester monomer!
The content is 5 to 50% by weight. If the spray amount is less than 5%, the objectives of the present invention, such as melting of the copolymer, reduction of bulk, imparting polarity, imparting flexibility, etc., will not be achieved satisfactorily;
If the amount exceeds % by weight, the miscibility of ethylene with the copolymer of radically configurable acid anhydride will be less than f.

In addition to the radically polymerizable ester monomer, Polymer (2) also contains acrylamide 1:, acrylonitrile, acrylic acid, methacrylamide, methacrylonitrile, methacrylic acid, crotonic acid, fumaric acid, alkyl vinyl ether (alkyl methyl, ethyl butyl). etc.) and a second component such as vinyl alkoxysilane.

The MFR (190°C) of the copolymer containing units based on the radically polymerizable Nisdel monomer is limited by the above-mentioned range of the resulting composition. 500g/10 minutes.

Copolymer 11 can be produced in accordance with the method for producing Copolymer I described above. That is, using a pre-type reactive group or a seed-type reactive group.

Ethylene compressed to 1,000 atmospheres or more and a radically polymerizable Nisdel monomer were injected into the reaction group, and at the same time, they were injected into the base circle through a separate pipe to initiate radical polymerization, typified by the organic peroxide used in Copolymer I. ride together by agent,
A copolymer is obtained. After separating unreacted monomers from the copolymer using ih separators, the copolymer is pelletized using an extruder, preferably an extruder with a vent.

More specifically, the above copolymer 1 is preferably polymerized under conditions of a polymerization pressure of 1500 to 3000 atm and an average polymerization temperature of 200 to 300°C. In order to reduce the odor based on the monomer, it is particularly preferable that the temperature at which one reactive group is released exceeds 250°C, and the polymerization temperature is preferably 240°C to 280°C.

If the combined pressure is less than 1,500 atm, the resulting copolymer will not have a large molecular weight and the consumption of the polymerization catalyst will increase significantly. Although there is no profit, the nail bed equipment becomes expensive and there is a lot of waste in terms of energy for one polymerization.

Furthermore, if the polymerization temperature is lower than 200° C., the polymerization reaction becomes unstable, and not only is it difficult to produce a stable copolymer, but there is also a risk of inducing 1M chemotactic reaction. Nail base temperature is 2
If the temperature exceeds 80° C., the molecular weight of the copolymer (5) may not increase and runaway reactions may occur.

In order to exhibit the adhesive properties targeted by the present invention, it is necessary that the composition consists of at least 120 to 80 parts by weight of the copolymer and 1180 to 20 parts by strain of the copolymer. If the amount of copolymer I in the composition is less than 20 parts, the adhesiveness based on the M pyrohydride group will be insufficient. Furthermore, if the amount of copolymer II is less than 20 parts by weight, the adhesion of the citrus resin composition of the present invention to the adherend will be insufficient and the adhesion will be reduced.

Although the reason for this is not clear, it is thought to be due to the flexibility and polarity of the copolymer.

Copolymer II constituting the resin composition of the present invention is a copolymer obtained by high-pressure radical copolymerization of ethylene, a radically polymerizable acid anhydride, and a radically polymerizable ester monomer as described above. Temperature is 180 to 2
Since the polymerization temperature can be set higher than that of 30°C, the separation efficiency between the produced copolymer and the monomer is high.

It is thought that the odor caused by the ester monomer is reduced.

Furthermore, the production of the resin composition includes the above-mentioned copolymer I20.
Generally, 180 to 20 parts by weight of the copolymer (1) and 180 to 20 parts by weight of the copolymer are kneaded using a Banbury mixer roll, various extruders, or the like. In some cases, it is also possible to tri-blend the respective pellets and additives without melt-mixing, and then directly mold them using a molding machine.

In particular, it is more desirable to reduce evaporation of the ester monomer by venting or the like during mixing.

In addition, the resin composition of the present invention may contain well-known additives and compounding agents as required. Those that cause the resin composition to react with the acid anhydride group which is the reactive group possessed by the copolymer of the present invention. It can also be used from a chemical perspective with reactive groups. Examples of additives and compounding agents include antioxidants (heat stabilizers)
, ultraviolet absorber (light stabilizer), antistatic agent, antifog agent, f
l Refueling agent, lubricant (slip agent, anti-blocking agent),
Non-volatile and organic fillers, reinforcing agents, colorants (dyes, face 14
1. Foaming agents, crosslinking agents, perfumes, etc.

Examples of heat-resistant stabilizers include phenolic stabilizers, sulfur-based stabilizers, and phosphorus-based stabilizers, and specifically, 2,6-di-t,-butyl-4-methylphenol. , stearyl-β-(3,5-di-t-butyl-
4-hydroxyphenyl)propionate, 1-(4-
hydroxy-3,5-di-t-butylaminophenyl)
3.5-dioctylthio-2,4,6-)riazine, 2
．． 2°-methylenebis(4-methyl-6t-butylphenol), 2.2°-methylenebis(4-ethyl-6-
t-butylphenol).

4.4'-thiobis(3-methyl-6-t-butylphenol), 1.1.3-)lis(2-methyl-4-hydroxy-5-1-butylphenyl)butane, 1.3.5
-trimedel-2,4゜6-tris(3,5-di-t-
butyl 4-hydroxybenzyl)benzene, tris(3
, 5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tetrakis]methylene-3(3゛5°-
Phenol-based stabilizers such as di-L-butyl-4-hydroxyphenyl)propionate] methane, sulfur-based stabilizers such as dilaurylthiodipropionate, distearylthiodipropionate, pentaerythritol tetralaurylthiopropionate, tris(nonyl) Phenyl) phosphite, distearlylbentaerythritol diphosph! Tetra(tridecyl)-1,13-tris(
2-Methyl-5-t-butyl-4-hydroquinphenyl)butane diphosphite, tetrakis(2,4-di-t
-butylphenyl) 4,4-biphenylene diphosphite, 9°10-di-hydro-9-oxa-10-phosphaphenanthrene-10-oxaf, and the like.

Examples of light stabilizers include salicylic acid-based, benzophenone-based, and benzotriazole-based stabilizers, and four specific examples include phenyl salicylate, p-ocdylsalicylate, monoglycol salicylate, p- Salicylic acid stabilizers such as -t-butylzalidilla-1, 2.4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2.2°-dihydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-〇-octyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2-human[oxy-
4-dodecyloxybenzophenone, benzophenone stabilizers, 2-(2'-hydroxy-5''-methylphenyl)benzo I-lyazole, 2-(2'-hydroxy-4'-n octyloxyphenyl)benzotriazole, etc. Examples include benzotriazole stabilizers and resorcinol monobenzoate.

Antistatic agents and antifogging agents include esters such as bentaerythritol monostearate, glycerin monostearate, glycerin mostearate, trimethylolpropane monostearate, sorbitan monopalmitate, polyethylene glycol monostearate, and lauryl sulfate. Soda, lauryl chlorosulfonate, sulfated oleic acid, sodium dodecylbenzenesulfonate, etc! oxide,
Monooleyl phosphate, dioleyl phosphate, monolauryl phosphate, dilauryl phosphate, monocetyl phosphate 1g dicetyl phosphate, m
Phosphorous oxides such as W monononylphenyl and dinonylphenyl phosphate, N-methyl-N-acetic acid soda oleic acid amide,
Amides such as N,N-jetanollauric acid amide,
Quaternary ammonium salts such as lauryl trimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, tanol methyl ammonium chloride, stearyl trimethyl ammonium methosulfate, betaines such as stearyl dimethyl betaine, lauryl dihydroxy betaine, lauryl dimethyl sulfobetaine, polyethylene glycol hef-ir Examples include on-line lightning protection agents.

As a flame retardant, chlorinated paraffin, J! j-Nonated polyethylene non-hydrochlorendic acid, tetrabrominated bisphenol A, tetrabrominated phthalic anhydride, dibromodichlorobroban exclusive halogen-based H refueling agent, Tris 20 Loeg~Lupofu J-to, Bischlorobrovir Kurojiru Phosphate, a phosphorus-based flame retardant exclusively made by Nisdel Phosphate. U-ized antimony,
Examples include non-halogen type WI fuel such as magnesium hydroxide.

Hydrocarbon-based lubricants (including slip agents and anti-blocking agents T in a broad sense) include liquid paraffin, natural paraffin, microwax, synthetic wax, low molecular weight polyethylene, etc., fatty acid-based products such as stearic acid,
Fatty acid amides such as stearic acid amide, valmitic acid amide, methylene bis stearyl amide, ethylene bis stearyl amide, oleic acid amide, alkylene bis fatty acid amides, etc. are used as fatty acid amide types, and fatty acid lower alcohol esters and fatty acid polyamides are used as Nisder type fatty acid amide. Hydrolic alcohol esters, polyglycol esters of fatty acids, etc., fatty acid lower alcohol nitrides such as butyl stearate, alcohols such as aliphatic alcohols, polyhydric alniol, polyglycols, etc., metal soaps, etc. can.

Fillers include carbon black, white carbon,
Calcium carbonate, hydrous basic magnesium carbonate, clay,
Silicate minerals, natural silicic acid, alumina hydrate, barium sulfate, calcium sulfate.

Metal powder, organic fillers (for example, wood flour, fruit shells, cellulose, etc.), etc., and asbestos as a reinforcing material. glass mj4
1. carbon fiber, stainless steel mta, aluminum fiber,
Potassium titanate fiber, aramid fiber, glass peas,
May show aluminum flakes etc.

Coloring agents (dyes, pigments) include titanium oxide, zinc oxide, barium sulfate, carbon blank, aniline black, lead white, cadmium yellow, lupine, zinc chromate, yellow ten, Hansa yellow, red iron oxide, litho roots. 1:, Alizarin Lake, Cadmium Red, Bengara, Ki→Kuri I
[Z] ζ, cobalt violet, ultramarine, Huvard blue. Indicates phthalocyanine blue, phthalocyanine clean, chrome green, aluminum powder, bronze powder, etc.1
Rir.

Examples of blowing agents include inorganic blowing agents such as ammonia carbonate, sodium bicarbonate, and sodium nitrite, nitroso blowing agents such as mite 1-r:I soventamide tetramine, dimethyl dinitrosoprephthalamide, and benzenesulfonyl. hydrazi 1
゛, p-h luenesulfonyl hydrazide. Examples include sulfohydrazide blowing agents such as p-poxybisbenzenesulfonyl hydrazide, disulfone hydrazide diphenyl sulfone, and azo yarn blowing agents such as azobisisobutyronitrile and azodicarbonamide.

As a crosslinking agent, the various peroxides mentioned above can be used as a radical polymerization initiator, and as a crosslinking aid, methacrylate-1-based compounds such as lauryl methacrylate, ethylene glycol dimethacrylate L/-1-, and trimethylolpropene trimethacrylate can be used. , allyl compounds such as diallyl fumarate, diallyl phthalate, triallyl isocyanurate, quinone dioxime compounds such as p-quinone dioxime, dibenzoylquinone dioxime, divinylbenzene, vinyltoluene, 1.2 polybucdiene, etc. The crosslinking efficiency can also be increased by using these compounds together.

In addition, l! which is a feature of this copolymer! IP! #, hydroxide group f
Various chemical crosslinking methods can be considered. Furthermore, regarding crosslinking, it is also possible to use a technique of crosslinking using high energy such as ionizing radiation (electron beam, X-ray, gamma ray, etc.) without using any of these crosslinking agents.

As the fragrance, natural fragrances such as musk, civet, castoreum, ambergris, various synthetic fragrances, masking agents, etc. can be used.

The composition of the present invention can be molded using a well-known method, for example, using a single screw extruder, a special extrusion W (for example, a three-stage extruder, a vented extruder, a multi-screw extruder, etc.). Extrusion molding, coextrusion molding, blow molding, coextrusion blow molding, injection molding, rotational molding, hot stamping molding, etc. can be carried out to form films, laminates, pipes, sheets, m-tube rings, etc. More special uses include fluid immersion and coating as an emulsion paint.

Although it is possible to use the composition as it is as a molded article, it is also possible to use it in combination with various base materials including polyolefin. In particular, polar materials such as metals, inorganic fillers, glass, polyamides, saponified ethylene-vinyl acetate copolymers, polyesters, polycarbonates, fluorine-based secondary resins, and paper can be mentioned. In its form, it can be mixed with inorganic fillers, blow, film, sheet, fiber (core-sheath).
It is possible to use it in multiple layers.

Hereinafter, explanation will be given according to examples. The present invention is not limited to these embodiments, and may take any form as long as it meets its purpose.

[Example] The volume of the copolymer used in the present invention is 41.

It was produced using an autoclave-type reactor divided into two zones. Unsaturated carboxylic anhydride or unsaturated carboxylic acid anhydride and other monomers and/or solvents are at the second stage pressure J1! Upstream of the reactor, ethylene was added to the first zone of the reactor. The purified copolymer was separated from unreacted slag using a high-pressure separator and a low-pressure separator, and was pelletized using an extruder to obtain a product. The following 6 copolymers were used as the produced copolymers.

(a) Ethylene-maleic anhydride copolymer (MF+18
．． 4. Ethylene content 95.4% by weight! IA water containing maleic acid (M4.6%) Average polymerization temperature +
210°C (b) Ethylene-maleic anhydride copolymer fM
FR82, ethylene containing FF 194.8% by weight, maleic anhydride containing FF 15.2% by weight) Average polymerization temperature: 2
IO℃ (C) Ethylene-itaconic anhydride copolymer (MF+(2
7,1, ethylene containing M196゜2% by weight, itaconic anhydride content 38% by weight) Average polymerization temperature: 2
10℃ (a) Ethylene-medyl acrylate copolymer (
MFRIO,2, ethylene content 91.2% by weight, methyl acrylate content 8.8% by weight) Average polymerization temperature: 270°C Outlet temperature: 280°C (A3 J-ethylene-ethyl acrylate conjugate (M
F R9,5, ethyl acrylate content 10.2% by weight) Average polymerization temperature, 270°C, Outlet temperature 280°C (1) Ethylene-methyl methacrylate copolymer (M
FR8.6, ethylene content 90.8% by weight, methyl methacrylate content 9.2% by weight) Average polymerization temperature: 270°C.

Outlet temperature, 280°C (1) Ethylene-methyl acrylate-maleic anhydride copolymer (MFR2.6, ethylene content 92.8% by weight, methyl acrylate content 5.2% by weight, maleic anhydride content 2. 0% by weight) Average polymerization temperature = 210°C, outlet temperature - 220°C (Example 1) 12 kg (40 ffin parts) of the above copolymer (a) and 18 kg (60 parts by weight) of the copolymer (a) were 2
After mixing with a 00 liter drum blender, 40 m
Mixing was carried out using an extruder in a twin-screw extrusion chamber equipped with mφ vent. The composition was laminated onto an aluminum foil having a thickness of 30 μm using a laminator having an extruder of 90 mmφ and a die width of 750 mm. The extrusion temperature was 280°C, and the extruder screw rotation speed was 60 r.
p m, the take-up speed was 80 m/min, and the total thickness of the obtained laminate was 60 μm.The resulting laminate was conditioned for 24 hours at 23° C. and 50% phase χ1μ degree. After that, it was cut into strips with a width of 15 mm and the 180 degree peel strength between the layers was measured.When peeled at a speed of 300 mm/min, it showed a strength of 380 g/15 mm width, indicating excellent interlayer adhesion. Next, the laminate was cut to an appropriate size and a sealed bag with a resin layer as the inner layer was manufactured.
00cc).

After heating at 40° C. for 30 minutes, the bag was opened and the odor was sensory evaluated. In the evaluation, six panelists selected in a preliminary test made a relative evaluation with a molded copolymer (1) in the same manner. Six out of six panelists evaluated that the laminate according to the present invention had less odor.

From the results below, it was confirmed that the composition according to the present invention had little odor and had excellent adhesive properties.

(Example 2, Comparative Example 4) A composition was produced in the same manner as in Example fIA1. The composition and copolymer were molded and evaluated for adhesive strength and odor in the same manner as in Example 1, except that kraft paper was used for the al. The results are shown in Table 1.

(Example 3. Comparative Example 1.2.3.5) In the same manner as in Example 1, the copolymers shown in Table 1 and the compositions obtained from the copolymers were molded, adhesive strength evaluated, and odor evaluated. Ta. The laminate obtained in Comparative Example 1 had excellent adhesion and odor, but had the drawback of lacking softness, which is the object of the present invention.

(Left below) (Reference Example I) Evaluation Fl of the composition used in Example 1 by coextrusion
The resin composition used in Example 1 and the saponified product of ethylene vinyl acetate copolymer (ethylene content = 32 mol%),
40 mm, 45 mm (45 m layer of composition of Example I)
Using a two-kami-layer co-extrusion molding machine with a die temperature of 220°C and a chill roll with water flowing through it. S30μ,
A 35 μm two-layer film was prepared and evaluated in a 180 degree peel test at a peel rate of 200 mm/min. Quarry strength is 280K
g/I 5ml TI.

b. The resin composition used in Example 1 and 6-nylon were molded using a two-layer co-extrusion molding machine of 40 mm and 45 mm (same as above), using a chill roll with a die temperature of 220°C and 5 water passages. A two-layer film of 2830 μm and 351 μm was prepared using a 180° peel test at a peel speed of 200 mm/min. The adhesive strength was 420Kg/15mm.

(Reference Example 2) The resin composition of the present invention is more flexible than Copolymer I and has excellent transparency.

In other words, the stiffness and haze of the resin composition of Example (a) ethylene-maleic anhydride copolymer and Example 1 as the copolymer (1) are shown below.1- [Effects of the Invention] The resin composition is ethylene-unsaturated carbon r1!, which is widely used as an adhesive resin when laminating polyolefin resins. (or its anhydride), and has significantly improved adhesion.It is also a 3-delta copolymer of ethylene-radical Φ7 polymerizable acid anhydride and radically polymerized Nisdel. The object of the present invention is to provide a low-cost, odorless adhesive resin composition based on a radically polymerizable Nisdel monomer while exhibiting white adhesive properties.

The resin composition of the present invention has excellent flexibility, strong adhesion to paper, metals such as aluminum, saponified products of ethylene-vinyl acetate copolymer, etc., and has little odor. Therefore, it is excellent in compatibility with nylon, polyester, etc. It is also possible to produce films and sheets that are transparent and can be safely used in the packaging fields of food, cosmetics, and pharmaceutical products.

Claims (1)

[Claims] 20 to 80 parts by weight of a copolymer comprising ethylene and a radically polymerizable acid anhydride; and 80 to 2 parts by weight of a copolymer comprising at least ethylene and a radically polymerizable ester monomer.
A resin composition comprising 0 parts by weight.