JPH07713B2 - Ethylene copolymer mixture - Google Patents

Description

TECHNICAL FIELD The present invention relates to an ethylene-based copolymer mixture having good heat resistance and capable of producing a crosslinked polymer.

[Conventional technology]

So far, unsaturated carboxylic acids copolymerized with polyvinyl alcohol having a saponification degree of 85% or less or its acid anhydrides
A composition comprising an olefin-based copolymer containing 10% by weight or less has been proposed (JP-A-55-127450).
However, this relates to a resin composition of a heat-retaining film, which is intended to enhance the uniform dispersibility of a heat-retaining polyvinyl alcohol and an olefin-based copolymer, and is used for an adhesive resin or crosslinking. It could not be used as a composition.

Furthermore, a resin composition for packaging materials comprising an ethylene-vinyl acetate copolymer and a copolymer of an olefin with an unsaturated carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride or a derivative thereof has also been proposed ( JP-A-55-131
No. 033 gazette), this composition is suitable for a packaging material of a packaged object which is required to be moisture-proof and easy to be cut with a blade while having gas permeation resistance. It cannot be used as a composition.

At present, there is a strong demand for polymer materials having good heat resistance and excellent adhesiveness to metals and the like in the fields of electric instruments and electronic instruments. Although there are many polymer materials that have good adhesiveness to metals and the like at room temperature, polyester resins and polyimide resins have been proposed as polymer materials that have excellent heat resistance and adhesiveness. However, polyester resins have drawbacks such as high water absorption and a large coefficient of thermal expansion at 20 ° C to 250 ° C. Further, the polyimide resin has a drawback in that it has poor surface activity and therefore has insufficient adhesiveness to a metal or the like.

Further, in these fields, thermosetting resins, room temperature curable resins, and photocurable resins are widely used. However, these curable resins have relatively long curing time, and therefore production efficiency is high. Not only bad, it also shortened the life of parts due to its hygroscopicity.

Based on these facts, the inventors of the present invention have conducted various searches as to how to easily obtain a resin mixture having excellent adhesion to metals and the like, and found that (A) at least an olefin and a compound represented by the following structural formula: Copolymer (A), In the formula, R ¹ is a hydrogen atom or a methyl machine, R ² is a linear or branched alkylene group having 1 to 12 carbon atoms, and R ³
Is a vinyl group, an allyl group or a methallyl group.

(B) Obtained by saponifying and neutralizing (1) a copolymer composed of at least an olefin and an unsaturated monocarboxylic acid, and (2) an olefinic copolymer composed of at least an olefin and an unsaturated carboxylic acid ester. And a (3) at least one copolymer selected from the group consisting of (3) a copolymer of an olefin and an unsaturated dicarboxylic acid or a half ester thereof, and (C) a reaction accelerator. The composition ratio of the copolymer (A) in the coalescence is 1 to 99% by weight, and the composition ratio of the reaction accelerator is 0.005 to 5.0 parts by weight based on 100 parts by weight of the total copolymer. I proposed it before (Japanese Patent Application No. 60-282097).

However, the obtained resin composition is not always satisfactory in adhesiveness at room temperature and high temperature.

[Problems to be solved by the invention]

From the above, the present invention does not have these drawbacks (problems), is not only excellent in heat resistance, but also improved hygroscopicity, further shortened curing time without the use of a reaction accelerator, Moreover, it is to obtain a mixture of ethylene-based polymers or a crosslinked product thereof which has good adhesiveness to various materials such as metals.

[Means and Actions for Solving Problems]

According to the present invention, these problems are (A) a copolymer (I) of at least ethylene with an anhydride of an α, β-unsaturated dicarboxylic acid, and (B) at least a radical copolymer with ethylene. A copolymer (II) with an unsaturated monomer having an epoxy group and (C) a copolymer (III) of ethylene and α, β-unsaturated carboxylic acid, and α, occupied in the copolymer (I), The copolymerization ratio of the anhydride of β-unsaturated dicarboxylic acid is 0.3 to 15 mol%, the copolymerization ratio of the unsaturated monomer having an epoxy group in the copolymer (II) is 0.3 to 10 mol%, The copolymerization ratio of the α, β-unsaturated carboxylic acid in the copolymer (III) is 0.3 to 20 mol%, and the copolymerization weight in the total amount of the copolymer (I) and the copolymer (II). The mixing ratio of the compound (I) is 5 to 95% by weight, and the epoxide in the copolymer (II) is Si group: The ratio of the carboxyl group in the copolymer (III) can be solved by an ethylene-based copolymer mixture having a molar ratio of 1: 0.05 to 1.5. Hereinafter, the present invention will be specifically described.

(A) Copolymer (I) The copolymer (I) used in the present invention is a copolymer of at least ethylene and an anhydride of α, β-unsaturated dicarboxylic acid. Considering the molding processability of this copolymer,
Those that melt at a temperature of 150 ° C. or less and have fluidity are preferable. In order to ensure this property, a radical-polymerizable monomer having a polar group (hereinafter referred to as “third monomer”) is further copolymerized with the ethylene and an anhydride of α, β-unsaturated dicarboxylic acid. desirable.

The unsaturated dicarboxylic acid anhydride used for producing the copolymer (I) generally has 4 to 20 carbon atoms, and particularly preferably 4 to 16 carbon atoms. Preferred α,
Typical examples of β-unsaturated dicarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, and 3,
Examples thereof include 6-endomethylene-1,2,3,6-tetrahydro-cis-phthalic anhydride.

Representative examples of the third comonomer include alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate and vinyl ester.

The alkyl (meth) acrylate usually has 4 to 40 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 4 to 16 carbon atoms. Among them, the number of carbon atoms in the alkyl group is 1
~ 4 are preferred. Representative examples of suitable alkyl (meth) acrylates are not preferable because the copolymer (I) from which methyl (meth) acrylate and ethyl (meth) acrylate are obtained has excellent thermal stability.

Moreover, the alkoxyalkyl (meth) acrylates generally have at most 20 carbon atoms. Further, it is desirable that the alkyl group has 1 to 8 (preferably 1 to 4) carbon atoms. Further, an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) is desirable. Representative examples of preferable alkoxyalkyl (meth) acrylates include:
Mention may be made of methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate.

The vinyl ester usually has at most 20 carbon atoms (preferably 4 to 10 carbon atoms). Representative examples of suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate and the like.

In the copolymer (I), the copolymer of the unsaturated dicarboxylic acid anhydride is 0.3 to 15 mol%, preferably 0.5 to 10 mol%, particularly preferably 0.5 to 7 mol%. The copolymerization ratio of the anhydride of unsaturated dicarboxylic acid of copolymer (I) is 0.
If it is less than 3 mol%, the adhesiveness and heat resistance are insufficient. On the other hand, it is not necessary to exceed 15 mol%, which is not preferable in terms of production and economy.

When the third comonomer is copolymerized in this copolymer, it is usually at most 20 mol%, preferably 0.5 to 20 mol%, particularly preferably 1.0 to 15 mol%.
Even if the third comonomer is copolymerized in an amount of more than 20 mol%, the characteristics of the present invention are exhibited, but if it exceeds 20 mol%, it is not preferable in terms of production and economy.

(B) Copolymer (II) Further, the copolymer (II) used in the present invention is at least ethylene and "an unsaturated monomer having an epoxy group capable of radical copolymerization" (hereinafter referred to as "epoxy compound"). It is a copolymer with. Further, a multi-component copolymer obtained by copolymerizing ethylene and an epoxy compound with the third comonomer can also be used for the same reason as above.

Representative examples of the epoxy compounds include unsaturated glycidyl esters and unsaturated glycidyl ethers whose general formulas are represented by the following formulas [(I) and (II)].

Typical examples of preferable epoxy compounds include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, and methallyl glycidyl ether.

In the copolymer (II), the copolymerization ratio of the epoxy compound is 0.3 to 10 mol%, preferably 0.3 to 8 mol%, and particularly preferably 0.4 to 7 mol%. Copolymer (II)
When the copolymerization ratio of the epoxy compound is less than 0.3 mol%, there is no problem in terms of adhesiveness, but heat resistance is insufficient. On the other hand, if it exceeds 10 mol%, not only the characteristics of the present invention cannot be further improved, but also there is a problem in terms of economy and production.

When using a copolymer of a third comonomer,
Like the above-mentioned copolymer (I), it is usually at most 20 mol%, preferably 0.3 to 20 mol%, and particularly preferably 1.0 to 15 mol%.

(C) Copolymer (III) Further, the copolymer (III) used in the present invention is at least ethylene and α, β-unsaturated carboxylic acid (that is, α, β-unsaturated monocarboxylic acid, α, β-unsaturated dicarboxylic acid). Further, a multi-component copolymer obtained by copolymerizing ethylene and α, β-unsaturated carboxylic acid with the above-mentioned third comonomer can also be used for the same reason as above.

The carbon number of the α, β-unsaturated carboxylic acid is generally 3 to
It is 20 and particularly preferably 3 to 16.

Representative examples of α, β-unsaturated monocarboxylic acids include acrylic acid, methacrylic acid and crotonic acid.
Further, as a typical example of α, β-unsaturated dicarboxylic acid,
Maleic acid, fumaric acid, citraconic acid, itaconic acid, 3,
Mention may be made of 6-methylene-1,2,3,6-tetrahydro-cyclo-phthalic acid.

In the copolymer (III), the copolymerization ratio of the α, β-unsaturated carboxylic acid is 0.3 to 20 mol%, preferably 0 to 15 mol%, and more preferably 0.5 to 15 mol%.
When a copolymer of a third comonomer is used, it is usually at most 20 mol%, preferably 0.3 to 20 mol%, particularly preferably 0.5 to 15 mol%, like the above-mentioned copolymer (I). Is.

Both the α, β-unsaturated dicarboxylic acid anhydride of the copolymer (I) and the α, β-unsaturated carboxylic acid of the copolymer (III) are the same as those of the copolymer (II). It serves as a cross-linking reaction point and imparts adhesiveness to a wide variety of base materials, and does not need to be excessive from either side. If the amount increases, the water absorption will increase, which not only adversely affects foaming during molding and water absorption after molding, but also adversely affects electrical properties, as well as manufacturing problems such as safety, separation and recovery, and economically. Is also disadvantageous and not preferable. On the other hand, if the amount is less than the lower limit, the crosslinking reaction is not sufficient and the heat resistance is insufficient, which is not preferable.

In addition, this copolymer (III) is prepared by saponifying a part or all of the ester groups in an ethylene-based copolymer consisting of ethylene and an unsaturated carboxylic acid ester, and adjusting the degree of neutralization such as demetallizing treatment. A copolymer having a carboxyl group can be produced.

The unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and particularly preferably 4 to 20 carbon atoms. Typical examples are methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-methoxyethyl (meth).
Examples thereof include acrylate and diethyl fumarate.

The content of unsaturated carboxylic acid ester in this copolymer is 1
-25 mol% is preferred. The saponification rate of the ester depends on the content of the ester and cannot be generally stated.
In terms of the carboxylic acid-containing unit in the copolymer after the neutralization treatment, 0.3 to 20 mol% is preferable, and 0.5 to 15 mol% is particularly preferable.

The saponification reaction is a widely known method, for example, a mixed solvent of toluene and isobutyl alcohol (mixing ratio 50: 5).
It can be carried out by adding a copolymer containing NaOH and an ester group in (0) and refluxing for 3 hours. The saponification rate can be adjusted arbitrarily depending on the amount of NaOH. Furthermore, after precipitating this saponified product with water or alcohol and passing the solvent through it, one day and one night,
Vacuum dry at 50 ° C. Disperse this polymer in water,
Sulfuric acid was added to this, and the copolymer (II
I) is obtained.

The copolymer (I) or the copolymer (III) is a chain transfer agent, if necessary, at a temperature of 120 to 260 ° C. under an ultrahigh pressure of 500 to 2500 kg / cm ² of each monomer (monomer). Radical polymerization using a free radical generator such as peroxide in an autoclave or tubular reactor equipped with a stirrer, or, if necessary, after that, an unsaturated carboxylic acid is graft-copolymerized in the presence of a free radical generator. Can be obtained by

According to the melt flow index (JIS K7210) of the copolymer (I) and the copolymer (II), the condition is 4
Measured by the following, hereinafter referred to as "MFR") is usually 0.1-10
00g / 10, 0.5-700g / 10min is desirable, especially 1.
0 to 500 g / 10 minutes is suitable. If a copolymer having an MFR of less than 0.1 g / 10 min and a copolymer having an MFR of more than 1000 g / 10 min is used, the moldability will be poor. The copolymer (III) has an MFR of 0.1 g / 10
It may be at least a minute, and may have a low molecular weight.

In producing the mixture of the present invention, by further adding (blending) the reaction accelerator described below, further promoting the crosslinking of the copolymer (I) and the copolymer (III) and the copolymer (II). You can

(D) Reaction Accelerator The reaction accelerator used in the present invention is widely known as a curing agent for epoxy resins, and a typical example thereof is “Epoxy Resin” edited by Hiroshi Kakiuchi (Shokoido, Showa Showa). Issued in 1954), pages 26 to 29, pages 32 to 35,
Examples thereof include those described on pages 109 to 128, 185 to 188, 330 and 331.

Typical examples of the reaction accelerator include a tertiary amine represented by the formula (III), an acid, an alkaline compound and an ammonium salt represented by the formula (IV).

In the formulas (III) and (IV), R ⁴ , R ⁵ , R ⁶ and R ⁷
May be the same or different and each is a hydrocarbon group selected from an alkyl group having 1 to 32 carbon atoms, an aryl group, an alkaryl group and an aralkyl group, and X is a halogen atom. In these formulas, a hydrocarbon group having 12 or less carbon atoms in R ⁴ to R ⁷ is preferable. Further, X is preferably a chlorine atom or a bromine atom.

Representative examples of the reaction accelerator include ethanolamine, diethanolamine, triethanolamine, dimethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, N, N-dimethylaminoethanol, N, N-diethylaminoethanol. , Morpholine, biperidine, pyridine, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminomethacrylate, N, N-diethylaminoethyl acrylate, trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylbenzylamine, Hexamethylenetetramine, triethylenediamine, tertiary amines such as N, N-dimethylpiperazine and N-methylmorpholine, acidic compounds such as p-toluenesulfonic acid and potassium hydroxide, or alkaline compounds. Compounds as well as trimethylbenzylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride and cetyltrimethylammonium halide ammonium salt such as chloride, zinc chloride and the like more. Especially, N, N-dimethylbenzylamine and p-toluenesulfonic acid are preferable.

(E) Mixing ratio In producing the ethylene copolymer mixture of the present invention, the mixing ratio of the copolymer (I) in the total amount of the copolymer (I) and the copolymer (II) is 5 to 5. It is 95% by weight, preferably 10 to 90% by weight, particularly preferably 20 to 90% by weight. When the mixing ratio of the copolymer (I) in the total amount of the copolymer (I) and the copolymer (II) is less than 5% by weight, adhesiveness to a metal is not a problem, but polyester, cellophane, polyimide Adhesion with such as is not good. On the other hand, 95
If the content is more than wt%, the adhesion will be satisfactory, but the heat resistance will be poor.

The epoxy group in the copolymer (II): copolymer (II
The mixing ratio of the carboxyl groups in I) is 1: 0.05 by molar ratio.
It is 1.5, preferably 0.05 to 1.2, and particularly preferably 0.1 to 1.0. When the molar ratio of the epoxy group in the copolymer (II) to the carboxyl group in the copolymer (III) is less than 1: 0.05, the heat resistance is poor and the crosslinking reaction requires a long time. On the other hand, if it exceeds 1: 1.5, adhesion to metal is not a problem, but adhesion to polyester, cellophane, polyimide, etc. is poor, and adhesion at high temperature (100 ° C) is not good.

When a reaction accelerator is added, the mixing ratio with respect to 100 parts by weight of the total amount of the copolymer (I), the copolymer (II) and the copolymer (III) is generally 5.0 parts by weight at most. 0.01 to 5.0 parts by weight is preferable, and 0.01 to 2.0 parts by weight is particularly preferable. Even if the reaction accelerator is blended in an amount of more than 5.0 parts by weight, the low-temperature cross-linking promoting effect is exhibited, but not only the cross-linking adhesion inhibiting effect by the reaction promoting agent itself may occur, but the reaction promoting agent may also form a molded article. It is not preferable because it causes bleeding on the surface and a good molded product cannot be obtained.

(F) Mixing method In order to produce the mixture of the present invention, the above copolymer (I), copolymer (II) and copolymer (III), or these copolymers and a reaction accelerator are uniformly added. Can be mixed with.

As a mixing method, a dry blend using a mixer such as a Henschel mixer which is usually performed in the field of olefin polymers may be used, and a Banbury mixer, a kneader, a twin screw extruder, a single screw extruder, a roll mill, etc. A method of melting and mixing using a mixer may be used. At this time
A uniform mixture can be produced by dry-blending in advance and melt-mixing the obtained mixture.

It should be noted that, when mixing in a molten state, it is necessary to carry out under conditions in which the respective copolymers used do not substantially undergo a crosslinking reaction (if a reaction occurs during mixing, a uniform mixture cannot be obtained. However, this is not preferable because not only the moldability is deteriorated when the mixture is molded and processed, but also the desired shape of the molded product and heat resistance and adhesiveness when the molded product is crosslinked are deteriorated.) Therefore, in the case of melt-mixing, depending on the viscosity of each of the copolymer (I), the copolymer (II) and the copolymer (III), it is generally room temperature (25 ° C) to 150 ° C, Preferably 70
It is desirable to carry out at a relatively low temperature of up to 140 ° C, preferably 70 to 130 ° C, in a short time of about several minutes.

As a measure of "substantially not cross-linking", the total amount of the above-mentioned copolymer (I), copolymer (II) and copolymer (III) is "extracted in boiling toluene for 3 hours, It is preferable that the "residue having a diameter of 0.1 μm or more" (hereinafter referred to as "extraction residue") is generally 15% by weight or less,
Weight% or less is suitable, and especially 5 weight% or less is optimal.

(G) Method for producing crosslinked product, molding method, etc. The mixture obtained as described above can be formed into a molded product by almost all existing molding methods. For example, in the method of casting and heating the mixture, desired moldings can be obtained by heating and crosslinking by cast molding, compression molding, transfer molding, powder molding and the like. In the method of kneading and molding to obtain a precursor and then crosslinking, a molded article may be obtained by injection molding, extrusion molding, laminate molding, and roll processing, and then heated and crosslinked. After obtaining a sheet or film by extrusion molding, vacuum forming,
A molded product can be obtained by pressure molding or the like, and a crosslinked polymer molded by heating this can be obtained,
The composition is first formed into a film using a T-die film forming machine, and the film is formed from aluminum, paper, copper,
After laminating on one side or both sides to various substrates such as polyimide resin, nylon, polysulfone, etc., by heating or by making a roll of the composition or a calender roll to prepare a sheet of an appropriate thickness and adhering these It can be adhered by sandwiching it between the desired base materials and hot pressing at high temperature. Alternatively, a composite material having high heat resistance and high adhesive strength can be obtained by performing a two-layer or multi-layer lamination by a method similar to a method generally known as extrusion lamination and then performing heat treatment at a high temperature.

The crosslinked film of the composition can also be produced by arranging rolls having different temperatures from low temperature to 230 to 260 ° C. or less one after another and raising the temperature while applying a slight tension. Alternatively, the crosslinked film or sheet can also be prepared by sandwiching the uncrosslinked T-die film or sheet obtained by the above-mentioned method with a film such as Teflon and pressing with heat. Although these are cross-linked films, they have adhesiveness, and can be firmly adhered by sticking various substrates and heating, and of course, they have remarkable heat resistance.

Furthermore, when a chemical foaming agent is mixed when the above composition is prepared, a crosslinked foamed film or sheet, or a heat-resistant crosslinkable foamed composite material (sandwich) can be obtained by attaching a base material on both sides without using an adhesive. Can be built.

The heating temperature for crosslinking varies slightly depending on the comonomer composition ratio of each olefin-based copolymer used, but is generally 150 ° C or higher, and particularly preferably 160 ° C or higher.

The heating time varies greatly depending on the heating temperature and the composition ratio of the olefin-based copolymer, but is on the order of several seconds to several tens of minutes.

[Examples and Comparative Examples]

Hereinafter, the present invention will be described in more detail with reference to Examples.

The adhesive strength in the examples and comparative examples is JIS K685.
According to 4, the T-type peeling was performed under the condition that the pulling speed was 100 mm / min and the measurement was performed. The heat resistance was such that the sheet was left for 30 minutes in a constant temperature oven at 260 ° C., and the state of the sheet after standing was observed.

In addition, in Examples and Comparative Examples, Table 1 shows the copolymerization ratios and types of the second comonomer and the third comonomer of each ethylene copolymer used, and their MFRs. In Table 1, "MAH" is maleic anhydride, "IAH" is itaconic anhydride, "GMA" is glycidyl methacrylate, "AGE" is allyl glycidyl ether, and "MAA" is Methacrylic acid, "AA" acrylic acid, "EA" ethyl acrylate, "MMA" methyl methacrylate, "VA" vinyl acetate.

Examples 1 to 8 and Comparative Examples 1 to 7 Copolymers (I) and copolymers (II) whose types and copolymerization ratios and MFRs of the respective second and third comonomers are shown in Table 1. And copolymer (II
Dry blending was carried out for 5 minutes using a Henschel mixer at the respective mixing amounts of I) and the reaction accelerator shown in Table 2. A mixture was produced by kneading each of the obtained mixtures at 140 ° C. or lower using a uniaxial extruder having a cylinder portion having a diameter of 30 mm. Using a T-die film forming machine with a cylinder diameter of 40 mm, the C ₁ , C ₂ , C _{3 of the} cylinder and the temperature of the dies were adjusted to 110 for each of the obtained mixtures.
C., 115.degree. C., 120.degree. C., and 125.degree. C. were set, and film formation was carried out.

The obtained film is a copper foil (thickness 35 μm) or a polyimide film (Toray DuPont, trade name Kapton)
100 H, thickness 25 μm) copper foil / mixture / copper foil (Example 1)
No. 4 and Comparative Examples 1 to 4) and a polyimide film / mixture / polyimide film (Examples 5 to 8 and Comparative Examples 5 to 7) sandwich at 230 ° C. and 2
Preheat 1.5 minutes each at a temperature of 30 ℃ (bonding temperature), press at these temperatures under a pressure of 20 kg / cm ^{2 for} the time shown in Tables 3 and 4, and have a thickness of 0.15 to 0.22. mm adhesive plates were produced. The adhesive strength of each obtained adhesive plate was high in each Example as shown in Tables 3 and 4. The extraction residues of each sample at this time are shown in Tables 3 and 4.

Further, Teflon sheets were placed on the upper and lower sides of the film (not heated) produced by the T-die, and a film having a thickness of 0.15 mm was produced at a temperature of 200 ° C. and 230 ° C. by the same method as that for the adhesive plate. The heat resistance of each of the obtained films was tested.

Although the heat resistance test of each film of the mixture obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was still thick, a part of the film of the mixture obtained in Comparative Example 4 was used. Melted.

From these results, the mixture of the present invention containing a copolymer having a carboxyl group not only has excellent adhesive strength not only at room temperature but also at a temperature of 100 ° C., and also has good heat resistance. That is clear.

Example 9 200 g of ethylene-methyl methacrylate copolymer having an MFR of 109 g / 10 minutes and a copolymerization ratio of methyl methacrylate of 7.6 mol%, and 1.5 l of a mixed solvent of toluene / isobutyl alcohol = 50/50 and water. Sodium oxide (0.5 mol with respect to methyl methacrylate in the copolymer) was placed in a 3 l separable flask and the temperature was raised with stirring to completely dissolve it. The reaction was carried out for 3 hours while stirring at the boiling point of the mixed solvent. The mixed solvent having the obtained reaction product was gradually added to 2 l of methyl alcohol while stirring to precipitate a reaction product (particles). The precipitated reaction product was filtered and dried under reduced pressure at a temperature of 60 ° C. overnight. The saponification rate of the obtained reaction product (polymer) was 42% with respect to methyl methacrylate.

100 g of this reaction product was dispersed in 1 part of water, sulfuric acid was added in an equimolar amount to the metal of carboxylic acid while stirring, and the reaction was carried out at 60 ° C. for 1 hour. Then, after passing the obtained reaction product, it was washed with water three times, and it was confirmed that no sulfate was found in the washing liquid. As a result, a copolymer (hereinafter referred to as "III-4") in which all the metal salts of carboxylic acid in the polymer were converted into carboxylic acid groups by absorption of infrared spectrophotometry was obtained.

The mixing ratio (by weight) of this copolymer (ie III
-4): I-1: II-1 was used at 10:50:40 using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and the rotation speed was 4 at 120 ° C.
The mixture was prepared by kneading for 3 minutes under conditions of 0 revolutions / minute. This mixture was rolled into a sheet (thickness 1.
0mm) was created.

The obtained sheet was interposed between the above-mentioned two copper foils, pressed under the same conditions as in Example 1, and the adhesive strength was measured. 8.6kg / 25mm at room temperature, 0.8kg / 25mm at 100 ℃
Met. The extraction residue of the sheet in this adhesive was 96.2%.

Example 10 Example 1 was repeated except that 0.5 part by weight of N, N-dimethylbenzylamine (reaction accelerator) was added to the mixture of Example 1.
Dry blending was performed in the same manner as in. This mixture was mixed using a Labo Plastomill at a temperature of 110 ° C. or lower at a rotor rotation speed of 40 rpm for 3 to 4 minutes to prepare a mixture.

This mixture is placed between two Teflon sheets (which do not adhere to the mixture), and the temperature is 110 ° C for 2 minutes, 20 kg / cm ²
Pressing was carried out for 3 minutes under pressure to prepare a film of the mixture having a thickness of 0.15 mm. Then, this sample was interposed between the two copper foils used in Example 1 and adhered at a temperature of 170 ° C. for 10 minutes to prepare an adhesive plate having a thickness of 0.18 mm. When the adhesive strength of the obtained adhesive plate was measured in the same manner as in Example 1, it was 8.3 kg / 25 mm at room temperature and 0.82 kg / 25 mm at a temperature of 100 ° C. The extraction residue of the film in the adhesive plate was 90.6%. The extraction residue of the film prepared in the same manner as above except that N, N-dimethylbenzylamine was not added was 76.6%. From these, it can be seen that the crosslinking is increased by adding the reaction accelerator.

Examples 11 to 14 Copolymers (I), Copolymers (II) and Copolymers (III) whose types are shown in Table 5 are mixed in a Laboplast mill in a weight ratio of 50:40:10. The mixture was prepared by mixing in a rotor at a temperature below 120 ° C. and 40 rpm for 3-4 minutes. Each of the resulting mixtures was coated with a Teflon-coated roll at 85 ° C to a thickness of 0.5-1.0.
Each mm sheet was created. Sandwich each of the resulting sheets between Teflon sheets.
A sheet was prepared by pressing under a pressure of 20 kg / cm ² for 0 minutes. Extraction residue of each of these sheets and
Leave for 24 hours under the conditions of ℃ and 53% relative humidity ”[hereinafter referred to as“ condition (a) ”],” Leave for 24 hours under the conditions of temperature of 21 ° C. and relative humidity of 57% ”[hereinafter“ condition (b) ) ”],“ Leave for 550 hours under conditions of temperature of 21 ° C. and relative humidity of 97% ”[hereinafter referred to as“ condition (c) ”], and“ Leave in boiling water for 2 hours ”[hereinafter“ condition ( d) ”] was measured. The results are shown in Table 5.

Each sheet was immersed in a solder bath at 260 ° C. for 3 minutes, but no change was observed in any of the sheets.

A mixture in which the mixing ratio of I-1, II-2 and III-1 shown in Table 1 is 50:40:10 [hereinafter referred to as "mixture (1)"], I-2, II-1. And a mixture in which the mixing ratio of III-3 is 50:40:10 [hereinafter referred to as "mixture (2)"
], A mixture having a mixing ratio of I-1 and II-2 of 50:50 [hereinafter referred to as "mixture (3)"] and I-
2. A mixture having a mixing ratio of 50:50 with II-1 [hereinafter referred to as "mixture (4)"] was previously dry blended for 5 minutes using a Henschel mixer, and then at 110 ° C using a Labo Plastomill. It was manufactured by kneading. Mixture (1) to mixture (4) and I-1 alone, II-
The cross-linking curve was determined at a temperature of 190 ° C. by using a carastometer (manufactured by Toyo Baldwin Co., Ltd., model JSR-III type) for 1 alone and III-3 alone. The results are shown in FIG. In FIG. 1, “a” is the mixture (1),
"B" is the mixture (2), "a '" is the mixture (3),
"B '" is mixture (4), "c" is mixture I-1 alone,
“D” is the cross-linking curve of II-1 alone and “e” is the cross-linking curve of III-3 alone.

From FIG. 1, the mixture (1) and the mixture (2), which are the ethylene-based copolymer mixture of the present invention, are the mixtures in which the copolymer having a carboxyl group is not used, that is, the mixture (3) and the mixture (4). It is clear from the comparison of a and b with a'and b'that the crosslinking reaction is fast and the reaction proceeds efficiently because the torque rises faster and the torque value is higher. Is. Further, no increase in torque was observed with each copolymer alone, and it is clear that the crosslinking reaction did not occur.

〔The invention's effect〕

The ethylene-based copolymer mixture obtained by the present invention has good flowability and excellent processability, so that various molded products such as films, sheets and pipes can be easily produced.

Further, the cross-linked polymer obtained by cross-linking the mixture obtained according to the present invention has excellent electrical insulation properties like general thermoplastic resins.

The most distinctive effect is that it has excellent heat resistance and adhesiveness as described below.

1) Regarding heat resistance, it generally does not cause discoloration, foaming or deformation even at a temperature of 260 ° C or higher, and even at 300 ° C or higher for a short time.

2) Regarding the adhesiveness, when a mixture or a precursor (for example, a film or sheet) according to the present invention obtained by molding is brought into close contact with a third substance and then crosslinked by heating, it strongly adheres to the third substance. Is to do. The third substance includes metals and alloys such as aluminum, copper, iron, stainless steel, brass, galvanized iron, tin plate, glass ceramics, amide,
Examples thereof include imide resins, polysulfones, polyesters, polycarbonates, polyurethanes, cellophane, various papers, and modified polyolefin polymers obtained by grafting monomers having polar groups, such as synthetic resins having polar groups.

Since the mixture obtained by the present invention and the crosslinked product thereof have the above effects, they can be widely and effectively utilized in various fields.

In addition to heat resistance and adhesiveness, it has excellent electrical insulation properties such as volume and surface resistivity, and has excellent electrical properties such as low dielectric constant and dielectric loss tangent. Adhesive strength water resistance, organic solvent resistance, acid resistance, alkali resistance, etc. Has excellent chemical resistance, boiling resistance (moisture resistance), and excellent etching and plating characteristics. Therefore, it can be used for printed circuit board laminates and flexible wiring boards. It is suitable for various electric machines and electronic devices such as electronic materials such as sealing materials for electrolytic capacitors. It is also used as a material for automobile parts that require heat resistance and adhesiveness.

[Brief description of drawings]

FIG. 1 shows mixtures (1) to (4) and I-
FIG. 3 is a cross-sectional curve diagram of 1 alone, II-1 alone, and III-3 alone. In this figure, the vertical axis represents torque (Kg-cm) and the horizontal axis represents crosslinking time (minutes).

Claims (1)

[Claims] 1. A copolymer (I) of at least ethylene and an anhydride of an α, β-unsaturated dicarboxylic acid, and (B) an unsaturated monomer having an epoxy group capable of being radically copolymerized with at least ethylene. (II) and (C) a copolymer (III) of ethylene and an α, β-unsaturated carboxylic acid, which is an anhydride of α, β-unsaturated dicarboxylic acid in the copolymer (I). The copolymerization ratio of the product is 0.3 to 15 mol%, the copolymerization ratio of the unsaturated monomer having an epoxy group in the copolymer (II) is 0.3 to 10 mol%, and the copolymerization ratio is in the copolymer (III). The copolymerization ratio of the α, β-unsaturated carboxylic acid is 0.3 to 20 mol%, and the mixing ratio of the copolymer (I) in the total amount of the copolymer (I) and the copolymer (II) is 5 to 95% by weight, and the epoxy group in the copolymer (II): the cap in the copolymer (III). Proportion of Bokishiru groups in a molar ratio of 1: ethylene copolymer mixture is 0.05 to 1.5.