JPH0657737B2 - Olefin-based copolymer mixture - Google Patents

Description

TECHNICAL FIELD The present invention relates to a mixture capable of producing a heat-resistant cross-linking polymer, which has a relatively simple cross-linking property and further has an excellent adhesion property to a metal or the like. The object of the present invention is to provide a mixture which gives good results and has a heat resistance as well as a crosslinked product having good transparency.

Conventional technology So far, unsaturated carboxylic acids or their acid anhydrides copolymerized with polyvinyl alcohol having a saponification degree of 85% or less have been used.
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.

Further, in the field of laminated glass, a polymer material having good adhesiveness with glass and excellent penetration resistance is desired.

From these facts, it is possible to easily obtain a resin mixture having excellent adhesiveness. The following four olefin-based copolymers; (A) a copolymer composed of at least an olefin and glycidylalkyl (meth) acrylate; (B) A copolymer comprising at least an olefin and an unsaturated monocarboxylic acid, (C) a copolymer obtained by saponifying and neutralizing an olefinic copolymer comprising at least an olefin and an unsaturated carboxylic acid ester, (D) at least an olefin And a unsaturated dicarboxylic acid or a half ester thereof, the weight composition ratio of the copolymer (A) is 1/99 to 99 /
Copolymer (A) and copolymer (B), such as 1
A crosslinkable composition selected from the composition of (A) and a copolymer (C) and the composition of a copolymer (A) and a copolymer (D).

Has been proposed (Japanese Patent Application No. 60-80303).

However, the transparency of the resulting resin mixture is not always satisfactory.

Problems to be Solved by the Invention From the above, the present invention does not have these drawbacks (problems) and has not only excellent heat resistance, but also improved transparency, further shortened curing time, and It is to obtain a mixture or cross-linked product of an olefin-based polymer having good adhesiveness to various materials such as metal and glass.

Means and Actions for Solving Problems According to the present invention, the problems are (A) (1) a copolymer comprising at least an olefin and an unsaturated monocarboxylic acid, [hereinafter referred to as “copolymer ( a) ”],
(2) A copolymer obtained by saponifying an olefin-based copolymer composed of at least an olefin and an unsaturated carboxylic acid ester, and subjecting to demetalization (hereinafter referred to as "copolymer (b)") and (3 ) At least one copolymer (I) selected from the group consisting of a copolymer of at least an olefin and an unsaturated dicarboxylic acid, an anhydride thereof or a half ester thereof (hereinafter referred to as "copolymer (c)"). , (B) a copolymer of at least an olefin and an unsaturated monomer having an epoxy group capable of radical copolymerization (II) [hereinafter referred to as "copolymer (d)"], and (C) a carboxylic acid ester plasticizer In a total amount of the copolymer (I) [that is, the copolymer (a) or the copolymer (c)] and the copolymer (II) [that is, the copolymer (d)]. Copolymer (I)
Is 1 to 99% by weight, and the mixing ratio of the carboxylic acid ester plasticizer is 1 to 50 parts by weight based on 100 parts by weight of the total amount of these copolymers. can do. Hereinafter, the present invention will be specifically described.

(A) Copolymer (a) The copolymer (a) is a copolymer of at least an α-olefin and an unsaturated monocarboxylic acid. Considering molding processability, it is preferable that the copolymer melts at a temperature of 150 ° C. or lower and has fluidity. In order to ensure this property, it is preferable to copolymerize a radical-polymerizable comonomer having a polar group (hereinafter referred to as “third component”).

The unsaturated monocarboxylic acid that can be used in the present invention generally has 3 to 20 carbon atoms, and particularly preferably 3 to 10 carbon atoms. Representative examples include acrylic acid, methacrylic acid, crotonic acid, monoalkylmalates, monoalkylfumarates and the like.

The α-olefin has 2 to 12 carbon atoms (preferably,
2 to 8) α-olefins are preferable, and examples thereof include ethylene, propylene, butene-1, and the like, with ethylene being particularly preferable.

The third component is a radically polymerizable vinyl compound containing a polar group, and examples thereof include unsaturated carboxylic acid esters, vinyl esters, and alkoxyalkyl (meth) acrylates.

The unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and particularly preferably 4 to 20 carbon atoms. As a typical example,
Those having good heat stability such as methyl (meth) acrylate and ethyl (meth) acrylate are preferable, and those having poor heat stability such as t-butyl (meth) acrylate cause foaming and are not preferable.

Moreover, the alkoxyalkyl (meth) acrylates usually have at most 20 carbon atoms. In addition, an alkyl group having 1 to 8 (preferably 1 to 4) carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4) Is desirable. Representative examples of preferred alkoxy (meth) alkyl acrylates include methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate. The vinyl ester generally has at most 20 carbon atoms (preferably 4 to 10 carbon atoms). Representative examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and the like.

In the copolymer (a), the amount of the third component is preferably 25 mol% or less, and particularly preferably 2 to 20 mol%. twenty five
The characteristics of the present invention are exhibited even if the amount exceeds 25% by mole,
However, it is not preferable in terms of production and economy.

The amount of bonds in the unsaturated monocarboxylic acid copolymer (a) is 0.5
It is desirable that the amount is not less than mol% and not more than 25 mol%, and particularly preferably 1.0 mol% to 15 mol%. The unsaturated monocarboxylic acid monomer was added to the olefin copolymer at 0.5
The present invention also includes those obtained by graft-copolymerizing at least mol% as described below, but block or random copolymers are preferable, and random copolymers are particularly preferable.

The unsaturated monocarboxylic acid serves as a cross-linking reaction point with the below-mentioned copolymer (d) and imparts adhesiveness to a wide variety of base materials, and it is necessary to be excessive from both sides. There is no. 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 it is less than 0.5 mol%, there is no problem in terms of adhesion, but heat resistance becomes insufficient, which is not preferable.

The copolymer (a) comprises an α-olefin and an unsaturated carboxylic acid, or a mixture of these and a third component in an amount of 500 to 2500 Kg /
Under ultra high pressure of cm ² , at a temperature of 120-260 ℃, if necessary, using a chain transfer agent, in an autoclave or tubular reactor with a stirrer, radical polymerization using a free radical generator such as peroxide, or as needed. Accordingly, it can be obtained by graft-copolymerizing an unsaturated carboxylic acid in the presence of a free radical generator.

(B) Copolymer (b) Further, the copolymer (b) used in the present invention is one of the above-mentioned α-olefin and one of the ester groups in the olefinic copolymer composed of an unsaturated carboxylic acid ester. It is a copolymer obtained by saponifying all or part of it and performing a neutralization reaction such as demetallizing treatment. It is preferable that the copolymer melts at a temperature of 150 ° C. or lower and has fluidity.

Examples of the α-olefin include compounds of the same type as the copolymer (a). The unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and particularly preferably 4 to 20 carbon atoms.
Representative examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, diethyl fumarate and the like.

The content of unsaturated carboxylic acid ester in the copolymer (b) is preferably 1 to 25 mol%. The saponification rate of the ester cannot be generally determined because it depends on the content of the ester, but the saponification rate is 0.5 to 20 mol% in terms of the carboxylic acid-containing unit in the copolymer after the neutralization treatment. Is preferred, especially 1 to 15
Molar% is preferred.

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,
Copolymer (b) is obtained by adding sulfuric acid to this and stirring for 1 hour at 70 ° C. to carry out a demetallizing treatment (= neutralization reaction).

(C) Copolymer (c) Further, the copolymer (c) used in the present invention is a copolymer of the aforementioned α-olefin and an unsaturated dicarboxylic acid, an anhydride thereof or a half ester thereof. (The third component may be included). That is, an α-olefin and an unsaturated dicarboxylic acid, an anhydride thereof or a half ester thereof, or those obtained by directly copolymerizing these with the third component is preferable, and an α-olefin and an anhydride of the unsaturated dicarboxylic acid are used. An olefin-based copolymer (which may contain the third component) may be modified so that a part or all of the acid anhydride group is dicarboxylic-oxidized or half-esterified. A material that melts at a temperature of 150 ° C or lower is preferable. Examples of the α-olefin and the third component include the same types of compounds as the copolymer (a).

When the copolymer (c) is produced by a direct copolymerization method, unsaturated dicarboxylic acid, its anhydride or its monoester is selected as the comonomer.

The unsaturated dicarboxylic acid usually has at most 20 carbon atoms, and particularly preferably has 4 to 16 carbon atoms. As typical examples of the dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 3,6-endomethylene-1,2,
3,6-Tetrahydro-cis-phthalic acid (nadic acid)
Can be given.

The unsaturated dicarboxylic acid monoester generally has at most 40 carbon atoms, particularly 5 to 20 carbon atoms. As a typical example thereof, one in which one of the carboxyl groups of the dicarboxylic acid is half-esterified by a typical example of the alcohol described below can be mentioned. Representative examples of the alcohol include primary alcohols having at most 20 carbon atoms such as methanol, ethanol, propanol, butanol and the like. As typical examples of half esters, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester,
Examples thereof include maleic acid monobutyl ester and itaconic acid monoethyl ester.

The copolymer of "unsaturated dicarboxylic acid or its half ester" (hereinafter referred to as "unsaturated dicarboxylic acid component")
The amount of bonds in (c) is preferably 0.5 mol% or more and 20 mol% or less. More preferably, it is 1.0 to 15 mol%.
It is also possible to use a copolymer obtained by grafting an unsaturated dicarboxylic acid component onto a copolymer of an olefin and the third component in an amount of 0.5 mol% or more as described below. The unsaturated dicarboxylic acid component serves as a cross-linking reaction point with the copolymer (d) described below and imparts adhesiveness to various base materials, and is excessive from both sides. No need.

When the copolymer (c) used in the present invention is obtained by modifying the copolymer of unsaturated dicarboxylic acid anhydride, the starting olefin-based copolymer is α-olefin and unsaturated dicarboxylic acid. Anhydride or a copolymer obtained by copolymerizing these with the third component and a copolymer of an α-olefin and the unsaturated dicarboxylic acid ester are graft-copolymerized with an anhydride of the unsaturated dicarboxylic acid. Selected from the copolymers thus obtained.

The modification is carried out, for example, by hydrolysis and / or half-esterification with the alcohols mentioned.

As a result of the modification, the copolymer (c) thus obtained contains a structural unit in which a carboxyl group is bonded to adjacent carbon atoms and / or a structural unit in which a carboxyl group and a carboalkoxy group are bonded to adjacent carbon atoms. It becomes a copolymer.

Copolymer of the sum of these structural units modified (c)
The proportion in the above is preferably 0.5 to 20 mol%, and more preferably 1.0 to 15 mol%.

In the copolymer (c), an unsaturated carboxylic acid ester used as a copolymerization component of an unsaturated dicarboxylic acid, or its anhydride or its half ester, or an unsaturated dicarboxylic acid, its anhydride or its monoester is grafted. Α used as a starting material for copolymerization
As the unsaturated carboxylic acid ester used in the copolymer of olefin and unsaturated carboxylic acid ester, the same unsaturated carboxylic acid ester as described above can be used.

The content of the unsaturated carboxylic acid ester in the copolymer (c) is preferably 25 mol% or less, and particularly preferably 2 to 20 mol%. If the amount exceeds 25 mol%, the characteristics of the present invention will be exhibited, but in that region, the production is difficult and there is no economical advantage.

In producing the copolymer (c), various known methods (for example, solution method, suspension method, melting method) can be adopted.

Of these production methods, the melting method will be described as an example. An unsaturated dicarboxylic acid is added to the copolymer of the α-olefin and the unsaturated carboxylic acid ester (hereinafter referred to as “copolymer (c ′)”). In the case of graft-copolymerizing the anhydride of the above, a melt kneader (for example, an extruder) used in the field of general synthetic resins is used, and the copolymer, the anhydride of the unsaturated dicarboxylic acid and the radical described below are used. It can be obtained by treating the initiator while melt-kneading. The kneading temperature at this time varies depending on the kinds of the copolymer and the radical initiator to be used, but is in the temperature range from the melting point of the copolymer used to 330 ° C. or less. Generally, it is 120 to 270 ° C. Examples of the radical initiator include 2,5-dimethyl-2,5-di (tertiary butylperoxy) hexane, 2,5-dimethyl-5,5-di (tertiary butylperoxy) hexyne-3 and benzoylperoxide. An organic peroxide such as oxide can be given.

When the copolymer (c) is produced by the graft method, the proportion of the unsaturated dicarboxylic acid anhydride used relative to 100 parts by weight of the copolymer (c ') is as described above. Considering the physical properties and economical efficiency of the coalescence, usually 7.0 parts by weight or less is preferable, and 5.0 parts by weight or less is preferable.

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

As a typical example of this epoxy compound, one having a general formula represented by the following formula [(I) and (II)] can be mentioned.

Typical examples of the epoxy compounds represented by the formulas (I) and (II) include glycidyl methacrylate, glycidyl acrylate, α-methylglycidyl acrylate,
Examples include α-methylglycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether and methallyl glycidyl ether.

Melt index of these copolymers (a), copolymers (b), copolymers (c) and copolymers (d) (according to JIS K-7210, temperature 190 ° C and load 2.16 Kg Measured with the following, `` M.
"I.") is usually 0.1 g / 10 minutes or more, and
It is preferably 5 g / 10 minutes or more, and particularly preferably 1.0 to 50 g / 10 minutes or more.

(E) Carboxylic Acid Ester Plasticizer Further, as the carboxylic acid ester plasticizer used in the present invention, those generally used for plastics are used. The plasticizers are described in "Handbook Rubber / Plastic Blended Chemicals" edited by Rubber Digest Co., Ltd. (Rubber Digest Co., published in 1974), pp. 145 to 191 and their types and physical properties.

Typical examples of the carboxylic acid ester plasticizer include phthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, trimellitic acid, citric acid, oleic acid, ricinoleic acid, stearic acid and lauric acid. Examples include esters of carboxylic acids and alcohols having 2 to 40 carbon atoms. Typical examples of these plasticizers include di (iso) butyl phthalate, dihexyl phthalate, diisodecyl phthalate, butyl octyl phthalate, di-2-octyl phthalate, octyl decyl phthalate, butyl phthalyl phthalate. Butyl
Glycolate, di- (2-ethylhexyl) adipate, octyl decyl adipate, benzyl octyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, di (iso) octyl sebacate, di- (2-ethylhexyl) ) Malate,
Dinonyl malate, di- (2-ethylhexyl) fumarate, tri- (2-ethylhexyl) trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-butyl citrate,
Acetyl tri- (2-ethylhexyl) citrate,
Methoxy ethyl oleate, tetrahydro furfuryl oleate, butyl acetyl ricinoleate, glyceryl monoricinolate, glyceryl monostearate, diethylene glycol distearate. In addition, butyl coconut alkyl phthalate, esters of vegetable oil fatty acids, polyethylene glycol cis- (2-ethyl hexoate) can also be used.

To produce the mixture of the present invention, at least one of the above copolymer (a) or copolymer (c) and a copolymer (d)
And a carboxylic acid ester-based plasticizer, which are obtained by uniformly mixing the mixture within the range of the mixing ratio described below, but by further mixing a reaction accelerator described below or an organic peroxide, the above-mentioned copolymer (a) The crosslinking of the copolymer (d) with any one of the copolymer (b) and the copolymer (c) can be promoted.

(F) 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 primary, secondary or tertiary amines represented by the formula (III), acids, alkaline compounds and ammonium salts represented by the formula (IV). .

In the formulas (III) and (IV), R ⁶ , R ⁷ , R ⁸ and R
⁹ may be the same or different and each is a hydrogen atom, a hydrocarbon group selected from an alkyl group having 1 to 32 carbon atoms, an aryl group, an alkaryl group and an aralkyl group, but not all hydrogen atoms at the same time. X is a halogen atom. In these formulas, the carbon number of R ⁶ to R ⁹ is
12 or less hydrocarbon groups are preferred. 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, M, 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.

(G) Organic Peroxide Furthermore, the organic peroxide used in the present invention is not particularly limited, but it is preferable that the decomposition temperature (the temperature at which the half-group is 1 minute) be 120 ° C. or higher, particularly 130 A temperature of at least ° C is suitable. Representative examples of suitable organic peroxides are ketone peroxides such as 1,1-bis-tertiary-butylperoxy-3,3,5-trimethylcyclohexane,
2,5-dimethylhexane-2; hydroperoxide such as 5-dihydroperoxide, 2,5-dimethyl-
Examples thereof include peroxyesters such as 2,5-di-tertiary butylperoxyhexane and diacyl peroxides such as benzoyl peroxide.

Further, polyfunctional substances such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, triallyl trimellitate and metaphenylene bismaleimide which are used as a crosslinking aid in the usual rubber field may be blended. .

(H) mixing ratio copolymer (a) in the mixture of the present invention, the copolymer (b) and the copolymer (c) and the copolymer (a) in the total amount of the copolymer (d) The mixing ratio of the copolymer (b) and the copolymer (c) is 1 to 99% by weight as a total amount thereof, preferably 2 to 98% by weight, particularly preferably 5 to 95% by weight, and particularly preferably
10 to 90% by weight is preferred. Even when the mixing ratio of the copolymer (a) or the copolymer (c) in the copolymer (a) or the copolymer (d) is less than 1% by weight as a total amount thereof,
Even if it exceeds 99% by weight, the crosslinkability of the mixture is insufficient and the heat resistance of the obtained crosslinked product is not good.

Further, the carboxylic acid ester plasticizer, the reaction accelerator (when added) and the organic peroxide (when added) relative to 100 parts by weight of the total amount of the copolymer (a) or the copolymer (d) are as follows. On the street.

The amount of the carboxylic acid ester plasticizer is 1 to 50 parts by weight, preferably 1 to 40 parts by weight, and particularly preferably 2 to 35 parts by weight. If the mixing ratio of the carboxylic acid ester plasticizer is less than 1 part by weight, when the resulting mixture is crosslinked, the effect of improving the transparency of the crosslinked product is poor. On the other hand, even if added in an amount of more than 50 parts by weight, the transparency is not further improved, bleeding occurs, and the mechanical properties and heat resistance of the crosslinked product deteriorate.

When adding a reaction accelerator, the mixing ratio is
The amount is 0.005 to 5.0 parts by weight, preferably 0.01 to 5.0 parts by weight, and particularly preferably 0.01 to 2.0 parts by weight. 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 inhibitory effect by the reaction promoting agent itself may occur, but the reaction promoter may not May cause bleeding on the surface,
It is not preferable because a good molded product cannot be obtained.

Furthermore, when an organic peroxide is added, its mixing ratio is generally 0.001 to 10.0 parts by weight, preferably 0.005 to 10.0 parts by weight, and particularly preferably 0.01 to 7.0 parts by weight. If the organic peroxide is added in excess of 10.0 parts by weight, crosslinking will occur rapidly and it will be difficult to control crosslinking.

(J) Production of Mixture In producing the mixture of the present invention, the copolymer (a)
Or any one of the copolymers (c), the copolymer (d), the carboxylic acid ester plasticizer, the reaction accelerator or the organic peroxide (when both are added) may be used alone. Well, two or more kinds may be used in combination.

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 more uniform mixture can be produced by dry-blending in advance and melt-mixing the obtained mixture, and further by using a static mixer or the like at the tip of the extruder.

In addition, when mixing in a molten state, it is necessary to perform it under the condition that the olefin-based copolymer used does not substantially undergo a crosslinking reaction.

However, if a reaction occurs during mixing, a uniform composition cannot be obtained, and therefore not only the moldability at the time of molding the composition is deteriorated, but also the shape of the desired molded article or the molded article is cross-linked. In this case, heat resistance and the like are reduced, which is not preferable.

Therefore, in the case of melt-mixing, it depends on the viscosity of the olefin-based copolymer at each temperature, but generally 25 ° C (room temperature) to
It is desirable to carry out at a relatively low temperature of 200 ° C., preferably 70 to 180 ° C., preferably 70 to 160 ° C., in a short time of about several minutes.
For this reason also, the softening temperature or the normal crystal melting temperature of the olefin-based copolymer is 160 ° C. or lower, particularly 140 ° C. or lower is suitable, and it is convenient that the fluidity is as large as possible.

In addition, in the case of producing the mixture of the present invention, of the antioxidants, ultraviolet deterioration inhibitors, foaming agents, foaming aids, metal deterioration inhibitors, flame retardants and pressure-sensitive adhesives that are commonly used in the field of olefin polymers. Fillers such as additives and carbon black can be added.

(K) Method for producing crosslinked product (crosslinked polymer) The mixture obtained as described above can be formed into a molded article 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 cross-linking after obtaining a kneaded and molded precursor, a molded article may be obtained by injection molding, extrusion molding, laminate molding, and roll processing, and then heated and cross-linked. 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 by using a T-die film forming machine or the like, and the film or sheet is laminated on one or both sides of various substrates such as aluminum, paper, copper, polyimide resin, nylon and polysulfone. A sheet having an appropriate thickness may be prepared by heating or by rolling the composition with a roll or a calender roll, and the composition may be sandwiched between the substrates to be bonded and then hot-pressed at a high temperature for bonding. . Or
A composite material having a large heat resistance and a large adhesive strength can be obtained by carrying out a two-layer or multi-layer lamination by a method similar to a method generally known as extrusion lamination and then performing a heat treatment at a high temperature.

Further, the crosslinked film of the composition can also be formed by sandwiching the uncrosslinked T-die film or sheet obtained by the above-mentioned method with a film such as Teflon and heating and pressing the film. it can.
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.

The heating temperature for crosslinking varies slightly depending on the type and proportion of each comonomer composition of each olefin-based copolymer used, but is generally 150 ° C or higher, especially 160 ° C.
The above is desirable.

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.

In producing the crosslinked product of the present invention, the mixture is extruded, injection-molded, blow-molded, laminate-molded, roll-processed, vacuum-molded, pre-formed into a film by pressure molding, etc. Linear crosslinking may be performed.

(J) Electron beam cross-linking The electron beam cross-linking method includes various types of electrons such as Cockcroft type, Cockcroft Walton type, Bandegraph type, insulating core transformer type, linear type, dynamitron type, high frequency type, and electro curtain type. There is a method of emitting an electron beam from a linear accelerator. The irradiation dose can be varied within a wide range depending on the required performance of the irradiated object. Generally 0.5-200Mrad, 1.0-200Mr
ad is preferable, and 1.0 to 150 Mrad is particularly preferable.
If the irradiation dose is less than 0.5 Mrad, the degree of crosslinking will be insufficient.
On the other hand, if it exceeds 200 Mrad, molecular breakage occurs and the physical properties of the crosslinked product deteriorate. The acceleration voltage is usually 50 to 1000 KV, preferably 100 to 1000 KV, and particularly preferably 100 to 800 KV.

As an atmosphere for crosslinking, it is desirable to carry out in an inert gas if necessary. Typical examples of the inert gas include nitrogen, carbon dioxide gas, helium and the like.

The cross-linked product thus obtained may be further heated as described above.

In order to sufficiently express the adhesiveness and heat resistance of the crosslinked polymer comprising the mixture of the present invention, the gel fraction of the crosslinking reaction product of the olefinic copolymer is preferably 10% or more, 30
% Or more is suitable, and especially a gel fraction of 50% or more is optimum, and it is necessary to adopt such conditions. Also,
According to JIS K-7210, the fluidity index under a load of 2.16 kg and a temperature of 190 ° C is 0.01 g / 10 minutes or less.

The gel fraction was measured by placing the crosslinked polymer sample in a 300-mesh wire net, soxhlet-extracting with boiling toluene for 6 hours, and then drying the wire wire at 80 ° C for 16 hours, measuring the weight, and remaining in the wire net. The weight is calculated and displayed as a weight percentage.

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

The copolymers used in Examples and Comparative Examples
The physical properties and production methods of (a), copolymer (b), copolymer (c) and copolymer (d) are shown below.

[(A) copolymer (a)]

As the copolymer (a), the copolymerization ratio of methacrylic acid is 6.0.
Mol%, and the copolymerization ratio of methyl methacrylate is
3.5 mol% ethylene-methacrylic acid-methyl methacrylate terpolymer [MI 22.5 g / 10 min, melting point
79.5 ° C., hereinafter referred to as “(a-1)” and an ethylene-acrylic acid copolymer having a copolymerization ratio of acrylic acid of 8.1 mol% [MI 270 g / 10 minutes, melting point 84.0 ° C., hereinafter “(a
-2) ”is used].

[(B) copolymer (b)]

As the copolymer (b), an ethylene-methyl methacrylate copolymer having a copolymerization ratio of methyl methacrylate of 8.5 mol% [MI 20.6 g / 10 minutes, melting point 83.2 ° C.] 5.0 Kg
Was placed in a mixture 50 having a toluene: isobutyl alcohol ratio (volume) of 6: 4. Further, sodium hydroxide was added in an amount of 0.5 times the molar amount of methyl methacrylate, which is a copolymerization component in the copolymer, and the reaction was carried out for 3 hours while stirring under reflux conditions. Then, the mixture was cooled to 60 ° C. and water 10 was added with stirring to obtain polymer particles. The polymer particles were washed with a large amount of water to completely remove unreacted sodium hydroxide, and then dried at 60 ° C. under reduced pressure for 12 hours. According to the infrared absorption spectrum, 41% of methyl methacrylate was a metal salt.

4.0 Kg of this copolymer was dispersed in 50 parts of water, 1.25 times mol of hydrochloric acid was added to the metal salt, and the mixture was stirred at 60 ° C. for 3 hours and then washed with water 3 times to remove hydrochloric acid in the washing liquid. I confirmed that it was not recognized. The polymer thus obtained [hereinafter referred to as (b-1)] was dried at 60 ° C. under reduced pressure for one day. It was confirmed by infrared absorption spectrum that all the metal salts were carboxyl groups.

((C) copolymer (c))

Further, as the copolymer (c), the copolymerization ratio of methyl methacrylate is 8.2 mol%, the copolymerization ratio of maleic anhydride is 1.6 mol% ethylene-methylmethacrylate-maleic anhydride ternary copolymer Combined [MI 82.2g / 10
Min., Melting point 79.3 ° C., hereinafter referred to as “(c-1)”, ethylene-ethyl acrylate-having a copolymerization ratio of ethyl acrylate of 9.5 mol% and a copolymerization ratio of maleic anhydride of 2.6 mol%. Maleic anhydride terpolymer (MI 210 g / 10 min, melting point 69.1 ° C) 5.0 Kg was dissolved in 50 toluene, and 20 parts of water and 3 parts of maleic anhydride were added.
A double mole of triethylamine was added, and the mixture was heated at a temperature of 80 ° C. for 5 hours with stirring. Then, hydrochloric acid was added to neutralize the mixture, and hydrochloric acid was added to the mixture until it became weakly acidic, and the mixture was allowed to stand overnight. Then, hexane was added as a precipitation solvent to precipitate the polymer, and hexane was exchanged several times to wash the polymer. After that, the polymer was vacuum dried at a temperature of 40 ° C. overnight.

The hydrolysis rate of this polymer [hereinafter referred to as "(c-2)"] was calculated from the decrease in absorption due to the acid anhydride at 1760 cm ^-1 by IR measurement. As a result, 100% hydrolysis and dicarboxylic acid oxidation were carried out. Was there. In addition, the copolymerization ratio of methyl methacrylate is 8.7 mol%, and the copolymerization ratio of maleic anhydride is 1.8 mol%, ethylene-methyl methacrylate-maleic anhydride terpolymer [MI 115
5.0 kg was dissolved in 50 toluene, and methyl alcohol 20 and triethylamine 200 ml were added, and the mixture was reacted for 6 hours under the reflux condition of methyl alcohol. Then, hexane was added as a precipitation solvent to precipitate the polymer, and hexane was exchanged several times to wash the polymer. Then, the polymer was vacuum-dried at 40 ° C. overnight.

The half-esterification rate of the obtained polymer [hereinafter referred to as (c-3)] was calculated from the decrease in absorption due to the acid anhydride at 1760 cm ⁻¹ by IR measurement, and it was found to be 83% maleic anhydride. Was half-esterified. Further, as the copolymer (c), 100 parts by weight of an ethylene-methyl methacrylate copolymer having a copolymerization ratio of methyl methacrylate of 9.8 mol% (MI 109 g / 10 min, melting point 73.2 ° C.) was used with a Banbury mixer. 40 at 185 ℃
While kneading at rotation / minute, after adding 3.0 parts by weight of maleic anhydride, 0.75 parts by weight of dicumyl peroxide was added in 5 batches, kneading for 10 minutes, and using a vacuum dryer.
After drying under reduced pressure at 160 ° C. for 6 hours, a copolymer grafted with maleic anhydride was obtained. The grafted maleic anhydride was 1.8% by weight based on the copolymer.
This copolymer was hydrolyzed under the same conditions as in the above (c-2). The hydrolysis rate of the obtained hydrolyzate [hereinafter referred to as "(c-4)"] was 92% of the theoretical value.

[(D) copolymer (d)]

Further, as the copolymer (d), the copolymerization ratio of allyl glycidyl ether is 3.2 mol%, and the copolymerization ratio of methyl methacrylate is 8.2 mol% ethylene-
A copolymerization ratio of allyl glycidyl ether-methyl methacrylate terpolymer [MI 130 g / 10 min, melting point 73.2 ° C., hereinafter referred to as "(d-1)"] and glycidyl methacrylate is 2.3 mol%, and The copolymerization ratio of vinyl acetate is 2.0 mol% ethylene-glycidyl methacrylate-vinyl acetate terpolymer [MI 7.2
g / 10 minutes, melting point 94.5 ° C., hereinafter referred to as (d-2) ”.

Also, as a carboxylic ester plasticizer, dibutyl
Phthalates (hereinafter "DBP"), di-2-ethylhexyl phthalate (hereinafter "DOP") and dioctyl sebacate (hereinafter "DOS") were used.

Examples 1 to 8 and Comparative Examples 1 to 5 Copolymers (a) whose types and amounts are shown in Table 1
Further, the copolymer (c) and the copolymer (d) and the carboxylic acid ester plasticizer were dry blended in advance for 3 minutes using a Henschel mixer to prepare a mixture. Using a single-screw extruder having a cylinder portion having a diameter of 30 mm, the mixture was mixed at a temperature of 120 ° C. or lower to obtain a mixture having a ratio shown in Table 1. These mixtures have a cylinder diameter of
Using a 40mm T-die film forming machine, C in the cylinder part
₁ , C ₂ , C ₃ and die temperature 110 ℃, 1 respectively
Film formation was carried out at 15 ° C., 120 ° C. and 125 ° C., and in each case, a clean film having a gel thickness of 30 μm to 1.0 mm and no fish eyes was obtained.

These films are made into a copper foil / film / copper foil sandwich on a copper foil having a thickness of 35 μm, and are preheated at a temperature of 200 ° C. and 230 ° C. for 0.5 minutes and pressed at a pressure of 20 Kg / cm ² for different times, 0.1
An 8 mm adhesive plate was obtained. The adhesive strength of the obtained adhesive plate at room temperature (23 ° C) (T-type peeling JIS K6854, tensile speed is 100 mm
/ Min) was large as shown in Table 1. The gel fraction of each sample at this time is also shown in Table 1.

Further, Teflon sheets were placed on the upper and lower sides of the non-crosslinked T die film, and a sheet having a thickness of 0.19 mm was prepared at a temperature of 200 ° C. and 230 ° C. in the same manner as the adhesive plate. These are 200 ℃, 2
The film was allowed to stand in a constant temperature oven at 50 ° C. for 30 minutes and the state of the film was observed. The results are shown in Tables 2 and 3.

In addition, the non-crosslinked T-die film is a glass plate (thickness: 2 m
m) was pressed in a sandwich form under the same conditions as above to obtain a plate having a thickness of 4.17 mm. The haze (haze value, measured according to ASTM D-1003) when this sample was annealed at 60 ° C. for 36 hours was measured. Examples 1 to 8 containing a plasticizer
It is clear that, as shown in Table 1, the transparency is superior to Comparative Examples 1 to 5 in which no plasticizer is added.

In the heat resistance test, even if the film was soaked at a temperature of 200 ° C. for 10 minutes and 30 minutes and at a temperature of 250 ° C. for 3 minutes, no abnormal change was observed in the film in any of the Examples and Comparative Examples. Could not be acknowledged (as it was in its original form).

Examples 9 to 12 The samples shown in Table 2 (however, the mixing ratio is 50:50 by weight) and 100 parts by weight of the total amount of these copolymers as DBP as a plasticizer (however carried out In Example 11, 10 parts by weight of DOP) was added, and a mixture was obtained by mixing at a speed of 120 ° C. or lower at 40 revolutions / minute for 3 to 4 minutes using a mixin grouter of Labo Plastomil. next,
0.5 by using 85 ℃ roll (Teflon coating)
A sheet having a thickness of ~ 1.0 mm was prepared. These were sandwiched between Teflon sheets and pressed at a temperature of 190 ° C. for 10 minutes at a pressure of 20 kg / cm ² to prepare a crosslinked sheet.

Table 2 shows the data of gel fraction, heat resistance and volume resistivity [room temperature (21 ° C.), relative humidity: 53% and 97%] of these crosslinked sheets.

The volume resistivity (electrical insulation) is Yokogawa Hurret-Packart Model 4329A, and the test voltage is 500.
V, charge time 30 seconds, measurement time 2 minutes after charge
It was measured under the conditions of 30 seconds and disk charge of 2 minutes.

The heat resistance test was performed in a constant temperature oven (230 ° C)
No deformation was observed in any of the pressed sheets when left for 0 minutes (the original shape).

Example 13 Uncrosslinked T-die film obtained in Example 5 (thickness 150 μm
m) Energy Science Incorporated
An electron curtain type electron beam accelerator manufactured by (Energy Seiences Incorporated) was used to perform electron beam irradiation in a nitrogen atmosphere at an accelerating voltage of 175 KV and an irradiation dose of 5 Mrad. The gel fraction of this irradiated film was 29.6%.

This irradiated film was preheated to a sandwich of copper foil / film / copper foil as in Example 5 at a temperature of 230 ° C. and preheated to 0.5.
Min, and pressed at a pressure of 20 kg / cm ² for 10 minutes to obtain a 0.20 mm adhesive plate. The adhesive strength of the obtained adhesive plate at room temperature is 3.6 Kg /
The value was 25 mm, which was a remarkably large value. The gel fraction at this time was 84.9%.

The electron beam-irradiated film was pressed with a glass plate under the same conditions as in Example 5 to obtain a 4.14 mm plate. This sample was allowed to stand in an atmosphere of 120 ° C. (in a constant temperature oven) for 1 hour, then the temperature was lowered by 15 ° C. per hour, and when it reached 60 ° C., it was annealed for 36 hours. Then, the temperature was naturally cooled to room temperature, and the haze was measured and found to be 0.4%.

The same film as described above was pressed with a glass plate under the same conditions as in Example 5 without irradiating with an electron beam, and the thickness was
A 4.13 mm plate was obtained. When this sample was treated under the same conditions as above, the haze was 1.1. From this, it is understood that the transparency is further improved by irradiating the electron beam.

Examples 14 to 17 (a-2) and (d-2), (c-2) and (d-2) are mixed in a mixing ratio of 70:30 by weight, and the total amount of these copolymers is 100% by weight. As a plasticizer, 10 parts by weight of DOS and 0.8 parts by weight of N, N-dimethylbenzylamine (however, Examples 16 and 17 were not compounded) were dry blended for 5 minutes using a Henschel mixer. Each of the obtained mixtures was kneaded at 40 ° C./min for 3 minutes at a temperature of 120 ° C. using a Laminoplast mill mixin grouter. Each of the obtained mixtures was sandwiched between Teflon sheets and pressed at 120 ° C. under a pressure of 20 kg / cm ² for 2 minutes, and 1
An 80 μm film was made. Each film has a thickness of 35μ
m copper foil is sandwiched with copper foil / film / copper foil, preheated at a temperature of 170 ° C for 0.5 minutes, and pressed under a pressure of 20 Kg / cm ² for 10 minutes to obtain an adhesive plate with a thickness of 0.21 mm. Obtained.
The adhesive strength of each obtained adhesive plate was measured in the same manner as in Examples 1 to 8. The adhesive strength of each sample and the gel fraction of each film are shown in Table 3.

In addition, the non-crosslinked film is interposed between glass plates (thickness: 2 mm) and pressed under the same conditions as above, and the thickness is 4.13 mm.
Got the plate. The haze (cloudiness value) of each of these samples was measured under the same conditions as in Examples 1 to 8. Third each haze
Shown in the table.

From the above results, Examples 14 and 15 to which N, N-dimethylbenzylamine was added as a reaction accelerator were compared with Examples 16 and 17 corresponding to those to which N, N-dimethylbenzylamine was not added, respectively, at low temperature. Highly crosslinkable (high gel fraction). Moreover, it is clear that the transparency is excellent.

The mixing ratio (weight ratio) of (a-2) and (d-2) is 50:
50 copolymer components and the total amount of these copolymers 10
A mixture consisting of 10 parts by weight of DBP as a plasticizer (hereinafter referred to as "a") to 0 parts by weight, and the mixing ratio (weight ratio) of (b-1) and (d-2) is 50:50. A mixture comprising a certain copolymerization component and 10 parts by weight of DOP as a plasticizer for 100 parts by weight of the total amount of these copolymers (hereinafter referred to as "b"), (c-3) and (d-1). Mixing ratio with (weight ratio)
Is 50:50 and a mixture of 10 parts by weight of DOP as a plasticizer per 100 parts by weight of the total amount of these copolymers (hereinafter referred to as "c") and (a-2) alone. (Hereinafter referred to as "d"), (b-1) alone (hereinafter referred to as "e")
, (C-3) alone (hereinafter referred to as "f") and (d-2) alone (hereinafter referred to as "g"), respectively, a curast meter (manufactured by Toyo Baldwin Co., Ltd., model JSR-III).
Type) was used to determine the cross-linking curve at a temperature of 190 ° C. The results are shown in FIG.

From FIG. 1, it is clear that the mixture of the copolymers containing the plasticizers such as a, b, and c shows an increase in torque, and the crosslinking reaction is progressing. With the polymer alone, no increase in torque was observed, and it is clear that the crosslinking reaction did not occur.

EFFECTS OF THE INVENTION The uncrosslinked composition obtained by the present invention has good flowability and excellent processability, and therefore various molded products such as films, sheets and pipes can be easily produced.

Further, the cross-linked polymer obtained by the present invention has excellent electrical insulating properties like general thermoplastic resins.

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

1) Regarding heat resistance, it generally does not cause discoloration, foaming or deformation even at a temperature of 250 ° C or higher, and even at 300 ° C or higher for a short time. In particular, the heat resistance of the product obtained is excellent even when molded under the commonly used molding conditions.

2) Regarding the transparency, even if it is bonded to glass and heat-treated at 60 ° C for 36 hours and then cooled (natural cooling), no whitening is observed and transparency is excellent.

3) The heat resistance of the film or sheet is good, so peeling does not occur at high temperatures.

4) Due to the excellent water resistance of the film or sheet,
No peeling occurs in high humidity or in water.

5) Regarding the adhesiveness, when the uncrosslinked composition according to the present invention or the precursor obtained by molding (for example, a film or sheet) is brought into close contact with the third substance and then crosslinked by heating, the third substance Is to adhere strongly. As the third substance, aluminum, copper, iron,
Modified polyolefin polymers obtained by grafting metals and alloys such as stainless steel, brass, galvanized iron, tinplate, glass, ceramics, amide, imide resin, polyester, cellophane, various papers and monomers having polar groups Examples thereof include synthetic resins having a polar group.

Since the composition obtained by the present invention and the crosslinked product thereof have the above-mentioned 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. It has excellent chemical resistance, excellent moisture resistance, and excellent etching characteristics and plating characteristics. Therefore, it can be used to seal printed circuit board laminates, flexible wiring boards, and electrolytic capacitors. It is suitable for various electric and electronic devices such as electronic materials such as materials. Furthermore, it has good adhesion to glass,
Moreover, because of its excellent transparency, there are glass for windshields of automobiles, glass for buildings, glass for ships, and interlayer films of glass for vehicles other than automobiles.

[Brief description of drawings]

FIG. 1 shows a mixture of (a-2), (a-2) and DBP (a), (b-1), (d-2) and a mixture of DOP (b) and (c-3), (d). -1) and a mixture with DOP (c) and (a-2) alone (d), (b-
1) Single (e), (c-3) Single (f) and (d-
2) It is a crosslinking curve of (g) alone. In this figure, the vertical axis represents torque (Kg-cm) and the horizontal axis represents crosslinking time (minutes).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hitoshi Funada Oita-shi, Oita Prefecture Nakanosu 2 Showa Denko KK Oita Laboratories (56) References JP-A-59-56442 (JP, A) JP-A-55 -131033 (JP, A) JP-A-55-127450 (JP, A) JP-A-61-238846 (JP, A)

Claims (1)

[Claims] 1. (A) (1) A copolymer comprising at least an olefin and an unsaturated monocarboxylic acid, and (2) an olefinic copolymer comprising at least an olefin and an unsaturated carboxylic acid ester is saponified and deoxidized. Copolymers obtained by metal treatment and (3) at least one copolymer selected from the group consisting of copolymers of at least olefin and unsaturated dicarboxylic acid, its anhydride or its half ester (I) A mixture of (B) a copolymer (II) of at least an olefin and an unsaturated monomer having an epoxy group capable of radical copolymerization, and (C) a carboxylic acid ester-based plasticizer, and a copolymer (I) Copolymer (II)
The mixing ratio of the copolymer (I) in the total amount of
It is 99% by weight, and the mixing ratio of the carboxylic acid ester plasticizer with respect to 100 parts by weight of the total amount of these copolymers is 1 to
50 parts by weight of olefin-based copolymer mixture.