JPS6356520A - Crosslinkable compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound, consisting of a copolymer of an olefin and unsaturated (di)carboxylic acid and a polyfunctional epoxy resin, capable of providing a crosslinkable polymer having excellent heat resistance and having good adhesion to metal, etc. CONSTITUTION:The aimed composition, consisting of a crosslinkable compound composed of (A) a copolymer having 15,000-150,000mol.wt. consisting of (i) a copolymer of an olefin and unsaturated monocarboxylic acid, (ii) a copolymer obtained by saponifying and neutralizing an olefinic copolymer of an olefin and unsaturated carboxylic acid and/or (iii) a copolymer of an olefin and unsaturated dicarboxylic acid (half ester) and (B) epoxy resin containing >=2 epoxy groups in one molecule and containing 5-80wt% component (B).

Description

DETAILED DESCRIPTION OF THE INVENTION ,--1 The present invention relates to a mixture capable of producing a heat-resistant crosslinked polymer, which not only has heat resistance sufficient to withstand hanging, but also has crosslinking properties. The object of the present invention is to provide a crosslinked product which is relatively simple and which also provides good adhesion to metals and the like.

So far, compositions consisting of polyvinyl alcohol with a degree of saponification of 85% or less and an olefin copolymer containing 10% by weight or less of a copolymerized unsaturated carboxylic acid or its acid anhydride have been developed. It has been proposed (Japanese Unexamined Patent Publication No. 55-12745
0), but this is related to a resin composition for a heat-retaining film, and its purpose is to improve the uniform dispersibility of heat-retaining polyvinyl alcohol and olefin copolymer. It could not be used as a resin or a crosslinking composition.

Furthermore, resin compositions for packaging materials comprising ethylene-vinyl acetate copolymers and copolymers of olefins and unsaturated carboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, or derivatives thereof have also been proposed ( Japanese Unexamined Patent Publication 1973-
131033), this composition is suitable as a packaging material for packaged items that requires moisture resistance, which is easy to cut with a knife, etc., while having gas permeation resistance. It cannot be used as a composition.

Currently, there is a strong demand for polymeric materials that have good heat resistance and excellent adhesion to metals and the like in the fields of electrical and electronic devices. There are many polymer materials that have good adhesion to metals and the like at room temperature, and polyester resins and polyimide resins have been proposed as polymer materials that have excellent heat resistance and adhesion. However, polyester resin has drawbacks such as high water absorption and a large coefficient of thermal expansion at 20°C to 250°C. Furthermore, polyimide resins have drawbacks such as insufficient adhesion to metals and the like due to poor surface activity.

Furthermore, thermosetting resins, room temperature curing resins, and photocuring resins are widely used in these fields, but these curing resins have relatively long curing times, making manufacturing efficiency difficult. Not only is this bad, but it also shortens the life of parts due to its hygroscopic properties.

The results show that the present invention does not have these drawbacks (problems) and not only has excellent heat resistance, but also improved moisture absorption, shortened curing time, and the ability to cure materials such as metals. It is an object of the present invention to obtain a mixture or a crosslinked product of an olefin polymer that also has good adhesion to various materials.

. According to the invention and the present invention, the above problems are solved by (I) (1) A copolymer consisting of at least an olefin and an unsaturated monocarboxylic acid [hereinafter referred to as "copolymer (A)"]
(2) At least mo? A copolymer obtained by saponifying and neutralizing an olefin copolymer consisting of L/fin and an unsaturated carboxylic acid ester [hereinafter referred to as "copolymer (B)"], and (3) at least an olefin. and an unsaturated dicarboxylic acid or its halfester [hereinafter referred to as "copolymer (C)"]. and (II) a crosslinkable composition consisting of an epoxy resin having at least two epoxy groups in one molecule, wherein the mixing ratio of the epoxy resin in the mixture is 5 to 80% by weight. can do. The present invention will be explained in detail below.

(A) Copolymer (A) The copolymer (A) is a copolymer of at least an α-olefin and an unsaturated monocarboxylic acid.

In consideration of moldability, the copolymer is preferably one that melts at a temperature of 150° C. or lower and has fluidity.

In order to ensure this property, it is preferable to use a material copolymerized with a radically 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, preferably 3 to 10 carbon atoms. Representative examples include acrylic acid, methacrylic acid, and crotonic acid. It will be done.

The α-olefin is preferably an α-olefin having 2 to 12 carbon atoms (preferably 2 to 8 carbon atoms), examples of which include ethylene, propylene, butene-1, etc., with ethylene being particularly preferred. be.

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

The unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and preferably 4 to 20 carbon atoms. As the representative side, those with good thermal stability such as methyl (meth)acrylate and ethyl (meth)acrylate are preferable, and 1-
Materials with poor thermal stability such as butyl (meth)acrylate are undesirable because they cause foaming.

Furthermore, the alkoxyalkyl (meth)acrylate usually has at most 20 carbon atoms. Moreover, those in which the alkyl group has 1 to 8 carbon atoms (suitably, 1 to 4 carbon atoms) are preferable, and those in which the alkoxy group has 1 to 8 carbon atoms (suitably, 1 to 4 carbon atoms) are preferable. Representative examples of preferable alkoxy(meth)alkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate, and butoxyethyl acrylate. In addition, the number of carbon atoms in vinyl ester is generally at most 20 (
Typical examples include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl bivalate.

In the copolymer (A), the amount of the third component is preferably 25 mol% or less, particularly preferably 2 to 20 mol%, and even if it exceeds 25 mol%, the characteristics of the present invention are expressed, but It is not necessary to exceed 25 mol%, which is unfavorable from the viewpoint of production and economy.

The amount of bonds in the copolymer (A) of unsaturated monocarboxylic acid is
The content is desirably 0.5 mol% or more and 25 mol% or less, and particularly preferably 1.0 mol% to 15 mol%. Although the present invention also includes graft copolymerization of 0.5 mol % or more of an unsaturated monocarboxylic monomer to an olefin copolymer as described below, block or random copolymers are preferable, particularly random copolymers. Polymers are preferred.

The unsaturated monocarboxylic acid is used as a crosslinking reaction site with the epoxy resin described later and to provide adhesiveness to a wide variety of base materials, and from either point of view, it is not necessary to have an excessive amount. If this happens, water absorption becomes high, which not only has negative effects such as foaming during molding and deterioration of electrical properties due to water absorption after molding, but also causes manufacturing problems such as safety, separation, and recovery, and is also economically problematic. This is disadvantageous and undesirable. On the other hand, if it is less than 0.5 mol %, there will be no problem in terms of adhesiveness, but it will be insufficient in terms of heat resistance, which is not preferable.

The copolymer (A) is a mixture of an α-olefin and an unsaturated carboxylic acid, or a mixture of these and a third component.
Under ultra-high pressure of 500Kg/c rn”, 120~28
Radical polymerization at a temperature of 0°C, optionally with a chain transfer agent, in a stirred autoclave or tubular reactor, using a free radical generator such as peroxide, or optionally followed by a free radical generator. It can be obtained by graft copolymerizing an unsaturated carboxylic acid in the coexistence of an unsaturated carboxylic acid.

(B) Copolymer (B) Furthermore, the copolymer (B) used in the present invention is
A copolymer obtained by saponifying some or all of the ester groups in an olefin copolymer consisting of the above-mentioned α-olefin and an unsaturated carboxylic acid ester, and performing a neutralization reaction such as demetalization treatment. It is preferable to melt at a temperature of 150°C or less and have fluidity.

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

The content of the unsaturated carboxylic acid ester in the copolymer (B) is preferably 1 to 25 mol%. , in terms of carboxylic acid-containing units in the copolymer after neutralization, is preferably from 0.5 to 20 mol%, particularly preferably from 1 to 15 mol%.

The saponification reaction can be carried out by a widely known method, for example, by adding NaOH and a copolymer containing an ester group to a mixture of toluene and isobutyl alcohol (mixing ratio 50:50) and refluxing for 3 hours. The saponification rate can be arbitrarily adjusted by adjusting the amount of NaOH. Furthermore, this saponified product is precipitated with water or alcohol, and after filtering the solvent, it is vacuum-dried at 50° C. day and night. The olefin copolymer (B) is obtained by dispersing this polymer in water, adding sulfuric acid thereto, and stirring the mixture at 70° C. for 1 hour to perform a metal removal treatment (=neutralization reaction).

(C) Copolymer (C) In addition, the copolymer (C) used in the present invention is a copolymer of the above-mentioned α-olefin and an unsaturated dicarboxylic acid or its monoester (the above-mentioned third In other words, a direct copolymerization of an α-olefin and an unsaturated dicarboxylic acid or a monoester thereof, or a direct copolymerization of these and the third component is preferable. An olefinic copolymer of a saturated dicarboxylic acid anhydride (which may contain the third component) may be modified to dicarboxylate or halfesterize some or all of the acid anhydride groups. Good, one that melts at a temperature of 150°C or less is good.

α-olefin and copolymer (A) as the third component
The same type of compounds can be mentioned.

When producing the copolymer (C) by a direct copolymerization method,
Unsaturated dicarboxylic acids or monoesters thereof are selected as comonomers.

The number of carbon atoms in the unsaturated dicarboxylic acid is usually at most 20.
4 to 12 are particularly preferred. Representative examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and 3,6-endomethylene-1,2,3,6-titrahydrosis-phthalic acid (nadic acid).

The unsaturated dicarboxylic acid monoester generally has at most 40 carbon atoms, particularly those having 5 to 20 carbon atoms. A typical example thereof is one in which one of the carboxyl groups of the dicarboxylic acid is halfesterified with a representative example of an alcohol described below. Representative examples of the alcohol include some alcohols having at most 20 carbon atoms, such as methanol, ethanol, propatool, and butanol. Typical examples of Hafestel include maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester, maleic acid monobutyl ester, and itacon-derived monoethyl ester.

The copolymer of "unsaturated dicarboxylic acid or its monoester" (hereinafter referred to as "unsaturated dicarboxylic acid component") (
The amount of bonding in C) is preferably 0.5 mol% or more and 20 mol% or less, more preferably 1.0 to 15 mol%. In addition, a copolymer of an olefin and the third component grafted with 0.5 mol % or more of an unsaturated dicarboxylic acid component as described later may also be used. The unsaturated dicarboxylic acid component serves as a crosslinking reaction site with the epoxy resin described below and to provide adhesiveness to various base materials, and there is no need for it to be present in excess in either respect.

When the copolymer (C) used in the present invention is obtained by modifying a copolymer of an unsaturated dicarboxylic acid anhydride, the starting olefin copolymer is an α-olefin and an unsaturated dicarboxylic acid. Graft copolymerizing the anhydride of the unsaturated dicarboxylic acid onto the anhydride or a copolymer obtained by copolymerizing these and the third component, and a copolymer of α-olefin and the unsaturated dicarboxylic ester. It is selected from copolymers obtained by

Modification is carried out, for example, by hydrolysis and/or halfesterification with the alcohols mentioned above.

As a result of modification, the copolymer (C) obtained in this way has
A copolymer containing a structural unit in which a carboxyl group is bonded to an adjacent carbon atom and/or a structural unit in which a carboxyl group and a carbalkoxy group are bonded to an adjacent carbon atom.

The total proportion of these modified structural units in the olefin copolymer (C) is preferably 0.5 to 20 mol%, more preferably 1.0 to 20 mol%. be.

In the copolymer (C), unsaturated dicarboxylic acid, its anhydride, or its monoester used as a copolymerization component or unsaturated dicarboxylic acid, its anhydride, or its monoester are grafted together. α- used as starting material for polymerization
Used for copolymers of olefins and unsaturated carboxylic acid esters.

As the unsaturated carboxylic ester, the same unsaturated carboxylic ester as described above can be used.

The content in the copolymer is preferably 25 mol% or less, particularly preferably 2 to 20 mol%. Even if it exceeds 25 mol %, the characteristics of the present invention will be exhibited, but production will be difficult in that range and there will be no economic advantage.

In the case of graft copolymerization, any of various known production methods (eg, solution method, suspension method, melt method) can be employed.

Among these production methods, to explain the melt method as an example, when graft copolymerizing an anhydride of an unsaturated dicarboxylic acid to the copolymer of the α-olefin and an unsaturated carboxylic acid ester, a general synthesis method is used. Melting mixers used in the resin field (e.g. extrusion 4!1)
It can be obtained by melt-kneading the copolymer, an anhydride of an unsaturated dicarboxylic acid, and a radical initiator described below using the above-mentioned method. The crosstalk temperature in this case varies depending on the type of copolymer and radical initiator used, but it ranges from 330 to 330 degrees above the melting point of the copolymer used.
The temperature range is below ℃. Generally, the temperature is 120 to 270°C. As a radical initiator.

Organics such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-5,5-di(tert-butylperoxy)hexane-3, and benzoyl peroxide. Examples include overbreeding products.

In this case, the ratio of the unsaturated dicarboxylic acid anhydride to 100 parts of the above-mentioned copolymer is usually 0.01 to 0.01 from the viewpoint of the physical properties and economical efficiency of the resulting graft copolymer.
The amount is preferably 5.0 parts by weight, preferably 0.05 to 5.0 parts by weight, and particularly preferably 0.1 to 5.0 parts by weight.

In addition, the melt index (JIS K-7210
Measured at a temperature of 190°C and a load of 2.18 kg, hereinafter rM, 1. J) are usually 0.5.
g/10 minutes or more, preferably 5.0 g/710 minutes or more, particularly preferably 50 g/1G minute or more. Further, the average molecular weight is 15,000 to 150,000, preferably 20,000 to 150,000, particularly 2
0,000 to 120,000 is suitable. If a copolymer (A), copolymer (B), or copolymer (C) with an average molecular weight of less than 15,000 or more than 150,000 is used, it may be difficult to use extrusion molding, lamination molding, etc. as described below. molded products (e.g. films, sheets)
Good molded products cannot be obtained when manufacturing.

(D) Epoxy resin The epoxy resin used in the present invention has at least two epoxy groups in one molecule. Generally, the softening temperature indicated by the Durand method is 170°C or lower, preferably 180°C or lower. If an epoxy resin whose softening temperature exceeds 170° C. is used, a reaction occurs during mixing in a molten state, making it impossible to obtain a homogeneous mixture.

This epoxy resin is described in the “Encyclopedia Off Polymer Science and Technology (
Eneyelopedia of Po17merSc
Interscience Publishers, Inc. (Division Off John Wiley and Sons, Inc.) (In
Terscie-nce Publisher d
ivision of John Wile7
& 5onsInc, ), published in 1987],
Volume 6, pages 208 to 271, edited by Shunsuke Murahashi, Ryohei Oda, and Minoru Iki, Plastic Handbook (
Asakai Shoten, published in February 1980), pages 272 to 291, Hiroshi Kakiuchi (ed.) "Epoxy Resin" (Shokodo, published in June 1980), pages 68 to 105, etc., for manufacturing methods, softening, and uses. etc. are listed.

Examples of this epoxy resin include a reaction product between an active hydrogen compound (e.g., bisphenol A) and epichlorohydrin, a reaction product between a novolac resin and epichlorohydrin, a reaction product between an oxycarboxylic acid (e.g., oxybenzoic acid) and epichlorohydrin, and a reaction product between a polyphenol and epichlorohydrin. Reaction products with epichlorohydrin, resorcinol-acetone resins with epichlorohydrin, polyhydric phenols with epichlorohydrin, aromatic carboxylic acids with epichlorohydrin, alicyclic hydrocarbons (e.g. cyclohexene, dicyclopenta Examples include epoxy resins obtained by oxidizing gen, cyclopentene).

To produce the mixture of the present invention, the copolymer (A),
It is obtained by uniformly mixing at least one of the copolymer (B) and the copolymer (C) with an epoxy resin.

(E) Mixing ratio The mixing ratio of the epoxy resin in the mixture of the present invention is 5
~80% by weight (that is, the mixing ratio of the olefin copolymer is 95~20% by weight as a total amount), and 10~80% by weight.
70% by weight is preferable, and 15 to 60% by weight is particularly preferable.0 When the composition ratios are greatly different or when the viscosity difference is large, it is difficult to obtain a uniform composition, so it is preferable to use something with a viscosity as close as possible. , the composition ratio is l:1
It is also possible to create the desired composition by creating a high-concentration masterbatch that is close to 100% and then diluting it.

(F) Production of the mixture The mixing method may be tri-blending using a mixer such as a Henschel mixer, which is commonly used in the field of olefin polymers, or a Banbury mixer, Niegoo, twin screw extruder, single A method of melt-mixing using a mixer such as a shaft extruder or roll mill may also be used.
By triblending in advance and melt-mixing the resulting mixture, and by using a static mixer or the like at the tip of an extruder, a more homogeneous mixture can be produced.

In addition, when mixing in a molten state, it is necessary to carry out the mixing under conditions where the olefin copolymer and the epoxy resin to be used do not substantially undergo a crosslinking reaction.

If a reaction occurs during mixing, it will not be possible to obtain a homogeneous composition, and this will not only impair moldability during molding of the composition, but also cause problems with the desired shape of the molded product and cross-linking of the molded product. This is not preferable because it will reduce the heat resistance etc.

Therefore, when melt-mixing, it depends on the viscosity of the olefin copolymer and epoxy resin at each temperature, but generally 25°C (room temperature) to 200°C, preferably 70 to 18°C.
It is desirable to carry out the reaction at a relatively low temperature of 0°C, preferably 70 to 160°C, and for a short time of about several minutes.

For this purpose, the softening temperature or crystal melting temperature of the olefin copolymer and epoxy resin is preferably 160°C or lower, particularly preferably 140°C or lower, and it is advantageous for the fluidity to be as high as possible.

1. When producing the mixture of the present invention, antioxidants, ultraviolet deterioration inhibitors, blowing agents, foaming aids, metal deterioration inhibitors, flame retardants, and adhesives commonly used in the field of olefin polymers may be used. Additives such as carbon black and fillers can be added. Additionally, reaction accelerators (e.g. tri-n-butylamine, N,N-dimethylbenzylamine, p-)luenesulfonic acid, N-methylmorpholine) may be added to control the reaction rate, thereby impairing the properties of the mixtures of the invention. May be added as long as it does not.

(G) Method for producing crosslinked product (crosslinked polymer) The composition obtained as described above can be made into a molded article by almost all existing molding methods. For example, the method of casting and heating the mixture includes cast molding, compressing,
A desired molded product can be obtained by heating and crosslinking by transfer molding, powder molding, etc. In the method of crosslinking after obtaining a precursor by kneading and molding, the molded product is obtained by injection molding, extrusion molding, lamination molding, or roll processing, and then crosslinked by heating. After that, a molded product is obtained by vacuum forming, pressure forming, etc., and by heating this, a molded crosslinked polymer can be obtained. Form the film,
This film is laminated on one or both sides of various substrates such as aluminum, paper, copper, polyimide resin, nylon, polysulfone, etc., and then heated or the composition is rolled or calendered into sheets of appropriate thickness. It is possible to bond them by preparing them in advance, sandwiching them between the base materials to which they are to be bonded, and pressing them under high temperature heat. Alternatively, a composite material with high heat resistance and high adhesive strength can be obtained by performing two-layer or multi-layer lamination using a method similar to that generally known as extrusion lamination and then heat-treating at a high temperature.

Further, a crosslinked film of the composition can also be produced by arranging rolls having different temperatures one after another from a low temperature to 230 to 280°C or lower, and raising the temperature while applying a slight tension. Alternatively, a crosslinked film or sheet can also be produced by sandwiching the uncrosslinked T-die film or sheet obtained by the above method between Teflon or other films and hot pressing.

Although these are crosslinked films, they have adhesive properties, and can be firmly bonded by bonding various base materials together and heating them, and of course have remarkable heat resistance.

Furthermore, by mixing a chemical foaming agent when making the above composition, you can create a cross-linked foam film or sheet, or by attaching a base material on both sides, you can create a heat-resistant cross-linked foam composite (sandwich) without using an adhesive. can be built.

The heating temperature for crosslinking varies slightly depending on the comonomer composition of each olefin copolymer used and the type and proportion of the epoxy resin, but generally 150
℃ or more, particularly preferably 1eO ℃ or more.

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

In addition, in order to sufficiently exhibit adhesiveness and heat resistance of the crosslinked polymer made of the composition of the present invention, the gel fraction of the crosslinked reaction product of the epoxy resin and other olefin copolymer should be 10
% or more, preferably 50% or more, especially 70% or more
% or more is optimal, and it is necessary to adopt such conditions.

In addition, according to JIS K-7210, the load is 2.18K.
g, the fluidity index under the condition of temperature 190℃ is 0.01g
/10 minutes or less.

The gel fraction was determined by placing the crosslinked polymer sample in a 300-mesh wire mesh, performing Soxhlet extraction with boiling toluene for 6 hours, drying it in the wire mesh at 80°C for 18 hours, and measuring the weight. The weight is calculated and expressed as a weight percentage.

In addition, the second comonomer and the third comonomer of each olefin copolymer used in Examples and Comparative Examples
Copolymerization ratio of comonomers and their types, saponification rate, degree of neutralization, hydrolysis ring ＼-phesterification rate, and M
, 1. are shown in Table 1.

Examples 1 to 4, Comparative Example 1 Copolymer (A) and copolymer (B) shown in Table 1
Or copolymer (C) and epoxy resin [manufactured by Nippon Ciba Geigy Co., Ltd., trade name Araldite 8084, x poxy equivalent weight 900 to 1,000 g/eq, Duran melting point 9G-104°C, hereinafter referred to as "epoxy resin (I)"
] and N,N-dimethylbenzylamine (however, the amount of amine used is 0.5 parts by weight per 100 parts by weight of the total amount of all olefin copolymer and epoxy resin) in a predetermined ratio. The mixtures were blended and mixed at a temperature below 140 DEG C. using a single-screw extruder with a cylinder part having a diameter of 30 m2 to obtain compositions having the ratios shown in Table 2. Using a T-die film forming machine with a diameter of 40 cm, the temperatures of cylinder parts C1, C2, C3 and the die were set to 110°C, 115°C, and 120°C, respectively.
The temperature was set at 125°C, and film molding was performed, and in all cases, clean films with a thickness of 60 to 200 microns and no gel or fish eyes were obtained.

These films are coated with copper foil/copper foil with a thickness of 35IL layer.
Composition/Copper foil sandwich, 180℃ and 200℃
A bonded plate of 0.22 mm was obtained by preheating at a temperature of 1.5 minutes and pressing at a pressure of 20 kg/cm for varying times.

The adhesive strength of the obtained adhesive plate at room temperature (T-type peeling JI
The tensile speed of S K8854 (100 mm/min) was high as shown in Table 2. The gel fraction of each sample at this time is also shown in Table 2.

Further, Teflon sheets were placed above and below the non-crosslinked T-die film, and sheets with a thickness of 0.15mm were prepared at temperatures of 180°C and 200°C in the same manner as for adhesive plates. These were immersed in a 280°C solder bath for 1 to 5 minutes, and the state of the film was observed. The results are shown in Table 2.

(Left below) Examples 5 to 7 Copolymer (A) and copolymer (B) shown in Table 1
Or copolymer (C) and epoxy resin [epoxy resin trade name Araldite EC manufactured by Nippon Ciba Geigy Co., Ltd.
N1299, x-boxy equivalent weight 235 g/eq.

Duran melting point 96℃, hereinafter referred to as "epoxy resin (II)"
A composition was obtained by mixing 70:30 ratio of 0
Next, these were sandwiched between Teflon sheets and heated at a temperature of 180 to 200°C -c 30 N8
Press at a pressure of 0 minutes, 2 (1 Kg/c rn') 1.
A crosslinked sheet with a thickness of 0 to 1.5 mm was created.

Table 3 shows data on gel fraction, heat resistance, electrical properties, and volume resistivity after boiling in boiling water for 2 hours for these crosslinked sheets.

In addition, these compositions were sandwiched between Teflon sheets and heated at 120°C for 2 minutes at 50K.
Press with pressure of g/c ml, 80-250gra
created a film. This film is made into a sandwich of copper foil/composition/copper foil on a copper foil with a thickness of 35 mm, and 1
30-60 minutes at a temperature of 80-200℃, 20Kg/cr
Pressing was carried out at a pressure of n' to obtain an adhesive plate with a thickness of 0.15 to 0.28 am. The adhesive strength of the obtained adhesive board at room temperature (
T-type peeling JIS K8854) Peeling speed 100mm/
The amount was large as shown in Table 3.

(Leaving space below) Example 8 An uncrosslinked T-die film containing 150% by weight of copolymer A-obtained in Example 1 and 50% by weight of epoxy resin was pressed onto copper foil at 180°C for 30 minutes or at 200°C. Bonding was carried out at a temperature of 5 to 20 Kg/c for 10 minutes.

These were sampled in a tanzak shape with a width of 25 mm.

After repeating the heat cycle operation 10 times by leaving it in an oven at a high temperature of 150 to 250 °C for 10 minutes, quickly taking it out, immersing it in dry ice methanol at -80 °C and leaving it for 10 minutes, it was heated to room temperature (21 °C). The results of measuring the adhesive strength are shown in Table 4. These results show that the adhesive strength remains strong even after extremely severe heat cycles.

(Leaving space below) Table 4 Example 9 20g of the above α-olefin copolymer (87.4 mol% ethylene, 8.5 mol% ethyl acrylate, 3.1 mol% maleic anhydride) was added to 200 servings of toluene. dissolve,
To this were added 100 cc of water and triethylamine in an amount three times the mole of the maleic anhydride portion, and the mixture was heated at a temperature of 80° C. for 5 hours with forced stirring.

Thereafter, hydrochloric acid was added to neutralize the mixture, and further hydrochloric acid was continuously added until it became weakly acidic, and the mixture was left for one day and night. Thereafter, hexane was added as a precipitation solvent to precipitate the polymer, and the hexane was exchanged several times to wash the polymer. Thereafter, the polymer was vacuum dried at a temperature of 40° C. for a day and a night.

The hydrolysis rate was calculated from the decrease in absorption due to acid anhydride at 1780 cm-'' measured by IR measurement.
It was 100% hydrolyzed.

Example 10 An example of the halfesterization reaction is shown below.

Copolymer (89.7 mol% ethylene, 8.7 mol% methyl methacrylate, 11.8 mol% maleic anhydride)
20g was dissolved in 200ml of toluene, 100ml of methanol and 1ml of triethylamine were added, and the mixture was reacted for 6 hours under refluxing conditions of methanol.

Thereafter, hexane was added as a precipitation solvent to precipitate the polymer, and the hexane was exchanged several times to wash the polymer. Thereafter, the polymer was vacuum dried at 40° C. for one day and night.

Regarding the Hafestelization rate, see IR measurement 171
Calculating from the decrease in absorption due to acid anhydride at 30 cm°1, 83% of maleic anhydride was halfesterized.

0 N,N-dimethylbenzylamine was added to a 50:50 (weight ratio) mixture of copolymer A-1 and epoxy resin (I).
゜5 parts by weight added (hereinafter referred to as "a"), copolymer B-1 and epoxy resin (II) (7) 70: 30
(weight ratio) (hereinafter referred to as "b").

70:3 of copolymer C-3 and epoxy resin (II)
0 (weight ratio) (hereinafter referred to as rcJ), copolymer C-4 shown in Example 11 below and epoxy resin (I
A mixture of 70:30 (weight ratio) of I) (hereinafter referred to as rd
J), copolymer B-1 alone (hereinafter referred to as reJ), epoxy resin (II) alone (hereinafter referred to as "f")
A crosslinking curve was determined at a temperature of 200° C. using a curelastometer (manufactured by Toyo Baldwin, model JSRIII). The results are shown in Figure 1. From Figure 1, it can be seen that when used alone, like copolymer B-1 or epoxy resin (II), there is no increase in torque because there is no crosslinking, but copolymer A-1 and epoxy resin (1), copolymer B-1 and epoxy resin (II), copolymer C-3
In the case of a mixture (composition) such as copolymer C-4 and epoxy resin (II) shown in Example 11 below, a crosslinking reaction occurs at this temperature and the torque increases. It is clear that

Example 11 Ethylene/methyl methacrylate copolymer containing 9.6 mol% methyl methacrylate (M,!, = 109 g71
0 minutes) in Laboplastomill (185℃, 40rpm)
3. Maleic anhydride while kneading with. After adding OPHR,
Dicumyl peroxide 0.75 PHR was added in 5 portions, kneaded for 10 minutes, and then dried using a vacuum dryer.
It was dried under reduced pressure at 0°C for 6 hours to obtain a copolymer grafted with maleic anhydride (average molecular weight: 92,000). The amount of grafting was 2.1% by weight. This copolymer was 100% hydrolyzed in the same manner as in Example 9 to obtain copolymer C-4.

Comparative Example 2 Copolymer (ethylene 82.8 mol%, methyl methacrylate 14.1 mol%, maleic anhydride 3.1 mol%, M, 1. 1000 g/10 min or more, molecular weight 820
0) was halfesterized in the same manner as in Example 10 to obtain copolymer C-5. Note that 86% of maleic anhydride was converted into halfester.

Copolymer C-5 and epoxy resin [manufactured by Nippon Ciba Geigy Co., Ltd., trade name: Araldai] ECN1299
x boxy fi1 235g/e (!, Duran melting point 9
℃] at a ratio of 70:30, and using a single-screw extruder with a part of the cylinder diameter of 30 mm,
Although it was mixed at a temperature below ℃, it could not be pelletized.
Further, the tri-blend sample was formed into a film using a T-die film forming machine with a cylinder diameter of 40 m5, with various temperature conditions and extrusion conditions of the cylinder part and die, but a uniform film could not be obtained.

The uncrosslinked composition obtained by the present invention has good fluidity and excellent processability, so it can be used in various molded products, such as
Films, sheets, pipes, etc. can be easily produced.

Further, the crosslinked polymer obtained by the present invention has excellent electrical insulation properties like general thermoplastic resins.

The most distinctive effects are excellent heat resistance and adhesive properties as described below.

l) # Regarding thermal properties, it generally does not cause discoloration, foaming, or deformation even at temperatures of 260° C. or higher, even 300° C. or higher for a short period of time.

2) Regarding adhesion, 1) 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 a third substance and then crosslinked by heating, the third component The problem is that they are strongly adhered to each other.

[Brief explanation of drawings]

Figure 1 shows a mixture (a) consisting of copolymer A-1 and epoxy resin (1), a mixture (a) consisting of copolymer A-1 and epoxy resin (II), and a mixture (a) consisting of copolymer A-1 and epoxy resin (II).
), a mixture (b) consisting of copolymer C-3 and epoxy resin (II), a mixture (C) consisting of copolymer C-3 and epoxy resin (II), copolymer C-
4 and epoxy resin (II) (d), copolymer B-1 alone (e) and epoxy resin C
AI) Single (f) crosslinking curve. In this figure, the vertical axis is torque (Kg・CJ), and the horizontal axis is crosslinking time (
minute).

Claims (1)

[Claims] (I) Saponifying (1) a copolymer comprising at least an olefin and an unsaturated monocarboxylic acid, (2) an olefin copolymer comprising at least an olefin and an unsaturated carboxylic acid ester, At least one selected from the group consisting of a copolymer obtained by neutralization and (3) a copolymer of at least an olefin and an unsaturated dicarboxylic acid or a half ester thereof, having an average molecular weight of 15,000 to 150,000. and (II) a crosslinkable mixture consisting of an epoxy resin having at least two epoxy groups in one molecule, and the mixing ratio of the epoxy resin in the mixture is 5 to 80% by weight. .