JPS63101413A - Olefin copolymer mixture - Google Patents

Abstract

PURPOSE:To obtain the title mixture which has excellent crosslinkability and can give a crosslinked product excellent in heat resistance, bondability and transparency, by mixing a copolymer comprising an olefin and an unsaturated monocarboxylic acid, etc. with a copolymer of an olefin with an epoxy group- containing unsaturated monomer and an organic peroxide. CONSTITUTION:100pts.wt. total of 1-99wt% at least one copolymer (A) selected from among a copolymer (a) obtained by radical-polymerizing a 2-12C alpha-olefin with a 3-20C unsaturated monocarboxylic acid and, optionally, a polar group- containing radical-polymerizable vinyl compound at 120-260 deg.C and an ultrahigh pressure of 500-25,000kg/cm<2>, a copolymer (b) obtained by saponifying a copolymer comprising a 2-12C alpha-olefin and a 4-40C unsaturated carboxylic ester and neutralizing the saponificate and a copolymer (c) of an alpha-olefin with an unsaturated dicarboxylic acid or its anhydride or half-ester and 99-1wt% copolymer of an olefin with a radical-polymerizable epoxy group-containing unsaturated monomer is mixed with 0.001-10.0pts.wt. organic peroxide (C) by melting.

Description

[Detailed Description of the Invention] LjL-Standing Plate±! The present invention relates to a mixture that can produce a heat-resistant crosslinked polymer, which is relatively easy to crosslink, provides good adhesion to metals, etc., and is resistant to solder. The purpose of this invention is to provide a crosslinked product that has sufficient heat resistance to withstand high temperatures.

[Tairibai] 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.

Based on these facts, some of the inventors of the present invention searched various ways to easily obtain a resin mixture that not only has excellent adhesion to metals etc. but also has good heat resistance. and a compound represented by the following structural formula (I) (A), (wherein R is a vinyl group, an allyl group, or a methallyl group), and (B) (1) at least an olefin and an unsaturated (2) a copolymer obtained by saponifying and neutralizing an olefinic copolymer consisting of at least an olefin and an unsaturated carboxylic acid ester; and (3) a copolymer consisting of at least an olefin. A composition comprising at least one copolymer selected from the group consisting of unsaturated dicarboxylic acids or copolymers thereof with halfester, and the copolymer (
A crosslinkable composition having a composition ratio of 1 to 99% by weight has good adhesion not only to metals but also to other substances,
Moreover, it was found that it has excellent heat resistance and is an economically advantageous (simple) composition, which was previously proposed (Japanese Patent Application No. tO-28752Ei).

However, when crosslinking the resulting composition, there is a problem that the crosslinkability is not necessarily satisfactory (for example, the crosslinking time is relatively long). Based on these facts, we previously proposed a composition obtained by further incorporating a reaction accelerator into the composition (Japanese Patent Application No. 1980-
No. 282097).

Although the crosslinkability of the mixture can be improved, the problem is that the transparency is not necessarily satisfactory.

From the above, the present invention does not have these drawbacks (problems), that is, it has good crosslinking properties, and the resulting crosslinked product not only has good heat resistance, but also has good resistance to metals and other materials. The object of the present invention is to obtain a mixture that has excellent adhesion to various substances and has good transparency.

According to the method for fortune-telling and the present invention, these problems are solved by (A) (1)
) A copolymer consisting of at least an olefin and an unsaturated monocarboxylic acid (hereinafter referred to as "copolymer (a)"),
(2) A copolymer obtained by saponifying and neutralizing an olefin copolymer consisting of at least an olefin and an unsaturated carboxylic acid ester [hereinafter referred to as "copolymer (b)"], and (3) A copolymer of at least an olefin and an unsaturated dicarboxylic acid, its anhydride, or its halfester [hereinafter referred to as "copolymer (C)"]
At least one copolymer selected from the group consisting of
I), (B) A copolymer with an unsaturated polymer having an epoxy group capable of radical copolymerization with at least an olefin (■) [
Hereinafter referred to as "copolymer (d)"] and (C) an organic peroxide. )] and copolymer (■) [i.e., copolymer (d)], the mixing ratio of copolymer (I) is 1 to 99% by weight, and the proportion of these copolymers is 1 to 99% by weight. The total proportion of organic peroxides based on the total amount of 100 parts by weight of the olefinic copolymer mixture is 0.001 to 10.0 parts by weight. The present invention will be specifically explained below.

(A) Copolymer (a) Copolymer (a) is a copolymer of at least an α-olefin and an unsaturated monocarboxylic acid. Considering moldability, the copolymer should preferably melt at a temperature of 150°C or lower and have fluidity. In order to ensure this property,
It is preferable to use a copolymerized comonomer 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, crotonic acid, monoalkyl Examples include malate and monoalkyl fumarate.

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. It is.

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 number of carbon atoms in the unsaturated carboxylic acid ester is usually 4 to 40, and 4 to 20 carbon atoms are particularly preferred. Representative examples include carbon atoms with good thermal stability such as methyl (meth)acrylate and ethyl (meth)acrylate. Those with poor thermal stability such as t-butyl (meth)acrylate are not preferred 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 preferred alkoxy(meth)alkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate, and butkiethyl acrylate. Also,
The vinyl ester generally has at most 20 carbon atoms (preferably from 4 to 10(i)); representative examples 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, 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 unsaturated monocarboxylic acid bonded in the copolymer (a) is
The content is desirably 0.5 mol% or more and 25 mol% or less, and particularly preferably 1.0 mol% to 15 mol%. In addition, unsaturated monocarboxylic acid mono? The present invention also includes graft copolymerization of 0.5 mol% or more of - to an olefin copolymer as described below, but block or random copolymers are preferred, and random copolymers are particularly preferred. .

The unsaturated monocarboxylic acid serves as a crosslinking reaction site with the copolymer (d) described below and to provide adhesiveness to a wide variety of base materials, and from both points of view, it is necessary to have an excess amount. If the amount increases, water absorption will increase, which will not only have a negative effect on electrical properties such as foaming during molding and water absorption after molding, but also lead to manufacturing problems such as safety and recovery. On the other hand, if it is less than 0.5 mol %, there is no problem in terms of adhesiveness, but it is not preferable because it is disadvantageous in terms of heat resistance.

The co-monomer (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/crn', 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 that it melts at a temperature of 150°C or less and has 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%. is preferably 0.5 to 20 mol %, particularly preferably 1 to 15 mol %, in terms of carboxylic acid-containing units in the copolymer after neutralization treatment.

The saponification reaction can be carried out using a widely known method, for example, using a mixed solvent of toluene and isobutyl alcohol (mixing ratio: 50
: 50) by adding NaOH and a copolymer containing an ester group and refluxing for 3 hours. The saponification rate can be arbitrarily adjusted by adjusting the amount of Na0)1. 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. Copolymer (b) is obtained by dispersing this polymer in water, adding sulfuric acid thereto, and stirring at 70° C. for 1 hour to perform a metal removal treatment (=neutralization reaction).

(C) Copolymer (c) As a result, the copolymer (C) used in the present invention consists of the above-mentioned α-olefin and unsaturated dicarboxylic acid,
It is sufficient that it is a copolymer (which may contain the third component) with its anhydride or its halfester, that is, an α-olefin and an unsaturated dicarboxylic acid, its anhydride or its halfester, or a copolymer thereof with the third component. It is preferable to directly copolymerize the components, or by modifying an olefinic copolymer of an α-olefin and an anhydride of the unsaturated dicarboxylic acid (which may also contain the third component) to form an acid. Part or all of the anhydride group may be dicarboxylated or halfesterified, and those that melt at a temperature of 150° C. or lower are preferable.

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

When producing the copolymer (e) by a direct copolymerization method,
Unsaturated dicarboxylic acids, their anhydrides or their halfesters 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 acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and 3,6-endomethylene-1,2,3,8-tetrahydro-cis-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. Typical examples of the alcohol include primary alcohols having at most 20 carbon atoms, such as methanol, ethanol, propatool, and butanol. A representative example of Hafestel is maleic acid monomethyl ester.

Examples include monoethyl maleate, monoisopropyl maleate, monobutyl maleate, and monoethyl itaconate.

"Unsaturated dicarboxylic acid, its anhydride or its halfester" (hereinafter referred to as "unsaturated dicarboxylic acid component")
The amount of bonding in the copolymer (C) is 0.5 mol% or more, 2
It is preferably 0 mol% or less.

More preferably, it is 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 copolymer (d) described below and to provide adhesiveness to various base materials, and is present in excess from both points of view. There's no need.

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 acid 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.

A copolymer of the sum of these modified structural units (C
) is preferably 0.5 to 20 mol%, more preferably 1.0 to 15 mol%.

In the copolymer (C), graft copolymerization of unsaturated dicarboxylic acid, its anhydride, or unsaturated carboxylic acid ester or unsaturated dicarboxylic acid, its anhydride, or its monoester used as a copolymerization component of its halfester. α used as a starting material to
-Used in 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 of unsaturated carboxylic acid ester in the copolymer is 2
It is preferably 5 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 producing the copolymer (C), various known methods (for example, solution method, suspension method, melt method) can be employed.

Among these manufacturing methods, the melting method will be explained as an example. An unsaturated dicarboxylic acid is added to the copolymer of the α-olefin and unsaturated carboxylic acid ester [hereinafter referred to as "copolymer (c') J"]. When graft copolymerizing an acid anhydride, the copolymer, the unsaturated dicarboxylic acid anhydride, and the It can be obtained by processing a radical initiator while melt-kneading it. The kneading temperature at this time varies depending on the type of copolymer and radical initiator used, but
The temperature range is from above the melting point of the copolymer used to below 330°C. Generally, the temperature is 120 to 270°C. As a radical initiator, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-5,5-di(tert-butylperoxy)hexane-3
and organic peroxides such as penzoyl peroxide.

When producing a copolymer by the melt grafting method, the ratio of the unsaturated dicarboxylic acid anhydride to 100 parts by weight of the copolymer (Co) is as described above, but the physical properties of the resulting graft copolymer and considering the economical aspects,
It is preferably 7.0 parts by weight or less, especially 5.
The amount is preferably 0 parts by weight or less.

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

Representative examples of this epoxy compound include those whose general formulas are represented by the following formulas [formula (■) and formula (H)].

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

These copolymers (a), copolymers (b), copolymers (
C) and copolymer (d) melt index (JI
In accordance with S K-7210, the temperature was 190°C and the load was 2.18Kg, hereinafter referred to as rM, 1. J) are usually 0.1 g/10 minutes or more, and 0.5 g
/ 10 minutes or more is desirable, especially i, o g /
It is preferable that the time is more than 0 minutes.

(E) Organic peroxide Furthermore, the organic peroxide used in the present invention is not particularly limited, but it is particularly desirable to have a decomposition temperature (temperature at which the half-depleted group is reduced in 1 minute) of 130°C or higher, and in particular 14
A temperature of 0°C or higher is preferable.

Representative examples of suitable organic peroxides include 1. l-bis-
Ketone peroxides such as tertiary-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-
dimethylhexane-2; hydroperoxide such as 5-sibide lobaroxide, 2,5-dimethyl-2
, 5-di-tert-butyl peroxyhexane, and diacyl peroxides such as benzoyl peroxide.

Additionally, polyfunctional substances such as triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, triallyl trimellitate, trimethylolpropane trimethacrylate and metaphenylene bismaleimide are used as crosslinking aids in the conventional rubber field. may be blended.

(F) Mixing ratio of copolymer (1) [i.e., copolymer (a) to copolymer (C)] and copolymer (II) in the mixture of the present invention.
) (that is, copolymer (d)), the mixing ratio of copolymer (I) in the total amount is 1 to 99% by weight,
2 to 88% by weight is desirable, 5 to 95% by weight is preferred, and especially 10 to 90% by weight is preferred. Even if the mixing ratio of copolymer (r) in the total amount of copolymer (I) and copolymer (II) is less than 1% by weight or more than 99% by weight, the crosslinkability of the mixture is insufficient. Therefore, the heat resistance of the resulting crosslinked product is poor.

The mixing ratio of the organic peroxide to 100 parts by weight of the total amount of these copolymers is 0.001 to 10.0 parts by weight, preferably 0.005 to 1000 parts by weight, particularly 0.001 to 10.0 parts by weight. 1 to 7.0 parts by weight of O is suitable. If the mixing ratio of the organic peroxide is less than 0.001 parts by weight with respect to the total amount of 100 parts by weight of these copolymers, crosslinking properties are poor and a crosslinked product with good adhesiveness cannot be obtained.
If more than 0.00 parts by weight is added, crosslinking will occur rapidly, it will be difficult to control the crosslinking, and the resulting crosslinked product will have poor physical properties, which is not preferable.

(G) Production of mixture In producing the mixture of the present invention, the copolymer (a
) to copolymer (C) and copolymer (d
) and organic peroxides may be used alone or in combination of two or more.

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 mixer such as a Banbury mixer, Niegoo, twin-screw extruder, axle-shaft extruder, or roll mill. A method of melting and mixing using a blender may also be used.
By tri-blending in advance and melt-mixing the resulting mixture, a more homogeneous mixture can be produced by using a static mixer or the like at the tip of an extruder.

In addition, when mixing in a molten state, it is necessary to perform the mixing under conditions where the olefin copolymer used and the organic peroxide 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 the moldability of the composition when molding it, but also cause problems such as cross-linking and the shape of the desired 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 used at each temperature, but generally it is 25°C.
It is desirable to conduct the reaction at a relatively low temperature of (room temperature) to 200°C, preferably 70 to 180°C, preferably 70 to 160°C, in a short time of about several minutes.

For this reason, the softening temperature or crystal melting temperature of the olefin copolymer is usually 160°C or lower, especially 14
The temperature is preferably 0°C or lower, and the fluidity is preferably as high as possible.

In addition, 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 are used. Additives such as carbon black and fillers can be added.

(H) Method for producing crosslinked product (crosslinked polymer) The mixture 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, compression molding,
A desired molded product can be obtained by heating and crosslinking by transfer molding, powder molding, etc. In the method of cross-linking after obtaining a precursor by cross-wiring and molding, it is sufficient to obtain a molded product by injection molding, extrusion molding, lamination molding, or roll processing, and then heat and cross-link it, or form a sheet or film by extrusion molding. 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 260°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 somewhat depending on the comonomer composition ratio of each olefin copolymer used, but it is generally 150°C or higher, and preferably 180°C or higher.

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 producing a crosslinked product from the mixture of the present invention, the mixture is first produced into a sheet or film by the extrusion molding, injection molding, blow molding, laminating molding, roll processing, vacuum forming, pressure forming, etc. Electron beam crosslinking may also be performed.

(J) Electron beam crosslinking There are various methods for carrying out the electron beam crosslinking, such as Cockcroft type, Cockcroft-Walton type, bumpgraph type, insulated core transformer type, linear type, dynamidron type, high frequency type, and electrocurtain type. One example is a method of emitting an electron beam from an electron beam accelerator. The irradiation dose can vary within a wide range depending on the required performance of the irradiated object. Generally it is 0.5 to 200 M rad,
1.0 to 200 Mrad is preferable, especially 1.0
~150 Mrad is preferred. Irradiation dose is 0.5M
If it is less than rad, the degree of crosslinking is insufficient. On the other hand, 200
When Mrad is exceeded, molecular cleavage occurs and the physical properties of the crosslinked product deteriorate. In addition, the acceleration voltage is usually 50-100KV, preferably 100-1000KV, and especially 100-100KV.
300Kv is preferred.

The atmosphere during crosslinking is preferably an inert gas, if necessary. Representative examples of this inert gas include nitrogen, carbon dioxide, helium, and the like.

The crosslinked product thus obtained may be further heated as described above.

In addition, in order to fully develop the adhesiveness and heat resistance of the crosslinked polymer consisting of the mixture 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 2.16K.
g, and the fluidity index under the condition of temperature 190°C is 0. O1g
/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 16 hours, and measuring the weight. The weight is calculated and expressed as a weight percentage.

The present invention will now be explained in more detail with reference to Examples.

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, half-varnish chilling rate such as hydrolysis, N, 1. are shown in Table 1.

Examples 1 to 7, Comparative Examples 1 to 5 Copolymers (A) and copolymers (B) shown in Table 1
° or copolymer (C) and copolymer (El) and an organic peroxide (dicumyl peroxide) or an organic peroxide and a crosslinking aid (triallyl isocyanurate) are triblended in a predetermined ratio, Using a single-screw extruder with a Gorses cylinder diameter, the mixtures were mixed at a temperature of 120° C. or lower to obtain mixtures having the ratios shown in Tables 2 and 3. Using a T-die film forming machine with a cylinder diameter of 40vs, these mixtures were molded into C1 and C
2, the temperature of C3 and the die was 110℃, 11
Film molding was performed at temperatures of 5°C, 120°C, and 125°C.

In all cases, clean films with a thickness of 60 to 200 gra and no gel or fish eyes were obtained.

These films were sandwiched between copper foil/film/copper foil with a thickness of 35 cm and heated at 18°C and 17°C.
Preheat for 0.5 minutes at temperatures of 0℃, 180℃ and 190℃,
Press at a pressure of 20Kg/cm" for different times, and press 0.1
A 9 mm adhesive plate was obtained. Room temperature of the obtained adhesive board (23℃
) (T type side #JIS K8854° tensile speed 100 mm/min) was high as shown in Tables 2 and 3. The gel fraction of each sample at this time is also shown in Tables 2 and 3.

Further, Teflon sheets were placed above and below the non-crosslinked T-die film, and sheets with a thickness of 0.19 mm were prepared at temperatures of 170°C, 180°C, and 190°C in the same manner as for adhesive plates. These are 200℃, 250℃, 300℃
The film was immersed in a solder bath for 3 to 30 minutes, and the state of the film was observed. The results are shown in Tables 2 and 3 in comparison with those without added organic peroxide.

In addition, the non-crosslinked T-die film was attached to a glass plate (thickness:
2 mm) in a sandwich shape under the same conditions as above to obtain a plate with a thickness of 4.12 mm. This sample was naturally cooled to room temperature, and the haze (haze value AST) l D-10
03) was measured. As shown in Tables 2 and 3, those to which organic peroxides have been added are
Clearly, transparency is excellent! be.

(Left below) Examples 8 to 11 Copolymers (A) and copolymers (B) shown in Table 1
Or copolymer (C) and copolymer (D) 50:5
0 (weight ratio) and 2.0 parts by weight of organic peroxide and mixed by mixing for 3 to 4 minutes at 40 revolutions/min at a temperature below 120 °C using a mixing rotor of a Lab Blast Mill. I got it.

A sheet with a thickness of 0.5 to 1.0 Ilg was then prepared using an 85° C. roll (Teflon coated). These were sandwiched between Teflon sheets and heated to 190℃ for 10 minutes to produce 20Kg/cm''.
A crosslinked sheet was created by pressing at a pressure of

Table 4 shows data on the gel fraction, heat resistance, electrical properties (humidity 53-97%), and volume resistivity after boiling in boiling water for 2 hours of these crosslinked sheets.

(Left below) Example 12 Uncrosslinked T-die film obtained in Example 1 (thickness + 50 #
Energy Sciences Incorporated (LI11)
Electron beam irradiation was performed using an electrocurtain type electron beam accelerator manufactured by Orated) 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 35.5%.

This irradiated film was pressed in the same manner as in Example 1 in the form of a copper foil/film/copper foil sandwich at a temperature of 180°C for 0.5 minutes and a pressure of 20 kg/cm for 20 minutes. An adhesive plate was obtained.The adhesive strength of the obtained adhesive plate at room temperature was 8.2 Kg/25 mm, which was a significantly large value.The gel fraction at this time was 99.
．． The electron beam irradiation film was pressed with a glass plate under the same conditions as in Example 1 to obtain a 4.13 mm plate. This sample was naturally cooled to room temperature, and the haze (haze value) was measured to be 0.6%.

Comparative Example 6 50% by weight copolymers A-2 and 5 as in Example 1
0% by weight of copolymer D-2 (no organic peroxide added)
A film (thickness: 140 gm+) was prepared in the same manner as in Example 1. This film was subjected to electron beam irradiation under the same conditions as in Example 12. The gel fraction of this electron beam irradiated film was 34.7%, which was not much different from that of the film to which peroxide was added. Furthermore, an adhesive plate was made from this film using the same method as in Example 12. When the adhesive strength of this adhesive plate was measured, it was 7.9Kg72.5m+++.

The gel fraction was 68.2%.

The electron beam irradiated film was pressed with a glass plate under the same conditions as in Example 12 to obtain a 4.12 mm plate.

This sample was naturally cooled to room temperature and the haze (haze value) was measured and found to be 3.1%.

Example 13 Ethylene/methyl methacrylate copolymer containing 8.6 mol% methyl methacrylate (M, 1.=10t3g/
10 minutes) in a lab blast mill (185℃, 40rpff)
After adding 3.0 PHR of maleic anhydride while kneading in step 1), 0.75 PHR of dicumyl peroxide was added in 5 portions, kneaded for 10 minutes, and then dried under reduced pressure at 180° C. for 6 hours. When measured using an infrared spectrophotometer, a copolymer C-5 grafted with 2.2% by weight of maleic anhydride was obtained.

The ratio of this copolymer C-5 and copolymer D-2 was 50:50.
2.0 parts by weight of dicumyl peroxide was added to 100 parts by weight of the total amount (% by weight), and crosslinking was carried out in the same manner as in Example 8. The gel fraction of this crosslinked product was 97.8%.

The uncrosslinked mixture was also sandwiched between copper foils (thickness 35 lumens) and preheated at a temperature of 190° C. for 1.5 minutes. Pressing was carried out at this temperature for 10 minutes under a pressure of 20 kg/cm' to obtain an adhesive plate having a thickness of 0.21 mm. The peel strength of this adhesive plate was 8.3 kg/25 mm.

Example 14 Ethylene copolymer (87.9 mol% ethylene.

8.5 mol% ethyl acrylate, 2. maleic anhydride.
6 mol %) was dissolved in 20 volumes of toluene, 100 cc of water and triethylamine in an amount three times the mole of maleic anhydride were added thereto, and the mixture was heated at 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 in stirrups all 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-' in IR measurement.
It was 100% hydrolyzed.

Example 15 An example of the halfesterization reaction is shown below.

Copolymer (88.6 mol% ethylene, 8.7 mol% methyl methacrylate, 2.7 mol% maleic anhydride) 20
Dissolve 200 grams of toluene and add 1 ounce of methanol.
1 ran of 00IlfL triethylamine was added and reacted for 8 hours under methanol reflux conditions.

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 Hafestel conversion rate, IR measurement 1780
As calculated from the decrease in absorption due to the acid anhydride of ``c+++-'', 83% of maleic anhydride was halfesterized.

A-2 and D-2 (hereinafter referred to as "a"), B-1 and D-2
(hereinafter referred to as rbJ): 50:50 (weight ratio)
2.0 parts by weight of dicumyl peroxide were added to each of a and b (hereinafter referred to as "a'").
” and “b””) and 2,5-dimethyl-2
, 2.0 parts by weight of 5-di(tertiary-butylperoxy)hexyne-3 (hereinafter referred to as "aoo" and "bo")
”) using a Curelastometer (manufactured by Toyo Baldwin Co., Ltd.).

A crosslinking curve was obtained at a temperature of 190° C. using a 190° C. The results are shown in Figure 1. From Figure 1, it can be seen that in the case of a or b, in which no organic peroxide is added, the torque increases gradually, but in cases a',
It is clear that when organic peroxides are added, such as ", bo, and b", the torque increases rapidly and the crosslinking rate increases significantly.

Fish and shellfish J and flat mold The uncrosslinked composition obtained by the present invention has good fluidity and excellent processability, so that it can be easily manufactured into various molded products such as films, sheets, pipes, etc.

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.

Regarding heat resistance, it generally does not cause discoloration, foaming, or deformation even at temperatures of 300°C or higher, or even 380°C or higher for short periods of time, and in particular, it can be obtained even when molded under normal molding conditions. The product has good heat resistance.

2) Regarding adhesiveness, when the uncrosslinked composition according to the present invention or a 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 substance The problem is that they are strongly adhered to each other.

Third substances include metals and alloys such as aluminum, copper, iron, stainless steel, brass, galvanized iron, and tinplate, glass ceramics, amide, imide resin, polysulfone, polyester, polycarbonate,
Examples include synthetic resins having polar groups such as polyurethane, cellophane, various papers, and modified polyolefin polymers obtained by grafting monomers having polar groups.

The composition and its crosslinked product obtained by the present invention have the above-mentioned effects and can be widely and effectively utilized in a wide range of fields.

l1lF# In addition to heat resistance and adhesive properties, it has high electrical insulation properties such as volume and surface resistivity, and has excellent electrical properties such as low dielectric constant and dielectric loss tangent, and has adhesive strength that is water resistant, organic solvent resistant, acid resistant, and alkali resistant. It has excellent chemical resistance such as It is suitable for various electrical and electronic devices such as electronic materials such as plates and sealing materials for electrolytic capacitors. It is also used as a material for automobile parts that require heat resistance and adhesive properties.

[Brief explanation of the drawing]

Figure 1 shows A-2 and D-2 (a), B-1 and D-2 (
b) and these (a) and (b) plus p-toluenesulfone ugliness ((a') and (b')
) and those to which N,N'-dimethylbenzylamine was added ((a") and (b")). In this figure, the vertical axis is torque (Kg-cm) and the horizontal axis is crosslinking time (minutes).

Claims (1)

[Claims] (A) 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, a copolymer obtained by neutralization; 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, its anhydride, or its half ester. , (B) a copolymer (II) with an unsaturated monomer having an epoxy group capable of radical copolymerization with at least an olefin, and (C) an organic peroxide, and the copolymer (I) in the mixture Copolymer (I) in the total amount of and copolymer (II)
An olefin copolymer mixture having a mixing ratio of 1 to 99% by weight, and a mixing ratio of organic peroxide to 100 parts by weight of the total amount of these copolymers is 0.001 to 10.0 parts by weight.