JPS62129341A - Crosslinkable composition - Google Patents

Abstract

PURPOSE:To obtain a composition capable of giving crosslinked products of outstanding heat resistance and high adhesivity to metals, etc., by blending a copolymer from olefin and glycidyl ether, a second copolymer of olefin/ unsaturated monocarboxylic acid, etc. CONSTITUTION:The objective composition can be obtained by blending (A) a copolymer from at least olefin and a compound of formula (R is vinyl, allyl or methallyl) and (B) one or more copolymers selected from (i) a second or more copolymers selected from (i) a second copolymer from at least olefin and unsaturated monocarboxylic acid, (ii) a third copolymer derived from neutralization following saponification of an olefin copolymer from at least olefin and unsaturated carboxylic ester, and (iii) a fourth copolymer from at least olefin and unsaturated dicarboxylic acid or its half ester so as to be 1-99wt% for the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION (11) The present invention relates to a composition capable of producing a heat-resistant crosslinked polymer. More specifically, (A) an olefin copolymer of at least an olefin and a glycidyl ether (A) and (B) (1) an olefin copolymer of at least an olefin and an unsaturated monocarboxylic acid; (2) an olefin copolymer of at least an olefin and an unsaturated monocarboxylic acid; An olefin copolymer obtained by saponifying and neutralizing a copolymer consisting of an unsaturated carboxylic acid ester and (3)
The present invention relates to a crosslinkable composition comprising at least one copolymer (B) selected from the group consisting of copolymers comprising at least an olefin and an unsaturated dicarboxylic acid or halfester, and which has excellent heat resistance. First, it is an object of the present invention to provide a crosslinked product that provides good adhesion to metals and the like.

Differential velocity J and lΔ Until now, adhesive thermoplastic polymer compositions have been known that are made by mixing an epichlorohydrin polymer with a thermoplastic polymer having alcoholic hydroxyl groups in the molecule; Moreover, since it contains chlorine, its heat resistance is limited and is not sufficient. In addition, the chlorine in the composition not only poses problems in terms of hygiene and pollution due to the generation of toxic gas during incineration, but also the high cost of epichlorohydrin polymers has limited its use.

In addition, unsaturated carboxylic acid or its acid anhydride copolymerized with polyvinyl alcohol having a degree of saponification of 85% or less
A composition comprising an olefin-based copolymer containing less than % by weight has been proposed (Japanese Patent Laid-Open No. 127450/1983), but this relates to a resin composition for a heat-retaining film, and is a composition with a heat-retaining property. The purpose of this was to improve the uniform dispersibility of polyvinyl alcohol and an olefin copolymer, and it could not be used as an adhesive 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 No. 55-
131033), this composition is suitable as a packaging material for packaged items that requires gas permeation resistance and moisture resistance that is easy to cut with a knife, etc., and is suitable for use with adhesive resins or crosslinked resins. It cannot be used as a composition for use.

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 etc. at room temperature, but #
Polyester resins and polyimide resins have been proposed as polymeric materials that have excellent thermal properties and adhesive properties. However, polyester resin has high water absorption and can reach up to 20'C! It has drawbacks such as a large coefficient of thermal expansion at temperatures ranging from 250°C to 250°C. Furthermore, polyimide resins have drawbacks such as insufficient adhesion to metals and the like due to poor surface activity.

− tries to do ′. Based on the above, the present invention provides an olefin polymer composition that does not have these drawbacks (problems) and has not only excellent heat resistance but also good adhesion to various materials such as metals. Or to obtain a crosslinked product.

According to the present invention, the above problems are solved by (A) a copolymer (A) consisting of at least an olefin and a compound represented by the following structural formula (1) [hereinafter referred to as "olefin"]. (1) A copolymer consisting of at least an olefin and an unsaturated monocarboxylic acid. [Hereinafter referred to as "olefin copolymer (B)"] (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 "olefin copolymer (C)")] and (3) a copolymer of at least an olefin and an unsaturated dicarboxylic acid or its halfester [hereinafter referred to as "olefin copolymer (D)"]. A composition comprising at least one copolymer selected from the group consisting of at least one copolymer (
A) can be solved by a crosslinkable composition having a composition ratio of 1 to 99% by weight. The present invention will be explained in detail below.

(A) Olefin copolymer (A) The olefin copolymer (A) of the present invention has at least α-
It is a copolymer of olefin and glycidyl ether,
It is preferable that the material melts at a temperature of 150° C. or lower and has fluidity. For this purpose, it is desirable to include a third component such as an unsaturated luponic acid ester, vinyl ester, or alkoxyalkyl acrylate.

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.

As the glycidyl ether, the glycidyl ether has the following general formula % formula % (I) in which R is a vinyl group, an allyl group or a methallyl group, vinyl glycidyl ether,
Examples include allyl glycidyl ether and methallyl glycidyl ether.

The amount of the epoxy-containing monomer (glycidyl ether) is preferably 0.1 mol% or more and 17 mol% or less. The higher the amount, the better from the viewpoints of adhesiveness and heat resistance, but if it is less than 0.1 mol%, not only will the adhesiveness not be improved much, but the olefin copolymer (A) and other olefins will not be improved much. Even if the composition with the copolymer or the reaction conditions are changed, sufficient heat resistance cannot be obtained. On the other hand, if it exceeds 17 mol%, the water absorption of the copolymer increases, which not only causes undesirable effects such as foaming during molding and deterioration of electrical properties due to water absorption after molding, but also reduces safety φ separation.・It is undesirable because it causes manufacturing problems such as recovery and is economically disadvantageous.

Incidentally, a copolymer obtained by graft-polymerizing a glycidyl monomer onto a copolymer of ethylene and the third component and containing 0.1 mol % or more of the glycidyl monomer can also be used.

The unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, particularly preferably 4 to 20 carbon atoms. As typical examples, those with good thermal stability such as methyl (meth)acrylate and ethyl (meth)acrylate are preferable, and those with poor thermal stability such as t-butyl (meth)acrylate are preferable because they cause foaming. do not have.

Furthermore, the alkoxyalkyl acrylate usually has at most 20 carbon atoms. Furthermore, the alkyl group preferably has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), and the alkoxy group has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms).
4) is desirable. Representative examples of preferred glycidyl ethers include methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and butkiethyl acrylate.

Furthermore, the number of carbon atoms in vinyl ester is generally at most 20.
(preferably 4 to 10). Typical examples include vinyl acetate and vinyl propionate.

The copolymer (A) is produced, for example, under high pressure (500 to 250
0Kg/cm') at a temperature of 120-280°C,
By radical polymerization or in the presence of a free radical generator such as glycidyl ether or peroxide, the olefinic copolymer of α-olefin and the third component is processed using a -screw or twin-screw extruder, a kneader (Brabender), etc. ) etc., but if the sum of the third component and glycidyl ether in the copolymer (A) exceeds 70% by weight, the softening point of the polymer will be high. This is not only undesirable because the fluidity at temperatures below 150°C is impaired, but also economically unfavorable.

On the other hand, if it is less than 5% by weight, the crystal melting temperature becomes high and low-temperature fluidity is impaired, which is not preferable.

The glycidyl ether mentioned above is an olefin copolymer (B
), serves as an active site for crosslinking with the olefin copolymer (C) or olefin copolymer (D), and as an adhesion agent with various substrates, but glycidyl ether If the bonding amount of A), olefin copolymer (B), olefin copolymer (
Even if the composition with C) or the olefin copolymer (D) is changed, the number of substantial crosslinking points is insufficient, which is not preferable from the viewpoint of heat resistance.

In addition, the melt index of the olefin copolymer (A)
(according to JIS K-7210, temperature is 180°)
C and a load of 2.113Kg (hereinafter referred to as "MI") is usually 0.5g710 minutes or more, and 5.0g7
10 minutes or more is desirable, and 50 g/10 minutes or more is particularly suitable. Regarding this MI, conventional olefin copolymers (B) and olefin copolymers (C
) and the olefin copolymer (0).

(B) Olefin copolymer (B) Further, the olefin copolymer (B) is a copolymer of the α-olefin and an unsaturated monocarboxylic acid, and 150
It is preferable to melt at a temperature below °C and have fluidity.
Those containing ingredients are preferred.

The number of carbon atoms in the unsaturated monocarboxylic acid that can be used in the present invention is generally 3 to 20, particularly 3 to 10 (
Typical examples include agrilic acid, methacrylic acid, isocrotonic acid, crotonic acid, and ethacrylic acid.

Further, a copolymer of an α-olefin and an unsaturated carboxylic acid such as the olefin copolymer (B) can be used, for example, from mono-v-500 to 2500Kg/ Qrn' (7
) Radical polymerization can be carried out using a free radical generator such as peroxide in an autoclave with a stirrer or a tubular reactor, using a chain transfer agent if necessary, under ultra-high pressure and at a temperature of 120 to 260 °C. .

In the olefin copolymer (B), the amount of the third component is preferably 70% by weight or less, particularly 10 to 6% by weight.
0% by weight is preferred. Although the characteristics of the present invention can be achieved even if the content exceeds 70% by weight, it is not necessary to exceed 70% by weight, which is not preferable from the viewpoint of production and economy.

The amount of unsaturated monocarboxylic acid bonded in the olefin copolymer CB) is desirably 0.1 mol% or more and 75 mol% or less, particularly 0.5 mol% or more! 5 mol% is preferred. It is also possible to use an olefin copolymer grafted with 0.1 mol % or more of an unsaturated monocarboxylic acid monomer.

The unsaturated monocarboxylic acid is the olefin copolymer (
It serves as a crosslinking reaction point with A) and to provide adhesiveness to a wide variety of base materials, and there is no need for it to be present in excess from either point of view. If the amount increases, water absorption increases, which not only has negative effects such as foaming during molding and deterioration of electrical properties due to water absorption after molding, but also production problems such as safety, separation, and recovery, and economic problems. This is also disadvantageous and undesirable. On the other hand, if it is less than 0.1 mol %, there will be no problem in terms of adhesiveness, but it will be insufficient in terms of heat resistance, which is not preferable.

(C) Olefin copolymer (C) Furthermore, the olefin copolymer (C) used in the present invention is an olefin copolymer consisting of the above α-olefin and an unsaturated carboxylic acid ester. It is a copolymer obtained by saponifying some or all of the ester groups and performing a neutralization reaction such as demetalization treatment, and 1
It is preferable that the material melts at a temperature of 50° C. or lower and has fluidity.

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

The content of unsaturated carboxylic acid ester in the olefin copolymer (C) is preferably 1 to 25 mol%.

The saponification rate of ester depends on the content of ester, but it is 2
0 to 80% is preferred.

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:
This can be done by adding NaOH and a copolymer containing an ester group to 50) and refluxing for 3 hours. Saponification rate is Ma
c)! The amount can be adjusted arbitrarily. 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 (C) 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).

CD) Olefin copolymer (D) The olefin copolymer (D) is a copolymer of the above α-olefin and an unsaturated dicarboxylic acid or a monoester thereof (which may also contain the third component) Alternatively, an olefinic copolymer of an α-olefin and an anhydride of the unsaturated dicarboxylic acid (which may contain the third component) may be modified to remove some or all of the acid anhydride groups. may be dicarboxylated or halfesterized.

It is preferable to use one that melts at a temperature of 150°C or lower.

Examples of the α-olefin and the third component include the same types of compounds as the olefin copolymer (A).

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 (methyl)hymic acid.

In the olefin copolymer (1111), the amount of the third component is desirably 70% by weight or less, particularly preferably 10 to 80% by weight. Even if the content exceeds 70% by weight, the characteristics of the present invention are exhibited, but it is not necessary to exceed 70% by weight, which is unfavorable in terms of production and economy.

The amount of unsaturated acid anhydride groups bonded in the copolymer (D) is 0.
It is preferably 1 mol% or more and 75 mol% or less.

More preferably, it is 0.5 mol% to 15 mol%. Note that a copolymer of an olefin and the third component grafted with 0.1 mol % or more of unsaturated acid anhydride groups may also be used. The unsaturated acid anhydride group serves as a crosslinking reaction site with the olefin copolymer (A) and provides adhesion to various base materials, and from both points of view, it is not excessive. It doesn't have to be in

The olefin copolymer (D) used in the present invention is obtained by modifying the acid anhydride group in the above copolymerization.

Denaturation is carried out, for example, by hydrolysis and/or halfesterization with alcohols, typical examples of which are methanol, ethanol, propatool,
Examples include general alcohols having at most 20 carbon atoms, such as butanol.

Of the olefin copolymers (D) obtained in this way, the halfesterized acid anhydride and its dicarboxylic acid monoester (septumerium) generally have at most 40 carbon atoms. , especially those with 5 to 20 pieces. Typical examples thereof include those in which the carboxylic acid group of any of the representative dicarboxylic acids is halfesterified with the representative example of the -class alcohol; representative examples include maleic acid monomethyl ester,
Examples include monoethyl maleate, monoimpropyl maleate, monobutyl maleate, and monoethyl itaconate.

Incidentally, in the above example, an olefin copolymer (D) is obtained by modifying an olefin copolymer containing an acid anhydride group. It is also possible to copolymerize as an independent copolymerization component (for example, maleic acid ester) without modification. For example, α-olefin, alkyl (meth)acrylate,
The four components of maleic anhydride and maleic ester may be copolymerized.

(E) Production of composition In producing the composition of the present invention, the olefin copolymer (A) and the olefin copolymer (B), the olefin copolymer (C), or the olefin copolymer are used. (D
) are mixed evenly.

The mixing method may be a tri-blend 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 screw extruder, roll mill, etc. A method of melting and mixing using a mixer may also be used. At this time,
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, the olefin copolymer (A) and the olefin copolymer (B), the olefin copolymer (C), or the olefin copolymer (D) are substantially crosslinked. It is necessary to carry out the reaction under non-reactive conditions.

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, the olefin copolymer (A), olefin copolymer (B), olefin copolymer (C), and olefin copolymer (D)
Depending on the viscosity at each temperature, 25°C (room temperature) to 150°
The temperature is preferably 140°C or less.

For this purpose, the softening temperature or normal crystal melting temperature of the olefin copolymer (A), olefin copolymer (B), olefin copolymer (C), and olefin copolymer (D) is l 20 '0 or less, especially 10
The temperature is preferably 0°C or lower, and the fluidity is preferably as high as possible.

The composition ratio (mixing ratio) of the olefin copolymer (A) in the resulting mixture (composition) is 1 to 99.
% by weight, preferably from 2 to 98% by weight, particularly from 5 to 98% by weight.
95% by weight is preferred. Since it is difficult to obtain a uniform composition when the composition ratio is greatly different or when there is a large difference in viscosity, it is necessary to use something with a viscosity as close as possible.
The desired composition can also be produced by preparing a highly concentrated masterbatch with a composition ratio of nearly 1:1 and diluting it.

When producing the composition of the present invention, antioxidants, ultraviolet deterioration inhibitors, foaming agents, foaming aids, metal deterioration inhibitors, flame retardants,
Additives such as adhesives and fillers such as carbon black may be added as long as they do not impair the properties of the composition of the present invention.

CF) Method for producing crosslinked product (crosslinked polymer) A molded crosslinked polymer can be obtained by casting and heating the composition obtained as described above, and First, a film was formed using a T-die film forming machine, and this film was laminated on one or both sides to various base materials such as aluminum, paper, cellophane, copper, polyimide resin film, PET, PBT, nylon, and polysulfone. Afterwards, the composition can be bonded by heating or by preparing a sheet of appropriate thickness using a roll or calendar roll, sandwiching these between the substrates to be bonded, and pressing them with high temperature heat. can. 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 240°C or less, 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;
It can be firmly bonded by bonding various base materials together and heating them, and of course has 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. Pipes can be made in the same way.

The heating temperature for crosslinking varies slightly depending on the comonomer composition of each olefin copolymer used, but
Generally, the temperature is 155°C or higher, particularly preferably 170°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 hours.

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 olefin copolymer (A) and other olefin copolymers must be adjusted. is preferably 10% or more, preferably 50% or more, particularly a gel fraction of 70% or more is optimal, and it is necessary to adopt such conditions.

Also, according to J Is, -7210, the load is 2.18
Kg, the fluidity index under the condition of temperature 190°C is 0.0
1 g/10 minutes or less.

The gel fraction was determined by placing the cross-linked polymer sample in a 300-mesh wire mesh, performing Sonxhlet extraction with elevated toluene for 6 hours, drying it in the wire mesh at 80°C for 18 hours, and then measuring the weight. The weight remaining in the wire mesh was calculated and expressed as a weight percentage.

Example 7 and L 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, etc./＼-phesterification rate and M
I is shown in Table 1.

Example 1, Comparative Example 1 The olefin copolymer (A) [hereinafter referred to as "copolymer (A)"] and the olefin copolymer (B) [hereinafter referred to as "copolymer (A)]" shown in Table 1 were used. olefin copolymer (C) [hereinafter referred to as "copolymer (C)"]
Or olefin copolymer (D) [hereinafter referred to as “copolymer (D)”
D)", the diameter of part of the cylinder is 301
Mixing was carried out using an 11 m single screw extruder at a temperature of 140° C. or lower to obtain a mixed composition having the ratio shown in Table 2.

Using these T-die film forming machines with a cylinder diameter of 40 mm, the temperatures of cylinder parts C1, C2, C3 and the die were set to 110°C, 115°C, 120°C, and 1, respectively.
Film molding was carried out at 25°C, and clear films with a thickness of 60 to 100 microns and no gel or fish eyes were obtained.

These films are coated with aluminum foil (70 microns)
Preheat at 160°C, 180°C, and 240°C for 1.5 minutes and press at 20 kg/cm' for different times.
A 0.23 mm adhesive plate was obtained. The adhesive strength (T-type peeling IJIS KEi854) of the obtained adhesive plate at room temperature was extremely high as shown in Table 2. In addition, the gel fraction of each sample at this time is also shown in Table 2. In addition, Teflon sheets were placed above and below the non-crosslinked T-die film at 160°C, 180°C, and 2°C.
At 40°C, 0.23ma using the same method as when making the adhesive board.
A sheet with + thickness was created. These were heated at 200℃, 2
50°C1300°C, 3-30°C in solder bath at 350°C
These were soaked for a minute and the state of the film was observed. The results are as follows: Examples 2 to 7 Olefin copolymer (A) and olefin copolymer (
B), a 50:50 mixed composition with the olefin copolymer (C) or the olefin copolymer (D) was heated in a lab blast mill at a temperature of 110°C or less at a rotor rotation speed of 40
A composition was obtained by mixing with rotating force for 3 to 4 minutes. Next, sheets with a thickness of 1.5 am are made using rolls at 85°C, sandwiched between Teflon sheets, and heated at a temperature of 180 to 240°C for 30 minutes to 20 minutes.
A crosslinked sheet was prepared by pressing at a pressure of 20 kg/cm' for an hour.

Table 3 shows data on gel fraction, heat resistance, electrical properties (humidity 53 to 97%), and volume resistivity after boiling in boiling water for 2 hours for these crosslinked sheets.

(Left below) Example 8 The uncrosslinked T-die film obtained in Example 1 was pressed onto aluminum foil at 230°C for 10 to 30 minutes or at 300°C.
Positive pressure bonding was carried out at 5-20 Kg/cm' for 3-10 minutes at C. These were sampled in a tanzak shape with a width of 25+ am, and 10
After repeating the heat cycle operation 5 to 10 times, in which the head is quickly removed and immersed in dry ice methanol at -80°C and left for 10 minutes, it is heated to room temperature (21'C).
Table 4 shows the results of measuring the adhesive strength.

This result shows that the adhesive strength remains strong even after extremely severe heat cycles.

Example 9 50 pieces of A-3 and D-3 molded in the same manner as Example 1
A T-die film of a mixed composition of 230 mm was sandwiched between aluminum foils (100 pm).
Adhesion was performed using a press at a pressure of 20 kg/cm' for 5 minutes at °C. This sandwich sample was cut into 25 mm wide tanzak shapes and immersed in boiling water for up to 48 hours.

After that, leave it in a constant temperature room at 21°C and 54% humidity for 2 hours.
Adhesive strength was measured by the type jlI release test method. The adhesive strength after 4 hours and 48 hours of immersion was 9.8, respectively.
It was 8,8Kg and 725mm. Even when the crosslinked product of the present invention was immersed in boiling water, the adhesive strength remained constant regardless of the immersion time and was very strong.

(Left below) Table 4 Example 10 The α-olefin copolymer (89 mol% ethylene,
8.5 mol% ethyl acrylate, 1 maleic anhydride,
5 mol %) was dissolved in 200 m of toluene, 100 cc of water and 3 times the mole of triethylamine as the maleic anhydride moiety 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 the mixture was further added with hydrochloric acid and left overnight until it became weakly acidic. Thereafter, hexane was added as a precipitation solvent to precipitate the polymer, and the hexane was exchanged several times to wash with poly. Thereafter, the polymer was vacuum dried at 40°C overnight.

Regarding the hydrolysis rate, IR measurement was conducted at 17130 cm.
Calculated from the decrease in absorption due to acid anhydride,
It was 100% hydrolyzed.

Example 11 An example of the halfesterization reaction is shown below.

Copolymer (88 mol% ethylene, ethyl acrylic b, kQ
I; hand” 1) to senior minister-ni de 17 iso vertical
Dissolve 20g of water) in 200ml of toluene, add 100ml of methanol and 100ml of triethylamine.
rnl was added and reacted for 6 hours under methanol reflux conditions. Thereafter, the precipitation solvent was removed, hexane was added to precipitate the polymer, and the hexane was exchanged several times to wash the polymer. Thereafter, the polymer was vacuum dried at 40°C overnight.

For the Hafestelization rate, see IR measurement 178
Calculating from the decrease in absorption due to acid anhydride at 0 cm-', 70% of maleic anhydride was halfesterized.

A-3 and B-2 (hereinafter referred to as raJ), A-3 and C-1
(hereinafter referred to as rbJ) and A-2 and D-2 (hereinafter referred to as r
cJ), A-3 alone (hereinafter referred to as rdJ), and B-2 alone (hereinafter referred to as "e") using a castometer (manufactured by Toyo Baldwin, model number JSR-m type) is used,
A crosslinking curve was determined at a temperature of 200'0(7). The results are shown in Figure 1.

From this Figure 1, it can be seen that when the olefin copolymer alone does not crosslink, as in A-3 or B-2, there is no increase in torque, but A-3 and B-2, A-3 and C −
In the case of a mixture (composition) like No. 1, it is clear that a crosslinking reaction occurs at this temperature and the torque increases.

The uncrosslinked composition obtained by the present invention has good fluidity and excellent processability, so 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.

1) Regarding thermal properties, generally no discoloration, foaming or deformation occurs even at temperatures of 300°C or higher, even 360°C or higher for short periods of time.

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

The compositions and crosslinked products thereof obtained according to the present invention have the above-mentioned effects, and therefore can be widely and effectively utilized in a wide variety of fields.

In addition to heat resistance and adhesion, it has high electrical insulation properties such as volume and surface resistivity, and has excellent electrical properties such as low dielectric constant and :A electric dissipation tangent, and has adhesive strength of 1 water resistance, organic solvent resistance, and acid resistance. , has excellent chemical resistance such as alkali resistance,
Also, heat cycle resistance of adhesive strength, boiling resistance (#humidity)
Because of its outstanding properties such as excellent etching and plating properties, it is suitable for use in a variety of electrical and electronic equipment, including electronic materials such as printed circuit board laminates and flexible wiring boards. suitable. In addition, heat resistance,
Used as a material for automobile parts that require adhesive properties.

[Brief explanation of drawings]

Figure 1 shows A-3 and B-2 (a), A-3 and C-1 (
b) and a mixture of A-2 and D-2 (c), as well as A-3 alone (d) and B-2 alone (e). In this figure, the vertical axis is torque (Kg - c
m), and the horizontal axis is the crosslinking time (minutes).

Claims (1)

[Claims] (A) A copolymer (A) consisting of at least an olefin and a compound represented by the following structural formula (I), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a vinyl group, an allyl group or a methallyl group) and (B) (1) a copolymer consisting of at least an olefin and an unsaturated monocarboxylic acid, (2) an olefin system consisting of at least an olefin and an unsaturated carboxylic acid ester A copolymer obtained by saponifying and neutralizing a copolymer, and (3) at least one copolymer selected from the group consisting of a copolymer of at least an olefin and an unsaturated dicarboxylic acid or a half ester thereof. A crosslinkable composition comprising a copolymer (A) in a proportion of 1 to 99% by weight.