JPH0311307B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a composition capable of producing a heat-resistant crosslinked polymer. More specifically, an (ethylene)-based copolymer (A) of at least (ethylene) and glycidyl (meth)acrylate
and an (ethylene)-based copolymer (B) of at least (ethylene) and an unsaturated monocarboxylic acid, or a composition comprising the copolymer (A) and at least (ethylene) and an unsaturated carboxylic acid ester. Obtained by saponifying and neutralizing a copolymer (ethylene)
A composition comprising a copolymer (C) or a crosslinkable composition comprising the copolymer (A) and a copolymer (D) comprising at least (ethylene) and an unsaturated dicarboxylic acid or a half ester. The object of the present invention is to provide a crosslinked product that not only has excellent heat resistance but also has good adhesion to metals and the like. Prior Art Until now, adhesive thermoplastic polymer compositions have been known that are made by mixing an epichlorohydrin polymer with a thermoplastic polymer having an alcoholic hydroxyl group in the molecule. Furthermore, 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. Furthermore, a composition comprising polyvinyl alcohol with a degree of saponification of 85% or less and an olefinic copolymer containing 10% by weight or less of a copolymerized unsaturated carboxylic acid or its acid anhydride has been proposed (Unexamined Japanese Patent Publication No. Akira
55-127450), which relates to a resin composition for a heat-retaining film, and is intended to improve the uniform dispersibility of polyvinyl alcohol and olefin copolymer, which have heat-retaining properties. 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 Patent Application Laid-open No. 52-62362), 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 synthetic resin or a crosslinking 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. Problems to be Solved by the Invention From the above, the present invention does not have these drawbacks (problems) and has not only excellent heat resistance but also good adhesion to various materials such as metals. (Ethylene) polymer composition or crosslinked product. Means and Effects for Solving the Problems According to the present invention, the above problems are solved by using the following four ethylene copolymers; (A) consisting of at least ethylene and glycidyl alkyl (meth)acrylate; (B) Ethylene-based copolymer obtained by radical polymerization under high pressure (hereinafter referred to as "copolymer (A)"), (B) consisting of at least ethylene and an unsaturated monocarboxylic acid, obtained by radical polymerization under high pressure. Copolymer [hereinafter referred to as "copolymer (B)"]
(C) An ethylene copolymer consisting of at least ethylene and an unsaturated carboxylic acid ester, obtained by saponifying and neutralizing an ethylene copolymer obtained by radical polymerization under high pressure [hereinafter referred to as "copolymer"] (C)”
] and (D) an ethylene copolymer consisting of at least ethylene and an unsaturated dicarboxylic acid obtained by radical polymerization under high pressure, or a half-esterified ethylene copolymer thereof [hereinafter referred to as "copolymer"]
(D)], the weight composition ratio with copolymer (A) is 1/99 to 9.
9/1 copolymer (A) and copolymer (B), copolymer (A) and copolymer (C), and copolymer (A) and copolymer
This problem can be solved by using a crosslinkable composition selected from (D) that is capable of crosslinking. The present invention will be specifically explained below. (A) (Ethylene)-based copolymer (A) The (ethylene)-based copolymer (A) of the present invention is a copolymer of at least (ethylene) and glycidyl alkyl (meth)acrylate. It is preferable to use one that melts at a certain temperature and has fluidity. For this purpose, it is desirable to include a third component such as an unsaturated carboxylic acid ester or a vinyl ester. Examples of the glycidyl alkyl (meth)acrylate include those represented by the following general formula. (Here, R ₁ is H or a methyl group and R ₂ is a linear or branched alkyl group having 1 to 12 carbon atoms.)
Examples include butenetricarboxylic acid monoglycidyl ester, glycidyl methacrylate, glycidyl acrylate, glycidyl tarotonate, glycidyl ethacrylate, and itaconic acid glycidyl ester. The amount of the epoxy-containing monomer is preferably 0.1 mol% or more and 17 mol% or less. The higher the amount, the better from the viewpoints of adhesion and heat resistance, but if it is less than 0.1 mol%, not only will the adhesion not be improved much, but the composition and reaction conditions with the copolymer (A) will change. However, sufficient heat resistance cannot be obtained. On the other hand, 17 mol%
If it exceeds this, the water absorption of the copolymer will increase, which will not only cause undesirable effects such as foaming during molding and deterioration of electrical properties due to absorption after molding, but also problems with manufacturing issues such as safety, separation, and recovery. This is not desirable because it causes problems and is disadvantageous economically. As the unsaturated carboxylic acid ester, those with good thermal stability such as methyl (meth)acrylate and ethyl (meth)acrylate are preferable, and t-
Materials with poor thermal stability such as butyl (meth)acrylate are undesirable because they cause foaming. Examples of vinyl esters include vinyl acetate and vinyl propionate. The copolymer (A) can be prepared, for example, under high pressure (500 to 2500
Copolymer (A) can be produced by radical polymerization at a temperature of 120 to 260°C (kg/cm ² ).
If the sum of the third component and glycidyl alkyl (meth)acrylate exceeds 70% by weight, the softening point of the polymer will become high and the fluidity at temperatures below 150°C will be impaired, which is not only undesirable but also economically undesirable. I also don't like it. 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 above-mentioned glycidyl alkyl (meth)acrylate can be used as an active site for crosslinking with copolymer (B), copolymer (C), or copolymer (D), and as an adhesive agent for various substrates. Although it plays a role,
If the amount of glycidyl acrylate bound is less than 0.4% by weight, even if the comonomer composition of copolymer (B), copolymer (C) or copolymer (D) is changed or the copolymer
Even if the composition of (A) and copolymer (B), copolymer (C), or copolymer (D) is changed, the number of substantial crosslinking points is insufficient,
Unfavorable in terms of heat resistance. In addition, the melt index (JIS
Compliant with K-7210, temperature is 190℃ and load is
Measured at 2.16Kg (hereinafter referred to as "MI") is usually 0.5g/
The heating time is 10 minutes or more, preferably 5.0 g/10 minutes or more, and particularly preferably 50 g/10 minutes or more. Furthermore, this
Regarding MI, the same applies to conventional copolymers (B), copolymers (C), and copolymers (D). (B) (ethylene) copolymer (B) Also, (ethylene) copolymer (B) is (ethylene)
and an unsaturated monocarboxylic acid,
It is preferable to melt at a temperature of 150°C or less and have fluidity.
Those containing ingredients are preferred. Examples of unsaturated monocarboxylic acids that can be used in the present invention include acrylic acid and methacrylic acid. In addition, a copolymer of (ethylene) and an unsaturated carboxylic acid such as copolymer (B) can be used in the same way as the above-mentioned copolymer (A).
Radical polymerization is carried out under an ultra-high pressure of 2500 Kg/cm ² at a temperature of 120 to 260 °C, using a chain transfer agent as necessary, in an autoclave with a stirrer or a tubular reactor, and using a free radical generator such as peroxide. be able to. In the copolymer (B), the amount of the third component is preferably 70% by weight or less, particularly preferably 10 to 60% by weight. 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 bound in the copolymer (B) is preferably 0.1 mol% or more and 75 mol% or less, particularly preferably 0.5 mol% to 15 mol%. The unsaturated monocarboxylic acid serves as a crosslinking reaction site with the above copolymer (A) and to provide adhesiveness to a wide variety of base materials, and from both points of view, there is no need for it to be in excess. do not have. 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 not desirable. 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) (ethylene) copolymer (C) Furthermore, the (ethylene) copolymer (C) used in the present invention is composed of the above (ethylene) and an unsaturated carboxylic acid ester (ethylene). It is a copolymer obtained by saponifying some or all of the ester groups in the copolymer and performing a neutralization reaction such as demetalization treatment.It melts at a temperature of 150℃ or less and has good fluidity. It is better to have Examples of unsaturated carboxylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, hydroxymethyl (meth)acrylate,
Examples include diethyl fumarate. The content of unsaturated carboxylic acid ester in the (ethylene) copolymer (C) is preferably 1 to 25 mol%.
The saponification rate of ester is preferably 20 to 80%, although it depends on the ester content. The saponification reaction can be carried out by a widely known method, for example, by adding a copolymer containing NaOH and an ester group to a mixed solvent 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 was precipitated with water or alcohol, and after filtering the solvent, it was heated at 50°C overnight.
Dry in vacuum. The (ethylene) copolymer (C) is obtained by dispersing this polymer in water, adding sulfuric acid to it, and stirring at 70°C for 1 hour to perform a metal removal treatment (=neutralization reaction). (D) (ethylene)-based copolymer (D) (ethylene)-based copolymer (D) is an (ethylene)-based copolymer containing (ethylene) and an unsaturated acid anhydride group (the third component ) is modified so that some or all of the acid anhydride groups are dicarboxylic acids or half esters,
It is best to use one that melts at a temperature of 150℃ or less. Examples of the third component include the same type of compound as the (ethylene) copolymer (A). Examples of unsaturated acid anhydride groups include maleic anhydride, tetrahydrophthalic anhydride, maleobimaric anhydride, 4-methylcyclohex-4-ene-1,
Examples include 2-carboxylic anhydride, bicyclo 2,2,1-hept-5-ene-2,3-dicarboxylic anhydride, and the like. In the copolymer (D), the amount of the third component is desirably 70% by weight or less, particularly preferably 10 to 60% 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
It is preferably 0.1 mol% or more and 75 mol% or less. More preferably, it is 0.5 mol% to 15 mol%. The unsaturated acid anhydride group serves as a crosslinking reaction site with the above (ethylene) copolymer (A) and to provide adhesiveness to various substrates. It doesn't need to be excessive either. (Ethylene) copolymer (D) used in the present invention
is obtained by modifying the acid anhydride group in the above copolymerization. The modification is carried out, for example, by hydrolysis and/or half-esterification with an alcohol, and examples of the alcohol include primary alcohols such as methanol, ethanol, propanol, and butanol. In addition, in the above, by modifying the (ethylene) copolymer containing an acid anhydride group, (ethylene)
Although an example of obtaining a copolymer (D) has been shown, it is also possible to copolymerize the parts constituting the copolymer as an independent copolymer component (e.g., maleic ester) without modifying the maleic anhydride group. It's okay. For example, the four components of (ethylene), alkyl (meth)acrylate, maleic anhydride, and maleic ester may be copolymerized. (E) Production of composition In producing the composition of the present invention, the above copolymer (A) and copolymer (B), copolymer (C) or copolymer are used.
Mix (D) uniformly. The mixing method may be dry blending using a mixer such as a Henschel mixer, which is commonly used in the field of olefin polymers, or mixing using a Banbury mixer, twin screw extruder, single screw extruder, roll mill, etc. A method of melting and mixing using a machine may also be used. At this time, a more uniform mixture can be produced by performing dry blending in advance and melt-mixing the resulting mixture, and by using a static mixer or the like at the tip of the extruder. In addition, when mixing in a molten state, the copolymer (A) and copolymer (B), copolymer (C), or copolymer (D) may be mixed under conditions that do not substantially cause a crosslinking reaction. is necessary. 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 copolymer (A), copolymer (B), copolymer (C) and copolymer (D)
Depending on the viscosity at each temperature, 25℃ (room temperature) ~ 150℃
The temperature is preferably 140°C or lower, especially 140°C or lower. For this purpose, the softening temperature or normal crystal melting temperature of copolymer (A), copolymer (B), copolymer (C), and copolymer (D) is 120°C or lower, especially 100°C or lower. It is preferable that the fluidity is as large as possible. The mixing composition of copolymer (A) and copolymer (B), copolymer (C), or copolymer (D) is 99:1 to 1:1.
99 (preferably 2:98 or 98:2, suitably 5:95 or 95:5), but if the composition ratio is significantly different or the viscosity difference is large, a uniform composition can be obtained. Since this is difficult, it is also possible to create the desired composition by using something with a viscosity as close as possible, or by creating a high-temperature master batch with a composition ratio close to 1:1 and then diluting it. can. When producing the composition of the present invention, antioxidants, ultraviolet deterioration inhibitors, foaming agents, foaming aids, metal deterioration inhibitors, flame retardants, and adhesives commonly used in the field of olefinic polymers are used. Additives such as carbon black and fillers may be added as long as they do not impair the properties of the composition of the present invention. (F) Method for producing crosslinked product (crosslinked polymer) By casting and heating the composition obtained as described above, a shaped crosslinked polymer can be obtained, and the composition First, a film is formed using a T-die film forming machine, and this film is laminated on one or both sides to various base materials such as aluminum, paper, cellophane, copper, polyimide resin film, PET, PBT, nylon, and polysulfone. After that, by heating, or by preparing a sheet of an appropriate thickness from the composition using a roll or calender roll, sandwiching these between the substrates to be bonded, and bonding them by hot pressing at a high temperature. Can be done. Or, after performing two-layer or multi-layer lamination in a manner similar to the method generally known as extrusion lamination,
By heat-treating at high temperatures, a composite material with high heat resistance and adhesive strength can be obtained. Further, a crosslinked film of the composition can also be produced by arranging rolls of film at different temperatures one after another from a low temperature to 230 to 240°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.
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 crosslinked foamed film or sheet, or by attaching a base material on both sides, you can create a heat-resistant crosslinked foamed composite material (sandermanch) 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 the copolymer (A), copolymer (B), copolymer (C), or copolymer (D), 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 of copolymer (A), copolymer (B), copolymer (C), or copolymer (D), but is on the order of several seconds to several hours. It is. In addition, in order to sufficiently exhibit adhesiveness and heat resistance of the crosslinked polymer made of the composition of the present invention, it is necessary to combine copolymer (A) with copolymer (B), copolymer (C), or copolymer. The gel fraction of the crosslinking reaction product (D) is preferably 10% or more, preferably 50% or more, and especially optimally contains 70% or more of gel, and it is necessary to adopt such conditions. be. In addition, according to JIS K-7210, load 2.16Kg, temperature
The fluidity index under the condition of 190°C is 0.01 g/10 minutes or less. In addition, the gel fraction is 300% for the crosslinked polymer sample.
It was placed in a mesh wire mesh, subjected to Soxhlet extraction with boiling toluene for 6 hours, then dried at 80°C for 16 hours in the wire mesh, and then weighed.The weight remaining in the wire mesh was calculated and expressed as weight percentage. It is something. Examples and Comparative Examples In addition, the second comonomer that is a comonomer of the copolymer (A), copolymer (B), copolymer (C), and copolymer (D) used in the examples and comparative examples, Table 1 shows the copolymerization ratio of the third comonomer, its type, saponification rate, degree of neutralization, half-esterification rate such as hydrolysis, and MI. Example 1, Comparative Example 1 Regarding A-4 and B-2 listed in Table 1,
Using a single-screw extruder with a cylinder diameter of 30 mm, mix at a temperature of 140°C or less, 50:50, 30:70.
A mixed composition was obtained. Using these T-die film forming machines with a cylinder diameter of 40 mm, the temperatures of C ₁ , C ₂ , C ₃ of the cylinder part and the die were set to 110°C, 115°C, 120°C, respectively.
Film molding was performed at a temperature of 125°C, and clear films with a thickness of 60 to 100 microns and no gel or fish eyes were obtained. These films were preheated to aluminum foil (70 microns) at 160℃, 180℃, and 240℃ for 1.5 minutes and then pressed.
Pressing was performed at 20 kg/cm ² for different times to obtain a 1.5 mm adhesive plate. The adhesive strength (T-peel JIS K6854) 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, and
Then, I made a 1.5mm thick sheet using the same method as when making the adhesive board. These are 200℃, 250℃,
These were immersed in a solder bath at 300°C and 350°C for 3 to 30 minutes, and the state of the film was observed. The results are shown in Table 2.

【table】

【table】

[Table] ** ○: Original shape △: Slightly deformed ×: Modified examples 2 to 7 Copolymer (A) and copolymer (B), copolymer (C) or copolymer (D) A composition was obtained by mixing a 50:50 mixed composition of the following with a laboplasto mill at a temperature of 110° C. or lower and a rotor rotation speed of 40 revolutions/minute for 3 to 4 minutes. Next, make sheets with a thickness of 1.5 mm using a roll at 85℃, sandwich these between Teflon sheets like a sandwich, and heat them at a temperature of 180 to 240℃ for 30 minutes.
A crosslinked sheet was prepared by pressing at a pressure of 20 kg/cm ² for 2 hours. Data on the gel fraction, tensile strength, isot impact (-40℃), hardness, electrical properties (humidity 53-97%), and volume resistivity after boiling in boiling water for 2 hours of these crosslinked sheets were collected in the third section. Shown in the table.

[Table] Examples 8 to 14 50:50 compositions of various combinations of copolymer (A) and copolymer (B), copolymer (C), or copolymer (D) were prepared in advance. , T-die films were formed in the same manner as in Example 1, and these films were used to mold glass, cellophane, 6-nylon, polycarbonate, Bakelite, polyethylene, and polypropylene in the same manner as in Example 1. They were heated using a lamination press at 120 to 150°C for 20 to 30 minutes, and bonded with or without pressure (in the case of glass). The 180 degree peel strength of these adhesives was measured using a Tensilon (tensile testing machine) at a tensile speed of 100 mm/min. Table 4 shows these adhesive strengths and gel fractions. The glass was crosslinked by heating without applying pressure using a sandwich structure of glass/adhesive layer (film of copolymer composition)/aluminum foil, and aluminum was used as a support during peeling. The cellophane was formed into a sandwich of cellophane/adhesive layer/cellophane and was pressed and heated at a pressure of 10 kg/cm ² . The 6-nylon was bonded in the form of a sandwich of 6-nylon/adhesive layer/aluminum foil by heating at a pressure of 10 kg/cm ² . Aluminum foil was used as a support. The same process was carried out for polycarbonate and Bakelact. Polyethylene and polypropylene are made of polyethylene or polypropylene/adhesive layer/polyethylene or polypropylene sandwich shape and pressure 10Kg/
The adhesive was bonded by applying pressure (heating) at cm ² and the adhesive strength was measured. The results obtained are shown in Table 4.

[Table] Example 15 Laboplasto Mill 95℃, 40 rotations/min, A-4
and B-2, A-3 and C-3, A-4 and D-4, and A-2 and D-2 at a ratio of 1:1 for 3 minutes to prepare mixed compositions. At the same time, 3% by weight of Cellmic CAP-500, a product of Sankyo Kasei Co., Ltd., was mixed in as a foaming agent. A press sheet having a thickness of 1 mm was prepared from these mixed compositions by pressing at 110°C. When this press sheet containing the foaming agent was placed on aluminum foil and heated in an oven at 230°C for 5 minutes, a foam with an expansion ratio of about 30 times was obtained. The gel fraction of this foam is 83%, and
Adhesion was 6.5Kg/25mm. Further, the uncrosslinked press sheet containing the foaming agent was sandwiched between aluminum foils to form a sandwich, and this was pressed at 110° C. for 1 minute at a pressure of 5 kg/cm ² to adhere the aluminum foils to both sides. The thickness of the adhesive resin was 0.5 mm. When this was heated in an oven at 230° C. for 5 minutes at normal pressure, a sandwich-like foam was obtained. The gel fraction of these was 89% or more, and the adhesive strength was 4.7Kg/25mm or more. Even when these foams were placed in an oven at 350°C, no deformation or coloring occurred and they showed excellent heat resistance. Example 16 Similar to Example 15, A-4 and B-4 containing 3% by weight of Cellmic CAP-500 were prepared using Labo Plastomill.
A 1:1 mixed composition of 2 was prepared. 5 of these
The blowing agent copolymer mixture was pressed onto paper/sample/paper sandwiches at 110° C. and a pressure of 5 kg/cm ² for 1 minute. When these were heated in an oven at 1 atm at 190°C for 10 minutes, a sandwich-like foam was obtained. These adhesive strengths were so strong that in all cases, the base material (paper), not the adhesive interface, was destroyed. Even when this foam was left in an atmosphere at a temperature of 250° C. or more for more than one hour, no deformation occurred. Note that similar adhesive strength was obtained even when the foam was bonded to paper after it was made. Example 17 The uncrosslinked T-die film obtained in Example 1 was pressed onto aluminum foil at 230°C for 10 to 30 minutes or 300 minutes.
Adhesion was carried out at 5-20 Kg/cm ² pressure for 3-10 minutes at ℃.
These were sampled in a tanzak shape with a width of 25 mm,
After repeating the heat cycle operation 5 to 10 times by leaving it in an oven at a high temperature of 150 to 300 degrees Celsius for 10 minutes, quickly taking it out, immersing it in dry ice methanol at -80 degrees Celsius, and leaving it for 10 minutes, it was heated to room temperature (21 degrees Celsius). ) The results of measuring the adhesive strength are shown in Table 5. This result shows that the adhesive strength remains strong even after extremely severe heat cycles. Example 18 A-4 and D- molded in the same manner as Example 1
A T-die film of a 50:50 mixed composition of No. 4 was sandwiched between aluminum foils (100 μm) in the shape of a sandwich sandwich and adhered by pressing at 230° C. for 5 minutes at a pressure of 20 kg/cm ² . This sandwich-like sample was cut into 25 mm wide tanzak shapes and immersed in boiling water for up to 48 hours. Thereafter, the adhesive strength was measured by the T-peel test method after being left in a constant temperature room at 21° C. and 54% humidity for 2 hours. Adhesion strength after 4 hours and 48 hours of immersion, respectively.
It was 10.2, 9.3Kg/25mm. 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.

【table】

[Table] Example 19 3 to 5% by weight of antimony trioxide as a flame retardant for a 1:1 composition of A-4 and D-4, AFR1002
(manufactured by Asahi Glass Co., Ltd.) in an amount of 9 to 30% by weight was mixed at 110° C. for 4 minutes at 40 revolutions/minute using a Laboplasto Mill. This mixture was rolled into a sheet with a thickness of 1.5 mm (100°C), and sandwiched between aluminum foil and a Teflon sheet in the shape of a sandwich.
Obtained by pressing at a pressure of Kg/cm ² . The adhesive strength of the former sample was measured using the T-peel method, and the temperature dependence of flammability and electrical properties of the latter sample was measured using ASTM D635. The results are shown in Table 6. Example 20 Using the same method as Example 17, the composition was the same as Example 19, and 3% by weight of the above-mentioned Cellmic CAP-500 was added.
Mixed and cross-linked and foamed in the same manner as in Example 15,
The foaming state and combustibility were evaluated and the results are shown in Table 7.

【table】

[Here, C〓 is an amount proportional to the concentration of uncrosslinked epoxy groups, and C〓 is an amount proportional to the concentration of epoxy groups after crosslinking. Also, 〓 _a is the absorption of 850 cm ^-1 of (), 〓 _b is the absorption of 4250 cm ^-1 of (), and furthermore, 〓 _a is the absorption of 850 ^-1 I of (), and 〓 _b is The absorption of () is 4250cm ^-1 . ]

The reaction rate is expressed as C〓−C〓/C〓×100, and from the respective infrared absorption spectra in Figures 1 and 2, the 82
% decreased, indicating that a crosslinking reaction was occurring. Effects of the Invention 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. (1) Regarding heat resistance, it generally does not cause discoloration, foaming, or deformation even at temperatures of 300°C or higher, or even 360°C or higher for short periods of time. (2) Regarding adhesiveness, if 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, This is due to strong adhesion to the third substance.
Third substances include metals and alloys such as aluminum, copper, iron, stainless steel, brass, galvanized iron, and tinplate, glass ceramics, amide, imide resin, polysulfone,
Examples include synthetic resins having polar groups such as polyester, polycarbonate, polyurethane, cellophane, various papers, and modified polyolefin polymers obtained by grafting monomers having polar groups. The compositions and crosslinked products thereof obtained by the present invention have the above-mentioned effects and can be widely and effectively utilized in a wide range of fields. In addition to heat resistance and adhesion, it has high electrical insulation properties such as volume and surface resistivity, excellent electrical properties such as low dielectric constant and low dielectric loss tangent, and adhesive strength such as water resistance, organic solvent resistance, acid resistance, alkali resistance, etc. It has excellent chemical resistance, excellent adhesive strength, heat cycle resistance, and boiling resistance (moisture resistance), as well as excellent etching and plating properties, making it suitable for printed circuit boards. It is suitable for various electrical and electronic devices such as electronic materials such as laminates and flexible wiring boards. In addition, heat resistance,
It is used as a material for automobile parts that require adhesive properties.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of a non-crosslinked film of a mixture of A-4 and B-2, and FIG. 2 is an infrared absorption spectrum diagram of a crosslinked film of the mixture. In these figures, the vertical axis shows transmittance, and the horizontal axis shows frequency (cm ^-1 ).

Claims (1)

[Scope of Claims] 1. The following four ethylene copolymers: (A) An ethylene copolymer comprising at least ethylene and glycidyl alkyl (meth)acrylate and obtained by radical polymerization under high pressure; (B) (C) Ethylene copolymer consisting of at least ethylene and an unsaturated monocarboxylic acid and obtained by radical polymerization under high pressure; (C) Ethylene copolymer consisting of at least ethylene and an unsaturated carboxylic acid ester and obtained by radical polymerization under high pressure. (D) An ethylene copolymer obtained by radical polymerization under high pressure, consisting of at least ethylene and an unsaturated dicarboxylic acid, or a half-esterified version of this copolymer. In the ethylene copolymer, the weight composition ratio with copolymer (A) is 1/99 to 9
9/1 copolymer (A) and copolymer (B), copolymer (A) and copolymer (C), and copolymer (A) and copolymer
A crosslinkable composition selected from the compositions of (D).