JPH0445123A - Thin article of crosslinkable resin composition - Google Patents

Abstract

PURPOSE:To provide the subject thin article having excellent heat resistance, good adhesivity to metal and excellent mechanical strength such as toughness and rigidity and useful for packaging materials by compounding a phthalate compound and plural kinds of different ethylenic copolymers. CONSTITUTION:The objective thin article having a thickness of 10mum-5mm is prepared of a composition comprising 1-99wt.% of (i) a phthalate compound having at least two reactive allyl groups in one molecule and/or a polymer thereof and (ii) a copolymer of ethylene with an alpha,beta-unsaturated dicarboxylic acid and/or an anhydride thereof or with a mixture thereof with an unsaturated carboxylate ester and (iii) a copolymer of ethylene with an epoxy group- containing ethylenic unsaturated monomer or with a mixture thereof with an unsaturated carboxylate ester and/or a vinyl ester, wherein the carboxyl groups and the anhydride thereof in the copolymer are 0.1-20moles per mole of the epoxy group in the copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides heat resistance, adhesion and mechanical properties (among others,
This invention relates to thin-walled resin compositions with excellent toughness and rigidity.

More specifically, the resin composition is composed of a phthalate compound and two specific ethylene copolymers, and has excellent heat resistance, adhesiveness, and mechanical properties (particularly toughness and rigidity), as well as good crosslinking properties. Regarding thin items.

[Conventional technology]

Because diallyl phthalate resin has excellent mechanical properties, electrical properties, heat resistance, moisture resistance, chemical resistance, weather resistance, etc., it has been proposed to be used in decorative boards, laminates, various molding materials, etc. (For example, JP-A-48-5494).

Further, (A) an ethylene copolymer of at least ethylene and an α,β-unsaturated dicarboxylic acid and/or an anhydride thereof; and (B) an ethylene copolymer of at least ethylene and an ethylenically unsaturated monomer containing an epoxy group. It is well known that crosslinked copolymer compositions have excellent adhesion and heat resistance, as well as good flexibility, and are therefore used for electrical insulation materials, various laminates, etc. (e.g. , JP 60-240747, JP 61-2388
No. 46, No. 62-129341, No. 62-14101
No. 9, No. 83-83122, No. 63-101413, No. 63-159420, No. 63-317542,
No. 63-317543 and Japanese Unexamined Patent Publication No. 1-90237).

[Problem to be solved by the invention]

Since the diallyl phthalate resin is hard and brittle, it is difficult to continuously mold it into a film or sheet like a normal thermoplastic resin.

Furthermore, since compositions of two types of ethylene copolymers are too soft, their application to fields where mechanical properties are required for films and sheets is currently limited.

Based on the above, the present invention improves the above-mentioned drawbacks of compositions of diallyl phthalate resin and two types of ethylene polymers when producing thin products (i.e., sheets not films), and also improves heat resistance, The object is to obtain a thin crosslinkable resin composition having excellent adhesiveness and mechanical properties (particularly toughness and rigidity).

[Means and effects for solving the problems] According to the present invention, these problems are solved by: (A) a phthalate compound having at least two reactive allyl groups in one molecule and/or a polymer thereof; (B) A copolymer of ethylene and α,β-unsaturated dicarboxylic acid and/or its anhydride, or a copolymer of these and an unsaturated carboxylic acid ester [hereinafter referred to as “ethylene copolymer (I)”] and ( C) Consists of an ethylenically unsaturated monomer containing ethylene and an epoxy group, or a copolymer of these with an unsaturated carboxylic acid ester and/or vinyl ester [hereinafter referred to as "ethylene copolymer (■)"] A composition in which the composition ratio of the phthalate compound and/or its polymer is 1 to 99%.
% by weight, and the ratio of the carboxyl group and/or its anhydride in the ethylene copolymer (I) to 1 mole of epoxy group in the ethylene copolymer (El) is 0.
A resin composition having a thickness of 1 to 20 moles is molded to a thickness of 1
A thin product of a crosslinkable resin composition having a thickness of Oun to 5 mm,
It can be solved by The present invention will be specifically explained below.

(A) Phthalate compounds and polymers thereof Among the phthalate compounds and polymers thereof used in the present invention, phthalate compounds include diallyl orthophthalate (DAP), diallyl isophthalate (DA I
P) and diallyl terephthalate (DATP).

In addition, the a=product is a homopolymer obtained by polymerizing only one type of these phthalate compounds, and a copolymer obtained by copolymerizing at least two types of these phthalate compounds. It is a thing.

All of these polymers can be produced by either a solution polymerization method or a bulk polymerization method. Incidentally, as the polymerization catalyst, a radical generator described below is preferably used.

The viscosity of the polymer at 20°C is usually 50 to 130 cp.
s, particularly preferably 60 to 120 cps.

(B) Ethylene copolymer (1) In addition, the ethylene copolymer (1) used in the present invention
1) is a copolymer of ethylene and "α,β-unsaturated dicarboxylic acid and/or its anhydride" [hereinafter referred to as "unsaturated dicarboxylic acid component"], and these (i.e.
It is a multi-component copolymer of ethylene, an unsaturated dicarboxylic acid component) and an unsaturated carboxylic acid ester.

Among the unsaturated dicarboxylic acid components, the α,β-unsaturated dicarboxylic acid usually has at most 20 carbon atoms, and preferably 4 to 16 carbon atoms. Representative examples of the dicarboxylic acids include maleic acid, fumaric acid, itaconic acid 1, citraconic acid, and 3,6-endomethylene-2,3,4,8
-tetrahydro-cis-phthalic acid.

Among the unsaturated dicarboxylic acid components of the present invention, the α, β-
Anhydrides of unsaturated dicarboxylic acids are preferred, and maleic anhydride is particularly preferred.

Additionally, the number of carbon atoms in unsaturated carboxylic acid esters is generally 4.
~40 pieces, preferably 4 to 30 pieces, and particularly preferably 4 to 20 pieces.

Representative examples of suitable unsaturated carboxylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl acrylate, and 2-methylhexyl acrylate, with methyl methacrylate being most preferred.

The copolymerization ratio of the unsaturated dicarboxylic acid component of the ethylene copolymer (I) of the present invention is usually 0.1 to 20 mol%,
0.1 to 15 mol % is preferred, particularly 0.1 to 10 mol 96. If an ethylene copolymer (T) in which the copolymerization ratio of the unsaturated dicarboxylic acid component is less than 0.1 mol % is used, the crosslinking density with the ethylene copolymer (II) described later will be low, and the resulting composition The heat resistance of the product becomes insufficient. On the other hand, ethylene copolymer (1) exceeding 20 mol%
If a polymer is used, it is not only difficult to produce a polymer and stable production is difficult, but even if it is obtained, the acid anhydride group absorbs a lot of moisture from the air, causing the composition to deteriorate. This is undesirable because foaming occurs when the composition is manufactured by kneading or when the resulting composition is molded. Further, the copolymerization ratio of the unsaturated carboxylic acid ester is generally at most 50 mol%, preferably 45 mol% or less, and particularly preferably 40 mol% or less. If the ethylene copolymer (I) in which the copolymerization ratio of unsaturated carboxylic acid ester exceeds 50 mol % is used, the characteristics of the present invention can be expressed, but it is not preferable in terms of production and economy.

The melt flow index of the ethylene copolymer (1) (according to JIS K7210, the conditions in Table 1 are 4)
Measured at rM, 1. J] is generally 0.5 to 500 g/10 minutes, preferably 1.0 to 500 g/10 minutes, especially 5
．． 0 to 400 g/10 minutes is suitable.

(C) Ethylene copolymer (II) Furthermore, the ethylene copolymer (II) used in the present invention is an ethylenically unsaturated monomer containing ethylene and an epoxy group, or a combination of these and the unsaturated carboxylic acid ester. and/or a copolymer with vinyl ester.

The general formula of a typical example of the ethylenically unsaturated monomer containing an epoxy group, which is a comonomer component of the ethylene copolymer (II), is R-0 shown by the following formula [formula (I) and formula (II)]. -CH2-CQ-/CH, (II) Representative examples of the unsaturated monomer include glycidyl (meth)acrylate, allyl glycidyl ether, and methacryl glycidyl ether.

Further, as a typical example of the vinyl ester as a comonomer component, those having at most 20 carbon atoms are generally preferred, and those having 4 to 18 carbon atoms are particularly preferred. Suitable vinyl esters include vinyl acetate, vinyl propionate, and vinyl butyrate, with vinyl acetate being most suitable.

The copolymerization ratio of the ethylenically unsaturated monomer containing an epoxy group in the ethylene copolymer (II) of the present invention is usually 0.
．． 2 to 20 mol%, preferably 0.2 to 5 mol%, particularly preferably 0.5 to 15 mol%. If the copolymerization ratio of the ethylenically unsaturated monomer containing an epoxy group in the copolymer is less than 0.2 mol%, the crosslinking density with the above-mentioned ethylene copolymer (1) will be low, and the resulting composition heat resistance becomes insufficient. On the other hand, if it exceeds 20 mol %, although the characteristics of the present invention are exhibited, it is difficult to produce the copolymer and there are economical problems. In addition, the copolymerization ratio of unsaturated carboxylic acid ester and vinyl ester is generally at most 50 mol% as their total amount, and 45
It is preferably at most mol%, particularly preferably at most 40 mol%. If the copolymerization ratio of unsaturated carboxylic acid ester and vinyl ester or their total amount exceeds 50 mol%, production becomes difficult.

M of the ethylene copolymer (II), 1. is usually 0.5 to
500[/lo min], preferably 1.0 to 500 g/IO min, and particularly preferably 5.0 to 400 i/10 min.

In producing the resin composition of the present invention, a radical initiator described below may be further blended in order to increase the crosslinking density and improve the heat resistance and mechanical properties of the resulting composition.

(D) Radical initiator The radical initiator is generally a radical polymerization initiator,
Furthermore, it is widely used as a crosslinking agent for rubbers and polymers, and organic peroxides are preferably used. Among these, those with a half-life of 1 minute of 120°C or more are preferred, and those with a half-life of 130 to 200°C are particularly preferred. Representative examples of preferred organic peroxides include diacyl peroxides such as benzoyl peroxide, ketone peroxides such as 1,1-bis-tertiary-butylperoxy-3,3,5-trimethylcyclohexane, and dicumyl. Dialkyl peroxides such as peroxide, hydroperoxides such as 2,5-dimethylhexane-2,5-hydroperoxide and 2,5-dimethyl-2,5
- Peroxy esters such as dibenzoyl peroxyhexane.

(E) Composition ratio In the composition of the present invention, the composition ratio of the phthalate compound and/or its polymer in the composition is 1 to 9.
9% by weight, preferably 2 to 98% by weight, particularly preferably 5 to 95% by weight. The composition ratio of the phthalate compound and/or its polymer in the composition is 1
If the amount is less than % by weight, a composition with sufficient rigidity cannot be obtained. On the other hand, if it exceeds 99% by weight, a composition with satisfactory adhesiveness and flexibility cannot be obtained.

Further, the ratio of carboxyl groups and/or their anhydride groups in the ethylene copolymer (I) to 1 mole of epoxy groups in the ethylene copolymer (II) is 0.1 to 20 moles, and 0.1 to 20 moles. 2 to 15 moles are preferred, especially 05 to 2 moles.
Moles are preferred. A composition obtained even if the ratio of carboxyl groups and/or its anhydride groups in the ethylene copolymer (1) to 1 mole of epoxy groups in the ethylene copolymer (II) is less than the lower limit or exceeds the upper limit. The crosslinking density is low, making it impossible to obtain a mixture with sufficient heat resistance.

In addition, when blending a radical initiator, its composition ratio is ethylene copolymer (I), ethylene copolymer (■)
, total amount of phthalate compounds and their polymers 100
At most 10 parts by weight (preferably 50 parts by weight)
parts by weight or less). If the upper limit is exceeded, not only will the cost increase, but a rapid crosslinking reaction may occur.

(F) Production of Composition In order to produce the composition of the present invention, a phthalate compound and/or a polymer thereof, an ethylene copolymer (1) and an ethylene copolymer (It), or these and a radical The initiator may be mixed uniformly. Second, some of the composition components are mixed together (for example, ethylene copolymer (1) and ethylene copolymer (II) are mixed), and the remaining composition components are mixed into this mixture. Good too.

The mixing method for producing the composition of the present invention may be tri-blending using a mixer such as a Henschel mixer, which is commonly used in the field of polyolefin resins, a Banbury mixer, a kneader 1 single-screw mixer, etc. Ethylene copolymer (I), ethylene copolymer (I
I) and the phthalate compound and/or its polymer can be mixed at a temperature at which both are melted. Furthermore, by using a static mixer or the like at the tip of the extruder, a more homogeneous mixture can be produced. Furthermore, a more homogeneous mixture can be produced by triblending in advance and kneading the resulting mixture in a molten state.

In addition, when crosslinking in a molten state, it is necessary to conduct the crosslinking under conditions in which each component is not substantially crosslinked. If crosslinking occurs during mixing, a homogeneous mixture cannot be obtained. This is not preferable because it not only impairs the moldability when the composition is molded into a thin product, but also reduces the shape of the intended molded product and the heat resistance when crosslinking the molded product. Therefore, when mixing in a molten state, depending on the viscosity of each component,
It is preferable to carry out the reaction at a temperature in the range of .degree. C. (room temperature) to 150.degree. C., particularly preferably 25.degree. C. to 140.degree.

Furthermore, if the total viscosity of each component differs greatly, it is difficult to obtain a uniform mixture. Therefore, it is necessary to select a material whose viscosity ratio is as close to 1 as possible.

Furthermore, additives such as antioxidants, ultraviolet absorbers, antistatic agents, electrical property improvers, flame retardants, processability improvers, pigments, talc, mica, calcium carbonate, barium sulfate, silicon An appropriate amount of an inorganic filler such as calcium acid may also be added.

(G) Production of thin-walled products The resin composition obtained as described above is processed into thin-walled products of the present invention (
film or sheet).

In order to crosslink the thin object of the present invention, the thin object is first molded using a method of casting and heating the composition, a T-die film molding machine, etc., and then the thin object is made of a metal such as aluminum or copper. One side of various base materials such as foils, plates, films or sheets of synthetic resins such as polyimide, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polyamide resin (PA), polysulfone resin, paper, cellophane, etc. After stacking both sides, there is a method of heating it in an oven, or heating it while applying pressure with a press or roll. Although the heating temperature cannot be unconditionally limited depending on the types of components, their composition ratios, and whether or not a radical initiator is used, it is generally 120 to 250°C (preferably 150°C).
~250°C). Other methods include irradiation with ultraviolet rays and radiation.

[Examples and comparative examples]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the heat resistance is 300°C.
sample (100 m thick) in a solder bath.

2.5 x 2.5 cm), and the deformation after 3 minutes was observed with the naked eye. In addition, to determine the gel fraction, 1 g of the sample was placed in a 300-mesh stainless steel wire mesh, boiled in xylene for 8 hours, and then dried in a vacuum drying mold for 24 hours. He led the way. Furthermore, adhesion is indicated by the 90 degree peel strength (JIS K6854) of a 1.5 m11 adhesive plate obtained by pressing a film on aluminum foil (thickness 70 μs) at a temperature of 200°C under a pressure of 20 kg/c-. Ta.

In addition, tensile strength at break was measured according to Monthly S K7113.

The physical properties, manufacturing method, etc. of ethylene copolymer (1) and ethylene copolymer (II) used in Examples and Comparative Examples are shown below.

[(A) Ethylene copolymer (I)]

The ethylene copolymer (T) was obtained by copolymerizing ethylene, maleic anhydride, and methyl methacrylate using high-pressure low-density polyethylene manufacturing equipment, and the copolymerization ratio of maleic anhydride was 3.0. mole%
and the copolymerization ratio of methyl methacrylate is 37.0
An ethylene-maleic anhydride-methyl methacrylate ternary copolymer (hereinafter referred to as rP E (A) J) having mol % and M and I of 2.5 g/10 min was copolymerized in the same manner. The copolymerization ratio of maleic anhydride obtained by doing this is 0.8 mol%, the copolymerization ratio of methyl methacrylate is 2.5 mol%, and M, 1.
is 17 g/10 minutes of ethylene-maleic anhydride-methyl methacrylate terpolymer [hereinafter r P E (
B) J] and the copolymerization ratio of acrylic acid produced by copolymerizing ethylene and acrylic acid in the same manner is 3.4 mol%, and M, 1. 8.
An ethylene-acrylic acid copolymer [hereinafter referred to as rPE(C)J] having a rate of 2 g/10 minutes was used.

[(B) Ethylene copolymer (■)]

In addition, as the ethylene copolymer (II), the copolymerization ratio of ethylene and glycidyl methacrylate or glycidyl methacrylate obtained by copolymerizing these and vinyl acetate using high-pressure low density polyethylene production equipment is 2. .5 mol%, and M, 1.
The copolymerization ratio of ethylene-glycidyl methacrylate copolymer [hereinafter referred to as rPE(1)J] is 2.3 mol %, and the copolymerization ratio of vinyl acetate is 1 g/10 min. .9 mol%, and M, 1. 6. An ethylene-glycidyl methacrylate-vinyl acetate ternary copolymer [hereinafter referred to as r P E (2) J] having a temperature of Ijg/10 minutes was used.

[(C) Phthalate compound]

Further, as a phthalate compound, a polymer substance of diallyl phthalate (monomer content: 3.5% by weight, hereinafter referred to as rDAPJ) having a viscosity of 90 cps at 20° C. was used.

Examples 1 to 10, Comparative Examples 1 to 7 Ethylene copolymer (1) and ethylene copolymer (I
I), a phthalate compound (DAP) whose blending amount is shown in Table 1, and 2.0 parts by weight of dicumyl peroxide (as a radical initiator) were triblended for 5 minutes using a Henschel mixer.

Each of the obtained mixtures was melt-kneaded using a Brabender at 100° C. and 40 revolutions/minute for 10 minutes to produce a composition. In addition, the ethylene copolymer (
Table 1 shows the ratio of carboxyl groups or acid anhydride groups in the ethylene copolymer (1) to 1 mole of Epoquin groups in II).

Each composition thus obtained was extruded using an extruder (diameter: 40 mm) equipped with a T-die to a thickness of 0.1 mm.

A film having a width of 30c+n was molded at a resin temperature of 120°C. The gel fraction of each film obtained was almost 0%.
Met.

Each film thus obtained was crosslinked while heating at 200° C. for 10 minutes using a thermal oven, and the heat resistance and gel fraction after this treatment were measured.

Furthermore, the adhesiveness and flexural modulus described above were measured. The results are shown in Table 2.

Table (Part 1) Table (Part 2) The above results, especially from Table 2, show that even if the compositions shown in the comparative examples have high mechanical strength, they are inferior in both adhesion and heat resistance, and are not suitable for practical use. It is clear that this is not the case.

〔Effect of the invention〕

The resin composition of the present invention exhibits the following effects.

(1) Excellent heat resistance.

(2) Good adhesion to metal.

(3) Excellent mechanical strength (particularly toughness and rigidity).

The thin resin composition of the present invention can be used in many directions in order to exhibit the above-mentioned effects. In addition to general films or sheets, it is also promising as a material (such as bags) that requires heat resistance.

Claims (1)

[Scope of Claims] (A) A phthalate compound having at least two reactive allyl groups in one molecule and/or a polymer thereof; (B) Ethylene and an α,β-unsaturated dicarboxylic acid and/or a polymer thereof;
or their anhydrides, or copolymers of these with unsaturated carboxylic esters (I) and (C) ethylenically unsaturated monomers containing ethylene and epoxy groups, or these with unsaturated carboxylic esters and/or vinyl It is a composition consisting of a copolymer (II) with an ester, and the composition ratio of the phthalate compound and/or its polymer is 1 to 99%.
% by weight, and the ratio of the carboxyl group and/or its anhydride in the copolymer (I) to 1 mole of the epoxy group in the copolymer (II) is 0.1 to 20 moles. A thin product of a crosslinkable resin composition formed by molding and having a thickness of 10 μm to 5 mm.