JPH0441538A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition excellent in heat resistance, adhesion to metal, toughness, rigidity, etc., by mixing a phthalate compound with two specified ethylene copolymers and an alpha,beta-unsaturated acid compound in a specified weight ratio. CONSTITUTION:A phthalate compound having a plurality of reactive allyl groups in the molecule (e.g. diallyl o-phthalate) and/or its polymer (A), a copolymer (B) of ethylene with an alpha,beta-unsaturated dicarboxylic acid (anhydride) and optionally an unsaturated carboxylic acid ester, a copolymer (C) of ethylene with an epoxy-containing ethylenically unsaturated monomer and optionally an unsaturated carboxylic acid ester and/or a vinyl ester and an alpha,beta-unsaturated carboxylic acid (anhydride) or an unsaturated carboxylic acid ester (D) are mixed together in such amounts that D/(A+D) is 1-40wt.%, the total of components B and C is 1-99wt.% based on the whole mixture, and the molar ratio of the carboxyl (anhydride) groups of component B to the epoxy groups of component C is 0.1-20.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition having excellent heat resistance, adhesiveness and mechanical properties (particularly toughness and rigidity). More specifically, it is a resin composition that is composed of a phthalate compound and two specific ethylene copolymers, has excellent heat resistance, adhesive properties, and mechanical properties (especially toughness and rigidity), and has good crosslinkability. Regarding.

[Conventional technology]

It is well known that diallyl phthalate resin has excellent mechanical properties, electrical properties, heat resistance, moisture resistance, chemical resistance, weather resistance, etc., and is therefore used in decorative laminates, laminates, and various molding materials. [For example, pages 702 to 723 of "Engineering Plastics Encyclopedia," co-edited by Ihonai, Oyanagi, and Seno, Shihodo Publishing, published December 15, 1988].

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 81-2388
No. 48, No. 82-129341, No. 82-14101
No. 9, No. 83-83122, No. 63-101413, No. 63-159420, No. 63-317542,
No. 83-317543 and Japanese Unexamined Patent Publication No. 1-90237).

[Problem to be solved by the invention]

However, it has been pointed out that diallyl phthalate resin has poor adhesion to metals and is hard and brittle. For this reason, at present, the use of the resin in composite materials containing metal as a constituent element is extremely limited. For example, copper-clad laminates for printed circuits cannot be used for this purpose because the adhesive strength between the copper foil and diallyl phthalate resin is weak and practical beer strength cannot be obtained.

Furthermore, the use of flexible printed circuit boards is limited because diallyl phthalate resin is hard, brittle, and has poor flexibility.

Furthermore, the crosslinked product of the above-mentioned composition with the two types of ethylene copolymers is currently too soft, so its application to fields where excellent mechanical strength is required is currently limited.

From the above, the present invention does not have these drawbacks (problems), that is, it not only has excellent adhesive properties, but also has good mechanical properties (particularly toughness and rigidity), and also has good heat resistance. Diaryl phthalate decorative boards with a metal core can be produced without using any adhesives, and can also be applied to copper-clad laminates for printed circuits. The object of the present invention is to obtain a resin composition that makes it possible to significantly expand the uses of phthalate resins.

[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 or a polymer thereof; ) Copolymers of ethylene and α, β-unsaturated dicarboxylic acids and/or their anhydrides, or these and unsaturated carboxylic esters [hereinafter referred to as “ethylene copolymers (I)”], (C) Ethylenically unsaturated monomer 1 containing ethylene and epoxy groups or a copolymer of these with an unsaturated carboxylic acid ester and/or vinyl ester [hereinafter referred to as "ethylene copolymer (■)"] and (D ) at least one unsaturated compound selected from the group consisting of α, β-unsaturated carboxylic acids, their anhydrides, and unsaturated carboxylic acid esters; The mixing ratio of unsaturated compounds in the total amount of saturated compounds is 1 to 40% by weight, and the mixing ratio of ethylene copolymer (I) and ethylene copolymer (II) in the total mixture is 1 to 40% by weight. 1 to 9 as the total amount of
9% by weight, and the ratio of the carboxyl group or anhydride of the ethylene copolymer (I) and the unsaturated compound to 1 mole of epoxy group in the ethylene copolymer (II) is 0.1 to 20 moles. The problem can be solved by a resin composition, which is. The present invention will be explained in detail 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) and diallylisophthalate (DAIP).
and diallyl terephthalate (DATP).

In addition, the polymer includes 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.

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

Among the unsaturated dicarboxylic acid components, the α,β-unsaturated dicarboxylic acid usually has at least 20 carbon atoms, and preferably 4 to 16 carbon atoms. Representative examples of the dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and 3,6-nintomethylene-2.3,4.6-
Examples include titrahydrosis-phthalic acid.

Among the unsaturated dicarboxylic acid components of the present invention, the α, β-
Anhydrides of unsaturated dicarboxylic acids are preferred, with maleic anhydride being 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 nocarboxylic acid component in the ethycine-based copolymer (I) of the present invention is usually 0.1 to 20 mol 9o, preferably 0.1 to 15 mol %, particularly 0.1 to 20 mol %. 10 mol% is suitable. An ethylene copolymer (I) having a copolymerization ratio of less than 0.1 mol % of the unsaturated carbonic acid component is used. In this case, the crosslinking density with the ethylene copolymer (U) described later becomes low, and the heat resistance of the resulting composition becomes insufficient. On the other hand, ethylene copolymer (I) exceeding 20 mol%
If a polymer is used, it is not only difficult to produce the 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 product is manufactured by kneading, etc., and when the resulting product is molded. In addition, the copolymerization ratio of unsaturated carboxylic acid ester is generally
At most 50 mol%, preferably 45 mol% or less, especially 40 mol%? . The following is preferred. If an ethylene copolymer (I) in which the copolymerization ratio of unsaturated carboxylic acid ester exceeds 50 moles is used, the characteristics of the present invention may not be achieved, and it is not preferable from the viewpoint of production and economy.

The melt flow index of the ethylene copolymer (I) [according to JIS K7210 or under the conditions in Table 1 or 4]
Measured at rM, 1. J] is generally 05 to 500 g, /I from the point of view of formability and mechanical strength.
0 minutes, 10-5 [10g/10 minutes is desirable,
Particularly suitable is 50 to 400 g/10 minutes.

(C) Ethylene-based copolymer (b) Furthermore, the ethyl 7-based copolymer 1) used in the present invention is an ethylenically unsaturated monomer containing ethylene and an epoxy group, or a combination of these and the unsaturated carboxyl group. It is a copolymer with acid ester and/or vinyl ester.

The general formula of a typical example of an ethylenically unsaturated monomer containing an epoxy group, which is a comonomer component of the ethylene copolymer (II), is represented by the above formula [formula (I) and formula (n)]. Representative examples of saturated monomers include glycidyl (meth)crylate, 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 ethylene copolymer of the present invention (former epoxy group-containing ethylenically unsaturated monomer is usually 0.2
-20 mol%, preferably 0.2-15 mol%,
Particularly suitable is 0.5 to 15 mol96. If the copolymerization ratio of the ethylenically unsaturated monomer containing an epoxy group in the copolymer is less than 0.2 mol 96, the crosslink density with the ethylene copolymer (I) will be low, and the resulting composition The heat resistance will be 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 less than mol%, particularly preferably less than 40 mol%. If the copolymerization ratio of unsaturated carboxylic acid ester and vinyl ester exceeds 50 mol% in total, production becomes difficult.

M of the ethylene copolymer (n), 1. is usually 0.5 to 5 for the same reason as the above-mentioned ethylene copolymer (I).
00 g/10 min, preferably 1.0 to 500 g/lO min, particularly preferably 5.0 to 400 g/l O min.

(D) Unsaturated compound Also, the unsaturated compound used in the present invention is α5 β
- selected from the group consisting of unsaturated carboxylic acids, their anhydrides and unsaturated carboxylic esters.

The α,β-unsaturated carboxylic acid generally has at most 40 carbon atoms, and preferably 3 to 20 carbon atoms. Representative examples of the unsaturated carboxylic acid include αβ-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, monoalkyl maleate, and monoalkyl fumarate, and comonomer components of the ethylene copolymer (I). Examples include α,β-unsaturated dicarboxylic acids in which the following is described. Further, the anhydride is an anhydride of the unsaturated dicarboxylic acid.

Further, as representative examples of α,β-unsaturated carboxylic acid esters, unsaturated carboxylic acid esters, methoxyethyl acrylate, ethoxyethyl acrylate, and Examples include alkoxyalkyl (meth)acrylates having at most 20 carbon atoms such as butquinethyl acrylate (preferably, the alkyl group and alkoxy group have 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms). .

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 mixture.

(E) Rancal initiator The radical initiator is generally used as a radical polymerization initiator,
Furthermore, it is widely used as a crosslinking agent for rubbers and polymers, and a#1 peroxide is preferably used. Among them, those with a half-life of 1 minute or 120°C or more are preferable.
Particularly suitable is a temperature of 130 to 200°C. Representative examples of preferred organic peroxides include diacyl peroxides such as benzoyl peroxide, ketone peroxides such as 1,1-bis-tert-butylperoxy-3,3,5-trimethylcyclohexane, dialkyl peroxides such as milbaroxide, hydroperoxides such as 2,5-dimethylhexane-2,5-hydroperoxide and 2,5-dimethyl-2,
Examples include peroxy esters such as 5-dihenzoyl peroxyhexane.

CF) Mixing ratio In the composition of the present invention, the composition ratio of the unsaturated compound in the total amount of the phthalate compound, its polymer, and the unsaturated compound is 1 to 40% by weight, particularly 2 to 40% by weight. % weight is good. If the composition ratio of the unsaturated compound in the total amount of the phthalate compound, its polymer, and the unsaturated compound is less than 1% by weight, the ethylene copolymer (I) and the ethylene copolymer (II) sufficient affinity cannot be obtained. On the other hand, if it exceeds 40% by weight,
The moldability is poor and a uniform composition cannot be obtained.

Furthermore, the ethylene copolymer (I) in the entire mixture
The mixing ratio of the ethylene copolymer (IT) is 1 to 99% by weight as a total amount thereof, and preferably 2 to 95% by weight. If the mixing ratio of the ethylene copolymer (I) and the ethylene copolymer (II) in the entire composition is less than 1% by weight, the resulting mixture will not have sufficient adhesion and flexibility. On the other hand, if it exceeds 99% by weight,
The resulting composition has poor rigidity.

Further, 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 (II) is 0.1 as a total amount.
~20 mol, preferably 02 to 15 mol, especially 0
5 to 5 mol is suitable. Crosslinking of the composition obtained even if the ratio of the carboxyl group and/or its anhydride of the ethylene copolymer (I) to 1 mole of the epoxy group of the ethylene copolymer (n) is less than the lower limit or exceeds the upper limit. A mixture with low density and sufficient heat resistance cannot be obtained.

Furthermore, when blending (mixing) a radical initiator, the mixing ratio is the total amount of the ethylene copolymer (I), the ethylene copolymer (H), the phthalate compound, its polymer, and the unsaturated compound. The amount is at most 10 parts by weight per 100 parts by weight (preferably 0.1 to 5.0 parts by weight). However, if the amount exceeds the upper limit, a rapid crosslinking reaction may occur.

(G) Production of a acid product To produce the composition of the present invention, a phthalate compound and/' or a polymer thereof, an ethylene copolymer (■)
, the ethylene copolymer (b), the unsaturated compound, or these and a radical initiator may be uniformly mixed. At this time, some of the composition components are roughly mixed together (for example, ethylene! Mix the Ti polymer (I) and the ethylene copolymer (II)], and the remaining composition components may be mixed into this mixture.

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 Bambanow mixer, a kneader 1 single-screw mixer, etc. Ethylene copolymer (I), ethylene copolymer (I
1) and the phthalate compound and/or its polymer can be mixed at a temperature at which they melt. 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 uniform MN product can be produced by roughening and triblending and kneading the resulting mixture in a molten state.

In addition, when kneading in a molten state, it is necessary that each component be mixed under conditions that do not substantially cause crosslinking. If crosslinking occurs during kneading, a uniform iJ2g product cannot be obtained. For this reason, it is undesirable to deteriorate the moldability when the composition is molded and pressurized, and the shape of the intended molded product and the heat resistance when crosslinking the molded product are deteriorated. Therefore, when mixing in a molten state, depending on the viscosity of each mixed component,
It is preferable to carry out the reaction at a temperature in the range of ℃ (room temperature) to 150 ℃, particularly preferably 25 ℃ to 140 ℃.

Further, if the total viscosity of each mixed 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 Appropriate inorganic fillers such as calcium chloride
It is also possible to mix 5 amounts.

()I) Method for producing crosslinked product The resin composition of the present invention can be crosslinked by, for example, casting a mixture and heating it, using a film molding machine such as a T-die film molding machine, or by forming a film or sheet. This film or sheet is made of metal foil such as aluminum or copper, polyimide, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PB).
T), polyamide resin (PA), synthetic resin film or sheet such as polysulfone resin, paper, cellophane, etc., after being laminated on one or both sides of various base materials, such as
There are methods to heat it in an oven, or to heat it without applying pressure with a press or roll. The heating temperature cannot be unconditionally limited depending on the types of mixed components, their composition ratios, and whether or not a radical initiator is used, and is generally 120 to 250°C (preferably 150 to 250°C).
It is. 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 knots thick, 2.5X2.
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 for 8 hours in Kinshin, and then dried in a vacuum drying mold for 24 hours. He led the way. Furthermore, the adhesion was determined by applying 200 parts of film to aluminum foil (thickness: 70 parts).
The 90 degree peel strength (IIS
K61154).

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

The physical properties and manufacturing method of the ethylene copolymer (I) and the ethylene copolymer (b) used in the Examples and Comparative Examples are shown below.

[(8) 1-ethylene copolymer (I)] The ethylene copolymer (I) is produced by copolymerizing ethylene, maleic anhydride, and methyl methacrylate using high-pressure low-density polyethylene production equipment. The copolymerization ratio of the obtained maleic anhydride is 3.0 mol 0
6, and the copolymerization ratio of methyl methacrylate is 37.
An ethylene-maleic anhydride-methyl methacrylate ternary copolymer (hereinafter referred to as rPE(A)J) having an Ml of 0 mol % and a Ml of 2.5 g/10 min was copolymerized in the same manner. The copolymerization ratio of maleic anhydride obtained by
．． or 17 g/10 minutes of ethylene-maleic anhydride-methyl methacrylate terpolymer [hereinafter r P
E (B)J] and similarly produced by copolymerizing ethylene and acrylic acid), the copolymerization ratio of acrylic acid is 34 moles? ] and M
, 1. A urethane-acrylic acid J-% polymer (hereinafter referred to as rPE(C)J) having a yield of 8.2 sr/10 minutes was used.

[(B) Ethylene copolymer (■)]

In addition, as the ethylene copolymer (II), copolymerization of ethylene and glycidyl methacrylate, or glycidyl methacrylate obtained by copolymerizing these and vinyl acetate using the production equipment for low-density polyethylene using the 1. The proportion is 2.5 mol 9o, and M,
Ethylene-grindyl methacrylate copolymer c with an I of 3.1 g/10 min, hereinafter referred to as rPE(I)J]
and the copolymerization ratio of glycidyl methacrylate 23
The mole is 9 degrees, and the copolymerization ratio of vinyl acetate is 19 mole O.
0, and M, 1. An ethylene-glycidyl methacrylate-vinyl acetate ternary copolymer (hereinafter referred to as r P E (2) J) having a yield of 6.8 g/10 minutes was used.

[(C) Phthalate compound]

Further, as a phthalate compound, a polymer substance of diallyl phthalate (called rDAPJ having a monomer weight of 3.5 weight OO1 or less) having a viscosity at 120° C. (90 EL) S was used.

[(D) Unsaturated compound]

In addition, as an unsaturated compound, maleic anhydride [hereinafter [M
AHJ] was used.

Examples 1 to 13, Comparative Examples 1 to 8 Ethylene copolymer (I) and ethylene copolymer (I) whose types and amounts are shown in Table 1
I) and a phthalate compound (DAP) and an unsaturated compound (MAR) as shown in Table 1 and 20 parts by weight of dicumyl peroxide (as a radical initiator) for 5 minutes using a Henschel mixer. Triblending was carried out. Each of the resulting mixtures was blended using a brahender at 100° C. for 10
The composition was prepared by melt mixing for a minute. In addition, the epoxy group 1 in the ethylene copolymer (II) in each mixture
Table 1 shows the ratio of carboxyl groups or acid anhydride groups in the ethylene copolymer (I) to moles.

[Reference example]

The obtained composition was crosslinked using a press machine at 200°C under the conditions of 100 kg/cJ (gauge pressure) to create a crosslinked film, which was then subjected to DJ determination and evaluation of heat resistance, adhesion, and tensile strength at break. I did this.

Furthermore, the gel fraction was measured. The results are shown in Table 2.

/ (Part 1) Condolence Table (Part 2) From the above results, especially from Table 2, the compositions shown in the comparative examples have good mechanical strength, but are poor in both adhesion and heat resistance. It is obvious that this is not practical.

〔Effect of the invention〕

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

(I) Excellent heat resistance.

(2) Good adhesion to metal.

(3) Mechanical strength (particularly toughness and rigidity) is poor.

Because the resin composition of the present invention exhibits the above-mentioned effects, it has good heat resistance and adhesive properties, such as decorative boards and laminates, and is promising in fields where mechanical properties are required.

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), (C) ethylenically unsaturated monomers containing ethylene and epoxy groups, or these with unsaturated carboxylic esters and/or vinyl A composition comprising (II) a copolymer with an ester and (D) at least one unsaturated compound selected from the group consisting of α,β-unsaturated carboxylic acids, their anhydrides and unsaturated carboxylic acid esters. The mixing ratio of the unsaturated compound in the total amount of the phthalate compound, its polymer, and the unsaturated compound is 1 to 40% by weight, and the proportion of the copolymer (I) and copolymer (I) in the total mixture is 1 to 40% by weight. The mixing ratio of II) is 1 to 99% by weight in total, and the ratio of carboxyl groups or their anhydrides in copolymer (I) to 1 mole of epoxy groups in copolymer (II) is 0.
．． A resin composition having a content of 1 to 20 moles.