JPH04159347A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. excellent in flexibility, abrasion resistance, tensile properties, appearance, etc., by compounding a reaction product of an ethylene copolymer ionomer with an olefinic copolymer having epoxy groups on its side chains with an ethylene-vinyl acetate copolymer. CONSTITUTION:100 pts.wt. reaction product of an ethylene copolymer ionomer (consisting of 40-99wt.%, pref. 60-90wt.%, ethylene, 1-50wt.%, pref. 2-40wt.%, unsatd. carboxylic acid, and up to 50wt.% other unsatd. compds.) with an olefinic copolymer having epoxy groups on its side chains (e.g. an ethylene-vinyl acetate-glycidyl methacrylate copolymer) in a wt. ratio of the former to the latter of (90:10) to (99.1:0.1) is compounded with 100-700 pts.wt. copolymer comprising an ethylene-vinyl acetate copolymer or an ethylene-(meth)acrylic ester copolymer (having an ethylene content of 55-95wt.%, pref. 10-40wt.%).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to an ethylene copolymer resin composition having excellent flexibility, abrasion resistance, tensile properties, appearance, etc.

[Prior Art] Ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) and copolymer of ethylene with (meth)acrylic acid ester such as methyl acrylate, ethyl acrylate, methyl methacrylate (hereinafter, abbreviated as EVA) (Sometimes abbreviated as EEA, etc.)
has excellent flexibility, weather resistance, hygiene, light weight, low-temperature properties, tear strength, stress cracking properties, etc., and is useful for artificial turf, automobile mudguards, agricultural films, civil engineering sheets, flexible containers, and foams. etc., are widely used for various purposes.

[Problems to be Solved by the Invention] However, these EVA, EEA, etc. have poor abrasion resistance, so when used for civil engineering sheets such as tunnel water stop sheets, there is a problem of damage due to contact with rock, etc. There is.

In addition, in these applications and flexible container applications, antistatic agents are blended to prevent dust from adhering, but during long-term storage, the antistatic agent migrates to the sheet surface and precipitates. Another problem has arisen in that the appearance is significantly impaired.

In order to solve these problems, we have developed products with good wear resistance and
Ethylene copolymer ionomers (hereinafter abbreviated as ionomers), which have good compatibility with antistatic agents, are often blended. However, ionomers such as EVA, E
Due to the poor compatibility with EA etc., sheets made from the mixture improve the above-mentioned problems, but the elongation value becomes smaller and new problems such as holes and tears occur in the sheet when the sheet is applied. A problem has emerged.

Therefore, for these uses, EVA or EEA
There has been a need for a method to improve the compatibility of ionomers and the like.

[Means for Solving the Problems] As a result of intensive study, the inventors found that EVA, EEA
It has been found that this problem can be solved by using a composition proposed by the present applicant modified with an olefin polymer having an epoxy group in the side chain (Japanese Patent Application Laid-open No. 2-138354) as an ionomer to be blended into the ionomer. Ta.

Therefore, the present invention provides an ethylene copolymer ionomer (A
) and an olefin copolymer (B) having epoxy groups in its side chains (A) and (B) = 90 to 99.9:0.
1~】0 (weight ratio) of ethylene containing 55 to 95% by weight of the reaction product.
This is a resin composition containing 100 to 700 parts by weight of vinyl acetate copolymer or ethylene/(meth)acrylic acid ester copolymer (C).

The ionomer (A) used in the present invention contains ethylene and an unsaturated carboxylic acid salt as essential polymer components, and optionally includes an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, etc. may contain an unsaturated compound as a polymerization component. Such ionomers generally include neutralizing at least a portion of the unsaturated carboxylic acid component of a copolymer of ethylene and an unsaturated carboxylic acid, optionally with other unsaturated compounds, with metal ions and/or organic amines. Alternatively, it can be obtained by saponifying at least a portion of the unsaturated carboxylic ester acid component of a copolymer consisting of ethylene, an unsaturated carboxylic ester, and optionally another unsaturated compound.

Ethylene and unsaturated carboxylic acid, which are the raw materials for the ionomer,
In copolymers containing other unsaturated compounds as optional components, the unsaturated carboxylic acid preferably has about 3 to 8 carbon atoms, and specifically includes acrylic acid, methacrylic acid, fumaric acid, itaconic acid, and anhydride. Maleic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, etc. are used. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferably used. Such unsaturated carboxylic acids may be randomly copolymerized or graft copolymerized, but from the viewpoint of transparency, random copolymerization is better; As an optional component, other unsaturated compounds as the third component include esters of unsaturated carboxylic acids, alkenyl esters of saturated carboxylic acids, etc.
More specific examples include methyl acrylate, ethyl acrylate, isobutyl acrylate, acrylobutyl, 2-ethylhexyl acrylate, methyl methacrylate, and vinyl acetate.

These ethylene-unsaturated carboxylic acid copolymers include:
Ethylene content is 40-99% by weight, preferably 60-99% by weight
99% by weight, and unsaturated carboxylic acid from 1 to 50% by weight,
An ethylenically unsaturated carboxylic acid copolymer, preferably present in an amount of 2 to 40% by weight,
If present, the third component is desirably present in an amount up to 50% by weight, preferably up to 40% by weight.

As neutralizing components in the ethylenically unsaturated carboxylic acid copolymer, Na'', K'', Lj', Ca''
, Mg", 2n", Cu"3, Co", Nj~, Mn"
, monovalent to trivalent metal cations such as Al″3, and/or organic amines such as n-hexylamine, hexamethylene diamine, 1,3-bisaminomethylcyclohexane, metaxylene diamine, etc. The carboxyl salt produced by neutralization acts as a catalyst for the bonding reaction between the carboxyl group of the ionomer and the epoxy group of the olefin copolymer.The reaction occurs even in the absence of a neutralizing component, but crosslinking This tends to occur unevenly (the degree of improvement in mechanical strength at high temperatures is small).The neutralizing component can be used alone or in combination of two or more components.

A suitable ionomer is based on a copolymer of ethylene and an unsaturated carboxylic acid synthesized by high-pressure radical polymerization, or a third component used as necessary, and has some or all of the acidic groups removed. It is an ionomer neutralized with cations. The degree of neutralization used is usually 5 to 100%, preferably 10 to 90%. The melting point of such ionomers is generally about 70 to 105°C. As for its flow characteristics, the melt flow rate (MFR) measured at 190°C and a load of 2160g is 0. Old ~ 11000
It is preferred to use dg/min, especially 0.1 to 200 dg/min.

The olefin copolymer having an epoxy group in the side chain used in the present invention is particularly suitable for a-olefin and glycidyl acrylate or glycidyl methacrylate (
(hereinafter referred to as glycidyl (meth)acrylate) or a copolymer with glycidyl ether is suitable. As the α-olefin, α-olefins having 2 to 8 carbon atoms are preferred, examples of which include ethylene, propylene, butene-1
etc.

Examples of glycidyl (meth)acrylate and glycidyl ether include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, and 2-methylallyl glycidyl ether.

The monomers constituting the olefin copolymer having an epoxy group in its side chain do not need to be two components.

In addition to the olefin and epoxy group-containing monomers, a third component such as an unsaturated carboxylic acid ester or vinyl ester can be included as a two-monomer component. Examples of these include those exemplified above as the third component of the copolymer that is the raw material for the ionomer. These copolymers have an olefin content of 40 to 99% by weight, for example.
, preferably 50-98% by weight, 0.5-20% by weight, preferably 1-15% by weight of glycidyl (meth)acrylate or glycidyl ether, and 0% of a third component such as an unsaturated carboxylic acid ester or vinyl ester. ~49,
5% by weight, preferably 0 to 40% by weight is suitably used.

Note that the olefin copolymer having an epoxy group in the side chain can be a random copolymer, a block copolymer, or a graft copolymer, but random copolymers are preferable in terms of uniformity of crosslinking. is preferred, the olefin copolymer has, for example, 500 to 3000 K g/c
It is obtained by radical polymerization under a pressure of m' and a temperature of 150 to 280°C.

When an ethylene copolymer is used as the copolymer, the melt flow rate measured at 190° C. under a load of 2160 g is 0.01 to 11000 d/min, particularly 0.1 to 11000 d/min.
Preferably, one with a rate of 200 dg/min is selected.

In the present invention, the reaction mechanism between the ionomer component and the olefin copolymer having an epoxy group in the side chain is that the carboxyl group of the ionomer component reacts with the epoxy group in the side chain of the olefin copolymer, and the ionomer molecular chains are separated. It is thought that a crosslinked product bonded by covalent bonds via the olefin copolymer is formed. At this time, by-products such as water and gas are not produced due to the zero reaction, which is thought to be caused by the carboxylic acid salt in the ionomer acting as a catalyst for the reaction, and therefore, no foaming is caused by the by-products.

The ethylene content of EVA or EEA used in the present invention is 55 to 95% by weight, preferably 60 to 90% by weight, and the content of vinyl acetate or (meth)acrylic acid ester is 5 to 45% by weight, preferably is 10 to 40% by weight. If the ethylene content is higher than the above range, the compatibility with component (A) will not be sufficient, and if the ethylene content is lower than the above range, the thermal stability will be poor, the adhesive will be strong and it will be too soft as a molding material, etc. This is not preferable because it causes the following drawbacks.

Examples of (meth)acrylic esters that are copolymerization components such as EEA include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, jilt-butyl acrylate, and methyl methacrylate. .

Melt flow rate of EVA or EEA (19
0℃, load 2160g'T' measurement) is 0.1 to 400
dg/min, preferably 1 to 150 dg/min, melt flow rate (hereinafter abbreviated as MFR)
If it is smaller than this, the fluidity of the resin composition will be reduced, and the moldability will be significantly inhibited. On the other hand, if it is larger than this, the strength of the resin composition will decrease. Ionomer (A)
and an olefin copolymer with epoxy groups in the side chain (B
) The blending ratio of (A): (B) = 90 to 90 by weight
99.9:0.1-10, preferably 95-99:1
~5. If the blending ratio of (B) is too low, the improvement efficiency will not be substantially recognized, and if it is higher than the above range, the reaction will occur excessively, resulting in gelation of the reaction product. The trend becomes remarkable, and E
The appearance of molded products after mixing with VA, EEA, etc. will be impaired. Reaction product 100 consisting of (A) and (B)
The blending ratio of EVA or EEA (C) to parts by weight is 100 to 700 parts by weight, preferably 200 to 50 parts by weight.
0 parts by weight is desirable. If the blending ratio of (C) is less than the above range, the molded product will become too rigid and the characteristics of (C) will be lost; if it is greater than the above range, the abrasion resistance will not be sufficient, and an antistatic agent may not be added. In the system, appearance defects are likely to occur due to bleeding.

The reaction product of (A) and (B) does not necessarily need to be produced before blending component (C), and may be produced in the presence of component (C). ) (C) may be mixed in any order, and of course may be mixed at the same time. Industrially, it is economical to adopt a method of simultaneously mixing (A), (B), and (C). The above mixing can be carried out using a conventional mixing device such as a single screw extruder, a twin screw extruder, or a Banbury mixer.

Other thermoplastic resins and rubbers can be blended into the resin composition of the present invention as long as the purpose thereof is not impaired. In addition, various additives such as antioxidants, weather stabilizers, pigments, dyes, antistatic agents, crosslinking agents, blowing agents, and various fillers may be added to the resin composition of the present invention, depending on the purpose of use. Although it is different, the melt flow rate at 190°C and 2160g load is 0. It is preferable to adjust the rate to 200 dg/min, preferably 0.1 to 1100 d/min).

[Effects of the Invention] According to the present invention, a resin composition having excellent flexibility, abrasion resistance, tensile properties, and appearance can be provided. In particular, compared to systems containing component (B), the tensile properties are improved without substantially impairing excellent properties such as wear resistance, making it possible to prevent molded products from breaking due to insufficient elongation. .

Utilizing such properties, the resin composition of the present invention can be used for artificial turf,
It can be suitably used for civil engineering sheets, flexible containers, etc.

[Example] Next, the present invention will be explained by examples.

In addition, the composition of the resin used for blending the resin composition of the example,
The physical properties are as follows.

Ionomer 1 Base polymer: Ethylene-methacrylic acid copolymer Ethylene content 85% by weight Methacrylic acid content 15% by weight Metal ion 2n Degree of ionization 60% A, F, Rldg/min Ionomer 2 Base polymer: Ethylene-methacrylic acid copolymer ethylene Content 90% by weight Methacrylic acid content IO weight% Metal ion Zn Ionization degree 72% M, F, Rldg 1 minute ionomer 3 Base polymer m: Ethylene-methacrylic acid copolymer Ethylene content 85% by weight Methacrylic acid content 15% by weight Metal ion Na Ionization degree 40% M, F, R2dg/min EVA-1 (ethylene-vinyl acetate copolymer) Vinyl acetate content 12wt%, M, F, Rl 2dg/min EVA-2 (ethylene-vinyl acetate copolymer) Contains vinyl acetate! 25 wt%, M, F, I'l・2 dg/min) EEA-1 (ethylene-ethyl acrylate copolymer) Ethyl acrylate content 9 wt%, M, F, R 5 dg/min EEA-2 (ethylene-ethyl acrylate copolymer Coalescence) Ethyl acrylate content 25wt%, M, F, R5d
g/min EVAGMA (Ethylene-vinyl acetate-glycidyl methacrylate copolymer) Vinyl acetate content 5% by weight, glycidyl methacrylate content 8% by weight M, F, R 6 dg/min Also, in this example, a test method for the produced resin composition is as follows.

M, F, R (melt flow properties) Measured according to JIS K-6710 at a load of 2160 g and a measurement temperature of 190°C.

Observation 1 Based on JIS K-7160, a test piece with a thickness of 3 mm was measured.

・ JIS with a thickness of 2 mm based on JIS K-6760
Measurements were made on the No. 2 test piece under conditions of a tensile speed of 200 mm/min.

Shore D Measurement was performed on a 3 mm thick test piece based on JIS K-7215.

Taper wear (w) Using a wear wheel based on JIS K-7204 (S-1
1. The amount of wear (Ilgl) after 1000 rotations was measured for a test piece with a thickness of 3 cm.

A test piece with a thickness of 3 mm was left in an oven set at 50°C ± 3°C for 40θ hours, and changes in appearance due to bleeding of the antistatic agent were observed with the naked eye. Those with Ol were marked as ×, and those in the middle were marked as △.

叉JJL２”.

Ionomer 1 in the amount shown in Table 1, 9.95 kg, and an olefin copolymer having an epoxy group in the side chain -r
EVAGMA, 0.05 kg, antistatic agent [Resistat PL139 J I fatty acid mono- and diglyceride borate ester, molecular weight 408, manufactured by Dai-Kogyo Seiyaku)
0.05kg and EVA-130kg at 1509. The mixture was put into a Henschel vessel and 5 molecules were prepared and kneaded in an atmosphere at 23°C.

This mixture was melt-mixed and pelletized using a 40wmφ extruder equipped with a single screw with L/D=28 under conditions of a tie temperature of 200° C. and a screw rotation speed of 30 rpm. Regarding this pellet, M, F, H
Measurements were made. Further, it was formed into a plate shape of a predetermined thickness by heat press molding, and its bending rigidity, tensile strength, elongation, hardness, taper wear, and bleed resistance were evaluated. The results are shown in Table-1.

Example L Example 22 Evaluation was conducted in exactly the same manner as in Example 1, except that the blending ratio of ionomer 1 and EVAGMA was changed. The results are shown in Table-1.

Evaluation was conducted in exactly the same manner as in Example 1 for 115 units, except that the blending ratio of Ionomer 1 and EVAGMA was changed. The results are shown in Table-1.

5.2A In Example 2, evaluation was conducted in exactly the same manner as in Example 2, except that the amount of EVAi was reduced. The results are shown in Table-1.

Shigo! 22 In Example-2, evaluation was performed in exactly the same manner as in Example-2, except that Ionomer 2 was used instead of Ionomer 1. The results are shown in Table-1.

In Example 2, evaluation was carried out in exactly the same manner as in Example 2, except that Ionomer 3 was used instead of Ionomer 1. The results are shown in Table-1.

11522 In Example-2, EVA-1 was replaced with EVA-1.
Evaluation was carried out in the same manner as in Example 2 except that Example 2 was used. The results are shown in Table-1.

Example-8 In Example-2, EEA was used instead of EVA-1.
1° in the same manner as in Example-2 except that -1 was used.
We conducted an evaluation. The results are shown in Table 1.

Example-9 In Example-2, EEA-1 was used instead of EVA-1.
Evaluation was carried out in the same manner as in Example 2 except that Example 2 was used. The results are shown in Table 1.

Comparative Example-1 In Example-2, except that EVAGMA was not used,
Evaluation was performed in exactly the same manner as in Example-2.

The results are shown in Table-2.

Gloss Point 21 Evaluation was carried out in the same manner as in Example 2, except that the content of EVA-1 was increased. The results are shown in Table-2.

In Example 2, evaluation was carried out in exactly the same manner as in Example 2, except that the content of EVAGMA was increased. The results are shown in Table 1.

A formulation of EVA-1 alone was evaluated. The results are shown in Table-2.

Comparative Example-5 In Example-1, low-density polyethylene (density 0.923 g/cc, M F
Evaluation was performed in exactly the same manner as in Example-1 except that R3,0) was used. The results are shown in Table-2.

Table-1 Table-1 (continued) Table-2 As is clear from the results of Unmeasurable Table-1i5 and Table-2, (B
Resin compositions that do not contain the olefin copolymer having an epoxy group in the side chain (component ) have a lack of elongation, which is thought to be due to low compatibility. On the other hand, in the resin composition of the present invention prepared by blending the above component (B) in a specific amount, a resin composition having excellent flexibility, abrasion resistance, and tensile properties can be obtained.

Claims (1)

[Claims] (1) Ethylene copolymer ionomer (A) and olefin copolymer (B) having an epoxy group in the side chain (A)
):(B)=90-99.9:0.1-10 (weight ratio)
100 to 700 parts by weight of ethylene/vinyl acetate copolymer or ethylene/(meth)acrylate copolymer (C) having an ethylene content of 55 to 95% by weight per 100 parts by weight of the reaction product. A resin composition formed by blending in the proportion of.