JP2934207B2 - Ionomer resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ionomer resin containing a fluorine compound, and more particularly to a thermoplastic resin having improved physical properties and the like.

[0002]

2. Description of the Related Art Ionomers (polymers in which organic and inorganic components are linked by covalent and ionic bonds)
Generally has a polar group in the molecular chain of polyolefin, and has a structure in which a part of the molecular chain is cross-linked by a metal ion or the like.

[0003] By the way, ionomers typified by Du Pont's trade name "Surlyn" are polymers having some features not found in conventional polyolefin polymers and the like, and are attracting attention in recent years. It is. That is, this "Surlyn" is obtained by reacting a metal ion of sodium or zinc with an ethylene-methacrylic acid copolymer and ion-crosslinking, and its features are transparency and moderate flexibility. , Heat resistance, abrasion resistance, heat sealability, adhesion to metals, etc., melt strength, oil resistance,
Since it requires chemical resistance and can be molded and processed as well as ordinary polyolefin polymers,
Packaging materials such as films and sheets, coating materials,
It is used for various applications such as molded articles such as golf balls and toys, and coating layers of laminates. However, ionomers such as "Surlyn" are not necessarily said to have good water resistance, especially water resistance of adhesive strength, and have a defect that the bonded surface is liable to peel when humid or immersed in water. doing.

On the other hand, block copolymers having a relatively high styrene content are transparent impact-resistant resins, and these resins are trade names "K Resin" (manufactured by Philips Petroleum Co.) and "Clearylene" (Electric). (Manufactured by Kagaku Co., Ltd.) and used in the field of packaging materials such as sheets, films and hollow products. However, these resins also have defects in water resistance, solvent resistance, heat resistance, and the like.

[0005]

The object of the present invention is to improve the water resistance, solvent resistance, and temperature resistance characteristics of ionomers such as "Surlyn".

[0006]

According to the ionomer resin of the present invention, the polymer contains 50 to 95% by weight of an olefin monomer unit and 5 to 50% by weight of a polymerizable monomer unit having at least one carboxyl group. A copolymer (b-1);
It consists of a 5: 5 ratio of a copolymer (b-2) containing 50 to 95% by weight of a polymerizable monomer unit containing fluorine and 5 to 50% by weight of a polymerizable monomer unit having at least one carboxyl group. It is characterized in that the mixture is ion-crosslinked with a metal ion or a base. Here, each monomer unit refers to a structural unit in which each of the above monomers is linearly bonded by olefinic addition polymerization.

By the way, the present inventors have confirmed that the above object can be achieved if the ionomer resin is copolymerized using a fluorine-containing monomer as one of its monomer components. The present invention has been made based on this.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The ionomer resin according to the present invention is composed of a copolymer (b-1) and another copolymer (b-2).
It is obtained by ion-crosslinking a mixture having a ratio of 5 with a metal ion or a base described below. The following are mentioned as each monomer component in these. (1) Olefin monomers such as ethylene, propylene and butene; and (2) Polymerizable monomers having one or more carboxyl groups are α, β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid. (3) Examples of the fluorine-containing polymerizable monomer such as an acid or unsaturated dicarboxylic acid include a fluoroolefin monomer shown in Table 1 below and a fluorinated (meth) acrylate shown in Table 2 below.

[0009]

[Table 1]

[0010]

[Table 2]

Other than these, certain monomer components useful as ionomer resins are described in JP-B-39-6810, and the disclosed olefin monomers and polymerizable monomers having at least one carboxyl group are disclosed therein. Etc. can also be used in the present invention.

In order to produce each of the above-mentioned copolymers in the present invention, if the copolymer is (b-1), for example, a copolymer of ethylene and acrylic acid may be added to a monovalent, divalent or trivalent metal compound. May be reacted. In this case, these metal compounds represent 1 to 100 mol% of the carboxylic acid groups in the copolymer.
Is neutralized, so that the ethylene-acrylic acid copolymer is obtained as ion-crosslinked.

Here, some specific examples of the copolymer in the present invention are as follows. The percentage in parentheses is% by weight, and the parenthesis at the end indicates a crosslinked metal or a crosslinked base. (B-1) Example of copolymer No. 1 ethylene (80%)-acrylic acid (20%) copolymer (Ca) No. 2 ethylene (90%)-methacrylic acid (10%) copolymer ( No.3 Propylene (60%)-itaconic acid (40%) copolymer (Zn) No.4 Ethylene (50%)-2-ethylhexylmethate (30%)-maleic acid (20%) copolymer Merged (NH ₄ ) No. 5 Butene (20%)-methyl methacrylate (60
%)-Acrylic acid (40%) copolymer (Fe)

(B-2) Example of copolymer No. 6 Heptadecafluorooctylethyl methacrylate (80%)-methacrylic acid (20%) copolymer (Ca) No. 7 Trifluoroisopropyl-α-cyanoacrylate (80%)-acrylic acid (20%) copolymer (diethylamine) No.8 hexafluorobutyl methacrylate (50%)
-Styrene (20%)-maleic acid (30%) copolymer (Z
n) No.9 tetrafluoroethylene (80%)-acrylic acid (20%) copolymer (NH ₄ ) No.10 hexafluoropropylene (60%)-itaconic acid (40%) copolymer (Fe)

The metal ions used in the production of these ionomers are, as described above, the periodic tables I, II, III, IV
-1,2 and trivalent ions of metals of groups A and VI;
Specific examples thereof include monovalent ions such as Na ⁺ , Li ⁺ , K ⁺ , and Ag ⁺ , Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , Zn ²⁺ , Sr
Divalent ions such as ²⁺ and Hg ^2+, and ³ ions such as Al ³⁺ and Fe ³⁺
Valence ions. These are reacted with the copolymer as compounds such as hydroxides, alcoholates and lower carboxylic acid groups. In addition, in the production of the ionomer, a base may be used as described above, and examples of the base include ammonia and amine, which may be reacted with the copolymer.

The ratio of each monomer component (composition ratio) of the polymer of the present invention is as follows. (B-1) Copolymer: olefin monomer / polymerizable monomer having one or more carboxyl groups = 50 to 95/5 to 5
(B-2) Copolymer: polymerizable monomer containing fluorine / polymerizable monomer having one or more carboxyl groups = 50 to
95/5 to 50

However, when the polymerizable monomer having one or more carboxyl groups is less than 5% by weight, ionic crosslinking hardly occurs, and conversely, 50% by weight
Above, there may be inconveniences such as poor flexibility and difficult processing due to too strong ionic crosslinking. Further, when the polymerizable fluorine monomer is 5% by weight or less, water resistance,
Heat resistance and oil resistance are inferior, and conversely, if it is 50% by weight or more, the adhesiveness tends to deteriorate.

The copolymer composition of the present invention is blended with each of the copolymers (b-1) and (b-2) to form an ionomer. In this case, (b-1) / (b-2) ≒ 5/5
It is. (B-2) When the proportion of the copolymer is considerably less than 50% by weight, water resistance, heat resistance and solvent resistance become insufficient.

The resin composition of the present invention can be prepared by an apparatus generally used for mixing high-molecular substances according to the composition ratio of each component. Examples of the mixing device include an extruder, a mixing roll, a Banbury mixer, and a kneader. In the present invention, a melt mixing method using an extruder is particularly preferable. In addition, the ionomer resin of the present invention includes reinforcing agents or fillers such as calcium carbonate, silica, carbon black, glass fiber, and clay, to the extent that their properties are not impaired, process oil, polyethylene glycol, and phthalic acid esters. It is also possible to add plasticizers. In addition, an antioxidant, an ultraviolet absorber, a coloring agent, a foaming agent, and the like can be added as additives.

Now, an example of the production of the copolymer (b-1) is shown in the following (1) and (2). (1) Preparation of chromium catalyst component Into a 200 ml flask purged with argon, 10 stainless steel balls having a diameter of 5 to 10 mm were put.
6 g (4 mmol) and 100 ml of toluene were charged and ball-milled for 10 hours while stirring at room temperature. Then, toluene was added thereto to make the total amount 200 ml. As a result, a black-purple gel-containing chromium catalyst-containing component was obtained.

(2) Production of copolymer 300 ml of toluene, 3.4 ml of acrylic acid, and 10 mmol of ethyl aluminum dichloride as Lewis acid were added to a pressure-resistant glass container having an inner volume of 500 ml and purged with argon, followed by stirring at 20 ° C. for 5 minutes to react. I let it. Then, the above (1)
0.01 mmol of the chromium catalyst component prepared in 1) and 1 mmol of diethylaluminum monochloride were added, ethylene was continuously introduced, and the copolymerization reaction was carried out at 20 ° C. for 3 hours while maintaining the internal pressure at 2 kg / cm ² G. After completion of the reaction, ethylene was depressurized and the product was poured into methanol to precipitate. The obtained solid was collected by filtration, deashed and washed with a mixed solution of hydrochloric acid and methanol to remove soluble components, and then subjected to acetone extraction for 5 hours to remove an amorphous polymer. Further, the extraction residue was dried under reduced pressure at 80 ° C. for 2 hours to obtain 6.6 g of a white copolymer. The catalytic activity (polymerization activity) is 12.7 kg / g
It was chrome. Similarly, in order to produce the (b-2) copolymer, a fluorine-containing monomer may be introduced instead of continuously introducing ethylene in the above (b-2) production example.

[0022]

EXAMPLES Examples 1 to 4 The physical properties of the previously prepared copolymer itself or the copolymer composition were measured. The results were as shown in Table 3.

[0023]

[Table 3]

[0024]

The ionomer resin of the present invention has good adhesion to metals, paper, etc., and has good water resistance, oil resistance and oil repellency. Further, the ionomer resin of the present invention can be molded by various conventional molding methods such as extrusion molding, injection molding, calendar molding, etc., and various molded products such as machine parts, automobile parts, electric parts, toys, industrial It can be used in various fields such as parts, belts, hoses, footwear, medical supplies, vibration-proof rubber, daily necessities, sundries, building materials, sheets, films, hollow molded products, solution-type and hot-melt type adhesives and adhesives. It is useful.

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Claims (1)

(57) [Claims] 1. A polymerizable monomer unit having 50 to 95% by weight of an olefin monomer unit and at least one carboxyl group.
(B-1) containing 50 to 95% by weight of a polymerizable monomer unit containing fluorine and 5 to 50% by weight of a polymerizable monomer unit having at least one carboxyl group. An ionomer resin obtained by subjecting a mixture having a ratio of 5: 5 to the copolymer (b-2) to be ion-crosslinked with a metal ion or a base.