JPS6322850A - Thermoplastic polymer composition containing ionomer - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to improved thermoplastic polymer compositions, and more particularly to (a) an ionomer component.

(b) A block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound contains a component of a modified block copolymer in which one dicarboxylic acid group is bonded to a molecular unit containing a derivative group thereof. A thermocilic polymer composition with improved physical properties.

(Conventional Technique 4#) Ionomers, represented by DuPont's product name "Surlyn", are polymers that have several characteristics not found in conventional polyolefin polymers, and have attracted attention in recent years. It is a material that has

The above "Sarson" is obtained by ionic crosslinking by reacting ethylene-methacrylic acid copolymer with metal ions such as aluminum and zinc, and its characteristics include transparency and moderate flexibility. It has properties such as heat resistance, cold resistance, abrasion resistance, heat sealability, adhesion to metals, melt strength, oil resistance, and chemical resistance, and can be molded and processed in the same way as ordinary polyolefin polymers. Possible packaging materials such as films, seams, coatings, and soles.

It is used for various applications such as molded products such as golf poles and toys, and adhesive layers for laminates.

However, ionomers such as "Surlyn" mentioned above,
It does not have good cold resistance, especially water resistance in terms of adhesive strength, and has the disadvantage that the adhesive surface tends to peel off when exposed to high humidity or when soaked in water.

On the other hand, styrene-
Butadiene block copolymers are polymeric materials that have received attention in recent years. Among these styrene-butadiene block copolymers, those with a relatively low styrene content and having two or more polystyrene blocks and one or more polybutadiene blocks have the properties of thermoplastic elastomers. , which has the advantages of the rubber elasticity of vulcanized rubber and the processability of thermoplastics, is used as a molding material for shoe soles and as a modifier for polystyrene resins and polyolefin resins. Examples of such thermoplastic nystomeric styrene-butadiene block copolymers include the trade names "Tuffprene" (manufactured by Asahi Kasei Kogyo Co., Ltd.) and "Turublane TJ".
(manufactured by Nippon Elastomers) and "Kraton" (Shell Chemical Exhibition) are well-known.

In addition, the block copolymer with a relatively high styrene content is a transparent impact-resistant resin), trade name ``K-Resin'' (Philips Petroleum Co., Ltd.).

It is used mainly in packaging materials such as sheets, films, and hollow products.

(Problems to be Solved by the Invention) A block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound, of which the styrene-butadiene block copolymer is a typical example, can be used with a styrene resin, etc. as described above. Friends with good compatibility.

Although it is used as a modifier for these, its compatibility with the ionomer is not necessarily good. Compositions of ionomers and the above block copolymers are disclosed in JP-A-52-4
No. 7863 discloses its use as a foam,
Although there is some mutual modification effect due to blending, there is not much improvement in adhesion, etc.

(Means for Solving the Problems) Therefore, as a result of intensive research by the present inventors to improve the compatibility between Fi, ionomer and the above block copolymer and enhance mutual modification effects, the above block copolymer A modified block copolymer made by subjecting a copolymer to an addition reaction of an unsorated dicarboxylic acid or its derivative? The present inventors have found that the above object can be achieved by using the present invention, and have completed the present invention.

In other words, one aspect of the present invention is.

(a) Ingredients: α, β-N12 Unfavorable 2! ■Carbon beating gang 1
A copolymer with a monomer that can be synthesized is used as a base polymer.

The content of any one of monovalent, divalent, and trivalent metal ions in this polymer exceeds 50% by weight and 99% by weight of an ionomer that is ionically crosslinked with two or more.
below.

Component (b): A block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound in which the content of the vinyl aromatic compound is 5 to 95% by weight, and a molecular unit containing a dicarboxylic acid group or a derivative group thereof. This is an ionomer-containing thermoplastic polymer composition comprising 1 to 50 ionomers bonded per molecule of the block copolymer and at least 1 weight and less than 50 weight of the phosphor-modified block copolymer.

The present invention will be explained in more detail below.

The ionomer (a) F& of the present invention is a copolymer with a copolymerizable monomer of α,β-unsaturated carboxylic acid as a heptad containing a carboxyl group as a base polymer. This polymer is ionically crosslinked by two or more of the monovalent, divalent and pentavalent metal ions contained in the polymer.

The above-mentioned substrate 1 combination includes olefins such as ethylene, propylene, butene, and non-polar monomers such as styrene;
Copolymers with α, β-unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid and α, β-, β-dicarboxylic acids such as maleic acid are usually used, and 1% contains 50% olefin.
molar or more, α, β-unsaturated unsaturated carboxylic acid 2
An olefin-α,β-unsaturated carboxylic acid copolymer having a content of ˜25 moles is preferred.

The ionomer is produced by reacting the above-mentioned base polymer, such as a copolymer of haolefin with α,β-unsaturated carboxylic acid, with a monovalent to trivalent metal compound, as shown in Japanese Patent Publication No. 39-6810. obtained by These metal compounds contain 10 to 1 of the carboxylic acid groups in the copolymer.
00 mol are added to neutralize and participate in ionic crosslinking.

An example of the olefin-α,β-unsaturated carbonate copolymer is an ethylene-acrylic copolymer.

Examples include ethylene-methacrylic acid copolymer, ethylene-itaconic acid copolymer, ethylene-maleic acid copolymer, ethylene-acrylic acid-methacrylic acid copolymer, ethylene-propylene-methacrylic acid copolymer, etc. The ethylene-acrylic acid copolymer t7t containing saturated monocarboxylic acid rR is preferably an ethylene-methacrylic acid copolymer.

In addition, the metal ions used in the production of the above ionomer are listed in 1.1 of the Periodic Table 17). II, III, IV-A
Mono- to trivalent ions of metals of the O and II groups, such as Na", Li", K", Os",
Monovalent ions such as Ag+, Mg", Ca", Ba
”, Zn”, Sr”, Hg!+.

Examples include divalent ions such as Fe"x and trivalent ions such as AZ"I Fe"x. These are reacted with the base polymer as compounds such as hydroxide, alcoholade, and lower carboxylic acid groups.

Furthermore, the above ionomer contains an olefin-α,β-unsaturated carboxylic acid ester copolymer 1, such as ethylene-methyl methacrylate copolymer or ethylene-acrylic, ruba-methyl copolymer, in water of a mono- to trivalent metal. It can also be produced by saponifying it with an oxide, or by partially neutralizing the saponified product with agar to partially convert it into a carboxylic acid, and these can also be used as component (a) of the composition of the present invention.

Commercially available ionomers that can be used in the present invention include, in addition to the trade name "Surlyn".

Examples include the product name "Corpolen" (manufactured by Asahi Dow).

Two or more ionomers can be mixed and used in the composition of the present invention.

Next, in the present invention, the block copolymer (b) component is a block copolymer (hereinafter referred to as "block copolymer") consisting of a vinyl aromatic compound and a conjugated diene compound as a base.
It is a polymer in which a molecular unit containing a dicarboxylic acid group or a derivative group thereof, preferably a dicarboxylic acid anhydride group, is bonded to a dicarboxylic acid group or a derivative group thereof.

The block copolymer serving as the base has a vinyl aromatic compound content of 5 to 95% by weight, preferably 15 to 85% by weight. Then, a polymer block mainly composed of a vinyl aromatic compound (one or more A, preferably two or more A,
Polymer block (B)t mainly composed of a conjugated diene compound
-Contains one or more polymer blocks, and the M amount ratio of each polymer block is
Preferably A/B is in the range of 10/90 to 9 fl/10. In the above range, if the content of the vinyl aromatic compound is 70% by weight or less, or more specifically, 50% by weight or less, a rubbery block copolymer is obtained, and the content of the vinyl aromatic compound is 70% by weight or less. If it exceeds %, it becomes a #finger-like block copolymer. This state is maintained even after modification with dicarboxylic acid groups or derivatives thereof. Furthermore, the specific properties of the composition of the present invention, such as hardness, vary from the vinyl aromatic compound-containing iK of the block copolymer.

In block A of the block copolymer, the content of the vinyl aromatic compound is 60% by weight or more, preferably 80% by weight or more, particularly preferably 100% by weight,
In block B, the vinyl aromatic compound content j1 is 40% by weight or less, preferably 30% by weight or less. If a minor component exists in each block, its distribution is random.

Cheebird, partially block-like primary may be a combination thereof. Each polymer block is 2111! If it is l1 or more, the same structure or a different structure may be used.

Examples of vinyl aromatic compounds constituting the block copolymer include styrene, α-methylstyrene, vinyltoluene, etc., and examples of conjugated diene compounds include butadiene,
Examples include isoprene, 1.3-pentadiene, and the like. As the block copolymer of the present invention, a styrene-butadiene block copolymer is preferred.

The number average molecular weight of block A or B is 1000-300
．． 000. It is preferably in the range of 5,000 to 100,000, and the number average molecular weight of the entire block copolymer is 1,000.
0-5oooooo, preferably 20000-3000
00 Ashi 1 molecular weight distribution! d1.01-10. Furthermore, the molecular structure of the block copolymer is linear, monobranched,
Either a radial pattern obtained by using all polyfunctional coupling agents or any combination thereof may be used. The conditions for the polymer structure of the block copolymer described above are the conditions most desired for the modified block copolymer to achieve the effects of the present invention. Furthermore, block copolymers having 211 or more different structures can be combined.

The block valve type fraction of the above structure is usually used for benzene, toluene, hexane, cyclo'f "j"etc.'7)
It is obtained by an anionic living polymerization method using a vinyl aromatic compound and a conjugated diene compound as monomers in an inert hydrocarbon solvent, using a right-wall lithium compound such as butyllithium as a catalyst. Furthermore, by reacting the block copolymer having a lithium active end obtained by the above method with a polyfunctional coupling agent 1 such as 4-carbon, silicon tetrachloride, etc., 1-branched, radial, etc. It is also possible to form a block copolymer of In the present invention, any polymer obtained by any polymerization method can be used as long as it falls within the above range.

Next, the modified block copolymer of the present invention is obtained by subjecting the above block copolymer to a total addition reaction with an unsaturated dicarboxylic acid or its derivative. - A derivative of the compound is added to the conjugated diene moiety of the block copolymer at the active unsaturated bond position.

In order for the composition of the present invention to have the desired properties, it is preferable to add 1 to 50, preferably 1 to 20 unsaturated dicarboxylic acids or derivatives thereof per molecule of the block copolymer. Even if the number of additions is as small as 1 or 2, significant improvement effects can still be achieved. Even if the number of additions exceeds 50, there is little effect compared to VC.

Examples of unsaturated rhodicarboxylic acids or derivatives thereof include c.
Maleic a, m-hydric maleic acid, fumaric acid.

Itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and its anhydride, endo-cis-bicyclo(
2,2,1)-5-heptene-2,3-dicarboxylic acid and acid anhydrides of these dicarboxylic acids.

There are esters, amides, and imides, and maleic acid, fumaric acid, and maleic anhydride are preferred.

The modified block copolymer is composed of, for example, a block valve type nine polymer and an unsaturated dicarboxylic acid or a derivative thereof.

It can be obtained by reacting in a molten or solution state with or without a radical initiator. The method for producing these block copolymers is not particularly limited in the present invention.

Production methods in which the resulting modified block copolymer contains undesirable components such as gel, or in which flowability is reduced and processability is deteriorated are not preferred. As an example of a preferred method, the addition reaction is carried out in an extruder or the like as shown in Japanese Patent Application No. 53-99102 in the presence of a radical inhibitor under melt mixing conditions that do not substantially generate radicals. There are several methods.

In the composition of the present invention, by mixing the components (a) and (b), the metal ions in the component (a) can be mixed with the dicarboxylic dispersion group or its derivative group in the modified block copolymer of the component (b). The components (a) and (b) are co-ionically crosslinked by the metal ions, thereby greatly improving the compatibility of the components in one fraction. The co-ionic cross-linking described above can be confirmed using, for example, an infrared spectrophotometer.

In the present invention, as the modified block copolymer of component (b), it is also possible to use a secondary ionic crosslinked product which has been pre-ionically crosslinked with mono- to pentavalent metal ions. When a modified block copolymer that has been ionically crosslinked in advance is used, the hardness, tensile stress, etc. of the composition are significantly improved, and a tough material can be obtained.

The composition of the present invention contains component (a) in an amount exceeding 50% by weight.
The amount of component (b) is 1M or more and less than 50% by weight. If the amount of component (b) is less than 1% by weight, no effect of improving adhesion is observed, and if it is more than 50% by weight, the tensile strength decreases, which is not preferable.

The composition of the present invention can be prepared using a conventional apparatus capable of mixing polymeric substances depending on the composition ratio of each component.

For example, there is one mixing device.

Extruder, mixing roll, Banbury mixer.

Examples include a kneader, and in the present invention, a melt mixing method using an extruder is particularly preferred.

In addition, the thermoplastic polymer composition of the present invention has the property JX
It is also possible to add reinforcing agents or fillers such as calcium carbonate, silica, carbon black, glass fiber, clay, process oil, polyethylene glycol, phthalate FX, etc. (D plasticizers) to the extent that they do not damage the Other additives 1 such as heat stabilizers, antioxidants, ultraviolet absorbers 1 colorants, pigments, etc. may also be added.

It is also possible to add a foaming agent to the composition of the present invention to form a foam.

(Effects of the Invention) In the present invention, the ionomer of the component (a) is the main component, and the modified block co-electronic a-form of the component (b) is contained in an amount of at least 1% by weight and less than 50% by weight, preferably from 1 to 40% by weight. In particular, the characteristics of ionomers such as heat sealability, melt strength, oil resistance, etc. are all maintained, while flexibility, adhesive strength, water resistance, etc. are improved.

Firstly, the composition of the present invention has good adhesion to various materials such as metals, various thermoplastic composites, and paper, and has good adhesion to these materials and one or more types of laminated materials. It is useful as a junction layer in a laminate of materials, and particularly its water resistance can be fully demonstrated.

Furthermore, the composition of the present invention is not only a useful material in itself, but also can be made into a composition with various thermoplastic polymers or other useful materials.

Zarani1 The composition of the present invention can be molded using various conventional molding methods1.
For example, extrusion molding, injection molding, calendar molding, etc.
Can be molded into various molded products.

For example, 1 mechanical parts, automobile parts, electrical parts, toys.

For various fields such as industrial parts, belts, hoses, footwear, medical supplies, anti-vibration rubber, daily necessities, miscellaneous goods, building materials, sheets, films, blow molded products, and solution-type and real-melt adhesives and pressure-sensitive adhesives. These are useful compositions available.

(Examples) Hereinafter, some examples will be shown, but these are intended to specifically explain the VC of the present invention and are not intended to limit the scope of the present invention. Note that U is also shown for reference.

Reference Example [Preparation of Modified Block Copolymer] Using Sample P, which is a thermoplastic elastomer of styrene-butadiene block copolymer, maleic anhydride was grafted by the method described below to obtain modified block copolymer 7. The combination (sample P) was obtained. The sample pFi was obtained using n-butyllithium as a polymerization catalyst in a hexane solution, and it is believed to have the following structure based on the rapid synthesis method and analysis results.

Polymer structure: B+-8t-Bt-8t (linear) B, = 113N Lid - 〇31/(5) = 1672
(Chibird) S, = 17% by weight (5)/(8)
= 0/17B, -49 weight i% (2)/(5) = 4
675 (Chee Bird) St = '6M amount - 031/(8)
=Q/16, Bn... Polymer block mainly composed of butadiene Sn... Polymer block mainly composed of styrene The integer n represents the order along the molecular chain.

(5) - Butadiene content (wt% relative to the entire block copolymer) (3) Styrene content (weight 1 ms relative to the entire block copolymer > (in the following examples) ) Styrene content: 38M Tiblock styrene content: 33M - weight average molecular weight (Mw) 281,000 number average molecules'! #L (Mn) =
620 o.

Melt Index: 11. Of/10101
1 (JIS-6870, load 15 kg, 200C) For 100 M parts of sample p, 1.5 parts by weight of maleic anhydride, 0.3 parts BHT (butyl hydroxytoluene) as a gelling inhibitor, and 0. .2 parts by weight of phenothiazine? r was added, and these were mixed uniformly using a mixer f.

This mixture was fed to a 40 mm extruder (single screw, full-flight screw, L/D=24) under nitrogen atmosphere at a cylinder temperature of 190-210 c.

A denaturation reaction was performed. The obtained polymer was dried under reduced pressure to remove unreacted maleic anhydride.

The analysis results of the modified block copolymer (sample P) are as follows.

Melt index is 7.3t/10 yrria
,) The amount of toluene insoluble matter was determined by titration with sodium methylate, and the amount of maleic anhydride added was 100 parts by weight of the block copolymer and 0.70 parts by weight of 7'C.

In addition, sample q (styrene/butadiene/styrene = 5
7/26757 structure styrene-butadiene block copolymer, melt index 8.4P/10 decoy),
Using sample r (commercially available styrene-butadiene block copolymer Asabrene T-431 styrene content 50% by weight, melt index 10.3 t/10M),
By a method using an extruder similar to that used to obtain sample P,
Samples Q and R'(H) of modified block copolymers were obtained by addition of maleic anhydride. Their melt index.

Addition of maleic anhydride 'my+' is shown in Table 1.

Table 1 X block copolymer 100 parts by weight Examples 1 to 4
．． Comparative Examples 1 to 3 (a) As the component ionomer, Kobolene QD-400t manufactured by Asahi Dow was used, (b) As the modified block copolymer for ff, sample P, sample Q, ionic crosslinked product PA, and comparison friend were used. For this purpose, it was possible to knead the compositions shown in Table 1 and Table 2 using unmodified block copolymers Sample P and Sample Q using a 180C mixing roll.

As shown in Table 2, the compositions containing the paternal block copolymers of Examples 1 to 3, compared to the compositions containing the unmodified block copolymers of Comparative Examples 1 to 3 and the ionomer alone,
It has excellent adhesion strength and water resistance with nylon (non-stretched sheet of nylon-6). In addition, Example 1
Compositions Nos.-3 have better tensile strength than the corresponding compositions of Comparative Examples 1-3. Furthermore, Example 4 shows that sample pl sodium methylate provides ionic cross-linking (CH3
ONa/Kjl anhydride group=0.4) L sample p-A'f: The tensile strength was improved by the composition used, and the water resistance of the adhesive strength was also good.

Table 2

Claims (8)

[Claims] (1) Component (a): A copolymer of α,β-unsaturated carboxylic acid and other monomers is used as the base polymer, and the monovalent, divalent and trivalent More than 50% by weight and not more than 99% by weight of an ionomer that is ionically crosslinked with one or more metal ions, and (b) component: content of vinyl aromatic compound is 5 to 95% by weight. In a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound, the number of molecular units containing a dicarboxylic acid group or its derivative group is 1 per molecule of the block copolymer.
~1% by weight or more of a modified block copolymer with ~50 units bonded5
ionomer-containing thermoplastic polymer composition comprising less than 0% by weight. (2) The composition according to claim 4, wherein the base polymer is an olefin-α,β-unsaturated monocarboxylic acid copolymer. (3) Olefin-α,β-unsaturated monocarboxylic acid copolymer is ethylene-acrylic acid copolymer or ethylene-acrylic acid copolymer
The composition according to claim 2, which is a methacrylic acid copolymer. (4) The composition according to claim 1, wherein the content of α,β-unsaturated carboxylic acid as a monomer unit in the base polymer is 0.2 to 25 mol. (5) The composition according to any one of claims 1 to 4, wherein the dicarboxylic acid group or its derivative group is a dicarboxylic acid anhydride group. (6) The content of the vinyl aromatic compound in the block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound is 5
70% by weight of a composition according to any one of claims 1 to 5. (7) The vinyl aromatic compound content of the block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound is 7
The composition according to any one of claims 1 to 5, which has a content of more than 0% by weight and less than 95% by weight. (8) Due to the metal ions in component (a), component (a) and (
2. The composition according to claim 1, wherein component b) is co-ionically crosslinked.