JPS6219785B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel thermoplastic polymer composition containing a chlorine-containing hydrocarbon polymer, and more particularly to a modified thermoplastic polymer composition containing a chlorine-containing hydrocarbon polymer and a dicarboxylic acid group or a derivative group thereof. The present invention relates to a thermoplastic polymer composition with improved compatibility, comprising a vinyl aromatic compound and a conjugated diene compound block copolymer. Chlorine-containing hydrocarbon polymers, especially polyvinyl chloride, are polymers with excellent tensile strength, transparency, water resistance, flame retardance, etc., and are relatively inexpensive as polymeric materials, so they are used in various molded products. It is widely used in special fields. However, polyvinyl chloride has drawbacks such as poor impact resistance, poor performance especially at low temperatures, and poor processability because the processing temperature and polymer decomposition temperature are close to each other. Therefore, plasticizers such as dioctyl phthalate and dibutyl phthalate are added, and various polymers such as ABS resin and ethylene-vinyl acetate copolymer are added as impact modifiers. In addition, Japanese Patent Publication No. 1867-1982 and Japanese Patent Application Laid-open No. 11486-1987 show that a vinyl aromatic compound-conjugated diene compound block copolymer is useful as a modifier for polyvinyl chloride. ing. On the other hand, vinyl aromatic compound-conjugated diene compound block copolymers, particularly styrene-butadiene block copolymers, which are representative thereof, are materials that have been attracting attention in recent years. A polymer that contains two or more polystyrene blocks and one or more polybutadiene blocks and has a relatively low styrene content exhibits properties as a thermoplastic elastomer, exhibits rubber elasticity without vulcanization, and is similar to plastic. It is used as a material for various molding as it can be molded into various shapes. Also, styrene-butadiene block copolymers with relatively high styrene content are known as transparent impact-resistant styrenic resins. Although attempts have already been made to improve the properties of polyvinyl chloride-based polymers and vinyl aromatic compound-conjugated diene compound block copolymers as described above, Vinyl polymers and vinyl aromatic compounds
The compatibility with the conjugated diene compound block copolymer is not always satisfactory, and the reality is that blends of the two already have poor transparency and insufficient improvement in impact resistance. It was hot. The present inventors have improved the compatibility between a chlorine-containing hydrocarbon polymer, of which the above-mentioned polyvinyl chloride polymer is a typical example, and a vinyl aromatic compound-conjugated diene compound block copolymer, and further As a result of intensive studies to improve mechanical properties such as impact resistance, we found that the above-mentioned block copolymer,
It has been discovered that by introducing a dicarboxylic acid group or a derivative group thereof, compatibility can be improved and a useful composition can be obtained, and the present invention has been achieved. The gist of the present invention is that a block copolymer consisting of (a) component: a chlorine-containing hydrocarbon polymer, and (b) component: a vinyl aromatic compound and a conjugated diene compound contains a dicarboxylic acid group or a derivative group thereof. A thermoplastic polymer composition comprising a modified block copolymer formed by bonding molecular units. The present invention will be explained in detail below. The chlorine-containing hydrocarbon polymer, which is the component (a) of the composition of the present invention, is a hydrocarbon polymer containing chlorine in its molecule, and examples thereof include vinyl chloride homopolymer; Copolymers of vinyl chloride and other monomers, such as vinyl chloride-vinylidene chloride copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-acrylic acid ester copolymers, Examples include vinyl chloride-maleic acid ester copolymers; graft copolymers based on these; and chlorinated polyolefins, such as chlorinated polyethylene and chlorinated polypropylene. These chlorine-containing hydrocarbon polymers generally have a molecular weight of 10,000 to 500,000, preferably 20,000 to 200,000. In addition, the polymer of component (a) above, especially the polymer containing vinyl chloride, may contain dibutyl phthalate, dibutyl sebacate, diethyl carbonate, dibutyl phenyl phosphate,
dihexyl phthalate, dioctyl adipate,
Dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, etc. can be added, and these plasticizers for vinyl chloride polymers (referred to as component (c)) are added to 100 parts by weight of component (a). On the other hand, it can be blended in an amount of 1 to 100 parts by weight. Next, the modified block copolymer which is component (b) of the present invention is a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound as a base, and a molecule containing a dicarboxylic acid group or a derivative group thereof. It is a combination of units. The block copolymer serving as the base contains one or more, preferably two or more, polymer blocks mainly composed of a vinyl aromatic compound, and one or more polymer blocks mainly composed of a conjugated diene compound. It is something. The content of vinyl aromatic compounds in this block copolymer is generally from 5 to 95% by weight, preferably from 15 to 85% by weight. Among these, the content of vinyl aromatic compounds is
Below 70% by weight, preferably below 60% by weight, the block copolymer is elastomeric, whereas polymers with a content of vinyl aromatic compounds above 70% by weight are transparent impact-resistant resins. These conditions are maintained even after the modified block copolymer is produced. Also, when the composition of the present invention is used, it exhibits slightly different performance depending on the content of the vinyl aromatic compound in the block copolymer. In the block copolymer, the ratio of the polymer block mainly consisting of a vinyl aromatic compound to the polymer block mainly consisting of a conjugated diene compound is preferably in the range of 10/90 to 90/10. In a polymer block mainly composed of a vinyl aromatic compound, the content of the vinyl aromatic compound is 60% by weight or more, preferably 80% by weight or more, particularly preferably 100% by weight, while the content is mainly composed of a conjugated diene compound. In the polymer block, the content of vinyl aromatic compounds is not more than 40% by weight, preferably not more than 30% by weight. The distribution of minor components in each polymer block may be random, tapered (monomer components increase or decrease along the molecular chain), partially block-like, or a combination thereof. When there are two or more polymer blocks, they may have the same structure or different structures. Vinyl aromatic compounds constituting the block copolymer include styrene, α-methylstyrene, vinyltoluene, etc., and conjugated diene compounds include butadiene, isoprene, 1,3-pentadiene, etc. In the present invention, as the base block copolymer, a styrene-butadiene block copolymer having a type 4 structure of butadiene-styrene-butadiene-styrene is particularly effective. In the block copolymer, the number average molecular weight of each polymer block is 1,000 to 300,000, preferably 5,000.
~100,000, and the number average molecular weight of the entire block copolymer is 10,000 to 500,000, preferably 20,000.
~300,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is in the range of 1.01 to 10. Furthermore, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. The above-mentioned limitations on the polymer structure of the book copolymer are necessary for the modified block copolymer to achieve the effects of the present invention. Not only one type of block copolymer may be used, but two or more types having different structures may be used in combination. Next, the modified block copolymer of the present invention is obtained by adding an unsaturated dicarboxylic acid or a derivative thereof to the above block copolymer, and these unsaturated dicarboxylic acids or derivatives thereof are , is added to the conjugated diene moiety of the block copolymer at the active unsaturated bond position. On average, one or more of these bonds to each molecule of the block copolymer, and
0.05 to 20 parts by weight, preferably 0.1 to 20 parts by weight
It is necessary to add within the range of 10% by weight in order for the resulting polymer composition to have the desired properties. Examples of the unsaturated dicarboxylic acids or derivatives thereof include maleic acid, fumaric acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1]
-5-heptene-2,3-dicarboxylic acid, etc.
There are acid anhydrides, esters, amides, etc. of these dicarboxylic acids, and among these, maleic acid, fumaric acid, and maleic anhydride are preferred. The modified block copolymer of the present invention can be obtained by reacting a block copolymer with an unsaturated dicarboxylic acid or a derivative thereof in a molten state or a solution state, with or without using a radical initiator. It will be done. The method for producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gel, or may have poor flowability and poor processability. It is not preferable to use a manufacturing method that deteriorates the radicals. For example, as shown in Japanese Patent Application No. 53-99102 related to the previously filed application, in the presence of a radical inhibitor in an extruder or the like, the radicals are substantially eliminated. A method in which the addition reaction is carried out under melt-mixing conditions that prevent the addition reaction from occurring is preferred. Furthermore, this modified block copolymer has the dicarboxylic acid group or its derivative group as a crosslinking position,
Ionic crosslinking of mono-, di- and trivalent metal ions can also be used. This ionic crosslinked product is obtained by crosslinking the above-mentioned modified block copolymer with one or a mixture of two or more of monovalent, divalent, and trivalent metal ions through ionic bonds. It can be obtained by reacting a modified block copolymer with any one or a mixture of two or more of monovalent, divalent and trivalent metal compounds as a crosslinking agent compound. In the above ionic crosslinked product, the dicarboxylic acid group or its derivative group of the modified block copolymer is
Ionization is achieved by adding a crosslinker compound. The amount of ionization can be adjusted by adjusting the amount of the crosslinking agent compound added, and the amount is measured using, for example, an infrared spectrophotometer. The amount of the crosslinking agent compound to be added is such that part or all of the dicarboxylic acid groups or derivative groups thereof contained in the modified block copolymer are ionized, and the ionization reaction proceeds almost quantitatively. In order to obtain the desired amount of ionization, an excess of the crosslinking agent over the theoretical amount may be necessary. In order to effectively obtain an ionic crosslinked product, it is preferable that the molar ratio between the metal compound and the dicarboxylic acid group or its derivative group contained in the modified block copolymer is 0.1 to 3.0. The crosslinking agent compound used to obtain the ionic crosslinked product by adding it to the modified block copolymer may be any one of the metal compounds of Groups 1, 2, and 3 of the periodic table; A mixture of two or more types is preferred, and specific examples thereof include sodium compounds, potassium compounds, magnesium compounds, calcium compounds, zinc compounds, and aluminum compounds. Preferred examples of these metal compounds are hydroxides, alcoholates, and carboxylates. A specific method for obtaining an ionic crosslinked product of a modified block copolymer is to add a crosslinking agent compound to a molten modified block copolymer, or to dissolve the modified block copolymer in an appropriate solvent. Examples include a method in which a crosslinking agent compound is added to this solution to cause a crosslinking reaction, and a method in which a modified block copolymer is used as a latex and a crosslinking agent is added thereto. It can be used as a method to obtain a crosslinked product. The composition of the present invention is characterized by improved compatibility between components (a) and (b). The composition of component (a) and component (b) can be in any ratio, but a composition in which component (a) accounts for about 50% by weight or more, preferably 60% by weight or more is a chlorine-containing carbonized A hydrogen-based polymer composition with improved impact resistance, processability, etc., in which component (b) is about 50% by weight or more, preferably 60% by weight or more, is a vinyl aromatic compound. -This is a composition in which the oil resistance, flame retardance, etc. of the conjugated diene compound block copolymer are improved, and both components have good compatibility according to the present invention, so it can be said that it is a useful composition. . The composition of the present invention may further contain, as additives, inorganic or organic granular or fibrous fillers, various antioxidants, lubricants, adhesives, colorants, and the like. The composition of the present invention can be molded as a thermoplastic polymer composition by injection molding, extrusion molding, compression molding, or other molding methods. In addition, the composition of the present invention can be used for footwear, daily necessities,
It can be used as an adhesive or pressure-sensitive adhesive, paint, etc. in molded sheets for miscellaneous goods, industrial materials, packaging materials such as films, hot melts, solutions, etc. Some examples are shown below, but these are for explaining the present invention in detail, and the scope of the present invention is not limited thereto.
Needless to say. Reference Example 1 [Preparation of modified block copolymer] “Tuffprene A” (sample p), a thermoplastic elastomer of styrene-butadiene block copolymer (manufactured by Asahi Kasei Industries, styrene content: 40
Weight%, melt index (G conditions)...
...10g/10min) to obtain a modified block copolymer grafted with maleic anhydride (sample P) by the method shown below. 2.0 parts by weight of maleic anhydride and 0.3 parts by weight of BHT as anti-gelling agent for 100 parts by weight of sample p.
(butyl hydroxytoluene) and 0.2 parts by weight of phenothiazine were added, and these were mixed uniformly using a mixer. This mixture was supplied to a 40 mm extruder (single screw, full flight type screw, L/D=24) under a nitrogen atmosphere, and a modification reaction was carried out at a cylinder temperature of 190 to 220°C. 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:
The index was 7.8 g/10 min, the toluene insoluble content was 0.05% by weight, and the amount of maleic anhydride added was 1.10 parts by weight per 100 parts by weight of the block copolymer, as determined by titration with sodium methylate. In addition, a block copolymer resin (sample q) of styrene-butadiene-styrene = 40/20/40 obtained by polymerizing styrene and butadiene using a butyllithium catalyst in cyclohexane (melt Index 7.2g/
A modified block copolymer resin (sample Q) to which maleic anhydride was added was obtained using the same extruder as that used to obtain sample A. Sample Q had an added amount of maleic anhydride of 0.93 parts by weight per 100 parts by weight of the block copolymer, and a melt index of 5.3 g/10 min. The added amount of maleic anhydride in the above-mentioned modified block copolymer sample P and sample Q is such that on average one or more maleic anhydride is bonded to each molecule of the block copolymer, which satisfies the requirements of the present invention. It was hot. Examples 1 to 4 and Comparative Examples 1 to 3 Using modified block copolymers Sample P and Sample Q, compositions with polyvinyl chloride shown in Table 1 (Examples 1 to 4) were heated at 175°C. Obtained using a mixing roll. In addition, 2 parts by weight of a vinyl chloride stabilizer was added to the total amount of these compositions. For comparison, Comparative Example 1 was prepared in the same manner using unmodified block copolymer samples p and q.
-3 compositions were obtained. The Izot impact strength and haze (0.3 mm thick sheet) of compression molded products of these compositions were measured, and the results are shown in Table 1. Note that measured values for polyvinyl chloride are also shown as a reference example. The compositions of Examples 1 to 4 all had improved compatibility with polyvinyl chloride, and the corresponding Comparative Examples 1 to 3
The results show that the composition using the modified block copolymer of the present invention is useful, as it has better transparency and improved impact resistance than the composition of the present invention.

【table】

[Table] Examples 5 and 6 and Comparative Examples 4 and 5 Using the modified block copolymer P, a composition containing a large amount of the modified block copolymer shown in Table 2 was prepared.
Prepared using a mixing roll at 175°C. Similarly, Comparative Example 4 was prepared using unmodified block copolymer sample P instead of modified block copolymer P.
and 5 compositions were prepared. Table 2 shows the physical properties of these compositions and of unmodified block copolymer sample p as a reference example. As is clear from the haze (measured on a 0.3 mm thick sheet) and oil resistance values shown in Figure 2, the compositions using the modified block copolymers of Examples 5 and 6 were superior to the corresponding unmodified block copolymers. Compared to the compositions of Comparative Examples 4 and 5 using copolymers, the compatibility of both phases is improved, the transparency of the composition is good, and the oil resistance is improved.

[Table] Example 7 and Comparative Example 6 Using Sample P of a modified block copolymer and Sample P of an unmodified block copolymer, the chlorinated polyethylene shown in Table 3 (Elastrene...manufactured by Showa Denko) was tested. The composition was prepared by mixing in a Brabender plastograph at 200°C. Table 3 shows the oil resistance test results of these compositions. As is clear from the results in Table 3, the composition using the modified block copolymer of Example 7 was the same as that of Comparative Example 6.
It has improved oil resistance compared to the composition.

【table】

【table】

Claims (1)

[Claims] 1. Component (a): a chlorine-containing hydrocarbon polymer; component (b): a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound; A thermoplastic polymer composition comprising a modified block copolymer formed by bonding molecular units containing the same. 2. The composition according to claim 1, wherein the chlorine-containing hydrocarbon polymer as component (a) is a homopolymer of vinyl chloride. 3. The composition according to claim 1, wherein the chlorine-containing hydrocarbon polymer as component (a) is a copolymer of vinyl chloride and another monomer copolymerizable with vinyl chloride. 4. The composition according to claim 1, wherein the chlorine-containing hydrocarbon polymer as component (a) is a chlorinated polyolefin polymer. 5. Claim 1, wherein the modified block copolymer of component (b) contains 0.05 to 20 parts by weight of a molecular unit containing a dicarboxylic acid group or its derivative group per 100 parts by weight of the block copolymer. Compositions as described. 6. The composition according to claim 1 or 5, wherein the dicarboxylic acid derivative group of component (b) is a dicarboxylic acid anhydride group. 7. Claims in which the modified block copolymer of component (b) is ionicly crosslinked with mono-, di- or trivalent metal ions using the dicarboxylic acid group or its derivative group as the cross-linking site. The composition according to any one of items 1 to 6. 8. A composition according to any one of claims 1 to 7, comprising 1 to 50% by weight of component (a) and 99 to 50% by weight of component (b). 9 Component (a) exceeding 50% by weight and not exceeding 99% by weight and component (b)
The composition according to any one of claims 1 to 7, comprising less than 50% by weight and 1% by weight or more. 10 The composition further contains plasticizers for vinyl chloride polymers 1 to 1 as component (c) per 100 parts by weight of component (a).
A composition according to claim 8 or 9, comprising 100 parts by weight. 11. The composition according to any one of claims 1 to 10, wherein the content of the vinyl aromatic compound in the block copolymer as component (b) is 5 to 70% by weight. 12. The composition according to any one of claims 1 to 10, wherein the content of the vinyl aromatic compound in the block copolymer as component (b) is more than 70% by weight and not more than 95% by weight.