JPS5840343A - Polymer composition containing filler - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having improved tensile strength, 300% tensile modulus, hardness and resistance to oil, weather and thermal aging, consisting of a specified modified block copolymer, a reinforcing resin, a filler and a softening agent. CONSTITUTION:5-200pts.wt. filler such as carbon black and 0-200pts.wt. softening agent such as naphthenic process oil are blended with 100pts.wt. mixture of 95-0wt% reinforcing resin such as PS and 5-100wt% modified block copolymer to which is bonded a molecular unit contg. a carboxyl (derivative) group, said copolymer being obtd. from an addition reaction between an unsaturated carboxylic acid (derivative) and a block copolymer having a number- average MW of 20,000-500,000 and a ratio of weight-average MW to number- average MW of 1.05-10 and composed of at least one arom. vinyl compd. polymer block A and at least one olefin compd. polymer block B which is hydrogenated to such an extent that the degree of unsaturation does not exceed 20%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to filler-containing polymeric compositions with improved physical properties. ! Specifically, it is a modified block copolymer in which molecular units containing a carboxylic acid group and a derivative group thereof are bonded to a vinyl aromatic compound-oleayne compound block copolymer.

It contains a filler, and if necessary, a reinforcing resin and a softening agent. For molding with improved physical properties,
The present invention relates to a filler-containing polymer composition suitable as a material.

In recent years, various block copolymers consisting of polymer blocks that are thermodynamically rubbery at room temperature (soft segments) and polymer blocks that are glassy or crystalline (hard segments) have been developed by vulcanization. Even without rubber, it has rubber elasticity similar to conventional rubber at room temperature and fluidity similar to conventional plastic at processing temperatures, and is attracting attention as a thermoplastic elastomer to which plastic processing technology can be applied. .

Among such thermoplastic elastomers, vinyl aromatic compound-conjugated diene compound block copolymers, such as sterene-butadiene block copolymers and styrene-isoprene block copolymers, have elasticity and feel that are closest to those of conventional vulcanized rubber. Because of this, it is considered suitable as a material for various rubber molded products such as footwear, industrial goods, and daily necessities, for which vulcanized rubber has traditionally been used.

However, the drawbacks of these block copolymers are that
When inorganic fillers or reinforcing resins are added to improve rigidity, tensile strength may decrease or permanent elongation at break may increase.

The present inventors have improved the interstitial point in a polymer composition consisting of the vinyl aromatic compound-conjugated diene compound block copolymer, an inorganic photonic agent, and a reinforcing resin and a softener blended as necessary. As a result of extensive research, we have arrived at the present invention.

That is, the present invention has (a) at least 41 vinyl aromatic compound polymer blocks A and at least one olefin compound polymer block B, and the degree of unsaturation of block B is 20
Molecular units containing carboxylic acid groups or derivative groups thereof are bonded to a block copolymer which is a polymer block of not more than 96 olefin compounds! Polymer block copolymer 5
~100% by weight and (b) reinforcing resin 95~0% by weight total amount 100
c) filler 5 to 2001i parts by weight and (d)
A filled, agent-containing polymer composition comprising 0 to 200 parts by weight of a softener.

The present invention will be described in detail below.

The modified block copolymer which is the component (a) of the composition of the present invention comprises at least 411 vinyl aromatic compound polymer blocks A and at least one olefin compound polymer block in which the degree of unsaturation does not exceed 2096. A block copolymer consisting of B (hereinafter referred to as this).

It is a modified block copolymer in which a molecular unit containing a carboxylic acid group or a derivative thereof is bonded to a "basic block copolymer" (referred to as a "basic block copolymer"). Here, the olefin compound polymer block refers to monoolefins such as ethylene, propylene, 1-butene, and inbutylene, or conjugated diolefins such as butadiene, itaprene, and 1g3-pentadiene.

1e Polymerized or copolymerized form of one or more olefin compounds selected from non-conjugated diolefins such as 1e4-hexadiene, norbornene, and norbornene derivatives m
The unsaturated FIILFi content of the block is 20% or less. Therefore, when the above-mentioned diolefin a is used as a constituent monomer of an olefin compound polymer block, the cine saturation is increased by a method such as hydrogenation until the degree of unsaturation in the block portion does not exceed 20%. Measures must be taken to reduce this.

Furthermore, vinyl aromatic compounds are randomly copolymerized in the olefin compound polymer block, which improves stuttering properties. In the present invention, examples of the "block copolymer serving as a base" include hydrogenated block copolymers of a vinyl aromatic compound and a conjugated diene compound, block copolymers of a vinyl aromatic compound and a monoolefin, etc. Can be mentioned. The modified block copolymer used in the present invention can be produced by adding an unsaturated carboxylic acid or a derivative thereof to the above-mentioned "base block copolymer".

In the present invention, the most preferable modified block copolymer as component (1) is a block copolymer (hereinafter referred to as "block copolymer") composed of a vinyl aromatic compound polymer block and a polymer block mainly composed of a conjugated diene compound. (referred to as "block copolymer as a precursor") is selectively hydrogenated to a degree of unsaturation of the conjugated diene moiety not exceeding 20%. It is a modified block copolymer obtained by bonding through an addition reaction.

"Block copolymer as a precursor" has at least 4
It contains 11, preferably 2 or more vinyl aromatic compound polymer blocks and at least 411 conjugated diene-based polymer blocks. Here, the polymer block mainly composed of conjugated diene has a weight ratio of vinyl aromatic compound to conjugated diene compound of 0/100 to 50.
150. Preferably, in a polymer block having a composition range of 0/100 to 30/70, the distribution of the vinyl aromatic compound in this block is random, tapered (the monomer component increases or decreases along the molecular chain). thing)
.

It may be partly block-shaped or any combination thereof. In addition, in the "block copolymer as a precursor" in the present invention, the content of the vinyl aromatic compound is contained in the transition region between the vinyl aromatic compound polymer block and the polymer block mainly composed of a conjugated diene compound. A copolymer block of a vinyl aromatic compound and a conjugated diene compound having a weight of more than 50% may be present, but such a polymer block shall be included in the above-mentioned polymer block mainly composed of a conjugated diene compound. .

In the "block copolymer as a precursor", the weight ratio of the content of the vinyl aromatic compound and the content of the conjugated diene compound is preferably in the range of 10790 to 90710 -I
More preferably, the range is from s/85 to 85/15. Such a block copolymer exhibits properties as a thermoplastic elastomer when the content of the vinyl aromatic compound is about 60% by weight or more, preferably 55% by weight or less, and is classified as a "precursor". It is suitably used as a block copolymer.

As the vinyl aromatic compound forming the "block copolymer as a precursor", one selected from among styrene, a-methylstyrene, and vinyltoluene, or two or more types of Fi, among which styrene is particularly preferred. Conjugated diene compounds include butadiene, isoprene, 1*3-
II or more selected from pentadiene, among others, butadiene and/or isoprene are particularly preferred. The above block copolymer #'i has a number average molecular weight in the range of 20*000 to 5009000 and a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) of 1
．． A cape circumference of 0S to 1O is preferred. In addition, the molecular structure of the block copolymer may be linear, monobranched, radial, or a combination thereof.Furthermore, when butadiene is used as the conjugated diene compound in the block copolymer, the microstructure of the butadiene moiety The 1*2 bond amount of the structure is preferably in the range of 10 to 805%. If the modified block copolymer needs to have rubber elasticity,
1) The 2-kite content is 35-55% Il! I particularly like the song.

When the block copolymer contains two or more vinyl aromatic compound polymer blocks or fCFi conjugated diene compound-based polymer blocks, each block may have the same structure, Each structure such as monomer component content, distribution in their molecular chains, block molecular weight, microstructure, etc. may be different.

Methods for producing "block copolymers as precursors" include 1, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43
-14979 Publication, Special Publication No. 49-36957,
Examples include methods described in Japanese Patent Publication No. 4B-2423, Japanese Patent Publication No. 48-4106, and the like.

All of these methods use an organic lithium compound or the like as an anionic polymerization initiator in a hydrocarbon solvent, and if necessary, an ether compound such as diethyl ether or tetrahydrofuran, trinoethylamine, or NtN* as a vinylizing agent.
Using a tertiary amine such as N't,N'-tetramethylethylenediamine, a Lewis base such as a phosphine compound such as hexamethylphosphoamide, or a polyfunctional compound such as silicon tetrachloride or ezoxidized soybean oil as a coupling agent. A block copolymer having a linear, branched or radial structure is obtained by block copolymerization of a vinyl aromatic compound and a conjugated diene compound. In the present invention, F! Any material obtained by any polymerization method can be used as long as it falls within the above range. j
! ! Furthermore, it is also possible to use not only one type of block copolymer Fi, but also a mixture of two or more types.

C) "Block copolymer as r precursor".

A ``block copolymer serving as a base'' can be obtained by carrying out water treatment using a known method 1, for example, the method described in Japanese Patent Publication No. 42-8704. "Block copolymer as a base" means that at least 80% of the aliphatic double bonds based on the conjugated diene compound in the polymer block mainly composed of the conjugated diene compound of the "block copolymer as the precursor" In other words, the degree of unsaturation in the block morphologically converted into olefin compound polymer block B by hydrogenation of one combined block mainly composed of a conjugated diene compound exceeds 209. It is necessary that there be no.

If the degree of unsaturation of the olefin compound polymer block exceeds 20%, it is not preferable because the weather resistance and heat aging resistance of the molded article of the unsaturated 2-ester resin composition will be poor. On the other hand, the hydrogen of the aromatic double bond based on the vinyl aromatic compound copolymerized in the vinyl aromatic compound monopolymer block and the vinyl aromatic compound copolymerized in the polymer block mainly composed of a conjugated diene compound if necessary. Although there is no particular restriction on the addition rate, it is preferable that the hydrogenation rate is 1 to 20X or less. The unsaturated gIL of the olefin compound 1 combined block is
It can be measured by instrumental analysis using an infrared spectrophotometer (IR), a nuclear gas resonance device (NMR), etc., or a satisfactory analysis using an iodometric titration method.

The "substrate block copolymer" is then subjected to an addition reaction with an unsaturated carboxylic acid 1 + chlorine derivative to synthesize the modified block copolymer used in the present invention. Examples of unsaturated carboxylic acids or conductors at that time include maleic acid, leicic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1y2-dicarboxylic acid, endo-cis-bicyclo(2s2t'l)5 −
Examples include hebutene-293-dicarboxylic acid, acid anhydrides, esters, amides, and imides of these dicarboxylic acids, acrylic acid, methacrylic acid, and esters and amides of these monocarboxylic acids. These can be used not only alone but also as a mixture of two or more.

Among these, derivatives of unsaturated dicarboxylic acids are preferred, and maleic anhydride is particularly preferred.

Modified block copolymer Fi, r Obtained by adding an unsaturated carboxylic acid or a conductor to a base block copolymer in a solution or melt state with or without the use of a radical initiator. . The method for producing these modified block copolymers is not particularly limited in the present invention. A manufacturing method that deteriorates workability is not preferred. The preferred method is
For example, there is a method in which a "substrate block copolymer" is reacted with an unsaturated carboxylic acid or a conductor at that time in the presence of a radical initiator in an extrusion tank.

The amount of molecular units containing carvone isthmus groups or derivative groups thereof contained in the modified block copolymer, that is, the amount of unsaturated cargen a12 or the conductor added thereto, the average value of the entire modified block copolymer used in the present invention As,
1 or more, preferably 3 to 200, preferably 5 per polymer molecule of the "substrate block copolymer"
At other amounts added, ˜50, the properties of the composition of the invention are lost. In particular, the above conditions are necessary to obtain uniformity of the composition, uniform mechanical strength, and surface Elk 1% property.

The content of molecular units containing a carboxylic acid group or its O derivative group in the modified block copolymer can be easily determined by a method such as an infrared spectrophotometer or titration.

ta, in the present invention, the unmodified block copolymer can be used within a range in which the amount of unsaturated carbon tR or its derivative in the modified block copolymer used as component (a) satisfies the above range as an overall average value. May include merging. Furthermore, two or more different modified block copolymers can be used in combination.

In the method for producing a modified block copolymer as described above,
Generally, unreacted unsaturated carboxylic acids or derivatives thereof remain in the modified block copolymer, but this unreacted carboxylic acid or its derivatives may be completely removed or may be left as is.

In the present invention, the total amount of the modified block copolymer tf (layer) component and the reinforcing resin (b) component is 5 to 100%.
It is used in a range of 1% by weight.

Next, in a preferred embodiment of the present invention, reinforcing resin #i used as component (b), for example, an olefin resin.

Styrene resin, acrylate resin, vinyl chloride resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene sulfide resin, polyphenylene ether resin.

Selected from thermoplastic resins such as polyacetal resin and polyurethane resin. Among these, the present olefin resin and styrene resin are preferred, and polystyrene and high-impact polystyrene are particularly preferred.

The reinforcing resin of the present invention has the hardness of the modified block copolymer,
It is used as necessary for the purpose of improving heat resistance, oil resistance, etc. 1 In the present invention, the total amount with the Fi(j) component is 0 to 0.
It is used in an amount of 95% by weight, preferably in the range of 0 to 50% by weight.

Next, the filler used as component (C) in the present invention is:
It is selected from any inorganic or organic compound commonly used as a filler in rubber or plastic applications. Examples of these fillers are -t
Carbon black, white carbon, clay, talc, calcium carbonate, magnesium carbonate, glass iron, aramid fiber, etc. can be produced.

The filler is used as an essential component of the composition of the present invention for the purpose of improving the hardness, heat resistance, and oil resistance of the modified block copolymer. Total amount of 1oo111kmTori~200 parts by weight,
It is preferably used in a range of 10 to 100 parts by weight. If the amount of the filler is less than 5 parts by weight, no reinforcing effect will be observed, and if it exceeds 200 parts by weight, the rubber elasticity will decrease, and processability will deteriorate, which is not preferable.

Next, in a preferred embodiment of the composition of the present invention (d)
The softeners blended as ingredients are generally used to improve the hardness, rigidity, and fluidity of rubber or plastic. Examples include #
i, aromatic process oils, naphthenic process oils, ester plasticizers such as vaseline, paraffin, polyethylene wax, linseed oil, soybean oil, polyethylene wax, dioctyl phthalate, dioctyl adipate, etc. Among these, process oils are preferred, and naphthenic process oils are particularly preferred.

In the present invention, the softener is used to improve the fluidity and bending resistance of the composition.
It is added as necessary for the purpose of improving rebound elasticity, etc., and its blending amount is 100% in total of component (1) and component (b).
The amount is in the range of 0 to 200 parts by weight, preferably 0 to 50 parts by weight, based on the weight sK.

The composition of the present invention is characterized by the use of a modified block copolymer, which increases the tensile strength compared to compositions using an unmodified block copolymer.

300% improved tensile stress, hardness, oil resistance, etc. Furthermore, in the modified block copolymer used in the present invention, the degree of unsaturation of the olefin compound polymer block is 20.
%, the composition has excellent weather resistance and heat aging resistance.

The composition of the present invention can be used as a material for molding, for example, footwear, belts/hoses, industrial goods, and toys.

Used for daily necessities, sponges, sports goods, balls, packing, etc. Various molded products Fi, compression molding,
It can be manufactured by a molding method such as extrusion molding or injection molding. It can also be used by processing it into a foam or the like.

The present invention will be explained in more detail with reference to some examples below, but it goes without saying that these are merely illustrative and do not limit the scope of the present invention.

Examples 1 to 7 and Comparative Examples 1 to 7 (υ Hydrogenated block copolymer 1Ml Nippyl lithium was used as the polymerization medium, and tetrahydro-72 was added to the vinyl content in n-hexane or Schiff-tetrahexane solvent. As a regulator, a block copolymer shown in Table 1 was synthesized by anionic block copolymerization of butadiene and styrene.

Table 1 Styrene-butadiene block copolymer The vinyl content of the butadiene portion was measured by the Hampton method.

Next, combine the blocks shown in Table 1 with n-hex/
and hydrogen pressure in a mixed solvent of cyclohexane and cobalt naphthenate and triethylaluminum as catalysts?
Q/cm', temperature [hydrogenation was performed at 50°C for 5 hours,
Approximately 909 of the double bonds in the butadiene block portion were hydrogenated.

A selectively hydrogenated block copolymer was synthesized in which the benzene ring of the styrene block portion remained almost unhydrogenated. The metal remaining on the catalyst was removed by washing with an aqueous salt solution and methanol.

(2) Preparation of modified block copolymer 2.
5 parts by weight of Louis anhydride/acid.

After uniformly mixing 0.1 part by weight of Perhexa 25B (manufactured by Nippon Oil & Fats Co., Ltd.), a screw extruder (
Single shaft, screw diameter 20m+, L/D=24. (full-flight type screw).

The maleation reaction was carried out at a cylinder temperature of 250°C. Unreacted maleic anhydride was removed under reduced pressure from the obtained modified block copolymer, and 226-sheeter diary-petyl-4-methylphenol was added as a stabilizer to 1 polymer 1.
0.5 parts by weight per 00 parts by weight. When this modified block copolymer was analyzed, the results shown in Table 2 of ζ filter 1 were obtained.

Table 2 F block copolymer Measured using a titration trap.

(3B) Preparation of composition Modified block copolymer M(1) *M (厘)? M
Examples 1 to 7 were prepared by mixing OII) and various filler-containing polymer compositions shown in Table 3 in a kneader.
A composition was obtained. For comparison, we used a sample (υI(1)) which is an untrained block copolymer.

Corresponding compositions of Comparative Examples 1 to 7 were obtained. Table 3K shows the physical property #1 constant results of the compression molded products of each composition of Examples, and Table 4 shows the results of each composition of Comparative Examples.

As is clear from the results in Tables 3 and 4, the filler-containing compositions of Examples 9111 to 7 using the modified block copolymers of the present invention were different from the filler-containing compositions of Examples 9111 to 7 using the unmodified block copolymers of Comparative Examples 1 to 7. Compared to the Friend composition, it has superior tensile strength, 300X tensile stress, hardness, etc., and the reinforcing effect of the filler is large.

It is a useful composition with a low permanent elongation at break.

Example 8 and Comparative Example 8 The compositions of Example 1 and Comparative Example 1 were tested for weather resistance and heat aging resistance. In the weather resistance test, the tensile strength of the compression molded product was measured after being exposed to weather conditions for 100 hours.

In addition, the heat aging resistance test was performed by leaving the compression molded product in an atmosphere at 100°C for 100 hours and measuring the tensile strength after death.

The results are shown in Table 5, and it can be seen that the compression molded product #i of the composition of the present invention was inferior in weather resistance and heat aging resistance.

Margin below

Claims (1)

[Scope of Claims] /,, (a) has at least one vinyl aromatic compound polymer block and at least one olefin compound polymer block B, and the degree of unsaturation of the block B is 2096. 5 to 100% by weight of a modified block copolymer in which a molecular unit containing a carginic acid group or a derivative group thereof is bonded to a block copolymer that is an olefin compound polymer block that does not exceed 5 to 100% by weight, and (b) reinforcing resin 95 ~O total amount of % by weight 100
C) filler 5 to 200 parts by weight and (d)
Filler-containing polymer composition 2 comprising 0 to 200 parts by weight of a softener The composition according to claim 1, wherein the carbic acid derivative group is a dicarboxylic acid anhydride group.