JPH0562624B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Fields] The present invention has excellent weather resistance, heat resistance, mechanical strength, impact resistance, rubber elasticity, paintability, oil resistance, and adhesive properties, and is suitable for electric wires, cables, insulated cords, insulated sheets,
The present invention relates to a thermoplastic polymer composition suitable for laminate adhesive sheets, films, tubes, automobile parts, electrical parts, etc. [Conventional technology] Polyamide has traditionally had a number of excellent properties such as heat resistance, oil resistance, abrasion resistance and mechanical strength.
Specifically, nylon 6, nylon
66, nylon 610, nylon 612, nylon 11, nylon 12, etc. are commercially available, and are widely used as engineering plastics as various molding materials in the fields of automobiles, home appliances, electrical/electronic, mechanical parts, etc. However, although these nylons have excellent heat resistance, the heat distortion temperature (18.5Kg/
^cm2 ) is less than 100℃ and its continuous use is 5000
The temperature is also below 100°C, and in applications requiring heat resistance, it is known to add various additives such as glass fiber and mineral fillers to improve the heat distortion temperature. In addition, these nylons have low impact strength, which can be said to be a drawback of plastic materials in general, especially at low temperatures, so a number of improvement studies have been conducted to improve their functionality, and polymer blends have been proposed as a way to improve their impact resistance. Various modification methods have been proposed, for example, in JP-A-52-150457, JP-A-58-7443, and JP-A-59-56451. Among these proposals, the composition described in JP-A-52-150457 proposes a composition consisting of a hydrogenated block copolymer and polyamide having a specific structure,
Further, the composition described in JP-A-58-7443 is a modified hydrogenated block copolymer in which a polar thermoplastic polymer having a polar functional group such as polyamide and a molecular unit containing a carboxylic acid group or a derivative group thereof are bonded. The patent proposes a composition consisting of a polymer, and specifically discloses a polyamide having a melting point of 150 to 270°C as the polyamide provided here. And furthermore, JP-A-59-
The composition described in No. 56451 proposes a composition comprising polyamide and a maleic anhydride-modified hydrogenated polymer in which maleic anhydride is added with ene to the remaining double bonds of the hydrogenated polymer. [Problems to be Solved by the Invention] However, although the composition proposed here consisting of a polyamide and a hydrogenated polymer or a modified hydrogenated polymer provides a composition useful as a direction for modifying polyamide resins in general, However, this prior art does not necessarily provide an improved and good composition when processing characteristics and physical properties due to the properties of each polyamide are taken into consideration. The present invention takes this point into consideration, and as a polyamide,
When we investigated the modification of polyamide with excellent heat resistance and a melting point of 280°C or higher, we found that the composition obtained by the above-mentioned prior art still had an insufficient balance of physical properties among impact resistance, mechanical strength, and rigidity. It has been found that this is due to the structure of the hydrogenated polymer or modified hydrogenated polymer used as the catalyst. [Means and effects for solving the problem] The present invention was made to solve the problems that were difficult to solve with the conventional modified polyamide materials described above, and in particular, it is necessary to maintain the performance of high melting point polyamide. At the same time, the molding material is mainly composed of high-melting-point polyamide, which has improved impact resistance at low temperatures and an excellent balance between impact resistance and rigidity, and has excellent heat resistance, as well as hydrogenated material with excellent mechanical strength and oil resistance. This was created based on the need for a molding material whose main component is a polymer, and a hydrogenated block copolymer with a specific structure and/or a modified hydrogenated block copolymer with a specific structure can meet the above needs. The present inventors have discovered that it is a composition that can be used in a practical manner, and that it is a practically useful composition. That is, the present invention comprises (a) a polymer block B mainly composed of at least one hydrogenated conjugated diene compound and a polymer block A mainly composed of at least one vinyl aromatic compound,
A hydrogenated block copolymer having at least one polymer block B disposed at the end of a polymer chain, and/or the hydrogenated block copolymer in the presence of an unsaturated carboxylic acid or a derivative thereof and an organic peroxide. radical modification, (i) the ratio of the molecular weight distribution (w/n) of the hydrogenated block copolymer after modification/the molecular weight distribution (w/n) of the hydrogenated block copolymer before modification is 1.2 or more; (ii) ) A modified hydrogenated block copolymer characterized in that 0.1 to 10 parts by weight of an unsaturated carboxylic acid or a derivative thereof is added per 100 parts by weight of the hydrogenated block copolymer 5 to 95% by weight (b) 1 ,4-diaminobutane and or 1,2
- A thermoplastic polymer composition comprising 95 to 5% by weight of polyamide obtained by condensation of diaminoethane and adipic acid. The present invention will be described in detail below. The hydrogenated block copolymer used as component (a) in the present invention is a polymer block B mainly composed of at least one hydrogenated conjugated diene compound.
and a polymer block A mainly composed of at least one vinyl aromatic compound, and has a structure in which at least one polymer block B is arranged at the end of the polymer chain. Expressed as a general formula, it is expressed as follows. (B-A) _{o o} ≧1 ( _B -A)— _{o B o} ≧1 ( _B ^- _{A )} — _{n -A ) - n _} ^_ _{_} And B-A, B-A-B-A, B-A-B, B-A-B-A-B, and a hydrogenated block copolymer consisting of a mixture thereof. Furthermore, this hydrogenated block copolymer contains 5 to 60% by weight, preferably 10 to 40% by weight of a vinyl aromatic compound.Moreover, referring to the block structure, the polymer block A, which is mainly composed of a vinyl aromatic compound, contains a vinyl aromatic compound. , having a structure of a vinyl aromatic compound polymer block or a copolymer block of a vinyl aromatic compound containing more than 50% by weight and preferably 70% by weight or more and a hydrogenated conjugated diene compound. Further, preferably, the polymer block B mainly composed of a hydrogenated conjugated diene compound contains more than 50% by weight of the hydrogenated conjugated diene compound polymer block or the hydrogenated conjugated diene compound. is 70% by weight
It has the structure of a copolymer block of the hydrogenated conjugated diene compound and vinyl aromatic compound contained above. In addition, polymer block A mainly composed of these vinyl aromatic compounds and polymer block B mainly composed of hydrogenated conjugated diene compounds are hydrogenated conjugated diene compounds in the molecular chains of the polymer blocks, respectively. Alternatively, the distribution of the vinyl aromatic compound may be random, tapered (the monomer component increases or decreases along the molecular chain), partially block-like, or any combination thereof, and the vinyl aromatic compound When there are two or more polymer blocks mainly consisting of a polymer block and two or more polymer blocks mainly consisting of a hydrogenated conjugated diene compound, each block may have the same structure or may have a different structure. As the vinyl aromatic compound constituting the hydrogenated block copolymer, one or more kinds are selected from, for example, styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Among them, styrene is preferable. Further, examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-
One or more types are selected from 1,3-butadiene and the like, and among them, butadiene, isoprene, and a combination thereof are preferred. The microstructure of a polymer block mainly composed of a conjugated diene compound before hydrogenation can be arbitrarily selected; for example, in a polybutadiene block, the 1,2-microstructure is 20 to 50%.
%, preferably 25-45%. The number average molecular weight of the hydrogenated block copolymer is
The range is 500 to 1,000,000, preferably 10,000 to 800,000, more preferably 30,000 to 300,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is 10.
It is as follows. The molecular structure of the hydrogenated block copolymer provided in the present invention may be linear, branched, radial, or any combination thereof, and any molecular structure having the above-mentioned structure and essential structure may be used. For example, by the method described in Japanese Patent Publication No. 40-23798, a vinyl aromatic compound-conjugated diene compound is prepared in an inert solvent using a lithium catalyst or the like. A block copolymer was synthesized, and then, for example,
It can be synthesized by hydrogenation in the presence of a hydrogenation catalyst in an inert solvent by the method described in Japanese Patent Application Laid-Open No. 59-133203. In this case, at least 80% of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and the polymer block mainly composed of the conjugated diene compound is morphologically olefinic. The compound can be converted into polymer block B. In addition, the hydrogenation rate of aromatic double bonds based on the vinyl aromatic compound copolymerized into the block A mainly composed of a vinyl aromatic compound and, if necessary, the polymer block B mainly composed of a conjugated diene compound. Although there is no particular restriction on the hydrogenation rate, it is preferable that the hydrogenation rate be 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like. Furthermore, the modified hydrogenated block copolymer to which an unsaturated carboxylic acid or a derivative thereof is added, which is used as component (a), is a hydrogenated block copolymer having the above-mentioned structure added to an α,β-unsaturated carboxylic acid. or its anhydride, ester, etc. (hereinafter referred to as α,β-unsaturated carboxylic acids) and radical modification in the presence of an organic peroxide, and the resulting modified hydrogenated block copolymer is (i) Molecular weight distribution (w/n) of hydrogenated block copolymer after modification/molecular weight distribution (w/n) of hydrogenated block copolymer before modification
Mn) ratio of 1.2 or more (ii) Hydrogenated block copolymer 100
It is characterized in that 0.1 to 10 parts by weight of an unsaturated carboxylic acid or a derivative thereof is added per part by weight. Examples of α,β-unsaturated carboxylic acids that can be used for radical modification include maleic acid, maleic anhydride, fumaric acid, itaconic acid, acrylic acid, acrylic ester, crotonic acid, cis-4- Examples include cyclohexene-1,2-dicarboxylic acid and its anhydride, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid and its anhydride, maleimide, etc. Among these, maleic anhydride is preferred. Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and dicumyl peroxide. , 5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, n-butyl 4,4-bis(tert-butylperoxy)valerate, 1,1-bis(tert-
butylperoxy)3,3,5-trimethylcyclohexane, etc., and can be suitably selected from among these. The method for producing the modified hydrogenated block copolymer is not particularly limited in the present invention, but the modified hydrogenated block copolymer obtained may have a structure deviating from the above-mentioned characteristics, or may have a structure such as a gel. Production methods that include undesirable components or that significantly increase the melt viscosity and deteriorate processability are not preferred. An example of a preferred production method is to melt-knead the hydrogenated block copolymer, α,β-unsaturated carboxylic acids, and organic peroxide described above at a temperature of 150 to 350°C in an extruder, and then radically modify the copolymer. There is a way. The obtained modified hydrogenated block copolymer may be ionomerized with a monovalent or higher valent metal ion. The modified hydrogenated block copolymer thus obtained has the following properties: (i) molecular weight distribution of hydrogenated block copolymer after modification (w/n)/molecular weight distribution of hydrogenated block copolymer before modification (w/n); /n) is preferably 1.2 or more (ii) The amount of α,β-unsaturated carboxylic acids added to the hydrogenated block copolymer is 0.1 to 10 parts by weight per 100 parts by weight of the hydrogenated block copolymer. Preferably,
Further, 0.2 to 5 parts by weight is preferred. When a modified hydrogenated block copolymer that does not have these two characteristics is used as a composition, its improvement effect is slight compared to the hydrogenated block copolymer before modification. Next, the polyamide used as component (b) of the present invention is a high melting point polyamide with a melting point of 280°C or higher, and has a higher heat distortion temperature than nylon 66, and has excellent heat resistance. By blending the above-mentioned component (a), a resin composition with improved impact resistance-rigidity balance and excellent heat resistance can be obtained, and furthermore, mechanical strength and oil resistance can be improved. Provides an excellent elastomer composition. The polyamide used as the component (b) is, for example, disclosed in JP-A No. 56-149431, JP-A No.
1,4- by the method described in No. 58-83029.
It is obtained by condensing diaminobutane and/or 1,2-diaminoethane with adipic acid, and those having a number average molecular weight of 10,000 or more and a melting point of 280°C or more are preferably used. The composition of each component of the thermoplastic polymer composition composed of the above-mentioned components (a) and (b) may be any desired composition depending on the stiffness and flexibility of the composition to be obtained by the functions of each of the above-mentioned components. However, the content of either component in the composition must be at least 5% by weight; if the content is less than this, the improvement effect will not be observed, and the composition will have the desired properties of heat resistance and impact resistance. It is not possible to obtain a resin composition with an excellent balance of strength and rigidity and an elastomer composition with excellent mechanical strength and oil resistance. More specifically, (a) component 95-75% by weight, (b)
A composition obtained by blending 5 to 25% by weight of the components is useful as a good rubber-like composition with improved oil resistance, and further contains (a) 5% to 75% by weight of the components, and (b) A composition obtained by blending the components in an amount of more than 25% by weight and less than 95% by weight is useful as a resin-like or hard rubber-like composition having a good balance between natural impact resistance and rigidity. The composition obtained in the present invention may optionally contain other polyolefin resins, polyolefin rubbers, those modified with unsaturated carboxylic acids, styrene/maleic anhydride copolymers, polyphenylene ethers, and other resins. , flame retardant, glass fiber,
Various fillers such as carbon fiber and mineral fillers, antioxidants, heat stabilizers, ultraviolet absorbers,
It is also possible to suitably add a hindered amine light stabilizer, a coloring agent, etc. The method for producing the composition of the present invention involves mixing components (a) and (b) using a Henschel mixer, blender, etc., and then melt-kneading them using a continuous kneader such as a single-screw extruder or twin-screw extruder. In addition, various molding methods can be applied. [Effects of the Invention] The composition obtained by the present invention has excellent weather resistance, heat resistance, mechanical strength, impact resistance, rubber elasticity, paintability, oil resistance, and adhesiveness, so it can be used for covering various electric wires and cables. It can be suitably used by forming materials, insulating cords, insulating sheets, tubes, tapes, films, laminated product adhesive sheets, automobile parts, electrical/electronic parts, etc. [Examples] Examples are shown below, but these are intended to explain the present invention more specifically, and the present invention is not limited to these examples. Reference Example 1 A hydrogenated block copolymer as shown in Table 1 was synthesized. The catalyst used for hydrogenation was a Ti-based catalyst described in JP-A-59-133203, and the hydrogenation rate was 95 in both cases.
It was between % and 99%.

[Table] Reference Example 2 Hydrogenated block copolymer 100 synthesized in Reference Example 1
Parts by weight, 2 to 10 parts by weight of maleic anhydride, 2,5-
Using 0.1 to 1.0 parts by weight of dimethyl-2,5-di(tert-butylperoxy)hexane, in an extruder
The mixture was melt-kneaded at 230-350°C to obtain modified hydrogenated block copolymers as shown in Table 2.

【table】

[Table] Note: The amount of maleic anhydride added was measured by titration with sodium methylate.
Reference Example 3 A high melting point polyamide was synthesized by the following method. In an autoclave, 1,4-diaminobutane/adipic acid (1,4-diaminobutane 5 mol
% excess) and incubate at 200-220℃ in the presence of _N2 .
The prepolymer was synthesized by heating for a period of time. Then, after pulverizing the prepolymer, further
Solid phase polycondensation was carried out by heating at 260° C. for 4 hours under N ₂ blowing and normal pressure to obtain white nylon 46. Analysis of this product revealed a reduced viscosity of 3.7 and a melting point of 290°C. In the same manner, polycondensation was carried out using 1,2-diaminoethane as a diamine component to obtain nylon 26. Analysis of this product revealed a reduced viscosity of 3.1 and a melting point of 302°C. Examples 1 to 4, Comparative Examples 1 to 4 Nylon 46 (melting point 290°C), Nylon 26 (melting point 302
℃) and hydrogenated block copolymers were blended in the composition shown in Table 3, melt-kneaded in a 50 mmφ twin-screw extruder, and various physical properties were measured. The results are listed in Table 3. These results show that various physical properties are improved by providing a hydrogenated block copolymer having the specific structure defined in the present invention. Examples 5-9, Comparative Examples 5-8 Nylon 46 (melting point 290°C), Nylon 26 (melting point 302
The modified hydrogenated block copolymer was blended with the composition shown in Table 4, melt-kneaded in a 50 mmφ twin-screw extruder, and various physical properties were measured. The results are listed in Table 4. These results show that various physical properties are improved by providing a modified hydrogenated block copolymer having the specific structure defined in the present invention. It has been found that improvements in various physical properties vary not only with the amount of maleic anhydride added, but also with the structure and molecular weight distribution of the modified polymer provided.

【table】

【table】

【table】

[Table] Examples 10 to 12, Comparative Examples 9 to 12 Hydrogenated block copolymer (polymer number 2, 4),
Modified hydrogenated block copolymer (polymer number 8,
9, 10, 12), nylon 46, and nylon 26 were blended in the composition shown in Table 5 to prepare an elastomer composition, and its physical properties were measured. The results are listed in Table 5.
These results show that by providing a hydrogenated block copolymer or a modified hydrogenated block copolymer having the specific structure defined in the present invention, the oil resistance and mechanical strength of the elastomer composition can be improved.

【table】

Claims (1)

[Scope of Claims] 1 (a) a polymer block B mainly composed of at least one hydrogenated conjugated diene compound;
a hydrogenated block copolymer consisting of a polymer block A mainly composed of at least one vinyl aromatic compound, and at least one polymer block B disposed at the end of the polymer chain; The copolymer is radically modified in the presence of an unsaturated carboxylic acid or its derivative and an organic peroxide, and (i) molecular weight distribution (w/n) of the hydrogenated block copolymer after modification/hydrogenation before modification. Molecular weight distribution of block copolymer (w/
n) has a ratio of 1.2 or more, and (ii) an unsaturated carboxylic acid or a derivative thereof is added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the hydrogenated block copolymer. Polymer 5~
95% by weight (b) 1,4-diaminobutane and or 1,2
- A thermoplastic polymer composition comprising 95 to 5% by weight of polyamide obtained by condensation of diaminoethane and adipic acid.