JPH01149853A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition, consisting of a specific modified polyphenylene ether, polyamide, A-B-A' type block copolymer elastomer and modified hydrogenated A-B-A' type block copolymer elastomer and having excellent low-temperature fracture resistance. CONSTITUTION:A composition consisting of (A) 5-90wt.% modified substance obtained by reacting (A1) 100 pts.wt. polyphenylene ether prepared by oxidatively polymerizing phenols (e.g., 2,6-dimethylphenol) with (A2) 0.05-20 pts.wt. substituted olefinic compound (e.g., acrylic acid) having one or more carboxylic acid, carboxylic acid anhydride and imide groups in the presence of a radical forming agent, (B) 1-20wt.% A-B-A' type copolymer elastomer (A and A' are vinyl aromatic block; B is polymerized conjugated diene block) and (C) 1-20wt.% modified polymer obtained by introducing a monomer component having carboxylic acid, catboxylic acid anhydride groups, etc., into the hydrogenated substance of the component (B).

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention has excellent properties such as heat resistance, dimensional stability, impact resistance, and melt flowability, and also shows no brittle fracture in a falling ball or falling weight test at low temperatures. Regarding thermoplastic resin compositions having excellent low-temperature fracture resistance that do not cause
The present invention relates to a thermoplastic resin composition comprising a -B-A' type block copolymer elastomer and a modified hydrogenated A-B-A' type block copolymer elastomer.

<Prior Art> In recent years, there has been much research into creating new materials by blending two or more types of polymers. Among these, polymer blend materials that combine polyamide and polyphenylene ether as main components have good affinity for both polymers, and have excellent moldability, wear resistance, and
Chemical resistance and excellent heat resistance of polyphenylene ether,
Numerous studies have been reported for the possibility of obtaining materials that have both dimensional stability and water resistance.

Among these, a blend system with particularly good balance of properties is one that uses polyamide and a specific modified polyphenylene ether and further incorporates a rubber component as a third component.A typical example is a blend system that uses polyamide and a specific modified polyphenylene ether. , a combination of styrene-butadiene-styrene bronoch copolymer (for example, Japanese Patent Application No. 1983)
-146433), polyamide, acid-modified polyphenylene ether, hydrogenated styrene-butadiene-styrene block copolymer combination (e.g., JP-A-62-138553), polyamide, acid-modified polyphenylene ether, acid-modified hydrogen A combination of styrene-butadiene-styrene block copolymer (
For example, Japanese Patent Laid-Open No. 62-68850) can be cited.

<Problems to be solved by the invention> The above-mentioned prior art is based on a combination of polyamide and acid-modified polyphenylene ether, and aims to develop characteristics by selectively blending certain rubber components. It has given fairly good results in terms of basic properties such as heat resistance, dimensional stability, moldability, and impact resistance typified by Izot impact strength.

However, the above-mentioned conventional materials are not necessarily satisfactory in a falling ball test or a falling weight test, which are considered to be close to practical evaluation when assuming use in exterior parts such as automobile fenders, door panels, and bumpers. In other words, all of the above conventional materials exhibit extremely brittle properties, such as brittle fracture when subjected to a falling ball or falling weight test in the low temperature range of 0°C to -30°C, with cracks occurring in a wider area than the impact area of the ball or weight. It shows. This property severely limits its use in large parts such as automobile exterior parts, and there is currently a strong desire to improve this low-temperature breakdown resistance.

<Means for Solving the Problems> Therefore, the present inventors investigated to improve the above-mentioned low-temperature fracture resistance and obtain a truly useful nylon/borifue elm/ether/rubber blend material. A-B-A' type block copolymer elastomer and modified A-B as components
- By using both of the A' type block copolymer elastomers together, it is impossible to imagine that when each is used alone =
4- It was discovered that lateral low-temperature fracture resistance was improved and the present invention was achieved.

That is, the present invention provides (4) a polyphenylene ether obtained by oxidative polymerization of one or more phenols represented by the following formula (I), and a carboxylic acid group and a carboxylic acid anhydride for 100 ffili parts of the polyphenylene ether. Modified polyphenylene ether 5-901t obtained by reacting 0.05-20 parts by weight of a substituted olefin compound having at least some functional groups selected from group and imide group in the molecule in the coexistence of a radical generator (I%, (2) polyamide 5-90% by weight, (C) A-B-A' type block copolymer elastomer (here, A18' is a vinyl aromatic hydrocarbon block, and B is a polymerized It is a conjugated diene block.) 1-2
0% by weight and (1) hydrogenated A-B-A in which part or all of the intermediate polymer block part B in the block copolymer elastomer is hydrogenated.
Modified hydrogenated A-B-A' type block copolymer elastomer 1 to 1, in which a structural unit containing a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, or an imide group is bonded to the ' type block copolymer elastomer. The present invention provides a resin composition comprising 20% by weight.

(Here, R1, R2, 1(3, R4 are selected from a water atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group, an aryl group, and a halogen atom, and R1-R4 may be the same or different) Good.) Used in the present invention (4
) The polyphenylene ether which is the raw material for the modified polyphenylene 7: r--f component can be obtained by oxidative polymerization of the phenols shown in the above-mentioned formula.

Specific examples of phenols include 2,6-dimethylphenol, 2,6-dinitylphenol, 2,6-sibutylphenol, 2,6-dipropylphenol, and 2,6-dipropylphenol.
-diphenylphenol, 2-methyl-6-nitylphenol, 2-methyl-6-tolylphenol, 2-methyl-6-medoxyphenol, 2-methyl-6-butylphenol, 2,6-simethoxyphenol, 2 ,3.
Examples include 6-dolimethylphenol and 2,3.5.6-titramethylphenol. Either a homopolymer made by polymerizing these phenols alone or a copolymer made by polymerizing a mixture of two or more of these phenols can be used in the present invention. In particular, homopolymers obtained by polymerizing 2,6-dimethylphenol and copolymers obtained by copolymerizing a mixture of 2,6-dimethylphenol and 2.3.6-dolimethylphenol are preferably used.

Modifying components of the modified polyphenylene ether used in the present invention include carboxylic acid groups, carboxylic acid anhydride groups, imide groups,
A substituted olefin compound having at least one functional group selected from epoxy groups; specific examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, and glutaconic anhydride. Examples include acids, citraconic anhydride, aconitic anhydride, maleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, and the like. The amount of these substituted olefin compounds to be used is within the range of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 10*m parts of polyunisene ether. If the amount of the substituted olefin compound used is less than 0.005 parts by weight, the impact resistance and heat resistance of the composition obtained by kneading the modified polyphenylene ether, polyamide, and modified polyolefin will be insufficient, and the amount used will be less than 20 parts by weight. If it exceeds this, the fluidity of the composition will decrease and the moldability will be impaired, which is not preferable.

The reaction between the polyphenylene ether and the substituted olefin compound is carried out in the presence of a radical generator, and examples of suitable radical generators include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and t-butyl cumyl peroxide. oxide, cumene hydroperoxide, 2
5-Dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexane-3, azobisisobutyronitrile, etc. The radical generator is preferably used in an amount of 5 to 30 parts by weight based on 1003 mt parts of the substituted olefin compound, but the type and amount of the radical generator used are not limited thereto.

Regarding the method of reacting polyphenylene ether with a substituted olefin compound, there is a method of reacting it in a solution using an appropriate solvent, or a method of reacting polyphenylene ether with a substituted olefin compound at a high temperature of 200 to 350°C in the absence of a solvent.
There is a method in which a mixture of radical generators is reacted while being melt-mixed for 10 seconds to 30 minutes, and any method may be used.

The proportion of the modified polyphenylene ether thus obtained in the final resin composition is 5 to 90% by weight, preferably 10 to 80% by weight. If the amount of modified polyphenylene ether is less than 5% by weight, the resin composition will lack heat resistance and dimensional stability, and if it exceeds 90% by weight, the moldability of the resin composition will be impaired, which is not preferable.

The polyamide component (B) used in the present invention is a polyamide whose main components are an amino acid, a lactam, or a diamine and a dicarboxylic acid. Specific examples of constituent components include ε-caprolactam, enantlactam, ω
- Lactams such as laurocyctam, amino acids such as ε-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2.2゜4-/ 2.4.4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-quinlylenediamine, (1), 3-bisaminomethylcyclohexane, 1.
Diamines such as 4-bis-aminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronecyamine, adipic acid, superric acid, azelaic acid, sebacic acid, dodecanoic acid, l,4-cyclohexane dicarboxylic acid acid, 1
．． There are dicarboxylic acids such as 3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and dimer acid. These components are subjected to polymerization either alone or in the form of a mixture of two or more, and both the polyamide homopolymer and copolymer thus obtained can be used in the present invention. Polyamides particularly useful in the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene diamine (nylon 610), polyundecaneamide (nylon 11), and polydodecanamide. (nylon 12), and copolymers and mixtures of these polyamides. The degree of polymerization of the polyamide used here is not limited, and any polyamide having a relative viscosity of 1% concentrated sulfuric acid solution at 25° C. within the range of 1.5 to 5.0 can be used.

The proportion of polyamide in the resin composition of the present invention is 5 to 5.
It is 90% by weight, preferably 10 to 80% by weight. If the polyamide content is less than 5% by weight, the melt flowability and chemical resistance of the resin composition will be insufficient, and if the polyamide content exceeds 90% by weight, the water resistance and dimensional stability will be insufficient.

In the present invention, the block copolymer elastomer used as the component (0) is an A-B-A' type block copolymer elastomer consisting of a vinyl aromatic hydrocarbon and a conjugated diene, and the terminal block A and A ′ may be the same or different, and is a thermoplastic homopolymer or copolymer derived from a vinyl aromatic hydrocarbon in which the aromatic moiety may be monocyclic or polycyclic.Such a vinyl aromatic hydrocarbon Examples include styrene, α-methylstyrene, vinyl/l/toluene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and mixtures thereof.The intermediate electropolymer block B is composed of a conjugated diene hydrocarbon. Examples include polymers derived from 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, and mixtures thereof.

A, -B-A' of working components in the resin composition of the present invention
The proportion of the type block copolymer elastomer is 1 to 20% by weight, preferably 2 to 15% by weight. If the content of the A-B-A' type block copolymer elastomer is less than 1% by weight, the low-temperature fracture resistance and impact resistance of the resin composition will decrease, which is undesirable.On the other hand, if it exceeds 20% by weight, the resin composition will deteriorate. It is not preferable because it impairs the heat resistance and fluidity of the material.

Modified hydrogenated A used as (f) component of the present invention
-B-A' type block copolymer elastomer is the above-mentioned A-B
- Part or all of the intermediate polymer block portion B of the A' type block copolymer elastomer is
Hydrogenated A-B-A' type block copolymer elastomer obtained by hydrogenation according to the method shown in Specification No. 23, including carboxylic acid groups, carboxylic anhydride groups, carboxylic ester groups, and imide groups. This is an acid-modified polymer obtained by introducing a monomer component having at least one functional group selected from the following (hereinafter referred to as a functional group-containing component).

Examples of functional group-containing components include acrylic acid, methacrylic acid, maleic acid, 7-malic acid, itaconic acid, crotonic acid, methyl maleic acid, methyl 7-malic acid, mesaconic acid,
citraconic acid, glutaconic acid, methyl hydrogen maleate,
Methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl itaacrylate, hydroxyethyl methacrylate, amine ethyl methacrylate ,
Dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, 7traconic anhydride, endobicyclo-(2-2.I)-5-heptene-2.3-dicarboxylic acid, poly/tobicyclo-(2. 2++ 1)-5-hep-2,3-dicarboxylic anhydride, maleimide, N
-Ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, etc.

The method of introducing these functional group-containing components is not particularly limited, and the method includes mixing with the main components vinyl aromatic hydrocarbons and conjugated dienes and copolymerizing them during the production of the A-B-A' type block copolymer elastomer. Methods such as graft introduction using a hydrogenated A-B-A' block copolymer elastomer or a radical initiator can be used. The amount of the functional group-containing component introduced is o, ot-to weight %, preferably within the range of 0.02 to 8 weight % relative to the entire modified hydrogenated A-B-A' block copolymer elastomer. is appropriate.

The proportion of the modified hydrogenated A-B-A' type block copolymer elastomer of the component (■) in the resin composition of the present invention is 1 to 2.
0ffi amount%, preferably 2 to 15% by weight. The modified hydrogenated A-B-A' type block copolymer elastomer is I
If the amount of N is less than %, the low temperature fracture resistance and impact resistance of the resin composition will deteriorate, which is undesirable. On the other hand, if it exceeds 20% by weight, the heat resistance and fluidity of the resin composition will be impaired, which is undesirable.

In the present invention, it is extremely important to use both the C'l component and the 0 component in combination. This is because the A-B-A' type block copolymer elastomer and the modified hydrogenated A-B - When each of the A' type block copolymer elastomers is used alone, all of them result in brittle fracture in the falling ball and falling weight tests at low temperatures of -30°C, and only materials with low low-temperature fracture resistance can be obtained. Only when polyphenylene ether and polyphenylene ether This is thought to be because the component 0, which has a strong affinity for polyamide, and the component 0, which has a strong affinity for the polyamide, efficiently reinforce the polyphenylene ether phase and the polyamide phase, respectively.

Modified polyphenylene ether, polyamide, A-B-
A' type block copolymer elastomer and modified hydrogenated A-
There are no particular limitations on the mixing method for the B-A' type block copolymer elastomer, and the mixture of powders, pieces, and pellets of each resin is mixed using a single or twin screw extruder, a Banbury mixer, a kneader, or a mixing roll. Examples include a method in which the mixture is fed to a commonly known melt mixer and kneaded at a temperature of 220 to 350°C. Furthermore, there is no particular limitation on the mixing order of the four types of resins, and the four types of resins may be mixed all at once, or two or three types of resins may be mixed in advance and then mixed with other resins that remain. You may take the method of implementing

In the resin composition of the present invention, other additives such as pigments, dyes, reinforcing agents, fillers, heat resistant agents, oxidative deterioration inhibitors, weathering agents, and lubricants may be added during mixing and molding of the resin as long as they do not impair its physical properties. , a mold release agent, a crystal nucleating agent, a plasticizer, a flame retardant, a fluidity improver, an antistatic agent, etc. can be added and introduced.

Molded products made from the resin composition of the present invention by methods such as injection molding, blow molding, and extrusion molding have excellent heat resistance, water resistance, dimensional stability, and impact resistance, as well as particularly low-temperature fracture resistance. These are particularly useful as exterior parts such as automobile facades, door panels, quarter panels, bumpers, spoilers, YH-K caps, fuel lids, side sealners, etc., and general mechanical parts such as sheep.

<Example> The present invention will be explained in more detail with reference to Examples below.

The various properties described in Examples and Comparative Examples e were evaluated by the following methods.

(I) Tensile properties: AST
MD638 (2) Bending characteristics:
ASTM D790(3) Izot impact strength: ASTM D256(4) Heat distortion temperature: ASTM D648(5) Low temperature fracture resistance:
Using Takashima type falling weight tester, 80 x 80 x 31
A square plate of 1111 was cooled to -30° C., and a drop weight test was performed by dropping a weight of 110 mm weight and a probe diameter of 12.711 mm from a height of 50 scratches.

A total of 10 samples were tested, and the number of samples that suffered ductile fracture was shown to evaluate the resistance to low temperature fracture.

Reference example f (manufacture of polyphenylene ether) 1 liter of a toluene solution containing 7.62 kg of anhydrous cuprous chloride and 10 y of di-t-butylamine was charged into a polymerization tank, and then 55% by weight
A toluene solution 41 of 2,6-dimethylphenol was added, the temperature was maintained at 30°C, and the mixed solution was stirred while blowing oxygen to perform oxidative polymerization. After polymerization, an acetic acid aqueous solution was added to deactivate the catalyst to stop the reaction, and after concentrating the reaction solution, a large amount of methanol was added to precipitate the polymer. Polyphenylene ether was obtained by filtering, washing and drying the precipitated polymer.

Reference Example 2 (Production of modified polyphenylene ether) 100 parts of the polyphenylene ether obtained in Reference Example 1, 1 part by weight of maleic anhydride, and 2°5-dimethyl-2,5
- A mixture of o, i parts by weight of di-t-butylperoxyhexane is fed into the hopper of an extruder, and the cylinder temperature is 32
Maleic anhydride-modified polyphenylene ether (A-1) was obtained by melt-kneading at 0°C.

The reaction between polyphenylene ether and maleic anhydride was confirmed by observing the IR of the modified polyphenylene ether after extracting the modified polyphenylene ether with methanol as a solvent at a bath ratio of 30:1 for 48 hours.
This was confirmed by analyzing the νc=00 absorption peak in the 00α−1 region.

Reference Example 3 The same operation as shown in Reference Example 2 was carried out except that the type and amount of the olefin compound were changed, and modified polyphenylene ether A-2 and olefin compound A-3 were added.
Disease (part by weight vs. polyphenylene ether A-2N-phenyl 3.0 Maleimide Reference Example 4.5 (Production of modified hydrogenated A-B-A' type block copolymer elastomer) Hydrogenated polystyrene manufactured by Shell Chemical Co. Polybutadiene-borimethylene copolymer "Krayton" G 165
2 100 parts by weight, 3 parts by weight of maleic anhydride and 2 parts by weight
, 0.3 parts by weight of 5-dimethyl-2,5-di-t-butylperoxyhexane was supplied to the hopper of an extruder and melt-kneaded at a cylinder temperature of 250°C to produce maleic anhydride-modified hydrogenated polystyrene. -Polybutadiene-polystyrene copolymer (D-1) was obtained.

Also, Shell Chemical Company's ``Krayton'' G
1657 and itaconic anhydride, 2,5-dimethyl-
A hydrogenated polystyrene-bolybutadiene-boristyrene copolymer (D-2) modified with itaconic anhydride was prepared using 2,5-di-t-butylperoxyhexane as a raw material in the same manner.
I got it.

Example I 6650 parts by weight of nylon with a relative viscosity of 2.9, 40M modified polyphenylene ether (A-1) obtained in Reference Example 1
Part i, polystyrene-polybutadiene-polystyrene copolymer ('Califlex') manufactured by Shell Chemical Co.
1' R-1102) (C-1) 5 parts by weight and 5 parts by weight of the modified copolymer (D-1) obtained in Reference Example 4 were triblended using a Henschel mixer, and then 30Hφ
Supplied to the hopper of a twin-screw extruder, the cylinder temperature was 280℃.
The mixture was melt-kneaded and pelletized under the conditions of .degree. C. and screw rotation speed of 20 rpm. After vacuum drying the pellets at 100°C for 24 hours, the cylinder temperature was 280°C and the mold temperature was 80°C.
Injection molding was performed at ℃ to obtain test pieces for evaluating various physical properties. The properties of the test pieces are shown in Table 1, and the resin composition obtained here has excellent strength, heat resistance, and impact resistance, and especially has extremely good low-temperature fracture resistance, making it of high practical value. It turned out to be the material.

Comparative Example 1 Melt mixing, Injection molding and property evaluation were performed, and the results shown in Table 1 were obtained.The resin compositions obtained here all showed brittle fracture in the low-temperature drop weight test, and the low-temperature fracture resistance was insufficient.

Comparative Example 2 The polystyrene-polybutadiene-polystyrene copolymer (C-1) was not used, but the amount of the modified copolymer (D-1) was 10! Melt kneading, injection molding, and property evaluation were carried out in exactly the same manner as in Example 1 except that the imaginary part was used. The results shown in Table 1 were obtained, and this product also lacked low-temperature fracture resistance.

Examples 2-6 Polyamide, modified polyphenylene ether, A-B-A
Molded pieces obtained by melt mixing and injection molding with various types and blending amounts of the 'type block copolymer elastomer and the modified water accumulation A-B-A' type block copolymer elastomer. The characteristics are summarized in Table 1. All of the resin compositions obtained here were found to be useful materials with excellent strength, heat resistance, impact resistance, and low-temperature fracture resistance.

<Effects of the Invention> The characteristics of the present invention are polyamide, polyphenylene ether,
In a blend system consisting of rubber, A is especially used as a rubber component.
-B -A' type block copolymer elastomer and modified hydrogenated A-
The point is that both of the B-A' type block copolymer elastomer are used together. Only when these two are used together, a remarkable improvement in low-temperature fracture resistance that is unimaginable when used individually is achieved, and a polyamide/polyphenylene ether/rubber blend molding material with high practical value can be obtained. It was done.

Patent application Daitoshi Co., Ltd. 26 (Complete)

Claims (1)

[Scope of Claims] (A) A polyphenylene ether obtained by oxidative polymerization of one or more phenols represented by the following formula (I), and a carboxylic acid group and a carboxylic acid based on 100 parts by weight of the polyphenylene ether. Modified polyphenylene ether obtained by reacting 0.05 to 20 parts by weight of a substituted olefin compound having at least one functional group selected from anhydride group and imide group in the molecule in the coexistence of a radical generator. 5 to 90% by weight, (B) 5 to 90% by weight of polyamide, (C) A-B-A' type block copolymer elastomer (here, A
, A' is a vinyl aromatic hydrocarbon block, and B is a polymerized conjugated diene block. ) 1 to 20% by weight and (D) hydrogenation A-B in which part or all of the intermediate polymer block part B in the block copolymer elastomer is hydrogenated.
- Modified hydrogenated A-B-A' in which a structural unit containing a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, or an imide group is bonded to an A' type block copolymer elastomer
A resin composition comprising 1 to 20% by weight of a type block copolymer elastomer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (Here, R^1, R^2, R^3, R^4 are hydrogen atoms,
R^1 to R^4 selected from alkyl groups having 1 to 10 carbon atoms, haloalkyl groups, aryl groups, and halogen atoms;
may be the same or different. )