JPH0238441A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in heat resistance and impact resistance by mixing a polyamide resin with an ABS resin and a specified multiphase structure thermoplastic resin. CONSTITUTION:95-20wt.% mixture comprising at most 30wt.% vinyl cyanide compound, 30-80wt.% aromatic vinyl compound and 0-70wt.% alkyl unsaturated carboxylate compound is polymerized in the presence of 5-80wt.% conjugated diene rubber to obtain an ABS resin (a) which is a graft copolymer. 100 pts.wt. mixture of 99-1wt.% polyamide resin (b) (e.g., nylon 6) with 1-99wt.% component (a) is mixed with 0.1-100 pts.wt. multiphase structure thermoplastic resin (c) comprising 5-95wt.% carboxylated vinyl copolymer and 95-5wt.% vinyl (co)polymer obtained by (co)polymerizing a vinyl monomer, wherein one polymer forms a matrix and the other polymer forms a dispersed phase of a particle diameter of 0.001-10mum.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a thermoplastic resin composition with excellent heat resistance and impact resistance, and is applicable to a wide range of fields such as automobile parts, electrical and electromechanical parts, etc. It is used.

<Conventional technology> Polyamide resin has good moldability, thermal stability, abrasion resistance,
It has excellent properties such as solvent resistance and is widely used in various molded products. However, there have been problems with impact resistance, which has limited its use.

On the other hand, although ABS resin has excellent impact resistance, it has the disadvantage of poor solvent resistance.

If a thermoplastic resin that solves the above problems can be obtained by compensating for the disadvantages of polyamide resin and ABS resin with each other's strengths, it is expected that new applications will open up.

<Problems to be Solved by the Invention> However, since polyamide resins and ABS resins have different chemical structures, their compatibility is extremely poor, making it difficult to obtain a composition that combines the advantages of each by simply mixing the two. I couldn't come.

<Means for Solving the Problems> The present invention has been made as a result of intensive research to solve the above problems.
By blending a specific multiphase thermoplastic resin with polyamide resin and ABS resin as a compatibilizer, the compatibility between the two is improved, and the polyamide resin has excellent moldability.
We have now completed a thermoplastic resin composition that has thermal stability, abrasion resistance, solvent resistance, and the excellent impact resistance of ABS resin.

That is, the present invention comprises (I) 99 to 1% by weight of polyamide resin, (II) AB
S resin 1 to 99% by weight and the above (I) + (II)
Based on 100 parts by weight, (m) 95 to 95% by weight of a vinyl polymer or copolymer obtained by polymerizing or copolymerizing 5 to 95% by weight of a carboxyl group-containing vinyl copolymer and a vinyl monomer.
5% by weight, and 0.1 to 100 parts by weight of a multiphase thermoplastic resin in which one polymer is a matrix and the other polymer forms a dispersed phase with a particle size o, oot ~ 10 gm is blended. and (I) 99 to 1% by weight of polyamide resin, (II) AB
S resin 1 to 99% by weight and the above (I) + (II)
Based on 100 parts by weight, (m) 95 to 95% by weight of a vinyl polymer or copolymer obtained by polymerizing or copolymerizing 5 to 95% by weight of a carboxyl group-containing vinyl copolymer and a vinyl monomer.
5% by weight, and 0.1 to 100 parts by weight of a multiphase thermoplastic resin in which one polymer is a matrix and the other polymer forms a dispersed phase with a particle size of 0.001 to 10 gm, and (I) + (II) + (I[I) 1oo
This is a thermoplastic resin composition comprising 100 parts by weight or less of (IV) elastomer based on the weight part.

Next, each component of the thermoplastic resin composition of the present invention will be explained.

Examples of the polyamide resin (I) include nylon 6, nylon 6/6, nylon 6/10, nylon 6/12, nylon 11. Aliphatic polyamide resins such as nylon 12, nylon 4 and 6, etc.; aromatic polyamide resins such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, xylene group-containing polyamide, and modified products thereof; Examples include mixtures thereof. Particularly preferred polyamide resins include nylon 6 and nylon 6.6.

The ABS resin (II) is a graft copolymer (a) obtained by polymerizing a vinyl cyanide compound, an aromatic vinyl compound, and optionally an unsaturated carboxyl alkyl ester compound in the presence of a conjugated diene rubber. It is. If necessary, a copolymer (b) obtained by polymerizing two or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds can also be included. .

Conjugated diene rubber in graft copolymer (a) and -
The composition ratio with the compound described in L is not particularly limited as long as it has properties as an ABS resin, but a composition ratio of 5 to 80% by weight of the conjugated diene rubber and 95 to 20% by weight of the above-mentioned compound is preferable. Further, the composition ratio of the above-mentioned compounds is preferably 30% by weight or less of the vinyl cyanide compound, 30 to 80% by weight of the aromatic vinyl compound, and 0 to 70% by weight of the unsaturated carboxylic acid alkyl ester compound. The particle size of the conjugated diene rubber is not particularly limited, but it is preferably 0.05 to Igm. The composition ratio of the above-mentioned compounds in the copolymer (b) is: 0 to 30% by weight of vinyl cyanide compound, 50 to 90% by weight of aromatic vinyl compound, and 0 to 40% by weight of unsaturated carboxylic acid alkyl ester compound.
Preferably, it is % by weight. Intrinsic viscosity of copolymer (b) [30°C, dimethylformamide (DMF)]
Nemo is not particularly limited, but preferably 0.25 to 1.0.

Examples of the conjugated diene rubber include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylatetrile; aromatic vinyl compounds include styrene, α-methylstyrene, vinyltoluene, dimethylstyrene, and chlorostyrene; and examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate and ethyl. Acrylate, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, etc. may be mentioned.

Examples of methods for producing ABS resins include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and emulsion-suspension polymerization.

Among the components of the multiphase thermoplastic resin (III), the carboxyl group-containing vinyl copolymer is a combination of a vinyl monomer and an unsaturated carboxyl group-containing monosulfur by radical polymerization.
It is an original or multi-element copolymer. Examples of the vinyl monomer of the copolymer include styrene, nuclear-substituted styrene, vinyl aromatics such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorstyrene, and α-ethylstyrene, (meth)acrylonitrile,
(meth)acrylic acid ester, maleic acid diester,
Examples include fumaric diester and butadiene, with styrene and (meth)acrylic ester being particularly preferred.

Examples of unsaturated carboxyl group-containing monomers include (meth)acrylic acid, itaconic acid, crotonic acid, maleic anhydride, maleic acid, maleic acid monoester, fumaric acid,
Examples include fumaric acid monoester, and (meth)acrylic acid is particularly preferred.

When copolymerizing the vinyl monomer and the unsaturated carboxyl-containing monomer, the carboxyl-containing monomer is
Preferably it is present in an amount of 40% by weight.

Vinyl (co), another component of multiphase thermoplastic resin
Polymers include styrene, nuclear substituted styrenes such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorstyrene, α-substituted styrene,
For example, vinyl aromatic monomers such as α-methylstyrene and α-ethylstyrene, (meth)acrylonitrile monomers, (meth)acrylic acid ester monomers, maleic acid diester monomers, fumaric acid diester monomers , and a (co)polymer obtained by mixing one or more types of butadiene monomers. Then, either the carboxyl group-containing vinyl copolymer or the vinyl (co)polymer forms a matrix, and the other is uniformly dispersed in a spherical shape in the matrix to form a multiphase thermoplastic resin. The particle diameter of the dispersed polymer is 0.001 to 10 μm, preferably 0.01 to 5 gm. Dispersed resin particle size 0
．． If it does not reach 0.001 μm or exceeds 10 gm, the polyamide resin and ABS resin will not be sufficiently compatible, resulting in a decrease in impact resistance and delamination of the thermoplastic resin composition.

Furthermore, the number average degree of polymerization of both the carboxyl group-containing vinyl copolymer and the vinyl (co)polymer is 10 to 10,0.
00, preferably in the range of 50 to 5,000. If the number average degree of polymerization is less than 10, it is not possible to improve the impact resistance of the thermoplastic resin composition of the present invention, but it is not preferable because the heat resistance decreases. Also, the number average degree of polymerization is 1
If it exceeds 0,000, the melt viscosity increases, moldability decreases, and surface gloss decreases, which is not preferable.

The multiphase structure thermoplastic resin contains 5 to 95% by weight of a carboxyl group-containing vinyl copolymer, and 95% by weight of a vinyl (co)polymer.
~5% by weight, preferably carboxyl group-containing vinyl copolymer lO~9()% by weight, vinyl (co)polymer 90
~10% by weight. When the carboxyl group-containing vinyl copolymer is less than 5% by weight, the compatibilizing effect with the polyamide resin can be sufficiently exhibited, and when the carboxyl group-containing vinyl copolymer exceeds 95% by weight, ABS This is not preferable because the effect of making it compatible with the resin cannot be fully exhibited.

Multiphase structured thermoplastic resins are produced by grafting or blocking methods. These may be carried out by any generally well-known method such as chain transfer method or ionizing radiation irradiation method, preferably the method shown below.

The reason for this is that the grafting or tuloc efficiency is high and secondary aggregation due to heat does not occur, so performance is more effectively expressed. The polymerization method may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

Hereinafter, typical examples of the method for producing a thermoplastic resin having a multiphase structure will be shown in the case of a kraft copolymer and a block copolymer.

First, an example of producing a graft copolymer will be explained. That is,
First, vinyl monomers are (co)polymerized using an ordinary radical polymerization initiator under conditions that do not cleave the peroxide bonds of a radically (co)polymerizable organic peroxide, thereby producing vinyl containing peroxide bonds. A system (co)polymer is obtained, and then an unsaturated carboxyl group-containing monomer and one or more other vinyl monomers are copolymerized under conditions such that the peroxide bonds are cleaved. Kraft copolymers can be obtained efficiently.

In addition, unsaturated carboxyl group-containing monomers are either (co)
It may be introduced into the polymer portion.

Further, as the radical (co)polymerizable organic peroxide referred to here, specifically, t-butyl peroxyallyl carbonate, t-amyl peroxyallyl carbonate, t-
-hexylperoxyallyl carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-hexylperoxyethyl carbonate, t-tutylberoxyethyl fumarate, t-amylberoxyethyl fumarate rate, t-hexylberoxyethyl fumarate, t-butylperoxyisopropyl fumarate, t-
amylperoxyisopropyl fumarate, t-hexylperoxyisopropyl fumarate, t-butylperoxycyclohexyl fumarate, t-amylperoxycyclohexyl fumarate, t-hexylperoxycyclohexyl fumarate, 7-butylperoxyacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, t-
Butylperoxyacryloyloxyethoxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethyl carbonate, 7-hexylperoxyacryloyloxyethoxyethyl carbonate, t-butylberoxymethacryloyloxyethyl carbonate, t
-Amylperoxyacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, t-butylberoxymethacryloyloxyethoxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyl Examples include roxyethoxyethyl carbonate, t-butylperoxycrotonate, t-amylperoxycrotonate, and t-hexylperoxycrotonate. Among these, 7-butyl peroxyallyl carbonate, t-
butylperoxyisopropyl fumarate and t-butylberoxymethacryloyloxyethyl carbonate.

Next, an example of manufacturing a block copolymer will be explained. That is,
First, when vinyl monomers are (co)polymerized using polycarbonate as a polymerization initiator, a peroxide bond-containing vinyl (co)polymer with peroxide groups introduced into the chain is obtained. When an unsaturated carboxyl group-containing monomer and one or more other vinyl monomers are added and copolymerized, the peroxide bonds are cleaved and a block copolymer can be efficiently obtained.

The unsaturated carboxyl group-containing monomer may be introduced into either (co)polymer portion. In addition, the polymeric peroxide referred to here is a compound having two or more peroxide bonds in one molecule, and specifically, for example, (n = 2 to 40 in all of the above). can.

The resin composition of the present invention may also contain an elastomer (IV). Next, this elastomer will be explained. That is, the elastomer in the present invention is a normal elastomer (C) having a glass transition temperature or rubber elasticity of 0°C or lower.
Specific examples include styrene-butadiene rubber, di-1-lyl rubber, butadiene rubber, chloroprene rubber, ethylene propylene terpolymer, butyl rubber, imprene rubber, silicone rubber, polyvinyl chloride, ethylene propylene rubber, ethylene-distillate, and acid. Examples include vinyl copolymers, ethylene-ethyl acrylate copolymers, ethylene propylene rubber, chlorinated polyethylene, styrene elastomers, olefin elastomers, urethane nylastores, and polyester elastomers.

The composition of the polyamide resin (I) and ABS resin (II) in the thermoplastic resin composition of the present invention is such that the former has a composition of 1 to 9
9% by weight, preferably 5-95% by weight, the latter 99-1% by weight
% by weight, preferably 95 to 5% by weight, and further contains the multiphase thermoplastic resin (III) as component (I) + (I
I) 0.1 to 100 parts by weight, preferably 1 to 90 parts by weight, per 100 parts by weight. If the polyamide resin is less than 1% by weight, the solvent resistance and heat resistance will be insufficient, and if the ABS resin is less than 1% by weight, the impact resistance will be insufficient. If the multiphase structure thermoplastic resin (m) is less than 1.1 parts by weight, the compatibility between the polyamide resin and the ABS resin will be insufficient, and if it exceeds 100 parts by weight, the heat resistance will decrease, which is undesirable. .

In the present invention, component (I) + (II) + (
m) 100 parts by weight or less of elastomer (IT) may be blended with respect to 100 parts by weight. If the amount of the elastomer exceeds 100 parts by weight, the heat resistance will deteriorate, which is not preferable.

In the composition of the present invention, the above (I) + (II) + (■)
or the above (I)+ (II)+
Up to 150 parts by weight of an inorganic filler can be blended with respect to ioo parts by weight of the resin component containing (m) + (IV).

Examples of the above-mentioned inorganic fillers include powder-like, tabular, scaly, acicular, spherical or hollow, and fibrous fillers, and specific examples include calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, and silica sand. , glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, etc.; mica, glass plate, sericite, pyrophyllite, aluminum flakes, etc. flat or scale-like fillers such as metal foil and graphite; hollow fillers such as rainbow balloons, metal balloons, glass balloons, and pumice; glass fibers;
carbon fiber, graphite fiber, whiskers, metal fiber,
Examples include mineral tags such as silicon carbide #ll #I, asbestos, and wolstonite.

If the amount of filler added exceeds 150 parts by weight, the impact strength of the molded article will decrease, which is not preferable.

In addition, the surface of the inorganic filler is treated with stearic acid, oleic acid, palmitic acid or their metal salts, paraffin wax, polyethylene wax or modified products thereof, organic silane, organic borane, organic titanate, etc. It is preferable to apply

The thermoplastic resin composition of the present invention comprises a polyamide resin, A
BS resin and multiphase structure thermoplastic resin at a temperature of 200 to 30
It is manufactured by mixing under melting at 0°C.

The melt-mixing order may be such that all the components are melt-mixed at the same time, or the polyamide resin or ABS resin and the multiphase thermoplastic resin are melt-mixed in advance, and then the other resin is melt-mixed. Good too.

The melt-mixing method can be carried out using a commonly used kneading machine such as a Banbury Mixer-1 pressurized kneader, a kneading extruder, a twin-screw extruder, or a mixing roll.

In the present invention, other thermoplastic resins such as polyester resins, polyphenylene sulfite resins, polysulfone resins,
Or inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based,
Organic fillers such as wood flour, antioxidants, UV inhibitors,
Additives such as lubricants, coupling agents, dispersants, blowing agents, crosslinking agents, and coloring agents may be added.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

Seven pieces 1 (Multiphase structure thermoplastic resin-A (III)
(Manufacturing) In a stainless steel reactor equipped with a thermometer, stirrer and condenser, add 1% polyvinyl alcohol aqueous solution IO parts by weight, 10% tertiary calcium phosphate aqueous solution 1 phosphorus monomer 45 parts by weight, methacrylic acid monomer 5,000 records, t
- A mixed solution of 1.4 parts by weight of phthylberoxyisopropyl fumarate (70% purity) and 0.5 parts by weight of 3,55-trimethylhexanoyl peroxyte (75% purity) was charged, and air inside the reactor was charged. After replacing the reactor with nitrogen gas, the temperature was maintained at 70'C with stirring, and polymerization was carried out for 6 hours. Thereafter, 45 parts by weight of styrene monomer and 15 parts by weight of acrylonitrile monomer were added, the temperature was raised to 75°C, polymerization was completed for 4 hours, and the polymer was cooled, filtered, washed with water, and dried to obtain the desired product. A multiphase structured thermoplastic resin A (m) was obtained.

This multiphase thermoplastic resin was examined using a scanning electron microscope (rJEO).
L JSM T0n (observed with I J (product name, manufactured by JEOL Ltd.), particle size 1), 1 to 0.5 gm
It was a heat-off resin with a multiphase structure in which a truly spherical resin styrene-acrylonitrile copolymer was dispersed. The matrix was a styrene-methacrylic acid copolymer.

Part 7 2 (Manufacture of multi-phase structured thermoplastic resin-B (m)) In a stainless steel reactor equipped with a thermometer, stirrer and condenser, add 10 parts by weight of 1% polyvinyl alcohol aqueous solution and 10% tribasic calcium phosphate main solution IO. Parts by weight, 2 parts water
80 parts by weight was added. Next, a mixed solution of 35 parts by weight of styrene monomer, 15 parts by weight of acrylonitrile monomer, and 4.2 parts by weight of polymeric peroxide (f) (60% purity) was charged, and the air in the reactor was replaced with nitrogen gas. After that, the temperature was maintained at 75° C. without stirring, and polymerization was carried out for 3 hours. After that, 45 parts by weight of styrene monomer and 5 parts by weight of methacrylic acid monomer were added, the temperature was raised to 80°C, polymerization was completed for 4 hours, and the polymer was cooled, filtered, washed with water, dried, and the desired product was obtained. A multiphase structured thermoplastic resin B (m) was obtained.

This multiphase thermoplastic resin was examined using a scanning electron microscope (rJEO).
L JSM T300 J (product name, manufactured by JEOL Ltd.) 1 particle size 0.1-0.5 JL
It was a thermoplastic resin with a multiphase structure in which a styrene-acrylonitrile copolymer having a true spherical shape of m was dispersed. The matrix was a styrene-methacrylic acid copolymer.

Examples 1 to 8 Polyamide nylon 6.6 [manufactured by Toshiku Co., Ltd.], trade name [Amilan CM3001-NJ] and ABS resin [manufactured by Asahi Kasei Co., Ltd.]
Co., Ltd. under the trade name [SLILAC-ABSIOIJ] and the multiphase structure thermoplastic resin obtained in Reference Example were melt-mixed in the proportions shown in Table 1.

The melt-mixing method was carried out using a co-directional twin-screw extruder with a screw diameter of 3011111 and set at a cylinder temperature of 2506C.
manufactured by Plastic Engineering Research Institute Co., Ltd.] and melted and mixed in a cylinder. After the mixed resin is granulated,
It was dried at 150°C for 3 hours and a test piece was prepared by injection molding. The size of the test piece is as follows.

Izotsu impact test piece 12.7mo+X 651X
6.4 am (with notch) Weighted deflection temperature test piece 12.7n+mX 1:10
mmX 6.4 mm The test method is as follows.

(1) Izot impact test (notched): JIS
K7110 (2) Loaded deflection temperature: JIS K7207 Chemical wax The test piece was immersed in methanol at 75°C for 30 days, and then its appearance was observed.

The results are shown in Table 1. In Table 1, 0ΔX indicates the following results.

○・・・No change.

△・・・Cracks have occurred on the surface or some parts have eluted.

×: Significant surface elution.

In addition, it was determined whether the resin peeled off in layers from the fractured part of the test piece, and this was used as a measure of compatibility.

Examples 9 to 13 In addition to the above examples, Table 2 shows an example in which an ethylene-propylene terpolymer [manufactured by Mitsui Petrochemicals Co., Ltd., trade name [972D J in Mitsui Elas 1-mer] was added as an elastomer. show.

Examples 14 to 19 In addition to the above examples, the average fiber length was 5.0 mm and the diameter was 10 mm.
Table 3 shows an example in which glass fibers of JJ and m were blended.

Comparative Examples 1 to 7 Table 4 shows examples in which a styrene-maleic anhydride copolymer and a styrene-acrylonitrile-matacrylic acid copolymer were used in place of the multiphase thermoplastic resin in the composition of the present invention.

Comparing Tables 1, 2, 3, and 4, it is clear that the resin composition of the present invention is superior.

(Effects of the Invention) The thermoplastic resin composition of the present invention is a resin composition that takes advantage of the respective advantages of polyamide resin and ABS resin and has excellent heat resistance, impact resistance, and adhesiveness. Widely used for automobile parts, electrical/electronic parts, industrial parts, etc.

Claims (2)

[Claims] (1) (I) 99-1% by weight of polyamide resin, (II
) Polymerization or copolymerization of 1 to 99% by weight of ABS resin and 100 parts by weight of (I) + (II) above, and 5 to 95% by weight of (III) carboxyl group-containing vinyl copolymer and a vinyl monomer. 95 to 5% by weight of a vinyl polymer or copolymer obtained by
Multiphase structure thermoplastic resin forming a dispersed phase of 0 μm 0
．． A thermoplastic resin composition containing 1 to 100 parts by weight. (2) (I) Polyamide resin 99-1% by weight (II)
Polymerize or copolymerize 1 to 99% by weight of ABS resin and 100 parts by weight of the above (I) + (II) with 5 to 95% by weight of (III) a carboxyl group-containing vinyl copolymer and a vinyl monomer. 95 to 5% by weight of a vinyl-based polymer or copolymer obtained by A thermoplastic resin composition comprising 0.1 to 100 parts by weight of a structural thermoplastic resin and 100 parts by weight of the above (I) + (II) + (III), and 100 parts by weight or less of (IV) an elastomer.