JPH07122007B2 - Improved hard thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a hard thermoplastic resin composition having remarkably improved thermal stability.

[Conventional technology]

Like ABS resin and impact-resistant polystyrene resin, the matrix is a styrene resin, and many kinds of butadiene or butyl acrylate polymer particles grafted with a polymer containing vinylidene aromatic hydrocarbon such as styrene are dispersed particles. The hard thermoplastic resin having excellent impact resistance has been already developed and is widely used mainly as a molding material. Examples of these resins include acrylonitrile-styrene copolymers, styrene-based polymers such as polystyrene as resins used for the matrix and graft, and a part of styrene of these two styrene-based polymers as alpha. A variety of modified styrene polymers substituted with one or more monomers selected from methylstyrene, methylmethacrylate, maleic anhydride, phenylmaleimide, and methacrylic acid are used. As a united, polybutadiene,
A butadiene copolymer such as a copolymer of butadiene and a crosslinkable monomer, for example, divinylbenzene, and a modified butadiene polymer obtained by substituting a part of butadiene in the butadiene polymer with styrene, acrylonitrile, etc. are used. Furthermore, as the butyl acrylate-based polymer, a copolymer containing butyl acrylate as a main component and other components such as allyl methacrylate, vinyl acrylate, ethylene dimethacrylate, divinylbenzene, and butadiene as a minor component is also available. It is used.

[Problems to be solved by the invention]

ABS resin and other hard thermoplastic resins with excellent impact resistance such as the above examples are excellent in impact resistance, rigidity, heat resistance and fluidity, but on the other hand, they tend to discolor due to heat. There is. That is, since the thermal stability is not good, there is a problem in hue, it is difficult to obtain a bright hue and a stable hue, and there is a problem that the application is limited.

As a conventional method for solving such a problem, for example, a method of adding a hindered phenol such as octadecyl (3,5-ditertiarybutyl-4-hydroxyphenyl) bropionate and a hindered phenol Further, a method of using phosphite or thioethers in combination is generally used. However, the addition of hindered phenols alone is not sufficient in the initial hue and the effect of sustaining thermal stability, and in order to improve the thermal stability, the amount of hindered phenols used should be 1 relative to the resin.
When it is used in an amount exceeding the amount by weight, the effect of sustaining the thermal stability is certainly improved to some extent, but there is a problem that the presumed initial hue is probably deteriorated due to the reaction product of the hindered phenol itself. When hindered phenols and phosphites or thioethers are used in combination, the initial hue and the effect of maintaining thermal stability are both improved compared to hindered phenols alone, but the improvement effect is still unsatisfactory. If the amount of phosphite or thioether is increased with the expectation of further improvement, conversely, there arises a problem that both the initial hue and the effect of sustaining thermal stability decrease.

On the other hand, in recent years, 2,2'-oxamidobis- [ethyl-3-
(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] (hereinafter abbreviated as OBP) was developed,
Polyolefin resin mainly composed of polypropylene is used to prevent deterioration mainly by a copper component and other transition metal components. OBP is also suggested to be used for other resins including ABS resin,
Little is disclosed about how to use it. In fact
Even if OBP is added to the ABS resin, the effect of maintaining the initial hue and thermal stability is not large.

As another proposal for improving the thermal stability of ABS resin, for example, as disclosed in Japanese Laid-Open Patent Publication No. 60-106835, ABS resin latex produced by emulsion polymerization is first coagulated with acid, and then base and water-soluble 2 Add valent metal, then filter,
A method of washing and drying, in the same manner as disclosed in JP-A-59-155410, when an alphamethylstyrene-acrylonitrile polymer is produced by an emulsion polymerization method in the intermediate step of making an ABS resin, a persulfate salt is added at the beginning of the polymerization. Used as a catalyst,
There is also an attempt to improve thermal stability by devising resin coagulation, washing or polymerization conditions, such as a method using an oil-soluble catalyst in the latter stage of polymerization, but the manufacturing method becomes complicated and the improvement effect It has the drawback of not being ridiculous.

[Means for solving problems]

An object of the present invention is to provide a composition in which the persistence effect of initial hue and thermal stability of a vinylidene aromatic hydrocarbon-containing resin blend shown below, which is an ABS resin or a similar resin, is significantly improved. Is.

That is, according to the present invention, when such vinylidene aromatic hydrocarbon-containing resin blend is added with the above-mentioned OBP and a specific divalent metal compound described below in an addition amount within a specific range, a continuous effect of initial hue and thermal stability is obtained. Is based on the finding that both are significantly improved.

According to the present invention, it is possible to easily provide a hard thermoplastic resin composition having a remarkably excellent initial hue and a long lasting effect of thermal stability by a simple method.

The hard thermoplastic resin composition according to the present invention comprises: [I] (A) (1) Vinylidene aromatic hydrocarbon 10 to 10
0% by weight, (2) acrylonitrile 0-40% by weight,
(3) A thermoplastic polymer comprising 0 to 90% by weight of methyl methacrylate, (4) 0 to 40% by weight of a maleimide compound, and (5) 0 to 30% by weight of an ethylene compound copolymerizable therewith (hereinafter referred to as vinylidene). Abbreviated as aromatic hydrocarbon-containing polymer) 30 to 95 wt% (B) (1) 0 to 100 wt% butadiene, (2) 0 to 98.8 wt% butyl acrylate, (3) Monoethylene copolymerizable with these Based compounds (0 to 40% by weight), (4) based on 0 to 5% by weight of compounds having two or more ethylenic unsaturated bonds copolymerizable therewith (hereinafter abbreviated as rubber type polymer), In the presence of (1) vinylidene aromatic hydrocarbon 10 to 100% by weight,
(2) Acrylonitrile 0-40% by weight, (3) Methyl methacrylate 0-90% by weight, (4) Maleimide compound 0-40% by weight, (5) Monoethylene compound 0-30 copolymerizable with these %, (6) Graft copolymer obtained by polymerizing a mixed monomer (hereinafter abbreviated as graft monomer mixture) consisting of 0 to 5% by weight of a compound having two or more ethylenic unsaturated bonds copolymerizable with these (hereinafter referred to as graft monomer mixture). Hereinafter, abbreviated as vinylidene aromatic hydrocarbon-containing graft product) 70-5
The rubber-based polymer contained in this is 2 to 40% by weight.
100 parts by weight of a resin mixture (hereinafter, abbreviated as vinylidene aromatic hydrocarbon-containing blend) such that the content of the mixture becomes 100% by weight [II] 2,2'-oxamidebis- [ethyl-3- (3,5
-Ditertiarybutyl-4-hydroxyphenyl) propionate] 0.001 to 2.0 parts by weight [III] Divalent metal oxide, hydroxide, carbonate or organic carvone selected from the group consisting of magnesium, calcium, strontium and barium. An acid salt (hereinafter abbreviated as a divalent metal compound used in the present invention) is 0.01 to 5.0 parts by weight.

First, the raw material of the vinylidene aromatic hydrocarbon-containing polymer [I] (A) used in the present invention will be described below.

Vinylidene aromatic hydrocarbon has the chemical formula (R ₁ and R ₂ each represent a hydrogen group or a methyl group), and typical examples thereof include styrene and alphamethylstyrene, and other examples include paramethylstyrene and metamethylstyrene. .

In addition, the maleimide compound has a chemical formula (R ₃ represents a phenyl group, a substituted phenyl group, a cyclohexyl group or an alkyl group), phenylmaleimide is a typical example, and isopropylmaleimide, 2,6
Examples are dimethylphenylmaleimide, chlorophenylmaleimide, cyclohexylmaleimide.

Ethylene compounds copolymerizable with these are compounds having a copolymerizable ethylenic unsaturated bond, such as dibutyl itaconate, methyl acrylate, butyl acrylate, and 2
-Ethylhexyl methacrylate, methacrylic acid,
Acrylic acid, diethyl itaconate, maleic anhydride,
Examples are dimethyl fumarate, methacrylonitrile, and allyl methacrylate.

Examples of such vinylidene aromatic hydrocarbon-containing polymers include acrylonitrile-styrene copolymers, acrylonitrile-styrene-alphamethylstyrene copolymers,
Acrylonitrile-styrene-methylmethacrylate copolymer, acrylonitrile-styrene-alphamethylstyrene-methylmethacrylate copolymer, acrylonitrile-styrene-phenylmaleimide copolymer,
Acrylonitrile-styrene-alphamethylstyrene-phenylmaleimide copolymer, styrene-phenylmaleimide copolymer, polystyrene, styrene-maleic anhydride copolymer, styrene-methylmethacrylate-
There are maleic anhydride copolymers, styrene-methacrylic acid copolymers, and the like. Among these examples, 6 types of copolymers containing acrylonitrile and styrene have good physical properties,
Particularly preferred.

Such a polymer is usually produced by a known method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. There are a thermal polymerization method and a catalytic polymerization method for the polymerization, and as the catalyst, azobisisobutyronitrile, azobiscyclohexanonitrile, tertiary butyl peroxybenzoate, 1,1-
Bis-tert-butyl peroxycyclohexane, benzoyl peroxide, bis-tert-butyl peroxy ester of 1,4-cyclohexanedicarboxylic acid,
Tertiary butyl hydroperoxide, cumene hydroperoxide, potassium persulfate and the like are usually used in an amount of 1.0% by weight or less based on the polymer.

When a solvent is used, ethylbenzene, toluene, methyl ethyl ketone and the like are preferable.

Further, in the polymerization, if necessary, normal octyl mercaptan, normal dodecyl mercaptan, tertarydodecyl mercaptan, 2-ethylhexyl thioglylate, terpinolene, etc. are usually used in an amount of 2.0% by weight or less as a chain transfer agent.

As an emulsifier when a polymer is produced by an emulsion polymerization method,
For example, carboxylic acid type anion activators such as potassium stearate, potassium oleate, sodium laurate, and disproportionated potassium rosinate, sodium bis (2-ethylhexyl) sulfosuccinate, sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate. Such non-carboxylic acid type anionic activators, nonionic activators such as polyoxyethylene lauryl ether and polyoxyethylene nonylphenyl ether are usually used in an amount of about 0.03 to 5% by weight based on the weight of the polymer. Also, a pH adjusting agent,
For example, potassium bicarbonate, dibasic sodium phosphate, sodium orthophosphate, etc. can also be used. When a polymer is produced by an emulsion polymerization method, as a method of adding a raw material monomer to a polymerization apparatus, there are a batch charging method, a divided charging method, a continuous charging method, and the like. However, there is also a method of continuously charging the rest. The emulsifier, chain transfer agent, catalyst, etc. may be added as a batch charging method, a divided charging method, a continuous charging method, or the like, or a combination of these methods may be used.

Next, the raw material of the above-mentioned rubber polymer which will be the base of the vinylidene aromatic hydrocarbon-containing graft product [I] (B) used in the present invention will be explained.

The copolymerizable monoethylenic compound is a compound having one copolymerizable ethylenic unsaturated bond, and examples thereof include styrene, acrylonitrile, methyl acrylate, methyl methacrylate, isoprene, dibutyl fumarate and dicyclopentadienyl acrylate. Here is an example.

Compounds having two or more copolymerizable ethylenic unsaturated bonds include divinylbenzene, allyl methacrylate, vinyl acrylate, polypropylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol bis (methoxy fumarate). Rate) is an example.

In the present invention, as the rubber polymer, a polymer mainly containing butadiene and a polymer mainly containing butyl acrylate are used.

Butadiene 10 for butadiene-based polymers
In addition to 0% of polymer, butadiene is 70% by weight or more, monoethylene compound such as styrene and acrylonitrile which is copolymerized with butadiene is 30% by weight or less, and polyvinylidene compound such as divinylbenzene is 0 to 0.2% by weight. A degree of butadiene copolymer is preferred. In the case of a polymer mainly composed of butyl acrylate, butyl acrylate 85 to 99.8% by weight, butadiene 0 to 10% by weight, monoethylene compound such as styrene, isobutyl acrylate, dicyclopentadienyl acrylate 0 to 15% by weight, poly Vinylidene compounds such as allyl methacrylate and butyl acrylate copolymer containing about 0.013 to 3% by weight of triallyl cyanurate are particularly preferable.

The rubber polymer is usually produced by an emulsion polymerization method.
The preferred particle size range of the rubber-based polymer used is usually 0.15
~ 1.5μ.

As a catalyst for producing a rubber polymer, potassium persulfate, cumene hydroperoxide, tertiary butyl hydroperoxide, azobisisobutyronitrile, etc., as well as a reducing agent for redox polymerization and its adjustment As the component, ferrous sulfate, ferric sulfate, sodium bisulfite, glucose, sodium formaldehyde sulfoxylate, sodium pyrophosphate, sodium salt of ethylenediaminetetraacetic acid, etc. are appropriately used as necessary.

In addition, as an emulsifier, carboxylic acid type anion activators such as potassium stearate, sodium oleate, ammonium laurate, and disproportionated potassium rosinate, sodium bis (2-ethylhexyl) sulfosuccinate, sodium dodecylbenzenesulfonate, etc. Non-carboxylic acid anion activators, nonionic activators such as polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, etc. are usually 0.
It is used in the range of 02-5% by weight.

If necessary, a chain transfer agent such as tertiary dodecyl mercaptan, 2-ethylhexyl thioglycolate, terpinolene, etc. is appropriately used.

Next, the graft monomer mixture used in the above graft product [I] (B) will be described.

Vinylidene aromatic hydrocarbons and maleimide compounds are
It is the same as that described for the raw material of the polymer [I] (A), and styrene and alphamethylstyrene are typical examples of the former and phenylmaleimide is typical example of the latter.

The monoethylene compound which can be copolymerized with these is a compound having one copolymerizable ethylenic unsaturated bond, and is methacrylic acid, acrylic acid, methacrylonitrile, diethyl maleate, glycidyl methacrylate, 2-hydroxyethyl acrylate, An example is N-butoxymethyl acrylamide.

Examples of compounds having two or more ethylenic unsaturated bonds copolymerizable with them include divinylbenzene, ethylene dimethacrylate, allyl methacrylate, dimethacryloxyethyl phthalate, triallyl cyanurate, and diethylene glycol bis (butoxy fumarate). This is an example.

An emulsion polymerization method is convenient as a method for producing the graft product [I] (B) from the rubber polymer and the graft monomer mixture.

As a catalyst for producing the graft product [I] (B), potassium persulfate, cumene hydroperoxide, diisopropylbenzene hydroperoxide, decanoyl peroxide, and the like, as well as a reducing agent for redox polymerization and its preparation may be used. As a component therefor, ferrous sulfate, ferric sulfate, glucose, sodium formaldehyde sulfoxylate, sodium pyrophosphate, sodium salt of ethylenediaminetetraacetic acid, etc. are appropriately used as necessary.

Also, potassium laurate, potassium stearate as an emulsifier,
Carboxylic acid anion activators such as potassium oleate, sodium palmitate, sodium stearyl lactate, potassium 12-hydroxystearate, and disproportionated potassium rosinate; non-carboxylic acid anions such as sodium dodecyl sulfate and sodium dodecylbenzene sulfonate. Nonionic activator such as activator, polyoxyethylene lauryl ether, polyoxyethylene tertiaryoctyl phenyl ether is 0.03 to 10.0 based on the rubber polymer.
Used by weight%

Further, usually, as a chain transfer agent, tershalide decyl mercaptan, normal dodecyl mercaptan, normal octyl mercaptan, 2-ethylhexyl thioglycolate, terpinolene and the like 0.03 ~ 5.0 wt% based on the weight of the graft product [I] (B) Used to a degree.

When an emulsion of the graft product [I] (B) is produced by graft polymerization, a rubber-based polymer emulsion is usually added to a polymerization apparatus, and a graft monomer mixture or the like is added thereto to carry out polymerization. As a method of adding the catalyst and the chain transfer agent, there are methods such as a batch charging method, a multiple charging method during polymerization, and a continuous charging method during polymerization.

The content of the rubber polymer in the graft product is preferably 20 to 85% by weight, and particularly preferably 45 to 80% by weight.

The graft product [I] (B) produced by the emulsion polymerization method and the polymer [I] (A) produced by employing the emulsion polymerization method are usually used individually or after mixing, It is filtered, washed and dried. Typical examples of the coagulation method include an acid coagulation method using sulfuric acid and hydrochloric acid, a salt coagulation method using calcium chloride, magnesium sulfate, magnesium chloride, strontium nitrate, barium chloride and the like, and a thermal coagulation method using steam. When an aqueous solution of the compound of the divalent metal such as calcium chloride, magnesium sulfate, magnesium chloride, strontium nitrate, barium chloride is used as a coagulant, the carboxylic acid contained in the graft product or the polymer is used. The anionic anionic activator enters the solidified product as the divalent metal carboxylic acid salt, which is eventually contained in the hard thermoplastic resin composition of the present invention.

Further, after the coagulation step, if desired, it can be carried out in an extruder, and it is particularly convenient to carry out filtration, washing and drying in the extruder.

The OBP [II] used in the present invention is used in an amount of 0.001 to 2.0, preferably 0.01 to 0.5% by weight based on the vinylidene aromatic hydrocarbon-containing blend [I]. When the OBP is less than 0.001% by weight, the effect of improving the thermal stability is achieved, and when it is more than 2.0% by weight, the hue is rather deteriorated. As a method of using OBP, it is general to add it to the blend [I], but to add it in the kneading step of the blend, to add it to the graft [I] (B), or to add the graft [I ] (B)
Of adding to a graft monomer mixture used in the production of a polymer, a method of adding to a rubber polymer, a method of adding to a polymer [I] (A) before forming a blend [I], a rubber polymer or a polymer A method of adding [I] (A) to the raw material monomer mixture, and further a polymerization step of the graft product [I] (B),
A method such as addition in the polymerization step of the rubber-based polymer or the polymerization step of the polymer [I] (A) is also a preferable method, and it is added in any step of the step of producing the hard thermoplastic resin composition of the present invention It is also possible to do so.

When zinc is used instead of the divalent metal of the divalent metal compound used in the present invention, for example, when zinc stearate is used, the effect of sustaining the initial hue and thermal stability is poor. or,
Instead of the divalent metal compound used in the present invention, the same 2
Not only the initial thermal stability and the sustained effect of thermal stability cannot be improved even by using salts formed from a valent metal and a strong acid, such as calcium dodecylbenzene sulfonate, barium lauryl sulfate and magnesium nitrate, but they often deteriorate on the contrary. .

The blending amount of the vinylidene aromatic hydrocarbon-containing graft used in the hard thermoplastic resin composition of the present invention is 2 when the rubber polymer occupies the vinylidene aromatic hydrocarbon-containing resin blend of the present invention. The amount is up to 40% by weight. If it is less than 2% by weight, the impact strength will be insufficient, and if it is 40% by weight or more, the rigidity will be insufficient.

The organic carboxylic acid in the organic carboxylic acid salt of a divalent metal used in the present invention means an organic acid having a carboxyl group. Examples of such an organic acid include aliphatic carboxylic acids,
There are aromatic carboxylic acids and their substituted carboxylic acids, including stearic acid, palmitic acid, lauric acid, 2-ethylhexanoic acid, oleic acid, disproportionated rosin acid, stearyl lactic acid, 12-hydroxystearic acid, citric acid, and tert-acid. Ributylbenzoic acid and paraoxybenzoic acid are examples.

Examples of the divalent metal compound used in the present invention include calcium stearate, calcium laurate, calcium 2-ethylhexanoate, calcium oleate, disproportionated calcium rosinate, calcium stearyl lactate, and tert-butylbenzoic acid as organic carboxylates. calcium,
Magnesium stearate, magnesium laurate,
Representative examples are magnesium oleate, strontium stearate, barium stearate, barium laurate, and (2) Other compounds are magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide. Calcium carbonate and barium hydroxide are typical. The organic carboxylic acid salt may be used in the present invention as the compound itself, or in the case of producing the graft product [I] (B) or the polymer [I] (A), as described above. When using a systemic anion activator and using a compound such as calcium chloride, magnesium sulfate or magnesium chloride as a coagulating agent in a molar ratio of about 0.5 times or more with respect to the carboxylic acid anion present in the emulsion to be coagulated, a carboxylic acid system is used. Most of the carboxylate anion in the anion activator is bound to the divalent metal cation in the water-soluble divalent metal compound to form an organic carboxylate and remains in the coagulated product, which may be used. . For example, when potassium stearate is used as the carboxylic acid anion activator and magnesium sulfate is used as the coagulant, magnesium stearate is produced and remains in the coagulated product.

The divalent metal compound used in the present invention is 0.01 to 5.0 with respect to 100 parts by weight of the vinylidene aromatic hydrocarbon-containing blend [I].
Parts by weight, preferably 0.1 to 3.0 parts by weight are used. here
If it is less than 0.01 parts by weight, the thermal stability of the hard thermoplastic resin composition of the present invention is impaired, and if it is more than 5.0 parts by weight, there are disadvantages such as excessive lubricity and the appearance of white spots. .

The organic carboxylic acid salt itself is added in the blend [I] or in a kneading device therefor, in the graft [I] (B), or in the polymer [I] (A). It can be added at various stages such as addition.

The hard thermoplastic resin composition of the present invention, ABS resin, impact-resistant polystyrene resin and these are usually maleimide compounds, methylmethacrylate, alphamethylstyrene, maleic anhydride, resins modified with methacrylic acid, etc. Various known additives as added may be added as required.

These additives include (1) substances that impart lubricity,
(2) Substances for improving fluidity, (3) Substances for preventing oxidative deterioration due to heat and aging, (4) Substances for preventing deterioration by ultraviolet rays, (5) Preventing electrification and conductivity. Substance for imparting properties, (6) substance for imparting flame retardancy, (7) substance for neutralizing acidic substances,
(8) Fillers, (9) substances for surface treatment and gloss improvement of various fillers, (10) to improve strength, heat distortion temperature, lubricity, flame retardancy, antistatic property and other properties. There are various polymers and fiber materials, (11) colorants, (12) foaming agents.

(1) Examples of substances that impart lubricity include metal soaps such as zinc stearate, aluminum stearate, and 12
-Lithium hydroxystearate, lead stearate,
Lipophilic substances such as octadecyl phosphate such as zinc, calcium and magnesium (additives are usually 3.0% or less), metal-free fatty derivatives such as stearic acid,
Examples are lipophilic substances such as octadecyl alcohol, butyl stearate, palmitic acid amide, ethylene bis stearamide, low molecular weight polyethylene, and paraffin (addition amount is usually 5% or less).

(2) Substances for improving fluidity include butylbenzyl phthalate, tricresyl phosphate, triphenyl phosphate, dilauryl azelate, tris (2-ethylhexyl) trimellitate, poly (butylene adipate), and bisphenol A. Lipophilic substances such as diglycidyl ether are mentioned, and the addition amount is usually 5%.
It is the following.

(3) Phenolic compounds such as 2,6-ditertiarybutyl-4-methylphenol, octadecyl (3,
5-ditertiarybutyl-4-hydroxyphenyl) propionate, triethylene glycol bis [3- (3
-Tertiarybutyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], 2-tertiarybutyl-6- (3 -Tert-butyl-2-hydroxy-5-
Lipophilic substances such as methylbenzyl) -4-methylphenylacrylate (usually 1% or less), substantially trivalent phosphorus-containing organic compounds such as trisnonylphenyl phosphite, cyclic neopentane tetra Irbis (octadecyl phosphite), 4,4'-
Butylidene bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite, tris (2,4
-Ditertiarybutylphenyl) phosphite, 9,10
-Lipophilic substances such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (addition amount is usually 2% or less), thioether compounds such as dioctadecyl thiopropionate, pentaerythritol-
Tetrakis- (beta-dodecyl-thiopropionate), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,4-bis- (n-octylthio) -6- (4-hydroxy-) Lipophilic substances such as 3,5-ditertiarybutylanilino) -1,3,5-triazine (usually 2% or less), compounds that form chelate compounds with metals, such as dibenzoylmethane. Oily substances (addition amount is usually less than 2%), hydrophilic substances such as ethylenediaminetetraacetic acid sodium salt, nitrilotriacetic acid sodium salt (addition amount is usually 0.5%)
Below).

(4) Examples of substances that prevent deterioration due to ultraviolet rays include 2-hydroxy-4-methoxybenzophenone and 2-
(2'-hydroxy-5'-methylphenylbenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, A lipophilic substance such as 6-tetramethyl-4-piperidyl) sebacate may be mentioned, and the addition amount thereof is usually 1% or less.

(5) Organic substances such as beta-hydroxyalkyl-N-ethanolamine, an adduct of 1,2-epoxydodecane and monoethanolamine, and beta (dodecyl) are used as substances for preventing charging and imparting conductivity. Hydrophilic substances such as (methyl-amino) propionic acid (addition amount is usually 3% or less), metals such as copper powder, nickel flakes, stainless fiber (addition amount is usually
150% or less), carbons such as conductive carbon black (usually 50% or less).

(6) Examples of the substance for imparting flame retardancy include decabromodiphenyl ether, tetrabromobisphenol A, brominated epoxy resin, bis (2,4,6-tribromophenoxy) ethane, zinc borate, and antimony oxide. The amount added is usually 30% or less.

(7) Examples of the substance for neutralizing the acidic substance include basic magnesium aluminum hydroxycarbonate (chemical formula Mg _4.2 Al (OH) _12.4 CO ₃ ), dibutyltin maleate, etc., and the addition amount is usually 1.5% or less. Is.

(8) Examples of the filler include talc, mica, alumina and silica (the amount added is usually 70% or less).

(9) Examples of substances for surface treatment and gloss improvement of various fillers include various silane coupling agents, various titanates, and various zirconates, and the addition amount is usually 2% or less.

(10) As various polymers and fiber materials, polymers such as polycarbonate, poly (phenylene ether), polyvinyl chloride, chlorinated polyethylene, polymethylmethacrylate, polyurethane, silicone, polyethylene glycol (addition amount is usually 200 %), Fiber materials such as glass fiber, asbestos, polyacrylonitrile fiber, carbon fiber, etc. (usually 200% or less).

In the above description of the additives, the addition amounts are all based on the vinylidene aromatic hydrocarbon-containing blend based weight. These additive substances are added to (1) a blend [I], (2) a blend [I] and an extruder, and (3) a graft [I] (B). There are methods, (4) addition to the graft monomer mixture, (5) addition to the rubber-based polymer, (6) addition to the polymer [I] (A), and other polymers [I] ( A) is prepared by polymerization, a rubber-based polymer is prepared by polymerization, a graft product [I] (B) is prepared, or a blended product [I] is kneaded in a batch manner or continuously. There are various methods such as methods.

The methods of adding these additive substances at various stages as described above include (1) a method of adding the substances themselves,
(2) There is a method of adding the lipophilic substance as described above by dissolving it in a solvent or a monomer, and (3) a method of dissolving or dispersing the hydrophilic substance as described above in water or an aqueous medium and adding it. In this case, the solvent, the volatile monomer, water and other volatile substances are usually removed by evaporation from the vent of the extruder.

In addition, among the above-mentioned additives, the compounds described in and of (3) substances for preventing oxidative deterioration due to heat and aging, that is, organic compounds and thioether compounds containing substantially trivalent phosphorus At least one of the belonging compounds is usually preferably added.

〔Example〕

The present invention will be described below with reference to examples showing preferred embodiments, but the present invention is not limited to these examples.

In the description of the examples, parts or% are based on weight.

Example 1 (a) An emulsion of a vinylidene aromatic hydrocarbon-containing polymer (H1) was obtained by the following formulation.

Polymer composition is about 27% acrylonitrile, 73 styrene
%, And the yield was 96%.

Polymerization conditions: Polymerization was carried out at 60 ° C. for 5 hours. The polymerization rate was 97%.

(B) An emulsion of a vinylidene aromatic hydrocarbon-containing graft product (G1) obtained by grafting acrylonitrile-styrene copolymer on polybutadiene was prepared by the following formulation.

Polymerization conditions: Polymerization was performed at 65 ° C for 5.5 hours. The polymerization rate was 96%.

After the completion of polymerization, mix 75 parts of H1 emulsion (solid content) and 25 parts of G1 emulsion (solid content) at 90 ° C.
By mixing with an aqueous solution of sulfuric acid 0.1% and sodium chloride 0.1% heated at 90 ° C at 90 ° C, coagulating, filtering, washing with water and drying, a vinylidene aromatic hydrocarbon-containing blend (FH
The powder of 1) was obtained.

(C) Pellets of the hard thermoplastic resin composition were obtained with the following formulation using a twin-screw vent extruder.

(D) Thermal stability test A disc with a diameter of 5 cm and a thickness of 2 mm was molded by injection molding and left in an oven at 170 ° C for 60 minutes and 120 minutes, then the test piece was taken out and the yellow index (YI ) Was measured. The results are shown in Table 1.

Example 2 (a) An emulsion of a polymer (H2) was obtained by a formulation using 20 parts of acrylonitrile, 65 parts of styrene part and 15 parts of phenylmaleimide instead of 100 parts of the monomer in Example 1 (a). .

The composition of the polymer is acrylonitrile 19%, styrene 66%,
Phenylmaleimide was 15% and the yield was 95%.

(B) Instead of the polybutadiene latex in Example 1 (b), the composition was 85% butyl acrylate, 14.6% butadiene, 0.2% divinylbenzene, 0.2% allyl methacrylate, concentration 50%, average particle size 0.31μ. Graft polymerization was carried out in the same manner using the latex of 1. to prepare an emulsion of the graft product (G2).

After the completion of the polymerization, H2 emulsion and G2 were added in the same manner as in Example 1.
The powder of blend (FH2) was obtained by mixing and processing the emulsion of.

(C) In the same manner as in Example 1 with the following formulation, pellets of a hard thermoplastic resin composition were obtained.

(D) Thermal stability test A test was conducted in the same manner as in Example 1. The results (Y1) are shown in Table 2.

Example 3 (a) An emulsion of a polymer (H3) of 25 parts of styrene, 70 parts of methyl methacrylate and 5 parts of alphamethylstyrene was obtained instead of 100 parts of the monomer in Example 1 (a). The composition of the polymer is 69% methyl methacrylate,
Styrene 26%, alpha methyl styrene 5%, yield 94%
Met.

(B) Graft polymerization was carried out in the same manner by using 12 parts of styrene and 28 parts of methyl methacrylate instead of the monomer in Example 1 (b) to prepare an emulsion of the graft product (G3).

After the completion of polymerization, the emulsion of H3 and the emulsion of G3 were mixed and treated in the same manner as in Example 1 to obtain a powder of a blend (FH3).

(C) Pellets of a hard thermoplastic resin composition were produced with the following formulation in the same manner as in Example 1 (Experiment Nos. 1 to 4 are also examples of the present invention).

(D) Thermal stability test A test was conducted in the same manner as in Example 1. The results (Y1) are shown in Table 3.

Example 4 An experiment was performed in the same manner as in Example 1 except that 25 parts of acrylonitrile and 3 parts of methyl acrylate were used instead of 28 parts of acrylonitrile of Example 1 (a). The results are shown in Table 4.

Example 5 An emulsion of polymer (H4) was prepared by substituting 100 parts of styrene (100 parts) for 100 parts of the monomer in (a) of Example 1. Graft polymerization was also carried out in the same manner as in Example 2 (b) except that 40 parts of the monomer was replaced with styrene (40 parts).
A graft product (G4) was produced. Thereafter, a blended product (FH4) was produced in the same manner as in Example 1. Next, Example 3 (c)
FH4 was used instead of FH3 of Experiment No., and pellets of the hard thermoplastic resin composition were produced in the same manner. After this, a thermal stability test was conducted in the same manner as in Example 1 (d). The results are shown in Table 5.

Claims (1)

[Claims] 1. [I] (A) (1) 10 to 100% by weight of vinylidene aromatic hydrocarbon, (2) 0 to 40% by weight of acrylonitrile, (3) 0 to 90% by weight of methyl methacrylate,
(4) Maleimide compound 0 to 40% by weight, (5) Thermoplastic polymer consisting of ethylene compound 0 to 30% by weight copolymerizable therewith 30 to 95% by weight (B) (1) Butadiene 0 to 100 % By weight, (2) 0 to 98.8% by weight of butyl acrylate, (3) 0 to 40% by weight of a monoethylene compound copolymerizable therewith, (4) 2 or more ethylenically unsaturated bonds copolymerizable with them. Based on a polymer consisting of 0 to 5% by weight of the compound (hereinafter referred to as a rubber-based polymer) in the presence of (1) vinylidene aromatic hydrocarbon 10 to 100% by weight,
(2) Acrylonitrile 0-40% by weight, (3) Methyl methacrylate 0-90% by weight, (4) Maleimide compound 0-40% by weight, (5) Monoethylene compound 0-30 copolymerizable with these %, (6) 70 to 5% by weight of a graft copolymer obtained by polymerizing a mixed monomer of 0 to 5% by weight of a compound having two or more ethylenic unsaturated bonds copolymerizable therewith. The rubber-based polymer contained in 2 to 40
100 parts by weight of a resin mixture such that the amount of [II] 2,2'-oxamidobis- [ethyl-3- (3,5-
Ditertiarybutyl-4-hydroxyphenyl) propionate] 0.001 to 2.0 parts by weight [III] magnesium, calcium, strontium,
A hard thermoplastic resin composition comprising 0.01 to 5.0 parts by weight of a divalent metal oxide, hydroxide, carbonate or organic carboxylate selected from the group consisting of barium.