JPS63260948A - High-rigidity, high-impact strength, weather-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in notched Izod strength and heat resistance, by mixing a specified thermoplastic resin with a phosphoric ester, an organic carboxylic acid, an ultraviolet absorber and an ultraviolet stabilizer. CONSTITUTION:100pts.wt. thermoplastic resin comprising 10-97wt.% graft copolymer obtained by graft-polymerizing 20-900pts.wt. mixture comprising 40-90wt.% aromatic vinyl monomer (a), 0-40wt.% vinyl cyanide monomer (b) and 0-40wt.% vinyl monomer (c) with 100pts.wt. rubber-like polymer comprising 60-99.99wt.% (1-13C) alkyl acrylate, 0-40wt.% vinyl or vinylidene monomer and 0.01-20wt.% crosslinking compound having at least two C-C unsaturated bonds in the molecule, 0-80wt.% copolymer comprising 40-90wt.% component (a), 0-40wt.% component (b) and 0-40wt.% component (c) and 5-90wt.% polycarbonate is mixed with 0.01-1.0pt.wt. organic phosphoric (phosphorous) ester and/or acid phosphoric (phosphorous) ester, 0.01-5pts.wt. organic carboxylic acid (anhydride), 0.05-5pts.wt. ultraviolet absorber and 0.05-5pts.wt. hindered amine ultraviolet stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a weather-resistant resin composition having high rigidity (and high impact strength).

The resin obtained from the composition according to the present invention is suitable for applications that are mainly used outdoors, such as various automobile parts, building materials, and coating materials, and that require impact resistance strength equivalent to that of conventional ABS resins. .

(Prior art and problems to be solved by the present invention) A in which resin is grafted onto rubber such as polybutadiene, SBR, etc.
BS resin has excellent physical properties such as impact resistance and moldability balance, so it is widely used in various office equipment, home appliances, etc. However, it leaves a large amount of unsaturated bonds in the rubber component. Therefore, it is susceptible to deterioration due to ultraviolet rays, ozone in the air, oxygen, etc., and due to the deterioration of physical properties caused by this, it has the disadvantage that there is a limit to its use outdoors. In order to improve this drawback, many attempts have been made to replace the gum component in ABS with a saturated rubber that is less susceptible to deterioration, such as acrylic rubber containing acrylic ester as a main component. When acrylic rubber is used as a component,
Weather resistance is significantly improved compared to when the component is unsaturated rubber, but on the other hand, when comparing the same rubber content, it has the disadvantage of low impact strength (especially notched Izod strength), and is equivalent to 8BS. In order to obtain the impact strength of the resin, the rubber content must be increased, and in this case, the rigidity and heat resistance of the resin will be greatly reduced.

On the other hand, polycarbonate is known as a resin with excellent impact strength, rigidity, and heat resistance, but although it has good DuPont impact and notch-free Izod strength, it does not have the presence of notches, which corresponds to the impact resistance when a molded product is damaged. The 1zod strength has thickness dependence, especially when the thickness is 174 inches.
It has the property of having low zod strength.

Polymer alloys containing acrylic rubber-containing resin (hereinafter abbreviated as AAS) and polycarbonate as constituent components have been known (Japanese Patent Publication No. 52-35697, Japanese Patent Application Laid-open No. 61-72).
054, JP-A-6L-148258), but these are
Although it contains ABS resin as a component and has an excellent balance of moldability, heat resistance, and impact resistance, it has poor weather resistance because it contains butadiene rubber.

Alloys of AAS and polycarbonate that do not contain ABS are also known (Special Publication No. 48-29308, Special Publication No. 49
-18779, JP-A-54-55, JP-A-58-17
43) However, these have some difficulty in moldability, so it is necessary to raise the molding temperature, and in that case, or when boiling in the molding machine, thermal decomposition of the polycarbonate is likely to be induced, resulting in As a result, flanche formation and strength reduction may occur.

The present inventor conducted intensive research to obtain a weather-resistant resin with excellent impact resistance and rigidity without these disadvantages, and found that AAS
and polycarbonate in a certain composition ratio, organic phosphate ester, organic phosphite ester, acid phosphate ester, acid phosphite ester and/or their metal salts, organic carboxylic acid and/or organic carboxylic acid. Surprisingly, the notched 1zod strength of the compound containing acid anhydride cannot be explained by the mere additive effect of both AAS (notched 1zod strength is low) and polycarbonate (notched 1zod strength is also low). Thickness 1
/4 inch), and has high rigidity, as well as a weather-resistant resin with good thermal stability during molding, leading to the present invention.

That is, the present invention comprises: Component A: 60 to 99.99% by weight of an acrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms, 0 to 40% by weight of a vinyl or vinylidene monomer copolymerizable therewith, and 100 parts by weight of a rubbery polymer consisting of 0.01 to 20% by weight of a crosslinkable compound having two or more carbon-carbon unsaturated bonds in one molecule, 40 to 90% by weight of an aromatic vinyl monomer, and cyanide. A graft copolymer obtained by graft polymerizing 20 to 900 parts by weight of a monomer mixture for graft polymerization consisting of 0 to 40% by weight of a vinyl monomer and 0 to 40% by weight of a vinyl monomer copolymerizable with these. 10 to 97% by weight of a polymer, component B: 40 to 90% by weight of an aromatic vinyl monomer, 0 to 40% by weight of a vinyl cyanide monomer, and 0 to 40% by weight of a vinyl monomer copolymerizable with these. Copolymer consisting of 0-8%
0% by weight, component C: 100 parts by weight of a thermoplastic resin consisting of 5 to 90% by weight of polycarbonate, an organic phosphoric acid ester,
Organic phosphites, acid phosphates, acid phosphites and/or metal salts thereof 0.01-1.
0 parts by weight, organic candade amine ultraviolet stabilizer 0.0
This is a weather-resistant resin composition with high rigidity and impact strength, containing 5 to 5 parts of the resin.

The present invention will be explained in detail below.

In the resin composition of the present invention, the resin component may consist only of component A and component C, but an aromatic vinyl monomer may be mixed therein as component B in an amount of 80% by weight or less. However, the excellent properties of the weather-resistant resin of the present invention are not impaired even if the weather-resistant resin of the present invention is used.

First, component A will be explained. The rubber component in component A is mainly composed of an acrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms, preferably methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethyl-hexyl acrylate. Vinyl or vinylidene monomers copolymerizable with, for example, styrenic monomers such as styrene, α-methylstyrene, and vinyltoluene, vinyl cyanide monomers such as acrylonitrile and α-chloroacrylonitrile, and carbon atoms of 1 to 1. 4
methacrylic acid alkyl ester having an alkyl group of
ff1 body, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylic acid amide,
It is also possible to copolymerize N,N'-dimethylacrylamide, vinylnorbornene, etc. in an amount not exceeding 40% by weight.

If it exceeds 40% by weight, the properties of the rubber such as rubber elasticity may be impaired, which is not preferable.

In an uncrosslinked state, acrylic rubber easily deforms during molding and processing, which can cause poor appearance of the molded product.
Impact strength is significantly reduced.

Therefore, during polymerization of rubber, two or more ;C=
It is necessary to add a crosslinking compound having a C unsaturated bond to carry out a certain degree of crosslinking simultaneously with polymerization. Examples of such crosslinking compounds include divinylbenzene, ethylene glycol diacrylate, diethylene glycol diacrylate-1, and diacrylate compounds such as triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate. Triacrylate compounds such as acrylate, ethylene glycol dimethacrylate,
Dimethacrylate compounds such as diethylene glycol dimethacrylate and triethylene glycol dimethacrylate, diaryl compounds such as diaryl phthalate and diaryl maleate, aryl unsaturated carboxylic acids such as aryl acrylate and aryl methacrylate, dicyclopentadiene, ethylidene norbornene, Examples include vinylnorbornene, norbornadiene, triallyl cyanurate, triallyl isocyanurate, and the like. The amount of these crosslinkable compounds to be used should be within a range of 20% by weight, preferably 10% by weight, in the rubber; if it exceeds 20% by weight, the rubber elasticity will drop significantly. Further, if it is less than 0.01% by weight, sufficient crosslinking effect cannot be obtained.

Although there are no particular limitations on the rubber polymerization method, emulsion polymerization is preferably carried out because it is easy to obtain rubber with a desired particle size. In this case, it is advantageous that the emulsion graft polymerization of the resin component can be carried out concurrently with the polymerization of the rubber.

Emulsifiers that can be used in the emulsion polymerization method include fatty acid soaps such as sodium stearate and potassium oleate, organic sulfonic acids such as disproportionated potassium rosinate, potassium lauryl sulfate, sodium dioctyl sulfosuccinate, and sodium dodecylbenzenesulfonate. Although fatty acid soaps or disproportionated rosin acid soaps may cause hydrolysis of acrylic acid alkyl esters, they should be prepared at around neutral pH 1, preferably at pH 4.
Preferred are organic sulfonate salts that can be polymerized in ~8.

Polymerization initiators that can be used in the emulsion polymerization method include peroxides such as benzoyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, hydrogen peroxide, sodium peroxide, ammonium persulfate, and potassium persulfate. azo catalysts such as azobisisobutyronitrile and reducing agents such as formaldehyde sulfoxylates, L-ascorbic acid, glucose, metal salts such as ferrous sulfate, cobalt chloride, pyrophosphoric acid or ethylenediamine 4 Examples include redox catalysts that use a chelating agent such as disodium acetate.

Among these, potassium persulfate, etc. may significantly lower the pH in the polymerization system due to decomposition, and sodium acetate, sodium carbonate, and hydrogen carbonate are used as buffering agents to avoid demulsification and corrosion of polymerization equipment. Preferably, a small amount of a salt of a weak acid, such as sodium, is added. Polymerization temperature is 30
~100°C, particularly preferably about 40~80°C.

In emulsion polymerization, it is possible to obtain a desired rubber particle size by using a known seed polymerization method.
It is appropriately controlled by the method and speed of monomer addition, the amount of emulsifier added, etc.

The preferred rubber particle diameter is 0.05-5μ, more preferably 0.1-3μ. If it is less than 0.05μ, the impact strength is insufficient, and if it exceeds 5μ, the gloss decreases, which is not preferable.

In component A, among the monomer mixture for graft polymerization to be graft-polymerized to rubber, the aromatic vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-7' tylstyrene, and chlorostyrene. Among them, styrene and α-methylstyrene are particularly preferred. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred. Vinyl monomers that can be copolymerized with these include acrylic acid alkyl esters having an alkyl group having 1 to 13 carbon atoms, methacrylic acid alkyl esters having an alkyl group having 1 to 4 carbon atoms, acrylic acid, methacrylic acid, etc. Examples include vinyl carboxylic acid monomers, acrylic acid amide, methacrylic acid amide, N-alkyl substituted maleimide, N-aromatic substituted maleimide, and the like. The amount of these monomer mixtures to be used is 20 to 900 parts by weight, preferably 50 to 500 parts by weight, per 100 parts by weight of rubber. The sex is also low. If the amount exceeds 900 parts by weight, the impact resistance will be insufficient.

The proportion of the aromatic vinyl monomer in the sit mixture compound is 40 to 90% by weight, but if it is less than 40 parts by weight, the moldability and dimensional stability of the resulting molded product will be impaired.

Furthermore, the proportion of vinyl cyanide monomer and other vinyl monomers in the monomer mixture is 0 to 40% by weight, respectively.
However, if it exceeds 40% by weight, moldability deteriorates, which is not preferable.

When grafting a monomer mixture for graft polymerization onto rubber, there are no particular restrictions on the polymerization method, but for rubbers obtained by emulsion polymerization, graft polymerization by emulsion polymerization or suspension polymerization is recommended from the viewpoint of operability. It is preferable to do so.

Suspension stabilizers that can be used in the suspension polymerization method include polyvinyl alcohol, methyl cellulose, carboxyethyl cellulose, gelatin, calcium phosphate, magnesium carbonate, bentonite, talc, and the like.

Emulsifiers that can be used in the emulsion polymerization method include fatty acid soaps such as sodium stearate and potassium oleate, organic sulfonic acids such as disproportionated potassium rosinate, potassium lauryl sulfate, sodium dioctyl sulfosuccinate, and sodium dodecylbenzenesulfonate. Examples include salt.

Addition methods for the monomer mixture for graft polymerization include bulk addition,
Although there are methods such as partial addition and continuous batch addition of all the monomers for graft polymerization, continuous batch addition is most preferable in order to effectively carry out graft copolymerization to the rubbery polymer. The polymerization temperature is preferably about 30 to 80°C, particularly about 50 to 75°C.

In addition, in performing graft polymerization to rubber in the present invention, sulfur compounds such as normal decyl mercaptan, t-dodecyl mercaptan, nonyl mercaptan, xantho, and gendisulfide, terpenes, tetrahydronaphthalene, and 9,10-dihydro anthracene are used. Chain transfer agents such as hydrocarbon compounds may also be used.

Next, component B will be explained. The aromatic vinyl monomers used in component B include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-7'tylstyrene, and chlorostyrene, and their substituted products. Among these, styrene and α-methylstyrene are particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile. Among these, acrylonitrile is particularly preferred.

Vinyl monomers that can be copolymerized with these have 1 to 1 carbon atoms.
acrylic acid ester monomer having 13 alkyl groups,
Methacrylic acid ester monomers having an alkyl group having 1 to 4 carbon atoms, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylic acid amide, acenaphthylene, N-vinylcarbazole, N-alkyl Examples include substituted maleimide, N-aromatic substituted maleimide, and the like.

The proportion of aromatic vinyl monomer in component B is 40 to 9
0% by weight, and that of vinyl cyanide monomer and other vinyl monomers is 0 to 40% by weight, respectively.The reason for limiting the range in this way is that This is because it was taken into consideration.

Any known polymerization method can be employed for the polymerization, such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, and precipitation polymerization of the produced polymer in a nonsolvent.

Next, the C component will be explained.

Polycarbonates that can be used as component C include bisphenol A, (4,4'-dihydroxydiphenyl)
ether and 2,2-(4,4'-dihydroxy-3
．． 5. It is a polymer with carbonate bonds synthesized from bisphenols such as 3',5'-tetrobromodiphenyl)propane and phosgene or diphenyl carbonate, and it is also a copolycarbonate (homo-bonded copolycarbonate) made from different bisphenols as raw materials. Modified polycarbonate resins such as polymers) or heterobond copolymers having carbonate bonds and other bonds, such as ester bonds, urethane bonds or siloxane bonds in the main chain, can be used as well.

In the composition of the present invention, the resin component is A consisting of A and B components.
It is composed of ASIO to 97% by weight, preferably 30 to 90% by weight, and polycarbonate as component C, 5 to 90% by weight, preferably 10 to 70% by weight. If the AAS content is less than 10% by weight, the moldability is extremely poor, and if it exceeds 97% by weight, that is, if the polycarbonate content is 5% by weight.
If it is less than that, the effect of improving rigidity is low.

In the composition of the present invention, examples of organic phosphate esters used as additives include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, Examples include trinonylphenyl phosphate, talesyl diphenyl phosphate, xylenyl diphenyl phosphate, octyl diphenyl phosphate, trilauryl phosphate, tricetyl phosphate, tristearyl phosphate, trioleyl phosphate, and halogen-substituted phosphates thereof.

Organic bone phosphate esters include trimethyl phosphite, triethyl phosphite, tributyl phosphite,
trioctyl phosphite, triisodecyl phosphite, triphenyl phosphite, tricresyl phosphite, tricylenyl phosphite, trinonylphenyl phosphite, talesyl diphenyl phosphite, trilauryl phosphite, tricetyl phosphite, tristearyl phosphite, trioleyl phosphite, di-2-ethylhexylhydrogen phosphite,
Examples include dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, triphenyl trithiophosphite, trilauryl trithiophosphite, tristearyl trithiophosphite, and halogen-substituted phosphites thereof.

Examples of acidic phosphoric acid esters include monomethyl 7-sidophosphate, dimethyl acid phosphate, monoisobrobyl acid phosphate, diisopropyl acid phosphate, monobutyl acid phosphate, dibutyl acid phosphate, monooctyl 7-sidophosphate, dioctyl acid phosphate, mono- Lauryl acid phosphate, dilauryl acid phosphate, monostearyl acid phosphate, distearyl acid phosphate, monophenylacenodophosphate, diphenyl acid phosphate, monocresyl acid phosphate, dibutyl acid phosphate, monononylphenyl acid phosphate, dinonylphenyl acid phosphates and their halogen-substituted acid phosphates.

Acidic phosphate esters include monomethyl acid phosphite, dimethyl acid phosphite, monoisopropyl acid phosphite, diisopropyl acid phosphite, monobutyl acid phosphite, dibutyl acid phosphite, monooctyl acid phosphite, dioctyl acid phosphite, Monolauryl acid phosphite, dilauryl acid phosphite, monostearyl acid phosphite, distearyl acid phosphite, monophenyl acid phosphite, diphenyl acid phosphite, monocresyl acid phosphite, dibutyl acid phosphite, monononylphenyl These include acid phosphites, dinonylphenyl acid phosphites, and their halogen-substituted acid phosphites.

Examples of the metal salts of acidic phosphates and acidic phosphates include Mg salts, zn salts, and aluminum salts of the acidic phosphates and acidic phosphates.

The amount of these added is 0.01 to 1.0 parts by weight, preferably 0.05 to 0.0 parts by weight, per 100 parts by weight of the resin component.
It is 8 parts by weight. If it is less than 0.01 part by weight, the effect of improving retention thermal stability during molding is small, and if it exceeds 1.0 part by weight, it may cause flash.

Specific examples of organic carboxylic acids and/or their anhydrides that are similarly used as additives in the present invention include terephthalic acid, cyclopenkunetetracarboxylic acid, trimellitic acid, transanicosotonic acid, and homophthalic acid. , diphenic acid, maleic acid, itaconic acid, ββ′ dithiodipropionic acid, furoic acid, etc., and their anhydrides include maleic anhydride, styrene-maleic anhydride copolymer, phthalic anhydride, trimellitic anhydride, pyroanhydride, etc. Examples include mellitic acid, diphenic anhydride, cyclobencunecarboxylic anhydride, benzophenonetetracarboxylic anhydride, norbornene 2,3 dicarboxylic anhydride, methylendomethylenetetrahydrophthalic anhydride, and the like. The amount of these additives added is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, per 100 parts by weight of the resin component. The reason for limiting the amount used is the same as described above.

In the present invention, [organic phosphate ester, organic phosphite ester, acid phosphate ester, acid surface phosphate ester and/or metal salt thereof] and [organic carboxylic acid and/or
or organic carboxylic acid anhydride” must be used in combination. If you try to achieve the effect only with the former phosphorus compound,
It is necessary to use more than 1.0 parts by weight of the phosphorus compound, which tends to cause flashing during molding retention.

From the composition of the present invention, a weather-resistant resin with extremely high notched 1zod strength (especially in the case of a thickness of 174 inches) and good rigidity and heat resistance can be obtained.Although the mechanism of its characteristic development is not clear, it has certain properties. AAS and polycarbonate mixed in a composition ratio form a special morphology to increase strength, and the addition of the aforementioned phosphorus compound prevents deterioration during molding retention and maintains physical properties at a high level. considered to be a thing. It is also possible that these phosphorus compounds and the like make some contribution to the formation of the morphology.

The composition of the present invention contains a UV absorber and a hindered amine UV stabilizer for the following reasons. It is generally said that saturated rubbers such as acrylic rubbers are less susceptible to deterioration due to light than polybutadiene rubbers, but when exposed to long-term irradiation with ultraviolet light of 300 nm or less, the polymer main chain breaks. Natural light does not have much light in this wavelength range, so it is not a big problem in practice, but in order to withstand longer outdoor use, it may be necessary to add UV absorbers or UV stabilizers. There is.

Preferred ultraviolet absorbers in the present invention are 2-(
2'-Hydroxy-5'-methylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)=5-chloro-benzotriazole, 2-(2'- Hydroxy-3'-[-butyl-5
'-Methylphenyl)-5-chloro-benzotriazole, 2-(2'-hydroxy-3-5'-di-t-amylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5 '-di-t-butylphenyl)-benzotriazole, 2-(2'-hydroxy-5'-t
-butylphenyl)-benzotriazole, 2-(2'
-hydroxy-5'- to -octylphenyl)-benzotriazole, 2-[2-hydroxy-3,←-bis(
α,α-dimethylbenzyl)phenyl)-2H-penztriazole, 2,2-methylenebis(4-(1,l.

3.3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2゜4-dihydroxy-benzophenone, 2-hydroxy-4-methoxybeny/sophenone, 2-hydroxy-4-methoxybenzophenone -5-sulfonic acid, 2-hydroxy-4-benzyloxybenzophenone, 2,2
'-dihydroxy-4-methoxyhensiphenone, 2-
Hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxypenzophenone, phenyl salicylate, 4-t-butylphenyl salicylate, 2. 4-di-t-butylphenyl-3
',5'-di-t-butyl-4'-hydroxybenzoate, ethyl-2-dia2-3,3-diphenylacrylate, bis(5-benzoyl-4-hydroxy-2-
methoxyphenyl)methane, 2-ethoxy-2'-ethyloxalic acid bisanilide, 2-ethoxy-
Examples include 5-t-butyl-2'-ethyloxalink aifudobisanilide. In addition, as a hindered amine ultraviolet stabilizer, bis(2,2,6,6-tetramethyl-4-piperidyl)sebaque, t, bis(2,2
, 6,6-tetramethyl-4-piperidyl)adipate, dimethyl succinate-1-(2-hydroxyethyl)-
4-hydroxy-2,2,6,6-titramethylpiperidine polycondensate, 2-(3,5-di-t-butyl-4-
Bis(hydroxybenzyl)-2-n-butylmalonate (
1,2,2,6,6-pankumethyl-4-piperidyl)
, poly((6-(1,l.

3.3-tetramethylbutyl)imino-1,3゜5-triazine-2,4-diyl)((2,2゜6.6-tetramethyl-4-piperidyl)imino]hexamethylene(
(2,2,6,6-tetramethyl-4-piperidyl)imino)), 2.2.6° 6-tetramethyl-4-piperiditul (N-methyl) and a mixture of tridecyl alcohol and 1,2° 3. Condensation product with 4-butane-tetra-carboxylin acid, 2.2.6.6-tetramethyl 4h'' compound of helicinol and tridecyl alcohol, and 1.2.3.4-butane-tetra Condensation product with carboxylin acindo, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, l, 2,2.6.6 -bentamethyl-4-piperidyl methacrylate, 2,2.
6,6-tetramethyl-4-piperidyl methacrylate and the like are preferably used.

Ultraviolet absorbers and hindered amine ultraviolet stabilizers are very effective when used in combination, and the amount used is
0.05 to 5 parts by weight or 0.1 to 3 parts by weight, respectively.

If the amount is less than 0.05 parts by weight, the effect will be low, and if it exceeds 5 parts by weight, the softening point temperature of the resin will drop significantly and the gloss will deteriorate. It also causes flash.

The composition of the present invention includes the above-mentioned A component, B component, C component, "
Organic phosphate esters, organic phosphites, acid phosphates, acid phosphites and/or metal salts thereof,” “organic carboxylic acids and/or organic carboxylic acid anhydrides,” ultraviolet absorbers, and hindered amines. Although an ultraviolet stabilizer is mixed therein, there are no particular restrictions on the mixing method, and known means can be used. Examples of such means include a Banbury mixer, a Henschel mixer, a tumbler mixer, a mixing roll, and a single-screw or twin-screw extruder. As for the mixing form, there are methods of obtaining the composition by ordinary melt mixing, melt kneading at various stages using master pellets, etc., and blending in a solution.

Furthermore, stabilizers, flame retardants, desensitizers, lubricants, colorants, and fillers such as talc, silica, clay, and calcium carbonate may be added to the composition of the present invention, if necessary.

(Examples) Hereinafter, the present invention will be further explained by examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded. Note that all parts and percentages in the examples are expressed on a weight basis.

200ml of ion-exchanged pure water in an autoclave equipped with a stirrer
1 part, 0.6 part of sodium acetate, and 0.5 part of sodium dodecylbenzenesulfonate, and heated to 70°C with stirring.
After the temperature was raised to 0.1, and 0.15 parts of potassium persulfate was added, a mixture of 100 parts of butyl acrylate, 2.5 parts of divinylbenzene, and 0.15 parts of triallyl isocyanurate was continuously added over 3 hours. After the addition, stirring was continued for an additional 5 hours at 70°C. The polymerization rate of butyl acrylate is 99
．． It was 7%. The weight average particle size of the rubber latex synthesized here was determined to be 0.12μ using a calibration curve showing the relationship between absorbance and weight average particle size using polystyrene latex with a known weight average particle size. Further, when the latex was observed using an electron microscope, the particle diameter was found to be almost uniform. The rubber latex obtained here is
It is called x-■.

(2) Rubber polymerization (seed 2) L obtained in (1)
10 parts of x-■ in terms of solid content, 170 parts of ion-exchanged pure water, 0.4 parts of sodium acetate, and 0.2 parts of sodium dodecylbenzenesulfonate were placed in an autoclave equipped with a stirrer, heated to 70°C, and then filtered. After adding 0.12 parts of potassium sulfate, a mixture of 100 parts of butyl acrylate, 2 parts of divinylbenzene, and 0.2 parts of triallyl isocyanurate was continuously added over 6 hours. 3 more at 70℃ after addition
Polymerization was continued with stirring for an hour. The polymerization rate of butyl acrylate was 98.2%, and the particle size was 0.26μ, which was almost uniform. The obtained rubber latex is Lx-■
shall be.

(3) Rubber charging (3rd seed) 10 parts of Lx-■ in terms of solid content, 170 parts of ion-exchanged pure water, 0.4 parts of sodium acetate, and 0.2 parts of sodium dodecylbenzenesulfonate in an autoclave equipped with a stirrer. After raising the temperature to 70°C and adding 0.10 parts of potassium persulfate, a mixture of 100 parts of butyl acrylate, 2 parts of divinylbenzene, and 1-0.4 parts of triallyl isocyanurate was added continuously for 7 hours. added to. After addition, keep at 70°C for an additional 3 hours.
Polymerization was completed. The final polymerization rate of butyl acrylate is 9
9.1%, particle size is almost uniform, average particle size 0.0
It was 5μ. The obtained rubber latex is designated as Lx-〇.

Pressure-go J! Goshihito Otsu L1 gold Lx-■, Lx-■ are 45 parts and 5 parts, respectively, in terms of solid content.
5 parts of ion-exchanged pure water, 300 parts of ion-exchanged pure water, and 0.5 parts of sodium dodecylbenzenesulfonate were placed in an autoclave equipped with a stirrer, and after raising the temperature to 50°C, 0.3 parts of sodium formaldehyde sulfoxylate, 75 parts of ethylene, and 25 parts of acrylonitrile were added. 1 part, 0.3 parts of t-dodeosylmercabutane, and 0.18 parts of t-butylperl-xyacetate are added continuously over a period of 5 hours. After the addition, 0.1 part of t-butyl peroxyacetate was added, the temperature was raised to 75°C, and stirring was continued for an additional 3 hours. The polymerization rates of styrene and acrylonitrile were determined by gas chromatography.
．． Values of 0% and 97.0% were obtained. The obtained latex was coagulated with calcium chloride, washed with water, and dried to obtain a graft copolymer as a white powder. This will be referred to as polymer (2).

Experimental Example 2 Synthesis of Component A In Experimental Example 1(3), 100 parts of Lx-■ was used as the rubber latex in terms of solid content, and all operations were the same as in Experimental Example 1(3) except that Lx-■ was not used at all. A graft copolymer (Polymer ■) was obtained.

, Example 3 Synthesis of A Synthesis In Experimental Example 1(3), all operations were performed in the same manner as in Experimental Example 1(3), except that 100 parts of Lx-■ was used in terms of solid content as the rubber latex, and the graft copolymer ( Polymer (■) was obtained.

Experimental Example 4 Synthesis of B composition 60 parts of styrene, 30 parts of acrylonitrile, α-methyl, 10 parts of styrene, 0.5 part of sodium dodecylbenzenesulfonate, and 250 parts of ion-exchanged pure water were charged into an autoclave equipped with a stirrer, and 70 parts of styrene was charged. After raising the temperature to 0.degree. C., 0.1 part of potassium persulfate was added to initiate polymerization. Six hours after the start of the polymerization, 0.05 part of potassium persulfate was further added, and the temperature was raised to 80°C and maintained for 2 hours to complete the polymerization. The polymerization rate was 99.5%. The obtained latex was coagulated with calcium chloride, washed with water, and dried to obtain a white powder copolymer, which was designated as Polymer (2).

Oarashi Tekjou Niko A component, B component, C component (Kijin Panrai I-Ni-1130
0W) in the proportions shown in the table, and to this were added 0.03 parts of triisodecyl phosphite, 0.04 parts of monoisopropyl acid phosphate, and 0.0 parts of trimellitic anhydride.
03 parts, norbornene anhydride 2,3 dicarboxylic acid 0.04
Part, styrene-maleic anhydride copolymer (S
MA resin, molecular weight 2000) 0.1 part, pentaerythrityl-tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) 0. parts, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-
10.5 parts of tetrakis(2-yl)phenol, tetrakis(2,2
,6,6-tetramethyl-4-piperidyl) -1,2
, 0.5 part of 3,4-butanetetracarboxylate was added thereto, followed by mixing using a Henschel mixer. This mixture was extruded into pellets using a screw extruder equipped with a 30 mφ devolatilization device. This pellet is made into an injection molding machine for 27
After molding at 0°C, physical properties were measured and the results are shown in Table 1.

Other additives were added in the same manner as in the examples.Triisodecyl phosphite, monoisopropyl acid phosphate, trimellitic anhydride, norbornene anhydride.2.
The same formulation as in Example was carried out except that 3 dicarboxylic acid and styrene-maleic anhydride copolymer were not added at all, pelletization and molding were carried out, and physical properties were measured. The results are shown in Table 1.

1 Comparison 1 -1300 (Bellet) was molded on Kijin Panlite, and the physical property measurement results are shown in Table 1.

This served as a control for the test.

Physical properties were measured by the following method.

1) Izod strength: Measured according to ASTM-D256.

2) Bending: Measured according to ASTM D-790.

3) Vicat softening point temperature: ASTM D at 5kg load
-1525.

4) Retention thermal stability: inside the cylinder of the molding machine (280°C)
After staying for 35 seconds and 600 seconds, it is molded and Iz
Changes in od intensity were investigated.

5) Weather resistance: Carbon Arc Sunshine Weather)
- 83℃ (WE-5IIN-DC type)
Iz of 600 hours after irradiating the Izod piece with light (no rain)
This was investigated by measuring the od intensity.

6) Electron microscopy: After staining the rubber particles by mixing the sample latex with a 1% uranyl acetate solution at a volume ratio of 1:1, drop it onto a collodion membrane and dry it, then use a transmission electron microscope JE? Observation was made using 12QOCX at an accelerating voltage of 100 kV.

(Effects of the Invention) The composition of the present invention, that is, a blend of AAS and polycarbonate at a certain composition ratio, contains a(sub)phosphoric acid ester, an acidic(sub)phosphoric acid ester, and an organic carboxylic acid (anhydride). It is clear from Table 1 that the blended resin provides a weather-resistant resin that has extremely high notched 1zod strength, is rigid, and has excellent thermal stability during molding.

Patent applicant: Denki Kagaku Kogyo Co., Ltd. Procedural amendment May 1, 1986 Commissioner of the Patent Office Kuro 1) Mr. Akio 1. Display of incident 3. Person who makes corrections Relationship to the case Patent applicant Claims column and Detailed description of the invention column of the specification 5. Contents of correction (1) The scope of claims is amended as shown in the attached sheet.

(2) "Boiling distillation" on page 4, line 19 of the specification is replaced with "retention"
(3) "97% by weight" on page 6, line 9 of the specification is corrected to "95% by weight."

(4) "10-97% by weight" on page 17, line 4 of the specification is corrected to "10-95% by weight."

(5) “97% by weight” on page 17, line 8 of the specification is changed to “95% by weight”
Correct to ``% by weight''.

(6) "rO,05μ" on page 30, line 8 of the specification is rO,
Corrected to 50μ.

(7) “Experimental Example 1 (3)” on page 31, line 12 of the specification
is corrected to "Experimental Example 1 (3) and".

(8) Table 1 on page 36 of the specification and Table 1 on page 37 (
(Continued) shall be corrected as shown in the attached sheet.

Claims Component A: A rubber-like substance consisting of 60 to 99.99% by weight of an acrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms, and 0.01 to 20% by weight of vinyl or vinylisopropylene copolymerizable therewith. Graft polymerization consisting of 100 parts by weight of a polymer, 40 to 90% by weight of an aromatic vinyl monomer, 0 to 40% by weight of a vinyl cyanide monomer, and 0 to 40% by weight of a vinyl monomer copolymerizable with these. 10 to 95% by weight of a graft copolymer obtained by graft polymerization of 20 to 900 parts by weight of a monomer mixture for use, and component B: 40 to 90% by weight of aromatic vinyl monomer, vinyl cyanide monomer. Copolymer 0-8 consisting of 0-40% by weight and 0-40% by weight of a vinyl monomer copolymerizable with these
0% by weight, component C: 100 parts by weight of a thermoplastic resin consisting of 5 to 90% by weight of polycarbonate, an organic phosphoric acid ester,
Organic phosphites, acid phosphates, acid phosphites and/or metal salts thereof 0.01-1.
0 parts by weight, organic carboxylic acid and/or organic carboxylic acid anhydride o, oi - 5 parts by weight, ultraviolet absorber 0.05 - 5 parts by weight, and hindered amine ultraviolet stabilizer 0.05 - 5 parts by weight
A weather-resistant resin composition with high rigidity and impact strength, containing 5 parts by weight.

Claims (1)

[Claims] Component A: 60 to 99.99% by weight of an acrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms, and 0 to 40% by weight of a vinyl or vinylidene monomer copolymerizable therewith. and 100 parts by weight of a rubbery polymer consisting of 0.01 to 20% by weight of a crosslinkable compound having two or more carbon-carbon unsaturated bonds in one molecule, 40 to 90% by weight of an aromatic vinyl monomer, A graft obtained by graft polymerization of 20 to 900 parts by weight of a monomer mixture for graft polymerization consisting of 0 to 40% by weight of a vinyl cyanide monomer and 0 to 40% by weight of a vinyl monomer copolymerizable with these. 10 to 97% by weight of copolymer, component B: 40 to 90% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and 0 to 40% of vinyl monomer copolymerizable with these. Copolymer consisting of 0-8% by weight
and component C: 5 to 90% by weight of polycarbonate, to 100 parts by weight of a thermoplastic resin, an organic phosphoric acid ester, an organic phosphorous acid ester, an acidic phosphoric acid ester, an acidic phosphite and/or Those metal salts 0
．． 01 to 1.0 parts by weight, organic carboxylic acid and/or organic carboxylic acid anhydride 0.01 to 5 parts by weight, ultraviolet absorber 0
．． A weather-resistant resin composition comprising: 0.05 to 5 parts by weight, and 0.05 to 5 parts by weight of a hindered amine ultraviolet stabilizer.