JPH0747677B2 - Matte resin composition with excellent impact resistance and processability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention provides impact resistance and processability by blending a rubber-reinforced styrene-based thermoplastic resin with a specific graft polymer and a specific copolymer. The present invention relates to an excellent matte resin composition.

<Prior art> Rubber-reinforced styrene thermoplastic resins such as high-impact polystyrene (HIPS), ABS resin, MBS resin, AES resin, and AAS resin have excellent moldability and physical property balance, and are used in many fields. Particularly in the vehicle field, it is widely used for interior and exterior parts of automobiles, and has become a representative resin material for automobiles along with polypropylene and the like.

Recently, the interior parts for automobiles are required to have a matt finish in order to emphasize safety and harmony with other parts.

As a method of obtaining a matte part, there are a method of improving from the mold surface such as thin embossing and a method of modifying from the material side. In the improvement from the mold surface, the resin is completely adhered to the mold at the time of molding, so the mold surface is heavily worn, frequent embossing is required, and the gloss condition also depends on the molding conditions. It On the other hand, from the material side, a method of adding a filler and addition of a rubbery polymer have been proposed, but addition of a filler is not preferable in terms of appearance and physical properties, and in the case of adding a rubbery polymer, the processability is poor, and the flow There is a defect that marks and weld marks are generated.

In recent years, a matting composition prepared by blending a copolymer composed of styrene with an unsaturated carboxylic acid or an unsaturated epoxy compound has been proposed, but it has a problem of poor balance between impact resistance and processability.

Therefore, under the present circumstances, it is desired to develop a composition having a good balance between impact resistance and processability and excellent matte properties.

<Means for Solving Problems> As a result of earnest studies on the above problems, the present inventors have found that a rubber-reinforced styrene thermoplastic resin (A) and an ethylene-α-olefin rubber (b-1) are present. Below, a graft polymer (B) obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound and / or an unsaturated carboxylic acid alkyl ester compound (b-2) and an unsaturated epoxy compound (b-3), and an aromatic One or more compounds (c-1) selected from the group consisting of group vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid alkyl ester compounds and unsaturated carboxylic acid compounds, unsaturated epoxy compounds, hydroxyl group-containing compounds, nitrogen-containing compounds Copolymer (C) with one or more compounds (c-2) selected from the group consisting of base-containing compounds
And (A), (B) and (C) as 100 parts by weight, (A) 40 to 99.8 parts by weight, (B) 0.1
The present invention provides a matte resin composition having excellent impact resistance and processability, which is characterized in that the content is -50 parts by weight and (C) 0.1-50 parts by weight.

Hereinafter, the composition of the present invention will be described in detail.

Rubber-reinforced styrene-based thermoplastic resin (A) Rubber-reinforced styrene-based thermoplastic resin (A) in the present invention
Means an aromatic vinyl compound (a-2) or an aromatic vinyl compound (a-2) and a vinyl cyanide compound and / or an unsaturated carboxylic acid alkyl ester compound in the presence of the rubbery polymer (a-1). It is a resin obtained by polymerizing (a-3). The resin is composed of a (co) polymer (a-2 homopolymer or a-2-a-3 copolymer) produced as a by-product during polymerization, or a separately produced above compound (co). It may include a polymer.

There is no particular limitation on the composition ratio of the rubbery polymer (a-1) and the compound (a-2 or the total of a-2 and a-3) in the resin (A), but the composition ratio of impact resistance and processability is not limited. From the standpoint of balance, the content of the rubbery polymer is preferably 5 to 70% by weight.

Examples of the rubbery polymer (a-1) include polybutadiene, butadiene-styrene polymer, butadiene-acrylonitrile polymer, polyisoprene, polychloroprene, ethylene-propylene polymer, ethylene-propylene-non-conjugated diene polymer, polybutyl. Acrylate, ethylene
Examples thereof include vinyl acetate polymers and chlorinated polyethylene, and one kind or two or more kinds can be used.

In particular, conjugated diene rubbers such as polybutadiene, butadiene-styrene polymer, butadiene-acrylonitrile polymer and ethylene-propylene polymer, ethylene-
Ethylene-α-olefin based rubbers such as propylene-non-conjugated diene polymers are preferred.

Examples of the aromatic vinyl compound (a-1) include styrene and α
-Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, α
-Methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromstyrene, dibromostyrene, vinylnaphthalene, etc. are exemplified, and one kind or two or more kinds can be used. Particularly preferred is styrene.
Examples of the vinyl cyanide compound, which is the compound (a-3) capable of forming the rubber-reinforced styrene-based thermoplastic resin (A) together with the aromatic vinyl compound (a-2), include acrylonitrile, methacrylonitrile, and ethacrylonitrile. , Fumaronitrile, etc. are exemplified, and one kind or two or more kinds can be used. Acrylonitrile is particularly preferable.

As the unsaturated carboxylic acid alkyl ester compound, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and the like are exemplified, and one kind or two or more kinds can be used. Methyl methacrylate is particularly preferable.

The composition ratio of the compound used is not particularly limited, but from the viewpoint of impact resistance, processability, heat resistance, chemical resistance, etc., the aromatic vinyl compound (a-2) 30 to 100% by weight, particularly 50 to 80% by weight, vinyl cyanide compound and / or unsaturated carboxylic acid alkyl ester compound (a-3) 0 to 70% by weight, particularly 20 to 50% by weight are preferable.

Examples of the method for producing the rubber-reinforced styrene thermoplastic resin (A) include an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution gun method, an emulsion-suspension polymerization method, and a bulk-suspension polymerization method. .

Graft polymer (B) The graft polymer (B) in the present invention means ethylene-
Aromatic vinyl compound, vinyl cyanide compound and / or unsaturated carboxylic acid alkyl ester compound (b-2) and unsaturated epoxy compound (b-3) are polymerized in the presence of α-olefin rubber (b-1). It is a graft polymer obtained by.

The ethylene-α-olefin rubber (b-1) constituting the graft polymer (B) is a binary copolymer (EPR) consisting of ethylene and propylene or butene, ethylene, propylene or butene and a non-conjugated diene. It is a terpolymer (EPDM) or the like, and is used alone or in combination of two or more.

As the non-conjugated diene in the terpolymer (EPDM),
Dicyclopentadiene, ethylidene norbornene, 1.4
-Hexadiene, 1.4-cycloheptadiene, 1.5-cyclooctadiene and the like.

The molar ratio of ethylene to propylene or butene in the binary copolymer (EPR) and the ternary copolymer (EPDM) is preferably in the range of 5: 1 to 1: 3.

Further, in the terpolymer (EPDM), the proportion of the non-conjugated diene is preferably in the range of 2 to 50 in terms of iodine value.

An aromatic vinyl compound constituting the graft polymer (B),
The vinyl cyanide compound or the unsaturated carboxylic acid alkyl ester compound is the compound described in the section of the rubber-reinforced styrene-based thermoplastic resin described above.

The unsaturated epoxy compound (b-3) constituting the graft polymer (B) is a compound having one or more polymerizable unsaturated bond and one or more epoxy group in each molecule. Examples of such unsaturated epoxy compounds include those represented by the general formula (Wherein R represents a hydrocarbon group having a polymerizable ethylenically unsaturated bond) and an unsaturated glycidyl ester represented by the general formula (Here, R is the same as that of the formula [I], X is —CH ₂ —O
-Or An unsaturated glycidyl ether represented by the formula: and a general formula (Here, R is the same as that of the formula [I], R'is hydrogen or a methyl group), and the like epoxy alkene.

Specifically, glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid, mono-, di- and triglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo [2.2 .1] Mono- and diglycidyl esters of hept-5-ene-2,3-dicarboxylic acid (trade name nadic acid), endo-cis-bicyclo [2.2.1] hept-5-en-2-methyl- Mono- and diglycidyl esters of 2,3-dicarboxylic acid (trade name: methyl nadic acid), mono- and diglycidyl esters of allyl succinic acid, glycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene -P-glycidyl Ter or p-glycidyl styrene, 3.4-epoxy-1-butene, 3.4-epoxy-3-methyl-1-butene, 3.4-epoxy-1-pentene, 3.4-epoxy-3-methyl -1-Pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like can be mentioned.

The composition ratio of the ethylene-α-olefin rubber and each compound when polymerizing the graft polymer (B) is not particularly limited, but from the viewpoint of physical properties of the final resin composition, the ethylene-α-olefin rubber (b-1 ) 10 to 2000 parts by weight of aromatic vinyl compound and vinyl cyanide compound and / or unsaturated carboxylic acid alkyl ester compound (b-2) and 0.5 to 800 parts by weight of unsaturated epoxy compound (b-3) per 100 parts by weight. Is preferred. Particularly, 20 to 1000 parts by weight of the compound (b-2) and 1 to 400 parts by weight of the unsaturated epoxy compound (b-3) are preferable per 100 parts by weight of the rubber (b-1).

Also, the polymerization method for obtaining the graft polymer (B) is not particularly limited, and emulsion polymerization method, bulk polymerization method, suspension polymerization method,
Known methods such as a solution polymerization method can be used.

Copolymer (C) The copolymer (C) in the present invention is one or more compounds (c-1) selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and unsaturated carboxylic acid alkyl ester compounds. ) And one or more compounds (c-2) selected from the group consisting of unsaturated carboxylic acid compounds, unsaturated epoxy compounds, hydroxyl group-containing compounds, and nitrogen-containing base-containing compounds.

The aromatic vinyl compound, vinyl cyanide compound or unsaturated carboxylic acid alkyl ester compound is the compound mentioned in the section of the rubber-reinforced styrene thermoplastic resin described above.

Examples of unsaturated carboxylic acid compounds include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, and one or more of them can be used.

As the unsaturated epoxy compound, a graft polymer (B)
Are the compounds listed in the section.

Examples of the hydroxyl group-containing compound include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate, and one kind or two or more kinds can be used.

As the nitrogen-containing base-containing compound, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, Examples of N-vinylimidazole, N-vinylindole, N-vinylcarbazole, N-vinylpyrrole, p-aminostyrene, p-dimethylaminostyrene can be used alone or in combination of two or more.

The composition ratio of the compound (c-1) and the compound (c-2) constituting the copolymer (C) is not particularly limited, but the final composition may have impact resistance, processability, matteness, etc. From the surface, the compound (c
-1) 99 to 30% by weight, particularly 95 to 50% by weight, compound (c-
2) 1 to 70% by weight, particularly 5 to 50% by weight is preferable.

Further, the compound (c-1) and the compound in the compound (c-2) are also not particularly limited, but as the compound (c-1), an aromatic vinyl compound alone, an unsaturated carboxylic acid alkyl ester compound alone or an aromatic compound is used. A combination of a vinyl compound and / or an unsaturated carboxylic acid alkyl ester compound and a vinyl cyanide compound is preferable.

As a method for producing the copolymer (C), an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or a combination of these methods is used.

Preferred examples of the copolymer (C) include styrene- (meth) acrylic acid copolymer, acrylonitrile-styrene- (meth) acrylic acid copolymer, methylmethacrylate- (meth) acrylic acid copolymer, styrene- Methyl methacrylate- (meth) acrylic acid copolymer, styrene-
Glycidyl methacrylate copolymer, methyl methacrylate-glycidyl methacrylate copolymer, styrene-
Acrylonitrile-glycidyl methacrylate copolymer, styrene-methyl methacrylate-glycidyl methacrylate copolymer, styrene-hydroxyethyl (meth) acrylate copolymer, acrylonitrile-styrene-hydroxyethyl (meth) acrylate copolymer,
Styrene-dimethylaminoecyl (meth) acrylate copolymer, acrylonitrile-styrene-dimethylaminoethyl (meth) acrylate copolymer, styrene-diethylaminoethyl (meth) acrylate copolymer, acrylonitrile-styrene-diethylaminoethyl (meth) Acrylate copolymers, styrene-2-vinylpyridine copolymers, acrylonitrile-styrene-2-vinylpyridine copolymers and the like can be mentioned, and one kind or two or more kinds can be used.

Resin Composition The resin composition of the present invention comprises the rubber-reinforced styrene thermoplastic resin (A), the graft polymer (B) and the copolymer (C) described above, and the compounding ratio thereof is (A), (B)
And the total of (C) is 100 parts by weight, (A) 40 to 99.
8 parts by weight, (B) 0.1 to 50 parts by weight and (C) 0.1 to 50 parts by weight.

If the rubber-reinforced styrene-based thermoplastic resin (A) is less than 40 parts by weight, the balance between impact strength and workability will be deteriorated, and if it exceeds 99.8 parts by weight, the matting effect will be insufficient. Preferably 70-
It is 99 parts by weight. If the amount of the graft polymer (B) or the copolymer (C) is less than 0.1 parts by weight or more than 50 parts by weight, the balance between impact strength and processability is poor. Preferably 0.5 each
~ 15 parts by weight.

There is no particular limitation on the mixing method of the rubber-reinforced styrene thermoplastic resin (A), the graft polymer (B) and the copolymer (C), and they are mixed in a latex state or in a state of powder, beads, pellets or the like. I can do things. The order of mixing them is also not particularly limited, and may be a method of collectively mixing the three components or a method of premixing the two components and mixing the remaining one component. As a melt-kneading method, a known method such as a Banbury mixer, a roll or an extruder can be adopted.

At the time of mixing, if necessary, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a dye, a pigment, a plasticity, a flame retardant,
Additives such as release agents can be added. Further, a thermoplastic resin such as polyacetal, polycarbonate, polybutylene terephthalate, polyphenylene oxide, polymethylmethacrylate, or polyvinyl chloride can be appropriately blended.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the number of parts and the percentage are all shown on a weight basis. Reference Example 1. Rubber-reinforced styrene thermoplastic resin (A) A-1: ABS resin A reactor substituted with nitrogen has an average particle size of 0.4 μm and a gel content. Rate 8
After charging 100% of polybutadiene latex having 0% solid content of 50%, 0.3 part of potassium persulfate and 100 parts of pure water, the temperature was raised to 65 ° C. with stirring. After that, a mixed monomer solution consisting of 15 parts of acrylonitrile, 35 parts of styrene and 0.2 part of t-dodecyl mercaptan and disproportionated potassium rosinate 2
30 parts of an emulsifier aqueous solution containing 10 parts of each was continuously added over 4 hours, and then the polymerization system was heated to 70 ° C. and aged for 3 hours to complete the polymerization to obtain an ABS graft copolymer latex.

Separately, 0.3 part of potassium persulfate and 120 parts of pure water were charged into a reactor purged with nitrogen, and then the temperature was raised to 65 ° C. with stirring. After that, 30 parts of acrylonitrile, 70 parts of styrene and 0.3 part of t-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of disproportionated potassium rosinate were continuously added for 4 hours each, and then the polymerization system was added. After heating to 70 ° C and aging for 3 hours to complete the polymerization, an acrylonitrile-styrene copolymer latex is obtained, mixed with the graft copolymer latex, and then subjected to usual salting-out / drying treatment to obtain a rubber content of 15%. I got ABS resin.

A-2: Heat-resistant ABS resin In a reactor purged with nitrogen, pure water 150 parts, potassium persulfate 0.5
And 2 parts of sodium lauryl sulfate were charged, and the temperature was raised to 70 ° C. with stirring. Then 30 parts of acrylonitrile,
A mixed monomer solution consisting of 70 parts of α-methylstyrene and 0.2 parts of t-dodecyl mercaptan was continuously added over 5 hours, and then the polymerization system was heated to 75 ° C. and aged for 5 hours to complete the polymerization, and acrylonitrile A -α-methylstyrene copolymer latex was obtained.

Then, mixed with the above-mentioned graft copolymer latex,
A heat resistant ABS resin having a rubber content of 15% was obtained after usual salting out and drying treatment.

A-3: AES resin Based on a known suspension polymerization method, an ethylene-propylene-ethylidene norbornel polymer (propylene content 43%,
A graft polymer consisting of iodine value 9, Mooney viscosity 87) 50%, styrene 34% and acrylonitrile 16% was obtained.

Then, the above-mentioned acrylonitrile-styrene copolymer latex was mixed with a copolymer obtained by subjecting it to a salting out and drying treatment to obtain an AES resin having a rubber content of 20%.

Reference Example 2 Graft polymer (B) B-1: 50 parts of ethylene-propylene-dicyclopentadiene (iodine value 10, Mooney viscosity 60, propylene content 40%),
40 parts of styrene, 17 parts of acrylonitrile and 7 parts of glycidyl methacrylate were polymerized by a known solution polymerization method to obtain a polymer B-1.

B-2: Ethylene-propylene-ethylidene norbornene (iodine value 8, Mooney viscosity 61, propylene content 43%) 20
Parts, styrene 75 parts, acrylonitrile 25 parts, and glycidyl methacrylate 10 parts were polymerized by a known solution polymerization method to obtain a polymer B-2.

Reference Example 3 Copolymer (C) C-1: After 120 parts of pure water and 0.3 part of potassium persulfate were charged in a reactor substituted with nitrogen, the temperature was raised to 65 ° C. with stirring. Thereafter, 30 parts of acrylonitrile, 65 parts of styrene, 5 parts of methacrylic acid and 0.3 part of t-dodecyl mercaptan, and 30 parts of an emulsifier aqueous solution containing 2 parts of sodium dodecylbenzenesulfonate are continuously added for 4 hours, respectively. After that, the temperature of the polymerization system was raised to 70 ° C. and aged for 3 hours to complete the polymerization.

C-2: Acrylonitrile-styrene-glycidyl was prepared by changing 30 parts of acrylonitrile to 25 parts, 65 parts of styrene to 60 parts, and further changing 5 parts of methacrylic acid to 15 parts of glycidyl methacrylate and polymerizing in the same manner as C-1. A methacrylate copolymer was obtained.

C-3: An acrylonitrile-styrene-hydroxyethyl acrylate copolymer was produced in the same manner as C-1, except that 5 parts of methacrylic acid was replaced with 5 parts of hydroxyethyl acrylate.

C-4: A reactor purged with nitrogen was charged with 120 parts of pure water and 0.3 part of potassium persulfate, and then heated to 65 ° C. with stirring. After that, 30 parts of an emulsifier aqueous solution containing 25 parts of acrylonitrile, 60 parts of styrene, 15 parts of 2-vinylpyridine and 0.3 part of t-dodecyl mercaptan and 2 parts of disproportionated potassium rosinate were each added for 4 hours. After continuous addition, the polymerization system was heated to 70 ° C. and aged for 3 hours to complete the polymerization.

C-5: Acrylonitrile-styrene-diethylaminoethyl methacrylate copolymer was produced in the same manner as C-4 except that 15 parts of 2-vinylpyridine was replaced with 15 parts of diethylaminoethyl methacrylate.

Examples and Comparative Examples Rubber-reinforced styrenic thermoplastic resin (A
-1 to 3), a graft polymer (B-1 to 2) and a copolymer (C-1 to 5) or a known matting agent at a composition ratio shown in Tables -1 to 3, respectively, and a Banbury mixer. After kneading, pelletized. Various test pieces were prepared from the obtained pellets according to a conventional method, and each characteristic was measured. The obtained results are shown in Tables 1-3.

Impact resistance (notched Izod): ASTM D-256, 1 /
8 ″, “Kg · cm / cm”, 23 ℃ Workability: Koka type flow tester, 210 ℃ × 30kg / cm
² (* Comparative examples 9-10 using heat-resistant ABS resin, Examples 5-8
230 ℃ × 60kg / cm ²⁾ in, "cc / min" Gloss: 3.5 ounces using an injection molding machine 60 mm × 60 mm thickness 3m
A test plate of m is molded, and the gloss of the central part of the test plate is measured with a digital variable angle gloss meter UGV-4D manufactured by Suga Test Instruments Co., Ltd.
It was measured at °. "%"<Effect of the Invention> The composition of the present invention is characterized by being excellent in the balance of impact resistance and processability and in matting properties, as compared with the conventionally known compositions.

Claims (1)

[Claims] 1. A rubber-reinforced styrene thermoplastic resin (A),
In the presence of ethylene-α olefin rubber (b-1),
Aromatic vinyl compound and vinyl cyanide compound and / or unsaturated carboxylic acid alkyl ester compound (b-
2) and a graft polymer (B) obtained by polymerizing an unsaturated epoxy compound (b-3), and one or more selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and an unsaturated carboxylic acid alkyl ester compound. Of the compound (c-1) of (1) and one or more compounds (c-2) selected from the group consisting of unsaturated carboxylic acid compounds, unsaturated epoxy compounds, hydroxyl group-containing compounds, and nitrogen-containing base-containing compounds ( C), and (A) 40 to 99.8 parts by weight, (B) 0.1 to 50 parts by weight and (C) 0.1 to 10 parts by weight, with (A), (B) and (C) as 100 parts by weight in total. A matte resin composition excellent in impact resistance and processability, which is characterized by being 50 parts by weight.