JPH01306457A - Lusterless resin composition excellent in impact resistance and processability - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in delustered nature and balance between impact resistance and processability by incorporating a rubber- reinforced styrene-based thermoplastic resin with each specified amount of each specific graft polymer and copolymer. CONSTITUTION:The objective composition can be obtained by incorporating (A) 40-99.8 pts.wt. of a rubber-reinforced styrene-based thermoplastic resin with (B) 0.1-50 pts.wt. of a graft polymer prepared by polymerization, in the presence of B1: an ethylene-alpha-olefin rubber, of B2: at least one kind of compound selected from aromatic vinyl compounds, vinyl cyanide compounds, etc., and B3: a unsaturated epoxy compound, and (C) 0.1-50 pts.wt. of a copolymer from C1: at least one kind of compound selected from aromatic vinyl compounds, vinyl cyanide compounds, etc., and C2: at least one kind of compound selected from unsaturated carboxylic acid compounds unsaturated epoxy compounds, hydroxyl group- contg. compounds, etc.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to a rubber-reinforced styrenic thermoplastic resin blended with a specific graft polymer and a specific copolymer to improve impact resistance and processability. This invention relates to an excellent matte resin composition.

<Conventional technology> Rubber-reinforced styrenic thermoplastic resins such as high-impact polystyrene (H-PS), ABS resin, MBS resin, ABS resin, and AAS resin have excellent moldability and physical property balance, and are applied in many fields. There is. 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 others.

Recently, there has been a demand for automobile interior parts to be matte due to the emphasis on safety and harmony with other parts.

Methods for obtaining matte parts include a method of improving from the mold surface, such as thin embossing, and a method of modifying from the material surface. When improving the mold surface, the special molding resin is completely adhered to the mold, which causes severe wear on the mold surface and requires frequent embossing, and the gloss condition also depends on the molding conditions. Ru. On the other hand, from the materials perspective, adding fillers and adding rubbery polymers have been proposed, but adding fillers is unfavorable in terms of appearance and physical properties, and adding rubbery polymers has poor processability and flow. There is a drawback that marks and weld marks occur.

In recent years, matte compositions containing copolymers of styrene and unsaturated carboxylic acids or unsaturated epoxy compounds have been proposed, but these compositions have the problem of poor balance between impact resistance and processability.

Therefore, it is currently desired to develop a composition that has an excellent balance between impact resistance and processability as well as excellent matte properties.

<Means for Solving the Problems> As a result of intensive research into the above-mentioned problems, the present inventors found that rubber-reinforced styrene thermoplastic resin (A) and ethylene-α olefin rubber (b-1) In the presence of one or more compounds (b-2) selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid alkyl ester compounds and unsaturated epoxy compounds (b-
3) and one or more compounds (C-1) selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, an unsaturated carboxylic acid alkyl ester compound and an unsaturated carboxylic acid. one or more compounds selected from the group consisting of compounds, unsaturated epoxy compounds, hydroxyl group-containing compounds, and nitrogen-containing base-containing compounds (C-
2) and a copolymer (C), and (A), (
G) and (Q) is 100 parts by weight, (A)
49 to 99.8 parts by weight, 0.1 to 50 parts by weight of (03), and 0.1 to 50 parts by weight of (C), providing a matte resin composition with excellent impact resistance and processability. It is something to do.

The composition of the present invention will be explained in detail below.

O Rubber-reinforced styrenic thermoplastic resin (A) The rubber-reinforced styrenic thermoplastic resin (A) in the present invention refers to an aromatic vinyl compound (a-1) in the presence of a rubbery polymer (a-1).
2) or a resin obtained by polymerizing an aromatic vinyl compound (a-2) and a vinyl cyanide compound and/or an unsaturated carboxylic acid alkyl ester compound (a-3).

In addition, such a resin is a by-product during polymerization (i. polymer (a-2 homopolymer or a-1-a-8 copolymer) or a (co)polymer made of the above-mentioned compound produced separately. May include coalescence.

Rubbery polymer (a-1) and compound (
There is no particular restriction on the composition ratio of a-2 or the sum of a-2 and a-3, but it is preferably 5 to 70% by weight of the rubbery polymer from the standpoint of balance between impact resistance and processability. .

As the rubbery polymer (a-1), polybutadiene, butadiene-styrene polymer, butadiene-acrylonitrile polymer, polyisoprene, polychloroprene, ethylene-propylene polymer, ethylene-propylene-nonconjugated diene polymer, polybutyl Examples include acrylate-1, ethylene-vinyl acetate polymer, and chlorinated polyethylene, and one or more of them can be used.

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

As the aromatic vinyl compound (a-1), styrene, α
-Methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, α
-Methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromustyrene, dibromustyrene, vinylnaphthalene, etc. are exemplified, and - or two types can be used. Styrene is particularly preferred.

A rubber-reinforced styrenic thermoplastic resin (compound (a-2) that can form a gradient
-3) As the hibinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, etc. are exemplified, and -m or two or more thereof can be used. Acrylonitrile is particularly preferred.

Examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate.
Examples include butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc., and one or more types can be used. Particularly preferred is methyl methacrylate.

There is no particular restriction on the composition ratio of the compound used, but from the viewpoint of impact resistance, processability, heat resistance, mulberry resistance, etc., 30 to 100% by weight of the aromatic vinyl compound (a-2'), especially 5
0 to 80% by weight, vinyl cyanide compound and/or unsaturated carboxylic acid alkyl ester compound (a-3)
i: 70% by weight, particularly preferably 20 to 50% by weight.

Examples of methods for producing the rubber-reinforced styrenic thermoplastic resin (A) include emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. .

0 graft polymer (g) The graft polymer (B) in the present invention is ethylene-
In the presence of the α-olefin rubber (b-1), one or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid alkyl ester compounds (b=2) and unsaturated Epoxy compound <b-a
) is a graft polymer obtained by polymerizing.

The ethylene-α olefin rubber (b-1) constituting the graft polymer 03) is a binary copolymer (EPR) consisting of ethylene and propylene or butene, or a tripolymer consisting of ethylene, propylene or butene, and a non-conjugated diene. These are original copolymers (EPDM), etc., and one or more types are used.

Examples of the non-conjugated diene in the terpolymer (EPDM) include dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, 1,4-cyclohebutadiene, and 1.5-cyclooctadiene.

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

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

aromatic vinyl compound constituting the graft polymer (B),
Examples of the vinyl cyanide compound or the unsaturated carboxylic acid alkyl ester compound include the compounds listed in the section of the rubber-reinforced styrenic thermoplastic resin above.

The unsaturated epoxy compound (b-3) constituting the graft polymer 03) is a compound having one or more each of one or more polymerizable unsaturated bonds and one or more epoxy groups in one molecule. Examples of unsaturated epoxy compounds such as 0 include unsaturated glycidyl esters represented by the general formula (where R represents a hydrocarbon group having a polymerizable ethylenically unsaturated bond) and general formula ( Here, R is the same as in formula (1), and X is a divalent group) and unsaturated glycidyl ethers represented by the general formula , R' is hydrogen or a methyl group).

Specifically, glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid, mono-, di- and triglycidyl esters of butene I dicarboxylic 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-ene-2-
Mono- and diglycidyl esters of methyl-2,3-dicarboxylic acid (trade name methylnadic acid), mono- and diglycidyl esters of allylsuccinic acid, glycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether , styrene-p-glycidyl ether or p-glycidylstyrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-I-butene, 3,4-epoxy-i-pentene, 3,4 -epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, and vinylcyclohexene monoxide.

There is no particular restriction on the composition ratio of the ethylene-α olefin rubber and each compound when polymerizing the graft polymer (B), but the composition ratio of the ethylene-α olefin rubber (b-1) is not particularly limited in terms of the physical properties of the final resin composition. 100? 10 to 2000 parts by weight of one or more compounds (b-2) selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid alkyl ester blends, and unsaturated epoxy compound Cb per i part -3) It is preferably 0.5 to 800 parts by weight. Especially per 100 parts by weight of rubber (b-1),
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 preferred.

Further, the compound (b-2) is 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, and there is no particular restriction on its composition, but the aromatic A combination of a vinyl compound and a vinyl cyanide compound and/or an unsaturated carboxylic acid alkyl ester compound is preferred.

Furthermore, there are no particular limitations on the polymerization method for obtaining the graft polymer (T), including emulsion polymerization, bulk polymerization, suspension polymerization,
Known methods such as solution type method may be used.

Copolymer (C) in the present invention refers to one or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl ester compounds (C-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.

Examples of the aromatic vinyl compound, vinyl cyanide compound, or unsaturated carboxylic acid alkyl ester compound include the compounds listed in the section of the rubber-reinforced styrenic thermoplastic resin above.

Examples of the unsaturated carboxylic acid compound include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, and -i or two or more thereof can be used.

As the unsaturated epoxy compound, graft polymer 03>
These are the compounds listed in the section.

Examples of hydroxyl group-containing compounds include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
)・ are exemplified, and - species or two or more species can be used.

Examples of nitrogen-containing base-containing compounds include dimethylamine ethyl acrylate, dietylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, pressure methyl-5-vinylpyridine, N-vinylimidazole, N-vinylindole, N-vinylcarbazole, N-vinylpyrrole,
Examples include p-aminostyrene and p-dimethylaminostyrene, and one or more types can be used.

The compound (c-1) constituting the copolymer (C) and the compound (
There is no particular restriction on the composition ratio with C-2), but from the viewpoint of impact resistance, processability, matting properties, etc. of the final composition, it is preferable to use compound (C-2).
1) 99-30% by weight, especially 95-50% by weight, compound (C-2) 1-70% by weight, especially 5-50% by weight.

In addition, there are no particular limitations on the compounds in compound (c-1) and compound (c-2), but compound (c-i) may be an aromatic vinyl compound alone, an unsaturated carboxylic acid alkyl ester compound alone, or an aromatic vinyl compound alone. A combination of a vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound and a vinyl cyanide compound is preferred.

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.

Copolymers (preferred examples of Q include styrene-(meth)acrylic acid copolymer, acrylonitrile monostyrene-(meth)acrylic acid copolymer, methyl methacrylate-(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-dimethylaminoethyl (meth)acrylate copolymer, acrylonitrile-styrene-dimethylaminoethyl (meth)acrylate copolymer, styrene-diethylaminoethyl (meth)acrylate copolymer, acrylonitrile-styrene-diethylaminoethyl (meth)acrylate copolymer, styrene-2-
Examples include vinylpyridine copolymer, acrylonitrile-styrene-2-vinylpyridine copolymer, and -W or two or more thereof can be used.

0 Resin Composition The resin composition of the present invention consists of the above-mentioned rubber-reinforced styrenic thermoplastic resin (A), graft polymer (B), and copolymer (C), and the blending ratio thereof is (A). ,(B)
and (C) as 100 parts by weight, (A) 40
~99.8 ffl parts, 0.1 to 50ii parts of 03) and 1 to 50 parts of (C)o.

When the rubber-reinforced styrenic thermoplastic resin (A) has an electric field of less than 40 parts, the balance between impact strength and processability is poor. When the amount of graft polymer 03) or copolymer (C) is less than 0.1 part by weight or more than 50 parts by weight, impact strength and rubber-reinforced styrenic thermoplastic resin (A), graft polymer (B), and copolymer There are no particular restrictions on the mixing method for (C), and it can be mixed in the form of latex, powder, beads, pellets, or the like. There is also no particular restriction on the order of mixing them, and either the three components may be mixed at once, or the two components may be premixed, and then one component may be mixed later. As the melt-kneading method, known methods such as a Banbury mixer, roll, extruder, etc. can be employed.

In addition, when mixing, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, dyes, pigments, plasticizers, flame retardants,
Additives such as a mold release agent can be added. Further, thermoplastic resins such as polyacetal, polycarbonate, polybutylene terephthalate, polyphenylene oxide, polymethyl methacrylate, and polyvinyl chloride can also be appropriately blended.

Next, the present invention will be specifically explained using Examples and Comparative Examples. Note that all parts and percentages are expressed on a weight basis.

Reference example 1. Rubber-reinforced styrenic thermoplastic resin (A)A
-1: ABS resin Polybutadiene latex 1 with an average particle size of 0.4μ, a gel content of 80%, and a solid content of 50% was placed in a reactor purged with nitrogen.
After charging 0.00 parts of potassium persulfate, 0.3 parts of potassium persulfate, and 100 parts of pure water, the temperature was raised to 65° C. while stirring. Thereafter, a mixed monomer solution consisting of 15 parts of acrylonitrile, 35 parts of styrene, and 0.2 parts of t-dodecylmercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of disproportionated potassium rosinate were each continuously added over a period of 4 hours, and then polymerization was carried out. system to 70
The temperature was raised to .degree. C., and the mixture was aged for 3 hours to complete polymerization, thereby obtaining an ABS graft copolymer latex.

Separately, 0.3 parts of potassium persulfate and 120 parts of pure water were charged into a reactor purged with nitrogen, and the temperature was raised to 65°C while stirring. Then 17 parts of acrylonitrile, 7 parts of styrene
A mixed monomer solution consisting of 0 parts and 0.3 parts of 1-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of disproportionated potassium rosinate were each added continuously over a period of 4 hours, and then the polymerization system was heated to 70°C. The temperature was raised and the polymerization was completed by aging for 3 hours to obtain an acrylonitrile-styrene copolymer latex. After mixing with the graft copolymer latex, AB with a rubber content of 15% was obtained by ordinary salting out and drying treatments.
S resin was obtained.

A-J: fFl thermal ABS resin After 150 parts of pure water, 0.5 parts of potassium persulfate, and 2 parts of sodium lauryl sulfate were charged into a reactor purged with nitrogen, the temperature was raised to 70'G while stirring. Thereafter, a mixed monomer solution consisting of 30 parts of acrylonitrile, 70 parts of α-methylstyrene, and 0.2 parts of t-dodecylmercaptan was continuously added over 5 hours, and then the polymerization system was heated to 75°C and aged for 5 hours. Polymerization was completed in this manner to obtain an acrylonitrile-α-methylstyrene copolymer latex.

Then, mixed with the aforementioned graft copolymer latex,
After conventional salting-out and drying treatments, a heat-resistant ABS resin with a rubber content of 15% was obtained.

A-3: ABS resin Based on the known suspension polymerization method, ethylene-propylene-ethylidene norbornel polymer (propylene content 43%)
, iodine number 9, Mooney viscosity 87) 50%, styrene 3
A copolymer obtained by graph salting out and drying and containing 4% of acrylonitrile and 16% of acrylonitrile was mixed to obtain an ABS resin with a rubber content of 20%.

Reference Example 2 Graft polymer (T) B-1: Ethylene-propylene-dicyclopentadiene (iodine value 10, Mooney viscosity 60, propylene content 40%)
Polymer B-1 was obtained by polymerizing 50 parts of styrene, 40 parts of styrene, 17 parts of acrylonitrile, and 7 parts of glycidyl methacrylate by a known solution polymerization method.

B-2 = Ethylene-propylene-ethylidene norbornene (iodine value 8A-2-viscosity 61, propylene content 43%) 2
0 parts, 75 parts of styrene, 25 parts of acrylonitrile, and 10 parts of glycidyl methacrylate were polymerized by a known solution polymerization method to obtain Polymer B-2.

Reference Example 3 Copolymer (C) C-1: 120 parts of pure water and 0.3 parts of potassium persulfate were charged into a reactor purged with nitrogen, and then the temperature was raised to 65°C while stirring. After that, 30 parts of acrylonitrile, 65 parts of styrene,
5 parts of methacrylic acid and 0.0 parts of t-dodecyl mercaptan.
A mixed monomer solution consisting of 3 parts and 30 parts of an emulsifier aqueous solution containing 2 parts of sodium dodecylbenzenesulfonate were each added continuously over a period of 4 hours, and then the polymerization system was heated at 70°.
The temperature was raised to C and aged for 3 hours to complete polymerization.

C-2: 30 parts of acrylonitrile was changed to 25 parts, 65 parts of styrene was changed to 60 parts, and 5 parts of methacrylic acid was changed to 15 parts of glycidyl methacrylate, and polymerization was carried out in the same manner as in C and -t to obtain acrylonitrile-styrene. - A glycidyl methacrylate copolymer was obtained.

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

C-4: After 120 parts of pure water and 0.3 parts of potassium persulfate were charged into a reactor purged with nitrogen, the temperature was raised to 65°C while stirring. Thereafter, a mixed monomer solution consisting of 25 parts of acrylonitrile, 60 parts of styrene, 15 parts of 2-vinylpyridine, and 0.3 parts of t-dodecylmercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of disproportionated potassium rosinate were each added for 4 hours. After continuous addition, the temperature of the polymerization system was raised to 70'C, and the polymerization was completed by aging for 3 hours.

C-5; Same as C-4 except that 15 parts of 2-vinylpyridine was replaced with 15 parts of diethylaminoethyl methacrylate,
An acrylonitrile-styrene-diethylaminoethyl methacrylate copolymer was produced.

Examples and Comparative Examples Rubber-reinforced styrenic thermoplastic resin (A
-1 to 3), graft polymers (B-1 to 2), copolymers (C-1 to 5), or known matting agents in the composition ratios shown in Tables 1 to 3, respectively, and Banbury mixer. −
After mixing, it was pelletized. Various test pieces were prepared from the obtained pellets according to conventional methods, and various properties were measured. The obtained results are shown in Tables 1 to 3, respectively.

oi1iJ impact resistance (notched Izot)': ASTM
D-256.1/8′ Mewa 9.231LO workability:
Koka type flow tester, 210°C x 30 Ky/cm
2 (*230'c x 60 cy/an2 in Comparative Examples 9-10 and Examples 5-8 using heat-resistant ABS resin
), "En-" O Gloss: A 60n x 60WM thick 3 yxx test plate was molded using a 3.5 oz injection molding machine, and the gloss in the center of the test plate was measured using a Suga Test Instruments Digital Variable Gloss Meter UGv. -4D at an incident angle of 60°. ×
<Effects of the Invention> The composition of the present invention is characterized by an excellent balance between impact resistance and processability as well as excellent matte properties compared to conventionally known compositions.

Claims (1)

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