JPH03199255A - Aromatic polycarbonate-based resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition, composed of an aromatic polycarbonate-based resin having specific terminal group composition, ABS-based or polystyrene-based resin and epoxy group- or oxazolinyl group-containing copolymer and having low gloss and high impact strength. CONSTITUTION:A resin composition obtained by blending (A) 3-97 pts.wt. aromatic polycarbonate resin having phenolic terminal groups expressed by formula I (R1 is H or <=20C alkyl which may be substituted with halogen) and nonphenolic terminal groups expressed by formula II (R2 is same as R1) at >=1/19, preferably >=1/10, especially (1/5)-1 ratio of the (formula I)/(formula II) with (B) 97-3 pts.wt. ABS-based resin or polystyrene-based resin and (C) a copolymer (preferably glycidyl methacrylate/styrene copolymer, etc.) having epoxy groups and/or oxazolinyl groups in an amount of 0.5-100 pts.wt. based on 100 pts.wt. total amount of the components (A) and (B).

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an aromatic polycarbonate resin composition,
More specifically, the present invention relates to an aromatic polycarbonate resin composition that has low gloss and has an impact strength of 1Ω.

(Problems to be solved by the prior art and the invention) Aromatic polycarbonate is a resin with excellent mechanical strength and is widely used as an engineering plastic. Blends of are known.

Blend with ABS resin (Special Publication No. 38-15
225 Publication and Special Publication No. 51-11142〉
Or a blend with polystyrene (Special Publication No. 43-62
95 Bow Publication and Japanese Patent Publication No. 44-11551g> or λ11. Blending with such ABS resin or Haphoris Brene improves the moldability of the aromatic polycarbonate resin, and also! ! A molded product with improved i6 impact strength can be obtained. 33 for these molded products
Among them, the one with high impact strength is -B gloss.

On the other hand, 127t! has low gloss and high impact strength, which is required for many applications including automobile interior parts.
It is l. However, an aromatic polycarbonate molding material #1 that has low gloss and high impact strength has not yet been obtained.

Therefore, an object of the present invention is to provide an aromatic polycarbon II-based resin composition that has low gloss and high impact strength.

(Means for solving the problem) The present inventors have developed aromatic polycarbonate resin and ABS.
In J3 blend with resin or polystyrene resin, adjust the ratio of phenolic end groups and non-phenolic end groups of aromatic polycarbonate resin, and add a copolymer having epoxy group or oxazolinyl group. It was discovered that by doing so, it is possible to impart properties of low gloss and high impact strength to a molded article, and the present invention was completed.

That is, the present invention provides (8) a phenolic end group represented by the following formula: and a non-phenolic end group represented by the following formula (in the above formula, R1 and R2 can be the same or different from each other, Each is a hydrogen atom or an alkyl group having 20 or less carbon atoms, and may be substituted with halogen> Aromatic polycarbonate resin whose ratio (I)/(ff) is 1/19 or more 3 to 97 (B) 97 to 3 parts by weight of ABS resin or polystyrene resin, and (C) a copolymer having 8 epoxy groups or A-kylysilinyl groups, in a total of (A) and (8). A Z6 group polycarbonate resin composition containing 0.5 to 100 parts by weight per 100 parts by weight is provided.

The aromatic polycarbonate resin as component (A) used in the present invention usually has the formula % (each R is phenylene, halogen-substituted phenylene, or 0
1-2o alkyl direct phenylene, A and 8 represent a hydrogen atom, a 01-12 hydrocarbon group containing no aliphatic unsaturation, or a group forming a cycloalkane group together with adjacent carbon atoms. Mainly has a position. The present invention is characterized in that such an aromatic polycarbonate is used in which the ratio (end group ratio) of phenol ↑ raw terminal j% (I) and non-phenolic terminal group (n) is adjusted.

The end group ratio of aromatic polycarbonate 1 can be easily adjusted by producing aromatic polycarbonate by a transesterification method and changing the molar ratio of the raw materials diphenyl carbonate and diphenol (e.g. bisphenol A) at that time. I can do it. For example, when bisphenol A and diphenyl carbonate 1 to 1 are subjected to upward sprue exchange, the terminal end of the polycarbonate is a phenolic residue derived from bisphenol A or a phenyl group derived from Schiff T nyl carbonate. Therefore, when the molar ratio of bisphenol A is increased during the transesterification reaction, the proportion of phenol↑([terminal groups) increases in the produced polycarbonate. Branched polycarbonate is
By reacting polyfunctional aromatic compounds with diphenols and/or carbonate precursors, branched thermoplastic randomly branched polycarbonates are obtained.

Conventionally commonly used aromatic polycarbonates 1-,
Particularly in aromatic polycarbonates made by the phosgene method, the ratio of phenolic end groups to non-phenolic end groups is 1/20 or less.

In short, polycarbonate is made by reacting bisphenol 8 and phosgene, but by adding a small amount of phenol to the raw materials or during the reaction, the polymer ends are blocked with phenol (the hydroxyl groups react). ing.

In this defense, iJ3 refers to aromatic polycarbonate 1 to 7.
The ratio of 1-nor↑4 end groups to non-phenolic end groups, z4f(i)/(It), is at least 1719, preferably at least 1710, especially at least 175, up to 110.

When the terminal monomerization is less than 1719, low gloss, impact resistance, or excellent molding amount cannot be obtained.

The degree of 01-1 group of the phenolic end group is 3 in FTIR.
It is determined by measuring the absorption intensity at BOOcrtr-1. The total terminal group concentration can be determined by determining the average molecular weight based on the IV (intrinsic viscosity) value measured with a meblen chloride solution.When converting the IV value to the average molecular weight, use the 5chnell formula. Using.

-40,83 IV=1.23X10 M (M-viscosity average molecular weight) Next, component (B) used in the present invention will be described. Component (B) is an ABS resin or a polystyrene resin.

The ABS resin used in the present invention is a copolymer containing (a) a rubbery polymer, (b) an aromatic hynyl monopendicular component, and (C) a vinyl cyanide monomer component.

(a) Rubbery polymers used in the present invention include polybutadiene, polyisoprene, ethylene-butadiene random copolymers and butadiene copolymers, hydrogenated products of the block copolymers, acrylic "1 nitrile- Diene rubbers such as butadiene copolymers and butadiene-isoprene copolymers, ethylene-butene random and block copolymers, ethylene-butene random and block copolymers, ethylene and α-
Copolymer with olefin, edylene-methacrylate,
Copolymers of ethylene-vinyl acrylate and ethylenically unsaturated carboxylic acid esters, copolymers of ethylene and vinyl fatty acids such as ethylene-vinyl acetate, ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene to kylidiene Ethyl-propylene non-co-IQ terpolymers such as copolymers, butylene-
Examples include isoprene copolymers, and these may be used alone or in combination of two or more. Preferred rubbery polymers are ethylene-propylene rubber, ethylene-propylene non-conjugated genter polymer, and diene rubber, and particularly preferred are polybutadiene and ethylene-butadiene copolymer, and styrene in this ethylene-butadiene copolymer is The I content is preferably 50% by weight or less.

(b) Examples of the vinyl cyanide monomer component include acrylonitrile and methacrylate trile, and one or more of these may be used.

(C) Aromatic vinyl monomer components include, for example, styrene, α-methylstyrene, o-, m-6, p-methylethylene, vinylxylene, monochlorostyrene, dichloro[1-styrene, monoprostyrene, diproprostyrene, Examples include styrene, fluorostyrene, p-tert-bubblestyrene, ethylstyrene, vinylxylene, etc., and one or more of these may be used. Preferred are ethylene and α-methylethylene.

In addition to the above-mentioned components (a), (b) and (C), the AB, S-based resin of component (B) in the present invention contains (d) a monomer copolymerizable with these components. It can be used within the range that does not impair the purpose of the invention. Other copolymerizable monomers include α,β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate-1, α,β-unsaturated carboxylic acid Nisdels such as bubl(meth)acrylate, 2-ethyl(meth)acrylate, and 2-ethylhexyl methacrylate;α,β-unsaturated such as maleic anhydride, teric itaconic acid, etc. Dicarphonic acid anhydrides: maleimide, N-methylmaleimide,
N-ethylmaleimide, N-phenylmaleimide, N-
Examples include imide compounds of α,β unsaturated dicarboxylic acids such as 0-chlorophenylmaleimide; these monomers may be used alone or in combination of two or more.

In the ABS resin of component (8), each component (a).

The composition ratio of (b) and (C) is not particularly limited, and each component is blended depending on the purpose.

In addition, ABS resins include (a) a graft copolymer obtained by graft copolymerizing other components in the presence of a rubbery polymer, or this graft copolymer and (b) vinyl cyanide monomer and (C ) A blend with a copolymerization product of aromatic vinyl ll11, etc. is preferable, and more preferably A
They are BS resin and AES resin.

Regarding the manufacturing method of ABS resin of component (B), especially lj
There is no limitation, and commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. It is also possible to obtain the ABS resin of component (8) by blending separately copolymerized resins.

Next, the polystyrene resin that can be used in the present invention is known per se and has the general formula (in the formula, R is hydrogen) or an alkyl group having 1 to 4 carbon atoms, and X is a halogen atom or a carbon atom number. at least 25% by weight of repeating 4M structural units derived from a vinyl aromatic compound represented by a substituent which is an alkyl group of 1 to 4, and p is an integer of 1 to 5; You must have at least the following. Such polystyrene resins include, for example, homopolymers of styrene or its derivatives, as well as polybutadiene, polyisoprene, bubble rubber, and EP.
DM, ethylene-propylene copolymer, natural rubber, mixtures of natural or synthetic elastomeric substances such as shrimp chlorohydrin, or modified ↑%L, styrenic polymers, and styrene-containing 4j copolymers, For example, styrene-acryloni i-lyl copolymer (SAND, styrene-
Mention may be made of butadiene copolymer, styrene-maleic anhydride copolymer, soubrene-acrylonitrile-butadiene copolymer (8BS). Preferred styrenic polymers for the present invention are homoponosbrene and rubber-reinforced polystyrene. be.

Such ABS resin or polybrene resin, Zunawara component (B), has a ratio of 97 to 3 parts by weight per 3 to 97 parts by weight of component (8), preferably 10 to 90 parts by weight of component (A).
Add 90 to 10 parts by weight to Chihaya part.

Further, as component (B), both ABS resin and polystyrene resin can be used.

Next, component (C) used in the present invention will be described. The copolymer having an epoxy group or oxazononyl group as component (C) refers to a copolymer of an unsaturated L-mer having an epoxy group or an A-xylysilinyl group and another unsaturated L-mer.

Examples of unsaturated polymers having an epoxy group or an oxazolinyl group include the following.

Preferred epoxy group-containing unsaturated supermers include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate, and glycidyl itaconate. Preferred unsaturated heptadmers containing an oxylizolinyl group include those represented by the general formula, in which Z contains a polymerizable double bond. Preferred substituents Z are as follows.

1 CI+2 = CR' - C12 = CR' -
CCl2 -cR'0'R' In these formulas, R' is a hydrogen atom or an alkyl group or alkoxy group containing 1 to 6 carbon atoms, such as a methyl group,
i- and n-propyl groups or divalent groups.

A particularly preferred compound is a vinyl oxazoline represented by -Monken, where R' has the above meaning and is preferably a hydrogen atom or a mebble group.

Examples of other heptadmers that can be copolymerized with these epoxy group- or sacillinyl group-containing unsaturated heptadmers include the following: styrene-based heptadmers 1 such as styrene, α-methylsubrene, and Particularly preferred are side-chain alkyl-substituted styrenes such as α-ethylstyrene, nuclear alkyl-substituted subrenes such as vinyltoluene, p-methylstyrene, and halogenated styrenes such as heptanochlorostyrene, dichlorostyrene, tribromostyrene, tetrabromostyrene. Styrene; ethylene, propylene, 1-butene, 1-benzone, 4-noblue 1-
Pentene, 1-hexene, 1-octene, 1-decene,
α-olefins such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene: butadiene, isoprene, 1,4-hexylydiene, 5-ethylidene-2-nor-11ζ runene, 5-vinyl-2-norbornene Dienes such as vinyl acetate, acrylic acid (salt), methacrylic acid salt>, acrylic ester, methacrylic acid-■-ster, maleic acid (anhydride), maleic acid-
[Ster, 2-norbornene-5,6-dicarboxylic acid (
unsaturated carboxylic acids such as anhydrides or one thereof; and vinyl cyanide Enomers such as acrylonitrile.

Moreover, the copolymer of component (C) can also have both an epoxy group and an oxysilinyl group.

Examples of particularly preferred copolymers of component (C) include glycidyl methacrylate (GMA)/styrene copolymers, vinyloxazoline/styrene copolymers, GMA/styrene/acrylonitrile (AN) copolymers, and vinyloxazoline/styrene copolymers. It is a styrene/AN copolymer.

The above component (C) is the above-mentioned component (A) and (8).
It is added in an amount of 0.5 to 100 parts by weight, preferably 1 to 40 parts by weight, based on a total of 100 parts by weight. If the amount of additive/III is too small, the sufficient effect of the invention will not be exhibited, and if it is too large, fluidity, heat resistance, etc. will be reduced.

In addition, the resin composition of the present invention may be used with J3, as long as its physical properties are not impaired. , a heat resisting agent, an oxidative deterioration inhibitor, a weathering agent, a lubricant, a molding agent, a crystal nucleating agent, a molding agent, a fluidity improver, an antistatic agent, etc. may be added.

Reinforcing fillers include finely divided aluminum, iron or nickel, metal oxides and non-metals, e.g. carbon filaments, silicates, e.g. mica, aluminum silicates (clays).
, talc, asbestos, butane dioxide, wollastonite, tubaculite, potassium titanate and titanate whiskers, glass flakes, glass peas and glass fibers and polymer fibers, or combinations thereof. .

The reinforcing filler, which can have a reinforcing effect, accounts for 1 to 60% by weight of the total weight of the silk composition.

A preferred range is 5-50% by weight.

The toughening agent is glass.

When the composition of the present defense includes a polycarbonate consisting of brominated hisphenol, the resulting thermal
In order to synergistically enhance 4, inorganic or organic antimony compounds may be further incorporated into the compositions of the present invention.

Hindered phenol, i as a stabilizer and antioxidant
T-sphite, metal phosphate, metal phosphite, etc. can be mixed.

When producing the resin composition of the present invention, each component can be mixed by a conventionally known method. For example, after mixing each component in fractions with a high-speed mixer such as a Turnpull mixer, Henshi 1 Lumiki 1 No, ribbon blender, or Super Mixer, the ingredients can be mixed in fractions using a turnpull mixer, a high-speed mixer such as a Henshi 1 Lumiki 1 No, a ribbon blender, or a Super Mixer.
A method of melting and kneading with 1[1-l] or the like is appropriately selected.

(Example) The aromatic polycarbonate (component (^)) according to the present invention used in the following examples was obtained by ester exchange of diphenyl carbonate 1 ~ and hisphenol A, The viscosity measured in methylene chloride at 25°C was 0.50 dl/(). The molar ratio of Schifnyl carbonate to bisphenol was adjusted to separate the phenolic and non-phenolic end groups. The ratio is about 3
/7 and 1/1, and convert this into P C (30
) and P C (!+0).

For comparison, bisphenol A was polymerized by the phosgene method, and aromatic polycarbonate t~(
Lexan 141, trademark, General Electric Company, intrinsic viscosity 0.51 dl at 25°C in methylene chloride
/(]) was used. This is expressed as PC(1).

As component (B), the following were used: ABS resin: HRG 370 (trademark: manufactured by Vineral Electric Co., Ltd.) SAN 580 (trademark: manufactured by General Electric Co., Ltd.), Polysbrene resin: HTPS (trademark: T644, high impact polystyrene, manufactured by Mitsubishi Monsanto Chemical) The following was used as component (C); c -1
: CP-1005SA (trademark; manufactured by NOF ■, 5
Monomer % epoxy compound-containing styrene-acrylonitrile copolymer> C-2: RAS-1005 (manufactured by Nippon Shokubai Chemical Co., Ltd.,
Styrene-acrylonitrile copolymer containing 5% by weight of oxazoline compound) c-3: CP-10053 (trademark: manufactured by NOF Corporation,
Styrenic copolymer containing 5% by weight of glycidyl methacrylate> c-4: CX-RPS-1005 (trademark; manufactured by Nippon Shokubai Chemical Co., Ltd., styrenic copolymer containing 5% by weight of oxazoline compound) Examples 1- 5 and Comparative Examples 1 to 9 The components in the proportions (weight ratio) shown in the table were melt-kneaded using a 50InIn twin-screw extruder at a temperature set at 260'C and a rotational speed of 29Orpm to produce pellets. Using this pellet, a molded product was prepared under the conditions of a set temperature of 260° C. and a mold temperature of 60° C., and the notched Izot impact strength J3 and gloss were measured. Note that Izotsu 1 to impact strength (with 1/8" notch) was based on AS-rM D256.

In addition, the glossiness of the surface of the molded product (50 x 50 x 3 mm square plate) was measured using a digital variable angle gloss meter (UGV-40, manufactured by Suga Test Instruments).The results are shown in the table.

(Effects of the Invention) The resin composition of the present invention has characteristics similar to those of aromatic polycarbonate resins, ABS resins, or polystyrene resins, and has both impact resistance and low gloss. Therefore, its uses are wide and its industrial value is high.

Claims (1)

[Claims] (A) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A phenolic terminal group represented by (I), and the following formula: ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ Non-phenolic terminal group represented by (II) (in the above formula, R_1 and R_2 can be the same or different from each other, each having a hydrogen atom or up to 20 carbon atoms) 3 to 97 parts by weight of an aromatic polycarbonate resin whose ratio (I)/(II) is 1/19 or more; (B) an ABS resin or a polystyrene resin; 97-3
parts by weight, and (C) an aromatic polycarbonate resin composition containing 0.5 to 100 parts by weight of a copolymer having an epoxy group or an osazolinyl group based on a total of 100 parts by weight of (A) and (B). thing.