JPS6246579B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermoplastic resin compositions having improved impact strength. More particularly, the present invention relates to polycarbonate resin mixtures having improved room temperature impact strength and good compatibility. Aromatic carbonate polymers are well-known commercially available materials that have a wide range of uses in plastics technology. Such carbonate polymers can be synthesized with 2, such as 2,2-bis(4-hydroxyphenyl)propane, in the presence of an acid binder.
Polymer phenols can be made by reacting them with carbonate precursors such as phosgene. Generally speaking, aromatic polycarbonate resins offer high resistance to mineral acid attack, are easily moldable, physiologically harmless, and strain resistant. Also, polycarbonate resin is about 1/8 to 1/4
It is also well known to have high impact strength below a critical thickness between in. Above this average thickness, the impact strength of the polycarbonate resin is low, and defective molded products are brittle. Furthermore, the impact strength of polycarbonate resin decreases when the temperature drops below about -5°C.
It decreases rapidly after aging the polymer at high temperatures above 100℃. These properties necessarily limit the field of application of unmodified aromatic polycarbonate resins. Therefore, in an effort to improve the impact behavior of polycarbonate resins, it has been proposed to add modifiers to polycarbonate. Goldblum's U.S. Pat. No. 3,431,224 proposes adding a modifier in a certain proportion, and the modifier is polyethylene, polypropylene, polyisobutylene, a copolymer of ethylene and ethyl acrylate, a copolymer of ethylene and propylene. It consists of at least one member of the group consisting of polymers, cellulose esters, polyamides, polyvinyl acetals, alkyl cellulose esters, and polyurethane elastomers. Results using such modifiers are generally excellent for parts with thin cross-sections, e.g. 1/8 inch thick, but moldings thicker than 1/4 inch tend to fail when these modifiers are used. Such damage is one type of undesirable brittleness. Liyu U.S. Pat. No. 4,245,058 teaches that compositions consisting of high molecular weight aromatic polycarbonates, acrylate copolymers and polyolefins have improved aging impact strength, low and high temperature impact strength and good weld line strength. It describes what is shown when compared with unmodified polycarbonate. In U.S. Pat. No. 3,864,428, Nakamura et al.
They describe compositions consisting of a graft copolymer based on aromatic polyester, aromatic polycarbonate and butadiene, in which the polycarbonate constitutes 10 to 75% by weight of the total mixture, and state that these have good room temperature impact strength. ing. Finally, Floms et al., in U.S. Pat.
~8% by weight aromatic polycarbonate and 100%
A high impact strength composition consisting of a core-shell copolymer having a core of butazine groups, the balance for % has been published. A thermoplastic interpolymer of a diene-vinyl aromatic copolymer and an acrylate or methacrylate comonomer, and an impact modifier combination consisting of a poly(ethylene terephthalate) resin or an amorphous copolyester resin, and a poly(ester-carbonate) copolymer. It has now been discovered that a polycarbonate resin having enhanced room temperature impact strength in a thin-walled molded section can be provided by incorporating a certain proportion of . When the aforementioned modifiers are added to polycarbonate resins within certain ranges, the mixture formed has good weld seam strength and improved impact strength at room temperature when compared to unmodified polycarbonate resins. According to the present invention, the above-mentioned desirable properties are present in (a) (i) an aromatic polycarbonate resin, and (ii) a copoly(ester-carbonate resin), and (b) (i) a poly(ethylene terephthalate) resin and an amorphous polycarbonate resin. a polyester resin selected from the group consisting of copolyester resins, and (ii) alone or in a mixture with at least one monomeric compound selected from monomers further containing one vinylidene group; A thermoplastic interpolymer of a monomer selected from at least one of ₁ to _C6 alkyl acrylate, C1 _{to C6} alkyl methacrylate, acrylic acid, methacrylic acid and mixtures of the above monomers, and a diene vinyl aromatic copolymer. The amounts of modifiers used can vary widely, but in general the best results are obtained when the composition is With about 55-90% by weight of aromatic polycarbonate resin component (a)
The results are obtained when containing amounts of (a)(i) varying from about 10 to 90% by weight of (a), preferably 20 to 80% by weight of (a).
The amount of (b) is about 10-45% by weight of (a) and (b). (b)
The amount of (b)(ii) therein is from about 10 to about 40% by weight. Addition of modifier to aromatic polycarbonate resin
(a) This can be achieved by any method as long as complete distribution of the modifier in (i) is obtained. Generally copoly(ester)
carbonate) is first mixed with an aromatic polycarbonate resin to form a polycarbonate resin mixture, and then the modifier combination is added. But this is not critical. Mixing of these materials can be accomplished by a variety of methods commonly used to incorporate plasticizers or fillers into thermoplastic polymers, including kneading rolls, dough mixers, Banbury mixers, extruders, and other mixing equipment. including but not limited to.
The mixture formed can be processed by any conventional method used for molding or manipulating thermoplastics. The materials can be molded using compression, injection, calendering, extrusion, and blow molding techniques alone or in any combination. Multi-stage processing methods such as extrusion blow molding or extrusion injection can also be used, for example for multilayer containers. In addition to the polymers mentioned above, the resin mixtures made according to the invention can also contain other additives to provide lubrication, reinforcement, antioxidant protection, and to provide color to the material. Other additives, such as mold release agents and stabilizers, are well known to those skilled in the art and can be incorporated without departing from the scope of the invention. Aromatic polycarbonates can be made by reacting dihydric phenols with carbonate precursors such as phosgene, haloformates or carbonate esters. Generally speaking, such carbonate polymers have the formula (In the formula, A is a divalent aromatic group of divalent phenol used in the polymer production reaction.) It can be represented as having a repeating structural unit. The carbonate polymers used to make the resin mixtures of this invention have an intrinsic viscosity in the range of about 3.0 to about 1.00 dl/g (25°C
) when measured in methylene chloride. Dihydric phenols that can be used to make such aromatic carbonate polymers include mononuclear or polynuclear aromatic compounds containing as functional groups two hydroxy groups, each of which is directly bonded to a carbon atom of the aromatic nucleus. There is. Typical dihydric phenols include: 2,2-bis-(4-hydroxyphenyl)propane, hydroquinone, resorcinol, 2,2-bis-(4-hydroxyphenyl)pentane, 2. 4'-(dihydroxydiphenyl)methane, bis(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-5-nitrophenyl)methane, 1,1-bis- (4-hydroxyphenyl)ethane, 3,3-bis-(4-hydroxyphenyl)pentane, 2,2-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, bis-(4-hydroxydiphenyl)sulfone, Bis-(3,5-diethyl-4-hydroxyphenyl)sulfone, 2,2-bis-(3,5-dimel-4-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylsulfone, 5'-Chloro-2,4'-dihydroxydiphenyl sulfone, bis-(4-hydroxyphenyl)diphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodif enyl ether, 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, etc. Other dihydric phenols suitable for use in making the polycarbonates described above are described in U.S. Pat.
No. 2999835, No. 3038365, No. 3334154 and No.
Described in No. 4131575. These aromatic polycarbonates can be prepared by known methods, such as the above-mentioned literature and US Pat.
4,018,750 and 4,123,436 by reacting a dihydric phenol with a carbonate precursor such as phosgene, or simply by transesterification as described in U.S. Pat. No. 3,153,008. Alternatively, it can be made by other methods known to those skilled in the art. When a carbonate copolymer or interpolymer rather than a homopolymer is desired for use in preparing the polycarbonate mixtures of the present invention, two or more different dihydric phenols can be used, or the dihydric phenols and Glycol or hydroxy or acid terminated polyesters or copolymers with dibasic acids can be used. Also useful are branched polycarbonates, such as those described in US Pat. No. 4,001,184, and mixtures of linear and branched polycarbonates are also available. Additionally, mixtures of any of the above materials may be used in the practice of this invention to obtain aromatic polycarbonates. In any case, the preferred aromatic carbonate polymer for use as component (a)(i) herein is derived from 2,2-bis-(4-hydroxyphenyl)propane (bisphenol-A). It is a homopolymer. The copoly(ester-carbonate) copolymer resins (a)(ii) used in this invention generally contain repeating carbonate groups. carboxylate group containing an aromatic carbocyclic group in the linear polymer chain;
At least some of the carboxylate groups and at least some of the carbonate groups can be represented as a copolyester in which at least some of the carbonate groups are bonded directly to the ring carbon atoms of the aromatic carbocyclic group. These poly(ester-carbonate) copolymers are generally made by reacting a difunctional carboxylic acid, a dihydric phenol, and a carbonate precursor. Here, the dihydric phenol useful in blending the poly(ester-carbonate) to be used as component (a)(ii) has the general formula In the above formula, A is an aromatic group such as phnylene, biphenylene, naphthylene, anthrylene, etc. E can be an alkylene or alkylidene group such as a methylene, ethylene, propylene, propylidene, isopropylidene, butylene, butylidene, isobutylidene, amylene, isoamylene, amylidene, isoamylidene group, and the like. When E is an alkylene or alkylidene group, it also represents an aromatic bond,
Two or more alkylene or alkylidene groups bonded by non-alkylene or non-alkylidene groups such as tertiary amino bonds, ether bonds, carbonyl bonds, silicon-containing bonds, or bonded by sulfur-containing bonds such as sulfides, sulfoxides, sulfones, etc. It may consist of a base. Furthermore, E is an alicyclic group (e.g. cyclopentyl, cyclohexyl), a cyclohexylidene group such as cyclohexylidene, a sulfur-containing bond such as sulfide, sulfoxide or sulfone, an ether bond,
It may be a carbonyl group, a tertiary nitrogen group, or a silicon-containing bond such as a silane or siloxy.
Other groups that E may represent will occur to those skilled in the art. R is hydrogen or a monovalent hydrocarbon group such as an alkyl group (methyl, ethyl, propyl, etc.), an aryl group (phenyl, naphthyl, etc.), an aralkyl group (benzyl, ethyl phenyl, etc.), or an alicyclic group (cyclopentyl, cyclohexyl, etc.) It is.
Y is an inorganic atom such as chlorine, bromine, or fluorine; an inorganic group such as a nitro group; an organic group such as R above; or
It can be an oxy group such as OR; Y need only be inert to and unaffected by the reaction components and conditions.
m is any integer from 0 to the number of available positions on A for substitution, p is any integer from 0 to the number of available positions on E, and t is at least 1. are equal numbers, s is 0 or 1, and u is any integer including 0. When more than one Y substituent is present in the dihydric phenol compound represented by the above formula, they may be the same or different. The same is true for the R substituents. When s is 0 and u is non-zero in the formula, the aromatic rings are directly attached without an intervening alkylene or other bond. The positions of the hydroxyl group and Y on the aromatic nuclear residue A can vary in the ortho, meta or para positions, and two or more ring carbon atoms of the aromatic hydrocarbon residue are substituted with Y and the hydroxyl group. When present, each group can be in an adjacent, asymmetric or symmetrical relationship. Examples of dihydric phenol compounds that can be used in the present invention include: 2,2-bis-(4-hydroxyphenyl)propane (bisphenol-A), 2,4'-dihydroxydiphenylmethane. , bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-5-nitrophenyl)methane, bis-(4-hydroxy-2,6-dimethyl-
3-methoxyphenyl)methane, 1,1-bis-(4-hydroxyphenyl)ethane, 1,2-bis-(4-hydroxyphenyl)ethane, 1,1-bis-(4-hydroxy-2 -chlorophenyl)-ethane, 1,1-bis-(2,5-dimethyl-4-hydroxyphenyl)ethane, 1,3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2- Bis-(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis-(4-hydroxynaphthyl)propane, 2. 2-bis-(4-hydroxyphenyl)pentane, 3,3-bis-(4-hydroxyphenyl)pentane, 2,2-bis-(4-hydroxyphenyl)heptane, bis-(4-hydroxyphenyl)pentane enyl) phenylmethane, bis-(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis-(4-hydroxyphenyl)-
1,2-bis-(phenyl)propane, 2,2-bis-(4-hydroxyphenyl)-1
-Phenylpropane, etc. Also, dihydroxybenzene represented by hydroquinone and resorcinol, dihydroxydiphenyl such as 4,4'-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 2,4'-
Dihydroxydiphenyl; also includes dihydroxynaphthalene such as 2,6-dihydroxynaphthalene. Also useful are divalent phenols in which E is a sulfur-containing group, such as dihydroxyarylsulfones, such as bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, 5-chloro-2, Examples include 4'-dihydroxydiphenyl sulfone, 3-chloro-bis-(4-hydroxyphenyl) sulfone, and 4,4'-dihydroxytriphenyl disulfone. The preparation of these and other useful sulfones is described in US Pat. No. 2,288,282. Not only polysulfones but also substituted sulfones using halogen, nitrogen, alkyl groups, etc. are useful. As the divalent phenol here, US patent No.
Dihydroxy aromatic ethers such as those described in No. 3,148,172 are useful. Dihydroxy aromatic ethers may be prepared as described in US Pat. No. 2,739,171. Examples of such compounds include: 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxytriphenyl ether, 4,3'-, 4,2'-, 4,1'-, 2・2′−,
Dihydroxy diphenyl ether such as 2,3'-, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, 4,4'-dihydroxy-2,5-dimethyldiphenyl ether, 4,4'-dihydroxy -3,3'-diisobutyl diphenyl ether, 4,4'-dihydroxy-3,3'-diisopropyl diphenyl ether, 4,4'-dihydroxy-3,3'-dinitro diphenyl ether, 4,4'- Dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-3,3'-difluorodiphenyl ether, 4,4'-dihydroxy-2,3'-dibromodiphenyl ether, 4,4 '-dihydroxydinaphthyl ether, 4,4'-dihydroxy-3,3'-dichlorodinaphthyl ether, 2,4-dihydroxytetraphenyl ether, 2,4'-dihydroxypentaphenyl ether, 4,4'- Dihydroxy-2,6-dimethoxydiphenyl ether, 4,4'-dihydroxy-2,5-diethoxy-
Diphenyl ether etc. Mixtures of dihydric phenols may also be used, and reference herein to dihydric phenols is intended to include mixtures of such materials. For preparing the polyester-carbonates useful in formulating the compositions of this invention, any difunctional carboxylic acid or reactive derivative thereof conventionally used in making polyesters, such as acid halides, can be used. Commonly usable carboxylic acids include aliphatic carboxylic acids, aliphatic-aromatic carboxylic acids, or aromatic carboxylic acids. Aromatic dicarboxylic acids or their reactive derivatives such as aromatic diacid halides are preferred because they produce aromatic polyester-carbonates that are most useful from a physical property standpoint in the practice of this invention. be. Such carboxylic acids can be represented by the general formula ^R2 ( ^-R1 ) _-qCOOH . In the above formula, R ¹ is an alkylene, alkylidene or alicyclic group in the same manner as shown for E in the above formula; an alkylene, alkylidene or alicyclic group containing an ethylenically unsaturated bond; phenylene, naphthylene, bisphenylene, Aromatic groups such as substituted phenylene;
Represents two or more aromatic groups connected via a non-aromatic bond as defined by E in the formula; or a divalent aliphatic-aromatic hydrocarbon group such as an aralyl or alkaryl group. R ² is a carboxyl group or a hydroxyl group. q represents 1 when R ² is a hydroxyl group, and represents 0 or 1 when R ² is a carboxyl group. Therefore 2
Functional carboxylic acids are either monohydroxy monocarboxylic acids or dicarboxylic acids. Aromatic dicarboxylic acids or their reactive derivatives such as acid halides are preferred for the present invention. In these preferred aromatic dicarboxylic acids, for example as represented by the formula, R ² is a carboxyl group and R ¹ is an aromatic group such as phenylene, biphenylene, naphthylene, substituted phenylene, etc., connected via a non-aromatic bond. Two or more aromatic groups or divalent aliphatic-aromatic groups. Non-limiting examples of suitable and preferred aromatic dicarboxylic acids that may be used in preparing the polyester-carbonate resins of the present invention include phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, o-, m-, and p-phenylene dicarboxylic acids. Includes acetic acid, polynuclear aromatic acids such as diphenic acid and 1,4-naphthalic acid. These acids can be used individually or as a mixture of two or more different acids. Carbonate precursors can be either carbonyl halides, carbonate esters or haloformates. Carbonyl halides that can be used here include carbonyl chloride and carbonyl bromide. Examples of carbonate esters that can be used here include diphenyl carbonate, di(halophenyl) carbonate such as di(chlorophenyl) carbonate, di(bromophenyl) carbonate, di(trichlorophenyl) carbonate, di(tribromophenyl) carbonate, etc. , di(alkylphenyl)
Carbonates include di(tolyl) carbonate, di(naphthyl) carbonate, di(chloronaphthyl) carbonate, phenyltolyl carbonate, chloronaphthylchlorophenyl carbonate, and the like. Suitable haloformates for use herein include bishaloformates of divalent phenols, such as the bischloroformate of hydroquinone, or haloformates of glycols, such as ethylene glycol, neopentyl glycol, polyethylene glycol, etc. . Although other carbonate precursors will occur to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred. The preparation of polyester-carbonates that can be used in the compositions of the present invention is disclosed in U.S. Pat. No. 3,030,331.
No. 3169121, No. 3207814, No. 4194038 and No. 4156069. Polyester-carbonates useful in the practice of this invention include aromatic polyester-carbonates derived from dihydric phenols, aromatic dicarboxylic acids or their reactive derivatives such as aromatic diacid halides, and phosgene. A truly useful group of aromatic polyester-carbonates are:
Bisphenol-A, isophthalic acid, terephthalic acid or a mixture of isophthalic acid and terephthalic acid,
or reactive derivatives of these acids such as those derived from terephthaloyl dichloride, isophthaloyl dichloride, or mixtures of isophthaloyl chloride and terephthaloyl chloride, and phosgene. The molar ratio of dihydroxydiaryl units to benzenedicarboxylate units to carbonate units is 1:0.30 to 0.90:0.70.
~0.10, and the molar range of terephthalate units to isophthalate units is ~9:1.
It can be in the range of 3:7. The impact modifier combination (b) of the invention should be present in a small proportion of the total composition. Impact modifier combination (b)
(i) a poly(ethylene terephthalate) resin or an amorphous copolyester resin. Firstly, regarding poly(ethylene terephthalate) resins, such resins are currently very well known to those skilled in the art.
The production of poly(ethylene terephthalate) resins as well as other polyalkylene terephthalate resins is extensively described in Finnfield, US Pat. No. 2,465,319 and Pengilly, US Pat. No. 3,047,539. polyethylene terephthalate)
is preferred and fresh or waste polymers can be used, although other polyalkylene terephthalates or mixtures of polyalkylene terephthalates such as poly(1,4-butylene terephthalate) can also be used. In another embodiment, modifier component (b) herein
As (i), an amorphous copolyester resin can be used instead of poly(ethylene terephthalate). The amorphous copolyester resin has a glycol portion consisting of 1,4-cyclohexanedimethanol and ethylene glycol (in this case, the molar ratio of 1,4-cyclohexanedimethanol to ethylene glycol in the glycol portion is about 4:1 to 1: 4)
and an acid moiety consisting of terephthalic acid or isophthalic acid or a mixture of both acids,
It is not limited to this. Copolyester component (b)(i) is U.S. Patent No. 2901466
It can be made by methods well known to those skilled in the art, such as by condensation reactions as described in No.
More particularly, an acid or a mixture of acids or an alkyl ester of an aromatic dicarboxylic acid or a mixture thereof, e.g. dimethyl terephthalate, is placed in a flask with a dihydric alcohol at a temperature sufficient to initiate condensation of the copolymer, e.g. Heat to ℃. The temperature is then increased to about 250-300°C, vacuum is applied, and the condensation reaction is allowed to proceed until substantially complete. The condensation reaction can be facilitated by the use of a catalyst, the choice of catalyst being determined by the type of reaction components. The various catalysts used here are very well known to those skilled in the art and are too numerous to exemplify each. However, in general when using alkyl esters of dicarboxylic acid compounds, esterification type catalysts such as NaHTi in n-butanol are used.
(OC ₄ H ₉ ) ₆ is preferred. When a free acid is to be reacted with a free glycol, no catalyst is generally added until the main condensation reaction has been accomplished. The reaction generally involves starting in the presence of excess glycol and initially heating to a temperature sufficient to cause most of the condensation, followed by evaporation of the excess glycol. The entire reaction is carried out with stirring under an inert atmosphere. The temperature can then be increased to advantage, with or without applying vacuum immediately. As the temperature increases further, the pressure is advantageously reduced significantly and the condensation proceeds until the desired degree of polymerization is achieved. The product can be considered complete at this stage or can be further polymerized in the solid phase in well-known manner. For example, the highly monomeric condensation product formed can be cooled, ground, and the powder heated to a temperature slightly lower than that used during the last step of the melt phase polymerization, thereby forming solid particles. coagulation can be avoided. Solid phase polymerization is carried out until the desired degree of polymerization is achieved. Solid phase polymerization, among others, produces high degrees of polymerization without the attendant deterioration that often occurs when the last stage of melt polymerization is continued at temperatures high enough to achieve the desired degree of polymerization. Solid phase processes are advantageously carried out under normal atmospheric pressure or under large vacuum, using an inert atmosphere and stirring. The copolyester used as component (b)(i) in this invention has an intrinsic viscosity of at least about 0.4 dl/g as measured in 60/40 phenol/tetrachloroethane or other similar solvent at about 25°C.
The relative amounts of 1,4-cyclohexanedimethanol to ethylene glycol in the glycol moiety are such that the molar ratio of 1,4-cyclohexanedimethanol to ethylene glycol is 1 to give a polyester copolymer with suitable properties and heat deflection temperatures. :
It can be varied as long as it is between 4 and 4:1. Preferred polyesters for use as amorphous polyester copolymer component (b)(i) in the present invention have glycol moieties containing more ethylene glycol than 1,4-cyclohexanedimethanol, e.g. more than 50/50; Particularly preferred is about 70 moles of ethylene glycol to 30 moles of 1,4 cyclohexanedimethanol, and a copolyester as described above in which the acid moiety is terephthalic acid.
This type of copolyester is available from Eastman Chemical Company under the trade name KODAR PETG6763.
available on the market. Modifier combination (b) also comprises as component (ii) a diene-vinyl aromatic copolymer and an acrylic or methacrylic monomer alone or with other monomers containing one vinylidene group and copolymerizable with these. It also contains a thermoplastic interpolymer. The interpolymer consists solely of, or consists primarily of, a diene-vinyl aromatic copolymer latex and a _C1 - _C6 alkyl acrylate, a _C1 - _C6 alkyl methacrylate, acrylic acid, methacrylic acid, or any mixture thereof. It is a thermoplastic resin composition formed from a monomer material further comprising other copolymerizable monomers having one vinylidene group as the only aliphatic carbon-to-carbon bond polymerization-reactive unsaturated group. The monomeric material or monomer mixture is copolymerized with the copolymer by emulsion polymerization. The diene-vinyl aromatic copolymers used to form the latex include polymerized diene units such as butadiene, isoprene, 1,3-pentadiene, etc., and polymerized vinyl aromatic compound units such as styrene, α- methylstyrene,
It may contain units such as vinyltoluene and p-methylstyrene. Preferred copolymers are about 10-50% by weight
of styrene and about 90-50% butadiene, ranging from about 25,000 to 1,500,000, preferably about
It is a styrene-butadiene copolymer with a molecular weight in the range of 150,000 to 500,000. The copolymer solids are dispersed in water to form a latex having about 15 to 75 parts by weight of solids. Solid copolymer latexes in water contain a dispersant, such as sodium oleate, to keep the copolymer in suspension. The copolymer latex contains _C1 - _C6 alkyl acrylate, _C1 - _C6 alkyl methacrylate, acrylic acid or methacrylic acid monomers or mixtures thereof, neat or with acrylonitrile, vinylidene chloride, styrene or other similar A comonomer having one vinylidene group, such as an unsaturated compound, is further mixed and added. The monomer is preferably methyl methacrylate, or at least 55% by weight, preferably 75% by weight, of monomeric methyl methacrylate in a mixture with the other monomers mentioned above. The amount of monomer or monomer mixture added for polymerization with the copolymer latex ranges from about 65 to 85 parts by weight of the monomer mixture to 15 to 75 parts by weight of solids in the latex. Copolymerization of a monomer or monomer mixture with a copolymer solid suspended in water takes place at temperatures in the range of 15°C to 80°C in the presence of a polymerization modifier that acts as a free radical generating catalyst and a chain transfer agent. Close. Any of the well-known free radical generating catalysts that polymerize methyl methacrylate or acrylate itself can be utilized in emulsion polymerization. Suitable catalysts are, for example, catalysts of the organic peroxide type, such as methyl ethyl ketone peroxide and benzoyl peroxide; of the hydroperoxide type, such as potassium persulfate, or azoisobutyronitrile. Therefore, not only ordinary water-soluble catalysts but also monomer-soluble catalysts can be used. The amount of catalyst used is usually 0.05 to 0.5 parts by weight of the monomers used. Water-soluble forms of the catalyst may be added to the diluted copolymer latex before adding the monomers, whereas catalysts that are soluble in the monomers are usually added to the monomers before contacting the monomers with the latex. Suitable polymerization modifiers for use in this process are organic sulfur compounds such as thio acids, high molecular weight mercaptans such as benzyl mercaptan, aliphatic mercaptans having at least 6 carbon atoms per molecule such as octyl, dodecyl and tertiary dodecyl mercaptan, Mixtures of mercaptans such as those obtained from lauryl alcohol, nitrohydrazine, amino compounds, carbon tetrachloride and similar well-known polymerization modifiers or modifiers. n
Alkyl mercaptans with low water solubility, such as -dodecyl mercaptan or tertiary dodecyl mercaptan, are preferred. The amount of modifier added to control the polymerization rate is approximately 0.2-5% by weight of the monomers used.
is within the range of Preferably, the modifier is added to the monomers before mixing the latex and monomers. Latexes of butadiene-styrene, or other diene-vinyl aromatic copolymers, are usually prepared with a sufficient amount of a dispersant, such as sodium oleate, sodium lauryl sulfate, etc., to keep the copolymer in suspension in the liquid medium. contains. Prior to adding the monomer or monomer mixture to the latex, additional dispersant of the same or generally similar type is added to the latex. The monomers, catalyst and polymerization modifier in admixture with the latex are then emulsion polymerized in a suitable reactor under controlled temperature conditions of 15-80°C.
Coagulation of the copolymerized product is carried out, for example, with calcium chloride solution, followed by filtering, washing and drying. These materials can range in physical properties from relatively rigid compositions to rubbery compositions.
A preferred commercially available interpolymer of the type described above is available from Rohm and Haas Chemical Company under the trade name Acryloid KM611. Additional information about these interpolymers and their manufacture can be found in U.S. Pat.
2943074 and 2857360,
These are incorporated herein by reference. The compositions of the present invention are made by dry blending the aromatic polycarbonate resin with the poly(ester-carbonate) copolymer resin and then dry blending them with the impact modifier combination until a complete dispersion is obtained. be able to. The resin mixture is then extruded and cut to form pellets, which are then shaped in a conventional manner. Extrusion and molding cycles should preferably be conducted at temperatures below about 525°C to obtain the highest impact strength enhancement for the resin mixtures of this invention. This is because processing at temperatures above about 550° will adversely affect the impact strength values of the target composition. The resistance to impact failure of polycarbonate resin mixtures made in accordance with the present invention is 2.5″ x 0.5″ x
The notched Izot impact test, ASTM D56, was performed on molded specimens in the form of 0.125" rods. The specimens were mounted according to the ASTM D256 method and tested at room temperature. were measured on all specimens according to ASTM D256 method.In order to better understand how to carry out the present invention, the following non-limiting examples are included. Percentages are by weight unless otherwise noted. Each polycarbonate resin mixture was extruded on a Stirling extruder and molded on a 3oz Van Dorn injection molding machine, with processing temperatures for each operation listed below. Examples 1-6 Many of the compositions made in the examples below contain 30
Approximately 0.5 when measured in methylene chloride at °C
A copolyester-carbonate copolymer having an intrinsic viscosity (iv) of dl/g was included. This copolyester-carbonate copolymer was made as follows. In a reaction vessel, 16 methylene chloride, 8 parts water, 1906 g (8.36 mol) bisphenol-A,
24 ml of triethylamine, 3.4 g of sodium glyconate, and 65 g of p-tert-butylphenol chain terminator were added. With a pH of about 9-10.5, 2
1089.6 g (5.37 moles) of a mixture of 15% isophthaloyl dichloride and 85% terephthaloyl dichloride in methylene chloride of 1089.6 g (5.37 moles) was added with a 35% aqueous solution of caustic soda controlling the pH to about 9-10.5.
Added in minutes. After adding the diacid dichloride mixture, it was added at a rate of 36 g/min for 12 minutes while controlling the pH to about 10-11 with a 35% aqueous solution of caustic soda. The polymer mixture was diluted with 2 portions of methylene chloride and the saline phase was separated. once the formed polymer phase is 0.1
of HCl, three times with water, and then recovered by high steam precipitation to yield a white powder. The preferred poly(ester-carbonate) copolymers have a ratio of dihydroxydiaryl units to benzenedicarboxylate units to carbonate units of about 1:0.6 to 0.75:0.4.
~0.25 and a molar ratio of terephthalate units to isophthalate units of approximately 8.5:1.5. The following resin mixture was made. 2,2-bis-(4-hydroxyphenyl) having an intrinsic viscosity (iv) of about 0.46 to about 0.49 dl/ as measured in methylene chloride solution at 25°C.
An aromatic polycarbonate resin made from propane (General Electric Company, LEXAN 3250) was mixed with a poly(ester-carbonate) resin as described above in a laboratory tumbler until well mixed. Poly(ethylene terephthalate) resin (scrap available from Gutdeyer) and styrene-butadiene methyl methacrylate thermoplastic interpolymer (Acryloid KM-611 from Rohm & Haas Chemical Company) were then added and all components were combined with additives. Mix until complete dispersion. The mixture formed was fed to a Stirling extruder operated at the temperatures shown in the table below. The formed extrudate was cut into pellets. The thickness of the pellets as described above
Injection molded into 0.125in specimens. Table 1 shows the Izot impact strength of the measured samples. The weld line strength of the specimens was measured using the same method as the notched Izot specimens on specimens made from double gate moldings. When the polymer melt was injected through the gate, it formed a weld line in the center of the sample. Measurement is ASTM D256
Follow the instructions. The number in the title indicates the percentage of the sample that was ductile, and the title H indicates that the sample failed in the form of a hinge, indicating an improvement over brittle failure. The labeled samples contained no modifier, but were aromatic polycarbonates containing incomplete modifier combinations as indicated. The formulations used and the results obtained are shown in Table 1.

【table】

TABLE These data show that compositions made within the scope of the present invention are superior to unmodified aromatic polycarbonate resins as well as for each of the control compositions B-D in which some or all of the impact modifiers are not present. This shows the overall impact strength improvement shown. In the comparison between Example 2 and Example 3, high treatment temperature,
This clearly shows the adverse effect that molding temperatures above 525° can have on the impact strength of these compositions.
In Example 2, using a molding temperature of 550°, the impact resistance was three times greater than that obtained with the same composition molded at 500° (Example 3). Furthermore, these data demonstrate the overall improvement in impact strength provided by the compositions of the present invention over a wide composition range. In particular, when comparing Example 6, which has the extreme composition range, to Examples 1-4, which have intermediate amounts of each component, these data show that equally excellent impact strength improvements are obtained. The specifications and publications of each of the aforementioned patents are specifically incorporated herein by reference. Although the invention has been described with reference to certain preferred embodiments, many modifications will be made and will be taught to those skilled in the art. For example, instead of bisphenol-A polycarbonate, one containing units derived from tetramethylbisphenol-A or dixylenol sulfone can be used. Poly(ester-carbonates) based on terephthalate and isophthalate units
Alternatively, naphthanate units can be used in place of either. Isoprene-styrene copolymers can be used instead of butadiene-styrene copolymers. Such obvious modifications are within the scope of this invention.

Claims (1)

[Claims] 1. A polycarbonate resin mixture comprising (a)(i) an aromatic polycarbonate resin; and (ii) a poly(ester-carbonate) copolymer resin;
and (b)(i) a polyester resin selected from the group consisting of a poly(ethylene terephthalate) resin and an amorphous copolyester resin; and (ii) a diene-vinyl aromatic copolymer; and
At least one selected from _C1 - _C6 alkyl acrylate, _C1 - _C6 alkyl methacrylate, acrylic acid, methacrylic acid, and any mixture thereof, or at least one monomer containing one vinylidene group. comprising a homogeneous blend of an impact modifier combination consisting of a thermoplastic interpolymer of selected monomers in the form of a mixture with other monomers of (b) to 55 to 90% by weight of component (a); Ingredients 45~
The proportion of (a) (i) is 10% by weight, and the component (a) (i) is
10 to 90% by weight, and the component (b)(ii) is 10% by weight in component (b).
~40% by weight, and the amorphous copolyester resin of (b)(i) above has a molar ratio of (i) 1,4-cyclohexanedimethanol to ethylene glycol of 1:4 to 1:4, respectively.
(ii) an acid moiety consisting of an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and mixtures of the two acids; A resin mixture characterized in that it consists of a derivatized polyester copolymer. 2 Aromatic polycarbonate resin (a)(i) has the formula (In the formula, A is a divalent aromatic group of divalent phenol)
Resin mixture as described in Section. 3. Claim 2 in which A is derived from 4,4'-dihydroxy-di(mononuclear) arylalkane
Resin mixture as described in Section. 4. The resin mixture according to claim 1, wherein the aromatic polycarbonate resin (a)(i) comprises poly(2,2-dihydroxydiphenylpropane) carbonate. 5 Poly(ester-carbonate) copolymer component (a)(ii) is derived from (a) a dihydric phenol, (b) at least one aromatic dicarboxylic acid or a reactive derivative thereof, and (c) a carbonate precursor A resin mixture according to claim 1. 6 The poly(ester-carbonate) copolymer is derived from bisphenol-A, terephthaloyl dichloride, isophthaloyl dichloride, and phosgene, and the molar ratio of dihydroxy-diaryl units to benzene dicarboxylate units to carbonate units is 1. :0.6-0.75:0.4-0.25, and the molar ratio of terephthalate units to isophthalate units is 8.5:1.5. 7. The resin mixture of claim 1, wherein impact modifier combination component (b)(i) comprises poly(ethylene terephthalate). 8. The resin mixture according to claim 1, wherein the amorphous copolyester copolymer comprises poly((0.7)ethylene-co-(0.3)-1,4-cyclohexane dimethylene terephthalate). 9. In the thermoplastic interpolymer, the diene-vinyl aromatic copolymer comprises polymerized diene units selected from the group consisting of butadiene, isoprene and 1,3-pentadiene, and styrene,
A resin mixture according to claim 1 comprising polymerized units of a vinyl aromatic compound selected from the group consisting of alpha-methylstyrene, vinyltoluene and paramethylstyrene. 10 In the thermoplastic interpolymer, the diene-vinyl aromatic copolymer is composed of a styrene-butadiene copolymer consisting of 90 to 50% by weight of butadiene and 10 to 50% by weight of styrene, and the above copolymer is A resin mixture according to claim 1 having a molecular weight in the range of 1,500,000. 11. In thermoplastic interpolymers, consisting essentially of a monomer mixture consisting of at least 55% by weight of methyl acrylate in the form of a mixture with other monomers selected from acrylonitrile, vinylidene chloride and styrene, and methyl methacrylate A resin mixture according to claim 1, in which the monomers are selected from the group. 12 In the thermoplastic interpolymer, the diene-vinyl aromatic copolymer comprises 10 to 75 parts by weight, and the monomer comprises 65 to 85 parts by weight, based on the total weight of the interpolymer. 1
Resin mixture as described in Section.