JPS58145756A - Acrylate core shell polymer, polycarbonate composition containing abs and olefin-acrylate copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Polycarbonate is a member of the family of engineering thermoplastics that can be used in a variety of applications.

Molding polycarbonate into complex shapes usually requires high temperatures to provide adequate melt flow to ensure that the mold is filled with melt. high temperature, i.e. about 35
The use of temperatures higher than 0° C. is not preferred because the materials used in (1) and (1) 4-carbonate are not stable at high temperatures.

The applicant has proposed that multiphase composite copolymers of acrylates and methacrylates: copolymers of acrylonitrile, butadiene and alkenyl aromatic compounds; and copolymers of olefins and acrylates, when used with large amounts of It has been found that this results in a molding material with good processability as evidenced by a high melt flow index.

By selecting the preferred compositions encompassed by the present invention, it is possible to obtain polycarbonate molding compositions whose impact strength remains significant, but whose melt viscosity is reduced and which is easily processed at low temperatures. These materials are particularly advantageous when molding complex shapes or detailed designs.

It was observed that the melt flow was reduced, and at the same time, a molding material with good impact strength in the thick portion and good weld line strength was obtained.

U.S. Pat. No. 3,13θ, L7 describes materials consisting of polycarbonate and ABS copolymers. West German patent no. i, i o q, g g q,
The materials listed are polycarbonate and styrene-acrylonitrile-styrene resin. U.S. Patent No. 3, g g
0.7 g No. 3 describes a specific group of IJ-/>-bonate transparent materials that can be used even if they contain an ABS polymer. Additionally, a large number of multiphase composite copolymers of polycarbonates, acrylates, and methano-1j-lates, as well as copolymers of olefins and acrylates, have been available on the market for over a year.

The material of the present invention comprises ial high molecular weight aromatic polycarbonate resin; ibl
C,-, a multiphase composite copolymer consisting of acrylates and C1-, methacrylate; lcl-copolymer of crinitrile, butadiene and alkenyl aromatic compounds; This is a thermoplastic molding material made of a copolymer of acrylate.

The polycarbonate resin is represented by the formula: (wherein A is a divalent aromatic group of dihydric phenol). Preferred polycarbonate resins are those of the formula: 1, where 1 and 2 are hydrogen, (lower) alkyl or phenyl, and n is at least 30 or preferably from I10 to qθθ. be. The term (lower)alkyl includes alkyl groups having number of carbon atoms/-A.

In the present invention, a high molecular weight thermoplastic aromatic polycarbonate is defined as having a number average molecular weight of approximately g, o o o to u θ0.
θ00 or more, preferably about /9.000~gθθ0
1,V determined in methylene chloride at 0 and 25 °C
.

Homopolycarbonates and copolycarbonates with θ30 to 10 dlll and mixtures thereof. These beaucarbonates are dihydric phenols, 2-bis(couhydroxyphenyl)furopane, bis(4L-hydroxyphenyl)methane, λ, unice(IJ-hydroxy-3-methylphenyl)propane, g, *-His(4-hydroxyphenyl)butane 1.2. ,,:1-C3,! ;,3',:Da'-tetrachloroge Ql-dihydroxyphenyl)propane, 2-(3,5,3',5'-tetrabromo-
4Z, 4'-dihydroxydiphenyl)propane,
Oyohi (3,3'-dichloro-4Z,'+'-dihydroxyphenyl)methane is derived. Other dihydric phenols suitable for use in the preparation of the above-described bocarbonates are described in U.S. Pat. No. 2.999. g J No. 3, No. 3.02 g, 3 A No. 5, No. 3.33 'l,
/311 and 1I, /31. s7! It is stated in No. r.

These aromatic polycarbonates can be prepared using known methods such as carbonate precursors such as dihydric phenols, such as phosgene, and the above-cited references and U.S. Pat.
0/g, '730 and No. 11. / 23. '1
3B or by reacting according to the method shown in US Pat. / 53.00 g
2, as well as other methods known to those skilled in the art.

Aromatic polycarbonates utilized in the present invention also include those described in U.S. Pat. Included are polymeric derivatives of dihydric phenols, dicarboxylic acids, and carbonic acid, such as those described in No. /bq, /, 2/.

Where carbonate copolymers are preferred over the use of homopolymers for the preparation of aromatic polycarbonates utilized in the practice of this invention, two or more different dihydric phenols or dihydric phenols and glycol or acid-terminated polyesters may be used. It is also possible to use copolymers of or with dibasic acids.

Mixtures of any of the above materials from which aromatic polycarbonates are obtained can also be used in the practice of this invention.

Branched polycarbonates, such as those described in U.S. Pat. It can be used when implementing.

01~. Multiphase composite copolymers consisting of acrylates and C1-5 methacrylates are disclosed in U.S. Pat. No. 2 A O, 1,93 and U.S. Pat.
oqt,.

It is described in No. 202. These copolymers are approximately '
75-99. g wound I C8-5 alkyl acrylate,
about 25 to qS weight percent of a first elastomer phase polymerized with a monomer system consisting of a θ/~S crosslinking monomer and a θ/~S grafting monomer, and the elastomer The final rigid thermoplastic phase polymerized in the presence of the phase consists of about 75-5% by weight.

The crosslinking monomer is a multiethylenically unsaturated monomer having multiple addition polymerizable reactive groups that all polymerize at substantially the same reaction rate. Suitable crosslinking monomers include polyacrylic and polymethacrylic esters of polyols, such as butylene diacrylate and dimethacrylate, trimethylolpropane trimethacrylate, and the like; di- and trivinylbenzene, vinylester acrylate and methacrylate, and the like. A preferred crosslinking monomer is butylene diacrylate.

The coupling monomer has a large number of reactive groups capable of addition polymerization. Accordingly, at least one of these reactive groups is a polyethylenically unsaturated monomer that polymerizes at a substantially different rate of polymerization than at least one other reactive group. The effect of the grafting monomer is to provide a residual amount of unsaturation within the elastomer phase, particularly at the final stage V) of the polymerization, and thus at or near the surface of the elastomer particles.

When the rigid thermoplastic phase is subsequently polymerized on the elastomer surface, the unsaturated addition-polymerizable reactive groups left by the grafting monomers are involved in the subsequent reaction, and at least a portion of the rigid phase is polymerized on the surface of the elastomer. chemically bond. Effective grouting monomers are less preferred than allyl group-containing monomers of allyl esters of ethylenically unsaturated acids, such as oriru acrylate, oriru methacrylate, diryoryl, but are polymerizable. Also preferred are diallyl esters of polycarboxylic acids that do not contain unsaturation.

Preferred grafting monomers are allyl methacrylate and diester lumale-1.

The most preferred copolymers are those consisting of only two stages (v), the first stage consisting of a copolymer of about 6θ to 95% by weight, with 95 to qq, g parts by weight of butyl acrylate. , 0/~, 2.5 ffi amount % of bunalene dichloromethane acrylate as crosslinking agent, θ/~, 2. It is a product obtained by polymerizing allyl methacrylate or diallyl maleate as a grafting agent in the amount of sx, and the final stage is about 60 to 100
It is a 1-fC product in which M amount % of methyl methacrylate is polymerized.

Acrylonitrile-butadiene-alkenyl aromatic compound copolymers are well known. Preferred Kyodo 1 combinations are those made from acrylonitrile-butadiene, nitrogen-styrene, and acrylonitrile-butadiene-alphamethylstyrene. The general method for producing these materials is as follows: 1) U.S. Pat. It is described in Rootsu 0.33/issue.

The preferable weight fraction of the acrylonitrile-butadiene-alkenyl aromatic compound copolymer ranges from 20 to qθ:
15-30: bS-30, preferably each 2S-35:
Yu0~, 25:3-5~da0.

Copolymers of olefins and acrylates are copolymers of C2~, onfines and CI~, and acrylates, and those used in carrying out the present invention are olefins such as ethylene, propylene, imbutylene, pentene, etc. It is a copolymer of C2~, acrylate is ethyl acrylate; n-butyl acrylate; /, 3-butylene diacrylate; methyl acrylate; /, gobutanediol diacrylate and 4-butyl acrylate 1) 1 note of yona acrylate. .

The IJ weight fraction of the olefin-acrylate copolymer based on the total mass of the copolymer ranges from about 1.theta. to about 30% by weight. The olefinic portion can be rubbed in the range of about 70 to about 90 degrees.

A preferred olefin-acrylate copolymer is an ethylene-ethyl acrylate copolymer, in which the weight ratio of ethylene to ethyl acrylate moieties is about lIS2/. These olefin rate copolymers are either commercially available or prepared by methods well known to those skilled in the art.In general, the materials of the present invention contain from 5 to 95 parts by weight, More preferred (
-< is g5~95 parts by weight polycarbonate wheat, 2 attacks~3
5 parts by weight, more preferably 5 to 70 parts by weight of a copolymer of ac-10 nitrile-butadiene-arykenyl aromatic compound, θS~/3 parts by weight, more preferably 7 to 72 parts by weight of C1~ 5. Acrylate and C + ~, a multiphase composite copolymer consisting of methacrylate and 05 to 70 parts by weight,
More preferably / ~ 51 parts ~, olefin C
, ~, it is a copolymer of 1/-ite. All parts by weight are polycarbonate, acrylonitrile in the material.
The amount is per 700 parts of the total of phytadiene-alkenyl aromatic copolymer, multiphase composite copolymer, and olefin-acrylate copolymer.

The materials of the invention include reinforcing fillers, such as aluminum,
Ferrous metals, aluminum alloys, etc. and non-metals, and evaporated carbon filaments, silicates, such as acicular calcium silicate, acicular calcium sulfate, wollastonite, asbestos, titanium dioxide, bentonite, chao-)night titanium acidity 1) Rum and titanic acid Vines containing salt whiskers, glass flakes and fibers and mixtures thereof. If the filler does not increase the strength and stiffness of the compound, it is simply a filler and not a reinforcing agent as intended here. In particular, reinforcing fillers increase flexural strength, flexural modulus, tensile strength, and heat deflection temperature. Reinforcing fillers are generally required to be present in amounts that exhibit at least a reinforcing effect; Approximately/~60 of the family
The vine contains % of heavy weight.

%, the preferred reinforcing agent is glass (P), and it is preferred to use glass fiber filaments consisting of relatively soda-free lime-aluminum borosilicate glass. This is known as "E" glass. However, if electrical properties are not of great importance, other glasses may be useful, such as a slightly soda-laden glass known as "C" glass. Made by blowing, flame blowing and mechanical tension.

The preferred filaments for reinforcement are those made by mechanical tension. The diameter of the filament is approximately 0003 to 0009 inches, but the present invention is not limited thereto.

It goes without saying that glass fibers include all glass fiber materials including glass silk and the glass fiber fabrics, rovings, stable fibers and glass fiber mats obtained therefrom. The length of the crow filaments and whether they are bundled into fibers, twisted into threads, robes or rovings, woven into cloaks, etc. are not limited by the present invention. However, when using glass fiber filaments, they are first assembled into bundles known as strands.

Binding agents are applied to the glass filaments to bind the filaments into strands that can be used. The strands can then be cut to various desired lengths. The length of the strand is about //g' to about /#,
It is advantageous to use lengths preferably shorter than //II''. These are called chopped strands. Some of these binders are polymers, such as polyvinyl acetate, certain polyester resins, polycarbohydrates, Starch, acrylic, melamine or polyvinyl alcohol.Preferably, the material contains about/to about 0.1% glass fiber by weight.

A flame retardant amount of flame retardant is also added to the resin component θ5- in the material of the present invention.
The vine used in an amount of 50% by weight. Examples of suitable flame retardants are described in U.S. Pat. No. 3,936.400 and U.S. Pat. Other conventional non-reinforcing fillers, antioxidants, extrusion promoters, light stabilizers, blowing agents, such as U.S. Pat. No. 4.21.3, cited in reference. If desired, these compounds may be added to the material of the present invention.

The method of manufacturing the material of the present invention is a conventional method. Preferably, each component is added as a component of a blend premix and mixed, for example by passing through an extruder or by plasticizing in a mill at a temperature depending on the particular composition. The mixed material is cooled, cut into shaped granules and shaped into the desired σ) shape.

The invention will be explained in more detail in the following examples.

All parts are based on weight t.

ASTM 0251. The term double gate (1)G) is used in the examples to refer to the weld line strength of the samples produced by double gate molding, tested according to the following. The number on the upper right of the impact data in the example is the ductility of the sample 6
It is a fraction. The term MFI refers to the melt flow index, converted to grams per 10 minutes, obtained according to AS1'Ml)/U3g at conditions 01300°C. Notched Izo1 units are feet/bonds/inches; beauty values are feet/pounds.

Example 7 A coloring material of 150θOg had an intrinsic viscosity of θl11. measured in methylene chloride at 25'C. dl, Q, Nibis(4'-hydroxyphenyl)propane polycarbonate h9/weight, n-butyl acrylate vs. methyl meth/y II v-t (AcryloidKM 33
0, Pencil Pani (Rohm & Haas, Philadelphia, State) with a weight ratio of approximately Q:/3it.
parts, acrylonitrile-butadiene-styrene (acrylonitrile/phtadiene/styrene 30/211/11
b, kralastic Ll, S, S, chemicals) copolymer s fc and ethylene-ethyl acrylate copolymer (Bakelil, e DPD
b/b 9, Union Carbide, Danbury, Conn.) by mechanically mixing the ingredients in a tumbler, then extruding and pelletizing the material. Injection mold the pellet, //g″×S″×l/2″ and //!”x 5'x
//2" test pieces were produced. Izod impact values are shown in Table 1.

Table / A' 21. /, 2.71oc13.0°
poa100B210 /'Ag""
l Otsu 0 q%10013, l, 1IOI) 10
0 c3/llllAg1001O O,93θq100 D2512. and AlI3 copolymer 3.0 (kralastic 5LS) control: polycarbonate 95; It is only the unique mixture of all the components of the present invention that provides a compositional distribution with very good processability, as indicated by high MFI, while maintaining or even improving it.

Example 2: 76 parts by weight of the polycarbonate of Example/, 3.0 parts by weight of the polyphasic copolymer of Example 1 and IO A 150θθg molding material containing parts by weight of the ethylene-ethyl acrylate copolymer of Example 1 was prepared using the same procedure as used in Example 1. Table of test results
Shown below.

Table YuE q72 iθq10° 11003.
3゜F1/IA3/1A7100/yu, gloo
3. Same as U O Branch Public St E.

As the data show, high melt flow indices can be obtained in the unfavorable region of compositional parameters. However, the impact resistance is significantly reduced. The effect of olefinic acrylate components on melt flow is illustrated by this data.

Obviously, the present invention may be modified in light of the above teachings. It is therefore a matter of course that the particular embodiments of the invention may be varied within the scope of the claims.

Patent Applicant General Electric Company Agent ('7630) Tokuji Ikunuma

Claims (1)

[Claims] (c(at high molecular weight aromatic pho++ carbonate resin;
bl C+ ~ 5 crylate C7 ~, methacrylate E multiphase composite copolymer; tel crylinitol II, butadiene, yohyl kenyl aromatic compound copolymer; and idl C2 ~, olefin and C1 ~! A thermoplastic molding material made of a copolymer of I-cho acrylate. A thermoplastic molding material according to Claims No. (C), in which component (C1 is acrylonitrile, butadiene, and styrene). The thermoplastic molding material according to claim 2, which is a divalent aromatic group) is represented by the formula: (wherein, [t
l and I (, ' are hydrogen, (lower) alkyl or phenyl, and n is at least <+/00) Material. (,9 multiphase composite copolymer is methyl methacrylate #,
Thermoplastic molding material according to claim 11-1, comprising rhin-butyl and IJl/-. (Ro1 polycarbonate tree, 2-vinu (q
Thermoplastic molding material according to claim 1, which is derived from -hydroxyphenyl)propane. (The thermoplastic molding material described in claim C) characterized by a reinforcing filler with a reinforcement amount of 71. Thermoplastic molding material. 19) Claim No. 1 characterized by a flame retardant amount of a flame retardant.
The thermoplastic molding material described in item C. (10) The thermoplastic molding material according to claim 1, which contains a flame retardant in a flame retardant amount.