JPS5865747A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To provide a polycarbonate resin compsn. consisting of polycarbonate resin, acrylic rubber and modified ethylene copolymer and capable of producing molding products with excellent impact resistance and weld strength. CONSTITUTION:The compsn. is prepared by blending 100pts.wt. polycarbonate resin, 0.5-50pts.wt. acrylic rubber (e.g. Metaprene W-530 made by Mitsubishi Rayon Co.) and about 0.05-25pts.wt. modified ethylene copolymer (obtaned by grafting about 0.05-1.5wt% alpha,beta-unsatd. carboxylic acid or deriv. thereof to a copolymer of ethylene and 3C or higher alpha-olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polycarbonate resin compositions. Specifically, the present invention relates to a polycarbonate resin composition for producing a molded article with improved thickness dependence in m* impact resistance and chemical resistance, and with little deterioration in physical properties at the weld area.

Polycarbonate resin is an excellent engineering plastic, but its drawbacks are that its impact resistance is highly dependent on thickness and that its chemical resistance is insufficient, and improvements in stiffness are desired.

As a polycarbonate resin composition with improved thickness dependence in impact resistance, a composition in which acrylic rubber is blended with polycarbonate resin (41 Kosho at-Koku 30♂
(see Japanese Patent Publication No. 2003-110016), and a copolymer K of ethylene and an α-olefin having 3 or more carbon atoms in a polycarbonate resin,
A composition containing a modified ethylene copolymer obtained by graft polymerization of an α,β-unsaturated carboxylic acid or a derivative thereof (see Japanese Patent Application Laid-open No. Sho! J-/J7T4TR) is known.

In these compositions, the thickness dependence of impact resistance has been improved; however, in the former composition, chemical resistance has not been improved.

There is a drawback that the strength and quality of the molded product decreases significantly when gasoline gets on it. First, the latter composition has the disadvantage that when it is mixed with a molded article, the physical properties of the sea urchin part are greatly reduced, and the weld part is noticeable and the appearance is poor.

The inventors of the present invention have repeatedly carried out electrical resistance tests in order to obtain a polycarbonate resin composition free of the unusual defects described above. As a result, when polycarbonate resin is combined with one acrylic rubber and one modified ethylene copolymer described above, the polycarbonate resin is Compared to a composition containing only acrylic rubber, chemical resistance is greatly improved, and a composition with excellent physical properties in the weld area can be obtained.In addition, only one combination of modified ethylene and polycarbonate resin is blended. The present invention was completed based on the knowledge that it is possible to obtain a composition that has significantly improved physical properties and appearance of the weld area, and also has improved chemical resistance, compared to conventional compositions. .

That is, the present invention aims to provide a polycarbonate resin composition of great industrial value.
Its purpose is to use polycarbonate resin 10O
For N negative part, (,) Acrylic Go A 01j-j
0Nit part, and (b) a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, a derivative thereof of α,β-unsaturated caronic acid is added to the copolymer in an amount of 0.0
j〜／、! Weight% modified ethylene copolymer obtained by graft polymerization 0. ! -Jjffi is blended with a polycarbonate resin composition that lasts a long time.

9 below provides a detailed explanation of the present invention.

The polycarbonate resin used in the present invention is:

It is a resin having repeating units represented by the general formula, and is a polymeric carbonate ester of a dihydroxydiaryl compound represented by the general formula.

Specific examples of the dihydroxydiaryl compound represented by the above general formula are bis(terhydroxyphenyl)methane and /,/-bis(terhydroxyphenyl)ethane.

-, -monobis(terhydroxyphenyl)propane, 1. Corbis(4t-hydroxyphenyl)butane.

λ1.2-bis(terhydroxyphenyl)mectane, bis(4t-hydroxyphenyl)phenylmethane, co, corbis(4t-human 4x-3-methylphenyl)propane, /, /-bis(a-hydroxy-3- tertiary-butylphenyl)propane, co-corbis(4t-hydroxy-3-butyl-p-mophenyl)propane, 1,-1bis(a-hydroxy-J,j-dibromophenyl)propane, 1, corbis(a-hydroxy-J , j-dichlorophenyl)propane.

1, l-bis(4t-hydroxyphenyl)cyclopentane.

Bis(hydroxyaryl)cycloalkanes such as /,/-bis(4t-hydroxyphenyl)cyclohexane.

@, 4t'-dihydroxycyphelether, 4t, 4
Dihydroxydiarylethyls such as t/-dihydroxy-3,34-dimethyldiphenyl ether, 41. g/-dihydroxydiphenyl sulfite@.

4t,4t'-dihydroxy-3,3'-dimethyldiphenylsulfide, 4t,4t'-dihydroxydiphenylsulfo aM/)
", a,v-dihydroxy-J,J'-dihydroxyschiff+3-lsulfoxides such as J'-dihydroxydiphenylsulfoxide, daβ'-dihydroxydiphenylsulfone, a,4t'
Examples include dihydroxysulfones such as -dihydroxy-3,3'-dimethyldiphenylsulfone.

Among these polycarbonate resins.

Polycarbonate resins made from 2/-bis(4t-hydroxyphenyl)furonokun (so-called bisphenol A) are preferred.

Examples of methods for producing polycarbonate resin include a phosgene method in which bisphenol A is reacted with phosgene tri, and a transesterification method in which bisphenol A is reacted with a carbonate ester such as diphenyl carbonate.

Acrylic dandruff is a rubber-like elastic material obtained by polymerization of acrylic acid ester or copolymerization mainly consisting of acrylic dandruff.A typical example is a rubber-like elastic material obtained by polymerizing acrylic acid ester or copolymerization mainly consisting of butyl acrylate and a small amount of butyl acrylate. Polymers obtained by polymerizing crosslinking monomers such as diacrylate,
A graft monomer like methyl methacrylate! A rubber-like monomer obtained by graft polymerization of - is opened.

In addition to butyl acrylate, examples of the acrylic ester include methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate, and monoethylhexyl acrylate. As a crosslinking agent, in addition to butylene diacrylate, there are also esters of polyol and acrylic acid or methacrylic acid, such as divinylbenzene, vinyl acrylate, vinyl methacrylate, etc. Vinyl compound, allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, monoallyl maleate, monoallyl fumarate,
Allyl compounds such as triallyl cyanurate are included.

Moreover, as the above-mentioned graft polymerizable monomer.

Methyl methacrylate [in addition to ethyl methacrylate,
Examples include methacrylic acid esters such as butyl methacrylate, hexyl methacrylate, coethylhexyl acrylate, and lauryl methacrylate, styrene, and acrylonitrile. A part of this graft polymerizable monomer can be co-merged using 1 lkK for polymerizing the above-mentioned acrylic ester and crosslinkable monomer.

The above-mentioned acrylic rubbers are 1, for example, manufactured by Mitsubishi Rayon, Metablane W-jJO% W-3θO, Rohm.
Manufactured by Ant Haas, acryloid K M -j j
'sKM-323% is also commercially available as Hitachi Chemical Co., Ltd., Pitax v-t4toi, Kanebuchi Chemical Co., Ltd., and Kane Ace FM1.

Modified ethylene copolymer consists of ethylene and α having 3 or more carbon atoms.
- Copolymer with olefin (hereinafter referred to as unmodified ethylene copolymer) k.

It was obtained by grafting a derivative of α,β-unsaturated carboxylic acid onto an unmodified ethylene copolymer at a concentration of 0.0 j −/j %.

The unmodified ethylene copolymer, which is the raw material for the above-mentioned modified ethylene copolymer, is prepared by using a Ziegler-Natsuta catalyst, especially a vanadium compound such as vanadium oxytrichloride or vanadium tetrachloride, and an organic aluminum compound. jO mol% or more, preferably 10 to 3 mol%,
! θ mol% or less, preferably 20~! Mol% carbon number 3
Stones are copolymerized with the above α-olefins.

α-olefin having 3 or more carbon atoms; 1. Examples include propylene, butene-11hexene-/, y'-ni-7, termethylbutene-/, g-methylpentene-l, but propylene or butene-7 is preferable. Examples of suitable unmodified ethylene copolymers include a series of resins commercially available from Mitsui Petrochemical Industries Ltd. under the trademark 7mer, such as py-r-port,
141090. Mu-0090° corner Toughmer A series (ethylene-butene/copolymer), Tough→-P02
IO, PO4tlO1POlslθ, POlrθ, etc.F
) /7W-PSiIJ, <(ethylene-propylene copolymer), etc.

α to be graft-polymerized to the unmodified ethylene copolymer,
Examples of β-unsaturated carboxylic acids or derivatives thereof (hereinafter simply referred to as unsaturated carboxylic acids) include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid or ζ
Examples include anhydrides or esters of acids such as i.

Among these, maleic anhydride is preferred.゛The amount of unsaturated carboxylic acid that is craft-polymerized into the unmodified ethylene copolymer is 0.0 per unmodified ethylene copolymer.
j~/, j Jukuramaru. If this amount is too small, the effect of improving the impact resistance of polycarbonate will be small.
Only molded products with a small tensile elongation rate could be obtained;
This is undesirable because it causes peeling, and conversely, if it is present too much, it causes coloring when added to polycarbonate, which is undesirable. Preferably, θ is in the range 1 of 7 to %/heavy lid.

Graft polymerization is carried out by adding an unsaturated carboxylic acid to an unmodified ethylene copolymer and melt-kneading the mixture at a temperature of usually /10 to JOO°C according to a conventional method. In order to efficiently cause #i1 polymerization during this graft polymerization, an organic peroxide such as α,α'-bis-t-butylperoxy-P-diisopropylbenzene is added to the unmodified ethylene copolymer.

It may be used in an amount of about 0.00/-0, Oj weight %.

Modified ethylene comonomer Fi used in the present invention, crystallinity (
Journal of Polymer Science, @Volume XV1 (
I91 pg/ 7~J 4'1i (according to rJY Ei
(measured by line method) is 7% or less, preferably it/~J! %, and melt index (58%) is preferable.
Measured at 0°C according to TM D I211 I7te)
is 0.07~! O1 is preferably q O0/~koO.

A modified ethylene copolymer of 11Il may be used as a modified ethylene copolymer having such a crystallinity and melt index, and Kameno having a crystallinity and melt index within the above range may be used as an unmodified ethylene copolymer.

In the present invention, a polycarbonate resin composition is prepared by melt-mixing a polycarbonate resin, the above-mentioned acrylic rubber, and a modified ethylene copolymer.

Melt mixing can be carried out according to conventional methods.

For example, using equipment such as a single screw or multi-screw extruder or a double screen electric mixer,
O-JJθ°C, preferably J! θ~! It is best to carry out once for 0.1 to 75 minutes, preferably 7 to 10 minutes, at a temperature of 10''C@degrees.

The amount of acrylic rubber used is the polycarbonate tree a/θO
Q, 1 to 50 parts by weight.

Preferably it is about /-7.0 weight S. Too much Kl
)%A, the effect of improving the physical properties of the weld part cannot be expected. On the other hand, if there is a large amount of K in the sand blast, K may impair the mechanical properties inherent to the polycarbonate resin. In addition, the amount of modified ethylene copolymer used is 1% of polycarbonate resin.
001 parts by weight of %o3~ parts by weight, preferably /~
of! The weight is about S. If it is too low, the effect of improving the impact resistance and chemical resistance cannot be expected.
If it is too much, it will impair the physical properties of the weld part.

The polycarbonate resin composition of the present invention can contain a soryamide resin, a polyester polycarbonate resin, a t-lyacetal resin suspension, and polyethylene terephthalate.

It is preferable to use the same weight or less as the polyvarnish such as polybutylene terephthalate, preferably 0 parts by weight or less to 100 parts by weight of the polycarbonate oil, and it is preferable to use polyethylene terephthalate.

In addition, the polycarbonate resin composition of the present invention may contain fine reinforcing agents such as glass fiber, carbon fiber, and metal fiber, and fillers such as silica, alumina, silica alumina, clays, glass beads, and carbon black. Well-known additives such as flame retardants such as aromatic compounds, stabilizers such as phosphorous esters and phosphoric esters, other lubricants, ultraviolet absorbers, and coloring agents may be added.・ 11HnEI:j 58-G5747 (5) The polycarbonate resin composition of the present invention can be used to produce molded products with excellent impact resistance and chemical resistance, and with little deterioration in physical properties at welded parts, so it can be used for injection molding and extrusion. By various molding methods such as molding and compression molding, molded products suitable for use as automobile parts, electrical and electronic parts, and other industrial materials can be obtained.

Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples, which do not go beyond the gist of the invention. indicates "parts by weight" and "% by weight".

Further, the isot impact strength is a constant value, and the tensile elongation rate and tensile strength are constant values.

The tensile stretch wheel of the weld part was constant for test pieces in which molten resin was injected from both ends of the gold specimen to form a weld part in the center of the test piece in the molding of the test piece specified in ABTM D431. The appearance of the weld area is determined by the naked eye of the test piece.
,Ta.

The tensile elongation rate of chemical resistance is determined by testing a tensile test piece defined by MST (MI) ≦ J/ such that the amount of bending distortion is 0.2%.
After bending it and immersing it in gasoline for 1 minute,
JJtl: This is a value measured on a test piece that was left to dry for a period of time.

Production example of modified ethylene copolymer 3.6 Butene with crystallinity of -0% and melt index of -/
100 parts of ethylene-butene/copolymer containing ffi/4' mol % and α,α'-bis-,-j,-4butylpayaoxy-P-diisopropylbenzene O0Q dissolved in a small amount of acetone. parts and maleic anhydride o, z m
were blended in a Henschel 2 xer, and this blend was melt-kneaded, extruded, and pelletized at 230°C using an Ou Il extruder to form a modified ethylene copolymer 1.
-1 again.

After crushing a portion of the pellets, unreacted maleic anhydride was extracted with acetone, and after press molding, maleic anhydride was determined by infrared spectroscopy. It turned out that there was a problem.

Example 1-Co and Comparative Example/~3 To 700 parts of polycarbonate tree NI (manufactured by Mitsubishi Chemical Industries, Ltd., Novarexfu O Coco) with an average molecular weight of 000, acrylic rubber (manufactured by Rohm and Haas Co., Ltd., Acryloid KM) was added. 310% or Mitsubishi Rayon ■, Metablane Wj-2), and the modified ethylene comonomer produced in the above production example were mixed in the amounts shown in the table below, and 4tom
The mixtures were melt-mixed and extruded using a yx (s extruder) at a temperature of 0.degree. C., and then pelletized to obtain polycarbonate resin composition pellets.

This pellet was molded using a 3.6 oz injection molding machine (Toshiba Kisago 8-718) and gold mt for molding test pieces for measuring physical properties.
Injection molding was performed at a resin temperature of -210°C, a mold temperature of 20°C, an injection time of 0 seconds, and a cooling time of 30 seconds.The physical properties of the obtained test pieces were as shown in Table 7 below.

For comparison, in the case of only polycarbonate resin,
Results obtained when only one of acrylic rubber (Metablen w rJy ) or modified ethylene copolymer was used are also shown.

/ 1. / 7 / / Example J-da and Comparative Example 4t-4 700 parts of the polycarbonate resin used in Example /, 10 parts of polybutylene terephthalate (manufactured by Mitsubishi Chemical Corporation, Nopad Wool! θ10) with intrinsic viscosity /, / Examples or polyethylene terephthalate with an intrinsic viscosity of 0.2!
(manufactured by Mitsubishi Chemical Industries, Ltd., NOVAPETS) 107rijO part (Example DA).

The acrylic rubber shown in the table below (Acryloid KM 37θ, manufactured by Rohm & Heath Co., Ltd.) and the modified ethylene copolymer produced according to the above production example were mixed, and a polycarbonate resin was prepared in the same manner as in Example 1. Composition pellets were produced [5. Injection molding was performed.

The physical properties of the obtained test piece were as shown in Table 2 below.

For comparison, a case where a composition consisting of only 10 parts of polycarbonate and 30 parts of polyethylene terephthalate was used, and a case where a composition containing only one of iK acrylic rubber or modified ethylene copolymer was used. The results are also listed.

Claims (1)

[Claims] (1) For 10σ weight part of polycarbonate resin, (a
) Acrylic rubber o, -t-jox* part, and (b
) An α,β-unsaturated carboxylic acid or a derivative thereof is added to a copolymer of ethylene and an α-olefin having 3 or more carbon atoms in an amount of θ, Oj~8! Modified ethylene copolymer obtained by graft polymerization to 0. A polycarbonate resin composition containing 11 parts by weight of j-1.