JPS60135454A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent mechanical properties, chemical resistance, appearance and moldability, containing an arom. polycarbonate resin, an arom. satd. polyester resin, a polyolefin and a specified arylate ester copolymer. CONSTITUTION:A thermoplastic resin compsn. contains 60-90wt% arom. polycarbonate resin, 8-30wt% arom. satd. polyester resin, 1-20wt% polyolefin and 1.0-20wt% acrylate ester copolymer of an acrylate ester contg. a 1-5C (un)saturated linear or branched aliph. hydrocarbon group with a methacrylate ester contg. a 1-5C (un)saturated linear or branched aliph. hydrocarbon group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition that exhibits various mechanical properties, particularly excellent impact resistance at low temperatures, chemical resistance and appearance, as well as good moldability. In detail, A, aromatic polycarbonate resin 60-90 ivt%, B, aromatic saturated polyester resin 8-30-1%, and C,
It contains 1 to 20 wt% of polyolefin and 1 to 20-1% of acrylic ester copolymer, and the acrylic ester copolymer is a saturated or unsaturated linear or branched chain having 1 to 5 carbon atoms. It is characterized by being a copolymer of an acrylic ester having an aliphatic hydrocarbon group and (1) a methacrylic ester having a saturated or unsaturated straight chain or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms. It is a thermoplastic resin composition with excellent low-temperature 11i4 impact resistance.

As is well known, aromatic polycarbonate resins are tough, have excellent impact resistance for 1 hour, have excellent electrical properties, and have good thermal stability, so they are widely used as useful engineering plastics. On the other hand, it has disadvantages such as high melt viscosity and poor moldability, thickness dependence of impact resistance, and problems with chemical resistance such as cranking when it comes into contact with aromatic solvents or gasoline. The reality is that its scope of application is limited for several reasons.

In order to improve these drawbacks, proposals have been made to blend different types of resins into aromatic polycarbonate resins. For example, Japanese Patent Publication No. 40-17663 discloses polyolefin, Japanese Patent Publication No. 40-24191 discloses ethylene-propylene copolymer, Japanese Patent Publication No. 38-15225 discloses BS resin, and Japanese Patent Publication No. 39-71 describes polyolefin. is an MBS resin, and Japanese Patent Publication No. 48-29308 teaches the addition of ■^S resin, which improves moldability and impact resistance, but lowers the heat distortion temperature and improves compatibility. There are various defects such as surface peeling phenomenon caused by defects and weakness of the weld portion, and improvements cannot necessarily be said to be sufficient for practical use. Furthermore, Japanese Patent Publication No. 36-14035 proposes blending an aromatic polyester resin with an aromatic polycarbonate resin to improve solvent resistance, but these resins have poor compatibility and the resulting composition has low impact resistance, and no improvement has been achieved in the thickness dependence of impact strength. Furthermore, Japanese Patent Publication No. 39-20434 proposes a ternary composition containing an aromatic polycarbonate resin, an aromatic saturated polyester resin, and a polyolefin, and although the moldability and solvent resistance have been improved to some extent, This composition has poor induction resistance at low temperatures, which is currently required in the market, and also causes noticeable flow marks at the gate, resulting in poor product appearance and poor performance when used with paint applied. There is a drawback that the flow mark part is more likely to peel off than other parts.

The present inventors have developed a resin composition that has well-balanced molding processability of aromatic polycarbonate + 11 resin as well as various mechanical properties, thermal properties, and chemical properties, and in particular, a resin composition that has low-temperature impact resistance and impact strength that are thickness-dependent. The present inventors have discovered a quaternary thermoplastic resin composition that has significantly improved properties and chemical resistance, and has significantly reduced or eliminated flow marks at the gate area, leading to the completion of the present invention.

The present invention will be explained in detail below.

The aromatic polycarbonate resin of the present invention is an optionally branched thermoplastic polycarbonate polymer made by reacting an aromatic dihydroxy or a small amount of a polyhydroxy compound with a diester of phosgene or carbonic acid. An example of an aromatic dihydroxy compound is
2.2-bis(4-hydroxyphenyl)propane (bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A, bis(4-hydroxyphenyl)-P-diisopropylbenzene, hydroquinone, resorcinol, 4.4'-dihydroxy diphenyl, etc., and bisphenol A is particularly preferred. In addition, to obtain a branched aromatic polycarbonate resin,
Phloroglucin, 4,6-dimedyru 2.4.6-)
(4-hydroxyphenyl)hebutene-2,4,6
-Simethyl-2.4.6- Tri(4-hydroxyphenyl)hebutane, 2.6-Simethyl-2.4.6-
1-li(4-hydroxyphenyl)hebutene-3,4
, 6-dimethyl-2.4.6-tri(4-hydroxyphenyl)hebutane, ■.

3.5-1-li(4-hydroxyphenyl)henzene, 1.1.1-tri(4-hydroxyphenyl)ethane, etc., polyhydroxy compounds, and 3゜3
-bis(4-hydroxyaryl)oxindole (
= isatin bisphenol), 5-chloroisatin, 5
, 7-cycloisotin, 5-bromysatin, etc. as part of the dihydroxy compound, for example, 0.2 to 2 mol%.
is replaced with a polyhydroxy compound. Furthermore, monovalent aromatic hydroxy compounds suitable for controlling molecular weight include m- and p-methylphenol, t- and p-propylphenol, p-bromophenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. is preferred. Typical aromatic polycarbonate resins include bis(4-hydroxyphenyl)alkane-based dihydroxy compounds, especially polycarbonate resins whose main raw material is bisphenol A. Branched polycarbonate obtained by combining a small amount of trivalent thunol compound i can also be mentioned.Aromatic polycarbonate resin is used as a mixture of two or more types. Good too.

The aromatic saturated polyester resin used in the present invention is
It is a polymer obtained by reacting aromatic dicarboxylic acid or its diester with glycol, alkyl, or kylene oxide by a known method. Specifically, it is a polymer obtained by reacting terephthalic acid or dimethyl terephthalate as the main component of aromatic dicarboxylic acid. Examples include polyethylene terecrate and polytetramethylene terephthalate obtained by reacting this with ethylene glycol, butanediol, ethylene oxide, etc. The aromatic saturated polyester resin may be a copolymer or may be used in the form of a mixture of two or more types. The aromatic saturated polyester resin used in the present invention is prepared at 30°C in a mixed solvent of phenol and tetrachloroethylene in a weight ratio of 6:4.
Intrinsic viscosity (intrinsic viscosity) measured at 0.8 or higher, usually 1
．． It is preferable to have a value of 0 to 1.5, and if it is less than 0.8, the improvement in impact strength and chemical resistance will be insufficient.

The polyolefin of the present invention includes polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-
1. Ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc., with a low glass transition temperature, -40°C or lower Particularly preferred are those.

The 0, acrylic acid ester copolymer used in the present invention is an acrylic ester having a saturated or unsaturated straight or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms, and ■ a carbon number It is a copolymer with a methacrylic acid ester having 1 to 5 saturated or unsaturated linear or branched aliphatic hydrocarbon groups.

Here, as acrylic esters having a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms, methyl acrylate, ethyl acrylate, isobutyl acrylate, diacrylic #-1,4 -butanediol, 〇-butyl acrylate, diacrylic acid-1,
Examples include 3-butanediol. Also, carbon number 1~
As the methacrylic ester (2) having a saturated or unsaturated straight or branched aliphatic hydrocarbon group in No. 5, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 1,3-butylene dimethacrylate, isobutyl methacrylate Examples include.

The acrylic ester moiety in the present acrylic ester copolymer is preferably in the range of about 50 to 85 wt%, such as a copolymer with a weight ratio of 0-butyl tecrylate: methyl methacrylate of 3:2. is exemplified. As such an acrylic ester copolymer, a resin commercially available from Rohm & Haas under the trade name [Balaroid KM330J] is suitably used.

To the above in the thermoplastic resin composition of the present invention.

Aromatic polycarbonate resin is 60-90 wt%, B
, aromatic saturated polyester resin is 8-30 wt%, C
, 1 to 20 wt% of polyolefin, and 1.0 to 2 Qwt% of acrylic acid ester copolymer.

If the aromatic polycarbonate 1M fat is less than 60-1%, the heat resistance will not reach the level required for engineering plastics, and the dimensional stability will be poor, and if it exceeds 90-t%, the improvement in moldability will be insufficient. , chemical resistance is also insufficient. 8ivt% aromatic saturated polyester resin
If the amount is less, the improvement of chemical resistance will be insufficient, and 3
If it exceeds 0-1%, it causes poor dimensional stability. Further, if the polyolefin content is less than 1 wt%, no improvement in chemical resistance or impact resistance will be achieved, and if it exceeds 20-t%, it will cause poor heat resistance. Furthermore, if the acrylic ester copolymer content is less than 1iyt%, it is difficult to improve flow marks at the gate.

The thermoplastic resin composition of the present invention as described above may contain various additives such as stabilizers, pigments, dyes, flame retardants, and lubricants, reinforcing materials such as inorganic or organic fiber substances, glass beads, etc., as desired. Various fillers may be blended, and other resin components may also be blended within a range that does not impair the characteristics of the present invention. For example, polycarbonate made from bisphenol A or tetrabromobisphenol A.
Examples include adding oligomers to improve moldability, W# flame resistance, and surface properties, and adding heat-resistant polyesters such as polyester carbonate and polyarylate (for example, product name: U Polymer, Unitika 01) to improve heat resistance. It will be done.

In preparing the thermoplastic resin composition of the present invention,
Any conventionally known method may be used, and methods of kneading using an extruder, Banbury mixer, rolls, etc. may be selected as appropriate.

Hereinafter, it will be explained by examples and comparative examples, but "%"
and [molecular weight] are on a weight basis unless otherwise specified.

Examples 1 to 3 and Comparative Examples 1 to 3 Aromatic polycarbonate resin made from bisphenol A (produced by Mitsubishi Gas Chemical Co., Ltd., trade name Newpiron 5-iooo, molecular weight 28,000), polyethylene terephthalate (produced by Toyobo Co., Ltd.) Special product, product name: Univent RT-580, intrinsic viscosity 1.2 at 30°C, in a mixed solvent of phenol/tetrachloroethylene (6/4 wt ratio), polyethylene (
Manufactured by Mitsui Petrochemical ■, product name: Hize Sox 7000F)
and acrylic ester copolymer (Rohm & Haas ■
(trade name: Valaloid kM330) manufactured by Valoid Co., Ltd., in the proportions shown in Table 1 were placed in a blender and mixed for 30 minutes.

Feeding the resulting mixture into a 408-vented extruder;
The mixture was melted and kneaded at a cylinder temperature of 260°C to form pellets. After drying this pellet in a hot air dryer at 120° C. for 5 hours or more, a test piece for measuring physical properties was molded by injection molding. The test results are shown in Table 1.

For comparison, aromatic polycarbonate resin China, Germany (comparative example -
1), a composition of aromatic polycarbonate resin and polyethylene terephthalate (Comparative Example-2), and a composition in which the acrylic ester copolymer was removed from the resin component of the Example (Comparative Example-3). The physical properties were measured using the method. The test results are shown in Table 1.

Examples 4 and 5 and Comparative Examples 4 and 5 In Examples 1 to 3, ethylene-propylene copolymer (manufactured by Mitsui Petrochemicals @ Xun, trade name: Tafmer P-680, and Nippon Gosei) was used instead of polyethylene. Rubber a1M,
The same resin components were used, except for using JSREP 07C (trade name: JSREP 07C), mixed in the proportions shown in Table 1, pelletized using a vented extruder, and molded into test pieces for measuring physical properties in the same manner. The measurement results are shown in Table 1.

For comparison, Table 1 also shows the results of the same procedure as above for Comparative Examples 4 and 5, in which the acrylic ester copolymer was removed from the resin components of Examples.

Examples 6 and 7 and Comparative Examples 6 and 7 In Examples 1 to 3, polybutylene terephthalate (produced by Toyobo Co., Ltd.,
Product name: Tough Pair) N-1200, intrinsic viscosity 1.2
at 30°C, phenol/tetrachlorethylene
The same resin components were used except that a mixed solvent with a ratio of 6/dwt) was used, mixed at the ratio shown in Table 1, and the physical properties were determined by the same operation except that the cylinder temperature of the vented extruder was set at 250°C. A test piece for measurement was molded. The measurement results are shown in Table 1.

For comparison, the above also applies to a resin composition of aromatic polycarbonate resin and polybutylene terephthalate (Comparative Example-6) and a resin composition in which the acrylic acid ester copolymer was removed from the resin component of the example (Comparative Example-7). The results obtained in the same manner as above are also listed in Table 1.

Example-8 and Comparative Example-8 The same resin components as in Example-6 or 7 except that ethylene-propylene copolymer (manufactured by Mitsui Petrochemicals, trade name: Tafmer p-680) was used instead of polyethylene. were mixed in the proportions shown in Table 1, formed into pellets using a vented extruder, and molded into test pieces for measuring physical properties in the same manner. The measurement results are shown in Table 1.

For comparison, Table 1 also shows the results of the same procedure as above for the resin component of Example 8 except that the acrylic ester copolymer was removed (Comparative Example 8).

Examples 9 and 10 The resin components used in Examples 1 to 8 were mixed in the proportions shown in Table 1, and test pieces for measuring physical properties were formed in the same manner as Examples 1 to 8. Physical properties were measured. The results are shown in Table 1.

Hand νε Main City Masho (self-proposal) January 22, 1985 1, Description of the case 1988 Patent Application No. 243299 2, Name of the invention Thermoplastic resin composition 3, Relationship with the person making the amendment ( Patent Applicant) 4. Subject of Amendment 5. The following amendments will be made to the "Detailed Description of the Invention" column of the description of the contents of the amendment.

■Correct "thickness dependence" in the first line of page 4 to "1 thickness dependence".

■Delete "7" in the row of Hysenox "7000F" in the ratio-4 column of Table 1 on pages 16-17.

■ Insert [7] in the row of ethylene resin rP-680J in the ratio-4 column of Table 1 on pages 16-17.

(2) Correct "65" in the row of polycarbonate 1-resin in column 7 of Table 1 on pages 16-17 to [66].

(1) Correct "168" in the row of Polycarbonate 1-Resin in column 9 of Table 1 on pages 16-17 to "66".

(2) Correct ``68'' in the column 10 of Table 1 on pages 16-17 for polycarbofluoride 1 to resin to ``64''.

that's all

Claims (1)

[Claims] ^, Aromatic polycarbonate resin 60~90w 1%
, B, aromatic saturated polyester resin 8-30Ht%,
C, polyolefin 1-20w 1%, and D, acrylic ester copolymer 1.0-20w 1%, and the acrylic ester copolymer has 1 to 5 carbon atoms.
Acrylic acid ester having a saturated or unsaturated straight-chain or branched aliphatic hydrocarbon group; and ■ Methacrylic ester having a saturated or unsaturated straight-chain or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms. A thermoplastic resin composition with excellent low-temperature impact resistance characterized by being a copolymer of