JP2002105301A - Rubber reinforced polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber reinforced polycarbonate resin composition having excellent thermal stability without reducing flowability, impact resistance, thermal resistance and steam resistance and capable of preventing deficiencies such as yellowing of color tone in the case of receiving an excess heat history in drying and molding process. SOLUTION: This rubber reinforced polycarbonate resin composition comprises 99.5-90 wt.% of a polycarbonate resin and 0.5-10 wt.% of a rubber modified (meth)acrylate polymer, and 100 pts.wt. of the rubber modified (meth) acrylate polymer includes (a) 3-20 pts.wt. of 6-[3-(3-t-butyl-4-hydroxy-5- methylphenyl)propoxy]-2,4,6,8,10-tetra-t-butylbenz[d,f][1.3.2]dioxapho sphepin and (b) 10-70 pts. of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-reinforced polycarbonate resin composition having excellent low-temperature impact resistance, heat resistance and thermal stability. More specifically, the present invention relates to a rubber-reinforced polycarbonate resin composition in which problems such as yellowing of the color tone have been improved even after receiving an excessive heat history in drying and molding.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in impact resistance, heat resistance, and transparency, and are used for electric / electronic, optical, building materials,
It is widely used in various fields such as medicine, food, and vehicles. However, polycarbonate resins are inferior in impact resistance and fluidity at low temperatures, and therefore, conventionally, a modifying material such as a rubber-modified (meth) acrylate has been blended into the polycarbonate resin.

However, although the rubber-reinforced polycarbonate resin containing the modifier has improved impact resistance and fluidity at low temperatures, it suffers from an excessive heat history such as being exposed to high temperatures for a long time in drying and molding. Thus, there is a problem that the rubber component in the modifier deteriorates and the color tone of the rubber-reinforced polycarbonate resin changes.

[0004]

In order to prevent this yellowing, an antioxidant has been incorporated. As antioxidants, phosphorus-based and phenol-based antioxidants are known, but even if they are individually added to rubber-reinforced polycarbonate resin, the effect of preventing yellowing is poor, and when added in large amounts to increase the effect, There is a problem that the thermal stability such as steam resistance is poor. In addition, even when a phosphorus-based antioxidant and a phenol-based antioxidant were used in combination, the effect of preventing discoloration was slightly observed as compared with the case where each antioxidant was used alone, but a remarkable improvement effect was not obtained. .

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned problems, and as a result, a specific phosphorus-based antioxidant and a phenol-based antioxidant have been used in a specific ratio in a rubber-reinforced polycarbonate resin. By doing so, it was found that a fluid-reinforced, impact-resistant, heat-resistant, and even a rubber-reinforced polycarbonate resin composition having a high degree of thermal stability was obtained without deteriorating the steam resistance, and the present invention was completed. Reached.

That is, the present invention relates to a rubber-reinforced polycarbonate resin composition comprising 99.5 to 90% by weight of a polycarbonate resin and 0.5 to 10% by weight of a rubber-modified (meth) acrylic polymer. ) Per 100 parts by weight of the acrylic polymer, (a) 6- [3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,6,8,10-tetra-t
-Bityldibenz [d, f] [1.3.2] dioxaphosphepin: 3 to 20 parts by weight, and (b) octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate: Provides a rubber-reinforced polycarbonate resin composition prepared to contain 10 to 70 parts.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polycarbonate resin used in the present invention is a polymer obtained by a phosgene method of reacting various dihydroxydiaryl compounds with phosgene, or a transesterification method of reacting a dihydroxydiaryl compound with a carbonate such as diphenyl carbonate. A typical example is an aromatic polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

The above dihydroxydiaryl compounds include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) in addition to bisphenol A.
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxy diaryl ethers such as 3,3'-dimethyl diphenyl ether; dihydroxy diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide; 4,4'-dihydroxy diphenyl sulphoxide; 4,4'-dihydroxy-3,3 Dihydroxydiarylsulfoxides such as'-dimethyldiphenylsulfoxide; and dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

These may be used alone or as a mixture of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl and the like may be used as a mixture.

Further, the above-mentioned dihydroxyaryl compound and a phenol compound having three or more valences as shown below may be mixed and used. Phloroglucin, 4,6-dimethyl-2,4,6-tri-
(4-hydroxyphenyl) -heptene, 2,4,6-
Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -Ethane and 2,2-bis-
[4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

The viscosity average molecular weight of the polycarbonate resin is usually from 10,000 to 100,000, preferably 15,000.
３５35,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as required.

The rubber-modified (meth) acrylic polymer used in the present invention comprises an acrylate ester and / or a methacrylate ester as an essential component and, if desired, an aromatic vinyl such as styrene or a butadiene. It is a polymer composed of unsaturated hydrocarbons and other copolymerizable monomers. Further, the morphology is not limited, but a core-shell type may be used in which the hard segment is a continuous layer and the soft segment is a dispersion layer, or the reverse layer.

Preferably, core-shell type methyl methacrylate / butadiene rubber, methyl methacrylate / glycidyl methacrylate / styrene / acrylate rubber, and methyl methacrylate / styrene / silicone / acrylate rubber can be used.

The compounding amount of the rubber-modified (meth) acrylic polymer mixed with the polycarbonate resin is 0.5 to 10% by weight. When the content is less than 0.5% by weight, the impact strength in a low-temperature atmosphere is inferior, and when it exceeds 10% by weight, heat resistance is inferior. More preferably, it is 0.7 to 7% by weight, further preferably 1 to 5% by weight. Within this range, the balance between impact strength and heat resistance in a low-temperature atmosphere is further improved.

The 6- [3- (3-t) used in the present invention
-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,6,8,10-tetra-t-bityldibenz [d, f] [1.3.2] dioxaphosphepin Is a rubber-modified (meth) acrylic polymer 10
It is 3 to 20 parts by weight per 0 parts by weight. If the amount is less than 3 parts by weight, thermal stability is poor, and if it exceeds 20 parts by weight, steam resistance is poor, which is not preferable. More preferably 4 to
It is 15 parts by weight, more preferably 5 to 10 parts by weight. In this range, the thermal stability is further improved without impairing the physical properties of the rubber-reinforced polycarbonate resin composition and without impairing the steam resistance.

Octadecyl-3- used in the present invention
(3,5-di-t-butyl-4-hydroxyphenyl)
The amount of propionate is 10 to 70 parts per 100 parts by weight of the rubber-modified (meth) acrylic polymer. If the amount is less than 10 parts by weight, the thermal stability is poor, and if it is more than 70 parts by weight, the steam resistance is poor. More preferably 15 to 65 parts by weight, even more preferably 30 to 60 parts by weight.
Parts by weight. In this range, the thermal stability is further improved without impairing the physical properties of the rubber-reinforced polycarbonate resin composition and without impairing the steam resistance.

The method of mixing the various components of the rubber-reinforced polycarbonate resin composition of the present invention is not particularly limited, and the components are mixed by a known mixer, for example, a tumbler / ribbon blender, and then melted by a single or twin screw extruder. Kneading can be performed.

Further, if necessary, known additives, for example, additives such as a releasing agent, an ultraviolet absorber, a flame retardant, and a dye / pigment may be added as long as the effects of the present invention are not impaired.

[0019]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In addition, "part" and "%" are based on weight unless otherwise noted.

(Examples 1 to 6 and Comparative Examples 1 to 9) Polycarbonate resins (Calibur 200-20, manufactured by Sumitomo Dow, viscosity average molecular weight 19000) synthesized from bisphenol A and phosgene and various compounds are shown in Tables 1 to 6. Compounding was performed based on the compounding amounts shown in FIG. 37m
The mixture was melt-kneaded at a cylinder temperature of 280 ° C. using a twin-screw extruder having a diameter of m (KTX-37 manufactured by Kobe Steel Ltd.) to obtain pellets.

The details of the raw materials used are as follows. 1. 1. Polycarbonate resin: abbreviated as PC Sumitomo Dow Co. Caliber 200-20 (viscosity average molecular weight: 19000) Rubber-modified (meth) acrylic polymer: Core shell type methyl methacrylate / butadiene rubber: Abbreviated as E-1 (Kuraha Chemical Industry Co., Ltd., Paraloid E)
XL2602) Core shell type methyl methacrylate / glycidyl methacrylate / styrene / acrylate rubber: Abbreviated as E-2 (PARALOID EX manufactured by Kureha Chemical Industry Co., Ltd.)
L2314) Core shell type methyl methacrylate / styrene /
2. Silicon acrylate rubber: Abbreviated as E-3 (METABLEN S2001 manufactured by Mitsubishi Rayon Co.) Antioxidant 6- [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propoxy] -2,4,6,8,10
-Tetra-t-bityldibenz [d, f] [1.3.
2] Dioxaphosphepin: abbreviated as AO-1 (SUMILIZER GP manufactured by Sumitomo Chemical Co., Ltd.) Octadecyl-3- (3,5-di-t-butyl-4-)
(Hydroxyphenyl) propionate: Abbreviated as AO-2 (Irganox 1 manufactured by Ciba Specialty Chemicals)
076) tetrakis (2,4-di-t-butylphenyl)-
4,4′-biphenylenephosphonite: Abbreviated as AO-3 (Irgaphos P-EP manufactured by Clariant Japan)
Q FF) 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite: abbreviated as AO-4 (HP-10 manufactured by Asahi Denka Kogyo Co., Ltd.) 2-t-butyl-6- (3- t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate: abbreviated as AO-5 (Sumilyzer GM manufactured by Sumitomo Chemical Co., Ltd.) 2- [1- (2-hydroxy-3,5-di- [t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate AO-6 (Sumitomo Chemical Co., Ltd. Sumilizer GS) bis (2,6-di-t-butyl-4-methylphenyl) Pentaerythritol diphosphite: Abbreviated as AO-7 (Adeka Stab PEP36 manufactured by Asahi Denka Kogyo KK)

Various pellets obtained at 125 ° C. for 4 hours
After drying, the injection molding machine (J100 manufactured by Japan Steel Works, Ltd.)
-E-C5), injection pressure 1600Kg
/ Cm ^TwoStandard color plate (50x90x3m)
m) was molded. Further, the obtained various pellets are heated to 140 ° C.
After drying for 19 hours under the same conditions, heat stability
A strike color plate was formed.

The color plate was heated at a temperature of 23 ° C. and a humidity of 50
% In a constant temperature room for 24 hours, and colorimetry was performed using a high-speed spectrophotometer (CMS-35SP JC2 type manufactured by Murakami Color Research Laboratory). JIS from each colorimetric data
The color difference (ΔE) was determined according to Z8730 (color difference according to L * a * b * color system), and the thermal stability was evaluated. In addition, 10
A material having the following color difference (ΔE) was evaluated as good.

A standard color plate was prepared using a pressure cooker (TPC-411 manufactured by Tabai Espec Corp.).
It was left at 30 ° C. and 99% RH for 24 hours. For each of the obtained standard color plate after the steam test and the untreated standard color plate, the molecular weight of the polycarbonate resin was measured using a Cannon-Fenske viscosity tube (20).
° C methylene chloride falling time is 120 ± 5 seconds). The calculation method is as follows: (1) The intrinsic viscosity ([η]) is determined from the following formula. η _sp / c = [η] + 0.45 [η] ² c where η _sp / c is the reduced viscosity. c is the sample weight in 100 ml methylene chloride. (0.5g
Reference) eta _sp (specific viscosity) = η _rel (relative _{viscosity) -1 = (t s / t} 0) -1 t s is falling seconds of the sample solution. t ₀ is the number of seconds of methylene chloride falling. Therefore, (2) H. Using Schnell's equation, the average molecular weight M is determined from [η]. [Η] = 1.23 × 10 ⁻⁴ M ^0.83 The difference in molecular weight between the untreated product and the product subjected to the steam test was defined as the steam resistance.

The obtained various pellets are placed at 125 ° C. for 4 hours.
After drying, the injection molding machine (J100 manufactured by Japan Steel Works, Ltd.)
-E-C5), injection pressure 1600Kg
/ Cm ^TwoThe test piece for impact strength evaluation (63 × 12.7)
x3.2 mm), a test piece for evaluating heat resistance (125 × 1
(2.7 x 6.4 mm).

The test piece for impact strength evaluation was left in a constant temperature room at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and then left at −30 ° C. for 3 hours using a low-temperature bath, and then subjected to ASTM D-25.
6, and the low-temperature impact strength was evaluated.

A test piece for heat resistance evaluation was left in a constant temperature room at a temperature of 23 ° C. and a humidity of 50% for 24 hours.
The heat resistance was evaluated according to D-648.

[0028]

[Table 1] Table 1 * 1: Number of parts per 100 parts of the used modified (meth) acrylic polymer * 2: ○: Color difference of 5 or less (good) Δ: Color difference of more than 5 to 10
Less than ×: color difference of more than 10 (bad) * 3: ○: molecular weight difference of 3000 or less (good) ×: molecular weight difference of more than 3000 (bad)

[0029]

[Table 2] Table 2 * 1: Number of parts per 100 parts of the used modified (meth) acrylic polymer * 2: ○: Color difference of 5 or less (good) Δ: Color difference of more than 5 to 10
Less than ×: color difference of more than 10 (bad) * 3: ○: molecular weight difference of 3000 or less (good) ×: molecular weight difference of more than 3000 (bad)

[0030]

[Table 3] Table 3 * 1: Number of parts per 100 parts of the used modified (meth) acrylic polymer * 2: ○: Color difference of 5 or less (good) Δ: Color difference of more than 5 to 10
Less than ×: color difference of more than 10 (bad) * 3: ○: molecular weight difference of 3000 or less (good) ×: molecular weight difference of more than 3000 (bad)

[0031]

The rubber-reinforced polycarbonate resin composition of the present invention has excellent thermal stability without lowering fluidity, impact resistance, heat resistance and steam resistance. Therefore, it is possible to prevent problems such as yellowing of the color tone even when receiving an excessive heat history in drying and forming.

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[Procedure amendment]

[Submission date] November 8, 2000 (200.11.
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

That is, the present invention relates to a rubber-reinforced polycarbonate resin composition comprising 99.5 to 90% by weight of a polycarbonate resin and 0.5 to 10% by weight of a rubber-modified (meth) acrylic polymer. ) Per 100 parts by weight of the acrylic polymer, (a) 6- [3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,6,8,10-tetra-t
- Bed Chirujibenzu [d, f] [1.3.2] dioxaphosphepin: 3-20 parts by weight, and (b) octadecyl-3- (3,5-di -t- butyl-4-hydroxyphenyl ) Propionate: Provides a rubber-reinforced polycarbonate resin composition prepared to contain 10 to 70 parts.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

The 6- [3- (3-t) used in the present invention
- butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,6,8,10- tetra -t- Bed chill <br/> dibenz [d, f] [1.3.2] dioxa The compounding amount of the phosphepin is the same as that of the rubber-modified (meth) acrylic polymer 10
It is 3 to 20 parts by weight per 0 parts by weight. If the amount is less than 3 parts by weight, thermal stability is poor, and if it exceeds 20 parts by weight, steam resistance is poor, which is not preferable. More preferably 4 to
It is 15 parts by weight, more preferably 5 to 10 parts by weight. In this range, the thermal stability is further improved without impairing the physical properties of the rubber-reinforced polycarbonate resin composition and without impairing the steam resistance.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

The details of the raw materials used are as follows. 1. 1. Polycarbonate resin: abbreviated as PC Sumitomo Dow Co. Caliber 200-20 (viscosity average molecular weight: 19000) Rubber-modified (meth) acrylic polymer: Core shell type methyl methacrylate / butadiene rubber: Abbreviated as E-1 (Kuraha Chemical Industry Co., Ltd., Paraloid E)
XL2602) Core shell type methyl methacrylate / glycidyl methacrylate / styrene / acrylate rubber: Abbreviated as E-2 (PARALOID EX manufactured by Kureha Chemical Industry Co., Ltd.)
L2314) Core shell type methyl methacrylate / styrene /
2. Silicon acrylate rubber: Abbreviated as E-3 (METABLEN S2001 manufactured by Mitsubishi Rayon Co.) Antioxidant 6- [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propoxy] -2,4,6,8,10
- tetra -t- Bed Chirujibenzu [d, f] [1.3.
2] Dioxaphosphepin: abbreviated as AO-1 (SUMILIZER GP manufactured by Sumitomo Chemical Co., Ltd.) Octadecyl-3- (3,5-di-t-butyl-4-)
(Hydroxyphenyl) propionate: Abbreviated as AO-2 (Irganox 1 manufactured by Ciba Specialty Chemicals)
076) tetrakis (2,4-di-t-butylphenyl)-
4,4′-biphenylenephosphonite: Abbreviated as AO-3 (Irgaphos P-EP manufactured by Clariant Japan)
Q FF) 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite: abbreviated as AO-4 (HP-10 manufactured by Asahi Denka Kogyo Co., Ltd.) 2-t-butyl-6- (3- t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate: abbreviated as AO-5 (Sumilyzer GM manufactured by Sumitomo Chemical Co., Ltd.) 2- [1- (2-hydroxy-3,5-di- [t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate AO-6 (Sumitomo Chemical Co., Ltd. Sumilizer GS) bis (2,6-di-t-butyl-4-methylphenyl) Pentaerythritol diphosphite: Abbreviated as AO-7 (ADK STAB PEP36 manufactured by Asahi Denka Kogyo Co., Ltd.)

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BN122 BN162 BN172 CG001 CG011 CG021 CG031 EJ067 EW026 FD076 FD077

Claims (5)

[Claims] 1. A rubber-reinforced polycarbonate resin composition comprising 99.5 to 90% by weight of a polycarbonate resin and 0.5 to 10% by weight of a rubber-modified (meth) acrylic polymer. Polymer 100
(A) 6- [3- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) propoxy]-
2,4,6,8,10-tetra-t-bityldibenz [d, f] [1.3.2] dioxaphosphepin: 3 to
20 parts by weight, and (b) octadecyl-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate: a rubber-reinforced polycarbonate resin composition prepared to contain 10 to 70 parts. 2. The rubber-reinforced polycarbonate resin composition according to claim 1, wherein the compounding amount of the rubber-modified (meth) acrylic polymer is 1 to 5% by weight. 3. The rubber-reinforced polycarbonate resin composition according to claim 1, wherein the rubber-modified (meth) acrylic polymer is a polymer containing methyl methacrylate and butadiene as essential components. 4. A polymer wherein the rubber-modified (meth) acrylic polymer is composed of an acrylate ester and / or a methacrylate ester and, if desired, an aromatic vinyl or other copolymerizable monomer. The rubber-reinforced polycarbonate resin composition according to claim 1 or 2, wherein 5. The rubber-modified (meth) acrylic polymer is methyl methacrylate / butadiene rubber, methyl methacrylate / glycidyl methacrylate / styrene.
The rubber reinforced polycarbonate resin composition according to claim 1 or 2, wherein the rubber reinforced polycarbonate resin composition is at least one selected from acrylate rubber and methyl methacrylate / styrene / silicon / acrylate rubber.