JP2001187838A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having excellent impact resistance. SOLUTION: This polycarbonate resin composition is obtained by blending polycarbonates with a thermoplastic resin other than polycarbonates, wherein a polycarbonate (A) produced by a phosgene method is included at a content of 10-90 wt.% based on the total of the polycarbonate (A) and the thermoplastic resin other than polycarbonates, and a polycarbonate (B) produced by an ester interchange method is included at a content of 0.01-30 wt.% based on the polycarbonate (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition having excellent impact resistance.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as engineering plastics because of their excellent mechanical strength. In particular, polycarbonate resins produced by the phosgene method are most widely used because of their high molecular weight and excellent impact resistance and transparency.

[0003] It is known to blend polycarbonate resins with various resins in order to improve the impact strength and molding processability of polycarbonate resins. For example, blends with ABS resins (JP-B-38-15225, Tokiko Sho 51-11
No. 142) and a blend with polystyrene (Japanese Patent Publication No. Sho 4)
JP-A-3-6295, JP-B-44-11551)
Has been proposed.

[0004]

However, the improvement by the prior art is still not enough, and further improvement in impact resistance is desired for many applications.

Accordingly, an object of the present invention is to provide a polycarbonate resin composition having excellent impact resistance.

Means for Solving the Problems In order to solve the above-mentioned problems, a polycarbonate resin composition of the present invention is a polycarbonate resin composition comprising a polycarbonate resin and a thermoplastic resin other than the polycarbonate resin, The blending ratio of the polycarbonate resin (A) produced by the phosgene method is in the range of 10 to 90% by weight based on the total amount of the polycarbonate resin (A) and the thermoplastic resin other than the polycarbonate resin, and the transesterification method. Polycarbonate resin (B) produced by
With respect to the polycarbonate resin (A)
It is characterized in that it is contained in the range of up to 30% by weight.

Although the present invention is not limited to any theory, the reason why the polycarbonate resin produced by the phosgene method cannot be blended well with other thermoplastic resins is that the molecular terminals of the polycarbonate resin are not sufficiently blended. This is presumed to be due to the low hydroxyl group concentration and poor reactivity with the compatibilizer. Therefore, in the present invention, a small amount of the polycarbonate resin (B) produced by the transesterification method is used as a compatibilizer. That is, the polycarbonate resins (A) and (B) are compatible with each other because they are polycarbonate resins. Since the polycarbonate resin (B) has a high hydroxyl group concentration, it has excellent reactivity with a compatibilizer unlike the polycarbonate (A) resin. Therefore, when a small amount of the polycarbonate resin (B) is used in the mixed system of the polycarbonate resin (A) and the other thermoplastic resin, this plays a role as a compatibilizing agent, so that the compatibility between the polycarbonate resin and the other resin is reduced. It is believed that improved properties are obtained.

JP-A-3-172347 and JP-A-3-199255 disclose resin compositions in which a polycarbonate resin having a high hydroxyl group concentration is blended with a polyester, ABS resin or styrene resin. However, although there is a certain effect on the improvement of impact resistance, the effect is still not enough.
It is conceivable that the high hydroxyl group concentration causes adverse effects such as the progress of transesterification during kneading. On the other hand, in the present invention, since only a small amount of the polycarbonate resin (B) having a high hydroxyl group concentration is used as a compatibilizer, the good physical properties (impact resistance and transparency) of the polycarbonate resin (A) are It can be reflected in the base resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the terminal hydroxyl group concentration of a polycarbonate resin is 3600 cm ^{-1 of} FT-IR.
Can be determined by measuring the absorption intensity at

The polycarbonate resin has the general formula

[0010]

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(R ¹ and R ² are divalent organic groups,
R ³ and R ⁴ are a hydrogen atom, a monovalent organic group or a group which forms a cycloalkane group with an adjacent carbon atom. ) Is mainly provided. Among them, an aromatic polycarbonate resin in which R ¹ and R ² are a phenylene group, a halogen-substituted phenylene group, or an alkyl-substituted phenylene group having 1 to 20 carbon atoms is preferable. In particular, a polycarbonate resin starting from bisphenol A in which R ¹ and R ² are phenylene groups and R ³ and R ⁴ are methyl groups is preferable.

The polycarbonate resin (A) of the present invention is not particularly limited as long as it is produced by the phosgene method, but the ratio of hydroxyl terminal to non-hydroxyl terminal is 5:95.
It is preferably less than. The phosgene method is a method in which a dioxy compound such as bisphenol A is reacted with phosgene to produce a polycarbonate resin.However, a small amount of phenol is added to the raw material or during the reaction so that the polymer end is sealed with phenol and the terminal hydroxyl group is added. The concentration will be lower. Generally, a polycarbonate resin obtained by the phosgene method has a relatively high molecular weight and is excellent in impact resistance and transparency.

The polycarbonate resin (B) of the present invention is not particularly limited as long as it is produced by a transesterification method, but the ratio of hydroxyl terminal to non-hydroxyl terminal is 5:
It is preferably 95 or more. The transesterification method
For example, it is a method of performing transesterification using a dioxy compound such as bisphenol A and diphenyl carbonate as raw materials. Since the molecular terminal of the polycarbonate resin obtained in this case is a phenolic residue derived from a dioxy compound or a phenyl group derived from diphenyl carbonate, the terminal hydroxyl group ( Phenolic residues). The ratio of the hydroxyl group terminal to the non-hydroxyl group terminal of the polycarbonate resin (B) is from 5:95 to
It is preferably 100: 0, and 10:90 to 90:
More preferably, it is 10.

The amount of the polycarbonate resin (B) is 0.01 to 30% by weight based on the polycarbonate resin (A).
And preferably 1 to 15% by weight, and 5 to 1% by weight.
More preferably, it is 0% by weight. If the polycarbonate resin (B) is too small, the polycarbonate resin (A)
Cannot act as a compatibilizer. If the amount of the polycarbonate resin (B) is too large, the ratio of the polycarbonate resin (A) is reduced, so that the physical properties of the entire composition are inferior.

The other thermoplastic resin blended with the polycarbonate resin in the present invention is mainly blended for modifying and improving the polycarbonate resin.
Although it is not particularly limited as long as it is a thermoplastic resin other than the polycarbonate resin, for example, polyphenylene ether, polyester, nylon, ABS resin (acrylonitrile-butadiene-styrene copolymer), styrene resin, olefin resin, etc. Can be mentioned.
These resins can be used in combination of two or more kinds.

The polyphenylene ether is represented by the following general formula:

[0017]

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(R ¹ , R ² and R ³ are the same or different and represent a monovalent group such as an alkyl group, an aryl group, a halogen, a hydrogen, etc.).

Examples of the polyester include saturated polyesters such as polyethylene terephthalate and polybutylene terephthalate; and polyarylates obtained by reacting a dihydric phenol with an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.

As nylon, 6-nylon, 66-
Nylon, 6/66 copolymer nylon, 46-nylon,
Examples include polyamides such as 12-nylon. Examples of the olefin resin include polyethylene, polypropylene, polybutene-1, poly4-methylpentene-1 and other α.
-Polymers of olefins, preferably polypropylene. The olefin-based resin does not need to be a homopolymer, and may be a copolymer with another α-olefin. For example, in the case of polypropylene, another α-olefin may be contained preferably in a range of up to 20% by weight. Other preferred α-olefins for polypropylene include ethylene and the like. The copolymer may be any of a random copolymer, a block copolymer or a graft copolymer.

Further, these thermoplastic resins may be appropriately modified, for example, may be modified with an unsaturated carboxylic acid or an anhydride thereof. Examples of the unsaturated carboxylic acid or its anhydride include acrylic acid, monocarboxylic acid such as methacrylic acid, maleic acid, fumaric acid, dicarboxylic acid such as itaconic acid, maleic anhydride, and dicarboxylic anhydride such as itaconic anhydride. And dicarboxylic anhydrides are particularly preferred.

When the total amount of the polycarbonate resin (A) and the other thermoplastic resin is 100 parts by weight, the mixing ratio of the polycarbonate resin (A) is 1
It can be used in the range of 0 to 90% by weight, and can be appropriately selected depending on the desired physical properties and applications.
Preferably it is 20 to 80% by weight, more preferably 3 to 80% by weight.
0 to 70% by weight.

When the total amount of the polycarbonate resin composition of the present invention is 100% by weight, a preferable blending ratio of the thermoplastic resin is 5 to 95% by weight, more preferably 10 to 90% by weight, and most preferably. Is from 10 to 50% by weight.

The polycarbonate resin composition of the present invention may further contain a compatibilizer. By using the compatibilizer, the compatibility between the other thermoplastic resin and the polycarbonate resin can be increased. Examples of such a compatibilizer include a compound having an oxazoline group and a compound having an epoxy group.

As the compound having an oxazoline group,
Examples thereof include a 2-oxazoline compound and a polymer containing an oxazoline group. As the 2-oxazoline compound, specifically, 2,2′-methylenebis (2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-ethylenebis (4-methyl-2 -Oxazoline), 2,2'-propylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'- Octamethylene bis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p- Phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2 '
-P-phenylenebis (4-phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2
-Oxazoline), 2,2'-m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2 '
-M-phenylenebis (4-phenylenebis-2-oxazoline), 2,2′-o-phenylenebis (2-oxazoline), 2,2′-o-phenylenebis (4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like.

Examples of the polymer having an oxazoline group include a copolymer of a vinyl monomer having an oxazoline ring and another monomer copolymerizable with the monomer.

The vinyl monomer having an oxazoline ring is a compound having a polymerizable vinyl group bonded to the oxazoline ring, and is specifically represented by the following general formula (1).

[0028]

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[Wherein, R ₁ represents a hydrogen atom or an alkyl group, X independently represents a hydrogen atom or a hydrocarbon group having 18 or less carbon atoms, and n represents an integer of 1 to 5. Among the vinyl monomers of the general formula (1), 2-isopropenyl-2-oxazoline represented by the following formula (2) and 2-isopropenyl- represented by the following formula (3) are particularly preferred.
4,4-Dimethyl-2-oxazoline is preferred.

[0030]

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[0031]

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The compound having an epoxy group can be obtained by reacting the active hydrogen of a phenolic hydroxyl group or the amino group of an aniline with a slightly large amount of epichlorohydrin in the presence of an alkali. Are commercially available.

The compounds having an epoxy group which can be used in the present invention include these commercially available epoxy resins, for example, bisphenol A type, bisphenol F
And bisphenol-based epoxy resins such as bisphenol S type, biphenyl type and diphenyl ether type, and polyfunctional phenol type epoxy resins such as orthocresol novolak type, DPP novolak type and trishydroxyphenylmethane type. In addition, a polymer containing an epoxy group can also be used. For example, a homopolymer of an epoxy group-containing unsaturated monomer, a copolymer of two or more epoxy group-containing unsaturated monomers, one or more And a copolymer comprising the above epoxy group-containing unsaturated monomer and another monomer.

Examples of the epoxy group-containing unsaturated monomer include glycidyl (meth) acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, and glycidyl itaconate. Can be

Other unsaturated monomers include aromatic vinyl monomers such as styrene; vinyl cyanide monomers such as acrylonitrile; vinyl acetate, acrylic acid (salt), methacrylic acid (salt), acrylic acid Unsaturated carboxylic acids such as esters, methacrylic esters, (anhydride) maleic acid, maleic esters, 2-norbornene-5,6-dicarboxylic acids (anhydrides) and derivatives thereof; ethylene, propylene, 1-butene, 1 -Pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1
Α-olefins such as tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; butadiene;
Isoprene, 1,4-hexadiene, 5-ethylidene-
Diene components such as 2-norbornene and 5-vinyl-2-norbornene are exemplified. Examples of copolymers include GM
A (glycidyl methacrylate) / St (styrene),
GMA / St / MMA (methyl methacrylate) / MA
(Maleic acid), GMA / St / acrylonitrile, G
MA / MMA / acrylonitrile, GMA / MMA, G
MA / MMA / St, vinyl oxazoline / St, vinyl oxazoline / MMA, ethylene / GMA, ethylene / vinyl acetate / GMA, and the like.

The amount of the above-mentioned compatibilizer used is 0.0 to the total of the polycarbonate resin and the other thermoplastic resin.
It is preferably from 1 to 20% by weight, more preferably from 0.1 to 10% by weight.

The polycarbonate resin composition of the present invention contains a pigment, a dye, a reinforcing agent, a filler, a heat-resistant agent, an antioxidant, a weathering agent, a lubricant, a release agent, a crystal nucleating agent, a plasticizer, and a fluidizer. Additives such as an improving agent and an antistatic agent can be appropriately blended.

In order to produce the polycarbonate resin composition of the present invention, each component can be mixed by a conventionally known method. For example, there is a method in which each component is dispersed and mixed by a high-speed mixer such as a turnbull mixer, a Henschel mixer, a ribbon blender, and a super mixer, and then melt-kneaded by an extruder, a Banbury mixer, a roll, or the like.

[0039]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

In the examples, "parts" means "parts by weight" unless otherwise specified. Examples 1-2, Comparative Examples 1-4 Each component was mixed with the composition shown in Table 1, and Examples 1-2,
The polycarbonate resin compositions of Comparative Examples 1 to 4 were prepared, and the Izod impact strength (with 1/8 notch) was measured according to ASTM.
It measured according to D256.

[0041]

[Table 1]

As shown in Table 1, Examples 1 and 2
In this case, since the polycarbonate resin (B) produced by the transesterification method is contained in an appropriate amount, a polycarbonate resin composition having excellent impact resistance is obtained. On the other hand, in Comparative Examples 2 and 4, which do not contain the polycarbonate resin (B), and Comparative Examples 1 and 3, in which the blending amount of the polycarbonate resin (B) is too large, the impact resistance is inferior to Examples 1 and 2. It has become something.

[0043]

According to the present invention, a polycarbonate resin composition having excellent impact resistance can be obtained.

Continued on front page F-term (reference) 4J002 BB03X BB12X BB17X BN15X CD053 CD063 CD073 CD193 CD203 CF06X CF07X CF16X CG00W CH07X CL01X CL03X CL05X CM013 EU226

Claims (5)

[Claims] 1. A polycarbonate resin composition comprising a polycarbonate resin and a thermoplastic resin other than the polycarbonate resin, wherein the proportion of the polycarbonate resin (A) produced by the phosgene method is the same as that of the polycarbonate resin (A). And the thermoplastic resin other than the polycarbonate resin is in the range of 10 to 90% by weight, and the polycarbonate resin (B) produced by the transesterification method is further reduced by 0 to the polycarbonate resin (A). 0.1 to 30% by weight of the polycarbonate resin composition. 2. The polycarbonate resin composition according to claim 1, wherein the ratio of the hydroxyl terminal to the non-hydroxy terminal of the polycarbonate resin (A) is less than 5:95. 3. The polycarbonate resin composition according to claim 1, wherein the ratio of the hydroxyl terminal to the non-hydroxy terminal of the polycarbonate resin (B) is 5:95 or more. 4. The polycarbonate according to claim 1, wherein the thermoplastic resin other than the polycarbonate resin is at least one of polyphenylene ether, polyester, nylon, ABS resin, styrene resin, and olefin resin. -Based resin composition. 5. The method according to claim 1, further comprising a compatibilizer.
5. The polycarbonate resin composition according to any one of items 1 to 4.