JP2014231581A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which is improved in chemical resistance against chemicals, e.g. antiseptic solutions, while retaining excellent original capabilities of polycarbonate resins, including transparency, impact resistance, heat resistance, thermal stability, and suppresses occurrence of defects, e.g. cracks. even when a chemical, e.g. an antiseptic solution, adheres to a molding obtained from the resin composition.SOLUTION: A polycarbonate resin composition consists of 100 pts. wt. of a polycarbonate resin (A), 0.01-20 pts. wt. of a specified alkyl ketene dimer (B) and 0.01-2 pts. wt. of a full ester (C) of pentaerythritol with 12-30C saturated and/or unsaturated fatty acids.

Description

  The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition having excellent transparency, impact resistance, heat resistance, thermal stability, and chemical resistance against chemicals such as disinfectants.

  Polycarbonate resin is a thermoplastic resin that excels in transparency, impact resistance, heat resistance, thermal stability, etc., and is widely used in fields such as electricity, electronics, ITE, machinery, automobiles, tableware, medicine containers, and medical equipment. It is used. And, for example, in the recent pandemic of influenza, especially in applications such as electricity, electronics, medical equipment, etc., sterilization cleaning and cleaning processing of various places are frequently performed with chemicals such as various disinfectants. It has become to. However, if chemicals such as disinfectant solution adhere to polycarbonate resin molded products, defects such as cracks may occur from the adhered part, and chemical resistance, in particular chemicals such as disinfectant solution, will not occur. There is a demand for a polycarbonate resin having excellent chemical resistance to the above.

So far, a resin composition in which a polyester resin is blended with a polycarbonate resin has been proposed for the purpose of improving the above-mentioned problems. However, by blending polyester resin,
(1) Although the solvent resistance against general detergents and cleaning agents is slightly improved, the effect of improving the chemical resistance against chemicals such as disinfectant is not sufficient,
(2) While greatly reducing the transparency, which is an advantage of polycarbonate resin,
(3) The impact resistance of the polycarbonate resin is impaired.
There was a problem.

Furthermore, a method of blending an impact resistance improving material such as MBS with a resin composition comprising a polycarbonate resin and a polyester resin has been proposed in order to improve the impact strength among the above problems (Patent Document 1). However, there is a problem that coloring caused by MBS and a problem that the polyester resin decomposes due to transesterification are expected, and further improvement is expected.

Japanese Patent Publication No.55-9435

  An object of the present invention is to provide a polycarbonate resin composition having excellent chemical resistance against chemicals such as disinfectants while maintaining the transparency, impact properties, heat resistance, thermal stability, etc. inherent to the polycarbonate resin. .

  As a result of intensive studies in view of such conventional problems, the present inventors have found that a full ester of a specific alkyl ketene dimer, pentaerythritol, and a saturated or unsaturated fatty acid having 12 to 30 carbon atoms in the polycarbonate resin. Surprisingly, the polycarbonate resin has excellent chemical resistance against chemicals such as disinfectants, in addition to the excellent transparency, impact resistance, heat resistance, thermal stability, and other properties inherent to polycarbonate resins. As a result, the present invention has been completed.

That is, the present invention relates to 100 parts by weight of the polycarbonate resin (A), 0.01 to 20 parts by weight of the alkyl ketene dimer (B) represented by the following general formula 1, and pentaerythritol and saturated or unsaturated having 12 to 30 carbon atoms. The present invention provides a polycarbonate resin composition comprising 0.01 to 2 parts by weight of a full ester (C) with a fatty acid.
General formula 1:

（一般式１において、Ｒは、同一でも異なっても良いが、炭素数６〜３３のアルキル基をあらわす。）

(In General Formula 1, R may be the same or different, but represents an alkyl group having 6 to 33 carbon atoms.)

  The polycarbonate resin composition of the present invention has improved chemical resistance against chemicals such as disinfectant while maintaining the excellent transparency, impact resistance, heat resistance, thermal stability, etc. inherent to the polycarbonate resin. Therefore, even if chemicals such as a disinfectant adhere to the molded product obtained from such a resin composition, the occurrence of defects such as cracks can be suppressed.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) 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 ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include 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 (A) is not particularly limited, but is usually in the range of 10,000 to 100,000, more preferably 14,000 to 30,000, and even more preferably 16,000 to 26,000 in terms of moldability and strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

The alkyl ketene dimer (B) used in the present invention is a compound represented by the following general formula 1.
General formula 1:

  In general formula 1, R may be the same or different, but an alkyl group having 6 to 33 carbon atoms, preferably an alkyl group having 10 to 21 carbon atoms, and most preferably an alkyl having 14 to 16 carbon atoms in R. It is a group.

  The compounding quantity of an alkyl ketene dimer (B) is 0.01-20 weight part per 100 weight part of polycarbonate resin (A). If it is less than 0.01 parts by weight, the chemical resistance is poor, and if it exceeds 20 parts by weight, granulation processing becomes difficult and it is not possible to obtain pellets of the resin composition. A preferable compounding amount is 0.01 to 10 parts by weight, and more preferably 0.1 to 10 parts by weight.

As the full ester (C) of pentaerythritol and saturated or unsaturated fatty acid having 12 to 30 carbon atoms used in the present invention, pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, pentaerythritol tetrabehenate Etc. These can be used alone or in combination of two or more. Particularly preferred is pentaerythritol tetrastearate.

The full ester of pentaerythritol and a saturated or unsaturated fatty acid having 12 to 30 carbon atoms is 0.01 to 2 parts by weight per 100 parts by weight of the polycarbonate resin (A). If the amount is less than 0.01 parts by weight, the chemical resistance is poor, and if it exceeds 2 parts by weight, the material slips in the cylinder during the injection molding process, which makes it extremely difficult to form. Preferably it is 0.1-1.5 weight part, Most preferably, it is 0.3-1.0 weight part.

Examples of the chemicals that can be applied to the polycarbonate resin composition obtained by the present invention and molded articles and sheets thereof include alkylpolyaminoethylglycine-based disinfectants classified as amphoteric surfactants. These are commercially available under the trade names such as Tego 51 (manufactured by Alfresa Pharma), alkyd, usnon, lage, kinsar G, conknol, satenidin, nissan anon, hygiel, hyperle, pearl, hishi punch, fast-I, etc. . High chemical resistance to chemicals against these disinfectants.

There are no particular restrictions on the method of blending the various blending components (A), (B), and (C) of the present invention, and these can be mixed with any mixer such as a tumbler, ribbon blender, high-speed mixer, etc. It can be melt-kneaded with a screw or twin screw extruder. Moreover, there is no restriction | limiting in particular also about the mixing | blending order of these compounding components, collective mixing, and division | segmentation mixing.

  In addition, other known additives such as mold release agents, UV absorbers, antistatic agents, dyes and pigments, spreading agents (epoxy soybean oil, liquid paraffin, etc.) and reinforcing materials (glass fibers) may be used at the time of mixing. , Carbon fiber, talc, mica, etc.) and other resins can be blended.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified.

The compounding components used are as follows.
Polycarbonate resin (A):
Polycarbonate resin synthesized from bisphenol A and phosgene (Caliber 200-20 manufactured by Sumika Stylon Polycarbonate Co., Ltd.)
Viscosity average molecular weight: 19000, hereinafter abbreviated as PC)
Alkyl ketene dimer (B):
AKD1840 (hereinafter abbreviated as AKD) manufactured by Eiheng Chemical Company
The ingredients are as follows:

上記一般式でＲは炭素数が１５〜１８のアルキル基であるアルキルケテンダイマー。

R is an alkyl ketene dimer in which R is an alkyl group having 15 to 18 carbon atoms.

Full ester (C) of pentaerythritol and saturated or unsaturated fatty acid having 12 to 30 carbon atoms:
Roxyol VPG861 (hereinafter abbreviated as PETS) manufactured by Cognis was used.
Polybutyl terephthalate resin:
600FP manufactured by Polyplastics (hereinafter abbreviated as PBT)

  The above-mentioned various blending components are collectively put into a tumbler at the blending ratios shown in Tables 1 and 2, and after dry mixing for 10 minutes, using a twin-screw extruder (Kobe Steel KTX37), a melting temperature of 280 ° C. To obtain pellets of polycarbonate resin composition.

(Evaluation of chemical resistance of molded products)
The pellets of the various resin compositions obtained above were each dried at 125 ° C. for 4 hours, and then set using an injection molding machine (Japan Steel Works J-100E-C5) at a set temperature of 280 ° C. and an injection pressure of 1600 kg / cm ^2. A test piece (127 × 13 × 3.2 mm) was prepared.
The obtained test piece was subjected to arbitrary distortion using a chemical test jig for cantilever beams (see FIG. 1), and the following chemicals were respectively applied to the center of the test piece.
Evaluation chemical (disinfectant)
A 10-fold diluted solution (Tego 51: Purified water = 600 ml: 6000 ml) was prepared with purified water manufactured by Alfresa Pharma Co., Ltd. (see below for details). Abbreviation).
Tego 51: Alkyldiaminoethylglycine hydrochloride:
Formula _{[RNH · CH 2 · CH 2} · NH · CH 2 · CH 2 · NH · CH 2 · COOH] · HCl (R is _{C 8 H 17 ~C 16 H 33} , mainly _C 12 _{H 25} and _C 14 _{H 29} Consist of)
The test piece after the chemical application was allowed to stand for 48 hours in an atmosphere at 23 ° C., and the critical strain (%) was determined from the position of cracks and cracks on the test piece according to the following formula.

(formula)

From the critical strain determined by the above formula, the chemical resistance was determined according to the following criteria, and a critical strain of more than 0.7% (◯ to と し た) was considered acceptable.
Determination of chemical resistance:
◎: Critical strain is 1.0% or more ○: Critical strain is 0.7% or more to less than 1.0% △: Critical strain is 0.5% or more to less than 0.7% ×: Critical strain is 0.3 % Or more to less than 0.5% XX: Critical strain is less than 0.3%

(Evaluation of notched Charpy impact strength and deflection temperature under load)
The pellets of the various resin compositions obtained above were each dried at 125 ° C. for 4 hours, and then set using an injection molding machine (Japan Steel Works J-100E-C5) at a set temperature of 280 ° C. and an injection pressure of 1600 kg / cm ^2. A test piece in accordance with the ISO test method was prepared using the obtained test piece, and the Charpy impact strength with notch and the deflection temperature under load were measured in accordance with ISO 179-1 and ISO 75-2. An impact strength of 10 KJ / m ² or more and a deflection temperature under load of 105 ° C. or more were regarded as acceptable.

(Evaluation of transparency of molded products)
The pellets of the various resin compositions obtained above were each dried at 125 ° C. for 4 hours, and then set using an injection molding machine (Japan Steel Works J-100E-C5) at a set temperature of 280 ° C. and an injection pressure of 1600 kg / cm ^2. A test piece for transparency evaluation (150 × 90 × 3.0 mm) was prepared.
Using the obtained test piece, the light transmittance of a test piece thickness of 3 mm was measured according to JIS K 7361, and the light transmittance was determined to be 80% or more.

  In the case where the polycarbonate resin composition satisfies the constituent requirements of the present invention (Examples 1 to 4), good results were exhibited over each of transparency, chemical resistance, impact strength, and heat resistance. .

On the other hand, in the case where the polycarbonate resin composition does not satisfy the constituent requirements of the present invention, each case has some drawbacks.
In Comparative Examples 1 and 2, the alkyl ketene dimer was not added, and the case was less than the range defined by the present invention, and the chemical resistance was poor.
In Comparative Example 3, the number of alkyl ketene dimers was larger than the range defined by the present invention, so that pellets could not be produced due to difficulty in granulation.
Comparative Example 4 was a case where the full ester of pentaerythritol and a saturated or unsaturated fatty acid having 12 to 30 carbon atoms was less than the range defined by the present invention, and was inferior in chemical resistance.
Comparative Example 5 is a case where a polyester resin which has been proposed for the purpose of improving chemical resistance and solvent resistance has been blended, and was inferior in transparency, impact resistance, heat resistance and chemical resistance.

Claims (4)

100 parts by weight of polycarbonate resin (A), 0.01 to 20 parts by weight of alkyl ketene dimer (B) represented by the following general formula 1, and full ester of pentaerythritol and saturated or unsaturated fatty acid having 12 to 30 carbon atoms ( A polycarbonate resin composition comprising 0.01 to 2 parts by weight of C).
General formula 1:

(In General Formula 1, R may be the same or different, but represents an alkyl group having 6 to 33 carbon atoms.)   2. The polycarbonate resin composition according to claim 1, wherein the alkyl ketene dimer (B) is an alkyl group having 10 to 21 carbon atoms represented by R in the general formula 1. 3.   The polycarbonate resin composition according to claim 1 or 2, wherein the compounding amount of the alkyl ketene dimer (B) is 0.03 to 5 parts by weight per 100 parts by weight of the polycarbonate resin (A). The polycarbonate resin composition according to claim 1, wherein the full ester of the pentaerythritol and a saturated or unsaturated fatty acid having 12 to 30 carbon atoms is pentaerythritol tetrastearate.