JP2017082111A - Polycarbonate resin composition for film insert molding - Google Patents

Abstract

SOLUTION: A polycarbonate resin composition for film insert molding contains 100 pts.wt. of a polycarbonate resin (A), 0.1 to 1 pt.wt. of a glycerine fatty acid ester having the melting point of 70°C or more (B) as a flowability modifier and 0.01 to 1 pt.wt. of a phosphorous-based antioxidant (C).EFFECT: A transparent polycarbonate resin composition can be used for a body of a device requiring inside visibility or components transmitting light of a light source without shielding or the like as it has not only excellent flowability, but also high impact performance and is excellent in transparency and is suitably used for a transparent member of a game machine or film insert molding as it is excellent in high impact performance.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition that is excellent in the balance of fluidity, transparency, and impact strength and is suitably used for film insert molding without impairing the original properties of the polycarbonate resin.

  2. Description of the Related Art Conventionally, a high design property is often required for a decorative part of a game machine called a so-called pachinko machine. In the past, methods for plating and coating the surface of molded resin products have been used to provide design properties, but there are significant environmental impacts such as waste liquid treatment, and alternative technologies have been sought. The use of film is drawing attention. Film insert molding is suitable for providing designability using a decorative film. Film insert molding is a method of preparing a decorative film preformed in a desired shape and manufacturing a resin molded product in which the base resin of the component and the decorative film are integrated by heat welding, It is advantageous as a method that is not necessary. For these reasons, film insert molding using a decorative film has attracted attention as a method for imparting design properties to game machine exterior parts and the like. A transparent thermoplastic resin is insert-molded into a gold, silver or metallic film to make an exterior part. As a technique related to film insert molding, for example, there is a report of a metallic decorative film suitable for film insert molding (Patent Document 1).

  On the other hand, polycarbonate resins have been widely used in the gaming machine field, OA field, automobile field, and the like because of their high impact strength. In recent years, the flow from inorganic materials to resins has been increasing for reasons such as weight reduction, freedom of design, and cost reduction. The point which prevents is mentioned. In some cases, the high impact strength of polycarbonate resin can prevent breakage, but higher strength high molecular weight polycarbonate resin may cause problems such as poor moldability and productivity due to fluidity problems during injection molding. is there. When polycarbonate resin is used as the above-mentioned film insert molding resin, for example, coexistence of at least two or more characteristics such as moldability, adhesion to a film, impact resistance, transparency, and fluidity is a problem. Become.

  As a method for increasing the fluidity of the polycarbonate resin, a method of adding a flow modifier to the polycarbonate resin composition is known. For example, there is a report that fluidity is improved by adding a small amount of triphenyl phosphate or polycaprolactone having a specific structure (see Patent Documents 2 and 3). However, a major disadvantage of such an improvement method is that even if the addition amount is only 1%, the impact strength is lowered and the impact strength, which is an important characteristic of the polycarbonate resin, is lost.

  It is conceivable that the impact strength is reduced because the flow modifier is thermally decomposed at the molding processing temperature to reduce the molecular weight of the polycarbonate resin. On the other hand, when a polycaprolactone-based polymer is added to a polycarbonate resin, the hydrolyzability is lowered, and thus a good material cannot be obtained.

  Until now, there has not been known a polycarbonate resin composition that can be suitably used for film insert molding, which is particularly demanding in recent years and has an excellent balance of fluidity, transparency and impact strength.

Patent No. 3727128 Japanese Patent Laid-Open No. 7-3140 JP-A 63-6051

  It is an object of the present invention to provide a polycarbonate resin composition for film insert molding that has an excellent balance of fluidity, transparency and impact strength without impairing the original properties of the polycarbonate resin.

  As a result of intensive studies in view of such problems, the present inventors have determined that a specific glycerin fatty acid ester (B) and a phosphorus-based antioxidant (100% by weight) as a fluidity modifier are used for 100 parts by weight of the polycarbonate resin (A). It was found that by blending a predetermined amount of C) as an essential component, a polycarbonate resin composition excellent in the balance of fluidity, transparency and impact strength can be obtained without impairing the original properties of the polycarbonate resin. It came to be completed.

  That is, in the polycarbonate resin composition for film insert molding of the present invention, 0.1 part of glycerin fatty acid ester (B) having a melting point of 70 ° C. or more as a fluidity modifier is 100 parts by weight of the polycarbonate resin (A). The present invention provides a polycarbonate resin composition for film insert molding, which comprises ˜1 part by weight and 0.01 to 1 part by weight of a phosphorus-based antioxidant (C).

  The polycarbonate resin composition for film insert molding of the present invention is excellent in the balance of fluidity, transparency and impact strength without impairing the original properties of the polycarbonate resin. Is preferably used. In particular, the present invention can be applied to exterior parts that require internal visibility, exterior parts that transmit light without shielding light from the light source, and the like.

  Hereinafter, embodiments will be described in detail. However, more detailed explanation than necessary may be omitted. For example, detailed descriptions of already well-known matters and repeated descriptions for substantially the same configuration may be omitted. This is to avoid the following description from becoming unnecessarily redundant and to facilitate understanding by those skilled in the art.

  In addition, the inventors provide the following explanation for those skilled in the art to fully understand the present invention, and are not intended to limit the subject matter described in the claims.

  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 ' Dihydroxydiaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone Rusuruhon, and the like can be mentioned.

  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 16,000 to 30,000, and even more preferably 18,000 to 24,000 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 present inventors use a glycerin fatty acid ester having a melting point of 70 ° C. or more as a fluidity modifier in combination with a phosphorus-based antioxidant, whereby a polycarbonate resin composition having an excellent balance of fluidity, transparency and impact strength. It has been newly found that can be obtained. The glycerin fatty acid ester (B) as a fluidity modifier used in the present invention is a glycerin fatty acid ester (B) having a melting point of 70 ° C. or higher. As the glycerin fatty acid ester, monoesters of glycerin and hydroxy-modified fatty acid are preferable, and among them, glycerin monobehenate (melting point: 74-80 ° C.), glycerin mono-12-hydroxystearate (melting point: 71-77 ° C.) Is mentioned. These may be used in combination. Examples of commercially available products include Riquemar B-100 (glycerin monobehenate) from Riken Vitamin Co., Ltd., Riquemar HC-100 (glycerin mono-12-hydroxystearate), and the like. When a glycerin fatty acid ester having a temperature of less than 70 ° C. is used, it is not preferable because the molded article may be inferior in transparency, colorability, or impact strength.

  The compounding quantity of the glycerol fatty acid ester (B) used by this invention is 0.1-1 weight part per 100 weight part of polycarbonate resin (A). If it is less than 0.1 part by weight, the fluidity may be inferior. If it exceeds 1 part by weight, impact strength may not be obtained, which is not preferable. A preferable compounding amount is 0.15 to 0.8 part by weight, and more preferably 0.2 to 0.5 part by weight.

Examples of the phosphorus antioxidant used in the present invention include those composed of one or more compounds represented by the following general formulas 1, 2 and 3.
General formula 1:

（一般式１において、Ｒ１〜４は炭素数１〜２０のアルキル基、またはアルキル基で
置換されてもよいアリール基を示す。）
一般式２：

(In General Formula 1, R1-4 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group.)
General formula 2:

（一般式２において、Ｒ５、Ｒ６は炭素数１〜２０のアルキル基、またはアルキル基で置換されてもよいアリール基を、ａ、ｂは整数０〜３を示す。）
一般式３：

(In General Formula 2, R5 and R6 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and a and b represent integers 0 to 3.)
General formula 3:

（一般式３において、Ｒ７は炭素数１〜２０のアルキル基、またはアルキル基で置換されてもよいアリール基を、ｃは０〜３の整数を示す。）

(In General Formula 3, R7 represents an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and c represents an integer of 0 to 3)

  Examples of the compound of the general formula 1 include [1,1′-biphenyl] -4,4′-diylbis [bis (2,4-di-t-butylphenoxy) phosphine], for example, BASF Irgafos P-EPQ (trade name) manufactured by Adeka and P-EPQ (trade name) manufactured by Adeka Corporation are commercially available.

  Examples of the compound of the general formula 2 include 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro. [5,5] undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, etc. ADK STAB PEP-36A and ADK STAB PEP-8 ("ADEKA STAB" is a registered trademark) manufactured by ADEKA Corporation are commercially available. Among these, 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane is Is preferred.

  Examples of the compound of the general formula 3 include triphenyl phosphite, tricresyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and trisnonylphenyl phosphite. Among these, tris (2,4-di-t-butylphenyl) phosphite is particularly suitable. For example, Irgafos 168 manufactured by BASF ("Irgafos" is a registered trademark of BASF Societas Europea) is commercially available. Is available.

  The compounding quantity of the phosphorus antioxidant (C) used by this invention is 0.01-1 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the thermal stability is poor, which is not preferable. On the other hand, when the amount exceeds 1 part by weight, the thermal stability becomes insufficient at the time of retention during the molding process, and it is not preferable because it turns yellow. More preferably, it is 0.05-0.8 weight part.

  There are no particular restrictions on the blending method of the various blending components (A), (B) and (C) of the present invention, and these are mixed by an optional 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. When mixing, other known additives such as mold release agents, ultraviolet absorbers, antistatic agents, antioxidants, thermal stabilizers, dyes and pigments, epoxy soy oil, liquid paraffin as necessary Etc.), reinforcing materials (glass fiber, carbon fiber, talc, mica, etc.) and other resins can be blended. As a film insert molding method, a known method can be used.

  As described above, the embodiments have been described as examples of the technology disclosed in the present application. However, the technology in the present invention is not limited to this, and can also be applied to embodiments in which changes, replacements, additions, omissions, etc. are made as appropriate.

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

The compounding components used are as follows.
1. 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”)
2. Glycerin fatty acid ester (B) as a fluidity modifier:
2-1. Glycerin monobehenate (melting point 74-80 ° C)
Riquemar B-100 (Riken Vitamin Co., Ltd., hereinafter abbreviated as “GMS-1”)
2-2. Glycerin mono 12-hydroxystearate (melting point 71-77 ° C.)
Riquemar HC-100 (Riken Vitamin Co., Ltd., hereinafter abbreviated as “GMS-2”)
3. Phosphorous antioxidant (C):
PEP-Q (manufactured by Adeka, hereinafter abbreviated as “AO”)
[1,1′-biphenyl] -4,4′-diylbis [bis (2,4-di-t-
Butylphenoxy) phosphine]
4). Other Glycerol monostearate (melting point 63-68 ° C)
Riquemar S-100 (manufactured by Riken Vitamin Company, hereinafter abbreviated as “GMS-3”)
Epoxidized soybean oil (manufactured by Adeka, hereinafter abbreviated as ESO)

  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 260 ° C. To obtain pellets of polycarbonate resin composition.

(1) Evaluation of transparency)
The pellets of the various resin compositions obtained above were each dried at 120 ° C. for 4 hours, and then set at a setting temperature of 290 ° C. and an injection pressure of 1600 kg / cm ² using an injection molding machine (Japan Steel Works J-100E2-P). A test piece (2 mmt) was prepared. Using the obtained test pieces of various resin compositions, the light transmittance of a test piece thickness of 2 mm was measured in accordance with JIS K7361.
(2) Evaluation of melt flow rate (MFR)
After drying the pellets of the various resin compositions obtained at 120 ° C. for 4 hours,
The melt flow rate (MFR) was evaluated under test conditions of a test temperature of 300 ° C. and a test load of 1.2 kg in accordance with ISO 1133. A value of 30 or more was considered good, and a value less than 30 was judged as bad.

(3) Evaluation of notched Izod impact strength The pellets of various resin compositions obtained above were each dried at 120 ° C. for 4 hours, and then set using an injection molding machine (J-1002-P manufactured by Nippon Steel). A test piece according to the ASTM standard D-256 test method was prepared at a temperature of 290 ° C. and an injection pressure of 1600 kg / cm ² , and a notched Izod impact strength was measured at −20 ° C. using the obtained test piece. . When the notched Izod impact strength was minus 20 ° C., 50 kgf · cm / cm or more was considered good, and less than that was regarded as bad.

  In the case where the polycarbonate resin composition satisfies the constituent requirements of the present invention (Examples 1 to 6), good results were exhibited in each of transparency, fluidity (MFR), and impact strength.

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 the examples (Comparative Example 1 and Comparative Example 3) in which the glycerin fatty acid ester (B) is less than the range defined by the present invention, the fluidity (MFR) was inferior.
In the examples where the glycerin fatty acid ester (B) is larger than the range defined by the present invention (Comparative Example 2 and Comparative Example 4), the impact strength was inferior.
In the example (Comparative Example 5) in which the phosphorus-based antioxidant is less than the range defined by the present invention, the impact strength was inferior.
In the example (Comparative Example 6) in which the phosphorus-based antioxidant is more than the range defined by the present invention, the impact strength was inferior.
In the example (Comparative Example 7) in which the glycerin fatty acid ester (B) has a melting point of 70 ° C. or lower, the impact strength was inferior.

  As described above, the embodiments have been described as examples of the technology in the present invention. To that end, a detailed explanation was provided. Accordingly, the components described in the detailed description include not only components essential for solving the problem but also components not essential for solving the problem in order to illustrate the above technique. obtain. Therefore, it should not be immediately recognized that these non-essential components are essential as the non-essential components are described in the detailed description.

  Moreover, since the above-mentioned embodiment is for demonstrating the technique in this invention, a various change, replacement, addition, abbreviation, etc. can be performed in a claim or its equivalent range.

  The polycarbonate resin composition for film insert molding of the present invention is excellent in the balance of fluidity, transparency and impact strength without impairing the original properties of the polycarbonate resin. Is preferably used. In particular, it can be applied to exterior parts that require internal visibility and exterior parts that transmit light without shielding the light from the light source, and the industrial utility value is extremely high.

Claims (3)

  0.1 to 1 part by weight of a glycerin fatty acid ester (B) having a melting point of 70 ° C. or higher as a fluidity modifier and 100 parts by weight of a phosphorus-based antioxidant (C) with respect to 100 parts by weight of the polycarbonate resin (A) A polycarbonate resin composition for film insert molding, comprising 0.01 to 1 part by weight.   The polycarbonate resin composition for film insert molding according to claim 1, wherein the glycerin fatty acid ester (B) is at least one of glycerin monobehenate or glycerin mono-12-hydroxystearate. The polycarbonate for film insert molding according to claim 1, wherein the phosphorus-based antioxidant (C) is one or more compounds selected from compounds represented by the following general formulas 1, 2 and 3. Resin composition.
General formula 1

(In General Formula 1, R1-4 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group.)
General formula 2

(In General Formula 2, R5 and R6 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and a and b represent integers 0 to 3.)
General formula 3

(In General Formula 3, R7 represents an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and c represents an integer of 0 to 3)