JP2010254776A - Polycarbonate resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly durable polycarbonate resin composition for use in an insect-repellent sleeve for a fluorescent lamp, etc., and a molded product. <P>SOLUTION: The resin composition includes (i) 100 pts.wt. polycarbonate resin having a viscosity average molecular weight of 1.5×10<SP>4</SP>-5.0×10<SP>4</SP>, (ii) 0.01-0.5 pts.wt. compound represented by formula (1) [wherein R<SP>a</SP>, R<SP>b</SP>, R<SP>c</SP>, R<SP>d</SP>, R<SP>e</SP>, R<SP>f</SP>, R<SP>g</SP>, R<SP>h</SP>, R<SP>i</SP>and R<SP>j</SP>are each independently a hydrogen atom or monovalent substituent] and (iii) 0.001-0.1 pts.wt. phosphorus stabilizer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composition and a molded article containing a polycarbonate resin. More specifically, the present invention relates to a resin composition having excellent transparency, molding processability, and toughness possessed by a polycarbonate resin, and a molded product thereof. The molded article of the present invention is useful in the optical field, electrical and electronic field, medical field, automobile field and the like, and is particularly useful as an insect repellent sleeve for fluorescent lamps.

Ultraviolet rays are known to have light-inducing properties against pests and the like. Particularly in fluorescent lamps, light emission by so-called UV-A causes light induction of pests and the like, and safety, hygiene, and disgust given to humans are problematic.
As disclosed in Patent Document 1, it has already been proposed to add an ultraviolet absorber to a polycarbonate resin. However, the main purpose of the development of the conventional UV absorber is to protect the polycarbonate resin from UV degradation, and not the purpose of reducing the light inductive properties of insects and the like due to the light that has passed through the polycarbonate resin. Therefore, most conventional ultraviolet absorbers need to be added in a large amount in order to achieve the purpose of insect repellent, and most of them do not reach the target insect repellent effect even if added in a large amount. Further, the degree of freedom is small with respect to the thickness of the molded product. For example, when the molded product is thinned for the purpose of cost reduction, there is a problem that the purpose of insect prevention cannot be achieved.

On the other hand, in recent years, proposals have been made on ultraviolet absorbers for insect repellent. Patent Document 2 proposes that insect protection is performed with an ultraviolet absorber that absorbs a wavelength of 410 nm. However, in order to achieve the insect repellent effect, the light transmittance around 420 nm is particularly important, and this proposal has an insufficient insect repellent effect, and the insect repellent effect cannot be achieved particularly with a thin molded product.
Patent Document 3 proposes an ultraviolet absorber having an absorption maximum at 400 nm or more. However, this proposal has a problem that the durability of the ultraviolet absorbent itself is insufficient, and the ultraviolet absorbent itself is decomposed by ultraviolet absorption.
Patent Document 4 proposes an ultraviolet absorber that can maintain long-wave ultraviolet absorption ability for a long time.

Japanese Patent Application Laid-Open No. 07-196904 International Publication No. 2006/087872 Pamphlet JP 2007-254533 A JP 2008-273927 A

  An object of the present invention is to provide a resin composition and a molded article containing a polycarbonate resin and having an excellent insect-proofing effect. An object of the present invention is to provide a resin composition and a molded product that are capable of reducing the thickness of the molded product even with an appropriate addition amount as an insect-repellent sleeve for fluorescent lamps and that have excellent long-term durability.

  The present inventors diligently studied an ultraviolet absorbent having an insect repellent effect suitable for use in a polycarbonate resin. As a result, a compound represented by the following formula (1) was used as the ultraviolet absorbent, and a phosphorus stabilizer was further used. It was found that a resin composition having an excellent insecticidal effect can be obtained when used in combination, and the present invention was completed.

[R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ and R ^j each independently represent a hydrogen atom or a monovalent substituent. ]
Here, a person skilled in the art, during heat processing (pellet, extrusion molding), phosphoric acid produced in a trace amount from a phosphorus-based stabilizer used for stabilizing polycarbonate hydrolyzes the compound of the above formula (1). In view of this, the structure of the present invention cannot be easily recalled. However, by defining the content of the phosphorus stabilizer in the polycarbonate resin and the compound of the formula (1), such an influence is also caused. However, it was found that there were special effects such as insect repellent effect and long-term durability.

That is, according to the present invention, the following inventions are provided.
1. (I) For 100 parts by weight of the polycarbonate resin having a viscosity average molecular weight in the range of 1.5 × 10 ^{4 to} 5.0 × 10 ⁴ , (ii) the compound represented by the above formula (1) 0.01 to 0. A resin composition containing 5 parts by weight and (iii) 0.001 to 0.1 parts by weight of a phosphorus-based stabilizer.
2. 2. The resin composition according to item 1, further comprising (iv) 0.01 to 0.5 parts by weight of a benzotriazole type ultraviolet absorber with respect to 100 parts by weight of the polycarbonate resin.
3. 2. The resin composition according to item 1, further comprising (v) 0.01 to 2 parts by weight of a saturated fatty acid ester with respect to 100 parts by weight of the polycarbonate resin.
4). 4. The resin composition according to any one of items 1 to 3, wherein the phosphorus stabilizer is a phosphite compound or a phosphonite compound.
5). 5. A molded article formed from the resin composition according to any one of items 1 to 4.
6). 6. The molded article according to item 5, wherein the thickness is 0.2 to 3.0 mm, and the light transmittance at a wavelength of 420 nm is 40% or less.
7). An insect repellent sleeve for a fluorescent lamp formed from the resin composition according to any one of the preceding items 1 to 4.
8). The insect-repellent sleeve for fluorescent lamps according to the above item 7, which has a thickness of 0.2 to 1.0 mm.
9. 9. A lighting fixture comprising the insect repellent sleeve for fluorescent lamps according to 7 or 8 above.

  The resin composition and molded product of the present invention have an excellent insect repellent effect, can reduce the thickness of the molded product, and are excellent in long-term durability.

  Hereinafter, the present invention will be described in detail.

(Polycarbonate resin)
The polycarbonate resin used in the present invention is an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. Specific examples of the dihydric phenol used here include, for example, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxy). Phenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) phenylmethane, 2,2-bis ( 4-hydroxy-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-3,5-dichlorophenyl) Bis (hydroxyaryl) alkanes such as propane, 1,1-bis (hydroxyphenyl) cyclopentane, bis (hydroxyphenyl) cycloalkanes such as 1,1-bis (hydroxyphenyl) cyclohexane, 4,4′-dihydroxy Dihydroxy ethers such as diphenyl ether and 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, dihydroxys such as 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide Diaryl sulfides, 4,4′-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4, '- dihydroxy diaryl sulfones such dihydroxy-3,3'-dimethyl diphenyl sulfone and the like. These dihydric phenols may be used alone or in combination of two or more.
Among the dihydric phenols, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferably used as the main dihydric phenol component, particularly 70 mol% or more, particularly 80 mol in the total dihydric phenol component. % Or more is preferably bisphenol A. Most preferred is an aromatic polycarbonate resin in which the dihydric phenol component is substantially bisphenol A.

Polycarbonate resins are useful for lighting fixtures because they are superior in transparency compared to other thermoplastic resins and have higher impact strength and flame retardancy. In particular, fluorescent lamp sleeves are also useful for preventing glass scattering when broken.
The basic means for producing the polycarbonate resin will be briefly described. In the solution method using phosgene as a carbonate precursor, the reaction of a dihydric phenol component and phosgene is usually performed in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In addition, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used for promoting the reaction, and a terminal terminator such as an alkyl-substituted phenol such as phenol or p-tert-butylphenol is used as a molecular weight regulator. It is desirable to use it. The reaction temperature is preferably 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more.

  In the transesterification method (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined proportion of a dihydric phenol component and a carbonic acid diester are stirred with heating in the presence of an inert gas, and the resulting alcohol or phenols are distilled. It is a method to make it come out. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. The reaction is carried out while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, a normal transesterification reaction catalyst can be used. Examples of the carbonic acid diester used for the transesterification include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and the like, and diphenyl carbonate is particularly preferable.

The molecular weight of the polycarbonate resin used in the present invention is a range of 1.5 × 10 ^{4 to} 5.0 × 10 ⁴ in terms of viscosity average molecular weight, and a range of 1.8 × 10 ^{4 to} 3.0 × 10 ⁴ is present. The range of 2.0 × 10 ^{4 to} 2.6 × 10 ⁴ is particularly preferable. When the viscosity is within the above range, the molding process and stability of the polycarbonate resin at the time of extrusion molding are excellent, and the mechanical strength of the resulting molded product is good. Here, for the viscosity average molecular weight (M) of the polycarbonate resin, the specific viscosity (η _sp ) obtained from a solution of 0.7 g of the polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer is inserted into the following equation. It is what I asked for.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(UV absorber)
The ultraviolet absorber used in the present invention is a compound represented by the following formula (1).

R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ and R ^j each independently represent a hydrogen atom or a monovalent substituent.
R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ and R ^j are preferably a hydrogen atom, an alkyl group having 10 or less carbon atoms, or an alkoxy having 10 or less carbon atoms. Group, a hydroxy group and a halogen atom, more preferably a hydrogen atom and an alkoxy group having 10 or less carbon atoms. More preferred is a hydrogen atom, and particularly preferred is a case where all represent a hydrogen atom.
Examples of the compound represented by the formula (1) include, for example, Example 4 on page 43, left line 43 to right line 8 of JP-A-2000-264879, and page 4, right column, line 5 of JP-A 2003-155375. It can be synthesized with reference to the example in the 30th line, “Bioorganic & Medicinal Chemistry”, 2000, Vol. 8, pp. 2095-2103, “Bioorganic & Medicinal Chemistry Letters”, 2003, Vol. 13, pages 4077-4080. . For example, UV-1 used in the examples can be synthesized by reacting 2,5-thiophene dicarbonyl dichloride with anthranilic acid.

(Phosphorus stabilizer)
Specific examples of the phosphorus stabilizer used in the present invention include phosphite compounds represented by the following formula (2).

[Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or these Halo, alkylthio (the alkyl group has 1 to 30 carbon atoms) or a hydroxy substituent, and three R ^{1 's} are the same or different from each other, and a cyclic structure can be selected by being derived from dihydric phenols. ]
Moreover, the phosphite compound represented by following formula (3) can be mentioned.

[Wherein R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, or an alkyl group having 7 to 30 carbon atoms. An aralkyl group, a cycloalkyl group having 4 to 20 carbon atoms, and a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms; The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group or those substituted with an alkyl group. ]
Moreover, the phosphite compound represented by following formula (4) can be mentioned.

[Wherein R ⁴ and R ⁵ are each an alkyl group having 12 to 15 carbon atoms. R ⁴ and R ⁵ are the same or different from each other. ]
Examples of the phosphonite stabilizer include a phosphonite compound represented by the following formula (5) and a phosphonite compound represented by the following formula (6).

[In the formula, Ar ¹ and Ar ² represent an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, or a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms. The four Ar ¹ are the same or different from each other. Or two Ar ² are mutually the same or different. ]
Preferred examples of the phosphite compound corresponding to the above formula (2) include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenylmono (tridecyl) ) Phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite.

Preferred specific examples of the phosphite compound corresponding to the above formula (3) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc., preferably distearyl pentaerythritol diphosphite, bis ( Examples include 2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
Preferable specific examples of the phosphite compound corresponding to the above formula (4) include 4,4′-isopropylidenediphenol tetratridecyl phosphite. Such phosphite compounds can be used alone or in combination of two or more.
More preferable phosphite compounds for the above phosphite compounds include compounds represented by the following formula (7) (C-7 component) and compounds represented by the following formula (8) (C-8 component). Can do.

(In formula (7), R ⁶ and R ⁷ are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 aralkyl groups are shown.)

(In Formula (8), R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R < ¹¹ >, R <^14> , R <^15> and R <^16> are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 6 to 20 carbon atoms. Cycloalkyl group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents a hydrogen atom or Indicates a methyl group.)
In formula (7), R ⁶ and R ⁷ are preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound of formula (7) (C-7 component) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-) -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert) -Butylphenyl) phosphite and the like, and tris (2,4-di-tert-butylphenyl) phosphite is particularly preferable.

  On the other hand, the phosphorus compound of the formula (8) can be produced by a known method. For example, there is a method of reacting a bisphenol compound represented by the following formula (9) with phosphorus trichloride to obtain the corresponding phosphoric acid chloride, and then reacting it with a phenol represented by the following formula (10).

(In Formula (9), R < ⁸ >, R <^9> , R < ¹⁰ > and R < ¹¹ > are respectively independently a hydrogen atom, a C1-C12 alkyl group, a C6-C20 cycloalkyl group, C6-C6. 20 represents an aryl group or an aralkyl group having 7 to 20 carbon atoms, R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents a hydrogen atom or a methyl group.)

(In formula (10), R <^14> , R <^15> and R <^16> are respectively independently a hydrogen atom, a C1-C12 alkyl group, a C6-C20 cycloalkyl group, and a C6-C20 aryl. Group or an aralkyl group having 7 to 20 carbon atoms.)
Specific examples of the compound of the above formula (9) include 2,2′-methylenebisphenol, 2,2′-methylenebis (4-methylphenol), 2,2′-methylenebis (6-methylphenol), 2,2 '-Methylenebis (4,6-dimethylphenol), 2,2'-ethylidenebisphenol, 2,2'-ethylidenebis (4-methylphenol), 2,2'-isopropylidenebisphenol, 2,2'-methylenebis ( 4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dihydroxy-3,3'-di (α-methylcyclohexyl) ) -5,5′-dimethylphenylmethane, 2,2′-methylenebis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis (4,6-di-tert-butylphenol) And 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), and the like can be preferably used.

  More preferably, the compound of the formula (9) is 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2 '-Methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), and 2,2'-butylidene-bis (4-methyl-6) -Tert-butylphenol).

  On the other hand, specific examples of the compound of the formula (10) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-tert-butyl. -4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert -Butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-4-s-butylphenol, etc. Can be preferably used. A more preferable example of the compound of the above formula (10) is a case having two or more alkyl substituents.

  In addition, preferred specific examples of the phosphonite compound (component C-5) corresponding to the above formula (5) include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2 , 4-Di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6 -Di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylpheny ) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl)- 4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite and the like, and tetrakis (di-tert-butylphenyl) -biphenylenedi Phosphonite is preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylene diphosphonite is more preferred. The tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically tetrakis (2,4-di-tert-butylphenyl) -4,4. '-Biphenylene diphosphonite (C-5-1 component), tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphosphonite (C-5-2 component), and tetrakis ( Three mixtures of 2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite (C-5-3 component) are preferred. In the case of three kinds of mixtures, the mixing ratio is preferably in the range of 100: 37 to 64: 4 to 14 by weight ratio of the C-5-1 component, the C-5-2 component and the C-5-3 component. The range of 100: 40 to 60: 5 to 11 is more preferable.

  Preferable specific examples of the phosphonite compound (C-6 component) corresponding to the above formula (6) include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4 -Di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butyl) Phenyl) -3-phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl- Phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert) Butylphenyl) -3-phenyl-phenylphosphonite and the like, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, and bis (2,4-di-tert-butylphenyl) -phenyl- More preferred is phenylphosphonite. The bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4- One or two of phenyl-phenylphosphonite (C-6-1 component) and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite (C-6-2 component) Can be used in combination, but a mixture of the two is preferred. In the case of two kinds of mixtures, the mixing ratio is preferably in the range of 5: 1 to 4 by weight, and more preferably in the range of 5: 2 to 3.

On the other hand, as a phosphate stabilizer, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, Dioctyl phosphate, diisopropyl phosphate and the like can be mentioned, and trimethyl phosphate is preferred.
The phosphorus heat stabilizer is preferably a phosphite compound or a phosphonite compound. At least one compound selected from the group consisting of the above C-5 component, C-6 component and C-7 component is preferred, and in particular, a phosphorus system comprising the above C-5 component, C-6 component and C-7 component Stabilizer compositions are preferred.

The phosphorus stabilizer composition comprising the C-5 component, the C-6 component, and the C-7 component has a C-5 component of 40 to 80% by weight and a C-6 component of 100% by weight. A phosphorus stabilizer composition in which 0 to 25% by weight and the C-7 component is 5 to 50% by weight is preferable. More preferably, the C-5 component is 40 to 80% by weight, the C-6 component is 5 to 25% by weight, and the C-7 component is 5 to 50% by weight. Most preferably, the C-5 component is 55 to 50% by weight. 80 wt%, C-6 component is 5-25 wt%, and C-7 component is 5-45 wt%.
The amount of the phosphorus stabilizer or the composition thereof is in the range of 0.001 to 0.1 parts by weight, more preferably in the range of 0.002 to 0.08 parts by weight, with respect to 100 parts by weight of the polycarbonate resin. A range of 0.01 to 0.06 parts by weight is most preferred. If the content of the phosphorus stabilizer is less than 0.001 part by weight, the thermal stability effect is not exhibited, which is not preferable, and if it exceeds 0.1 part by weight, the moist heat resistance is decreased, which is not preferable.

(Antioxidant)
The resin composition of the present invention can contain a phenolic antioxidant. Various types of such phenolic antioxidants can be used.
Specific examples of the phenol-based antioxidant include vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- ( 3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) ), 4,4′-methylenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl) -6-cyclohexylphenol), 2,2'-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2, 2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [2-tert-butyl -4-methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [ 5,5] undecane, 4,4-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4- Methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6-di-tert-butylphenol), 4, 4'-tri-thiobis (2,6-di-tert-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-tert-butyla) Nilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) Isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di) -Tert-butyl-4-hydroxyphenyl) propionate] methane and the like, and can be preferably used.

  More preferably, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl) -2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Further, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate is preferable.

The resin composition of the present invention can contain a sulfur-based antioxidant. Specific examples of such sulfur-based antioxidants include dilauryl-3,3′-thiodipropionic acid ester, ditridecyl-3,3′-thiodipropionic acid ester, dimyristyl-3,3′-thiodipropionic acid ester. , Distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4 -(3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. be able to. More preferably, a pentaerythritol tetra ((beta) -lauryl thiopropionate) ester can be mentioned.
As a ratio of the phenolic antioxidant and the sulfurous antioxidant, the phenolic antioxidant or the sulfurous antioxidant is 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the polycarbonate resin. It is preferable that More preferably, it is 0.005-0.05 weight part with respect to 100 weight part of polycarbonate resin. More preferably, it is 0.01-0.03 weight part.

(UV absorber)
The resin composition of the present invention can contain a benzotriazole-based ultraviolet absorber. Examples of the benzotriazole ultraviolet absorber preferably used in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl). Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy- 3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 "-tetraphthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H- Benzotriazol-2-yl) phenol], typified by condensates with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol Benzotriazole-based ultraviolet absorbers.
The ratio of the benzotriazole ultraviolet absorber is preferably 0.01 to 0.5 parts by weight, more preferably 0.02 to 0.4 parts by weight, and still more preferably 0.05 to 100 parts by weight of the polycarbonate resin. ˜0.35 parts by weight, particularly preferably 0.1 to 0.3 parts by weight.

(Release agent)
The resin composition of the present invention may contain a release agent. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound (silicone oil) , Silicone resins and the like modified with functional group-containing compounds such as acid modification can also be used), fluorine compounds (fluorine oils typified by polyfluoroalkyl ethers), paraffin wax, beeswax and the like. .
Preferred release agents include saturated fatty acid esters, such as glycerin monoesters such as glycerin monostearate, polyglycerin fatty acid esters such as decaglycerin decastate and decaglycerin tetrastearate, stearic acid stearate, etc. Lower fatty acid esters, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The release agent is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 1 part by weight, and 0.03 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Is more preferable, and it is especially preferable that it is 0.05-0.3 weight part.

(Bluing agent)
In addition, the resin composition of the present invention can be blended with a bluing agent in order to counteract the yellowish color based on an ultraviolet absorber or the like. Any bluing agent can be used without any problem as long as it is used for polycarbonate resin. In general, anthraquinone dyes are preferred because they are readily available. Specific examples of the bluing agent include the general name Solvent Violet 13 [CA. No. (Color Index No) 60725; Trade names “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Violet 31 [CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33 [CA. No. 60725; trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA. No. 61500; trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation, generic name Solvent Violet 36 [CA. No. 68210; Trade name: “Macrolex Violet 3R” manufactured by Bayer, Inc., generic name: Solvent Blue 97 [trade name: “Macrolex Blue RR” manufactured by Bayer, Inc.], and generic name: Solvent Blue 45 [CA. No. 61110; trade name “Terrazol Blue RLS” manufactured by Sand Corp.], Ciba Specialty Chemicals' Macrolex Violet, Terrazol Blue RLS, etc., particularly Macrolex Blue RR, Macrolex Violet B and Terrazol Blue RLS is preferred. These bluing agents are usually blended in the polycarbonate resin at a concentration of 0.3 to 1.2 ppm.

(Thermoplastic resin)
The resin composition of the present invention can contain various thermoplastic resins and other additives depending on the purpose.
Examples of thermoplastic resins other than polycarbonate resin include polyethylene resin, polypropylene resin, polystyrene resin, polyacryl styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, etc. General-purpose plastics, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, polyamide resin, cyclic polyolefin resin, engineering plastics represented by polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), poly So-called super engineering plastics such as ether ether ketone, polyether imide, polysulfone, polyether sulfone, polyphenylene sulfide, etc. It can be mentioned. Furthermore, thermoplastic elastomers such as styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

  Other various additives include, for example, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass bead, glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled Fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, aramid particle, aramid fiber, polyarylate fiber, graphite, conductive carbon black, various whiskers Etc.), flame retardants (halogen, phosphate ester, metal salt, red phosphorus, silicon, metal hydrate, etc., including anti-dripping agents), other thermal stabilizers, other UV absorption Agent, light stabilizer, lubricant, colorant (carbon black, acid Pigments and dyes such as titanium), light diffusing agents (acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers , Crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers typified by graft rubber, infrared absorbers, and photochromic agents. it can. Various additives can be added to the thermoplastic resin composition of the present invention without departing from the object of the present invention.

(Molding)
The resin composition of the present invention can be molded by various methods such as extrusion molding, injection molding, injection press molding, inflation molding and blow molding to obtain a molded product. Of these, extrusion molding, injection molding, and injection press molding are preferable. Extrusion molding and injection press molding are particularly preferable as a method for obtaining a thin product in a large area.
The molded article of the present invention preferably has a thickness of 0.2 to 3.0 mm. The molded article preferably has a light transmittance at 420 nm of 40% or less. When the light transmittance is high, a sufficient insect repellent effect is not exhibited, which is not preferable when used as a molded product for insect repellent.
The molded article of the present invention is particularly preferably used as an insect repellent sleeve for fluorescent lamps. The thickness of the insect-repellent sleeve for fluorescent lamps is preferably 0.2 to 1.0 mm, more preferably 0.5 to 0.7 mm. When the thickness of the molded product is thin, the strength is insufficient or a sufficient insect-proof effect cannot be exhibited. On the other hand, when the molded product is thick, coloring is conspicuous and the weight of the product increases, leading to an increase in cost.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, a part is a weight part, and evaluation was implemented by the following method.

(1) Viscosity average molecular weight The specific viscosity at 20 ° C. of a solution obtained by dissolving 0.7 g of polycarbonate resin or extruded product in 100 ml of methylene chloride was measured and calculated from the following formula.
η _sp /c=[η]+0.45×[η] ² c
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
η _sp : specific viscosity [η]: intrinsic viscosity c: constant (= 0.7)
M: Viscosity average molecular weight

(2) Light transmittance The light-transmittance at 420 nm was measured with a U-4100 type spectrophotometer manufactured by Hitachi, Ltd. for the molded extruded product.

(3) Durability test About a test sample of a 0.6 mm thick extruded product, 60 W / m ² (300 to 400 nm), temperature 60 ° C., no humidity, 200 hr with a xenon weather meter XL75 (Suga Test Instruments Co., Ltd.) The test was conducted under the following conditions. The strength of the molded product was confirmed by visual observation and further hammering.
○: Not colored and not destroyed by hammering ×: Colored or destroyed by hammering (with reduced strength)

(4) Insect-proof test Using the polycarbonate resins and additives of Examples 1 to 9 and Comparative Examples 1 to 4 as raw materials, a sleeve having a thickness of 0.6 mm and an outer shape of 32 mm was prepared by extrusion molding, and 40 W was further formed on the sleeve. A white fluorescent lamp was put in and a lighting fixture sealed with a cap was created.
Similarly, a sleeve was prepared using 100 parts by weight of PC-1, 0.02 parts by weight of HS-1, 0.10 parts by weight of L-1 and 0.0001 parts by weight of BL-1 as raw materials, and further sleeves A lighting fixture for confirming the insecticidal effect was prepared by putting a 40 W white fluorescent lamp in the tube and sealing with a cap.
The insect repellent test was performed by arranging one lighting fixture selected from the lighting fixtures of Examples 1 to 9 and Comparative Examples 1 to 4 and a lighting fixture for confirming the insect repellent effect at intervals of 50 cm, and flying insects flying for 30 minutes each. Counted the number of. The number of flying insects flying to the former lighting fixture was divided by the number of flying insects flying to the latter lighting fixture for confirmation of insecticidal effect, and the insecticidal effect index was obtained.
○: Insect-proof effect index that does not attract flying insects Less than 0.1 △: Insect-proof effect index that does not attract flying insects 0.1 to less than 0.5 ×: Insect-proof effect index that attracts flying insects 0.5 or more

(5) Stability of polymer The stability of the polymer during extrusion molding was evaluated as follows.
○: No problem △: Slight resin dripping occurred and temperature adjustment required ×: Yellowing occurred

[Examples 1 to 9, Comparative Examples 1 to 4]
The polycarbonate resin and additives in the table were kneaded with a twin-screw extruder JSW TEX-30α at a cylinder temperature of 300 ° C., and the strands were cut to obtain pellets. The obtained pellets were dried at 120 ° C. for 4 hours, and extrusion molding was performed with a Nakatani single-screw extruder, and an extruded product having a thickness of 0.6 mm and a width of 20 cm (however, Example 3 was a molded product having a thickness of 3 mm). In Example 4, a film having a thickness of 0.2 mm was prepared. The above evaluation was performed on this extruded product. The results are shown in Table 1.
The polycarbonate resin, ultraviolet absorber, phosphorus stabilizer, mold release agent, and bluing agent shown in Table 1 are as follows.

(1) Polycarbonate resin PC-1: Powdered polycarbonate resin having a repeating unit of bisphenol A having a viscosity average molecular weight of 23,800 obtained by interfacial polymerization from p-tert-butylphenol and phosgene PC-2: p-tert- Powdered polycarbonate resin containing bisphenol A having a viscosity average molecular weight of 18,500 obtained by interfacial polymerization from butylphenol and phosgene as a repeating unit PC-3: Viscosity average obtained by interfacial polymerization from p-tert-butylphenol and phosgene Powdered polycarbonate resin containing bisphenol A having a molecular weight of 25,200 as a repeating unit (2) Compound of formula (1) (ultraviolet absorber)
UV-1: 2,2 ′-(thiophene-2,5-diyl) bis (4H-benzo [d] [1,3-oxazin-4-one]

(3) Phosphorus stabilizer HS-1: 71:15:14 (weight ratio) mixture of the following P-1 component, P-2 component and P-3 component (manufactured by Clariant Japan Co., Ltd .: Sandstub P) -EPQ (product name))
P-1 component: tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3'-biphenylenedi Phosphonite and tetrakis (2,4-di-t-butylphenyl) -3,3′-biphenylenediphosphonite 100: 50: 10 (weight ratio) mixture P-2 component: bis (2,4-di -Tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite 5: 3 (weight ratio) mixture P-3 component: Tris (2,4-di-tert-butylphenyl) phosphite (4) Benzotriazole type UV absorber UV-2: 2,2′-methylenebis [4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol) -2-ylphenol] (Asahi Denka Kogyo Co., Ltd .: ADK STAB LA-31)
(Other UV absorbers)
UV-3: 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one) (manufactured by Siatech: CYASORB UV-3638 (trade name))
(5) Saturated fatty acid ester L-1: Glycerin monostearate (Riken Vitamin Co., Ltd. product: Riquemar S-100A (trade name))
(Bluing agent)
BL-1: anthraquinone compound (manufactured by Bayer: Macrolex Violet B (trade name))

  The resin composition of the present invention is useful as an insect repellent sleeve for fluorescent lamps.

Claims (9)

(I) With respect to 100 parts by weight of the polycarbonate resin having a viscosity average molecular weight in the range of 1.5 × 10 ^{4 to} 5.0 × 10 ⁴ , (ii) the compound represented by the following formula (1) 0.01 to 0. A resin composition containing 5 parts by weight and (iii) 0.001 to 0.1 parts by weight of a phosphorus-based stabilizer.

[R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ and R ^j each independently represent a hydrogen atom or a monovalent substituent. ] The resin composition according to claim 1, further comprising (iv) 0.01 to 0.5 parts by weight of a benzotriazole type ultraviolet absorber with respect to 100 parts by weight of the polycarbonate resin. The resin composition according to claim 1, further comprising (v) 0.01 to 2 parts by weight of a saturated fatty acid ester with respect to 100 parts by weight of the polycarbonate resin. The resin composition according to any one of claims 1 to 3, wherein the phosphorus stabilizer is a phosphite compound or a phosphonite compound. The molded article formed from the resin composition as described in any one of Claims 1-4. The molded article according to claim 5, wherein the molded article has a thickness of 0.2 to 3.0 mm and a light transmittance of 40% or less at a wavelength of 420 nm. The insect-repellent sleeve for fluorescent lamps formed from the resin composition as described in any one of Claims 1-4. The insect repellent sleeve for fluorescent lamps according to claim 7, which has a thickness of 0.2 to 1.0 mm. A lighting fixture comprising the insect repellent sleeve for a fluorescent lamp according to claim 7 or 8.