JP5663600B2 - Polycarbonate resin composition and molded article - Google Patents

Description

  The present invention relates to a resin composition excellent in molding heat resistance, repro resistance, dry heat resistance, weather resistance, releasability and boiling water resistance. The present invention also relates to a resin composition in which there is no cracking of a molded product during injection molding or extrusion molding, and there is little contamination of a mold, a die, a molding roll or the like due to sublimation of an additive or the like. Moreover, this invention relates to the resin composition which has the corrosion inhibitory effect of metal parts, such as a metal mold | die which resin contacts. Furthermore, this invention relates to the molded article formed from this resin composition.

Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc., and are therefore widely used in electrical, mechanical, automotive, building materials, medical applications, and the like. However, when a molded article of polycarbonate resin is used outdoors for a long period of time, such as for automotive parts or building materials, dry heat resistance, weather resistance, and water resistance may be problematic. In addition, thermal stability during injection molding and extrusion molding, cracking of molded products, contamination of molds and rolls due to sublimation of additives, etc., and corrosion of metal parts in contact with resin may be problematic. .
Conventionally, various additives have been used to solve these problems. Patent Document 1 discloses a fragrance with improved molding heat resistance, dry heat resistance and wet heat fatigue resistance while maintaining weather resistance by combining specific phosphorus stabilizers, phenol stabilizers, ultraviolet absorbers and mold release agents. A group polycarbonate resin composition is shown. Patent Document 2 discloses a polycarbonate that can reduce contamination of a die when formed into a sheet by extrusion while maintaining weather resistance and mechanical properties by combining an ultraviolet absorber, a specific internal mold release agent and a specific phosphorus stabilizer. A resin composition is shown. Patent Document 3 is excellent in thermal stability and water resistance not only during granulation but also during molding and recycling by combining a specific phosphorus stabilizer, a specific phenol stabilizer and an epoxy compound. It has been shown that polycarbonate resin compositions can be provided.

  However, the techniques of Patent Documents 1 and 2 are not satisfactory with respect to boiling water resistance and thermal stability during extrusion, and the metal parts such as molds and molding rolls that are in contact with the resin during molding are corroded. There is. In addition, the technology of Patent Document 3 is not satisfactory with respect to weather resistance and dry heat resistance, and there is a problem that the molded product breaks during injection molding processing and extrusion molding processing, and due to sublimation of additives, molds, dies and molding rolls. Etc. are contaminated.

JP 2002-194200 A Japanese Patent No. 3827924 Japanese Patent No. 3285690

Accordingly, an object of the present invention is to provide a resin composition excellent in molding heat resistance, repro resistance, dry heat resistance, weather resistance, mold release and boiling water resistance. Another object of the present invention is to provide a resin composition in which a molded product is not cracked during injection molding or extrusion molding. Moreover, the objective of this invention is providing the resin composition with few contaminations, such as a metal mold | die by the sublimation of an additive etc., a die, and a forming roll. Furthermore, the objective of this invention is providing the resin composition which has the corrosion inhibitory effect of metal parts, such as a metal mold | die which a resin contacts.
The present invention adopts the following configuration in order to solve the above problems.

1. [A] 100 parts by weight of a polycarbonate resin (component A) having a viscosity average molecular weight of 2.2 × 10 ^{4 to} 3.2 × 10 ⁴ , where the polycarbonate resin (component A) is composed of a dihydric phenol, a carbonate precursor, , 70 mol% or more of the dihydric phenol is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A),
[B] A phosphorus stabilizer (component B) represented by the following formula (1): 0.005 to 0.2 parts by weight,
[C] A phenol-based stabilizer (C component) represented by the following formula (2): 0.005 to 0.2 parts by weight,
[D] At least one ultraviolet ray selected from the group consisting of a benzotriazole ultraviolet absorber having a molecular weight of 400 or more, a triazine ultraviolet absorber having a molecular weight of 400 or more, and a cyclic iminoester ultraviolet absorber represented by the following formula (3) Absorbent (component D) 0.01 to 0.5 parts by weight,
[E] pentaerythritol tetrastearate (E component) 0.005 parts by weight, and contains [F] a copolymer of styrene and glycidyl methacrylate (F component) 0.003 to 0.2 parts by weight And
The E component and the F component have a limit stress when the bisphenol A type polycarbonate resin sheet having a viscosity average molecular weight of 24,500 produced by the melt extrusion method is treated at a temperature of 120 ° C. for 24 hours in a quarter ellipse test method. The resin composition which is 12 MPa or more.

[Wherein R _{1 to} R ₄ are each independently substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms. Or an aryl group having 5 to 20 carbon atoms. ]

[Wherein, R ₁ and R ₂ each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, and R ₃ and R ₄ each independently represents an alkylene group having 1 to 5 carbon atoms. Represent. ]

[Ar is a divalent aromatic hydrocarbon residue having 6 to 12 carbon atoms and may contain a hetero atom. n represents 0 or 1. ]

2. 2. The resin composition according to item 1 above, wherein the polycarbonate resin (component A) has a viscosity average molecular weight of 2.3 × 10 ⁴ to 3.0 × 10 ⁴ .
3. A molded article formed from the resin composition according to item 1.
4). 4. The molded article according to 3 above, which is a sheet or film having a thickness of 0.1 to 30 mm.
5. 5. The molded product according to item 3 or item 4, which is a building material and a transparent member for vehicles.

The resin composition of the present invention is excellent in molding heat resistance, repro resistance, dry heat resistance, weather resistance, releasability and boiling water resistance. In addition, the resin composition of the present invention has few cracks in the molded product during injection molding or extrusion molding, and there is little contamination of the mold, die, molding roll, etc. due to sublimation of additives and the like. Furthermore, the resin composition of the present invention has an effect of inhibiting corrosion of metal parts such as a mold that the resin contacts.
Moreover, since the molded article formed from the resin composition has good transparency, hue, and boiling water resistance, it can be suitably used for a transparent member for a vehicle represented by a building member and a glazing material. In addition to building materials and transparent members for vehicles, spectacle lenses, protective glasses, goggles, nameplates, solar cell covers or solar cell substrates, display device covers, touch panels, and pachinko machine parts (circuit covers, It can be used for a wide range of applications such as chassis and pachinko ball conveyance guides). That is, the resin composition of the present invention can be suitably used in a wide range of applications because of its excellent characteristics, and the industrial effects that it exhibits are exceptional.

The schematic diagram of the jig | tool for a quarter ellipse test method for measuring a limit stress. The schematic diagram of the metal mold | die (cavity size side 42mm x length 24mm x depth 3mmt, the insert (20mmphi) insertion for corrosion evaluation created with metal mold | die material NAK80) used for metal mold | die corrosion evaluation.

  Below, the polycarbonate resin composition of this invention is demonstrated in detail.

[Polycarbonate resin]
Polycarbonate resin (A component), a dihydric phenol is reacted with a carbonate precursor to give al is by more than 70 mol% of the dihydric phenol is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A ) . Other components include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) 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, Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, 1,1-bis (hydroxyphenyl) cyclopentane, 1,1- Bis (hydroxyphenyl) cycloalkanes such as bis (hydroxyphenyl) cyclohexane, dihydroxyaryl ethers such as 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4 ′ -Dihydroxydiphenyl sulfide, dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Examples thereof include dihydroxydiaryl sulfoxides such as sulfoxide, and dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone. It is used these dihydric phenols alone, but it may also be used alone or in combination.
The dihydric phenol is preferably one in which 80 mol% or more is bisphenol A. Most preferred is an aromatic polycarbonate resin in which the dihydric phenol component is substantially bisphenol A.

  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 in 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 (A component) is the viscosity average molecular weight (M) at ^{2.2 × 10 4 ~3.2 × 10 4} , 2.3 × 10 4 ~3.0 × 10 4 virtuous preferable . A polycarbonate resin having such a viscosity average molecular weight (M) is preferable because it has a certain mechanical strength with respect to the obtained molded product while maintaining a relatively good fluidity during extrusion and molding.

The viscosity average molecular weight referred to in the present invention refers to M obtained by inserting a specific viscosity (η _SP ) measured using a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
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

[Phosphorus stabilizer]
The phosphorus stabilizer (component B) used in the present invention is a compound represented by the following formula (1).

In the formula, each of R _{1 to} R ₄ may be independently substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms. It is a good aryl group having 5 to 20 carbon atoms.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, t-butyl group, pentyl group, hexyl group, octyl group, and decyl group.
Examples of the aryl group having 5 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthryl group. Examples of the substituent for the aryl group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.

As a phosphorus stabilizer (component B), tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4, 3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl- Mention may be made of phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite. Particularly preferred is tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite.
Content of a phosphorus stabilizer (B component) is 0.005-0.2 weight part with respect to 100 weight part of polycarbonate resin (A component). If it is less than 0.005 parts by weight, the thermal stability is insufficient. On the other hand, if the amount exceeds 0.2 parts by weight, the color of the polycarbonate resin and the decrease in water resistance are remarkable. The content of the component B is more preferably 0.01 to 0.1 parts by weight, particularly preferably 0.02 to 0.08 parts by weight with respect to 100 parts by weight of the component A.

[Phenolic stabilizer]
The phenol-based stabilizer (component C) is a compound represented by the following formula (2).

In the formula, R ₁ and R ₂ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, and R ₃ and R ₄ each independently represent an alkylene group having 1 to 5 carbon atoms. .
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. Examples of the alkylene group having 1 to 5 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group.

As the phenol-based stabilizer (component C), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3 5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1-dimethyl- 2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane and the like can be mentioned. Particularly preferred is octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.
Content of a phenol type stabilizer (C component) is 0.005-0.2 weight part with respect to 100 weight part of polycarbonate resin (A component). If it is less than 0.005 parts by weight, the thermal stability is insufficient. Moreover, when it exceeds 0.2 weight part, coloring of a polycarbonate resin, a crack of a molded product, etc. may be caused. The content of component C is more preferably 0.01 to 0.1 parts by weight, still more preferably 0.01 to 0.08 parts by weight, and particularly preferably 0 to 100 parts by weight of component A. 0.01 to 0.06 parts by weight.

[Ultraviolet absorber]
The UV absorber (component D) is selected from the group consisting of a benzotriazole UV absorber having a molecular weight of 400 or more, a triazine UV absorber having a molecular weight of 400 or more, and a cyclic imino ester UV absorber represented by the following formula (3). It is.
As a benzotriazole ultraviolet absorber having a molecular weight of 400 or more, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylenebis [4- ( 1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2,2′-methylenebis [4-tert-butyl-6- (2H-benzotriazole-2) -Yl) phenol], 2,2′-octylidenebis [4-methyl-6- (2H-benzotriazol-2-yl) phenol] and the like. Particularly preferred is 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol].

As triazine-based ultraviolet absorbers having a molecular weight of 400 or more, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-[(octyl) oxy] -phenol and the like. Particularly preferred is 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.
The cyclic imino ester-based ultraviolet absorber is a compound represented by the following formula (3).

Ar is a divalent aromatic hydrocarbon residue having 6 to 12 carbon atoms and may contain a hetero atom. n represents 0 or 1.
Examples of the divalent aromatic hydrocarbon residue include a phenylene group, a naphthalenediyl group, and an anthracenediyl group. The aromatic hydrocarbon residue may have a substituent. As substituents, methyl groups, ethyl groups, propyl groups, butyl groups, t-butyl groups, pentyl groups, hexyl groups, octyl groups, decyl groups and other alkyl groups having 1 to 10 carbon atoms, and halogens such as chlorine atoms and bromine atoms Atom.

As a compound represented by the formula (3), 2,2′-bis (3,1-benzoxazin-4-one) (when n = 0 in the above formula (3)), 2,2′-p-phenylene Bis (3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5-naphthalene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2 -Nitro-p-phenylene) bis (3,1-benzoxazin-4-one), and 2,2 '-(2- Chloro-p-phenylene) bis (3,1-benzoxazin-4-one) and the like. Particularly preferred is 2,2′-p-phenylenebis (3,1-benzoxazin-4-one).
By blending the specific ultraviolet absorber as described above, weather resistance can be imparted and contamination of rolls and the like can be suppressed during molding.

  Content of a ultraviolet absorber (D component) is 0.01-0.5 weight part with respect to 100 weight part of polycarbonate resin (A component). If it is less than 0.01 part by weight, the ultraviolet absorption performance is small, and sufficient weather resistance cannot be obtained. In addition, when the amount exceeds 0.5 parts by weight, the UV absorber itself is often colored yellow due to its nature, and since the polycarbonate resin is colored yellow, it is possible to add a large amount of blueing agent to counteract the yellowishness Necessary. As a result, problems such as deterioration of transparency of the molded product and increase in the volatile content of the ultraviolet absorber during molding cause mold contamination. The content of component D is preferably 0.05 to 0.3 parts by weight, more preferably 0.1 to 0.3 parts by weight, with respect to 100 parts by weight of component A.

[Release agent]
The resin composition of the present invention, it contains pentaerythritol tetrastearate (E component) as a release agent.
Pentaerythritol tetrastearate used as a release agent in the present invention (E component), to bisphenol A type polycarbonate resin sheet with a viscosity average molecular weight 24,500 prepared by melt extrusion methods, 1 elliptical Test Method 4 minutes The critical stress when treated at 120 ° C. for 24 hours is 12 MPa or more.
The test method for the above critical stress is usually performed as follows because pentaerythritol tetrastearate is a solid having a melting point of 60 ° C. or higher. That is, the solid of pentaerythritol tetrastearate is heated to a molten state, and is applied to the entire surface of a predetermined polycarbonate resin sheet placed in a jig for a quarter ellipse test method. The sheet is then stored in a 120 ° C. gear oven for 24 hours and heat treated. The sheet after such treatment is cooled, and after removing pentaerythritol tetrastearate on the surface, the critical stress of pentaerythritol tetrastearate is evaluated from the crack generation position. If pentaerythritol tetrastearate easily flows down from the sheet surface during storage in a gear oven because the viscosity at 120 ° C. is too low, a gauze impregnated with pentaerythritol tetrastearate is placed on the sheet surface. Process with. Further, the liquid already applied at room temperature is applied to the entire surface of the sheet without heating, or the gauze soaked with the liquid is placed on the surface of the sheet for evaluation. In addition, the polycarbonate resin sheet used in such a test method has a very low residual strain. Usually, a sheet produced by the melt extrusion method can be used as it is because the residual strain is extremely low. However, if the strain is large, it is necessary to test by reducing the residual strain by annealing or the like. . In the examples described later, the maximum value of the limit stress measured by the 1/4 ellipse test method jig shown in FIG. 1 is 47 MPa.

The present invention is based on the finding that the crack resistance of a molded product can be improved satisfactorily when the critical stress of pentaerythritol tetrastearate (component E) exceeds a specific value. It is considered that cracking of the molded product occurs when pentaerythritol tetrastearate remaining on the mold surface comes into direct contact with a high-temperature polycarbonate resin having a large amount of distortion and stress during molding.
The esterification rate of pentaerythritol tetrastearate (component E) is not particularly limited, but the esterification rate is preferably 60% or more, more preferably 80% or more, and still more preferably 85% or more. An ester having a low esterification rate and a high hydroxyl value cannot satisfy the above limit stress of 12 MPa or more. However, in the present invention, the full ester (E component) does not necessarily have an esterification rate of 100%, may be 80% or more, and preferably 85% or more.
Content of pentaerythritol tetrastearate (E component) is 0.005-0.5 weight part with respect to 100 weight part of polycarbonate resin. If it is less than 0.005 parts by weight, the releasability is not sufficiently improved. On the other hand, if it exceeds 0.5 parts by weight, the transparency of the molded product is impaired by the coloring of the polycarbonate resin. The content of the E component is more preferably 0.01 to 0.4 parts by weight, still more preferably 0.05 to 0.3 parts by weight with respect to 100 parts by weight of the A component.

[Epoxy compounds]
The resin composition of the present invention, you containing a copolymer of styrene and glycidyl methacrylate (F component).
A copolymer of styrene and glycidyl methacrylate (component F) is a bisphenol A type polycarbonate resin sheet having a viscosity average molecular weight of 24,500 produced by a melt extrusion method at a temperature of 120 ° C. in a quarter ellipse test method. The critical stress when treated for 24 hours is 12 MPa or more.
A polycarbonate resin composition containing a copolymer of styrene and glycidyl methacrylate (F component) gives good boiling water resistance and is molded in applications exposed to high-temperature and high-humidity environments such as transparent members for vehicles. The mold corrosion of the machine is suppressed, and the molded article has good crack resistance. Particularly when used in combination with the phosphorus stabilizer of the present invention, good boiling water resistance can be imparted.

The present invention is based on the finding that the cracking resistance of a molded article can be improved satisfactorily when the limit stress of a copolymer of styrene and glycidyl methacrylate (F component) exceeds a specific value. It is considered that cracking of the molded product occurs when a copolymer of styrene and glycidyl methacrylate remaining on the mold surface is in direct contact with a high-temperature polycarbonate resin in which distortion and stress remain largely during molding.
Copolymers of styrene and glycidyl methacrylate (component F) basically have all epoxy functional groups for the purpose of imparting good boiling water resistance and for the purpose of inhibiting mold corrosion. Is applicable. However, in the case of the resin composition of the present invention, in addition, the critical stress needs to be 12 MPa or more.
Content of the copolymer (F component) of styrene and glycidyl methacrylate is 0.003-0.2 weight part with respect to 100 weight part of polycarbonate resin. If it is less than 0.003 parts by weight, the boiling water resistance improving effect is not sufficient. On the other hand, if the amount exceeds 0.2 parts by weight, the heat resistance of the polycarbonate resin deteriorates, resulting in problems such as causing coloring of the molded product. The content of the component F is preferably 0.005 to 0.1 parts by weight, more preferably 0.007 to 0.05 parts by weight with respect to 100 parts by weight of the component A.

[Other additives]
In the resin composition of the present invention, a bluing agent can be blended in order to cancel the yellowishness of the lens based on the polycarbonate resin or the ultraviolet absorber. Any bluing agent can be used without any problem as long as it is used for polycarbonate resin. In general, anthraquinone dyes are easily available and preferred.
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, generic name Solvent Blue97 [tradename: “Macrolex Blue RR” manufactured by Bayer, Inc.] and generic name, SolventBlue45 [CA. No. 61110; trade name “Tetrazole Blue RLS” manufactured by Sand Corp.] is a typical example. These bluing agents are usually blended in the polycarbonate resin at a concentration of 0.05 to 3.0 ppm. With such a blending amount, a natural transparency can be imparted to the molded product.

In the resin composition of the present invention, other heat stabilizers, antistatic agents, flame retardants, heat ray shielding agents, fluorescent whitening agents, pigments, light diffusing agents, and reinforcing fillings are provided as long as the object of the present invention is not impaired. Agents, other resins, elastomers, and the like can be blended.
Various products can be manufactured by injection molding the resin composition of the present invention to obtain a molded product. In such injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas assist injection molding, insert molding, in-mold coating molding, heat insulation mold molding, rapid heating / cooling mold molding, two-color molding. , Sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.
In addition, the resin composition of the present invention can be used in the form of various shaped extruded products, sheets, films and the like by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can also be made into a hollow molded product by rotational molding, blow molding or the like. The sheet or film preferably has a thickness of 0.1 to 30 mm, more preferably 0.3 to 10 mm, and still more preferably 0.5 to 5 mm. A sheet having a thickness of 0.5 to 10 mm is defined as a polycarbonate resin sheet, and a sheet having a thickness of 0.1 to 0.5 mm is defined as a polycarbonate resin film.

  The resin composition of the present invention is excellent in molding heat resistance, repro resistance, dry heat resistance, weather resistance, releasability and water resistance. The resin composition of the present invention has few cracks in a molded product during injection molding or extrusion molding, and less contamination of a mold, a die, a molding roll, or the like due to sublimation of an additive or the like. Moreover, since the resin composition of this invention has the corrosion inhibitory effect of metal parts, such as a metal mold | die which resin contacts, it is used suitably in various transparent members. As various transparent members, it can use suitably for the transparent member for vehicles represented by the building member and the glazing material, for example. In addition to building materials and transparent members for vehicles, spectacle lenses, protective glasses, goggles, nameplates, solar cell covers or solar cell substrates, display device covers, touch panels, and pachinko machine parts (circuit covers, It can be used for a wide range of applications such as chassis and pachinko ball conveyance guides).

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Evaluation was carried out by the following method.

[Evaluation method]
(1) Limit stress of copolymer of pentaerythritol tetrastearate (E component), styrene and glycidyl methacrylate (F component) Installed in the jig for the quarter ellipse test method shown in FIG. Was measured. As a test piece, it was cut out from a polycarbonate resin sheet (bending elastic modulus Eb = 2,040 MPa) having a viscosity average molecular weight of 24,500 and a thickness of 1 mm produced by extrusion molding using a T-die into a size of 120 mm in length and 40 mm in width. The test piece was used. The polycarbonate resin sheet (symbol 7) is attached to a jig, fixed with a press fitting (symbol 5) along an elliptical curved surface, and pentaerythritol tetrastearate and styrene and glycidyl methacrylate previously melted on the sheet surface . Each copolymer was coated. The horizontal distance X (cm) from the center of the ellipse (symbol 1) of the part (symbol 8) that is held in a gear oven at 120 ° C. for 24 hours and cracked with the least distortion (symbol 6; that is, from the ellipse minor axis) The horizontal distance to the crack occurrence point was measured. In the jig used in the test, the relationship between the distance X and the strain ε of the polycarbonate resin sheet is as follows.
^{ε = 0.02 × (1-0.0084X 2)} -3/2 t
t: thickness of the polycarbonate resin sheet (cm)
X: Horizontal distance (cm) from the center of the ellipse to the cracked part with the least distortion
Since t = 0.1 in the test of the present invention, the strain ε was obtained from the following equation.
^{ε = 2 × (1-0.0084X 2)} -3/2 × 10 -3
Further, the critical stress for occurrence of cracks was determined from the value of ε according to the following formula.
Critical stress (MPa) = ε × Eb
Eb: Flexural modulus (MPa) of polycarbonate resin

(2) Molding heat resistance Molded in a molding cycle of 60 seconds on an injection molding machine with a maximum clamping force of 85 Ton and a cylinder temperature of 350 ° C and a mold temperature of 80 ° C. 90 mm × width 50 mm × thickness 2 mm). Further, the resin was retained in the cylinder of the injection molding machine for 10 minutes and then molded to obtain a “molded plate after retention” (length 90 mm × width 50 mm × thickness 2 mm). The hue (L, a, b) of the molded plate before and after the residence was measured by the C light source reflection method using SE-2000 manufactured by Nippon Denshoku Co., Ltd., and the color difference ΔE was determined by the following formula. It shows that it is excellent in molding heat resistance, so that (DELTA) E is small.
ΔE = {(L−L ′) ² + (aa ′) ² + (b−b ′) ² } ^1/2
Hue of “molded plate before stay”: L, a, b
Hue of “molded plate after residence”: L ′, a ′, b ′
(3) Reproducibility The virgin pellets obtained in each example were repelleted twice at an extrusion temperature of 270 ° C. with a 30 mm diameter single screw extruder. The yellowness (b) of the obtained pellet was measured by a C light source reflection method using SE-2000 manufactured by Nippon Denshoku Co., Ltd., and the degree of discoloration Δb between the virgin pellet and the twice repellet was determined. The smaller the Δb, the better the change in hue.
Δb = b′−b
"Virgin pellet hue": b
"Twice repellet hue": b '

(4) Dry heat resistance Molded plate obtained by molding in a molding cycle of 60 seconds on a cylinder temperature of 350 ° C. and a mold temperature of 80 ° C. on an injection molding machine with a maximum clamping force of 85 Ton (length 90 mm × width 50 mm) × 2 mm thickness) was treated for 1,000 hours under a condition of a temperature of 130 ° C. using a hot air dryer, and the difference ΔYI in the yellowness (YI) of the flat plate before and after the dry heat treatment was determined. It shows that dry-heat resistance is excellent, so that (DELTA) YI is small.
YI = [100 (1.28X−1.06Z)] / Y
ΔYI = YI of the molded plate after treatment-YI of the molded plate before treatment
(5) Weather resistance Molded plate obtained by molding in a molding cycle of 60 seconds on a cylinder temperature of 350 ° C. and a mold temperature of 80 ° C. on an injection molding machine with a maximum clamping force of 85 Ton (length 90 mm × width 50 mm) X thickness 2 mm) using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd .: WEL-SUN: HC-B), black panel temperature 63 ° C., humidity 50%, water spray for 18 minutes and no spray for 102 minutes The treatment was performed for 1,000 hours under the conditions of a total of 120 minutes. The hue change (ΔYI) before and after the treatment is expressed by the following formula based on ASTM-E1925 from X, Y and Z values obtained by measuring transmitted light using SE-2000 manufactured by Nippon Denshoku Co., Ltd. Asked. It shows that it is excellent in a weather resistance, so that (DELTA) YI is small.
YI = [100 (1.28X−1.06Z)] / Y
ΔYI = YI of the molded plate after treatment-YI of the molded plate before treatment

(6) Boiling water resistance Molded plate obtained by molding in a molding cycle of 60 seconds on a cylinder temperature of 350 ° C and a mold temperature of 80 ° C on an injection molding machine with a maximum clamping force of 85 Ton (length 90 mm x width 50 mm × thickness 2 mm) was processed for 48 hours under the conditions of a temperature of 120 ° C. and a humidity of 100% using an autoclave SN510 manufactured by Yamato Scientific Co., Ltd. The Haze before and after the treatment was measured according to ISO14782 using NDH-2000 manufactured by Nippon Denshoku Co., Ltd., and the change in the Haze before and after the treatment (ΔHaze) was determined by the following formula. It shows that it is excellent in boiling-water resistance, so that (DELTA) Haze is small.
ΔHaze = Haze of the molded plate after treatment −Haze of the molded plate before treatment
(7) Releasability When molding a cup-shaped molded product of 70mmφ × 20mm, 4mm thickness under the conditions of cylinder temperature 300 ° C, mold temperature 80 ° C, injection pressure 118MPa with an injection molding machine with maximum clamping force 75Ton The projecting load applied to the projecting pin was measured, and an average value obtained by molding 30 shots was shown as a release load. It shows that it is excellent in mold release property, so that a mold release load is small.

(8) Cracking during molding A cup-shaped molded product was continuously formed into 1,000 shots under the same conditions as those for the above-mentioned releasability, and x indicates that cracking occurred immediately after molding, and no cracking occurred. Was marked as ○.
(9) Mold corrosiveness Maximum using a mold having the shape shown in FIG. 2 (cavity size width 42 mm × length 24 mm × depth 3 mmt, insert for corrosion evaluation (20 mmφ) inserted in mold steel NAK80) After 500 shots of continuous molding using an injection molding machine with a clamping force of 85 Ton, remove the corrosion evaluation insert from the mold and place it in a thermo-hygrostat set to 50 ° C x 90% RH for 2 hours. Was visually observed to determine the presence or absence of corrosion on the mold mirror surface. The criteria for determination are as follows.
○: Corrosion is 5% or less of the mirror surface. Δ: Corrosion is observed in the range of more than 5% of the mirror surface and 50% or less. ×: Corrosion is observed in the range of 50% or more of the mirror surface.

(10) Roll stain during sheet molding When the fogging condition (dirt) of a roll after forming a flat sheet is continuously formed for 6 hours by the following melt-extrusion method, Was evaluated with the naked eye, where no effect was observed but the cloudiness was noticeable and the cloudiness was not noticeable.
Melt extrusion method: Melted polycarbonate resin composition having a width of 1,000 mm by using a vented T-die extruder with an extruder temperature of 250 to 300 ° C., a die temperature of 260 to 300 ° C., and a vacuum degree of the vent portion being maintained at 26.6 kPa. The first roll to the third roll are all mirror metal rolls (roll diameter 300 mm), and the temperatures of the first roll, the second roll and the third roll are set to 140 ° C., 150 ° C. and 145 ° C., respectively. Then, the extruded molten polycarbonate resin composition is sandwiched between the first roll and the second roll and pressed with a linear pressure of 6 MPa · cm, and the gap between the second roll and the third roll is changed to the third roll. It was allowed to pass while being contacted, and was taken up by a take-up roll to form a polycarbonate resin sheet (thickness 2 mm).

Examples 1-4, Comparative Examples 1-11
Various additives shown in Table 1 were added to 100 parts by weight of the polycarbonate resin in the blending amounts shown in Table 1, mixed with a blender, and then melt-kneaded using a vent type twin screw extruder to obtain pellets. The vent type twin screw extruder used was TEX30α (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The kneading zone was of one type before the vent opening. Extrusion conditions were a discharge rate of 30 kg / h, a screw rotation speed of 300 rpm, a vent vacuum of 2 kPa, and an extrusion temperature of 290 ° C. from the first supply port to the die part.
The obtained pellets were dried at 120 ° C. for 5 hours with a hot air circulation dryer, and then various evaluations were performed using the pellets. The evaluation results are shown in Table 1.
Each symbol in the table represents the following compound.

[A] Polycarbonate resin (component A)
A-1: Polycarbonate resin powder having a viscosity average molecular weight of 23,900 produced from bisphenol A and phosgene by an interfacial condensation polymerization method A-2: Viscosity average molecular weight produced by an interfacial condensation polymerization method from bisphenol A and phosgene 27,000 Polycarbonate resin powder

[B] Phosphorus stabilizer (component B)
B-1: Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite (phosphorus stabilizer other than component B)
B-2: Tris (2,4-di-t-butylphenyl) phosphite

[C] Phenolic stabilizer (component C)
C-1: Pentaerythritol-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (phenolic stabilizer other than component C)
C-2: n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate C-3: 2,2-thio [diethylbis-3 (3,5-di-t-butyl) -4-hydroxyphenyl)

[D] UV absorber (component D)
D-1: 2,2′-p-phenylenebis (3,1-benzoxazin-4-one)
D-2: 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]
D-3: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (UV absorber other than component D)
D-4: (2- (2-hydroxy-5-tert-octylphenyl) benzotriazole

[E] release agent; pentaerythritol tetrastearate (E component)
E-1: Pentaerythritol tetrastearate having a critical stress value of 18 MPa according to the above evaluation method (manufactured by Cognis Japan Co., Ltd .: Roxyol VPG861)
(Releasing agent other than E component)
E-2: Glycerin mono fatty acid ester having a critical stress value of 11 MPa according to the above evaluation method (manufactured by Riken Vitamin Co., Ltd .: Riquemar S-100A)

[F] Copolymer of styrene and glycidyl methacrylate (F component)
F-1: Copolymer of styrene and glycidyl methacrylate having a critical stress value of 47 MPa according to the above evaluation method (manufactured by NOF Corporation: Marproof G-0250SP)
(Epoxy compounds other than component F)
F-2: Epoxidized soybean oil having a critical stress value of 2 MPa according to the above evaluation method (manufactured by NOF Corporation: New Sizer 510R)
(Other additives)
G-1: Brewing agent (anthraquinone compound, manufactured by Bayer Co., Ltd .: Macrolex Violet B)

  From Table 1, it can be seen that the resin composition of the present invention is excellent in molding heat resistance, repro resistance, dry heat resistance, weather resistance, mold releasability and boiling water resistance. In addition, it can be seen that the resin composition of the present invention is less contaminated with molds, dies, molding rolls and the like due to sublimation of additives and the like during injection molding and extrusion. Furthermore, it turns out that the resin composition of this invention has the corrosion inhibitory effect of metal parts, such as a metal mold | die which resin contacts in the case of a shaping | molding process.

  Since the molded article obtained from the resin composition of the present invention has good transparency, hue, and boiling water resistance, it can be suitably used for a transparent member for a vehicle represented by a building member and a glazing material. In addition to building materials and transparent members for vehicles, spectacle lenses, protective glasses, goggles, nameplates, solar cell covers or solar cell substrates, display device covers, touch panels, and pachinko machine parts (circuit covers, It can be used for a wide range of applications such as chassis and pachinko ball conveyance guides).

1 Ellipse center 2 Ellipse major axis radius (10cm)
3 Ellipse minor axis radius (4cm)
4 Jig width (4cm)
5 Presser brackets (each 1 cm wide)
6 Horizontal distance from the center of the ellipse to the cracked part with the least distortion (cm)
7 Polycarbonate resin sheet 8 Cracked part with minimal distortion 9 Gate 10 Sprue 11 Corrosion evaluation insert (steel NAK80, 20mmφ)

Claims (5)

[A] 100 parts by weight of a polycarbonate resin (component A) having a viscosity average molecular weight of 2.2 × 10 ^{4 to} 3.2 × 10 ⁴ , where the polycarbonate resin (component A) is composed of a dihydric phenol, a carbonate precursor, , 70 mol% or more of the dihydric phenol is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A),
[B] A phosphorus stabilizer (component B) represented by the following formula (1): 0.005 to 0.2 parts by weight,
[C] A phenol-based stabilizer (C component) represented by the following formula (2): 0.005 to 0.2 parts by weight,
[D] At least one ultraviolet ray selected from the group consisting of a benzotriazole ultraviolet absorber having a molecular weight of 400 or more, a triazine ultraviolet absorber having a molecular weight of 400 or more, and a cyclic iminoester ultraviolet absorber represented by the following formula (3) Absorbent (component D) 0.01 to 0.5 parts by weight,
[E] pentaerythritol tetrastearate (E component) 0.005 parts by weight, and contains [F] a copolymer of styrene and glycidyl methacrylate (F component) 0.003 to 0.2 parts by weight And
The E component and the F component have a limit stress when the bisphenol A type polycarbonate resin sheet having a viscosity average molecular weight of 24,500 produced by the melt extrusion method is treated at a temperature of 120 ° C. for 24 hours in a quarter ellipse test method. The resin composition which is 12 MPa or more.

[Wherein R _{1 to} R ₄ are each independently substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms. Or an aryl group having 5 to 20 carbon atoms. ]

[Wherein, R ₁ and R ₂ each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, and R ₃ and R ₄ each independently represents an alkylene group having 1 to 5 carbon atoms. Represent. ]

[Ar is a divalent aromatic hydrocarbon residue having 6 to 12 carbon atoms and may contain a hetero atom. n represents 0 or 1. ] The resin composition according to claim 1, wherein the polycarbonate resin (component A) has a viscosity average molecular weight of 2.3 × 10 ⁴ to 3.0 × 10 ⁴ .   A molded article formed from the resin composition according to claim 1.   The molded article according to claim 3, which is a sheet or film having a thickness of 0.1 to 30 mm.   The molded article according to claim 3 or 4, which is a building material and a transparent member for a vehicle.

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