JP7236882B2 - Polycarbonate resin composition - Google Patents

Description

The present disclosure maintains high total light transmittance while suppressing light transmittance in a specific ultraviolet region, that is, a wavelength around 420 nm, which is regarded as harmful light, and improves impact strength and molding retention stability. The present invention relates to an excellent polycarbonate resin composition.

Molded articles formed using synthetic resin (plastic) are more difficult to break than glass materials, and are easy to color and various molding processes. For example, synthetic resins have been used instead of glass materials for optical moldings such as spectacle lenses, camera lenses, front panels of various displays, and light source covers.

Synthetic resin molded articles are susceptible to deterioration due to long-term exposure to sunlight or ultraviolet rays, and discoloration such as yellowing is unavoidable. In order to suppress deterioration such as discoloration, an ultraviolet absorber is added to synthetic resin moldings for the purpose of improving light resistance.

In addition, recently, for the purpose of protecting the eyes, studies have also been made on imparting ultraviolet absorbing power to synthetic resin molded articles. It has been pointed out that ultraviolet rays have an adverse effect on the eyes. In addition, blue light emitted from, for example, natural light, liquid crystal displays of office equipment, displays of mobile devices such as smartphones and mobile phones, etc., is also concerned about the effects on the eyes, such as eye fatigue and pain. For example, it has been pointed out that when the eyes are exposed to blue light for a long period of time, they are subject to eye fatigue and oxidative stress due to the generation of active oxygen, particularly excessive singlet oxygen. It is known that the production of singlet oxygen is promoted by short-wave blue light, which has high energy among ultraviolet light and visible light.

In the retina, a waste product called lipofuscin accumulates in the retinal pigment epithelium with aging, and it is believed that this acts as a photosensitizer to generate singlet oxygen. This lipofuscin has the property that its absorption increases with decreasing wavelength over the visible to ultraviolet region. On the other hand, lutein is known as a substance that suppresses oxidative stress caused by singlet oxygen. Lutein is present in the retina, but it is degraded by light in the ultraviolet to blue region.

Therefore, in order to suppress the generation of singlet oxygen by lipofuscin and to suppress the deterioration of lutein, which suppresses oxidative stress, a wavelength of 400 to 420 nm, which is the wavelength range where the light absorption properties of lutein and lipofuscin overlap, Cutting in front of the retina is very effective.

Furthermore, recent studies have shown that exposure of retinal tissue to short-wavelength light at 411 nm causes stronger oxidative stress in neuronal retinal cells than exposure to light of 470 nm wavelength, leading to signs of cell death. In addition, it has been pointed out that the distortion of the structure of the retinal tissue is caused, and it is considered to be one of the factors for the progression of age-related macular degeneration.

In addition, it has been pointed out that the irradiation of light with a wavelength of 400 to 420 nm initiates the generation of reactive oxygen species, DNA damage, and cell death of lens epithelial cells, which are the causes of cortical cataracts. Blocking the potentially triggering short wavelength light of 400-420 nm is very important to keep the eyes healthy. In other words, suppressing the light transmittance of wavelength light around 420 nm is very important for keeping the eyes healthy.

Patent Documents 1 and 2 propose the use of an ultraviolet absorber that imparts the ability to absorb light with a wavelength of 400 to 420 nm to a plastic molded product.

Patent Documents 3 and 4 disclose a plastic that suppresses absorption of light with a wavelength of 420 nm or more while sufficiently efficiently absorbing a wavelength of 400 to 420 nm, is less affected by harmful light, suppresses yellowing, and has an excellent appearance. A lens is suggested.

Japanese Patent No. 5620033 Japanese Patent No. 4334633 WO2016/021664 WO2016/174788

Patent Document 1 proposes a technique of using 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-chlorobenzotriazole as an ultraviolet absorber and combining it with a resin material such as episulfide resin. . Further, Patent Document 2 proposes a technique of blending a specific benzotriazole-based ultraviolet absorber.

However, when the benzotriazole-based ultraviolet absorber described in Patent Documents 1 and 2 is added to the resin to sufficiently absorb light with a wavelength in the vicinity of 400 to 420 nm, the absorption efficiency in that wavelength region is low. It is necessary to add a large amount of the agent, and at the same time, due to its optical properties, it absorbs a large amount of light with a wavelength longer than around 420 nm, so there is a problem of yellowing of the molded product.

Patent Documents 3 and 4 propose transparent plastic moldings that suppress the transmittance of the wavelength of 420 nm. However, the plastic molded articles such as plastic lenses specifically shown in these proposals are molded articles made of thermosetting resins with insufficient impact strength.

In general, polycarbonate resins are said to be superior in mechanical properties such as impact strength as compared with other thermoplastic resins and thermosetting resins. However, when polycarbonate resin and various additives are used in combination to impart various functions other than impact resistance, the mechanical properties of the molded product may deteriorate depending on the type and amount of the additive. The heat stability during processing deteriorates, and as a result, problems such as coloration of the molded product and deterioration of physical properties often occur.

As mentioned above, there have been proposals for transparent plastic molded articles that suppress the transmittance of wavelengths around 420 nm, which are considered harmful. There was no specific proposal for obtaining a polycarbonate resin composition having excellent impact strength. Furthermore, there is a strong demand for a polycarbonate resin composition that suppresses the light transmittance of wavelengths around 420 nm, has excellent impact strength, high total light transmittance, and excellent retention stability during molding and extrusion. was rare.

Therefore, the object of the present disclosure is to maintain a high total light transmittance while suppressing the light transmittance of a specific ultraviolet region, that is, a wavelength around 420 nm, which is considered to be harmful light, and to achieve impact resistance strength and molding. An object of the present invention is to provide a polycarbonate resin composition having excellent retention stability.

式１中、
Ｒ^１～Ｒ^５はそれぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、及び水酸基のいずれかを示し、かつ、前記炭化水素基には、酸素含有基が含まれてもよく、
Ｒ^６～Ｒ^９はそれぞれ独立に、水素原子、又は、Ｒ－Ｓ－で表わされる硫黄含有基のいずれかを示し、かつ、Ｒ^６～Ｒ^９の少なくとも一つは、Ｒ－Ｓ－で表わされる硫黄含有基であり、Ｒは、炭素原子数１～２４の炭化水素基である。
〈態様２〉
前記紫外線吸収剤（Ｂ１）のＲ－Ｓ－で表わされる硫黄含有基のＲが、炭素原子数１～２４のアルキル基を示す、態様１に記載の組成物。
〈態様３〉
前記紫外線吸収剤（Ｂ１）のＲ－Ｓ－で表わされる硫黄含有基が、Ｒ^６又はＲ^９に結合した、態様１又は２に記載の組成物。
〈態様４〉
前記紫外線吸収剤（Ｂ１）におけるＲ^１～Ｒ^５の炭化水素基が、炭素原子数１～１２のアルキル基である、態様１～３のいずれかに記載の組成物。
〈態様５〉
前記紫外線吸収剤（Ｂ１）におけるＲ^１～Ｒ^５の炭化水素基が、炭素原子数１～４のアルキル基である、態様１～３のいずれかに記載の組成物。
〈態様６〉
前記紫外線吸収剤（Ｂ１）におけるＲ^１～Ｒ^５のうちの少なくとも一つが、メチル基である、態様１～５のいずれかに記載の組成物。
〈態様７〉
前記紫外線吸収剤（Ｂ１）におけるＲ^１～Ｒ^５のうちの少なくとも一つが、メチル基であり、かつ、残りのＲ^１～Ｒ^５の炭化水素基のうちの少なくとも一つがブチル基である、態様１～５のいずれかに記載の組成物。
〈態様８〉
前記ポリカーボネート樹脂（Ａ）１００質量部に対して、前記紫外線吸収剤（Ｂ１）を０．２～１．４質量部含む、態様１～７のいずれかに記載の組成物。
〈態様９〉
前記ポリカーボネート樹脂（Ａ）１００質量部に対して、前記添加剤（Ｂ）として、リン系熱安定剤（Ｂ２）を０．０１～０．１質量部含む、態様１～８のいずれかに記載の組成物。
〈態様１０〉
前記ポリカーボネート樹脂（Ａ）１００質量部に対して、前記添加剤（Ｂ）として、脂肪酸エステル系離型剤（Ｂ３）を０．０３～０．５質量部含む、態様１～９のいずれかに記載の組成物。
〈態様１１〉
前記ポリカーボネート樹脂（Ａ）１００質量部に対して、前記添加剤（Ｂ）として、ヒンダードフェノール系酸化防止剤（Ｂ４）を０．０１～０．３０質量部含む、態様１～１０のいずれかに記載の組成物。
〈態様１２〉
前記ポリカーボネート樹脂（Ａ）１００質量部に対して、前記添加剤（Ｂ）として、エポキシ基含有化合物（Ｂ５）を０．００１～０．０２質量部含む、態様１～１１のいずれかに記載の組成物。
〈態様１３〉
前記ポリカーボネート樹脂（Ａ）１００質量部に対して、前記添加剤（Ｂ）として、前記紫外線吸収剤（Ｂ１）以外の紫外線吸収剤（Ｂ６）を０．０５～０．３質量部を含む、態様１～１２のいずれかに記載の組成物。
〈態様１４〉
加熱溶融成形品の成形材料として用いる、態様１～１３のいずれかに記載の組成物。
〈態様１５〉
眼鏡レンズ成形品の成形材料として用いる、態様１～１３のいずれかに記載の組成物。 <Aspect 1>
0.2 to 1.5 parts by mass of the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A) having a viscosity average molecular weight of 21,000 to 26,000, and the additive (B ), a polycarbonate resin composition containing 0.2 parts by mass or more of an ultraviolet absorber (B1) having a benzotriazole skeleton represented by the following formula 1:

In formula 1,
R ¹ to R ⁵ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydroxyl group, and the hydrocarbon group may include an oxygen-containing group. ,
R ⁶ to R ⁹ each independently represent either a hydrogen atom or a sulfur-containing group represented by R—S—, and at least one of R ⁶ to R ⁹ is represented by R—S— and R is a hydrocarbon group having 1 to 24 carbon atoms.
<Aspect 2>
The composition according to aspect 1, wherein R of the sulfur-containing group represented by RS- of the ultraviolet absorber (B1) represents an alkyl group having 1 to 24 carbon atoms.
<Aspect 3>
The composition according to aspect 1 or 2, wherein the sulfur-containing group represented by R—S— of the ultraviolet absorber (B1) is bonded to R ⁶ or R ⁹ .
<Aspect 4>
The composition according to any one of aspects 1 to 3, wherein the hydrocarbon groups of R ¹ to R ⁵ in the ultraviolet absorber (B1) are alkyl groups having 1 to 12 carbon atoms.
<Aspect 5>
The composition according to any one of Embodiments 1 to 3, wherein the hydrocarbon groups of R ¹ to R ⁵ in the ultraviolet absorber (B1) are alkyl groups having 1 to 4 carbon atoms.
<Aspect 6>
The composition according to any one of aspects 1 to ⁵ , wherein at least one of R ¹ to R 5 in the ultraviolet absorber (B1) is a methyl group.
<Aspect 7>
An embodiment in which at least one of R ¹ to R ⁵ in the ultraviolet absorber (B1) is a methyl group, and at least one of the remaining hydrocarbon groups of R ¹ to R ⁵ is a butyl group. 6. The composition according to any one of 1-5.
<Aspect 8>
The composition according to any one of aspects 1 to 7, comprising 0.2 to 1.4 parts by mass of the ultraviolet absorber (B1) with respect to 100 parts by mass of the polycarbonate resin (A).
<Aspect 9>
According to any one of aspects 1 to 8, containing 0.01 to 0.1 parts by mass of a phosphorus-based heat stabilizer (B2) as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). composition.
<Aspect 10>
Any one of aspects 1 to 9, wherein 0.03 to 0.5 parts by mass of a fatty acid ester release agent (B3) is contained as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The described composition.
<Aspect 11>
Any one of aspects 1 to 10, wherein 0.01 to 0.30 parts by mass of a hindered phenol-based antioxidant (B4) is included as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The composition according to .
<Aspect 12>
Aspects 1 to 11, wherein 0.001 to 0.02 parts by mass of an epoxy group-containing compound (B5) is contained as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). Composition.
<Aspect 13>
An embodiment in which 0.05 to 0.3 parts by mass of an ultraviolet absorber (B6) other than the ultraviolet absorber (B1) is contained as the additive (B) with respect to 100 parts by weight of the polycarbonate resin (A). 13. The composition according to any one of 1 to 12.
<Aspect 14>
The composition according to any one of aspects 1 to 13, which is used as a molding material for hot-melt molded articles.
<Aspect 15>
The composition according to any one of aspects 1 to 13, which is used as a molding material for spectacle lens moldings.

According to the present disclosure, while suppressing the light transmittance of a specific ultraviolet region, that is, the light transmittance of a wavelength near 420 nm, which is regarded as harmful light, a high total light transmittance is maintained, and impact resistance strength and molding retention stability are achieved. It is possible to provide a polycarbonate resin composition having excellent properties.

In addition, according to the present disclosure, various heat-melt molded products, for example, front plates of various displays such as personal computers and car navigation systems, front plates and covers of light emitters, light source covers, multi-purpose sheets (for example, injection-molded flat plates, extrusion-molded A flat plate or film) and a polycarbonate resin composition used as a molding material for molding spectacle lenses can be provided.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the spirit of the invention.

式１中、
Ｒ^１～Ｒ^５はそれぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、及び水酸基のいずれかを示し、かつ、前記炭化水素基には、酸素含有基が含まれてもよく、
Ｒ^６～Ｒ^９はそれぞれ独立に、水素原子、又は、Ｒ－Ｓ－で表わされる硫黄含有基のいずれかを示し、かつ、Ｒ^６～Ｒ^９の少なくとも一つは、Ｒ－Ｓ－で表わされる硫黄含有基であり、Ｒは、炭素原子数１～２４の炭化水素基である。 The polycarbonate resin composition of one embodiment of the present disclosure has a viscosity average molecular weight of 21,000 to 26,000 with respect to 100 parts by mass of the polycarbonate resin (A), and 0.2 to 1 of the additive (B). A polycarbonate resin composition containing .5 parts by mass and containing 0.2 parts by mass or more of an ultraviolet absorber (B1) having a benzotriazole skeleton represented by the following formula 1 as the additive (B):

In formula 1,
R ¹ to R ⁵ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydroxyl group, and the hydrocarbon group may include an oxygen-containing group. ,
R ⁶ to R ⁹ each independently represent either a hydrogen atom or a sulfur-containing group represented by R—S—, and at least one of R ⁶ to R ⁹ is represented by R—S— and R is a hydrocarbon group having 1 to 24 carbon atoms.

The polycarbonate resin composition of the present disclosure maintains high total light transmittance while suppressing light transmittance in a specific ultraviolet region, that is, a wavelength around 420 nm, which is regarded as harmful light, and impact resistance strength, Excellent molding retention stability. Although not limited by the principle, the principle of action of the polycarbonate resin composition of the present disclosure is believed to be as follows.

The polycarbonate resin composition of the present disclosure contains a polycarbonate resin having a specific viscosity-average molecular weight and a specific UV absorber represented by Formula 1 above. By adopting this UV absorber, it is possible to maintain a high total light transmittance while sufficiently suppressing the light transmittance at wavelengths around 420 nm, even though the amount is lower than that of conventional benzotriazole-based UV absorbers. I think we can.

Further, in such an ultraviolet absorber, at least one of R ⁶ to R ⁹ in Formula 1 has a sulfur-containing group represented by a specific R—S—. Since the ultraviolet absorber has such a specific sulfur-containing group, heat resistance and compatibility with polycarbonate resin are improved, and even if the amount of the ultraviolet absorber added is large, impact resistance strength is improved. We believe that this will have the effect of suppressing the decline.

In addition, when a polycarbonate resin composition containing a general UV absorber is extruded or molded, the UV absorber itself to be blended tends to volatilize and solidify easily. The vent pipe and the volatile substance trap device installed in the middle of the vent pipe were easily clogged. In other words, in order to use conventional UV absorbers and exhibit sufficient UV absorbency, it was necessary to incorporate a large amount of UV absorbers in consideration of volatile matter during molding. This is thought to be a factor in lowering the impact strength and the like of the molded article obtained from the resin composition. On the other hand, the specific ultraviolet absorber of the present disclosure has a higher molecular weight than conventional ultraviolet absorbers, is excellent in heat resistance and compatibility with polycarbonate resins, and is difficult to volatilize from the composition, so a low amount is enough ultraviolet light. It is considered that the absorption capacity can be exhibited and the impact resistance strength of the molded product will not be lowered. In addition, compared to conventional UV absorbers, the UV absorber of the present disclosure is less likely to volatilize during molding processes involving heating and melting such as extrusion, and is less likely to solidify or crystallize. can be mitigated.

<<Polycarbonate resin composition>>
The polycarbonate resin composition of the present disclosure is excellent in various performances.

<Light shielding performance of 420 nm or less>
The polycarbonate resin composition of the present disclosure can block light around 420 nm. For example, when a 2 mm thick sheet obtained from a polycarbonate resin composition is used, the spectral light transmittance of light of 420 nm in such a sheet is 70% or less, less than 70%, 65% or less, or 60% or less. be able to. There is no particular limit to this lower limit, but for example, it can be specified as 0.1% or more, 0.5% or more, 1% or more, 3% or more, 5% or more, 7% or more, or 10% or more. can.

The polycarbonate resin composition of the present disclosure can also block light around 400 nm. For example, when a 2 mm thick sheet obtained from a polycarbonate resin composition is used, the spectral light transmittance at 400 nm of the sheet is 1% or less, 1% or less, 0.9% or less, or 0.8% or less. can be This lower limit is not particularly limited, but can be defined as 0% or more, 0% or more, or 0.1% or more, for example.

<Total light transmittance>
The polycarbonate resin composition of the present disclosure has excellent transparency. For example, when a 2 mm thick sheet obtained from a polycarbonate resin composition is used, the total light transmittance of the sheet can be 87% or more, 87% or more, 88% or more, or 89% or more. This upper limit is not particularly limited, but can be defined as less than 100%, 99% or less, or 98% or less, for example.

<Impact resistance>
The polycarbonate resin composition of the present disclosure has excellent impact resistance. For example, the molded article obtained from the polycarbonate resin composition should achieve more than 55 kJ/m ² , 60 kJ/m ² or more, 70 kJ/m ² or more, or 80 kJ/m ^{2 or} more in the Charpy impact strength test described later. can be done. This upper limit is not particularly limited, but can be defined as, for example, 150 kJ/m ² or less, 120 kJ/m ² or less, or 100 kJ/m ² or less.

<Heat-resistant>
The polycarbonate resin composition of the present disclosure has excellent heat resistance. The heat resistance is intended to mean that the molded product is less deformed at high temperatures, and can be evaluated, for example, by the load deflection temperature test described later. A molded product obtained from the polycarbonate resin composition can achieve a temperature of more than 124° C., 125° C. or higher, or 126° C. or higher in the deflection temperature test under load. This upper limit is not particularly limited, but can be defined as, for example, 135° C. or less, 132° C. or less, or 130° C. or less.

<Mold retention stability>
The polycarbonate resin composition of the present disclosure is excellent in molding retention stability. For example, a molded article obtained from a polycarbonate resin composition can achieve a color difference (ΔE) of 0.75 or less, less than 0.75, 0.72 or less, or 0.70 or less in a molding retention test described later. can. This lower limit is not particularly limited, but can be defined as 0.40 or more, 0.45 or more, or 0.50 or more, for example.

<Polycarbonate resin (A)>
The polycarbonate resin that can be blended in the polycarbonate resin composition of the present disclosure is not particularly limited as long as it has a viscosity average molecular weight of 21,000 to 26,000.

(viscosity average molecular weight)
The viscosity-average molecular weight is more preferably 21,500 to 25,000, particularly preferably 22,000 to 24,000, from the viewpoint of impact resistance, melt fluidity, molding processability, and the like. .

Here, the viscosity average molecular weight (M) of the polycarbonate resin is the specific viscosity (ηsp) 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 calculated from Equations 2 and 3 of:
ηsp/c=[η]+0.45×[η] ² c Equation 2
[η]=1.23×10 ⁻⁴ M ^0.83 Equation 3
where [η] is the limiting viscosity and c is 0.7.

As the polycarbonate resin in the composition of the present disclosure, for example, an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor can be used.

(dihydric phenol)
Specific examples of dihydric phenols include 2,2-bis(4-hydroxyphenyl)propane (sometimes referred to as bisphenol A), 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 , bis(hydroxyaryl)alkanes such as 2-bis(4-hydroxy-3,5-dibromophenyl)propane and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; Bis(hydroxyphenyl)cycloalkanes such as 1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(hydroxyphenyl)cyclohexane; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 ,3′-dimethyldiphenyl ether and other dihydroxyaryl ethers; 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide and other dihydroxydiaryl sulfides; dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;4,4'-dihydroxydiphenylsulfone,4,4'-dihydroxy- and dihydroxydiarylsulfones such as 3,3'-dimethyldiphenylsulfone. These dihydric phenols may be used alone or in combination of two or more.

Among the dihydric phenols mentioned above, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is preferable from the viewpoint of impact resistance and the like. The proportion of bisphenol A in the total dihydric phenol component is preferably 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more, 90 mol% or more, 95 mol% or more, or more preferably 100%.

(Method for producing polycarbonate resin)
The method for producing the polycarbonate resin is not particularly limited, but it can be produced, for example, by the following method.

For example, a solution process using phosgene as the carbonate precursor can be employed. In this method, the reaction between the dihydric phenol component and phosgene is usually carried out 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. Examples of organic solvents include halogenated hydrocarbons such as methylene chloride and chlorobenzene.

Also, optionally, catalysts such as tertiary amines, quaternary ammonium salts, etc. can be used to promote the reaction, and catalysts such as phenol, p-tert-butylphenol, etc. can be used to control the molecular weight. A terminal terminator such as alkyl-substituted phenol can be used.

The reaction temperature is usually 0 to 40° C., the reaction time can be 1 minute to 5 hours, and the pH is preferably maintained at 10 or higher during the reaction.

A transesterification method (melting method) using a carbonic acid diester can also be used as a carbonate precursor. In this method, in the presence of an inert gas, a dihydric phenol component and a carbonic diester in a predetermined ratio are heated and stirred to distill off the resulting alcohol or phenol.

Although the reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, it is usually in the range of 120 to 350°C. The reaction is carried out under reduced pressure from the initial stage while distilling off the alcohol or phenols produced. In addition, a conventional transesterification reaction catalyst can be used to promote the reaction.

Carbonic acid diesters used in this transesterification reaction include, for example, diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, with diphenyl carbonate being particularly preferred.

<Additive (B)>
The polycarbonate resin composition of the present disclosure contains a predetermined amount of additive (B).

This additive (B) is an additive that can be blended with polycarbonate, and may be composed of a plurality of additives. Preferably, this additive (B) is the following ( It means an additive indicated by B1) to (B7).

The total amount of additive (B) is 0.2 to 1.5 parts by mass with respect to 100 parts by mass of polycarbonate resin (A). The total amount of additive (B) is preferably 0.3 to 1.4 parts by mass, more preferably 0.4 to 1.3 parts by mass, from the viewpoint of impact resistance, heat resistance, etc. It is preferably 0.6 to 1.2 parts by mass, particularly preferably 0.8 to 1.1 parts by mass.

式１中、Ｒ^１～Ｒ^５はそれぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、及び水酸基のいずれかを示し、炭化水素基には、酸素含有基が含まれてもよい。Ｒ^６～Ｒ^９はそれぞれ独立に、水素原子、又は、Ｒ－Ｓ－で表わされる硫黄含有基のいずれかを示し、Ｒ^６～Ｒ^９の少なくとも一つは、Ｒ－Ｓ－であり、Ｒは、炭素原子数１～２４の炭化水素基である。 (Ultraviolet absorber (B1) represented by Formula 1)
The composition of the present disclosure contains, as an additive (B), an ultraviolet absorber (B1) having a specific benzotriazole skeleton represented by Formula 1 below. This ultraviolet absorber (B1) contains 0.2 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A) from the viewpoint of sufficient suppression effect of light transmittance around 420 nm and impact resistance. Preferably 0.2 to 1.4 parts by mass, more preferably 0.3 to 1.3 parts by mass, still more preferably 0.4 to 1.2 parts by mass, particularly preferably 0.6 to 1.2 parts by mass. 1 part by weight, most preferably 0.8 to 1.0 part by weight of:

In Formula 1, R ¹ to R ⁵ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydroxyl group, and the hydrocarbon group may include an oxygen-containing group. good. R ⁶ to R ⁹ each independently represent either a hydrogen atom or a sulfur-containing group represented by R—S—, at least one of R ⁶ to R ⁹ is R—S—, and R is a hydrocarbon group having 1 to 24 carbon atoms.

Examples of hydrocarbon groups include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups. Alkyl groups include linear or branched chains, and are not particularly limited, but examples include methyl group, ethane-1-yl group, propan-1-yl group, 1-methylethan-1-yl group, butan-1-yl group. , butan-2-yl group, 2-methylpropan-1-yl group, 2-methylpropan-2-yl group, pentan-1-yl group, pentan-2-yl group, hexane-1-yl group, heptane -1-yl group, octan-1-yl group, 1,1,3,3-tetramethylbutan-1-yl group, nonan-1-yl group, decan-1-yl group, undecane-1-yl group , dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptadecan-1-yl group, octadecane-1-yl group, nonadecan-1-yl group, eicosan-1-yl group, heneicosan-1-yl group, docosan-1-yl group, tricosan-1-yl group, tetracosan-1-yl group, benzyl group, α,α-dimethyl A benzyl group and the like can be mentioned. Alkenyl groups include straight or branched chains, and are not particularly limited, but examples include vinyl, prop-1-en-1-yl, allyl, isopropenyl, but-1-en-1-yl, but -2-en-1-yl group, but-3-en-1-yl group, 2-methylprop-2-en-1-yl group, 1-methylprop-2-en-1-yl group, pent-1 -en-1-yl group, pent-2-en-1-yl group, pent-3-en-1-yl group, pent-4-en-1-yl group, 3-methylbut-2-en-1 -yl group, 3-methylbut-3-en-1-yl group, hex-1-en-1-yl group, hex-2-en-1-yl group, hex-3-en-1-yl group, hex-4-en-1-yl group, hex-5-en-1-yl group, 4-methylpent-3-en-1-yl group, 4-methylpent-3-en-1-yl group, hept- 1-en-1-yl group, hept-6-en-1-yl group, octa-1-en-1-yl group, octa-7-en-1-yl group, non-1-en-1- yl group, non-8-en-1-yl group, dec-1-en-1-yl group, dec-9-en-1-yl group, undec-1-en-1-yl group, undec-10 -en-1-yl group, dodec-1-en-1-yl group, dodec-11-en-1-yl group, tridec-1-en-1-yl group, tridec-12-en-1-yl group, tetradeca-1-en-1-yl group, tetradeca-13-en-1-yl group, pentadec-1-en-1-yl group, pentadec-14-en-1-yl group, hexadec-1- en-1-yl group, hexadec-15-en-1-yl group, heptadedec-1-en-1-yl group, heptadedec-16-en-1-yl group, octadec-1-en-1-yl group , octadec-9-en-1-yl group, octadec-17-en-1-yl group, nonadecan-1-en-1-yl group, eicos-1-en-1-yl group, heneicosa-1-ene -1-yl group, docos-1-en-1-yl group, tricosa-1-en-1-yl group, tetracos-1-en-1-yl group and the like. Alkynyl groups include straight or branched chains, and are not particularly limited, but examples include ethynyl, prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl. group, but-3-yn-1-yl group, 1-methylprop-2-yn-1-yl group, pent-1-yn-1-yl group, pent-4-yn-1-yl group, hexa- 1-yn-1-yl group, hex-5-yn-1-yl group, hept-1-yn-1-yl group, hept-6-yn-1-yl group, octa-1-yn-1- yl group, octa-7-yn-1-yl group, non-1-yn-1-yl group, non-8-yn-1-yl group, deca-1-yn-1-yl group, deca-9 -yn-1-yl group, undec-1-yn-1-yl group, undec-10-yn-1-yl group, dodec-1-yn-1-yl group, dodec-11-yn-1-yl group, tridec-1-yn-1-yl group, tridec-12-yn-1-yl group, tetradeca-1-yn-1-yl group, tetradeca-13-yn-1-yl group, pentadeca-1- yn-1-yl group, pentadeca-14-yn-1-yl group, hexadec-1-yn-1-yl group, hexadec-15-yn-1-yl group, heptadeca-1-yn-1-yl group , heptadeca-16-yn-1-yl group, octadec-1-yn-1-yl group, octadec-17-yn-1-yl group, nonadeca-1-yn-1-yl group, eicos-1-yne -1-yl group, heneicosa-1-yn-1-yl group, docos-1-yn-1-yl group, tricosa-1-yn-1-yl group, tetracos-1-yn-1-yl group, etc. are mentioned.

Examples of the alicyclic hydrocarbon group include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

Examples of aromatic hydrocarbon groups include, but are not particularly limited to, groups containing aromatic ring residues such as phenyl residues, naphthalene residues, and anthracene residues. Examples of monovalent aromatic hydrocarbon groups include, but are not limited to, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5 -dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propyl phenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-pentylphenyl group, 4-tert-pentylphenyl group, 2,4-bis(4-tert-pentyl)phenyl group, 1,1,3,3-tetramethylbutylphenyl group, 2-methyl-5-tert-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-heptylphenyl group, 4-octylphenyl group, 4-nonylphenyl group, 4-decanylphenyl group, 4-undecylphenyl group, 4-dodecylphenyl group, 4-tridecylphenyl group, 4-tetradecylphenyl group, 4-pentadecylphenyl group, 4 -hexadecylphenyl group, 4-heptadecylphenyl group, 4-octadecylphenyl group, 4-biphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3- ethoxyphenyl group, 4-ethoxyphenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-hydroxyphenyl group, 1 -naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group and the like, and the divalent aromatic hydrocarbon group is not particularly limited, but for example, 1,4- Phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,8-naphthylene group, 2,7-naphthylene group, 2,6-naphthylene group, 1,4-naphthylene group, 1,3-naphthylene group group, 9,10-anthracenylene group, 1,8-anthracenylene group, 2,7-anthracenylene group, 2,6-anthracenylene group, 1,4-anthracenylene group, 1,3-anthracenylene group and the like.

Examples of oxygen-containing groups include, but are not limited to, hydroxy, alkoxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, iso-butoxy, tert. -butoxy group, sec-pentyloxy group, iso-pentyloxy group, tert-pentyloxy group, 1-hexyloxy group, 2-hexyloxy group, 3-hexyloxy group, 1-heptyloxy group, 2-heptyloxy group, 3-heptyloxy group, 4-heptyloxy group, 1-octyloxy group, 2-octyloxy group, 3-octyloxy group, 4-octyloxy group, 1-nonyloxy group, 2-nonyloxy group, 3- nonyloxy group, 4-nonyloxy group, 5-nonyloxy group, 1-decyloxy group, 2-decyloxy group, 3-decyloxy group, 4-decyloxy group, 5-decyloxy group, 1-undecyloxy group, 1-dodecyloxy group , 1-tridecyloxy group, 1-tetradecyloxy group, 1-pentadecyloxy group, 1-hexadecyloxy group, 1-heptadecyloxy group, 1-octadecyloxy group, phenoxy group, methylphenoxy group, dimethyl phenoxy group, naphthoxy group, phenylmethoxy group, phenylethoxy group, acetoxy group, acetyl group, aldehyde group, carboxy group, urea group, urethane group, amide, imide, ether group, carbonyl group, ester group, oxazole group, morpholine group , carbamate group, carbamoyl group, polyoxyethylene group and the like.

As the hydrocarbon group represented by R ¹ to R ⁵ in Formula 1, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or a butyl group is particularly preferable. Furthermore, at least one of R ¹ to R ⁵ is preferably a methyl group, and at least one of the remaining R ¹ to R ⁵ is more preferably a butyl group. Furthermore, it is most preferred that at least one of ^R2 and ^R4 is selected from such alkyl groups and ^R1 is a hydroxyl group.

Further, the ultraviolet absorber (B1) has a sulfur-containing group represented by RS-. Due to the presence of this sulfur-containing group, when the ultraviolet absorber (B1) is blended with a polycarbonate resin having a specific viscosity average molecular weight, high total light transmittance, excellent impact resistance and molding retention stability are obtained. While maintaining, the transmittance of light of 400 nm, especially light of 400-420 nm can be suppressed.

In formula 1 above, the sulfur-containing group represented by R—S— is positioned at any one of R ⁶ to R ^9. From the viewpoint of making it easier to develop the above performance, R ⁶ or R ⁹ position. R is an alkyl group having 1 to 24 carbon atoms, but from the viewpoint of making it easier to express the above performance, an alkyl group having 1 to 18 carbon atoms is more preferable, and 1 to 12 carbon atoms. is more preferred, and an alkyl group having 1 to 8 carbon atoms is particularly preferred. Also, the alkyl group is preferably linear.

Furthermore, the introduction of a sulfur-containing group represented by RS- surprisingly increases the molecular weight of the UV absorber itself, but compared to conventional UV absorbers, extruders and molding used for extrusion and molding processing It has been found that clogging of the vacuum vent line system leading to the machine (eg, such systems include vent lines and volatile trap devices) can be reduced. The reason for this is that, in addition to the fact that the molecular weight is increased by the amount of the sulfur-containing group and the volatility is suppressed, the ultraviolet absorber (B1 ), but solidification or crystallization is less likely to proceed than with other conventional UV absorbers, so it is presumed that this is the reason why deposits are bulky and difficult to grow in the system.

(optional additive)
The composition of the present disclosure may contain, as the additive (B), one or more additives such as those exemplified below other than the ultraviolet absorber (B1). In this case, the additive other than the ultraviolet absorber (B1) is, from the viewpoint of mechanical properties such as impact resistance and heat resistance, for example, 0.01 to 0 per 100 parts by mass of the polycarbonate resin (A). .5 parts by mass, preferably 0.02 to 0.4 parts by mass, more preferably 0.03 to 0.3 parts by mass, It is more preferably blended in the range of 0.04 to 0.25 parts by mass, and particularly preferably in the range of 0.05 to 0.2 parts by mass.

a. Phosphorus heat stabilizer (B2)
The composition of the present disclosure may contain a phosphorus-based heat stabilizer. Phosphorus-based heat stabilizers include, for example, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, for example, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, Phite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyl diphenylphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis( nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite Phyto, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, 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, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite and bis(2,4-di-tert- butylphenyl)-3-phenyl-phenylphosphonite and the like. These can be used singly or in combination of two or more.

Among these, tris(2,4-di-tert-butylphenyl) phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, bis(2,6- Di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite are preferred; bis(2,6-di-tert-butyl-4-methyl Phenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite are more preferred; tris(2,4-di-tert-butylphenyl)phosphite is particularly preferred.

The content of the phosphorus-based heat stabilizer is 0.01 to 0.1 mass per 100 parts by mass of the polycarbonate resin (A) from the viewpoint of molding retention stability, mechanical properties such as impact resistance, and heat resistance. parts, more preferably 0.01 to 0.05 parts by mass, even more preferably 0.015 to 0.03 parts by mass.

b. Fatty acid ester release agent (B3)
For example, the composition of the present disclosure can be blended with a fatty acid ester release agent in order to improve the release performance of the molded product from the mold during melt molding.

Fatty acid ester release agents include, for example, (i) an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated or unsaturated fatty acid having 10 to 30 carbon atoms, and (ii) 1 to 30 carbon atoms. At least one release agent selected from the group consisting of partial esters or full esters of 25 polyhydric alcohols and saturated or unsaturated fatty acids having 10 to 30 carbon atoms is used.

(i) Esters of monohydric alcohols having 1 to 20 carbon atoms and saturated or unsaturated fatty acids having 10 to 30 carbon atoms include stearyl stearate, palmityl palmitate, butyl stearate, and methyl laurate. , isopropyl palmitate, etc. Among them, stearyl stearate is preferable.

(ii) Examples of partial esters or full esters of polyhydric alcohols having 1 to 25 carbon atoms and saturated or unsaturated fatty acids having 10 to 30 carbon atoms include glycerin monostearate, glycerin distearate, glycerin tristearate, Stearate, glycerin monobehenate, glycerin tribehenate, glycerin trisorbate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, sorbitan monostearate, 2- Full esters of dipentaerythritol such as ethylhexyl stearate and dipentaerythritol hexastearate, partial esters of dipentaerythritol and the like.

Among these fatty acid esters, pentaerythritol tetrastearate, glycerin tristearate, and a mixture of glycerin tristearate and stearyl stearate are preferably used. A mixture of glycerin tristearate and stearyl stearate is particularly preferred. The mixing weight ratio (former/latter) is preferably 45-15/55-85, more preferably 40-15/60-85.

From the viewpoint of impact resistance, heat resistance, releasability, discoloration resistance, etc., the content of the fatty acid ester release agent is preferably 0.03 to 0.03 parts per 100 parts by mass of the polycarbonate resin (A). It is 5 parts by mass, more preferably 0.08 to 0.4 parts by mass, still more preferably 0.1 to 0.3 parts by mass.

The fatty acid ester release agent can be used in combination with other known release agents known to those skilled in the art. It is preferably 45 parts by mass, and is preferably the main component (50% or more) of the release agent.

From the viewpoint of molding retention stability at high temperatures, etc., the content of trace metal impurities, particularly tin (Sn), in the fatty acid ester release agent is preferably smaller, for example, preferably 200 ppm or less. It is more preferably 100 ppm or less, further preferably 50 ppm or less, and particularly preferably 1 ppm or less. The amount of various metals in the release agent can be analyzed by ICP (inductively coupled plasma) analysis.

c. Hindered phenolic antioxidant (B4)
A composition of the present disclosure may contain a hindered phenolic antioxidant. The addition of such an antioxidant can exhibit, for example, an effect (dry heat resistance) of suppressing color deterioration during molding and discoloration when the molded product is used at high temperatures for a long period of time.

Hindered phenol stabilizers include, for example, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer) propionate, 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), 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, 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), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and tetrakis[methylene-3-(3′,5′ -di-tert-butyl-4-hydroxyphenyl)propionate]methane and the like. All of these are available as commercial products. The above hindered phenol-based stabilizers can be used alone or in combination of two or more.

The content of the hindered phenol antioxidant is preferably 0.01 to 0.30 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A) from the viewpoint of impact resistance, dry heat resistance, etc. It is preferably 0.02 to 0.25 parts by mass, more preferably 0.03 to 0.15 parts by mass.

d. Epoxy group-containing compound (B5)
The composition of the present disclosure may contain an epoxy group-containing compound. Such an epoxy group-containing compound is blended for the purpose of suppressing mold corrosion and for the purpose of improving moist heat resistance, and basically all compounds having an epoxy functional group can be applied.

Specific examples of preferable epoxy group-containing compounds include, for example, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexylcarboxylate, 2,2-bis(hydroxymethyl)-1-butanol of 1,2- Epoxy-4-(2-oxiranyl)cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, copolymers of styrene and glycidyl methacrylate, and the like.

From the viewpoint of impact resistance, heat resistance, mold retention stability, transparency, mold corrosion inhibition effect, moist heat resistance improvement effect, etc., the content of the epoxy group-containing compound is 100 parts by mass of the polycarbonate resin (A). On the other hand, it is preferably 0.001 to 0.02 parts by mass, more preferably 0.004 to 0.15 parts by mass, and still more preferably 0.005 to 0.1 parts by mass.

e. UV absorber (B6) other than UV absorber (B1)
The composition of the present disclosure includes, in addition to the ultraviolet absorber (B1), a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a cyclic iminoester-based ultraviolet absorber, or a cyanoacrylate-based ultraviolet absorber. agents and the like can be contained.

For example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3', 5′-dicumylphenyl)phenylbenzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-(1 , 1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazol- 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-amylphenyl ) benzotriazole, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, 2-(2′-hydroxy-5′-tert-butylphenyl)benzotriazole, 2-(2′ -hydroxy-4'-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazine-4 -on), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole and the like. These can be used singly or in a mixture of two or more.

Among them, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3', 5′-dicumylphenyl)phenylbenzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-(1 , 1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)- 5-methylphenyl]benzotriazole is preferred; 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetra methylbutyl)-6-(2H-benzotriazol-2-yl)phenol] is more preferred.

In the composition of the present disclosure, the content of the UV absorber (particularly the benzotriazole-based UV absorber) other than the UV absorber (B1) is determined from the viewpoint of impact resistance, heat resistance, transparency, moldability, and hue. , With respect to 100 parts by mass of the polycarbonate resin (A), it is preferably 0.05 to 0.3 parts by mass, more preferably 0.1 to 0.25 parts by mass, and 0.15 to 0.15 parts by mass. It is more preferably 25 parts by mass.

f. Bluing agent (B7)
The composition of the present disclosure may contain a bluing agent in order to cancel the yellowness of the molded article caused by the polycarbonate resin or the ultraviolet absorber. The bluing agent is not particularly limited as long as it is used for polycarbonate resin. Anthraquinone dyes are generally preferred because they are easily available.

Specific bluing agents include, for example, general name Solvent Violet 13 (CA. No (color index No) 60725; trade name "Macrolex Violet B" manufactured by Bayer; "Diaresin Blue G" manufactured by Mitsubishi Chemical Corporation; Sumitomo Chemical Co., Ltd. "Sumiplast Violet B"), generic name Solvent Violet 31 (CA. No 68210; trade name Mitsubishi Chemical Co., Ltd. "Diaresin Violet D"), generic name Solvent Violet 33 (CA. No 60725; trademark name Mitsubishi Chemical Corporation "Diaresin Blue J"), general name Solvent Blue 94 (CA. No 61500; trademark name Mitsubishi Chemical Corporation "Diaresin Blue N"), general name Solvent Violet 36 (CA. No 68210; trademark name Bayer "Macrolex Violet 3R"), general name Solvent Blue 97 (trade name Bayer "Macrolex Blue RR") and general name Solvent Blue 45 (CA. No 61110; trade name Clariant "Polythin Threne Blue RLS") is a representative example.

The bluing agent can be usually contained in the polycarbonate resin at a concentration of 0.3 to 1.2 ppm in consideration of the luminous transmittance and the like.

The composition of the present disclosure may further include other heat stabilizers, antistatic agents, flame retardants, heat ray shielding agents, fluorescent brighteners, pigments, light diffusing agents, etc., as long as the objects of the present disclosure are not impaired. agents, reinforcing fillers, other resins and elastomers, and the like.

Other heat stabilizers include, for example, sulfur-based heat stabilizers. Examples of sulfur-based heat stabilizers include pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropionate), pentaerythritol-tetrakis(3-stearylthiopropionate ), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate and the like. Pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, among others Pionates are preferred. Particularly preferred is pentaerythritol-tetrakis(3-laurylthiopropionate). The thioether compounds are commercially available from Sumitomo Chemical Co., Ltd. as Sumilizer TP-D (trade name) and Sumilizer TPM (trade name), and are readily available.

The content of the sulfur-based heat stabilizer in the composition of the present disclosure is preferably 0.001 to 0.2 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A).

〈Heating and melting molded product〉
The heat-melt molded product is intended to be a transparent molded product obtained by heat-melt molding the polycarbonate resin composition of the present disclosure, for example, by a molding method involving heat-melting such as injection molding, extrusion molding, and rotational molding. . Specifically, for example, planar molded products used as front plates of various displays such as personal computers and car navigation systems, covers and front plates of various light emitters, and covers and front plates of various light sources (e.g., injection molded flat plates, extrusion molding flat plates (eg, extrusion-molded sheets); planar molded articles used as window glass (eg, injection-molded sheets, extrusion-molded sheets); and optical lenses such as spectacle lenses. Further, the surfaces of these molded products may be subjected to surface shaping, and the flat molded products may be further press-molded to give curved or three-dimensional shapes. All of these various molded articles have excellent impact strength, maintain high light transmittance, and have the effect of suppressing light transmittance at 400 nm, and particularly at 400 to 420 nm.

The thickness of the molded product is not particularly limited, but from the viewpoint of the practical strength of the molded product, it is preferably 0.3 mm or more, more preferably 0.5 mm or more, and 1.0 mm or more. More preferably, it is particularly preferably 2 mm or more. Although the upper limit of the thickness is not particularly limited, it is preferably 10 mm or less, more preferably 7 mm or less, and even more preferably 5 mm or less from the viewpoint of moldability.

〈Glasses lens〉
Spectacle lenses, which are a type of heat-melt molded product, include, for example, finished lenses in which the convex and concave surfaces of the lens are optically finished by transferring the glass mold surface at the time of molding, and are molded according to the desired power. mentioned. Further, for example, a semi-finished lens in which only the convex surface is optically finished in the same manner as the finished lens, and the concave surface side is optically finished according to the desired dioptric power according to an order or the like can be mentioned.

The semi-finished lens is ground or cut by a curve generator or an NC-controlled cutting tool or the like in accordance with necessary concave surface processing, and smoothing (finning) is performed as necessary. The surface that has been cut, ground, and smoothed (finned) is polished using a polishing dish with an abrasive and a polishing cloth, or a flexible polishing tool, etc., and mirror-finished to an optical finish. be done.

After that, both the finished lens and the polished semi-finished lens are washed and inspected for scratches and foreign matter. Furthermore, optionally, for example, a dyeing step to give the lens a desired color, a hard coating step to form a hardened film to cover the scratch susceptibility of the plastic lens, a lens surface reflection to reduce the transmittance After undergoing processes such as the formation of an anti-reflection film to improve the product, it is shipped as a finished product and used by each user.

Spectacle lenses formed using the polycarbonate resin composition of the present disclosure can be used for vision correcting lenses, sunglasses, protective spectacles, and the like. All spectacle lenses maintain a high light transmittance and have the effect of suppressing the light transmittance around 420 nm, particularly 400 nm to 420 nm.

EXAMPLES Hereinafter, the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited to these.

<<Examples 1 to 12 and Comparative Examples 1 to 7>>
The polycarbonate resin composition obtained by the production method shown below was subjected to the following evaluations, and the results are shown in Table 1. Here, the numerical values of the polycarbonate resin and various additives in Table 1 are all parts by mass.

<Charpy impact strength (impact resistance)>
The pellets obtained in each example are dried at 120 ° C. for 5 hours with a hot air dryer, and are used with a J75EIII injection molding machine manufactured by Japan Steel Works, Ltd. at a cylinder temperature of 280 ° C. and a mold temperature of 70 to 75 ° C. A test piece having a width of 10 mm, a length of 80 mm, and a thickness of 4 mm was molded at a cycle of 1 minute, and the notched Charpy impact strength was measured according to ISO179.

<Load Deflection Temperature (Heat Resistance)>
The pellets obtained in each example were dried at 120 ° C. for 5 hours with a hot air dryer, and were molded with a J75EIII injection molding machine manufactured by The Japan Steel Works, Ltd. at a cylinder temperature of 280 ° C. and a mold temperature of 70 to 75 ° C. A test piece having a width of 10 mm, a length of 80 mm, and a thickness of 4 mm was molded at a minute cycle, and the deflection temperature under load was measured under a load of 1.80 MPa in accordance with ISO 75-1 and 75-2.

<Total light transmittance>
The pellets obtained in each example were dried at 120° C. for 5 hours in a hot air dryer, and a cylinder temperature of 350° C. and a mold temperature of 80° C. were cycled for 1 minute using a J75EIII injection molding machine manufactured by The Japan Steel Works, Ltd. A three-stage plate having a width of 50 mm, a length of 90 mm, and a thickness of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the gate side was molded, and this was used as a test piece. . The total light transmittance at a 2 mm thick portion of the three-stage plate was measured according to JIS K7361 using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

<Spectral light transmittance>
The pellets obtained in each example were molded with an injection molding machine (cylinder temperature: 350°C, 1 minute cycle) to obtain a flat plate for measurement (length 90 mm x width 50 mm x thickness 2 mm). The spectral light transmittance of the measurement flat plate in the wavelength range of 300 nm to 500 nm was measured with Cary 5000 manufactured by Varian to obtain the spectral light transmittances at 420 nm and 400 nm.

<Molding retention test>
A molding retention test, which corresponds to a molding heat resistance test, was conducted to evaluate the molding retention stability. The pellets obtained in each example were dried at 120 ° C. for 5 hours with a hot air dryer, and an injection molding machine J85-ELIII manufactured by The Japan Steel Works, Ltd. was used at a cylinder temperature of 350 ° C. and a mold temperature of 80 ° C., 1 A three-stage plate having a width of 50 mm, a length of 90 mm, and a thickness of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the gate side was molded in a minute cycle. After 20 shots were continuously molded, the resin was retained in the cylinder of the injection molding machine at a cylinder temperature of 350°C for 10 minutes, and the hue (L, a, b) of the 2 mm thick portion of the test piece before and after retention was measured as follows: In accordance with JIS K-7105, Color-Eye 7000A manufactured by Gretag Macbeth was used for measurement by the C light source transmission method, and the color difference ΔE' was obtained by the following equation 4. A smaller ΔE′ indicates better retention stability during molding.

ΔE′={(ΔL′) ² +(Δa′) ² +(Δb′) ² } ^1/2 Equation 4
Color of molded plate before residence: L'', a'', b''
Color of formed plate after residence: L''', a''', b'''
ΔL': L''-L'''
Δa′: a″−a′″
Δb′: b″−b′″

<Synthesis of UV absorber (B1)>
As the ultraviolet absorber (B1), a compound represented by the following formula 5 obtained in Synthesis Example 1 below was used.

(Synthesis example 1)
2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole (5.00 g, 15.8 mmol), octanethiol (7.63 g, 52.1 mmol), carbonic acid Potassium (7.20 g, 52.1 mmol) and potassium iodide (0.18 g, 1.1 mmol) were reacted in 50 mL of DMF at 150° C. for 20 hours. After completion of the reaction, purification was performed to obtain a compound (UV-1) represented by the following formula 5. In addition, the results of each analysis of such compounds are shown below:

Analysis by FT-IR (KBr) 3125 cm ^-1 : OH stretching vibration 1438, 1391 cm ^-1 : triazole ring stretching vibration 661 cm ^-1 : CS stretching vibration

Analysis by ¹ H-NMR (CDCl ₃ 400 MHz) δ 0.88 (t, 3H, CH ₃ (CH ₂ ) ₇ —S), 1.27 (m, 8H, CH ₃ ( CH ₂ ) ₄ (CH ₂ ) _{3 -} S ), _1.49 (m, 11H, -Ph-OH- _CH3 -C( CH3 ) ₃ , _CH3 ( _CH2 ) _4CH2 ( _CH2 ) _2- S), 1.75 (quin, 2H, _CH3 ( _CH2 ) 5CH2CH2 _- S ₎ , 2.38 (s, 3H,-Ph-OH- CH3 _- C( _{CH3 ) 3} ), 3 .03 (t, 2H, _CH3 ( _CH2 ) _{5CH2CH2 -} S), 7.16 (s _, 1H ), 7.37 (d, 1H), 7.70 (s, 1H), 7.81 (d, 1H), 8.05 (s, 1H), (insg.5arom.C H ), 11.61 (s, 1H, —Ph— OH —CH ₃ —C(CH ₃ ) ₃ )

Analysis by ¹³ C-NMR (CDCl ₃ 400 MHz) δ 14.0 ( CH ₃ (CH ₂ ) ₇ -S), 20.0 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 22 .6 (-Ph-OH- _CH3 - C ( _CH3 ) ₃ ), 28.7 ( _CH3 ( CH2 _{) 5CH2CH2 -} S), 31.9 ₍ -Ph-OH- _CH3 -C( CH3 _{) 3 )} , 33.2( _CH3 ( _CH2 ) _5CH2CH2 - S ₎ , 35.4( _CH3 ( _{CH2 ) 5CH2CH2} - _S ), 113.6, 117.5 _, 119.3, 128.7, 129.3 ( C _Harom ), 141.2, 143.4 ( Carom ), 125.4 ( Carom _- N), 128.3 ( _Carom - CH3 ), _138.0 ( Carom _- S), 139.1 ( Carom _- C( _CH3 ) ₃ ), 146.7 ( Carom _- OH)

(Example 1)
The compound obtained in Synthesis Example 1 as an ultraviolet absorber was added to 100 parts of polycarbonate resin powder (PC-1) having a viscosity average molecular weight of 23,900 obtained by interfacial polymerization of bisphenol A and phosgene in a conventional manner. (UV-1) 0.22 parts, phosphorus heat stabilizer (P-1) 0.03 parts, fatty acid ester release agent (R-1) 0.1 part as a release agent, and bluing agent ( 0.00025 parts of BL-1) was added to each of them, and after sufficiently mixing them in a tumbler, they were pelletized with a 30 mmφ vented twin-screw extruder at a temperature of 290° C. and a degree of vacuum of 4.7 kPa.

(Examples 2 to 12, Comparative Examples 1 to 7)
The same operation as in Example 1 was performed except that the amounts of various materials shown in Table 1 were used. Table 1 shows the evaluation results. The components corresponding to each symbol listed in Table 1 are shown below.

(Polycarbonate resin powder)
PC-1: Aromatic polycarbonate resin powder having a viscosity average molecular weight of 23,900 obtained by interfacial polymerization of bisphenol A and phosgene (manufactured by Teijin Chemicals Ltd.: Panlite (trademark) L-1250WP).

PC-2: Aromatic polycarbonate resin powder having a viscosity-average molecular weight of 22,200 obtained by interfacial polymerization of bisphenol A and phosgene (manufactured by Teijin Chemicals Ltd.: Panlite (trademark) L-1225WP).

PC-3: Aromatic polycarbonate resin powder having a viscosity-average molecular weight of 19,700 obtained by interfacial polymerization of bisphenol A and phosgene (manufactured by Teijin Chemicals Ltd.: Panlite (trademark) L-1225WX).

(Ultraviolet absorber)
UV-1; 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-octylsulfanylbenzotriazole (compound obtained in Synthesis Example 1).

UV-2; 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (manufactured by BASF Corporation: Tinuvin (trademark) 329).

UV-3; 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (manufactured by BASF Corporation: Tinuvin (trademark) 326).

(Phosphorus heat stabilizer)
P-1; tris(2,4-di-tert-butylphenyl)phosphite (BASF Corporation: Irgafos (trademark) 168).

P-2: Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (manufactured by ADEKA Corporation: ADEKA STAB (trademark) PEP-36).

(Fatty acid ester release agent)
R-1: A mixture of stearic acid triglyceride and stearyl stearate (Rikemar (trademark) SL-900 manufactured by Riken Vitamin Co., Ltd.).

R-2; Pentaerythritol tetrastearate (manufactured by Emery Oleochemicals Co., Ltd.: Roxyol (trademark) VPG861).

(Antioxidant)
H-1: Hindered phenolic antioxidant; Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox (trademark) 1076 manufactured by BASF Corporation).

H-2; hindered phenolic antioxidant; pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (Irganox (trademark) 1010 manufactured by BASF Corporation).

(Epoxy group-containing compound)
C-1; Copolymer of styrene and glycidyl methacrylate (manufactured by NOF Corporation: Marproof (trademark) G-0250SP).

(Bluing agent)
BL-1; Bluing agent (manufactured by Bayer KK: Macrolex Violet (trademark) B).

<result>
As can be seen from the results in Table 1, the polycarbonate resin compositions of Examples 1 to 12 containing a predetermined amount of a specific ultraviolet absorber (B1) have the effect of suppressing light transmittance at 400 nm, particularly at 420 nm, and It was confirmed that the impact strength and molding retention stability were also excellent.

High total light transmittance and excellent mold retention stability during molding and extrusion are important in polycarbonate resin compositions as molding materials for transparent plastic molded products including spectacle lenses. It is a characteristic.

The polycarbonate resin composition of the present invention maintains high total light transmittance while suppressing light transmittance at wavelengths around 420 nm, particularly 400 to 420 nm, and is excellent in impact resistance strength and molding retention stability. Front panels for various displays such as personal computers and car navigation systems, front panels and covers for light emitters, light source covers, multi-purpose sheets (for example, injection-molded flat panels, extruded flat panels or films), and eyeglass lenses that utilize these features. It is widely used industrially as a molding material for obtaining heat-melted molded products such as.

Claims (14)

With respect to 100 parts by mass of an aromatic polycarbonate resin (A) obtained by reacting a carbonate precursor selected from phosgene or a carbonate diester having a viscosity average molecular weight of 21,000 to 26,000 with a dihydric phenol , 0.2 to 1.5 parts by mass of an additive (B), and 0.2 to 1 part of an ultraviolet absorber (B1) having a benzotriazole skeleton represented by the following formula 1 as the additive (B) .4 parts by mass, and the additives (B) other than the ultraviolet absorber (B1) include a phosphorus stabilizer (B2), a fatty acid ester release agent (B3), a hindered phenol antioxidant (B4 ), an epoxy group-containing compound (B5), an ultraviolet absorber (B6) other than the ultraviolet absorber (B1), and a bluing agent (B7) selected from the group consisting of a polycarbonate resin composition:

In formula 1,
R ¹ to R ⁵ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydroxyl group, and the hydrocarbon group may include an oxygen-containing group. ,
R ⁶ to R ⁹ each independently represent either a hydrogen atom or a sulfur-containing group represented by R—S—, and at least one of R ⁶ to R ⁹ is represented by R—S— and R is a hydrocarbon group having 1 to 24 carbon atoms. 2. The composition according to claim 1, wherein R of the sulfur-containing group represented by RS- of the ultraviolet absorber (B1) represents an alkyl group having 1 to 24 carbon atoms. The composition according to claim 1 or 2, wherein said R ⁶ or R ⁹ is a sulfur-containing group represented by RS- . The composition according to any one of claims 1 to 3, wherein the hydrocarbon groups of R ¹ to R ⁵ in the ultraviolet absorber (B1) are alkyl groups having 1 to 12 carbon atoms. The composition according to any one of claims 1 to 3, wherein the hydrocarbon groups of R ¹ to R ⁵ in the ultraviolet absorber (B1) are alkyl groups having 1 to 4 carbon atoms. The composition according to any one of claims 1 to ⁵ , wherein at least one of R ¹ to R 5 in said UV absorber (B1) is a methyl group. Claims 1 to 5, wherein at least one of R ¹ to R ⁵ in said UV absorber (B1) is a methyl group, and at least one of the remaining R ¹ to R ⁵ is a butyl group. The composition according to any one of Any one of claims 1 to 7 , comprising 0.01 to 0.1 parts by mass of a phosphorus-based heat stabilizer (B2) as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The described composition. Any one of claims 1 to 8 , wherein 0.03 to 0.5 parts by mass of a fatty acid ester release agent (B3) is contained as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The composition according to . Any of claims 1 to 9 , comprising 0.01 to 0.30 parts by mass of a hindered phenolic antioxidant (B4) as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The composition according to 11. The epoxy group-containing compound (B5) as the additive (B) is contained in an amount of 0.001 to 0.02 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), according to any one of claims 1 to 10 . composition. 0.05 to 0.3 parts by mass of an ultraviolet absorber (B6) other than the ultraviolet absorber (B1) as the additive (B) with respect to 100 parts by weight of the polycarbonate resin (A). Item 12. The composition according to any one of items 1 to 11 . The composition according to any one of claims 1 to 12 , which is used as a molding material for hot-melt molded articles. The composition according to any one of claims 1 to 12 , which is used as a molding material for spectacle lens moldings.