JP2020132839A - Polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition which maintains high total light transmittance while reducing light transmittance of a wavelength in a specific ultraviolet region, namely, in the vicinity of 420 nm that seems harmful light, and which has excellent impact strength, molding retention stability and drying resistance.SOLUTION: A polycarbonate resin composition includes 0.1-1.5 pts.mass of an additive (B) and includes, as the additive (B), 0.1 pts.mass or more of an ultraviolet absorber (B1) having a benzotriazole skeleton represented by formula 1 relative to 100 pts.mass of a polycarbonate resin (A) having a viscosity average molecular weight of 21,000-26,000.SELECTED DRAWING: None

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 impact resistance, molding retention stability, and so on. The present invention relates to a polycarbonate resin composition having excellent dry heat resistance.

Molded products formed using synthetic resin (plastic) are more difficult to crack than glass materials, and are easy to color and various molding processes, so that they are being replaced with glass materials. For example, synthetic resins have been used in place of glass materials for optically molded products such as spectacle lenses, camera lenses, front plates of various displays, and light source covers.

Synthetic resin molded products are liable to deteriorate due to long-term exposure to sunlight or ultraviolet rays, and discoloration such as yellowing is unavoidable. In order to suppress such deterioration such as discoloration, an ultraviolet absorber is blended in the synthetic resin molded product for the purpose of improving the light resistance.

In addition, recently, for the purpose of protecting the eyes, studies have been conducted to impart ultraviolet absorption ability to synthetic resin molded products. It has been pointed out that ultraviolet rays have an adverse effect on the eyes. Further, for example, natural light, a liquid crystal display of an office device, a blue light emitted from a display of a portable device such as a smartphone or a mobile phone, and the like may cause eye fatigue and pain, and may affect the eyes. For example, it has been pointed out that when the eyes are exposed to blue light for a long period of time, they are subjected to eye strain and oxidative stress due to the generation of active oxygen, especially excess singlet oxygen. It is known that the production of this singlet oxygen is promoted by short-wavelength blue light, which has strong energy among ultraviolet rays and visible light.

In the retina, it is thought that a waste product called lipofuscin accumulates in the retinal pigment epithelium with aging, and this acts as a photosensitizer to generate singlet oxygen. This lipofuscin has a property that absorption increases as the wavelength becomes shorter from visible light to the 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 is degraded by light in the ultraviolet to blue regions.

Therefore, in order to suppress the generation of singlet oxygen by lipofuscin and the deterioration of lutein that suppresses oxidative stress, a wavelength of 400 to 420 nm, which is a wavelength range in which the light absorption characteristics of lutein and lipofuscin overlap, is used. It is very effective to cut before the retina.

Further recent studies have shown that exposure of retinal tissue to 411 nm short wavelength light causes stronger oxidative stress on neuronal retinal cells than exposure to 470 nm wavelength light, indicating signs of cell death. It has been pointed out that the structure of the retinal tissue is distorted, and it is considered to be one of the factors that promote age-related macular degeneration.

In addition, it has been pointed out that irradiation with wavelength light of 400 to 420 nm initiates the production of active oxygen species, DNA damage, and cell death of lens epithelial cells, which are the causes of cortical cataracts. Blocking short wavelength light of 400-420 nm, which can be a trigger, is very important for keeping the eye healthy. In other words, suppressing the light transmittance of light having a wavelength near 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 having a wavelength of 400 to 420 nm to a plastic molded product.

Patent Documents 3 and 4 describe a plastic that absorbs wavelengths of 400 to 420 nm sufficiently efficiently, suppresses absorption of wavelength light of 420 nm or more, is less affected by harmful light, suppresses yellowing, and has an excellent appearance. Lenses have been proposed.

Japanese Patent No. 5620033 Japanese Patent No. 4334633 International Publication No. 2016/021664 International Publication No. 2016/174788

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 for 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 the wavelength light in the vicinity of 400 to 420 nm, the absorption efficiency in the wavelength region is low, so that the ultraviolet rays are absorbed. It is necessary to increase the amount of the agent added, and at the same time, due to its optical characteristics, it absorbs more light having a wavelength longer than around 420 nm, so that there is a problem that the molded product turns yellow.

Patent Documents 3 and 4 propose transparent plastic molded products that suppress the transmittance at a wavelength of 420 nm. However, the plastic molded products such as plastic lenses specifically shown in these proposals are molded products made of thermosetting resins having insufficient impact resistance.

Generally, it is said that polycarbonate resin is superior in mechanical properties such as impact resistance to other thermoplastic resins and thermosetting resins. However, when a polycarbonate resin and various additives are used in combination in order to impart various functions other than impact resistance, there is a problem that the mechanical properties of the molded product deteriorate depending on the type and amount of the additives, or molding. Thermal stability during processing deteriorates, and as a result, problems such as coloring of molded products and deterioration of physical properties often occur.

As mentioned above, there have been proposals for transparent plastic molded products that suppress the transmittance of wavelengths around 420 nm, which are considered harmful, but while suppressing the light transmittance of wavelengths around 420 nm, they are resistant. There was no specific proposal for obtaining a polycarbonate resin composition having excellent impact strength. Furthermore, a polycarbonate resin composition that suppresses light transmittance at wavelengths around 420 nm, has excellent impact resistance, has high total light transmittance, and has excellent molding retention stability and dry heat resistance during molding and extrusion. Was strongly desired.

Therefore, an object of the present disclosure is to maintain 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 to have impact resistance and molding. It is an object of the present invention to provide a polycarbonate resin composition having excellent retention stability and dry heat resistance.

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、水素原子が炭素原子数１〜１８のアルキル基に置換されてもよい炭素原子数６〜２４の芳香族基である。
〈態様２〉
前記紫外線吸収剤（Ｂ１）の芳香族基が、フェニル残基を示す、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０．１〜１．４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>
The additive (B) is contained in an amount of 0.1 to 1.5 parts by mass 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) is contained. ), A polycarbonate resin composition containing 0.1 part 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 independently represent any one of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a hydroxyl group, and the hydrocarbon group may contain an oxygen-containing group. ,
R ^{6 to} R ⁹ each independently represent either a hydrogen atom or a sulfur-containing group represented by RS-, and at least one of R ^{6 to} R ⁹ is represented by RS-. It is a sulfur-containing group, and R is an aromatic group having 6 to 24 carbon atoms in which a hydrogen atom may be replaced with an alkyl group having 1 to 18 carbon atoms.
<Aspect 2>
The composition according to aspect 1, wherein the aromatic group of the ultraviolet absorber (B1) exhibits a phenyl residue.
<Aspect 3>
The composition according to aspect 1 or 2, wherein the sulfur-containing group represented by RS- 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 group of R ^{1 to} R ⁵ in the ultraviolet absorber (B1) is an alkyl group having 1 to 12 carbon atoms.
<Aspect 5>
The composition according to any one of aspects 1 to 3, wherein the hydrocarbon group of R ^{1 to} R ⁵ in the ultraviolet absorber (B1) is an alkyl group 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>
Aspects 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. The composition according to any one of 1 to 5.
<Aspect 8>
The composition according to any one of aspects 1 to 7, which contains 0.1 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>
The invention according to any one of aspects 1 to 8, wherein 0.01 to 0.1 parts by mass of a phosphorus-based heat stabilizer (B2) is contained as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). Composition.
<Aspect 10>
In any of aspects 1 to 9, the fatty acid ester-based release agent (B3) is contained in an amount of 0.03 to 0.5 parts by mass as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The composition described.
<Aspect 11>
Any of aspects 1 to 10, wherein 0.01 to 0.30 parts by mass of a hindered phenolic antioxidant (B4) is contained as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The composition according to.
<Aspect 12>
The embodiment 1 to 11, wherein the epoxy group-containing compound (B5) is contained in an amount of 0.001 to 0.02 parts by mass 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 mass of the polycarbonate resin (A). 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 a heat-melt molded product.
<Aspect 15>
The composition according to any one of aspects 1 to 13, which is used as a molding material for an spectacle lens molded product.

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

Further, 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, and multipurpose sheets (for example, injection molded flat plates, extrusion molded). Flat plate or film), and a polycarbonate resin composition used as a molding material for molding an optic lens 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 can be variously modified and implemented within the scope of the gist 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、水素原子が炭素原子数１〜１８のアルキル基に置換されてもよい炭素原子数６〜２４の芳香族基である。 In the polycarbonate resin composition of one embodiment of the present disclosure, the additive (B) is 0.1 to 1 with respect to 100 parts by mass of the polycarbonate resin (A) having a viscosity average molecular weight of 21,000 to 26,000. A polycarbonate resin composition containing 0.5 parts by mass and containing 0.1 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 independently represent any one of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a hydroxyl group, and the hydrocarbon group may contain an oxygen-containing group. ,
R ^{6 to} R ⁹ each independently represent either a hydrogen atom or a sulfur-containing group represented by RS-, and at least one of R ^{6 to} R ⁹ is represented by RS-. It is a sulfur-containing group, and R is an aromatic group having 6 to 24 carbon atoms in which a hydrogen atom may be replaced with an alkyl group having 1 to 18 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 has impact resistance. Excellent molding retention stability and dry heat resistance. Although not limited by the principle, the principle of action of the polycarbonate resin composition of the present disclosure is considered 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 ultraviolet absorber represented by the above formula 1. By adopting this UV absorber, a high total light transmittance is maintained while sufficiently suppressing the light transmittance of wavelengths around 420 nm, although the amount is lower than that of the conventional benzotriazole-based UV absorber. I think I can do it.

Further, in such an ultraviolet absorber, in particular, at least one of R ^{6 to} R ⁹ in the formula 1 has a sulfur-containing group represented by a specific RS-. Since the UV absorber has such a specific sulfur-containing group, heat resistance and compatibility with the polycarbonate resin are improved, and even if the amount of the UV absorber added is large, the impact resistance is high. We believe that the effect of suppressing the decrease can be obtained.

Further, when a polycarbonate resin composition containing a general ultraviolet absorber is extruded or molded, the ultraviolet absorber itself to be blended tends to volatilize and solidify. Therefore, for example, a vacuum connected to an extruder or a molding machine. The vent pipe and the volatile trap device installed in the middle of the vent pipe were easily blocked. In other words, in order to use the conventional UV absorber to exert sufficient UV absorbing ability, it was necessary to add a large amount of UV absorber in consideration of the volatile matter during molding, so polycarbonate. It is considered that this was a factor that lowered the impact resistance and the like of the molded product obtained from the resin composition. On the other hand, the specific ultraviolet absorber of the present disclosure has a higher molecular weight than the conventional ultraviolet absorber, has excellent heat resistance and compatibility with the polycarbonate resin, and is hard to volatilize from the composition. Therefore, a small amount of sufficient ultraviolet rays is sufficient. It is believed that it can exhibit its absorbency and does not reduce the impact resistance of the molded product. Further, the ultraviolet absorber of the present disclosure is less likely to volatilize during molding processing involving heating and melting such as extrusion, and is less likely to solidify or crystallize than the conventional ultraviolet absorber, so that there is also a problem of blocking the vacuum vent pipe or the like. It 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 in the vicinity of 420 nm. For example, when a sheet having a thickness of 2 mm obtained from a polycarbonate resin composition is used, the spectral light transmittance of light at 420 nm in the sheet is 70% or less, less than 70%, 65% or less, or 60% or less. be able to. There is no particular limitation on this lower limit, but for example, it may 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. it can.

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

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

<Impact resistance>
The polycarbonate resin composition of the present disclosure has excellent impact resistance. For example, the molded product obtained from the polycarbonate resin composition, in Charpy impact strength test described below, 55 kJ / ^{m 2} greater, 60 kJ / ^{m 2} or more, 70 kJ / ^{m 2} or more, or to achieve a 80 kJ / ^{m 2} or more 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 cause less deformation of the molded product under high temperature, and can be evaluated by, for example, a deflection temperature test under load described later. The molded product obtained from the polycarbonate resin composition can achieve more than 124 ° C., 125 ° C. or higher, or 126 ° C. or higher in such a deflection temperature test under load. The upper limit is not particularly limited, but can be specified as, for example, 135 ° C. or lower, 132 ° C. or lower, or 130 ° C. or lower.

<Molding retention stability>
The polycarbonate resin composition of the present disclosure is excellent in molding retention stability. For example, a molded product 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. it can. The lower limit is not particularly limited, but may be specified as, for example, 0.40 or more, 0.45 or more, or 0.50 or more.

<Dry heat resistance>
The polycarbonate resin composition of the present disclosure is excellent in dry heat resistance. The dry heat resistance is intended to mean that when the molded product is left at a high temperature for a long period of time, there is little change in hue or deterioration of the molded product. For example, a molded product obtained from a polycarbonate resin composition achieves a yellowing degree (ΔYI) of 3.0 or less, less than 3.0, 2.5 or less, or 2.0 or less in a dry heat resistance test described later. be able to. The lower limit is not particularly limited, but may be specified as, for example, 0.1 or more, 0.3 or more, or 0.5 or more.

<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 is a polycarbonate resin having 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, and particularly preferably 22,000 to 24,000, from the viewpoints 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 prepared by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer. It is calculated from Equations 2 and 3:
ηsp / c = [η] +0.45 × [η] ² c ... Equation 2
[Η] = 1.23 × 10 ^-4 M ^0.83 … Equation 3
Here, [η] is the ultimate 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 divalent phenol with a carbonate precursor can be used.

(Divalent phenol)
Specific examples of the divalent phenol include 2,2-bis (4-hydroxyphenyl) propane (sometimes referred to as bisphenol A), bis (4-hydroxyphenyl) methane, and 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-3,5-dichlorophenyl) propane and other bis (hydroxyaryl) alkanes; 1, Examples include bis (hydroxyphenyl) cycloalkanes such as 1-bis (hydroxyphenyl) cyclopentane, 1,1-bis (hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3. , 3'-Dihydroxyaryl ethers such as dimethyldiphenyl ethers; 4,4'-dihydroxydiphenyl sulfides, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfides and other dihydroxydiaryl sulfides; Examples include dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;4,4'-dihydroxydiphenylsulfone,4,4'-dihydroxy- Examples thereof include dihydroxydiaryl sulfones such as 3,3'-dimethyldiphenyl sulfone. These divalent phenols may be used alone or in combination of two or more.

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

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

For example, a solution method using phosgene as a carbonate precursor can be adopted. In this method, the reaction between the divalent phenol component and phosgene is usually carried out in the presence of an acid binder and an organic solvent.

As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.

Further, optionally, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used for promoting the reaction, and for adjusting the molecular weight, for example, phenol, p-tert-butylphenol, etc. A terminal terminator such as an alkyl-substituted phenol can be used.

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

A transesterification method (melting method) using a carbonic acid diester can also be used as the carbonate precursor. This method is a method in which a predetermined ratio of the dihydric phenol component and the carbonic acid diester are stirred while heating in the presence of an inert gas to distill off the produced alcohol or phenols.

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 under reduced pressure from the initial stage while distilling off the produced alcohols or phenols. In addition, a normal transesterification reaction catalyst can be used to accelerate the reaction.

Examples of the carbonic acid diester used in this transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, and diphenyl carbonate is particularly preferable.

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

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

The total amount of the additive (B) is 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). The total amount of the additive (B) is preferably 0.2 to 1.3 parts by mass, more preferably 0.3 to 1.2 parts by mass, from the viewpoint of impact resistance, heat resistance, dry heat resistance and the like. Yes, more preferably 0.4 to 0.9 parts by mass, and particularly preferably 0.4 to 0.7 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、水素原子が炭素原子数１〜１８のアルキル基に置換されてもよい炭素原子数６〜２４の芳香族基である。 (Ultraviolet absorber (B1) represented by Equation 1)
The composition of the present disclosure contains, as an additive (B), an ultraviolet absorber (B1) having a specific benzotriazole skeleton represented by the following formula 1. This ultraviolet absorber (B1) contains 0.1 part by mass or more with respect to 100 parts by mass of the polycarbonate resin (A) from the viewpoint of a sufficient suppressing effect of light transmittance near 420 nm and impact resistance. It preferably contains 0.1 to 1.4 parts by mass, more preferably 0.2 to 1.2 parts by mass, further preferably 0.3 to 1.1 parts by mass, and particularly preferably 0.4 to 0. Contains 8 parts by mass, most preferably 0.4 to 0.6 parts by mass:

In Formula 1, R ^{1 to} R ⁵ independently represent any one of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a hydroxyl group, and the hydrocarbon group may contain an oxygen-containing group. Good. R ^{6 to} R ⁹ each independently represent either a hydrogen atom or a sulfur-containing group represented by RS-, and at least one of R ^{6 to} R ⁹ is RS-, and R Is an aromatic group having 6 to 24 carbon atoms in which a hydrogen atom may be substituted with an alkyl group having 1 to 18 carbon atoms.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group and the like. The alkyl group includes a linear group or a branched group, and is not particularly limited, but for example, a methyl group, an ethane-1-yl group, a propane-1-yl group, a 1-methylethane-1-yl group, a butane-1-yl group. , Butan-2-yl group, 2-methylpropan-1-yl group, 2-methylpropan-2-yl group, pentane-1-yl group, pentane-2-yl group, hexane-1-yl group, heptane -1-yl group, octane-1-yl group, 1,1,3,3-tetramethylbutane-1-yl group, nonane-1-yl group, benzyl-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, heptadecane-1-yl group, octadecane-1-yl group, Examples thereof include a nonadecan-1-yl group, an eikosan-1-yl group, a benzyl group, an α, α-dimethylbenzyl group and the like. The alkenyl group includes a linear group or a branched group, and is not particularly limited, but for example, a vinyl group, a propa-1-ene-1-yl group, an allyl group, an isopropenyl group, a pig-1-en-1-yl group, a pig. -2-En-1-yl group, porcine-3-ene-1-yl group, 2-methylpropa-2-ene-1-yl group, 1-methylpropa-2-ene-1-yl group, penta-1 -En-1-yl group, penta-2-en-1-yl group, penta-3-en-1-yl group, penta-4-en-1-yl group, 3-methylbut-2-ene-1 -Il group, 3-methylbut-3-en-1-yl group, hexa-1-en-1-yl group, hexa-2-en-1-yl group, hexa-3-en-1-yl group, Hexa-4-en-1-yl group, hexa-5-en-1-yl group, 4-methylpenta-3-ene-1-yl group, 4-methylpenta-3-en-1-yl group, hepta- 1-en-1-yl group, hepta-6-en-1-yl group, octa-1-en-1-yl group, octa-7-en-1-yl group, nona-1-en-1-yl group Il group, nona-8-en-1-yl group, deca-1-en-1-yl group, deca-9-en-1-yl group, undeca-1-en-1-yl group, undeca-10 -En-1-yl group, dodeca-1-en-1-yl group, dodeca-11-en-1-yl group, trideca-1-en-1-yl group, trideca-12-en-1-yl group Group, tetradeca-1-en-1-yl group, tetradeca-13-en-1-yl group, pentadeca-1-en-1-yl group, pentadeca-14-en-1-yl group, hexadeca-1- En-1-yl group, hexadeca-15-en-1-yl group, heptadeca-1-en-1-yl group, heptadeca-16-en-1-yl group, octadeca-1-en-1-yl group , Octadeca-9-en-1-yl group, octadeca-17-en-1-yl group, nonadeca-1-en-1-yl group, Eikosa-1-en-1-yl group and the like. The alkynyl group includes a straight chain or a branched chain, and is not particularly limited, but for example, ethynyl, propa-1-in-1-yl group, propa-2-in-1-yl group, porcine-1-in-1-yl group. Group, porcine-3-in-1-yl group, 1-methylprop-2-in-1-yl group, penta-1-in-1-yl group, penta-4-in-1-yl group, hexa- 1-in-1-yl group, hexa-5-in-1-yl group, hepta-1-in-1-yl group, hepta-6-in-1-yl group, octa-1-in-1- Il group, octa-7-in-1-yl group, nona-1-in-1-yl group, nona-8-in-1-yl group, deca-1-in-1-yl group, deca-9 -In-1-yl group, Undeca-1-in-1-yl group, Undeca-10-in-1-yl group, Dodeca-1-in-1-yl group, Dodeca-11-in-1-yl group Group, trideca-1-in-1-yl group, trideca-12-in-1-yl group, tetradeca-1-in-1-yl group, tetradeca-13-in-1-yl group, pentadeca-1- In-1-yl group, pentadeca-14-in-1-yl group, hexadeca-1-in-1-yl group, hexadeca-15-in-1-yl group, heptadeca-1-in-1-yl group , Heptadeca-16-in-1-yl group, Octadeca-1-in-1-yl group, Octadeca-17-in-1-yl group, Nonadeca-1-in-1-yl group, Eikosa-1-in -1-Il group and the like can be mentioned.

The alicyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

The aromatic hydrocarbon group is not particularly limited, and examples thereof include groups containing aromatic ring residues such as phenyl residue, naphthalene residue, and anthracene residue. The monovalent aromatic hydrocarbon group is not particularly limited, and is, for example, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, 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 Examples thereof include −naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl 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 Groups, 9,10-anthracenylene group, 1,8-anthrasenylene group, 2,7-anthrasenylene group, 2,6-anthrasenylene group, 1,4-anthrasenylene group, 1,3-anthrasenylene group and the like.

The oxygen-containing group is not particularly limited, but for example, a hydroxy group, an alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, and a 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 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, morpholin group , Carbamate group, carbamoyl group, polyoxyethylene group and the like.

As the hydrocarbon groups of R ^{1 to} R ⁵ in the 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 methyl, also, at least one of the remaining R ¹ to R ⁵ is more preferably a butyl group. Further, it is most preferable that at least one of R ² and R ⁴ is selected from such an alkyl group and R ¹ 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 an ultraviolet absorber (B1) is blended with a polycarbonate resin having a specific viscosity average molecular weight, it has high total light transmittance, excellent impact resistance, molding retention stability, and While maintaining the dry heat resistance, it is possible to suppress not only the light beam of 400 nm but also the light transmittance of 400 to 420 nm in particular.

In the above formula 1, the sulfur-containing group represented by R—S— is located in any of R ^{6 to} R ⁹ , but from the viewpoint of facilitating the development of the above performance, R ⁶ or R ⁹ It is preferably in position.

The aromatic group of R of the sulfur-containing group is not particularly limited, and examples thereof include the monovalent aromatic hydrocarbon group described above. Among them, for example, a phenyl residue, a naphthalene residue, a biphenyl residue, and an anthracene residue are preferable, and a phenyl residue is more preferable, from the viewpoint of making it easier to express the above-mentioned performance. Here, the residue is intended as a group containing an aromatic moiety, for example, in the case of a phenyl residue, it is intended as a benzene ring moiety. Further, the hydrogen atom of the aromatic group of R may be substituted with an alkyl group having 1 to 18 carbon atoms, and from the viewpoint of facilitating the development of the above-mentioned performance, the hydrogen of the aromatic group The number of carbon atoms of the alkyl group that can be substituted with an atom is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4.

The introduction of the sulfur-containing group represented by RS-surprisingly increases the molecular weight of the UV absorber itself, but in comparison with conventional UV absorbers, it is used in extruders and molding machines for extrusion and molding. It has been found that clogging of the connected vacuum vent piping system (for example, such a system includes a vent piping and a volatile trap device) can be suppressed. The reason for this is that the molecular weight is increased by the amount of the sulfur-containing group and the volatility is suppressed, and the ultraviolet absorber (B1) that has entered as a volatile substance in the vacuum vent piping system connected to the extruder or molding machine. ), However, it is presumed that the cause is that the deposits are bulky and difficult to grow in the system because solidification or crystallization is difficult to proceed as compared with other conventional ultraviolet absorbers.

Furthermore, as a result of diligent studies, the R of the sulfur-containing group is higher than that of the ultraviolet absorber when the R of the sulfur-containing group is an aliphatic group, that is, when the substituent containing a sulfur atom does not have an aromatic group. However, it has been found that the ultraviolet absorber of the present disclosure containing an aromatic group can improve the dry heat resistance of the polycarbonate resin composition.

(Any additive)
The composition of the present disclosure may contain one or more additives (B) other than the ultraviolet absorber (B1) as exemplified below. In this case, the additives other than the ultraviolet absorber (B1) are used from the viewpoints of mechanical properties such as impact resistance, heat resistance, dry heat resistance, etc., for example, with respect to 100 parts by mass of the polycarbonate resin (A). It can be blended in the range of 01 to 0.5 parts by mass, preferably in the range of 0.02 to 0.4 parts by mass, and preferably in the range of 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 blended in the range of 0.05 to 0.2 parts by mass.

a. Phosphorus heat stabilizer (B2)
A phosphorus-based heat stabilizer can be added to the composition of the present disclosure. Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof. Specifically, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phos. Fight, 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-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphos Fight, 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 can be mentioned. These can be used alone 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 is preferred; bis (2,6-di-tert-butyl-4-methyl) Phenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite is 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 by mass with respect to 100 parts by mass of the polycarbonate resin (A) from the viewpoints of mechanical properties such as molding retention stability and impact resistance, and heat resistance. It is preferably parts, more preferably 0.01 to 0.05 parts by mass, and even more preferably 0.015 to 0.03 parts by mass.

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

Examples of the fatty acid ester-based release agent include (i) an ester of a monovalent alcohol having 1 to 20 carbon atoms and a saturated or unsaturated fatty acid having 10 to 30 carbon atoms, and (ii) 1 to 1 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) Examples of the ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated or unsaturated fatty acid having 10 to 30 carbon atoms include stearyl stearate, palmityl palmitate, butyl stearate, and methyl laurate. , Isopropyl palmitate and the like, and among them, stearyl stearate is preferable.

(Ii) Examples of the partial ester or full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated or unsaturated fatty acid having 10 to 30 carbon atoms include glycerin monostearate, glycerin disstearate, and glycerintri. Steerate, Glycerin Monobehenate, Glycerin Tribehenate, Glycerin Trisorbinate, Pentaerythritol Monostearate, Pentaerythritol Tetrastearate, Pentaerythritol Tetrapelargonate, Propropylene Glycol Monostearate, Solbitan Monostearate, 2- Examples thereof include a total ester of dipentaerythritol such as ethylhexyl stearate and dipentaerythritol hexastearate, and a partial ester of dipentaerythritol.

Among these fatty acid esters, pentaerythritol tetrastearate, glycerin tristearate, and a mixture of glycerin tristearate and stearyl steerate are preferably used. In particular, a mixture of glycerin tristearate and stearyl stearate is preferably used. The mixed weight ratio (former / latter) is preferably 45 to 15/55 to 85, more preferably 40 to 15/60 to 85.

The content of the fatty acid ester-based mold release agent is preferably 0.03 to 0. With respect to 100 parts by mass of the polycarbonate resin (A) from the viewpoints of impact resistance, heat resistance, mold release resistance, discoloration resistance and the like. It is 5 parts by mass, more preferably 0.08 to 0.4 parts by mass, and further preferably 0.1 to 0.3 parts by mass.

The fatty acid ester-based release agent can be used in combination with other known release agents known to those skilled in the art, but even in that case, the content of the fatty acid ester-based release agent is 0.02 to 0. It is preferably 45 parts by mass, and preferably the main component (50% or more) of the release agent.

From the viewpoint of molding retention stability at high temperature, the content of trace metal impurities, particularly tin (Sn), in the fatty acid ester-based mold release agent is preferably smaller, for example, 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 hindered phenolic antioxidant can be added to the composition of the present disclosure. The polycarbonate resin composition of the present disclosure has, for example, dry heat resistance such that the deterioration of hue during molding is small, or discoloration due to long-term use of the molded product at high temperature is small. In order to impart a high degree of dry heat resistance, it is effective to add such an antioxidant.

Examples of the hindered phenol-based stabilizer include n-octadecyl-β- (4'-hydroxy-3', 5'-di-tert-butylfel) propionate and 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 are exemplified. All of these are available as commercial products. The above-mentioned hindered phenol-based stabilizer can be used alone or in combination of two or more.

The content of the hindered phenolic 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 and the like. It is preferably 0.02 to 0.25 parts by mass, and more preferably 0.03 to 0.15 parts by mass.

d. Epoxy group-containing compound (B5)
Epoxy group-containing compounds can be added to the compositions of the present disclosure. The epoxy group-containing compound is blended for the purpose of suppressing mold corrosion and improving the heat resistance to moisture and humidity, 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, and 1,2-bis (hydroxymethyl) -1-butanol 1,2-. Examples thereof include an epoxy-4- (2-oxylanyl) cyclosexan adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate.

The content of the epoxy group-containing compound is 100 parts by mass of the polycarbonate resin (A) from the viewpoints of impact resistance, heat resistance, molding retention stability, transparency, mold corrosion suppressing effect, moisture heat resistance improving effect, and the like. 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 further preferably 0.005 to 0.1 parts by mass.

e. UV absorbers (B6) other than UV absorbers (B1)
In addition to the ultraviolet absorber (B1), the compositions of the present disclosure include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, or cyanoacrylate-based ultraviolet absorbers. It can contain agents and the like.

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-benzotriazole-2-yl) phenol], 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazo- Le, 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) benzotriazol, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4) -On), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazole and the like can be mentioned. These can be used alone or in admixture 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-benzotriazole-2-yl) phenol], 2- [2-Hydroxy-3- (3,4,5,6-tetrahydrophthalimidemethyl)- 5-Methylphenyl] benzotriazole is preferred; 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetra) Methylbutyl) -6- (2H-benzotriazole-2-yl) phenol] is more preferred.

In the composition of the present disclosure, the content of the ultraviolet absorber (particularly the benzotriazole-based ultraviolet absorber) other than the ultraviolet absorber (B1) is determined from the viewpoints of impact resistance, heat resistance, transparency, molding processability, and hue. The amount 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 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is more preferably 25 parts by mass.

f. Brewing agent (B7)
The composition of the present disclosure may contain a brewing agent in order to counteract the yellowness of the molded product caused by the polycarbonate resin or the ultraviolet absorber. The brewing agent is not particularly limited as long as it is used for a polycarbonate resin. Generally, anthraquinone dyes are preferable because they are easily available.

Specific brewing agents include, for example, the generic name Solvent Violet13 (CA.No (color index No.) 60725; brand name "Macrlex Violet B" manufactured by Bayer, "Dialezin Blue G" manufactured by Mitsubishi Chemical Corporation, etc. Sumitomo Chemical Co., Ltd. "Sumiplast Violet B"), Generic name Solvent Violet31 (CA. No 68210; Trade name "Dialesin Violet D" manufactured by Mitsubishi Chemical Co., Ltd.), Generic name Solvent Violet33 (CA. No 60725; Trademark) Name Mitsubishi Chemical Co., Ltd. "Dialesin Blue J"), Generic name Solvent Blue94 (CA.No 61500; Trade name Mitsubishi Chemicals Co., Ltd. "Dialesin Blue N"), Generic name Solvent Bayeret36 (CA.No 68210; Trademark Bayer "Macrolex Violet 3R"), generic name Solvent Blue97 (brand name Bayer "Macralex Blue RR") and generic name Solvent Blue45 (CA.No 61110; brand name Clariant "Polysynthslen Blue") RLS ”) is a typical example.

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

The compositions of the present disclosure further include other heat stabilizers, antistatic agents, flame retardants, heat ray shielding agents, optical brighteners, pigments, light diffusing agents, and strengthening fillers, to the extent that they do not impair the object of the present disclosure. , Other resins, elastomers, etc. can be contained.

Examples of other heat stabilizers include sulfur-based heat stabilizers. Examples of the sulfur-based heat stabilizer include pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), and pentaerythritol-tetrakis (3-stearylthiopropionate). ), Dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate and the like. Among them, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipro Pionate is preferred. Particularly preferred is pentaerythritol-tetrakis (3-laurylthiopropionate). The thioether compound is commercially available from Sumitomo Chemical Co., Ltd. as Sumilyzer TP-D (trade name), Sumilyzer TPM (trade name), and the like, and can be easily obtained.

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).

<Heat melt molded product>
The heat-melt molded product is intended to be a transparent molded product obtained by subjecting the polycarbonate resin composition of the present disclosure to a molding method involving heat-melting such as injection molding, extrusion molding, or rotary molding. .. Specifically, for example, flat-shaped molded products (for example, injection-molded flat plates, extrusion-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. Flat plates (for example, extrusion-molded sheets); flat-shaped molded products (for example, injection-molded sheets, extrusion-molded sheets) used as window glasses; optical lenses such as eyeglass lenses and the like. Further, the surface of the molded product may be surface-molded, or the flat-shaped molded product may be further press-molded to give a curved surface shape or a three-dimensional shape. All of these various molded products have excellent impact resistance, maintain high light transmittance, and have an effect of suppressing light transmittance of 400 nm as well as particularly 400 to 420 nm.

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

<Glasses lens>
As a spectacle lens which is a kind of heat-melt molded product, for example, a finish lens in which both the convex surface and the concave surface of the lens are optically finished by transferring the glass mold surface at the time of molding and molded according to a desired power is used. Can be mentioned. Further, for example, a semi-finish lens in which only the convex surface is optically finished in the same manner as the finish lens and the concave surface side is optically finished in accordance with a desired power by an order or the like can be mentioned.

The semi-finish lens is ground or cut by a curve generator, an NC-controlled cutting tool, or the like according to the required concave surface processing, and is subjected to smoothing processing (fining) as necessary. This cut, ground, or smoothed surface is polished using a polishing dish or a flexible polishing tool with an abrasive and a polishing cloth interposed, and is mirror-finished and optically finished. Be done.

After that, both the finish lens and the polished semi-finish lens are cleaned and inspected for scratches and foreign matter. Further, optionally, for example, a dyeing step of coloring a lens as desired, a hard coating process of forming a cured film to cover the susceptibility to scratches of a plastic lens, and a reduction of surface reflection of the lens to reduce transmittance. After performing the process of forming an antireflection film to improve it, it is shipped as a finished product and used by each user.

The spectacle lens formed by using the polycarbonate resin composition of the present disclosure can be used for a vision correction lens, sunglasses, protective spectacles and the like. All of the spectacle lenses maintain a high light transmittance and have an effect of suppressing the light transmittance in the vicinity of 420 nm, particularly in the range of 400 nm to 420 nm.

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

<< Examples 1 to 12 and Comparative Examples 1 to 9 >>
The polycarbonate resin composition obtained by the production method shown below was evaluated as follows, 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 were dried at 120 ° C. for 5 hours in a hot air dryer, and then in 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 formed in a 1-minute cycle, and the notched Charpy impact strength was measured in accordance with ISO179.

<Deflection temperature under load (heat resistance)>
The pellets obtained in each example were dried at 120 ° C. for 5 hours with a hot air dryer, and then with a J75EIII injection molding machine manufactured by Japan Steel Works, Ltd., a cylinder temperature of 280 ° C. and a mold temperature of 70 to 75 ° C., 1 A test piece having a width of 10 mm, a length of 80 mm, and a thickness of 4 mm was formed in a minute cycle, and the deflection temperature under load with a load of 1.80 MPa was measured in accordance with ISO75-1,75-2.

<Total light transmittance>
The pellets obtained in each example were dried at 120 ° C. for 5 hours in a hot air dryer, and the cylinder temperature was 350 ° C. and the mold temperature was 80 ° C. for 1 minute cycle using a J75EIII injection molding machine manufactured by 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 formed and used as a test piece. .. The total light transmittance of the 3-stage plate at a thickness of 2 mm was measured using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361.

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

<Molding retention test>
In order to evaluate the molding retention stability, a molding retention test corresponding to the molding heat resistance test was performed. The pellets obtained in each example were dried at 120 ° C. for 5 hours in a hot air dryer, and the cylinder temperature was 350 ° C. and the mold temperature was 80 ° C. using the injection molding machine J85-ELIII manufactured by 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) was formed by 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 hues (L, a, b) of the test piece having a thickness of 2 mm before and after the retention were determined. According to JIS K-7105, it was measured by the C light source transmission method using Color-Eye7000A manufactured by Gretag Macbeth, and the color difference ΔE'was determined by the following formula 4. The smaller ΔE'is, the better the molding retention stability is.

ΔE'= {(ΔL') ² + (Δa') ² + (Δb') ² } ^1/2 ... Equation 4
Hue of "molded plate before retention": L'', a'', b''
Hue of "molded plate after retention": L''', a''', b'''
ΔL': L''-L'''
Δa': a''-a'''
Δb': b''-b'''

<Dry heat resistance test>
The pellets obtained in each example were dried at 120 ° C. for 5 hours in a hot air dryer, and the cylinder temperature was 350 ° C. and the mold temperature was 80 ° C. using the injection molding machine J85-ELIII manufactured by 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) is formed in a minute cycle, and this is used as a test piece. And said.

In the dry heat resistance test, the obtained test piece was treated with a hot air dryer at 130 ° C. for 500 hours. The hue of the 2 mm-thick part of the test piece before and after the treatment was measured by the C light source transmission method using Color-Eye7000A manufactured by Gretag Macbeth, and the yellowing degree (ΔYI) before and after the test was measured based on the following formula 5. I asked. The smaller ΔYI is, the more the hue does not change, indicating that the dry heat resistance is excellent.

ΔYI = YI-YI ₀ ... Equation 5
ΔYI: Yellowness before and after the test YI: Yellowness after the test YI ₀ : Yellowness before the test

<Synthesis of UV absorber>
As the ultraviolet absorber (B1), the compounds represented by the following formulas 6 and 7 obtained by the following Synthesis Examples 1 and 2 were used. Further, as an example of the ultraviolet absorber (B6) other than the ultraviolet absorber (B1), the compound represented by the following formula 8 obtained by the following Synthesis Example 3 was used.

(Synthesis Example 1)
2- (2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole (25.0 g, 79.2 mmol), benzenethiol (17.4 g, 158.3 mmol), potassium carbonate (24) .1 g, 174.2 mmol) and potassium iodide (0.9 g, 5.5 mmol) were reacted in 62.5 g of DMF at 125 ° C. for 12 hours. After completion of the reaction, purification was performed to obtain a compound (UV-1) represented by the following formula 6. In addition, the results of each analysis of such compounds are shown below:

Analysis by ^{FT-IR (KBr) 3000cm -1} : O-H stretching vibration 1445,1390cm ^-1: triazole ring stretching vibration 665cm ^-1: C-S stretching vibration

_{^{1 H-NMR (CDCl 3 400MHz}} ) Analysis _{δ 1.48 (s, 9H, -Ph} -OH-CH 3 -C (C H 3) 3), 2.37 (s, 3H, -Ph-OH- _{C H 3 -C (CH 3)} 3), 7.16 (s, 1H), 7.38 (d, 4H), 7.48 (s, 2H), 7.68 (s, 1H), 7. 83 (d, 1H), 8.03 (d, 1H), (insg.10arom.C H), 11.55 (s, 1H, -Ph-O H -CH 3 -C (CH 3) 3)

_{^{13 C-NMR (CDCl 3 400MHz}} ) Analysis by _{δ 20.9 (-Ph-OH- C H} 3 -C (CH 3) 3), 29.5 (-Ph-OH-CH 3 -C (C H 3 ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 116.8, 118.0, 119.3, 128.3, 128.8, 129.6, 132. _{7 (CH arom), 125.5,141.2,143.2 (} C arom), 129.8 (C arom -CH 3), 139.2 (C arom -S), 139.2 (S- C _{arom), 139.2 (C arom -C} (CH 3) 3), 146.7 (C arom -OH)

(Synthesis Example 2)
2- (2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole (25.0 g, 79.2 mmol), 4-isopropylbenzenethiol (24.1 g, 158.3 mmol) ), Potassium carbonate (24.1 g, 174.2 mmol) and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125 ° C. for 12 hours. After completion of the reaction, purification was performed to obtain a compound (UV-2) represented by the following formula 7. In addition, the results of each analysis of such compounds are shown below:

Analysis by ^{FT-IR (KBr) 3000cm -1} : O-H stretching vibration 1446,1389cm ^-1: triazole ring stretching vibration 666cm ^-1: C-S stretching vibration

_{^{1 H-NMR (CDCl 3 400MHz}} ) Analysis by _{δ 1.30 (d, 6H, (} C H 3) 2 CH-Ph-S -), 1.48 (s, 9H, -Ph-OH-CH 3 - _{C (C H 3) 3)} , 2.37 (s, 3H, -Ph-OH-C H 3 -C (CH 3) 3), 2.95 (m, 1H, (CH 3) 2 C H - Ph-S-), 7.16 (s, 1H), 7.28 (s, 2H), 7.36 (d, 1H), 7.45 (s, 2H), 7.57 (s, 1H) , 7.81 (d, 1H), 8.02 (d, 1H), (insg.9arom.C H), 11.58 (s, 1H, -Ph-O H -CH 3 -C (CH 3) ₃ )

_{^{13 C-NMR (CDCl 3 400MHz}} ) Analysis by _{δ 20.9 (-Ph-OH- C H} 3 -C (CH 3) 3), 23.9 ((C H 3) 2 CH-Ph-S-) _{, 29.5 (-Ph-OH-CH} 3 -C (C H 3) 3), 33.9 ((CH 3) 2 C H-Ph-S -), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 115.3, 117.8, _119.3 , 127.9, _128.7 , 129.2, _129.6 , 133.6 (CH _arom ), 125.4 _{141.4,143.3 (C arom), 128.3 (} C arom -CH 3), 138.5 (C arom -S), 138.5 (S- C arom), 139.1 (C arom - _{C (CH 3) 3),} 146.7 (C arom -OH), 149.7 (C arom - C H)

(Synthesis Example 3)
2- (2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole (5.00 g, 15.8 mmol), octanethiol (7.63 g, 52.1 mmol), carbonate 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-3) represented by the following formula 8. This compound corresponds to an ultraviolet absorber (B6) other than the ultraviolet absorber (B1) of the present application. In addition, the results of each analysis of such compounds are shown below:

Analysis by FT-IR (KBr) 3125cm ^-1 : OH expansion and contraction vibration 1438, 1391cm ^-1 : Triazole ring expansion and contraction vibration 661cm ^-1 : CS expansion and contraction vibration

_{^{1 H-NMR (CDCl 3 400MHz}} ) Analysis by _{δ 0.88 (t, 3H, C} H 3 (CH 2) 7 -S), 1.27 (m, 8H, CH 3 (C H 2) 4 (CH _{2) 3 -S), 1.49 (} m, 11H, -Ph-OH-CH 3 -C (C H 3) 3, CH 3 (CH 2) 4 C H 2 (CH 2) 2 -S), _{1.75 (quin, 2H, CH 3} (CH 2) 5 C H 2 CH 2 -S), 2.38 (s, 3H, -Ph-OH-C H 3 -C (CH 3) 3), 3 _{.03 (t, 2H, CH 3} (CH 2) 5 CH 2 C H 2 -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-O H -CH 3 -C (CH 3) 3 )

_{^{13 C-NMR (CDCl 3 400MHz}} ) Analysis by _{δ 14.0 (C H 3 (CH} 2) 7 -S), 20.0 (-Ph-OH- C H 3 -C (CH 3) 3), 22 _{.6 (-Ph-OH-CH 3} - C (CH 3) 3), 28.7 (CH 3 (C H 2) 5 CH 2 CH 2 -S), 31.9 (-Ph-OH-CH 3 _{-C (C H 3) 3)} , 33.2 (CH 3 (CH 2) 5 C H 2 CH 2 -S), 35.4 (CH 3 (CH 2) 5 CH 2 C H 2 -S), _{113.6,117.5,119.3,128.7,129.3 (C H arom), 141.2,143.4} (C arom), 125.4 (C arom -N), 128.3 _{(C arom - C H 3)} , 138.0 (C arom -S), 139.1 (C arom -C (CH 3) 3), 146.7 (C arom -OH)

(Example 1)
The compound obtained in Synthesis Example 1 as an ultraviolet absorber on 100 parts of a polycarbonate resin powder (PC-1) having a viscosity average molecular weight of 23,900 obtained by polymerizing bisphenol A and phosgen by a conventional method by an interfacial polymerization method. (UV-1) 0.12 parts, phosphorus-based heat stabilizer (P-1) 0.03 parts, fatty acid ester-based mold release agent (R-2) 0.2 parts as a release agent, and brewing agent ( BL-1) 0.00015 parts were added, and the mixture was sufficiently mixed with a tumbler, and then pelletized with a 30 mmφ vent type twin-screw extruder at a temperature of 290 ° C. and a vacuum degree of 4.7 kPa.

(Examples 2 to 12, Comparative Examples 1 to 9)
The same operation as in Example 1 was performed except that various materials were used in the amounts shown in Table 1. The evaluation results are shown in Table 1. The components corresponding to each symbol shown in Table 1 are shown below.

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

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

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

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

UV-2; 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5- (4'-isopropylphenyl) sulfanilbenzotriazole (compound obtained in Synthesis Example 2).

UV-3; 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-octylsulfanilbenzotriazole (compound obtained in Synthesis Example 3).

UV-4; 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole (manufactured by BASF Corporation: Tinuvin ™ 329).

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

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

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

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

R-2; pentaerythritol tetrastearate (manufactured by Emery Oleo Chemicals Co., Ltd .: Roxyol ™ VPG861).

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

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

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

(Bluing agent)
BL-1; brewing agent (manufactured by Bayer Corporation: 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 the specific ultraviolet absorber (B1) have an effect of suppressing the light transmittance of not only 400 nm but also 420 nm in particular, and also have an effect of suppressing light transmittance. It was confirmed that it is also excellent in impact strength, molding retention stability, and dry heat resistance.

High total light transmittance and excellent molding retention stability during molding and extrusion are regarded as important for polycarbonate resin compositions as molding materials in transparent plastic molded products including spectacle lenses. It is a characteristic. Further, when the molded product is used in a high temperature environment such as in an automobile in summer, not only the heat resistance of the molded product itself (the molded product is less deformed under high temperature) but also the molded product itself Dry heat resistance (when left at high temperature for a long period of time, there is little change in hue or deterioration of the molded product) is required.

The polycarbonate resin composition of the present invention maintains high total light transmittance while suppressing light transmittance in the vicinity of 420 nm, particularly in the wavelength range of 400 to 420 nm, and has impact resistance, molding retention stability, and dry heat resistance. Because of its superiority, the front plate of various displays such as personal computers and car navigation systems, the front plate and cover of the illuminant, the light source cover, and the multipurpose sheet (for example, injection-molded flat plate, extrusion-molded flat plate or film) take advantage of these features. It is widely used industrially as a molding material for obtaining heat-melt molded products such as spectacle lenses.

Claims (15)

The additive (B) is contained in an amount of 0.1 to 1.5 parts by mass 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) is contained. ), A polycarbonate resin composition containing 0.1 part 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 independently represent any one of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a hydroxyl group, and the hydrocarbon group may contain an oxygen-containing group. ,
R ^{6 to} R ⁹ each independently represent either a hydrogen atom or a sulfur-containing group represented by RS-, and at least one of R ^{6 to} R ⁹ is represented by RS-. It is a sulfur-containing group, and R is an aromatic group having 6 to 24 carbon atoms in which a hydrogen atom may be replaced with an alkyl group having 1 to 18 carbon atoms. The composition according to claim 1, wherein the aromatic group of the ultraviolet absorber (B1) represents a phenyl residue. The composition according to claim 1 or 2, wherein the sulfur-containing group represented by RS- of the ultraviolet absorber (B1) is bonded to R ⁶ or R ⁹ . The composition according to any one of claims 1 to 3, wherein the hydrocarbon group of R ^{1 to} R ⁵ in the ultraviolet absorber (B1) is an alkyl group having 1 to 12 carbon atoms. The composition according to any one of claims 1 to 3, wherein the hydrocarbon group of R ^{1 to} R ⁵ in the ultraviolet absorber (B1) is an alkyl group 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 the ultraviolet absorber (B1) is a methyl group. Claims ^{1 to 5} 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 R ^{1 to} R ⁵ is a butyl group. The composition according to any one of. The composition according to any one of claims 1 to 7, which contains 0.1 to 1.4 parts by mass of the ultraviolet absorber (B1) with respect to 100 parts by mass of the polycarbonate resin (A). One of claims 1 to 8, wherein 0.01 to 0.1 parts by mass of a phosphorus-based heat stabilizer (B2) is contained as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The composition described. Any of claims 1 to 9, which contains 0.03 to 0.5 parts by mass of a fatty acid ester-based release agent (B3) 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 10, wherein 0.01 to 0.30 parts by mass of a hindered phenolic antioxidant (B4) is contained as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). The composition described in polycarbonate. The invention according to any one of claims 1 to 11, wherein 0.001 to 0.02 parts by mass of the epoxy group-containing compound (B5) is contained as the additive (B) with respect to 100 parts by mass of the polycarbonate resin (A). Composition. Claimed to contain 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 mass of the polycarbonate resin (A). Item 8. The composition according to any one of Items 1 to 12. The composition according to any one of claims 1 to 13, which is used as a molding material for a heat-melt molded product. The composition according to any one of claims 1 to 13, which is used as a molding material for an spectacle lens molded product.