WO2019172015A1 - Styrene-based resin composition for optical applications, and optical component - Google Patents
Styrene-based resin composition for optical applications, and optical component Download PDFInfo
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- WO2019172015A1 WO2019172015A1 PCT/JP2019/007240 JP2019007240W WO2019172015A1 WO 2019172015 A1 WO2019172015 A1 WO 2019172015A1 JP 2019007240 W JP2019007240 W JP 2019007240W WO 2019172015 A1 WO2019172015 A1 WO 2019172015A1
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- resin composition
- styrene
- optical
- transmittance
- mass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Definitions
- the polymerization reaction is first controlled by adjusting the polymerization temperature to achieve the target molecular weight, molecular weight distribution, and reaction conversion rate using a well-known complete mixing tank type stirring tank or tower reactor in the polymerization process. Is done.
- the polymerization solution containing the polymer exiting the polymerization step is transferred to the devolatilization step, and unreacted monomers and polymerization solvent are removed.
- the devolatilization process includes a vacuum devolatilization tank with a heater, a vented devolatilization extruder, and the like.
- the polymer in the molten state that has exited the devolatilization step is transferred to the granulation step.
- the molten resin is extruded in a strand form from a porous die and processed into a pellet shape by a cold cut method, an air hot cut method, or an underwater hot cut method.
- Phosphorous antioxidants and phenolic antioxidants can be added by adding and mixing in the polymerization process, devolatilization process, granulation process of styrene resin, or by extruders or injection molding machines during molding.
- a method of mixing, a method of diluting and mixing a resin composition in which a hydrophilic additive is adjusted to a high concentration with an additive-free styrenic resin to a desired content, and the like are not particularly limited.
- anthraquinone compounds include the following. The names listed below are COLOR
- the styrenic resin composition may contain mineral oil as long as the colorless transparency of the present invention is not impaired. Also includes additives such as internal lubricants such as stearic acid and ethylene bisstearylamide, sulfur antioxidants, lactone antioxidants, UV absorbers, hindered amine stabilizers, antistatic agents, external lubricants, etc. It may be. As the external lubricant, ethylene bisstearylamide is suitable, and the content is preferably 30 to 200 ppm in the resin composition.
- the light guide plate receives light from the end surface (side surface) of the plate-shaped molded product, and guides light to the front surface (light emitting surface) of the molded product by a reflection pattern formed on the rear surface (non-light emitting surface) of the molded product. It is a member that has the function of emitting surface light.
- the reflective pattern can be formed by a method such as a screen printing method, an injection molding method, a laser method, or an ink jet method. When processing the plate-shaped molded product into the light guide plate, it is preferable to polish the light incident surface or the entire end surface to a mirror surface.
- Examples 1 to 4 Comparative Examples 1 to 3
- the phosphorous antioxidant and phenolic antioxidant of (b) used in Table 2 were 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy), respectively.
- injection molding was performed at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. to form a plate-shaped molded article having a thickness of 127 ⁇ 127 ⁇ 3 mm.
- the obtained molded product was stored in an oven at 80 ° C. for 1000 hours.
- a 115 ⁇ 85 ⁇ 3 mm thickness test piece was cut out from the plate-shaped molded product, the end surface was polished by buffing, and a mirror surface was formed on the end surface.
- a plate-shaped molded article having the same was prepared.
- the polished plate-like molded product was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation, with an incident light having a size of 20 ⁇ 1.6 mm and a spread angle of 0 °, and a wavelength at an optical path length of 115 mm.
- the spectral transmittance from 350 nm to 800 nm was measured.
- each evaluation is shown by the following criteria.
- delta), (circle), and (double-circle) are set, evaluation is high in order of x, (triangle
- the molded product of the example was excellent in initial uniform surface light emission and excellent in long-term uniform surface light emission.
- optical styrenic resin composition and molded article of the present invention are excellent in initial uniform surface luminescence and long-term uniform surface luminescence, and thus, for example, televisions, desktop personal computers, notebook personal computers. It can be suitably used for light guide plate applications such as cellular phones and car navigation systems.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided are: a styrene-based resin composition having excellent initial uniform surface light-emission properties and excellent long-term uniform surface light-emission properties; and an optical component. A styrene-based resin composition for optical applications, which contains (a) a styrene-based resin, (b) a phosphorus-containing antioxidant agent and/or a phenol-type antioxidant agent and (c) an anthraquinone-type compound, the styrene-based resin composition being characterized in that the content of the component (b) is 0.02 to 1% by mass relative to 100% by mass of the styrene-based resin composition and the content of the component (c) is 0.1 to 90 ppb relative to the total mass of the resin components.
Description
本発明は、光学用スチレン系樹脂組成物及び光学部品に関する。
The present invention relates to an optical styrene resin composition and an optical component.
スチレン系樹脂は、透明性、剛性、低吸水性、寸法安定性などの特性に優れ、成形加工性に優れることから、射出成形、押出成形、ブロー成形などの各種成形方法により、電気製品や各種工業材料、食品包装容器、雑貨等として広く用いられている。また、透明性を生かした用途として、導光板等の光学部材にも用いられている。
Styrenic resins have excellent properties such as transparency, rigidity, low water absorption, and dimensional stability, and are excellent in molding processability. Therefore, various types of molding methods such as injection molding, extrusion molding, blow molding, etc. Widely used as industrial materials, food packaging containers, miscellaneous goods and the like. Moreover, it is used also for optical members, such as a light-guide plate, as an application using transparency.
液晶ディスプレイのバックライトには光源を表示装置の正面に配置する直下型バックライトと側面に配置するエッジライト型バックライトがある。導光板はエッジライト型バックライトに組み込まれ、側面からの光を液晶パネルに導く役割を果たし、テレビ、デスクトップ型パーソナルコンピューターのモニター、ノート型パーソナルコンピューター、携帯電話機、カーナビゲーションなど幅広い用途で使用される。そのような導光板に用いられるスチレン系樹脂組成物として、長期間の使用においても透過率の変化が小さいスチレン系樹脂組成物が特許文献１に記載されている。
There are two types of backlights for liquid crystal displays: a direct type backlight that arranges the light source in front of the display device and an edge light type backlight that arranges the light source on the side. The light guide plate is incorporated in the edge-light type backlight and plays the role of guiding the light from the side to the liquid crystal panel, and is used in a wide range of applications such as televisions, desktop personal computer monitors, notebook personal computers, mobile phones, car navigation systems. The As a styrene resin composition used for such a light guide plate, Patent Document 1 describes a styrene resin composition having a small change in transmittance even after long-term use.
しかしながら、上記文献記載の従来技術では、長期間の使用における透過率の変化を抑制できる一方で、均一面発光性及び長期的な均一面発光性が十分でないという問題があった。
However, the conventional technique described in the above-mentioned document has a problem that uniform surface luminescence and long-term uniform surface luminescence are not sufficient while it is possible to suppress a change in transmittance during long-term use.
本発明は上記事情に鑑みてなされたものであり、初期の均一面発光性に優れ、且つ長期的な均一面発光性に優れるスチレン系樹脂組成物及び光学部品を提供するという課題を達成することを目的とする。
The present invention has been made in view of the above circumstances, and achieves the problem of providing a styrenic resin composition and an optical component that are excellent in initial uniform surface luminescence and excellent in long-term uniform surface luminescence. With the goal.
本発明によれば、（ａ）スチレン系樹脂と、（ｂ）リン系酸化防止剤及び／又はフェノール系酸化防止剤と、（ｃ）アントラキノン系化合物を含み、スチレン系樹脂組成物１００質量％中の前記（ｂ）の含有量は０．０２～１質量％であり、樹脂成分全質量に対する前記（ｃ）の含有量は０．１～９０ｐｐｂであることを特徴とする光学用スチレン系樹脂組成物が提供される。
According to the present invention, (a) a styrene-based resin, (b) a phosphorus-based antioxidant and / or a phenol-based antioxidant, and (c) an anthraquinone-based compound, the styrene-based resin composition in 100% by mass The content of the (b) is 0.02 to 1% by mass, and the content of the (c) is 0.1 to 90 ppb with respect to the total mass of the resin component. Things are provided.
本発明者らは、上記課題を達成するため、鋭意研究を進めたところ、特定量のリン系酸化防止剤及び／又はフェノール系酸化防止剤と、アントラキノン系化合物を併用することで、前記目的が達成されることを見出し、本発明の完成に至った。
In order to achieve the above-mentioned problems, the present inventors have conducted extensive research. As a result, the object can be achieved by using a specific amount of a phosphorus-based antioxidant and / or a phenol-based antioxidant in combination with an anthraquinone-based compound. As a result, the present invention has been completed.
以下、本発明の種々の実施形態を例示する。以下に示す種々の実施形態は互いに組み合わせ可能である。
好ましくは、光路長１１５ｍｍでの波長３８０ｎｍ～７８０ｎｍの平均透過率が８０％以上である（但し前記平均透過率は、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行って得た１２７×１２７×３ｍｍ厚みの板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出しの端面をバフ研磨によって研磨し作成した端面に鏡面を有する試験片を用いて測定するものとする）。
好ましくは、波長４８０ｎｍの透過率（ｔ４８０）と波長５８０ｎｍの透過率（ｔ５８０）の比率が、以下の関係である。
０．９６＜ｔ５８０／ｔ４８０＜１．０４
好ましくは、（ａ）スチレン系樹脂と、（ｂ）リン系酸化防止剤及び／又はフェノール系酸化防止剤と、（ｃ）アントラキノン系化合物を含み、スチレン系樹脂組成物１００質量％中の前記（ｂ）の含有量は０．０２～１質量％であり、光路長１１５ｍｍでの波長３８０ｎｍ～７８０ｎｍの平均透過率が８０％以上であり（但し前記平均透過率は、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行って得た１２７×１２７×３ｍｍ厚みの板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出しの端面をバフ研磨によって研磨し作成した端面に鏡面を有する試験片を用いて測定するものとする）、波長４８０ｎｍの透過率（ｔ４８０）と波長５８０ｎｍの透過率（ｔ５８０）の比率が、以下の関係である。
０．９６＜ｔ５８０／ｔ４８０＜１．０４
好ましくは、上記光学用スチレン系樹脂組成物からなる光学部品。 Hereinafter, various embodiments of the present invention will be exemplified. The various embodiments described below can be combined with each other.
Preferably, the average transmittance at a wavelength of 380 nm to 780 nm at an optical path length of 115 mm is 80% or more (provided that the average transmittance is 127 obtained by injection molding at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. A test piece having a thickness of 115 × 85 × 3 mm is cut out from a plate-shaped molded product having a thickness of × 127 × 3 mm, and the measurement is performed using a test piece having a mirror surface on the end surface that is created by polishing the end surface by buffing.
Preferably, the ratio between the transmittance at a wavelength of 480 nm (t480) and the transmittance at a wavelength of 580 nm (t580) is as follows.
0.96 <t580 / t480 <1.04
Preferably, (a) a styrene-based resin, (b) a phosphorus-based antioxidant and / or a phenol-based antioxidant, and (c) an anthraquinone-based compound, The content of b) is 0.02 to 1% by mass, and the average transmittance at a wavelength of 380 nm to 780 nm at an optical path length of 115 mm is 80% or more (provided that the average transmittance is a cylinder temperature of 230 ° C., a mold) A test piece of 115 × 85 × 3 mm thickness was cut out from a 127 × 127 × 3 mm thickness plate-like molded product obtained by injection molding at a temperature of 50 ° C. and the end surface was polished by buffing and had a mirror surface on the end surface. The ratio between the transmittance at a wavelength of 480 nm (t480) and the transmittance at a wavelength of 580 nm (t580) is as follows.
0.96 <t580 / t480 <1.04
Preferably, an optical component comprising the optical styrene resin composition.
好ましくは、光路長１１５ｍｍでの波長３８０ｎｍ～７８０ｎｍの平均透過率が８０％以上である（但し前記平均透過率は、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行って得た１２７×１２７×３ｍｍ厚みの板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出しの端面をバフ研磨によって研磨し作成した端面に鏡面を有する試験片を用いて測定するものとする）。
好ましくは、波長４８０ｎｍの透過率（ｔ４８０）と波長５８０ｎｍの透過率（ｔ５８０）の比率が、以下の関係である。
０．９６＜ｔ５８０／ｔ４８０＜１．０４
好ましくは、（ａ）スチレン系樹脂と、（ｂ）リン系酸化防止剤及び／又はフェノール系酸化防止剤と、（ｃ）アントラキノン系化合物を含み、スチレン系樹脂組成物１００質量％中の前記（ｂ）の含有量は０．０２～１質量％であり、光路長１１５ｍｍでの波長３８０ｎｍ～７８０ｎｍの平均透過率が８０％以上であり（但し前記平均透過率は、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行って得た１２７×１２７×３ｍｍ厚みの板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出しの端面をバフ研磨によって研磨し作成した端面に鏡面を有する試験片を用いて測定するものとする）、波長４８０ｎｍの透過率（ｔ４８０）と波長５８０ｎｍの透過率（ｔ５８０）の比率が、以下の関係である。
０．９６＜ｔ５８０／ｔ４８０＜１．０４
好ましくは、上記光学用スチレン系樹脂組成物からなる光学部品。 Hereinafter, various embodiments of the present invention will be exemplified. The various embodiments described below can be combined with each other.
Preferably, the average transmittance at a wavelength of 380 nm to 780 nm at an optical path length of 115 mm is 80% or more (provided that the average transmittance is 127 obtained by injection molding at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. A test piece having a thickness of 115 × 85 × 3 mm is cut out from a plate-shaped molded product having a thickness of × 127 × 3 mm, and the measurement is performed using a test piece having a mirror surface on the end surface that is created by polishing the end surface by buffing.
Preferably, the ratio between the transmittance at a wavelength of 480 nm (t480) and the transmittance at a wavelength of 580 nm (t580) is as follows.
0.96 <t580 / t480 <1.04
Preferably, (a) a styrene-based resin, (b) a phosphorus-based antioxidant and / or a phenol-based antioxidant, and (c) an anthraquinone-based compound, The content of b) is 0.02 to 1% by mass, and the average transmittance at a wavelength of 380 nm to 780 nm at an optical path length of 115 mm is 80% or more (provided that the average transmittance is a cylinder temperature of 230 ° C., a mold) A test piece of 115 × 85 × 3 mm thickness was cut out from a 127 × 127 × 3 mm thickness plate-like molded product obtained by injection molding at a temperature of 50 ° C. and the end surface was polished by buffing and had a mirror surface on the end surface. The ratio between the transmittance at a wavelength of 480 nm (t480) and the transmittance at a wavelength of 580 nm (t580) is as follows.
0.96 <t580 / t480 <1.04
Preferably, an optical component comprising the optical styrene resin composition.
本発明の耐熱スチレン系樹脂組成物は、初期の均一面発光性に優れ、且つ長期的な均一面発光性に優れるスチレン系樹脂組成物及び光学部品が得られる。
The heat-resistant styrene-based resin composition of the present invention provides a styrene-based resin composition and an optical component that are excellent in initial uniform surface luminescence and excellent in long-term uniform surface luminescence.
以下、本発明を詳細に説明する。
Hereinafter, the present invention will be described in detail.
＜＜スチレン系樹脂＞＞
本発明のスチレン系樹脂は、スチレン系単量体を重合して得ることができる。スチレン系単量体とは、芳香族ビニル系モノマーである、スチレン、α－メチルスチレン、ｏ－メチルスチレン、ｐ－メチルスチレン、ｍ－メチルスチレン、エチルスチレン、ｐ－ｔ－ブチルスチレン等の単独又は２種以上の混合物であり、好ましくはスチレンである。また、本発明の特徴を損ねない範囲でスチレン系単量体と共重合可能な単量体と共重合してもよく、例えば、アクリル酸やメタクリル酸等の（メタ）アクリル酸類、アクリロニトリル、メタクリロニトリル等のシアン化ビニルモノマーや無水マレイン酸、フマル酸等のα，β－エチレン不飽和カルボン酸類、フェニルマレイミド、シクロヘキシルマレイミド等のイミド系モノマー類が挙げられる。なお、これらの中でもスチレン系単量体のみからなる重合体が好ましく、特にスチレンホモポリマーが好ましい。
スチレン系樹脂組成物は、スチレン系樹脂と、各種添加剤とで構成されていることが好ましく、スチレン系樹脂組成物１００質量％中のスチレン系樹脂の割合は、例えば９０～９９．９６質量％であり、９５～９９．９６質量％が好ましい。スチレン系樹脂の割合は、具体的には例えば、９０、９１、９２、９３、９４、９５、９６、９７、９８、９９、９９．９６質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 << Styrenic resin >>
The styrene resin of the present invention can be obtained by polymerizing a styrene monomer. Styrene monomers are aromatic vinyl monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, pt-butylstyrene, etc. Or it is a mixture of two or more, preferably styrene. Further, it may be copolymerized with a monomer copolymerizable with a styrenic monomer within a range not impairing the characteristics of the present invention. For example, (meth) acrylic acids such as acrylic acid and methacrylic acid, acrylonitrile, methacrylate, etc. Examples thereof include vinyl cyanide monomers such as nitrile, α, β-ethylenically unsaturated carboxylic acids such as maleic anhydride and fumaric acid, and imide monomers such as phenylmaleimide and cyclohexylmaleimide. Among these, a polymer composed only of a styrene monomer is preferable, and a styrene homopolymer is particularly preferable.
The styrene resin composition is preferably composed of a styrene resin and various additives, and the ratio of the styrene resin in 100% by mass of the styrene resin composition is, for example, 90 to 99.96% by mass. 95 to 99.96% by mass is preferable. Specifically, the ratio of the styrenic resin is, for example, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.96% by mass, and any of the numerical values exemplified here is 2 It may be within a range between the two.
本発明のスチレン系樹脂は、スチレン系単量体を重合して得ることができる。スチレン系単量体とは、芳香族ビニル系モノマーである、スチレン、α－メチルスチレン、ｏ－メチルスチレン、ｐ－メチルスチレン、ｍ－メチルスチレン、エチルスチレン、ｐ－ｔ－ブチルスチレン等の単独又は２種以上の混合物であり、好ましくはスチレンである。また、本発明の特徴を損ねない範囲でスチレン系単量体と共重合可能な単量体と共重合してもよく、例えば、アクリル酸やメタクリル酸等の（メタ）アクリル酸類、アクリロニトリル、メタクリロニトリル等のシアン化ビニルモノマーや無水マレイン酸、フマル酸等のα，β－エチレン不飽和カルボン酸類、フェニルマレイミド、シクロヘキシルマレイミド等のイミド系モノマー類が挙げられる。なお、これらの中でもスチレン系単量体のみからなる重合体が好ましく、特にスチレンホモポリマーが好ましい。
スチレン系樹脂組成物は、スチレン系樹脂と、各種添加剤とで構成されていることが好ましく、スチレン系樹脂組成物１００質量％中のスチレン系樹脂の割合は、例えば９０～９９．９６質量％であり、９５～９９．９６質量％が好ましい。スチレン系樹脂の割合は、具体的には例えば、９０、９１、９２、９３、９４、９５、９６、９７、９８、９９、９９．９６質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 << Styrenic resin >>
The styrene resin of the present invention can be obtained by polymerizing a styrene monomer. Styrene monomers are aromatic vinyl monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, pt-butylstyrene, etc. Or it is a mixture of two or more, preferably styrene. Further, it may be copolymerized with a monomer copolymerizable with a styrenic monomer within a range not impairing the characteristics of the present invention. For example, (meth) acrylic acids such as acrylic acid and methacrylic acid, acrylonitrile, methacrylate, etc. Examples thereof include vinyl cyanide monomers such as nitrile, α, β-ethylenically unsaturated carboxylic acids such as maleic anhydride and fumaric acid, and imide monomers such as phenylmaleimide and cyclohexylmaleimide. Among these, a polymer composed only of a styrene monomer is preferable, and a styrene homopolymer is particularly preferable.
The styrene resin composition is preferably composed of a styrene resin and various additives, and the ratio of the styrene resin in 100% by mass of the styrene resin composition is, for example, 90 to 99.96% by mass. 95 to 99.96% by mass is preferable. Specifically, the ratio of the styrenic resin is, for example, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.96% by mass, and any of the numerical values exemplified here is 2 It may be within a range between the two.
スチレン系樹脂が、スチレン系単量体と（メタ）アクリル酸とを共重合して得られるスチレン－（メタ）アクリル酸共重合樹脂である場合、スチレン系樹脂のスチレン系単量体単位の含有量が８０．０～９９．９質量％、（メタ）アクリル酸単位の含有量が０．１～２０．０質量％であることが好ましい。ただし、スチレン系単量体単位と（メタ）アクリル酸単位の含有量の合計を１００質量％とする。（メタ）アクリル酸とは、アクリル酸、メタクリル酸等であり、メタクリル酸が好ましい。
When the styrene resin is a styrene- (meth) acrylic acid copolymer resin obtained by copolymerizing a styrene monomer and (meth) acrylic acid, the content of the styrene resin unit of the styrene resin The amount is preferably 80.0 to 99.9% by mass, and the content of (meth) acrylic acid units is preferably 0.1 to 20.0% by mass. However, the total content of styrene monomer units and (meth) acrylic acid units is 100% by mass. (Meth) acrylic acid is acrylic acid, methacrylic acid or the like, with methacrylic acid being preferred.
スチレン系樹脂中の（メタ）アクリル酸単位含有量の測定は室温で実施する。スチレン系樹脂０．５ｇを秤量し、トルエン／エタノール＝８／２（体積比）の混合溶液に溶解後、水酸化カリウム０．１ｍｏｌ／Ｌエタノール溶液にて中和滴定を行い、終点を検出し、水酸化カリウムエタノール溶液の使用量より、（メタ）アクリル酸単位の質量基準の含有量を算出する。なお、電位差自動滴定装置を使用することができ、京都電子工業株式会社製ＡＴ－５１０により測定を行うことができる。スチレン系樹脂中の（メタ）アクリル酸単位の含有量は、スチレン系樹脂の重合時における原料のスチレン系単量体と（メタ）アクリル酸単量体との組成比によって調整することができるが、相溶する範囲において（メタ）アクリル酸単位を含有するスチレン系樹脂と（メタ）アクリル酸単位を含有しないスチレン系樹脂とをブレンドして調整することもできる。
The measurement of the (meth) acrylic acid unit content in the styrene resin is performed at room temperature. Weigh 0.5 g of styrene resin, dissolve in toluene / ethanol = 8/2 (volume ratio) mixed solution, then perform neutralization titration with potassium hydroxide 0.1 mol / L ethanol solution to detect the end point. From the amount of potassium hydroxide ethanol solution used, the mass-based content of (meth) acrylic acid units is calculated. An automatic potentiometric titrator can be used, and measurement can be performed with AT-510 manufactured by Kyoto Electronics Industry Co., Ltd. The content of the (meth) acrylic acid unit in the styrenic resin can be adjusted by the composition ratio of the raw styrene monomer and the (meth) acrylic acid monomer during the polymerization of the styrene resin. In a compatible range, a styrene resin containing a (meth) acrylic acid unit and a styrene resin not containing a (meth) acrylic acid unit can be blended and adjusted.
スチレン系樹脂の重合方法としては、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等公知のスチレン重合方法が挙げられる。品質面や生産性の面では、塊状重合法、溶液重合法が好ましく、連続重合であることが好ましい。溶媒として例えばベンゼン、トルエン、エチルベンゼン及びキシレン等のアルキルベンゼン類やアセトンやメチルエチルケトン等のケトン類、ヘキサンやシクロヘキサン等の脂肪族炭化水素等が使用できる。
Examples of the polymerization method of the styrene resin include known styrene polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. In terms of quality and productivity, bulk polymerization and solution polymerization are preferable, and continuous polymerization is preferable. Examples of the solvent include alkylbenzenes such as benzene, toluene, ethylbenzene and xylene, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and cyclohexane.
スチレン系樹脂の重合時に、必要に応じて重合開始剤、連鎖移動剤を使用することができる。重合開始剤としては、ラジカル重合開始剤が好ましく、公知慣用の例えば、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、２，２－ジ（ｔ－ブチルパーオキシ）ブタン、２，２－ジ（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）プロパン、１，１－ジ（ｔ－アミルパーオキシ）シクロヘキサン等のパーオキシケタール類、クメンハイドロパーオキサイド、ｔ－ブチルハイドロパーオキサイド等のハイドロパーオキサイド類、ｔ－ブチルパーオキシアセテート、ｔ－アミルパーオキシイソノナノエート等のアルキルパーオキサイド類、ｔ－ブチルクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ジクミルパーオキサイド、ジ－ｔ－ヘキシルパーオキサイド等のジアルキルパーオキサイド類、ｔ－ブチルパーオキシアセテート、ｔ－ブチルパーオキシベンゾエート、ｔ－ブチルパーオキシイソプロピルモノカーボネート等のパーオキシエステル類、ｔ－ブチルパーオキシイソプロピルカーボネート、ポリエーテルテトラキス（ｔ-ブチルパーオキシカーボネート）等のパーオキシカーボネート類、Ｎ，Ｎ'－アゾビス（シクロヘキサン－１－カルボニトリル）、Ｎ，Ｎ'－アゾビス（２－メチルブチロニトリル）、Ｎ，Ｎ'－アゾビス（２，４－ジメチルバレロニトリル）、Ｎ，Ｎ'－アゾビス［２－（ヒドロキシメチル）プロピオニトリル］等が挙げられ、これらの１種あるいは２種以上を組み合わせて使用することができる。連鎖移動剤としては、脂肪族メルカプタン、芳香族メルカプタン、ペンタフェニルエタン、α－メチルスチレンダイマー及びテルピノーレン等が挙げられる。
A polymerization initiator and a chain transfer agent can be used as needed during the polymerization of the styrene resin. As the polymerization initiator, a radical polymerization initiator is preferable. For example, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, 2,2- Peroxyketals such as di (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-di (t-amylperoxy) cyclohexane, cumene hydroperoxide, t-butyl hydroperoxide, etc. Alkyl peroxides such as hydroperoxides, t-butylperoxyacetate, t-amylperoxyisononanoate, t-butylcumyl peroxide, di-t-butylperoxide, dicumylperoxide, di-t -Dialkyl peroxides such as hexyl peroxide, t-butylperoxyacetate Peroxyesters such as t-butyl peroxybenzoate and t-butylperoxyisopropyl monocarbonate, peroxycarbonates such as t-butyl peroxyisopropyl carbonate and polyether tetrakis (t-butyl peroxycarbonate) N, N′-azobis (cyclohexane-1-carbonitrile), N, N′-azobis (2-methylbutyronitrile), N, N′-azobis (2,4-dimethylvaleronitrile), N, N '-Azobis [2- (hydroxymethyl) propionitrile] and the like can be mentioned, and these can be used alone or in combination. Examples of the chain transfer agent include aliphatic mercaptan, aromatic mercaptan, pentaphenylethane, α-methylstyrene dimer, terpinolene and the like.
連続重合の場合、まず重合工程にて公知の完全混合槽型攪拌槽や塔型反応器等を用い、目標の分子量、分子量分布、反応転化率となるよう、重合温度調整等により重合反応が制御される。重合工程を出た重合体を含む重合溶液は、脱揮工程に移送され、未反応の単量体及び重合溶媒が除去される。脱揮工程は加熱器付きの真空脱揮槽やベント付き脱揮押出機などで構成される。脱揮工程を出た溶融状態の重合体は造粒工程へ移送される。造粒工程では、多孔ダイよりストランド状に溶融樹脂を押出し、コールドカット方式や空中ホットカット方式、水中ホットカット方式にてペレット形状に加工される。
In the case of continuous polymerization, the polymerization reaction is first controlled by adjusting the polymerization temperature to achieve the target molecular weight, molecular weight distribution, and reaction conversion rate using a well-known complete mixing tank type stirring tank or tower reactor in the polymerization process. Is done. The polymerization solution containing the polymer exiting the polymerization step is transferred to the devolatilization step, and unreacted monomers and polymerization solvent are removed. The devolatilization process includes a vacuum devolatilization tank with a heater, a vented devolatilization extruder, and the like. The polymer in the molten state that has exited the devolatilization step is transferred to the granulation step. In the granulation step, the molten resin is extruded in a strand form from a porous die and processed into a pellet shape by a cold cut method, an air hot cut method, or an underwater hot cut method.
＜＜リン系酸化防止剤／フェノール系酸化防止剤＞＞
本発明のスチレン系樹脂組成物は、リン系酸化防止剤及びフェノール系酸化防止剤の少なくとも一方を必須成分として含有する。好ましくは、リン系酸化防止剤及びフェノール系酸化防止剤の両方を含有する。 << Phosphorus antioxidant / Phenolic antioxidant >>
The styrene resin composition of the present invention contains at least one of a phosphorus antioxidant and a phenol antioxidant as an essential component. Preferably, both a phosphorus antioxidant and a phenolic antioxidant are contained.
本発明のスチレン系樹脂組成物は、リン系酸化防止剤及びフェノール系酸化防止剤の少なくとも一方を必須成分として含有する。好ましくは、リン系酸化防止剤及びフェノール系酸化防止剤の両方を含有する。 << Phosphorus antioxidant / Phenolic antioxidant >>
The styrene resin composition of the present invention contains at least one of a phosphorus antioxidant and a phenol antioxidant as an essential component. Preferably, both a phosphorus antioxidant and a phenolic antioxidant are contained.
リン系酸化防止剤は、スチレン系樹脂組成物１００質量％中０．０２～１質量％含有することが好ましく、０．０２～０．５０質量％含有することがより好ましく、０．０２～０．３０質量％含有することがさらに好ましい。また、フェノール系酸化防止剤は、スチレン系樹脂組成物１００質量％中０．０２～１質量％含有することが好ましく、０．０２～０．５０質量％含有することがより好ましく、０．０２～０．３０質量％含有することがさらに好ましい。リン系又はフェノール系酸化防止剤を上記含有量で添加した場合、長期的な均一面発光性に優れるからである。スチレン系樹脂組成物１００質量％中のリン系酸化防止剤及びフェノール系酸化防止剤の含有量は、それぞれ、具体的には例えば、０．０２、０．０３、０．０４、０．０５、０．０６、０．０７、０．０８であり、０．０９、０．１０、０．１５、０．２０、０．２５、０．３０、０．３５、０．４０、０．４５、０．５０、０．５５、０．６０、０．６５、０．７０、０．７５、０．８０、０．８５、０．９０、０．９５、１質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The phosphorus-based antioxidant is preferably contained in an amount of 0.02 to 1% by mass, more preferably 0.02 to 0.50% by mass, and more preferably 0.02 to 0% in 100% by mass of the styrene resin composition. More preferably, the content is 30% by mass. Further, the phenolic antioxidant is preferably contained in an amount of 0.02 to 1% by mass, more preferably 0.02 to 0.50% by mass in 100% by mass of the styrene resin composition, and 0.02%. More preferably, it is contained in an amount of ˜0.30% by mass. This is because when a phosphorus-based or phenol-based antioxidant is added in the above-described content, long-term uniform surface light emission is excellent. Specifically, the content of the phosphorus antioxidant and the phenolic antioxidant in 100% by mass of the styrene resin composition is, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1% by mass, exemplified here It may be within a range between any two of the numerical values.
リン系酸化防止剤とは、三価のリン化合物である亜リン酸エステル類である。リン系酸化防止剤は、例えば、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）フォスファイト、２，２'－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチル－１－フェニルオキシ）（２－エチルヘキシルオキシ）ホスホラス、ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト、４，４'－ビフェニレンジホスフィン酸テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）、３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ〔５．５〕ウンデカン、サイクリックネオペンタンテトライルビス（２，４－ジ－ｔ－ブチルフェニルフォスファイト）、ジステアリルペンタエリスリトールジフォスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス－[２－メチル－４，６－ビス－（１，１－ジメチルエチル）フェニル]エチルフォスファイト、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド、テトラキス（２，４－ジ－ｔｅｒｔ－ブチル－５－メチルフェニル）－４，４'－ビフェニレンジホスホナイト等が挙げられる。リン系酸化防止剤としては、耐加水分解性に優れたものが好ましく、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）フォスファイト、２，２'－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチル－１－フェニルオキシ）（２－エチルヘキシルオキシ）ホスホラス、ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト、３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ〔５．５〕ウンデカンであることが好ましい。特に好ましくは、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）フォスファイトである。リン系酸化防止剤は、単独でもよいが二種以上を併用してもよい。
Phosphorous antioxidants are phosphites that are trivalent phosphorus compounds. Phosphorus antioxidants include, for example, tris (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2- Ethylhexyloxy) phosphorus, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis (2 , 6-Di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, cyclic neopentanetetraylbis (2,4-di -T-butylphenyl phosphite), distearyl pentaerythritol diphosphite, bis (nonylphenyl) pe Taerythritol diphosphite, bis- [2-methyl-4,6-bis- (1,1-dimethylethyl) phenyl] ethyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, and the like. As the phosphorus-based antioxidant, those excellent in hydrolysis resistance are preferable, such as tris (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-). Butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, 3,9-bis (2,6-di-tert-butyl-4-methyl) Phenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane is preferred. Particularly preferred is tris (2,4-di-tert-butylphenyl) phosphite. Phosphorous antioxidants may be used alone or in combination of two or more.
フェノール系酸化防止剤とは、基本骨格にフェノール性水酸基を持つ酸化防止剤である。フェノール系酸化防止剤は、例えば、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、３，９－ビス[２－〔３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ〕－１，１－ジメチルエチル]－２，４，８，１０－テトラオキサスピロ[５．５]ウンデカン、エチレンビス（オキシエチレン）ビス〔３－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート〕、４，６－ビス（オクチルチオメチル）－ｏ－クレゾール、４，６－ビス〔（ドデシルチオ）メチル〕－ｏ－クレゾール、２，４－ジメチル－６－（１－メチルペンタデシル）フェノール、ペンタエリスリトールテトラキス[３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート]、ＤＬ－α－トコフェロール、２－ｔ－ブチル－６－（３－ｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェニルアクリレート、２－〔１－（２－ヒドロキシ－３，５－ジ－ｔ－ペンチルフェニル）エチル〕－４，６－ジ－ｔ－ペンチルフェニルアクリレート、４，４'－チオビス（６－ｔ－ブチル－３－メチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、４，４'－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、ビス－[３，３－ビス－（４'－ヒドロキシ－３'－ｔｅｒｔ―ブチルフェニル）－ブタン酸]－グリコールエステル等が挙げられる。好ましくは、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、３，９－ビス[２－〔３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ〕－１，１－ジメチルエチル]－２，４，８，１０－テトラオキサスピロ[５．５]ウンデカン、エチレンビス（オキシエチレン）ビス〔３－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート〕、ペンタエリスリトールテトラキス[３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート]である。フェノール系酸化防止剤は、単独でもよいが二種以上を併用してもよい。
The phenolic antioxidant is an antioxidant having a phenolic hydroxyl group in the basic skeleton. Examples of the phenolic antioxidant include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, ethylenebis (oxyethylene) bis [3- (5 -Tert-butyl-4-hydroxy-m-tolyl) propionate], 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis [(dodecylthio) methyl] -o-cresol, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphen L) propionate], DL-α-tocopherol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2- Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (6-tert-butyl-3-methylphenol), 1,1 , 3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), bis- [3,3-bis- ( And 4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester. Preferably, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methyl) Phenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4 -Hydroxy-m-tolyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. The phenolic antioxidant may be used alone or in combination of two or more.
上記のようにリン系酸化防止剤及びフェノール系酸化防止剤には非常に多様なものがその中でも、リン系酸化防止剤が、以下に示す（Ｂ１－１）～（Ｂ１－４）の中から選ばれる少なくとも１種であり、フェノール系酸化防止剤が、以下に示す（Ｂ２－１）～（Ｂ２－４）の中から選ばれる少なくとも１種であることが特に好ましい。
As described above, there are a great variety of phosphorus-based antioxidants and phenol-based antioxidants. Among them, phosphorus-based antioxidants are among the following (B1-1) to (B1-4). It is particularly preferable that the phenolic antioxidant is at least one selected from the following (B2-1) to (B2-4).
（Ｂ１－１）トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）フォスファイト
（Ｂ１－２）２，２'－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチル－１－フェニルオキシ）（２－エチルヘキシルオキシ）ホスホラス
（Ｂ１－３）ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト
（Ｂ１－４）３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ〔５．５〕ウンデカン (B1-1) Tris (2,4-di-tert-butylphenyl) phosphite (B1-2) 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2- Ethylhexyloxy) phosphorus (B1-3) bis (2,4-dicumylphenyl) pentaerythritol diphosphite (B1-4) 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane
（Ｂ１－２）２，２'－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチル－１－フェニルオキシ）（２－エチルヘキシルオキシ）ホスホラス
（Ｂ１－３）ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト
（Ｂ１－４）３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ〔５．５〕ウンデカン (B1-1) Tris (2,4-di-tert-butylphenyl) phosphite (B1-2) 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2- Ethylhexyloxy) phosphorus (B1-3) bis (2,4-dicumylphenyl) pentaerythritol diphosphite (B1-4) 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane
（Ｂ２－１）オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート
（Ｂ２－２）３，９－ビス［２－〔３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ〕－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン
（Ｂ２－３）エチレンビス（オキシエチレン）ビス〔３－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート〕
（Ｂ２－４）ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］ (B2-1) Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (B2-2) 3,9-bis [2- [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (B2-3) ethylenebis (oxyethylene) bis [ 3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate]
(B2-4) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
（Ｂ２－２）３，９－ビス［２－〔３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ〕－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン
（Ｂ２－３）エチレンビス（オキシエチレン）ビス〔３－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート〕
（Ｂ２－４）ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］ (B2-1) Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (B2-2) 3,9-bis [2- [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (B2-3) ethylenebis (oxyethylene) bis [ 3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate]
(B2-4) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
リン系酸化防止剤及びフェノール系酸化防止剤の添加方法としては、スチレン系樹脂の重合工程、脱揮工程、造粒工程で添加混合する方法や成形加工時の押出機や射出成形機などで添加混合する方法、親水性添加剤を高濃度に調整した樹脂組成物を無添加のスチレン系樹脂によって目的の含有量に希釈混合する方法などが挙げられ、特に限定されることではない。
Phosphorous antioxidants and phenolic antioxidants can be added by adding and mixing in the polymerization process, devolatilization process, granulation process of styrene resin, or by extruders or injection molding machines during molding. A method of mixing, a method of diluting and mixing a resin composition in which a hydrophilic additive is adjusted to a high concentration with an additive-free styrenic resin to a desired content, and the like are not particularly limited.
＜＜アントラキノン系化合物＞＞
本発明のスチレン系樹脂組成物は、アントラキノン系化合物を必須成分として含有する。スチレン系樹脂組成物中における樹脂成分全質量に対するアントラキノン系化合物の含有量は、０．１～９０ｐｐｂが好ましく、１～７０ｐｐｂがより好ましく、５～５０ｐｐｂがさらに好ましく、１５～４５ｐｐｂが特に好ましい。アントラキノン系化合物を上記含有量で添加した場合、初期及び長期的な均一面発光性が優れるからである。上記アントラキノン系化合物の含有量は、具体的には例えば、０．１，０．２，０．３，０．４，０．５，０．６，０．７，０．８，０．９，１，２，３，４，５，６，７，８，９，１０，１５，２０，２５，３０，３５，４０，４５，５０，５５，６０，６５，７０，７５，８０，８５，９０ｐｐｂであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 << Anthraquinone compound >>
The styrene resin composition of the present invention contains an anthraquinone compound as an essential component. The content of the anthraquinone compound with respect to the total mass of the resin component in the styrene resin composition is preferably 0.1 to 90 ppb, more preferably 1 to 70 ppb, further preferably 5 to 50 ppb, and particularly preferably 15 to 45 ppb. This is because when the anthraquinone compound is added in the above-described content, the initial and long-term uniform surface light emission properties are excellent. Specifically, the content of the anthraquinone compound is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9. , 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 , 90 ppb, and may be within a range between any two of the numerical values exemplified here.
本発明のスチレン系樹脂組成物は、アントラキノン系化合物を必須成分として含有する。スチレン系樹脂組成物中における樹脂成分全質量に対するアントラキノン系化合物の含有量は、０．１～９０ｐｐｂが好ましく、１～７０ｐｐｂがより好ましく、５～５０ｐｐｂがさらに好ましく、１５～４５ｐｐｂが特に好ましい。アントラキノン系化合物を上記含有量で添加した場合、初期及び長期的な均一面発光性が優れるからである。上記アントラキノン系化合物の含有量は、具体的には例えば、０．１，０．２，０．３，０．４，０．５，０．６，０．７，０．８，０．９，１，２，３，４，５，６，７，８，９，１０，１５，２０，２５，３０，３５，４０，４５，５０，５５，６０，６５，７０，７５，８０，８５，９０ｐｐｂであり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 << Anthraquinone compound >>
The styrene resin composition of the present invention contains an anthraquinone compound as an essential component. The content of the anthraquinone compound with respect to the total mass of the resin component in the styrene resin composition is preferably 0.1 to 90 ppb, more preferably 1 to 70 ppb, further preferably 5 to 50 ppb, and particularly preferably 15 to 45 ppb. This is because when the anthraquinone compound is added in the above-described content, the initial and long-term uniform surface light emission properties are excellent. Specifically, the content of the anthraquinone compound is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9. , 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 , 90 ppb, and may be within a range between any two of the numerical values exemplified here.
アントラキノン系化合物としては、例えば以下の物が挙げられる。なお、以下に挙げる名称はＣＯＬＯＲ ＩＮＤＥＸ ＧＥＮＥＲＩＣ ＮＡＭＥである。Ｄｉｓｐｅｒｓｅ Ｂｌｕｅ１４、Ｄｉｓｐｅｒｓｅ Ｂｌｕｅ６０、Ｄｉｓｐｅｒｓｅ Ｂｌｕｅ１９７、Ｄｉｓｐｅｒｓｅ Ｂｌｕｅ１９８、Ｄｉｓｐｅｒｓｅ Ｂｌｕｅ３３４、Ｄｉｓｐｅｒｓｅ Ｂｌｕｅ７２、Ｓｏｌｖｅｎｔ Ｂｌｕｅ１１、Ｓｏｌｖｅｎｔ Ｂｌｕｅ３５、Ｓｏｌｖｅｎｔ Ｂｌｕｅ３６、Ｓｏｌｖｅｎｔ Ｂｌｕｅ４５、Ｓｏｌｖｅｎｔ Ｂｌｕｅ５９、Ｓｏｌｖｅｎｔ Ｂｌｕｅ６３、Ｓｏｌｖｅｎｔ Ｂｌｕｅ６７、Ｓｏｌｖｅｎｔ Ｂｌｕｅ７８、Ｓｏｌｖｅｎｔ Ｂｌｕｅ８３、Ｓｏｌｖｅｎｔ Ｂｌｕｅ８７、Ｓｏｌｖｅｎｔ Ｂｌｕｅ９４、Ｓｏｌｖｅｎｔ Ｂｌｕｅ９５、Ｓｏｌｖｅｎｔ Ｂｌｕｅ９７、Ｓｏｌｖｅｎｔ Ｂｌｕｅ１０４、Ｓｏｌｖｅｎｔ Ｂｌｕｅ１０５、Ｓｏｌｖｅｎｔ Ｂｌｕｅ１２２、Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ１３、Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ３３、Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ３４、Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ１４、Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ３１、Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ３６、Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ３７、Ｄｉｓｐｅｒｓｅ Ｖｉｏｌｅｔ２６、Ｄｉｓｐｅｒｓｅ Ｖｉｏｌｅｔ２８、Ｄｉｓｐｅｒｓｅ Ｖｉｏｌｅｔ３１、Ｄｉｓｐｅｒｓｅ Ｖｉｏｌｅｔ５７、Ｓｏｌｖｅｎｔ Ｇｒｅｅｎ３、Ｓｏｌｖｅｎｔ Ｇｒｅｅｎ２０、Ｓｏｌｖｅｎｔ Ｇｒｅｅｎ２８。
Examples of anthraquinone compounds include the following. The names listed below are COLOR | INDEX | GENERIC | NAME. Disperse Blue14, Disperse Blue60, Disperse Blue197, Disperse Blue198, Disperse Blue334, Disperse Blue72, Solvent Blue11, Solvent Blue35, Solvent Blue36, Solvent Blue45, Solvent Blue59, Solvent Blue63, Solvent Blue67, Solvent Blue78, Solvent Blue83, Solvent Blue87, Solvent Blue94 , Solvent Blue95, Solvent Blue97, Solvent Blue104, Solvent Blue105, Solvent Blue12 , Solvent Violet13, Solvent Violet33, Solvent Violet34, Solvent Violet14, Solvent Violet31, Solvent Violet36, Solvent Violet37, Disperse Violet26, Disperse Violet28, Disperse Violet31, Disperse Violet57, Solvent Green3, Solvent Green20, Solvent Green28.
＜＜その他の添加剤＞＞
スチレン系樹脂組成物には、本発明の無色透明性を損なわない範囲でミネラルオイルを含有しても良い。また、ステアリン酸、エチレンビスステアリルアミド等の内部潤滑剤や、イオウ系酸化防止剤、ラクトン系酸化防止剤、紫外線吸収剤、ヒンダードアミン系安定剤、帯電防止剤、外部潤滑剤等の添加剤が含まれていても良い。また、外部潤滑剤としては、エチレンビスステアリルアミドが好適であり、含有量としては樹脂組成物中に３０～２００ｐｐｍであることが好ましい。 << Other additives >>
The styrenic resin composition may contain mineral oil as long as the colorless transparency of the present invention is not impaired. Also includes additives such as internal lubricants such as stearic acid and ethylene bisstearylamide, sulfur antioxidants, lactone antioxidants, UV absorbers, hindered amine stabilizers, antistatic agents, external lubricants, etc. It may be. As the external lubricant, ethylene bisstearylamide is suitable, and the content is preferably 30 to 200 ppm in the resin composition.
スチレン系樹脂組成物には、本発明の無色透明性を損なわない範囲でミネラルオイルを含有しても良い。また、ステアリン酸、エチレンビスステアリルアミド等の内部潤滑剤や、イオウ系酸化防止剤、ラクトン系酸化防止剤、紫外線吸収剤、ヒンダードアミン系安定剤、帯電防止剤、外部潤滑剤等の添加剤が含まれていても良い。また、外部潤滑剤としては、エチレンビスステアリルアミドが好適であり、含有量としては樹脂組成物中に３０～２００ｐｐｍであることが好ましい。 << Other additives >>
The styrenic resin composition may contain mineral oil as long as the colorless transparency of the present invention is not impaired. Also includes additives such as internal lubricants such as stearic acid and ethylene bisstearylamide, sulfur antioxidants, lactone antioxidants, UV absorbers, hindered amine stabilizers, antistatic agents, external lubricants, etc. It may be. As the external lubricant, ethylene bisstearylamide is suitable, and the content is preferably 30 to 200 ppm in the resin composition.
紫外線吸収剤は、紫外線による劣化や着色を抑制する機能を有するものであって、例えば、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系、ベンゾエート系、サリシレート系、シアノアクリレート系、蓚酸アニリド系、マロン酸エステル系、ホルムアミジン系などの紫外線吸収剤が挙げられる。これらは、単独又は２種以上組み合わせて用いることができ、ヒンダートアミン等の光安定剤を併用してもよい。
The ultraviolet absorber has a function of suppressing deterioration and coloring caused by ultraviolet rays. For example, benzophenone, benzotriazole, triazine, benzoate, salicylate, cyanoacrylate, oxalic anilide, malonic ester UV absorbers such as those of formaldehyde and formamidine. These can be used alone or in combination of two or more thereof, and a light stabilizer such as hindered amine may be used in combination.
本発明のスチレン系樹脂組成物は、射出成形、押出成形、圧縮成形、ブロー成形等、目的に応じた成形方法で成形することができ、その形状は制限されるものではない。例えば板状成形品であれば、導光板等に加工することができる。得られた成形品は、導光板等の成形品内部に光を透過させることによって機能する光学用部材として用いられる。導光板等の光学部材では、光の透過する距離（光路長）が長いため、均一面発光性に優れることが好ましい。ここで、均一面発光性に優れるとは、透過性が優れ、光の吸収率の波長依存性が小さい材料であることを意味する。
The styrenic resin composition of the present invention can be molded by a molding method according to the purpose such as injection molding, extrusion molding, compression molding, blow molding, and the shape is not limited. For example, if it is a plate-shaped molded product, it can be processed into a light guide plate or the like. The obtained molded product is used as an optical member that functions by transmitting light into the molded product such as a light guide plate. An optical member such as a light guide plate is preferably excellent in uniform surface light-emitting properties because a light transmission distance (optical path length) is long. Here, the phrase “excellent in uniform surface light emission” means that the material is excellent in transparency and has a small wavelength dependency of light absorption.
透過率については、光路長１１５ｍｍでの波長３８０ｎｍ～７８０ｎｍの平均透過率が８０％以上であることが好ましく、８２．５％以上であることがより好ましく、８４％以上であることがさらに好ましい。但し、上記平均透過率は、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行って得た１２７×１２７×３ｍｍ厚みの板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出しの端面をバフ研磨によって研磨し作成した端面に鏡面を有する試験片を用いて測定するものとする。また、８０℃で１０００時間保管後と初期の平均透過率の差の絶対値は２．０％以下であることが好ましく、１．５％以下であることがより好ましく、１．２％以下であることがさらに好ましい。
Regarding the transmittance, the average transmittance at a wavelength of 380 nm to 780 nm at an optical path length of 115 mm is preferably 80% or more, more preferably 82.5% or more, and further preferably 84% or more. However, the average transmittance is obtained by cutting out a 115 × 85 × 3 mm thick test piece from a 127 × 127 × 3 mm thick plate-shaped product obtained by injection molding at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. It is assumed that measurement is performed using a test piece having a mirror surface on the end surface prepared by polishing the end surface of the substrate by buffing. Further, the absolute value of the difference in average transmittance after storage at 80 ° C. for 1000 hours is preferably 2.0% or less, more preferably 1.5% or less, and 1.2% or less. More preferably it is.
光の吸収率の波長依存性は、例えば、波長４８０ｎｍの透過率（ｔ４８０）と波長５８０ｎｍの透過率（ｔ５８０）の比率（ｔ５８０／ｔ４８０）により評価することができる。本発明においては、比率（ｔ５８０／ｔ４８０）は、０．９６＜ｔ５８０／ｔ４８０＜１．０４であることが好ましく、０．９７＜ｔ５８０／ｔ４８０＜１．０３であることがより好ましく、０．９８＜ｔ５８０／ｔ４８０＜１．０２であることがさらに好ましく。ここで、光の吸収率の波長依存性が小さいとは、上記比率（ｔ５８０／ｔ４８０）が原則１に近いことを意味する。上記比率（ｔ５８０／ｔ４８０）は、具体的には例えば、０．９７、０．９８、０．９９、１．００、１．０１、１．０２、１．０３であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。
The wavelength dependency of the light absorption rate can be evaluated by, for example, the ratio (t580 / t480) of the transmittance (t480) at a wavelength of 480 nm and the transmittance (t580) at a wavelength of 580 nm. In the present invention, the ratio (t580 / t480) is preferably 0.96 <t580 / t480 <1.04, more preferably 0.97 <t580 / t480 <1.03, and More preferably, 98 <t580 / t480 <1.02. Here, the fact that the wavelength dependency of the light absorption rate is small means that the ratio (t580 / t480) is close to 1 in principle. Specifically, the ratio (t580 / t480) is, for example, 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, and the numerical values exemplified here It may be within the range between any two.
光路長１１５ｍｍの透過率は、次の手順にて測定を行った。スチレン系樹脂組成物のペレットを用い、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行い、１２７×１２７×３ｍｍ厚みの板状成形品を成形した。ここで長期の熱安定性を評価するサンプルは、８０℃のオーブン内に１０００時間保管した。次に、板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出し、端面をバフ研磨によって研磨し、端面に鏡面を有する板状成形品を作成した。研磨後の板状成形品について、日本分光株式会社製の紫外線可視分光光度計Ｖ－６７０を用いて、大きさ２０×１．６ｍｍ、広がり角度０°の入射光において、光路長１１５ｍｍでの波長３５０ｎｍ～８００ｎｍの分光透過率を測定した。
The transmittance with an optical path length of 115 mm was measured by the following procedure. Using pellets of the styrene-based resin composition, injection molding was performed at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. to form a plate-shaped molded article having a thickness of 127 × 127 × 3 mm. Here, a sample for evaluating long-term thermal stability was stored in an oven at 80 ° C. for 1000 hours. Next, a test piece having a thickness of 115 × 85 × 3 mm was cut out from the plate-shaped molded product, and the end surface was polished by buffing to produce a plate-shaped molded product having a mirror surface on the end surface. The polished plate-like molded product was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation, with an incident light having a size of 20 × 1.6 mm and a spread angle of 0 °, and a wavelength at an optical path length of 115 mm. The spectral transmittance from 350 nm to 800 nm was measured.
導光板は、板状の成形品の端面（側面）から光を入射し、成形品の後面（非発光面）に形成された反射パターンにより、成形品の前面（発光面）に光を導き、面発光させる機能を持った部材である。反射パターンは、スクリーン印刷法、射出成形法、レーザー法やインクジェット法などの方法によって形成することができる。板状の成形品から導光板に加工する際、光の入射面或いは端面全面を研磨処理して、鏡面とすることが好ましい。また、出射光の均一性を高めるために、板状成形品の前面（発光面）にプリズムパターン等を設けることができる。板状成形品の前面あるいは後面のパターンは、板状成形品の成形時に形成させることができ、例えば射出成形では金型形状、押出成形ではロール転写などによって、パターンを形成させることができる。
The light guide plate receives light from the end surface (side surface) of the plate-shaped molded product, and guides light to the front surface (light emitting surface) of the molded product by a reflection pattern formed on the rear surface (non-light emitting surface) of the molded product. It is a member that has the function of emitting surface light. The reflective pattern can be formed by a method such as a screen printing method, an injection molding method, a laser method, or an ink jet method. When processing the plate-shaped molded product into the light guide plate, it is preferable to polish the light incident surface or the entire end surface to a mirror surface. Moreover, in order to improve the uniformity of the emitted light, a prism pattern or the like can be provided on the front surface (light emitting surface) of the plate-shaped molded product. The pattern on the front surface or the rear surface of the plate-shaped molded product can be formed at the time of molding the plate-shaped molded product. For example, the pattern can be formed by a mold shape in injection molding or roll transfer in extrusion molding.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
（スチレン系樹脂の製造）
完全混合型撹拌槽である第１反応器と第２反応器及び静的混合器付プラグフロー型反応器である第３反応器を直列に接続して重合工程を構成し、表１に示す条件によりスチレン系樹脂の製造を実施した。各反応器の容量は、第１反応器を３９リットル、第２反応器を３９リットル、第３反応器を１６リットルとした。表１に記載の原料組成にて、原料溶液を作成し、第１反応器に原料溶液を表１に記載の流量にて連続的に供給した。重合開始剤は、第１反応器の入口で表１に記載の添加濃度（原料スチレン及びメタクリル酸の合計量に対する質量基準の濃度）となるように原料溶液に添加し、均一混合した。表１に記載の重合開始剤は次の通り
重合開始剤：２，２－ジ（４，４－ｔ－ブチルパーオキシシクロヘキシル）プロパン（日油株式会社製パーテトラＡを使用した。）
なお、第３反応器では、流れの方向に沿って温度勾配をつけ、中間部分、出口部分で表１の温度となるよう調整した。
続いて、第３反応器より連続的に取り出した重合体を含む溶液を直列に２段より構成される予熱器付き真空脱揮槽に導入し、表１に記載の樹脂温度となるよう予熱器の温度を調整し、表１に記載の圧力に調整することで、未反応スチレン及びエチルベンゼンを分離した後、多孔ダイよりストランド状に押し出しして、コールドカット方式にて、ストランドを冷却及び切断しペレット化した。 (Manufacture of styrene resin)
The polymerization reactor is configured by connecting a first reactor, which is a complete mixing tank, a second reactor, and a third reactor, which is a plug flow reactor with a static mixer. The styrene resin was manufactured by the above. The capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor. A raw material solution was prepared with the raw material composition described in Table 1, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 1. The polymerization initiator was added to the raw material solution at the inlet of the first reactor so that the addition concentration shown in Table 1 (concentration based on mass with respect to the total amount of raw styrene and methacrylic acid) was mixed. The polymerization initiators listed in Table 1 are as follows: Polymerization initiator: 2,2-di (4,4-t-butylperoxycyclohexyl) propane (Pertetra A manufactured by NOF Corporation was used).
In the third reactor, a temperature gradient was provided along the flow direction, and the temperature in Table 1 was adjusted at the intermediate part and the outlet part.
Subsequently, the solution containing the polymer continuously taken out from the third reactor was introduced into a vacuum devolatilization tank with a preheater constituted by two stages in series, and the preheater was adjusted to the resin temperature shown in Table 1. By adjusting the temperature and adjusting to the pressure shown in Table 1, unreacted styrene and ethylbenzene are separated and then extruded into a strand shape from a perforated die, and the strand is cooled and cut by a cold cut method. Pelletized.
完全混合型撹拌槽である第１反応器と第２反応器及び静的混合器付プラグフロー型反応器である第３反応器を直列に接続して重合工程を構成し、表１に示す条件によりスチレン系樹脂の製造を実施した。各反応器の容量は、第１反応器を３９リットル、第２反応器を３９リットル、第３反応器を１６リットルとした。表１に記載の原料組成にて、原料溶液を作成し、第１反応器に原料溶液を表１に記載の流量にて連続的に供給した。重合開始剤は、第１反応器の入口で表１に記載の添加濃度（原料スチレン及びメタクリル酸の合計量に対する質量基準の濃度）となるように原料溶液に添加し、均一混合した。表１に記載の重合開始剤は次の通り
重合開始剤：２，２－ジ（４，４－ｔ－ブチルパーオキシシクロヘキシル）プロパン（日油株式会社製パーテトラＡを使用した。）
なお、第３反応器では、流れの方向に沿って温度勾配をつけ、中間部分、出口部分で表１の温度となるよう調整した。
続いて、第３反応器より連続的に取り出した重合体を含む溶液を直列に２段より構成される予熱器付き真空脱揮槽に導入し、表１に記載の樹脂温度となるよう予熱器の温度を調整し、表１に記載の圧力に調整することで、未反応スチレン及びエチルベンゼンを分離した後、多孔ダイよりストランド状に押し出しして、コールドカット方式にて、ストランドを冷却及び切断しペレット化した。 (Manufacture of styrene resin)
The polymerization reactor is configured by connecting a first reactor, which is a complete mixing tank, a second reactor, and a third reactor, which is a plug flow reactor with a static mixer. The styrene resin was manufactured by the above. The capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor. A raw material solution was prepared with the raw material composition described in Table 1, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 1. The polymerization initiator was added to the raw material solution at the inlet of the first reactor so that the addition concentration shown in Table 1 (concentration based on mass with respect to the total amount of raw styrene and methacrylic acid) was mixed. The polymerization initiators listed in Table 1 are as follows: Polymerization initiator: 2,2-di (4,4-t-butylperoxycyclohexyl) propane (Pertetra A manufactured by NOF Corporation was used).
In the third reactor, a temperature gradient was provided along the flow direction, and the temperature in Table 1 was adjusted at the intermediate part and the outlet part.
Subsequently, the solution containing the polymer continuously taken out from the third reactor was introduced into a vacuum devolatilization tank with a preheater constituted by two stages in series, and the preheater was adjusted to the resin temperature shown in Table 1. By adjusting the temperature and adjusting to the pressure shown in Table 1, unreacted styrene and ethylbenzene are separated and then extruded into a strand shape from a perforated die, and the strand is cooled and cut by a cold cut method. Pelletized.
（実施例１～４、比較例１～３）
表２に示す含有量にて、（ａ）スチレン系樹脂ＰＳ－１と、（ｂ）リン系酸化防止剤／フェノール系酸化防止剤、（ｃ）アントラキノン系化合物をスクリュー径４０ｍｍの単軸押出機を用いて、シリンダー温度２３０℃、スクリュー回転数１００ｒｐｍで溶融混錬してペレットを得た。表２で用いた（ｂ）のリン系酸化防止剤及びフェノール系酸化防止剤はそれぞれ、２，２'－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチル－１－フェニルオキシ）（２－エチルヘキシルオキシ）ホスホラス（株式会社ＡＤＥＫＡ製 アデカスタブＨＰ－１０）、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート（ＢＡＳＦジャパン株式会社製 Ｉｒｇａｎｏｘ １０７６）であり、（ｃ）のアントラキノン系化合物はＳｏｌｖｅｎｔ Ｖｉｏｌｅｔ３３（三菱ケミカル株式会社製 Ｂｌｕｅ Ｊ）である。 (Examples 1 to 4, Comparative Examples 1 to 3)
A single-screw extruder having a screw diameter of 40 mm with (a) a styrene resin PS-1 and (b) a phosphorus antioxidant / phenolic antioxidant and (c) an anthraquinone compound at the contents shown in Table 2. Was melt kneaded at a cylinder temperature of 230 ° C. and a screw rotation speed of 100 rpm to obtain pellets. The phosphorous antioxidant and phenolic antioxidant of (b) used in Table 2 were 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy), respectively. ) Phosphorus (ADEKA STAB HP-10 manufactured by ADEKA Corporation), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF Japan Ltd.), and (c) The anthraquinone compound is Solvent Violet 33 (Blue J, manufactured by Mitsubishi Chemical Corporation).
表２に示す含有量にて、（ａ）スチレン系樹脂ＰＳ－１と、（ｂ）リン系酸化防止剤／フェノール系酸化防止剤、（ｃ）アントラキノン系化合物をスクリュー径４０ｍｍの単軸押出機を用いて、シリンダー温度２３０℃、スクリュー回転数１００ｒｐｍで溶融混錬してペレットを得た。表２で用いた（ｂ）のリン系酸化防止剤及びフェノール系酸化防止剤はそれぞれ、２，２'－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチル－１－フェニルオキシ）（２－エチルヘキシルオキシ）ホスホラス（株式会社ＡＤＥＫＡ製 アデカスタブＨＰ－１０）、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート（ＢＡＳＦジャパン株式会社製 Ｉｒｇａｎｏｘ １０７６）であり、（ｃ）のアントラキノン系化合物はＳｏｌｖｅｎｔ Ｖｉｏｌｅｔ３３（三菱ケミカル株式会社製 Ｂｌｕｅ Ｊ）である。 (Examples 1 to 4, Comparative Examples 1 to 3)
A single-screw extruder having a screw diameter of 40 mm with (a) a styrene resin PS-1 and (b) a phosphorus antioxidant / phenolic antioxidant and (c) an anthraquinone compound at the contents shown in Table 2. Was melt kneaded at a cylinder temperature of 230 ° C. and a screw rotation speed of 100 rpm to obtain pellets. The phosphorous antioxidant and phenolic antioxidant of (b) used in Table 2 were 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy), respectively. ) Phosphorus (ADEKA STAB HP-10 manufactured by ADEKA Corporation), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF Japan Ltd.), and (c) The anthraquinone compound is Solvent Violet 33 (Blue J, manufactured by Mitsubishi Chemical Corporation).
また、得られたペレットを用いて、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行い、１２７×１２７×３ｍｍ厚みの板状成形品を成形した。長期の熱安定性を評価するため、得られた成形品を８０℃のオーブン内で１０００時間保管した。保管前の初期の成形品と保管後の成形品について光学特性を評価するため、板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出し、端面をバフ研磨によって研磨し、端面に鏡面を有する板状成形品を作成した。研磨後の板状成形品について、日本分光株式会社製の紫外線可視分光光度計Ｖ－６７０を用いて、大きさ２０×１．６ｍｍ、広がり角度０°の入射光において、光路長１１５ｍｍでの波長３５０ｎｍ～８００ｎｍの分光透過率を測定した。
Further, by using the obtained pellets, injection molding was performed at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. to form a plate-shaped molded article having a thickness of 127 × 127 × 3 mm. In order to evaluate long-term thermal stability, the obtained molded product was stored in an oven at 80 ° C. for 1000 hours. In order to evaluate the optical properties of the initial molded product before storage and the molded product after storage, a 115 × 85 × 3 mm thickness test piece was cut out from the plate-shaped molded product, the end surface was polished by buffing, and a mirror surface was formed on the end surface. A plate-shaped molded article having the same was prepared. The polished plate-like molded product was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation, with an incident light having a size of 20 × 1.6 mm and a spread angle of 0 °, and a wavelength at an optical path length of 115 mm. The spectral transmittance from 350 nm to 800 nm was measured.
表２においては、各評価について下記のような基準により示した。なお、×、△、○、◎を設定し、×が最も劣り、◎が最も優れ、×、△、○、◎の順に評価が高くなる。
透過性
◎：透過率が８４％以上
○：透過率が８２．５％以上、８４％未満
△：透過率が８０％以上、８２．５％未満
×：透過率が８０％未満
波長依存性
◎：０．９８＜ｔ５８０／ｔ４８０＜１．０２
○：０．９７＜ｔ５８０／ｔ４８０≦０．９８、又は、１．０２≦ｔ５８０／ｔ４８０＜１．０３
△：０．９６＜ｔ５８０／ｔ４８０≦０．９７、又は、１．０３≦ｔ５８０／ｔ４８０＜１．０４
×：ｔ５８０／ｔ４８０≦０．９６、又は、ｔ５８０／ｔ４８０≧１．０４
均一面発光性
透過性及び波長依存性の２つの評価を併せて評価した項目である。
◎：透過性及び波長依存性が共に◎
○：透過性と波長依存性の両方が○以上、且つ、少なくとも一方が○
△：透過性と波長依存性の両方が△以上、且つ、少なくとも一方が△
×：透過性と波長依存性の少なくとも一方が×
長期均一面発光性
初期の均一面発光性、及び長期熱安定性試験後（８０℃、１０００時間後）の面均一発光性について総合評価した項目である。
◎：初期の均一面発光性が◎且つ長期熱安定性試験後の均一面発光性が○以上
○：初期の均一面発光性が○且つ長期熱安定性試験後の均一面発光性が△以上
△：初期の均一面発光性が△且つ長期熱安定性試験後の均一面発光性が△
×：初期の均一面発光性が×又は長期熱安定性試験後の均一面発光性が× In Table 2, each evaluation is shown by the following criteria. In addition, x, (triangle | delta), (circle), and (double-circle) are set, evaluation is high in order of x, (triangle | delta), (circle), and (double-circle) in which x is the inferior and is the best.
Transmittance ◎: Transmittance is 84% or more ○: Transmittance is 82.5% or more and less than 84% Δ: Transmittance is 80% or more and less than 82.5% ×: Transmittance is less than 80%
Wavelength dependence ◎: 0.98 <t580 / t480 <1.02
○: 0.97 <t580 / t480 ≦ 0.98 or 1.02 ≦ t580 / t480 <1.03
Δ: 0.96 <t580 / t480 ≦ 0.97 or 1.03 ≦ t580 / t480 <1.04
X: t580 / t480 ≦ 0.96 or t580 / t480 ≧ 1.04
It is the item which evaluated two evaluation of uniform surface-emitting transmittance | permeability and wavelength dependence collectively.
A: Both transmittance and wavelength dependence are A
○: Both transparency and wavelength dependence are ○ or more, and at least one is ○
Δ: Both transmittance and wavelength dependency are Δ or more, and at least one is Δ
×: At least one of transparency and wavelength dependency is ×
Long-term uniform surface light- emitting property This is a comprehensive evaluation of the initial uniform surface light-emitting property and the surface uniform light-emitting property after a long-term thermal stability test (after 80 ° C., 1000 hours).
◎: Initial uniform surface luminescence is ◎ and uniform surface luminescence after long-term thermal stability test is ◯ or more ○: Initial uniform surface luminescence is ○ and uniform surface luminescence after long-term thermal stability test is △ or more Δ: Uniform surface light emission after initial long-term thermal stability test Δ
×: Initial uniform surface light emission is × or uniform surface light emission after a long-term thermal stability test is ×
透過性
◎：透過率が８４％以上
○：透過率が８２．５％以上、８４％未満
△：透過率が８０％以上、８２．５％未満
×：透過率が８０％未満
波長依存性
◎：０．９８＜ｔ５８０／ｔ４８０＜１．０２
○：０．９７＜ｔ５８０／ｔ４８０≦０．９８、又は、１．０２≦ｔ５８０／ｔ４８０＜１．０３
△：０．９６＜ｔ５８０／ｔ４８０≦０．９７、又は、１．０３≦ｔ５８０／ｔ４８０＜１．０４
×：ｔ５８０／ｔ４８０≦０．９６、又は、ｔ５８０／ｔ４８０≧１．０４
均一面発光性
透過性及び波長依存性の２つの評価を併せて評価した項目である。
◎：透過性及び波長依存性が共に◎
○：透過性と波長依存性の両方が○以上、且つ、少なくとも一方が○
△：透過性と波長依存性の両方が△以上、且つ、少なくとも一方が△
×：透過性と波長依存性の少なくとも一方が×
長期均一面発光性
初期の均一面発光性、及び長期熱安定性試験後（８０℃、１０００時間後）の面均一発光性について総合評価した項目である。
◎：初期の均一面発光性が◎且つ長期熱安定性試験後の均一面発光性が○以上
○：初期の均一面発光性が○且つ長期熱安定性試験後の均一面発光性が△以上
△：初期の均一面発光性が△且つ長期熱安定性試験後の均一面発光性が△
×：初期の均一面発光性が×又は長期熱安定性試験後の均一面発光性が× In Table 2, each evaluation is shown by the following criteria. In addition, x, (triangle | delta), (circle), and (double-circle) are set, evaluation is high in order of x, (triangle | delta), (circle), and (double-circle) in which x is the inferior and is the best.
Transmittance ◎: Transmittance is 84% or more ○: Transmittance is 82.5% or more and less than 84% Δ: Transmittance is 80% or more and less than 82.5% ×: Transmittance is less than 80%
Wavelength dependence ◎: 0.98 <t580 / t480 <1.02
○: 0.97 <t580 / t480 ≦ 0.98 or 1.02 ≦ t580 / t480 <1.03
Δ: 0.96 <t580 / t480 ≦ 0.97 or 1.03 ≦ t580 / t480 <1.04
X: t580 / t480 ≦ 0.96 or t580 / t480 ≧ 1.04
It is the item which evaluated two evaluation of uniform surface-emitting transmittance | permeability and wavelength dependence collectively.
A: Both transmittance and wavelength dependence are A
○: Both transparency and wavelength dependence are ○ or more, and at least one is ○
Δ: Both transmittance and wavelength dependency are Δ or more, and at least one is Δ
×: At least one of transparency and wavelength dependency is ×
Long-term uniform surface light- emitting property This is a comprehensive evaluation of the initial uniform surface light-emitting property and the surface uniform light-emitting property after a long-term thermal stability test (after 80 ° C., 1000 hours).
◎: Initial uniform surface luminescence is ◎ and uniform surface luminescence after long-term thermal stability test is ◯ or more ○: Initial uniform surface luminescence is ○ and uniform surface luminescence after long-term thermal stability test is △ or more Δ: Uniform surface light emission after initial long-term thermal stability test Δ
×: Initial uniform surface light emission is × or uniform surface light emission after a long-term thermal stability test is ×
実施例の成形品は、初期の均一面発光性に優れ、且つ長期的な均一面発光性に優れていた。
The molded product of the example was excellent in initial uniform surface light emission and excellent in long-term uniform surface light emission.
本発明の光学用スチレン系樹脂組成物及び成形品は、初期の均一面発光性に優れ、且つ長期的な均一面発光性に優れることから、例えば、テレビ、デスクトップ型パーソナルコンピューター、ノート型パーソナルコンピューター、携帯電話機、カーナビゲーションなどの導光板用途で好適に用いることができる。
The optical styrenic resin composition and molded article of the present invention are excellent in initial uniform surface luminescence and long-term uniform surface luminescence, and thus, for example, televisions, desktop personal computers, notebook personal computers. It can be suitably used for light guide plate applications such as cellular phones and car navigation systems.
Claims (5)
- （ａ）スチレン系樹脂と、（ｂ）リン系酸化防止剤及び／又はフェノール系酸化防止剤と、（ｃ）アントラキノン系化合物を含み、
スチレン系樹脂組成物１００質量％中の前記（ｂ）の含有量は０．０２～１質量％であり、
樹脂成分全質量に対する前記（ｃ）の含有量は０．１～９０ｐｐｂであることを特徴とする光学用スチレン系樹脂組成物。 (A) a styrene resin, (b) a phosphorus antioxidant and / or a phenol antioxidant, and (c) an anthraquinone compound,
The content of (b) in 100% by mass of the styrene resin composition is 0.02 to 1% by mass,
An optical styrenic resin composition, wherein the content of (c) relative to the total mass of the resin component is 0.1 to 90 ppb. - 光路長１１５ｍｍでの波長３８０ｎｍ～７８０ｎｍの平均透過率が８０％以上であることを特徴とする請求項１に記載の光学用スチレン系樹脂組成物（但し前記平均透過率は、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行って得た１２７×１２７×３ｍｍ厚みの板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出しの端面をバフ研磨によって研磨し作成した端面に鏡面を有する試験片を用いて測定するものとする）。 The optical styrene resin composition according to claim 1, wherein an average transmittance at a wavelength of 380 nm to 780 nm at an optical path length of 115 mm is 80% or more (provided that the average transmittance is a cylinder temperature of 230 ° C, A test piece of 115 × 85 × 3 mm thickness was cut out from a 127 × 127 × 3 mm thick plate-shaped product obtained by injection molding at a mold temperature of 50 ° C., and the end surface was polished by buffing and mirrored on the end surface. It shall be measured using a test piece having
- 波長４８０ｎｍの透過率（ｔ４８０）と波長５８０ｎｍの透過率（ｔ５８０）の比率が、以下の関係であることを特徴とする請求項１又は請求項２に記載の光学用スチレン系樹脂組成物。
０．９６＜ｔ５８０／ｔ４８０＜１．０４ The optical styrene-based resin composition according to claim 1 or 2, wherein the ratio of the transmittance at a wavelength of 480 nm (t480) to the transmittance at a wavelength of 580 nm (t580) is as follows.
0.96 <t580 / t480 <1.04 - （ａ）スチレン系樹脂と、（ｂ）リン系酸化防止剤及び／又はフェノール系酸化防止剤と、（ｃ）アントラキノン系化合物を含み、
スチレン系樹脂組成物１００質量％中の前記（ｂ）の含有量は０．０２～１質量％であり、
光路長１１５ｍｍでの波長３８０ｎｍ～７８０ｎｍの平均透過率が８０％以上であり（但し前記平均透過率は、シリンダー温度２３０℃、金型温度５０℃にて射出成形を行って得た１２７×１２７×３ｍｍ厚みの板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出しの端面をバフ研磨によって研磨し作成した端面に鏡面を有する試験片を用いて測定するものとする）、
波長４８０ｎｍの透過率（ｔ４８０）と波長５８０ｎｍの透過率（ｔ５８０）の比率が、以下の関係であることを特徴とする光学用スチレン系樹脂組成物。
０．９６＜ｔ５８０／ｔ４８０＜１．０４ (A) a styrene resin, (b) a phosphorus antioxidant and / or a phenol antioxidant, and (c) an anthraquinone compound,
The content of (b) in 100% by mass of the styrene resin composition is 0.02 to 1% by mass,
The average transmittance at a wavelength of 380 nm to 780 nm at an optical path length of 115 mm is 80% or more (however, the average transmittance is 127 × 127 × obtained by injection molding at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. 115 mm x 85 mm x 3 mm thickness test piece cut out from a 3 mm thick plate-shaped molded article, and the end face of the cut end face polished by buffing shall be measured using a test piece having a mirror surface on the end face).
An optical styrene-based resin composition, wherein the ratio of the transmittance at a wavelength of 480 nm (t480) to the transmittance at a wavelength of 580 nm (t580) is as follows.
0.96 <t580 / t480 <1.04 - 請求項１～請求項４に記載の光学用スチレン系樹脂組成物からなる光学部品。 An optical component comprising the optical styrenic resin composition according to any one of claims 1 to 4.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5034340A (en) * | 1973-06-21 | 1975-04-02 | ||
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| WO2013151055A1 (en) * | 2012-04-02 | 2013-10-10 | Ｐｓジャパン株式会社 | Polystyrene-based resin composition and light guide plate formed by molding same |
| JP2014173034A (en) * | 2013-03-11 | 2014-09-22 | Ps Japan Corp | Polystyrene resin composition for light guide plate and light guide plate |
| JP2015195151A (en) * | 2014-03-31 | 2015-11-05 | Ｐｓジャパン株式会社 | light guide plate |
| WO2017188325A1 (en) * | 2016-04-28 | 2017-11-02 | 富士フイルム株式会社 | Composition, composition housing, and method for manufacturing composition |
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| JP6000978B2 (en) | 2011-12-20 | 2016-10-05 | 東洋スチレン株式会社 | Styrenic resin composition for optics, molded product and light guide plate |
| WO2014010137A1 (en) * | 2012-07-13 | 2014-01-16 | 東洋スチレン株式会社 | Styrene-based resin composition for optical applications, molded product, and light guide plate |
| JP6204726B2 (en) | 2013-07-09 | 2017-09-27 | 住化ケムテックス株式会社 | Blue light cut resin composition |
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2019
- 2019-02-26 WO PCT/JP2019/007240 patent/WO2019172015A1/en active Application Filing
- 2019-02-26 JP JP2020504939A patent/JP7229226B2/en active Active
- 2019-02-26 CN CN201980009841.XA patent/CN111655784B/en active Active
- 2019-02-26 KR KR1020207028242A patent/KR20200128551A/en not_active Application Discontinuation
- 2019-03-04 TW TW108107077A patent/TWI800610B/en active
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| JPS5034340A (en) * | 1973-06-21 | 1975-04-02 | ||
| JP2002012686A (en) * | 2000-06-29 | 2002-01-15 | Asahi Kasei Corp | Resin sheet or film |
| JP2002228830A (en) * | 2000-11-13 | 2002-08-14 | Orient Chem Ind Ltd | Colorant for laser light transmissive colored resin composition and its pertinent technique |
| JP2007224221A (en) * | 2006-02-27 | 2007-09-06 | Denki Kagaku Kogyo Kk | Optical molded item |
| JP2012149157A (en) * | 2011-01-19 | 2012-08-09 | Toyo Styrene Co Ltd | Styrene-based resin composition, plate-like molded article and light guide plate |
| JP2012149156A (en) * | 2011-01-19 | 2012-08-09 | Toyo Styrene Co Ltd | Styrene-based resin composition, plate-like molded article and light guide plate |
| JP2013082800A (en) * | 2011-10-07 | 2013-05-09 | Denki Kagaku Kogyo Kk | Styrenic resin composition for light guide, and light guide |
| WO2013151055A1 (en) * | 2012-04-02 | 2013-10-10 | Ｐｓジャパン株式会社 | Polystyrene-based resin composition and light guide plate formed by molding same |
| JP2014173034A (en) * | 2013-03-11 | 2014-09-22 | Ps Japan Corp | Polystyrene resin composition for light guide plate and light guide plate |
| JP2015195151A (en) * | 2014-03-31 | 2015-11-05 | Ｐｓジャパン株式会社 | light guide plate |
| WO2017188325A1 (en) * | 2016-04-28 | 2017-11-02 | 富士フイルム株式会社 | Composition, composition housing, and method for manufacturing composition |
Also Published As
| Publication number | Publication date |
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| KR20200128551A (en) | 2020-11-13 |
| TW201938673A (en) | 2019-10-01 |
| CN111655784A (en) | 2020-09-11 |
| TWI800610B (en) | 2023-05-01 |
| JP7229226B2 (en) | 2023-02-27 |
| CN111655784B (en) | 2023-04-28 |
| JPWO2019172015A1 (en) | 2021-02-18 |
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