TW201712064A - Styrene-based optical resin composition - Google Patents
Styrene-based optical resin composition Download PDFInfo
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Abstract
Description
本發明涉及能夠抑制因環境變化引起的白化現象的透明的苯乙烯系樹脂組成物。 The present invention relates to a transparent styrene resin composition capable of suppressing whitening caused by environmental changes.
對於苯乙烯系樹脂而言,具有優異的透明性、剛性、低吸水性、尺寸穩定性等特性,且成型加工性優異,因此通過注射成型、擠出成型、吹塑成型等各種成型方法,可廣泛用作電器產品和各種工業材料、食品包裝容器、雜貨等。另外,作為發揮透明性的用途,也可用於導光板等光學部件。 The styrene-based resin has excellent properties such as transparency, rigidity, low water absorbability, dimensional stability, and excellent moldability. Therefore, various molding methods such as injection molding, extrusion molding, and blow molding can be used. Widely used as electrical products and various industrial materials, food packaging containers, groceries, etc. Moreover, it can also be used for optical components, such as a light guide plate, as the use which exhibits transparency.
作為液晶顯示器的背光燈,存在著將光源配置於顯示裝置的正面的直下型背光模組和將光源配置於側面的側光(Light edge)型背光模組。導光板組裝於側光型背光模組上,將來自側面的光導至液晶面板而發揮作用,可在電視、桌上型個人電腦的顯示器、筆記型個人電腦、手機、汽車導航(car navigation)等廣泛用途中使用。導光板一直使用以PMMA(聚甲基丙烯酸甲酯)為代表的丙烯樹脂,但吸水性高,因此具有成型品發生彎曲的問題或尺寸發生變化的情況。 As a backlight of a liquid crystal display, there is a direct type backlight module in which a light source is disposed on a front surface of a display device, and a light edge type backlight module in which a light source is disposed on a side surface. The light guide plate is assembled on the edge light type backlight module, and the light from the side is guided to the liquid crystal panel to function, and can be used in a television, a desktop personal computer display, a notebook personal computer, a mobile phone, a car navigation, etc. Used in a wide range of applications. The propylene resin typified by PMMA (polymethyl methacrylate) has been used for the light guide plate, but the water absorbing property is high, so that the molded article may be bent or the size may be changed.
為此,提出使用改善了這些特性的作為苯乙烯和(甲基)丙烯酸甲酯的共聚物的MS樹脂。專利文獻1提出了MS樹脂的吸水性和成型時的變色降低等改良技術。 For this reason, an MS resin which is a copolymer of styrene and methyl (meth) acrylate which has improved these characteristics has been proposed. Patent Document 1 proposes an improved technique such as water absorption of an MS resin and reduction in discoloration during molding.
然而,專利文獻1中公開了苯乙烯-(甲基)丙烯酸酯系聚合物樹脂的重量平均分子量(Mw)6~17萬、殘餘單體量3000ppm以下、並且低聚物量2%以下的導光板,但其吸水性高,且尺寸穩定性不如以苯乙烯系單體為原料的苯乙烯系樹脂的傾向。 However, Patent Document 1 discloses a light guide plate having a weight average molecular weight (Mw) of 6 to 170,000, a residual monomer amount of 3,000 ppm or less, and an oligomer content of 2% or less of a styrene-(meth)acrylate polymer resin. However, it has high water absorbability and is inferior in dimensional stability to a styrene-based resin using a styrene-based monomer as a raw material.
另一方面,以苯乙烯系單體為原料的苯乙烯系樹脂的吸水性雖低,但苯乙烯系樹脂存在因溫度和濕度、溫水浸漬(非專利文獻1)等環境變化而使成型品發生白濁的問題(白化現象),作為優點的透明性根據用途的不同而被損壞。具體而言,成型品曝露於從高溫高濕環境變化為室溫環境,或者,從室溫環境變化為低溫環境的情況下,在苯乙烯系樹脂中均勻存在的水分變成不穩定而發生相分離從而生成圓盤狀的缺陷,其結果,成型品內部出現白濁的現象。另外,將苯乙烯系樹脂的成型品在熱水中浸漬規定時間以上之後,取出成型品時會發生白化,這也是因如同前述機理而產生的現象。 On the other hand, the styrene-based resin having a styrene-based monomer as a raw material has a low water absorption property, but the styrene-based resin has a molded product due to environmental changes such as temperature, humidity, and warm water immersion (Non-Patent Document 1). The problem of white turbidity (whitening phenomenon) occurs, and the transparency as an advantage is damaged depending on the use. Specifically, when the molded article is exposed to a high temperature and high humidity environment to a room temperature environment, or when the temperature changes from a room temperature environment to a low temperature environment, the water uniformly present in the styrene resin becomes unstable and phase separation occurs. As a result, a disk-shaped defect is generated, and as a result, white turbidity appears inside the molded article. In addition, when the molded article of the styrene resin is immersed in hot water for a predetermined period of time or more, whitening occurs when the molded article is taken out, which is also caused by the above mechanism.
如果成型品發生白濁,則如導光板這樣光路長的情況下,存在因光散射而使透射率大幅降低,顯示器的亮度下降的問題。 When the molded article is white turbid, if the optical path is long such as a light guide plate, there is a problem that the transmittance is largely lowered by light scattering, and the brightness of the display is lowered.
【專利文獻1】日本特開2003-075648號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-075648
【非專利文獻1】纖維學會雜誌,34卷,6號,245~253頁,1978年 [Non-Patent Document 1] Journal of the Fiber Society, Vol. 34, No. 6, pp. 245-253, 1978
本發明的課題在於提供抑制了因環境變化引起的白化現象的透明的苯乙烯系樹脂組成物。 An object of the present invention is to provide a transparent styrene resin composition that suppresses whitening caused by environmental changes.
根據本發明,提供一種光學用苯乙烯系樹脂組成物,其含有重量平均分子量為15萬~70萬的苯乙烯系樹脂和親水性添加劑,其中,所述親水性添加劑為選自環氧乙烷(ethylene oxide)的平均加成摩爾數為3~150的聚氧乙烯型表面活性劑和平均分子量為200~10000的聚乙二醇中的至少1種,HLB值為5~20,且在所述苯乙烯系樹脂組成物100質量%中的含量為0.4~2.0質量%。 According to the present invention, there is provided a styrene resin composition for optical use comprising a styrene resin having a weight average molecular weight of 150,000 to 700,000 and a hydrophilic additive, wherein the hydrophilic additive is selected from the group consisting of ethylene oxide. (ethylene oxide) having an average addition mole number of 3 to 150 polyoxyethylene surfactants and at least one of polyethylene glycol having an average molecular weight of 200 to 10,000, and an HLB value of 5 to 20, and The content in 100% by mass of the styrene resin composition is 0.4 to 2.0% by mass.
本發明的發明人等為了抑制因環境變化引起的白化現象而進行深入研究,首先瞭解到添加親水性添加劑對白化現象的抑制有效。可是,進一步進行研究 發現僅添加親水性並不能有效抑制白化現象。因此,進行進一步研究,結果可知:當(1)親水性添加劑具有特性的構成,(2)該HLB值為特定範圍內的值,且(3)該含量為特定範圍的量時,能夠維持苯乙烯系樹脂組成物的耐熱性的同時白化現象的抑制效果變得極高,並且也沒有損壞苯乙烯系樹脂的透明性。能得到這種效果的作用效果尚不明確,但是只有在上述3個條件齊全的情況下才能夠有效發揮,因此可以認為是由於這3個條件引起的相乘效果。 The inventors of the present invention have conducted intensive studies to suppress the whitening phenomenon caused by environmental changes. First, it has been found that the addition of a hydrophilic additive is effective for suppressing the whitening phenomenon. However, further research It was found that the addition of only hydrophilicity did not effectively inhibit whitening. Therefore, further studies have revealed that (1) the hydrophilic additive has a characteristic configuration, (2) the HLB value is a value within a specific range, and (3) the content is a specific range, and benzene can be maintained. The effect of suppressing the whitening phenomenon of the heat resistance of the ethylene-based resin composition is extremely high, and the transparency of the styrene-based resin is not impaired. The effect of obtaining such an effect is not clear, but it can be effectively exerted only when the above three conditions are complete, and therefore it can be considered that the multiplication effect due to these three conditions.
以下,例示本發明的各種實施方式。 Hereinafter, various embodiments of the present invention will be exemplified.
優選的,所述親水性添加劑是環氧乙烷的平均加成摩爾數為10~60的聚氧乙烯型表面活性劑,且在所述苯乙烯系樹脂組成物100質量%中的含量是0.6~1.4質量%。 Preferably, the hydrophilic additive is a polyoxyethylene type surfactant having an average addition mole number of ethylene oxide of 10 to 60, and the content in the 100% by mass of the styrene resin composition is 0.6. ~1.4% by mass.
優選的,所述親水性添加劑是環氧乙烷的平均加成摩爾數為13~35的聚氧乙烯型表面活性劑,且在所述苯乙烯系樹脂組成物100質量%中的含量是0.6~0.9質量%。 Preferably, the hydrophilic additive is a polyoxyethylene type surfactant having an average addition mole number of ethylene oxide of 13 to 35, and the content in the 100% by mass of the styrene resin composition is 0.6. ~0.9% by mass.
優選的,所述親水性添加劑的HLB值為10~18。 Preferably, the hydrophilic additive has an HLB value of 10-18.
優選的,所述聚氧乙烯型表面活性劑是聚氧乙烯型非離子性表面活性劑。 Preferably, the polyoxyethylene type surfactant is a polyoxyethylene type nonionic surfactant.
優選的,聚氧乙烯型非離子性表面活性劑是選自下述通式(1)表示的聚氧乙烯烷基醚和/或以下述通式(2)表示的聚氧乙烯脂肪酸酯中的1種以上。 Preferably, the polyoxyethylene type nonionic surfactant is selected from the group consisting of polyoxyethylene alkyl ethers represented by the following formula (1) and/or polyoxyethylene fatty acid esters represented by the following formula (2). One or more.
(式中,R表示碳原子數8~20的烷基。另外,可以是具有多個聚氧乙烯烷 基醚骨架的6價為止的多價聚氧乙烯烷基醚、具有多個聚氧乙烯脂肪酸酯骨架的6價為止的多價聚氧乙烯脂肪酸酯。n為整數且表示環氧乙烷單元的加成摩爾數。) (wherein R represents an alkyl group having 8 to 20 carbon atoms. Further, it may have a plurality of polyoxyethylene oxides A polyvalent polyoxyethylene alkyl ether having a valence of about 6 valences of a group ether skeleton, and a valence polyvalent polyoxyethylene fatty acid ester having a plurality of polyoxyethylene fatty acid ester skeletons. n is an integer and represents the number of moles of addition of the ethylene oxide unit. )
優選的,所述親水性添加劑是平均分子量為200~10000的聚乙二醇,且在所述苯乙烯系樹脂組成物100質量%中的含量為0.6~1.4質量%。 Preferably, the hydrophilic additive is polyethylene glycol having an average molecular weight of 200 to 10,000, and the content in the 100% by mass of the styrene resin composition is 0.6 to 1.4% by mass.
優選的,所述親水性添加劑是平均分子量為200~1800的聚乙二醇。 Preferably, the hydrophilic additive is polyethylene glycol having an average molecular weight of 200 to 1800.
優選的,所述親水性添加劑在所述苯乙烯系樹脂組成物100質量%中的含量是0.6~0.9質量%。 Preferably, the content of the hydrophilic additive in 100% by mass of the styrene resin composition is 0.6 to 0.9% by mass.
另外,所述苯乙烯系樹脂是將苯乙烯系單體和(甲基)丙烯酸共聚而得的苯乙烯-(甲基)丙烯酸共聚樹脂,苯乙烯系樹脂的苯乙烯系單體單元的含量為90.0~99.9質量%、(甲基)丙烯酸單元的含量為0.1~10.0質量%。其中,苯乙烯系樹脂的苯乙烯系單體單元和(甲基)丙烯酸單元的含量的總計為100質量%。 Further, the styrene resin is a styrene-(meth)acrylic copolymer resin obtained by copolymerizing a styrene monomer and (meth)acrylic acid, and the content of the styrene monomer unit of the styrene resin is The content of the (meth)acrylic acid unit is from 0.10 to 99.9% by mass and the content of the (meth)acrylic acid unit is from 0.1 to 10.0% by mass. The total content of the styrene monomer unit and the (meth)acrylic acid unit of the styrene resin is 100% by mass.
另外,所述苯乙烯系樹脂是將苯乙烯系單體和(甲基)丙烯酸共聚而得的苯乙烯-(甲基)丙烯酸共聚樹脂,苯乙烯系樹脂的苯乙烯系單體單元的含量為40.0~99.0質量%、(甲基)丙烯酸單元的含量為1.0~60.0質量%。其中,苯乙烯系樹脂的苯乙烯系單體單元和(甲基)丙烯酸單元的含量的總計為100質量%。 Further, the styrene resin is a styrene-(meth)acrylic copolymer resin obtained by copolymerizing a styrene monomer and (meth)acrylic acid, and the content of the styrene monomer unit of the styrene resin is 40.0 to 99.0% by mass and the content of the (meth)acrylic acid unit is 1.0 to 60.0% by mass. The total content of the styrene monomer unit and the (meth)acrylic acid unit of the styrene resin is 100% by mass.
另外,還含有6-〔3-(3-三級丁基-4-羥基-5-甲基苯基)丙氧基〕-2,4,8,10-四-三級丁基苯並〔d,f〕〔1,3,2〕二氧磷雜環庚烷(6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin)。 In addition, it also contains 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butylbenzo[ d,f][1,3,2]6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10- Tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin).
另外,含有磷系抗氧化劑及/或受阻酚(hindered phenol)系抗氧化劑。 Further, it contains a phosphorus-based antioxidant and/or a hindered phenol-based antioxidant.
另外,一種成型品,由上述光學用苯乙烯系樹脂組成物構成。 Further, a molded article is composed of the above-mentioned optical styrene resin composition.
另外,一種導光板,由上述的成型品構成。 Further, a light guide plate is composed of the above-mentioned molded article.
本發明的苯乙烯系樹脂組成物相較於PMMA或MS樹脂,其吸水性低且廉價,不產生作為苯乙烯系樹脂的缺點的因環境變化而引起的白化現象,無色透明性優異,所以能夠適用於發揮苯乙烯系樹脂本身的透明性的用途。 The styrene resin composition of the present invention has low water absorption and low cost compared to PMMA or MS resin, and does not cause whitening due to environmental changes as a disadvantage of the styrene resin, and is excellent in colorless transparency. It is suitable for use in the transparency of the styrene resin itself.
以下,對本發明的實施方式進行詳細說明。 Hereinafter, embodiments of the present invention will be described in detail.
本發明的苯乙烯系樹脂可聚合苯乙烯系單體而得到。苯乙烯系單體是指,作為芳香族乙烯基系單體的苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯等的單獨或2種以上的混合物,優選是苯乙烯。另外,在不影響本發明特徵的範圍內可以與苯乙烯系單體進行共聚,可舉出丙烯酸、甲基丙烯酸等丙烯酸單體,丙烯腈、甲基丙烯腈等氰化乙烯基單體,丙烯酸丁酯、丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯等丙烯酸系單體或馬來酸酐、富馬酸等α,β-乙烯不飽和羧酸類,苯基馬來醯亞胺、環己基馬來醯亞胺等醯亞胺系單體類。 The styrene resin of the present invention can be obtained by polymerizing a styrene monomer. The styrene-based monomer is preferably a single or a mixture of two or more of styrene, α-methylstyrene, o-methylstyrene, and p-methylstyrene as the aromatic vinyl monomer. Styrene. Further, the styrene-based monomer may be copolymerized in a range that does not impair the characteristics of the present invention, and examples thereof include an acrylic monomer such as acrylic acid or methacrylic acid, a vinyl cyanide monomer such as acrylonitrile or methacrylonitrile, and acrylic acid. Acrylic monomer such as butyl ester, ethyl acrylate, methyl acrylate or methyl methacrylate; α,β-ethylene unsaturated carboxylic acid such as maleic anhydride or fumaric acid, phenyl maleimide or cyclohexyl A quinone imine monomer such as maleimide.
苯乙烯系樹脂組成物由苯乙烯系樹脂和各種添加劑構成為佳,在苯乙烯系樹脂組成物100質量%中的苯乙烯系樹脂的比例可以為90~99.6質量%,優選為95~99.6質量%。作為苯乙烯系樹脂的比例,具體而言,例如為90、91、92、93、94、95、96、97、98、99、99.6質量%,也可以為在此所例示數值中的任意2個數值範圍之內。 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 may be 90 to 99.6% by mass, preferably 95 to 99.6. %. Specifically, the ratio of the styrene-based resin is, for example, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 99.6 mass%, and may be any of the numerical values exemplified herein. Within a range of values.
作為苯乙烯系樹脂,將苯乙烯系單體和(甲基)丙烯酸共聚而得的苯乙烯-(甲基)丙烯酸共聚樹脂時,苯乙烯系樹脂的苯乙烯系單體單元的含量為90.0~99.9質量%,(甲基)丙烯酸單元的含量為0.1~10.0質量%為佳。其中,苯乙烯系單體單元和(甲基)丙烯酸單元的含量的總計為100質量%。(甲基)丙烯酸是指,丙烯酸、甲基丙烯酸等,在此優選為甲基丙烯酸。 When the styrene-based (meth)acrylic copolymer resin obtained by copolymerizing a styrene-based monomer and (meth)acrylic acid is used as the styrene-based resin, the content of the styrene-based monomer unit of the styrene-based resin is 90.0~ The content of the (meth)acrylic acid unit is preferably from 0.1 to 10.0% by mass based on 99.9% by mass. Here, the total content of the styrene monomer unit and the (meth)acrylic unit is 100% by mass. (Meth)acrylic acid means acrylic acid, methacrylic acid, etc., and methacrylic acid is preferable here.
苯乙烯系樹脂中的(甲基)丙烯酸單元含量的測定是在室溫下實施。稱量0.5g的苯乙烯系樹脂,並溶解在甲苯/乙醇=8/2(體積比)的混合溶液後,用0.1mo1/L的氫氧化鉀乙醇溶液進行中和滴定,檢測終點,根據氫氧化鉀乙醇溶液的使用量,計算(甲基)丙烯酸單元的質量基準的含量。在此,可使用電位差自動滴定裝置,利用京都電子工業株式會社製AT-510進行測定。苯乙烯系樹脂中的(甲基)丙烯酸單元的含量可通過苯乙烯系樹脂聚合時的原料即苯乙烯系單體和(甲基)丙烯酸單體的組成比進行調整,但也可以在相溶的範圍內混合含有(甲基)丙烯酸單元的苯乙烯系樹脂和不含有(甲基)丙烯酸單元的苯乙烯系樹脂來進行調整。 The measurement of the (meth)acrylic acid unit content in the styrene resin was carried out at room temperature. 0.5 g of a styrene-based resin was weighed and dissolved in a mixed solution of toluene/ethanol = 8/2 (volume ratio), and then neutralized and titrated with a 0.1 mol/L potassium hydroxide ethanol solution to determine the end point, according to hydrogen. The amount of the potassium oxide ethanol solution used was calculated from the mass basis of the (meth)acrylic acid unit. Here, the measurement can be performed by using an electric potential automatic titrator and using AT-510 manufactured by Kyoto Electronics Industry Co., Ltd. The content of the (meth)acrylic acid unit in the styrene resin can be adjusted by the composition ratio of the styrene monomer and the (meth)acrylic monomer which are raw materials in the polymerization of the styrene resin, but it is also compatible. The styrene resin containing a (meth)acrylic acid unit and the styrene-based resin containing no (meth)acrylic acid unit were mixed in the range of adjustment.
作為苯乙烯系樹脂,將苯乙烯系單體和(甲基)丙烯酸酯共聚而得的苯乙烯-(甲基)丙烯酸酯共聚樹脂時,優選的苯乙烯系樹脂的苯乙烯系單體單元的含量為40.0~99.0質量%,(甲基)丙烯酸酯單元的含量為1.0~60.0質量%。其中,苯乙烯系單體單元和(甲基)丙烯酸酯單元的含量的總計為100質量%。(甲基)丙烯酸酯是,甲基丙烯酸甲酯、甲基丙烯酸乙酯等甲基丙烯酸酯,丙烯酸甲酯、丙烯酸乙酯等的丙烯酸酯等。 When a styrene-based (meth) acrylate copolymer resin obtained by copolymerizing a styrene-based monomer and a (meth) acrylate is used as the styrene-based resin, a styrene-based monomer unit of a styrene-based resin is preferable. The content is 40.0 to 99.0% by mass, and the content of the (meth) acrylate unit is 1.0 to 60.0% by mass. Here, the total content of the styrene monomer unit and the (meth) acrylate unit is 100% by mass. The (meth) acrylate is a methacrylate such as methyl methacrylate or ethyl methacrylate, or an acrylate such as methyl acrylate or ethyl acrylate.
苯乙烯系樹脂中的(甲基)丙烯酸酯單元的含量可利用熱裂解氣相色譜儀按以下條件進行測定。 The content of the (meth) acrylate unit in the styrene resin can be measured by a pyrolysis gas chromatograph under the following conditions.
熱解爐:PYR-2A(株式會社島津製作所製) Pyrolysis furnace: PYR-2A (made by Shimadzu Corporation)
熱解爐溫度設定:525℃ Pyrolysis furnace temperature setting: 525 ° C
氣象色譜儀:GC-14A(株式會社島津製作所製) Gas Chromatograph: GC-14A (made by Shimadzu Corporation)
柱:玻璃製3mm徑×3m Column: 3mm diameter × 3m made of glass
填充劑:FFAP Chromsorb WAW 10% Filler: FFAP Chromsorb WAW 10%
注射、檢測器溫度:250℃ Injection, detector temperature: 250 ° C
柱溫:120℃ Column temperature: 120 ° C
載氣:氮 Carrier gas: nitrogen
作為苯乙烯系樹脂的聚合方法,可舉出塊狀聚合法、溶液聚合法、懸浮聚合法、乳化聚合法等公知的苯乙烯聚合方法。考慮到品質和生產率,塊狀聚合法、溶液聚合法為佳,優選連續聚合。作為溶劑例如可使用苯、甲苯、乙苯以及二甲苯等烷基苯類,丙酮、甲基乙基酮等酮類,己烷、環己烷等脂肪族烴 等。 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 view of quality and productivity, a bulk polymerization method or a solution polymerization method is preferred, and continuous polymerization is preferred. 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. Wait.
苯乙烯系樹脂聚合時,可根據需要使用聚合引發劑、鏈轉移劑。作為聚合引發劑,自由基聚合引發劑為佳,可舉出公知慣用的物質,例如,1,1-二(三級丁基過氧基)環己烷(1,1-di(t-butylperoxy)cyclohexane)、2,2-二(三級丁基過氧基)丁烷(2,2-di(t-butylperoxy)butane)、2,2-二(4,4-二-三級丁基過氧基環己基)丙烷(2,2-di(4,4-di-t-butyl peroxy cyclohexyl)propane)、1,1-二(叔戊基過氧基)環己烷(1,1-di(t-amyl peroxy)cyclohexane)等過氧基縮酮類,過氧化氫異丙苯(Cumene hydroperoxide),過氧化叔丁醇(t-butyl hydroperoxide)等氫過氧化物(Hydroperoxide)類,過氧乙酸叔丁酯(t-Butyl peroxyacetate)、叔戊基過氧基異壬酸酯(t-amyl(peroxy isononanoate))等烷基過氧化物(Alkyl peroxide)類,過氧化三級丁基異丙苯(t-butyl cumyl peroxide)、過氧化二叔丁酯(Di-t-butyl peroxide)、過氧化二異丙苯(Dicumyl peroxide)、過氧化二叔己酯(Di-t-hexyl peroxide)等過氧化二烷基酯類,過氧乙酸叔丁酯(t-butylperoxy acetate)、三級丁基過氧苯甲酸酯(t-butyl peroxybenzoate)、三級丁基過氧異丙基單碳酸酯(t-butyl peroxyisopropylmonocarbonate)等過氧酯類,三級丁基過氧異丙基碳酸酯(t-butylperoxy isopropyl carbonate)、聚醚四(三級丁基過氧基碳酸酯)(Polyether tetrakis(t-butyl peroxy carbonate))等過氧碳酸酯類,N,N’-偶氮雙(環己烷-1-甲腈)(N,N’-azobis(cyclohexane-1-carbonitrile))、N,N’-偶氮雙(2-甲基丁腈)(N,N’-azobis(2-methyl butyronitrile))、N,N’-偶氮雙(2,4-二甲基戊腈)(N,N’-azobis(2,4- dimethyl valeronitrile))、N,N’-偶氮雙〔2-(羥基甲基)丙腈〕(N,N’-azobis[2-(hydroxymethyl)propionitrile])等,可使用這些中的1種或組合2種以上使用。作為鏈轉移劑可舉出,脂肪族硫醇、芳香族硫醇、五苯基乙烷、α-甲基苯乙烯二聚體以及異松油烯(Terpinolene)等。 When the styrene resin is polymerized, a polymerization initiator or a chain transfer agent may be used as needed. As the polymerization initiator, a radical polymerization initiator is preferred, and a conventionally known one may be mentioned, for example, 1,1-di(tri-butylperoxy)cyclohexane (1,1-di(t-butylperoxy). Cyclohexane), 2,2-di(t-butylperoxy)butane, 2,2-di(4,4-di-tertiary butyl) 1,2-di(4,4-di-t-butyl peroxy cyclohexylpropane), 1,1-di(tert-amylperoxy)cyclohexane (1,1- Hydroperoxides such as di(t-amyl peroxy)cyclohexane), hydroperoxides such as Cumene hydroperoxide and t-butyl hydroperoxide, Alkyl peroxides such as t-Butyl peroxyacetate and t-amyl (peroxy isononanoate), tertiary butyl peroxide T-butyl cumyl peroxide, Di-t-butyl peroxide, Dicumyl peroxide, Di-t-hexyl peroxide Such as dialkyl peroxides, t-butylperoxy acetate, tertiary butyl peroxygen Peroxy esters such as t-butyl peroxybenzoate, t-butyl peroxyisopropylmonocarbonate, t-butylperoxy isopropyl Peroxycarbonate such as carbonate, polyether tetrakis (t-butyl peroxy carbonate), N,N'-azobis(cyclohexane-1- N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylbutyronitrile), N,N'-azobis(2,4-dimethylvaleronitrile) (N,N'-azobis(2,4- Dimethyl valeronitrile)), N,N'-azobis[2-(hydroxymethyl)propionitrile], etc., one of these or Two or more types are used in combination. The chain transfer agent may, for example, be an aliphatic thiol, an aromatic thiol, pentaphenylethane, an α-methylstyrene dimer or a terpinolene.
進行連續聚合時,首先用聚合步驟採用公知的完全混合槽型攪拌槽或塔型反應器等,為了達到目標分子量、分子量分佈、反應轉化率而通過調節聚合溫度等控制聚合反應。將含有經聚合步驟的聚合物的聚合溶液移送至脫揮步驟,除去未反應的單體和聚合溶劑。脫揮步驟由帶有加熱器的真空脫揮槽和帶有排氣孔的脫揮擠出機等構成。將經脫揮步驟的熔融狀態的聚合物移送至造粒步驟。造粒步驟中,從多孔模頭將熔融樹脂擠出成繩股狀,通過***方式、空中熱切割方式、水中熱切割方式加工成顆粒形狀。 In the case of the continuous polymerization, the polymerization reaction is first controlled by a polymerization step by adjusting the polymerization temperature or the like in order to achieve the target molecular weight, the molecular weight distribution, and the reaction conversion rate by using a known fully mixed tank type stirred tank or a column type reactor. The polymerization solution containing the polymer of the polymerization step is transferred to a devolatilization step to remove unreacted monomers and a polymerization solvent. The devolatilization step is constituted by a vacuum devolatilization tank with a heater, a devolatilizing extruder with a vent hole, and the like. The molten state polymer in the devolatilization step is transferred to the granulation step. In the granulation step, the molten resin is extruded into a strand shape from a porous die, and processed into a pellet shape by a cold solution method, an air thermal cutting method, or an underwater hot cutting method.
本發明的苯乙烯系樹脂的重量平均分子量為15萬~70萬,18萬~50萬為佳。如果小於15萬,則成型品的強度變得不足,如果超過70萬則成型性顯著降低。苯乙烯系樹脂的重量平均分子量可通過聚合步驟的反應溫度、滯留時間、聚合引發劑的種類以及添加量、鏈轉移劑的種類以及添加量、聚合時使用的溶劑的種類以及量等來控制。 The styrene resin of the present invention has a weight average molecular weight of 150,000 to 700,000 and preferably 180,000 to 500,000. If it is less than 150,000, the strength of the molded article becomes insufficient, and if it exceeds 700,000, the moldability is remarkably lowered. The weight average molecular weight of the styrene resin can be controlled by the reaction temperature in the polymerization step, the residence time, the type and amount of the polymerization initiator, the type and amount of the chain transfer agent, the type and amount of the solvent used in the polymerization, and the like.
至於重量平均分子量(Mw)及Z平均分子量(Mz)、數平均分子量(Mn),使用凝膠滲透色譜法(GPC)並按以下條件測定。 The weight average molecular weight (Mw), the Z average molecular weight (Mz), and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
GPC儀種類:昭和電工株式會社製Shodex GPC-101 GPC type: Shodex GPC-101, manufactured by Showa Denko Co., Ltd.
柱:聚合物實驗室公司製PLgel 10μm MIXED-B Column: PLgel 10μm MIXED-B manufactured by Polymer Labs
移動相:四氫呋喃 Mobile phase: tetrahydrofuran
試樣濃度:0.2質量% Sample concentration: 0.2% by mass
溫度:爐溫40℃,注入口35℃,檢測器35℃ Temperature: furnace temperature 40 ° C, injection port 35 ° C, detector 35 ° C
檢測器:示差折射計 Detector: differential refractometer
本發明的分子量是基於單分散聚苯乙烯的溶出曲線計算各溶出時間的分子量且作為以聚苯乙烯換算的分子量來計算而得的值。 The molecular weight of the present invention is a value calculated by calculating the molecular weight of each elution time based on the dissolution profile of monodisperse polystyrene and calculating the molecular weight in terms of polystyrene.
親水性添加劑是指,具有能夠與水相互作用(氫鍵)的親水基團的化合物。親水基團優選為聚醚鏈。聚醚鏈是醚鍵相連而成的骨架結構,例如可舉出通過環氧乙烷(以下有時記載為E0)、環氧丙烷、環氧丁烷等環氧烷烴的加成反應而合成的聚氧乙烯鏈、聚氧丙烯鏈、聚氧丁烯鏈,或者通過甘油的脫水縮合等合成的聚丙三醇鏈,聚氧乙烯鏈為佳。聚醚鏈在1分子中可以有1組,也可以有多組。 The hydrophilic additive refers to a compound having a hydrophilic group capable of interacting (hydrogen bonding) with water. The hydrophilic group is preferably a polyether chain. The polyether chain is a skeleton structure in which an ether bond is bonded, and is, for example, synthesized by an addition reaction of an alkylene oxide such as ethylene oxide (hereinafter sometimes referred to as E0), propylene oxide or butylene oxide. A polyoxyethylene chain, a polyoxypropylene chain, a polyoxybutylene chain, or a polyglycerol chain synthesized by dehydration condensation of glycerin or the like, preferably a polyoxyethylene chain. The polyether chain may have one group or more groups in one molecule.
這樣的各種親水性添加劑之中,在本發明中,添加選自環氧乙烷的平均加成摩爾數為3~150的聚氧乙烯型表面活性劑和平均分子量200~10000的聚乙二醇中的至少1種。為了提高白化現象的抑制效果,發現在試驗中必須使用這樣的特定構成的親水性添加劑。 Among the various hydrophilic additives, in the present invention, a polyoxyethylene surfactant selected from the group consisting of ethylene oxide having an average addition mole number of 3 to 150 and a polyethylene glycol having an average molecular weight of 200 to 10,000 are added. At least one of them. In order to improve the inhibitory effect of the whitening phenomenon, it has been found that such a specific composition of a hydrophilic additive must be used in the test.
另外,親水性添加劑的HLB值為5~20。為了提高白化現象的抑制效果,發現在試驗中必須使用這樣的具有特定HLB值的親水性添加劑。HLB值優選為8 ~20,更優選為10~20,最優選為10~18。HLB(Hydrophilic-lipophilic blance)值是表示添加劑的親水性的值,HLB值如果為8~10則在水中穩定分散,如果超過10則從具有透明感的分散狀態變為呈透明地完全溶解的狀態。在具有聚醚鏈的非離子性表面活性劑中利用HLB值=(親水基團部分的分子量)/(添加劑的分子量)×20來進行計算,不含有親水基團的烷烴這樣的親水性添加劑HLB值=0,對於僅具有親水基團的聚乙二醇,HLB值=20,對於非離子性表面活性劑HLB值為0~20之間。 Further, the hydrophilic additive has an HLB value of 5 to 20. In order to enhance the inhibitory effect of the whitening phenomenon, it was found that such a hydrophilic additive having a specific HLB value must be used in the test. The HLB value is preferably 8 ~20, more preferably 10-20, most preferably 10-18. The HLB (Hydrophilic-lipophilic blance) value is a value indicating the hydrophilicity of the additive, and if the HLB value is 8 to 10, it is stably dispersed in water, and if it exceeds 10, it is changed from a dispersed state having a transparent feeling to a state of being completely transparent and transparent. . In the nonionic surfactant having a polyether chain, the HLB value = (molecular weight of the hydrophilic group portion) / (molecular weight of the additive) × 20 is calculated, and the hydrophilic additive HLB such as an alkane having no hydrophilic group is calculated. The value is 0. For polyethylene glycol having only a hydrophilic group, the HLB value is 20, and for the nonionic surfactant, the HLB value is between 0 and 20.
親水性添加劑以使在苯乙烯系樹脂組成物100質量%中的含量為0.4~2.0質量%的方式添加。為了維持苯乙烯系樹脂組成物的耐熱性同時提高白化現象的抑制效果,發現實驗室需要以成為這樣的含量的方式進行添加。在苯乙烯系樹脂組成物100質量%中的親水性添加劑的含量優選為0.7~1.6質量%或0.6~1.4質量%,進一步優選為0.6~0.9質量%。 The hydrophilic additive is added so that the content in the 100% by mass of the styrene resin composition is 0.4 to 2.0% by mass. In order to maintain the heat resistance of the styrene resin composition and to suppress the whitening phenomenon, it has been found that the laboratory needs to be added in such a manner. The content of the hydrophilic additive in 100% by mass of the styrene resin composition is preferably 0.7 to 1.6% by mass or 0.6 to 1.4% by mass, and more preferably 0.6 to 0.9% by mass.
親水性添加劑在溫度200℃、氮氣環境下的加熱損失為10質量%以下為佳。在溫度200℃、氮氣環境氣下的加熱損失可利用熱重量分析(TGA)求得,在氮氣環境下從室溫狀態以10℃/分鐘的升溫速度加熱,由溫度200℃下的重量損失量求得。在溫度200℃、氮氣環境下的加熱損失超過10質量%的添加劑,其揮發性高、在苯乙烯系樹脂的成型加工時產生氣體,有可能使模具、輥受到污染。 The heat loss of the hydrophilic additive at a temperature of 200 ° C and a nitrogen atmosphere is preferably 10% by mass or less. The heating loss at a temperature of 200 ° C under a nitrogen atmosphere can be obtained by thermogravimetric analysis (TGA), and is heated from a room temperature state at a temperature increase rate of 10 ° C / min under a nitrogen atmosphere, and a weight loss at a temperature of 200 ° C. Seek. The additive having a heating loss of more than 10% by mass in a nitrogen atmosphere at a temperature of 200 ° C has high volatility and generates gas during molding processing of the styrene resin, which may contaminate the mold and the roll.
作為親水性添加劑的添加方法,沒有特別限定,可舉出利用苯乙烯系樹脂 的聚合步驟、脫揮步驟、造粒步驟添加混合的方法;利用成型加工時的擠出機等添加混合的方法;通過無添加的苯乙烯系樹脂將調整為高濃度的親水性添加劑的樹脂組成物稀釋混合成目標含量的方法等。 The method of adding the hydrophilic additive is not particularly limited, and examples thereof include styrene resin. a polymerization step, a devolatilization step, a granulation step, a method of adding a mixture; a method of adding and mixing by an extruder or the like at the time of molding processing; and a resin composition adjusted to a high concentration of a hydrophilic additive by a styrene-based resin without addition A method in which the substance is diluted and mixed into a target content.
例如可舉出將含有0.5~50.0質量%的親水性添加劑的苯乙烯系樹脂組成物和無添加的苯乙烯系樹脂利用擠出機或注射成型機而混合,得到目標濃度的苯乙烯系樹脂組成物、成型品、導光板的方法。 For example, a styrene resin composition containing 0.5 to 50.0% by mass of a hydrophilic additive and a non-added styrene resin are mixed by an extruder or an injection molding machine to obtain a styrene resin having a target concentration. The method of the object, the molded article, and the light guide plate.
作為聚氧乙烯型表面活性劑,可舉出聚氧乙烯型非離子性表面活性劑、聚氧乙烯型陰離子性表面活性劑、聚氧乙烯型陽離子性表面活性劑、聚氧乙烯型兩性表面活性劑等,聚氧乙烯型非離子性表面活性劑為佳。 Examples of the polyoxyethylene type surfactant include a polyoxyethylene type nonionic surfactant, a polyoxyethylene type anionic surfactant, a polyoxyethylene type cationic surfactant, and a polyoxyethylene type amphoteric surface active agent. A polyoxyethylene type nonionic surfactant is preferred as the agent.
聚氧乙烯型非離子性表面活性劑可舉出下述通式(1)表示的聚氧乙烯烷基醚或下述通式(2)表示的聚氧乙烯脂肪酸酯、聚氧乙烯固化蓖麻油,聚氧乙烯山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯,但選自聚氧乙烯烷基醚和/或聚氧乙烯脂肪酸酯中的1種以上為佳。另外,即便使用在一分子中具有多個聚氧乙烯烷基醚骨架的多價聚氧乙烯烷基醚或在一分子中具有多個聚氧乙烯脂肪酸酯骨架的多價聚氧乙烯脂肪酸酯也能夠實現本發明的目的。聚氧乙烯烷基醚、聚氧乙烯脂肪酸酯的價數是指,在一分子中存在的聚氧乙烯烷基醚骨架或聚氧乙烯脂肪酸酯骨架的數量。 The polyoxyethylene type nonionic surfactant may, for example, be a polyoxyethylene alkyl ether represented by the following formula (1) or a polyoxyethylene fatty acid ester represented by the following formula (2) or a polyoxyethylene cured product. The sesame oil, the polyoxyethylene sorbitan fatty acid ester, and the polyoxyethylene sorbitan fatty acid ester are preferably one or more selected from the group consisting of polyoxyethylene alkyl ethers and/or polyoxyethylene fatty acid esters. Further, even a polyvalent polyoxyethylene alkyl ether having a plurality of polyoxyethylene alkyl ether skeletons in one molecule or a polyvalent polyoxyethylene fatty acid having a plurality of polyoxyethylene fatty acid ester skeletons in one molecule is used. Esters can also achieve the objects of the present invention. The valence of the polyoxyethylene alkyl ether and the polyoxyethylene fatty acid ester means the number of the polyoxyethylene alkyl ether skeleton or the polyoxyethylene fatty acid ester skeleton present in one molecule.
(式中,R表示碳原子數8~20的烷基。另外,可以是具有多個6價為止的聚氧乙烯烷基醚骨架的多價聚氧乙烯烷基醚,也可以是具有多個6價為止的聚氧乙烯脂肪酸酯骨架的多價聚氧乙烯脂肪酸酯。N為整數且表示環氧乙烷單元的加成摩爾數。) (In the formula, R represents an alkyl group having 8 to 20 carbon atoms. Further, it may be a polyvalent polyoxyethylene alkyl ether having a plurality of polyoxyethylene alkyl ether skeletons having a hexavalent number, or may have a plurality of A polyvalent polyoxyethylene fatty acid ester of a polyoxyethylene fatty acid ester skeleton having a valence of six. N is an integer and represents the number of moles of addition of an ethylene oxide unit.
聚氧乙烯烷基醚是使環氧乙烷與醇加成而得,聚氧乙烯脂肪酸酯是使環氧乙烷與脂肪酸加成或使脂肪酸和聚乙二醇直接酯化而得,環氧乙烷的平均加成摩爾數為3~150。為了提高白化現象的抑制效果,從實驗結果可知需要使平均加成摩爾數在這樣的特定範圍內。平均加成摩爾數優選為7~100,進一步優選為10~60,更優選為10~50,最優選為13~35。 Polyoxyethylene alkyl ether is obtained by adding ethylene oxide and alcohol, and polyoxyethylene fatty acid ester is obtained by adding ethylene oxide with fatty acid or directly esterifying fatty acid and polyethylene glycol. The average addition mole number of oxyethane is from 3 to 150. In order to improve the inhibitory effect of the whitening phenomenon, it is understood from the experimental results that the average addition mole number is required to be within such a specific range. The average addition mole number is preferably from 7 to 100, more preferably from 10 to 60, still more preferably from 10 to 50, most preferably from 13 to 35.
作為本發明的聚氧乙烯型表面活性劑,具體而言例如可舉出,十二烷基聚氧乙烯醚、十六烷基聚氧乙烯醚、十八烷基聚氧乙烯醚、辛基十二烷基聚氧乙烯醚、十四烷基聚氧乙烯醚、2-乙基己基聚氧乙烯醚等烷基聚氧乙烯醚,聚氧乙烯山梨糖醇酐單月桂酸酯、聚氧乙烯山梨糖醇酐三硬脂酸等的聚氧乙烯山梨糖醇酐脂肪酸酯,聚氧乙烯山梨糖醇四油酸酯等的聚氧乙烯山梨糖醇脂肪酸酯,聚乙二醇單月桂酸酯、聚乙二醇單硬脂酸酯、聚乙二醇二硬脂酸酯、聚乙二醇單油酸酯等的聚氧乙烯脂肪酸酯,聚氧乙烯固化蓖麻油、聚氧乙烯單甲基醚、聚氧乙烯二甲基醚、聚氧乙烯甘油醚、聚氧乙烯四油酸酯、聚氧乙烯三異硬脂酸酯、聚氧乙烯椰子脂肪酸甘油酯等。 Specific examples of the polyoxyethylene surfactant of the present invention include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, octadecyl polyoxyethylene ether, and octyl ten. Alkyl polyoxyethylene ether such as dialkyl polyoxyethylene ether, tetradecyl polyoxyethylene ether or 2-ethylhexyl polyoxyethylene ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbent Polyoxyethylene sorbitan fatty acid ester such as sugar anhydride tristearic acid, polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitol tetraoleate, polyethylene glycol monolaurate Polyethylene glycol fatty acid esters such as polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene cured castor oil, polyoxyethylene monomethyl Ethyl ether, polyoxyethylene dimethyl ether, polyoxyethylene glyceryl ether, polyoxyethylene tetraoleate, polyoxyethylene triisostearate, polyoxyethylene coconut fatty acid glyceride, and the like.
本發明中使用的聚乙二醇的平均分子量為200~10000。200~4000為佳,200~1800為更佳,300~1000為最佳。如果聚乙二醇的平均分子量小於200,則在成型加工時產生氣體,污染模具或輥,因而不優選。另外,如果大於10000,則防止白化現象的效果有降低的趨勢,並且與苯乙烯系樹脂的相溶性降低,苯乙烯系樹脂組成物、其成型品產生白濁。平均分子量是根據利用鄰苯二甲酸酐吡啶法測定的羥基的濃度(基於JIS K1557)而計算得到的值。 The polyethylene glycol used in the present invention has an average molecular weight of 200 to 10,000, preferably 200 to 4,000, more preferably 200 to 1800, and most preferably 300 to 1,000. If the average molecular weight of the polyethylene glycol is less than 200, gas is generated during the molding process, and the mold or the roll is contaminated, which is not preferable. In addition, when it is more than 10,000, the effect of preventing the whitening phenomenon tends to be lowered, and the compatibility with the styrene resin is lowered, and the styrene resin composition and the molded article thereof are white turbid. The average molecular weight is a value calculated based on the concentration of a hydroxyl group (based on JIS K1557) measured by a phthalic anhydride pyridine method.
本發明的苯乙烯系樹脂組成物在不影響本發明的無色透明性的範圍內可以含有礦物油。另外,也可以含有硬脂酸、亞乙基雙硬脂酸醯胺等內部潤滑劑、受阻酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、內酯系抗氧化劑、受阻胺系穩定劑、紫外線吸收劑、防靜電劑等的添加劑。另外,作為外部潤滑劑,亞乙基雙硬脂酸醯胺為佳,在樹脂組成物中含有30~200ppm為佳。 The styrene resin composition of the present invention may contain mineral oil insofar as it does not affect the colorless transparency of the present invention. Further, it may contain an internal lubricant such as stearic acid or ethylene bis-stearate, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a lactone-based antioxidant, or a hindered amine-based stabilizer. Additives such as ultraviolet absorbers and antistatic agents. Further, as the external lubricant, ethylene bis-stearate is preferred, and it is preferably 30 to 200 ppm in the resin composition.
對於本發明的苯乙烯系樹脂組成物而言,由於作為苯乙烯系樹脂的特徵的透射率、色調、透明性等光學特性的惡化小,所以可在發揮透明性的領域,例如作為光學用材料在光學用途優選使用。作為光學用途,可舉出透鏡、導光板、膜、光纖、光波導等。 In the styrene-based resin composition of the present invention, since the deterioration of optical characteristics such as transmittance, color tone, and transparency as a characteristic of the styrene-based resin is small, it is possible to exhibit transparency, for example, as an optical material. It is preferably used in optical applications. Examples of the optical use include a lens, a light guide plate, a film, an optical fiber, and an optical waveguide.
通過在本發明的苯乙烯系樹脂組成物中加入(c)6-〔3-(3-三級丁基-4- 羥基-5-甲基苯基)丙氧基〕-2,4,8,10-四-三級丁基二苯並〔d,f〕〔1,3,2〕二氧磷雜環庚烷(6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin)(下稱“化合物X”)、(d)磷系抗氧化劑、(e)受阻酚系抗氧化劑中的至少一個,從而能夠賦予長期的熱穩定性。如光學用途那樣在長期間使用的領域,長期熱穩定性是重要特性之一。長期熱穩定性顯示長期間使用時的因熱引起的色調和透射率的變化,熱穩定性優異的苯乙烯系樹脂組成物的色調和透射率的變化小。對於長期熱穩定性,可以通過加速試驗,在樹脂不變形的程度的高溫度條件(60~90℃)下保管成型品,以色調和透射率經時變化來進行評價。 By adding (c) 6-[3-(3-tertiary butyl-4-) to the styrene resin composition of the present invention Hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxane (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2 At least one of dioxaphosphepin (hereinafter referred to as "compound X"), (d) a phosphorus-based antioxidant, and (e) a hindered phenol-based antioxidant can impart long-term thermal stability. Long-term thermal stability is one of the important characteristics in fields that are used for a long period of time like optical applications. The long-term thermal stability shows a change in color tone and transmittance due to heat during long-term use, and a change in color tone and transmittance of the styrene-based resin composition excellent in thermal stability is small. For the long-term thermal stability, the molded article can be stored under high temperature conditions (60 to 90 ° C) to the extent that the resin is not deformed by an accelerated test, and the color tone and the transmittance are evaluated over time.
化合物X是在相同分子內具有受阻酚系抗氧化劑的骨架和磷系抗氧化劑的骨架的加工穩定劑。 The compound X is a processing stabilizer having a skeleton of a hindered phenol-based antioxidant and a skeleton of a phosphorus-based antioxidant in the same molecule.
作為化合物X,在苯乙烯系樹脂組成物100質量%中的含量為0.02~0.40質量%為佳,0.05~0.20質量%為更佳。如果化合物X的含量小於0.02質量%,則長期熱穩定性差,初期色調和透射率也變差。另外,即使超過0.40質量%,長期的熱穩定性也惡化。長期的熱穩定性顯示長期間使用時的因熱引起的色調和透射率的變化,熱穩定性優異的苯乙烯系樹脂組成物的色調和透射率的變化小。長的熱穩定性可通過加速試驗,在樹脂不變形的程度的高溫度條件(60~90℃)下保管成型品,以色調和透射率的經時變化來進行評價。苯乙烯系樹脂組成物100質量%中的化合物X的含量,具體而言例如為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質量%,也可以為在這裏例示的數值中的任意2個範圍內的值。 The content of the compound X in 100% by mass of the styrene resin composition is preferably 0.02 to 0.40% by mass, more preferably 0.05 to 0.20% by mass. If the content of the compound X is less than 0.02% by mass, the long-term thermal stability is poor, and the initial color tone and transmittance are also deteriorated. In addition, even if it exceeds 0.40 mass%, long-term thermal stability deteriorates. The long-term thermal stability shows a change in color tone and transmittance due to heat during long-term use, and a change in color tone and transmittance of the styrene-based resin composition excellent in thermal stability is small. The long thermal stability can be evaluated by accelerating the test, and the molded article is stored under high temperature conditions (60 to 90 ° C) in which the resin is not deformed, and the change in color tone and transmittance is measured with time. The content of the compound X in 100% by mass of the styrene resin composition is specifically 0.02, 0.03, 0.04, for example. 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40% by mass, and may be a value within any two of the numerical values exemplified herein.
通過在本發明的苯乙烯系樹脂組成物中加入化合物X,從而能夠賦予長期熱穩定性,並且即便加入磷系抗氧化劑和/或受阻酚系抗氧化劑,也能夠賦予長期熱穩定性。 By adding the compound X to the styrene resin composition of the present invention, long-term heat stability can be imparted, and even if a phosphorus-based antioxidant and/or a hindered phenol-based antioxidant is added, long-term heat stability can be imparted.
磷系抗氧化劑優選在苯乙烯系樹脂組成物100質量%中含有0.02~0.50質量%,更優選含有0.05~0.40質量%,進一步優選含有0.05~0.30質量%。如果小於0.02質量%,則長期的熱穩定性差,初期色調和透射率也差。即便超過0.50質量%,長期的熱穩定性也惡化。苯乙烯系樹脂組成物100質量%中的磷系抗氧化劑的含量,具體而言例如為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質量%,也可以為在這裏例示的數值中的任意2個範圍內的值。 The phosphorus-based antioxidant is preferably contained in an amount of 0.02 to 0.50% by mass, more preferably 0.05 to 0.40% by mass, even more preferably 0.05 to 0.30% by mass, based on 100% by mass of the styrene resin composition. If it is less than 0.02% by mass, the long-term thermal stability is poor, and the initial color tone and transmittance are also inferior. Even if it exceeds 0.50 mass%, long-term thermal stability deteriorates. The content of the phosphorus-based antioxidant in 100% by mass of the styrene resin composition is specifically 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, for example. 0.40, 0.45, and 0.50% by mass, and may be values in any two of the numerical values exemplified herein.
受阻酚系抗氧化劑優選在苯乙烯系樹脂組成物100質量%中含有0.02~0.50質量%,更優選含有0.02~0.30質量%,進一步優選含有0.05~0.30質量%。如果小於0.02質量%,則長期的熱穩定性差,初期色調和透射率也差。即便超過0.50質量%,長期熱穩定性也惡化。在苯乙烯系樹脂組成物100質量%中的受阻酚系抗氧化劑的含量,具體而言例如為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質量%,也可以為在這裏例示的數值中的任意2個範圍內的值。 The hindered phenol-based antioxidant is preferably contained in an amount of 0.02 to 0.50% by mass, more preferably 0.02 to 0.30% by mass, even more preferably 0.05 to 0.30% by mass, based on 100% by mass of the styrene resin composition. If it is less than 0.02% by mass, the long-term thermal stability is poor, and the initial color tone and transmittance are also inferior. Even if it exceeds 0.50 mass%, long-term thermal stability deteriorates. The content of the hindered phenol-based antioxidant in 100% by mass of the styrene resin composition is specifically 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, for example. 0.35, 0.40, 0.45, and 0.50% by mass, and may be values in any two of the numerical values exemplified herein.
磷系抗氧化劑是指三價的磷化合物的亞磷酸酯類。磷系抗氧化劑,例如可舉出,三(2,4-二-三級丁基苯基)亞磷酸酯、2,2’-亞甲基雙(4,6-二-三級丁基-1-苯基氧)(2-乙基己基氧基)磷、雙(2,4-二枯基苯基)季戊四醇二亞磷酸酯、4,4’-聯苯基二膦酸四(2,4-二-三級丁基苯基)、3,9-雙(2,6-二-三級丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺〔5.5〕十一烷、環新戊烷四基雙(2,4-二-三級丁基苯基亞磷酸酯)、雙十八烷基季戊四醇二亞磷酸酯、雙(壬基苯基)季戊四醇二亞磷酸酯、雙-[2-甲基-4,6-雙-(1,1-二甲基乙基)苯基]乙基亞磷酸酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、四(2,4-二-三級丁基-5-甲基苯基)-4,4’-聯苯基二亞膦酸酯等。作為磷系抗氧化劑,耐水解性優異的磷系抗氧化劑為佳,優選三(2,4-二-三級丁基苯基)亞磷酸酯、2,2’-亞甲基雙(4,6-二-三級丁基-1-苯基氧)(2-乙基己基氧)磷、雙(2,4-二枯基苯基)季戊四醇二亞磷酸酯、3,9-雙(2,6-二-三級丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺〔5.5〕十一烷。特別優選為三(2,4-二-三級丁基苯基)亞磷酸酯。磷系抗氧化劑可以單獨使用也可以並用二種以上。 The phosphorus-based antioxidant refers to a phosphite of a trivalent phosphorus compound. Examples of the phosphorus-based antioxidant include tris(2,4-di-tertiary butylphenyl)phosphite and 2,2'-methylenebis(4,6-di-tertiarybutyl- 1-phenyloxy)(2-ethylhexyloxy)phosphorus, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, 4,4'-biphenyldiphosphonic acid tetrakis(2, 4-di-tertiary butylphenyl), 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa- 3,9-diphosphorus [5.5]undecane, cyclopentane tetrakis(2,4-di-tert-butylphenylphosphite), dioctadecylpentaerythritol diphosphite , bis(nonylphenyl)pentaerythritol 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'-biphenyl Diphosphonite and the like. As the phosphorus-based antioxidant, a phosphorus-based antioxidant excellent in hydrolysis resistance is preferable, and tris(2,4-di-tri-butylphenyl)phosphite and 2,2'-methylenebis (4, 6-di-tertiary butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, 3,9-double (2 , 6-di-tertiary butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. Particularly preferred is tris(2,4-di-tertiary butylphenyl) phosphite. The phosphorus-based antioxidants may be used singly or in combination of two or more.
受阻酚系抗氧化劑是指,在基本骨架具有酚性羥基的抗氧化劑。受阻酚系抗氧化劑,例如可舉出,十八烷基-3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯、3,9-雙[2-〔3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基〕-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、亞乙基雙(氧基亞乙基)雙〔3-(5-三級丁基-4-羥基-間甲苯基)丙酸酯〕、4,6-雙(辛基硫代甲基)-鄰甲酚、4,6-雙〔(十二烷基硫代)甲基〕-鄰甲酚、2,4-二甲基-6-(1-甲基十五烷基)苯酚、 四〔亞甲基-3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯〕甲烷、DL-α-生育酚、2-三級丁基-6-(3-三級丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-〔1-(2-羥基-3,5-二-叔戊基苯基)乙基〕-4,6-二-叔戊基苯基丙烯酸酯、4,4’-硫代雙(6-三級丁基-3-甲基苯酚)、1,1,3-三(2-甲基-4-羥基-5-三級丁基苯基)丁烷、4,4’-亞丁基雙(3-甲基-6-三級丁基苯酚)、雙-[3,3-雙-(4’-羥基-3’-三級丁基苯基)-丁酸]-乙二醇酯等。優選為十八烷基-3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯、3,9-雙[2-〔3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基〕-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、亞乙基雙(氧基亞乙基)雙〔3-(5-三級丁基-4-羥基-間甲苯基)丙酸酯〕。受阻酚系抗氧化劑可以單獨使用也可以並用二種以上。 The hindered phenol-based antioxidant refers to an antioxidant having a phenolic hydroxyl group in the basic skeleton. The hindered phenol-based antioxidant may, for example, be octadecyl-3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate or 3,9-bis[2-[3 -(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[ 5.5] undecane, ethylene bis(oxyethylene) bis[3-(5-tris-butyl-4-hydroxy-m-tolyl)propionate], 4,6-bis (octyl) Thiomethyl)-o-cresol, 4,6-bis[(dodecylthio)methyl]-o-cresol, 2,4-dimethyl-6-(1-methylpentadecane Phenol, Tetrakis[methylene-3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate]methane, DL-α-tocopherol, 2-tris-butyl-6-(3 -tertiary butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl) 4-,6-di-tert-amylphenyl acrylate, 4,4'-thiobis(6-tri-butyl-3-methylphenol), 1,1,3-tris(2- Methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylene bis(3-methyl-6-tertiary butylphenol), bis-[3,3-double -(4'-Hydroxy-3'-tris-butylphenyl)-butyric acid]-ethylene glycol ester or the like. Preferred is octadecyl-3-(3,5-di-tertiarybutyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-tri-butyl)- 4-hydroxy-5-methylphenyl)propenyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, ethylene Bis(oxyethylene)bis[3-(5-tris-butyl-4-hydroxy-m-tolyl)propionate]. The hindered phenol antioxidant may be used singly or in combination of two or more.
作為化合物X、磷系抗氧化劑以及受阻酚系抗氧化劑的添加方法,沒有特別限定,可舉出利用苯乙烯系樹脂的聚合步驟、脫揮步驟、造粒步驟添加混合的方法;用成型加工時的擠出機、注射成型機等添加混合的方法;通過無添加的苯乙烯系樹脂將調整為高濃度這些添加劑的樹脂組成物稀釋混合成目標含量的方法等。 The method of adding the compound X, the phosphorus-based antioxidant, and the hindered phenol-based antioxidant is not particularly limited, and examples thereof include a method of adding and mixing by a polymerization step, a devolatilization step, and a granulation step of a styrene resin; A method of adding and mixing by an extruder, an injection molding machine, or the like; a method of diluting and mixing a resin composition adjusted to a high concentration of these additives into a target content by a styrene-based resin which is not added.
紫外線吸收劑是具有抑制因紫外線引起的劣化或著色的功能的紫外線吸收劑,例如可舉出二苯甲酮系、苯並***系、三嗪系、苯甲酸酯系、水楊酸酯系、氰基丙烯酸酯系、草酸苯胺系、丙二酸酯系、甲脒系等紫外線吸收劑。它們可以單獨使用或組合2種以上使用,也可以並用受阻胺等光穩定劑。 The ultraviolet absorber is a UV absorber having a function of suppressing deterioration or coloration by ultraviolet rays, and examples thereof include a benzophenone type, a benzotriazole type, a triazine type, a benzoate type, and a salicylate. A UV absorber such as a cyanoacrylate, an oxalic acid aniline, a malonate or a formazan. These may be used alone or in combination of two or more kinds, or a light stabilizer such as a hindered amine may be used in combination.
本發明的苯乙烯系樹脂組成物可以利用注射成型、擠出成型、吹塑成型、壓縮成型等根據目的的各種成型方法而得到成型品。成型品的形狀可以是根據目的而形成的形狀,並沒有限定。例如如果為板狀成型品,則可用作導光板。作為形成導光板的方法,已知有在板狀成型品的背面(射出光的面的相反側)設置點圖案等反射圖案。用樹脂板加工成導光板時,對光的入射面或樹脂板的端面整面進行研磨處理而形成鏡面為佳。另外,為了提高發射光的均勻性,而可以在板狀成型品的表面(能夠發射光的面)設置棱鏡圖案。板狀成型品的表面或背面的圖案可以在板狀成型品的成型時形成,例如如果是注射成型則為模具形狀,如果是擠出成型則通過輥轉印等而形成圖案。 The styrene resin composition of the present invention can be obtained by various molding methods such as injection molding, extrusion molding, blow molding, and compression molding according to the purpose. The shape of the molded article may be a shape formed according to the purpose, and is not limited. For example, if it is a plate-shaped molded article, it can be used as a light guide plate. As a method of forming the light guide plate, it is known to provide a reflection pattern such as a dot pattern on the back surface of the plate-shaped molded article (on the side opposite to the surface on which the light is emitted). When the resin sheet is processed into a light guide plate, it is preferable to polish the light incident surface or the entire surface of the resin sheet to form a mirror surface. Further, in order to improve the uniformity of the emitted light, a prism pattern may be provided on the surface of the plate-shaped molded article (the surface on which light can be emitted). The pattern on the front surface or the back surface of the plate-shaped molded article can be formed at the time of molding the plate-shaped molded article. For example, if it is injection-molded, it is a mold shape, and if it is extrusion-molded, a pattern is formed by roll transfer or the like.
本發明的苯乙烯系樹脂組成物的維卡軟化溫度是95~104℃為佳,97~104℃為更佳。如果維卡軟化溫度小於95℃,則耐熱性不足,根據使用環境而成型品有可能變形。 The styrene resin composition of the present invention preferably has a Vicat softening temperature of 95 to 104 ° C and more preferably 97 to 104 ° C. If the Vicat softening temperature is less than 95 ° C, the heat resistance is insufficient, and the molded article may be deformed depending on the use environment.
作為本發明苯乙烯系樹脂組成物的霧度而言,形成4mm厚度的成型品時,5%以下為佳,1%以下為更佳。 When the molded article having a thickness of 4 mm is formed as the haze of the styrene resin composition of the present invention, 5% or less is preferable, and 1% or less is more preferable.
以下,舉出實施例具體說明本發明,但本發明並不限定於這些實施例。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
(苯乙烯系樹脂A-1~A-3的製造) (Manufacture of styrene resin A-1 to A-3)
將作為完全混合型攪拌槽的第1反應器和第2反應器以及作為帶有靜態混合器的活塞式流動型反應器的第3反應器以串聯的方式連接來構成聚合步驟,按照表1所示的條件實施苯乙烯系樹脂的製造。各反應器的容量分別為:第1反應器為39升、第2反應器為39升、第3反應器為16升。用表1記載的原料組成製備原料溶液,向第1反應器以表1記載的流量連續供給原料溶液。在第1反應器的入口,以成為表1記載的添加濃度(質量基準相對於原料苯乙烯和甲基丙烯酸的總計量的濃度)的方式向原料溶液添加聚合引發劑,並均勻混合。表1記載的聚合引發劑如下: The first reactor and the second reactor as a completely mixed agitation tank and the third reactor as a piston type flow reactor with a static mixer are connected in series to form a polymerization step, as shown in Table 1. The production of the styrene resin was carried out under the conditions shown. The capacities of the respective reactors were 39 liters in the first reactor, 39 liters in the second reactor, and 16 liters in the third reactor. The raw material solution was prepared using the raw material compositions described in Table 1, and the raw material solution was continuously supplied to the first reactor at the flow rate shown in Table 1. At the inlet of the first reactor, a polymerization initiator was added to the raw material solution so as to have an additive concentration (concentration based on the total amount of the raw material styrene and methacrylic acid) described in Table 1, and uniformly mixed. The polymerization initiators shown in Table 1 are as follows:
聚合引發劑-1:2,2-二(4,4-三級丁基過氧基環己基)丙烷(使用日油株式會社製PATORA A。) Polymerization Initiator-1: 2,2-bis(4,4-tri-butylperoxycyclohexyl)propane (PATORA A manufactured by Nippon Oil Co., Ltd.)
聚合引發劑-2:1,1-二(三級丁基過氧基)環己烷(使用日油株式會社製PERHEXA C。) Polymerization initiator-2: 1,1-di(tri-butylperoxy)cyclohexane (using PERHEXA C manufactured by Nippon Oil Co., Ltd.)
在此,在第3反應器中,以使沿著流動方向產生溫度梯度,在中間部分、出口部分以成為表1的溫度的方式進行調整。 Here, in the third reactor, a temperature gradient is generated along the flow direction, and the intermediate portion and the outlet portion are adjusted so as to have the temperature of Table 1.
接著,通過將利用第3反應器連續取出的含有聚合物的溶液導入到由串聯的2段構成的帶有預熱器的真空脫揮槽中,以成為表1記載的樹脂溫度的方式調整預熱器的溫度,並按表1記載的壓力進行調整,從而將未反應苯乙烯和乙基苯分離後,利用多孔模頭擠出為繩股狀,利用***方式將繩股(strand)冷卻並切斷,進行顆粒化。 Next, the polymer-containing solution continuously taken out by the third reactor was introduced into a vacuum devolatilization tank having a preheater consisting of two stages connected in series, and the preheating was adjusted so as to have the resin temperature shown in Table 1. The temperature of the heat exchanger was adjusted according to the pressures shown in Table 1, and the unreacted styrene and ethylbenzene were separated, and then extruded into a strand shape by a porous die, and the strands were cooled by a cold solution method. And cut and granulated.
【表1】
(實施例1-1~1-33、比較例1-1~1-9) (Examples 1-1 to 1-33, Comparative Examples 1-1 to 1-9)
以表2所示的含量,使用螺杆直徑為40mm的單軸擠出機,將苯乙烯系樹脂A-1~A-3和添加劑在料筒溫度230℃、螺杆轉速100rpm下熔融混煉,得到顆 粒。表2中使用的添加劑如下所示。 The styrene resin A-1 to A-3 and the additive were melt-kneaded at a cylinder temperature of 230 ° C and a screw rotation speed of 100 rpm using a single-screw extruder having a screw diameter of 40 mm as shown in Table 2. One grain. The additives used in Table 2 are as follows.
B-1:乙烯基十二烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=25(花王株式會社製EMULGEN 123P) B-1: Ethylene lauryl polyoxyethylene ether, ethylene oxide, average addition mole number = 25 (EMULGEN 123P, manufactured by Kao Corporation)
B-2:乙烯基十八烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=12(花王株式會社製EMULGEN 320P) B-2: Vinyl octadecyl polyoxyethylene ether Ethylene oxide average addition mole number = 12 (EMULGEN 320P manufactured by Kao Corporation)
B-3:乙烯基十二烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=9(花王株式會社製EMULGEN 109P) B-3: Ethylene lauryl polyoxyethylene ether, ethylene oxide, average addition mole number = 9 (EMULGEN 109P, manufactured by Kao Corporation)
B-4:乙烯基十六烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=7(花王株式會社製EMULGEN 210P) B-4: Ethylene cetyl polyoxyethylene ether Ethylene oxide average addition mole number = 7 (EMULGEN 210P manufactured by Kao Corporation)
B-5:乙烯基十二烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=30(花王株式會社製EMULGEN 130K) B-5: Ethylene lauryl polyoxyethylene ether, ethylene oxide, average addition mole number = 30 (EMULGEN 130K, manufactured by Kao Corporation)
B-6:乙烯基十二烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=47(花王株式會社製EMULGEN 150) B-6: Vinyl lauryl polyoxyethylene ether, ethylene oxide average addition mole number = 47 (EMULGEN 150, manufactured by Kao Corporation)
B-7:乙烯基十四烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=85(花王株式會社製EMULGEN 4085) B-7: Ethylene tetradecyl polyoxyethylene ether, ethylene oxide average addition mole number = 85 (EMULGEN 4085, manufactured by Kao Corporation)
B-8:聚乙二醇單月桂酸酯環氧乙烷平均加成摩爾數=12(花王株式會社製EMANON 1112) B-8: Polyethylene glycol monolaurate Ethylene oxide average addition mole number = 12 (Malay Co., Ltd. EMANON 1112)
B-9:乙烯基十八烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=6(花王株式會社製EMULGEN 306P) B-9: Vinyl octadecyl polyoxyethylene ether Ethylene oxide average addition mole number = 6 (EMULGEN 306P, manufactured by Kao Corporation)
B-10:聚氧乙烯固化蓖麻油(花王株式會社製EMANON CH-40) B-10: Polyoxyethylene-cured castor oil (EMANON CH-40, manufactured by Kao Corporation)
B-11:平均分子量為400的聚乙二醇(日油株式會社製PEG#400) B-11: Polyethylene glycol having an average molecular weight of 400 (PEG#400 manufactured by Nippon Oil Co., Ltd.)
B-12:平均分子量為300的聚乙二醇(日油株式會社製PEG#300) B-12: Polyethylene glycol having an average molecular weight of 300 (PEG#300 manufactured by Nippon Oil Co., Ltd.)
B-13:平均分子量為600的聚乙二醇(日油株式會社製PEG#600) B-13: Polyethylene glycol having an average molecular weight of 600 (PEG#600 manufactured by Nippon Oil Co., Ltd.)
B-14:平均分子量為1000的聚乙二醇(日油株式會社製PEG#1000) B-14: Polyethylene glycol having an average molecular weight of 1000 (PEG#1000 manufactured by Nippon Oil Co., Ltd.)
B-15:平均分子量為2000的聚乙二醇(日油株式會社製PEG#2000) B-15: Polyethylene glycol having an average molecular weight of 2000 (PEG#2000 manufactured by Nippon Oil Co., Ltd.)
B-16:平均分子量為3100的聚乙二醇(日油株式會社製PEG#4000) B-16: Polyethylene glycol having an average molecular weight of 3,100 (PEG #4000, manufactured by Nippon Oil Co., Ltd.)
B-17:平均分子量8800的聚乙二醇(日油株式會社製PEG#6000) B-17: Polyethylene glycol having an average molecular weight of 8800 (PEG#6000 manufactured by Nippon Oil Co., Ltd.)
B-18:聚氧乙烯單甲基醚(日油株式會社製UNIOX M-550) B-18: Polyoxyethylene monomethyl ether (UNIOX M-550 by Nippon Oil Co., Ltd.)
B-19:聚氧乙烯三異硬脂酸(日油株式會社製UNIOX GT-20IS) B-19: Polyoxyethylene triisostearic acid (UNIOX GT-20IS manufactured by Nippon Oil Co., Ltd.)
B-20:辛基十二烷基聚氧乙烯醚(花王株式會社製EMULGEN 2025G) B-20: Octyldodecyl polyoxyethylene ether (EMULGEN 2025G, manufactured by Kao Corporation)
B-21:聚氧乙烯甘油醚(日油株式會社製UNIOX G-750) B-21: Polyoxyethylene glyceryl ether (UNIOX G-750, manufactured by Nippon Oil Co., Ltd.)
B-22:聚氧乙烯四油酸(日油株式會社製UNIOX ST-30E) B-22: Polyoxyethylene tetraoleic acid (UNIOX ST-30E, manufactured by Nippon Oil Co., Ltd.)
B-23:十八烷基醇(花王株式會社製KALCOL 8098) B-23: octadecyl alcohol (KALCOL 8098, manufactured by Kao Corporation)
B-24:硬脂酸單甘油酯(花王株式會社製EXCEL S-95) B-24: Stearic acid monoglyceride (EXCEL S-95, manufactured by Kao Corporation)
B-25:平均分子量為60000的聚乙二醇(明成化學工業株式會社製ALKOX L-6) B-25: Polyethylene glycol having an average molecular weight of 60,000 (ALKOX L-6, manufactured by Mingcheng Chemical Industry Co., Ltd.)
B-26:平均分子量為500的聚甘油(阪本藥品工業株式會社製聚甘油#500) B-26: Polyglycerol having an average molecular weight of 500 (polyglycerin #500 manufactured by Sakamoto Pharmaceutical Co., Ltd.)
使用得到的顆粒,在料筒溫度230℃、模具溫度50℃下進行注射成型,形成127×127×3mm厚度的板狀成型品。 Using the obtained pellets, injection molding was carried out 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.
另外,實施例1-33是使用螺杆直徑40mm的單軸擠出機將苯乙烯系樹脂A-1和添加劑B-1在料筒溫度230℃、螺杆轉速100rpm下熔融混煉,一旦得到添加劑B-1的濃度20質量%的顆粒後,以使該顆粒和苯乙烯系樹脂A-1成為1: 24的比率的方式進行混合,並注射成型而得到的成型品。 Further, in Examples 1-33, the styrene resin A-1 and the additive B-1 were melt-kneaded at a cylinder temperature of 230 ° C and a screw rotation speed of 100 rpm using a single-axis extruder having a screw diameter of 40 mm, once the additive B was obtained. After the concentration of -1 is 20% by mass of the particles, the particles and the styrene resin A-1 are made into 1: A molded article obtained by mixing and molding by a ratio of 24 ratio.
苯乙烯系樹脂組成物的MFR(熔體質量流動速率)是在200℃、49N負載的條件下,基於JIS K 7210進行測定的。 The MFR (melt mass flow rate) of the styrene resin composition was measured based on JIS K 7210 under the conditions of a load of 49 ° C and 49 N.
從所得到的板狀成型品中切出115×85×3mm厚度的試驗片,通過拋光研磨對端面進行研磨,得到端面具有鏡面的板狀成型品。對於得到的板狀成型品,使用日本分光株式會社製的紫外線可視分光光度計V-670,在大小20×1.6mm、擴散角度0°的入射光下,測定光路長115mm下的波長350nm~800nm的分光透射率,根據JIS K7105計算C光源的視角2°下的YI值。得到的值為表2的“YI 115mm”。另外,表2所示的“透射率115mm”表示波長380nm~780nm的平均透射率。 A test piece having a thickness of 115 × 85 × 3 mm was cut out from the obtained plate-shaped molded article, and the end surface was polished by polishing to obtain a plate-shaped molded article having a mirror surface on the end surface. For the obtained plate-shaped molded product, an ultraviolet visible spectrophotometer V-670 manufactured by JASCO Corporation was used, and a wavelength of 350 nm to 800 nm at an optical path length of 115 mm was measured under incident light having a size of 20 × 1.6 mm and a diffusion angle of 0°. The spectral transmittance is calculated according to JIS K7105, and the YI value at a viewing angle of 2° of the C light source is calculated. The value obtained is "YI 115 mm" of Table 2. Further, "transmittance 115 mm" shown in Table 2 indicates an average transmittance of a wavelength of 380 nm to 780 nm.
進而,表2中的“霧度4mm”以如下方式獲得,即,使用上述步驟中得到的顆粒,在料筒溫度220℃、模具溫度40℃下進行注射成型,使55×50×4mm厚度的板狀成型品成型,使用由此得到的試驗片,利用NDH5000(日本電色工業株式會社製),基於JIS K-7105進行測定而得到值,表2的“YI 4mm”是使用該試驗片,採用測色色差計NDJ4000(日本電色工業株式會社製),用反射法進行測定而得到的值。 Further, "haze 4 mm" in Table 2 was obtained in the following manner, that is, using the pellets obtained in the above steps, injection molding was carried out at a cylinder temperature of 220 ° C and a mold temperature of 40 ° C to make a thickness of 55 × 50 × 4 mm. The test piece obtained by the use of the test piece obtained by the NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was measured by JIS K-7105 to obtain a value, and the test piece was used for "YI 4 mm" in Table 2. A value obtained by measurement using a colorimetric color difference meter NDJ4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) by a reflection method.
此外,為了確認基於環境變化而產生的白化現象,將在端面具有鏡面的板狀成型品在60℃、90%相對濕度的環境暴露150小時,在23℃、50%相對濕度的環境取出試驗片,觀察在成型品內部產生的白化現象,作為白化抑制效果如下進行判定。 In addition, in order to confirm the whitening phenomenon caused by environmental changes, the plate-shaped molded article having a mirror surface on the end surface was exposed to an environment of 60 ° C and 90% relative humidity for 150 hours, and the test piece was taken out at 23 ° C and 50% relative humidity. The whitening phenomenon generated inside the molded article was observed, and the whitening suppression effect was determined as follows.
◎:完全不產生白化 ◎: no whitening at all
○:取出1小時後稍有白化,但24小時後消失 ○: A little whitening after taking out for 1 hour, but disappearing after 24 hours
△:取出1小時後白化,但24小時後幾乎消失 △: whitening after taking out for 1 hour, but almost disappeared after 24 hours
×:取出1小時後顯著白化,即便經過24小時也不消失 ×: Significantly whitened after taking out for 1 hour, even if it does not disappear after 24 hours
對於維卡軟化溫度,根據JIS K-7206,以升溫速度50℃/hr、試驗負載50N求得。 The Vicat softening temperature was determined according to JIS K-7206 at a temperature increase rate of 50 ° C / hr and a test load of 50 N.
根據以下基準,進行綜合評價。 Comprehensive evaluation was carried out based on the following criteria.
S:白化抑制效果為◎且維卡軟化溫度為100℃以上 S: The whitening inhibition effect is ◎ and the Vicat softening temperature is 100 ° C or higher.
A:不能充分滿足S的條件,白化抑制效果為◎且維卡軟化溫度為98℃以上,或者白化抑制效果為○且維卡軟化溫度為100℃以上 A: The condition of S cannot be sufficiently satisfied, the whitening suppression effect is ◎ and the Vicat softening temperature is 98° C. or higher, or the whitening suppression effect is ○ and the Vicat softening temperature is 100° C. or higher.
B:不能充分滿足A的條件,白化抑制效果為◎且維卡軟化溫度為95℃以上,或者白化抑制效果為○且維卡軟化溫度為98℃以上,或者白化抑制效果為△且維卡軟化溫度為100℃以上 B: The condition of A cannot be sufficiently satisfied, the whitening suppression effect is ◎ and the Vicat softening temperature is 95° C. or higher, or the whitening suppression effect is ○ and the Vicat softening temperature is 98° C. or higher, or the whitening suppression effect is Δ and Vicat softening Temperature is above 100 °C
C:不能充分滿足上述任一條件 C: cannot fully satisfy any of the above conditions
表2中顯示各樹脂組成物的特性和評價結果。 The characteristics and evaluation results of the respective resin compositions are shown in Table 2.
實施例相關的成型品的白化抑制效果優異,透射率和YI值均不惡化且透明性和色調也優異。在不添加親水性添加劑或者添加量過少的比較例1-1、1-2、1-4中白化現狀的抑制不充分。在親水性添加劑過量添加的比較例1-3和1-5中,耐熱性過度降低。另外,比較例1-6和1-7中,分別添加作為親水性添加劑的十八烷基醇、硬脂酸單甘油酯進行試驗,但白化抑制效果不充分。此外,比較例1-8和1-9中,添加分子量大的聚乙二醇、聚甘油進行試驗,但親水性添加劑不與苯乙烯系樹脂相溶,成型品發生白濁。 The molded article according to the examples is excellent in the whitening suppressing effect, and the transmittance and the YI value are not deteriorated, and the transparency and the color tone are also excellent. In the comparative examples 1-1, 1-2, and 1-4 in which the hydrophilic additive was not added or the amount of addition was too small, the suppression of the whitening status was insufficient. In Comparative Examples 1-3 and 1-5 in which the hydrophilic additive was excessively added, the heat resistance was excessively lowered. Further, in Comparative Examples 1-6 and 1-7, octadecyl alcohol or stearic acid monoglyceride as a hydrophilic additive was separately added and tested, but the whitening inhibitory effect was insufficient. Further, in Comparative Examples 1-8 and 1-9, polyethylene glycol and polyglycerin having a large molecular weight were added and tested, but the hydrophilic additive was not compatible with the styrene resin, and the molded article was cloudy.
由以上結果可知,為了維持苯乙烯系樹脂組成物的耐熱性、透明性並且抑制白化現象,必須滿足以下3個條件:(1)親水性添加劑具有特性構成,(2)其HLB值為特定的範圍內的值,並且(3)其含量為特定範圍的量。參照實施例1-20~1-21可知,在苯乙烯系樹脂是苯乙烯系單體與(甲基)丙烯酸或者(甲基)丙烯酸酯的共聚物時也能夠得到相同的結果。 From the above results, in order to maintain the heat resistance and transparency of the styrene resin composition and to suppress the whitening phenomenon, it is necessary to satisfy the following three conditions: (1) the hydrophilic additive has a characteristic configuration, and (2) the HLB value is specific. A value within the range, and (3) an amount whose content is a specific range. Referring to Examples 1-20 to 1-21, the same results were obtained even when the styrene resin was a copolymer of a styrene monomer and (meth)acrylic acid or (meth)acrylate.
(實施例2-1~2-46) (Examples 2-1 to 2-46)
將作為完全混合型攪拌槽的第1反應器和第2反應器以及作為帶有靜態混合器的活塞式流動型反應器的第3反應器以串聯的方式連接來構成聚合步驟,按照表1所示的條件實施苯乙烯系樹脂的製造。各反應器的容量分別為:第1反應器為39升、第2反應器為39升、第3反應器為16升。用表1記載的原料組成製備原料溶液,向第1反應器以表1記載的流量連續供給原料溶液。 The first reactor and the second reactor as a completely mixed agitation tank and the third reactor as a piston type flow reactor with a static mixer are connected in series to form a polymerization step, as shown in Table 1. The production of the styrene resin was carried out under the conditions shown. The capacities of the respective reactors were 39 liters in the first reactor, 39 liters in the second reactor, and 16 liters in the third reactor. The raw material solution was prepared using the raw material compositions described in Table 1, and the raw material solution was continuously supplied to the first reactor at the flow rate shown in Table 1.
另外,在第3反應器的入口,將具有聚醚鏈的親水性添加劑以成為表3所示的種類和含量的方式添加。使用的添加劑和聚乙二醇的種類如下。 Further, at the inlet of the third reactor, a hydrophilic additive having a polyether chain was added so as to have the kind and content shown in Table 3. The types of additives and polyethylene glycols used are as follows.
B-1:平均分子量為400的聚乙二醇(日油株式會社製PEG#400) B-1: Polyethylene glycol having an average molecular weight of 400 (PEG#400 manufactured by Nippon Oil Co., Ltd.)
B-2:平均分子量為1000的聚乙二醇(日油株式會社製PEG#1000) B-2: Polyethylene glycol having an average molecular weight of 1000 (PEG#1000 manufactured by Nippon Oil Co., Ltd.)
B-3:平均分子量為2000的聚乙二醇(日油株式會社製PEG#2000) B-3: Polyethylene glycol having an average molecular weight of 2,000 (PEG#2000 manufactured by Nippon Oil Co., Ltd.)
B-4:乙烯基十二烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=25(花王株式會社製EMULGEN 123P) B-4: Ethylene lauryl polyoxyethylene ether, ethylene oxide, average addition mole number = 25 (EMULGEN 123P, manufactured by Kao Corporation)
B-5:乙烯基十二烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=12(花王株式會社製EMULGEN 320P) B-5: Vinyl lauryl polyoxyethylene ether, ethylene oxide average addition mole number = 12 (EMULGEN 320P, manufactured by Kao Corporation)
B-6:乙烯基十二烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=9(花王株式會社製EMULGEN 109P) B-6: Ethylene lauryl polyoxyethylene ether Ethylene oxide average addition mole number = 9 (EMULGEN 109P, manufactured by Kao Corporation)
B-7:乙烯基十二烷基聚氧乙烯醚環氧乙烷平均加成摩爾數=30(花王株式會社製EMULGEN 130K) B-7: Vinyl lauryl polyoxyethylene ether, ethylene oxide average addition mole number = 30 (EMULGEN 130K, manufactured by Kao Corporation)
B-8:聚乙二醇單月桂酸酯環氧乙烷平均加成摩爾數=12(花王株式會社製EMANON 1112) B-8: Polyethylene glycol monolaurate Ethylene oxide average addition mole number = 12 (Malay Co., Ltd. EMANON 1112)
接著,將連續取出至第3反應器的含有聚合物的溶液導入到由串聯的2段構成的帶有預熱器的真空脫揮槽中,將未反應苯乙烯和乙基苯分離後,擠出為繩股狀並冷卻後,進行切斷來製成顆粒。在此,第1階段的脫揮槽內的樹脂溫度設定為160℃,真空脫揮槽的壓力為65kPa,第2階段的脫揮層內的樹脂溫度設定為235℃,真空脫揮槽的壓力為0.8kPa。 Next, the polymer-containing solution continuously taken out to the third reactor is introduced into a vacuum devolatilization tank having a preheater consisting of two stages connected in series, and the unreacted styrene and ethylbenzene are separated and then extruded. After being stranded and cooled, the cut was made to form pellets. Here, the resin temperature in the devolatilization tank of the first stage is set to 160 ° C, the pressure of the vacuum devolatilization tank is 65 kPa, and the resin temperature in the devolatilization layer of the second stage is set to 235 ° C, and the pressure of the vacuum devolatilization tank It is 0.8 kPa.
接下來,以成為表3所示的含量,使用螺杆直徑40mm的單軸擠出機,將上述得到苯乙烯系樹脂的顆粒和作為追加添加劑的化合物X、添加劑D以及添加劑E在料筒溫度230℃、螺杆轉速100rpm下熔融混煉得到顆粒。將在表3中使用的化合物X、D以及E示於下文。在此,化合物X表示6-〔3-(3-三級丁基-4-羥基-5-甲基苯基)丙氧基〕-2,4,8,10-四-三級丁基二苯並〔d,f〕〔1,3,2〕二氧磷雜環庚烷,添加劑D表示磷系抗氧化劑,添加劑E表示受阻酚系抗氧化劑。 Next, the pellets of the styrene-based resin and the compound X, the additive D and the additive E as additional additives were obtained at a cylinder temperature of 230 using a uniaxial extruder having a screw diameter of 40 mm as shown in Table 3. The mixture was melt-kneaded at ° C and a screw rotation speed of 100 rpm to obtain pellets. The compounds X, D and E used in Table 3 are shown below. Here, the compound X represents 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tertiary butyl Benzo[d,f][1,3,2]dioxepane, additive D represents a phosphorus-based antioxidant, and additive E represents a hindered phenol-based antioxidant.
化合物X:6-〔3-(3-三級丁基-4-羥基-5-甲基苯基)丙氧基〕-2,4,8,10-四-三級丁基二苯並〔d,f〕〔1,3,2〕二氧磷雜環庚烷(住友化學株式會社製SUMILIZER GP) Compound X: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[ d,f][1,3,2]dioxaphosphane (SUMILIZER GP, manufactured by Sumitomo Chemical Co., Ltd.)
D-1:三(2,4-二-三級丁基苯基)亞磷酸酯(BASF Japan株式會社製Irgafos 168) D-1: tris(2,4-di-tertiary butylphenyl) phosphite (Irgafos 168, manufactured by BASF Japan Co., Ltd.)
D-2:2,2’-亞甲基雙(4,6-二-三級丁基-1-苯基氧)(2-乙基己基氧)磷(株式會社ADEKA製ADKSTAB HP-10) D-2: 2,2'-methylenebis(4,6-di-tert-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus (ADKSTAB HP-10, manufactured by ADEKA)
D-3:雙(2,4-二枯基苯基)季戊四醇二亞磷酸酯(Dover Chemical Corporation製Doverphos S-9228) D-3: bis(2,4-dicumylphenyl)pentaerythritol diphosphite (Doverphos S-9228, manufactured by Dover Chemical Corporation)
D-4:3,9-雙(2,6-二-三級丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺〔5.5〕十一烷(株式會社ADEKA製ADKSTAB PEP-36) D-4: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphorane [5.5] Undecane (ADKSTAB PEP-36 manufactured by ADEKA Co., Ltd.)
E-1:十八烷基-3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯(BASF Japan株式會社製Irganox 1076) E-1: octadecyl-3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate (Irganox 1076, manufactured by BASF Japan Co., Ltd.)
E-2:3,9-雙[2-〔3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基〕-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷(株式會社ADEKA製 ADKSTABAO-80) E-2: 3,9-bis[2-[3-(3-tri-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro[5.5]undecane (made by ADEKA Co., Ltd.) ADKSTABAO-80)
E-3:亞乙基雙(氧乙烯)雙〔3-(5-三級丁基-4-羥基-間甲苯基)丙酸酯〕(BASF Japan株式會社製Irganox 245) E-3: ethylene bis(oxyethylene) bis[3-(5-tris-butyl-4-hydroxy-m-tolyl)propionate] (Irganox 245, manufactured by BASF Japan Co., Ltd.)
另外,熔體質量流動速率(MFR)是根據JIS K 7210,在200℃、49N負載的條件下進行測定,維卡軟化溫度是根據JIS K 7206,在升溫速度50℃/hr、試驗負載50N下進行測定。 In addition, the melt mass flow rate (MFR) is measured according to JIS K 7210 under the conditions of 200 ° C and 49 N load, and the Vicat softening temperature is according to JIS K 7206, at a heating rate of 50 ° C / hr, and a test load of 50 N. The measurement was carried out.
另外,使用得到的顆粒,在料筒溫度230℃、模具溫度50℃下進行注射成型,形成127×127×3mm厚度的板狀成型品。為了評價長期的熱穩定性,而將得到的成型品在80℃的爐溫內保管1000小時。為了評價保管前的初期成型品和保管後的成型品光學特性,而從板狀成型品切出115×85×3mm厚度的試驗片,通過拋光研磨對端面進行研磨,製備在端面具有鏡面的板狀成型品。對於研磨後的板狀成型品,使用日本分光株式會社製的紫外線可視分光光度計V-670,在大小20×1.6mm、擴散角度0°的入射光下,測定光路長115mm下的波長350nm~800nm的分光透射率,根據JIS K7105計算C光源的視角2°下的YI值。表3所示的透射率是表示波長380nm~780nm的平均透射率。 Further, using the obtained pellets, injection molding was carried out 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 heat stability, the obtained molded article was stored in an oven temperature of 80 ° C for 1,000 hours. In order to evaluate the optical properties of the initial molded product before storage and the molded product after storage, 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 polishing to prepare a plate having a mirror surface at the end surface. Shaped product. For the plate-shaped molded product after polishing, an ultraviolet visible spectrophotometer V-670 manufactured by JASCO Corporation was used to measure a wavelength of 350 nm at an optical path length of 115 mm under incident light having a size of 20 × 1.6 mm and a diffusion angle of 0°. The spectral transmittance at 800 nm was calculated according to JIS K7105, and the YI value at a viewing angle of 2° of the C light source was calculated. The transmittance shown in Table 3 is an average transmittance indicating a wavelength of 380 nm to 780 nm.
接下來,基於下式計算△YI差。 Next, the ΔYI difference is calculated based on the following formula.
△YI差=(有追加添加劑的實施例中的相較於初期的YI差)-(沒有追加添加劑的實施例中的相較於初期的YI差) ΔYI difference = (the difference in the example in which the additive is added is compared with the initial YI) - (in the example without the additive, the phase difference is compared with the initial YI)
在一例中,在有追加添加劑的實施例2-2中,相較於初期的YI差的值為 1.1,沒有追加添加劑的實施例2-1中相較於初期的YI差為5.1,所以實施例2-2的△YI差為-4.0。該值表示有由追加添加劑(化合物X、磷系D、受阻酚系E)引起的長期的熱穩定性的提高效果,值越小,表示長期的熱穩定性提高效果越大。 In an example, in Example 2-2 in which an additive was added, the value compared with the initial YI difference was 1.1. In Example 2-1 without additional additives, the difference in YI from the initial stage was 5.1, so the difference in ΔYI of Example 2-2 was -4.0. This value indicates an effect of improving the long-term thermal stability caused by the additional additive (compound X, phosphorus-based D, and hindered phenol-based E), and the smaller the value, the greater the effect of improving the long-term thermal stability.
此外,為了確認因環境變化而產生的白化現象,將在端面具有鏡面的板狀成型品在60℃、90%相對濕度的環境暴露150小時,在23℃、50%相對濕度的環境取出試驗片,觀察在成型品內部產生的白化現象,作為白化抑制效果如下進行判定。 In addition, in order to confirm the whitening phenomenon due to environmental changes, the plate-shaped molded article having a mirror surface on the end surface was exposed to an environment of 60 ° C and 90% relative humidity for 150 hours, and the test piece was taken out at 23 ° C and 50% relative humidity. The whitening phenomenon generated inside the molded article was observed, and the whitening suppression effect was determined as follows.
◎:完全不產生白化 ◎: no whitening at all
○:取出1小時後稍有白化,但24小時後消失 ○: A little whitening after taking out for 1 hour, but disappearing after 24 hours
△:取出1小時後白化,但24小時後幾乎消失 △: whitening after taking out for 1 hour, but almost disappeared after 24 hours
×:取出1小時後顯著白化,即便經過24小時也不消失 ×: Significantly whitened after taking out for 1 hour, even if it does not disappear after 24 hours
根據以下基準,將白化抑制效果、△YI差、維卡軟化溫度的評價結果進行數值化。 The evaluation results of the whitening suppression effect, the ΔYI difference, and the Vicat softening temperature were numerically calculated based on the following criteria.
白化抑制效果的分數值(◎→3;○→2;△→1;×→0) The fractional value of the whitening inhibition effect (◎→3; ○→2; △→1; ×→0)
△YI差的分數值(-4.0以下→4;-3.5以下→3;-2.5以下→2;-1.5以下→1;除此以外→0) ΔYI difference score value (-4.0 or less→4; -3.5 or less→3; -2.5 or less→2; -1.5 or less→1; otherwise →0)
維卡軟化溫度的分數值(99℃以上→3;97℃以上→2;95℃以上→1;除此以外→0) The value of the Vicat softening temperature (99 °C or more → 3; 97 ° C or more → 2; 95 ° C or more → 1; other than → 0)
對於根據上述基準而得的分數值的總計,根據以下基準進行綜合評價。S:10;A:9;B:8;C:7;D:6以下 The total of the score values obtained based on the above criteria was comprehensively evaluated based on the following criteria. S: 10; A: 9; B: 8; C: 7; D: 6 or less
表3顯示各樹脂組成物的特性和評價結果。實施例2-1~2-42中,使用根據條件1製成的苯乙烯系樹脂A-1,實施例2-43~2-44中使用根據條件2製成的苯乙烯系樹脂A-2,實施例2-45~2-46中使用根據條件3製成的苯乙烯系樹脂A-3。 Table 3 shows the characteristics and evaluation results of the respective resin compositions. In Examples 2-1 to 2-42, styrene resin A-1 prepared according to Condition 1 was used, and styrene resin A-2 prepared according to Condition 2 was used in Examples 2-43 to 2-44. In the examples 2-45 to 2-46, the styrene resin A-3 prepared according to Condition 3 was used.
參照表3可知,全部實施例的白化抑制效果均優異。另外,比較實施例2-1~2-35和實施例2-36~2-42可知,化合物X的含量為0.02~0.40質量%時,長期的熱穩定性特別優異。另外,參照實施例2-43~2-46可知,苯乙烯系樹脂是苯乙烯系單體與(甲基)丙烯酸或者(甲基)丙烯酸酯的共聚物時也能夠得到同樣的結果。 Referring to Table 3, it was found that all of the examples had excellent whitening inhibitory effects. Further, in Comparative Examples 2-1 to 2-35 and Examples 2-36 to 2-42, it is understood that when the content of the compound X is 0.02 to 0.40% by mass, the long-term thermal stability is particularly excellent. Further, referring to Examples 2-43 to 2-46, the same results were obtained when the styrene resin was a copolymer of a styrene monomer and (meth)acrylic acid or (meth)acrylic acid ester.
(實施例3-1~3-36) (Examples 3-1 to 3-36)
除試驗3中不添加化合物X以外,採用與試驗2同樣的方法進行評價。實施例3-1~3-32中,使用根據條件1製成的苯乙烯系樹脂A-1,實施例3-33~3-34中使用根據條件2製成的苯乙烯系樹脂A-2,實施例3-35~3-36中使用根據條件3製成的苯乙烯系樹脂A-3。 Evaluation was carried out in the same manner as in Test 2 except that Compound X was not added in Test 3. In Examples 3-1 to 3-32, the styrene resin A-1 prepared according to Condition 1 was used, and in Example 3-33 to 3-34, the styrene resin A-2 prepared according to Condition 2 was used. In the examples 3-35 to 3-36, the styrene resin A-3 prepared according to Condition 3 was used.
將其結果示於表4。 The results are shown in Table 4.
參照表4可知,全部實施例的白化抑制效果均優異。另外,比較實施例3-1~3-24和實施例3-25~3-32可知,磷系D的含量為0.05~0.40質量%且苯酚系E的含量為0.02~0.30質量%時,長期熱穩定性特別優異。另外,參照實施例3-33~3-36可知,苯乙烯系樹脂是苯乙烯系單體和(甲基)丙烯酸或者(甲基)丙烯酸酯的共聚物時也能夠得到同樣的結果。 Referring to Table 4, all of the examples were excellent in whitening suppression effects. Further, in Comparative Examples 3-1 to 3-24 and Examples 3-25 to 3-32, it is understood that when the content of the phosphorus-based D is 0.05 to 0.40% by mass and the content of the phenol-based E is 0.02 to 0.30% by mass, the long-term The thermal stability is particularly excellent. Further, referring to Examples 3-33 to 3-36, the same results were obtained even when the styrene resin was a copolymer of a styrene monomer and (meth)acrylic acid or (meth)acrylic acid ester.
本發明的苯乙烯系樹脂組成物能夠防止因環境變化引起的白化現象,並且透明性和色調優異,所以在一直以來因環境變化而產生白化現象的用途中也能夠維持作為苯乙烯系樹脂的優點的透明性,能夠優選使用。 The styrene-based resin composition of the present invention can prevent the whitening phenomenon due to environmental changes, and is excellent in transparency and color tone. Therefore, it is possible to maintain the advantage of being a styrene-based resin in applications in which whitening has been caused by environmental changes. The transparency can be preferably used.
並且,由於長期熱穩定性優異的苯乙烯系樹脂組成物的色調變化小,所以與以往相比能夠在保持長期透明性和色調的情況下使用。 In addition, since the styrene resin composition having excellent long-term thermal stability has a small change in color tone, it can be used while maintaining long-term transparency and color tone as compared with the related art.
例如,可應用於電視機、桌上型個人電腦、筆記型個人電腦、手機、汽車導航等的導光板。 For example, it can be applied to a light guide plate of a television, a desktop personal computer, a notebook personal computer, a mobile phone, a car navigation, or the like.
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