TW201026766A - Styrene series resin composition - Google Patents

Styrene series resin composition Download PDF

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Publication number
TW201026766A
TW201026766A TW098128378A TW98128378A TW201026766A TW 201026766 A TW201026766 A TW 201026766A TW 098128378 A TW098128378 A TW 098128378A TW 98128378 A TW98128378 A TW 98128378A TW 201026766 A TW201026766 A TW 201026766A
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Taiwan
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mass
fine particles
styrene
resin fine
acrylate
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TW098128378A
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Chinese (zh)
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TWI527853B (en
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Hideo Matsuzaki
Rie Toshio
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Toagosei Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Abstract

Disclosed is a styrene system resin composition, that has high light diffusion properties, as well as excellent diffusion light transmittance, dimensional stability and shape stability, and that provides a molded body, for which scattered transmitted light does not take on a yellowish tinge and which is suitable as a light diffusion plate or the like, and a molded body comprised of the composition. The composition is a styrene system resin composition wherein the styrene system resin contains a crosslinked resin particulate comprised of a (meth)acrylic acid ester system resin having a volume-average particle diameter (dv) of 0.7-2.5 μm, a ratio (dv/dn) of the volume-average particle diameter (dv) to the number-average particle diameter (dn) of 1.2 or less, and a charge crosslinking point equivalent weight of 0.15 meq/g or greater.

Description

201026766 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種苯乙烯系樹脂組成物及由該組成物 所成的成形體。更詳言之，本發明係有關一種可賦予光擴 散性優異、且擴散光之透過性優異、沒有散射透過光被黃 化的情形、尺寸安定性及形狀安定性優異的成形體之苯乙 烯系樹脂組成物以及由該苯乙烯系樹脂組成物所成的成形 ❿ 體。 本發明由苯乙烯系樹脂組成物所成的成形體，可活化 前述優異的特性，有效地使用於液晶顯示裝置等之光擴散 板、菲涅耳（Fresnel )透鏡、凹凸式透鏡、照明器具、電 照看板等之光學用途。 【先前技術】 於液晶電視等之大型顯示裝置中，爲得充分的明亮度 φ 時，採用來自液晶面板正下方、以數條冷陰極管（CCFL )照射光、稱爲「正下方型」的照射方式，該「正下方型 」之光照射方式，必須具有爲使燈影像消失以使光均勻地 照射於液晶面板時之光擴散板。 近年來’於顯示裝置業界中，由於成本競爭變得愈來 愈爲嚴苛’對應於此’企求使用更少條數的更高出力之冷 陰極管’對液晶面板進行光照射。伴隨於此，欲使光之擴 散性變高、且板厚度變薄、予以低成本化時，亦企求不會 降低光擴散性之光擴散板。 -5- 201026766 此外’伴隨顯示裝置之大型化，企求尺寸安定性及形 狀安定性優異的光擴散板。 由於苯乙烯系樹脂與苯乙烯-甲基丙烯酸甲酯共聚合 樹脂（MS樹脂）、甲基丙烯酸甲酯系樹脂相比時較爲低 價’飽和吸濕量小 '尺寸安定性及形狀安定性優異，故使 用在苯乙烯系樹脂中配合有光擴散劑之苯乙烯系樹脂組成 -物’製造顯不裝置用之光擴散板。 另外’使配合有光擴散劑之苯乙烯系樹脂組成物使用 0 於透過型螢幕等螢幕透鏡、或照明器具、照明看板等之其 他光學用途，亦爲已知。 配合有光擴散劑之苯乙烯系樹脂組成物，（1)在由 苯乙烯系單體單位80〜99質量％、甲基丙烯酸單體單位 20〜1質量％及其他乙烯基化合物單體單位0〜10質量％所 成的苯乙烯系聚合物中，配合有折射率爲1.52以下、平 均粒徑爲1〜20 μπι之未熔融化合物的螢幕透鏡用成形體或 光擴散板用成形體等所使用的苯乙烯系樹脂組成物（參照 〇 專利文獻1 )，（ 2 )表層與裏層係由配合有相對於苯乙烯 系聚合物之折射率差爲0.005以內的交聯苯乙烯系聚合物 粒子等所成的未熔融化合物之苯乙烯系樹脂組成物所成， 中間層係由配合有相對於苯乙烯系聚合物之折射率差爲 0.05〜0.15之交聯甲基丙烯酸甲酯系聚合物粒子等所成的 未熔融化合物之苯乙烯系樹脂組成物所成的多層薄片（參 照專利文獻2 )，以及（3 )在具有1〜1 〇重量％ (甲基） 丙烯酸系單體單位之苯乙烯系單體-(甲基）丙烯酸系單 -6 - 201026766 體共聚物中，配合有折射率差爲0.04〜0.12、重量平均粒 徑爲1,0〜ΙΟμιη之有機交聯粒子的光擴散性苯乙烯系樹脂 組成物（參照專利文獻3)，係爲已知。 然而，前述（1)之苯乙烯系樹脂組成物，藉由配合 二氧化矽或交聯聚有機基矽氧烷所成的未熔融化合物，苯 — 乙烯系樹脂之強度顯著降低。而且，前述（〇之苯乙烯 ' 系樹脂組成物，由於使用使高純度水晶粉碎且在高溫的火 〇 焰中予以熔融球狀化後、進行分級，或使高純度水晶粉碎 後進行分級、所得的二氧化矽粒子或交聯聚有機基矽氧烷 粒子的高價粒子作爲未熔融化合物，即使基體之苯乙烯系 樹脂爲低價者，苯乙烯系樹脂組成物全體之成本變高，且 不易以經濟性價格提供光擴散性優異的苯乙烯系樹脂組成 物及由該組成物所成的成形體。其次，前述（1 )僅著重 於由二氧化矽或交聯聚有機基矽氧烷所成的未熔融化合物 之平均粒徑，完全沒有提及任何有關粒度分布。此外，前 〇 述（1)之苯乙烯系樹脂組成物，以未熔融化合物（二氧 化矽粒子或交聯聚有機基矽氧烷粒子）之平均粒徑爲1〜 2 0μπι較佳，以1.5〜19μιη更佳，於實施例中使用平均粒 徑爲2〜18μιη之未熔融化合物（二氧化矽粒子或交聯聚有 機基矽氧烷粒子）’惟使用平均粒徑爲3 μηι以上之未熔融 化合物時，不易藉由配合少量的未熔融化合物，製得光擴 散性優異的苯乙烯系樹脂組成物及成形體。 於前述（2)中，在中間層所配合的由交聯甲基丙烯 酸甲酯系聚合物粒子所成的未熔融化合物之平均粒徑爲2 201026766 〜ΙΟμιη、較佳者爲3〜8μιη，平均粒徑未達2μιη時，會有 光擴散性降低情形。然而，交聯甲基丙烯酸甲酯聚合物粒 子之平均粒徑大於2.5μπι時，藉由少量的配合量，實際上 不易製得光擴散性優異的苯乙烯系樹脂組成物或積層薄片 等。而且，於前述（2)中，沒有提及著重於有關作爲未 熔融化合物所使用的交聯苯乙烯系聚合物粒子或交聯甲基 丙烯酸甲酯系聚合物粒子之粒度分布。 於前述（3)之苯乙烯系樹脂組成物中，有機交聯粒 @ 子之重量平均粒徑以3〜8μιη較佳，於實施例中配合重量 平均粒徑爲3.1〜5.5μιη之有機交聯粒子。然而，使用平 均粒徑爲3μηι以上之有機交聯粒子時，實際上藉由少量的 配合，不易製得光擴散性優異的苯乙烯系樹脂組成物及成 形體。而且，於前述（3)中，亦沒有提及著重於作爲光 擴散劑使用的有機交聯粒子的粒度分布。 〔專利文獻〕 [專利文獻1]日本特開20 06-124522號公報 〇 [專利文獻2]日本特開2006-168088號公報 [專利文獻3]日本特開2007-204536號公報 【發明內容】 本發明之目的，係提供一種可賦予具有高光擴散性， 且擴散光之透過性優異、沒有散射透過光帶有黃化的問題 、尺寸安定性及形狀安定性優異的成形體或其他製品的苯 乙烯系樹脂組成物。 -8- 201026766 本發明之目的，係提供一種由該苯乙烯系樹脂組成物 所成的成形體。 在透明的樹脂中配合有光擴散劑粒子之樹脂組成物及 由該組成物所成的成形體之光擴散性能，與樹脂及光擴散 劑粒子之折射率差、光擴散劑粒子之粒徑、光擴散劑粒子 • 之含量等有關，且樹脂及光擴散劑粒子之折射率差愈大時 '、或光擴散劑粒子之粒徑愈大時，藉由1個光擴散劑粒子 φ 以使光擴散係數愈大。然而，由於光擴散劑粒子之粒徑愈 大時，光擴散劑粒子之質量愈大，故在樹脂中之光擴散劑 粒子的含量（質量）一定時，樹脂中所含的光擴散劑粒子 之個數變少，以各光擴散劑粒子之光擴散係數與在樹脂中 所含的光擴散劑粒子之個數的積爲基準，不一定全體的光 擴散性能皆必須變高。 另外，在透明的樹脂中所含的光擴散劑粒子之粒徑變 得過小時，波長較短的光被更強烈地散射，與散射光的波 Ο 長相關性變大，故散射透過光帶有黃色現象。 而且，透明的樹脂與光擴散劑粒子之折射率差變得過 大時，全光線透過率降低，例如使用作爲顯示裝置之光擴 散板、透過型螢幕、照明器具之外罩、照明看板等時，變 得無法得到充分的明亮度。 此外，在透明的樹脂中所含的光擴散劑粒子之耐熱性 不充分，熔融成形時等失去光擴散劑粒子原有的形態或特 性時，變得無法發揮作爲光擴散劑粒子之特性。 本發明人等考慮於苯乙烯系樹脂中含有光擴散劑粒子 -9- 201026766 ，製造光擴散性之苯乙烯系樹脂組成物時，爲具有高的光 擴散性，同時可防止散射透過光帶有黃色情形，維持高的 全光線透過率時，就每1個苯乙烯系樹脂中所含的光擴散 劑粒子之光擴散係數與樹脂中所含的光擴散劑粒子之個數 (量）的平衡性而言，光擴散劑粒子必須使用由在與苯乙 烯系樹脂間具有適合於光擴散的折射率差之特定材料所成 · 者，此時有最適合的粒徑範圍及粒度分布存在，遂而完成 © 另外，本發明人等檢討有關含有光擴散劑粒子之苯乙 烯系樹脂組成物於熔融成形時等，可維持光擴散劑粒子原 有的形態或特性的光擴散劑粒子之交聯度。 其次，有鑑於上述情形，再三深入硏究檢討的結果， 發現在苯乙烯系樹脂中含有體積平均粒徑爲0.7〜2.5μιη( 較佳者爲〇·8〜2·0μιη、更佳者爲0.9〜1 ·5μιη )，且體積平 均粒徑/數平均粒徑之値爲1.2以下（較佳者爲1.0 5以下 、更佳者爲1.02以下），粒度分布狹窄，具有特定的交 〇 聯度之（甲基）丙烯酸酯系樹脂所成的交聯樹脂微粒子作 爲光擴散劑時，即使進行熔融成形等，在不會損害前述交 聯樹脂粒子之前述形態或原有特性下仍可被維持，可得賦 予光擴散性優異，同時擴散光之透過性優異、不會有散射 透過光帶有黃色的問題、尺寸安定性及形狀安定性優異的 成形體等之苯乙烯系樹脂組成物，遂而完成本發明。 此外’本發明人等發現藉由相對於苯乙烯系樹脂，以 特定的比例配合由（甲基）丙烯酸酯系樹脂所成的前述交 -10- 201026766 聯樹脂微粒子時，可更爲順利地製得光擴散性及光透 優異，散射透過光不會產生光黃色化的前述苯乙烯系 組成物。 而且，本發明人等發現該交聯樹脂微粒子，以藉 散聚合法所製造的（甲基）丙烯酸酯系樹脂微粒子爲 粒子，於其中使含有交聯性單體之乙烯系單體吸收· ' 所得的交聯樹脂微粒子、及使藉由分散聚合法所製造 φ 有水解性矽烷基之（甲基）丙烯酸酯系樹脂微粒子交 得的交聯樹脂微粒子中一方或兩方，具備適合的本發 規定的平均粒徑、粒度分布及交聯度，良好地使用於 明之苯乙烯系樹脂組成物而得，以此等之各種見解爲 ，完成本發明。 換言之，本發明之苯乙烯系樹脂組成物’其特徵 對於全部構造單位之合計量1 00質量％而言，來自苯 系單體之構造單位的含有比例，爲8 0質量％以上的苯 Φ 系樹脂（A)、與交聯樹脂微粒子（B)所成的苯乙烯 脂組成物，其特徵爲該交聯樹脂微粒子（B)爲由（ )丙烯酸酯系樹脂所成的交聯樹脂微粒子（以下稱爲 件（bl )」），體積平均粒徑（dv)爲0.7〜2·5μιη ( 稱爲「要件（b2 )」），體積平均粒徑（dv )與數平 徑（dn)之比（dv/dn)爲1.2以下（以下稱爲「要件 )」）’且設定交聯點當量爲〇.15meq/g以上（以下 「要件（b4)」）。 其次，於本發明之苯乙烯系樹脂組成物中’前述 過性 樹脂 由分 種子 聚合 的具 聯所 明所 本發 基準 爲相 乙烯 乙烯 系樹 甲基 「要 以下 均粒 (b3 稱爲 苯乙 -11 - 201026766 烯系樹脂（A)及前述交聯樹脂微粒子（B)之含有比例， 於此等之合計爲100質量％時，各爲95.0〜99.5質量％及 0.5〜5.0質量％較佳，構成前述交聯樹脂微粒子（B )之來 自苯乙烯系單體之構造單位之含有比例，相對於全部構造 單位之合計量100質量％爲80質量％以上較佳。 此外，於本發明之苯乙烯系樹脂組成物中，前述交聯 _ 樹脂微粒子（B)以選自在藉由分散聚合法所製造的（甲 ^ 基）丙烯酸酯系樹脂微粒子所成的種子粒子中使含交聯性 @ 單體之乙烯系單體吸收·聚合所得的交聯樹脂微粒子（Ba )、及藉由分散聚合法所製造的具水解性矽烷基的（甲基 )丙烯酸酯系樹脂微粒子交聯所得的交聯樹脂微粒子（Bb )之交聯樹脂微粒子較佳。 其次’本發明之成形體，係由前述本發明之苯乙烯系 樹脂組成物所成的成形體，以使用於光學用途之成形體較 佳。 ❹ [發明效果] 本發明之苯乙烯系樹脂組成物，由於在苯乙烯系樹脂 (A)中含有具備前述要件（bl)〜（μ)之交聯樹脂微 粒子（B)、即具有本發明規定的特定之體積平均粒徑（ dv) ’且體積平均粒徑（dv)與數平均粒徑（dn)之比（ dv/dn )爲I.2以下、粒度分布狹窄、具有特定的設定交聯 點當量、耐熱性優異、由（甲基）丙烯酸酯系樹脂所成的 特定交聯樹脂微粒子（B)作爲光擴散劑，使用本發明之 -12- 201026766 苯乙烯系樹脂組成物，在加熱下進行熔融成形或其他成形 加工等處理時，在不會損害交聯樹脂微粒子之前述形態或 特性下仍可被維持，順利地製得具有高的光擴散性，且擴 散光之透過性優異，散射透過光不會帶有黃色之各種光學 用途中有效的成形體或製品。 * 由本發明之苯乙烯系樹脂組成物所成的成形體或製品 '，低吸濕性、尺寸安定性及形狀安定性優異。 〇 交聯樹脂微粒子（B)，由於使用藉由分散聚合法所 製造的（甲基）丙烯酸酯系樹脂微粒子所成的種子粒子中 使含有交聯性單體之乙烯系單體吸收•聚合所得的交聯樹 脂微粒子（Ba)、及使藉由分散聚合法所製造的具有水解 性矽烷基之（甲基）丙烯酸酯系樹脂微粒子交聯所得的交 聯樹脂微粒子（Bb)中任何一方或兩方，可以上述方法確 實且順利地製造本發明規定的前述具有特定的體積平均粒 徑（dv )、特定的體積平均粒徑（dv )與數平均粒徑（dn ® )之比例（dv/dn )、及特定的設定交聯點當量之該交聯 樹脂微粒子（Ba )及交聯樹脂微粒子（Bb )，故可確實地 、簡單地製得具有前述的高光擴散性能及良好的擴散光透 過性，且可賦予不會產生散射透過光具有黃色現象的成形 體之本發明苯乙烯系樹脂組成物。 由於本發明所使用的由（甲基）丙烯酸酯系樹脂所成 的交聯樹脂微粒子（B )，與前述專利文獻1所揭示的使 作爲光擴散劑使用的純水晶予以粉碎所成的二氧化矽或交 聯聚有機基矽氧烷等所成的未熔融化合物相比時爲低價者 -13- 201026766 ，故可提供一種經濟價格的具有前述優異特性之本發明苯 乙烯系樹脂組成物及成形體。 本發明之苯乙烯系樹脂組成物及由該組成物所成的成 形體，可使前述優異的特性活性化，有效地使用於液晶電 視等大型顯示裝置用之光擴散板、透過型螢幕等之螢幕透 鏡、照明器具、照明看板等之光學用途。 · 特別是於本發明之苯乙烯系樹脂組成物中，苯乙烯系 ’ 樹脂（A )及交聯樹脂微粒子（B )之含有比例，於此等合 @ 計爲100質量％時，各爲95.0〜99.5質量％及0.5〜5.0質 量％，不僅可以成本經減低、順利地製造具有習知的液晶 面板中使用的光擴散板所要求的物性（板厚1 .5mm之光擴 散率爲70%以上、全光線透過率爲60%〜65%及散射透過 光之黃色度爲20以下）之光擴散板，且使用以較少條數 的較高出力之冷陰極管所製作的近年來之液晶面板所使用 的具備光擴散板時要求的物性（光擴散率爲90%以上、全 光線透過率爲55%〜65%及散射透過光之黃色度爲1〇以下 Θ )之光的光擴散板。 [爲實施發明之形態] 於下述中詳細說明有關本發明。 本發明之苯乙烯系樹脂組成物，就苯乙烯系樹脂組成 物之熔融流動性、成形性、耐熱性、耐吸濕性、折射率等 而言，使用相對於構成該苯乙烯系樹脂（A)之全部構造 單位的合計量100質量％而言，來自苯乙烯系單體之構造 -14- 201026766 單位的含有比例爲80質量％以上之樹脂作爲苯乙烯系樹脂 (A)。來自苯乙烯系單體之構造單位的含有比例，較佳 者爲90質量％以上，更佳者爲95〜1〇〇質量％。 形成苯乙烯系樹脂（A)之苯乙烯系單體，例如苯乙 烯、α-甲基苯乙烯、p_甲基苯乙烯、〇_甲基苯乙烯、…甲 * 基苯乙烯、乙烯基甲苯、p-乙基苯乙烯、p-t-丁基-苯乙烯 、p-n-丁基苯乙烯、p_n_己基苯乙烯、p_辛基苯乙烯、2,4_ G 二甲基苯乙烯、P -甲氧基苯乙烯、P -苯基苯乙烯、〇 -氯化 苯乙烯、m-氯化苯乙烯、p_氯化苯乙烯、2,4-二氯化苯乙 烯等’苯乙烯系樹脂（A)可由1種或2種以上此等之苯 乙嫌系單體所成。 於此等之中，苯乙烯系樹脂（A )係由苯乙烯所成， 惟就苯乙烯系樹脂之取得容易性、成本、聚合性等而言較 佳。 苯乙烯系樹脂（A)具有來自苯乙烯系單體之構造單 Φ 位與來自除苯乙烯系單體外之單體的構造單位時，其他的 單體例如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（ 甲基）丙烯酸丁酯等之（甲基）丙烯酸酯類；（甲基）丙 烯腈等之氰化乙烯基單體；（甲基）丙烯酸、馬來酸酐、 馬來酸、衣康酸酐、衣康酸等之不飽和羧酸或其酸酐；馬 來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、N-環 己基馬來醯亞胺等含二羧酸醯亞胺基之單體等。此等之苯 乙烯系樹脂（A)，可含有1種或2種以上來自此等其他 單體之構造單位。 -15- 201026766 苯乙烯系樹脂（A)爲具有來自其他單體之構造單位 時’來自其他單體之構造單位爲來自（甲基）丙烯酸、馬 來酸酐之構造單位，就共聚合性、耐熱性、成本等而言較 佳。 本發明所使用的苯乙烯系樹脂（A)之分子量，沒有 特別的限制。就苯乙烯系樹脂組成物之成形加工性、特別 · 是熔融成形性、所得的成形體之強度等而言，以凝膠色層 ’ 分析法（GPC )測定的聚苯乙烯換算之重量平均分子量（ @[Technical Field] The present invention relates to a styrene resin composition and a molded body formed from the composition. More specifically, the present invention relates to a styrene system which is excellent in light diffusibility, excellent in diffused light transmittance, yellowed without scattering light, and excellent in dimensional stability and shape stability. A resin composition and a formed body composed of the styrene resin composition. The molded article formed of the styrene resin composition of the present invention can activate the above-mentioned excellent characteristics, and can be effectively used for a light diffusing plate such as a liquid crystal display device, a Fresnel lens, a concave-convex lens, a lighting fixture, or the like. Optical use such as electrophotography. [Prior Art] In a large-sized display device such as a liquid crystal television, in order to obtain a sufficient brightness φ, a light is emitted from a liquid crystal panel directly under a plurality of cold cathode tubes (CCFLs), which is called a "normally low type". In the irradiation method, the "next-down type" light irradiation method must have a light diffusion plate for causing the light image to disappear to uniformly illuminate the liquid crystal panel. In recent years, in the display device industry, cost competition has become more and more severe. In response to this, it has been desired to use a cold cathode tube of a lower number of outputs to lightly illuminate the liquid crystal panel. Along with this, in order to increase the light diffusibility and to reduce the thickness of the sheet and to reduce the cost, it is also desired to reduce the light diffusing property. -5- 201026766 In addition, as the size of the display device has increased, a light diffusing plate excellent in dimensional stability and shape stability has been sought. Since the styrene resin is relatively inexpensive compared with styrene-methyl methacrylate copolymer resin (MS resin) or methyl methacrylate resin, 'saturated moisture absorption is small' dimensional stability and shape stability Since it is excellent, it uses the styrene resin composition which melt|blends a styrene-type resin with the light-diffusion agent, and manufactures the light-diffusion board of the display apparatus. Further, it is also known to use a styrene resin composition containing a light diffusing agent for other optical applications such as a screen lens such as a transmissive screen, or a lighting fixture or a lighting panel. The styrene resin composition containing a light diffusing agent is (1) 80 to 99% by mass of the styrene monomer unit, 20 to 1% by mass of the methacrylic monomer unit, and other vinyl compound monomer units. In the styrene-based polymer to be used in an amount of 5% by mass or less, a molded article for a screen lens or a molded article for a light-diffusing sheet having an unmelted compound having a refractive index of 1.52 or less and an average particle diameter of 1 to 20 μm is used. The styrene resin composition (see Patent Document 1), (2) the surface layer and the inner layer are crosslinked styrene polymer particles having a refractive index difference of 0.005 or less with respect to the styrene polymer. The styrene-based resin composition of the unmelted compound is formed, and the intermediate layer is made of a crosslinked methyl methacrylate polymer particle having a refractive index difference of 0.05 to 0.15 with respect to the styrene polymer. a multilayer sheet formed of a styrene resin composition of an unmelted compound (see Patent Document 2), and (3) a styrene system having 1 to 1% by weight of a (meth)acrylic monomer unit monomer-( a light-diffusing styrene resin composition containing an organic crosslinked particle having a refractive index difference of 0.04 to 0.12 and a weight average particle diameter of 1,0 to ΙΟμηη in a methyl methacrylate-based single-6 - 201026766 bulk copolymer. (refer to Patent Document 3), it is known. However, in the styrene resin composition of the above (1), the strength of the styrene-based resin is remarkably lowered by the addition of the unmelted compound of cerium oxide or crosslinked polyorganosiloxane. Further, the above-mentioned styrene-based resin composition is obtained by pulverizing high-purity crystals and spheroidizing them in a high-temperature smoldering flame, and then classifying them, or pulverizing high-purity crystals and classifying them. The high-valent particles of the cerium oxide particles or the cross-linked polyorganosiloxane particles are not melted, and even if the styrene resin of the matrix is low, the cost of the styrene resin composition is high, and it is difficult to The styrene resin composition excellent in light diffusibility and the molded body formed from the composition are provided at an economical price. Second, the above (1) focuses only on cerium oxide or crosslinked polyorganosiloxane. The average particle diameter of the unmelted compound is not mentioned at all with respect to the particle size distribution. Further, the styrene resin composition of the above (1) is an unmelted compound (cerium oxide particles or crosslinked polyorganoquinone). The average particle diameter of the oxyalkylene particles is preferably from 1 to 2 0 μm, more preferably from 1.5 to 19 μm, and in the examples, an unmelted compound (cerium oxide having an average particle diameter of from 2 to 18 μm is used. When particles or crosslinked polyorganosiloxane particles are used, when an unmelted compound having an average particle diameter of 3 μη or more is used, it is difficult to obtain a styrene resin having excellent light diffusibility by blending a small amount of unmelted compound. In the above (2), the average particle diameter of the unmelted compound formed of the crosslinked methyl methacrylate polymer particles blended in the intermediate layer is 2 201026766 to ΙΟμιη, preferably 3~8μιη, when the average particle diameter is less than 2μηη, there is a case where the light diffusibility is lowered. However, when the average particle diameter of the crosslinked methyl methacrylate polymer particles is more than 2.5 μm, a small amount of the compounding amount is actually It is difficult to obtain a styrene resin composition or a laminated sheet which is excellent in light diffusibility, and in the above (2), there is no mention of focusing on crosslinked styrene polymer particles used as an unmelted compound or The particle size distribution of the crosslinked methyl methacrylate polymer particles. In the styrene resin composition of the above (3), the weight average particle diameter of the organic crosslinked particles is 3 to 8 μm. Preferably, in the examples, organic crosslinked particles having a weight average particle diameter of 3.1 to 5.5 μm are blended. However, when organic crosslinked particles having an average particle diameter of 3 μη or more are used, it is practically difficult to obtain light by a small amount of blending. A styrene-based resin composition and a molded article having excellent diffusibility. Further, in the above (3), there is no mention of focusing on the particle size distribution of the organic crosslinked particles used as the light diffusing agent. [Patent Literature] [Patent Literature] [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei. No. 2007-168088 (Patent Document 3) Japanese Patent Application Publication No. 2007-204536 (Invention) The object of the present invention is to provide a A styrene resin composition which has high light diffusibility, is excellent in diffused light transmittance, has no problem of yellowing of scattered light, and has a molded body or other product excellent in dimensional stability and shape stability. -8- 201026766 The object of the present invention is to provide a molded body composed of the styrene resin composition. The resin composition in which the light diffusing agent particles are blended in the transparent resin, and the light diffusing property of the molded body formed from the composition, the refractive index difference between the resin and the light diffusing agent particles, and the particle diameter of the light diffusing agent particles, When the content of the light diffusing agent particles is the same, and the refractive index difference between the resin and the light diffusing agent particles is larger, or the particle diameter of the light diffusing agent particles is larger, one light diffusing agent particle φ is used to light The larger the diffusion coefficient. However, as the particle size of the light diffusing agent particles is larger, the mass of the light diffusing agent particles is larger, so when the content (mass) of the light diffusing agent particles in the resin is constant, the light diffusing agent particles contained in the resin are The number of the light diffusing agent particles is less than the number of the light diffusing agent particles contained in the resin, and the light diffusing performance of all the light diffusing properties is not necessarily high. Further, when the particle diameter of the light diffusing agent particles contained in the transparent resin is too small, light having a short wavelength is more strongly scattered, and the correlation with the wavelength of the scattered light becomes large, so that the light is transmitted through the light band. There is a yellow phenomenon. Further, when the difference in refractive index between the transparent resin and the light diffusing agent particles is too large, the total light transmittance is lowered, and for example, when a light diffusing plate, a transmissive screen, a lighting fixture, a lighting panel, or the like as a display device is used, I can't get enough brightness. In addition, when the light diffusing agent particles contained in the transparent resin are insufficient in heat resistance, and the original form or characteristics of the light diffusing agent particles are lost during melt molding, the properties of the light diffusing agent particles are not exhibited. The present inventors have considered that when a light diffusing agent styrene resin composition is produced by containing a light diffusing agent particle -9-201026766 in a styrene resin, it has high light diffusibility and can prevent scattering light transmission. In the case of yellow, when the total light transmittance is maintained, the light diffusing coefficient of the light diffusing agent particles contained in each styrene resin is balanced with the number (quantity) of the light diffusing agent particles contained in the resin. In particular, the light diffusing agent particles must be made of a specific material having a refractive index difference suitable for light diffusion between the styrene resin, and the most suitable particle size range and particle size distribution are present. In addition, the inventors of the present invention have reviewed the degree of crosslinking of the light diffusing agent particles which maintain the original form or characteristics of the light diffusing agent particles during the melt molding, etc., in the styrene resin composition containing the light diffusing agent particles. . Next, in view of the above, the results of the review were further examined and found to contain a volume average particle diameter of 0.7 to 2.5 μm in the styrene resin (preferably 〇·8 to 2·0 μιη, and more preferably 0.9). 〜1·5μιη), and the volume average particle diameter/number average particle diameter is 1.2 or less (preferably 1.05 or less, more preferably 1.02 or less), and the particle size distribution is narrow, and has a specific cross-linking degree. When the crosslinked resin fine particles of the (meth)acrylate resin are used as a light diffusing agent, they can be maintained without being damaged by the above-described form or original characteristics of the crosslinked resin particles, even if they are melt-molded or the like. A styrene resin composition which is excellent in light diffusibility, is excellent in diffused light transmittance, has no problem of scattering yellow light, and has excellent dimensional stability and shape stability, and is completed. this invention. In addition, the present inventors have found that the blending of the above-mentioned -10-201026766 resin fine particles formed of a (meth) acrylate-based resin can be more smoothly produced by a specific ratio with respect to the styrene-based resin. It is excellent in light diffusibility and light transmission, and the styrene-based composition which does not cause light yellowing by scattering transmitted light. In addition, the present inventors have found that the (meth)acrylate resin fine particles produced by the dispersion polymerization method are particles of the crosslinked resin fine particles, and the vinyl monomer containing the crosslinkable monomer is absorbed therein. One or both of the obtained crosslinked resin fine particles and the crosslinked resin fine particles obtained by dispersing the (meth)acrylate resin fine particles of the φ hydrolyzable alkylene group produced by the dispersion polymerization method, and the like The predetermined average particle diameter, particle size distribution, and degree of crosslinking are preferably used in a styrene-based resin composition of the present invention, and the present invention has been completed in view of various findings. In other words, the styrene-based resin composition of the present invention is characterized in that the content ratio of the structural unit derived from the benzene-based monomer is 80% by mass or more based on the total amount of all the structural units of 100% by mass. The styrene resin composition of the resin (A) and the crosslinked resin fine particles (B) is characterized in that the crosslinked resin fine particles (B) are crosslinked resin fine particles composed of () an acrylate resin (hereinafter It is called (bl)"), and the volume average particle diameter (dv) is 0.7 to 2·5 μmη (referred to as "requirement (b2)"), and the ratio of the volume average particle diameter (dv) to the number of planes (dn) ( Dv/dn) is 1.2 or less (hereinafter referred to as "required")") and the cross-linking point equivalent is set to 〇.15 meq/g or more (hereinafter, "requirement (b4)"). Next, in the styrene-based resin composition of the present invention, the above-mentioned pass-through resin is polymerized by a seed-separating method, and the base is a vinylidene-based methyl group. -11 - 201026766 The ratio of the content of the olefinic resin (A) and the crosslinked resin fine particles (B) is preferably from 95.0 to 99.5 mass% and from 0.5 to 5.0 mass%, respectively, when the total amount thereof is 100% by mass. The content ratio of the structural unit derived from the styrene-based monomer constituting the crosslinked resin fine particles (B) is preferably 80% by mass or more based on 100% by mass of the total of all structural units. Further, the styrene of the present invention. In the resin composition, the crosslinked-resin fine particles (B) are made to contain crosslinkable @ monomer in seed particles selected from fine particles of (meth) acrylate-based resin produced by a dispersion polymerization method. A crosslinked tree obtained by crosslinking the crosslinked resin fine particles (Ba) obtained by absorption and polymerization of a vinyl monomer and the (meth)acrylate resin fine particles having a hydrolyzable alkylene group produced by a dispersion polymerization method The crosslinked resin fine particles of the lipid fine particles (Bb) are preferred. The molded article of the present invention is preferably a molded article obtained from the styrene resin composition of the present invention, which is preferably used for an optical use.发明 [Effect of the invention] The styrene resin composition of the present invention contains the crosslinked resin fine particles (B) having the above-mentioned requirements (b1) to (μ) in the styrene resin (A), that is, the present invention The specific volume average particle diameter (dv) 'and the ratio of the volume average particle diameter (dv) to the number average particle diameter (dn) (dv/dn) is I.2 or less, the particle size distribution is narrow, and the specific cross-linking is specified. The specific crosslinked resin fine particles (B) made of a (meth) acrylate resin are used as a light diffusing agent, and the styrene resin composition of -12-201026766 of the present invention is used under heating. When the treatment such as melt molding or other forming processing is performed, the shape and characteristics of the crosslinked resin fine particles are not impaired, and the light diffusing property is smoothly obtained, and the diffused light is excellent in permeability and scattering. Through The light does not have a molded article or product which is effective for various optical applications in yellow. * The molded article or product formed by the styrene resin composition of the present invention is excellent in low hygroscopicity, dimensional stability, and shape stability. The ruthenium crosslinked resin fine particles (B) are obtained by absorbing and polymerizing a vinyl monomer containing a crosslinkable monomer in seed particles formed by using (meth) acrylate resin fine particles produced by a dispersion polymerization method. The obtained crosslinked resin fine particles (Ba) and the crosslinked resin fine particles (Bb) obtained by crosslinking the (meth)acrylate resin fine particles having a hydrolyzable alkylene group produced by a dispersion polymerization method or Both of them can reliably and smoothly produce the above-mentioned specific volume average particle diameter (dv), specific volume average particle diameter (dv) and number average particle diameter (dn ® ) prescribed by the present invention (dv/). Dn), and the crosslinked resin fine particles (Ba) and the crosslinked resin fine particles (Bb) having a specific cross-linking point equivalent, so that the above-described high light diffusing property can be obtained reliably and simply The styrene resin composition of the present invention which is excellent in diffused light transmittance and which can provide a molded body which does not cause scattering of transmitted light and has a yellow color. The crosslinked resin fine particles (B) made of the (meth) acrylate-based resin used in the present invention are oxidized by the use of the pure crystal used as the light diffusing agent disclosed in Patent Document 1 When the unmelted compound formed by ruthenium or cross-linked polyorganosiloxane or the like is a low-cost product - 13 to 201026766, it is possible to provide the styrene resin composition of the present invention having the above-mentioned excellent characteristics at an economical price and Shaped body. The styrene resin composition of the present invention and the molded article formed from the composition can be used for a light diffusing plate, a transmissive screen, or the like for a large display device such as a liquid crystal television. Optical applications such as screen lenses, lighting fixtures, and lighting panels. In particular, in the styrene resin composition of the present invention, the content ratio of the styrene-based resin (A) and the crosslinked resin fine particles (B) is 95.0 each in the case of 100% by mass. ～99.5 mass% and 0.5 to 5.0 mass%, the physical properties required for a light diffusing plate used in a conventional liquid crystal panel can be manufactured at a reduced cost (the light diffusivity of a plate thickness of 1.5 mm is 70% or more) a light diffusing plate having a total light transmittance of 60% to 65% and a yellow light having a transmitted light having a yellowness of 20 or less, and using a liquid crystal panel made of a cold cathode tube having a relatively high number of outputs A light diffusing plate which is required to have a physical property (light diffusivity of 90% or more, total light transmittance of 55% to 65%, and yellowness of scattered light transmitted by 1 〇 or less) required for the light diffusing plate to be used. [Formation for Carrying Out the Invention] The present invention will be described in detail below. The styrene resin composition of the present invention is used to form the styrene resin (A) in terms of melt fluidity, moldability, heat resistance, moisture absorption resistance, refractive index, and the like of the styrene resin composition. The resin content of the structure of the styrene-based monomer-14-201026766 is 80% by mass or more of the styrene-based resin (A). The content ratio of the structural unit derived from the styrene monomer is preferably 90% by mass or more, and more preferably 95 to 1% by mass. a styrene-based monomer forming a styrene-based resin (A), such as styrene, α-methylstyrene, p-methylstyrene, fluorene-methylstyrene, methylated styrene, vinyltoluene , p-ethylstyrene, pt-butyl-styrene, pn-butylstyrene, p_n-hexylstyrene, p-octylstyrene, 2,4_ G dimethylstyrene, P-methoxy 'styrene-based resin (A) such as styrene, P-phenylstyrene, fluorene-chlorinated styrene, m-chlorostyrene, p-chlorinated styrene, 2,4-dichlorostyrene It can be formed from one or more of these styrene-based monomers. Among these, the styrene resin (A) is made of styrene, and it is preferable in terms of ease of availability, cost, polymerizability, and the like of the styrene resin. When the styrene resin (A) has a structural Φ position from a styrene monomer and a structural unit derived from a monomer other than the styrene monomer, other monomers such as methyl (meth)acrylate, (meth) acrylate such as ethyl methacrylate or butyl (meth) acrylate; vinyl cyanide monomer such as (meth) acrylonitrile; (meth)acrylic acid, maleic anhydride, horse An unsaturated carboxylic acid such as acid, itaconic anhydride or itaconic acid or an anhydride thereof; maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexyl A monomer containing a quinone dicarboxylate such as maleimide or the like. These styrene-based resins (A) may contain one or two or more structural units derived from such other monomers. -15- 201026766 When the styrene resin (A) has a structural unit derived from another monomer, the structural unit derived from other monomers is a structural unit derived from (meth)acrylic acid or maleic anhydride, and is copolymerizable and heat resistant. It is better in terms of sex, cost, and the like. The molecular weight of the styrene resin (A) used in the present invention is not particularly limited. The polystyrene-equivalent weight average molecular weight measured by the gel chromatography layer analysis method (GPC), the molding processability of the styrene resin composition, the melt moldability, the strength of the obtained molded body, and the like ( @

Mw )，以 50,000 〜1,000,000 較佳，以 1 00,000 〜500,000 更佳。 苯乙烯系樹脂（A)之分子量分布（Mw/Mn)爲1.5〜 3 . 5，就所得的成形體之強度等而言較佳。 而且，本乙燒系樹脂（A)之折射率，以1.55以上較 佳，以1.57以上更佳，以1.58〜1.62最佳。 此外，本說明書所指的折射率，係指以JIS K7015之 方法爲基準，使用Abbe折射率計' 以波長5 89nm、25t 0 所測定的折射率。 本發明之苯乙烯系樹脂組成物，含有滿足下述要件（ bl)〜（b4)之交聯樹脂微粒子（B)。 (bl)由（甲基）丙烯酸酯系樹脂所成的交聯樹脂微 粒子。 (b2)體積平均粒徑（dv)爲0.7〜2_5μιη。 (b3 )體積平均粒徑（dv )與數平均粒徑（dn )之比 例（dv/dn)爲1.2以下。 -16- 201026766 (b4)設疋父聯點當量爲〇_i5meq/g以上。 父聯樹脂微粒子（B)，係由以來自（甲基）丙烯酸 醋之構造單位爲主體的（甲基）丙烯酸酯系樹脂所構成（ 要件（bl))、構成該（甲基）丙烯酸酯系樹脂之來自（ 甲基）丙烯酸酯的構造單位之含有比例，較佳者爲50質 量％以上’更佳者爲80質量％以上，尤佳者爲90質量％以 上’最佳者爲95〜1 00質量％。特別是來自（甲基）丙烯 φ 酸酯之構造單位的含有比例爲80質量％以上時，可使交聯 樹脂微粒子（B)之折射率爲1.46〜1.49。 於構成交聯樹脂微粒子（B)之（甲基）丙烯酸酯系 樹脂中，來自（甲基）丙烯酸酯之構造單位的含有比例少 時，容易使交聯樹脂微粒子（B)之折射率變大，導致苯 乙烯系樹脂（A)與交聯樹脂微粒子（B)之折射率差變小 ，苯乙烯系樹脂組成物及由該組成物所成的成形體之光擴 散性降低，耐候性變得不充分。 Φ 爲使與苯乙烯系樹脂（A)之折射率差變大時，由（ 甲基）丙烯酸酯系樹脂所成的交聯樹脂微粒子（B)之折 射率，以1.51以下較佳，以1.46〜1.49更佳。 形成構成交聯樹脂微粒子（B)之（甲基）丙烯酸酯 系樹脂的（甲基）丙烯酸酯，例如單官能單體及交聯性單 體。前述交聯樹脂微粒子（B)，由於具備交聯構造，通 常具有來自交聯性單體之構造單位。該交聯構造可以具有 2個以上聚合性不飽和鍵之化合物爲基準者，亦可使用至 少具有1個聚合性不飽和鍵及水解性矽烷基之化合物、藉 -17- 201026766 由水解縮合之矽氧烷鍵爲基準者。 單官能單體例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、 甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯 、甲基丙烯酸第3 丁酯、甲基丙烯酸戊酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂酯等之甲 基丙烯酸的烷酯；丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯 、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第3-丁酯、丙烯 酸戊醋、丙烯酸2-乙基己酯、丙烯酸月桂酯、丙烯酸硬脂 ❹ 酯等之丙烯酸的烷酯；（甲基）丙烯酸環己酯、（甲基） 丙烯酸異冰片酯等（甲基）丙烯酸之含脂環基的酯；（甲 基）丙烯酸環氧丙酯、（甲基）丙烯酸四氫呋喃酯等（甲 基）丙烯酸之含雜環基的酯；（甲基）丙烯酸2-羥基乙酯 、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸3-羥基丙 酯等（甲基）丙烯酸之羥基烷酯；（甲基）丙烯酸2 -甲氧 基乙酯等之（甲基）丙烯酸的烷氧基烷酯等。此等之化合 物可單獨使用，亦可使用2種以上。而且，於此等之中， @ 就粒子之耐熱嵌段性、耐候性、折射率而言，以甲基丙烯 酸甲酯及甲基丙烯酸異丁酯較佳。 交聯性單體例如二（甲基）丙烯酸乙二醇酯、三（甲 基）丙烯酸三羥甲基丙烷酯、三（甲基）丙烯酸季戊四醇 酯、四（甲基）丙烯酸季戊四醇酯等（甲基）丙烯酸之多 元醇酯；（甲基）丙烯酸烯丙酯；（甲基）丙烯酸三甲氧 基矽烷基丙酯等（甲基）丙烯酸之烷氧基矽烷基烷酯等。 此等之化合物’可單獨使用，亦可2種以上使用。於此等 -18- 201026766 之中，爲可以高收率及高生產性進行合成交聯密度高 子時，以（甲基）丙烯酸之烷氧基矽烷基烷酯較佳。 前述（甲基）丙烯酸酯系樹脂，相對於來自構成 甲基）丙烯酸酯系樹脂之單官能（甲基）丙烯酸酯的 單位之全量爲1 〇 〇質量％而言，較佳者爲6 0質量％以 更佳者爲6 5質量％以上，最佳者爲7 0〜1 0 0質量％， 來自甲基丙烯酸甲酯之構造單位及/或來自甲基丙烯 φ 丁酯之構造單位所成的（甲基）丙烯酸酯系樹脂較佳 交聯樹脂微粒子（B)，可爲自表面至內部皆爲 組成的粒子，亦可爲芯殼型粒子。爲後者時，對於殻 數沒有特別的限制。 本發明所使用的交聯樹脂微粒子（B)，其體積 粒徑（dv)爲0.7〜2.5μιη (要件（b2))，以0.8〜2 較佳，以〇_9〜1 ·5μιη更佳。 交聯樹脂微粒子（Β)之體積平均粒徑（dv)過 〇 ’苯乙烯系樹脂組成物及由該組成物所得的成形體等 擴散性能無法爲充分的高値，產生散射透過光帶有黃 問題。另外，交聯樹脂微粒子（B )之體積平均粒徑 )過大時，會有苯乙烯系樹脂組成物及由該組成物所 成形體等之光擴散性能降低的情形。 本發明所使用的交聯樹脂微粒子（B )，以體積 粒徑（dv)與數平均粒徑（dn)之比例（dv/dn)爲1. 下（要件（b3 ))，以1.05以下較佳，以1.02以下 的粒 該（ 構造 上， 以由 酸異 〇 均勻 層之 平均 • 0 μιη 小時 之光 色的 (d ν 得的 平均 2以 更佳 -19- 201026766 體積平均粒徑（dv )與數平均粒徑（dn )之比例（ dv/dn)的値接近1時，係指粒度分布狹窄，交聯樹脂微 粒子（B)之尺寸一致。 本發明所使用的交聯樹脂微粒子（B)，以體積平均 粒徑（dv)與數平均粒徑（dn)之比例（dv/dn)爲1.2以 下，藉由極爲接近1時，粒度部分狹窄，具有均勻的尺寸 〇 此處，本說明書之交聯樹脂微粒子（B)之體積平均 @ 粒徑（dv )與數平均粒徑（dn )，使用掃描型電子顯微鏡 ，以攝影交聯樹脂微粒子（B)之粒子影像爲基準所計算 的體積平均粒徑（dv )及數平均粒徑（dn )，其詳細的計 算方法，如下述之實施例中記載。 本發明所使用的交聯樹脂微粒子（B)，係在苯乙烯 系樹脂（A )中配合交聯樹脂微粒子，且在高溫下進行成 形加工、特別是熔融成形時，爲防止交聯樹脂微粒子（B )之熔融、變形、形態變化、於粒子間之熔融凝聚等，充 〇 分發揮作爲光擴散劑之機能時，設定交聯點當量爲 0.15meq/g以上（要件（b4))，以0.3meq/g以上較佳， 以0.5 meq/g以上更佳。交聯樹脂微粒子（B)之設定交聯 點當量的上限値，沒有特別的限制，就不會使製造上造成 困難、及成本而言，較佳者爲l〇meq/g，更佳者爲5meq/g 〇 使用含有設定交聯點當量過小的交聯樹脂微粒子之苯 乙烯系樹脂組成物時，藉由熔融成形等進行成形加工時， -20- 201026766 交聯樹脂微粒子（B)會產生熔融、變形、形態變化、在 粒子間之溶融凝聚等情形’無法製得光擴散性優異的成形 體等。 此處’本說明書之「交聯樹脂微粒子（B)之設定交 聯點當量（meq/g )」，係指以製造交聯樹脂微粒子時所 使用的交聯性單體之交聯性反應基的當量爲基準之値，由 下述之數式（I )求取。 φ 交聯樹脂微粒子（B)之設定交聯點當量=(Dxn)/W (I) (式中’ D係表示製造交聯樹脂微粒子（b)時所使用的 交聯性單體之使用量（mmol )，η係表示每1分子交聯性 單體之交聯性反應基的數（當量），W係表示交聯樹脂微 粒子（B)之質量（g)) 由本發明之組成物求得交聯樹脂微粒子（B )的設定 交聯點當量時，可利用熱分解氣體色層分析法、ICP發光 分析法等。 φ 例如，使用具有2個交聯性反應基（甲基丙烯醯基） 之二甲基丙烯酸乙二醇酯 0.03mol ( 30mmol )作爲交聯性 單體，二甲基丙烯酸乙二醇酯之2個甲基丙烯醯基實質上 皆以與交聯反應（藉由加成反應之交聯反應）有關的條件 ，製得1 〇〇g交聯樹脂微粒子（B )時’交聯樹脂微粒子（ B)之設定交聯點當量爲（3〇mmolx2)/100g = 0.6meq/g。爲 自由基聚合反應時，甲基丙烯醯基實質上皆與交聯反應有 關。 而且，例如使用具有3個交聯性反應基之鍵結於矽原 -21 - 201026766 子的甲氧基之三甲氧基矽烷基丙基甲基丙烯酸酯 0.03 mol (30mmol)，甲基丙烯酸三甲氧基矽烷基丙酯中3個甲氧 基實質上皆以與交聯反應（藉由水解變換成矽烷醇基及形 成矽氧烷鍵）有關的條件，製得lOOg交聯樹脂微粒子（ B)時，交聯樹脂微粒子（B)之設定交聯點當量爲 (30mmolx3)/100g = 0.9meq/g。在適當的觸媒存在下，甲氧 基矽烷基實質上皆與交聯反應有關。 此外，無觸媒之甲氧基矽烷基之交聯反應極爲緩慢， © 與觸媒存在下相比時，由於實質上沒有進行交聯反應或僅 稍微進行交聯反應，以無觸媒條件化製造時，僅稍有甲氧 基矽烷基之導入量，一般而言設定交聯點當量爲0。 本發明所使用的交聯樹脂微粒子（B)，只要是由滿 足前述要件（bl)〜（b4)之（甲基）丙烯酸酯系樹脂所 成的交聯樹脂微粒子即可，其製造方法沒有特別的限制。 於本發明中，交聯樹脂微粒子（B)以使用 (i)在藉由分散聚合法所製造的（甲基）丙烯酸酯 © 系樹脂微粒子所成的種子粒子中使含交聯性單體之乙烯系 單體吸收·聚合所得的交聯樹脂微粒子（B a )，及 (i i )藉由分散聚合法所製造的具有水解性矽烷基之 (甲基）丙烯酸酯系樹脂微粒子交聯所得的交聯樹脂微粒 子（Bb) 較佳。交聯樹脂微粒子（B a )及交聯樹脂微粒子（Bb )，可單獨使用，或組合使用。 (甲基）丙烯酸系交聯樹脂微粒子之製造方法，一般 -22- 201026766 爲懸浮聚合法，一般而言藉由懸浮聚合時，不易 分布狹窄、尺寸一致的（甲基）丙烯酸酯系交聯 子。另外，採用分散聚合法時，可順利地製造粒 窄、尺寸一致的（甲基）丙烯酸酯系樹脂微粒子 而言，以使用前述的交聯樹脂微粒子（Ba)、及 聯樹脂微粒子（Bb )中任何一種或兩種較佳。特 較爲簡單且低成本製造滿足要件（bl)〜（b4) φ 交聯樹脂微粒子（Bb )較佳。 說明有關交聯樹脂微粒子（Ba)。 製造交聯樹脂微粒子（Ba )時所使用的（甲 酸酯系樹脂微粒子之種子粒子，可藉由在水/醇 劑中，使用含羧基之高分子單體作爲分散安定劑 甲基）丙烯酸酯爲主體的聚合性單體予以分散聚 地製造。 形成前述種子粒子之含羧基的高分子單體， © 分子末端或側鏈上具有自由基聚合性不飽和鍵者 有特別的限制。該自由基聚合性不飽和鍵，可使 乙烯基、末端（甲基）丙烯醯基、側鏈（甲基） 、末端苯乙稀基等。 前述含羧基之高分子單體，可使用使具羧基 單體、與含疏水性乙烯基單體之單體，在聚合引 下、較佳者在180°C以上之溫度下進行自由基聚 在末端具有次乙烯基型乙烯性不飽和化合物之化 下稱爲「高分子單體（mml )」）。 製造粒度 樹脂微粒 度分布狹 。就該點 前述的交 別是可以 者，故以 基）丙烯 系極性溶 ，使以（ 合，順利 只要是在 即可，沒 用末端次 丙烯醯基 之聚合性 發劑存在 合所得的 合物（以 -23- 201026766 具有羧基之聚合性單體，例如丙烯酸、甲基丙烯酸、 巴豆酸'丙烯氧基丙酸等之不飽和單羧酸；馬來酸、富馬 酸、中康酸、檸康酸、衣康酸、環己烷二羧酸等之不飽和 二羧酸；馬來酸酐、四氫苯二甲酸酐等之藉由水解生成羧 基的不飽和酸酐等。 疏水性乙烯基系單體，例如（甲基）丙烯酸甲酯、（ 甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯 酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸第3· 丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸2-乙基己酯 、（甲基）丙烯酸月桂酯、（甲基）丙烯酸硬脂酯等之（ 甲基）丙烯酸之烷酯；（甲基）丙烯酸環己酯、（甲基） 丙烯酸苯酯、（甲基）丙烯酸苯甲酯：苯乙烯、α-甲基苯 乙烯、ρ-甲基苯乙烯、〇-甲基苯乙烯、m-甲基苯乙烯、乙 烯基甲苯、p-乙基苯乙烯、p-t-丁基-苯乙烯、p-n-丁基苯 乙烯、p-n-己基苯乙烯、ρ-辛基苯乙烯、2，4-二甲基苯乙 烯等之苯乙烯系單體等。 而且，聚合引發劑例如過氧化苯甲醯基、過氧化月桂 醯基、〇-氯過氧化苯甲醯基、〇-甲氧基過氧化苯甲醯基、 過氧化3,5,5-三甲基己醯基、t-丁基過氧化-2-乙基己酸醋 、過氧化二-t-丁基、過氧化二-t-己基、過氧化二-t-戊基 、t-丁基過氧化三甲基乙酸酯等之有機過氧化物；偶氮雙 異丁腈、偶氮雙環己羰腈、偶氮雙（2,4-二甲基戊腈）等 之偶氣系化合物；過硫酸狎等之過硫化物系化合物等。 此外，前述含有羧基之高分子單體，可使用使含有具 -24- 201026766 羥基之聚合性單體、及疏水性乙烯基系單體之單體，在具 有羧基之連鏈移動劑及聚合引發劑存在下進行聚合，形成 在末端具有羧基、在側鏈具有羥基之第1聚合物後，使該 第1聚合物中所含的末端羧基、與具有環氧基之聚合性不 飽和化合物進行反應，形成第2聚合物，然後，使該第2 聚合物中所含的羥基、與二羧酸酐進行反應所得的化合物 (以下稱爲高分子單體（mm2 ))。 φ 具有羧基之連鏈移動劑，例如巯基醋酸、锍基丙酸、 锍基丁酸、硫代水楊酸等之硫醇化合物。 具有羥基之聚合性單體，例如（甲基）丙烯酸2-羥基 乙酯、（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥 基丙酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯酸3-羥基丁酯、（甲基）丙烯酸 4-羥基丁酯、聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單 (甲基）丙烯酸酯、在（甲基）丙烯酸2-羥基乙酯中加成 φ ε-己內酯所得的化合物等具有羥基之（甲基）丙烯酸酯； 〇-羥基苯乙烯、m-羥基苯乙烯、ρ_羥基苯乙烯、〇·羥基-α_ 甲基苯乙烯、m-羥基-α-甲基苯乙烯、ρ_羥基-α—甲基苯乙 烯、2-羥基甲基-α-甲基苯乙烯、3_羥基甲基-α_甲基苯乙 烯、4_羥基甲基-α-甲基苯乙烯、4-羥基甲基-1-乙烯萘、7-羥基甲基-1-乙烯萘、8-羥基甲基-1-乙烯萘、4-羥基甲基-1-異丙烯萘、7-羥基甲基-1-異丙烯萘、8_羥基甲基-卜異丙 烯萘、Ρ-乙烯基苯甲醇等。 疏水性乙烯基系單體及聚合引發劑，可各使用形成前 -25- 201026766 述高分子單體（mml)時所使用的化合物。 具有環氧基之聚合性不飽和化合物，例 烯酸環氧丙酯、（甲基）丙烯酸β-甲基環氧 )丙烯酸β-乙基環氧丙酯、（甲基）丙烯I 環氧基丁酯、（甲基）丙烯酸3-乙基-3，4-環 甲基）丙烯酸4-甲基-4,5-環氧基戊酯、（ 2,3-環氧基環己基甲酯、（甲基）丙烯酸3 基甲酯、〇-乙烯基苯甲基環氧丙醚、m-乙烯 丙醚、P-乙烯基苯甲基環氧丙醚、氧化2-乙 氧化3-乙烯基環己烯、氧化4-乙烯基環己烯 丙醚等。 二羧酸酐例如琥珀酸酐、苯二甲酸酐、 基琥珀酸酐、乙醯基蘋果酸酐等。 另外，前述含有羧基之高分子單體，亦 具羧基之聚合性單體、與疏水性乙烯基系單 用聚合引發劑進行聚合，形成具有羧基之第 使部分該第1聚合物中所含的羧基、與具有 性不飽和化合物進行反應所得的化合物（以 子單體（mm3 )」）。 具有羧基之聚合性單體、疏水性乙烯基 引發劑及具有環氧基之聚合性不飽和化合物 述例示的化合物。 前述高分子單體（mml) 、 （mm2)及 凝膠滲透色層分析法（GPC )所測定的以聚 如（甲基）丙 丙酯、（甲基 庚3-甲基-3,4-氧基丁酯、（ 甲基）丙烯酸 ，4-環氧基環己 基苯甲基環氧 烯基環己烯、 、烯丙基環氧 檸康酸酐、甲 可使用使含有 體之單體，使 1聚合物後， 環氧基之聚合 下稱爲「高分 系單體、聚合 ，可各使用前 (mm3)藉由 苯乙烯換算之 201026766 重量平均分子量（Mw)，較佳者爲1，000〜1 00,000，更 佳者爲3,000〜30,000。 形成前述之（甲基）丙烯酸酯系樹脂微粒子時所使用 的聚合性單體，係以（甲基）丙烯酸酯爲主體。換言之， 聚合性單體中所含的（甲基）丙烯酸酯之含有比例，較佳 者爲50質量％以上，更佳者爲70質量％以上，上限値通 常爲1 0 0質量％。 φ 前述之（甲基）丙烯酸酯，例如甲基丙烯酸甲酯、甲 基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲 基丙烯酸異丁酯、甲基丙烯酸第3-丁酯、甲基丙烯酸戊酯 、甲基丙烯酸2-乙基己酯、甲基丙烯酸月桂酯、甲基丙烯 酸硬脂酯等之甲基丙烯酸的烷酯；丙烯酸甲酯、丙烯酸乙 酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸 第3-丁酯、丙烯酸戊酯、丙烯酸2-乙基己酯、丙烯酸月桂 酯、丙烯酸硬脂酯等之丙烯酸的烷酯；（甲基）丙烯酸環 〇 己酯、（甲基）丙烯酸異冰片酯等之（甲基）丙烯酸的含 脂環基之酯等。此等之化合物，可單獨使用、亦可2種以 上組合使用。而且，前述之（甲基）丙烯酸酯以甲基丙烯 酸甲酯及甲基丙烯酸異丁酯較佳。 製造前述之（甲基）丙烯酸酯系樹脂微粒子時，高分 子單體之使用量相對於100質量份前述之聚合性單體而言 ，較佳者爲0.5〜50質量份，更佳者爲1.0〜20質量份。 而且，（甲基）丙烯酸酯系樹脂微粒子，通常在聚合引發 劑存在下製造。 -27- 201026766 前述之（甲基）丙烯酸酯系樹脂微粒子（種子粒子） ，藉由凝膠滲透色層分析法（GPC )所測定的以聚苯乙稀 換算的重量平均分子量（Mw)，較佳者爲1，0〇〇〜 2,000,000，更佳者爲 5,000 〜1,000,000。 此外，被由藉由前述分散聚合所得的（甲基）丙烯酸 酯系樹脂微粒子所成的種子粒子吸收、聚合的乙烯系單體 ，爲生成交聯樹脂微粒子（Ba)時，必須含有多官能乙稀 基單體。該多官能乙烯基單體，以使用聚合性優異的多官 能（甲基）丙烯酸酯化合物較佳。具體例如二（甲基）丙 烯酸乙二醇酯、二（甲基）丙烯酸丙二醇酯、二（甲基） 丙烯酸1,6-己二醇酯、二（甲基）丙烯酸聚乙二醇酯、二 (甲基）丙烯酸聚丙二醇酯等之二元醇之二（甲基）丙_ 酸酯類；三（甲基）丙烯酸三羥甲基丙烷酯、三羥甲基H 烷氧化乙烯改性物之三（甲基）丙烯酸酯、三（甲基）H 烯酸丙三醇酯、三（甲基）丙烯酸季戊四醇酯、四（甲基 )丙烯酸季戊四醇酯等3價以上的多元醇之三（甲基）H 烯酸酯、四（甲基）丙烯酸酯等的聚（甲基）丙稀酸醋， 此等可使用1種或2種以上。 於此等之中，二（甲基）丙烯酸乙二醇酯、三（甲s )丙烯酸三羥甲基丙烷酯，就可被種子粒子容易吸收、^ 高交聯密度、及聚合安定性優異等而言較佳。 被種子粒子吸收、聚合的乙烯基系單體，爲含有 之多官能乙烯基單體、同時含有單官能乙烯基單體， 被種子粒子吸收、及聚合安定性有利而言較佳。該胃胃_ -28- 201026766 乙烯基單體，係與構成種子粒子之（甲基）丙烯酸酯相同 或類似的（甲基）丙烯酸酯系單體，例如甲基丙烯酸甲酯 及甲基丙烯酸異丁酯較佳。藉由使用該含有該單官能乙烯 基單體之乙烯系單體，可良好地進行種子粒子之膨脹，藉 此可促進乙烯基系單體被種子粒子吸收，可製得充分進行 交聯的交聯樹脂微粒子（Ba)。而且，爲使苯乙烯系樹脂 (A )與交聯樹脂微粒子（Ba )之折射率差變大，可得較 φ 高的光擴散性時，以選擇可製得折射率較低的聚合物之單 官能乙烯基單體較佳，例如以使用甲基丙烯酸異丁酯、甲 基丙烯酸第3-丁酯等較佳。 有關製造交聯樹脂微粒子（Ba)時之種子粒子及乙烯 基系單體的使用比例，相對1質量份種子粒子而言，乙烯 基系單體以0.5〜10質量份較佳，以0.7〜5質量份更佳。 被種子粒子吸收之乙烯基系單體中的多官能乙烯基單 體之含有量’係使該乙烯基系單體被種子粒子吸收、聚合 ® 所得的交聯樹脂微粒子（Ba)之設定交聯點當量，爲本發 明所規定之値以上的量。 一般而言，相對乙烯基系單體之全部質量而言，多官 能乙烯基單體之使用量以3〜95質量％較佳，更佳者爲5 〜7 5質量％。 其次’說明有關交聯樹脂微粒子（Bb)。 製造交聯樹脂微粒子（Bb)時所使用的具有水解性矽 烷基之（甲基）丙烯酸酯系樹脂微粒子，係藉由使用含有 具水解性矽烷基之乙烯基單體、與（甲基）丙烯酸酯系單 -29- 201026766 體之單體混合物進行分散聚合所得者。而且，水解性矽烷 基係指可藉由水解縮合反應形成矽氧烷鍵、予以交聯的官 能基。 具有水解性矽烷基之乙烯基單體，可使用任何的具有 1個以上水解性矽烷基之乙烯基單體。例如，乙烯基三甲 氧基矽烷、乙烯基三乙氧基矽烷、乙烯基甲基二甲氧基矽 烷、乙烯基二甲基甲氧基矽烷等之乙烯基矽烷類；丙烯酸 三甲氧基矽烷基丙酯、丙烯酸三乙氧基矽烷基丙酯、丙烯 @ 酸甲基二甲氧基矽烷基丙酯等含有水解性矽烷基之丙烯酸 酯類；甲基丙烯酸三甲氧基矽烷基丙酯、甲基丙烯酸三乙 氧基矽烷基丙酯、甲基丙烯酸甲基二甲氧基矽烷基丙酯、 甲基丙烯酸二甲基甲氧基矽烷基丙酯等含有水解性矽烷基 之甲基丙烯酸酯類；三甲氧基矽烷基丙基乙烯醚等含有水 解性矽烷基之乙烯醚類；三甲氧基矽烷基^ —烷酸乙烯酯 等含有水解性矽烷基之乙烯酯類等。此等可單獨1種或2 種以上使用。 ® 於此等之中，具有水解性矽烷基之乙烯基單體’以含 有水解性矽烷基之丙烯酸酯、及含有水解性矽烷基之甲基 丙烯酸酯較佳。此等之單體，由於可製得與形成具有水解 性砂院基之（甲基）丙烯酸酯系樹脂微粒子的主體之（甲 基）丙烯酸酯系單體的共聚合性優異、耐候性優異的微粒 子，故較佳。特別是就與（甲基）丙嫌酸酯系單體之共聚 合性、分散聚合時之安定性及交聯性優異而言’以使用甲 基丙烯酸三乙氧基矽烷基丙醋（甲基丙嫌酸二甲氧基砂院 -30- 201026766 基丙酯）較佳。 具有水解性矽烷基之乙烯基單體的使用量’係使藉由 分散聚合所得的具有水解性矽烷基的（甲基）丙烯酸酯系 樹脂微粒子進行交聯所得的交聯樹脂微粒子（Bb)的設定 交聯點當量，在本發明所規定之値以上的量。 一般而言，相對於製造具有水解性矽烷基之（甲基） 丙烯酸酯系樹脂微粒子時所使用的單體混合物（包含高分 ❹ 子單體）之全部質量而言，具有水解性矽烷基之乙烯基單 體的使用量爲2〜50質量％，特別是以5〜25質量％較佳 〇 爲製造具有水解性矽烷基之（甲基）丙烯酸酯系樹脂 微粒子時的分散聚合，以在醇系溶劑、特別是醇與水之混 合溶劑中進行較佳。藉此，可容易地抑制聚合時粒子間之 凝聚情形，進行聚合後之交聯。而且，藉由調整醇與水之 比例，可控制粒徑、粒徑分布，故較佳。 ® 另外，製造具有水解性矽烷基之（甲基）丙烯酸酯系 樹脂微粒子時所使用的（甲基）丙烯酸酯系單體，例如（ 甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯 酸丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯 、（甲基）丙烯酸第3-丁酯、（甲基）丙烯酸戊酯、（甲 基）丙烯酸2-乙基己酯、（甲基）丙烯酸月桂酯、（甲基 )丙烯酸硬脂酯等（甲基）丙烯酸之烷酯；（甲基）丙烯 酸環己酯、（甲基）丙烯酸異冰片酯等（甲基）丙烯酸之 含脂環基的酯；（甲基）丙烯酸環氧丙酯、（甲基）丙烯 -31 - 201026766 酸四氫呋喃酯等（甲基）丙烯酸之含雜環基的酯；（甲基 )丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲 基）丙烯酸3-羥基丙酯等之（甲基）丙烯酸的羥基烷酯； (甲基）丙烯酸2-甲氧基乙酯等之（甲基）丙烯酸的烷氧 基烷酯等。此等之化合物，可單獨使用，或2種以上組合 使用。於此等之中，就耐熱性、耐候性及折射率而言，以 甲基丙烯酸甲酯、甲基丙烯酸異丁酯及甲基丙烯酸第3-丁 酯較佳。 @ 製造具有水解性矽烷基之（甲基）丙烯酸酯系樹脂微 粒子時所使用的（甲基）丙烯酸酯系單體之使用量，相對 於單體混合物（不含高分子單體）之全部質量而言，較佳 者爲50〜100質量％，更佳者爲80〜100質量％。 此外，製造具有水解性矽烷基之（甲基）丙烯酸酯系 樹脂微粒子時的分散聚合，以使用具有（甲基）丙烯醯基 之高分子單體型分散安定劑較佳。使用具有（甲基）丙烯 醯基之高分子單體型分散安定劑時，可藉由少量的使用， © 順利地製得具有目標之粒徑，且具有粒度分布狹窄的水解 性矽烷基之（甲基）丙烯酸酯系樹脂微粒子。另外，該高 分子單體型分散安定劑，以亦具有羧基更佳。 (甲基）丙烯醯基可鍵結於聚合物鏈末端及側鏈之任 何一個位置。特別是鍵結於側鏈之高分子單體型分散安定 劑，就可藉由使用更爲少量，安定地製造目的之具有水解 性矽烷基的（甲基）丙烯酸酯系樹脂微粒子而言較佳。 在側鏈上具有（甲基）丙烯醯基且具有羧基之高分子 -32- 201026766 單體的製造方法，例如藉由乳化聚合法合成含殘 物，然後，在該預聚物之部分羧基上加成甲基丙 丙酯等之含環氧基的（甲基）丙烯酸酯之方法。 簡單地製造高性能的高分子單體。含環氧基之（ 烯酸酯，藉由在每1條聚合物鏈上加成0.6〜1.1 造粒度分布更爲狹窄且粒徑更爲一致的微粒子， 前述高分子單體藉由凝膠滲透色層分析法（ 〇 測定的以苯乙烯換算之重量平均分子量（Mw) 爲 500 〜50,000，更佳者爲 1，000 〜10,000。 製造具有水解性矽烷基之（甲基）丙烯酸酯 粒子時所使用的具有（甲基）丙烯醯基及羧基的 體，以使該羧基中和、使用較佳。藉此可藉由經 基陰離子之靜電反發效果，可安定地製造具有水 基之（甲基）丙烯酸酯系樹脂微粒子。中和時所 量，係以羧基的2倍當量以下較佳。大於2倍當 ® 液之鹼性變強，於聚合中水解性矽烷基進行反應 聚情形。中和用之鹼，以使用容易除去的銨較佳 具有水解性矽烷基之（甲基）丙烯酸酯系樹 ，可藉由使前述含高分子單體之單體混合物，在 劑存在下進行聚合反應予以製造。該聚合引發劑 成前述高分子單體（mm 1)時所使用的化合物。 然後，使前述所得的具有水解性矽烷基之（ 烯酸酯系樹脂微粒子進行交聯反應，製造交聯樹 (Bb )。 基之預聚 烯酸環氧 該方法可 甲基）丙 個，可製 故較佳。 GPC )所 ，較佳者 系樹脂微 高分子單 中和的羧 解性矽烷 使用的鹼 量時反應 ，產生凝 〇 脂微粒子 聚合引發 可使用形 甲基）丙 脂微粒子 -33- 201026766 交聯反應係可藉由在含有具水解性矽烷基之（甲基） 丙烯酸酯系樹脂微粒的分散液中添加交聯用觸媒，藉由水 解性矽烷基間之縮合反應形成矽氧烷鍵予以進行。交聯用 觸媒’以使用鹼材料較佳，特別是使用乾燥時容易除去的 銨或低沸點胺更佳。 鹼材料之使用量，就矽烷基交聯度變高而言，相對於 具有水解性矽烷基之（甲基）丙烯酸酯系樹脂微粒子中之 矽烷基而言爲3倍當量以上較佳，以6倍當量以上更佳。 · 而且’本發明之苯乙烯系樹脂組成物，可含有如下述 之添加劑。於本發明中，前述交聯樹脂微粒子（B)亦可 含有抗氧化劑、光安定劑等之粒子。藉由含有此等之添加 劑，本發明之苯乙烯系樹脂組成物由於耐熱分解安定性、 耐候性特別優異，故較佳。Mw), preferably 50,000 to 1,000,000, more preferably 1 00,000 to 500,000. The molecular weight distribution (Mw/Mn) of the styrene-based resin (A) is preferably 1.5 to 3. 5, and the strength of the obtained molded body or the like is preferable. Further, the refractive index of the ethylbenzene-based resin (A) is preferably 1.55 or more, more preferably 1.57 or more, and most preferably 1.58 to 1.62. Further, the refractive index referred to in the present specification means a refractive index measured by a wavelength of 5 89 nm and 25 t 0 using an Abbe refractometer based on the method of JIS K7015. The styrene resin composition of the present invention contains crosslinked resin fine particles (B) satisfying the following requirements (b1) to (b4). (bl) Crosslinked resin microparticles composed of a (meth) acrylate resin. (b2) The volume average particle diameter (dv) is 0.7 to 2_5 μmη. (b3) The ratio of the volume average particle diameter (dv) to the number average particle diameter (dn) (dv/dn) is 1.2 or less. -16- 201026766 (b4) Let the parent joint point equivalent be 〇_i5meq/g or more. The parent-linked resin fine particles (B) are composed of a (meth) acrylate-based resin mainly composed of a structural unit derived from (meth)acrylic acid vine (requirement (bl)), and constitute the (meth) acrylate system. The content ratio of the structural unit derived from the (meth) acrylate of the resin is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The best is 95 to 1%. 00% by mass. In particular, when the content ratio of the structural unit derived from the (meth) propylene φ acid ester is 80% by mass or more, the refractive index of the crosslinked resin fine particles (B) can be 1.46 to 1.49. In the (meth) acrylate resin constituting the crosslinked resin fine particles (B), when the content ratio of the structural unit derived from the (meth) acrylate is small, the refractive index of the crosslinked resin fine particles (B) is likely to be increased. The difference in refractive index between the styrene resin (A) and the crosslinked resin fine particles (B) is small, and the light diffusibility of the styrene resin composition and the molded body formed from the composition is lowered, and the weather resistance is improved. insufficient. Φ When the refractive index difference with the styrene resin (A) is increased, the refractive index of the crosslinked resin fine particles (B) formed of the (meth) acrylate resin is preferably 1.51 or less, and 1.46. ~1.49 is better. A (meth) acrylate which forms a (meth) acrylate resin constituting the crosslinked resin fine particles (B), for example, a monofunctional monomer and a crosslinkable monomer. The crosslinked resin fine particles (B) usually have a structural unit derived from a crosslinkable monomer because they have a crosslinked structure. The cross-linking structure may be a compound having two or more polymerizable unsaturated bonds, or a compound having at least one polymerizable unsaturated bond and a hydrolyzable decyl group, and hydrolytic condensation by -17-201026766 The oxyalkylene bond is the benchmark. Monofunctional monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 3 butyl methacrylate, amyl methacrylate An alkyl ester of methacrylic acid such as 2-ethylhexyl methacrylate, lauryl methacrylate or stearyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid An alkyl ester of isobutyl acrylate, 3-butyl acrylate, pentyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, etc.; cyclohexyl (meth) acrylate, (A) An alicyclic ester-containing ester of (meth)acrylic acid such as isopropyl acrylate or a heterocyclic group-containing ester of (meth)acrylic acid such as glycidyl (meth) acrylate or tetrahydrofuran (meth) acrylate (hydroxy) (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, etc.; (meth)acrylic acid 2 -Methoxyethyl ester, etc. ) Alkoxyalkyl esters of acrylic acid. These compounds may be used singly or in combination of two or more. Further, among these, @ is preferably methacrylic acid methyl ester or isobutyl methacrylate in terms of heat resistance blockiness, weather resistance and refractive index of the particles. Crosslinkable monomers such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(methyl)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. a polyhydric alcohol ester of acrylic acid; allyl (meth) acrylate; an alkoxy decyl alkyl (meth) acrylate such as trimethoxy decyl propyl (meth) acrylate. These compounds ' may be used singly or in combination of two or more. Among these, in the case of -18-201026766, in order to carry out the synthesis of a cross-linking density high in a high yield and high productivity, an alkoxy decylalkyl (meth)acrylate is preferred. The (meth) acrylate-based resin is preferably 60% by mass based on the total amount of the unit of the monofunctional (meth) acrylate constituting the methyl acrylate-based resin. % is more preferably 65% by mass or more, and most preferably 70% to 100% by mass, a structural unit derived from methyl methacrylate and/or a structural unit derived from methacrylic acid φ butyl ester. The (meth) acrylate-based resin is preferably a cross-linking resin fine particle (B), and may be a particle having a composition from the surface to the inside, or may be a core-shell type particle. In the latter case, there is no particular limitation on the number of shells. The crosslinked resin fine particles (B) used in the present invention have a volume particle diameter (dv) of 0.7 to 2.5 μm (essential (b2)), preferably 0.8 to 2, more preferably 〇9 to 1 · 5 μm. The volume average particle diameter (dv) of the crosslinked resin fine particles (dv) is too high, and the diffusion property of the styrene resin composition and the molded body obtained from the composition is not sufficiently high, and the scattering transmitted light has a yellow problem. . When the volume average particle diameter of the crosslinked resin fine particles (B) is too large, the light diffusing performance of the styrene resin composition and the molded body of the composition may be lowered. The crosslinked resin fine particles (B) used in the present invention have a ratio of a volume particle diameter (dv) to a number average particle diameter (dn) (dv/dn) of 1. (equivalent (b3)) to 1.05 or less. Preferably, the particles are below 1.02 (structuralally, with an average of uniform layers of acid isoindole • 0 μιη hours of light color (d ν average 2 is better -19- 201026766 volume average particle size (dv) When the ratio of the number average particle diameter (dn) (dv/dn) is close to 1, the particle size distribution is narrow, and the crosslinked resin fine particles (B) have the same size. The crosslinked resin fine particles (B) used in the present invention The ratio of the volume average particle diameter (dv) to the number average particle diameter (dn) (dv/dn) is 1.2 or less, and when it is extremely close to 1, the particle size portion is narrow and has a uniform size. Here, the present specification Volume average @ particle diameter (dv) and number average particle diameter (dn) of crosslinked resin microparticles (B), using a scanning electron microscope, the volume average calculated based on the particle image of the photographic crosslinked resin microparticles (B) Particle size (dv) and number average particle diameter (dn), the detailed calculation method is as follows The crosslinked resin fine particles (B) used in the present invention are obtained by blending crosslinked resin fine particles in a styrene resin (A) and performing molding processing, particularly melt molding, at a high temperature. When the crosslinking, the morphological change, and the fusion between the particles are prevented, the cross-linking point equivalent is set to 0.15 meq/g or more. B4)) is preferably 0.3 meq/g or more, more preferably 0.5 meq/g or more, and the upper limit of the cross-linking point equivalent of the crosslinked resin fine particles (B) is not particularly limited, and the production is not made. In terms of difficulty and cost, it is preferably l〇meq/g, more preferably 5 meq/g, and when a styrene resin composition containing crosslinked resin fine particles having a too small cross-linking point is used, When the molding process is performed by melt molding or the like, -20-201026766 crosslinked resin fine particles (B) are melted, deformed, changed in morphology, and melted and aggregated between particles, etc., and a molded article excellent in light diffusibility cannot be obtained. 'This statement The "cross-linking point equivalent (meq/g) of the crosslinked resin fine particles (B)" is based on the equivalent of the crosslinkable reactive group of the crosslinkable monomer used in the production of the crosslinked resin fine particles. Then, it is obtained by the following formula (I): φ crosslinked resin fine particles (B) set crosslink point equivalent = (Dxn) / W (I) (wherein D represents the production of crosslinked resin fine particles (b) The amount of the crosslinkable monomer used (mmol), η represents the number (equivalent) of the crosslinkable reactive group per one molecule of the crosslinkable monomer, and W represents the crosslinked resin fine particles ( B) Mass (g)) When the crosslinked point equivalent of the crosslinked resin fine particles (B) is determined from the composition of the present invention, a thermal decomposition gas chromatography method, an ICP emission analysis method, or the like can be used. φ For example, 0.03 mol (30 mmol) of ethylene glycol dimethacrylate having two crosslinkable reactive groups (methacryl oxime) is used as a crosslinkable monomer, and ethylene glycol dimethacrylate Each of the methacrylic fluorenyl groups is substantially crosslinked with the resin microparticles (B) when a crosslinked reaction (crosslinking reaction by an addition reaction) is carried out to obtain 1 〇〇g of the crosslinked resin fine particles (B). The set cross-linking point equivalent is (3〇mmolx2)/100g = 0.6meq/g. In the case of radical polymerization, the methacrylanyl group is substantially related to the crosslinking reaction. Further, for example, a trimethoxymethoxyalkyl methacrylate having a methoxy group bonded to 矽原-21 - 201026766 having 3 crosslinkable reactive groups is used, 0.03 mol (30 mmol), trimethyl methacrylate The three methoxy groups in the alkyl propyl ester are substantially in the same conditions as the crosslinking reaction (by hydrolysis to a stanol group and a siloxane chain), and 100 g of the crosslinked resin fine particles (B) are obtained. The crosslinked point equivalent of the crosslinked resin fine particles (B) was (30 mmol x 3) / 100 g = 0.9 meq / g. The methoxydecylalkyl group is substantially related to the crosslinking reaction in the presence of a suitable catalyst. Further, the cross-linking reaction of the catalyst-free methoxydecyl group is extremely slow, and when compared with the catalyst, the catalyst is not subjected to a cross-linking reaction or a slight cross-linking reaction, and is carried out without catalyst. At the time of manufacture, only a small amount of the introduction amount of the methoxyalkyl group is generally set to the crosslinking point equivalent of 0. The crosslinked resin fine particles (B) used in the present invention may be any crosslinked resin fine particles formed of a (meth) acrylate resin satisfying the above requirements (b1) to (b4), and the production method thereof is not particularly limited. limits. In the present invention, the crosslinked resin fine particles (B) are made to contain a crosslinkable monomer in seed particles obtained by using (i) (meth)acrylate resin fine particles produced by a dispersion polymerization method. Crosslinked resin fine particles (B a ) obtained by absorption/polymerization of a vinyl monomer, and (ii) cross-linking of (meth)acrylate-based resin fine particles having a hydrolyzable alkylene group produced by a dispersion polymerization method The resin fine particles (Bb) are preferred. The crosslinked resin fine particles (B a ) and the crosslinked resin fine particles (Bb ) may be used singly or in combination. A method for producing (meth)acrylic crosslinked resin fine particles, generally -22-201026766 is a suspension polymerization method, and generally, it is difficult to distribute a narrow (meth)acrylate crosslinker having a uniform size by suspension polymerization. . In addition, when the dispersion polymerization method is used, it is possible to smoothly produce the (meth)acrylate resin fine particles having a narrow particle size and uniform size, and to use the above-mentioned crosslinked resin fine particles (Ba) and the secondary resin fine particles (Bb). Any one or two are preferred. It is particularly simple and low-cost to manufacture the satisfying requirements (b1) to (b4) φ of the crosslinked resin fine particles (Bb). Description of crosslinked resin microparticles (Ba). The seed particles of the formate resin fine particles used in the production of the crosslinked resin fine particles (Ba) can be obtained by using a carboxyl group-containing polymer monomer as a dispersion stabilizer methyl group in a water/alcohol agent. The main polymerizable monomer is produced by dispersion polymerization. The carboxyl group-containing polymer monomer forming the seed particles has a particular limitation in that it has a radical polymerizable unsaturated bond at a molecular terminal or a side chain. The radical polymerizable unsaturated bond may be a vinyl group, a terminal (meth) acryl group, a side chain (methyl), a terminal styrene group or the like. The carboxyl group-containing polymer monomer may be obtained by polymerizing a monomer having a carboxyl group and a monomer having a hydrophobic vinyl group under polymerization, preferably at a temperature of 180 ° C or higher. The term "polymer monomer (mml)" is referred to as a terminal vinyl group-containing ethylenically unsaturated compound. Manufacturing particle size The resin particle size distribution is narrow. In this case, the above-mentioned classification is possible, so that the propylene-based polar solution is dissolved, and the compound obtained by the polymerization of the terminal acrylonitrile-based polymer can be used as long as it is satisfactory. -23- 201026766 Polymerizable monomer having a carboxyl group, such as an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid 'acryloxypropionic acid; maleic acid, fumaric acid, mesaconic acid, and citrine An unsaturated dicarboxylic acid such as acid, itaconic acid or cyclohexanedicarboxylic acid; an unsaturated acid anhydride such as maleic anhydride or tetrahydrophthalic anhydride which is hydrolyzed to form a carboxyl group, etc. Hydrophobic vinyl monomer For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid 3. Butyl methacrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Ester; cyclohexyl (meth)acrylate, (meth) propylene Phenyl ester, benzyl (meth)acrylate: styrene, α-methylstyrene, ρ-methylstyrene, fluorene-methylstyrene, m-methylstyrene, vinyltoluene, p-B A styrene monomer such as styrene, pt-butyl-styrene, pn-butylstyrene, pn-hexylstyrene, ρ-octylstyrene or 2,4-dimethylstyrene. Further, a polymerization initiator such as benzammonium peroxide, laurel, phthalocyanine, benzyl-methoxybenzoyl peroxide, ruthenium peroxide, 3,5,5-three Methylhexyl decyl, t-butylperoxy-2-ethylhexanoic acid vinegar, di-t-butyl peroxide, di-t-hexyl peroxide, di-t-pentyl peroxide, t-butyl An organic peroxide such as oxidized trimethylacetate; an azo compound such as azobisisobutyronitrile, azobiscyclohexanecarbonylonitrile or azobis(2,4-dimethylvaleronitrile) a persulfate-based compound such as barium persulfate, etc. Further, the polymer monomer having a carboxyl group may be a single monomer containing a polymerizable monomer having a hydroxyl group of -24 to 201026766 and a hydrophobic vinyl monomer. Body Polymerization is carried out in the presence of a chain-linking agent having a carboxyl group and a polymerization initiator, and a terminal polymer having a carboxyl group at a terminal group and a hydroxyl group in a side chain is formed, and a terminal carboxyl group contained in the first polymer and a ring are formed. The polymerizable unsaturated compound of the oxy group is reacted to form a second polymer, and then the hydroxyl group contained in the second polymer and a compound obtained by reacting with a dicarboxylic acid anhydride (hereinafter referred to as a polymer monomer (mm2) )) φ a chain-linking agent having a carboxyl group, for example, a mercaptan compound such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid or thiosalicylic acid. A polymerizable monomer having a hydroxyl group, for example, (methyl) 2-hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, in (methyl) Addition of φ ε-caprolactone to 2-hydroxyethyl acrylate (meth) acrylate having a hydroxyl group; hydrazine-hydroxystyrene, m-hydroxystyrene, ρ-hydroxystyrene, hydrazine-hydroxy-α-methylstyrene, m-hydroxy-α-methylbenzene Ethylene, ρ-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylbenzene Ethylene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxyl Methyl-1-isopropene naphthalene, 8-hydroxymethyl-bupropenylnaphthalene, anthracene-vinylbenzyl alcohol, and the like. As the hydrophobic vinyl monomer and the polymerization initiator, each of the compounds used in the formation of the polymer monomer (mml) before the formation of -25-201026766 can be used. A polymerizable unsaturated compound having an epoxy group, exemplified by a propylene acrylate, a β-methyl propyl acrylate (meth) acrylate, a (meth) propylene I epoxy group Butyl ester, 4-methyl-4,5-epoxypentyl (3-ethyl-3,4-cyclomethyl)acrylate, (2,3-epoxycyclohexylmethyl ester, 3-methyl (meth)acrylate, fluorene-vinylbenzyl glycidyl ether, m-vinyl propyl ether, P-vinylbenzyl glycidyl ether, 2-ethoxylated 3-vinyl ring Hexene, oxidized 4-vinylcyclohexene propyl ether, etc. Dicarboxylic anhydride such as succinic anhydride, phthalic anhydride, succinic anhydride, ethenyl malic anhydride, etc. Further, the above-mentioned polymer monomer having a carboxyl group is also Polymerization of a carboxyl group-containing polymerizable monomer with a hydrophobic vinyl-based polymerization initiator to form a carboxyl group contained in the first polymer having a carboxyl group, and reacting with a functional unsaturated compound a compound (sub-monomer (mm3 )). A polymerizable monomer having a carboxyl group, a hydrophobic vinyl initiator, and an epoxy group. The polymerizable unsaturated compound is a compound exemplified by the above-mentioned polymer monomers (mml), (mm2) and gel permeation chromatography (GPC), such as poly(methyl)propyl propyl ester, (methyl). G 3-methyl-3,4-oxybutyl ester, (meth)acrylic acid, 4-epoxycyclohexylbenzyloxycycloalkenylcyclohexene, allyl epoxy citrate anhydride, A The monomer of the inclusion body can be used, and after the polymerization of the epoxy group, the polymerization of the epoxy group is referred to as "high-sequence monomer, polymerization, and the weight average molecular weight of 201026766 can be converted by styrene before each use (mm3). Mw), preferably from 1,000 to 1,00,000, more preferably from 3,000 to 30,000. The polymerizable monomer used in forming the aforementioned (meth)acrylate resin fine particles is (meth)acrylic acid. The ester is mainly the main component. In other words, the content of the (meth) acrylate contained in the polymerizable monomer is preferably 50% by mass or more, more preferably 70% by mass or more, and the upper limit 値 is usually 100% by mass. % φ The aforementioned (meth) acrylate, such as methyl methacrylate, methyl Ethyl acrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 3-butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, A An alkyl ester of methacrylic acid such as lauryl acrylate or stearyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 3-butyl acrylate, acrylic acid An alkyl ester of acrylic acid such as amyl ester, 2-ethylhexyl acrylate, lauryl acrylate or stearyl acrylate; (cyclo)methyl (meth)acrylate, isobornyl (meth)acrylate, etc. The alicyclic group-containing ester of acrylic acid, etc. These compounds may be used singly or in combination of two or more kinds. Further, the above (meth) acrylate is preferably methyl methacrylate or isobutyl methacrylate. When the (meth)acrylate resin fine particles are produced, the amount of the polymer monomer used is preferably 0.5 to 50 parts by mass, more preferably 1.0, based on 100 parts by mass of the above polymerizable monomer. ~20 parts by mass. Further, the (meth) acrylate resin fine particles are usually produced in the presence of a polymerization initiator. -27- 201026766 The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC), as described above for (meth)acrylate resin fine particles (seed particles) The best is 1,0〇〇~ 2,000,000, and the better is 5,000~1,000,000. In addition, the vinyl monomer which is absorbed and polymerized by the seed particles of the (meth)acrylate resin fine particles obtained by the dispersion polymerization is required to contain the polyfunctional B when the crosslinked resin fine particles (Ba) are formed. Dilute monomer. The polyfunctional vinyl monomer is preferably a polyfunctional (meth) acrylate compound excellent in polymerizability. Specifically, for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, two a di(methyl)propionate of a diol such as a (meth)acrylic acid polypropylene glycol ester; a trimethylolpropane tris(meth)acrylate; a trimethylol H alkoxide oxyethylene modified product Tris(methyl) acrylate, tris(methyl)H enoate, glyceryl tri(meth) acrylate, pentaerythritol tetrakis(meth)acrylate, etc. A poly(meth)acrylic acid vinegar such as an enoic acid ester or a tetra (meth) acrylate may be used alone or in combination of two or more. Among these, ethylene glycol di(meth)acrylate and trimethylolpropane tris(meth)acrylate are easily absorbed by seed particles, high crosslink density, and excellent polymerization stability. It is better. The vinyl monomer which is absorbed and polymerized by the seed particles is preferably a polyfunctional vinyl monomer containing a monofunctional vinyl monomer, is absorbed by the seed particles, and is excellent in polymerization stability. The stomach stomach _ -28- 201026766 A vinyl monomer which is the same or similar (meth) acrylate monomer as the (meth) acrylate constituting the seed particles, such as methyl methacrylate and methacrylic acid Butyl ester is preferred. By using the vinyl monomer containing the monofunctional vinyl monomer, the seed particles can be swollen well, whereby the vinyl monomer can be absorbed by the seed particles, and the cross-linking can be sufficiently obtained. Resin fine particles (Ba). Further, in order to increase the difference in refractive index between the styrene resin (A) and the crosslinked resin fine particles (Ba), it is possible to obtain a polymer having a lower refractive index when a light diffusing property higher than φ is obtained. The monofunctional vinyl monomer is preferably used, for example, isobutyl methacrylate or 3-butyl methacrylate. The ratio of the use of the seed particles and the vinyl monomer in the production of the crosslinked resin fine particles (Ba) is preferably 0.5 to 10 parts by mass, and 0.7 to 5 parts by mass based on 1 part by mass of the seed particles. Better quality. The content of the polyfunctional vinyl monomer in the vinyl monomer absorbed by the seed particles is a cross-linking of the crosslinked resin microparticles (Ba) obtained by the absorption of the vinyl monomer by the seed particles. The point equivalent is an amount above the enthalpy specified in the present invention. In general, the amount of the polyfunctional vinyl monomer used is preferably from 3 to 95% by mass, more preferably from 5 to 75% by mass, based on the total mass of the vinyl monomer. Next, the description relates to the crosslinked resin fine particles (Bb). The (meth)acrylate resin fine particles having a hydrolyzable alkylene group used in the production of the crosslinked resin fine particles (Bb) by using a vinyl monomer having a hydrolyzable alkylene group and (meth)acrylic acid The ester-based single-29-201026766 monomer mixture is obtained by dispersion polymerization. Further, the hydrolyzable decane group means a functional group which can be crosslinked by a hydrolysis condensation reaction to form a siloxane chain. As the vinyl monomer having a hydrolyzable alkylene group, any vinyl monomer having one or more hydrolyzable alkylene groups can be used. For example, a vinyl decane such as vinyl trimethoxy decane, vinyl triethoxy decane, vinyl methyl dimethoxy decane, vinyl dimethyl methoxy decane or the like; trimethoxy decyl propyl acrylate Acetate, triethoxy decyl propyl acrylate, acrylate @ acid methyl dimethoxy decyl propyl acrylate, etc.; hydrolyzable decyl acrylate; methacrylic acid trimethoxy decyl propyl methacrylate, methacrylic acid a methacrylate containing a hydrolyzable decyl group such as triethoxy decyl propyl propyl ester, methyl dimethoxy decyl propyl methacrylate or dimethyl methoxy decyl propyl methacrylate; A vinyl ether containing a hydrolyzable alkylene group such as a vinyl ether containing a hydrolyzable alkylene group such as a hydroxyalkylalkylpropyl vinyl ether; or a vinyl ester containing a hydrolyzable alkylene group such as a trimethoxysulfonylalkyl-alkanoate. These may be used alone or in combination of two or more. In the above, the vinyl monomer having a hydrolyzable alkylene group is preferably an acrylate containing a hydrolyzable alkylene group and a methyl acrylate containing a hydrolyzable alkylene group. These monomers are excellent in copolymerizability with a (meth)acrylate monomer which is a main body of a (meth)acrylate resin fine particle having a hydrolyzable sand-based resin group, and are excellent in weather resistance. Microparticles are preferred. In particular, in terms of copolymerizability with a (meth)propionic acid ester-based monomer, and stability and crosslinking property at the time of dispersion polymerization, it is used to use triethoxydecyl propyl acrylate (methyl group). Amorphous acid dimethoxy sand court -30- 201026766 propyl propyl ester) is preferred. The amount of the vinyl monomer having a hydrolyzable alkylene group is a crosslinked resin fine particle (Bb) obtained by crosslinking the (meth)acrylate resin fine particles having a hydrolyzable alkylene group obtained by dispersion polymerization. The amount of crosslinking point equivalent is set to be more than the amount specified in the present invention. In general, it has a hydrolyzable alkylene group with respect to the entire mass of the monomer mixture (including the high-component oxime monomer) used in the production of the (meth) acrylate-based resin fine particles having a hydrolyzable alkylene group. The vinyl monomer is used in an amount of 2 to 50% by mass, particularly preferably 5 to 25% by mass, based on the dispersion polymerization of the (meth)acrylate resin fine particles having a hydrolyzable alkylene group. It is preferred to use a solvent, particularly a mixed solvent of an alcohol and water. Thereby, the aggregation between the particles during the polymerization can be easily suppressed, and the crosslinking after the polymerization can be carried out. Further, by adjusting the ratio of the alcohol to the water, the particle size and the particle size distribution can be controlled, which is preferable. Further, a (meth) acrylate monomer used in the production of a (meth) acrylate resin fine particle having a hydrolyzable decyl group, for example, methyl (meth) acrylate or ethyl (meth) acrylate, Propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl ester, lauryl (meth)acrylate, alkyl (meth)acrylate such as stearyl (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate An alicyclic group-containing ester of (meth)acrylic acid; a glycidyl group of (meth)acrylic acid; a heterocyclic group-containing ester of (meth)acrylic acid such as (meth)acryl-31 - 201026766 acid tetrahydrofuran ester; a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate; (meth)acrylic acid 2 Alkoxyalkyl ester of (meth)acrylic acid such as methoxyethyl ester . These compounds may be used singly or in combination of two or more. Among these, methyl methacrylate, isobutyl methacrylate, and 3-butyl methacrylate are preferable in terms of heat resistance, weather resistance, and refractive index. @ The amount of the (meth) acrylate monomer used in the production of the (meth) acrylate resin fine particles having a hydrolyzable decyl group, relative to the total mass of the monomer mixture (excluding the polymer monomer) Preferably, it is 50 to 100% by mass, and more preferably 80 to 100% by mass. Further, in the case of producing a dispersion polymerization of a (meth) acrylate-based resin fine particle having a hydrolyzable decyl group, it is preferred to use a polymer monomer-type dispersion stabilizer having a (meth) acrylonitrile group. When a polymer monomer type dispersion stabilizer having a (meth) acrylonitrile group is used, it is possible to smoothly obtain a hydrolyzable decyl group having a target particle diameter and having a narrow particle size distribution by a small amount of use ( Methyl) acrylate resin fine particles. Further, the high molecular monomer type dispersion stabilizer preferably has a carboxyl group. The (meth)acrylonyl group may be bonded to any one of the end of the polymer chain and the side chain. In particular, a polymer monomer type dispersion stabilizer which is bonded to a side chain can be preferably used by using a smaller amount of a (meth) acrylate resin fine particle having a hydrolyzable decyl group for stable production. . A method for producing a monomer having a (meth)acrylinyl group and a carboxyl group in the side chain-32-201026766, for example, synthesizing a residue by emulsion polymerization, and then, on a part of the carboxyl group of the prepolymer A method of adding an epoxy group-containing (meth) acrylate such as methyl propyl propyl ester. Simply manufacture high performance polymer monomers. The epoxy group-containing (enoic acid ester) is obtained by adding 0.6 to 1.1 fine particles having a narrow particle size distribution and a uniform particle size to each of the polymer chains, and the polymer monomer is passed through a gel. The permeation chromatography method (the weight average molecular weight (Mw) in terms of styrene measured by hydrazine is from 500 to 50,000, more preferably from 1,000 to 10,000. When producing (meth) acrylate particles having hydrolyzable decyl group The body having a (meth)acryl fluorenyl group and a carboxyl group is preferably used for neutralizing and using the carboxyl group, whereby the water-based one can be stably produced by the electrostatic anti-initiation effect of the base anion ( The methyl acrylate-based resin fine particles are preferably used in an amount of 2 or less equivalents of the carboxyl group at the time of neutralization. When the amount is more than 2 times, the alkalinity of the liquid is increased, and the hydrolyzable decyl group is polymerized during polymerization. The base for neutralization is preferably a (meth) acrylate tree having a hydrolyzable decyl group which is easily removed, and the monomer mixture of the above polymer-containing monomer can be polymerized in the presence of a solvent. The reaction is produced. The polymerization The compound used in the above-mentioned polymer monomer (mm 1) is obtained. The hydrolyzable decyl group obtained by the above-mentioned (the acrylate resin fine particles are subjected to a crosslinking reaction to produce a crosslinked tree (Bb). The prepolymerized epoxide of the base may be methyl) propyl, which may be preferred. GPC), preferably, the reaction of the alkali amount of the carboxy-defected decane used for the single-neutralization of the resin micro-polymer, The methylated propyl granules can be used to initiate the polymerization of the condensed granules. The cross-linking reaction can be carried out by adding a dispersion to the dispersion of the (meth) acrylate-based resin particles having a hydrolyzable decyl group. The catalyst is used in combination with a condensation reaction between hydrolyzable decyl groups to form a decane bond. It is preferred to use a catalyst for crosslinking, and it is more preferable to use an ammonium or a low-boiling amine which is easily removed during drying. The amount of use of the alkali material is preferably 3 times by weight or more, more preferably 6 times or more, based on the alkylene group in the (meth)acrylate resin fine particles having a hydrolyzable alkylene group. More than the equivalent weight is better. Further, the styrene resin composition of the present invention may contain an additive as described below. In the present invention, the crosslinked resin fine particles (B) may contain particles such as an antioxidant or a light stabilizer. The styrene-based resin composition of the present invention is particularly excellent in heat-resistant decomposition stability and weather resistance by containing such an additive.

抗氧化劑例如磷系抗氧化劑、苯酚系抗氧化劑、硫系 抗氧化劑等。其中，磷系抗氧化劑例如磷酸、磷酸酯、亞 磷酸、亞磷酸酯等。 G 光安定劑例如雙（2,2,6,6-四甲基-4-哌啶基）癸酸酯 、雙（1，2,2,6,6-五甲基-4-哌啶基）癸酸酯、肆（2,2,6,6-四甲基-4-哌啶基）-1，2,3,4-丁烷四羧酸酯、肆（l,2,6,6,6-五甲基-4-哌啶基）-l，2,3,4-丁烷四羧酸酯、聚{[6-( 1，1，3,3-四甲基哌啶基）亞胺基]六亞甲基[(2,2,6,6_四甲 基哌啶基）亞胺基]}、聚甲基丙基-2-氧-[4- (2,2,6,6-四甲 基）哌啶醯基]矽氧烷等之受阻胺系化合物等。 本發明之苯乙烯系樹脂組成物中苯乙烯系樹脂（A ) -34- 201026766 及交聯樹脂微粒子（B)之含有比例，於此等之合計量爲 100質量％時，較佳者各爲94.0〜99.7質量％及0.3〜6.0 質量％、更佳者各爲9 5 · 0〜9 9 · 5質量％及0.5〜5 · 0質量％ 、尤佳者各爲96.0〜99.0質量％及1_0〜4.0質量％、最佳 者各爲96.5〜98.5質量％及1.5〜3.5質量％。上述之含有 比例各爲95.0〜99.5質量％及0.5〜5.0質量％時，適合於 形成板厚1 _5mm之光擴散率爲70 %以上，全光線透過率爲 φ 55%〜65%，且散射透過光之黃色度爲20以下之光擴散板 〇 交聯樹脂微粒子（B)之含量過少時，苯乙烯系樹脂 組成物及由該物所成的成形體等之光擴散性變得不充分。 而且，透過光亦有帶黃色情形。另外，交聯樹脂微粒子（ B)之含量過多時，會有苯乙烯系樹脂組成物及由該物所 成的成形體等之光透過性降低情形。 本發明之苯乙烯系樹脂組成物，可以前述之質量比混 _ 合苯乙烯系樹脂（A)與交聯樹脂微粒子（B)予以調整。 而且，本發明之苯乙烯系樹脂組成物，係使用部分的苯乙 烯系樹脂（A)、與全量的交聯樹脂微粒子（B)，預先調 整交聯樹脂微粒子（B)之含量比例高的主浴槽，然後， 混合該主浴槽與殘留部分之苯乙烯系樹脂（A)，可使苯 乙烯系樹脂（A)及交聯樹脂微粒子（B)在較佳的含有比 例下混合。The antioxidant is, for example, a phosphorus-based antioxidant, a phenol-based antioxidant, or a sulfur-based antioxidant. Among them, phosphorus-based antioxidants such as phosphoric acid, phosphoric acid ester, phosphorous acid, phosphite, and the like. G light stabilizers such as bis(2,2,6,6-tetramethyl-4-piperidyl) phthalate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ) phthalate, hydrazine (2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, hydrazine (l, 2, 6, 6) ,6-pentamethyl-4-piperidinyl)-l,2,3,4-butane tetracarboxylate, poly{[6-( 1,1,3,3-tetramethylpiperidinyl) Imino]hexamethylene[(2,2,6,6-tetramethylpiperidyl)imido]], polymethylpropyl-2-oxo-[4- (2,2,6 A hindered amine compound such as 6-tetramethyl)piperidinyl]oxane or the like. In the styrene resin composition of the present invention, the content ratio of the styrene resin (A) -34 to 201026766 and the crosslinked resin fine particles (B) is preferably 100% by mass or less. 94.0 to 99.7 mass% and 0.3 to 6.0 mass%, more preferably 9 5 · 0 to 9 9 · 5 mass% and 0.5 to 5 · 0 mass%, and particularly preferably 96.0 to 99.0 mass% and 1_0~ 4.0% by mass, and most preferably each is 96.5 to 98.5 mass% and 1.5 to 3.5 mass%. When the content ratio is 95.0 to 99.5 mass% and 0.5 to 5.0 mass%, respectively, the light diffusivity of forming a plate thickness of 1 _5 mm is 70% or more, the total light transmittance is φ 55% to 65%, and scattering is transmitted. When the content of the light-diffusing sheet having a light yellowness of 20 or less and the amount of the cross-linked resin fine particles (B) is too small, the light diffusibility of the styrene-based resin composition and the molded body formed from the material is insufficient. Moreover, the transmitted light also has a yellowish condition. When the content of the crosslinked resin fine particles (B) is too large, the light transmittance of the styrene resin composition and the molded article formed from the product may be lowered. The styrene resin composition of the present invention can be adjusted in the above-described mass ratio of the styrene-based resin (A) and the crosslinked resin fine particles (B). Further, in the styrene resin composition of the present invention, a part of the styrene resin (A) and the entire amount of the crosslinked resin fine particles (B) are used, and the ratio of the content ratio of the crosslinked resin fine particles (B) is adjusted in advance. In the bath, the main bath and the residual portion of the styrene resin (A) are mixed to mix the styrene resin (A) and the crosslinked resin fine particles (B) at a preferable content ratio.

此外，本發明之苯乙烯系樹脂組成物，爲微調整擴散 性能之色調時，視其所需亦可含有除交聯樹脂微粒子（B •35- 201026766 )以外之微粒子（以下稱爲「其他的微粒子」）。其他的 微粒子例如交聯苯乙烯微粒子、交聯聚有機基矽氧烷微粒 子、二氧化矽微粒子等。此等之其他微粒子可含有1種或 2種以上。 本發明之苯乙烯系樹脂組成物，在不會損害本發明目 的之範圍內，可含有添加劑。添加劑例如光安定劑、紫外 線吸收劑、抗氧化劑、抗靜電劑、平滑劑、難燃劑、著色 劑（染料、顏料）、螢光增白劑，選擇波長吸收劑、可塑 ❿ 劑等。 本發明之苯乙烯系樹脂組成物，可調製含有苯乙烯系 樹脂（A)、交聯樹脂微粒子（B )及視其所需選擇的添加 劑之混合物，使該混合物藉由習知的熔融混練方法製造。 製造裝置例如熔融押出機、各種混練機、混磨機等，可藉 由在苯乙烯系樹脂（A)之熔融溫度以上且較交聯樹脂微 粒子（B )之軟化溫度更低的溫度下進行熔融混練予以製 造。 〇 使用本發明之苯乙烯系樹脂組成物，相對於苯以乙烯 系樹脂等之成形用樹脂組成物而言，可藉由習知採用的各 種成形方法製造成形體。 爲製造成形體時之成形方法，視使用目的、用途等而 定予以適當選擇，沒有特別的限制，例如押出成形、射出 成形、壓縮成形、押出吹出成形、射出吹出成形、流延成 形、壓延成形、注模等之熔融成形。而且，亦可藉由熔融 成形所得的成形體，視其所需進行彎曲加工、真空成形、 -36- 201026766 吹出成形、壓製成形等之二次成形加工’形成目的之成形 體。爲光學用途時，視使用目的、用途而定，在成形體表 面上進行形成透鏡形狀、壓花形狀之加工方法，可調整光 學特性。 由本發明之苯乙烯系樹脂組成物所成的成形體，可有 效地使用於液晶顯示裝置等之光擴散板、菲涅耳透鏡、凹 凸式透鏡、照明器具、電照看板等之光學用途等。 φ 由本發明之苯乙烯系樹脂組成物所成的成形體，爲液 晶電視用之光擴散板時，對應於液晶面板所採用的背光方 式（光照射方式）等，例如（1 )板厚1 .5mm之光擴散率 爲70%以上、全光線透過率爲60%〜65%及散射透過光之 黃色度爲20以下之光擴散板，（2)光擴散率爲90%以上 、全光線透過率爲55%〜60%及散射透過光之黃色度爲10 以下之光擴散板等。 液晶面板由於視背光之燈的條數、出力等而定、對光 Φ 擴散板之要求性能不同，視要求性能而定各選擇適合的光 擴散板使用。 於光擴散板中，一般而Η光擴散率愈高時，全光線透 過率愈小，光之損失率愈大，惟以具有必要的光擴散性能 ，且全光線透過率更高，光之損失率小，黃色度低的光擴 散板較佳。 最近之液晶顯示裝置，就削減成本等而言，使用更少 條數之更高出力的冷陰極管以製作液晶面板予以進行，伴 隨於此，企求光擴散性更高的具有前述（2)之性能的光 -37- 201026766 擴散板。 藉由使用本發明之苯乙烯系樹脂組成物，不僅可順利 地製造習知的液晶面板所要求的前述（1)之光擴散板， 亦可以較習知更低的成本順利地製造光擴散率爲90 %以上 、確保必要的全光線透過率、且黃色度爲10以下低値的 前述（2)之光擴散板。 【實施方式】 於下述中，藉由實施例等具體地說明本發明有關本發 明，惟本發明不受下述之例所限制。 [實施例] 1 . 物性之評估方法 於下述例中，預聚物及高分子單體之重量平均分子量 (Mw)及數平均分子量（Μη)、交聯樹脂微粒子（Β) 之數平均粒徑（dn)、體積平均粒徑（dv)、體積平均粒 徑（dv)與數平均粒徑（dn)之比例（dv/dn)、以及由 苯乙烯系樹脂組成物所製造的成形體之全光線透過率、光 擴散率及透過光之黃色度（Yellow Index(YI))的測定方 法，如下所述。 (1)重量平均分子量（Mw )及數平均分子量（Μη ) 藉由凝膠滲透色層分析法（GPC )，求取以聚苯乙烯 換算之平均分子量（Mw)及數平均分子量（Μη)。 201026766 具體而言’ GPC裝置係使用 Tosoh c〇.製 8120GPC」（商品名），柱係使用4條「TSK ge MP-M」（商品名），使用四氫呋喃作爲展開溶劑 速0.6ml/分鐘、柱溫度4〇°C之條件進行測定。測定 使用使預聚物或高分子單體溶解於四氫呋喃之溶液 5mg/inl)。測定結果係使用以標準聚本乙稀所作成 線予以解析，且求取以聚苯乙嫌換算脂重量平均分 〇 Mw )及數平均分子量（Μη )。 (2)數平均粒徑（dn )、體積平均粒徑（dv )及 dv/dn ) 使以下述之合成例8〜1 2所得的種子粒子、合 〜48所得的交聯樹脂微粒子（B)及市售的交聯樹 子藉由使用日本電子社製電場放射掃描型電子顯 FE-SEM ) 「JSM-6330F」（型式名）之 SEM 法進 Ο 攝影。此時，藉由SEM法之照相攝影的倍率’係^ 照片中攝影有約50〜100個粒子的倍率，改變攝影 攝影粒子之延長數爲200個以上之張數的SEM照 如在1張照片中攝影有約50〜60個粒子時，改變 置攝影4張以上之SEM照片）。 然後，於前述SEM照片中，爲「粒子」時， 明確地確認全部粒徑（最大粒徑）爲0.2 μηι以上之 測定相當於由粒子之面積所求得的面積圓之粒徑（ 且以下述數式（II)及數式（III)爲基準，計算種 「HLC-1 super ，以流 速度係 (濃度 的檢測 子量（ 比例（ 成例13 脂微粒 微鏡（ 行照相 生1張 位置， 片（例 攝影位 有關可 粒子， di )， 子粒子 -39- 201026766 、交聯樹脂微粒子（B)及市售的交聯樹脂微粒子之數平 均粒徑（dn)及體積平均粒徑（dv)。 數平均粒徑（dn) = (SnidiUni) (H) 體積平均粒徑（<1ν) = (Σηί(Η3/Σηί)1/3 (in) 其次，自所求得的體積平均粒徑（dv )及數平均粒徑 (dn )之値’求取體積平均粒徑（dv )與數平均粒徑（dn )之比例（dv/dn )，作爲粒度分布之指標。比例（dv/dn )之値接近1時，係指粒度分布狹窄，粒子之尺寸一致， @ 另外，比例（dv/dn )之値遠離1時，係指粒度分布廣泛 ，粒子之尺寸不一致。 (3) 種子粒子之變動係數（Cv) 粒子之粒度分布的指標，除體積平均粒徑（dv )與數 平均粒徑（dn )之比例（dv/dn )以外，亦可使用變動係 數（Cv)。以下述合成例8〜12所調製的種子粒子之變動 係數（Cv) ’藉由下述之數式（IV)及（v)求取。 ❹ 變動係數（〇ν)(%)=ΐ〇〇σ/ίΐη (IV) σ(標準偏差）= (Σ(ίΗ-(1η)2/Σηί)丨/2 (V) (式中，爲求取σ時之上述數式（V)中之di及dn， 可利用前述（2)之粒徑（di)及數平均粒徑（dn)) (4) 成形體之全光線透過率 使用曰本電色社製霧度測定器「Haze Meter NDH2000 」（型式名）’測定以下述實施例及比較例所得的組成物 -40- 201026766 所成的板狀成形體（厚度1.5mm±0.05mm)之全光線透過 率（％ )。 (5) 成形體之光擴散率 使用村上色彩技術硏究所製變角光度計「 Goniophotometer GP-200」（型式名），自下述實施例及 比較例所得的組成物所成的板狀成形體（厚度1 . 5mm 土 φ 〇.〇5mm)之一面、朝厚度方向直角照射平行光，在另一面 測定透過擴散光之配向分布，求取成形體之光擴散率。 具體而言，有關自另一面側所出射的透過擴散光，測 定出射角度Θ各爲5度、20度及70度時之光度15、120及 17〇，自下述數式（VI)求取出射角度各爲5度、20度及 70度時之亮度B5、B2G及B70，然後，自下述數式（VII) 求取成形體之光擴散率。 亮度（Be) = le/cos0 (VI) φ 光擴散率（％) = [{(Β7〇 + Β2〇)/2}/Β5]χ100 (VII) (6) 透過光之黃色度（YellowIndex(YI)) 使用日本電色社製色差計「色差計 SE2000」（型式 名），有關由下述之實施例及比較例所得的組成物所成的 板狀成形體（厚度1.5mm±0.05mm)，測定透過光之黃色 度（Yellow Index(YI))。 2. 高分子單體之合成 -41 - 201026766 合成例1 (高分子單體水溶液（MM-l )之合成） 使藉由熱油、具備加熱裝置之容量500ml的加壓式攪 拌槽型反應器以3 -乙氧基丙酸乙酯塡滿。使反應器在約 250t下加溫，使反應器內壓力藉由壓力調節器來設定3-乙氧基丙酸乙酯之蒸氣壓以上。 然後，稱取甲基丙烯酸甲酯 20質量份、丙烯酸環己 酯 55質量份、丙烯酸 25質量份及過氧化物二-第3-丁 基 〇.1質量份且予以混合，調製單體混合液。其次，使該 © 單體混合液儲藏於原料桶中。 其次，使前述反應器內之壓力保持一定，且使前述單 體混合液自原料桶連續供應給反應器。此時，使單體混合 液在反應器內之平均滯留時間爲12分鐘以設定供應速度 。自反應器之出口連續取出相當於單體混合液之供應量。 於單體混合液之連續供應中，使反應器內溫度維持於 2 3 0± 2 °C。將自反應器之出口取出的反應液導入薄膜蒸發 器中，除去反應液中未反應單體等之揮發性成分，製得高 ® 分子單體。自單體混合液之供應開始90分鐘後，自薄膜 蒸發器之出口開始採取高分子單體，進行採取60分鐘。 有關前述高分子單體，藉由使用四氫呋喃溶劑之凝膠 滲透色層分析法（GPC )，測定其重量平均分子量（Mw ) 及數平均分子量（Μη)時，重量平均分子量（Mw)爲 1 0,600，數平均分子量（Μη)爲3,100。 此外，由前述高分子單體藉由1 H-NMR所測定的末端 乙烯性不飽和鍵之濃度與數平均分子量（Μη)所計算的末 -42- 201026766 端乙烯性不飽和鍵導入率爲9 8%。 使前述所得的高分子單體粉碎成碎片狀後，在附有冷 卻管之玻璃製燒瓶中加入高分子單體之粉碎物 1 〇〇質量 份、水 260質量份及25%敍水 22.5質量份，於90°C之溫 浴中進行加溫且攪拌，使高分子單體予以水溶化。確認高 分子單體溶解後，在高分子單體之濃度爲25質量％下加入 水，製造高分子單體水溶液（MM-1 )。該高分子單體水 溶液（MM-1 )在25°C之pH値爲8.0。 合成例2(高分子單體溶液（MM-2 )之合成） 在附有藉由定量幫浦的送液配管之玻璃製容器中，加 入丙二醇單甲醚乙酸酯 15質量份、甲基丙烯酸甲酯 18.19質量份、甲基丙烯酸2-羥基乙酯 39.39質量份及2-锍基丙酸1.77質量份進行攪拌，調製乙烯基單體混合液 74·35質量份。 © 另外，在附有藉由定量幫浦的送液配管之玻璃製容器 中，加入丙二醇單甲醚乙酸酯15質量份、及作爲聚合引 發劑之和光純藥工業社製 2,2’-偶氮雙（2-甲基丁腈）「 V-59」（商品名）0.17質量份，進行攪拌、溶解，調製引 發劑溶劑（p 1 ) 1 5.1 7質量份。 此外，在附有藉由定量幫浦的送液配管之玻璃製容器 中，加入丙二醇單甲醚乙酸酯 40質量份及上述聚合引發 劑〇·39質量份，進行攪拌、溶解，調製引發劑溶液（p2 )40.39質量份。 43- 201026766 在具備攪拌機、回流冷卻器、溫度計、氮氣導入管及 送液配管連結部之玻璃製反應器中，加入丙二醇單甲醚乙 酸酯 30質量份、甲基丙烯酸甲酯 12.13質量份及2-巯基 丙酸 1.77質量份，在攪拌下一邊吹入氮氣，一邊使反應 器溫度調整爲90°C。 然後，確認反應器內之混合液的溫度爲90°C之安定値 ，且開始將前述乙烯基單體混合液與前述引發劑溶液（pi )供應給前述反應器。此等之供應，藉由定量幫浦進行。 @ 換言之，以一定速度使前述乙烯基單體混合液在2小時內 進行供應，使前述引發劑溶液（P 1 )在3小時內進行供應 。前述引發劑溶液（pl)之供應完成後，直接開始將前述 引發劑溶液（p2 )供應給反應器。該引發劑溶液（pi )之 供應，亦藉由定量幫浦進行。換言之，以一定速度、在2 小時內進行供應前述引劑溶液（P2 )。於反應後，製得 在一末端具有羧基之預聚物作爲高分子單體之前驅體。使 反應液予以試樣化，藉由GPC測定分子量的結果，重量 ® 平均分子量（Mw)爲 4,000及數平均分子量（Μη)爲 2,200 ° 其次，吹入空氣取代吹入氮氣，在反應器內添加甲氧 基氫醌 〇.〇3質量份及溴化四丁銨（TBAB )0.81質量份’ 使反應器內溫昇溫至°C爲止。確認反應器內之混合液 的溫度爲11〇 °C之安定値，添加甲基丙烯酸環氧丙酯 5.67 質量份。在內溫11〇 °C下保持6小時’使甲基丙烯酸環氧 丙酯進行反應。藉由測定經試樣化的反應液之酸値’測定 -44- 201026766 對預聚物末端羧基之甲基丙烯酸環氧丙酯加成率的結果爲 98%。而且，藉由GPC進行分子量測定的結果，重量平均 分子量（Mw)爲4,800及數平均分子量（Μη)爲2,40 0。 於添加甲基丙烯酸環氧丙酯後經過7小時後，使內溫 保持於110°C下，添加琥珀酸酐 30.30質量份，在來自甲 基丙烯酸2-羥基乙酯之羥基上加成琥珀酸酐。於添加琥珀 酸酐後經過2小時，使反應液冷卻，含有羧基且在末端上 φ 具有，製得具有甲基丙烯醯基之高分子單體溶液。使該高 分子單體溶液在200°C下加熱20分鐘’製得固成分濃度 53.2質量％之高分子單體溶液（MM-2 )。使該高分子單體 溶液（MM-2)中之高分子單體的分子量進行GPC測定時 ，重量平均分子量（Mw)爲6,800及數平均分子量（Μη )爲 3,600 。 合成例3(高分子單體分散液（ΜΜ-3)之合成） © 在附有藉由定量幫浦的送液配管之玻璃製容器中’加 入甲基丙烯酸甲酯28.2質量份、甲基丙嫌酸異丁醋28.2 質量份、甲基丙烯酸 30.0質量份及硫醇酸2_乙基己酯 13.6質量份進行攪拌’調製單體混合液（100質量份）。 在具備攪拌機、回流冷卻器、溫度計、氮氣導入管及 送液配管連結部之玻璃製反應器中，加入離子交換水200 質量份，在攪拌下一邊吹入氮氣’一邊使反應器溫度調整 爲 8 0〇C。 確認反應器內溫度爲80 °C之安定値後’且在反應器中 -45- 201026766 添加在離子交換水3.0質量份中溶解有聚合引發劑之過硫 酸銨（APS ) 0.8質量份之引發劑水溶液，於5分鐘後開 始將前述單體混合液供應給反應器。單體混合液 1 〇〇質 量份，使用定量幫浦，以一定速度、於1 20分鐘供應給反 應器。供應完成後，亦使反應器內溫維持於8 ，於完成 供應的90分鐘後，添加在離子交換水 2.0質量份中溶解 有過氧化第3-丁基（氧化劑）0.1質量份之氧化劑水溶液 ，再於5分鐘後，添加在離子交換水 4.0質量份中溶解有 〇 氫硫化鈉（還原劑）0.3質量份之還原劑水溶液。然後， 在25分鐘內使反應器內溫維持於8 0 °C，調製預聚物之分 散液。其次，使少量的預聚物分散液予以試樣化，進行乾 燥後，藉由GPC測定進行測定分子量的結果，重量平均 分子量（Mw)爲3,900及數平均分子量（Μη)爲1，600。 使反應器內預聚物分散液之溫度維持於80°C下，吹入 空氣取代吹入氮氣，直接添加三乙胺 14.1質量份及甲氧 基氫醌 〇.〇3質量份。於15分鐘後，添加甲基丙烯酸環氧 Q 丙酯 9.47質量份，在內溫80°C下加熱2小時，在預聚物 之羧基上加成甲基丙烯酸環氧丙酯，製得高分子單體分散 液。藉由GPC分析，確認在高分子單體分散液沒有殘存 甲基丙烯酸環氧丙酯。使所得的高分子單體分散液在固成 分爲30質量％下，添加離子交換水，製得高分子單體分散 液（MM-3 )。 合成例4〜7(高分子單體液（MM-4 )〜（MM-7)之合成） -46 - 201026766 使用表1所示組成之單體混合液，進行與合成例3相 同的操作，調製預聚物之分散液。使少量的預聚物分散液 予以試樣化，進行乾燥後，藉由GPC測定進行測定分子 量的結果，各預聚物之重量平均分子量（Mw)及數平均 分子量（Μη)，如表1所示。 然後’使用預聚物分散液，三乙胺及甲基丙烯酸環氧 丙酯之添加量改成如表1所示之外，進行與合成例3相同 〇 的操作，製得固成分濃度爲30質量％之高分子單體分散液 (ΜΜ-4 )〜（ΜΜ-7 )。 以上述之合成例1〜7所得的高分子單體之製造原料 、物性等，如表1所示。In addition, when the styrene resin composition of the present invention is used to finely adjust the color tone of the diffusing property, it may contain fine particles other than the crosslinked resin fine particles (B • 35 - 201026766) (hereinafter referred to as "other". Microparticles"). Other fine particles are, for example, crosslinked styrene fine particles, crosslinked polyorganosiloxane fine particles, cerium oxide fine particles and the like. These other fine particles may contain one type or two or more types. The styrene resin composition of the present invention may contain an additive insofar as it does not impair the object of the present invention. Additives such as light stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, smoothing agents, flame retardants, colorants (dyes, pigments), fluorescent whitening agents, wavelength selective absorbers, plasticizing agents, and the like. The styrene resin composition of the present invention can prepare a mixture containing a styrene resin (A), a crosslinked resin fine particle (B), and an additive selected as desired, and the mixture can be melted and kneaded by a conventional method. Manufacturing. The production apparatus, for example, a melt extruder, various kneaders, a kneader, or the like, can be melted at a temperature lower than the melting temperature of the styrene resin (A) and lower than the softening temperature of the crosslinked resin fine particles (B). Hybrid to be manufactured. In the styrene-based resin composition of the present invention, the molded resin composition such as an ethylene-based resin can be produced by various conventional molding methods. The molding method for producing a molded article is appropriately selected depending on the purpose of use, use, and the like, and is not particularly limited, and is, for example, extrusion molding, injection molding, compression molding, extrusion blow molding, injection blow molding, casting molding, and calender molding. Melt molding such as injection molding. Further, the molded body obtained by melt molding may be subjected to bending processing, vacuum forming, secondary forming processing such as -36-201026766 blow molding, press molding, etc., to form a desired molded body. For optical use, the optical characteristics can be adjusted by forming a lens shape or an embossed shape on the surface of the molded body depending on the purpose of use and use. The molded article of the styrene-based resin composition of the present invention can be effectively used for optical applications such as a light diffusing plate such as a liquid crystal display device, a Fresnel lens, a concave-convex lens, a lighting fixture, and an electro-optical panel. φ When the molded article formed of the styrene-based resin composition of the present invention is a light-diffusing sheet for a liquid crystal television, it corresponds to a backlight method (light irradiation method) used for the liquid crystal panel, for example, (1) a sheet thickness of 1. 5mm light diffusing rate of 70% or more, total light transmittance of 60% to 65%, and diffused light transmitted by yellow light of 20 or less, (2) light diffusivity of 90% or more, total light transmittance It is a light diffusing plate of 55% to 60% and a yellowness of scattered light of 10 or less. The liquid crystal panel differs depending on the number of lamps of the backlight, the output, and the like, and the performance required for the light Φ diffusing plate is different, and the light diffusing plate suitable for each selection is selected depending on the required performance. In a light diffusing plate, generally, the higher the light diffusing rate, the smaller the total light transmittance, and the greater the light loss rate, but with the necessary light diffusing performance, and the higher light transmittance, the loss of light. A light diffusing plate having a small rate and a low yellowness is preferred. In the recent liquid crystal display device, a liquid crystal panel is produced by using a cold cathode tube having a lower output and a lower output, and the above-mentioned (2) is required to have higher light diffusibility. Performance of the light -37- 201026766 diffuser board. By using the styrene resin composition of the present invention, not only the light diffusing plate of the above (1) required for a conventional liquid crystal panel can be smoothly produced, but also the light diffusing rate can be smoothly produced at a lower cost than conventionally. The light diffusing plate of the above (2) which is 90% or more, ensures the required total light transmittance, and has a yellowness of 10 or less. [Embodiment] The present invention is specifically described by the following examples and the like, but the present invention is not limited by the following examples. [Examples] 1. Evaluation method of physical properties In the following examples, the weight average molecular weight (Mw) and the number average molecular weight (?n) of the prepolymer and the polymer monomer, and the number average particle size of the crosslinked resin microparticles (Β) The diameter (dn), the volume average particle diameter (dv), the ratio of the volume average particle diameter (dv) to the number average particle diameter (dn) (dv/dn), and the molded body produced from the styrene resin composition The method of measuring the total light transmittance, the light diffusivity, and the yellowness of the transmitted light (Yellow Index (YI)) is as follows. (1) Weight average molecular weight (Mw) and number average molecular weight (?η) The average molecular weight (Mw) and the number average molecular weight (?n) in terms of polystyrene were determined by gel permeation chromatography (GPC). 201026766 Specifically, 'GPC equipment is made of Tosoh c〇. 8120GPC" (trade name), and the column system uses four "TSK ge MP-M" (trade name), and uses tetrahydrofuran as the developing solvent speed of 0.6 ml/min. The measurement was carried out under the conditions of a temperature of 4 °C. The measurement was carried out using a solution in which a prepolymer or a polymer monomer was dissolved in tetrahydrofuran (5 mg/inl). The measurement results were analyzed by using a standard polyethylene sheet, and the average weight fraction (Mw) and the number average molecular weight (?n) of the weight of the polyphenylene styrene were determined. (2) Number average particle diameter (dn), volume average particle diameter (dv), and dv/dn) The seed particles obtained in the following Synthesis Examples 8 to 12, and the crosslinked resin fine particles (B) obtained in ～48 The SEM method of "JSM-6330F" (type name) was used for the photography of the cross-linked tree which was commercially available. At this time, the magnification of the photographing by the SEM method is a magnification of about 50 to 100 particles in the photograph, and the SEM of the number of extensions of the photographing photographing particles of 200 or more is changed as in one photograph. In the case of photography, there are about 50 to 60 particles, and the SEM photograph of 4 or more shots is changed. In the SEM photograph, in the case of "particles", it is confirmed that the measurement of the total particle diameter (maximum particle diameter) of 0.2 μm or more corresponds to the particle diameter of the area circle obtained from the area of the particles (and Based on the formula (II) and the formula (III), calculate the species "HLC-1 super , in the flow velocity system (the concentration of the detector (the ratio (in the case of 13 lipid micromirrors) The number average particle diameter (dn) and volume average particle diameter (dv) of the film (for example, the photographic particle, di), the subparticle-39-201026766, the crosslinked resin microparticle (B), and the commercially available crosslinked resin microparticles Number average particle size (dn) = (SnidiUni) (H) Volume average particle size (<1ν) = (Σηί(Η3/Σηί)1/3 (in) Second, from the volume average particle diameter ( Dv) and the number average particle diameter (dn) 求 'determine the ratio of the volume average particle diameter (dv) to the number average particle diameter (dn) (dv/dn) as an index of the particle size distribution. Proportion (dv/dn) When the 値 is close to 1, it means that the particle size distribution is narrow and the particle size is the same, @ In addition, when the ratio (dv/dn) is far from 1, the system is The particle size distribution is wide and the particle size is inconsistent. (3) Variation coefficient of seed particles (Cv) The index of particle size distribution of particles, except the ratio of volume average particle diameter (dv) to number average particle diameter (dn) (dv/dn) In addition to the coefficient of variation (Cv), the coefficient of variation (Cv) of the seed particles prepared in the following Synthesis Examples 8 to 12 can be obtained by the following equations (IV) and (v). (〇ν)(%)=ΐ〇〇σ/ίΐη (IV) σ(standard deviation)= (Σ(ίΗ-(1η)2/Σηί)丨/2 (V) (wherein, in order to obtain σ In the above formula (V), di and dn can be obtained by using the particle diameter (di) and the number average particle diameter (dn) of the above (2). (4) The total light transmittance of the molded body is used in Sakamoto Electric Co., Ltd. The haze meter "Haze Meter NDH2000" (type name) was measured for the total light transmission of the plate-shaped molded body (thickness: 1.5 mm ± 0.05 mm) formed by the composition -40 - 201026766 obtained in the following examples and comparative examples. Rate (%). (5) The light diffusivity of the molded body was measured using the Goniophotometer GP-200 (type name) manufactured by Murakami Color Technology Co., Ltd., from the following examples and The surface of the plate-shaped molded body (thickness: 1.5 mm, φ 〇. 〇 5 mm) formed by the composition obtained in the comparative example was irradiated with parallel light at a right angle in the thickness direction, and the distribution of the diffused light was measured on the other surface to obtain a shape. Specifically, the diffuse light emitted from the other surface side is measured for luminosity of 15, 120, and 17 出 at 5, 20, and 70 degrees, respectively, from the following numbers. In the formula (VI), the luminances B5, B2G, and B70 at which the angles of incidence are 5 degrees, 20 degrees, and 70 degrees are obtained, and then the light diffusivity of the molded body is obtained from the following formula (VII). Brightness (Be) = le/cos0 (VI) φ Light diffusivity (%) = [{(Β7〇+ Β2〇)/2}/Β5]χ100 (VII) (6) Yellowness of transmitted light (YellowIndex(YI) )) A plate-shaped molded body (thickness: 1.5 mm ± 0.05 mm) made of the composition obtained in the following examples and comparative examples, using a color difference meter "color difference meter SE2000" (type name) manufactured by Nippon Denshoku Co., Ltd. The yellowness of the transmitted light (Yellow Index (YI)) was measured. 2. Synthesis of a polymer monomer - 41 - 201026766 Synthesis Example 1 (Synthesis of a polymer monomer aqueous solution (MM-1)) A pressurized stirred tank reactor having a capacity of 500 ml by means of a hot oil and a heating device Filled with ethyl 3-ethoxypropionate. The reactor was warmed at about 250 t, and the pressure in the reactor was set to be above the vapor pressure of ethyl 3-ethoxypropionate by a pressure regulator. Then, 20 parts by mass of methyl methacrylate, 55 parts by mass of cyclohexyl acrylate, 25 parts by mass of acrylic acid, and 1 part by mass of peroxide di-t-butyl hydrazine were weighed and mixed to prepare a monomer mixture liquid. . Next, the © monomer mixture is stored in a raw material tank. Next, the pressure in the foregoing reactor is kept constant, and the above-mentioned monomer mixture is continuously supplied from the raw material tank to the reactor. At this time, the average residence time of the monomer mixture in the reactor was set to 12 minutes to set the supply rate. The supply amount corresponding to the monomer mixture is continuously taken out from the outlet of the reactor. In the continuous supply of the monomer mixture, the temperature in the reactor was maintained at 2 30 ± 2 °C. The reaction liquid taken out from the outlet of the reactor is introduced into a thin film evaporator to remove volatile components such as unreacted monomers in the reaction liquid to obtain a high-molecular monomer. After 90 minutes from the start of the supply of the monomer mixture, the polymer monomer was taken from the outlet of the film evaporator for 60 minutes. With respect to the above polymer monomer, the weight average molecular weight (Mw) and the number average molecular weight (?η) are measured by gel permeation chromatography (GPC) using a tetrahydrofuran solvent, and the weight average molecular weight (Mw) is 10,600. The number average molecular weight (?n) was 3,100. Further, the introduction ratio of the terminal-42-201026766 terminal ethylenically unsaturated bond calculated from the concentration of the terminal ethylenically unsaturated bond and the number average molecular weight (?η) determined by 1 H-NMR of the above polymer monomer was 9 8%. After the polymer monomer obtained as described above was pulverized into pieces, a pulverized product of a polymer monomer, 1 part by mass of water, 260 parts by mass of water, and 22.5 parts by mass of 25% water were added to a glass flask equipped with a cooling tube. The mixture was heated and stirred in a warm bath at 90 ° C to dissolve the polymer monomer in water. After confirming that the polymer monomer was dissolved, water was added to a polymer monomer concentration of 25% by mass to prepare a polymer monomer aqueous solution (MM-1). The aqueous polymer monomer solution (MM-1) had a pH of 8.0 at 25 °C. Synthesis Example 2 (Synthesis of Polymer Monomer Solution (MM-2)) In a glass container provided with a liquid supply pipe by a quantitative pump, 15 parts by mass of propylene glycol monomethyl ether acetate was added, and methacrylic acid was added. 18.19 parts by mass of methyl ester, 39.39 parts by mass of 2-hydroxyethyl methacrylate, and 1.77 parts by mass of 2-mercaptopropionic acid were stirred to prepare 74.35 parts by mass of a vinyl monomer mixture. In addition, 15 parts by mass of propylene glycol monomethyl ether acetate and 2,2'- of Wako Pure Chemical Industries, Ltd., which is a polymerization initiator, are added to a glass container with a liquid supply pipe for a quantitative pump. 0.17 parts by mass of azobis(2-methylbutyronitrile) "V-59" (trade name) was stirred and dissolved to prepare an initiator solvent (p 1 ) 1 5.1 7 parts by mass. In addition, 40 parts by mass of propylene glycol monomethyl ether acetate and 39 parts by mass of the above polymerization initiator are added to a glass container provided with a liquid supply pipe by a quantitative pump, and the mixture is stirred and dissolved to prepare an initiator. The solution (p2) was 40.39 parts by mass. 43-201026766, 30 parts by mass of propylene glycol monomethyl ether acetate and 12.13 parts by mass of methyl methacrylate were added to a glass reactor equipped with a mixer, a reflux condenser, a thermometer, a nitrogen gas introduction pipe, and a liquid supply pipe connection portion. 1.77 parts by mass of 2-mercaptopropionic acid, and the temperature of the reactor was adjusted to 90 ° C while blowing nitrogen gas under stirring. Then, it was confirmed that the temperature of the mixed liquid in the reactor was stabilized at 90 ° C, and the aforementioned vinyl monomer mixture and the aforementioned initiator solution (pi ) were started to be supplied to the aforementioned reactor. The supply of these is carried out by quantitative pumping. @ In other words, the vinyl monomer mixture was supplied at a constant rate for 2 hours, and the initiator solution (P 1 ) was supplied within 3 hours. After the supply of the aforementioned initiator solution (pl) is completed, the aforementioned initiator solution (p2) is directly supplied to the reactor. The supply of the initiator solution (pi) is also carried out by means of a metering pump. In other words, the aforementioned extract solution (P2) is supplied at a constant speed within 2 hours. After the reaction, a prepolymer having a carboxyl group at one end was prepared as a polymer monomer precursor. The reaction solution was sampled, and the molecular weight was measured by GPC. The weight® average molecular weight (Mw) was 4,000 and the number average molecular weight (?η) was 2,200 °. Next, air was blown in instead of blowing nitrogen gas, and the reactor was added. 3 parts by mass of methoxyhydroquinone. 及 and 0.81 parts by mass of tetrabutylammonium bromide (TBAB)' The internal temperature of the reactor was raised to °C. It was confirmed that the temperature of the mixture in the reactor was stabilized at 11 ° C, and 5.67 parts by mass of glycidyl methacrylate was added. The reaction was carried out at an internal temperature of 11 ° C for 6 hours to carry out the reaction of propyl methacrylate. The yield of the glycidyl methacrylate to the terminal carboxyl group of the prepolymer was determined by measuring the acid oxime of the sampled reaction solution -44-201026766. Further, as a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) was 4,800 and the number average molecular weight (?n) was 2,40. After 7 hours from the addition of the glycidyl methacrylate, the internal temperature was maintained at 110 ° C, 30.30 parts by mass of succinic anhydride was added, and succinic anhydride was added to the hydroxyl group derived from 2-hydroxyethyl methacrylate. After 2 hours from the addition of succinic anhydride, the reaction solution was cooled to contain a carboxyl group and φ was present at the terminal to prepare a polymer monomer solution having a methacryl oxime group. The polymer monomer solution was heated at 200 ° C for 20 minutes to obtain a polymer monomer solution (MM-2 ) having a solid concentration of 53.2% by mass. When the molecular weight of the polymer monomer in the polymer monomer solution (MM-2) was measured by GPC, the weight average molecular weight (Mw) was 6,800 and the number average molecular weight (?n) was 3,600. Synthesis Example 3 (Synthesis of Polymer Monomer Dispersion (ΜΜ-3)) © Adding 28.2 parts by mass of methyl methacrylate, methyl propyl in a glass container with a liquid supply pipe by a quantitative pump 28.2 parts by mass of succinic acid isobutyl vinegar, 30.0 parts by mass of methacrylic acid, and 13.6 parts by mass of 2-ethylhexyl thiolate were stirred to prepare a monomer mixture (100 parts by mass). 200 parts by mass of ion-exchanged water was added to a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas introduction pipe, and a liquid supply pipe connection portion, and the reactor temperature was adjusted to 8 while blowing nitrogen gas under stirring. 0〇C. After confirming that the temperature in the reactor is stabilized at 80 ° C and adding - 0.8 parts by mass of ammonium persulfate (APS ) in which the polymerization initiator is dissolved in 3.0 parts by mass of ion-exchanged water in the reactor The aqueous solution was started to supply the aforementioned monomer mixture to the reactor after 5 minutes. Monomer mixture 1 〇〇 mass fraction, supplied to the reactor at a constant speed and at a rate of 1 20 minutes using a quantitative pump. After the completion of the supply, the internal temperature of the reactor was maintained at 8, and after 90 minutes of completion of the supply, an oxidizing agent aqueous solution in which 0.1 parts by mass of peroxy-3-ethyl (oxidizing agent) was dissolved in 2.0 parts by mass of ion-exchanged water was added. Further, after 5 minutes, an aqueous solution of a reducing agent in which 0.3 parts by mass of sodium sulfonium hydrogen sulfide (reducing agent) was dissolved in 4.0 parts by mass of ion-exchanged water was added. Then, the internal temperature of the reactor was maintained at 80 ° C in 25 minutes to prepare a dispersion of the prepolymer. Next, a small amount of the prepolymer dispersion was sampled, and after drying, the molecular weight was measured by GPC measurement, and the weight average molecular weight (Mw) was 3,900 and the number average molecular weight (?n) was 1,600. The temperature of the prepolymer dispersion in the reactor was maintained at 80 ° C, and air was blown in instead of blowing nitrogen gas, and 14.1 parts by mass of triethylamine and 3 parts by mass of methoxyhydroquinone hydrazine were directly added. After 15 minutes, 9.47 parts by mass of methacrylic acid epoxy propyl ester was added, and the mixture was heated at an internal temperature of 80 ° C for 2 hours to form a glycidyl methacrylate on the carboxyl group of the prepolymer to obtain a polymer. Monomer dispersion. It was confirmed by GPC analysis that glycidyl methacrylate was not retained in the polymer monomer dispersion. The polymer monomer dispersion obtained was added with ion-exchanged water at a solid content of 30% by mass to obtain a polymer monomer dispersion (MM-3). Synthesis Examples 4 to 7 (Synthesis of Polymer Monomer Solution (MM-4) to (MM-7)) -46 - 201026766 The same operation as in Synthesis Example 3 was carried out using the monomer mixture liquid having the composition shown in Table 1, The dispersion of the prepolymer is prepared. A small amount of the prepolymer dispersion was sampled, dried, and the molecular weight was measured by GPC measurement. The weight average molecular weight (Mw) and the number average molecular weight (Μη) of each prepolymer were as shown in Table 1. Show. Then, using the prepolymer dispersion, the addition amount of triethylamine and glycidyl methacrylate was changed to the same as shown in Table 1, and the same operation as in Synthesis Example 3 was carried out to obtain a solid concentration of 30. Mass% of the polymer monomer dispersion (ΜΜ-4)~(ΜΜ-7). The raw materials, physical properties and the like of the polymer monomers obtained in the above Synthesis Examples 1 to 7 are shown in Table 1.

-47- 201026766 【一撇 合成例 卜 MM-7 31.6 31.6 〇 m 1 1 1 1 00 1 7500 1 [3000 1 [7.05 1 1 9-47 1 1 1 1 ο MM-6 38.05 38.05 1 1 1 1 00 | 6000 | 2900 [8.03 ] 1 4-73 i 1 —1 CS 1 MM-5 31.6 31.6 | 〇 m 1 1 1 1 00 8500 | 3000 | 7.05 1 4-73 1 倉 1 寸 「MM-4 | 33.2 1 33.2 1 1 1 1 | 13.6 1 3000 1600 | 9.40 1 9.47 1 —1 cs 1 MM-3 28.2 28.2 1 1 1 1 13.6 3900 1600 14.10 9.47 1 —1 (N 1 <N MM-2 30.32 1 1 1 1 39.39 | 1 3.54 I 1 4000 | 2200 | 1 5.67 | 30.30 6800 3600 MM-1 1 1 ^Ti r4 1 1 1 1 1 1 1 1 10600 3100 高分子單體液 單體混合液之組成(質量份） 甲基丙烯酸甲酯 甲基丙烯酸異丁酯 甲基丙烯酸 丙烯酸 丙烯酸環己酯 甲基丙烯酸2-羥基乙酯 2-锍基丙酸 硫醇酸2-乙基己酯 預聚物之物性 重量平均分子量Mw 數平均分子量Μη 高分子單體化學用原料(質量份） 三乙胺 甲基丙烯酸環氧丙酯 琥珀酸酐 高分子單體之物性 重量平均分子量Mw 數平均分子量Mn 晅要銎-κ 1:要逛¥¥-47- 201026766 [A 撇 synthesis example MM-7 31.6 31.6 〇m 1 1 1 00 1 7500 1 [3000 1 [7.05 1 1 9-47 1 1 1 1 ο MM-6 38.05 38.05 1 1 1 1 00 6000 | 2900 [8.03 ] 1 4-73 i 1 —1 CS 1 MM-5 31.6 31.6 | 〇m 1 1 1 1 00 8500 | 3000 | 7.05 1 4-73 1 Warehouse 1 inch "MM-4 | 33.2 1 33.2 1 1 1 1 | 13.6 1 3000 1600 | 9.40 1 9.47 1 —1 cs 1 MM-3 28.2 28.2 1 1 1 1 13.6 3900 1600 14.10 9.47 1 —1 (N 1 <N MM-2 30.32 1 1 1 1 39.39 | 1 3.54 I 1 4000 | 2200 | 1 5.67 | 30.30 6800 3600 MM-1 1 1 ^Ti r4 1 1 1 1 1 1 1 1 10600 3100 Composition of polymer monomer mixture (parts by mass) Methyl methacrylate isobutyl methacrylate methacrylic acid acrylate cyclohexyl methacrylate 2-hydroxyethyl ester 2-mercaptopropionic acid thiolate 2-ethylhexyl ester prepolymer physical weight average molecular weight Mw Number average molecular weight Μη Polymer monomer chemical raw material (parts by mass) Triethylamine methacrylate propylene acrylate succinic anhydride polymer monomer physical weight average molecular weight Mw To molecular weight Mn Xuan Qiong -κ 1: To visit ¥¥

_$φ^51ζ鑼-N鬆嵌鹋鄯 U 屮负扨阵__^鬆嵌鹋銶 (I e -48- 201026766 3 . 種子粒子之合成 合成例8 (種子粒子分散液（SD-1)之合成） 在附有藉由定量幫浦的送液配管之玻璃製容器中’加 入離子交換水32.6質量份、甲醇92·4質量份、甲基丙 烯酸甲酯75質量份及以合成例1所調製的高分子單體水 溶液（MM-1) 20質量份進行攪拌，調製單體混合液（220 質量份）。 φ 另外，在具備攪拌機、回流冷卻器、溫度計、氮氣導 入管及送液配管連結部之玻璃製反應器中’加入離子交換 水 150質量份、甲醇 320質量份、甲基丙烯酸甲酯 50 質量份及以合成例1所調製的高分子單體水溶液（MM-1 )40質量份，在攪拌下一邊吹入氮氣’一邊使反應器溫度 調整爲52°C。 確認反應器內溫度爲52 °C後，且在該反應器中添加作 爲聚合引發劑之3.0質量份日油社製過氧化三甲基乙酸第 ❹ 3-丁醋（商品名「Perbutyl PV」；過氧化三甲基乙酸第3- 丁酯之70%溶液）（以下簡稱爲「Perbutyl PV」），開始 聚合。確認於添加聚合引發劑後，反應液產生混濁情形， 慢慢地白化形成乳白色，生成樹脂微粒子。 添加聚合引發劑後，經過90分鐘後，開始將前述單 體混合液供應給反應器。換言之，使用定量幫浦，以一定 速度、於90分鐘將單體混合液 220份供應給反應器。供 應完成後，在30分鐘內使反應器內之溫度昇溫爲70 °C， 再於70°C下保持90分鐘。然後，使內溫冷卻至50°C爲止 -49- 201026766 ，在減壓下除去部分甲醇及水，使反應液之固成分濃度調 整爲35.0質量％，製造含有甲基丙烯酸酯系樹脂微粒子之 種子粒子分散液（SD-1 )。 使前述種子粒子分散液（SD-1)進行離心分離處理， 除去上層澄清液，回收微粒子。進行該微粒子之SEM觀 察，藉由影像求得的數平均粒徑（dn)爲1.68μιη，變動 係數（C ν )爲 3 · 5 0 %。 合成例9(種子粒子分散液（SD-2)之合成） 附有藉由定量幫浦的送液配管之玻璃製容器中，加入 離子交換水 42.9質量份、甲醇 89.6質量份、甲基丙烯 酸甲酯 75質量份及以合成例1所調製的高分子單體水溶 液（ΜΜ-1 ) 10質量份進行攪拌，調製單體混合液（217.5 質量份）。 另外，在具備攪拌機、回流冷卻器、溫度計、氮氣導 入管及送液配管連結部之玻璃製反應器中，加入離子交換 ® 水 150質量份、甲醇 320質量份、甲基丙烯酸甲酯 50 質量份及以合成例1所調製的高分子單體水溶液（ΜΜ-1 )40質量份，在攪拌下一邊吹入氮氣，一邊使反應器內溫 調整爲5 9.6 °C。 確認反應器內溫度爲5 9.6t之安定値後，且在該反應 器中添加3.0質量份作爲聚合引發劑之第過氧化三甲基乙 酸3-丁酯（使用「Perbutyl PV」），開始聚合。確認添加 聚合引發劑後，反應液產生混濁情形，慢慢地白化形成乳 -50- 201026766 白色，生成樹脂微粒子。 添加聚合引發劑後，經過90分鐘後，開始將前述單 體混合液供應給反應器。換言之，使用定量幫浦，以一定 速度、於90分鐘內將217.5份單體混合液供應給反應器 。供應完成後，在30分鐘內使反應器內之溫度昇溫爲 70°C，再於7CTC下保持90分鐘。然後，使內溫冷卻至 5 0°C爲止，在減壓下除去部分甲醇及水，使反應液之固成 〇 分濃度調整爲35.0質量％，製造含有甲基丙烯酸酯系樹脂 微粒子之種子粒子分散液（SD-2)。 使前述種子粒子分散液（SD-2 )進行離心分離處理， 除去上層澄清液，回收微粒子。進行該微粒子之SEM觀 察，藉由影像求得的數平均粒徑（dn)爲2.15μηι，變動 係數（C ν )爲 4.8 3 %。 合成例1〇(種子粒子分散液（SD-3)之合成） ® 除使用甲基丙烯酸甲酯 42.5質量份及甲基丙烯酸異 丁酯7.5質量份取代合成例8之玻璃製反應器中的甲基丙 烯酸甲酯 50質量份，使用甲基丙烯酸甲酯 63.75質量份 及甲基丙烯酸異丁酯1 1.25質量份取代玻璃製容器中所供 應的甲基丙烯酸甲酯 70質量份外，進行與實施例8相同 的操作，製造固成分濃度調整爲35.0質量％之含有（甲基 )丙烯酸酯系樹脂微粒子之種子粒子分散液（SD-3)。 使前述種子粒子分散液（SD-3)進行離心分離處理， 除去上層澄清液，回收微粒子。進行該微粒子之SEM觀 201026766 察，藉由影像求得的數平均粒徑（dn)爲1.39μιη，變動 係數（Cv)爲 3.16%。 合成例Π (種子粒子分散液（SD-4)之合成） 除使用甲基丙烯酸甲酯35.0質量份及甲基丙烯酸異 丁酯15.0質量份取代合成例8之玻璃製反應器中的甲基 丙稀酸甲醋50質量份，使用甲基丙嫌酸甲醋52.5質量 份及甲基丙烯酸異丁醋22.5質量份取代玻璃製容器中所 供應的甲基丙烯酸甲酯70質量份外，進行與實施例8相 同的操作，製造固成分濃度調整爲35.0質量％之含有（甲 基）丙烯酸酯系樹脂微粒子之種子粒子分散液（SD-4)。 使前述種子粒子分散液（SD-4)進行離心分離處理， 除去上層澄清液，回收微粒子。進行該微粒子之SEM觀 察，藉由影像求得的數平均粒徑（dn)爲1.22μιη，變動 係數（Cv )爲 2.78%。 合成例12 (種子粒子分散液（SD-5 )之合成） 在具備攪拌機、回流冷卻器、溫度計、氮氣導入管之 玻璃製反應器中，加入離子交換水 200質量份、甲醇 650質量份、甲基丙烯酸甲酯 50質量份、甲基丙烯酸異 丁酯 5 0質量份及以合成例1所調製的高分子單體水溶液 (MM-1) 200質量份，在攪拌下一邊吹入氮氣，一邊使反 應器內溫調整爲54°C。 確認反應器內溫度爲54°C之安定値後，且在該反應器 201026766 中添加3.0質量份聚合引發劑之過氧化三甲基乙酸第3-丁 酯（使用Perbutyl PV」），開始聚合。確認添加聚合引 發劑後，反應液產生混濁情形，慢慢地白化形成乳白色， 生成樹脂微粒子。 添加聚合引發劑後，經過180分鐘後，使反應器內之 溫度在60分鐘內昇成內溫65 °C，且在內溫65 °C下保持60 分鐘。然後，使內溫冷卻至50°C爲止，在減壓下除去部分 e 甲醇及水，使反應液之固成分濃度調整爲22.0質量％，製 造含有甲基丙烯酸酯系樹脂微粒子之種子粒子分散液（ SD-5 )。使前述種子粒子分散液（SD-5 )進行離心分離處 理，除去上層澄清液，回收微粒子。進行該微粒子之SEM 觀察，藉由影像求得的數平均粒徑（dn )爲0·78μιη，變 動係數（Cv)爲3.40%。 此外，使以該合成例12所得的種子粒子分散液（SD-5)中所含的甲基丙烯酸酯系樹脂微粒子（種子粒子）， Φ 以日本電子社製電場放射掃描型電子顯微鏡（FE-SEM ) 「JSM-6330F」（型式名）攝影。該照片如第1圖所示。 確認以前述合成例8〜1 2所得的種子粒子分散液（ SD-1)〜（SD-5)之內容，如下述表2所示。 -53- 201026766 合成例 (N SD-5 分散聚合法 MM-l Ο <N 離子交換水 +甲醇 oo d Ο rn SD-4 分散聚合法 MM-l § <n 離子交換水 +甲醇 <N fN oo (N m Ο 1 SD-3 1 分散聚合法 MM-l § 106.25 「18.75 | 離子交換水 +甲醇 σ\ cn 1-H \〇 rn m α\ SD-2 1 分散聚合法 MM-l cs 1 離子交換水 +甲醇 ^Ti ri ro 00 寸· m 〇〇 Q C/) 分散聚合法 MM-l cs 1 離子交換水Ί +甲醇 00 Οψ ΓΟ in m β 燦 锲 ¢1 1» mfi M 騷 m Uiml _ 腾 Φ 链 坭 避 M am mi 卜 w •N 蹵 <π 扭· a > 燦 嵌 m V—✓ m ISIC 氍 韜 6 謚 Φ 线 Φ 屮 屮铤 E 屮 rf Μ Φ务 m m Μ Ι1ΤΠΪ> imm Μ W. -N & El· Η*1 Μ, m tlmll W P Μ <1ml1 w t1mi1 w_$φ^51ζ锣-N loosely embedded 鹋鄯U 屮 negative 扨 __^松嵌鹋銶 (I e -48- 201026766 3 . Synthesis of seed particles Synthesis Example 8 (Seed particle dispersion (SD-1) Synthesis: 32.6 parts by mass of ion-exchanged water, 92. 4 parts by mass of methanol, 75 parts by mass of methyl methacrylate, and a synthesis example 1 were added to a glass container provided with a liquid supply pipe by a quantitative pump. 20 parts by mass of the prepared polymer monomer aqueous solution (MM-1) was stirred to prepare a monomer mixture (220 parts by mass). φ In addition, a stirrer, a reflux condenser, a thermometer, a nitrogen gas introduction pipe, and a liquid supply pipe were connected. In the glass reactor of the section, '150 parts by mass of ion-exchanged water, 320 parts by mass of methanol, 50 parts by mass of methyl methacrylate, and 40 parts by mass of the aqueous polymer monomer solution (MM-1) prepared in Synthesis Example 1 The temperature of the reactor was adjusted to 52 ° C while blowing nitrogen gas under stirring. After confirming that the temperature in the reactor was 52 ° C, 3.0 parts by mass of a polymerization initiator was added to the reactor. Trimethylacetic acid dihydrazide 3-butyl vinegar (trade name "Perbut Yl PV"; 70% solution of 3-butyl peroxy-3-acetate) (hereinafter referred to as "Perbutyl PV"), and polymerization was started. It was confirmed that the reaction liquid was turbid after the addition of the polymerization initiator, and slowly The whitening forms a milky white color to form resin fine particles. After the polymerization initiator is added, the monomer mixture liquid is supplied to the reactor after 90 minutes. In other words, the monomer mixture is used at a constant speed for 90 minutes using a quantitative pump. 220 parts were supplied to the reactor. After the supply was completed, the temperature in the reactor was raised to 70 ° C in 30 minutes, and then held at 70 ° C for 90 minutes. Then, the internal temperature was cooled to 50 ° C -49 - 201026766, a part of methanol and water were removed under reduced pressure, and the solid content concentration of the reaction liquid was adjusted to 35.0% by mass to prepare a seed particle dispersion (SD-1) containing methacrylate resin fine particles. The dispersion (SD-1) was subjected to centrifugation, and the supernatant liquid was removed to collect fine particles. The SEM observation of the fine particles was carried out, and the number average particle diameter (dn) obtained by the image was changed to 1.68 μm. The coefficient of motion (C ν ) is 3 · 50 %. Synthesis Example 9 (Synthesis of Seed Particle Dispersion (SD-2)) Ion-exchanged water is added to a glass container with a liquid supply pipe by a quantitative pump. 42.9 parts by mass, 89.6 parts by mass of methanol, 75 parts by mass of methyl methacrylate, and 10 parts by mass of the aqueous polymer monomer solution (ΜΜ-1) prepared in Synthesis Example 1 were stirred to prepare a monomer mixture (217.5 parts by mass). In addition, 150 parts by mass of ion exchange water, 320 parts by mass of methanol, and methyl methacrylate 50 were added to a glass reactor equipped with a mixer, a reflux condenser, a thermometer, a nitrogen gas introduction pipe, and a liquid supply pipe connection portion. In the mass part and 40 parts by mass of the aqueous polymer monomer solution (ΜΜ-1) prepared in Synthesis Example 1, the internal temperature of the reactor was adjusted to 5 9.6 ° C while blowing nitrogen gas under stirring. After confirming that the temperature in the reactor was 5 9.6 t of diazepam, 3.0 parts by mass of 3-butyl peroxytrimethylacetate (using "Perbutyl PV") as a polymerization initiator was added to the reactor to start polymerization. . After confirming the addition of the polymerization initiator, the reaction solution was turbid, and it was slowly whitened to form milk -50 - 201026766 white to form resin fine particles. After the addition of the polymerization initiator, after 90 minutes passed, the above-mentioned monomer mixture was supplied to the reactor. In other words, 217.5 parts of the monomer mixture was supplied to the reactor at a constant rate over 90 minutes using a metering pump. After the supply was completed, the temperature in the reactor was raised to 70 ° C in 30 minutes and held at 7 CTC for 90 minutes. Then, the internal temperature was cooled to 50 ° C, and a part of methanol and water were removed under reduced pressure, and the solid concentration of the reaction liquid was adjusted to 35.0% by mass to prepare seed particles containing methacrylate resin fine particles. Dispersion (SD-2). The seed particle dispersion (SD-2) was subjected to centrifugal separation treatment to remove the supernatant liquid and collect fine particles. The SEM observation of the fine particles was carried out, and the number average particle diameter (dn) obtained by the image was 2.15 μηι, and the coefficient of variation (C ν ) was 4.8 3 %. Synthesis Example 1 (Synthesis of Seed Particle Dispersion (SD-3)) ® In place of the use of 42.5 parts by mass of methyl methacrylate and 7.5 parts by mass of isobutyl methacrylate, the A in the glass reactor of Synthesis Example 8 was replaced. 50 parts by mass of methyl acrylate, 70.75 parts by mass of methyl methacrylate and 1 1.25 parts by mass of isobutyl methacrylate were used instead of 70 parts by mass of methyl methacrylate supplied in a glass container, and examples were carried out. In the same operation, a seed particle dispersion (SD-3) containing (meth) acrylate resin fine particles having a solid content concentration adjusted to 35.0% by mass was produced. The seed particle dispersion (SD-3) was subjected to centrifugal separation treatment to remove the supernatant liquid and collect fine particles. The SEM observation of the fine particles was carried out. 201026766, the number average particle diameter (dn) obtained by the image was 1.39 μm, and the coefficient of variation (Cv) was 3.16%. Synthesis Example (Synthesis of Seed Particle Dispersion (SD-4)) Methyl propyl in the glass reactor of Synthesis Example 8 was replaced by using 35.0 parts by mass of methyl methacrylate and 15.0 parts by mass of isobutyl methacrylate. 50 parts by mass of dilute acid vinegar, and 50 parts by mass of methyl methacrylate and 22.5 parts by mass of butyl methacrylate were used in place of 70 parts by mass of methyl methacrylate supplied in a glass container, and then carried out and implemented. In the same manner as in Example 8, a seed particle dispersion (SD-4) containing (meth)acrylate resin fine particles having a solid content concentration adjusted to 35.0% by mass was produced. The seed particle dispersion (SD-4) was subjected to centrifugal separation treatment to remove the supernatant liquid and collect fine particles. The SEM observation of the fine particles was carried out, and the number average particle diameter (dn) obtained by the image was 1.22 μm, and the coefficient of variation (Cv) was 2.78%. Synthesis Example 12 (Synthesis of Seed Particle Dispersion (SD-5)) 200 parts by mass of ion-exchanged water and 650 parts by mass of methanol were added to a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. 50 parts by mass of methyl acrylate, 50 parts by mass of isobutyl methacrylate, and 200 parts by mass of a polymer monomer aqueous solution (MM-1) prepared in Synthesis Example 1, while blowing nitrogen gas under stirring The internal temperature of the reactor was adjusted to 54 °C. After confirming that the temperature in the reactor was 54 ° C, and in the reactor 201026766, 3.0 parts by mass of a polymerization initiator of 3-methylbutyl peroxyacetate (using Perbutyl PV) was added to start polymerization. After confirming the addition of the polymerization initiator, the reaction solution was turbid, and it was slowly whitened to form milky white to form resin fine particles. After the addition of the polymerization initiator, after 180 minutes, the temperature in the reactor was raised to an internal temperature of 65 ° C in 60 minutes, and maintained at an internal temperature of 65 ° C for 60 minutes. Then, the internal temperature was cooled to 50° C., and a part of e methanol and water were removed under reduced pressure, and the solid content concentration of the reaction liquid was adjusted to 22.0% by mass to prepare a seed particle dispersion containing methacrylate resin fine particles. (SD-5). The seed particle dispersion (SD-5) was subjected to centrifugal separation treatment to remove the supernatant liquid and collect fine particles. The SEM observation of the fine particles was carried out, and the number average particle diameter (dn) obtained by the image was 0·78 μm, and the coefficient of variation (Cv) was 3.40%. Further, the methacrylate resin fine particles (seed particles) contained in the seed particle dispersion (SD-5) obtained in the synthesis example 12 were subjected to an electric field emission scanning electron microscope (FE- by Nippon Electronics Co., Ltd.). SEM) "JSM-6330F" (type name) photography. The photo is shown in Figure 1. The contents of the seed particle dispersions (SD-1) to (SD-5) obtained in the above Synthesis Examples 8 to 12 were confirmed as shown in Table 2 below. -53- 201026766 Synthesis Example (N SD-5 Dispersion Polymerization Method MM-l Ο <N Ion Exchange Water + Methanol oo d Ο rn SD-4 Dispersion Polymerization Method MM-l § <n Ion Exchange Water + Methanol < N fN oo (N m Ο 1 SD-3 1 Dispersion polymerization method MM-l § 106.25 "18.75 | Ion exchange water + methanol σ\ cn 1-H \〇rn m α\ SD-2 1 Dispersion polymerization method MM-l Cs 1 ion exchange water + methanol ^Ti ri ro 00 inch · m 〇〇QC/) Dispersion polymerization method MM-l cs 1 ion exchange water Ί + methanol 00 Οψ ΓΟ in m β 锲¢ 锲¢ 1 1» mfi M 骚 m Uiml _ Teng Φ Chain 坭 M M am mi 卜 • N 蹵 < π Twist · a > Can be embedded m V - ✓ m ISIC 氍韬 6 谥 Φ line Φ 屮屮铤 E 屮 rf Μ Φ mm Μ Ι 1 ΤΠΪ gt ; imm Μ W. -N & El· Η*1 Μ, m tlmll WP Μ <1ml1 w t1mi1 w

-54- 201026766 4. 交聯樹脂微粒子之合成 合成例13 (交聯樹脂微粒子（Ba-Ι)之合成 在不銹鋼製反應容器中加入甲基丙烯酸 份及東亞合成社製三羥甲基丙烷三丙烯酸_ 3 09」（商品名）50質量份，進行攪拌混合 中加入於離子交換水 100質量份中溶解有 社製、月桂基硫酸鈉「Emael 2F-30」（商品 〇 份的乳化劑水溶液，使用乳化器予以乳化， 體混合物之乳化液。 另外，在具備攪拌機、回流冷卻器、溫 入管及送液配管連結部之玻璃製反應器中， 水 299質量份、10%KOH水溶液 3.0質量 8所製造的種子粒子分散液（SD- 1 ) 28 5.7 進行攪拌，一邊使反應器內溫調整爲20°C。 在前述反應器中添加前述乙烯基單體混 ❹ ，再加入聚合引發劑之和光純藥工業社製： 2,4-二甲基戊腈）（商品名「V-65」）1質 器內溫爲20°C下進行攪拌12小時，在種子 烯基單體混合物及聚合引發劑。-54- 201026766 4. Synthesis of Crosslinked Resin Microparticles Synthesis Example 13 (Synthesis of Crosslinked Resin Microparticles (Ba-Ι) A methacrylic acid component and a trimethylolpropane triacrylate manufactured by Toagosei Co., Ltd. were added to a stainless steel reaction vessel. 50 parts by mass of _ 3 09" (product name), and 100 parts by mass of ion-exchanged water was added to the mixture to dissolve the emulsifier aqueous solution of "Melcuric sodium laurate" (Emael 2F-30). The emulsifier is emulsified and the emulsion of the mixture is made up. In a glass reactor equipped with a mixer, a reflux condenser, a warm inlet pipe, and a liquid supply pipe connection portion, 299 parts by mass of water and 3.0% by mass of a 10% KOH aqueous solution are used. Seed particle dispersion (SD-1) 28 5.7 While stirring, adjust the internal temperature of the reactor to 20 ° C. Add the aforementioned vinyl monomer to the reactor, and then add the polymerization initiator to the pure drug. Industrial Co., Ltd.: 2,4-Dimethylvaleronitrile (trade name "V-65") The internal temperature of the apparatus was stirred at 20 ° C for 12 hours in a seed ethylenic monomer mixture and a polymerization initiator.

然後，在反應器中藉由設置於液面上方 吹入氮氣，在2小時內使內溫由20°C昇溫至 使吸收於種子粒子中之乙烯基單體混合物予 內溫維持於7〇t下2小時。其次，在反應液 19質量份中溶解有作爲抗氧化劑之ADEK A ) 甲酯 50質量 i 「Aronix M- 。在該混合物 乳化劑之花王 名）1.5質量 調製乙烯基單 度計、氮氣導 加入離子交換 份及以合成例 質量份，一邊 合物之乳化液 2,2’-偶氮雙（ 量份，在反應 粒子中吸收乙 之氮氣導入管 70°C。藉此， 以聚合，再使 中加入在甲醇 製三乙二醇雙 •55- 201026766 (3-(3-第3-丁基-4-羥基-5-甲基苯基）丙酸酯「AO-70」 (商品名。以下簡稱爲「抗氧化劑」）1質量份之液體， 再於70 °C下保持30分鐘。然後，予以冷卻，製造含有交 聯樹脂微粒子（Ba-Ι )的分散液。 使前述交聯樹脂微粒子（Ba-1 )之分散液進行離心分 離處理，且除去上層澄清液，回收交聯樹脂微粒子之沉澱 塊。使經回收的交聯樹脂微粒子（Ba-Ι)之沉澱塊、與同 質量之離子交換水混合，予以再分散，然後，進行離心分 @ 離處理。其次，除去上層澄清液，直至經回收的沉澱塊在 155°C下予以加熱30分鐘時之不揮發成分爲98質量％以上 爲止，在80°C下進行乾燥。繼後，予以解碎，回收交聯樹 脂微粒子（Ba-Ι )。 進行前述交聯樹脂微粒子（Ba-Ι )之SEM觀察，藉 由影像所求得的數平均粒徑（dn )爲2.08μηι，體積平均 粒徑（dv )爲2.09μπι，體積平均粒徑（dv )與數平均粒 徑（dn)之比例（dv/dn)爲 1.00。 〇 而且，求取前述交聯樹脂微粒子（Ba-Ι )之設定交聯 點當量時，爲2.53meq/g。 合成例14〜16(交聯樹脂微粒子（Ba-2)〜（Ba-4)之合 成） 除吸收於種子粒子分散液（SD-1)之種子粒子中之單 體混合物的組成改爲如表3所示外，進行與合成例1 3相 同的操作，製造交聯樹脂微粒子（Ba-2 )〜（Ba-4 )。 -56- 201026766 進行前述交聯樹脂微粒子（Ba-2)〜（Ba-4)之SEM 觀察，藉由影像所求得的數平均粒徑（dn)、體積平均粒 徑（dv )、體積平均粒徑（dv )與數平均粒徑（dn )之比 例（dv/dn )，如表3所示。 而且，求取前述交聯樹脂微粒子（Ba-2)〜（Ba-4) 之設定父聯點當量時，如表3所不。 Q 合成例17 (交聯樹脂微粒子（Ba-5 )之合成） 除使用合成例10製造的種子粒子分散液（SD-3 ) 285·7質量份取代合成例13之種子粒子分散液（SD-1) 285·7質量份，且使吸收於種子粒子之乙烯基單體混合物 的組成改爲表3所示外，進行與合成例1 3相同的操作， 製造交聯樹脂微粒子（Ba_5)。 進行前述交聯樹脂微粒子（Ba-5 )之SEM觀察，藉 由影像所求得的數平均粒徑（dn )、體積平均粒徑（dv ) β 、體積平均粒徑（dv )與數平均粒徑（dn )之比例（ dv/dn )’如表3所示。 而且’求取前述交聯樹脂微粒子（Ba-5 )之設定交聯 點當量時’如表3所示。 合成例18及交聯樹脂微粒子（Ba-6)及（Ba-7)之 合成） 吏合成例n製造的種子粒子分散液（sd_4) 285·7質量份取代合成例13之種子粒子分散液（SD-1) -57- 201026766 285.7質量份，且使吸收於種子粒子之乙烯基單體混合物 的組成改爲表3所示外，進行與合成例1 3相同的操作， 製造交聯樹脂微粒子（Ba-6)及（Ba-7)。 進行前述交聯樹脂微粒子（Ba-6)及（Ba-7)之SEM 觀察，藉由影像所求得的數平均粒徑（dn)、體積平均粒 徑（dv )、體積平均粒徑（dv )與數平均粒徑（dn )之比 例（dv/dn )，如表3所示。Then, in the reactor, nitrogen gas was blown over the liquid surface, and the internal temperature was raised from 20 ° C in 2 hours until the internal temperature of the vinyl monomer mixture absorbed in the seed particles was maintained at 7 〇t. Next 2 hours. Next, 19 parts by mass of the reaction liquid was dissolved with ADEK A) methyl ester as an antioxidant 50 mass i "Aronix M-. In the name of the emulsifier of the mixture" 1.5 mass-modulated vinyl single-meter, nitrogen-guided addition of ions The exchanged parts and the synthetic mass parts, the emulsion of the monomer 2, 2'-azobis (volume, absorb the nitrogen gas of the reaction tube into a nitrogen gas introduction tube 70 ° C. Thereby, to polymerize, and then make Addition of triethylene glycol bis-55- 201026766 (3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate "AO-70" in methanol (trade name. 1 part by mass of the "antioxidant") was further kept at 70 ° C for 30 minutes, and then cooled to prepare a dispersion containing crosslinked resin fine particles (Ba-Ι). The crosslinked resin fine particles (Ba) -1) The dispersion is subjected to centrifugal separation treatment, and the supernatant liquid is removed to recover a precipitated block of crosslinked resin fine particles. The precipitated block of the recovered crosslinked resin fine particles (Ba-Ι) and ion exchange water of the same mass are used. Mixing, redispersing, and then centrifuging Next, the supernatant liquid was removed until the recovered precipitate was heated at 155 ° C for 30 minutes, and the nonvolatile content was 98% by mass or more, and dried at 80 ° C. Thereafter, it was decomposed and recovered. Crosslinked resin fine particles (Ba-Ι). The SEM observation of the crosslinked resin fine particles (Ba-Ι) was carried out, and the number average particle diameter (dn) obtained by the image was 2.08 μm, and the volume average particle diameter (dv) was obtained. The ratio of the volume average particle diameter (dv) to the number average particle diameter (dn) (dv/dn) is 1.00. 〇 Moreover, the cross-linking point equivalent of the crosslinked resin microparticles (Ba-Ι) is determined. In the case of the seed particles of the seed particle dispersion (SD-1) (Synthesis) The composition of the bulk mixture was changed to the same as in the above-mentioned Example 1, and the same procedure as in Synthesis Example 13 was carried out to produce crosslinked resin fine particles (Ba-2) to (Ba-4). -56- 201026766 The above-mentioned crosslinked resin fine particles were subjected. (Ba-2)~(Ba-4) SEM observation, the number average particle diameter (dn) obtained by image, volume flat The ratio of the particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter (dn) (dv/dn) is shown in Table 3. Further, the crosslinked resin fine particles (Ba-2) were obtained. (Ba-4) When the parental point equivalent is set, it is as shown in Table 3. Q Synthesis Example 17 (Synthesis of Crosslinked Resin Microparticles (Ba-5)) In addition to the seed particle dispersion (Synthesis) prepared using Synthesis Example 10 3) 285. 7 parts by mass of the seed particle dispersion (SD-1) of the synthesis example 13 was replaced by 28.5 parts by mass, and the composition of the vinyl monomer mixture absorbed in the seed particles was changed to that shown in Table 3 The crosslinked resin fine particles (Ba_5) were produced in the same manner as in Synthesis Example 13. The SEM observation of the crosslinked resin microparticles (Ba-5) was carried out, and the number average particle diameter (dn), the volume average particle diameter (dv) β, the volume average particle diameter (dv), and the number average particle obtained by the image were obtained. The ratio of the diameter (dn) (dv/dn )' is shown in Table 3. Further, the results are as shown in Table 3 when the cross-linking point equivalent of the crosslinked resin fine particles (Ba-5) is determined. Synthesis Example 18 and Synthesis of Crosslinked Resin Fine Particles (Ba-6) and (Ba-7) 种子 Synthesis of Seed Particle Dispersion (sd_4) by Synthetic Example n 285·7 parts by mass of seed particle dispersion of Substituted Synthesis Example 13 SD-1) -57-201026766 285.7 parts by mass, and the composition of the vinyl monomer mixture absorbed in the seed particles was changed to that shown in Table 3, and the same operation as in Synthesis Example 13 was carried out to produce crosslinked resin fine particles ( Ba-6) and (Ba-7). The SEM observation of the crosslinked resin microparticles (Ba-6) and (Ba-7) was carried out, and the number average particle diameter (dn), volume average particle diameter (dv), and volume average particle diameter (dv) obtained by the image were obtained. The ratio of the number average particle diameter (dn) (dv/dn) is shown in Table 3.

而且，求取前述交聯樹脂微粒子（Ba-6)及（Ba-7) Q 之設定交聯點當量時，如表3所示。 合成例20〜23 (交聯樹脂微粒子（B a-8)〜（B a-11)之 合成） 除合成例13之離子交換水的使用量由1〇〇質量份改 爲1 2 5質量份，使用合成例1 2製造的種子粒子分散液（ SD-5) 454.6質量份取代種子粒子分散液（SD-1) 285.7 質量份，且使吸收於種子粒子之乙烯基單體混合物的組成 © 改爲表4所示外，進行與合成例13相同的操作，製造交 聯樹脂微粒子（Ba-8 )〜（Ba-11 )。 進行前述交聯樹脂微粒子（Ba-8)〜（Ba-11)之 SEM觀察，藉由影像所求得的數平均粒徑（dn)、體積平 均粒徑（dv )、體積平均粒徑（dv )與數平均粒徑（dn ) 之比例（dv/dn)，如表4所示。 而且，求取前述交聯樹脂微粒子（Ba-8)〜（Ba-11 )之設定交聯點當量時’如表4所示。 -58- 201026766 另外，以合成例21所得的交聯樹脂微粒子（Ba-9 ) 以曰本電子社電場放射掃描型電子顯微鏡（FE-SEM ) 「 JSM-63 3 0F」（型式名）攝影。其照片如第2圖所示。 合成例24 (交聯樹脂微粒子（Ba-12 )之合成） 除合成例13之離子交換水的使用量由100質量份改 爲157質量份，使用合成例12製造的種子粒子分散液（ 參 SD-5 ) 227.3質量份取代種子粒子分散液（SD- 1 ) 28 5.7 質量份，且使吸收於種子粒子之乙烯基單體混合物的組成 改爲表4所示外，進行與合成例1 3相同的操作，製造交 聯樹脂微粒子（Ba-12)。 進行前述交聯樹脂微粒子（Ba-12)之SEM觀察，藉 由影像所求得的數平均粒徑（dn )、體積平均粒徑（dv ) 、體積平均粒徑（dv )與數平均粒徑（dn )之比例（ dv/dn )，如表4所示。 Φ 而且，求取前述交聯樹脂微粒子（Ba-12)之設定交 聯點當量時，如表4所示。 合成例25(交聯樹脂微粒子（B a-13)之合成） 除合成例13之離子交換水的使用量由100質量份改 爲525質量份，使吸收於種子粒子之乙烯基單體混合物的 組成改爲表4所示，聚合引發劑之2,2’-偶氮雙（2,4-二甲 基戊腈）（使用V-65 )之使用量由1質量份改爲3質量份 ，且沒有添加合成例1 3之抗氧化劑及甲醇外，進行與合 -59- 201026766 成例1 3相同的操作，製造交聯樹脂微粒子（Ba-1 3 )。 進行前述交聯樹脂微粒子（Ba-13 )之SEM觀察，藉 由影像所求得的數平均粒徑（dn )、體積平均粒徑（dv ) 、體積平均粒徑（dv )與數平均粒徑（dn )之比例（ dv/dn )，如表4所示。 而且’求取前述交聯樹脂微粒子（Ba-13 )之設定交 聯點當量時，如表4所示。 ❿ 合成例26(交聯樹脂微粒子（Ba_i4)之合成） 除合成例13之離子交換水的使用量由100質量份改 爲125質量份，使用合成例12製造的種子粒子分散液（ SD-5 ) 454.6質量份取代種子粒子分散液（SD- 1 ) 285.7 質量份’且使吸收於種子粒子之乙烯基單體混合物的組成 改爲表4所示外，進行與合成例i 3相同的操作，製造交 聯樹脂微粒子（Ba-1 4 )。 進行前述交聯樹脂微粒子（Ba-14)之SEM觀察，藉 馨 由影像所求得的數平均粒徑（dn )、體積平均粒徑（dv ) 、體積平均粒徑（dv )與數平均粒徑（dn )之比例（ dv/dn )，如表4所示。 而且，求取前述交聯樹脂微粒子（Ba-14 )之設定交 聯點當量時，如表4所示。 合成例27 (交聯樹脂微粒子（Ba-Ι5)之合成） 除合成例13之離子交換水的使用量由100質量份改 -60- 201026766 爲2 42.0質量份，使用合成例9製造的種子粒子分散液（ SD-2) 142.9質量份取代種子粒子分散液（SD-1) 285.7 質量份外，進行與合成例1 3相同的操作，製造交聯樹脂 微粒子（Ba-15 )。 進行前述交聯樹脂微粒子（Ba-15 )之SEM觀察，藉 由影像所求得的數平均粒徑（dn )、體積平均粒徑（dv ) 、體積平均粒徑（dv )與數平均粒徑（dn )之比例（ 瘳 dv/dn)，如表4所示。 而且，求取前述交聯樹脂微粒子（Ba-15)之設定交 聯點當量時，如表4所示。Further, when the cross-linking point equivalents of the crosslinked resin fine particles (Ba-6) and (Ba-7) Q were determined, they are shown in Table 3. Synthesis Examples 20 to 23 (Synthesis of Crosslinked Resin Microparticles (B a-8) to (B a-11)) The amount of ion-exchanged water used in Synthesis Example 13 was changed from 1 part by mass to 1 2 5 parts by mass. Using the seed particle dispersion (SD-5) manufactured in Synthesis Example 1 2, 454.6 parts by mass of the seed particle dispersion (SD-1), 285.7 parts by mass, and the composition of the vinyl monomer mixture absorbed by the seed particles was changed. In the same manner as in Synthesis Example 13, except that the conditions shown in Table 4 were carried out, crosslinked resin fine particles (Ba-8) to (Ba-11) were produced. The SEM observation of the crosslinked resin fine particles (Ba-8) to (Ba-11), the number average particle diameter (dn), the volume average particle diameter (dv), and the volume average particle diameter (dv) obtained by the image were obtained. The ratio to the number average particle diameter (dn) (dv/dn) is shown in Table 4. Further, when the crosslinked point equivalent of the crosslinked resin fine particles (Ba-8) to (Ba-11) was determined, the results are shown in Table 4. -58-201026766 In addition, the crosslinked resin fine particles (Ba-9) obtained in Synthesis Example 21 were photographed by a field emission scanning electron microscope (FE-SEM) "JSM-63 3 0F" (type name) of Sakamoto Electronics Co., Ltd. The photo is shown in Figure 2. Synthesis Example 24 (Synthesis of Crosslinked Resin Microparticles (Ba-12)) The amount of ion-exchanged water used in Synthesis Example 13 was changed from 100 parts by mass to 157 parts by mass, and the seed particle dispersion liquid produced in Synthesis Example 12 was used (see SD). -5) 227.3 parts by mass of the substituted seed particle dispersion (SD-1) 28 5.7 parts by mass, and the composition of the vinyl monomer mixture absorbed in the seed particles was changed to that shown in Table 4, and was carried out in the same manner as in Synthesis Example 13. The operation was carried out to produce crosslinked resin fine particles (Ba-12). The SEM observation of the crosslinked resin fine particles (Ba-12), the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter obtained by the image The ratio of (dn) (dv/dn) is shown in Table 4. Φ Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Ba-12) was determined, it is shown in Table 4. Synthesis Example 25 (Synthesis of Crosslinked Resin Microparticles (B a-13)) The amount of ion-exchanged water used in Synthesis Example 13 was changed from 100 parts by mass to 525 parts by mass to allow absorption of the vinyl monomer mixture of the seed particles. The composition was changed to that shown in Table 4, and the amount of 2,2'-azobis(2,4-dimethylvaleronitrile) (using V-65) of the polymerization initiator was changed from 1 part by mass to 3 parts by mass. Further, in the same manner as in Example 13 of the combination of -59-201026766, the crosslinking resin fine particles (Ba-1 3 ) were produced, except that the antioxidant of the synthesis example 13 and methanol were not added. The SEM observation of the crosslinked resin fine particles (Ba-13), the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter obtained by the image The ratio of (dn) (dv/dn) is shown in Table 4. Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Ba-13) was determined, the results are shown in Table 4. ❿ Synthesis Example 26 (Synthesis of Crosslinked Resin Microparticles (Ba_i4)) The amount of ion-exchanged water used in Synthesis Example 13 was changed from 100 parts by mass to 125 parts by mass, and the seed particle dispersion liquid (SD-5) produced in Synthesis Example 12 was used. 454.6 parts by mass of the substituted seed particle dispersion (SD-1) 285.7 parts by mass 'and the composition of the vinyl monomer mixture absorbed in the seed particles was changed to that shown in Table 4, and the same operation as in Synthesis Example i 3 was carried out, Crosslinked resin microparticles (Ba-1 4 ) were produced. The SEM observation of the crosslinked resin microparticles (Ba-14) was carried out, and the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle obtained by the image were determined by the image. The ratio of the diameter (dn) (dv/dn) is shown in Table 4. Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Ba-14) was determined, the results are shown in Table 4. Synthesis Example 27 (Synthesis of Crosslinked Resin Microparticles (Ba-Ι5)) The amount of ion-exchanged water used in Synthesis Example 13 was changed from 100 parts by mass to -60 to 201026766 to 2 42.0 parts by mass, and seed particles produced in Synthesis Example 9 were used. Dispersion (SD-2) 142.9 parts by mass of the substituted seed particle dispersion (SD-1) 287.8 parts by mass, the same operation as in Synthesis Example 13 was carried out to produce crosslinked resin fine particles (Ba-15). The SEM observation of the crosslinked resin fine particles (Ba-15), the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter obtained by the image The ratio of (dn) (瘳dv/dn) is shown in Table 4. Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Ba-15) was determined, the results are shown in Table 4.

-61 - 201026766 u谳 合成例 〇\ Ba-7 SD-4 | I 285.7 1 丨 1〇〇 1 1 § 1 丨 1-57 1 1 loo 1 fToi 1 〇〇 Ba-6 | SD-4 | 1 285.7 1 〇 1 1 CN 丨 1·52 1 1.00 |2.52 卜 Ba-5 SD-3 | 285.7 100 1 1 1 1-75 1.75 1.00 1 2.52 Ba-4 SD-1 | 285.7 1 〇 1 1 〇 | 2.10 | 2.10 | 1.00 0.51 <n Ba-3 SD-1] | 285.7 | 〇 1 g 1 丨 2.11 CN 1.00 1—< 寸 Ba-2 | SD-1 1 285.7 〇 1 1 | 2.02 | 2.03 1.00 2.52 CO Τ·*Η Ba-1 | SD-1 1 285.7」 Ο 1 1 2.08 | 2.09 1.00 2.53 交聯樹脂微粒子 原料之組成(質量份） 種子粒子分散液 種類 成4^旦分散液 坤、训里種子粒子之量 乙烯基系單體 甲基丙烯酸甲酯 甲基丙烯酸異丁酯 丄 三丙烯酸三羥甲基丙烷酯 二甲基丙烯酸乙二醇酯 交聯樹脂微粒子之物性 數平均粒徑如㈣） 體積平均粒徑(Μμιη) dv/dn 設定交聯點當量(meq/g) -62- 201026766 【寸漱 合成例 Ba-15 SD-2 142.9 1 1 1 3.04 I 1 3.06 I | 1.01 I 3.37 <N Ba-14 SD-5 | 454.6 〇 1 00 OS 1 <N 1 0.94 | 0.94 1 l.oo I 0.10 (N Ba-13 | SD-1 | 285.7 | 〇 On 1 1 |_L94 … 1 195 1 2.53 Ba-12 SD-5 | 227.3 | 1 § 1 1 1 1-1Q 1 1 1.01 1 0.35 m CN Ba-11 SD-5 454.6 1______ 〇 1 〇\ 1 1 0.97 1 1 0.97 1 l.oo 1 0.25 CN <N Ba-10 | SD-5 | | 454.6 1 〇 1 1 〇 1 | 0.96 1 1 0.96 1 I l.oo | 1 0.50 1 CN Ba-9 | SD-5 | 454.6 | Ο 1 g 1 1 | 0.95 1 0.96 1 1-Q1 1 1.01 Ba-8 SD-5 | 454.6 | Ο 1 1 1 | 0.94 1 0.94 I l.oo 1 2.52 交聯樹脂微粒子 原料之組成(質量份） 種子粒子分散液 種類 分散液 種子粒子之量 乙烯基系單體 甲基丙烯酸甲酯 甲基丙烯酸異丁酯 三丙烯酸三羥甲基丙烷酯 二甲基丙嫌酸乙二醇酯 聚合性光安定劑υ 交聯樹脂微粒子之物性 數平均粒徑ώι(μιη) 體積平均粒徑ίΐν(μηι) dv/dn 設定交聯點當量(meq/g) 添加量 题氍裝 M«ffi-«iyf χ&πΛ9(Νηι (i -63- 201026766 合成例28 (交聯樹脂微粒子（Bb-l )之合成） 在附有藉由定量幫浦的送液配管之玻璃製容器中，加 入甲醇2 6 9.4質量份、2 5 %銨水 0 · 2 8質量份及以合成例2 所調製的高分子單體水溶液（MM-2 ) 3.76質量份進行攪 拌，調製混合溶液（273.4質量份）。 另外，在具備攪拌機、回流冷卻器、溫度計、氮氣導 入管及送液配管連結部之玻璃製反應器中，加入離子交換 水 174.7質量份、甲醇 323.2質量份、25 %銨水 0.28質 @ 量份及以合成例2所調製的高分子單體水溶液（MM-2 ) 3.76質量份、甲基丙烯酸甲酯 50.0質量份及甲基丙烯酸 異丁酯 50.0質量份，在攪拌下一邊吹入氮氣，一邊使反 應器內溫調整爲50°C。 確認反應器內溫度爲5 0 °C之安定値後，且在該反應器 中投入1〇.〇質量份甲基丙烯酸三甲氧基矽烷基丙酯。於 1 〇分鐘後，添加作爲聚合引發劑之過氧化三甲基乙酸第 3 -丁醋（使用「Perbutyl PV」）2.4質量份，開始聚合。 〇 確認添加聚合引發劑後，反應液產生混濁情形，慢慢地白 化形成乳白色，生成樹脂微粒子。 添加聚合引發劑後，經過20分鐘後，開始將前述單 體混合液供應給反應器。換言之，使用定量幫浦，以一定 速度、於60分鐘內將273.4份單體混合液供應給反應器 。供應完成後，在160分鐘內使反應器內之溫度昇溫爲 5〇°C，調製具有水解性矽烷基之甲基丙烯酸酯系樹脂微粒 子之分散液。 -64- 201026766 自添加聚合引發劑後4小時後，於反應液中添加爲使 水解性矽烷基時作爲鹼性觸媒的25%銨水 32.8 5質量份。 然後，使反應器之內溫昇溫爲6(TC，在同溫下保持3小時 ，進行粒子交聯。此時，自銨水添加開始經過2.5小時， 添加抗氧化劑 1 · 〇質量份。 其次，使前述反應液冷卻，以200網目深層式濾芯（ Polynet )進行過濾。然後，回收交聯樹脂微粒子（經交聯 〇 的甲基丙烯酸烷酯系樹脂微粒子）。繼後，在155°c下加 熱30分鐘時之不揮發成分達到98質量％以上爲止，在 6 〇°C下進行乾燥。然後，進行解碎，製得交聯樹脂微粒子 (Bb-1 )。 進行前述交聯樹脂微粒子（Bb-Ι )之SEM觀察，藉 由影像所求得的數平均粒徑（dn )爲1.06μιη、體積平均 粒徑（dv)爲1·〇8μιη、體積平均粒徑（dv)與數平均粒 徑（dn)之比例（dv/dn)爲 1.02。 ® 而且，求取前述交聯樹脂微粒子（Bb-1)之設定交聯 點當量時，如表5所示爲1.06meq/g。 合成例29〜31 (交聯樹脂微粒子（Bb-2)〜（Bb-4)之合 成） 除爲使水解性矽烷基予以交聯時之鹼性觸媒的種類及 添加量改爲如表5所示外，進行與合成例2 8之操作，製 造由甲基丙烯酸烷酯系樹脂所成的交聯樹脂微粒子（Bb-2 )〜（Bb-4)。 -65- 201026766-61 - 201026766 u谳合成例〇\ Ba-7 SD-4 | I 285.7 1 丨1〇〇1 1 § 1 丨1-57 1 1 loo 1 fToi 1 〇〇Ba-6 | SD-4 | 1 285.7 1 〇1 1 CN 丨1·52 1 1.00 |2.52 卜Ba-5 SD-3 | 285.7 100 1 1 1 1-75 1.75 1.00 1 2.52 Ba-4 SD-1 | 285.7 1 〇1 1 〇| 2.10 | 2.10 1.00 0.51 <n Ba-3 SD-1] | 285.7 | 〇1 g 1 丨2.11 CN 1.00 1—< inch Ba-2 | SD-1 1 285.7 〇1 1 | 2.02 | 2.03 1.00 2.52 CO Τ· *Η Ba-1 | SD-1 1 285.7" Ο 1 1 2.08 | 2.09 1.00 2.53 Composition of crosslinked resin microparticle raw materials (parts by mass) Seed particle dispersion type into 4^dan dispersion liquid Kun, training seed particles Vinyl monomer methyl methacrylate isobutyl methacrylate trimethylolpropane triacrylate dimethacrylate crosslinked resin microparticles physical number average particle diameter (4)) volume average particle diameter (Μμιη) dv/dn Set the cross-linking point equivalent (meq/g) -62- 201026766 [Inch 漱 Synthesis Example Ba-15 SD-2 142.9 1 1 1 3.04 I 1 3.06 I | 1.01 I 3.37 <N Ba-14 SD-5 | 454.6 〇1 00 OS 1 <N 1 0.94 | 0.94 1 l.oo I 0.10 (N Ba-13 | SD-1 | 285.7 | 〇On 1 1 |_L94 ... 1 195 1 2.53 Ba -12 SD-5 | 227.3 | 1 § 1 1 1 1-1Q 1 1 1.01 1 0.35 m CN Ba-11 SD-5 454.6 1______ 〇1 〇\ 1 1 0.97 1 1 0.97 1 l.oo 1 0.25 CN < N Ba-10 | SD-5 | | 454.6 1 〇1 1 〇1 | 0.96 1 1 0.96 1 I l.oo | 1 0.50 1 CN Ba-9 | SD-5 | 454.6 | Ο 1 g 1 1 | 0.95 1 0.96 1 1-Q1 1 1.01 Ba-8 SD-5 | 454.6 | Ο 1 1 1 | 0.94 1 0.94 I l.oo 1 2.52 Composition of Crosslinked Resin Microparticles (Parts by Mass) Seed Particle Dispersion Type Dispersion Seed Particles The amount of vinyl monomer methyl methacrylate isobutyl methacrylate trimethylolpropane trimethyl propylene glycol methacrylate polymerized light stabilizer υ average number of crosslinked resin particles Particle size ώι(μιη) Volume average particle size ΐΐν(μηι) dv/dn Set cross-linking point equivalent (meq/g) Add amount of questions M氍ffi-«iyf χ&πΛ9(Νηι (i -63- 201026766 Synthetic Example 28 (crosslinked resin micro Synthesis of sub-(Bb-1)) In a glass container provided with a liquid supply pipe by a quantitative pump, methanol 4.6 parts by mass, 25 % ammonium water 0·28 parts by mass, and a synthesis example were added. 2.76 parts by mass of the prepared aqueous polymer monomer solution (MM-2) was stirred to prepare a mixed solution (273.4 parts by mass). Further, 174.7 parts by mass of ion-exchanged water, 323.2 parts by mass of methanol, and 0.28 mass of 25% ammonium water were added to a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas introduction pipe, and a liquid supply pipe connection portion. And 3.76 parts by mass of the aqueous polymer monomer solution (MM-2) prepared in Synthesis Example 2, 50.0 parts by mass of methyl methacrylate, and 50.0 parts by mass of isobutyl methacrylate, while blowing nitrogen gas while stirring The internal temperature of the reactor was adjusted to 50 °C. After confirming that the temperature in the reactor was 50 ° C, and in the reactor, 1 part by mass of trimethoxydecyl propyl methacrylate was charged. After 1 minute, 2.4 parts by mass of trimethylacetic acid trimethylacetate (using "Perbutyl PV") as a polymerization initiator was added to start polymerization. 〇 After the addition of the polymerization initiator, the reaction solution was turbid, and it was slowly whitened to form a milky white color to form resin fine particles. After the addition of the polymerization initiator, after 20 minutes passed, the above-mentioned monomer mixture was supplied to the reactor. In other words, a metered pump was used to supply 273.4 parts of the monomer mixture to the reactor at a rate of 60 minutes. After the completion of the supply, the temperature in the reactor was raised to 5 ° C in 160 minutes to prepare a dispersion of methacrylic resin fine particles having a hydrolyzable decyl group. -64-201026766 After 4 hours from the addition of the polymerization initiator, 52.8 parts by mass of 25% ammonium water as a basic catalyst when hydrolyzable decyl group was added was added to the reaction liquid. Then, the internal temperature of the reactor was raised to 6 (TC, and the mixture was kept at the same temperature for 3 hours to carry out particle crosslinking. At this time, the addition of the antioxidant 1 · 〇 parts by mass was started 2.5 hours after the addition of the ammonium water. The reaction solution was cooled, and filtered through a 200-mesh deep-layer filter (Polynet). Then, crosslinked resin fine particles (crosslinked sulfonated alkyl methacrylate resin fine particles) were recovered, and then heated at 155 ° C. The non-volatile content at 30 minutes is 98% by mass or more, and is dried at 6 〇 ° C. Then, it is pulverized to obtain crosslinked resin fine particles (Bb-1 ). The crosslinked resin fine particles (Bb- SEM) SEM observation, the number average particle diameter (dn) obtained by the image is 1.06 μm, the volume average particle diameter (dv) is 1·〇8 μιη, the volume average particle diameter (dv), and the number average particle diameter ( The ratio (dv/dn) of dn) was 1.02. Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Bb-1) was determined, it was 1.06 meq/g as shown in Table 5. Synthesis Example 29~ 31 (combination of crosslinked resin microparticles (Bb-2) to (Bb-4)) The type and amount of the basic catalyst when the decomposed decyl group was cross-linked were changed as shown in Table 5, and the operation of Synthesis Example 28 was carried out to produce a cross-linking of an alkyl methacrylate-based resin. Resin microparticles (Bb-2)~(Bb-4). -65- 201026766

進行前述交聯樹脂微粒子（Bb-2)〜（Bb-4)之SEM 觀察，藉由影像所求得的數平均粒徑（dn )、體積平均粒 徑（dv )、體積平均粒徑（dv )與數平均粒徑（dii )之比 例（dv/dn)，如表5所示。 而且，求取前述交聯樹脂微粒子（Bb-2 )〜（Bb-4 ) 之設定交聯點當量時，如表5所示。The SEM observation of the crosslinked resin fine particles (Bb-2) to (Bb-4) was carried out, and the number average particle diameter (dn), volume average particle diameter (dv), and volume average particle diameter (dv) obtained by the image were obtained. The ratio to the number average particle diameter (dii) (dv/dn) is shown in Table 5. Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Bb-2) to (Bb-4) was determined, the results are shown in Table 5.

合成例32 (交聯樹脂微粒子（Bb-5 )之合成） G 除甲基丙烯酸三甲氧基矽烷基丙酯之添加量改爲1.0 質量份外’進行與合成例28之操作，製造由甲基丙烯酸 院酯系樹脂所成的交聯樹脂微粒子（Bb-5)。 進行前述交聯樹脂微粒子（Bb-5 )之SEM觀察，藉 由影像所求得的數平均粒徑（dn )、體積平均粒徑（dv ) 、體積平均粒徑（dv )與數平均粒徑（dn )之比例（ dv/dn )，如表5所示。 而且’求取前述交聯樹脂微粒子（Bb-5 )之設定交聯 ® 點當量時，如表5所示。 -66 - 201026766 【5 ϊ 合成例 (Ν cn Bb-5 MM- 7.53 寸 32.85 1 1.00 S 0.12 | 1 Bb-4 1 MM-2 7.53 寸 〇 1 12.2 I 1.05 I I I 1.02 I 1.06 ο m Bb-3 | 1 MM-2 1 | 7.53 j 寸 〇 8.21 | 1 1 1.06 I 1.07 | ΐ·〇ι 1 1.06 | ο CN | Bb-2 | | MM-2 j i 7.53 j 寸 〇 16.43 | 1 1.08 1 〇 1.06 | 00 (Ν | Bb-1 | | MM-2 1 i 7.53 j 寸 〇 32.85 | 1 1.06 | 1.08 1 102 1 1.06 | 交聯樹脂微粒子 原料之組成(質量份） 高分子單體溶液 種類 溶液 高分子單體之量 1¾ 甲基丙烯酸甲酯 甲基丙烯酸異丁酯 甲基丙烯酸三甲氧基矽烷基丙酯 交聯用鹼性觸媒 25%銨水 三乙胺 交聯樹脂微粒子之物性 數平均粒徑(Ιη(μηι) 體積平均粒徑(Μμιη) dv/dn 設定交聯點當量(meq/g) 添加量 M- 恢 稍 裝 K! -67- 201026766 合成例33 (交聯樹脂微粒子（Bb-6 )之合成） 在具備攪拌機、回流冷卻器、溫度計、氮氣導入管及 送液配管連結部之玻璃製反應器中，加入離子交換水 134.0質量份 '甲醇 440.8質量份、25%銨水（中和用） 0.50質量份及以合成例3所調製的高分子單體水溶液（ MM-3) 6.67質量份、甲基丙烯酸甲酯 40.0質量份及甲基 丙烯酸異丁酯 50.0質量份，在攪拌下一邊吹入氮氣，一 邊使反應器內溫調整爲55°C。 @ 確認反應器內溫度爲5 5 °C之安定値後，且在該反應器 中投入1〇.〇質量份甲基丙烯酸三甲氧基矽烷基丙酯。於 1 〇分鐘後，添加作爲聚合引發劑之過氧化三甲基乙酸第 3-丁酯（使用「Perbutyl PV」）2.4質量份，開始聚合。 確認添加聚合引發劑後，反應液產生混濁情形，慢慢地白 化形成乳白色，生成樹脂微粒子。 其次，添加聚合引發劑後，經過4小時後，一邊使反 應液之內溫保持於5 5 °C、一邊進行攪拌，製得具有水解性 ® 矽烷基之樹脂微粒子的分散液。 然後，於反應液中添加爲使水解性矽烷基時作爲鹼性 觸媒的25%銨水 32_9質量份。然後，使反應器之內溫昇 溫爲68 °C，在同溫下保持3小時，進行粒子交聯。此時’ 自銨水添加開始經過2.5小時時，添加抗氧化劑1.0質量 份。 其次，使前述反應液冷卻，以200網目深層式濾芯（Synthesis Example 32 (Synthesis of Crosslinked Resin Microparticles (Bb-5)) G Except that the amount of addition of trimethoxydecyl propyl methacrylate was changed to 1.0 part by mass, the operation of Synthesis Example 28 was carried out, and methyl group was produced. Crosslinked resin fine particles (Bb-5) made of acrylic acid ester resin. The SEM observation of the crosslinked resin microparticles (Bb-5), the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter obtained by the image The ratio of (dn) (dv/dn) is shown in Table 5. Further, when the cross-linking ® point equivalent of the crosslinked resin fine particles (Bb-5) was determined, the results are shown in Table 5. -66 - 201026766 [5 ϊ Synthesis example (Ν cn Bb-5 MM- 7.53 inch 32.85 1 1.00 S 0.12 | 1 Bb-4 1 MM-2 7.53 inch 〇 1 12.2 I 1.05 III 1.02 I 1.06 ο m Bb-3 | 1 MM-2 1 | 7.53 j inch 〇 8.21 | 1 1 1.06 I 1.07 | ΐ·〇ι 1 1.06 | ο CN | Bb-2 | | MM-2 ji 7.53 j inch 〇 16.43 | 1 1.08 1 〇1.06 | 00 (Ν | Bb-1 | | MM-2 1 i 7.53 j inch 〇32.85 | 1 1.06 | 1.08 1 102 1 1.06 | Composition of crosslinked resin microparticles (parts by mass) Polymer monomer solution type solution polymer monomer Amount of 13⁄4 methyl methacrylate isobutyl methacrylate trimethoxy decyl propyl acrylate crosslinkable with basic catalyst 25% ammonium water triethylamine crosslinked resin microparticles physical number average particle size (Ιη (μηι) Volume average particle diameter (Μμιη) dv/dn Set crosslink point equivalent (meq/g) Addition amount M-Recovery K! -67- 201026766 Synthesis Example 33 (crosslinked resin microparticles (Bb-6) Synthesis) In a glass reactor equipped with a mixer, a reflux condenser, a thermometer, a nitrogen introduction tube, and a liquid supply pipe connection portion 134.0 parts by mass of ion-exchanged water, 440.8 parts by mass of methanol, 0.50 parts by mass of ammonium hydroxide (for neutralization), and 0.57 parts by mass of aqueous polymer monomer solution (MM-3) prepared in Synthesis Example 3, methacrylic acid 40.0 parts by mass of methyl ester and 50.0 parts by mass of isobutyl methacrylate were mixed with nitrogen gas while stirring to adjust the internal temperature of the reactor to 55 ° C. @ Confirm the stability of the reactor at a temperature of 5 5 ° C. Thereafter, 1 part by mass of trimethoxydecyl propyl methacrylate was added to the reactor. After 1 minute, 3-butyl peroxydiacetate as a polymerization initiator was added ( The polymerization was started by using 2.4 parts by mass of "Perbutyl PV". It was confirmed that the reaction liquid was turbid after the addition of the polymerization initiator, and the white color was gradually whitened to form resin fine particles. Next, after the addition of the polymerization initiator, after 4 hours, The mixture was stirred while maintaining the internal temperature of the reaction liquid at 5 5 ° C to obtain a dispersion of resin fine particles having hydrolyzable® decyl group. Then, 32-9 parts by mass of 25% ammonium water which is an alkaline catalyst when hydrolyzable decyl group is added is added to the reaction liquid. Then, the internal temperature of the reactor was raised to 68 ° C, and maintained at the same temperature for 3 hours to carry out particle crosslinking. At this time, 1.0 part by mass of an antioxidant was added after 2.5 hours from the start of the addition of the ammonium water. Secondly, the reaction liquid is cooled to a 200 mesh deep layer filter (

Pol ynet)進行過濾。然後，回收交聯樹脂微粒子（經交聯 -68- 201026766 的甲基丙烯酸烷酯系樹脂微粒子）。繼後，在155 °C下加 熱30分鐘時之不揮發成分達到98質量％以上爲止，在 6 0 °C下進行乾燥。然後，進行解碎，製得交聯樹脂微粒子 (Bb-6)。 進行前述交聯樹脂微粒子（Bb-6 )之SEM觀察，藉 由影像所求得的數平均粒徑（dn )、體積平均粒徑（dv ) 、體積平均粒徑（dv )與數平均粒徑（dn )之比例（ dv/dn )，如表6所示。 而且，求取前述交聯樹脂微粒子（Bb-6 )之設定交聯 點當量時，如表6所示。 合成例34〜38 (交聯樹脂微粒子（Bb-7 )〜（Bb-11 )之 合成） 除使合成例33之高分子單體液（MM-3)各改爲合成 例4〜6所製造的高分子單體液（MM-4 ) 、（MM-5)及 ❹ (MM-6 )，且於反應器中加入的離子交換水、甲醇、及 中和用25 %銨水之量如表6所示外，進行與合成例33之 操作，製造交聯樹脂微粒子（Bb-7)〜（Bb-11)。 進行前述交聯樹脂微粒子（Bb-7 )〜（Bb-11 )之 SEM觀察，藉由影像所求得的數平均粒徑（dn)、體積平 均粒徑（dv )、體積平均粒徑（dv )與數平均粒徑（dn ) 之比例（dv/dn )，如表6所示。 而且，求取前述交聯樹脂微粒子（Bb-7)〜（Bb-11 )之設定交聯點當量時’如表6所示。 -69 - 201026766 而且’使以合成例3 4所得的交聯樹脂微粒子（Bb-7 )以曰本電子社製電場放射掃描型電子顯微鏡（FE-SEM )「JSM-63 3 0F」（型式名）攝影。其照片如第3圖所示 合成例39 (交聯樹脂微粒子（Bb-12 )之合成） 除使合成例33之高分子單體液（MM-3)各改爲高分 子單體液（MM-4) 、（ MM-5 )及（MM-6 )，且於反應器 φ 中加入的離子交換水、甲醇、及中和用2 5 %銨水之量如表 6所示之量外，進行與合成例33之操作，製造交聯樹脂微 粒子（Bb-12 )。 進行前述交聯樹脂微粒子（Bb-12 )之SEM觀察，藉 由影像所求得的數平均粒徑（dn )、體積平均粒徑（dv ) 、體積平均粒徑（dv )與數平均粒徑（dn )之比例（ dv/dn )，如表6所示。 而且，求取前述交聯樹脂微粒子（Bb-Ι2)之設定交 〇 聯點當量時，如表6所示。 合成例40〜44(交聯樹脂微粒子（Bb-13)〜（Bb-17)之 合成） 除使合成例33之高分子單體液（MM-3 )各改爲高分 子單體液（MM-3 ) 、（ MM-4 )及（MM-7 )，且於反應器 中加入的離子交換水、甲醇、及中和用25%銨水之量如表 7所示外，進行與合成例33之操作，製造交聯樹脂微粒子 -70- 201026766 (Bb-1 3 )〜（Bb-1 7 )。 進行前述交聯樹脂微粒子（Bb-13)〜（Bb-17)之 SEM觀察，藉由影像所求得的數平均粒徑（dn)、體積平 均粒徑（dv )、體積平均粒徑（dv )與數平均粒徑（dn ) 之比例（dv/dn )，如表7所示。 而且，求取前述交聯樹脂微粒子（Bb-13)〜（Bb-17 )之設定交聯點當量時，如表7所示。 φ 而且，使以合成例4 1所得的交聯樹脂微粒子（Bb-1 4 )及以合成例43所得的交聯樹脂微粒子（Bb-1 6 )以日本 電子社製電場放射掃描型電子顯微鏡（FE-SEM ) 「JSM- 633 0F」（型式名）攝影。其照片如第4(Bb-14)圖及第Pol ynet) for filtering. Then, the crosslinked resin fine particles (the alkyl methacrylate resin fine particles of -68-201026766) were recovered. Thereafter, the nonvolatile matter was heated at 155 ° C for 30 minutes until the nonvolatile content reached 98% by mass or more, and dried at 60 ° C. Then, it was subjected to pulverization to obtain crosslinked resin fine particles (Bb-6). The SEM observation of the crosslinked resin microparticles (Bb-6), the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter obtained by the image The ratio of (dn) (dv/dn) is shown in Table 6. Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Bb-6) was determined, the results are shown in Table 6. Synthesis Examples 34 to 38 (Synthesis of Crosslinked Resin Microparticles (Bb-7) to (Bb-11)) The polymer monomer liquid (MM-3) of Synthesis Example 33 was changed to Synthesis Nos. 4 to 6 The polymer monomer liquid (MM-4), (MM-5) and ❹ (MM-6), and the amount of ion exchange water, methanol, and 25% ammonium water added to the reactor are as follows. Except as shown in Fig. 6, the operation of Synthesis Example 33 was carried out to produce crosslinked resin fine particles (Bb-7) to (Bb-11). The SEM observation of the crosslinked resin fine particles (Bb-7) to (Bb-11) was carried out, and the number average particle diameter (dn), volume average particle diameter (dv), and volume average particle diameter (dv) obtained by the image were obtained. The ratio (dv/dn) to the number average particle diameter (dn) is shown in Table 6. Further, when the crosslinked point equivalents of the crosslinked resin fine particles (Bb-7) to (Bb-11) were determined, the results are shown in Table 6. -69 - 201026766 - The electric field emission scanning electron microscope (FE-SEM) "JSM-63 3 0F" (type name) of the crosslinked resin fine particles (Bb-7) obtained in Synthesis Example 34 was used. )photography. The photograph is shown in Fig. 3, Synthesis Example 39 (Synthesis of Crosslinked Resin Fine Particles (Bb-12)), except that the polymer monomer liquid (MM-3) of Synthesis Example 33 was changed to a polymer monomer liquid (MM). -4), (MM-5) and (MM-6), and the amount of ion-exchanged water, methanol, and neutralized with 55% ammonium water added to the reactor φ is as shown in Table 6. The operation of Synthesis Example 33 was carried out to produce crosslinked resin fine particles (Bb-12). The SEM observation of the crosslinked resin microparticles (Bb-12) was carried out, and the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter obtained by the image were obtained. The ratio of (dn) (dv/dn) is shown in Table 6. Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Bb - Ι 2) was determined, the results are shown in Table 6. Synthesis Examples 40 to 44 (Synthesis of Crosslinked Resin Microparticles (Bb-13) to (Bb-17)) The polymer monomer solution (MM-3) of Synthesis Example 33 was changed to a polymer monomer solution (MM). -3), (MM-4) and (MM-7), and the amount of ion-exchanged water, methanol, and 25% ammonium water added to the reactor are as shown in Table 7, and the synthesis example is carried out. In the operation of 33, a crosslinked resin fine particle-70-201026766 (Bb-1 3 )~(Bb-1 7 ) was produced. The SEM observation of the crosslinked resin microparticles (Bb-13) to (Bb-17) was carried out, and the number average particle diameter (dn), volume average particle diameter (dv), and volume average particle diameter (dv) obtained by the image were obtained. The ratio (dv/dn) to the number average particle diameter (dn) is shown in Table 7. Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Bb-13) to (Bb-17) was determined, the results are shown in Table 7. In addition, the crosslinked resin fine particles (Bb-1 4 ) obtained in Synthesis Example 4 and the crosslinked resin fine particles (Bb-1 6 ) obtained in Synthesis Example 43 were subjected to an electric field emission scanning electron microscope (see Japanese Electric Co., Ltd.). FE-SEM ) "JSM-633 0F" (type name) photography. The photo is shown in Figure 4 (Bb-14) and

合成例45〜48(交聯樹脂微粒子（Bb-18)〜（Bb-21)之 合成） © 除使合成例33之高分子單體液（MM-3 )各改爲高分 子單體液（MM-5 )及（MM-7 )，且於反應器中加入的離 子交換水、甲醇、及中和用25 %銨水之量如表8所示，單 體之組成如表8所示外，進行與合成例3 3之操作，製造 交聯樹脂微粒子（Bb-18)〜（Bb-21)。 進行前述交聯樹脂微粒子（Bb-18 )〜（Bb-21 )之 SEM觀察，藉由影像所求得的數平均粒徑（dn)、體積平 均粒徑（dv )、體積平均粒徑（dv )與數平均粒徑（dn ) 之比例（dv/dn )，如表8所示。 -71 - 201026766 而且，求取前述交聯樹脂微粒子（Bb-18)〜（Bb-21 )之設定交聯點當量時，如表8所示。 而且，使以合成例46所得的交聯樹脂微粒子（Bb-19 )以日本電子社製電場放射掃描型電子顯微鏡（FE-S EM )「JSM-63 3 0F」（型式名）攝影。其照片如第6圖所示Synthesis Examples 45 to 48 (Synthesis of Crosslinked Resin Fine Particles (Bb-18) to (Bb-21)) © In addition, the polymer monomer liquid (MM-3) of Synthesis Example 33 was changed to a polymer monomer liquid ( MM-5) and (MM-7), and the amount of ion exchange water, methanol, and neutralized with 25% ammonium water added to the reactor are shown in Table 8, and the composition of the monomers is as shown in Table 8. The operation of Synthesis Example 3 was carried out to produce crosslinked resin fine particles (Bb-18) to (Bb-21). The SEM observation of the crosslinked resin fine particles (Bb-18) to (Bb-21), the number average particle diameter (dn), the volume average particle diameter (dv), and the volume average particle diameter (dv) obtained by the image The ratio (dv/dn) to the number average particle diameter (dn) is shown in Table 8. -71 - 201026766 Further, when the cross-linking point equivalent of the crosslinked resin fine particles (Bb-18) to (Bb-21) was determined, the results are shown in Table 8. Furthermore, the crosslinked resin fine particles (Bb-19) obtained in Synthesis Example 46 were imaged by an electric field emission scanning electron microscope (FE-S EM ) "JSM-63 3 0F" (type name) manufactured by JEOL Ltd. The photo is shown in Figure 6.

-72- 201026766 【9嗽 合成例 Os Bb-12 MM-4 6.67 〇 CN 0.26 I mi 1 464.0 | | 32.9 1 丨 1.46 | 1.46 I l.oo | | 0.59 1 00 Bb-11 1 MM-6 6.67 I 〇 <N 0.24 1 | 134.3 1 | 440.8 | 〇 〇 | 32.95 | 0.68 | 0.75 〇〇 卜 ro Bb-10 MM-5 6.67 I 〇 0.51 1 | 134.0 J | 440.8 | 〇 〇 | 32.9 | 0.80 | 0.96 1.20 οο *—Η ΓΟ Bb-9 MM-4 | I 6.67 I ο <Ν 0.26 1 | 198.1 | | 377.0 1 〇 〇 | 32.9 | 0.79 | 0.80 丨 1.01 1 1.18 iT) m Bb-8 MM-4 6.67 Ο oi 0.26 1 169.1 | 406.0 | 〇 〇 | 32.9 | 0.93 | 0.93 1.00 οο 荔 Bb-7 MM-4 6.67 ο <Ν 0.26 1 134.3 | | 440.8 | 〇 〇 | 32.9 1 1 I” 〇〇 I l.oo 丨 1.18 m Bb-6 MM-3 | 6.67 Ο CN 0.50 1 134.0 | | 440.8 | 〇 寸 〇 | 32.9 ra 1 1.13 〇 1 1.18 交聯樹脂微粒子 原料之組成(質量份） 高分子單體之分散液 種類 分散液 高分子單體之量 中和用25%銨水 聚合溶劑 甲醇 乙烯基系單體 甲基丙烯酸甲酯 甲基丙烯酸異丁酯 甲基丙烯酸三甲氧基矽烷基丙酯 交聯用鹼性觸媒 25%銨水 交聯樹脂微粒子之物性 數平均粒徑ώ(μιη) 體積平均粒徑(Ιν(μιη) dv/dn 設定交聯點當量(meq/g) 添加量 -73- 201026766 【卜« 合成例 Bb-17 MM-3 | 6.67 〇 (N | 0.50 1 197.8 | [377.0 1 〇 〇 | 32.9 1 | 0.66 1 1 0.68 1 | 1.03 | 丨 1.18 1 Bb-16 MM-7 | 6.67 〇 rj | 0.50 1 | 122.4 | [452.4 | 〇 〇 | 32.9 | | 0.42 1 0.60 1 1-43 00 Bb-15 MM-4 | 6.67 〇 CS 0.27 | mi 1 | 464.0 | 1 〇 | 32.9 1 | 1.20 1 ία I l.oo 1 1.18 寸 Bb-14 | | MM-4 | 6.67 〇 (N | 0.27 1 1 m-ι 1 | 464.0 | 1 CM | 32.9 1 | 1.33 1 丨 1.34 | Ο 1 2.96 〇 Bb-13 | | MM-4 | 6.67 〇 oi i 0.26 | 1 m-ι 1 | 464.0 | CN | 32.9 η 1—Η 1.00 0.24 交聯樹脂微粒子 原料之組成(質量份） 高分子單體之分散液 種類 分散液 高分子單體之量 中和用25%銨水 聚合溶劑 甲醇 乙烯基系單體 甲基丙烯酸甲酯 甲基丙烯酸異丁酯 甲基丙烯酸三甲氧基矽烷基丙酯 交聯用鹼性觸媒 25%銨水 交聯樹脂微粒子之物性 數平均粒徑(Ιιι(μιη) 體積平均粒徑(Μμιη) dv/dn 設定交聯點當量(meq/g) 添加量 201026766 [表8] 合成例 45 46 47 48 交聯樹脂微粒子 Bb-18 Bb-19 Bb-20 Bb-21 原料之組成(質量份） 高分子單體之分散液 種類 MM-7 MM-5 MM-7 MM-7 添加量 分散液 6.67 6.67 6.67 6.67 高分子單體之量 2.0 2.0 2.0 2.0 中和用25%錢水 0.50 0.51 0.50 0.50 聚合溶劑 水 197.8 197.8 81.8 52.8 甲醇 377.0 377.0 493.0 522.0 乙烯基系單體 甲基丙烯酸甲酯 40 40 40 40 甲基丙烯酸異丁酯 50 50 50 50 甲基丙烯酸三甲氧基矽烷丙酯 10 10 10 10 交聯用鹼性觸媒 25%銨水 32.95 32.9 32.9 32.9 交聯樹脂微粒子之物性 數平均粒徑d_m) 0.35 0.54 0.912 1.509 體積平均粒徑加㈣ 0.37 0.57 1.217 1.872 dv/dn 1.06 1.07 1.33 1.24 設定交聯點當量(meq/g) 1.18 1.18 1.18 1.18 5 . 苯乙烯系樹脂組成物之製造及評估 使用 Dongbu Hannong Chemicals製苯乙嫌系樹脂「 SOLARENEGPPSG-116HV」（商品名），製造苯乙烯系 樹脂組成物，且進行評估。而且，該苯乙烯系樹脂係由苯 乙烯單體所成的聚苯乙烯，以JIS K7015爲基準，使用波 長5 8 9nm之光、在25t下所測定的折射率爲1.59。 -75- 201026766 實施例ι(苯乙烯系樹脂組成物及成形體） 在苯乙烯系樹脂 5 8.8 g中添加以合成例1 3所製造的 交聯樹脂微粒子（Ba-1 ) 1.2g予以混合後，使用東洋精機 製作所社製混練機「LABO PLASTOMILL」（商品名）， 在200°C下進行熔融混練處理9分鐘（回轉速度50rpm ) 。然後，馬上取出，予以壓押延伸後進行切斷，製造粒料 狀苯乙烯系樹脂組成物。交聯樹脂微粒子（Ba-Ι )之含有 φ 量爲2質量％。 使前述苯乙烯系樹脂組成物體之粒料使用具備模具（ 尺寸：縱 120mm、橫 120mm、厚度 1.5mm)之壓縮成 型機「SFA-37」（型式名、神藤金屬工業所社製），在溫 度220°C、壓力5MPa之條件下進行壓縮成形，製造平板 狀成形體。使用微測定器測定成形體之板厚時，確認在 1.50mm土0,05mm 之範圍。 有關目u述成形體’測定其全光線透過率（％)、光擴 〇 散率（％ )及黃色度（Yellow Index(Yl))。結果如表1〇 所示。 實施例2〜1 3 (苯乙烯系樹脂組成物及成形體） 除使用以合成例1 4〜2 5所製造的交聯樹脂微粒子（ Ba-2 )〜（Ba-13 )取代交聯樹脂微粒子（Ba-1 )外，進 行與實施1相同的操作，各製造粒料狀苯乙烯系樹脂組成 物。 -76- 201026766 然後’使用前述苯乙烯系樹脂組成物之粒料’進行與 實施例1相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％ )及黃色度（Yellow Index(YI))。結果如表10 所示。 Ο »施例14(苯乙烯系樹脂組成物及成形體） 除在苯乙烯系樹脂 58.2g中添加以合成例19所製造 的交聯樹脂微粒子（Ba-7) 1.8g外，進行與實施1相同的 _作’各製造粒料狀苯乙烯系樹脂組成物。交聯樹脂微粒 子（Ba-7)之含有量爲3質量％。 使用前述苯乙稀系樹脂組成物之粒料，進行與實施例 1相同的操作，製造板厚爲1 ·5〇ιηπι±0.05mm之範圍的平板 狀成形體。 ® 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％ )及黃色度（Yellow Index(YI))。結果如表1 〇 所示。 實施例1 5及1 6 (苯乙烯系樹脂組成物及成形體） 除各使用以合成例21及24所製造的交聯樹脂微粒子 (Ba-9 )及（Ba-12 )取代交聯樹脂微粒子（Ba_7 )外， 進行與實施14相同的操作，各製造粒料狀苯乙烯系樹脂 組成物。 -77- 201026766 然後’使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例14相同的操作，製造板厚爲1.5 0mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％)、光擴 散率（％)及黃色度（YeU〇w Index(YI))。結果如表1〇 所示。 tfc較例1〜2(苯乙烯系樹脂組成物及成形體） _ 除各使用以合成例26及27所製造的交聯樹脂微粒子 (Ba-14)及（Ba_15)取代交聯樹脂微粒子（β^)外， 進行與實施1相同的操作，各製造粒料狀苯乙烯系樹脂組 成物。 然後’使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例1相同的操作，製造板厚爲1 5〇mm±〇 〇5ιηηι之範 圍的平板狀成形體。 有關前述成形體’測定其全光線透過率（％)、光擴 〇 散率（/。）及黃色度（Ye丨丨〇w Index(YI))。結果如表1〇 所示。 比較例3 (苯乙烯系樹脂組成物及成形體） 除使用Ganz Chemical Co·製交聯聚甲基丙烯酸甲酯 微粒子「GM-0806S」（商品名）（以下稱爲「交聯樹脂 微粒子（Bc-1)」）以取代交聯樹脂微粒子（β^)外， 進行與實施1相同的操 <乍，各製造粒料狀苯乙烯系樹脂組 -78- 201026766 成物。 然後’使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例1相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％)及黃色度（Yellow Index(YI))。結果如表10 所示。而且，測定成形體之光擴散率時，光擴散性過低， 〇 在射光面上之平行透過光的強度變高。因此，變得超過檢 測器之感度，無法測定光擴散率。 使前述交聯樹脂微粒子（Be-1)以日本電子社製電場 放射掃描型電子顯微鏡（FE-SEM) 「JSM-6330F」（型式 名）攝影。其照片如第7圖所示。其次，數平均粒徑（dn )、體積平均粒徑（dv)、體積平均粒徑（dv)與數平均 粒徑（dn )之比例（dWdn )，如表9所示。 Φ 比較例4 (苯乙烯系樹脂組成物及成形體） 除在苯乙烯系樹脂 58.2g中添加交聯樹脂微粒子（ Be-1) 1.8g外，進行與實施1相同的操作，製造粒料狀苯 乙烯系樹脂組成物。交聯樹脂微粒子（Be-Ι)之含有量爲 3質量％。 使用前述苯乙烯系樹脂組成物之粒料，進行與實施例 1相同的操作，製造板厚爲1.50mm±0.05mm之範圍的平板 狀成形體。 有關前述成形體，測定其全光線透過率（％)、光擴 -79- 201026766 散率（％ )及黃色度（YeUow hdexiΥΙ))。結果如表10 所示。 比較例5 (苯乙烯系樹脂組成物及成形體） 除在苯乙烯系樹脂 57_6g中添加交聯樹脂微粒子（-72- 201026766 [9嗽 Synthesis Example Os Bb-12 MM-4 6.67 〇CN 0.26 I mi 1 464.0 | | 32.9 1 丨 1.46 | 1.46 I l.oo | | 0.59 1 00 Bb-11 1 MM-6 6.67 I 〇<N 0.24 1 | 134.3 1 | 440.8 | 〇〇| 32.95 | 0.68 | 0.75 ro布ro Bb-10 MM-5 6.67 I 〇0.51 1 | 134.0 J | 440.8 | 〇〇| 32.9 | 0.80 | 0.96 1.20 Οο *—Η ΓΟ Bb-9 MM-4 | I 6.67 I ο <Ν 0.26 1 | 198.1 | | 377.0 1 〇〇| 32.9 | 0.79 | 0.80 丨1.01 1 1.18 iT) m Bb-8 MM-4 6.67 Ο Oi 0.26 1 169.1 | 406.0 | 〇〇 | 32.9 | 0.93 | 0.93 1.00 οο 荔Bb-7 MM-4 6.67 ο <Ν 0.26 1 134.3 | | 440.8 | 〇〇| 32.9 1 1 I” 〇〇I l.oo丨1.18 m Bb-6 MM-3 | 6.67 Ο CN 0.50 1 134.0 | | 440.8 | 〇 inch〇 | 32.9 ra 1 1.13 〇1 1.18 Composition of crosslinked resin fine particles (parts by mass) Type of dispersion of polymer monomer The amount of the polymer monomer in the dispersion is neutralized with 25% ammonium water polymerization solvent, methanol vinyl monomer, methyl methacrylate, isobutyl methacrylate Crosslinking of trimethoxydecyl propyl acrylate with a basic catalyst 25% ammonium water crosslinked resin microparticles physical number average particle diameter ώ(μιη) volume average particle diameter (Ιν(μιη) dv/dn set crosslinking point Equivalent (meq/g) Addition amount -73- 201026766 [Bu « Synthesis example Bb-17 MM-3 | 6.67 〇 (N | 0.50 1 197.8 | [377.0 1 〇〇 | 32.9 1 | 0.66 1 1 0.68 1 | 1.03 |丨1.18 1 Bb-16 MM-7 | 6.67 〇rj | 0.50 1 | 122.4 | [452.4 | 〇〇| 32.9 | | 0.42 1 0.60 1 1-43 00 Bb-15 MM-4 | 6.67 〇CS 0.27 | mi 1 464.0 | 1 〇| 32.9 1 | 1.20 1 ία I l.oo 1 1.18 inch Bb-14 | | MM-4 | 6.67 〇(N | 0.27 1 1 m-ι 1 | 464.0 | 1 CM | 32.9 1 | 1.33 1 丨 1.34 | Ο 1 2.96 〇Bb-13 | | MM-4 | 6.67 〇oi i 0.26 | 1 m-ι 1 | 464.0 | CN | 32.9 η 1—Η 1.00 0.24 Composition of crosslinked resin microparticles (mass parts) Polymer monomer dispersion type Dispersion polymer monomer amount neutralized with 25% ammonium water polymerization solvent methanol vinyl monomer methyl methacrylate isobutyl methacrylate methyl Crosslinking of trimethoxydecyl propyl acrylate with a basic catalyst 25% ammonium water crosslinked resin microparticles physical number average particle size (Ιιι(μιη) volume average particle size (Μμιη) dv/dn set crosslink point equivalent (meq/g) Addition amount 201026766 [Table 8] Synthesis Example 45 46 47 48 Crosslinked resin fine particles Bb-18 Bb-19 Bb-20 Bb-21 Composition of raw materials (parts by mass) Dispersion type of polymer monomer MM -7 MM-5 MM-7 MM-7 Addition Dispersion 6.67 6.67 6.67 6.67 Amount of Polymer Monomer 2.0 2.0 2.0 2.0 Neutralization with 25% Water 0.50 0.51 0.50 0.50 Polymer Solvent Water 197.8 197.8 81.8 52.8 Methanol 377.0 377.0 493.0 522.0 Vinyl monomer methyl methacrylate 40 40 40 40 Isobutyl methacrylate 50 50 50 50 Trimethoxy decyl methacrylate 10 10 10 10 Crosslinking alkaline catalyst 25% ammonium water 32.95 32.9 32.9 32.9 Physical properties of crosslinked resin microparticles Average particle size d_m) 0.35 0.54 0.912 1.509 Volume average particle size plus (4) 0.37 0.57 1.217 1.872 dv/dn 1.06 1.07 1.33 1.24 Set crosslink point equivalent (meq/g) 1.18 1.18 1.18 1.18 5 . Manufacture and evaluation of a styrene-based resin composition A styrene resin composition (SOLARENEGPPSG-116HV) (trade name) manufactured by Dongbu Hannong Chemicals was used to prepare a styrene-based resin composition. Further, the styrene resin is a polystyrene obtained from a styrene monomer, and has a refractive index of 1.59 measured at 25 t using light having a wavelength of 589 nm based on JIS K7015. -75-201026766 Example 1 (Styrene-based resin composition and molded article) After adding 1.2 g of crosslinked resin fine particles (Ba-1) produced in Synthesis Example 13 to 8.8 g of styrene-based resin, the mixture was mixed. The "LABO PLASTOMILL" (trade name) manufactured by Toyo Seiki Co., Ltd. was used, and the melt kneading treatment was carried out at 200 ° C for 9 minutes (rotation speed 50 rpm). Then, it was taken out immediately, and it was pressed and stretched, and then cut to produce a pelletized styrene resin composition. The content of φ of the crosslinked resin fine particles (Ba-Ι) was 2% by mass. In the pellets of the styrene-based resin composition, a compression molding machine "SFA-37" (type name, manufactured by Shinto Metal Industry Co., Ltd.) having a mold (size: 120 mm in length, 120 mm in width, and 1.5 mm in thickness) was used. Compression molding was carried out under the conditions of a pressure of 5 MPa at 220 ° C to produce a flat shaped body. When the thickness of the molded body was measured using a micrometer, it was confirmed to be in the range of 0,05 mm of 1.50 mm of soil. The molded article was measured for its total light transmittance (%), optical diffusivity (%), and yellowness (Yellow Index (Yl)). The results are shown in Table 1〇. Example 2 to 1 3 (Styrene-based resin composition and molded body) The crosslinked resin fine particles were replaced by the crosslinked resin fine particles (Ba-2) to (Ba-13) produced in Synthesis Examples 14 to 25 In the same manner as in Example 1, except for (Ba-1), a pellet-like styrene resin composition was produced. -76-201026766 Then, the same operation as in Example 1 was carried out by using the pellets of the styrene resin composition described above, and a flat molded body having a thickness of 1.50 mm ± 0.05 mm was produced. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 10. Ο»Example 14 (Styrene-based resin composition and molded body) Except that 1.8 g of the crosslinked resin fine particles (Ba-7) produced in Synthesis Example 19 was added to 58.2 g of the styrene-based resin, The same granules were used to produce a pelletized styrene resin composition. The content of the crosslinked resin fine particles (Ba-7) was 3% by mass. Using the pellets of the styrene-based resin composition described above, the same operation as in Example 1 was carried out to produce a flat shaped body having a thickness of 1 · 5 〇 η η ± 0.05 mm. ® For the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 1 。. Example 1 5 and 16 (styrene resin composition and molded body) The crosslinked resin fine particles (Ba-9) and (Ba-12) which were produced by using Synthesis Examples 21 and 24 were used in place of the crosslinked resin fine particles. In the same manner as in Example 14, except that (Ba_7), a pellet-like styrene resin composition was produced. -77-201026766 Then, the same operation as in Example 14 was carried out using the pellets of the styrene resin composition described above, and a flat plate-shaped molded body having a thickness of 1.50 mm ± 0.05 mm was produced. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (YeU〇w Index (YI)) were measured. The results are shown in Table 1〇. Tfc Comparative Examples 1 to 2 (styrene-based resin composition and molded body) _ In addition to cross-linking resin fine particles (Ba-14) and (Ba_15) produced by Synthesis Examples 26 and 27, crosslinked resin fine particles (β) were used. In the same manner as in the above, each of the pelletized styrene resin compositions was produced. Then, using the pellets of the styrene resin composition described above, the same operation as in Example 1 was carried out to produce a flat shaped body having a thickness of 15 〇 mm ± 〇 〇 5 ηηηι. The whole molded body was measured for its total light transmittance (%), optical diffusivity (/.), and yellowness (Ye丨丨〇w Index (YI)). The results are shown in Table 1〇. Comparative Example 3 (Styrene-based resin composition and molded body) In addition to the use of the crosslinked polymethyl methacrylate fine particles "GM-0806S" (trade name) manufactured by Ganz Chemical Co. (hereinafter referred to as "crosslinked resin fine particles (Bc) -1)") In place of the crosslinked resin fine particles (β^), the same operation as in the first embodiment was carried out, and each of the pelletized styrene resin groups -78-201026766 was produced. Then, using the pellets of the styrene resin composition described above, the same operation as in Example 1 was carried out to produce a flat molded body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 10. Further, when the light diffusivity of the molded body is measured, the light diffusibility is too low, and the intensity of the parallel transmitted light of the 〇 on the light-emitting surface becomes high. Therefore, the sensitivity of the detector is exceeded, and the light diffusivity cannot be measured. The crosslinked resin fine particles (Be-1) were imaged by an electric field emission scanning electron microscope (FE-SEM) "JSM-6330F" (type name) manufactured by JEOL Ltd. The photo is shown in Figure 7. Next, the ratio of the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter (dn) (dWdn) is shown in Table 9. Φ Comparative Example 4 (Styrene-based resin composition and molded article) The same operation as in Example 1 was carried out except that 1.8 g of crosslinked resin fine particles (Be-1) was added to 58.2 g of a styrene resin to produce pellets. A styrene resin composition. The content of the crosslinked resin fine particles (Be-Ι) was 3% by mass. Using the pellets of the styrene resin composition described above, the same operation as in Example 1 was carried out to produce a flat shaped body having a thickness of 1.50 mm ± 0.05 mm. Regarding the above-mentioned molded body, the total light transmittance (%), the optical expansion -79 - 201026766 diffusivity (%), and the yellowness (YeUow hdexiΥΙ) were measured. The results are shown in Table 10. Comparative Example 5 (Styrene-based resin composition and molded body) In addition to the cross-linking resin fine particles added to the styrene-based resin 57_6 g (

Bc-1) 2.4g外，進行與實施1相同的操作，製造粒料狀苯 乙烯系樹脂組成物。交聯樹脂微粒子（Be-1 )之含有量爲 4質量％。 ⑩ 使用前述苯乙烯系樹脂組成物之粒料，進行與實施例 1相同的操作，製造板厚爲1.50mm±0.05mm之範圍的平板 狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％ )及黃色度（Yellow Index(YI))。結果如表 10 所示。 比較例6 (苯乙烯系樹脂組成物及成形體） 〇 除使用積水化成品工業社製交聯聚甲基丙烯酸甲酯微 粒子「MBX-5」（商品名）（以下稱爲「交聯樹脂微粒子 C Bc-2 )」）取代交聯樹脂微粒子（Ba-〗）外，進行與實 施1相同的操作，製造粒料狀苯乙烯系樹脂組成物。 ’使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例1相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％)、光擴 -80 - 201026766 散率（％ )及黃色度（Yellow Index(YI))。結果如表j 〇 所示。 前述交聯樹脂微粒子（Bc-2)之數平均粒徑（dn)、 體積平均粒徑（dv )、體積平均粒徑（dv )與數平均粒徑 (dn)之比例（dv/dn)，如表9所示。 比較例7 Φ 除使用 Momentive Performance Materials 製砂樹脂微 粒子「Tospearl 1 1 10」（商品名）（以下稱爲「交聯樹脂 微粒子（Bc-3 )」）取代交聯樹脂微粒子（Ba-丨）外，進 行與實施1相同的操作，製造粒料狀苯乙烯系樹脂組成物 〇 然後，使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例1相同的操作，製造板厚爲1.50mm±0_05mm之範 圍的平板狀成形體。 Φ 有關前述成形體’測定其全光線透過率（％)、光擴 散率（％)及黃色度（Yellow Index(YI))。結果如表10 所示。而且，於測定成形體之光擴散率時，光擴散性過低 ，在射光面上之平行透過光的強度變得過高。因此，變得 超過檢測器之感度，無法測定光擴散率。 前述交聯樹脂微粒子（Bc-3)之數平均粒徑（dn)、 體積平均粒徑（dv)、體積平均粒徑（dv)與數平均粒徑 (dn )之比例（dv/dn )，如表9所示。 -81 - 201026766 比較例8 除沒有使用交聯樹脂微粒子下，使用僅由苯乙烯系樹 脂所成的粒料，進行與實施例1相同的操作，製造板厚爲 1.50mm±0.05mm之範圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％)、光擴 散率（％)及黃色度（Yellow Index(YI))。結果如表1〇 所示。 [表9] 交聯樹脂微粒子 Bc-1 Bc-2 Bc-3 數平均粒徑如㈣ 6.2 3.53 9.58 體積平均粒徑ίΜμιη) 7.25 4.07 9.6 dv/dn 1.17 1.15 1 φ -82- 201026766Bc-1) The same operation as in the first embodiment was carried out except for 2.4 g, and a pellet-shaped styrene-based resin composition was produced. The content of the crosslinked resin fine particles (Be-1) was 4% by mass. In the same manner as in Example 1, the pellets having a thickness of 1.50 mm ± 0.05 mm were produced by using the pellets of the styrene resin composition described above. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 10. Comparative Example 6 (Styrene-based resin composition and molded article) The cross-linked polymethyl methacrylate microparticle "MBX-5" (trade name) (hereinafter referred to as "crosslinked resin fine particles") was used. C Bc-2 )") A pellet-like styrene resin composition was produced in the same manner as in Example 1 except that the crosslinked resin fine particles (Ba-) were replaced. Using the pellets of the styrene resin composition described above, the same operation as in Example 1 was carried out to produce a flat plate-shaped molded body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the optical spread -80 - 201026766, and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table j 。. The ratio of the number average particle diameter (dn), the volume average particle diameter (dv), the volume average particle diameter (dv), and the number average particle diameter (dn) of the crosslinked resin fine particles (Bc-2) (dv/dn), As shown in Table 9. Comparative Example 7 Φ In addition to the use of Momentive Performance Materials sand resin fine particles "Tospearl 1 1 10" (trade name) (hereinafter referred to as "crosslinked resin fine particles (Bc-3)") in place of crosslinked resin fine particles (Ba-丨) The same operation as in the first embodiment was carried out to produce a pellet-like styrene resin composition. Then, the pellets of the styrene resin composition were used, and the same operation as in Example 1 was carried out to produce a sheet thickness of 1.50 mm ± A flat shaped body in the range of 0_05 mm. Φ The total optical transmittance (%), optical diffusivity (%), and yellowness (Yellow Index (YI)) of the molded body were measured. The results are shown in Table 10. Further, when the light diffusivity of the molded body is measured, the light diffusibility is too low, and the intensity of the parallel transmitted light on the light emitting surface is excessively high. Therefore, the sensitivity of the detector is exceeded, and the light diffusivity cannot be measured. a ratio (dv/dn) of the number average particle diameter (dn), volume average particle diameter (dv), volume average particle diameter (dv), and number average particle diameter (dn) of the crosslinked resin fine particles (Bc-3), As shown in Table 9. -81 - 201026766 Comparative Example 8 The same operation as in Example 1 was carried out except that the pellets composed only of the styrene resin were used without using the crosslinked resin fine particles, and the thickness of the sheet was 1.50 mm ± 0.05 mm. Flat shaped body. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 1〇. [Table 9] Crosslinked resin fine particles Bc-1 Bc-2 Bc-3 Number average particle diameter as (4) 6.2 3.53 9.58 Volume average particle diameter ίΜμιη) 7.25 4.07 9.6 dv/dn 1.17 1.15 1 φ -82- 201026766

[表 ι〇] 苯乙烯系樹脂組成物 / 或形體之 苯乙烯 系樹脂 (g) 交聯樹脂微粒子 全光線 透過率 (%) 光擴散 率(％) -- 黃色度 (YI) _ 配合量(g)(括號內爲 組成物中之含有率） 實施例1 58.8 Ba-1 1.2(2 質量％) 66.1 78.0 __J7.8 實施例2 58.8 Ba-2 1.2(2 Ms%) 66.5 78.5 __J8.3 實施例3 58.8 Ba-3 1.2(2 質量％) 65.2 81.0 16.7 實施例4 58.8 Ba-4 1.2(2 質量％) 65.1 80.5 --- 16.2 實施例5 58.8 Ba-5 1.2(2 質量％) 63.9 83.7 '·——. __1λ7 實施例6 58.8 Ba-6 1.2(2 質量％) 63.8 84.0 __i5.5 實施例7 58.8 Ba-7 1.2(2 質量％) 62.5 85.7 14.0 實施例8 58.8 Ba-8 1.2(2 質量％) 58.3 92.7 12.8 實施例9 58.8 Ba-9 1.2(2 質量％) 58.7 91.8 ' 10.2 實施例10 58.8 Ba-10 1.2(2 質量％) 58.7 91.9 10.0 實施例11 58.8 Ba-11 1.2(2 質量％) 58.5 92.1 9.6 實施例12 58.8 Ba-12 1.2(2 質量％) 60.0 91.2 L l〇 1 實施例13 58.8 Ba-13 1.2(2 質量％) 65.9 79.1 19.0 實施例14 58.2 Ba-7 i.B(3 ms%) 59.1 92.2 11.4 實施例15 58.2 Ba-9 1.8(3 質量％) 55.5 93.2 '—----- 9.2 實施例16 58.2 Ba-12 1.8(3 質量％) 56.9 93.5 --^ 8.5 比較例1 58.8 Ba-14 1-2(2 質量0/〇) 76.3 58.2 -- _383 比較例2 58.8 Ba-15 1·2(2 質量 ％) 70.4 69.9 20 7 比較例3 58.8 Bc-1 1.2(2 質量 ％) 84.0 無法測定 - 18〇 比較例4 58.2 Bc-1 1.8(3 Mm%) 76.0 62.0 19.6 比較例5 57.6 Bc-1 2.4(4 質量 ％) 67.6 73.0 —-17.3 比較例6 58.8 Bc-2 1.2(2 質量％) 80.9 53.2 21.6 比較例7 58.8 Bc-3 1.2(2 質量％) 72.6 無法測定 --'：：-- __Ζ5 比較例8 60 - 〇(〇質量％) 90.2 無法測定 3.3 ------ 將含有成本與耐候性優異的（甲基）丙烯酸酯系樹脂 所成的交聯樹脂微粒子作爲光擴散劑之組成物使用於形成 -83- 201026766 液晶面板用之光擴散板時，其含有率爲2〜3質量％ ’一般 而言以全光線透過率爲50〜70%、光擴散率爲75%以上及 透過光之黃色度（YI値）爲20以下較佳。 由表10之結果可知，實施例1〜16係藉由使使用的 苯乙烯系樹脂組成物具有本發明之構成，所得的成形體皆 具有55%〜70%範圍內的全光線透過率，與大於78%之高 光擴散率，以及19以下之低的透過光之黃色度（YI) ° 此等爲適合液晶面板等所使用的光擴散板等之性能。 @ 對此而言，比較例1係使用含有無法滿足設定交聯點 當量爲O.lOmeq/g之要件的交聯樹脂微粒子（Ba-14)之 苯乙烯系樹脂組成物之例。於比較例1中，所得的成形體 ，光擴散劑之含有率爲2質量％，光.擴散率爲58.2%之低 値，透過光之黃度（YI)爲38.3之高値，不爲企求。 此外，比較例2〜7係體積平均粒徑（dv )大於3 μιη ，使用含有無法滿足添要件（2 )的交聯樹脂微粒子（3^ B ) 、 （ Bc-1 ) 、 （ Bc-2 )或（Bc-3 )之苯乙烯系樹脂組 ❹ 成物的例。比較例8係不含交聯樹脂粒子之組成物的例。 比較例2,4,5及6中，光擴散劑之含有率爲2〜3質量％， 光擴散率爲73 %以下之低値，不夠充分。而且，比較例 3，7及8 ’由於平行透過光之強度過高，無法測定光擴散 率 。 實施例1 7 (苯乙烯系樹脂組成物及成形體） 在苯乙烯系樹脂59.4g中添加以合成例28所製造的 -84- 201026766 交聯樹脂微粒子（B b -1 ) 0 · 6 g外，進行與實施1相同的操 作，各製造粒料狀苯乙烯系樹脂組成物。交聯樹脂微粒子 (Bb-Ι )之含有量爲1質量％。 然後，使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例1相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 ❹ 散率（％ )及黃色度（Yellow Index(YI))。結果如表】】 所示。 實施例1 8 (苯乙烯系樹脂組成物及成形體） 在苯乙烯系樹脂58.8g中添加交聯樹脂微粒子（Bb_i )1.2g外’進行與實施1相同的操作，各製造粒料狀苯乙 烯系樹脂組成物。交聯樹脂微粒子（Bb-Ι)之含有量爲2 質量％。 Φ 使用前述苯乙烯系樹脂組成物之粒料，進行與實施例 1相冋的操作，製造板厚爲1.50mm±0.05mm之範圍的平板 狀成形體。 有關前述成形體，測定其全光線透過率（％)、光擴 散率（％ )及黃色度（Yellow Index(YI))。結果如表1 j 所示。 實施例19(苯乙烯系樹脂組成物及成形體） 在苯乙烯系樹脂58.2g中添加交聯樹脂微粒子（bh -85- 201026766 )1.8g外，進行與實施〗相同的操作，各製造粒料狀苯乙 烯系樹脂組成物。交聯樹脂微粒子（Bb-Ι )之含有量爲3 質量％。 使用前述苯乙烯系樹脂組成物之粒料，進行與實施例 1相同的操作，製造板厚爲丨·50111111^0·05111111之範圍的平板 狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％ )及黃色度（Yellow Index(YI))。結果如表 1 1 @ 所示。 實施例20〜22 (苯乙烯系樹脂組成物及成形體） 除使用以合成例29〜31所製造的交聯樹脂微粒子（[Table 〇] Styrene resin composition / or styrene resin (g) Crosslinked resin fine particles total light transmittance (%) Light diffusivity (%) -- Yellowness (YI) _ Complex amount ( g) (content in the composition in parentheses) Example 1 58.8 Ba-1 1.2 (2% by mass) 66.1 78.0 __J7.8 Example 2 58.8 Ba-2 1.2 (2 Ms%) 66.5 78.5 __J8.3 Implementation Example 3 58.8 Ba-3 1.2 (2% by mass) 65.2 81.0 16.7 Example 4 58.8 Ba-4 1.2 (2% by mass) 65.1 80.5 --- 16.2 Example 5 58.8 Ba-5 1.2 (2% by mass) 63.9 83.7 ' ·——. __1λ7 Example 6 58.8 Ba-6 1.2 (2% by mass) 63.8 84.0 __i5.5 Example 7 58.8 Ba-7 1.2 (2% by mass) 62.5 85.7 14.0 Example 8 58.8 Ba-8 1.2 (2 mass %) 58.3 92.7 12.8 Example 9 58.8 Ba-9 1.2 (2% by mass) 58.7 91.8 ' 10.2 Example 10 58.8 Ba-10 1.2 (2% by mass) 58.7 91.9 10.0 Example 11 58.8 Ba-11 1.2 (2% by mass 58.5 92.1 9.6 Example 12 58.8 Ba-12 1.2 (2% by mass) 60.0 91.2 L l〇1 Example 13 58.8 Ba-13 1.2 (2% by mass) 65.9 79.1 19.0 Example 14 58.2 Ba-7 iB (3 ms) %) 59.1 92.2 1 1.4 Example 15 58.2 Ba-9 1.8 (3 mass%) 55.5 93.2 '------ 9.2 Example 16 58.2 Ba-12 1.8 (3 mass%) 56.9 93.5 --^ 8.5 Comparative Example 1 58.8 Ba-14 1-2 (2 mass 0 / 〇) 76.3 58.2 - _383 Comparative Example 2 58.8 Ba-15 1·2 (2% by mass) 70.4 69.9 20 7 Comparative Example 3 58.8 Bc-1 1.2 (2% by mass) 84.0 Unable to measure - 18 〇 Comparative Example 4 58.2 Bc-1 1.8 (3 Mm%) 76.0 62.0 19.6 Comparative Example 5 57.6 Bc-1 2.4 (4% by mass) 67.6 73.0 -17.3 Comparative Example 6 58.8 Bc-2 1.2 (2% by mass) 80.9 53.2 21.6 Comparative Example 7 58.8 Bc-3 1.2 (2% by mass) 72.6 Unable to measure --'::-- __Ζ5 Comparative Example 8 60 - 〇 (〇% by mass) 90.2 Unable to measure 3.3 ------ Will contain The crosslinked resin fine particles formed of the (meth) acrylate-based resin having excellent cost and weather resistance are used as a composition of the light diffusing agent to form a light diffusing plate for a liquid crystal panel of -83 to 201026766, and the content thereof is 2 to 2. 3 mass% 'Generally, it is preferable that the total light transmittance is 50 to 70%, the light diffusivity is 75% or more, and the yellowness (YI値) of the transmitted light is 20 or less. As is clear from the results of Table 10, in Examples 1 to 16, the styrene resin composition to be used has the constitution of the present invention, and the obtained molded articles all have a total light transmittance in the range of 55% to 70%, and The high light diffusivity of more than 78% and the yellowness (YI) of the transmitted light of 19 or less are suitable for the performance of a light diffusing plate or the like used for a liquid crystal panel or the like. In this case, Comparative Example 1 is an example of a styrene resin composition containing crosslinked resin fine particles (Ba-14) which is incapable of satisfying the requirement of setting the crosslinking point equivalent to O.10 meq/g. In Comparative Example 1, the content of the obtained molded article, the light diffusing agent was 2% by mass, the light diffusing ratio was 58.2%, and the yellowness (YI) of the transmitted light was 38.3, which was not desirable. Further, Comparative Examples 2 to 7 have a volume average particle diameter (dv) of more than 3 μm, and contain crosslinked resin fine particles (3^B), (Bc-1), (Bc-2) which cannot satisfy the additive (2). Or an example of the styrene resin group composition of (Bc-3). Comparative Example 8 is an example of a composition containing no crosslinked resin particles. In Comparative Examples 2, 4, 5 and 6, the content of the light diffusing agent was 2 to 3 mass%, and the light diffusing rate was 73% or less, which was insufficient. Further, in Comparative Examples 3, 7 and 8', since the intensity of the parallel transmitted light was too high, the light diffusivity could not be measured. Example 1 7 (Styrene-based resin composition and molded article) -49-201026766 cross-linked resin fine particles (B b -1 ) 0 · 6 g other than the styrene-based resin was added to 59.4 g of the styrene resin. The same operation as in the first embodiment was carried out, and each of the pelletized styrene resin compositions was produced. The content of the crosslinked resin fine particles (Bb-Ι) was 1% by mass. Then, using the pellets of the styrene resin composition described above, the same operation as in Example 1 was carried out to produce a flat molded body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the optical diffusivity (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in the table]. Example 1 8 (Styrene-based resin composition and molded article) The same procedure as in Example 1 was carried out except that 1.2 g of crosslinked resin fine particles (Bb_i ) was added to 58.8 g of a styrene-based resin, and pelletized styrene was produced. A resin composition. The content of the crosslinked resin fine particles (Bb-Ι) was 2% by mass. Φ The pellets having a thickness of 1.50 mm ± 0.05 mm were produced by using the pellets of the styrene resin composition described above in the same manner as in Example 1. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 1 j. Example 19 (Styrene-based resin composition and molded article) The same operation as in the embodiment was carried out except that 1.8 g of crosslinked resin fine particles (bh - 85 - 201026766 ) was added to 58.2 g of a styrene resin, and pellets were produced. A styrene-based resin composition. The content of the crosslinked resin fine particles (Bb-Ι) was 3% by mass. Using the pellets of the styrene resin composition, the same operation as in Example 1 was carried out to produce a flat molded body having a thickness of 丨·50111111^0·05111111. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 1 1 @. Examples 20 to 22 (Styrene-based resin composition and molded body) Except using the crosslinked resin fine particles produced in Synthesis Examples 29 to 31 (

Bb-2)〜（Bb-4)取代交聯樹脂微粒子（Bb-Ι)外，進行 與實施18相同的操作，各製造粒料狀苯乙烯系樹脂組成 物。 然後，使用前述苯乙烯系樹脂組成物之粒料，進行與 © 實施例18相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％)及黃色度（Yellow Index(YI))。結果如表11 所示。 比較例9 (苯乙烯系樹脂組成物及成形體） 除使用以合成例32所製造的交聯樹脂微粒子（Bb-5 -86- 201026766 )取代交聯樹脂微粒子（Bb-1 )外，進行與實施1 8相同 的操作’各製造粒料狀苯乙烯系樹脂組成物。 然後’使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例18相同的操作，製造板厚爲15〇111111±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％ )及黃色度（Yellow Index(YI))。結果如表1 1 ❹ 所示。 [表 11 ] 苯乙烯系樹脂細成物 成形體之物性 苯乙烯 系樹脂 (g) 交聯樹脂微粒子 全光線透 過率(％) 光擴散 率(％) 黃色度 (YI) 種類 配合量(g)(括號內爲 組成物中之含有率） 實施例17 59.4 Bb-1 0.6(1 質量 ％) 65.6 80.1 19.8 實施例18 58.8 Bb-1 1.2(2 質量0/〇) 59.6 92.0 9.2 實施例19 58.2 Bb-1 1.8(3 質量％) 57.2 93.4 8.6 實施例20 58.8 Bb-2 1.2(2 質量 ％) 61.1 89.8 11.7 實施例21 58.8 Bb-3 1.2(2 質量0/〇) 63.4 83.4 18.3 實施例22 58.8 Bb-4 1.2(2 質量％) 59.8 91.9 9.5 比較例9 58.8 Bb-5 1.2(2 質量0/〇) 82.7 無法測定 42.1 由表1 1之結果可知，實施例1 7〜2 2係藉由將使用的 苯乙烯系樹脂組成物具有本發明之構成，所得的成形體皆 具有55%〜70%範圍內的全光線透過率，與超過80%之高 光擴散率，以及20%以下之低透過光的黃色度（YI) °此 等具有適合於液晶面板等所使用的光擴散板等之性能。 對此而言，比較例9係含有設定交聯點當量小於 -87- 201026766 0.1 5m eq/g、無法充分地予以交聯、不能滿足要件（b4 ) 的交聯樹脂微粒子（Bb-5 )之苯乙烯系樹脂組成物的例。 由比較例9之苯乙烯系樹脂組成物所得的成形體，平行透 過光之強度過高，無法測定光擴散率，透過光之黃色度爲 30以上（42.1 )之高値，不爲企求。 實施例23〜32 (苯乙烯系樹脂組成物及成形體） 除使用以合成例3 3〜42所製造的交聯樹脂微粒子（ ◎Bb-2) to (Bb-4) were subjected to the same operation as in Example 18 except that the crosslinked resin fine particles (Bb-fluorene) were replaced, and each of the pelletized styrene resin compositions was produced. Then, using the pellets of the styrene resin composition described above, the same operation as in Example 18 was carried out to produce a flat plate-shaped molded body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 11. Comparative Example 9 (Styrene-based resin composition and molded body) Except that the crosslinked resin fine particles (Bb-1) were replaced with the crosslinked resin fine particles (Bb-5-86-201026766) produced in Synthesis Example 32, The same operation as in '1' was carried out to produce a pellet-like styrene resin composition. Then, using the pellets of the styrene resin composition described above, the same operation as in Example 18 was carried out to produce a flat shaped body having a thickness of 15 〇 111111 ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 1 1 。. [Table 11] Physical properties of styrene resin fine molded article styrene resin (g) Crosslinked resin fine particles total light transmittance (%) Light diffusivity (%) Yellowness (YI) Type compounding amount (g) (The content in the composition in parentheses) Example 17 59.4 Bb-1 0.6 (1% by mass) 65.6 80.1 19.8 Example 18 58.8 Bb-1 1.2 (2 mass 0/〇) 59.6 92.0 9.2 Example 19 58.2 Bb -1 1.8 (3 mass%) 57.2 93.4 8.6 Example 20 58.8 Bb-2 1.2 (2 mass%) 61.1 89.8 11.7 Example 21 58.8 Bb-3 1.2 (2 mass 0/〇) 63.4 83.4 18.3 Example 22 58.8 Bb -4 1.2 (2% by mass) 59.8 91.9 9.5 Comparative Example 9 58.8 Bb-5 1.2 (2 mass 0 / 〇) 82.7 Unable to measure 42.1 From the results of Table 1 1, it is known that Examples 1 7 to 2 2 are used by The styrene resin composition has the constitution of the present invention, and the obtained molded body has a total light transmittance in the range of 55% to 70%, a high light diffusivity exceeding 80%, and a low transmitted light of 20% or less. Yellowness (YI) ° These have properties suitable for a light diffusing plate or the like used for a liquid crystal panel or the like. On the other hand, Comparative Example 9 contains crosslinked resin microparticles (Bb-5) which have a cross-linking point equivalent of less than -87 to 201026766 0.15 m eq/g, which cannot be sufficiently crosslinked and which cannot satisfy the requirement (b4). An example of a styrene resin composition. In the molded article obtained from the styrene resin composition of Comparative Example 9, the intensity of the parallel light transmission was too high, and the light diffusivity could not be measured, and the yellowness of the transmitted light was 30 or more (42.1), which was not desirable. Examples 23 to 32 (Styrene-based resin composition and molded body) In addition to the use of the crosslinked resin fine particles produced in Synthesis Examples 3 to 42 (◎

Bb-6 )〜（Bb-15 )取代交聯樹脂微粒子（Ba-Ι )外，進 行與實施1相同的操作，各製造粒料狀苯乙烯系樹脂組成 物。 然後’使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例18相同的操作，製造板厚爲15〇mm±〇 〇5mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 政率及黃色度（Yell〇w Index(YI))。結果如表12 ® 所示。 胃33 (苯乙烯系樹脂組成物及成形體） 除苯乙烯系樹脂及交聯樹脂微粒子（Bb-7 )之使用量 各爲59.4g及〇 6g外，進行與實施24相同的操作，各製 造粒料狀苯乙烯系樹脂組成物。 然後’使用前述苯乙烯系樹脂組成物之粒料，進行與 施传』1相同的操作，製造板厚爲1.50mm±0.05mm之範 -88- 201026766 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％)、光擴 散率（％)及黃色度（Yellow Index(YI))。結果如表12 所示。 實施例34 (苯乙烯系樹脂組成物及成形體） 除苯乙烯系樹脂及交聯樹脂微粒子（Bb-7)之使用量 Ο 各爲58_2g及1.8g外，進行與實施24相同的操作，各製 造粒料狀苯乙烯系樹脂組成物。 然後，使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例1相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％)及黃色度（Yellow Index(YI))。結果如表12 所示。 實施例3 5 (苯乙烯系樹脂組成物及成形體） 除苯乙烯系樹脂及交聯樹脂微粒子（Bb-7 )之使用量 各爲57.9g及2.1g外，進行與實施24相同的操作，各製 造粒料狀苯乙烯系樹脂組成物。 然後，使用前述苯乙烯系樹脂組成物之粒料’進行與 實施例1相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 -89 - 201026766 散率（％ )及黃色度（Yellow Index(YI))。結果如表12 所示。 實施例36(苯乙烯系樹脂組成物及成形體） 除苯乙烯系樹脂及交聯樹脂微粒子（Bb-7)之丨吏 各爲56.7g及3.3g外，進行與實施24相同的操作，各製 造粒料狀苯乙烯系樹脂組成物。 然後’使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例1相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％)、光擴 散率（％)及黃色度（Yellow Index(YI))。結果如表12 所示。 比較例1 0〜1 5 (苯乙烯系樹脂組成物及成形體） - 除各使用以合成例43〜48所製造的交聯樹脂微粒子 〇 (Bb-16)〜（Bb-21)取代交聯樹脂微粒子（Ba-Ι)外， 進行與實施1相同的操作，各製造粒料狀苯乙烯系樹脂組 成物。 然後，使用前述苯乙烯系樹脂組成物之粒料，進行與 實施例1相同的操作，製造板厚爲1.50mm±0.05mm之範 圍的平板狀成形體。 有關前述成形體，測定其全光線透過率（％ )、光擴 散率（％ )及黃色度（Yell〇w Index(YI))。結果如表12 -90 - 201026766 所示。 而且，比較例12於測定成形體之光擴散率時，光擴 散性過低，在射光面之平行透過光的強度變高。因此’變 得超過檢測器之感度，無法測定光擴散率。 [表 12] ___ 苯乙烯系樹脂組成物 成形體之物性 苯乙烯 系棚旨 (g) 交聯樹脂微粒子 全光線透 過率(％) 光擴散 率(％) 黃色度 (YI) 麵 配合量(g)(括號內爲 組成物中之含有率） 實施例23 58.8 Bb-6 1.2(2 質量 %) 1 60.2 91.0 9.8 實施例24 58.8 Bb-7 1.2(2 質量％) 59.7 92.3 8.3 實施例25 58.8 Bb-8 1·2(2 質量％) 59.5 92.3 9.2 實施例26 58.8 Bb-9 1.2(2 質量％) 60.3 90.7 12.0 實施例27 58.8 Bb-10 1.2(2 質量％) 60.6 89.4 13.9 實施例28 58.8 Bb-11 1.2(2 質量％) 60.6 89.9 13.1 實施例29 58.8 Bb-12 1.2(2 質量％) 60.8 90.7 10.6 實施例30 58.8 Bb-13 1.2(2 質量％) 1 62.6 87.8 12.3 實施例31 58.8 Bb-14 1.2(2 質量％) 60.5 92.7 8.6 實施例32 58.8 Bb-15 1.2(2 質量％) 62.0 87.0 13.0 實施例33 59.4 Bb-7 0.6(1 質量 ％) 66.3 79.8 19.0 實施例34 58.2 Bb-7 1_8(3 質量％) 57.3 93.7 8.3 實施例35 57.9 Bb-7 2.1(3.5 MS%) 55.5 93.8 9.3 實施例36 56.7 Bb-7 3.3(5.5 質量 ％) 49.4 93.4 13.5 比較例10 58.8 Bb-16 1.2(2 質量 ％) 65.7 78.3 24.5 比較例11 58.8 Bb-17 1.2(2 質量 ％) 64.3 76.0 35.0 比較例12 58.8 Bb-18 1.2(2 質量》/〇) 74.4 無法測定 74.9 比較例13 58.8 Bb-19 1.2(2 質量％) 65.8 69.3 45.7 比較例14 58.8 Bb-20 1.2(2 質量％) 67.1 71.9 35.4 比較例15 58.8 Bb-21 1.2(2質量％) 71.3 60.5 31.2 由表12之結果可知，實施例23〜32及34〜35係藉 -91 - 201026766 由使用的苯乙烯系樹脂組成物具有本發明之構成’所得的 成形體皆具有55 %〜65 %之範圍內的全光線透過率，與超 過8 7%之高光擴散率，以及14%以下之低的黃色度（YI ) 。此等具有適合於液晶面板等所使用的光擴散板等之性能 〇 對此而言，比較例10〜13係使用體積平均粒徑（dv )皆未達〇·7μιη，含有無法滿足要件（b2 )的交聯樹脂微 粒子（Bb-16) 、（ Bb-17 ) 、（ Bb-18 )或（Bb-19 )之苯 ❿ 乙烯系樹脂組成物之例。由比較例10〜13之苯乙烯系樹 脂組成物所得的成形體，不僅含有2質量％之光擴散劑， 且光擴散率爲未達80%之低値，透過光之黃度（YI)爲24 以上之高値，故不爲企求。 而且，比較例14及15，係使用（dv/dn)皆大於1.2 ，含有無法滿足前述要件（b3 )的交聯樹脂微粒子（Bb-20 )或（Bb-21 )之苯乙烯系樹脂組成物之例。由比較例 14及15之苯乙烯系樹脂組成物所得的成形體，不僅含有 參 2質量％之光擴散劑，且光擴散率爲未達72%之低値，透 過光之黃度（YI)爲31以上之高値，故不爲企求。 [產業上之利用價値] 藉由使用本發明之苯乙烯系樹脂組成物，在加熱下進 行熔融成形或其他的成形加工等，可製得具有高光擴散性 ，且擴散光之透過性優異，沒有散射透過光帶有黃色現象 ，尺寸安定性及形狀安定性優異的成形體等。本發明之苯 -92- 201026766 乙烯系樹脂組成物及由該組成物所成的成形體，可活化前 述之優異特性，有效地使用於液晶面板等之大型顯示裝置 用光擴散板、透過型螢幕等之螢幕透鏡、照明器具、照明 看板等之光學用途。 【圖式簡單說明】 [第1圖]係以合成例12所得的種子粒子分散液（SD-φ 5 )以FE-SEM攝影的影像。 [第2圖]係以合成例21所得的交聯樹脂微粒子（Ba-9 )以FE-SEM所攝影的影像。 [第3圖]係以合成例34所得的交聯樹脂微粒子（Bb-7 )以FE-SEM所攝影的影像。 [第4圖]係以合成例41所得的交聯樹脂微粒子（Bb-14)以FE-SEM所攝影的影像。 [第5圖]係以合成例4 3所得的交聯樹脂微粒子（B b -Φ 1 6 )所攝影的影像。 [第6圖]係以合成例4 6所得的交聯樹脂微粒子（B b _ 1 9 )所攝影的影像。 [第7圖]係使作爲交聯樹脂微粒子（Be·1)使用的 Ganz Chemical Co.製交聯聚甲基丙烯酸甲酯微粒子「GM· 0806S」（商品名）以FE-SEM所攝影的影像。 -93-Bb-6) to (Bb-15) were replaced with the crosslinked resin fine particles (Ba-Ι), and the same operation as in Example 1 was carried out to produce a pellet-like styrene resin composition. Then, using the pellets of the styrene resin composition described above, the same operation as in Example 18 was carried out to produce a flat shaped body having a thickness of 15 mm mm ± 5 mm. Regarding the molded body, the total light transmittance (%), the light expansion ratio, and the yellowness (Yell〇w Index (YI)) were measured. The results are shown in Table 12 ® . Stomach 33 (styrene-based resin composition and molded body) The same operation as in the case of Example 24 except that the amount of the styrene-based resin and the cross-linked resin fine particles (Bb-7) used was 59.4 g and 〇6 g, respectively. A pellet-like styrene resin composition. Then, using the pellets of the styrene resin composition described above, the same operation as in the teaching of "1" was carried out to produce a flat shaped body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 12. Example 34 (Styrene-based resin composition and molded article) The same operation as in Example 24 was carried out, except that the amount of styrene-based resin and cross-linked resin fine particles (Bb-7) used was 58-2 g and 1.8 g, respectively. A pelletized styrene resin composition was produced. Then, using the pellets of the styrene resin composition described above, the same operation as in Example 1 was carried out to produce a flat molded body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 12. Example 3 5 (Styrene-based resin composition and molded article) The same operation as in Example 24 was carried out, except that the amounts of the styrene-based resin and the cross-linked resin fine particles (Bb-7) were 57.9 g and 2.1 g, respectively. Each of the pelletized styrene resin compositions was produced. Then, the same operation as in Example 1 was carried out using the pellets of the styrene resin composition described above to produce a flat shaped body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the light spread -89 - 201026766 diffusivity (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 12. Example 36 (Styrene-based resin composition and molded article) The same operations as in Example 24 were carried out except that the styrene-based resin and the crosslinked resin fine particles (Bb-7) were each 56.7 g and 3.3 g. A pelletized styrene resin composition was produced. Then, using the pellets of the styrene resin composition described above, the same operation as in Example 1 was carried out to produce a flat molded body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yellow Index (YI)) were measured. The results are shown in Table 12. Comparative Example 1 0 to 1 5 (Styrene-based resin composition and molded body) - Crosslinking was carried out except for using crosslinked resin fine particles (Bb-16) to (Bb-21) produced in Synthesis Examples 43 to 48 A pellet-like styrene resin composition was produced in the same manner as in Example 1 except for the resin fine particles (Ba-Ι). Then, using the pellets of the styrene resin composition described above, the same operation as in Example 1 was carried out to produce a flat molded body having a thickness of 1.50 mm ± 0.05 mm. Regarding the molded body, the total light transmittance (%), the light diffusing ratio (%), and the yellowness (Yell〇w Index (YI)) were measured. The results are shown in Table 12 - 90 - 201026766. Further, in Comparative Example 12, when the light diffusivity of the molded body was measured, the light diffusibility was too low, and the intensity of the transmitted light in parallel with the light-emitting surface became high. Therefore, the sensitivity of the detector is exceeded, and the light diffusivity cannot be measured. [Table 12] ___ styrene-based resin composition molded article physical properties styrene-based (g) crosslinked resin fine particles total light transmittance (%) light diffusivity (%) yellowness (YI) surface blending amount (g (In the brackets, the content in the composition) Example 23 58.8 Bb-6 1.2 (2% by mass) 1 60.2 91.0 9.8 Example 24 58.8 Bb-7 1.2 (2% by mass) 59.7 92.3 8.3 Example 25 58.8 Bb -8 1·2 (2% by mass) 59.5 92.3 9.2 Example 26 58.8 Bb-9 1.2 (2% by mass) 60.3 90.7 12.0 Example 27 58.8 Bb-10 1.2 (2% by mass) 60.6 89.4 13.9 Example 28 58.8 Bb -11 1.2 (2% by mass) 60.6 89.9 13.1 Example 29 58.8 Bb-12 1.2 (2% by mass) 60.8 90.7 10.6 Example 30 58.8 Bb-13 1.2 (2% by mass) 1 62.6 87.8 12.3 Example 31 58.8 Bb- 14 1.2 (2% by mass) 60.5 92.7 8.6 Example 32 58.8 Bb-15 1.2 (2% by mass) 62.0 87.0 13.0 Example 33 59.4 Bb-7 0.6 (1% by mass) 66.3 79.8 19.0 Example 34 58.2 Bb-7 1_8 (3 mass%) 57.3 93.7 8.3 Example 35 57.9 Bb-7 2.1 (3.5 MS%) 55.5 93.8 9.3 Example 36 56.7 Bb-7 3.3 (5.5 mass%) 49.4 93.4 13.5 Comparative Example 10 58.8 Bb-16 1.2 (2% by mass) 65.7 78.3 24.5 Comparative Example 11 58.8 Bb-17 1.2 (2% by mass) 64.3 76.0 35.0 Comparative Example 12 58.8 Bb-18 1.2 (2 Mass "/〇) 74.4 Unable to measure 74.9 Comparative Example 13 58.8 Bb-19 1.2 (2% by mass) 65.8 69.3 45.7 Comparative Example 14 58.8 Bb-20 1.2 (2% by mass) 67.1 71.9 35.4 Comparative Example 15 58.8 Bb-21 1.2 (2% by mass) 71.3 60.5 31.2 As is clear from the results of Table 12, Examples 23 to 32 and 34 to 35 are from -91 to 201026766. The molded article obtained by using the styrene resin composition having the composition of the present invention has a range of 55% to 65%. The total light transmittance, with a high light diffusivity of over 8 7%, and a low yellowness (YI) of 14% or less. These have properties suitable for a light diffusing plate or the like used for a liquid crystal panel or the like. In contrast, in Comparative Examples 10 to 13, the volume average particle diameter (dv) is less than 〇·7 μm, and the content cannot be satisfied (b2). An example of a benzoquinone vinyl resin composition of crosslinked resin fine particles (Bb-16), (Bb-17), (Bb-18) or (Bb-19). The molded article obtained from the styrene resin compositions of Comparative Examples 10 to 13 contained not only 2% by mass of a light diffusing agent but also a light diffusing ratio of less than 80%, and a yellowness (YI) of transmitted light was More than 24 sorghum, so it is not for the sake of seeking. Further, in Comparative Examples 14 and 15, a styrene resin composition containing crosslinked resin fine particles (Bb-20) or (Bb-21) which does not satisfy the above requirement (b3) is used, using (dv/dn) of more than 1.2. An example. The molded body obtained from the styrene resin compositions of Comparative Examples 14 and 15 contained not only a light diffusing agent of 2% by mass, but also a light diffusing rate of less than 72%, and a yellowness (YI) of transmitted light. It is a high sorghum of 31 or more, so it is not for the sake of the enterprise. [Industrial use price] By using the styrene resin composition of the present invention, melt molding or other molding processing can be performed under heating, and high light diffusibility can be obtained, and the diffused light permeability is excellent. A molded body having a yellow phenomenon, excellent dimensional stability, and excellent shape stability, which is transmitted through the light. The benzene-92-201026766 ethylene resin composition of the present invention and the molded article formed from the composition can activate the above-mentioned excellent characteristics and can be effectively used for a light diffusing plate or a transmissive screen for a large display device such as a liquid crystal panel. Optical applications such as screen lenses, lighting fixtures, and lighting panels. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] An image photographed by FE-SEM using a seed particle dispersion (SD-φ 5 ) obtained in Synthesis Example 12. [Fig. 2] An image photographed by FE-SEM of the crosslinked resin fine particles (Ba-9) obtained in Synthesis Example 21. [Fig. 3] An image photographed by FE-SEM of the crosslinked resin fine particles (Bb-7) obtained in Synthesis Example 34. [Fig. 4] An image photographed by FE-SEM of the crosslinked resin fine particles (Bb-14) obtained in Synthesis Example 41. [Fig. 5] An image photographed by the crosslinked resin fine particles (B b - Φ 16 ) obtained in Synthesis Example 43. [Fig. 6] An image photographed by the crosslinked resin fine particles (B b _ 1 9 ) obtained in Synthesis Example 46. [Fig. 7] Image of FE-SEM photographed by cross-linked polymethyl methacrylate microparticle "GM·0806S" (trade name) manufactured by Ganz Chemical Co., which is used as the crosslinked resin fine particles (Be·1) . -93-

Claims (1)

201026766 七、申請專利範圍： 1. 一種苯乙烯系樹脂組成物，其相對於全部構造單 位之合計量100質量％而言，係含有來自苯乙烯系單體之 構造單位的含有比例爲80質量％以上的苯乙烯系樹脂（A )、交聯樹脂微粒子（B)所成的苯乙烯系樹脂組成物， 其特徵爲該交聯樹脂微粒子（B)爲由（甲基）丙烯酸酯 系樹脂所成的交聯樹脂微粒子，而體積平均粒徑（dv)爲 0.7〜2.5μιη’體積平均粒徑（dv)與數平均粒徑（dn)之 Q 比（dv/dn)爲1_2以下，且設定交聯點當量爲〇.i5meq/g 以上。 2 ·如申請專利範圍第1項之苯乙烯系樹脂組成物， 其中前述苯乙烯系樹脂（A)及前述交聯樹脂微粒子（B) 之含有比例’於此等之合計爲100質量％時各爲95.0〜 99.5質量％及0_5〜5.0質量％。 3. 如申請專利範圍第1或2項之苯乙烯系樹脂組成 物’其中’相對於全部構造單位的合計量100質量％而言 ❹ ，構成前述交聯樹脂微粒子（Β)之來自（甲基）丙烯酸 酯的構造單位之含有比例爲8 〇質量％以上。 4. 如申請專利範圍第1〜3項中任一項之苯乙烯系樹 脂組成物’其中前述交聯樹脂微粒子（Β )係由藉由分散 聚合法所製造的（甲基）丙烯酸酯系樹脂微粒子所成的種 子粒子上使含交聯性單體之乙烯系單體吸收•聚合所得的 交聯樹脂微粒子（Ba)、及藉由分散聚合法所製造的具水 解性矽烷基之（甲基）丙烯酸酯系樹脂微粒子交聯所得的 -94- 201026766 交聯樹脂微粒子（Bb )所選出之交聯樹脂微粒子。 5. 一種成形體，其特徵爲由如申請專利範圍第1〜4 項中任一項之苯乙烯系樹脂組成物所成。 6. 如申請專利範圍第5項之成形體，其係用於光學 用途之成形體。201026766 VII. Patent application range: 1. A styrene-based resin composition containing a content ratio of 80% by mass of a structural unit derived from a styrene-based monomer to 100% by mass of the total of all structural units A styrene resin composition comprising the styrene resin (A) and the crosslinked resin fine particles (B), wherein the crosslinked resin fine particles (B) are made of a (meth) acrylate resin. Crosslinked resin fine particles, and the volume average particle diameter (dv) is 0.7 to 2.5 μm, and the Q ratio (dv/dn) of the volume average particle diameter (dv) to the number average particle diameter (dn) is 1_2 or less, and the setting is performed. The joint equivalent is 〇.i5meq/g or more. (2) The styrene-based resin composition of the first aspect of the invention, wherein the content ratio of the styrene-based resin (A) and the cross-linked resin fine particles (B) is 100% by mass. It is 95.0 to 99.5 mass% and 0_5 to 5.0 mass%. 3. The styrene-based resin composition of the first or second aspect of the patent application, wherein 'in' is 100% by mass based on the total amount of all structural units, and the cross-linking resin fine particles (Β) are derived from (methyl) The content ratio of the structural unit of the acrylate is 8 〇 mass% or more. 4. The styrene-based resin composition of any one of the first to third aspects of the invention, wherein the cross-linked resin fine particles (Β) are a (meth) acrylate-based resin produced by a dispersion polymerization method. Crosslinked resin fine particles (Ba) obtained by absorbing and polymerizing a vinyl monomer containing a crosslinkable monomer on seed particles formed by fine particles, and a hydrolyzable alkylene group (methyl) produced by a dispersion polymerization method The crosslinked resin fine particles selected from the crosslinked resin fine particles (Bb) obtained by cross-linking the acrylate-based resin fine particles. A molded article comprising the styrene resin composition according to any one of claims 1 to 4 of the patent application. 6. The molded article of claim 5, which is a molded article for optical use. -95--95-
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US10633528B2 (en) 2014-12-19 2020-04-28 Ineos Styrolution Group Gmbh Light diffusing styrene copolymer compositions

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Publication number Priority date Publication date Assignee Title
TWI609907B (en) * 2012-04-27 2018-01-01 Toagosei Co Ltd Light diffusing resin composition and molded article thereof
US10633528B2 (en) 2014-12-19 2020-04-28 Ineos Styrolution Group Gmbh Light diffusing styrene copolymer compositions

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