JP6931350B2 - Resin composition for polarizer protective film, polarizer protective film - Google Patents
Resin composition for polarizer protective film, polarizer protective film Download PDFInfo
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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
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- 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
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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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
- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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Description
本発明は、偏光子保護フィルム用樹脂組成物及びその樹脂組成物を用いた偏光子保護フィルムに関するものである。 The present invention relates to a resin composition for a polarizer protective film and a polarizer protective film using the resin composition.
スマートフォンやタブレット端末、テレビ、パソコン、カーナビなどの液晶表示装置には、透明電極、液晶層、カラーフィルター等をガラス板で挟み込んだ液晶セルがあり、その液晶セルの両側には偏光板が使用されている。偏光板は、偏光子フィルムの両面に偏光子保護フィルムを貼り合わせた構成となっており、紫外線や熱、大気中の水分による影響を受け易い偏光子フィルムを偏光子保護フィルムで守っている。偏光子保護フィルムには、光学特性に優れるTAC(トリアセチルセルロース)フィルムが主に用いられてきたが、TACフィルムの課題として、TAC自身の高い吸水性により、寸法変形を発生し易い欠点がある。吸水性の高いTACフィルムの代替材としてアクリル系樹脂を使用した技術や、紫外線から偏光子フィルムを守る為に紫外線吸収剤を使用した技術があるが、寸法安定性や紫外線カット性能、透明性、外観のバランスに優れた偏光子保護フィルム用樹脂組成物及び偏光子保護フィルムは提案されていない。 Liquid crystal display devices such as smartphones, tablet terminals, televisions, personal computers, and car navigation systems have liquid crystal cells in which transparent electrodes, liquid crystal layers, color filters, etc. are sandwiched between glass plates, and polarizing plates are used on both sides of the liquid crystal cells. ing. The polarizing plate has a structure in which a polarizing element protective film is bonded to both sides of the polarizing element film, and the polarizing element film that is easily affected by ultraviolet rays, heat, and moisture in the atmosphere is protected by the polarizing element protective film. A TAC (triacetyl cellulose) film having excellent optical properties has been mainly used as a polarizer protective film, but as a problem of the TAC film, there is a drawback that dimensional deformation is likely to occur due to the high water absorption of TAC itself. .. There are technologies that use acrylic resin as an alternative to TAC film with high water absorption and technologies that use UV absorbers to protect the polarizing film from UV rays, but dimensional stability, UV cut performance, transparency, etc. No resin composition for a polarizer protective film and a polarizer protective film having an excellent balance of appearance have been proposed.
寸法安定性、紫外線カット性能、透明性、外観に優れた偏光子保護フィルム用樹脂組成物及びその樹脂組成物を用いた偏光子保護フィルムを提供することを課題とする。 An object of the present invention is to provide a resin composition for a polarizing element protective film having excellent dimensional stability, ultraviolet ray blocking performance, transparency, and appearance, and a polarizer protective film using the resin composition.
即ち、本発明は以下の通りである。
(1)スチレン系共重合体(A)10〜100質量%とメタクリル樹脂(B)0〜90質量%からなる熱可塑性樹脂組成物(C)100質量部に対して、紫外線吸収剤(D)0.1〜10質量部を含有し、スチレン系共重合体(A)は、波長200〜270nmの光線透過率が5%以下であり、紫外線吸収剤(D)は、JIS K0115に準拠して測定した波長380nmの吸光度が0.05以上である、偏光子保護フィルム用樹脂組成物。
(2)スチレン系共重合体(A)が、芳香族ビニル単量体単位45〜85質量%、(メタ)アクリル酸エステル単量体単位5〜45質量%、不飽和ジカルボン酸無水物単量体単位10〜30質量%からなり、JIS K7206に準拠して求めたビカット軟化温度が115℃以上であることを特徴とする(1)に記載の偏光子保護フィルム用樹脂組成物。
(3)スチレン系共重合体(A)が、JIS K7209に準拠して求めた飽和吸水率が1.0%以下であることを特徴とする(1)〜(2)記載の偏光子保護フィルム用樹脂組成物。
(4)(1)〜(3)いずれかに記載の偏光子保護フィルム用樹脂組成物からなる偏光子保護フィルム。That is, the present invention is as follows.
(1) An ultraviolet absorber (D) with respect to 100 parts by mass of a thermoplastic resin composition (C) composed of 10 to 100% by mass of a styrene-based copolymer (A) and 0 to 90% by mass of a methacrylic resin (B). The styrene-based copolymer (A) contains 0.1 to 10 parts by mass, the light transmittance at a wavelength of 200 to 270 nm is 5% or less, and the ultraviolet absorber (D) conforms to JIS K0115. A resin composition for a polarizer protective film having a measured absorbance at a wavelength of 380 nm of 0.05 or more.
(2) The styrene-based copolymer (A) contains 45 to 85% by mass of an aromatic vinyl monomer unit, 5 to 45% by mass of a (meth) acrylic acid ester monomer unit, and a single amount of unsaturated dicarboxylic acid anhydride. The resin composition for a polarizer protective film according to (1), which comprises 10 to 30% by mass of a body unit and has a Vicat softening temperature of 115 ° C. or higher determined in accordance with JIS K7206.
(3) The polarizer protective film according to (1) to (2), wherein the styrene-based copolymer (A) has a saturated water absorption rate of 1.0% or less determined in accordance with JIS K7209. Resin composition for use.
(4) A polarizer protective film comprising the resin composition for a polarizer protective film according to any one of (1) to (3).
本発明の樹脂組成物は、寸法安定性、紫外線カット性能、透明性、外観に優れた偏光子保護フィルム用途に有用である。 The resin composition of the present invention is useful for applications of polarizing element protective films having excellent dimensional stability, ultraviolet ray blocking performance, transparency, and appearance.
<用語の説明>
本願明細書において、例えば、「A〜B」なる記載は、A以上でありB以下であることを意味する。<Explanation of terms>
In the specification of the present application, for example, the description "A to B" means that it is A or more and B or less.
以下、本発明の実施形態について、詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
スチレン系共重合体(A)とは、芳香族ビニル単量体単位、(メタ)アクリル酸エステル単量体単位、不飽和ジカルボン酸無水物単量体単位を有する共重合体のことであり、例えばスチレン−メチルメタクリレート−無水マレイン酸共重合体がある。 The styrene-based copolymer (A) is a copolymer having an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid anhydride monomer unit. For example, there is a styrene-methylmethacrylate-maleic anhydride copolymer.
芳香族ビニル単量体単位としては、スチレン、o−メチルスチレン、m−メチルスチレン、p−メチルスチレン、2,4−ジメチルスチレン、エチルスチレン、p−tert−ブチルスチレン、α−メチルスチレン、α−メチル−p−メチルスチレン等の各スチレン系単量体に由来する単位が挙げられる。これらの中でも好ましくはスチレン単位である。これら芳香族ビニル単量体単位は、1種類でもよく、2種類以上の併用であってもよい。 As the aromatic vinyl monomer unit, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α Examples thereof include units derived from each styrene-based monomer such as -methyl-p-methylstyrene. Of these, the styrene unit is preferable. These aromatic vinyl monomer units may be one kind or a combination of two or more kinds.
(メタ)アクリル酸エステル単量体単位としては、メチルメタクリレート、エチルメタクリレート、n−ブチルメタクリレート、2−エチルヘキシルメタクリレート、ジシクロペンタニルメタクリレート、イソボルニルメタクリレートなどの各メタクリル酸エステル単量体、およびメチルアクリレート、エチルアクリレート、n−ブチルアクリレート、2−メチルヘキシルアクリレート、2−エチルヘキシルアクリレート、デシルアクリレート等の各アクリル酸エステル単量体に由来する単位が挙げられる。これらの中でも好ましくはメチルメタクリレート単位である。これら(メタ)アクリル酸エステル単量体単位は、1種類でもよく、2種類以上の併用であってもよい。 Examples of the (meth) acrylic acid ester monomer unit include each methacrylate ester monomer such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate, and Examples thereof include units derived from each acrylic acid ester monomer such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate. Of these, the methyl methacrylate unit is preferable. These (meth) acrylic acid ester monomer units may be one kind or a combination of two or more kinds.
不飽和ジカルボン酸無水物単量体単位としては、マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、アコニット酸無水物等の各無水物単量体に由来する単位が挙げられる。これらの中でも好ましくはマレイン酸無水物単位である。不飽和ジカルボン酸無水物単量体単位は、1種でもよく、2種類以上の併用であってもよい。 Examples of the unsaturated dicarboxylic acid anhydride monomer unit include units derived from each anhydride monomer such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and aconitic acid anhydride. Of these, the maleic anhydride unit is preferable. The unsaturated dicarboxylic acid anhydride monomer unit may be one kind or a combination of two or more kinds.
スチレン系共重合体(A)は、芳香族ビニル単量体単位、(メタ)アクリル酸エステル単量体単位、および不飽和ジカルボン酸無水物単量体単位以外の、共重合可能なビニル単量体の単位を共重合体中に発明の効果を阻害しない範囲で含んでもよく、好ましくは5質量%以下である。共重合可能なビニル単量体の単位としては、アクリロニトリル、メタクリロニトリル等のシアン化ビニル単量体、アクリル酸、メタクリル酸等のビニルカルボン酸単量体、N−メチルマレイミド、N−エチルマレイミド、N−ブチルマレイミド、N−シクロヘキシルマレイミド等のN−アルキルマレイミド単量体、N−フェニルマレイミド、N−メチルフェニルマレイミド、N−クロルフェニルマレイミド等のN−アリールマレイミド単量体等の各単量体に由来する単位が挙げられる。共重合可能なビニル単量体の単位は、2種類以上の併用であってもよい。 The styrene-based copolymer (A) is a copolymerizable vinyl unit amount other than the aromatic vinyl monomer unit, the (meth) acrylic acid ester monomer unit, and the unsaturated dicarboxylic acid anhydride monomer unit. The unit of the body may be contained in the copolymer as long as the effect of the invention is not impaired, and is preferably 5% by mass or less. Examples of the copolymerizable vinyl monomer unit include vinyl cyanide monomer such as acrylonitrile and methacrylonitrile, vinyl carboxylic acid monomer such as acrylic acid and methacrylic acid, N-methylmaleimide, and N-ethylmaleimide. , N-alkylmaleimide monomer such as N-butylmaleimide, N-cyclohexylmaleimide, N-arylmaleimide monomer such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, etc. Units derived from the body can be mentioned. The unit of the copolymerizable vinyl monomer may be a combination of two or more types.
スチレン系共重合体(A)の構成単位は、芳香族ビニル単量体単位45〜85質量%、(メタ)アクリル酸エステル系単量体単位5〜45質量%、不飽和ジカルボン酸無水物単量体単位10〜30質量%であり、好ましくは芳香族ビニル単量体単位50〜80質量%、(メタ)アクリル酸エステル単量体単位8〜38質量%、不飽和ジカルボン酸無水物単量体単位12〜25質量%である。 The constituent units of the styrene-based copolymer (A) are an aromatic vinyl monomer unit of 45 to 85% by mass, a (meth) acrylic acid ester-based monomer unit of 5 to 45% by mass, and an unsaturated dicarboxylic acid anhydride simple substance. The weight unit is 10 to 30% by mass, preferably the aromatic vinyl monomer unit is 50 to 80% by mass, the (meth) acrylic acid ester monomer unit is 8 to 38% by mass, and the unsaturated dicarboxylic acid anhydride is a single amount. The body unit is 12 to 25% by mass.
芳香族ビニル単量体単位が45質量%以上であれば、熱安定性、低吸湿性、紫外線カット性能、成形加工性に優れ、50質量%以上であれば、さらに熱安定性、低吸湿性、紫外線カット性能、成形加工性に優れる。芳香族ビニル単量体単位が85質量%以下であれば、透明性に優れ、80質量%以下であれば、さらに透明性に優れる。 When the aromatic vinyl monomer unit is 45% by mass or more, it is excellent in thermal stability, low hygroscopicity, ultraviolet ray blocking performance, and molding processability, and when it is 50% by mass or more, it is further thermal stability and low hygroscopicity. Excellent in UV protection and molding processability. When the aromatic vinyl monomer unit is 85% by mass or less, the transparency is excellent, and when it is 80% by mass or less, the transparency is further excellent.
(メタ)アクリル酸エステル単量体単位が5質量%以上であれば、透明性に優れ、8質量%以上であれば、さらに透明性に優れる。(メタ)アクリル酸エステル単量体単位が45質量%以下であれば、熱安定性、低吸湿性、紫外線カット性能、成形加工性に優れ、38質量%以下であれば、さらに熱安定性、低吸湿性、紫外線カット性能、成形加工性に優れる。 When the (meth) acrylic acid ester monomer unit is 5% by mass or more, the transparency is excellent, and when it is 8% by mass or more, the transparency is further excellent. When the (meth) acrylic acid ester monomer unit is 45% by mass or less, it is excellent in thermal stability, low hygroscopicity, ultraviolet ray blocking performance, and molding processability, and when it is 38% by mass or less, it is further thermally stable. Excellent in low hygroscopicity, UV blocking performance, and molding processability.
不飽和ジカルボン酸無水物単量体単位が10質量%以上であれば、耐熱性に優れ、12質量%以上であれば、さらに耐熱性に優れる。不飽和ジカルボン酸無水物単量体単位が30質量%以下であれば、熱安定性と成形加工性に優れ、25質量%以下であれば、さらに熱安定性と成形加工性に優れる。 When the unsaturated dicarboxylic acid anhydride monomer unit is 10% by mass or more, the heat resistance is excellent, and when it is 12% by mass or more, the heat resistance is further excellent. When the unsaturated dicarboxylic acid anhydride monomer unit is 30% by mass or less, the thermal stability and the molding processability are excellent, and when the unsaturated dicarboxylic acid anhydride monomer unit is 25% by mass or less, the thermal stability and the molding processability are further excellent.
スチレン系共重合体(A)の波長200〜270nmにおける光線透過率は5%以下であり、好ましくは3%以下、さらに好ましくは1%以下である。波長200〜270nmにおける光線透過率が5%以下であれば、共重合体単独で波長200〜270nmの紫外線を吸収する為、紫外線カット性能に優れる。また、共重合体自体に波長200〜270nmの紫外線カット性能があれば、波長200〜270nmの紫外線を吸収するような紫外線吸収剤を新たに添加する必要が無い為、透明性や色相、熱安定性に優れる。なお、波長200〜270nmの光線透過率は、溶融押出成形で作製した厚み60μmのフィルムを分光光度計(日本分光社製V−670)を用いて測定し、波長200nm〜270nmにおける光線透過率の平均値として算出した値のことである。 The light transmittance of the styrene-based copolymer (A) at a wavelength of 200 to 270 nm is 5% or less, preferably 3% or less, and more preferably 1% or less. When the light transmittance at a wavelength of 200 to 270 nm is 5% or less, the copolymer alone absorbs ultraviolet rays having a wavelength of 200 to 270 nm, so that the ultraviolet ray blocking performance is excellent. Further, if the copolymer itself has an ultraviolet ray blocking performance having a wavelength of 200 to 270 nm, it is not necessary to newly add an ultraviolet absorber that absorbs ultraviolet rays having a wavelength of 200 to 270 nm, so that the transparency, hue, and thermal stability are stable. Excellent in sex. The light transmittance at a wavelength of 200 to 270 nm was measured by measuring a film having a thickness of 60 μm produced by melt extrusion using a spectrophotometer (V-670 manufactured by JASCO Corporation) and measuring the light transmittance at a wavelength of 200 nm to 270 nm. It is a value calculated as an average value.
スチレン系共重合体(A)は、JIS K7206に準拠し荷重50N、昇温速度50℃/時間で求めたビカット軟化温度が115℃以上であることが好ましく、さらに好ましくは120℃以上、特に好ましくは125℃以上である。なお、ビカット軟化温度が高いほど耐熱性が良好となり、寸法安定性に優れる。 The styrene-based copolymer (A) preferably has a Vicat softening temperature of 115 ° C. or higher, more preferably 120 ° C. or higher, particularly preferably 120 ° C. or higher, as determined by a load of 50 N and a heating rate of 50 ° C./hour in accordance with JIS K7206. Is 125 ° C. or higher. The higher the Vicat softening temperature, the better the heat resistance and the better the dimensional stability.
スチレン系共重合体(A)は、JIS K7209に準拠して求めた飽和吸水率が1.0%以下であることが好ましく、さらに好ましくは0.9以下、特に好ましくは0.8以下である。なお、飽和吸水率が低いほど低吸湿性となり、寸法安定性に優れる。 The styrene-based copolymer (A) preferably has a saturated water absorption rate of 1.0% or less, more preferably 0.9 or less, and particularly preferably 0.8 or less, as determined in accordance with JIS K7209. .. The lower the saturated water absorption rate, the lower the hygroscopicity and the better the dimensional stability.
スチレン系共重合体(A)の重量平均分子量(Mw)は、10万〜30万であることが好ましく、さらに好ましくは11万〜25万である。重量平均分子量(Mw)が10万より小さいと強度が低くなり、30万を超えると成形加工性が悪くなる。スチレン系共重合体(A)の重量平均分子量(Mw)は、重合工程での重合温度、重合開始剤の種類及び添加量、連鎖移動剤の種類及び添加量、重合時に使用する溶媒の種類及び量等によって制御することができる。なお、重量平均分子量(Mw)とは、ゲルパーミエーションクロマトグラフィー(GPC)にて測定されるポリスチレン換算の値であり、下記記載の測定条件における測定値である。
装置名:SYSTEM−21 Shodex(昭和電工社製)
カラム:PL gel MIXED−Bを3本直列
温度:40℃
検出:示差屈折率
溶媒:テトラヒドロフラン
濃度:2質量%
検量線:標準ポリスチレン(PS)(PL社製)を用いて作製した。The weight average molecular weight (Mw) of the styrene-based copolymer (A) is preferably 100,000 to 300,000, more preferably 110,000 to 250,000. If the weight average molecular weight (Mw) is less than 100,000, the strength becomes low, and if it exceeds 300,000, the molding processability deteriorates. The weight average molecular weight (Mw) of the styrene-based copolymer (A) is determined by the polymerization temperature in the polymerization step, the type and amount of the polymerization initiator, the type and amount of the chain transfer agent, the type of the solvent used during the polymerization, and the amount. It can be controlled by the amount or the like. The weight average molecular weight (Mw) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and is a measured value under the measurement conditions described below.
Device name: SYSTEM-21 Shodex (manufactured by Showa Denko KK)
Column: 3 PL gel MIXED-B in series Temperature: 40 ° C
Detection: Differential Refractometer Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Made using standard polystyrene (PS) (manufactured by PL).
スチレン系共重合体(A)のASTM D1003に基づき測定した2mm厚みの全光線透過率は、88%以上であることが好ましく、さらに好ましくは89%以上であり、特に好ましくは90%以上である。2mm厚みの全光線透過率が88%以上であれば、メタクリル樹脂(B)に配合して得られる熱可塑性樹脂組成物(C)の透明性が良好となる。なお、全光線透過率は射出成形機(東芝機械社製IS−50EPN)を用いて、シリンダー温度230℃、金型温度40℃の成形条件で成形された縦90mm、横55mm、厚み2mmの鏡面プレートを、ASTM D1003に準拠し、ヘーズメーター(日本電色工業社製NDH−1001DP型)を用いて測定した値である。 The total light transmittance of the styrene copolymer (A) having a thickness of 2 mm measured based on ASTM D1003 is preferably 88% or more, more preferably 89% or more, and particularly preferably 90% or more. .. When the total light transmittance of the 2 mm thickness is 88% or more, the transparency of the thermoplastic resin composition (C) obtained by blending with the methacrylic resin (B) becomes good. The total light transmittance is a mirror surface of 90 mm in length, 55 mm in width, and 2 mm in thickness, which is molded by an injection molding machine (IS-50EPN manufactured by Toshiba Machine Co., Ltd.) under molding conditions of a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C. It is a value measured by using a haze meter (NDH-1001DP type manufactured by Nippon Denshoku Kogyo Co., Ltd.) on the plate in accordance with ASTM D1003.
スチレン系共重合体(A)の製造方法について説明する。重合様式においては特に限定はなく、溶液重合、塊状重合等公知の方法で製造できるが、溶液重合がより好ましい。溶液重合で用いる溶剤は、副生成物が出来難く、悪影響が少ないという観点から非重合性であることが好ましい。溶剤の種類としては、特に限定されるものではないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン等のケトン類、テトラヒドロフラン、1、4−ジオキサン等のエーテル類、トルエン、エチルベンゼン、キシレン、クロロベンゼン等の芳香族炭化水素等が挙げられるが、単量体や共重合体の溶解度、溶剤回収のし易さの観点から、メチルエチルケトン、メチルイソブチルケトンが好ましい。溶剤の添加量は、得られる共重合体量100質量部に対して、10〜100質量部が好ましく、さらに好ましくは30〜80質量部である。10質量部以上であれば、反応速度および重合液粘度を制御する上で好適であり、100質量部以下であれば、所望の重量平均分子量(Mw)を得る上で好適である。 A method for producing the styrene-based copolymer (A) will be described. The polymerization mode is not particularly limited and can be produced by a known method such as solution polymerization or bulk polymerization, but solution polymerization is more preferable. The solvent used in solution polymerization is preferably non-polymerizable from the viewpoint that by-products are difficult to form and adverse effects are small. The type of solvent is not particularly limited, but for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetophenone, ethers such as tetrahydrofuran, 1,4-dioxane, toluene, ethylbenzene, xylene and chlorobenzene. Examples thereof include aromatic hydrocarbons such as, but methyl ethyl ketone and methyl isobutyl ketone are preferable from the viewpoint of solubility of monomers and copolymers and ease of solvent recovery. The amount of the solvent added is preferably 10 to 100 parts by mass, more preferably 30 to 80 parts by mass, based on 100 parts by mass of the obtained copolymer. If it is 10 parts by mass or more, it is suitable for controlling the reaction rate and the viscosity of the polymer solution, and if it is 100 parts by mass or less, it is suitable for obtaining a desired weight average molecular weight (Mw).
重合プロセスは回分式重合法、半回分式重合法、連続重合法のいずれの方式であっても差し支えないが、所望の分子量範囲と透明性を得る上で回分式重合法が好適である。 The polymerization process may be any of a batch polymerization method, a semi-batch polymerization method, and a continuous polymerization method, but the batch polymerization method is preferable in order to obtain a desired molecular weight range and transparency.
重合方法は特に限定されないが、簡潔プロセスによって生産性良く製造することが可能であるという観点から、好ましくはラジカル重合法である。重合開始剤としては特に限定されるものではないが、例えばジベンゾイルパーオキサイド、t−ブチルパーオキシベンゾエート、1,1−ビス(t−ブチルパーオキシ)−2−メチルシクロヘキサン、t−ブチルパーオキシイソプロピルモノカーボネート、t−ブチルパーオキシ−2−エチルヘキサノエート、t−ブチルパーオキシアセテート、ジクミルパーオキサイド、エチル−3,3−ジ−(t−ブチルパーオキシ)ブチレート等の公知の有機過酸化物やアゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル、アゾビスメチルプロピオニトリル、アゾビスメチルブチロニトリル等の公知のアゾ化合物を用いることができる。これらの重合開始剤は2種以上を併用することも出来る。これらの中でも10時間半減期温度が、70〜110℃である有機過酸化物を用いるのが好ましい。 The polymerization method is not particularly limited, but a radical polymerization method is preferable from the viewpoint that it can be produced with high productivity by a simple process. The polymerization initiator is not particularly limited, but for example, dibenzoyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butylperoxy. Known organics such as isopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyacetate, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate, etc. Known azo compounds such as peroxides, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile can be used. Two or more of these polymerization initiators can be used in combination. Among these, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 70 to 110 ° C.
重量平均分子量(Mw)が10万〜30万のスチレン系共重合体(A)を得る方法については、重合温度、重合時間、および重合開始剤添加量の調整に加えて、溶剤添加量および連鎖移動剤添加量を調整することで得ることが出来る。連鎖移動剤としては、特に限定されるものではないが、例えば、n−ドデシルメルカプタン、t−ドデシルメルカプタンや2,4−ジフェニル−4−メチル−1−ペンテン等の公知の連鎖移動剤を用いることができる。 Regarding the method for obtaining the styrene-based copolymer (A) having a weight average molecular weight (Mw) of 100,000 to 300,000, in addition to adjusting the polymerization temperature, the polymerization time, and the amount of the polymerization initiator added, the amount of the solvent added and the chain It can be obtained by adjusting the amount of the transfer agent added. The chain transfer agent is not particularly limited, and for example, a known chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan, or 2,4-diphenyl-4-methyl-1-pentene may be used. Can be done.
重合終了後、重合液には本発明の効果を阻害しない範囲で、ヒンダードフェノール系化合物、ラクトン系化合物、リン系化合物、イオウ系化合物等の耐熱安定剤、滑剤や可塑剤、着色剤、帯電防止剤、鉱油等の添加剤を加えても構わない。その添加量は全単量体単位100質量部に対して0.2質量部未満であることが好ましい。これらの添加剤は単独で用いても、2種類以上を併用しても構わない。 After completion of the polymerization, heat-stabilizing agents such as hindered phenol-based compounds, lactone-based compounds, phosphorus-based compounds, and sulfur-based compounds, lubricants, plasticizers, colorants, and antistatic agents are added to the polymerization solution as long as the effects of the present invention are not impaired. Additives such as inhibitor and mineral oil may be added. The amount added is preferably less than 0.2 parts by mass with respect to 100 parts by mass of all the monomer units. These additives may be used alone or in combination of two or more.
重合液からスチレン系共重合体(A)を回収する方法については、特に限定はなく、公知の脱揮技術を用いることが出来る。例えば、重合液を二軸脱揮押出機にギヤーポンプを用いて連続的にフィードし、重合溶剤や未反応モノマー等の脱揮処理を行い、脱揮された溶融状態のスチレン系共重合体(A)は、造粒工程に移送され、多孔ダイよりストランド状に押出し、コールドカット方式や空中ホットカット方式、水中ホットカット方式にてペレット形状に加工することができる。なお、重合溶剤や未反応モノマー等を含む脱揮成分は、コンデンサー等を用いて凝縮させて回収し、凝縮液を蒸留塔にて精製することで、重合溶剤は再利用することが可能である。 The method for recovering the styrene-based copolymer (A) from the polymer solution is not particularly limited, and a known devolatilization technique can be used. For example, the polymerization solution is continuously fed to a twin-screw devolatilization extruder using a gear pump to carry out a volatilization treatment of a polymerization solvent, an unreacted monomer, etc., and the styrene-based copolymer (A) in a molten state is volatilized. ) Can be transferred to the granulation process, extruded into a strand shape from a porous die, and processed into a pellet shape by a cold cut method, an aerial hot cut method, or an underwater hot cut method. The volatilization component containing the polymerization solvent, unreacted monomer, etc. can be reused by condensing and recovering the volatilization component using a condenser or the like and purifying the condensate in a distillation column. ..
メタクリル樹脂(B)とは、(メタ)アクリル酸エステル単量体単位を有する重合体であり、例えば、ポリメチルメタクリレートがあり、市販されている一般的なものを使用することが出来る。また本発明においては、さらにスチレン系単量体単位を有することができ、スチレン系単量体単位は20質量%以下で用いることができる。 The methacrylic resin (B) is a polymer having a (meth) acrylic acid ester monomer unit, and for example, there is polymethylmethacrylate, and a general commercially available one can be used. Further, in the present invention, a styrene-based monomer unit can be further provided, and the styrene-based monomer unit can be used in an amount of 20% by mass or less.
メタクリル樹脂(B)には、本発明の効果を阻害しない範囲でヒンダードフェノール系化合物、ラクトン系化合物、リン系化合物、イオウ系化合物等の耐熱安定剤、滑剤や可塑剤、着色剤、帯電防止剤、鉱油等の添加剤を加えても構わない。 The methacrylic resin (B) contains heat-resistant stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, lubricants and plasticizers, colorants, and antistatic agents as long as the effects of the present invention are not impaired. Additives such as agents and mineral oils may be added.
紫外線吸収剤(D)とは、高分子材料の劣化要因となる紫外線を吸収する添加剤のことであり、例えば、ベンゾトリアゾール系、シアノアクリレート系、トリアジン系、ベンゾフェノン系、ベンゾエート系、サリシレート系、マロン酸エステル系、オキザニリド系(蓚酸アニリド系)等があり、市販されている一般的なものを使用することが出来る。いずれも紫外線を吸収して、高分子材料に対して無害な熱エネルギー等に転換する作用を持つ。 The ultraviolet absorber (D) is an additive that absorbs ultraviolet rays that cause deterioration of the polymer material. For example, benzotriazole type, cyanoacrylate type, triazine type, benzophenone type, benzoate type, salicylate type, There are malonic acid ester type, oxanilide type (ultraic acid anilide type), etc., and commercially available general ones can be used. Both have the effect of absorbing ultraviolet rays and converting them into heat energy that is harmless to polymer materials.
ベンゾトリアゾール系とは、例えば2−(2H−ベンゾトリアゾール−2−イル)−4−6−ビス(1−メチル−1−フェニルエチル)フェノール、2−(2H−ベンゾトリアゾール−2−イル)−p−クレゾール、2−〔5−クロロ(2H)−ベンゾトリアゾール−2−イル〕−4−メチル−6−(tert−ブチル)フェノール、2−(2H−ベンゾトリアゾール−2−イル)−4−(1,1,3,3−テトラメチルブチル)フェノール、2,2'−メチルレンビス〔6−(2H−ベンゾトリアゾール−2イル)−4−(1,1,3,3−テトラメチルブチル)フェノール〕、2−(2H−ベンゾトリアゾール−2−イル)−4−メチル−6−(3,4,5,6−テトラハイドロフタルイミディルメチル)フェノール、2−(3,5−ジ−tert−ペンチル−2−ヒドロキシフェニル)−2H−ベンゾトリアゾール、2−(2−ヒドロキシ−4−オクチルオキシフェニル)−2H−ベンゾトリアゾール、6−(2−ベンゾトリアゾイル)−4−t−オクチル−6'−t−ブチル−4'−メチル−2,2'−メチレンビスフェノール等がある。 The benzotriazole system is, for example, 2- (2H-benzotriazole-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2-yl)-. p-cresol, 2- [5-chloro (2H) -benzotriazole-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-Tetramethylbutyl) phenol, 2,2'-methyllenbis [6- (2H-benzotriazole-2yl) -4- (1,1,3,3-tetramethylbutyl) phenol ], 2- (2H-benzotriazole-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (3,5-di-tert-) Pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 6- (2-benzotriazoyl) -4-t-octyl-6' There are -t-butyl-4'-methyl-2,2'-methylenebisphenol and the like.
シアノアクリレート系とは、例えば2,2−ビス{〔2−シアノー3,3−ジフェニルアクリロイル〕オキシ〕メチル}プロパン−1,3−ジイル=ビス(2−シアノ−3,3−ジフェニルアクリラート)、2−シアノー3,3−ジフェニルアクリル酸エチル、2−シアノー3,3−ジフェニルアクリル酸2−エチルヘキシル等がある。 The cyanoacrylate system is, for example, 2,2-bis {[2-cyano-3,3-diphenylacryloyl] oxy] methyl} propane-1,3-diyl = bis (2-cyano-3,3-diphenylacryloyl). , 2-Cyano-3,3-diphenylacrylate ethyl, 2-cyano-3,3-diphenylacrylate 2-ethylhexyl and the like.
トリアジン系とは、例えば2−(4,6−ジフェニル―1,3,5−トリアジン−2−イル)−5−〔(ヘキシル)オキシ〕−フェノール、2−(4,6−ジフェニル−1,3,5−トリアジン−2−イル)−5−〔2−(2−エチルヘキサノイルオキシ〕エトキシフェノール、2,4,6−トリス(2−ヒドロキシ−4−ヘキシルオキシ−3−メチルフェニル)−1,3,5−トリアジン等がある。 The triazine system includes, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6-diphenyl-1, 3,5-Triazine-2-yl) -5- [2- (2-ethylhexanoyloxy] ethoxyphenol, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl)- There are 1,3,5-triazine and the like.
ベンゾフェノン系とは、例えばオクタベンゾン、2,2'−ジヒドロキシ−4,4'−ジメトキシベンフェノン、2,2'−4,4'−テトラヒドロベンフェノン、2,4−ジヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン−5−スルホン酸三水和物、4−ドデシルオキシ−2−ヒドロキシベンゾフェノン、4−ベンジルオキシ−2−ヒドロキベンゾフェノン、1,4−ビス(4−ベンゾイル−3−ヒドロキシフェノキシ)−ブタン、2,2'−ジヒドロキシ−4−メトキシベンゾフェノン等がある。 The benzophenone system includes, for example, octabenzone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-4,4'-tetrahydrobenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4. -Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydrokibenzophenone, 1,4-bis (4-bis) Benzoyl-3-hydroxyphenoxy) -butane, 2,2'-dihydroxy-4-methoxybenzophenone and the like.
ベンゾエート系とは、例えば2,4−ジ−tert−ブチルフェニル−3,5−ジ−tert−ブチル−4−ヒドロキシベンゾエート、ヘキサデシル3,5−ビス−tert−4−ヒドロキシベンゾエート等がある。 Examples of the benzoate system include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-bis-tert-4-hydroxybenzoate and the like.
サリシレート系とは、例えばフェニルサリシレート、4−tert−ブチルフェニルサリシレート等がある。 Examples of the salicylate system include phenyl salicylate and 4-tert-butylphenyl salicylate.
マロン酸エステル系とは、例えばマロン酸[(4−メトキシフェニル)−メチレン]−ジメチルエステル、テトラエチル−2,2−(1,4−フェニレン−ジメチリデン)−ビスマロネート等がある。 Examples of the malonic acid ester system include malonic acid [(4-methoxyphenyl) -methylene] -dimethyl ester, tetraethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate and the like.
オキザニリド系(蓚酸アニリド系)とは、例えば2−エチル−2'−エトキシ−オキザニリド等がある。 The oxanilide type (oxalic acid anilide type) includes, for example, 2-ethyl-2'-ethoxy-oxanilide and the like.
紫外線吸収剤(D)のJIS K0115に準拠して測定した波長380nmの吸光度は0.05以上であり、好ましくは0.1以上、さらに好ましくは0.15以上である。JIS K0115に準拠して測定した波長380nmの吸光度が0.05以上であれば、紫外線カット性能に優れる。また、波長380nmの吸光度が大きいほど、少ない配合量で紫外線カット性能を発揮する為、熱可塑性樹脂組成物(C)に配合した際の耐熱性の低下度合を小さくすることができ、加えて透明性や色相、外観にも優れる。 The absorbance at a wavelength of 380 nm measured according to JIS K0115 of the ultraviolet absorber (D) is 0.05 or more, preferably 0.1 or more, and more preferably 0.15 or more. If the absorbance at a wavelength of 380 nm measured in accordance with JIS K0115 is 0.05 or more, the ultraviolet ray blocking performance is excellent. Further, as the absorbance at a wavelength of 380 nm is larger, the ultraviolet ray blocking performance is exhibited with a smaller compounding amount, so that the degree of decrease in heat resistance when compounded in the thermoplastic resin composition (C) can be reduced, and in addition, it is transparent. It has excellent properties, hue, and appearance.
紫外線吸収剤(D)の分子量は、200g/mol以上であることが好ましく、さらに好ましくは300g/molである。紫外線吸収剤(D)の分子量が小さいと、熱可塑性樹脂組成物(C)に配合した際の耐熱性の低下度合が大きくなる場合や押出機や射出成形機などの成形加工時に揮散してしまうこともある。 The molecular weight of the ultraviolet absorber (D) is preferably 200 g / mol or more, and more preferably 300 g / mol. If the molecular weight of the ultraviolet absorber (D) is small, the degree of decrease in heat resistance when blended in the thermoplastic resin composition (C) becomes large, or the ultraviolet absorber (D) volatilizes during molding processing such as an extruder or an injection molding machine. Sometimes.
熱可塑性樹脂組成物(C)は、スチレン系共重合体(A)10〜100質量%とメタクリル樹脂(B)0〜90質量%からなり、好ましくはスチレン系共重合体(A)20〜100質量%とメタクリル樹脂(B)0〜80質量%であり、さらに好ましくはスチレン系共重合体(A)30〜100質量%とメタクリル樹脂(B)0〜70質量%である。熱可塑性樹脂組成物(C)におけるメタクリル樹脂(B)が90質量%を超えると、耐熱性が低くなり、また飽和吸水率が高くなる為、寸法安定性に劣る。 The thermoplastic resin composition (C) is composed of 10 to 100% by mass of the styrene-based copolymer (A) and 0 to 90% by mass of the methacrylic resin (B), preferably 20 to 100% by mass of the styrene-based copolymer (A). The mass% is 0 to 80% by mass of the methacrylic resin (B), and more preferably 30 to 100% by mass of the styrene-based copolymer (A) and 0 to 70% by mass of the methacrylic resin (B). If the methacrylic resin (B) in the thermoplastic resin composition (C) exceeds 90% by mass, the heat resistance becomes low and the saturated water absorption rate becomes high, so that the dimensional stability is inferior.
偏光子保護フィルム用樹脂組成物は、スチレン系共重合体(A)とメタクリル樹脂(B)からなる熱可塑性樹脂組成物(C)100質量部に対して、紫外線吸収剤(D)0.1〜10質量部を含有してなり、好ましくは紫外線吸収剤(D)0.5〜8質量部であり、さらに好ましくは紫外線吸収剤(D)1〜5質量部である。紫外線吸収剤(D)が0.1質量部以上であると、紫外線カット性能に優れ、10質量部以下であれば、寸法安定性、透明性、外観に優れる。 The resin composition for the polarizer protective film is 0.1 parts by mass of the ultraviolet absorber (D) with respect to 100 parts by mass of the thermoplastic resin composition (C) composed of the styrene copolymer (A) and the methacrylic resin (B). It contains 10 parts by mass, preferably 0.5 to 8 parts by mass of the ultraviolet absorber (D), and more preferably 1 to 5 parts by mass of the ultraviolet absorber (D). When the amount of the ultraviolet absorber (D) is 0.1 parts by mass or more, the ultraviolet ray blocking performance is excellent, and when it is 10 parts by mass or less, the dimensional stability, transparency and appearance are excellent.
偏光子保護フィルム用樹脂組成物は、波長200〜270nmの光線透過率が5%以下であるスチレン系共重合体(A)10〜100質量%とメタクリル樹脂(B)0〜90質量%からなる熱可塑性樹脂組成物(C)100質量部に対して、JIS K0115に準拠して測定した波長380nmの吸光度が0.05以上である紫外線吸収剤(D)0.1〜10質量部を含有していれば、特に製造方法は限定されない。例えば、スチレン系共重合体(A)とメタクリル樹脂(B)からなる熱可塑性樹脂組成物(C)に紫外線吸収剤(D)を添加し溶融押出混練する方法、スチレン系共重合体(A)の重合工程、脱揮工程、造粒工程で紫外線吸収剤(D)を添加混合した後にメタクリル樹脂(B)と溶融押出混練する方法、メタクリル樹脂(B)に紫外線吸収剤(D)を添加混合した後にスチレン系共重合体(A)と溶融押出混練する方法、スチレン系共重合体(A)とメタクリル樹脂(B)、紫外線吸収剤(D)を同時に溶融押出混練する方法等が挙げられる。なお、溶融押出混練方法については、公知の溶融混練技術を用いることができ、好適に使用できる溶融混練装置としては、単軸押出機、噛合形同方向回転または噛合形異方向回転二軸押出機、非または不完全噛合形二軸押出機等のスクリュー押出機、バンバリーミキサー、コニーダー及び混合ロール等がある。 The resin composition for a polarizer protective film comprises 10 to 100% by mass of a styrene-based copolymer (A) and 0 to 90% by mass of a methacrylic resin (B) having a wavelength of 200 to 270 nm and a light transmittance of 5% or less. For 100 parts by mass of the thermoplastic resin composition (C), 0.1 to 10 parts by mass of an ultraviolet absorber (D) having an absorbance of 0.05 or more at a wavelength of 380 nm measured in accordance with JIS K0115 is contained. If so, the manufacturing method is not particularly limited. For example, a method of adding an ultraviolet absorber (D) to a thermoplastic resin composition (C) composed of a styrene-based copolymer (A) and a methacrylic resin (B) and melt-extruding and kneading the styrene-based copolymer (A). A method of adding and mixing an ultraviolet absorber (D) in a polymerization step, a volatilization step, and a granulation step, and then melt-extruding and kneading the methacrylic resin (B). After that, a method of melt-extruding and kneading the styrene-based copolymer (A), a method of simultaneously melt-extruding and kneading the styrene-based polymer (A), the methacrylic resin (B), and the ultraviolet absorber (D) can be mentioned. As for the melt extrusion kneading method, a known melt kneading technique can be used, and as a melt kneading device that can be preferably used, a single-screw extruder, a meshing type co-directional rotation or a meshing type different direction rotating twin-screw extruder can be used. , Screw extruders such as non- or incompletely meshed twin-screw extruders, Banbury mixers, coniders and mixing rolls.
偏光子保護フィルム用樹脂組成物には、本発明の効果を阻害しない範囲でヒンダードアミン系光安定剤(HALS)を併用することもできる。ヒンダードアミン系光安定剤は、テトラメチルピペリジン骨格を基本骨格とした光安定剤である。光劣化によって生じたポリマーラジカルやポリオキシラジカル等のラジカルを捕捉しラジカル連鎖反応による劣化の進行を停止すると考えられている。ヒンダードアミン系光安定剤は、例えばコハク酸ジメチルと4−ヒドロキシ−2,2,6,6−テトラメチル−1−ピペリジンエタノールの重縮合物、オレフィン(C20−C24)・無水マレイン酸・4−アミノ−2,2,6,6−テトラメチルピペリジン共重合物、ジブチルアミン・1,3,5−トリアジン・N,N'−ビス(2,2,6,6−テトラメチル−4−ピペリジル−1,6−ヘキサメチレンジアミンとN−(2,2,6,6−テトラメチル−4−ピペリジル)ブチルアミンの重縮合物、ポリ[{6−(1,1,3,3−テトラメチルブチル)アミノ−1,3,5−トリアジン−2,4−ジイル}{2,2,6,6−テトラメチル−4−ピペリジル)イミノ}ヘキサメチレン{2,2,6,6−テトラメチル−4−ピペリジル)イミノ}]、ビス(2,2,6,6−テトラメチル−4−ピペリジル)セバケート、N,N'−ビス(2,2,6,6−テトラメチル−4−ピペリジル)−N,N'−ジホルミルヘキサメチレンジアミン、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)[[3,5−ビス(1,1−ジメチルエチル)−4−ヒドリキシフェニル]メチル]ブチルマロネート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)セバケート、テトラキス(2,2,6,6−テトラ−メチル−4−ピペリジル)−1,2,3,4−ブタンテトラカルボキシレート、2,2,4,4−テトラメチル−7−オキサ−3,20−ジアザ−ジスピロ−[5.1.11.2]−ヘネイコサン−21−オン、2,2,4,4−テトラメチル−21−オキソ−7−オキサ−3.20−ジアザジスピロ−ヘネイコサン−20−プロパン酸ドデシルエステル/テトラデシルエステル、2,2,4,4−テトラメチル−7−オキサ−3,20−ジアザ−20(2,3−エポキシ−プロピル)ジスピロ−[5.1.11.2]−ヘネイコサン−オン等がある。ヒンダードアミン系光安定剤の添加量は、熱可塑性樹脂組成物(C)100質量部に対して、5質量部未満であることが好ましい。 A hindered amine-based light stabilizer (HALS) can also be used in combination with the resin composition for a polarizer protective film as long as the effects of the present invention are not impaired. The hindered amine-based light stabilizer is a light stabilizer having a tetramethylpiperidine skeleton as a basic skeleton. It is thought that radicals such as polymer radicals and polyoxy radicals generated by photodegradation are captured and the progress of deterioration due to the radical chain reaction is stopped. Hindered amine-based photostabilizers include, for example, a polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, olefin (C20-C24), maleic anhydride, and 4-amino. -2,2,6,6-tetramethylpiperidine copolymer, dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1) , 6-Hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino -1,3,5-triazin-2,4-diyl} {2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl ) Imino}], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N '-Diformylhexamethylenediamine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydrideiphenyl] methyl] Butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetra-methyl-4-piperidyl) -1,2,3,4 -Butanetetracarboxylate, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro- [5.1.1.2] -Heneicosan-21-one, 2,2,4 , 4-Tetramethyl-21-oxo-7-oxa-3.20-diazadispiro-heneicosan-20-propanoic acid dodecyl ester / tetradecyl ester, 2,2,4,4-tetramethyl-7-oxa-3, There are 20-diaza-20 (2,3-epoxy-propyl) dispiro- [5.1.1.2] -heneicosan-on and the like. The amount of the hindered amine-based light stabilizer added is preferably less than 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition (C).
偏光子保護フィルム用樹脂組成物には、本発明の効果を阻害しない範囲でヒンダードフェノール系化合物、ラクトン系化合物、リン系化合物、イオウ系化合物などの耐熱安定剤、滑剤や可塑剤、着色剤、帯電防止剤、鉱油等の添加剤を配合してもよい。 Resin compositions for protector protective films include heat-resistant stabilizers such as hindered phenol-based compounds, lactone-based compounds, phosphorus-based compounds, and sulfur-based compounds, lubricants, plasticizers, and colorants as long as the effects of the present invention are not impaired. , Antistatic agent, mineral oil and other additives may be blended.
偏光子保護フィルムとは、例えばスマートフォンやタブレット端末、テレビ、パソコン、カーナビ等の液晶セルの両側に設けられた2枚の偏光板の中に使用されている偏光子フィルムを保護するフィルムのことである。偏光子フィルムは、ヨウ素で染色したPVA(ポリビニルアルコール)製フィルムを一軸延伸加工することによって偏光特性を持たせているが、紫外線や熱、大気中の水分による影響を受け易く、また薄く強度が弱い為、両面から偏光子保護フィルムで挟むことによって支持されている。 The polarizing element protective film is a film that protects the polarizing element film used in two polarizing plates provided on both sides of a liquid crystal cell such as a smartphone, a tablet terminal, a television, a personal computer, or a car navigation system. be. The polarizer film has polarization characteristics by uniaxially stretching a PVA (polyvinyl alcohol) film dyed with iodine, but it is easily affected by ultraviolet rays, heat, and moisture in the atmosphere, and is thin and strong. Since it is weak, it is supported by sandwiching it with a polarizing element protective film from both sides.
偏光子保護フィルム用樹脂組成物は、寸法安定性、紫外線カット性能、透明性、外観に優れている為、偏光子保護フィルムに好適に使用することが出来る。 Since the resin composition for a polarizer protective film is excellent in dimensional stability, ultraviolet ray blocking performance, transparency, and appearance, it can be suitably used for a polarizer protective film.
偏光子保護フィルム用樹脂組成物を用いた偏光子保護フィルムを得る方法については、特に限定はなく、溶融押出フィルム成形法や溶液流涎成形法などの公知の成形加工法を用いることが出来る。 The method for obtaining the polarizer protective film using the resin composition for the polarizer protective film is not particularly limited, and a known molding processing method such as a melt extrusion film molding method or a solution salivation molding method can be used.
以下、本発明をさらに詳しく説明するため実施例を挙げる。しかし、本発明はこれら実施例等になんら限定されるものではない。 Hereinafter, examples will be given to explain the present invention in more detail. However, the present invention is not limited to these examples and the like.
<スチレン系共重合体(A−1)の製造例>
マレイン酸無水物が20質量%濃度となるようにメチルイソブチルケトンに溶解させた20%マレイン酸無水物溶液と、t−ブチルパーオキシ−2−エチルヘキサノエートが2質量%となるようにメチルイソブチルケトンに希釈した2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液とを事前に調整し、重合に使用した。撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液2.6kg、スチレン26kg、メチルメタクレリレート11.4kg、t−ドデシルメルカプタン32g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて87℃まで昇温した。昇温後87℃を保持しながら、20%マレイン酸無水物溶液を1.5kg/時、および2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液を375g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液の分添を停止し、t−ブチルパーオキシイソプロピルモノカーボネートを30g添加した。20%マレイン酸無水物溶液は、そのまま1.5kg/時の分添速度を維持しながら、8.25℃/時の昇温速度で4時間かけて120℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で18kgになった時点で停止した。昇温後、1時間120℃を保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系共重合体(A−1)を得た。得られたスチレン系共重合体(A−1)の各種測定結果を表1に示す。<Production example of styrene-based copolymer (A-1)>
A 20% maleic acid anhydride solution dissolved in methyl isobutyl ketone so that the maleic acid anhydride has a concentration of 20% by mass, and methyl so that t-butylperoxy-2-ethylhexanoate has a concentration of 2% by mass. A 2% t-butylperoxy-2-ethylhexanoate solution diluted with isobutyl ketone was prepared in advance and used for polymerization. In a 120 liter autoclave equipped with a stirrer, 2.6 kg of a 20% maleic anhydride solution, 26 kg of styrene, 11.4 kg of methyl metaclerylate, 32 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone were charged, and the gas phase part was charged. Was replaced with nitrogen gas, and then the temperature was raised to 87 ° C. over 40 minutes with stirring. A 20% maleic anhydride solution at 1.5 kg / hour and a 2% t-butylperoxy-2-ethylhexanoate solution at 375 g / hour, respectively, while maintaining 87 ° C. after the temperature rise. The addition was continued over 8 hours continuously. Then, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 30 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 120 ° C. over 4 hours at a heating rate of 8.25 ° C./hour while maintaining the addition rate of 1.5 kg / hour as it was. The addition of the 20% maleic anhydride solution was stopped when the total amount of addition reached 18 kg. After the temperature was raised, the temperature was maintained at 120 ° C. for 1 hour to complete the polymerization. The polymer solution is continuously fed to a twin-screw devolatilization extruder using a gear pump, and methyl isobutyl ketone and a trace amount of unreacted monomer are devolatilized and extruded into strands to be extruded and cut to form pellet-shaped styrene. A system copolymer (A-1) was obtained. Table 1 shows various measurement results of the obtained styrene-based copolymer (A-1).
<スチレン系共重合体(A−2)の製造例>
20%マレイン酸無水物溶液と2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液は、実施例1と同様に調整した。撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液3.7kg、スチレン29kg、メチルメタクレリレート4kg、t−ドデシルメルカプタン35gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて90℃まで昇温した。昇温後90℃を保持しながら、20%マレイン酸無水物溶液を2.7kg/時、および2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液を500g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液の分添を停止し、t−ブチルパーオキシイソプロピルモノカーボネートを38g添加した。20%マレイン酸無水物溶液はそのまま2.7kg/時の分添速度を維持しながら、10℃/時の昇温速度で4時間かけて130℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で32.5kgになった時点で停止した。昇温後、1時間130℃を保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系共重合体(A−2)を得た。得られたスチレン系共重合体(A−2)の各種測定結果を表1に示す。<Production example of styrene-based copolymer (A-2)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as in Example 1. In a 120 liter autoclave equipped with a stirrer, 3.7 kg of a 20% maleic anhydride solution, 29 kg of styrene, 4 kg of methylmethacrylylate, and 35 g of t-dodecyl mercaptan were charged, and the gas phase part was replaced with nitrogen gas. The temperature was raised to 90 ° C. over 40 minutes with stirring. A 20% maleic anhydride solution at 2.7 kg / hour and a 2% t-butylperoxy-2-ethylhexanoate solution at 500 g / hour, respectively, while maintaining 90 ° C. after the temperature rise. The addition was continued over 8 hours continuously. Then, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 38 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 130 ° C. over 4 hours at a heating rate of 10 ° C./hour while maintaining the addition rate of 2.7 kg / hour. The addition of the 20% maleic anhydride solution was stopped when the total amount of the addition reached 32.5 kg. After the temperature was raised, the temperature was maintained at 130 ° C. for 1 hour to complete the polymerization. The polymer solution is continuously fed to a twin-screw devolatilization extruder using a gear pump, and methyl isobutyl ketone and a trace amount of unreacted monomer are devolatilized and extruded into strands to be extruded and cut to form pellet-shaped styrene. A system copolymer (A-2) was obtained. Table 1 shows various measurement results of the obtained styrene-based copolymer (A-2).
<スチレン系共重合体(A−3)の製造例>
20%マレイン酸無水物溶液と2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液は、実施例1と同様に調整した。撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液3.8kg、スチレン34.2kg、メチルメタクレリレート1.6kg、t−ドデシルメルカプタン33g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて90℃まで昇温した。昇温後90℃を保持しながら、20%マレイン酸無水物溶液を0.95kg/時、メチルメタクリレートを53g/時、および2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液を333g/時の分添速度で各々連続的に12時間かけて添加し続けた。その後、2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液の分添を停止し、t−ブチルパーオキシイソプロピルモノカーボネートを40g添加した。20%マレイン酸無水物溶液0.95kg/時、およびメチルメタクリレート53g/時の分添速度を維持しながら、5℃/時の昇温速度で7時間かけて125℃まで昇温した。20%マレイン酸無水物溶液の分添は積算で18kg、メチルメタクリレートの分添は積算で1kgになった時点で各々の分添を停止した。昇温後、1時間125℃を保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系共重合体(A−3)を得た。得られたスチレン系共重合体(A−3)の各種測定結果を表1に示す。<Production example of styrene-based copolymer (A-3)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as in Example 1. In a 120 liter autoclave equipped with a stirrer, 3.8 kg of a 20% maleic anhydride solution, 34.2 kg of styrene, 1.6 kg of methyl metaclerylate, 33 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone were charged and gas was charged. After replacing the phase part with nitrogen gas, the temperature was raised to 90 ° C. over 40 minutes with stirring. 333 g / hour of 20% maleic anhydride solution, 53 g / hour of methyl methacrylate, and 333 g / hour of 2% t-butylperoxy-2-ethylhexanoate solution while maintaining 90 ° C. after heating. The addition was continued for 12 hours each continuously at the hourly rate. Then, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The temperature was raised to 125 ° C. over 7 hours at a heating rate of 5 ° C./hour while maintaining the addition rate of 0.95 kg / hour of a 20% maleic anhydride solution and 53 g / hour of methyl methacrylate. When the total amount of the 20% maleic anhydride solution was 18 kg and the total amount of methyl methacrylate was 1 kg, the respective additions were stopped. After the temperature was raised, the temperature was maintained at 125 ° C. for 1 hour to complete the polymerization. The polymer solution is continuously fed to a twin-screw devolatilization extruder using a gear pump, and methyl isobutyl ketone and a trace amount of unreacted monomer are devolatilized and extruded into strands to be extruded and cut to form pellet-shaped styrene. A system copolymer (A-3) was obtained. Table 1 shows various measurement results of the obtained styrene-based copolymer (A-3).
<スチレン系共重合体(A−4)の製造例>
20%マレイン酸無水物溶液と2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液は、実施例1と同様に調整した。撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液3.6kg、スチレン14kg、メチルメタクレリレート17.7kg、t−ドデシルメルカプタン29gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて85℃まで昇温した。昇温後85℃を保持しながら、20%マレイン酸無水物溶液を2.0kg/時、スチレンを500g/時、および2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液を600g/時の分添速度で各々連続的に6時間かけて添加し続けた。その後、2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液の分添を停止し、t−ブチルパーオキシイソプロピルモノカーボネートを30g添加した。20%マレイン酸無水物溶液2.0kg/時、およびスチレン500g/時の分添速度を維持しながら、10℃/時の昇温速度で3時間かけて115℃まで昇温した。20%マレイン酸無水物溶液の分添は積算で18kg、スチレンの分添は積算で4.5kgになった時点で各々の分添を停止した。昇温後、1時間115℃を保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系共重合体(A−4)を得た。得られたスチレン系共重合体(A−4)の各種測定結果を表1に示す。<Production example of styrene-based copolymer (A-4)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as in Example 1. In a 120 liter autoclave equipped with a stirrer, 3.6 kg of 20% maleic anhydride solution, 14 kg of styrene, 17.7 kg of methylmethacrylylate, and 29 g of t-dodecyl mercaptan were charged, and the gas phase part was replaced with nitrogen gas. After that, the temperature was raised to 85 ° C. over 40 minutes with stirring. 2.0 kg / hour of 20% maleic anhydride solution, 500 g / hour of styrene, and 600 g / hour of 2% t-butylperoxy-2-ethylhexanoate solution while maintaining 85 ° C. after heating. The addition was continued for 6 hours continuously at the addition rate of. Then, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 30 g of t-butylperoxyisopropyl monocarbonate was added. The temperature was raised to 115 ° C. over 3 hours at a heating rate of 10 ° C./hour while maintaining the addition rate of 2.0 kg / hour of a 20% maleic anhydride solution and 500 g / hour of styrene. When the total amount of the 20% maleic anhydride solution was 18 kg and the total amount of styrene was 4.5 kg, the respective additions were stopped. After the temperature was raised, the temperature was maintained at 115 ° C. for 1 hour to complete the polymerization. The polymer solution is continuously fed to a twin-screw devolatilization extruder using a gear pump, and methyl isobutyl ketone and a trace amount of unreacted monomer are devolatilized and extruded into strands to be extruded and cut to form pellet-shaped styrene. A system copolymer (A-4) was obtained. Table 1 shows various measurement results of the obtained styrene-based copolymer (A-4).
<スチレン系共重合体(A−5)の製造例>
20%マレイン酸無水物溶液と2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液は、実施例1と同様に調整した。撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液2.3kg、スチレン25.2kg、メチルメタクレリレート11.4kg、t−ドデシルメルカプタン40g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて87℃まで昇温した。昇温後87℃を保持しながら、20%マレイン酸無水物溶液を1.5kg/時、および2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液を375g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液の分添を停止し、t−ブチルパーオキシイソプロピルモノカーボネートを30g添加した。20%マレイン酸無水物溶液は、そのまま1.5kg/時の分添速度を維持しながら、8.25℃/時の昇温速度で4時間かけて120℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で18kgになった時点で停止した。昇温後、1時間120℃を保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系共重合体(A−5)を得た。得られたスチレン系共重合体(A−5)の各種測定結果を表1に示す。<Production example of styrene-based copolymer (A-5)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as in Example 1. In a 120 liter autoclave equipped with a stirrer, 2.3 kg of a 20% maleic anhydride solution, 25.2 kg of styrene, 11.4 kg of methyl metaclerylate, 40 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone were charged and gas was charged. After replacing the phase part with nitrogen gas, the temperature was raised to 87 ° C. over 40 minutes with stirring. A 20% maleic anhydride solution at 1.5 kg / hour and a 2% t-butylperoxy-2-ethylhexanoate solution at 375 g / hour, respectively, while maintaining 87 ° C. after the temperature rise. The addition was continued over 8 hours continuously. Then, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 30 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 120 ° C. over 4 hours at a heating rate of 8.25 ° C./hour while maintaining the addition rate of 1.5 kg / hour as it was. The addition of the 20% maleic anhydride solution was stopped when the total amount of addition reached 18 kg. After the temperature was raised, the temperature was maintained at 120 ° C. for 1 hour to complete the polymerization. The polymer solution is continuously fed to a twin-screw devolatilization extruder using a gear pump, and methyl isobutyl ketone and a trace amount of unreacted monomer are devolatilized and extruded into strands to be extruded and cut to form pellet-shaped styrene. A system copolymer (A-5) was obtained. Table 1 shows various measurement results of the obtained styrene-based copolymer (A-5).
<スチレン系共重合体(A−6)の製造例>
20%マレイン酸無水物溶液と2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液は、実施例1と同様に調整した。撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液4kg、スチレン23.1kg、メチルメタクレリレート8.8kg、t−ドデシルメルカプタン28gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて90℃まで昇温した。昇温後90℃を保持しながら、20%マレイン酸無水物溶液を2.9kg/時、および2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液を500g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液の分添を停止し、t−ブチルパーオキシイソプロピルモノカーボネートを40g添加した。20%マレイン酸無水物溶液はそのまま2.9kg/時の分添速度を維持しながら、10℃/時の昇温速度で4時間かけて130℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で34.8kgになった時点で停止した。昇温後、1時間130℃を保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系共重合体(A−6)を得た。得られたスチレン系共重合体(A−6)の各種測定結果を表1に示す。<Production example of styrene-based copolymer (A-6)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as in Example 1. In a 120 liter autoclave equipped with a stirrer, 4 kg of 20% maleic anhydride solution, 23.1 kg of styrene, 8.8 kg of methylmethacrylylate, and 28 g of t-dodecyl mercaptan were charged, and the gas phase part was replaced with nitrogen gas. After that, the temperature was raised to 90 ° C. over 40 minutes with stirring. A 20% maleic anhydride solution was added at a rate of 2.9 kg / hour and a 2% t-butylperoxy-2-ethylhexanoate solution was applied at a rate of 500 g / hour while maintaining 90 ° C. after the temperature was raised. The addition was continued over 8 hours continuously. Then, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 130 ° C. over 4 hours at a heating rate of 10 ° C./hour while maintaining the addition rate of 2.9 kg / hour. The addition of the 20% maleic anhydride solution was stopped when the total amount of the addition reached 34.8 kg. After the temperature was raised, the temperature was maintained at 130 ° C. for 1 hour to complete the polymerization. The polymer solution is continuously fed to a twin-screw devolatilization extruder using a gear pump, and methyl isobutyl ketone and a trace amount of unreacted monomer are devolatilized and extruded into strands to be extruded and cut to form pellet-shaped styrene. A system copolymer (A-6) was obtained. Table 1 shows various measurement results of the obtained styrene-based copolymer (A-6).
メタクリル樹脂(B)は、三菱レイヨン社製「アクリペット VH5 000」(ビカット軟化温度107℃、MFR:5.5g/10min)を使用した。 As the methacrylic resin (B), "Acrypet VH5000" (Vicat softening temperature 107 ° C., MFR: 5.5 g / 10 min) manufactured by Mitsubishi Rayon Co., Ltd. was used.
紫外線吸収剤(D−1)は、BASF社製「ベンゾトリアゾール系紫外線吸収剤 Tinuvin326」(吸光度0.28、分子量316g/mol)を使用した。 As the ultraviolet absorber (D-1), "benzotriazole-based ultraviolet absorber Tinuvin 326" (absorbance 0.28, molecular weight 316 g / mol) manufactured by BASF was used.
紫外線吸収剤(D−2)は、シプロ化成社製「ベンゾフェノン系紫外線吸収剤 SEESORB106」(吸光度0.15、分子量246g/mol)を使用した。 As the ultraviolet absorber (D-2), "benzophenone-based ultraviolet absorber SEESORB106" (absorbance 0.15, molecular weight 246 g / mol) manufactured by Cipro Kasei Co., Ltd. was used.
紫外線吸収剤(D−3)は、BASF社製「ベンゾトリアゾール系紫外線吸収剤 Tinuvin234」(吸光度0.09、分子量448g/mol)を使用した。 As the ultraviolet absorber (D-3), "benzotriazole-based ultraviolet absorber Tinuvin234" (absorbance 0.09, molecular weight 448 g / mol) manufactured by BASF was used.
紫外線吸収剤(D−4)は、シプロ化成社製「ベンゾフェノン系紫外線吸収剤 SEESORB102」(吸光度0.01、分子量326g/mol)を使用した。 As the ultraviolet absorber (D-4), "benzophenone-based ultraviolet absorber SEESORB102" (absorbance 0.01, molecular weight 326 g / mol) manufactured by Cipro Kasei Co., Ltd. was used.
表1中の各種評価項目の測定条件は、以下の通りである。
(組成分析)
組成分析は、C−13NMR核磁気共鳴装置を用いて、下記記載の測定条件で実施した。
装置名:JNM−ECXシリーズFT−NMR(JEOL社製)
溶媒:重水素化クロロホルム
濃度:14質量%
温度:27℃
積算回数:8000回The measurement conditions for various evaluation items in Table 1 are as follows.
(Composition analysis)
The composition analysis was carried out using a C-13 NMR nuclear magnetic resonance apparatus under the measurement conditions described below.
Device name: JNM-ECX series FT-NMR (manufactured by JEOL)
Solvent: Deuterated chloroform Concentration: 14% by mass
Temperature: 27 ° C
Accumulation number: 8000 times
(重量平均分子量)
重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー(GPC)にて測定されるポリスチレン換算の値であり、下記記載の測定条件にて実施した。
装置名:SYSTEM−21 Shodex(昭和電工社製)
カラム:PL gel MIXED−Bを3本直列
温度:40℃
検出:示差屈折率
溶媒:テトラヒドロフラン
濃度:2質量%
検量線:標準ポリスチレン(PS)(PL社製)を用いて作製した。(Weight average molecular weight)
The weight average molecular weight (Mw) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and was carried out under the measurement conditions described below.
Device name: SYSTEM-21 Shodex (manufactured by Showa Denko KK)
Column: 3 PL gel MIXED-B in series Temperature: 40 ° C
Detection: Differential Refractometer Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Made using standard polystyrene (PS) (manufactured by PL).
(2mm厚みの鏡面プレートの全光線透過率)
2mm厚みの鏡面プレートの全光線透過率は、射出成形機(東芝機械社製IS−50EPN)を用いて、シリンダー温度230℃、金型温度40℃の成形条件で成形された縦90mm、横55mm、厚み2mmの鏡面プレートを、ASTM D1003に準拠し、ヘーズメーター(日本電色工業社製NDH−1001DP型)を用いて測定した。全光線透過率88%以上を合格とした。(Total light transmittance of 2 mm thick mirror plate)
The total light transmittance of the 2 mm thick mirror plate is 90 mm in length and 55 mm in width, which is molded using an injection molding machine (IS-50EPN manufactured by Toshiba Machine Co., Ltd.) under molding conditions of a cylinder temperature of 230 ° C and a mold temperature of 40 ° C. A mirror plate having a thickness of 2 mm was measured using a haze meter (NDH-1001DP type manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with ASTM D1003. A total light transmittance of 88% or more was regarded as acceptable.
(波長200〜270nmの光線透過率)
波長200〜270nmの光線透過率は、単軸押出機(東芝機械社製SE−65CA)を用いて、シリンダー温度260℃、Tダイ温度60℃の加工条件で作製した厚み60μmのフィルムを分光光度計(日本分光社製V−670)を用いて測定し、波長200nm〜270nmにおける光線透過率の平均値として算出した。波長200〜270nmの光線透過率5%以下を合格とした。(Light transmittance at wavelengths of 200 to 270 nm)
For the light transmittance at a wavelength of 200 to 270 nm, a film having a thickness of 60 μm produced under processing conditions of a cylinder temperature of 260 ° C. and a T-die temperature of 60 ° C. using a single-screw extruder (SE-65CA manufactured by Toshiba Machinery Co., Ltd.) is subjected to spectrophotometric intensity. It was measured using a meter (V-670 manufactured by JASCO Corporation) and calculated as the average value of the light transmittance at a wavelength of 200 nm to 270 nm. A light transmittance of 5% or less at a wavelength of 200 to 270 nm was regarded as acceptable.
(ビカット軟化温度)
ビカット軟化温度は、JIS K7206に準拠し荷重50N、昇温速度50℃/時間の条件で測定した。ビカット軟化温度115℃以上を合格とした。(Vicat softening temperature)
The Vicat softening temperature was measured according to JIS K7206 under the conditions of a load of 50 N and a heating rate of 50 ° C./hour. A Vicat softening temperature of 115 ° C. or higher was accepted.
(飽和吸水率)
飽和吸水率は、JIS K7209に準拠し温度23℃の水中に浸漬させた条件で測定した。飽和吸水率1.0%以下を合格とした。(Saturated water absorption rate)
The saturated water absorption rate was measured under the condition of being immersed in water at a temperature of 23 ° C. in accordance with JIS K7209. A saturated water absorption rate of 1.0% or less was regarded as acceptable.
<実施例・比較例>
前記製造例で記したスチレン系共重合体(A−1〜6)とメタクリル樹脂(B)、紫外線吸収剤(D−1〜4)を表2〜3で示した割合で混合した後、二軸押出機(東芝機械社製TEM−35B)にて、シリンダー温度230℃で溶融混練し樹脂組成物を得た。この樹脂組成物を単軸押出機(東芝機械社製SE−65CA)を用いて、シリンダー温度260℃、Tダイ温度60℃の加工条件にて、厚み60μmのフィルムを作製した。各種評価結果を表2〜3に示す。<Examples / Comparative Examples>
After mixing the styrene-based copolymer (A-1 to 6) described in the above production example, the methacrylic resin (B), and the ultraviolet absorber (D-1 to 4) at the ratios shown in Tables 2 to 3, two A resin composition was obtained by melt-kneading at a cylinder temperature of 230 ° C. using a shaft extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.). This resin composition was used in a single-screw extruder (SE-65CA manufactured by Toshiba Machine Co., Ltd.) to prepare a film having a thickness of 60 μm under processing conditions of a cylinder temperature of 260 ° C. and a T-die temperature of 60 ° C. The results of various evaluations are shown in Tables 2 and 3.
表2〜表3中の各種評価項目の測定条件は、以下の通りである。
(反り量)
反り量は、単軸押出機(東芝機械社製SE−65CA)を用いて、シリンダー温度260℃、Tダイ温度60℃の加工条件で作製した厚み60μmのフィルムを縦90mm、横90mmに切削後、環境試験機(エスペック社製PL−3KPH)にて温度85℃、湿度85%の条件下で72時間静置させた。その後、平坦なガラス基板上に試験後のフィルムを下に凸となる様に置き、フィルムの各頂点4箇所とガラス基板面との隙間、およびフィルム各辺の中央部(各辺を2等分する位置)4箇所とガラス基板面との隙間を計測し(計8箇所計測)、その平均値を反り量とした。反り量2mm以下を合格とした。The measurement conditions of various evaluation items in Tables 2 and 3 are as follows.
(Amount of warpage)
The amount of warpage is determined by cutting a film with a thickness of 60 μm produced under processing conditions of a cylinder temperature of 260 ° C. and a T-die temperature of 60 ° C. to 90 mm in length and 90 mm in width using a single-screw extruder (SE-65CA manufactured by Toshiba Machine Co., Ltd.). , It was allowed to stand for 72 hours under the conditions of a temperature of 85 ° C. and a humidity of 85% with an environmental tester (PL-3KPH manufactured by Espec). After that, the tested film is placed on a flat glass substrate so as to be convex downward, and the gap between each of the four vertices of the film and the glass substrate surface and the central portion of each side of the film (each side is divided into two equal parts). The gaps between the four locations and the glass substrate surface were measured (a total of eight locations were measured), and the average value was taken as the amount of warpage. A warp amount of 2 mm or less was regarded as acceptable.
(波長200〜270nmの光線透過率)
波長200〜270nmの光線透過率は、単軸押出機(東芝機械社製SE−65CA)を用いて、シリンダー温度260℃、Tダイ温度60℃の加工条件で作製した厚み60μmのフィルムを分光光度計(日本分光社製V−670)を用いて測定し、波長200nm〜270nmにおける光線透過率の平均値として算出した。波長200〜270nmの光線透過率5%以下を合格とした。(Light transmittance at wavelengths of 200 to 270 nm)
For the light transmittance at a wavelength of 200 to 270 nm, a film having a thickness of 60 μm produced under processing conditions of a cylinder temperature of 260 ° C. and a T-die temperature of 60 ° C. using a single-screw extruder (SE-65CA manufactured by Toshiba Machinery Co., Ltd.) is subjected to spectrophotometric intensity. It was measured using a meter (V-670 manufactured by JASCO Corporation) and calculated as the average value of the light transmittance at a wavelength of 200 nm to 270 nm. A light transmittance of 5% or less at a wavelength of 200 to 270 nm was regarded as acceptable.
(波長380nmの光線透過率)
波長380nmの光線透過率は、単軸押出機(東芝機械社製SE−65CA)を用いて、シリンダー温度260℃、Tダイ温度60℃の加工条件で作製した厚み60μmのフィルムを分光光度計(日本分光社製V−670)を用いて測定した。波長380nmの光線透過率10%以下を合格とした。(Light transmittance at wavelength of 380 nm)
For the light transmittance at a wavelength of 380 nm, a spectrophotometer (SE-65CA manufactured by Toshiba Machinery Co., Ltd.) was used to obtain a film having a thickness of 60 μm prepared under processing conditions of a cylinder temperature of 260 ° C. and a T-die temperature of 60 ° C. It was measured using V-670) manufactured by JASCO Corporation. A light transmittance of 10% or less at a wavelength of 380 nm was regarded as acceptable.
(全光線透過率、HAZE)
全光線透過率とHAZEは、単軸押出機(東芝機械社製SE−65CA)を用いて、シリンダー温度260℃、Tダイ温度60℃の加工条件で作製した厚み60μmのフィルムをASTM D1003に準拠し、ヘーズメーター(日本電色工業社製NDH−1001DP型)を用いて測定した。全光線透過率88%以上、HAZE3.0%以下を合格とした。(Total light transmittance, HAZE)
The total light transmittance and HAZE are based on ASTM D1003, which is a film with a thickness of 60 μm prepared by using a single-screw extruder (SE-65CA manufactured by Toshiba Machine Co., Ltd.) under processing conditions of a cylinder temperature of 260 ° C. and a T-die temperature of 60 ° C. Then, the measurement was performed using a haze meter (NDH-1001DP type manufactured by Nippon Denshoku Kogyo Co., Ltd.). A total light transmittance of 88% or more and a HAZE of 3.0% or less were accepted.
(外観)
外観は、単軸押出機(東芝機械社製SE−65CA)を用いて、シリンダー温度260℃、Tダイ温度60℃の加工条件で作製した厚み60μmのフィルムを縦90mm、横90mmに切削したサンプル50個を目視にて観察し、着色、気泡、焼けコンタミ、ブツなどの外観不良が発生したサンプル数を数えることによって、外観評価を行った。評価基準は以下の通りで、◎と○を合格とした。
◎:外観不良のサンプル数が0個
○:外観不良のサンプル数が1〜2個
△:外観不良のサンプル数が2〜5個
×:外観不良のサンプル数が6個以上(exterior)
The appearance is a sample obtained by cutting a 60 μm-thick film produced under the processing conditions of a cylinder temperature of 260 ° C. and a T-die temperature of 60 ° C. into a length of 90 mm and a width of 90 mm using a single-screw extruder (SE-65CA manufactured by Toshiba Machine Co., Ltd.). The appearance was evaluated by visually observing 50 pieces and counting the number of samples in which appearance defects such as coloring, air bubbles, burnt contamination, and lumps occurred. The evaluation criteria are as follows, and ◎ and ○ were accepted.
⊚: Number of samples with poor appearance is 0 ○: Number of samples with poor appearance is 1 to 2 Δ: Number of samples with poor appearance is 2 to 5 ×: Number of samples with poor appearance is 6 or more
実施例は、寸法安定性、紫外線カット性能、透明性、外観に優れたフィルムを得ることが出来た。一方、比較例では、寸法安定性、紫外線カット性能、透明性、外観のいずれかの物性が劣るものであった。 In the examples, a film having excellent dimensional stability, ultraviolet ray blocking performance, transparency, and appearance could be obtained. On the other hand, in the comparative example, any of dimensional stability, ultraviolet ray blocking performance, transparency, and appearance was inferior.
本発明の樹脂組成物を用いることで、寸法安定性、紫外線カット性能、透明性、外観に優れた偏光子保護フィルムを提供することが出来る。
By using the resin composition of the present invention, it is possible to provide a polarizer protective film having excellent dimensional stability, ultraviolet ray blocking performance, transparency, and appearance.
Claims (3)
スチレン系共重合体(A)が、スチレン単量体単位45〜69.9質量%、メチルメタクレリレート単量体単位5〜9.9質量%、マレイン酸無水物単量体単位20.2〜30質量%からなり、スチレン系共重合体(A)は、JIS K7206に準拠して求めたビカット軟化温度が115℃以上であり、
スチレン系共重合体(A)は、波長200〜270nmの光線透過率が5%以下であり、
紫外線吸収剤(D)は、JIS K0115に準拠して測定した波長380nmの吸光度が0.15以上であり、
波長380nmの光線透過率が1%以下である、偏光子保護フィルム用樹脂組成物。 UV absorber (D) 2-8 with respect to 100 parts by mass of the thermoplastic resin composition (C) consisting of 75 to 100% by mass of the styrene copolymer (A) and 0 to 25% by mass of the methacrylic resin (B). Contains parts by mass,
The styrene-based copolymer (A) contains 45 to 69.9% by mass of a styrene monomer unit, 5 to 9.9% by mass of a methylmethacrylylate monomer unit, and 20.2 % by weight of a maleic anhydride monomer. The styrene-based copolymer (A) is composed of about 30% by mass, and the Vicat softening temperature determined in accordance with JIS K7206 is 115 ° C. or higher.
The styrene-based copolymer (A) has a light transmittance of 5% or less at a wavelength of 200 to 270 nm.
The ultraviolet absorber (D) has an absorbance of 0.15 or more at a wavelength of 380 nm measured in accordance with JIS K0115.
Wavelength 380nm of light transmittance is Ru der than 1%, a polarizer protective film for the resin composition.
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