JP2008150484A - Composition for hard coat - Google Patents

Composition for hard coat Download PDF

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JP2008150484A
JP2008150484A JP2006339455A JP2006339455A JP2008150484A JP 2008150484 A JP2008150484 A JP 2008150484A JP 2006339455 A JP2006339455 A JP 2006339455A JP 2006339455 A JP2006339455 A JP 2006339455A JP 2008150484 A JP2008150484 A JP 2008150484A
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hard coat
parts
weight
film
colloidal silica
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Toshiyuki Otaki
俊之 大滝
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Momentive Performance Materials Japan LLC
Momentive Performance Materials Inc
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Momentive Performance Materials Japan LLC
Momentive Performance Materials Inc
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/046Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08Cellulose derivatives
    • C08J2301/10Esters of organic acids
    • C08J2301/12Cellulose acetate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00Characterised by the use 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; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard coat having excellent surface hardness, not generating a crack at curing and not causing a problem such as warpage and curl of a film relative to a plastic film. <P>SOLUTION: The composition for hard coat contains (A) hexa-functional urethaneacrylate: 20-70 pts.wt., (B) tetra-functional or more of (meth)acrylic monomer: 15-60 pts.wt., (C) colloidal silica surface-treated by a silane coupling agent having a reactive (meth)acrylate group in the molecule: 10-40 pts.wt., (D) a photopolymerization initiator, and (E) a dilution solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、フラットパネルディスプレイ等の光学用フィルム、さらにはポリカーボネート、アクリルに代表される透明プラスチック基材の表面保護コーティングに関する。   The present invention relates to an optical film such as a flat panel display, and further to a surface protective coating on a transparent plastic substrate represented by polycarbonate and acrylic.

コンパクトディスク、光磁気ディスク等をはじめとする光ディスクは、ポリカーボネートやポリメタクリレート等の透明性基板が使用されており、特に加工性、取扱い性、価格の面で優れているポリカーボネートが用いられている。しかしながら、軽量、耐衝撃性に優れるなどの長所を持つ反面、硬度や耐擦傷性が不十分で容易に傷がつきやすく、特に読み取り面に生じたスクラッチ傷や擦り傷の影響で情報の読み取りができなくなるという不具合があった。またDVDおよびブルーレイ、HDDVDに代表される次世代DVDにおいては、単位面積あたりの記録情報量が増加するに従い、読み取り面の微細な傷がさらに容易に読み取り不良に直結することになるために、ポリカーボネートのようなプラスチック透明保護基材上にさらにハードコート層を設けることが必要とされている。このようなハードコート剤の硬化皮膜に要求される性能として、充分な表面硬度、耐磨耗性、耐擦傷性、透明性等が挙げられる。このような要求に応えるべく、特許文献1では、特定のシランカップリング剤で処理されたコロイダルシリカを含有するアクリレート系組成物が提案されており、特許文献2〜4でもシリカを含有する特定組成のアクリレート系組成物が提案されている。   For optical disks such as compact disks and magneto-optical disks, transparent substrates such as polycarbonate and polymethacrylate are used, and in particular, polycarbonate which is excellent in terms of workability, handleability and cost is used. However, it has advantages such as light weight and excellent impact resistance, but it has insufficient hardness and scratch resistance and is easily scratched. In particular, it can read information due to scratches and scratches on the reading surface. There was a problem of disappearing. In next-generation DVDs such as DVD, Blu-ray, and HDDVD, polycarbonate increases because the amount of recorded information per unit area increases, and fine scratches on the reading surface are more easily connected to reading defects. It is necessary to further provide a hard coat layer on the transparent plastic protective base material. As the performance required for such a hard coating film, sufficient surface hardness, abrasion resistance, scratch resistance, transparency and the like can be mentioned. In order to meet such requirements, Patent Document 1 proposes an acrylate-based composition containing colloidal silica treated with a specific silane coupling agent, and Patent Documents 2 to 4 also include a specific composition containing silica. Acrylate compositions have been proposed.

一方、近年、液晶パネル等のフラットパネルディスプレイが各種開発されている。液晶パネルにおいては、偏光板を保護するため、光学特性に優れたトリアセチルセルロース(TAC)が用いられ、またプラズマディスプレイパネルにおいてはポリエチレンテレフタレート(PET)等のプラスチックフィルムの層が形成されている。このようなプラスチックフィルムはガラスに比べ柔らかく、表面に傷が付きやすいため、ハードコート層を設けることが必要である。特に、このような用途に用いられるプラスチックフィルム用のハードコートは、上述した従来のハードコートよりも一層の表面硬度が求められ、更に硬化収縮によるフィルムの反りやクラックを発生させないことが求められる。   On the other hand, in recent years, various flat panel displays such as liquid crystal panels have been developed. In the liquid crystal panel, triacetyl cellulose (TAC) having excellent optical properties is used to protect the polarizing plate, and in the plasma display panel, a plastic film layer such as polyethylene terephthalate (PET) is formed. Since such a plastic film is softer than glass and easily scratched on the surface, it is necessary to provide a hard coat layer. In particular, a hard coat for a plastic film used for such applications is required to have a higher surface hardness than the above-described conventional hard coat, and further, it is required not to cause warping or cracking of the film due to curing shrinkage.

かかるプラスチックフィルム用のハードコートとしては、特許文献5では、コロイダルシリカと、イソシアネート基と重合性不飽和基とを持つイソシアネート化合物等を含むハードコート剤が提案されているが、その表面硬度等は充分なものではなかった。
特開昭57−131214号公報 特開2002−245672号公報 特開2003−338089号公報 特開2006−63244号公報 特開2005−163035号公報
As a hard coat for such a plastic film, Patent Document 5 proposes a hard coat agent containing colloidal silica and an isocyanate compound having an isocyanate group and a polymerizable unsaturated group. It was not enough.
JP-A-57-13214 JP 2002-245672 A JP 2003-338089 A JP 2006-63244 A JP 2005-163035 A

本発明は上記従来技術の問題点を解決し、更に向上した表面硬度を有すると共に、硬化時にクラックが発生せず、プラスチックフィルムに対して反りやフィルムのカール等の問題を引き起こさないハードコートの提供を目的とする。   The present invention provides a hard coat that solves the above-mentioned problems of the prior art, has a further improved surface hardness, does not cause cracks during curing, and does not cause problems such as warping or curling of the plastic film. With the goal.

本発明者は、上記従来技術の問題を解決し、硬さと低硬化収縮を両立させたハードコート剤を提供すべく鋭意検討した結果、6官能ウレタンアクリレートと4官能以上のアクリルモノマー及び特定の表面処理コロイダルシリカを組み合わせることが極めて有効であることを見出し、本発明を完成するに至った。   As a result of diligent research to solve the above-described problems of the prior art and to provide a hard coating agent having both hardness and low curing shrinkage, the present inventors have found that a hexafunctional urethane acrylate, a tetrafunctional or higher acrylic monomer, and a specific surface. It has been found that combining treated colloidal silica is extremely effective, and the present invention has been completed.

即ち本発明は、
(A) 6官能ウレタンアクリレート;20〜70重量部
(B) 4官能以上の(メタ)アクリルモノマー;15〜60重量部
(C) 分子内に反応性(メタ)アクリレート基を有するシランカップリング剤にて表面処理されたコロイダルシリカ;10〜40重量部
(D) 光重合開始剤
(E) 希釈溶媒
を含有するハードコート用組成物である。
That is, the present invention
(A) Hexafunctional urethane acrylate; 20 to 70 parts by weight
(B) Tetrafunctional or higher (meth) acrylic monomer; 15-60 parts by weight
(C) Colloidal silica surface-treated with a silane coupling agent having a reactive (meth) acrylate group in the molecule; 10 to 40 parts by weight
(D) Photopolymerization initiator
(E) A hard coat composition containing a diluting solvent.

以下、本発明を詳細に説明する。本発明で用いる(A) 成分は6官能以上のウレタンアクリレートであり、1分子内に6個以上の反応性アクリレート基を有するウレタン骨格からなる。例えば特許2964267号記載のような形態によって用意でき、また単品もしくはアクリレートモノマーとの混合物として市販されているものを用いることができる。市販されているものの例としては、日本合成化学(株)製ウレタンアクリレート「紫光UV−1700B」、「紫光UV−6300B」、「紫光UV−7640B」、ダイセル・サイテック社製Ebecryl 1290、共栄社化学製「UA−306H」などが挙げられる。これら6官能以上の官能基を有するウレタンアクリレートは、硬度が高く、6官能アクリルモノマーよりも硬化収縮が少ない特徴を有する。   Hereinafter, the present invention will be described in detail. The component (A) used in the present invention is a urethane acrylate having 6 or more functional groups, and is composed of a urethane skeleton having 6 or more reactive acrylate groups in one molecule. For example, it can be prepared in the form described in Japanese Patent No. 2964267, or a commercially available product as a single product or a mixture with an acrylate monomer can be used. Examples of commercially available products include urethane acrylates “purple light UV-1700B”, “purple light UV-6300B”, “purple light UV-7640B” manufactured by Nippon Synthetic Chemical Co., Ltd. "UA-306H" etc. are mentioned. These urethane acrylates having 6 or more functional groups are characterized by high hardness and less cure shrinkage than hexafunctional acrylic monomers.

本発明に用いられる(B) 成分は、4官能以上の多官能性(メタ)アクリレートモノマーであり、従来よりハードコート用アクリル樹脂原料として用いられているジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート等が挙げられる。これらモノマーはハードコートの硬度を落とすことなく、硬化速度の向上、液の低粘度化、組成物の相溶性向上を達成することができる。特にジペンタエリスリトールヘキサアクリレートはそれ単独においては皮膜にクラックが生じるなどの不具合があるが、本系においては硬度の向上に特に有用である。   Component (B) used in the present invention is a tetrafunctional or higher polyfunctional (meth) acrylate monomer, and dipentaerythritol hexaacrylate, pentaerythritol pentaacrylate, which has been conventionally used as an acrylic resin raw material for hard coat, Examples include dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, and dipentaerythritol tetraacrylate. These monomers can achieve an improvement in the curing rate, a reduction in the viscosity of the liquid, and an improvement in the compatibility of the composition without reducing the hardness of the hard coat. In particular, dipentaerythritol hexaacrylate alone has defects such as cracks in the film, but is particularly useful for improving hardness in this system.

本発明に用いる(C) 成分の表面処理シリカとは、分子内に反応性(メタ)アクリレート基を有するシランカップリング剤にて表面処理されたコロイダルシリカであって、特開昭57−131214号公報、特開2000−289172号公報等に記載の周知のものである。本成分によりハードコート組成物の硬度を向上させるとともに、硬化収縮を抑え、かつ硬化時の皮膜のクラック発生を極力抑えることが可能になる。また本成分を添加することにより、上記の多官能性アクリル樹脂の曲げ等に関する機械的強度を向上させることができる。   The component (C) surface-treated silica used in the present invention is colloidal silica surface-treated with a silane coupling agent having a reactive (meth) acrylate group in the molecule, and disclosed in JP-A-57-131214. This is a well-known one described in Japanese Patent Laid-Open No. 2000-289172. This component improves the hardness of the hard coat composition, suppresses curing shrinkage, and suppresses the generation of cracks in the coating during curing as much as possible. Moreover, the mechanical strength regarding bending etc. of said polyfunctional acrylic resin can be improved by adding this component.

本発明において、(A) 〜(C) 成分の配合量は、(A) 成分20〜70重量部に対し、(B) 成分;15〜60重量部、(C) 成分;10〜40重量部である。この範囲を外れる場合、例えば(A)成分が少ない場合においては、硬度の不足が起こり、また硬化時の重合が完全に進行せず、機械的強度の不足が生じる。多い場合には皮膜にクラックが入りやすくなるなどの不具合がある。(B)成分が少ない場合においては、硬度の低下が生じ、また組成物の相溶性が損なわれる場合がある。多い場合においては硬化時に皮膜にクラックが入りやすくなり、皮膜の機械的強度が弱くなり脆くなる不具合がある。(C)成分が少ない場合においては硬度が下がり、フィルムにクラックが入りやすくなり、多くなると硬化時の重合反応が遅くなり、完全硬化に至らない分、硬度が下がる不具合がある。   In the present invention, the blending amount of the components (A) to (C) is (B) component: 15 to 60 parts by weight, (C) component; 10 to 40 parts by weight with respect to (A) component 20 to 70 parts by weight. It is. When outside this range, for example, when the amount of component (A) is small, insufficient hardness occurs, polymerization during curing does not proceed completely, and insufficient mechanical strength occurs. When there are many cases, there are defects such as cracks in the film. When the amount of the component (B) is small, the hardness is lowered and the compatibility of the composition may be impaired. In many cases, there is a problem that cracks are easily formed in the film during curing, and the mechanical strength of the film becomes weak and brittle. When the amount of the component (C) is small, the hardness is lowered and the film is likely to be cracked. When the amount is large, the polymerization reaction at the time of curing is delayed, and there is a problem that the hardness is lowered by the amount not completely cured.

またフィルムのカールを抑える目的で、(A)〜(C)の合計量100重量部に対して、20〜30重量部の、分子内に環構造を有する2官能のジメチロールジシクロペンタンジアクリレートを加えることもできるが、これより多くいれた場合においては、硬度の低下が著しくなる不具合がある。また環構造を有していない2官能アクリレートにおいては少量の添加においても硬度が下がる不具合が認められる。   In order to suppress curling of the film, 20-30 parts by weight of bifunctional dimethylol dicyclopentane diacrylate having a ring structure in the molecule with respect to 100 parts by weight of the total amount of (A) to (C). However, when it is added more than this, there is a problem that the hardness is remarkably reduced. Moreover, in the bifunctional acrylate which does not have a ring structure, the malfunction which hardness falls even if it adds a little is recognized.

本発明で用いる(D) 光重合開始剤としては、公知の一般に入手可能なものがいずれも使用可能であるが、特に可視領域における透明性を確保するために、UV吸収の最大波長ピークが400nm以下のものが望ましい。このような重合開始剤として、アセトフェノン系の1−ヒドロキシ−シクロヘキシル−フェニルケトン、2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン、2−ヒドロキシ−2−メチル−1−フェニル−プロパン−1−オン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタノン−1−オン、フォスフィンオキシド系の2,4,6−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、さらにはベンゾフェノンと重合促進剤のエチル−4−ジメチルアミノベンゾエート、2−エチルヘキシル−4−ジメチルアミノベンゾエートといった組み合わせのものも使用できる。これらは単独で用いられてもよいし、複数を組み合わせて光硬化時の光源に合わせて硬化条件の最適化を図ることもできる。特に液状で取扱が簡便な2−ヒドロキシ−2−メチル−1−フェニル−プロパン−1−オンは液体で取扱が簡便なため望ましく、上記にあげたような他重合開始剤をあらかじめ溶解させて使用することもできる。配合量は、光重合開始に必要な量であって特に制限されないが、一般的には(A) 〜(C) 成分の合計量100重量部に対して1〜10重量部が望ましく、硬化速度と経時安定性との兼ね合いから3〜8重量部がさらに望ましい。   As the (D) photopolymerization initiator used in the present invention, any known publicly available one can be used, but in order to ensure transparency particularly in the visible region, the maximum wavelength peak of UV absorption is 400 nm. The following are desirable: As such a polymerization initiator, acetophenone-based 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane -1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1-one, phosphine oxide-based 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, benzophenone and polymerization accelerators ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate Combinations such as these can also be used. These may be used singly or a plurality of them may be combined to optimize the curing conditions according to the light source during photocuring. In particular, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, which is liquid and easy to handle, is desirable because it is liquid and easy to handle, and is used by previously dissolving other polymerization initiators as described above. You can also The blending amount is an amount necessary for the initiation of photopolymerization and is not particularly limited, but generally 1 to 10 parts by weight is desirable with respect to 100 parts by weight of the total amount of the components (A) to (C), and the curing rate 3 to 8 parts by weight is more desirable in view of the balance with the stability over time.

本発明で用いる(E)希釈溶媒としては、イソプロパノール、ブタノール、1−メトキシー2−プロパノールなどのアルコール系溶媒、トルエン、キシレンなどの芳香族溶媒、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、酢酸エチル、酢酸ブチルなどのエステル系溶媒など公知の一般に入手可能なものが使用可能であり、単独でも混合溶媒系でも用いることが可能である。特にブタノール、1−メトキシー2−プロパノールはコロイダルシリカの表面処理および水を共沸留去する際にも用いることができ、合成プロセスが簡便にすることができ、さらにポリカーボネート基材の侵食を抑え、皮膜の透明性を容易に確保できるので望ましい。またメチルエチルケトンを用いた場合には、特別な密着性成分を入れなくともトリアセチルセルロースフィルムへの密着性を向上させうることが可能である。   The (E) dilution solvent used in the present invention includes alcohol solvents such as isopropanol, butanol and 1-methoxy-2-propanol, aromatic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ethyl acetate. Well-known generally available solvents such as ester solvents such as butyl acetate can be used, and they can be used alone or in a mixed solvent system. In particular, butanol and 1-methoxy-2-propanol can be used for surface treatment of colloidal silica and azeotropic distillation of water, the synthesis process can be simplified, and the erosion of the polycarbonate substrate is further suppressed. It is desirable because transparency of the film can be easily secured. Further, when methyl ethyl ketone is used, it is possible to improve the adhesion to the triacetyl cellulose film without adding a special adhesion component.

本発明の組成物に対して、基材への濡れ性、レベリング性を向上させるために界面活性剤を用いることができる。特にポリエーテル置換されたシリコーン系界面活性剤は組成物との相溶性が優れ、優れたレベリング性を付与することができる。このような界面活性剤としてはビックケミー・ジャパン製商品名「BYK300」、「BYK302」などが挙げられる。   For the composition of the present invention, a surfactant can be used in order to improve wettability and leveling to the substrate. In particular, polyether-substituted silicone surfactants have excellent compatibility with the composition and can impart excellent leveling properties. Examples of such surfactants include trade names “BYK300” and “BYK302” manufactured by Big Chemie Japan.

本発明のハードコート膜には、所望に応じて、帯電防止剤、艶消剤、紫外線安定剤および染料を含有していてもよい。ハードコート剤の光硬化に悪影響を与えず、透明または半透明性に悪影響を与えない限りで、これらの化合物のいずれも使用できる。さらに硬度を維持するために添加量はハードコート剤100重量部に対して0.1〜10重量部が望ましい。これより少ない場合には、帯電防止効果や紫外線吸収効果が期待できず、また多い場合においては硬度および耐擦傷性の低下が顕著となる。特にアクリル官能基といったバインダー樹脂と化学結合を伴う構造を有していない帯電防止剤、艶消剤、紫外線安定剤および染料においては硬度の低下がさらに顕著になるために、添加量はハードコート剤100重量部に対して5重量部以下が望ましい。   The hard coat film of the present invention may contain an antistatic agent, a matting agent, an ultraviolet stabilizer and a dye as desired. Any of these compounds can be used as long as it does not adversely affect the photocuring of the hard coating agent and does not adversely affect the transparency or translucency. Furthermore, in order to maintain hardness, the addition amount is desirably 0.1 to 10 parts by weight with respect to 100 parts by weight of the hard coating agent. When the amount is less than this, the antistatic effect and the ultraviolet ray absorbing effect cannot be expected, and when the amount is larger, the decrease in hardness and scratch resistance becomes remarkable. Especially for antistatic agents, matting agents, UV stabilizers and dyes that do not have a structure with a chemical bond with a binder resin such as an acrylic functional group, since the decrease in hardness becomes more remarkable, the amount added is a hard coating agent. 5 parts by weight or less is desirable with respect to 100 parts by weight.

本発明に用いるハードコート剤を製造するには、水性コロイドシリカ(コロイドシリカ水分散液)、シリル(メタ)アクリレート、6官能以上の官能基数を有するウレタンアクリレート、多官能価アクリルモノマーまたはその混合物、光開始剤および所望に応じて上述した他の添加剤のうち任意のものを配合させる。またコロイドシリカはアルコール溶媒にあらかじめ分散されているものでも同様に可能であり、アルコールとしてはメタノール、エタノール、イソプロピルアルコール、1−メトキシー2−プロパノール等があげられる。コロイドシリカの粒径は、皮膜透明性を確保するため1次粒子径が30nm以下、特に25nm以下のものが望ましい。   In order to produce the hard coating agent used in the present invention, aqueous colloidal silica (colloidal silica aqueous dispersion), silyl (meth) acrylate, urethane acrylate having 6 or more functional groups, a polyfunctional acrylic monomer or a mixture thereof, Any of the photoinitiators and other additives described above are incorporated as desired. Colloidal silica can be similarly dispersed in an alcohol solvent in advance, and examples of alcohol include methanol, ethanol, isopropyl alcohol, and 1-methoxy-2-propanol. The colloidal silica preferably has a primary particle size of 30 nm or less, particularly 25 nm or less in order to ensure film transparency.

第1の工程で、シリルアクリレートを水性コロイドシリカおよび水混和性アルコールの存在下で加水分解する。適当なアルコールとしては、例えば水混和性アルコール、具体的にはt−ブタノール、メタノール、エタノール、プロパノール、ブタノールなど、またはエーテルアルコール、例えばエトキシエタノール、ブトキシエタノール、メトキシプロパノールなどが挙げられる。水性コロイドシリカとシリルアクリレートを、加水分解が終わるまで加熱攪拌する。シリルアクリレートの加水分解は、大気条件下で行う、あるいは加水分解混合物を加熱還流することによって行うことができる。   In the first step, silyl acrylate is hydrolyzed in the presence of aqueous colloidal silica and water miscible alcohol. Suitable alcohols include, for example, water miscible alcohols, specifically t-butanol, methanol, ethanol, propanol, butanol and the like, or ether alcohols such as ethoxyethanol, butoxyethanol, methoxypropanol and the like. The aqueous colloidal silica and silyl acrylate are heated and stirred until hydrolysis is completed. Hydrolysis of silyl acrylate can be carried out under atmospheric conditions or by heating and refluxing the hydrolysis mixture.

第2の工程で、上記1の溶液にアクリル樹脂を添加し、反応に用いた水および溶媒を蒸留除去する。   In the second step, an acrylic resin is added to the above solution 1, and water and solvent used in the reaction are distilled off.

さらに第3の配合工程では、第2の工程のコロイドシリカが分散されたアクリル樹脂に、所望の光開始剤、光増感剤、レベリング剤などを添加する。   Further, in the third blending step, a desired photoinitiator, photosensitizer, leveling agent, and the like are added to the acrylic resin in which the colloidal silica in the second step is dispersed.

本発明において用いるハードコート剤への上述した成分の添加順序は重要ではないが、上述した加水分解シリルアクリレートとコロイドシリカの混合物に多官能価アクリルモノマーまたはその混合物を加えるのが好ましい。好ましくは、シリルアクリレートとコロイドシリカの混合物を適当な加水分解媒体、例えば前述した通りの水混和性アルコールの溶液中で攪拌しながら、この混合物に多官能価アクリルモノマーまたはその混合物を加える。また第1の工程において水混和性溶媒と水を共沸させて水を除く際に、水混和性溶媒が残っている段階で留めおき、そこにアクリル樹脂や光重合開始剤、レベリング剤を添加する方法も用いることができる。   The order of addition of the above-described components to the hard coat agent used in the present invention is not important, but it is preferable to add a polyfunctional acrylic monomer or a mixture thereof to the above-mentioned mixture of hydrolyzed silyl acrylate and colloidal silica. Preferably, the polyfunctional acrylic monomer or mixture thereof is added to the mixture while stirring the mixture of silyl acrylate and colloidal silica in a suitable hydrolysis medium, such as a solution of a water miscible alcohol as described above. Also, when removing water by azeotropically mixing the water-miscible solvent and water in the first step, keep it at the stage where the water-miscible solvent remains, and add acrylic resin, photopolymerization initiator, and leveling agent there. The method of doing can also be used.

本発明に用いるハードコート剤を製造する場合、水とアルコールの共沸混合物を上記配合物から蒸留除去する。最初の加水分解混合物にアルコールを使用しなかった場合には、十分な量のアルコールを加えて蒸留による水の除去を容易にすることができる。他の溶剤、例えば、トルエンまたは他の芳香族炭素水素を加えて水の除去を促進することもできる。   When producing the hard coat agent used in the present invention, an azeotropic mixture of water and alcohol is distilled off from the above blend. If no alcohol is used in the initial hydrolysis mixture, a sufficient amount of alcohol can be added to facilitate removal of water by distillation. Other solvents such as toluene or other aromatic hydrocarbons can be added to facilitate water removal.

本発明に用いるハードコート剤は、使用前にフィルターろ過されることが望ましい。フィルター材質はPTFE、ポリプロピレンなど、アクリル化合物によって容易侵食されないものが望ましく、ろ過時のフィルター径は0.2〜10ミクロン程度のものが入手も容易であり望ましい。特にフィルター径を2段階に分け、初期に2〜10ミクロン、後期に0.2〜1ミクロンのものを通すことにより、コロイドシリカの凝集物とアクリル樹脂由来のゲル物、および大気より混入する塵を効率良く除くことができ、最終的な皮膜の外観を良好に保つことができる。   The hard coat agent used in the present invention is preferably filtered before use. The material of the filter is preferably PTFE, polypropylene or the like that is not easily eroded by an acrylic compound, and the filter diameter during filtration is preferably about 0.2 to 10 microns because it is easily available. In particular, the filter diameter is divided into two stages, with the passage of 2 to 10 microns in the initial stage and 0.2 to 1 micron in the latter stage, so that colloidal silica aggregates and gels derived from acrylic resin and dust mixed in from the air are more efficient. It can be removed well and the final appearance of the film can be kept good.

上に述べたハードコート液をディップ、スピン、フロー、スプレーおよびはけ塗り等によりポリカーボネート基材表面に塗工し、光重合開始剤を適宜選択することにより、市販されている光照射装置で硬化することができる。   The hard coat solution described above is applied to the polycarbonate substrate surface by dipping, spinning, flow, spraying, brushing, etc., and cured with a commercially available light irradiation device by selecting a photopolymerization initiator as appropriate. can do.

また、本発明においてハードコート剤の形成厚さは3〜25μm、好ましくは10〜20μmである。膜厚が少なくなると、光硬化時に酸素による重合阻害の影響が大きくなり、窒素などの不活性ガス下による硬化システムが必要となり、さらにハードコート層が薄くなると傷つき防止性能自体が低下する。また膜厚が極度に大きくなると硬化収縮における基材の変形が大きくなる不具合がある。   In the present invention, the hard coat agent is formed with a thickness of 3 to 25 μm, preferably 10 to 20 μm. When the film thickness is reduced, the influence of polymerization inhibition by oxygen during photocuring increases, and a curing system under an inert gas such as nitrogen is required. Further, when the hard coat layer is thinned, the damage prevention performance itself is lowered. Further, when the film thickness becomes extremely large, there is a problem that the deformation of the base material during curing shrinkage becomes large.

以下、本発明の実施例を挙げるが、本発明は以下の実施例に限定されるものではない。また、実施例中、部は重量部を示す。
(調製例1)
イソプロピルアルコール1370部、日産化学工業(株)製スノーテックスO−40(40%コロイドシリカ水分散液)982部、γ−メタクリロキシプロピルトリメトキシシラン168部、4−ヒドロキシー2,2,6,6−テトラメチルピペリジン−1−オキシフリーラジカル0.88部の混合物を80℃に加熱して3時間攪拌還流させた。冷却後、プロピレングリコールモノメチルエーテル(以下PGM)280部を加え、イソプロピルアルコール1200部を減圧留去した。さらに400部のPGMを加え、残渣が700部となるようにIPAおよび水を減圧留去し、さらに500部のPGMを加えて55℃/50mmHgにて残渣が700部になるまで溶媒を留去した。105℃/1時間の条件で不揮発分を測定し、PGMを希釈剤として用いて、最終的に不揮発分60%の表面処理済みコロイダルシリカのPGM溶液を作成した(以下、FCS溶液と言う)。
Examples of the present invention will be described below, but the present invention is not limited to the following examples. Moreover, a part shows a weight part in an Example.
(Preparation Example 1)
1370 parts of isopropyl alcohol, 982 parts of Snowtex O-40 (40% colloidal silica aqueous dispersion) manufactured by Nissan Chemical Industries, Ltd., 168 parts of γ-methacryloxypropyltrimethoxysilane, 4-hydroxy-2,2,6,6 -A mixture of 0.88 parts of tetramethylpiperidine-1-oxy free radical was heated to 80 ° C and stirred and refluxed for 3 hours. After cooling, 280 parts of propylene glycol monomethyl ether (hereinafter PGM) was added, and 1200 parts of isopropyl alcohol were distilled off under reduced pressure. Further, 400 parts of PGM was added, and IPA and water were distilled off under reduced pressure so that the residue was 700 parts. Further, 500 parts of PGM was added, and the solvent was distilled off at 55 ° C./50 mmHg until the residue was 700 parts. did. The nonvolatile content was measured under the conditions of 105 ° C./1 hour, and finally a PGM solution of surface-treated colloidal silica having a nonvolatile content of 60% was prepared using PGM as a diluent (hereinafter referred to as FCS solution).

実施例1
次にFCS溶液20.1部に、日本合成化学(株)製ウレタンアクリレート「UV−1700B」18部、光重合開始剤の2−ヒドロキシ−2−メチル−1−フェニル−プロパンー1−オンを1.5部、メチルエチルケトン12.9部を加えて、ハードコート剤を得た。
Example 1
Next, 18 parts of urethane acrylate “UV-1700B” manufactured by Nippon Synthetic Chemical Co., Ltd., and 2-hydroxy-2-methyl-1-phenyl-propan-1-one as a photopolymerization initiator are added to 20.1 parts of FCS solution. 0.5 part and 12.9 parts of methyl ethyl ketone were added to obtain a hard coat agent.

このようにして得られたハードコート液を80ミクロン厚のトリアセチルセルロースフィルムにバーコーターで塗工し、60℃で3分間養生した後に、ヒュージョン社製光硬化システム(光源Hランプ)を用いて硬化させた。   The hard coat solution thus obtained was applied to an 80 micron thick triacetyl cellulose film with a bar coater, cured at 60 ° C. for 3 minutes, and then used with a light curing system (light source H lamp) manufactured by Fusion. Cured.

この試験片について、6cm角に切り出し、各種物性を調べた。
塗工厚み:
スペクトラ・コープ製光学膜厚測定装置を用い、解析ソフトASPECT PLUSを用いて、硬化後の膜厚を測定した。
鉛筆硬度:
湿度50%の環境下、500gの荷重をかけて5回引っ掻き試験を行い、傷がついた回数が1回以下の最高硬度を示した
クラック:光硬化後の塗膜外観において、ひび割れがおこっているかを目視にて確認した。
密着性:
光硬化後1日置いた皮膜について、カッターで100x100(幅1mm)の升目状の切り込みをいれ、テープ密着試験を行って、はがれていない領域が無い場合100/100、すべてはがれた場合0/100として表した。
外観:光硬化後の皮膜について、白濁、干渉縞が発生していないかを目視にて確認した。クラックの有無は除く。
カール:
光硬化後1日置いた皮膜について6cm角に切り出し、フィルムのカールの大小を曲率半径で表した。(小さい数字ほどカールが大きく、望ましくない)
結果を表1に示す。
The test piece was cut into a 6 cm square and examined for various physical properties.
Coating thickness:
The film thickness after curing was measured using analysis software ASPECT PLUS using an optical film thickness measuring device manufactured by Spectra Corp.
Pencil hardness:
A crack that showed a maximum hardness of less than 1 scratch under a 50% humidity environment with a load of 500 g, and cracks occurred in the appearance of the coating after photocuring. It was confirmed visually.
Adhesion:
A 100x100 (width 1 mm) grid cut was made with a cutter for the film that was placed for 1 day after photocuring, and a tape adhesion test was conducted. When there was no unpeeled area, 100/100, and when all peeled, 0/100 Expressed as:
Appearance: Regarding the film after photocuring, it was visually confirmed whether white turbidity or interference fringes were generated. Excluding the presence or absence of cracks.
curl:
The film placed for 1 day after photocuring was cut into a 6 cm square, and the curl size of the film was expressed by the curvature radius. (The smaller the number, the greater the curl, which is undesirable)
The results are shown in Table 1.

実施例2〜6
実施例1と同様に、FCS溶液にアクリル樹脂、光重合開始剤、メチルエチルケトンを加えて作成し、溶媒濃度が40%になるように調製したものを作成して、ヒュージョン社製光硬化システム(光源Hバルブ)を用いて硬化させて、同様の評価を行った。
用いたウレタンアクリレートは以下の通りである。
6官能ウレタンアクリレート(1);
日本合成化学工業製 紫光UV−1700B
6官能ウレタンアクリレート(2);
日本合成化学工業製 紫光UV−7640B
なお、6官能ウレタンアクリレート(1)においてはジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレートを含んでおり、6官能ウレタンアクリレート(2)においてはジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリアクリレートを含むものである。
Examples 2-6
In the same manner as in Example 1, an acrylic resin, a photopolymerization initiator, and methyl ethyl ketone were added to an FCS solution to prepare a solution having a solvent concentration of 40%. The same evaluation was performed using a H-bulb.
The urethane acrylate used is as follows.
Hexafunctional urethane acrylate (1);
Purple light UV-1700B made by Nippon Synthetic Chemical Industry
Hexafunctional urethane acrylate (2);
Purple light UV-7640B made by Nippon Synthetic Chemical Industry
The hexafunctional urethane acrylate (1) includes dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, and the hexafunctional urethane acrylate (2) includes dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and pentaerythritol. Tetraacrylate and pentaerythritol triacrylate are included.

実施例7
IPA120部、Nalcoag 1034A(35%コロイドシリカ水分散液) 60.6部、γ−メタクリロキシプロピルトリメトキシシラン5.4部、4−ヒドロキシー2,2,6,6−テトラメチルピペリジン−1−オキシフリーラジカル0.03部の混合物を80℃に加熱して3時間還流させた。冷却後、ジメチロールジシクロペンタンジアクリレート26.0部を加えて、減圧下で溶剤を蒸留した。約半分の溶剤を蒸留したところで、メトキシプロパノ−ル120部を加え、次いで溶剤のすべてを蒸留して透明な溶液を得た。
Example 7
IPA 120 parts, Nalcoag 1034A (35% colloidal silica aqueous dispersion) 60.6 parts, γ-methacryloxypropyltrimethoxysilane 5.4 parts, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy A mixture of 0.03 parts of free radicals was heated to 80 ° C. and refluxed for 3 hours. After cooling, 26.0 parts of dimethylol dicyclopentane diacrylate was added, and the solvent was distilled off under reduced pressure. When about half of the solvent had been distilled, 120 parts of methoxypropanol was added and then all of the solvent was distilled to give a clear solution.

この表面処理されたコロイドシリカ分散ジメチロールジシクロペンタンジアクリレート40部に、UV−1700B30部、ジペンタエリスリトールヘキサアクリレート40部、および2−ヒドロキシ−2−メチル−1−フェニル−プロパンー1−オンを5.0部、メチルエチルケトン66.5部を加えて、溶剤40%のハードコート溶液を調製した。   To 40 parts of this surface-treated colloidal silica-dispersed dimethylol dicyclopentane diacrylate, 30 parts of UV-1700B, 40 parts of dipentaerythritol hexaacrylate, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one were added. 5.0 parts and 66.5 parts of methyl ethyl ketone were added to prepare a 40% solvent hard coat solution.

このようにして得られたハードコート液について実施例1〜7と同様の評価を行った。   Evaluation similar to Examples 1-7 was performed about the hard coat liquid obtained in this way.

比較例1〜3、比較例6
アクリル樹脂、アクリルモノマーと光重合開始剤、およびメチルエチルケトンを混合し、溶媒40%の溶液を調製し、実施例1と同様の評価を行った。
Comparative Examples 1-3, Comparative Example 6
An acrylic resin, an acrylic monomer, a photopolymerization initiator, and methyl ethyl ketone were mixed to prepare a 40% solvent solution, and the same evaluation as in Example 1 was performed.

比較例4
IPA120部、Nalcoag 1034A(35%コロイドシリカ水分散液) 60.6部、γ−メタクリロキシプロピルトリメトキシシラン5.4部の混合物を80℃に加熱して3時間還流させた。冷却後、1,6−ヘキサンジオールジアクリレート26.0部を加えて、減圧下で溶剤を蒸留した。約半分の溶剤を蒸留したところで、メトキシプロパノ−ル120部を加え、次いで溶剤のすべてを蒸留して透明な溶液を得た。
Comparative Example 4
A mixture of 120 parts of IPA, 60.6 parts of Nalcoag 1034A (35% colloidal silica aqueous dispersion) and 5.4 parts of γ-methacryloxypropyltrimethoxysilane was heated to 80 ° C. and refluxed for 3 hours. After cooling, 26.0 parts of 1,6-hexanediol diacrylate was added, and the solvent was distilled off under reduced pressure. When about half of the solvent had been distilled, 120 parts of methoxypropanol was added and then all of the solvent was distilled to give a clear solution.

この表面処理されたコロイドシリカ分散1,6−ヘキサンジオールジアクリレート25部、ペンタエリスリトールトリアクリレート25部、および2−ヒドロキシ−2−メチル−1−フェニル−プロパンー1−オン5.0部を混合し、メチルエチルケトンを加えて、溶剤40%のハードコート溶液を調製して、実施例1と同様の評価を行った。   25 parts of this surface-treated colloidal silica dispersion 1,6-hexanediol diacrylate, 25 parts of pentaerythritol triacrylate, and 5.0 parts of 2-hydroxy-2-methyl-1-phenyl-propan-1-one were mixed. Then, methyl ethyl ketone was added to prepare a hard coat solution of 40% solvent, and the same evaluation as in Example 1 was performed.

比較例5
比較例4にて調製したコロイドシリカ分散1,6−ヘキサンジオールジアクリレート40部に「UV−1700B」30部、ジペンタエリスリトールヘキサアクリレート30部、および2−ヒドロキシ−2−メチル−1−フェニル−プロパンー1−オン5.0部を混合し、メチルエチルケトンを加えて、溶剤40%のハードコート溶液を調製して、実施例1と同様の評価をおこなった。
Comparative Example 5
40 parts of colloidal silica-dispersed 1,6-hexanediol diacrylate prepared in Comparative Example 4 30 parts of “UV-1700B”, 30 parts of dipentaerythritol hexaacrylate, and 2-hydroxy-2-methyl-1-phenyl- 5.0 parts of propan-1-one was mixed, methyl ethyl ketone was added to prepare a 40% solvent hard coat solution, and the same evaluation as in Example 1 was performed.

Figure 2008150484
Figure 2008150484

Figure 2008150484
Figure 2008150484

実施例8
実施例1および2において、シリコーン系界面活性剤を加えた。ビックケミー・ジャパン製商品名「BYK300」を0.8部加えたハードコート溶液を調製し、同様の評価を行ったところ、表面の感触がすべる皮膜が得られ、鉛筆硬度、密着性、外観、カール、ともに同等のものが得られた。
Example 8
In Examples 1 and 2, a silicone surfactant was added. A hard coat solution containing 0.8 parts of BYK300 brand name "BYK300" was prepared and evaluated in the same manner. A film with a slippery surface was obtained. Pencil hardness, adhesion, appearance, curl Both were equivalent.

実施例9
実施例1および2において、光重合開始剤を2,4,6−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイドに置き換えて、ハードコート溶液を調製し、光硬化時にヒュージョン社製光硬化システム(光源Dバルブ)を用いて硬化させたところ、実施例1と同様な評価結果が得られた。
Example 9
In Examples 1 and 2, the photopolymerization initiator was replaced with 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide to prepare a hard coat solution. ), The same evaluation results as in Example 1 were obtained.

実施例10
実施例1および2において、基材となるフィルムを東洋紡製100ミクロン厚PETフィルム(商品名「コスモシャインA4100」)を用い、易接着面に塗布して光硬化およびその後の評価を行った。鉛筆硬度が20ミクロン厚で6Hであるのに対し、比較例1において用いたハードコート剤を用いた場合には鉛筆硬度が20ミクロン厚で4Hであり、かつクラックが認められた。密着性はすべてにおいて100/100であった。
Example 10
In Examples 1 and 2, a 100 micron thick PET film (trade name “Cosmo Shine A4100”) manufactured by Toyobo Co., Ltd. was used as the base film, and photocuring and subsequent evaluation were performed on the easily adhesive surface. Whereas the pencil hardness was 20 microns and 6H, when the hard coating agent used in Comparative Example 1 was used, the pencil hardness was 20 microns and 4H, and cracks were observed. The adhesion was 100/100 in all cases.

Claims (7)

(A) 6官能ウレタンアクリレート;20〜70重量部
(B) 4官能以上の(メタ)アクリルモノマー;15〜60重量部
(C) 分子内に反応性(メタ)アクリレート基を有するシランカップリング剤にて表面処理されたコロイダルシリカ;10〜40重量部
(D) 光重合開始剤
(E) 希釈溶媒
を含有するハードコート用組成物。
(A) Hexafunctional urethane acrylate; 20 to 70 parts by weight
(B) Tetrafunctional or higher (meth) acrylic monomer; 15-60 parts by weight
(C) Colloidal silica surface-treated with a silane coupling agent having a reactive (meth) acrylate group in the molecule; 10 to 40 parts by weight
(D) Photopolymerization initiator
(E) A composition for hard coat containing a diluting solvent.
請求項1の成分(A) 、(B) および(C) 成分の合計100重量部に対して、2官能アクリルモノマーである、ジメチロールジシクロペンタンジアクリレート20〜30重量部を加え、成分(D) および(E) をさらに加えたものであるハードコート用組成物。   2 to 30 parts by weight of dimethylol dicyclopentane diacrylate, which is a bifunctional acrylic monomer, is added to 100 parts by weight of components (A), (B) and (C) in total. A composition for hard coat, further comprising D) and (E). シリコーン系界面活性剤をさらに含有させた請求項1又は2記載のハードコート用組成物。   The hard coat composition according to claim 1 or 2, further comprising a silicone-based surfactant. 希釈溶媒の少なくとも1種がメチルエチルケトンである請求項1〜3の何れか1項に記載のハードコート用組成物   The hard coat composition according to any one of claims 1 to 3, wherein at least one of the dilution solvents is methyl ethyl ketone. 透明支持基材上に請求項1〜4の何れか1項記載のハードコート用組成物を塗布後、光硬化してなる厚さ10〜20μmのハードコート層を有する積層体。   A laminate having a hard coat layer having a thickness of 10 to 20 µm, which is obtained by photocuring the hard coat composition according to any one of claims 1 to 4 on a transparent support substrate. 透明支持基材がトリアセチルセルロース(TAC)フィルムである請求項5記載の積層体。   The laminate according to claim 5, wherein the transparent support substrate is a triacetyl cellulose (TAC) film. 透明支持基材がポリエチレンテレフタレート(PET)フィルムであり、あらかじめ易接着処理を施した面に請求項1〜4の何れか1項記載のハードコート組成物を塗布後、光硬化してなる請求項5記載の積層体。   The transparent support base material is a polyethylene terephthalate (PET) film, and is obtained by photocuring after applying the hard coat composition according to any one of claims 1 to 4 to a surface which has been subjected to an easy adhesion treatment in advance. 5. The laminate according to 5.
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CN116406391A (en) * 2020-12-21 2023-07-07 东洋油墨Sc控股株式会社 Active energy ray-curable hard coating agent, hard coating layer, and laminate
CN115466565A (en) * 2022-09-19 2022-12-13 江苏天合蓝途新能源科技有限公司 Coating composition for photovoltaic module packaging, preparation method of composite material for packaging and photovoltaic module
CN115466565B (en) * 2022-09-19 2023-11-28 江苏天合蓝途新能源科技有限公司 Coating composition for packaging photovoltaic module, preparation method of composite material for packaging and photovoltaic module

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