JP2015214643A - Curable composition, substrate formed with surface layer film using the same, and method for manufacturing substrate formed with surface layer film - Google Patents
Curable composition, substrate formed with surface layer film using the same, and method for manufacturing substrate formed with surface layer film Download PDFInfo
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- JP2015214643A JP2015214643A JP2014097807A JP2014097807A JP2015214643A JP 2015214643 A JP2015214643 A JP 2015214643A JP 2014097807 A JP2014097807 A JP 2014097807A JP 2014097807 A JP2014097807 A JP 2014097807A JP 2015214643 A JP2015214643 A JP 2015214643A
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- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 239000000758 substrate Substances 0.000 title claims abstract description 51
- 239000002344 surface layer Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title description 19
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims description 48
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RYDOQJPDRXMRRP-UHFFFAOYSA-N 2-methylpropan-1-one Chemical compound CC(C)[C]=O RYDOQJPDRXMRRP-UHFFFAOYSA-N 0.000 description 1
- CUTWSDAQYCQTGD-UHFFFAOYSA-N 2-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)C(C)OC(=O)C=C CUTWSDAQYCQTGD-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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Abstract
Description
本発明は、硬化性組成物、可撓性基材上に当該硬化性組成物からなる硬化膜を形成して得られる表層膜形成基材及び表層膜形成基材の製造方法に関する。 The present invention relates to a curable composition, a surface layer film-forming substrate obtained by forming a cured film made of the curable composition on a flexible substrate, and a method for producing the surface layer film-forming substrate.
フィルムのような３０μｍから１００μｍ程度の厚さの膜を形成するための製造方法として、溶融押出成型法や溶液流延法などが一般的である。これらの方法を用いることで、フィルムなどの膜生成物が安価且つ高品質で大量生産可能となっている。このとき、溶液流延法では、キャスティングドラムやステンレス製の平滑ベルトなどの支持体上に塗材を流延してフィルムを作製するのが一般的である（例えば、特許文献１参照）。 As a manufacturing method for forming a film having a thickness of about 30 μm to 100 μm such as a film, a melt extrusion molding method, a solution casting method, or the like is generally used. By using these methods, film products such as films can be mass-produced at low cost and with high quality. At this time, in the solution casting method, a film is generally produced by casting a coating material on a support such as a casting drum or a stainless steel smooth belt (see, for example, Patent Document 1).
しかしながら、このような製造方法にて膜生成物を形成する塗材として硬化性組成物を用いる場合、塗膜の膜厚が厚くなると下層部まで反応が進まない場合がある。そのような場合、表層部と下層部とで硬化の進行度合いが異なってしまう。 However, when a curable composition is used as a coating material for forming a film product by such a production method, the reaction may not proceed to the lower layer when the coating film becomes thicker. In such a case, the progress of curing differs between the surface layer portion and the lower layer portion.
表層部と下層部とで硬化の進行度合いが異なると、基材全体がカールしてしまうことや、基材をロール状に巻取りした際に未反応部が起点となってブロッキングが生じてしまうことがある。 If the progress of curing is different between the surface layer portion and the lower layer portion, the entire base material may be curled, or blocking may occur due to the unreacted portion as the starting point when the base material is rolled up. Sometimes.
本発明は、表層膜の表面から下層部まで均一な硬化進行度が得られ、カールやブロッキングが抑えられた表層膜形成基材の製造に適した硬化性組成物、これを用いた表層膜形成基材の製造方法、並びに、当該硬化性組成物を硬化させて得られる樹脂硬化膜及びその製造方法を提供することを目的とする。 The present invention provides a curable composition suitable for the production of a base material for forming a surface layer film in which a uniform degree of curing is obtained from the surface of the surface layer film to the lower layer part and curling and blocking are suppressed, and surface layer film formation using the same It aims at providing the manufacturing method of a base material, the resin cured film obtained by hardening the said curable composition, and its manufacturing method.
本発明に係る硬化性組成物は、可撓性基材に塗布して硬化させることによって、厚さ３０μｍ以上１００μｍ以下の表層膜を形成するためのものであり、少なくとも、二官能以上の電離放射線硬化樹脂と、光重合開始剤とを含有し、光重合開始剤の配合比率が、二官能以上の電離放射線硬化樹脂を含む電離放射線硬化樹脂の全体の質量に対して、０．１質量％以上１０質量％以下であり、粘度が５０ｍＰａ・ｓ以上１００００ｍＰａ・ｓ以下であることを特徴とするものである。 The curable composition according to the present invention is for forming a surface layer film having a thickness of 30 μm or more and 100 μm or less by being applied to a flexible substrate and cured, and at least bifunctional or more ionizing radiation. A curing resin and a photopolymerization initiator are contained, and the blending ratio of the photopolymerization initiator is 0.1% by mass or more based on the total mass of the ionizing radiation curable resin including the bifunctional or higher ionizing radiation curable resin. It is 10 mass% or less, and a viscosity is 50 mPa * s or more and 10000 mPa * s or less, It is characterized by the above-mentioned.
また、本発明に係る表層膜形成機材の製造方法は、可撓性基材表面に、上記の硬化性組成物を塗布して塗布膜を形成する工程と、塗布膜を光硬化させる工程と備える。 Moreover, the manufacturing method of the surface layer film formation equipment which concerns on this invention is equipped with the process of apply | coating said curable composition to the surface of a flexible base material, and forming the coating film, and the process of photocuring the coating film. .
また、本発明に係る樹脂硬化膜は、上記の硬化性組成物を光硬化させることによって得られるものである。 Moreover, the resin cured film which concerns on this invention is obtained by photocuring said curable composition.
また、本発明に係る樹脂硬化膜の製造方法は、可撓性基材表面に、上記の硬化性組成物を塗布して塗布膜を形成する工程と、塗布膜を光硬化させる工程と、光硬化後の塗布膜を可撓性基材から剥離する工程とを備える。 The method for producing a cured resin film according to the present invention includes a step of applying the curable composition to the surface of a flexible substrate to form a coating film, a step of photocuring the coating film, And a step of peeling the cured coating film from the flexible substrate.
本発明によれば、表層膜の表面から下層部まで均一な硬化進行度が得られ、カールやブロッキングが抑えられた表層膜形成基材の製造に適した硬化性組成物、これを用いた表層膜形成基材の製造方法、並びに、当該硬化性組成物を硬化させて得られる樹脂硬化膜及びその製造方法を実現できる。 ADVANTAGE OF THE INVENTION According to this invention, the curable composition suitable for manufacture of the surface layer film formation base material from which the uniform hardening progress was obtained from the surface of the surface layer film to the lower layer part, and curl and blocking were suppressed, and the surface layer using this The manufacturing method of a film formation base material, the resin cured film obtained by hardening the said curable composition, and its manufacturing method are realizable.
以下に、本発明に係る硬化性組成物およびその硬化塗膜を有する表層膜形成基材、表層膜形成基材の製造方法の一例を説明するが、本発明はこれらに限定されるものではない。 Below, although an example of the manufacturing method of the surface layer film formation base material and surface layer film formation base material which have the curable composition which concerns on this invention, and its cured coating film is demonstrated, this invention is not limited to these. .
図１は、本発明の実施形態に係る表層膜形成基材の一例を示す概略図である。 FIG. 1 is a schematic diagram illustrating an example of a surface layer film-forming substrate according to an embodiment of the present invention.
表層膜形成基材３は、可撓性基材１と、可撓性基材１の少なくとも一方面に形成された硬化膜２とを備える。
The surface layer film-forming
可撓性基材１は、硬化性組成物中に含まれる各成分に溶解しない材質よりなるものであればよく、一般的な材料を用いることができる。中でも、平滑性、耐熱性を備え、機械的強度に優れたものが好ましい。可撓性基材１としては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリメチルアクリレート、ポリメチルメタクリレート、ポリアクリレート、ポリメタクリレート、ポリカーボネート、ポリアミド、ポリプロピレン、ポリビニルアセタール、ポリエーテルケトンなどの各種樹脂からなるフィルムなどを利用できる。
The
硬化性膜２は、二官能以上の電離放射線硬化樹脂と光重合開始剤とを少なくとも含有する硬化性組成物を、可撓性基材１の表面に塗布して硬化させたものである。
The
本発明の硬化性組成物に含まれる二官能以上の電離放射線硬化樹脂として、１分子中に２個以上の（メタ）アクリロイル基を分子中に有する多官能モノマーを用いることができる。例えば、１，４‐ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、３−メチルペンタンジオールジ（メタ）アクリレート、ジエチレングリコールビスβ‐（メタ）アクリロイルオキシプロピネート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリ（２−ヒドロキシエチル）イソシアネートジ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、２，３‐ビス（メタ）アクリロイルオキシエチルオキシメチル［２．２．１］ヘプタン、ポリ１，２−ブタジエンジ（メタ）アクリレート、１，２−ビス（メタ）アクリロイルオキシメチルヘキサン、ノナエチレングリコールジ（メタ）アクリレート、テトラデカンエチレングリコールジ（メタ）アクリレート、１，１０−デカンジオールジ（メタ）アクリレート、３，８−ビス（メタ）アクリロイルオキシメチルトリシクロ［５．２．１０］デカン、水素添加ビスフェノールＡジ（メタ）アクリレート、２，２−ビス（４−（メタ）アクリロイルオキシジエトキシフェニル）プロパン、１，４−ビス（（メタ）アクリロイルオキシメチル）シクロヘキサン、ヒドロキシピバリンサンエステルネオペンチルグリコールジ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、エポキシ変性ビスフェノールＡジ（メタ）アクリレートなどを挙げることができる。多官能モノマーは、単独で用いても良いし、２種類以上を併用して用いても良い。また、必要で有れば単官能の電離放射線硬化樹脂と併用して共重合させても良い。
As the bifunctional or higher ionizing radiation curable resin contained in the curable composition of the present invention, a polyfunctional monomer having two or more (meth) acryloyl groups in one molecule can be used. For example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (meth) acryloyloxypropionate, trimethylolethanetri (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2-hydroxyethyl) Socyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane,
なお、本発明において「（メタ）アクリロイル基」とは「アクリロイル基」と「メタクリロイル基」の両方を示している。また、「（メタ）アクリレート」とは「アクリレート」と「メタクリレート」の両方を示している。 In the present invention, “(meth) acryloyl group” means both “acryloyl group” and “methacryloyl group”. “(Meth) acrylate” refers to both “acrylate” and “methacrylate”.
また、上記二官能以上の電離放射線硬化樹脂を重合させて合成された多官能オリゴマーを用いることもできる。その際、重合に用いる多官能モノマーは単一成分でもよく、また、２種類以上の上記二官能以上の電離放射線硬化樹脂を共重合させた多官能ブロックオリゴマーを用いることもできる。 Moreover, the polyfunctional oligomer synthesize | combined by superposing | polymerizing the said bifunctional or more ionizing radiation hardening resin can also be used. In this case, the polyfunctional monomer used for the polymerization may be a single component, or a polyfunctional block oligomer obtained by copolymerizing two or more types of the above-mentioned bifunctional or higher ionizing radiation curable resins may be used.
また本発明は、硬化性組成物に含まれる二官能以上の電離放射線硬化樹脂が、ウレタンアクリレートモノマーあるいはオリゴマーの内少なくとも一つを含有しても良い。 In the present invention, the bifunctional or higher ionizing radiation curable resin contained in the curable composition may contain at least one of urethane acrylate monomers or oligomers.
可撓性基材上に表層膜形成を行うための硬化性組成物の成分として好ましい二官能以上の電離放射線硬化樹脂として、ウレタンアクリレートも挙げることができる。ウレタンアクリレートとしては、一般にポリエステルポリオールにイソシアネートモノマー、もしくはプレポリマーを反応させて得られた生成物に水酸基を有するアクリレートモノマーを反応させ容易に形成されるものを挙げることができる。例えば、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、ジペンタエリスリトールペンタアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートトルエンジイソシアネートウレタンプレポリマー、ジペンタエリスリトールペンタアクリレートトルエンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートイソホロンジイソシアネートウレタンプレポリマー、ジペンタエリスリトールペンタアクリレートイソホロンジイソシアネートウレタンプレポリマーなどを挙げることができる。また、これらの単量体は、１種または２種以上を混合して用いることができる。また、これらはモノマーとして用いてもよいし、一部が重合したオリゴマーとして用いても良い。 Urethane acrylate can also be mentioned as a bifunctional or higher ionizing radiation curable resin that is preferable as a component of the curable composition for forming the surface layer film on the flexible substrate. Examples of urethane acrylates include those that are easily formed by reacting an acrylate monomer having a hydroxyl group with a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. For example, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate Examples include isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate isophorone diisocyanate urethane prepolymer, and the like. Moreover, these monomers can be used 1 type or in mixture of 2 or more types. Moreover, these may be used as a monomer or may be used as a partially polymerized oligomer.
本発明の硬化性組成物に含まれる光重合開始剤は、電離放射線が照射された際にラジカルを発生するものであればよい。例えば、アセトフェノン類、ベンゾイン類、ベンゾフェノン類、ホスフィンオキシド類、ケタール類、アントラキノン類、チオキサントン類などを用いることができる。 The photoinitiator contained in the curable composition of this invention should just generate | occur | produce a radical when ionizing radiation is irradiated. For example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like can be used.
さらに具体的には、（２，４，６−トリメチルベンゾイル）ジフェニルホスフィンオキシドと、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］−フェニル｝−２−メチル−プロパン−１−オンなどの光重合開始剤を併用することができる。（２，４，６−トリメチルベンゾイル）ジフェニルホスフィンオキシドは、フォトブリーチング性を有しているため、光硬化性組成物の内部まで紫外線が届き、光硬化性組成物の下層部まで十分に硬化させることができる。また、（２，４，６−トリメチルベンゾイル）ジフェニルホスフィンオキシドは、安価で、耐光性が良好で黄変しにくく、かつ、揮発性が低い。しかしながら、（２，４，６−トリメチルベンゾイル）ジフェニルホスフィンオキシドを単独で用い、酸素存在下で光硬化させると、酸素阻害の影響により、表面が硬化しにくくなり、表面タック性（粘着性）が強くなるという問題がある。そこで、酸素阻害の影響を受けにくい開始剤である２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］−フェニル｝−２−メチル−プロパン−１−オンと併用することにより、酸素存在下で光硬化させても表面も内部も十分に硬化させることができる。このことにより、ロール・ツー・ロールで可撓性基材上へ表層膜を塗布する際にブロッキングを防止することができる。また、硬化性組成物の表面と内部とを十分に硬化できることにより、硬化収縮が表面側と裏面側とで同じになるため、カールすることを抑制することができる。 More specifically, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} Photopolymerization initiators such as 2-methyl-propan-1-one can be used in combination. Since (2,4,6-trimethylbenzoyl) diphenylphosphine oxide has photobleaching properties, ultraviolet rays reach the inside of the photocurable composition and sufficiently cure to the lower layer of the photocurable composition. Can be made. Further, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide is inexpensive, has good light resistance, hardly yellows, and has low volatility. However, when (2,4,6-trimethylbenzoyl) diphenylphosphine oxide is used alone and photocured in the presence of oxygen, the surface becomes difficult to cure due to the influence of oxygen inhibition, and surface tackiness (adhesiveness) is improved. There is a problem of becoming stronger. Therefore, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1 is an initiator that is not easily affected by oxygen inhibition. -By using together with ON, both the surface and the interior can be sufficiently cured even when photocured in the presence of oxygen. Thereby, blocking can be prevented when the surface layer film is applied onto the flexible substrate by roll-to-roll. Further, since the surface and the inside of the curable composition can be sufficiently cured, the curing shrinkage becomes the same on the front surface side and the back surface side, so that curling can be suppressed.
また、光重合開始剤の添加量は、電離放射線硬化材料１００質量％に対して０．１質量％以上１０質量％以下程度であり、この範囲の中でも１質量％以上７質量％以下程度であることが好ましい。 Moreover, the addition amount of a photoinitiator is about 0.1 mass% or more and 10 mass% or less with respect to 100 mass% of ionizing radiation hardening materials, and is 1 mass% or more and about 7 mass% or less also in this range. It is preferable.
光重合開始剤の添加量が電離放射線硬化材料１００重量％に対して０．１重量％未満であった場合、後述の硬化方法により硬化性組成物が十分に硬化せず、満足な特性の表面層形成基材を得られない。また、１０重量％を超えた場合、硬化は十分に進行するものの表面層形成基材中の光重合開始剤の残渣の影響により、硬化膜の機械特性が低下する。 When the addition amount of the photopolymerization initiator is less than 0.1% by weight with respect to 100% by weight of the ionizing radiation curable material, the curable composition is not sufficiently cured by the curing method described later, and the surface has satisfactory characteristics. A layer-forming substrate cannot be obtained. On the other hand, when the content exceeds 10% by weight, the curing proceeds sufficiently, but the mechanical properties of the cured film deteriorate due to the influence of the residue of the photopolymerization initiator in the surface layer forming substrate.
また、硬化性組成物の粘度は、５０ｍＰａ・ｓ以上１００００ｍＰａ・ｓ以下である。 Moreover, the viscosity of the curable composition is 50 mPa · s or more and 10,000 mPa · s or less.
硬化性組成物の粘度が５０ｍＰａ・ｓ未満であった場合、表層膜を厚さ３０μｍ以上で形成することができない、もしくはできたとしても形成方法が限定されてしまい、大面積での表層膜形成基材の作製はできなくなる。また、１００００ｍＰａ・ｓを超えた場合、表層膜を形成した面内で膜厚のばらつき無く均一に形成することができない。 When the viscosity of the curable composition is less than 50 mPa · s, the surface layer film cannot be formed with a thickness of 30 μm or more, or even if it can be formed, the formation method is limited, and the surface layer film is formed in a large area. The base material cannot be produced. On the other hand, when it exceeds 10,000 mPa · s, it cannot be formed uniformly without variation in film thickness within the surface on which the surface layer film is formed.
本発明の硬化性組成物は、溶剤を含んでいてもよい。溶剤として例えば、ジブチルエーテル、ジメトキシメタン、ジメトキシエタン、ジエトキシエタン、プロピレンオキシド、１，４−ジオキサン、１，３−ジオキソラン、１，３，５−トリオキサン、テトラヒドロフラン、アニソールおよびフェネトールなどのエーテル類、またアセトン、メチルエチルケトン、ジエチルケトン、ジプロピルケトン、ジイソブチルケトン、シクロペンタノン、シクロヘキサノン、メチルシクロヘキサノン、およびメチルシクロヘキサノンなどのケトン類、また蟻酸エチル、蟻酸プロピル、蟻酸ｎ−ペンチル、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン醸エチル、酢酸ｎ−ペンチル、およびγ−プチロラクトンなどのエステル類、さらにメチルセロソルブ、セロソルブ、ブチルセロソルブ、セロソルブアセテートなどのセロソルブ類、また炭酸ジメチルなどを用いることができる。これらの溶剤は単独、もしくは２種類以上を混合して用いることができる。 The curable composition of the present invention may contain a solvent. Examples of the solvent include ethers such as dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole and phenetole, Also, ketones such as acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, Esters such as methyl propionate, propion brewed ethyl, n-pentyl acetate, and γ-ptyrolactone, methyl cellosolve, cellosolve, butyl cellosolve, cello Cellosolves such as lube acetate and the like can be used dimethyl carbonate. These solvents can be used alone or in admixture of two or more.
また、本発明の硬化性組成物は、上記の溶剤を硬化性組成物全体の質量に対して１質量％以上５０質量％以下の配合比率で含有することが好ましい。溶剤を含有する場合、硬化性組成物の粘度が上述した範囲内となるように、配合比率を調整する。 Moreover, it is preferable that the curable composition of this invention contains said solvent by the compounding ratio of 1 to 50 mass% with respect to the mass of the whole curable composition. When the solvent is contained, the blending ratio is adjusted so that the viscosity of the curable composition is within the above-described range.
また、本発明の硬化性組成物は、添加剤として高分子系可塑剤、防汚剤、表面調整剤、レベリング剤、屈折率調整剤、密着性向上剤、硬化剤、光増感剤、導電材料などを加えても良い。 Further, the curable composition of the present invention includes, as additives, a polymeric plasticizer, an antifouling agent, a surface conditioner, a leveling agent, a refractive index adjuster, an adhesion improver, a curing agent, a photosensitizer, and a conductive agent. Materials etc. may be added.
次いで、本発明に係る表層膜形成基材の製造方法を説明する。 Subsequently, the manufacturing method of the surface layer film formation base material concerning the present invention is explained.
本発明に係る表層膜形成基材の製造方法は、少なくとも、可撓性基材の表面へ硬化性組成物を塗布する工程と、塗布膜を光硬化させる工程とを少なくとも備える。 The method for producing a surface film-forming substrate according to the present invention includes at least a step of applying a curable composition to the surface of a flexible substrate and a step of photocuring the coating film.
本発明の製造方法において、可撓性基材をロール・ツー・ロールで搬送しても良い。この場合、表層膜形成基材を効率的に製造することができる。 In the production method of the present invention, the flexible substrate may be conveyed by roll-to-roll. In this case, a surface layer film-forming substrate can be produced efficiently.
可撓性基材をロール・ツー・ロールで搬送する場合、可撓性基材の厚さは、ロール・ツー・ロールの基材搬送装置により連続的に搬送できる程度であれば良い。可撓性基材の厚さは、２５μｍ以上２００μｍ以下程度であることが好ましく、さらには４０μｍ以上１００μｍ以下程度がより好ましい。可撓性基材が２５μｍより薄い場合、可撓性基材にかかる張力により破断する可能性があり、可撓性基材が２００μｍより厚い場合、表層膜の形成工程において熱や光を減衰させる要因となる可能性がある。ただし、可撓性基材の厚さは上記範囲に限定されるものではない。 When the flexible base material is transported by roll-to-roll, the thickness of the flexible base material may be such that it can be continuously transported by a roll-to-roll base material transport device. The thickness of the flexible substrate is preferably about 25 μm to 200 μm, and more preferably about 40 μm to 100 μm. When the flexible substrate is thinner than 25 μm, it may break due to the tension applied to the flexible substrate. When the flexible substrate is thicker than 200 μm, heat and light are attenuated in the surface layer film forming process. It may be a factor. However, the thickness of the flexible substrate is not limited to the above range.
また、本発明の製造方法において、表層膜形成基材を作製した後、硬化性組成物により形成された塗布膜を可撓性基材から剥離することで、硬化膜の単体を得ることもできる。 Moreover, in the manufacturing method of this invention, after producing a surface layer film formation base material, the single-piece | unit of a cured film can also be obtained by peeling the coating film formed with the curable composition from a flexible base material. .
可撓性基材上に硬化性組成物を塗布する方法としては、適宜公知の塗布方法の中からウェットコーティング法と総称される方法を用いることができる。例えば、ディップコーティング法、スピンコーティング法、フローコーティング法、スプレーコーティング法、ロールコーティング法、グラビアロールコーティング法、エアドクターコーティング法、プレードコーティング法、ワイヤードクターコーティング法、ナイフコーティング法、リバースコーティング法、トランスファロールコーティング法、マイクログラビアコーティング法、キスコーティング法、キャストコーティング法、スロットオリフィスコーティング法、カレンダーコーティング法、ダイコーティング法、キャップコーティング法、アプリケータコーティング法などを用いることができる。中でも、ダイコーティング法、キャップコーティング法、ロールコーティング法などの塗布方法では、広い範囲の粘度の硬化性組成物について均一な塗布膜を形成できる。 As a method for applying the curable composition on the flexible substrate, a method generally referred to as a wet coating method among known application methods can be used. For example, dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure roll coating method, air doctor coating method, blade coating method, wire doctor coating method, knife coating method, reverse coating method, transfer A roll coating method, a micro gravure coating method, a kiss coating method, a cast coating method, a slot orifice coating method, a calendar coating method, a die coating method, a cap coating method, an applicator coating method and the like can be used. Among these, uniform coating films can be formed for curable compositions having a wide range of viscosities by coating methods such as die coating, cap coating, and roll coating.
上記の塗布方法により、可撓性基材の少なくとも片面上に硬化性組成物を塗布することにより塗膜を形成することができる。この際、乾燥後の膜厚が３０μｍ以上１００μｍ以下程度となるように、硬化性組成物の塗布を行うことが好ましい。 A coating film can be formed by applying the curable composition on at least one surface of the flexible substrate by the above application method. At this time, it is preferable to apply the curable composition so that the film thickness after drying is about 30 μm or more and 100 μm or less.
可撓性基材上に形成した塗膜中の溶剤を除去するために乾燥を行う。乾燥は、加熱、送風、熱風など、適宜公知の手法を用いて行うことができる。 Drying is performed to remove the solvent in the coating film formed on the flexible substrate. Drying can be performed using a known method as appropriate, such as heating, air blowing, and hot air.
乾燥させた塗膜を大気下で硬化させて硬化膜を形成する硬化方法としては、適宜公知の硬化方法を用いることができる。例えば、紫外線照射、電子線放射などを用いることができる。硬化膜を形成する硬化方法として、紫外線照射の場合、高圧水銀灯、低圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、などの光源を採用できる。また、電子線硬化の場合、コックロフトワルト型、バンデグラフ型、共振変圧型、絶縁コア変圧器型、直線型、ダイナミトロン型、高周波型、などの各種電子線加速器から放出される電子線などを用いることができる。用いる電子線は、５０ＫｅＶ以上１０００ＫｅＶ以下程度のエネルギーを有するのが好ましく、１００ＫｅＶ以上３００ＫｅＶ以下程度のエネルギーを有する電子線がより好ましい。 As a curing method for curing the dried coating film in the air to form a cured film, a known curing method can be used as appropriate. For example, ultraviolet irradiation, electron beam radiation, or the like can be used. As a curing method for forming a cured film, in the case of ultraviolet irradiation, a light source such as a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, or a xenon arc can be employed. In the case of electron beam curing, the electron beam emitted from various electron beam accelerators such as cockloftwald type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, high frequency type, etc. Can be used. The electron beam used preferably has an energy of about 50 KeV or more and 1000 KeV or less, and more preferably an electron beam having an energy of about 100 KeV or more and 300 KeV or less.
硬化膜の膜厚（硬化性組成物の乾燥後の膜厚）は、塗布精度、取扱いの観点から３０μｍ以上１００μｍ以下の範囲であることが好ましい。硬化膜の膜厚が３０μｍ未満では機械的強度が低いため取り扱い難い。また、硬化膜の膜厚が１００μｍより厚い場合では巻き取りや光硬化性組成物の塗布が困難となる。 The film thickness of the cured film (film thickness after drying of the curable composition) is preferably in the range of 30 μm or more and 100 μm or less from the viewpoint of coating accuracy and handling. If the thickness of the cured film is less than 30 μm, it is difficult to handle because the mechanical strength is low. Moreover, when the film thickness of a cured film is thicker than 100 micrometers, winding and application | coating of a photocurable composition will become difficult.
本発明では、可撓性基材を支持体として用いることにより、ロール・ツー・ロール方式で安価に生産可能であり、表層膜の表面から下層部まで均一な硬化進行度が得られ、カールやブロッキングが抑えられた３０μｍから１００μｍ程度の膜生成物の製造に適した硬化性組成物およびこれを用いて形成した表層膜形成基材を提供することができる。 In the present invention, by using a flexible base material as a support, it can be produced at a low cost by a roll-to-roll method, and a uniform degree of curing can be obtained from the surface of the surface layer film to the lower layer portion. It is possible to provide a curable composition suitable for the production of a film product of about 30 μm to 100 μm in which blocking is suppressed, and a surface layer film-forming substrate formed using the same.
以下、本発明を更に詳しく説明するために実施例を挙げるが、本発明はこれらの実施例にのみ限定されるものではない。 Hereinafter, examples will be given to describe the present invention in more detail, but the present invention is not limited to these examples.
＜実施例１＞
電離放射線硬化樹脂「ＵＡ１２２Ｐ」（新中村化学工業社製）６６．７重量部、光重合開始剤「イルガキュア１８４」（ＢＡＳＦ社製）３．３重量部、溶剤「メチルエチルケトン」３０重量部を混合、攪拌し、硬化性組成物を調製した。このときの硬化性組成物の粘度は１５０ｍＰａ・ｓであった。尚、「イルガキュア」は登録商標である。
<Example 1>
Ionizing radiation curable resin “UA122P” (manufactured by Shin-Nakamura Chemical Co., Ltd.) 66.7 parts by weight, photopolymerization initiator “Irgacure 184” (manufactured by BASF) 3.3 parts by weight, solvent “methyl ethyl ketone” 30 parts by weight, Stir to prepare a curable composition. The viscosity of the curable composition at this time was 150 mPa · s. “Irgacure” is a registered trademark.
次に上記硬化性組成物をアプリケータを用いて乾燥後の膜厚が５０μｍになるように、可撓性基材「ルミラー７５Ｔ６０」（東レ社製）の上に塗布し、塗膜を１００℃のオーブンにて２分間乾燥させた後、高圧水銀灯により２５０ｍＪ／ｃｍ２の紫外線を照射することにより、乾燥させた塗膜を硬化させて、大気下にて硬化膜を形成した。 Next, the curable composition was applied onto a flexible substrate “Lumirror 75T60” (manufactured by Toray Industries, Inc.) so that the film thickness after drying was 50 μm using an applicator, and the coating film was 100 ° C. After drying in an oven for 2 minutes, the dried coating film was cured by irradiating UV light of 250 mJ / cm 2 with a high-pressure mercury lamp to form a cured film in the atmosphere.
＜実施例２＞
電離放射線硬化樹脂「ＵＡ１２２Ｐ」（新中村化学工業社製）５３．４重量部、単官能電離放射線硬化樹脂「ライトアクリレート１３０Ａ」（共栄社化学社製）１３．３重量部、光重合開始剤「イルガキュア１８４」（ＢＡＳＦ社製）３．３重量部、溶剤「メチルエチルケトン」３０重量部を混合、攪拌し、硬化性組成物を調製した。このときの硬化性組成物の粘度は１２０ｍＰａ・ｓであった。
<Example 2>
Ionizing radiation curable resin “UA122P” (manufactured by Shin-Nakamura Chemical Co., Ltd.) 53.4 parts by weight, monofunctional ionizing radiation curable resin “light acrylate 130A” (manufactured by Kyoeisha Chemical Co., Ltd.) 13.3 parts by weight, photopolymerization initiator “Irgacure 184 "(BASF) 3.3 parts by weight and 30 parts by weight of solvent" methyl ethyl ketone "were mixed and stirred to prepare a curable composition. The viscosity of the curable composition at this time was 120 mPa · s.
次に上記硬化性組成物をアプリケータを用いて乾燥後の膜厚が５０μｍになるように、可撓性基材「ルミラー７５Ｔ６０」（東レ社製）の上に塗布し、塗膜を１００℃のオーブンにて２分間乾燥させた後、高圧水銀灯により２５０ｍＪ／ｃｍ２の紫外線を照射することにより、乾燥させた塗膜を硬化させて、大気下にて硬化膜を形成した。 Next, the curable composition was applied onto a flexible substrate “Lumirror 75T60” (manufactured by Toray Industries, Inc.) so that the film thickness after drying was 50 μm using an applicator, and the coating film was 100 ° C. After drying in an oven for 2 minutes, the dried coating film was cured by irradiating UV light of 250 mJ / cm 2 with a high-pressure mercury lamp to form a cured film in the atmosphere.
＜実施例３＞
電離放射線硬化樹脂「ＵＡ１２２Ｐ」（新中村化学工業社製）６０．４重量部、可塑剤「フタル酸ジメチル」６．７重量部、光重合開始剤「イルガキュア１８４」（ＢＡＳＦ社製）２．９重量部、溶剤「メチルエチルケトン」３０重量部を混合、攪拌し、硬化性組成物を調製した。このときの硬化性組成物の粘度は１３０ｍＰａ・ｓであった。
<Example 3>
Ionizing radiation curable resin “UA122P” (manufactured by Shin-Nakamura Chemical Co., Ltd.) 60.4 parts by weight, plasticizer “dimethyl phthalate” 6.7 parts by weight, photopolymerization initiator “Irgacure 184” (manufactured by BASF) 2.9 Part by weight and 30 parts by weight of the solvent “methyl ethyl ketone” were mixed and stirred to prepare a curable composition. The viscosity of the curable composition at this time was 130 mPa · s.
次に上記硬化性組成物をアプリケータを用いて乾燥後の膜厚が５０μｍになるように、可撓性基材「ルミラー７５Ｔ６０」（東レ社製）の上に塗布し、塗膜を１００℃のオーブンにて２分間乾燥させた後、高圧水銀灯により２５０ｍＪ／ｃｍ２の紫外線を照射することにより、乾燥させた塗膜を硬化させて、大気下にて硬化膜を形成した。 Next, the curable composition was applied onto a flexible substrate “Lumirror 75T60” (manufactured by Toray Industries, Inc.) so that the film thickness after drying was 50 μm using an applicator, and the coating film was 100 ° C. After drying in an oven for 2 minutes, the dried coating film was cured by irradiating UV light of 250 mJ / cm 2 with a high-pressure mercury lamp to form a cured film in the atmosphere.
＜比較例１＞
乾燥後の膜厚が１０μｍとなるように硬化性組成物を塗布したことを除いて、実施例１と同様の材料及び方法により、可撓性基材上への硬化性組成物の塗布を行った。
<Comparative Example 1>
The curable composition was applied onto the flexible substrate by the same material and method as in Example 1 except that the curable composition was applied so that the film thickness after drying was 10 μm. It was.
＜比較例２＞
乾燥後の膜厚が１５０μｍとなるように硬化性組成物を塗布したことを除いて、実施例１と同様の材料及び方法により、可撓性基材上への硬化性組成物の塗布を行った。
<Comparative Example 2>
The curable composition was applied on the flexible substrate by the same material and method as in Example 1 except that the curable composition was applied so that the film thickness after drying was 150 μm. It was.
（評価結果）
上記実施例、比較例により作製した表面層形成基材をそれぞれ２枚用意し、一方の表面層形成基材の可撓性基材面と他方の表面層形成基材の表層膜面を密着させて１ｋｇ／２５ｃｍ２にて加圧し、その際の両層のブロッキングの状態を暗室にて、３波長蛍光灯（ 松下電器産業株式会社製ナショナルパルック３波長形蛍光灯（ＦＬＲ４０Ｓ・ＥＸ−Ｎ／Ｍ−Ｘ）の直下４０ｃｍで目視観察し、評価した。その結果、実施例１、２、３、比較例１では両層面は密着しておらずブロッキング性は無かったが、比較例２では両層面が密着し貼りついていてブロッキングが起きていた。
(Evaluation results)
Prepare two surface layer-forming substrates prepared in the above examples and comparative examples, and make the surface of the flexible layer of one surface layer-forming substrate and the surface layer surface of the other surface-layer-forming substrate adhere to each other. Pressurize at 1kg / 25cm2 and set the blocking state of both layers at that time in a dark room with a three-wavelength fluorescent lamp (Matsushita Electric Industrial Co., Ltd. National Parook three-wavelength fluorescent lamp (FLR40S · EX-N / M- As a result, in Example 1, 2, 3 and Comparative Example 1, both layer surfaces were not in close contact and there was no blocking property, but in Comparative Example 2, both layer surfaces were Adhering and sticking, blocking occurred.
上記実施例、比較例により作製した表面層形成基材を５ｃｍ角に切り出し、１辺を定規で抑え、反対辺の浮き上がり高さを測定し、カール評価した。その結果、浮き上がり高さ（カール量）は実施例１、２、３、比較例２では１０ｍｍ、比較例１では２０ｍｍであった。 The surface layer-formed base material produced by the above Examples and Comparative Examples was cut into 5 cm squares, one side was suppressed with a ruler, the raised height of the opposite side was measured, and the curl was evaluated. As a result, the lifting height (curl amount) was 10 mm in Examples 1, 2, 3 and Comparative Example 2, and 20 mm in Comparative Example 1.
以上の評価結果から、実施例１〜３に係る硬化性組成物を用いた場合、ウェットコーティング法により、３０〜１００μｍの厚さで、カール及びブロッキングが抑制された自立膜を形成できることが確認された。 From the above evaluation results, when the curable compositions according to Examples 1 to 3 were used, it was confirmed that a self-supporting film in which curling and blocking were suppressed with a thickness of 30 to 100 μm could be formed by a wet coating method. It was.
また、上記実施例１から３により形成された表層膜形成基材はいずれも良好な面性、塗膜強度を示し、また表面タック性もなかった。これに対して、比較例１では、作製した表層膜（硬化膜）にはカールが強く発生し、表層膜形成基材全体を湾曲させると表層膜が追従しきれずに割れが発生した。また、比較例２では、作製した表層膜（硬化膜）は、表面の面性が悪く不均一な凹凸が発生した。また、紫外線照射による硬化性組成物の硬化が不十分であり、表層膜内部が未硬化状態となった。このように、実施例１〜３では、面性に優れ、表層膜（効果膜）の表層部から下層部まで均一な硬化進行度が得られることが確認された。 Further, the surface layer film-forming substrates formed in Examples 1 to 3 showed good surface properties and coating strength, and did not have surface tackiness. On the other hand, in Comparative Example 1, strong curling occurred in the produced surface layer film (cured film), and when the entire surface layer film-forming substrate was curved, the surface layer film could not follow and cracks occurred. Moreover, in the comparative example 2, the produced surface layer film (cured film) had poor surface properties and uneven unevenness occurred. Moreover, hardening of the curable composition by ultraviolet irradiation was inadequate, and the inside of the surface layer film was in an uncured state. Thus, in Examples 1-3, it was confirmed that it was excellent in surface property and a uniform degree of curing progress was obtained from the surface layer portion to the lower layer portion of the surface layer film (effect film).
本発明は、液晶表示装置などの表示装置部品や包装材、建築部材などに用いられる機能性フィルムなどに適用可能である。 The present invention can be applied to display device parts such as liquid crystal display devices, functional films used for packaging materials, building members, and the like.
１・・・・・可撓性基材
２・・・・・硬化膜
３・・・・・表層膜形成基材
DESCRIPTION OF
Claims (9)
少なくとも、二官能以上の電離放射線硬化樹脂と、光重合開始剤とを含有し、
前記光重合開始剤の配合比率が、前記二官能以上の電離放射線硬化樹脂を含む電離放射線硬化樹脂の全体の質量に対して、０．１質量％以上１０質量％以下であり、
粘度が５０ｍＰａ・ｓ以上１００００ｍＰａ・ｓ以下であることを特徴とする、硬化性組成物。 A curable composition for forming a surface layer film having a thickness of 30 μm or more and 100 μm or less by being applied to a flexible substrate and cured,
Containing at least a bifunctional or higher ionizing radiation curable resin and a photopolymerization initiator,
The blending ratio of the photopolymerization initiator is 0.1% by mass or more and 10% by mass or less with respect to the total mass of the ionizing radiation curable resin including the bifunctional or higher ionizing radiation curable resin.
A curable composition having a viscosity of 50 mPa · s or more and 10,000 mPa · s or less.
前記可撓性基材表面に、請求項１から５のいずれかに記載の硬化性組成物を塗布して塗布膜を形成する工程と、
前記塗布膜を光硬化させる工程と備える、表層膜形成基材の製造方法。 A method for producing a surface layer film-forming substrate in which a surface layer film is formed on a flexible substrate,
Applying the curable composition according to claim 1 to the surface of the flexible substrate to form a coating film;
A method for producing a surface layer film-forming substrate, comprising a step of photocuring the coating film.
可撓性基材表面に、請求項１から５のいずれかに記載の硬化性組成物を塗布して塗布膜を形成する工程と、
前記塗布膜を光硬化させる工程と、
光硬化後の塗布膜を前記可撓性基材から剥離する工程とを備える、樹脂硬化膜の製造方法。 A method for producing a cured resin film,
Applying a curable composition according to any one of claims 1 to 5 to a flexible substrate surface to form a coating film;
Photocuring the coating film;
A method for producing a cured resin film, comprising: a step of peeling a photocured coating film from the flexible substrate.
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