TW202323033A - Hard coat film and method for manufacturing the same - Google Patents

Hard coat film and method for manufacturing the same Download PDF

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TW202323033A
TW202323033A TW111138741A TW111138741A TW202323033A TW 202323033 A TW202323033 A TW 202323033A TW 111138741 A TW111138741 A TW 111138741A TW 111138741 A TW111138741 A TW 111138741A TW 202323033 A TW202323033 A TW 202323033A
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hard coat
film
compound
layer
mass
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中山雄二
江草直樹
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日商東洋油墨Ｓｃ控股股份有限公司
日商東洋科美股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/06—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood
    • B05D7/08—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood using synthetic lacquers or varnishes
    • B05D7/10—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood using synthetic lacquers or varnishes based on cellulose derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

This hard coat film has a triacetylcellulose film (1), a mixed layer (2), and a hard coat layer (3). The hard coat layer (3) is formed of a hard coat layer-forming composition that contains a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photoinitiator (C), and a solvent (D). The mass ratio of compound (B)/solvent (D) in the hard coat layer-forming composition is 0.03-0.20. The mixed layer (2) is a layer formed by swelling or dissolving the hard coat layer-forming composition on the triacetylcellulose film (1). When a cross section of the hard coat film in the thickness direction is observed by a scanning electron microscope, the film-thickness proportion of the mixed layer (2) in the total film thickness of the hard coat layer (3) and the mixed layer (2) is 65% or more.

Description

硬塗膜及其製造方法Hard coating film and its manufacturing method

本發明是有關於一種硬塗膜及其製造方法。The invention relates to a hard coating film and a manufacturing method thereof.

於作為電視、電腦、汽車導航系統、車載用儀表盤、行動電話等的圖像顯示裝置而使用的液晶顯示器、電漿顯示器、電致發光（Electroluminescent，EL）顯示器、後部投影顯示器、陰極射線管（Cathode Ray Tube，CRT）顯示器等各種顯示器中，出於保護顯示器等的表面的目的而使用硬塗膜。Liquid crystal displays, plasma displays, electroluminescent (EL) displays, rear projection displays, and cathode ray tubes used as image display devices for televisions, computers, car navigation systems, automotive dashboards, and mobile phones In various displays such as a Cathode Ray Tube (CRT) display, a hard coat film is used for the purpose of protecting the surface of the display or the like.

硬塗膜具有機械特性、尺寸穩定性、電絕緣性等優異的性質，因此作為以光學顯示材料為代表的包裝材料、電絕緣材料、各種照相材料、平面藝術（graphic arts）材料等多種用途的基材，廣泛使用透明的塑膠。 透明的塑膠中，就透明性、光的折射率、耐衝擊性、耐熱性、耐久性等方面而言，顯示器般的光學顯示材料大多使用三乙醯纖維素（Triacetyl Cellulose，TAC）膜。 The hard coat film has excellent properties such as mechanical properties, dimensional stability, and electrical insulation, so it is used as a packaging material represented by optical display materials, electrical insulation materials, various photographic materials, and graphic arts materials. As the substrate, transparent plastic is widely used. Among transparent plastics, in terms of transparency, light refractive index, impact resistance, heat resistance, durability, etc., most optical display materials like displays use triacetyl cellulose (TAC) film.

通常，硬塗膜是於作為基材的三乙醯纖維素膜上利用塗敷或印刷等方法將樹脂組成物形成硬塗層而製造。作為此種硬塗膜，例如於專利文獻1中揭示了一種硬塗組成物，其包含含有如下多官能性單體，即於1分子中具有兩個以上的(甲基)丙烯醯基的多官能性單體的電離放射線硬化型樹脂、光聚合起始劑、及溶劑。且記載了一種硬塗膜，其中，藉由將該硬塗組成物塗佈於基材，於與基材混合形成的混合層、及相對於該混合層形成於與基材側為相反之側的硬塗層的合計膜厚中混合層所佔的膜厚比率為32%以上且61%以下。Generally, a hard coat film is manufactured by forming a resin composition into a hard coat layer on a triacetyl cellulose film as a base material by methods such as coating or printing. As such a hard coat film, for example, Patent Document 1 discloses a hard coat composition comprising a polyfunctional monomer having two or more (meth)acryl groups in one molecule. Ionizing radiation curable resin of functional monomer, photopolymerization initiator, and solvent. Furthermore, a hard coat film is described, wherein a mixed layer formed by mixing with the base material by applying the hard coat composition to the base material, and formed on the side opposite to the base material side with respect to the mixed layer The film thickness ratio of the mixed layer in the total film thickness of the hard coat layer is 32% or more and 61% or less.

另外，硬塗膜中，因硬塗層的折射率與成為基材膜的三乙醯纖維素的折射率的折射率差、或以界面為界的折射率的不連續的變化，而導致於硬塗層表面處反射的光與於硬塗層和基材膜的界面處反射的光發生干涉，引起干涉不均（彩虹色的不均），從而有使顯示器的視認性劣化，而且損害顯示器的美觀的問題。In addition, in the hard coat film, due to the refractive index difference between the refractive index of the hard coat layer and the triacetyl cellulose used as the base film, or a discontinuous change in the refractive index with the interface as the boundary, the The light reflected at the surface of the hard coat layer interferes with the light reflected at the interface between the hard coat layer and the base film, causing interference unevenness (unevenness of the rainbow color), thereby deteriorating the visibility of the display and damaging the display aesthetic problems.

作為減少此種干涉不均的產生的方法，於專利文獻2中敘述了一種如下方法：藉由使用使基材溶解或膨潤的溶劑形成硬塗層而於硬塗層與基材的界面處不連續地形成微小的凹凸。於專利文獻3中敘述了一種如下方法：藉由將包含使基材溶解或膨潤的溶劑、及具有特定範圍的溶解度參數值的活性能量線硬化型化合物的組成物塗佈於該基材而形成硬塗層。 [現有技術文獻] [專利文獻] As a method of reducing the occurrence of such interference unevenness, a method is described in Patent Document 2: by forming a hard coat layer using a solvent that dissolves or swells the base material, the interface between the hard coat layer and the base material is not formed. Minute unevenness is continuously formed. Patent Document 3 describes a method in which a substrate is formed by applying a composition comprising a solvent for dissolving or swelling a substrate and an active energy ray-curable compound having a solubility parameter value within a specific range to the substrate. hard coat. [Prior art literature] [Patent Document]

[專利文獻1]日本專利特開2014-058601號公報 [專利文獻2]日本專利特開2003-131007號公報 [專利文獻3]日本專利特開2007-160513號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2014-058601 [Patent Document 2] Japanese Patent Laid-Open No. 2003-131007 [Patent Document 3] Japanese Patent Laid-Open No. 2007-160513

[發明所欲解決之課題] 然而，於此種先前的硬塗膜中，即便可減少干涉不均，但當減少干涉不均時，混合層的形成的控制及界面的凹凸等的控制變得困難，塗膜霧度的降低及耐擦傷性的惡化成為問題。即，現狀是無法同時滿足干涉不均的抑制與塗膜霧度及耐擦傷性。 進而，將三乙醯纖維素膜用作基材的硬塗膜的透濕度高，因此有於高溫高濕度環境下，因膜的吸濕而尺寸發生變化，從而產生變形、或密接性降低等問題。 [Problem to be Solved by the Invention] However, in such a conventional hard coat film, even if the interference unevenness can be reduced, the control of the formation of the mixed layer and the control of the unevenness of the interface become difficult, and the haze of the coating film is reduced. And deterioration of scratch resistance becomes a problem. That is, the current situation is that suppression of interference unevenness, coating film haze, and scratch resistance cannot be satisfied at the same time. Furthermore, a hard coat film using a triacetyl cellulose film as a base material has a high water vapor transmission rate, so in a high-temperature, high-humidity environment, the film may change in size due to moisture absorption, resulting in deformation or a decrease in adhesion. question.

因此，本發明的目的在於提供一種硬塗膜，其中，藉由使特定的硬塗層形成用組成物浸透於三乙醯纖維素膜中形成特定比率的混合層，可於不使塗膜霧度及耐擦傷性惡化的情況下（於設為實用上無問題的範圍內的同時）抑制干涉不均，進而密接性亦優異。 [解決課題之手段] Therefore, it is an object of the present invention to provide a hard coat film in which a mixed layer of a specific ratio is formed by impregnating a specific composition for forming a hard coat layer in a triacetyl cellulose film, thereby preventing the coating film from being fogged. When the degree and scratch resistance deteriorate (while setting it within a practically no problem range), the interference unevenness is suppressed, and the adhesion is also excellent. [Means to solve the problem]

為了解決所述課題，本發明者等人反覆進行了銳意研究，結果完成了以下發明。 [1]： 一種硬塗膜，具有三乙醯纖維素膜、混合層、及硬塗層，所述硬塗膜中， 所述硬塗層由硬塗層形成用組成物形成，所述硬塗層形成用組成物包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D）， 所述硬塗層形成用組成物中的化合物（B）/溶劑（D）的質量比為0.03～0.20， 所述混合層是使所述硬塗層形成用組成物於所述三乙醯纖維素膜中溶解或膨潤而形成的層， 於利用掃描式電子顯微鏡對硬塗膜觀察厚度方向上的剖面時，於所述硬塗層與所述混合層的合計膜厚中所述混合層所佔的膜厚比率為65%以上。 [2]： 如[1]所述的硬塗膜，其中，具有一個乙烯性不飽和基的化合物（B）為短邊2 cm×長邊4 cm×厚度80 μm的三乙醯纖維素膜的初期的質量（X1）、與將所述三乙醯纖維素膜於25℃的環境下在35 g的具有一個乙烯性不飽和基的化合物（B）中浸漬2小時後的三乙醯纖維素膜的質量（X2）的質量變化值[（X2）/（X1）]為1.2以上的具有一個乙烯性不飽和基的化合物（b1）。 [3]： 如[1]或[2]所述的硬塗膜，其中，溶劑（D）為短邊10 cm×長邊10 cm×厚度80 μm的三乙醯纖維素膜的初期的霧度值（Y1）、與對所述三乙醯纖維素膜於25℃的環境下滴加0.1 g的溶劑（D）並放置2分鐘後於60℃下加熱1分鐘後的三乙醯纖維素膜的霧度值（Y2）的霧度變化值[（Y2）-（Y1）]為0.10以上的溶劑（d1）。 [4]： 如[1]至[3]中任一項所述的硬塗膜，其中，具有一個乙烯性不飽和基的化合物（B）的含有率於化合物（A）與化合物（B）的合計100質量%中為3質量%～30質量%。 [5]： 如[1]至[4]中任一項所述的硬塗膜，其中，化合物（B）及溶劑（D）的合計含有率於硬塗層形成用組成物100質量%中為40質量%～70質量%。 [6]： 一種硬塗膜的製造方法，所述硬塗膜具有三乙醯纖維素膜、混合層、及硬塗層，所述硬塗膜的製造方法中， 於三乙醯纖維素膜上塗敷硬塗層形成用組成物，從而形成混合層、及硬塗層， 所述硬塗層形成用組成物包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D）， 所述硬塗層形成用組成物中的化合物（B）/溶劑（D）的質量比為0.03～0.20， 於利用掃描式電子顯微鏡對硬塗膜觀察厚度方向上的剖面時，於所述硬塗層與所述混合層的合計膜厚中所述混合層所佔的膜厚比率為65%以上。 [發明的效果] In order to solve the above-mentioned problems, the inventors of the present invention have made intensive researches and completed the following inventions as a result. [1]: A hard coat film having a triacetyl cellulose film, a mixed layer, and a hard coat layer, in which, The hard coat layer is formed from a composition for forming a hard coat layer, and the composition for forming a hard coat layer includes a compound (A) having three or more ethylenically unsaturated groups, a compound (A) having one ethylenically unsaturated group, (B), photopolymerization initiator (C), and solvent (D), The mass ratio of compound (B)/solvent (D) in the composition for forming a hard coat layer is 0.03 to 0.20, The mixed layer is a layer formed by dissolving or swelling the composition for forming the hard coat layer in the triacetylcellulose film, When the section in the thickness direction of the hard coat film was observed with a scanning electron microscope, the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer was 65% or more. [2]: The hard coat film according to [1], wherein the compound (B) having one ethylenically unsaturated group is a triacetylcellulose film having a short side of 2 cm x a long side of 4 cm x a thickness of 80 μm The initial mass (X1), and the triacetyl fiber after immersing the triacetyl cellulose film in 35 g of the compound (B) having an ethylenically unsaturated group at 25°C for 2 hours A compound (b1) having one ethylenically unsaturated group in which the mass change value [(X2)/(X1)] of the mass (X2) of the plain film is 1.2 or more. [3]: The hard coat film according to [1] or [2], wherein the solvent (D) is an initial mist of a triacetylcellulose film with a short side of 10 cm x a long side of 10 cm x a thickness of 80 μm Degree value (Y1), and triacetyl cellulose after adding 0.1 g of solvent (D) dropwise to the triacetyl cellulose film at 25°C and standing for 2 minutes, then heating at 60°C for 1 minute The solvent (d1) in which the haze change value [(Y2)-(Y1)] of the haze value (Y2) of the film is 0.10 or more. [4]: The hard coat film according to any one of [1] to [3], wherein the content of the compound (B) having one ethylenically unsaturated group is higher than that of the compound (A) and the compound (B) 3% by mass to 30% by mass in a total of 100% by mass. [5]: The hard coat film according to any one of [1] to [4], wherein the total content of the compound (B) and the solvent (D) is based on 100% by mass of the composition for forming a hard coat layer It is 40 mass % - 70 mass %. [6]: A method for producing a hard coat film, the hard coat film having a triacetyl cellulose film, a mixed layer, and a hard coat layer, in the method for producing the hard coat film, Coating a composition for forming a hard coat layer on a triacetyl cellulose film to form a mixed layer and a hard coat layer, The composition for forming a hard coat layer includes a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent (D), The mass ratio of compound (B)/solvent (D) in the composition for forming a hard coat layer is 0.03 to 0.20, When the section in the thickness direction of the hard coat film was observed with a scanning electron microscope, the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer was 65% or more. [Effect of the invention]

藉由使用本發明的硬塗層形成用組成物，能提供一種可於不使塗膜霧度及耐擦傷性惡化的情況下（於設為實用上無問題的範圍內的同時）抑制干涉不均、進而具有優異的密接性的硬塗膜。By using the composition for forming a hard coat layer of the present invention, it is possible to provide a method for suppressing interference without deteriorating the haze and scratch resistance of the coating film (while setting it within a practically non-problematic range). Uniform, and furthermore, a hard coat film having excellent adhesion.

以下對本發明的較佳的實施方式進行說明。另外，於本說明書中，使用「～」來確定的數值範圍設為包含「～」的前後所記載的數值作為下限值及上限值的範圍。另外，於本說明書中，「膜」或「片」不根據厚度來區分。換言之，本說明書的「片」亦包含厚度薄的膜狀的片，本說明書的「膜」亦包含具有厚度的片狀的膜。Preferred embodiments of the present invention will be described below. In addition, in this specification, the numerical range specified using "-" shall be the range including the numerical value described before and after "-" as a lower limit and an upper limit. In addition, in this specification, a "film" or a "sheet" is not distinguished by thickness. In other words, the "sheet" in this specification also includes a thin film-like sheet, and the "film" in this specification also includes a thick sheet-like film.

再者，本說明書中，於表述為「(甲基)丙烯酸」的情況下，只要無特別說明，則分別表示「丙烯酸或甲基丙烯酸」。 另外，有時將「具有三個以上的乙烯性不飽和基的化合物（A）」稱為「化合物（A）」，將「具有一個乙烯性不飽和基的化合物（B）」稱為「化合物（B）」，將「具有一個乙烯性不飽和基的化合物（b1）」稱為「化合物（b1）」。 本說明書中出現的各種成分只要無特別註釋，則可分別獨立地單獨使用一種或混合使用兩種以上。 In addition, in this specification, when expressing "(meth)acrylic acid", unless otherwise specified, it means "acrylic acid or methacrylic acid", respectively. In addition, "compound (A) having three or more ethylenically unsaturated groups" may be referred to as "compound (A)", and "compound (B) having one ethylenically unsaturated group" may be referred to as "compound (B)", and "compound (b1) having one ethylenically unsaturated group" is referred to as "compound (b1)". Unless otherwise specified, each component shown in this specification can be independently used individually by 1 type or in mixture of 2 or more types.

《硬塗膜》 本發明的硬塗膜是具有三乙醯纖維素膜、混合層、及硬塗層的硬塗膜。所述硬塗層由硬塗層形成用組成物形成，所述硬塗層形成用組成物包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D）。將硬塗層形成用組成物中的化合物（B）/溶劑（D）的質量比設為0.03～0.20。所述混合層是使所述硬塗層形成用組成物於所述三乙醯纖維素膜中溶解或膨潤而形成的層，於利用掃描式電子顯微鏡對硬塗膜的厚度方向上的剖面進行觀察時，於硬塗層與混合層的合計膜厚中所述混合層所佔的膜厚比率為65%以上。 "Hard Coating" The hard coat film of this invention is a hard coat film which has a triacetyl cellulose film, a mixed layer, and a hard coat layer. The hard coat layer is formed from a composition for forming a hard coat layer, and the composition for forming a hard coat layer includes a compound (A) having three or more ethylenically unsaturated groups, a compound (A) having one ethylenically unsaturated group, (B), photopolymerization initiator (C), and solvent (D). The mass ratio of the compound (B)/solvent (D) in the composition for hard-coat layer formation shall be 0.03-0.20. The mixed layer is a layer formed by dissolving or swelling the composition for forming the hard coat layer in the triacetyl cellulose film, and the cross-section in the thickness direction of the hard coat film is carried out using a scanning electron microscope. When observed, the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer was 65% or more.

＜三乙醯纖維素膜＞ 本發明中使用的三乙醯纖維素膜只要是可用作偏光板等基材的光學性透明的等級即可，三乙醯纖維素膜的厚度並無特別限制，但一般就強度或操作等作業性、薄層性等的方面而言，為10 μm～500 μm左右。特佳為20 μm～250 μm。 ＜Triacetylcellulose membrane＞ The triacetyl cellulose film used in the present invention may be of an optically transparent grade that can be used as a base material such as a polarizing plate. The thickness of the triacetyl cellulose film is not particularly limited, but it is generally determined in terms of strength, handling, etc. In terms of workability, thin layer, etc., it is about 10 μm to 500 μm. Most preferably, it is 20 μm to 250 μm.

＜硬塗層及混合層＞ 本發明的硬塗層由硬塗層形成用組成物形成，所述硬塗層形成用組成物包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D）。另外，混合層是使硬塗層形成用組成物於三乙醯纖維素膜中溶解或膨潤而形成的層。進而，於利用掃描式電子顯微鏡對硬塗膜觀察厚度方向上的剖面時，於硬塗層與混合層的合計膜厚中所述混合層所佔的膜厚比率為65%以上。 膜厚比率更佳為67%以上，進而佳為70%以上。另外，就硬塗性的觀點而言，較佳為90%以下。藉由混合層的膜厚比率為65%以上，可減少干涉不均，塗膜霧度及耐擦傷性不會降低，密接性亦良好。即，可於將塗膜霧度及耐擦傷性設為能夠實用的範圍的同時減少干涉不均，進而密接性亦優異。就干涉不均的減少優異的方面而言，所述膜厚比率較佳為高。 ＜Hard coat and mixed layer＞ The hard coat layer of the present invention is formed from a composition for forming a hard coat layer containing a compound (A) having three or more ethylenically unsaturated groups, a compound (A) having one ethylenically unsaturated group, Compound (B), photopolymerization initiator (C), and solvent (D). In addition, the mixed layer is a layer formed by dissolving or swelling the composition for forming a hard coat layer in a triacetyl cellulose film. Furthermore, when the cross section in the thickness direction of the hard coat film was observed with a scanning electron microscope, the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer was 65% or more. The film thickness ratio is more preferably at least 67%, and more preferably at least 70%. Moreover, it is preferable that it is 90% or less from a viewpoint of hard-coat property. When the film thickness ratio of the mixed layer is 65% or more, the interference unevenness can be reduced, the haze and scratch resistance of the coating film will not be reduced, and the adhesion is also good. That is, interference unevenness can be reduced, making a coating-film haze and scratch resistance into a practical range, and it is also excellent in adhesiveness. The film thickness ratio is preferably high in terms of excellent reduction of interference unevenness.

為了使所述混合層的膜厚比率為65%以上，重要的是使用包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D）的硬塗層形成用組成物。進而，能夠藉由化合物（B）及溶劑（D）的種類、以及該些的含量來進行控制。於化合物（B）為後述的化合物（b1）的情況、或/及溶劑（D）為後述的溶劑（d1）的情況下，特別容易使混合層的膜厚比率為65%以上，因此較佳。特佳為化合物（B）為化合物（b1），且溶劑（D）為溶劑（d1）。 另外，藉由對硬塗層形成用組成物的不揮發成分濃度進行調整、或者於在三乙醯纖維素膜上塗敷硬塗層形成用組成物後進行靜置等製造方法來提高基材滲透性，藉此亦能夠使混合層的膜厚比率為65%以上。 In order to make the film thickness ratio of the mixed layer 65% or more, it is important to use a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photo A composition for forming a hard coat layer of a polymerization initiator (C) and a solvent (D). Furthermore, it can control by the kind of compound (B) and solvent (D), and these content. When the compound (B) is the compound (b1) described later, or/and the solvent (D) is the solvent (d1) described later, it is particularly easy to make the film thickness ratio of the mixed layer 65% or more, so it is preferable. . Most preferably, the compound (B) is the compound (b1), and the solvent (D) is the solvent (d1). In addition, by adjusting the concentration of non-volatile components of the composition for forming a hard coat layer, or by applying a composition for forming a hard coat layer on a triacetyl cellulose film and then leaving it to stand, the substrate penetration can be improved. properties, thereby enabling the film thickness ratio of the mixed layer to be 65% or more.

（硬塗層形成用組成物） 硬塗層形成用組成物包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D）。 另外，化合物（B）較佳為後述的質量變化值[（X2）/（X1）]為1.2以上的具有一個乙烯性不飽和基的化合物。 另外，溶劑（D）較佳為後述的霧度變化值[（Y2）-（Y1）]為0.10以上的溶劑。 特佳為，化合物（B）為質量變化值[（X2）/（X1）]為1.2以上的具有一個乙烯性不飽和基的化合物（b1），溶劑（D）為霧度變化值[（Y2）-（Y1）]為0.10以上的溶劑（d1）。 藉此，基材滲透性提高，有效地減少干涉不均。 (Composition for forming a hard coat layer) The composition for forming a hard coat layer contains a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent (D ). In addition, the compound (B) is preferably a compound having one ethylenically unsaturated group whose mass change value [(X2)/(X1)] described later is 1.2 or more. In addition, the solvent (D) is preferably a solvent having a haze change value [(Y2)-(Y1)] described later of 0.10 or more. Particularly preferably, the compound (B) is a compound (b1) having one ethylenically unsaturated group with a mass change value [(X2)/(X1)] of 1.2 or more, and the solvent (D) is a haze change value [(Y2 )-(Y1)] is 0.10 or more solvent (d1). Thereby, the permeability of the base material is improved, and interference unevenness is effectively reduced.

就提高基材滲透性的觀點而言，硬塗層形成用組成物的不揮發成分濃度較佳為70質量%以下，更佳為60質量%以下。就抑制塗膜霧度的降低的觀點而言，不揮發成分較佳為25質量%以上，進而佳為35質量%以上。藉由對硬塗層形成用組成物的不揮發成分進行調整，容易將混合層的膜厚比率控制為65%以上。From the viewpoint of improving the substrate permeability, the non-volatile component concentration of the composition for forming a hard coat layer is preferably at most 70% by mass, more preferably at most 60% by mass. From the viewpoint of suppressing the reduction of the haze of the coating film, the non-volatile content is preferably at least 25% by mass, more preferably at least 35% by mass. By adjusting the non-volatile content of the composition for forming a hard-coat layer, it becomes easy to control the film thickness ratio of a mixed layer to 65% or more.

[化合物（A）] 化合物（A）是具有三個以上的乙烯性不飽和基的化合物。作為化合物（A），例如可列舉：季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷（ethylene oxide，EO）改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷（propylene oxide，PO）改質三羥甲基丙烷三(甲基)丙烯酸酯、三(丙烯醯氧基乙基)異氰脲酸酯、己內酯改質三(丙烯醯氧基乙基)異氰脲酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、烷基改質二季戊四醇三(甲基)丙烯酸酯、烷基改質二季戊四醇四(甲基)丙烯酸酯、烷基改質二季戊四醇五(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯、1,2,3-環己烷四(甲基)丙烯酸酯等多元醇與(甲基)丙烯酸的酯化合物； 聚胺基甲酸酯聚(甲基)丙烯酸酯、聚酯聚(甲基)丙烯酸酯、聚醚聚(甲基)丙烯酸酯、聚丙烯酸聚(甲基)丙烯酸酯、聚醇酸聚(甲基)丙烯酸酯、聚環氧聚(甲基)丙烯酸酯，聚螺縮醛聚(甲基)丙烯酸酯、聚丁二烯聚(甲基)丙烯酸酯、聚硫醇多烯聚(甲基)丙烯酸酯、多晶矽聚(甲基)丙烯酸酯等多官能化合物的聚(甲基)丙烯酸酯化合物； 由多元醇與多元酸及(甲基)丙烯酸合成的酯化合物、例如由三羥甲基乙烷/琥珀酸/丙烯酸=2/1/4（莫耳比）合成的酯化合物等。 [Compound (A)] The compound (A) is a compound having three or more ethylenically unsaturated groups. As the compound (A), for example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide (ethylene oxide, EO ) modified trimethylolpropane tri(meth)acrylate, propylene oxide (propylene oxide, PO) modified trimethylolpropane tri(meth)acrylate, tri(acryloxyethyl) iso Cyanurate, caprolactone-modified tris(acryloxyethyl)isocyanurate, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, di Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, alkyl modified dipentaerythritol tetra(meth)acrylate, alkyl modified Dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, 1,2,3-cyclohexane tetra(meth)acrylate and other polyols and (meth) Acrylic acid ester compounds; Polyurethane poly(meth)acrylate, polyester poly(meth)acrylate, polyether poly(meth)acrylate, polyacrylic acid poly(meth)acrylate, polyalkyd poly(meth)acrylate base) acrylate, polyepoxy poly(meth)acrylate, polyspiroacetal poly(meth)acrylate, polybutadiene poly(meth)acrylate, polythiol polyene poly(meth)acrylate Poly(meth)acrylate compounds of polyfunctional compounds such as acrylates and polysilicon poly(meth)acrylates; An ester compound synthesized from a polyhydric alcohol, a polybasic acid, and (meth)acrylic acid, for example, an ester compound synthesized from trimethylolethane/succinic acid/acrylic acid=2/1/4 (molar ratio), etc.

就密接性、耐擦傷性、及可靠性的方面而言，化合物（A）較佳為季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、聚胺基甲酸酯聚(甲基)丙烯酸酯、聚酯聚(甲基)丙烯酸酯、聚醚聚(甲基)丙烯酸酯、及聚丙烯酸聚(甲基)丙烯酸酯，更佳為季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、聚胺基甲酸酯聚(甲基)丙烯酸酯、及聚酯聚(甲基)丙烯酸酯。該些可任意組合。特佳為將具有胺基甲酸酯的聚胺基甲酸酯聚(甲基)丙烯酸酯與季戊四醇聚(甲基)丙烯酸酯或/及二季戊四醇聚(甲基)丙烯酸酯加以組合。The compound (A) is preferably pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate in terms of adhesion, scratch resistance, and reliability. , dipentaerythritol hexa(meth)acrylate, polyurethane poly(meth)acrylate, polyester poly(meth)acrylate, polyether poly(meth)acrylate, and polyacrylic poly(meth)acrylate Meth)acrylate, more preferably pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyurethane poly(meth)acrylate , and polyester poly(meth)acrylate. These can be combined arbitrarily. It is particularly preferable to combine polyurethane poly(meth)acrylate having urethane, pentaerythritol poly(meth)acrylate or/and dipentaerythritol poly(meth)acrylate.

化合物（A）的含有率於硬塗層形成用組成物100質量%中較佳為25質量%～60質量%，更佳為35質量%～55質量%。藉由為該範圍，塗膜強度提高，可形成能達成耐擦傷性或可靠性的塗膜，因此較佳。The content of the compound (A) is preferably from 25% by mass to 60% by mass, more preferably from 35% by mass to 55% by mass, in 100% by mass of the composition for forming a hard coat layer. Since the strength of a coating film improves by being this range, and the coating film which can achieve scratch resistance or reliability can be formed, it is preferable.

[化合物（B）] 化合物（B）是具有一個乙烯性不飽和基的化合物。 作為化合物（B），例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、甲氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸二甲基胺基乙酯、2-(甲基)丙烯醯氧基乙基酸式磷酸酯等酯化合物；苯乙烯、α-亞甲基等苯乙烯系化合物；γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基三乙氧基矽烷等矽烷化合物；(甲基)丙烯酸2-(N,N-二甲基胺基)乙酯、N-羥甲基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺、N-乙烯基-ε-己內醯胺、丙烯醯嗎啉等含氮化合物；(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸2,2,3,3,3-五氟丙酯等含氟化合物；聚合物的主鏈為矽酮成分且單末端經(甲基)丙烯酸酯基修飾的聚合性矽酮化物等。 [Compound (B)] Compound (B) is a compound having one ethylenically unsaturated group. Examples of the compound (B) include methyl (meth)acrylate, ethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Lauryl (meth)acrylate, Isobornyl (meth)acrylate, Benzyl (meth)acrylate, Phenoxyethyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, (Meth) ) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-(meth)propylene Ester compounds such as acyloxyethyl acid phosphate; styrene compounds such as styrene and α-methylene; γ-(meth)acryloxypropyltrimethoxysilane, γ-(methyl) Silane compounds such as acryloxypropyltriethoxysilane; 2-(N,N-dimethylamino)ethyl (meth)acrylate, N-methylol(meth)acrylamide, di Nitrogen-containing compounds such as ethyl (meth)acrylamide, N-vinyl-ε-caprolactam, acrylmorpholine; trifluoroethyl (meth)acrylate, (meth)acrylic acid 2,2, Fluorine-containing compounds such as 3,3,3-pentafluoropropyl ester; polymeric silicone compounds whose main chain is silicone and whose single end is modified with (meth)acrylate groups, etc.

關於化合物（B），就可容易將混合層的膜厚比率控制為65%以上，且干涉不均的減少優異的方面而言，較佳為設為短邊2 cm×長邊4 cm×厚度80 μm的三乙醯纖維素膜的初期的質量（X1）、與將所述三乙醯纖維素膜於25℃的環境下在35 g的具有一個乙烯性不飽和基的化合物（B）中浸漬2小時後的三乙醯纖維素膜的質量（X2）的質量變化值[（X2）/（X1）]為1.2以上的化合物（b1）。 質量變化值[（X2）/（X1）]更佳為2.0～10.0，進而佳為5.0以下。藉由滿足該條件的化合物（B），可使干涉不均的減少更優異。[（X2）/（X1）]的更佳的範圍為3.5～4.5。 Compound (B) is preferably 2 cm on the short side x 4 cm on the long side x thickness in terms of being able to easily control the film thickness ratio of the mixed layer to 65% or more and excellent in reducing interference unevenness The initial mass (X1) of the 80 μm triacetyl cellulose film, and the triacetyl cellulose film in the environment of 25 ℃ in 35 g of the compound (B) having one ethylenically unsaturated group The compound (b1) in which the mass change value [(X2)/(X1)] of the mass (X2) of the triacetylcellulose film after immersion for 2 hours is 1.2 or more. The mass change value [(X2)/(X1)] is more preferably from 2.0 to 10.0, more preferably at most 5.0. With the compound (B) satisfying this condition, the reduction of interference unevenness can be made more excellent. The more preferable range of [(X2)/(X1)] is 3.5-4.5.

例示化合物（B）的質量變化值[（X2）/（X1）]時，為丙烯醯嗎啉（3.9）、丙烯酸4-羥基丁酯（2.9）、丙烯酸四氫糠酯（1.5）、N-乙烯基-ε-己內醯胺（4.3）、二乙基丙烯醯胺（5.2）、丙烯酸月桂酯（1.0）、丙烯酸異冰片酯（1.0）、丙烯酸苯氧基乙酯（1.1），較佳為使用作為化合物（b1）的丙烯醯嗎啉、丙烯酸4-羥基丁酯、丙烯酸四氫糠酯、N-乙烯基-ε-己內醯胺、二乙基丙烯醯胺等。 就基材滲透性提高，有效地減少干涉不均的觀點而言，更佳為丙烯醯嗎啉、丙烯酸4-羥基丁酯或N-乙烯基-ε-己內醯胺，進而佳為丙烯醯嗎啉。 When the mass change value [(X2)/(X1)] of compound (B) is exemplified, it is acryloylmorpholine (3.9), 4-hydroxybutyl acrylate (2.9), tetrahydrofurfuryl acrylate (1.5), N- Vinyl-ε-caprolactam (4.3), diethylacrylamide (5.2), lauryl acrylate (1.0), isobornyl acrylate (1.0), phenoxyethyl acrylate (1.1), better As the compound (b1), acryloylmorpholine, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, N-vinyl-ε-caprolactam, diethylacrylamide and the like are used. From the perspective of improving the permeability of the substrate and effectively reducing interference unevenness, acryl morpholine, 4-hydroxybutyl acrylate or N-vinyl-ε-caprolactam is more preferred, and acrylamide is more preferred. Morpholine.

化合物（B）的含有率的下限值於化合物（A）與化合物（B）的合計100質量%中較佳為3質量%，更佳為4質量%，進而佳為5質量%。另外，化合物（B）的含有率的上限值於化合物（A）與化合物（B）的合計100質量%中較佳為30質量%，更佳為25質量%，進而佳為20質量%。藉由化合物（B）的含有率為3質量%以上，減少由基材滲透引起的干涉不均的效果變大，藉由為30質量%以下，耐擦傷性更優異，因此較佳。The lower limit of the content of the compound (B) is preferably 3% by mass, more preferably 4% by mass, and still more preferably 5% by mass, based on 100% by mass of the total of the compound (A) and the compound (B). The upper limit of the content of the compound (B) is preferably 30% by mass, more preferably 25% by mass, and still more preferably 20% by mass, based on 100% by mass of the total of the compound (A) and the compound (B). When the content of the compound (B) is 3% by mass or more, the effect of reducing interference unevenness caused by penetration of the base material becomes greater, and when it is 30% by mass or less, the scratch resistance is more excellent, so it is preferable.

[光聚合起始劑（C）] 光聚合起始劑（C）只要是具有可藉由光激發來起始自由基聚合的功能者，則並無特別限定，例如可列舉：苯乙酮化合物、安息香化合物、二苯甲酮化合物、氧化膦化合物、縮酮化合物、蒽醌化合物、噻噸酮化合物等。具體而言，可列舉：安息香甲醚、安息香***、安息香異丙醚、安息香丁醚、二乙氧基苯乙酮、苄基二甲基縮酮、1-羥基環己基苯基酮、二苯甲酮、2,4,6-三甲基安息香二苯基氧化膦、N,N-二甲基胺基苯甲酸異戊酯、2-氯噻噸酮、2,4-二乙基噻噸酮等。另外，亦可加入公知的有機胺作為增感劑。 [Photopolymerization initiator (C)] The photopolymerization initiator (C) is not particularly limited as long as it has the function of initiating radical polymerization by photoexcitation, for example, acetophenone compound, benzoin compound, benzophenone compound, Phosphine oxide compounds, ketal compounds, anthraquinone compounds, thioxanthone compounds, and the like. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diphenyl Methanone, 2,4,6-trimethylbenzoin diphenylphosphine oxide, isoamyl N,N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthene Ketones etc. In addition, known organic amines may also be added as sensitizers.

相對於化合物（A）與化合物（B）的合計100質量份，光聚合起始劑（C）的使用量較佳為0.1質量份～20質量份，更佳為1質量份～10質量份。藉由為該範圍，可獲得充分的聚合起始效果，有效地提高密接性或耐擦傷性。The usage-amount of a photoinitiator (C) is preferably 0.1-20 mass parts with respect to a total of 100 mass parts of compound (A) and compound (B), More preferably, it is 1-10 mass parts. By being in this range, sufficient polymerization initiation effect can be acquired, and adhesiveness and abrasion resistance can be improved effectively.

本發明中的硬塗層形成用組成物中，可於光聚合起始劑（C）中併用增感劑。 關於增感劑，可列舉：胺系增感劑、蒽系增感劑、噻噸酮系增感劑等。增感劑可單獨使用或併用兩種以上。 關於胺系增感劑，例如可列舉：三甲基胺、甲基二甲醇胺、三乙醇胺、對二乙基胺基苯乙酮、對二甲基胺基苯甲酸乙酯、對二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸乙酯、N,N-二甲基苄基胺、4'-雙(二乙基胺基)二苯甲酮等。 關於蒽系增感劑，例如可列舉：9,10-二丁氧基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-雙(2-乙基己氧基)蒽等。 關於噻噸酮系增感劑，例如可列舉：2,4-二乙基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮等噻噸酮系增感劑。作為市售品的代表例，胺系增感劑可例示EPA（日本化藥公司製造），蒽系增感劑可例示DBA、DEA（川崎化成工業公司製造），噻噸酮系增感劑可例示DETX、ITX（拉姆森（Lambson）公司製造）等。 增感劑較佳為噻噸酮系增感劑等。 In the composition for forming a hard coat layer in the present invention, a sensitizer may be used in combination with the photopolymerization initiator (C). Examples of the sensitizer include amine-based sensitizers, anthracene-based sensitizers, thioxanthone-based sensitizers, and the like. A sensitizer can be used individually or in combination of 2 or more types. Regarding the amine-based sensitizer, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoate Isoamyl aminobenzoate, ethyl 4-dimethylaminobenzoate, N,N-dimethylbenzylamine, 4'-bis(diethylamino)benzophenone, etc. Regarding anthracene-based sensitizers, for example, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-bis(2-ethoxyanthracene, Hexyloxy) anthracene, etc. As for the thioxanthone-based sensitizer, for example, thioxanthone-based sensitizers such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone are mentioned. As a representative example of commercially available products, amine-based sensitizers include EPA (manufactured by Nippon Kayaku Co., Ltd.); anthracene-based sensitizers include DBA and DEA (manufactured by Kawasaki Chemical Industry Co., Ltd.); Examples include DETX, ITX (manufactured by Lambson), and the like. The sensitizer is preferably a thioxanthone-based sensitizer or the like.

於使用增感劑的情況下，相對於化合物（A）與化合物（B）的合計100質量份，其含量較佳為0.1質量份～10質量份。When using a sensitizer, its content is preferably 0.1 mass parts - 10 mass parts with respect to a total of 100 mass parts of compound (A) and compound (B).

[溶劑（D）] 關於溶劑（D），例如可列舉：二丁基醚、二甲氧基乙烷、二乙氧基乙烷、環氧丙烷、1,4-二噁烷、1,3-二氧雜環戊烷、1,3,5-三噁烷、四氫呋喃、苯甲醚、苯***、丙二醇單甲醚等醚類； 丙酮、甲基乙基酮、甲基異丁基酮、二乙基酮、二丙基酮、二異丁基酮、環戊酮、環己酮、甲基環己酮等酮類； 甲酸乙酯、甲酸丙酯、甲酸戊酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、碳酸二甲酯、γ-丁內酯等酯類； 除所述以外的2-甲氧基乙酸甲酯、2-乙氧基乙酸甲酯、2-乙氧基乙酸乙酯、2-乙氧基丙酸乙酯、2-甲氧基乙醇、2-丙氧基乙醇、2-丁氧基乙醇、1,2-二乙醯氧基丙酮、乙醯丙酮、二丙酮醇、乙醯乙酸甲酯、乙醯乙酸乙酯等。該些可單獨使用一種或組合使用兩種以上。 [Solvent (D)] Regarding the solvent (D), examples include: dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane Alkanes, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, propylene glycol monomethyl ether and other ethers; Acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; Ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, γ-butyrolactone and other esters; Methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-methoxyethanol, 2 - Propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, etc. These can be used alone or in combination of two or more.

關於溶劑（D），對短邊10 cm×長邊10 cm×厚度80 μm的三乙醯纖維素膜的初期的霧度值（Y1）、及向所述三乙醯纖維素膜於25℃的環境下滴加0.1 g的溶劑（D）並放置2分鐘後於60℃下加熱1分鐘後的三乙醯纖維素膜的霧度值（Y2）進行測定。藉由所獲得的霧度變化值[（Y2）-（Y1）]為0.10以上，可容易將混合層的膜厚比率控制為65%以上，且干涉不均的減少優異，就此方面而言較佳。 霧度變化值[（Y2）-（Y1）]更佳為0.10以上且0.80以下，進而佳為0.45以下。藉由滿足該條件的溶劑（D），於不降低塗膜的霧度或耐擦傷性的情況下，基材滲透性提高，有效地減少干涉不均。 Regarding the solvent (D), the initial haze value (Y1) of a triacetyl cellulose film with a short side of 10 cm x a long side of 10 cm x a thickness of 80 μm, and the triacetyl cellulose film at 25°C The haze value (Y2) of the triacetyl cellulose film after adding 0.1 g of the solvent (D) dropwise and standing for 2 minutes at 60° C. for 1 minute was measured. With the obtained haze change value [(Y2)-(Y1)] being 0.10 or more, the film thickness ratio of the mixed layer can be easily controlled to be 65% or more, and the reduction of interference unevenness is excellent, which is relatively good. The haze change value [(Y2)-(Y1)] is more preferably from 0.10 to 0.80, more preferably from 0.45. With the solvent (D) that satisfies this condition, without reducing the haze or scratch resistance of the coating film, the permeability of the substrate is improved, and the interference unevenness is effectively reduced.

例示溶劑（D）的霧度變化值[（Y2）-（Y1）]時，為碳酸二甲酯（0.15）、乙酸乙酯（0.47）、丙酮（0.81）、甲基乙基酮（0.42）、1,3-二氧雜環戊烷（0.48）、甲基異丁基酮（0.01）、異丙醇（0.04）、丙二醇單甲醚（0.00），較佳為使用作為溶劑（d1）的碳酸二甲酯、乙酸乙酯、丙酮、甲基乙基酮或1,3-二氧雜環戊烷。 就於不降低塗膜的霧度或耐擦傷性的情況下，基材滲透性提高，有效地減少干涉不均的方面而言，更佳為碳酸二甲酯、甲基乙基酮、1,3-二氧雜環戊烷或乙酸乙酯，進而佳為碳酸二甲酯或甲基乙基酮。 When the haze change value [(Y2)-(Y1)] of the solvent (D) is shown as an example, it is dimethyl carbonate (0.15), ethyl acetate (0.47), acetone (0.81), methyl ethyl ketone (0.42) , 1,3-dioxolane (0.48), methyl isobutyl ketone (0.01), isopropanol (0.04), propylene glycol monomethyl ether (0.00), preferably used as solvent (d1) Dimethyl carbonate, ethyl acetate, acetone, methyl ethyl ketone or 1,3-dioxolane. In terms of improving the permeability of the substrate and effectively reducing interference unevenness without reducing the haze or scratch resistance of the coating film, dimethyl carbonate, methyl ethyl ketone, 1, 3-dioxolane or ethyl acetate, further preferably dimethyl carbonate or methyl ethyl ketone.

化合物（B）及溶劑（D）的合計含有率於硬塗層形成用組成物100質量%中較佳為40質量%～80質量%，更佳為40質量%～70質量%，進而佳為45質量%～65質量%。若為40質量%以上，則基材滲透性高，藉此密接性進一步提高，若為80質量%以下，則基材滲透性不會過高，可進一步抑制塗膜霧度或耐擦傷性的惡化。The total content of the compound (B) and the solvent (D) is preferably from 40% by mass to 80% by mass in 100% by mass of the composition for forming a hard coat layer, more preferably from 40% by mass to 70% by mass, still more preferably 45% by mass to 65% by mass. If it is 40% by mass or more, the permeability of the base material will be high, thereby further improving the adhesion. If it is 80% by mass or less, the permeability of the base material will not be too high, and the haze of the coating film and the effects of scratch resistance can be further suppressed. deterioration.

化合物（B）/溶劑（D）的質量比較佳為0.03～0.20，更佳為0.05～0.15。若為0.03以上，則基材滲透性充分，減少干涉不均的效果進一步提高，若為0.20以下，則耐擦傷性進一步提高。The mass ratio of compound (B)/solvent (D) is preferably from 0.03 to 0.20, more preferably from 0.05 to 0.15. If it is 0.03 or more, the permeability of the substrate is sufficient, and the effect of reducing interference unevenness is further enhanced, and when it is 0.20 or less, the scratch resistance is further improved.

本發明中的硬塗層形成用組成物中，根據需要可包含其他添加劑。關於其他添加劑，例如可列舉：塑化劑、表面調整劑、光穩定劑、抗氧化劑、聚合抑制劑。The composition for forming a hard coat layer in the present invention may contain other additives as necessary. Regarding other additives, for example, plasticizers, surface modifiers, light stabilizers, antioxidants, and polymerization inhibitors are mentioned.

＜硬塗膜的製造＞ 關於硬塗膜的製造方法，可利用在三乙醯纖維素膜上塗敷硬塗層形成用組成物等現有公知的方法來製造，並無特別限制。 例如，於將本發明的硬塗層形成用組成物塗敷於三乙醯纖維素膜上後，根據需要使溶劑乾燥。藉由對其照射活性能量線，而使所塗敷的硬塗層形成用組成物交聯硬化，從而獲得具有三乙醯纖維素膜、混合層、及硬塗層的硬塗膜。 藉此，於利用掃描式電子顯微鏡對硬塗膜的剖面進行觀察時，可獲得於硬塗層與混合層的合計膜厚中所述混合層所佔的膜厚比率為65%以上的硬塗膜。 另外，藉由在三乙醯纖維素膜上塗敷硬塗層形成用組成物並使其靜置，基材滲透性提高，容易使混合層的膜厚比率為65%以上，因此較佳。 ＜Manufacture of hard coating＞ The method for producing the hard coat film can be produced by a conventionally known method such as coating a composition for forming a hard coat layer on a triacetyl cellulose film, and is not particularly limited. For example, after applying the composition for forming a hard coat layer of the present invention on a triacetyl cellulose film, the solvent is dried if necessary. By irradiating it with active energy rays, the applied composition for forming a hard coat layer is crosslinked and cured, thereby obtaining a hard coat film having a triacetylcellulose film, a mixed layer, and a hard coat layer. Thereby, when observing the cross section of the hard coat film with a scanning electron microscope, it is possible to obtain a hard coat film in which the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer is 65% or more. membrane. In addition, by applying the composition for forming a hard coat layer on the triacetyl cellulose film and allowing it to stand still, the permeability of the base material is improved, and the film thickness ratio of the mixed layer can be easily made to be 65% or more, so it is preferable.

作為塗敷方法，可列舉：棒塗、刮塗、旋塗、反塗、模塗、噴塗、輥塗、凹版塗佈、微凹版塗佈、緣塗佈、氣刀塗佈、浸漬法等。Examples of coating methods include bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro gravure coating, edge coating, air knife coating, dipping and the like.

作為活性能量線，可使用電子束、或自氙氣燈、低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、碳弧燈、鎢燈等光源發出的紫外線。As active energy rays, electron beams or ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps can be used.

硬塗層的膜厚只要保有硬塗性則並無特別限定，通常為1 μm～20 μm，較佳為2 μm～15 μm。硬塗層與混合層的合計膜厚亦並無特別限制，但為了減少干涉不均，較佳為0.5 μm～100 μm，更佳為1.1 μm～30 μm，進而佳為1.2 μm～25 μm。 硬塗膜的膜厚並無特別限制，較佳為50 μm～300 μm，更佳為81 μm～100 μm，進而佳為82 μm～95 μm。 [實施例] The film thickness of the hard coat layer is not particularly limited as long as the hard coat property is maintained, but it is usually 1 μm to 20 μm, preferably 2 μm to 15 μm. The total film thickness of the hard coat layer and mixed layer is not particularly limited, but in order to reduce interference unevenness, it is preferably 0.5 μm to 100 μm, more preferably 1.1 μm to 30 μm, and still more preferably 1.2 μm to 25 μm. The film thickness of the hard coat film is not particularly limited, but is preferably 50 μm to 300 μm, more preferably 81 μm to 100 μm, and still more preferably 82 μm to 95 μm. [Example]

以下，列舉實施例、比較例來對本發明進行詳細說明，但本發明並不限定於以下例子。再者，只要無特別說明，則「份」意指「質量份」，「%」意指「質量%」。 另外，表中的調配量為質量份，除溶劑以外，為不揮發成分換算值。再者，表中的空欄表示未調配。 Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to the following example. In addition, unless otherwise specified, "part" means "mass part", and "%" means "mass %". In addition, the compounding quantity in a table|surface is a mass part, and it is a non-volatile matter conversion value except a solvent. Again, blank columns in the table represent no deployment.

＜化合物（B）的質量變化值[（X2）/（X1）]＞ 化合物（B）的質量變化值[（X2）/（X1）]是利用下述方法來求出。 首先，對短邊2 cm×長邊4 cm×厚度80 μm的三乙醯纖維素膜的初期的質量（X1）進行測定。繼而，將該三乙醯纖維素膜於25℃的環境下在35 g的具有一個乙烯性不飽和基的化合物（B）中浸漬2小時。然後，取出三乙醯纖維素膜，利用吸水紙（Kimtowel）輕輕擦拭後，測定三乙醯纖維素膜的質量（X2）。再者，作為三乙醯纖維素膜，使用厚度80 μm的三乙醯纖維素膜（富士軟片（股）製造）（後述的霧度亦使用該軟片）。 <Mass change value of compound (B) [(X2)/(X1)]> The mass change value [(X2)/(X1)] of the compound (B) was obtained by the following method. First, the initial mass (X1) of a triacetyl cellulose film with a short side of 2 cm x a long side of 4 cm x a thickness of 80 μm was measured. Next, the triacetylcellulose film was immersed in 35 g of the compound (B) having one ethylenically unsaturated group for 2 hours in a 25° C. environment. Then, the triacetyl cellulose film was taken out and lightly wiped with absorbent paper (Kimtowel), and then the mass (X2) of the triacetyl cellulose film was measured. In addition, as the triacetyl cellulose film, the triacetyl cellulose film (manufactured by Fuji Film Co., Ltd.) with a thickness of 80 μm was used (this film was also used for the haze described later).

＜溶劑（D）的霧度變化值[（Y2）-（Y1）]＞ 溶劑（D）的霧度變化值[（Y2）-（Y1）]是利用下述方法來求出。 首先，測定短邊10 cm×長邊10 cm×厚度80 μm的三乙醯纖維素膜的初期的霧度值（Y1）。繼而，對該三乙醯纖維素膜於25℃的環境下滴加0.1 g的溶劑（D），並放置2分鐘。然後於60℃下加熱1分鐘，恢復常溫後測定三乙醯纖維素膜的霧度值（Y2）。 <Change value of haze of solvent (D) [(Y2)-(Y1)]> The haze change value [(Y2)-(Y1)] of the solvent (D) was calculated|required by the following method. First, the initial haze value (Y1) of a triacetyl cellulose film having a short side of 10 cm x a long side of 10 cm x a thickness of 80 μm was measured. Next, 0.1 g of the solvent (D) was added dropwise to the triacetylcellulose film in an environment of 25° C., and left for 2 minutes. Then, it was heated at 60°C for 1 minute, and after returning to normal temperature, the haze value (Y2) of the triacetyl cellulose film was measured.

關於表1中使用的成分A～成分D，如下述所示。 ＜具有三個以上的乙烯性不飽和基的化合物（A）＞ ・UA-306H：（共榮社化學（股）製造：6官能丙烯酸胺基甲酸酯） ・M405：二季戊四醇六丙烯酸酯（東亞合成（股）製造：亞羅尼克斯（ARONIX）M405，6官能單體） ・PET30：季戊四醇三丙烯酸酯（日本化藥（股）製造：卡亞拉德（KAYARAD）PET30，3官能單體） Component A to component D used in Table 1 are as follows. <Compound (A) having three or more ethylenically unsaturated groups> ・UA-306H: (manufactured by Kyoeisha Chemical Co., Ltd.: 6-functional urethane acrylate) ・M405: Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.: ARONIX M405, hexafunctional monomer) ・PET30: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd.: KAYARAD PET30, trifunctional monomer)

＜具有一個乙烯性不飽和基的化合物（B）＞ 再者，括號內的數值是質量變化值[（X2）/（X1）]。 （具有一個乙烯性不飽和基的化合物（b1）） ・ACMO：丙烯醯嗎啉（KJ化學（KJ Chemicals）（股）製造：ACMO（Acryloylmorpholine），單官能單體，3.9） ・4-HBA：丙烯酸4-羥基丁酯（三菱化學（股）製造：4-HBA（4-hydroxybutyl acrylate），單官能單體，2.9）、 ・THF-A：丙烯酸四氫糠酯（共榮社化學（股）製造：萊易特丙烯酸酯（Light Acrylate）THF-A（Tetrahydrofurfuryl-Acrylate），單官能單體，1.5） ・NVP：N-乙烯基己內醯胺（亞什蘭（ASHLAND）製造：V-Cap/RC，單官能單體，4.3） ・DEAA：二乙基丙烯醯胺（KJ化學（股）製造：DEAA（Diethylacrylamide），單官能單體，5.2） （其他具有一個乙烯性不飽和基的化合物） ・LA：丙烯酸月桂酯（共榮社化學（股）製造：萊易特丙烯酸酯（Light Acrylate）L-A（lauryl-acrylate），單官能單體，1.0） ・IBXA：丙烯酸異冰片酯（大阪有機化學工業（股）製造：IBXA（Isobornyl acrylate），單官能單體，1.0） ・PEA：丙烯酸苯氧基乙酯（共榮社化學（股）製造：萊易特丙烯酸酯（Light Acrylate）PO-A，單官能單體，1.1） <Compound (B) having one ethylenically unsaturated group> It should be noted that the values in parentheses are mass change values [(X2)/(X1)]. (compound (b1) having one ethylenically unsaturated group) ・ACMO: Acryloylmorpholine (manufactured by KJ Chemicals Co., Ltd.: ACMO (Acryloylmorpholine), monofunctional monomer, 3.9) ・4-HBA: 4-hydroxybutyl acrylate (manufactured by Mitsubishi Chemical Co., Ltd.: 4-HBA (4-hydroxybutyl acrylate), monofunctional monomer, 2.9), ・THF-A: Tetrahydrofurfuryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.: Light Acrylate THF-A (Tetrahydrofurfuryl-Acrylate), monofunctional monomer, 1.5) ・NVP: N-vinylcaprolactam (manufactured by Ashland: V-Cap/RC, monofunctional monomer, 4.3) ・DEAA: Diethylacrylamide (manufactured by KJ Chemical Co., Ltd.: DEAA (Diethylacrylamide), monofunctional monomer, 5.2) (Other compounds having one ethylenically unsaturated group) ・LA: Lauryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.: Light Acrylate L-A (lauryl-acrylate), monofunctional monomer, 1.0) ・IBXA: Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.: IBXA (Isobornyl acrylate), monofunctional monomer, 1.0) ・PEA: Phenoxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.: Light Acrylate PO-A, monofunctional monomer, 1.1)

＜光聚合起始劑（C）＞ ・APO：二苯基-2,4,6-三甲基苯甲醯基氧化膦（大同化成工業（股）製造：DAIDO UV-CURE APO） ＜Photopolymerization initiator (C)＞ ・APO: Diphenyl-2,4,6-trimethylbenzoylphosphine oxide (manufactured by Daido Kasei Kogyo Co., Ltd.: DAIDO UV-CURE APO)

＜溶劑（D）＞ 再者，括號內的數值是霧度變化值[（Y2）-（Y1）]。 （具有一個乙烯性不飽和基的溶劑（d1）） ・DMC：碳酸二甲酯（dimethyl carbonate）（宇部興產（股）製造，0.15） ・乙酸乙酯（大賽璐（DAICEL）（股）製造，0.47） ・丙酮（三菱化學（股）製造，0.81） ・MEK：甲基乙基酮（methyl ethyl ketone）（丸善石油化學（股）製造，0.42） ・1,3-二氧雜環戊烷（東邦化學工業（股）製造，0.48） （其他溶劑） ・MIBK：甲基異丁基酮（methyl isobutyl ketone）（三菱化學（股）製造，0.01） ・IPA：異丙醇（Isopropanol）（岸田（KISHIDA）化學（股）製造，0.04） ・PGM：丙二醇單甲醚（propylene glycol monomethyl ether）（大伸化學（股）製造，0.00） <Solvent (D)> In addition, the numerical value in parentheses is a haze change value [(Y2)-(Y1)]. (solvent (d1) with one ethylenically unsaturated group) ・DMC: Dimethyl carbonate (manufactured by Ube Industries, Ltd., 0.15) ・Ethyl acetate (manufactured by DAICEL Co., Ltd., 0.47) ・Acetone (manufactured by Mitsubishi Chemical Co., Ltd., 0.81) ・MEK: methyl ethyl ketone (manufactured by Maruzen Petrochemical Co., Ltd., 0.42) ・1,3-Dioxolane (manufactured by Toho Chemical Industry Co., Ltd., 0.48) (other solvents) ・MIBK: Methyl isobutyl ketone (manufactured by Mitsubishi Chemical Co., Ltd., 0.01) ・IPA: Isopropanol (manufactured by KISHIDA Chemical Co., Ltd., 0.04) ・PGM: Propylene glycol monomethyl ether (manufactured by Daishin Chemical Co., Ltd., 0.00)

＜實施例1＞ 將作為化合物（A）的以季戊四醇三丙烯酸酯與六亞甲基二異氰酸酯的2：1加成物為主要成分的胺基甲酸酯預聚物（共榮社化學（股）製造：UA-306H，6官能丙烯酸胺基甲酸酯）50份、二季戊四醇六丙烯酸酯（東亞合成（股）製造：亞羅尼克斯（ARONIX）M405，6官能單體）30份、季戊四醇三丙烯酸酯（日本化藥（股）製造：卡亞拉德（KAYARAD）PET30，3官能單體）10份；作為化合物（B）的丙烯醯嗎啉（KJ化學（股）製造：ACMO，單官能單體）10份；作為光聚合起始劑（C）的二苯基-2,4,6-三甲基苯甲醯基氧化膦（大同化成工業（股）製造：DAIDO UV-CURE APO）3份；作為溶劑（D）的碳酸二甲酯（宇部興產（股）製造：DMC）100份加以混合，從而獲得硬塗層形成用組成物。 <Example 1> As the compound (A), a urethane prepolymer mainly composed of a 2:1 adduct of pentaerythritol triacrylate and hexamethylene diisocyanate (manufactured by Kyyoei Chemical Co., Ltd.: UA- 306H, 6-functional urethane acrylate) 50 parts, dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.: ARONIX M405, 6-functional monomer) 30 parts, pentaerythritol triacrylate (Japan Manufactured by Chemical Pharmaceutical Co., Ltd.: KAYARAD (KAYARAD) PET30, trifunctional monomer) 10 parts; acryloylmorpholine as compound (B) (manufactured by KJ Chemical Co., Ltd.: ACMO, monofunctional monomer) 10 parts 3 parts; 3 parts of diphenyl-2,4,6-trimethylbenzoylphosphine oxide (manufactured by Daido Chemical Industry Co., Ltd.: DAIDO UV-CURE APO) as a photopolymerization initiator (C); as The solvent (D) was mixed with 100 parts of dimethyl carbonate (manufactured by Ube Industries, Ltd.: DMC) to obtain a composition for forming a hard coat layer.

繼而，使用棒塗機No.10將所獲得的硬塗層形成用組成物塗佈於厚度80 μm的三乙醯纖維素膜（富士軟片（股）製造）上，並利用熱風烘箱乾燥1分鐘。然後，利用輸出80 w/cm的高壓水銀燈照射紫外線，使塗佈層硬化，從而獲得具有三乙醯纖維素膜、混合層、及硬塗層的硬塗膜。硬塗層與混合層的合計膜厚為9.0 μm，硬塗膜的膜厚為87.0 μm。另外，於硬塗層與混合層的合計膜厚中所述混合層所佔的膜厚比率為70.5%。Next, the obtained composition for forming a hard coat layer was coated on a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd.) with a thickness of 80 μm using a bar coater No. 10, and dried in a hot air oven for 1 minute. . Then, ultraviolet rays were irradiated with a high-pressure mercury lamp with an output of 80 W/cm to harden the coating layer, thereby obtaining a hard coat film having a triacetylcellulose film, a mixed layer, and a hard coat layer. The total film thickness of the hard coat layer and the mixed layer was 9.0 μm, and the film thickness of the hard coat film was 87.0 μm. Moreover, the film thickness ratio which the said mixed layer occupied in the total film thickness of a hard-coat layer and a mixed layer was 70.5%.

＜實施例2～實施例20、比較例1～比較例11＞ 如表1～表3所示般變更組成及調配量（質量份），除此以外，與實施例1同樣地製造實施例2～實施例20、比較例1～比較例11的硬塗層形成用組成物，從而獲得硬塗膜。將所獲得的硬塗膜的硬塗層與混合層的合計膜厚、硬塗膜的膜厚、於硬塗層與混合層的合計膜厚中所述混合層所佔的膜厚比率示於表1～表3中。 <Example 2 to Example 20, Comparative Example 1 to Comparative Example 11> Except for changing the composition and compounding amount (parts by mass) as shown in Tables 1 to 3, the hard coat layers of Examples 2 to 20 and Comparative Examples 1 to 11 were produced in the same manner as in Example 1. The composition is used to obtain a hard coating film. The total film thickness of the hard coat layer and the mixed layer of the obtained hard coat film, the film thickness of the hard coat film, and the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer are shown in Table 1 to Table 3.

[評價] 藉由以下方法對各實施例、比較例中獲得的硬塗膜進行測定及評價。將結果示於表1～表3中。 [evaluate] The hard coat film obtained by each Example and the comparative example was measured and evaluated by the following method. The results are shown in Tables 1 to 3.

[混合層的膜厚比率評價] 使用超薄切片機（ultra microtome）（徠卡顯微系統（Leica Microsystems）公司製造，型號：EM UC7）並利用鑽石刀對所獲得的硬塗膜的厚度方向上的剖面切削數次而使其平滑後，利用掃描電子顯微鏡（日本電子公司製造，型號：JSM-7800F）以加壓電壓5 kV進行剖面觀察。混合層的膜厚比率是根據下述式而算出。 混合層的膜厚比率（%）=混合層的膜厚（μm）/（硬塗層的膜厚（μm）+混合層的膜厚（μm））×100 [Evaluation of Film Thickness Ratio of Mixed Layer] The section in the thickness direction of the obtained hard coating film was cut several times with a diamond knife using an ultra microtome (manufactured by Leica Microsystems, model: EM UC7) to smooth it Then, the cross-section was observed with a scanning electron microscope (manufactured by JEOL Ltd., model: JSM-7800F) at a voltage of 5 kV. The film thickness ratio of the mixed layer was calculated from the following formula. Film thickness ratio of the mixed layer (%) = film thickness of the mixed layer (μm) / (film thickness of the hard coat layer (μm) + film thickness of the mixed layer (μm)) × 100

[硬塗膜的膜厚評價] 所獲得的硬塗膜的膜厚（μm）是使用數位顯微鏡（尼康（Nikon）公司製造，型號：MH-15M）來進行測定。 [Film thickness evaluation of hard coat film] The film thickness (μm) of the obtained hard coat film was measured using a digital microscope (manufactured by Nikon Corporation, model: MH-15M).

[密接性評價1] 使用所獲得的硬塗膜實施膠帶密接試驗。膠帶密接試驗是依照日本工業標準（Japanese Industrial Standards，JIS）K5600來實施。 以如下方式放入切刀，即以到達基材但不切斷硬塗膜的程度的深度且以寬1 mm間隔形成10格×10格共計100方格，將賽璐玢帶（25 mm寬，米其邦（Nichiban）公司製造）貼附於塗膜表面後，利用手迅速將賽璐玢帶剝離，藉此對殘留的方格的狀態進行評價。 ・評價基準 +++：無剝離（非常良好）。 ++：格的端部略微缺失（良好）。 +：觀察到1格～5格的剝離（實用上無問題）。 NG：觀察到6格以上的剝離（不可實用）。 [adhesion evaluation 1] A tape adhesion test was implemented using the obtained hard coat film. The adhesive tape test is carried out in accordance with Japanese Industrial Standards (JIS) K5600. Insert the cutter in such a way that the cellophane tape (25 mm wide , manufactured by Nichiban Co., Ltd.) was attached to the surface of the coating film, and the cellophane tape was quickly peeled off by hand to evaluate the state of the remaining squares. ・Evaluation criteria +++: No stripping (very good). ++: The end of the cell is slightly missing (good). +: Peeling of 1 to 5 squares is observed (no problem practically). NG: Peeling of 6 frames or more was observed (not practical).

[干涉不均評價] 將硬塗膜切成5 cm×5 cm，並利用砂紙對與塗敷面為相反之側的TAC基材表面往復摩擦10次左右，使表面平滑後，滴加黑色消光塗料並於70℃下乾燥2分鐘。藉由分光光度計（日立高新技術（Hitachi High-Technologies）公司製造，型號：U-4100）對其測定5°絕對反射率，觀察反射曲線有無波動。 ・評價基準 +++：未觀察到波動（非常良好）。 ++：低於所述基準。幾乎觀察不到波動（良好）。 +：低於所述基準。稍微觀察到波動（實用上無問題）。 NG：低於所述基準。觀察到波動（不可實用）。 [Evaluation of uneven interference] Cut the hard coating film into 5 cm×5 cm, and use sandpaper to reciprocate the surface of the TAC substrate on the opposite side to the coating surface for about 10 times to make the surface smooth, then add black matting paint and dry at 70°C Let dry for 2 minutes. Measure the absolute reflectance at 5° with a spectrophotometer (manufactured by Hitachi High-Technologies, model: U-4100), and observe whether there is any fluctuation in the reflectance curve. ・Evaluation criteria +++: No fluctuation observed (very good). ++: below the stated benchmark. Little fluctuation was observed (good). +: Below the benchmark. Slight fluctuations were observed (practical no problem). NG: Below the benchmark. Fluctuations observed (not practical).

[塗膜霧度評價1] 將硬塗膜切成10 cm×10 cm，使用分光霧度計（日本電色工業公司製造，SH7000）來測定霧度值。 ・評價基準 ++：小於0.5%（良好）。 +：0.5%以上且小於1.0%（實用上無問題）。 NG：1.0%以上（不可實用）。 [Coating film haze evaluation 1] The hard coat film was cut into 10 cm x 10 cm, and the haze value was measured using the spectroscopic haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., SH7000). ・Evaluation criteria ++: less than 0.5% (good). +: 0.5% or more and less than 1.0% (no problem practically). NG: More than 1.0% (not practical).

[耐擦傷性評價] 將安裝有#0000的鋼絲絨的1平方厘米的方形襯墊放置於試樣表面上，以負荷500 g往復10次後，藉由目視來評價外觀，並測定劃痕的條數。 ・評價基準 ++：劃痕0條（良好）。 +：劃痕1根以上且小於5根（實用上無問題）。 NG：劃痕5根以上（不可實用）。 [Evaluation of Scratch Resistance] Place a 1 square centimeter square pad with #0000 steel wool on the surface of the sample, reciprocate 10 times with a load of 500 g, then visually evaluate the appearance and measure the number of scratches. ・Evaluation criteria ++: 0 scratches (good). +: 1 or more scratches and less than 5 scratches (no practical problem). NG: 5 or more scratches (not practical).

[耐擦傷性評價2] 將耐擦傷性評價1的負荷500 g變更為負荷1 kg，除此以外，藉由同樣的方法來進行試驗。 ・評價基準 ++++：劃痕0條（優異）。 +++：劃痕3條以下（良好）。 ++：劃痕4條以上且6條以下（良好）。 +：劃痕7條以上且9條以下（實用上無問題）。 NG：劃痕10條以上（不可實用）。 [Scratch resistance evaluation 2] The test was performed by the same method except that the load of scratch resistance evaluation 1 was changed from 500 g to 1 kg. ・Evaluation criteria ++++: 0 scratches (excellent). +++: 3 or less scratches (good). ++: 4 or more and 6 or less scratches (good). +: 7 or more and 9 or less scratches (no practical problem). NG: 10 or more scratches (not practical).

[密接性評價2] 於進行所述密接性評價1後，進而對同樣的部位追加實施2次（合計3次）賽璐玢帶的剝離試驗，按照以下的基準評價殘留的方格的狀態。 ・評價基準 +++：無剝離（非常良好）。 ++：格的端部略微缺失（良好）。 +：觀察到1格～5格的剝離（實用上無問題）。 NG：觀察到6格以上的剝離（不可實用）。 [adhesion evaluation 2] After the Adhesiveness Evaluation 1, the peeling test of the cellophane tape was additionally implemented twice (3 times in total) on the same site, and the state of the grid remaining was evaluated according to the following criteria. ・Evaluation criteria +++: No stripping (very good). ++: The end of the cell is slightly missing (good). +: Peeling of 1 to 5 squares is observed (no problem practically). NG: Peeling of 6 frames or more was observed (not practical).

[表1] 表1. 實施例 1 2 3 4 5 6 7 8 9 10 硬塗層形成用組成物 化合物（A） UA-306H 50 50 50 50 50 50 50 50 50 50 M405 30 30 30 30 30 30 30 30 30 37 PET30 10 10 10 10 10 10 10 10 10 10 化合物（B） 化合物（b1） ACMO 10 10 10 10 10 3 4-HBA 10 THF-A 10 NVP 10 DEAA 10 其他 LA IBXA PEA 光聚合起始劑（C） APO 3 3 3 3 3 3 3 3 3 3 溶劑（D） 溶劑（d1） DMC 100 100 100 100 100 100 乙酸乙酯 100 丙酮 100 MEK 100 1,3-二氧雜環戊烷 100 其他 MIBK IPA PGM （B）+（D）含有率（%） 54.2 54.2 54.2 54.2 54.2 54.2 54.2 54.2 54.2 50.7 （B）／（D） 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.03 硬塗膜 硬塗層與混合層的合計膜厚[μm] 9.0 8.9 8.5 8.9 8.8 8.8 8.7 8.9 8.9 8.5 硬塗膜的膜厚[μm] 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 混合層的膜厚比率[%] 70.5 69.0 65.3 69.2 68.4 68.0 67.4 69.1 68.8 65.1 評價結果 密接性 ++ ++ ++ ++ ++ ++ ++ ++ ++ ++ 干涉不均 +++ +++ + +++ ++ +++ +++ +++ +++ + 塗膜霧度 ++ ++ ++ ++ ++ + + ++ + ++ 耐擦傷性 ++ ++ ++ ++ ++ ++ + ++ ++ ++ 耐擦傷性 1 kg NG10次 ++++ +++ +++ ++++ +++ +++ +++ +++ +++ ++++ 密接性 3次剝離 ++ + + ++ + + + + + ++ [Table 1] Table 1. Example 1 2 3 4 5 6 7 8 9 10 Composition for forming hard coat layer Compound (A) UA-306H 50 50 50 50 50 50 50 50 50 50 M405 30 30 30 30 30 30 30 30 30 37 PET30 10 10 10 10 10 10 10 10 10 10 Compound (B) Compound (b1) ACMO 10 10 10 10 10 3 4-HBA 10 THF-A 10 NVP 10 DEAA 10 other LA IBXA PEA Photopolymerization initiator (C) APOs 3 3 3 3 3 3 3 3 3 3 solvent (D) solvent (d1) DMC 100 100 100 100 100 100 ethyl acetate 100 acetone 100 MEK 100 1,3-dioxolane 100 other MIBK IPA PGM (B) + (D) content rate (%) 54.2 54.2 54.2 54.2 54.2 54.2 54.2 54.2 54.2 50.7 (B)/(D) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.03 Hard coating Total film thickness of hard coat layer and mixed layer [μm] 9.0 8.9 8.5 8.9 8.8 8.8 8.7 8.9 8.9 8.5 Film thickness of hard coat [μm] 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 Film thickness ratio of mixed layer [%] 70.5 69.0 65.3 69.2 68.4 68.0 67.4 69.1 68.8 65.1 Evaluation results Closeness ++ ++ ++ ++ ++ ++ ++ ++ ++ ++ uneven interference +++ +++ + +++ ++ +++ +++ +++ +++ + Coating Haze ++ ++ ++ ++ ++ + + ++ + ++ Scratch resistance ++ ++ ++ ++ ++ ++ + ++ ++ ++ Scratch resistance 1 kg NG10 times ++++ +++ +++ ++++ +++ +++ +++ +++ +++ ++++ Adhesive 3 peeling ++ + + ++ + + + + + ++

[表2] 表2. 實施例 11 12 13 14 15 16 17 18 19 硬塗層形成用組成物 化合物（A） UA-306H 50 50 50 50 50 50 50 50 50 M405 35 25 20 30 30 30 30 10 10 PET30 10 10 10 10 10 10 10 10 10 化合物（B） 化合物（b1） ACMO 5 15 20 10 10 10 10 30 4-HBA THF-A NVP DEAA 其他 LA 30 IBXA PEA 光聚合起始劑（C） APO 3 3 3 3 3 3 3 3 3 溶劑（D） 溶劑（d1） DMC 100 100 100 55 70 150 190 190 乙酸乙酯 丙酮 MEK 1,3-二氧雜環戊烷 其他 MIBK 190 IPA PGM （B）+（D）含有率（%） 51.7 56.7 59.1 41.1 46.2 63.2 68.3 75.1 75.1 （B）／（D） 0.05 0.15 0.20 0.18 0.14 0.07 0.05 0.16 0.16 硬塗膜 硬塗層與混合層的合計膜厚[μm] 8.7 9.1 9.2 8.5 8.6 9.1 9.2 8.4 8.4 硬塗膜的膜厚[μm] 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 混合層的膜厚比率[%] 67.3 71.1 72.2 65.2 66.7 71.7 72.1 65.1 65.2 評價結果 密接性 ++ ++ ++ + ++ ++ ++ ++ ++ 干涉不均 +++ +++ +++ +++ +++ +++ +++ + + 塗膜霧度 ++ ++ ++ ++ ++ ++ + + + 耐擦傷性 ++ ++ ++ ++ ++ ++ + + + 耐擦傷性 1 kg NG10次 ++++ ++++ +++ ++++ ++++ ++++ +++ ++ ++ 密接性 3次剝離 ++ ++ ++ + ++ ++ + + + [Table 2] Table 2. Example 11 12 13 14 15 16 17 18 19 Composition for forming hard coat layer Compound (A) UA-306H 50 50 50 50 50 50 50 50 50 M405 35 25 20 30 30 30 30 10 10 PET30 10 10 10 10 10 10 10 10 10 Compound (B) Compound (b1) ACMO 5 15 20 10 10 10 10 30 4-HBA THF-A NVP DEAA other LA 30 IBXA PEA Photopolymerization initiator (C) APOs 3 3 3 3 3 3 3 3 3 solvent (D) solvent (d1) DMC 100 100 100 55 70 150 190 190 ethyl acetate acetone MEK 1,3-dioxolane other MIBK 190 IPA PGM (B) + (D) content rate (%) 51.7 56.7 59.1 41.1 46.2 63.2 68.3 75.1 75.1 (B)/(D) 0.05 0.15 0.20 0.18 0.14 0.07 0.05 0.16 0.16 Hard coating Total film thickness of hard coat layer and mixed layer [μm] 8.7 9.1 9.2 8.5 8.6 9.1 9.2 8.4 8.4 Film thickness of hard coat [μm] 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 Film thickness ratio of mixed layer [%] 67.3 71.1 72.2 65.2 66.7 71.7 72.1 65.1 65.2 Evaluation results Closeness ++ ++ ++ + ++ ++ ++ ++ ++ uneven interference +++ +++ +++ +++ +++ +++ +++ + + Coating Haze ++ ++ ++ ++ ++ ++ + + + Scratch resistance ++ ++ ++ ++ ++ ++ + + + Scratch resistance 1 kg NG10 times ++++ ++++ +++ ++++ ++++ ++++ +++ ++ ++ Adhesive 3 peeling ++ ++ ++ + ++ ++ + + +

[表3] 表3. 比較例 1 2 3 4 5 6 7 8 9 10 11 12 13 硬塗層形成用組成物 化合物（A） UA-306H 50 50 50 50 50 50 50 50 50 50 50 50 50 M405 30 30 30 30 30 30 30 30 30 40 30 10 15 PET30 10 10 10 10 10 10 10 10 10 10 10 10 10 化合物（B） 化合物（b1） ACMO 10 10 10 10 30 25 4-HBA THF-A NVP DEAA 其他 LA 10 10 IBXA 10 10 PEA 10 10 光聚合起始劑（C） APO 3 3 3 3 3 3 3 3 3 3 3 3 3 溶劑（D） 溶劑（d1） DMC 100 100 100 100 100 100 乙酸乙酯 丙酮 MEK 1,3-二氧雜環戊烷 其他 MIBK 100 100 100 100 IPA 100 PGM 100 （B）+（D）含有率（%） 54.2 54.2 54.2 54.2 54.2 54.2 54.2 54.2 54.2 49.3 9.7 64.0 61.6 （B）／（D） 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0 0 0.30 0.25 硬塗膜 硬塗層與混合層的合計膜厚[μm] 7.8 7.7 7.9 7.6 7.8 8.0 7.0 7.0 7.0 7.8 7.3 9.3 9.2 硬塗膜的膜厚[μm] 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 混合層的膜厚比率[%] 47.3 46.1 49.8 45.6 47.1 50.0 0 0 0 47.0 22.1 73.4 73.0 評價結果 密接性 + + + + + + NG NG NG + NG ++ ++ 干涉不均 NG NG NG NG NG NG NG NG NG NG NG +++ +++ 塗膜霧度 ++ ++ ++ ++ ++ ++ ++ ++ ++ ++ NG ++ ++ 耐擦傷性 + + + + + + + + + + NG + + 耐擦傷性 1 kg NG10次 ++ ++ ++ ++ ++ ++ + + + ++ NG + ++ 密接性 3次剝離 + + + + + + NG NG NG + NG NG NG [table 3] table 3. comparative example 1 2 3 4 5 6 7 8 9 10 11 12 13 Composition for forming hard coat layer Compound (A) UA-306H 50 50 50 50 50 50 50 50 50 50 50 50 50 M405 30 30 30 30 30 30 30 30 30 40 30 10 15 PET30 10 10 10 10 10 10 10 10 10 10 10 10 10 Compound (B) Compound (b1) ACMO 10 10 10 10 30 25 4-HBA THF-A NVP DEAA other LA 10 10 IBXA 10 10 PEA 10 10 Photopolymerization initiator (C) APOs 3 3 3 3 3 3 3 3 3 3 3 3 3 solvent (D) solvent (d1) DMC 100 100 100 100 100 100 ethyl acetate acetone MEK 1,3-dioxolane other MIBK 100 100 100 100 IPA 100 PGM 100 (B) + (D) content rate (%) 54.2 54.2 54.2 54.2 54.2 54.2 54.2 54.2 54.2 49.3 9.7 64.0 61.6 (B)/(D) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0 0 0.30 0.25 Hard coating Total film thickness of hard coat layer and mixed layer [μm] 7.8 7.7 7.9 7.6 7.8 8.0 7.0 7.0 7.0 7.8 7.3 9.3 9.2 Film thickness of hard coat [μm] 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 87.0 Film thickness ratio of mixed layer [%] 47.3 46.1 49.8 45.6 47.1 50.0 0 0 0 47.0 22.1 73.4 73.0 Evaluation results Closeness + + + + + + NG NG NG + NG ++ ++ uneven interference NG NG NG NG NG NG NG NG NG NG NG +++ +++ Coating Haze ++ ++ ++ ++ ++ ++ ++ ++ ++ ++ NG ++ ++ Scratch resistance + + + + + + + + + + NG + + Scratch resistance 1 kg NG10 times ++ ++ ++ ++ ++ ++ + + + ++ NG + ++ Adhesive 3 peeling + + + + + + NG NG NG + NG NG NG

根據表1～表3的結果，確認到，根據本硬塗膜，可獲得兼具迄今為止難以兼顧的塗膜霧度、耐擦傷性、干涉不均、及密接性的優異的硬塗膜，所述本硬塗膜具有由硬塗層形成用組成物形成的硬塗層及混合層，所述硬塗層形成用組成物包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D），硬塗層形成用組成物中的化合物（B）/溶劑（D）的質量比為0.03～0.20，且於硬塗層與混合層的合計膜厚中所述混合層所佔的膜厚比率為65%以上。From the results of Tables 1 to 3, it was confirmed that according to the present hard coat film, an excellent hard coat film having both coating film haze, scratch resistance, interference unevenness, and adhesiveness, which have been difficult to achieve until now, can be obtained. The present hard coat film has a hard coat layer and a mixed layer formed of a composition for forming a hard coat layer containing a compound (A) having three or more ethylenically unsaturated groups, Compound (B) having one ethylenically unsaturated group, photopolymerization initiator (C), and solvent (D), and the mass ratio of compound (B)/solvent (D) in the composition for forming a hard coat layer is 0.03 to 0.20, and the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer is 65% or more.

1:三乙醯纖維素膜 2:混合層 3:硬塗層 1: Triacetyl cellulose membrane 2: mixed layer 3: Hard coating

圖1是表示本實施方式的硬塗膜的結構的一例的示意性剖面圖。FIG. 1 is a schematic cross-sectional view showing an example of the structure of the hard coat film according to the present embodiment.

1:三乙醯纖維素膜 1: Triacetyl cellulose membrane

2:混合層 2: mixed layer

3:硬塗層 3: Hard coating

Claims (6)

一種硬塗膜，具有三乙醯纖維素膜、混合層、及硬塗層，所述硬塗膜中， 所述硬塗層由硬塗層形成用組成物形成，所述硬塗層形成用組成物包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D）， 所述硬塗層形成用組成物中的化合物（B）/溶劑（D）的質量比為0.03～0.20， 所述混合層是使所述硬塗層形成用組成物於所述三乙醯纖維素膜中溶解或膨潤而形成的層， 於利用掃描式電子顯微鏡對硬塗膜觀察厚度方向上的剖面時，於所述硬塗層與所述混合層的合計膜厚中所述混合層所佔的膜厚比率為65%以上。 A kind of hard coat film, has triacetyl cellulose film, mixing layer and hard coat layer, in described hard coat film, The hard coat layer is formed from a composition for forming a hard coat layer, and the composition for forming a hard coat layer includes a compound (A) having three or more ethylenically unsaturated groups, a compound (A) having one ethylenically unsaturated group, (B), photopolymerization initiator (C), and solvent (D), The mass ratio of compound (B)/solvent (D) in the composition for forming a hard coat layer is 0.03 to 0.20, The mixed layer is a layer formed by dissolving or swelling the composition for forming the hard coat layer in the triacetylcellulose film, When the section in the thickness direction of the hard coat film was observed with a scanning electron microscope, the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer was 65% or more. 如請求項1所述的硬塗膜，其中，具有一個乙烯性不飽和基的化合物（B）為 短邊2 cm×長邊4 cm×厚度80 μm的三乙醯纖維素膜的初期的質量（X1）、與將所述三乙醯纖維素膜於25℃的環境下在35 g的具有一個乙烯性不飽和基的化合物（B）中浸漬2小時後的三乙醯纖維素膜的質量（X2）的質量變化值[（X2）/（X1）]為1.2以上的具有一個乙烯性不飽和基的化合物（b1）。 The hard coat film according to claim 1, wherein the compound (B) having an ethylenically unsaturated group is The initial mass (X1) of the triacetyl cellulose film of 2 cm on the short side x 4 cm on the long side x 80 μm in thickness is the same as that of a 35 g triacetyl cellulose film at 25°C. The mass change value [(X2)/(X1)] of the mass change value [(X2)/(X1)] of the mass (X2) of the triacetyl cellulose film after immersion in the compound (B) of ethylenically unsaturated group for 2 hours is 1.2 or more and has one ethylenically unsaturated group base compound (b1). 如請求項1或請求項2所述的硬塗膜，其中，溶劑（D）為 短邊10 cm×長邊10 cm×厚度80 μm的三乙醯纖維素膜的初期的霧度值（Y1）、與對所述三乙醯纖維素膜於25℃的環境下滴加0.1 g的溶劑（D）並放置2分鐘後於60℃下加熱1分鐘後的三乙醯纖維素膜的霧度值（Y2）的霧度變化值[（Y2）-（Y1）]為0.10以上的溶劑（d1）。 The hard coating film as described in claim 1 or claim 2, wherein the solvent (D) is The initial haze value (Y1) of a triacetyl cellulose film with a short side of 10 cm x a long side of 10 cm x a thickness of 80 μm, and the triacetyl cellulose film added dropwise at 25°C with 0.1 g The haze value (Y2) of the triacetyl cellulose film after leaving the solvent (D) for 2 minutes and heating at 60°C for 1 minute and the haze change value [(Y2)-(Y1)] is 0.10 or more solvent (d1). 如請求項1或請求項2所述的硬塗膜，其中，具有一個乙烯性不飽和基的化合物（B）的含有率於化合物（A）與化合物（B）的合計100質量%中為3質量%～30質量%。The hard coat film according to claim 1 or claim 2, wherein the content of the compound (B) having one ethylenically unsaturated group is 3 based on 100% by mass of the total of the compound (A) and the compound (B) Mass% to 30 mass%. 如請求項1或請求項2所述的硬塗膜，其中，化合物（B）及溶劑（D）的合計含有率於硬塗層形成用組成物100質量%中為40質量%～70質量%。The hard coat film according to claim 1 or claim 2, wherein the total content of the compound (B) and the solvent (D) is 40% by mass to 70% by mass based on 100% by mass of the composition for forming a hard coat layer . 一種硬塗膜的製造方法，硬塗膜具有三乙醯纖維素膜、混合層、及硬塗層，所述硬塗膜的製造方法中， 於三乙醯纖維素膜上塗敷硬塗層形成用組成物，從而形成混合層及硬塗層， 所述硬塗層形成用組成物包含具有三個以上的乙烯性不飽和基的化合物（A）、具有一個乙烯性不飽和基的化合物（B）、光聚合起始劑（C）、及溶劑（D）， 所述硬塗層形成用組成物中的化合物（B）/溶劑（D）的質量比為0.03～0.20， 於利用掃描式電子顯微鏡對硬塗膜觀察厚度方向上的剖面時，於所述硬塗層與所述混合層的合計膜厚中所述混合層所佔的膜厚比率為65%以上。 A kind of manufacture method of hard coat film, hard coat film has triacetyl cellulose film, mixing layer and hard coat layer, in the manufacture method of described hard coat film, A composition for forming a hard coat layer is applied on a triacetyl cellulose film to form a mixed layer and a hard coat layer, The composition for forming a hard coat layer includes a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent (D), The mass ratio of compound (B)/solvent (D) in the composition for forming a hard coat layer is 0.03 to 0.20, When the section in the thickness direction of the hard coat film was observed with a scanning electron microscope, the film thickness ratio of the mixed layer in the total film thickness of the hard coat layer and the mixed layer was 65% or more.
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