TW201819184A - Laminated film - Google Patents

Laminated film Download PDF

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TW201819184A
TW201819184A TW106125885A TW106125885A TW201819184A TW 201819184 A TW201819184 A TW 201819184A TW 106125885 A TW106125885 A TW 106125885A TW 106125885 A TW106125885 A TW 106125885A TW 201819184 A TW201819184 A TW 201819184A
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meth
layer
film
resin
acrylate
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TW106125885A
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TWI762500B (en
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藤長将司
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日商住友化學股份有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • 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
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

An object of the present invention is to provide a laminated film capable of maintaining a high polarization degree even in a wet heat environment. The laminated film comprises a polarizer layer in which dichroic dye is oriented in polyvinyl alcohol resin, a resin layer which comprises a resin film having a slow axis in a direction with respect to the absorption axis of polarizer layer, and an adhesive layer for adhering the polarizer layer and the resin layer, wherein the resin layer has a plasticizer, the adhesive layer has a cured product of the adhesive composition as a forming material, and the adhesive composition has a compound having at least one (meth)acryloyl group in the molecule.

Description

積層膜  Laminated film  

本發明係關於一種積層膜。 The present invention relates to a laminated film.

以往，偏光板係廣泛地被使用作為在液晶顯示裝置等顯示裝置中偏光的供給元件，並且作為偏光的檢測元件。偏光板已知有使用接著劑等在偏光膜(偏光件層)的一面或兩面貼合有保護膜之構成。 Conventionally, a polarizing plate has been widely used as a supply element for polarizing light in a display device such as a liquid crystal display device, and as a detecting element for polarized light. In the polarizing plate, a protective film is bonded to one surface or both surfaces of a polarizing film (polarizer layer) using an adhesive or the like.

作為偏光膜者，已知有在包含聚乙烯醇系樹脂之膜中配向有碘等二色性色素者。偏光膜中的碘係以碘錯合物的方式存在，碘錯合物本身亦依存於聚乙烯醇系樹脂的配向而配向。已知該碘錯合物會吸收可見光區域的光線，藉此，偏光膜顯示偏光特性(偏光度)。 As a polarizing film, it is known that a film containing a polyvinyl alcohol-based resin is provided with a dichroic dye such as iodine. The iodine in the polarizing film is present as an iodine complex, and the iodine complex itself is also aligned depending on the alignment of the polyvinyl alcohol resin. It is known that the iodine complex absorbs light in the visible light region, whereby the polarizing film exhibits polarization characteristics (polarity).

將偏光板應用於顯示裝置時，依照所需在設置有保護膜之偏光膜貼合具有光學特性之位相差板、光學補償膜等各種光學層(樹脂層)(例如，專利文獻1)。光學層中，為了提高膜的性能之目的，亦可含有塑化劑等添加劑。 When the polarizing plate is applied to a display device, various optical layers (resin layers) such as a phase difference plate having an optical property and an optical compensation film are bonded to a polarizing film provided with a protective film as required (for example, Patent Document 1). In the optical layer, an additive such as a plasticizer may be contained for the purpose of improving the performance of the film.

[先前技術文獻]  [Previous Technical Literature]   [專利文獻]  [Patent Literature]  

[專利文獻1]日本特開2008-80674號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-80674

然而，當專利文獻1所記載之偏光板放置於濕熱環境下(例如，室溫60℃、濕度95%的環境下)時，有偏光度降低之情形。 However, when the polarizing plate described in Patent Document 1 is placed in a hot and humid environment (for example, an environment of room temperature of 60 ° C and a humidity of 95%), the degree of polarization is lowered.

本發明係鑒於如此情形而以提供一種即便在濕熱環境下亦能夠保持較高的偏光度之積層膜為目的者。 The present invention has been made in view of such circumstances to provide a laminated film capable of maintaining a high degree of polarization even in a hot and humid environment.

為了解決上述的課題，本發明者等重複進行精心研討之結果，推論由於在濕熱環境下，光學層所含之塑化劑往偏光膜遷移，與有助於偏光之碘錯合物反應而使碘錯合物消失，結果係使所得之偏光板的偏光度降低。相對於此，藉由使介於偏光膜與光學層之間的接著劑層包含接著劑組成物的硬化物作為形成材料，接著劑組成物包含在分子內具有至少1個(甲基)丙烯醯基之化合物，預想可抑制塑化劑往偏光膜遷移，進而完成了本發明。 In order to solve the above problems, the inventors of the present invention have repeatedly conducted intensive studies and concluded that the plasticizer contained in the optical layer migrates to the polarizing film in a hot and humid environment, and reacts with the iodine complex which contributes to polarization. The iodine complex disappeared, and as a result, the degree of polarization of the obtained polarizing plate was lowered. On the other hand, the adhesive composition containing the adhesive composition between the polarizing film and the optical layer contains a cured product of the adhesive composition as a forming material, and the adhesive composition contains at least one (meth) acrylonitrile in the molecule. The compound of the base is expected to inhibit migration of the plasticizer to the polarizing film, thereby completing the present invention.

本發明的一態樣，係提供一種積層膜，其具有：偏光件層，係在聚乙烯醇系樹脂中配向有二色性色素；樹脂層，係將相對於偏光件層的吸收軸於斜交方向具有慢軸之樹脂膜作為形成材料者；及接著劑層，係將偏光件層與樹脂層接著者；其中，樹脂層包含塑化劑，接著劑 層包含接著劑組成物的硬化物作為形成材料，接著劑組成物包含在分子內具有至少1個(甲基)丙烯醯基之化合物。 According to an aspect of the present invention, there is provided a laminated film comprising: a polarizer layer which is provided with a dichroic dye in a polyvinyl alcohol resin; and a resin layer which is inclined with respect to an absorption axis of the polarizer layer a resin film having a slow axis in the direction of intersection as a material for forming; and an adhesive layer connecting the polarizer layer and the resin layer; wherein the resin layer contains a plasticizer, and the adhesive layer contains a cured product of the adhesive composition as The material is formed, and the adhesive composition contains a compound having at least one (meth) acrylonitrile group in the molecule.

本發明的一態樣，偏光件層及延伸膜皆可為長條狀。 In one aspect of the invention, both the polarizer layer and the stretch film may be elongated.

依照本發明的一態樣，能夠提供一種即便在濕熱環境下亦能夠保持較高偏光度之積層膜。 According to an aspect of the present invention, it is possible to provide a laminated film capable of maintaining a high degree of polarization even in a hot and humid environment.

1、2‧‧‧積層膜 1, 2‧‧ ‧ laminated film

11‧‧‧偏光件層 11‧‧‧ polarizer layer

21‧‧‧樹脂層 21‧‧‧ resin layer

23‧‧‧保護膜 23‧‧‧Protective film

31、33‧‧‧接著劑層 31, 33‧‧‧ adhesive layer

第1圖係顯示本實施形態的積層膜的層結構的一個例子之剖面示意圖。 Fig. 1 is a schematic cross-sectional view showing an example of a layer structure of a laminated film of the present embodiment.

第2圖係顯示本實施形態的積層膜的層結構的變形例之剖面示意圖。 Fig. 2 is a schematic cross-sectional view showing a modification of the layer structure of the laminated film of the embodiment.

<積層膜>  <Laminated film>  

第1圖係顯示本實施形態的積層膜的層結構的一個例子之剖面示意圖。如第1圖所示，本實施形態的積層膜1係具有偏光件層11、樹脂層21、及將偏光件層11與樹脂層21接著之接著劑層31。在其他實施形態，亦可進一步將保護膜積層在偏光件層11中與樹脂層21為相反之側。 Fig. 1 is a schematic cross-sectional view showing an example of a layer structure of a laminated film of the present embodiment. As shown in Fig. 1, the laminated film 1 of the present embodiment has a polarizer layer 11, a resin layer 21, and an adhesive layer 31 in which the polarizer layer 11 and the resin layer 21 are followed. In other embodiments, the protective film may be further laminated on the side opposite to the resin layer 21 in the polarizer layer 11.

本實施形態的積層膜可為長條狀，亦可為藉由將長條狀積層膜切斷成為預定長度而得到之片狀體。長條狀積層膜係包含長條狀偏光件層及長條狀樹脂層。針 對長條狀偏光件層及長條狀樹脂層係於後述進行說明。 The laminated film of the present embodiment may be in the form of a strip, or may be a sheet-like body obtained by cutting a long laminated film into a predetermined length. The long strip-shaped laminated film includes a long strip-shaped polarizer layer and a long strip-shaped resin layer. The long strip-shaped polarizer layer and the elongated resin layer will be described later.

[偏光件層]  [Polarizer layer]  

所謂偏光件層，係指具備將具有對光學軸為平行的振動面之直線偏光吸收，且使具有對光學軸為正交的振動面之直線偏光穿透的性質之光學膜。具體而言，本實施形態的偏光件層11係在聚乙烯醇系樹脂(以下有稱為「PVA系樹脂」之情形)中配向有二色性色素之膜。 The polarizer layer is an optical film having a property of absorbing linearly polarized light having a vibrating surface parallel to the optical axis and transmitting linearly polarized light having a vibrating surface orthogonal to the optical axis. Specifically, the polarizer layer 11 of the present embodiment is a film having a dichroic dye in a polyvinyl alcohol-based resin (hereinafter referred to as a "PVA-based resin").

偏光件層11的厚度較佳為30μm以下，更佳為25μm以下，又更佳為15μm以下，尤佳為10μm以下，特佳為7μm以下。 The thickness of the polarizer layer 11 is preferably 30 μm or less, more preferably 25 μm or less, still more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 7 μm or less.

偏光件層11係在PVA系樹脂中配向有二色性色素之膜時，亦可藉由將含有PVA系樹脂之坯膜進行延伸來得到偏光件層11。偏光件層11的厚度為7μm以下時，亦可將形成在基材上之含有PVA系樹脂的塗膜與基材一起延伸，隨後剝離基材而得到偏光件層11。 When the polarizer layer 11 is a film having a dichroic dye in a PVA-based resin, the polarizer layer 11 can be obtained by extending a green film containing a PVA-based resin. When the thickness of the polarizer layer 11 is 7 μm or less, the coating film containing the PVA resin formed on the substrate may be extended together with the substrate, and then the substrate may be peeled off to obtain the polarizer layer 11.

作為亦可使用在本實施形態之基材者，可舉出聚丙烯膜、聚對苯二甲酸乙二酯膜、聚碳酸酯膜、三乙酸纖維素膜、降莰烯膜、聚酯膜、聚苯乙烯膜等。 Examples of the substrate which can be used in the present embodiment include a polypropylene film, a polyethylene terephthalate film, a polycarbonate film, a cellulose triacetate film, a norbornene film, a polyester film, and Polystyrene film, etc.

作為在本實施形態所使用的PVA系樹脂者，可舉出將聚乙酸乙烯酯系樹脂皂化者。作為聚乙酸乙烯酯系樹脂，除了屬於乙酸乙烯酯的均聚物之聚乙酸乙烯酯，亦可列舉乙酸乙烯酯和能夠與其共聚合的其它單體之共聚物。作為能夠與乙酸乙烯酯共聚合的其它單體者，可 舉出不飽和羧酸、烯烴、乙烯醚、不飽和磺酸、具有銨基之丙烯醯胺等。 The PVA-based resin used in the present embodiment is saponified with a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to the polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith may be mentioned. Examples of the other monomer copolymerizable with vinyl acetate include an unsaturated carboxylic acid, an olefin, a vinyl ether, an unsaturated sulfonic acid, and an acrylamide having an ammonium group.

PVA系樹脂的皂化度較佳為80莫耳%以上，更佳為90莫耳%以上99.5莫耳%以下，又更佳為94莫耳%以上99莫耳%以下。皂化度為80莫耳%以上時，可提升所得到的積層膜1的耐濕熱性。又，皂化度為99.5莫耳%以下時，能夠得到具有充分的偏光性能之積層膜1。 The degree of saponification of the PVA-based resin is preferably 80 mol% or more, more preferably 90 mol% or more and 99.5 mol% or less, still more preferably 94 mol% or more and 99 mol% or less. When the degree of saponification is 80 mol% or more, the moist heat resistance of the obtained laminated film 1 can be improved. Further, when the degree of saponification is 99.5 mol% or less, the laminated film 1 having sufficient polarizing performance can be obtained.

PVA系樹脂亦可為一部分被改質之改質聚乙烯醇。例如亦可使用經由乙烯及丙烯等之烯烴改質者；經由丙烯酸、甲基丙烯酸及巴豆酸等之不飽和羧酸改質者；藉由不飽和羧酸的烷基酯、丙烯醯胺等而改質者。 The PVA-based resin may also be a modified polyvinyl alcohol which is partially modified. For example, those who have been modified with an olefin such as ethylene or propylene; those who have been modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid; or an alkyl ester of an unsaturated carboxylic acid, acrylamide or the like may be used. Revamped.

PVA系樹脂的改質比率較佳為未達30莫耳%，更佳為未達莫耳10%。使用改質比率未達30莫耳%的PVA系樹脂時，能夠充分地吸附二色性色素，得到具有充分的偏光性能之偏光件。 The modification ratio of the PVA-based resin is preferably less than 30 mol%, more preferably 10% less. When a PVA-based resin having a modification ratio of less than 30 mol% is used, the dichroic dye can be sufficiently adsorbed, and a polarizer having sufficient polarizing performance can be obtained.

PVA系樹脂的平均聚合度較佳為100以上10000以下，更佳為1500以上8000以下，又更佳為2000以上5000以下。平均聚合度為100以上時，能夠得到具有充分的偏光性能之偏光件。又，平均聚合度為10000以下時，對溶劑的溶解性變良好，且含有PVA系樹脂之膜的形成變容易。 The average degree of polymerization of the PVA-based resin is preferably from 100 to 10,000, more preferably from 1,500 to 8,000, still more preferably from 2,000 to 5,000. When the average degree of polymerization is 100 or more, a polarizer having sufficient polarizing performance can be obtained. In addition, when the average degree of polymerization is 10,000 or less, the solubility in a solvent is improved, and formation of a film containing a PVA-based resin is facilitated.

PVA系樹脂係能夠容易地取得市售品，作為市售品的較佳例，皆以商品名列舉：KURARAY股份有限公司製的"PVA124"及"PVA117"(皂化度皆為：98至99莫 耳%)、"PVA624"(皂化度：95至96莫耳%)、"PVA617"(皂化度：94.5至95.5莫耳%)；日本合成化學工業股份有限公司製的"N-300"及"NH-18"(皂化度皆為：98至99莫耳%)、"AH-22"(皂化度：97.5至98.5莫耳%)、"AH-26"(皂化度：97至98.8莫耳%)；日本VAM & POVAL股份有限公司的"JC-33"(皂化度：99莫耳%以上)、"JF-17"、"JF-17L"及"JF-20"(皂化度皆為：98至99莫耳%)、"JM-26"(皂化度：95.5至97.5莫耳%)、"JM-33"(皂化度：93.5至95.5莫耳%)、"JP-45"(皂化度：86.5至89.5莫耳%)等。 PVA-based resin can be easily obtained as a commercial product, and as a preferred example of a commercial product, "PVA124" and "PVA117" manufactured by KURARAY Co., Ltd. are listed as the product name: the degree of saponification is 98 to 99. Ear %), "PVA624" (saponification degree: 95 to 96 mol%), "PVA617" (saponification degree: 94.5 to 95.5 mol%); "N-300" and "Nippon Synthetic Chemical Industry Co., Ltd." NH-18" (saponification degree: 98 to 99 mol%), "AH-22" (saponification degree: 97.5 to 98.5 mol%), "AH-26" (saponification degree: 97 to 98.8 mol%) ); "JC-33" (saponification degree: 99% or more), "JF-17", "JF-17L" and "JF-20" of Japan VAM & POVAL Co., Ltd. (saponification degree: 98) Up to 99% by mole), "JM-26" (saponification degree: 95.5 to 97.5 % by mole), "JM-33" (saponification degree: 93.5 to 95.5 % by mole), "JP-45" (saponification degree: 86.5 to 89.5 mol%) and so on.

作為在本實施形態所使用的二色性色素者，可舉出碘或二色性有機染料等。作為二色性有機染料，能夠舉出紅BR、紅LR、紅R、粉紅LB、深紅(RUBIN)BL、棗紅GS、天藍LG、檸檬黃、藍BR、藍2R、藏青RY、綠LG、紫LB、紫B、黑H、黑B、黑GSP、黃3G、黃R、橘LR、橘3R、猩紅GL、猩紅KGL、剛果紅、亮紫BK、S超級藍G、超級藍GL、超級橘GL、直接天藍、直接久牢橘(DIRECT FAST ORANGE)S、久牢黑(FAST BLACK)。 Examples of the dichroic dye used in the present embodiment include iodine or a dichroic organic dye. Examples of the dichroic organic dye include red BR, red LR, red R, pink LB, deep red (RUBIN) BL, jujube GS, sky blue LG, lemon yellow, blue BR, blue 2R, navy blue RY, green LG, purple LB, Purple B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Bright Purple BK, S Super Blue G, Super Blue GL, Super Orange GL, direct sky blue, direct DIRECT FAST ORANGE S, and long dark black (FAST BLACK).

二色性色素可單獨使用1種類，亦可併用2種以上。 The dichroic dye may be used alone or in combination of two or more.

[樹脂層]  [resin layer]  

本實施形態的樹脂層21，係將相對於偏光件層11的吸收軸於斜交方向具有慢軸之樹脂膜作為形成材料。此種樹脂膜係能夠經由延伸處理進行製造，上述樹脂膜係相對 於偏光件層11的吸收軸於斜交方向殘留有拉伸應力。在該樹脂膜所殘留之殘留應力，可能成為偏光板的偏光度降低的原因之一。 In the resin layer 21 of the present embodiment, a resin film having a slow axis in the oblique direction with respect to the absorption axis of the polarizer layer 11 is used as a forming material. Such a resin film can be produced by an elongation treatment in which a tensile stress remains in the oblique direction with respect to the absorption axis of the polarizer layer 11. The residual stress remaining in the resin film may be one of the causes of a decrease in the degree of polarization of the polarizing plate.

樹脂層21係相對於偏光件層11的吸收軸於斜交方向具有慢軸，例如相對於偏光件層11的吸收軸，慢軸的角度較佳為45±10°或135±10°。藉由使慢軸的角度成為上述範圍，在快軸方向之光線的相位與在慢軸方向之光線的相位之差成為π/2。由於快軸與慢軸的相位差為π/2，將本實施形態的積層膜1應用在顯示裝置時，能夠使通過積層膜1之光線成為圓偏光。據此，即便隔著偏光玻璃觀看時，亦能夠成為具有優異的視認性之構成。 The resin layer 21 has a slow axis with respect to the absorption axis of the polarizer layer 11 in the oblique direction. For example, with respect to the absorption axis of the polarizer layer 11, the angle of the slow axis is preferably 45 ± 10° or 135 ± 10°. By setting the angle of the slow axis to the above range, the difference between the phase of the light beam in the fast axis direction and the phase of the light beam in the slow axis direction becomes π/2. When the laminated film 1 of the present embodiment is applied to a display device, the light passing through the laminated film 1 can be made into a circularly polarized light when the phase difference between the fast axis and the slow axis is π/2. According to this, even when viewed through a polarizing glass, it is possible to have a structure having excellent visibility.

本實施形態的樹脂層21，較佳為具有滿足下述式(1)至(4)的相位差特性及波長分散特性之相位差層。藉由樹脂層21滿足式(1)至(4)，在將本實施形態的積層膜1安裝於顯示裝置時，能夠有效地抑制隔著偏光玻璃從各種方向(方位角及極角)觀看畫面時之色調變化。藉此，能夠提升影像顯示裝置的視認性。 The resin layer 21 of the present embodiment preferably has a retardation layer satisfying the phase difference characteristics and the wavelength dispersion characteristics of the following formulas (1) to (4). When the laminated film 1 of the present embodiment is mounted on a display device by the resin layer 21, the laminated film 1 of the present embodiment can be effectively prevented from being viewed from various directions (azimuth and polar angle) via the polarizing glass. The color tone changes. Thereby, the visibility of the image display device can be improved.

(1)100nm≦Re(590)≦180nm、(2)0.5<Rth(590)/Re(590)≦0.8、(3)0.85≦Re(450)/Re(550)<1.00、及(4)1.00<Re(630)/Re(550)≦1.1 (1) 100 nm ≦R e (590) ≦ 180 nm, (2) 0.5 < R th (590) / R e (590) ≦ 0.8, (3) 0.85 ≦ R e (450) / R e (550) < 1.00 and (4) 1.00 <R e ( 630) / R e (550) ≦ 1.1

式中，Re(590)、Re(450)、Re(550)、Re(630)各自表示測定波長590nm、450nm、550nm、630nm中之面 內相位差值，Rth(590)表示測定波長590nm中之厚度方向相位差值。此等面內相位差值及厚度方向相位差值係指在溫度23℃、相對濕度55%的環境下所測定之值。 Wherein R e (590), R e (450), R e (550), and R e (630) each represent an in-plane retardation value in the measurement wavelengths of 590 nm, 450 nm, 550 nm, and 630 nm, and R th (590) The thickness direction phase difference value in the measurement wavelength of 590 nm is shown. These in-plane phase difference values and thickness direction phase difference values are values measured in an environment of a temperature of 23 ° C and a relative humidity of 55%.

面內相位差值Re、厚度方向相位差值Rth，係將面內慢軸方向的折射率設為nx，將面內快軸方向(與面內慢軸方向呈正交之方向)的折射率設為ny，將厚度方向的折射率設為nz，將光學膜的厚度設為d時，以下述式(S1)、式(S2)定義者。 The in-plane phase difference value R e and the thickness direction phase difference value R th are obtained by setting the refractive index in the in-plane slow axis direction to n x and the in-plane fast axis direction (in the direction orthogonal to the in-plane slow axis direction). When the refractive index is n y , the refractive index in the thickness direction is n z , and when the thickness of the optical film is d, it is defined by the following formulas (S1) and (S2).

(S1)Re=(nx-ny)×d (S1)R e =(n x -n y )×d

(S2)Rth=[{(nx+ny)/2}-nz]×d (S2)R th =[{(n x +n y )/2}-n z ]×d

從更有效地抑制在積層膜1的色調變化之觀點而言，式(1)中之Re(590)較佳為105至170nm。式(2)中之Rth(590)/Re(590)較佳為0.6至0.75。式(3)中之Re(450)/Re(550)較佳為0.86至0.98。式(4)中之Re(630)/Re(550)較佳為1.01至1.06。 From the viewpoint of more effectively suppressing the change in color tone of the laminated film 1, R e (590) in the formula (1) is preferably from 105 to 170 nm. R th (590) / R e (590) in the formula (2) is preferably from 0.6 to 0.75. The formula R e (3) in the (450) / R e (550 ) preferably 0.86 to 0.98. R e (630) / R e (550) in the formula (4) is preferably from 1.01 to 1.06.

例如藉由將含有後述樹脂之膜進行延伸，能夠製造樹脂層21。作為延伸處理，可舉出單軸延伸、雙軸延伸等。 For example, the resin layer 21 can be produced by stretching a film containing a resin described later. Examples of the stretching treatment include uniaxial stretching, biaxial stretching, and the like.

作為延伸方向者，可舉出未延伸膜的機械流動方向(MD)、與此正交的方向(TD)、斜交於機械流動方向(MD)之方向等。在此，所謂未延伸膜，係指狀態為未經延伸之膜。單軸延伸，係將未延伸膜在此等方向之中的任一方向進行延伸。另一方面，雙軸延伸可為在2個延伸方 向同時進行延伸之同時雙軸延伸，亦可為在預定方向進行延伸之後，在其它方向進行延伸之逐次雙軸延伸。 Examples of the direction of extension include a mechanical flow direction (MD) of the unstretched film, a direction orthogonal thereto (TD), a direction oblique to the mechanical flow direction (MD), and the like. Here, the unstretched film refers to a film in which the state is not extended. Uniaxial stretching extends the unstretched film in either of these directions. On the other hand, the biaxial extension may be a biaxial extension while extending simultaneously in two extending directions, or may be a sequential biaxial extension extending in other directions after extending in a predetermined direction.

延伸處理，係例如能夠藉由使用出口側的周速增大之二對以上的夾輥，而在縱軸方向(機械流動方向：MD)進行延伸，或是藉由使用夾頭把持未延伸膜的兩側端而在與機械流動方向呈正交的方向(TD)進行擴大來進行。此時，能夠藉由調整膜的厚度、或調整延伸倍率而將相位差值及波長分散控制在上述式(1)至(4)的範圍內。 The stretching treatment can be carried out, for example, by using two or more nip rolls whose peripheral speed is increased on the outlet side, in the longitudinal direction (mechanical flow direction: MD), or by using a chuck to hold the unstretched film. The both ends are expanded in a direction (TD) orthogonal to the mechanical flow direction. At this time, the phase difference value and the wavelength dispersion can be controlled within the range of the above formulas (1) to (4) by adjusting the thickness of the film or adjusting the stretching ratio.

又，藉由在樹脂添加波長分散調整劑，而能夠將波長分散值控制在上述式(3)至(4)的範圍內。 Further, by adding a wavelength dispersion adjusting agent to the resin, the wavelength dispersion value can be controlled within the range of the above formulas (3) to (4).

通常長條狀偏光膜(偏光件層)係在長邊方向具有吸收軸。從能夠以卷至卷之方式將長條狀樹脂層與長條狀偏光件層貼合，並且使偏光件層的吸收軸與樹脂層的慢軸所成的角度成為上述範圍的方式來配置兩者而言，樹脂層21較佳為藉由雙軸延伸進行斜延伸而製造者。 Usually, the long strip-shaped polarizing film (polarizer layer) has an absorption axis in the longitudinal direction. The two-layered resin layer and the long-length polarizer layer can be bonded together in a roll-to-roll manner, and the angle between the absorption axis of the polarizer layer and the slow axis of the resin layer is set to the above range. The resin layer 21 is preferably manufactured by obliquely extending by biaxial stretching.

作為形成樹脂膜之樹脂者，例如可舉出乙酸纖維素系樹脂、環烯烴系樹脂、聚烯烴系樹脂、丙烯酸系樹脂、聚醯亞胺系樹脂、聚碳酸酯系樹脂、聚酯系樹脂等。 Examples of the resin forming the resin film include a cellulose acetate resin, a cycloolefin resin, a polyolefin resin, an acrylic resin, a polyimide resin, a polycarbonate resin, a polyester resin, and the like. .

乙酸纖維素系樹脂係由纖維素的部分或完全乙酸酯化物所構成。作為乙酸纖維素系樹脂者，例如可舉出三乙酸纖維素、二乙酸纖維素等。 The cellulose acetate-based resin is composed of a partially or completely acetated cellulose. Examples of the cellulose acetate-based resin include cellulose triacetate and cellulose diacetate.

包含乙酸纖維素系樹脂之樹脂膜，係能夠容易地取得市售品，作為市售品的較佳例子，皆以商品名 舉出：富士FILM股份有限公司所販賣之"FUJITAC(註冊商標)TD80"、"FUJITAC(註冊商標)TD80UF"及"FUJITAC(註冊商標)TD80UZ"、由Konica Minolta Opto股份有限公司所販賣之"KC8UX2M"及"KC8UY"等。 A resin film containing a cellulose acetate-based resin can be easily obtained as a commercial product. As a preferred example of a commercial product, the product name is "FUJITAC (registered trademark) TD80 sold by Fuji FILM Co., Ltd. ", "FUJITAC (registered trademark) TD80UF" and "FUJITAC (registered trademark) TD80UZ", "KC8UX2M" and "KC8UY" sold by Konica Minolta Opto Co., Ltd.

形成樹脂膜之環烯烴系樹脂，係例如具有包含如降莰烯和多環降莰烯系單體的環狀烯烴(環烯烴)之單體單元的熱可塑性非晶性樹脂(亦稱為非晶性聚烯烴系樹脂)。環烯烴系樹脂可為上述環烯烴的開環聚合物之氫化物、使用2種以上環烯烴的開環共聚物之氫化物；亦可為環烯烴與鏈狀烯烴及/或具有乙烯基的芳香族化合物等之加成共聚物。又，亦可導入有極性基。 The cycloolefin-based resin forming the resin film is, for example, a thermoplastic amorphous resin having a monomer unit containing a cyclic olefin (cycloolefin) such as norbornene and a polycyclic norbornene-based monomer (also referred to as a non- Crystalline polyolefin resin). The cycloolefin resin may be a hydrogenated product of a ring-opening polymer of the above cycloolefin, a hydrogenated product of a ring-opening copolymer using two or more kinds of cyclic olefins, or a cycloolefin and a chain olefin and/or a vinyl group. An addition copolymer of a compound or the like. Further, a polar group may be introduced.

使用環烯烴與鏈狀烯烴及/或具有乙烯基的芳香族化合物之共聚物來構成樹脂膜時，作為鏈狀烯烴者，可舉出乙烯、丙烯等。又，作為具有乙烯基之芳香族化合物者，可舉出苯乙烯、α-甲基苯乙烯、苯環上有烷基取代之苯乙烯等。在此種共聚物，包含環烯烴之單體單元較佳為50莫耳%以下，更佳為15至50莫耳%。 When a resin film is formed by using a copolymer of a cyclic olefin and a chain olefin and/or an aromatic compound having a vinyl group, examples of the chain olefin include ethylene and propylene. Further, examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, and styrene having an alkyl group substituted on the benzene ring. In such a copolymer, the monomer unit containing a cycloolefin is preferably 50 mol% or less, more preferably 15 to 50 mol%.

特別是使用具有環烯烴、鏈狀烯烴及乙烯基的芳香族化合物之三元共聚物時，包含環烯烴的單體單元，能夠設為如上述之較少的量。在此種三元共聚物，由鏈狀烯烴所構成的單體之單元較佳為5至80莫耳%。又，包含具有乙烯基的芳香族化合物的單體單元較佳為5至80莫耳%。 In particular, when a terpolymer having an aromatic compound of a cycloolefin, a chain olefin, and a vinyl group is used, the monomer unit containing a cycloolefin can be set to a smaller amount as described above. In such a terpolymer, the unit of the monomer composed of a chain olefin is preferably from 5 to 80 mol%. Further, the monomer unit containing an aromatic compound having a vinyl group is preferably from 5 to 80 mol%.

環烯烴系樹脂係能夠容易地取得市售品，作 為市售品的較佳例，皆以商品名舉出：TOPAS ADVANCED POLYMERS GmbH製且在日本由POLY PLASTICS股份有限公司所販賣之"TOPAS(註冊商標)"、由JSR股份有限公司所販賣之"ARTON(註冊商標)"、由日本ZEON股份有限公司所販賣之"ZEONOR(註冊商標)"及"ZEONEX(註冊商標)"、由三井化學股份有限公司所販賣之"APEL(註冊商標)"等。 A commercially available product can be easily obtained as a cycloolefin resin, and a preferred example of a commercially available product is TOPAS (registered by TOPAS ADVANCED POLYMERS GmbH) and sold in Japan by POLY PLASTICS Co., Ltd. "Trademark"", "ARTON (registered trademark)" sold by JSR Co., Ltd., "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" sold by Japan ZEON Co., Ltd., by Mitsui Chemicals Co., Ltd. "APEL (registered trademark)" sold by the company.

本實施形態的樹脂層21為相位差層時，相位差層的厚度較佳為10μm以上且50μm以下。 When the resin layer 21 of the present embodiment is a phase difference layer, the thickness of the phase difference layer is preferably 10 μm or more and 50 μm or less.

本實施形態的樹脂層21係除了形成樹脂膜之樹脂以外，為了對樹脂膜賦予柔軟性且容易延伸之目的，亦可含有塑化劑。作為塑化劑者，能夠舉出乙二醇、甘油、丙二醇、二乙二醇、三乙二醇、四乙二醇、三羥甲基丙烷等多元醇。 The resin layer 21 of the present embodiment may contain a plasticizer for the purpose of imparting flexibility to the resin film in addition to the resin forming the resin film. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane.

塑化劑可只使用1種，亦可併用2種以上。特別是適合使用乙二醇和甘油。 The plasticizer may be used alone or in combination of two or more. In particular, it is suitable to use ethylene glycol and glycerin.

[接著劑層]  [adhesive layer]  

本實施形態的接著劑層31係包含接著劑組成物的硬化物作為形成材料(以下有將「接著劑組成物」稱為「本組成物」之情形)。接著劑組成物包含在分子內具有至少1個(甲基)丙烯醯基之化合物。在分子內具有至少1個(甲基)丙烯醯基之化合物，能夠舉出在分子內具有至少1個(甲基)丙烯醯氧基之化合物(以下，有稱為「(甲基)丙烯酸系化合物」之情形)，在分子內具有至少1個(甲基)丙烯醯胺基之 化合物(以下，有稱為「(甲基)丙烯醯胺系化合物」之情形)等。該等化合物為自由基聚合性化合物，可藉由照射活性能量線(例如，紫外線、可見光、電子射線、X射線等)而硬化。 In the adhesive layer 31 of the present embodiment, a cured product of the adhesive composition is used as a forming material (hereinafter, the "adhesive composition" is referred to as "the present composition"). The subsequent composition contains a compound having at least one (meth) acrylonitrile group in the molecule. A compound having at least one (meth) acryl fluorenyl group in the molecule, and a compound having at least one (meth) acryloxy group in the molecule (hereinafter referred to as "(meth)acrylic acid) In the case of the compound, a compound having at least one (meth)acrylamide group in the molecule (hereinafter referred to as "(meth)acrylamide compound)" or the like. These compounds are radically polymerizable compounds which can be cured by irradiation with active energy rays (for example, ultraviolet rays, visible light, electron rays, X-rays, etc.).

在本說明書中，所謂「(甲基)丙烯醯基」，係指甲基丙烯醯基或丙烯醯基。而且，所謂「(甲基)丙烯醯氧基」、「(甲基)丙烯醯胺基」亦與上述者同理。 In the present specification, the term "(meth)acryl fluorenyl" means a methacryl fluorenyl group or an acryl fluorenyl group. Further, the "(meth)acryloxy" and "(meth)acrylamide" are also the same as those described above.

接著劑層的厚度，較佳為0.01μm以上5μm以下，更佳為0.01μm以上2μm以下，又更佳為0.01μm以上1μm以下。接著劑層31的厚度為0.01μm以上時，能夠得到充分的接著性。又，接著劑層31的厚度為5μm以下時，積層膜1不易成為外觀不良。 The thickness of the subsequent layer is preferably 0.01 μm or more and 5 μm or less, more preferably 0.01 μm or more and 2 μm or less, and still more preferably 0.01 μm or more and 1 μm or less. When the thickness of the subsequent agent layer 31 is 0.01 μm or more, sufficient adhesion can be obtained. Moreover, when the thickness of the adhesive layer 31 is 5 μm or less, the laminated film 1 is less likely to be inferior in appearance.

接著劑層，較佳係選擇以使厚度成為2至3μm之方式將接著劑組成物塗佈於三乙酸纖維素膜上並使之硬化而得到之評估試樣，該評估試樣的透濕度成為300g/m2‧24小時以下者。透濕度的下限值並無特別限定，例如為50g/m2‧24小時。藉由使用透濕度成為如此之接著劑層，可使偏光度降低變更小。 Next, the agent layer is preferably selected so as to have a thickness of 2 to 3 μm, and the adhesive composition is applied to a cellulose triacetate film and hardened to obtain an evaluation sample, and the moisture permeability of the evaluation sample becomes 300g/m 2 ‧24 hours or less. The lower limit of the moisture permeability is not particularly limited and is, for example, 50 g/m 2 ‧24 hours. By using the moisture permeability to be such an adhesive layer, the change in the degree of polarization reduction can be made small.

評估試樣可以下述方式製作。首先，以使厚度成為2至3μm之方式將接著劑組成物塗佈於三乙酸纖維素膜上，形成接著劑組成物層。作為用以測定評估試樣的透濕度之三乙酸纖維素膜，係使用厚度為57.5μm，透濕度[藉由杯式法(JIS Z 0208，溫度40℃，濕度90%RH)所算出之值]為553g/m2‧24小時者。繼而，由接著劑組成 物層側，以累計光量成為400mJ/cm2之方式照射紫外線，使接著劑組成物層硬化而作為評估試樣。藉由杯式法(JIS Z 0208、溫度40℃、濕度90%RH)測定所得之評估試樣的透濕度。 The evaluation sample can be produced in the following manner. First, an adhesive composition is applied onto a cellulose triacetate film so as to have a thickness of 2 to 3 μm to form an adhesive composition layer. As a cellulose triacetate film for measuring the moisture permeability of the evaluation sample, a thickness of 57.5 μm and a moisture permeability [value calculated by a cup method (JIS Z 0208, temperature 40 ° C, humidity 90% RH)) were used. ] is 553g / m 2 ‧ 24 hours. Then, on the side of the adhesive composition layer, ultraviolet rays were irradiated so that the cumulative amount of light became 400 mJ/cm 2 , and the adhesive composition layer was cured to obtain an evaluation sample. The moisture permeability of the obtained evaluation sample was measured by a cup method (JIS Z 0208, temperature 40 ° C, humidity 90% RH).

(自由基聚合性化合物)  (radical polymerizable compound)  

作為本實施形態所使用之(甲基)丙烯酸系化合物者，可舉出在分子內具有至少1個(甲基)丙烯醯氧基之(甲基)丙烯酸酯單體、在分子內具有至少2個(甲基)丙烯醯氧基之(甲基)丙烯酸酯寡聚物等。該等係各自可單獨使用，亦可併用2種以上。併用2種以上時，(甲基)丙烯酸酯單體可為2種以上，(甲基)丙烯酸酯寡聚物亦可為2種以上，當然亦可併用(甲基)丙烯酸酯單體1種以上及(甲基)丙烯酸酯寡聚物1種以上。 Examples of the (meth)acrylic compound used in the present embodiment include a (meth) acrylate monomer having at least one (meth) acryloxy group in the molecule, and having at least 2 in the molecule. (Meth) propylene decyloxy (meth) acrylate oligomer, etc. Each of these systems may be used alone or in combination of two or more. When two or more types are used in combination, two or more kinds of (meth) acrylate monomers may be used, and two or more kinds of (meth) acrylate oligomers may be used. Of course, one type of (meth) acrylate monomer may be used in combination. One or more of the above (meth) acrylate oligomers.

作為上述(甲基)丙烯酸酯單體者，可列舉：在分子內具有1個(甲基)丙烯醯氧基之單官能(甲基)丙烯酸酯單體、在分子內具有2個(甲基)丙烯醯氧基之2官能(甲基)丙烯酸酯單體及在分子內具有3個以上(甲基)丙烯醯氧基之多官能(甲基)丙烯酸酯單體。 Examples of the (meth) acrylate monomer include a monofunctional (meth) acrylate monomer having one (meth) propylene decyloxy group in the molecule, and two molecules in the molecule (methyl group). A bifunctional (meth) acrylate monomer having an acryloxy group and a polyfunctional (meth) acrylate monomer having three or more (meth) acryloxy groups in the molecule.

作為單官能(甲基)丙烯酸酯單體者，可列舉：(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-或3-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2-羥基-3-苯氧基丙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸 異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸環己酯、1,4-環己烷二甲醇單丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸二環戊烯基氧基乙酯、(甲基)丙烯酸二甲基胺基乙酯、乙基卡必醇(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯、新戊四醇單(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸苯氧酯等。 Examples of the monofunctional (meth) acrylate monomer include tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2- or 3-hydroxypropyl (meth) acrylate. , 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, methyl (meth)acrylate, (A) Ethyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 1,4-cyclohexane dimethanol monoacrylate, dicyclopentanyl (meth) acrylate, (meth) acrylate Dicyclopentenyl ester, benzyl (meth)acrylate, isodecyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, Dimethylaminoethyl (meth) acrylate, ethyl carbitol (meth) acrylate, trimethylolpropane mono (meth) acrylate, neopentyl alcohol mono (meth) acrylate, Polyethylene glycol (meth) acrylate phenoxy ester and the like.

作為單官能(甲基)丙烯酸酯單體者，亦可使用含有羧基之(甲基)丙烯酸酯單體。作為含有羧基之單官能(甲基)丙烯酸酯單體者可列舉：2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、(甲基)丙烯酸羧乙酯、2-(甲基)丙烯醯氧基乙基琥珀酸、N-(甲基)丙烯醯氧基-N′,N′-二羧基甲基-對伸苯二胺、4-(甲基)丙烯醯氧基乙基偏苯三酸等。 As the monofunctional (meth) acrylate monomer, a carboxyl group-containing (meth) acrylate monomer can also be used. As the monofunctional (meth) acrylate monomer having a carboxyl group, 2-(meth) propylene oxiranyl ethyl phthalic acid, 2-(methyl) propylene oxiranyl ethyl hexahydroortho Phthalic acid, carboxyethyl (meth)acrylate, 2-(meth)acryloxyethyl succinic acid, N-(methyl)propenyloxy-N',N'-dicarboxymethyl- P-phenylenediamine, 4-(meth)acryloyloxyethyl trimellitic acid, and the like.

作為本實施形態所使用之(甲基)丙烯醯胺系化合物者，可舉出N-取代(甲基)丙烯醯胺化合物。N-取代(甲基)丙烯醯胺化合物係在N-位具有取代基之(甲基)丙烯醯胺化合物。此取代基的典型例為烷基。N-位的取代基可互相鍵結而形成環，構成該環之-CH2-亦可被氧原子取代。而且，構成該環之碳原子，亦可鍵結有如烷基、側氧基(=O)的取代基。N-取代(甲基)丙烯醯胺通常能夠藉由(甲基)丙烯酸或其氯化物與1級或2級胺的反應而製造。 The (meth) acrylamide compound used in the present embodiment may, for example, be an N-substituted (meth) acrylamide compound. The N-substituted (meth) acrylamide compound is a (meth) acrylamide compound having a substituent at the N-position. A typical example of such a substituent is an alkyl group. The substituent at the N-position may be bonded to each other to form a ring, and -CH 2 - constituting the ring may be substituted with an oxygen atom. Further, the carbon atom constituting the ring may be bonded to a substituent such as an alkyl group or a pendant oxy group (=O). N-substituted (meth) acrylamide can usually be produced by the reaction of (meth)acrylic acid or its chloride with a primary or secondary amine.

N-取代(甲基)丙烯醯胺化合物，較佳為下式(III)所示之化合物。下式(III)中，Q1表示氫原子或甲基，Q2表示氫原子或碳數1至6的烷基，Q3表示可具有羥基或胺基之碳數1至6的烷基，或是Q2與Q3互相鍵結，形成-CH2-可經氧原子取代之5員環或6員環。前述胺基的氫原子可經烷基取代。 The N-substituted (meth) acrylamide compound is preferably a compound represented by the following formula (III). In the following formula (III), Q 1 represents a hydrogen atom or a methyl group, Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q 3 represents an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group or an amine group. or Q 2 and Q 3 are bonded to each other to form a ring -CH 2- may be substituted by an oxygen atom of a 5- or 6-membered ring. The hydrogen atom of the aforementioned amine group may be substituted with an alkyl group.

作為Q3為具有羥基之烷基之例，可列舉羥烷基。Q3為具有胺基的烷基之例，可列舉：胺基烷基、N-烷基胺基烷基及N,N-二烷基胺基烷基。Q2與Q3可互相鍵結，形成-CH2-可經氧原子取代之5員環或6員環，該5員環或6員環之例，若舉出N-位鍵結羰基(C=O)之基形式者，可列舉：1-吡咯啶基(C4H8N-)、2-唑烷酮-3-基〔C2H4OC(=O)N-〕、哌啶基(C5H10N-)、嗎啉基(C2H4OC2H4N-)等。 Examples of the alkyl group in which Q 3 is a hydroxyl group include a hydroxyalkyl group. Q 3 is an alkyl group having an amine group, and examples thereof include an aminoalkyl group, an N-alkylaminoalkyl group, and an N,N-dialkylaminoalkyl group. Q 2 and Q 3 may be mutually bonded to form a ring -CH 2- may be substituted by an oxygen atom of a 5- or 6-membered ring, the 5-membered ring or a ring of six cases, if the bit include N- group bonded to a carbonyl ( The base form of C=O) can be exemplified by 1-pyrrolidinyl (C 4 H 8 N-), 2- Oxazolidin-3-yl [C 2 H 4 OC(=O)N-], piperidinyl (C 5 H 10 N-), morpholinyl (C 2 H 4 OC 2 H 4 N-), and the like.

作為Q2為氫原子、Q3為烷基之N-取代(甲基)丙烯醯胺化合物者，係有N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺等。同樣的，作為Q2及Q3皆為烷基之N-取代(甲基)丙烯醯胺者，可列舉N,N-二甲基(甲基)丙烯醯胺、N,N- 二乙基(甲基)丙烯醯胺等。 As an N-substituted (meth) acrylamide compound in which Q 2 is a hydrogen atom and Q 3 is an alkyl group, N-methyl(meth)acrylamide and N-ethyl(meth)acryl oxime are used. Amine, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) propylene hydride Amines, etc. Similarly, as the N-substituted (meth) acrylamide of the alkyl group in which both Q 2 and Q 3 are alkyl, N,N-dimethyl(meth) acrylamide, N,N-diethyl group can be cited. (Methyl) acrylamide and the like.

作為Q2為氫原子、Q3為具有羥基之烷基之N-取代(甲基)丙烯醯胺化合物者，係有N-羥甲基(甲基)丙烯醯胺、N-(2-羥基乙基)(甲基)丙烯醯胺、N-(2-羥基丙基)(甲基)丙烯醯胺等。作為Q2為氫原子、Q3為具有胺基之烷基的N-取代(甲基)丙烯醯胺化合物者，可列舉：N-[2-(N,N-二甲基胺基)乙基](甲基)丙烯醯胺、N-[2-(N,N-二乙基胺基)乙基](甲基)丙烯醯胺、N-[3-(N,N-二甲基胺基)丙基](甲基)丙烯醯胺、N-[1-甲基-1-(N,N-二甲基胺基)乙基](甲基)丙烯醯胺等。 As an N-substituted (meth) acrylamide compound in which Q 2 is a hydrogen atom and Q 3 is an alkyl group having a hydroxyl group, N-hydroxymethyl (meth) acrylamide, N-(2-hydroxyl group) Ethyl) (meth) acrylamide, N-(2-hydroxypropyl) (meth) acrylamide, and the like. Examples of the N-substituted (meth) acrylamide compound in which Q 2 is a hydrogen atom and Q 3 is an alkyl group having an amine group include N-[2-(N,N-dimethylamino)B. (M) propylene decylamine, N-[2-(N,N-diethylamino)ethyl](methyl) decylamine, N-[3-(N,N-dimethyl Amino)propyl](meth)acrylamide, N-[1-methyl-1-(N,N-dimethylamino)ethyl](meth)acrylamide, and the like.

作為Q2與Q3互相鍵結，形成-CH2-可經氧原子取代之5員環或6員環之N-取代(甲基)丙烯醯胺化合物者，可列舉：N-丙烯醯基吡咯啶、3-丙烯醯基-2-唑烷酮、4-丙烯醯基嗎啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶等。 As Q 2 and Q 3 are bonded to each other, may form a ring -CH 2- N- 6-membered ring or the substituted (meth) acrylamide compound are exemplified by an oxygen atom of a substituted 5: N- Bing Xixi yl Pyrrolidine, 3-propenyl-2- Oxazolidinone, 4-propenylmorphomorpholine, N-propenylhydrazine piperidine, N-methylpropenyl piperidine, and the like.

上述N-取代(甲基)丙烯醯胺化合物之中，較佳為如N-羥甲基丙烯醯胺及N-(2-羥基乙基)丙烯醯胺之N-羥烷基(甲基)丙烯醯胺，以及如N,N-二甲基丙烯醯胺及N,N-二乙基丙烯醯胺之N,N-二烷基(甲基)丙烯醯胺；特佳為N-(2-羥基乙基)丙烯醯胺或N,N-二甲基丙烯醯胺。 Among the above N-substituted (meth) acrylamide compounds, N-hydroxyalkyl (methyl) such as N-methylol acrylamide and N-(2-hydroxyethyl) acrylamide are preferred. Acrylamide, and N,N-dialkyl(meth) acrylamide such as N,N-dimethyl decylamine and N,N-diethyl acrylamide; particularly preferably N-(2 -Hydroxyethyl)propenylamine or N,N-dimethylpropenamide.

其他，如N-十二基(甲基)丙烯醯胺之具有長鏈烷基之N-烷基(甲基)丙烯醯胺和如N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺及N-(丁氧基甲基)丙烯醯胺之N-(烷氧基烷基)(甲基)丙烯 醯胺，可作為構成活性能量線硬化性化合物之N-取代(甲基)丙烯醯胺化合物使用。 Others, such as N-dodecyl (meth) acrylamide, N-alkyl (meth) acrylamides having long-chain alkyl groups and such as N-(methoxymethyl) acrylamide, N- N-(alkoxyalkyl)(methyl) of (ethoxymethyl) acrylamide, N-(propoxymethyl) acrylamide and N-(butoxymethyl) acrylamide Acrylamide can be used as an N-substituted (meth) acrylamide compound constituting an active energy ray-curable compound.

作為2官能(甲基)丙烯酸酯單體者，代表例者如：烷二醇二(甲基)丙烯酸酯、聚氧烷二醇二(甲基)丙烯酸酯、鹵代烷二醇二(甲基)丙烯酸酯、脂肪族多元醇之二(甲基)丙烯酸酯、氫化二環戊二烯或三環癸烷二烷醇之二(甲基)丙烯酸酯、二烷二醇或二烷二烷醇之二(甲基)丙烯酸酯、雙酚A或雙酚F的環氧烷加成物之二(甲基)丙烯酸酯、雙酚A或雙酚F之二(甲基)丙烯酸環氧酯等。 As a bifunctional (meth) acrylate monomer, representative examples include alkanediol di(meth)acrylate, polyoxyalkylene glycol di(meth)acrylate, halogenated alkanediol di(methyl). Acrylate, di(meth) acrylate of aliphatic polyol, di(meth) acrylate of hydrogenated dicyclopentadiene or tricyclodecane dialkyl alcohol, two Alkylene glycol or two Di(meth)acrylate of alkanediol, bis(meth)acrylate of an alkylene oxide adduct of bisphenol A or bisphenol F, bis(meth)acrylic acid of bisphenol A or bisphenol F Epoxy esters, etc.

作為2官能(甲基)丙烯酸酯單體者，可列舉：乙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯、二(三羥甲基丙烷)二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、聚矽氧二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇酯之二(甲基)丙烯酸酯、2,2-雙[4-(甲基)丙烯醯氧基乙氧基乙氧基苯基]丙烷、2,2-雙[4-(甲基)丙烯醯氧基乙氧基乙氧基環己基]丙烷、氫化二(甲基)丙烯酸二環戊二烯酯、三環癸烷二甲醇二(甲基)丙烯酸酯、1,3-二烷-2,5-二基二(甲基)丙烯酸酯[別稱：二烷二醇二(甲 基)丙烯酸酯]、羥基三甲基乙醛與三羥甲基丙烷之縮醛化合物[化學名：2-(2-羥基-1,1-二甲基乙基)-5-乙基-5-羥甲基-1,3-二烷]之二(甲基)丙烯酸酯、參(羥乙基)三聚異氫酸酯二(甲基)丙烯酸酯等。 Examples of the bifunctional (meth) acrylate monomer include ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and 1,4-butanediol II. (Meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, three Hydroxymethylpropane di(meth)acrylate, neopentyl alcohol di(meth)acrylate, di(trimethylolpropane)di(meth)acrylate, diethylene glycol di(meth)acrylic acid Ester, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di( Methyl) acrylate, polybutylene glycol di(meth) acrylate, polyoxy bis(meth) acrylate, bis(meth) acrylate of hydroxytrimethyl acetic acid neopentyl glycol ester, 2, 2-bis[4-(methyl)acryloxyethoxyethoxyethoxyphenyl]propane, 2,2-bis[4-(methyl)acryloxyethoxyethoxyethoxycyclohexyl] Propane, hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(methyl) Acrylate, 1,3-bis Alkane-2,5-diyldi(meth)acrylate [alias: two Alkanediol di(meth)acrylate], acetal compound of hydroxytrimethylacetaldehyde and trimethylolpropane [chemical name: 2-(2-hydroxy-1,1-dimethylethyl)- 5-ethyl-5-hydroxymethyl-1,3-di Alkanedi(meth)acrylate, hydroxy(hydroxyethyl)trimeric isocyanate di(meth)acrylate, and the like.

作為3官能以上的多官能(甲基)丙烯酸酯單體者，可列舉：如甘油三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二(三羥甲基丙烷)三(甲基)丙烯酸酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯及二新戊四醇六(甲基)甲基)丙烯酸酯之3官能以上的脂肪族多元醇的聚(甲基)丙烯酸酯。其他可列舉：3官能以上的鹵代多元醇之聚(甲基)丙烯酸酯、甘油的環氧烷加成物之三(甲基)丙烯酸酯、三羥甲基丙烷的環氧烷加成物之三(甲基)丙烯酸酯、1,1,1-參[(甲基)丙烯醯氧基乙氧基乙氧基]丙烷、參(羥乙基)三聚異氫酸酯三(甲基)丙烯酸酯類等。 Examples of the trifunctional or higher polyfunctional (meth) acrylate monomer include glycerol tri(meth) acrylate, trimethylolpropane tri (meth) acrylate, and bis (trimethylolpropane). Tris(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, two a trifunctional or higher aliphatic polyol of pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa(methyl)methyl acrylate Poly(meth) acrylate. Other examples include poly(meth)acrylates of a trifunctional or higher halogenated polyhydric alcohol, tris(meth)acrylates of alkylene oxide adducts of glycerin, and alkylene oxide adducts of trimethylolpropane. Tris(meth)acrylate, 1,1,1-gin[(methyl)acryloxyethoxyethoxyethoxy]propane, ginseng(hydroxyethyl)trimeric isocyanate tris(methyl) ) acrylates and the like.

作為(甲基)丙烯酸酯寡聚物者，可列舉：胺甲酸乙酯(甲基)丙烯酸酯寡聚物、聚酯(甲基)丙烯酸酯寡聚物、環氧(甲基)丙烯酸酯寡聚物等。 Examples of the (meth) acrylate oligomer include urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer, and epoxy (meth) acrylate oligo. Polymer, etc.

胺甲酸乙酯(甲基)丙烯酸酯寡聚物，係在分子內具有胺甲酸乙酯鍵結(-NHCOO-)及至少2個(甲基)丙烯醯氧基之化合物。具體而言，可列舉：在分子內具有至少1個(甲基)丙烯醯氧基及至少1個羥基之含羥基的(甲基)丙烯酸酯單體與聚異氰酸酯之胺甲酸乙酯化反應產物、和 多元醇與聚異氰酸酯反應所得之含末端異氰酸基的胺甲酸乙酯化合物與在分子內分別具有至少1個(甲基)丙烯醯氧基及至少1個羥基之(甲基)丙烯酸酯單體之胺甲酸乙酯化反應產物等。 The urethane (meth) acrylate oligomer is a compound having an urethane linkage (-NHCOO-) and at least two (meth) propylene oxime groups in the molecule. Specifically, a urethane reaction product of a hydroxyl group-containing (meth) acrylate monomer having at least one (meth) propylene fluorenyl group and at least one hydroxyl group in the molecule and a polyisocyanate may be mentioned. And a terminally isocyanate-containing urethane compound obtained by reacting a polyhydric alcohol with a polyisocyanate, and (meth)acrylic acid having at least one (meth) acryloxy group and at least one hydroxyl group in the molecule, respectively The urethane ethylation reaction product of the ester monomer, and the like.

作為胺甲酸乙酯化反應所使用之含羥基的(甲基)丙烯酸酯單體者，可列舉：(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2-羥基-3-苯氧基丙酯、甘油二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等。 Examples of the hydroxyl group-containing (meth) acrylate monomer used in the ureidoesterification reaction include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di(meth) acrylate, trimethylolpropane di(meth) acrylate, neopentyl Tetrahydrin tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like.

作為供給至與該含羥基的(甲基)丙烯酸酯單體進行胺甲酸乙酯化反應的聚異氰酸酯者，可列舉：二異氰酸六亞甲酯、離胺酸二異氰酸酯、異佛酮二異氰酸酯、二環己基甲烷二異氰酸酯、二異氰酸甲伸苯酯、二異氰酸伸苯二甲酯、將該等二異氰酸酯中之芳香族的異氰酸酯類氫化而得之二異氰酸酯(例如，氫化二異氰酸甲伸苯酯、氫化二異氰酸伸苯二甲酯等)、三苯基甲烷三異氰酸酯、二苯甲基苯三異氰酸酯等二-或三-異氰酸酯及使上述二異氰酸酯多聚化所得之聚異氰酸酯等。 Examples of the polyisocyanate supplied to the hydroxyethylation reaction of the hydroxyl group-containing (meth) acrylate monomer include hexamethylene diisocyanate, diisocyanate diisocyanate, and isophorone. Isocyanate, dicyclohexylmethane diisocyanate, methyl phenyl diisocyanate, terephthalic acid diisocyanate, diisocyanate obtained by hydrogenating aromatic isocyanates in such diisocyanates (for example, hydrogenation) Di- or tri-isocyanate such as methyl phenylisocyanate, hydrogenated diisocyanate, etc.), triphenylmethane triisocyanate, diphenylmethylbenzene triisocyanate, and polydiacetylate The obtained polyisocyanate or the like.

而且，作為用以藉由與聚異氰酸酯的反應而成為含末端異氰酸基的胺甲酸乙酯化合物而使用的多元醇類，除了芳香族、脂肪族及脂環式的多元醇之外，可列舉聚酯多元醇、聚醚多元醇等。作為芳香族的多元醇者，可列舉：1,4-苯二甲醇、1,3-苯二甲醇、1,2-苯二甲醇、4,4’ -萘二甲醇、3,4’-萘二甲醇等。作為脂肪族及脂環式的多元醇者，可列舉：1,4-丁二醇、1,6-己二醇、乙二醇、二乙二醇、三乙二醇、丙二醇、新戊二醇、三羥甲基乙烷、三羥甲基丙烷、二(三羥甲基丙烷)、新戊四醇、二新戊四醇、二羥甲基庚烷、二羥甲基丙酸、二羥甲基丁酸、甘油、氫化雙酚A等。 Further, as the polyol used to form the terminally isocyanate-containing urethane compound by the reaction with the polyisocyanate, in addition to the aromatic, aliphatic and alicyclic polyols, Polyester polyols, polyether polyols, and the like are listed. Examples of the aromatic polyol include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalene dimethanol, and 3,4'-naphthalene. Dimethanol and the like. Examples of the aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and neopentyl Alcohol, trimethylolethane, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, dimethylol heptane, dimethylolpropionic acid, two Hydroxymethyl butyric acid, glycerin, hydrogenated bisphenol A, and the like.

聚酯多元醇，係上述多元醇類與多元羧酸或其酸酐之脫水縮合反應所得者。作為多元羧酸或其酸酐者係有：琥珀酸、琥珀酸酐、己二酸、順丁烯二酸、順丁烯二酸酐、伊康酸、伊康酸酐、偏苯三酸、偏苯三酸酐、均苯四酸、均苯四酸酐、鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸、六氫鄰苯二甲酸、六氫鄰苯二甲酸酐等。 The polyester polyol is obtained by dehydration condensation reaction of the above polyol with a polyvalent carboxylic acid or an anhydride thereof. Examples of the polycarboxylic acid or its anhydride include succinic acid, succinic anhydride, adipic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, trimellitic acid, trimellitic anhydride, and benzene. Tetraacid, pyromellitic anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, and the like.

聚醚多元醇除了聚烷二醇之外，可列舉上述多元醇類或二羥苯類與環氧烷(alkylene oxide)反應所得之聚氧伸烷基改性多元醇等。 The polyether polyol includes, in addition to the polyalkylene glycol, a polyoxyalkylene-modified polyol obtained by reacting the above polyol or dihydroxybenzene with an alkylene oxide.

聚酯(甲基)丙烯酸酯寡聚物，係指在分子內具有至少2個酯鍵與至少2個(甲基)丙烯醯氧基之化合物。具體而言，係可藉由(甲基)丙烯酸、多元羧酸或其酸酐、及多元醇之脫水縮合反應而得到。作為脫水縮合反應所使用之多元羧酸或其酸酐，可列舉：琥珀酸、琥珀酸酐、己二酸、順丁烯二酸、順丁烯二酸酐、伊康酸、伊康酸酐、偏苯三酸、偏苯三酸酐、均苯四酸、均苯四酸酐、六氫鄰苯二甲酸、六氫鄰苯二甲酸酐、鄰苯二甲酸、鄰苯二甲酸 酐、間苯二甲酸、對苯二甲酸等。而且，作為脫水縮合反應所使用之多元醇，可列舉：1,4-丁二醇、1,6-己二醇、乙二醇、二乙二醇、三乙二醇、丙二醇、新戊二醇、三羥甲基乙烷、三羥甲基丙烷、二(三羥甲基丙烷)、新戊四醇、二新戊四醇、二羥甲基庚烷、二羥甲基丙酸、二羥甲基丁酸、甘油、氫化雙酚A等。 The polyester (meth) acrylate oligomer refers to a compound having at least two ester bonds and at least two (meth) acryloxy groups in the molecule. Specifically, it can be obtained by a dehydration condensation reaction of (meth)acrylic acid, a polyvalent carboxylic acid or an anhydride thereof, and a polyhydric alcohol. Examples of the polycarboxylic acid or an anhydride thereof used in the dehydration condensation reaction include succinic acid, succinic anhydride, adipic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and benzotriene. Acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc. . Further, examples of the polyhydric alcohol used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and neopentyl Alcohol, trimethylolethane, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, dimethylol heptane, dimethylolpropionic acid, two Hydroxymethyl butyric acid, glycerin, hydrogenated bisphenol A, and the like.

環氧(甲基)丙烯酸酯寡聚物，係可藉由在分子內至少具有2個(甲基)丙烯醯氧基之多縮水甘油醚與(甲基)丙烯酸之加成反應而得到。作為加成反應所使用之多縮水甘油醚者，可列舉：乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、雙酚A二縮水甘油醚等。 The epoxy (meth) acrylate oligomer can be obtained by an addition reaction of a polyglycidyl ether having at least two (meth) acryloxy groups in a molecule with (meth)acrylic acid. Examples of the polyglycidyl ether used in the addition reaction include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and double Phenol A diglycidyl ether and the like.

咸認在分子內具有至少1個(甲基)丙烯醯基之化合物，除了上述之與塑化劑的親和性低之外，在聚合時係形成交聯結構，因此塑化劑不易侵入包含該化合物之組成物的硬化物。藉此，可推測於濕熱環境下(例如，室溫60℃、濕度95%的環境下)，即使塑化劑由樹脂層21往偏光件層11(第1圖的箭號方向)遷移時，亦可抑制塑化劑的侵入。 A compound having at least one (meth) acrylonitrile group in the molecule, in addition to the above-mentioned affinity with a plasticizer, forms a crosslinked structure at the time of polymerization, so that the plasticizer is not easily invaded. A cured product of the composition of the compound. Therefore, it is presumed that when the plasticizer migrates from the resin layer 21 to the polarizer layer 11 (the arrow direction of FIG. 1) in a humid heat environment (for example, an environment of room temperature of 60 ° C and a humidity of 95%), It also inhibits the intrusion of plasticizers.

相對於本組成物100質量份，自由基聚合性化合物的含量較佳為1質量份以上70質量份以下，更佳為10質量份以上60質量份以下。 The content of the radically polymerizable compound is preferably from 1 part by mass to 70 parts by mass, more preferably from 10 parts by mass to 60 parts by mass, per 100 parts by mass of the composition.

本組成物中，自由基聚合性化合物可僅單獨使用1種，亦可併用2種以上。 In the present invention, the radically polymerizable compound may be used alone or in combination of two or more.

(其它成分)  (other ingredients)   (陽離子聚合性化合物)  (cationic polymerizable compound)  

本組成物除了上述含有自由基聚合性化合物，亦可視所需而含有陽離子聚合性開始劑。作為陽離子聚合性化合物，例如可舉出氧雜環丁烷化合物或環氧化合物等 In addition to the above-mentioned radical polymerizable compound, the composition may contain a cationic polymerizable starter as needed. Examples of the cationically polymerizable compound include an oxetane compound or an epoxy compound.

作為氧雜環丁烷化合物者可列舉例如：3-乙基-3-羥基甲基氧雜環丁烷等。 Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane and the like.

該等氧雜環丁烷化合物係能夠容易地取得市售品，以下以商品名舉出東亞合成股份有限公司所販售的市售品，如"ARON OXETANE(註冊商標)OXT-101"等。 Commercially available products such as "ARON OXETANE (registered trademark) OXT-101", etc., are commercially available under the trade name of the oxetane compound.

本組成物中，氧雜環丁烷化合物係可單獨使用1種，亦可併用2種以上。 In the present invention, the oxetane compound may be used alone or in combination of two or more.

又，本組成物係除了上述的自由基聚合性化合物以外，亦可依照所需而含有環氧化合物。環氧化合物係與氧雜環丁烷化合物同樣為陽離子聚合性化合物之一，能夠藉由照射活性能量線而硬化。藉由本組成物含有環氧化合物，能夠提升樹脂層21與偏光件層11的接著性。 Further, the present composition may contain an epoxy compound as needed in addition to the above-mentioned radically polymerizable compound. The epoxy compound is one of cationically polymerizable compounds similarly to the oxetane compound, and can be cured by irradiation with an active energy ray. By including the epoxy compound in the composition, the adhesion between the resin layer 21 and the polarizer layer 11 can be improved.

作為環氧化合物者，可舉出芳香族環氧化合物、具有脂環式環之多元醇的環氧丙基醚、脂肪族環氧化合物、脂環式環氧化合物等。 Examples of the epoxy compound include an aromatic epoxy compound, a glycidyl ether of a polyhydric alcohol having an alicyclic ring, an aliphatic epoxy compound, and an alicyclic epoxy compound.

作為芳香族環氧化合物者，可舉出如雙酚A的二環氧丙基醚、雙酚F的二環氧丙基醚及雙酚S的二環氧丙基醚之雙酚型環氧樹脂；如苯酚酚醛清漆環氧樹脂、 甲酚酚醛清漆環氧樹脂及羥基苯甲醛苯酚酚醛清漆環氧樹脂之酚醛清漆型的環氧樹脂；如四羥苯基甲烷的環氧丙基醚、四羥基二苯基酮的環氧丙基醚及環氧化聚乙烯基苯酚之多官能型的環氧樹脂等。 Examples of the aromatic epoxy compound include diglycidyl ether of bisphenol A, diepoxypropyl ether of bisphenol F, and bisphenol epoxy of diglycidyl ether of bisphenol S. Resin; such as phenol novolac epoxy resin, cresol novolac epoxy resin and hydroxybenzaldehyde phenol novolac epoxy resin novolac type epoxy resin; such as tetrahydroxyphenylmethane epoxy propyl ether, four A polyfunctional epoxy resin such as a glycidyl ether of hydroxydiphenyl ketone or an epoxidized polyvinyl phenol.

作為具有脂環式環之多元醇的環氧丙基醚者，可舉出藉由在觸媒的存在下，將芳香族多元醇在加壓下對芳香環選擇地進行氫化反應而得到的核氫化多羥基化合物，進行環氧丙基醚化而成者。作為芳香族多元醇，可舉出如雙酚A、雙酚F、雙酚S的雙酚型化合物；如苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、羥基苯甲醛苯酚酚醛清漆樹脂的酚醛清漆型樹脂；如四羥基二苯基甲烷、四羥基二苯基酮、聚乙烯基苯酚之多官能型的化合物等。 Examples of the glycidyl ether of the polyol having an alicyclic ring include a core obtained by selectively hydrogenating an aromatic ring under pressure in the presence of a catalyst. A hydrogenated polyhydroxy compound is obtained by epitaxially epoxidizing. Examples of the aromatic polyol include bisphenol type compounds such as bisphenol A, bisphenol F, and bisphenol S; and novolak type such as phenol novolak resin, cresol novolak resin, and hydroxybenzaldehyde phenol novolak resin. a resin; a polyfunctional compound such as tetrahydroxydiphenylmethane, tetrahydroxydiphenyl ketone or polyvinyl phenol.

藉由使該等芳香族多元醇的芳香環進行氫化反應而得到的脂環式多元醇、與表氯醇進行反應，能夠成為環氧丙基醚。 The alicyclic polyol obtained by hydrogenating the aromatic ring of the aromatic polyol and reacting with epichlorohydrin can be a glycidyl ether.

此種具有脂環式環之多元醇的環氧丙基醚之中，作為較佳者，可舉出經氫化的雙酚A的二環氧丙基醚。 Among the glycidyl ethers of such polyols having an alicyclic ring, preferred are diglycidyl ethers of hydrogenated bisphenol A.

作為脂肪族環氧化合物者，可舉出脂肪族多元醇或其環氧烷加成物的聚環氧丙基醚等。具體而言，可舉出使1,4-丁二醇的二環氧丙基醚；1,6-己二醇的二環氧丙基醚；甘油的三環氧丙基醚；三羥甲基丙烷的三環氧丙基醚；聚乙二醇的二環氧丙基醚；丙二醇的二環氧丙基醚；新戊二醇的二環氧丙基醚；如乙二醇、丙二醇或甘油的脂肪族多元醇與1種或2種以上的環氧烷(環氧乙烷和環氧丙 烷)進行加成在而得到的聚醚多元醇之聚環氧丙基醚等。 Examples of the aliphatic epoxy compound include polyepoxypropyl ether of an aliphatic polyol or an alkylene oxide adduct thereof. Specific examples thereof include diglycidyl ether of 1,4-butanediol; diepoxypropyl ether of 1,6-hexanediol; triepoxypropyl ether of glycerin; Triepoxypropyl ether of propane; diepoxypropyl ether of polyethylene glycol; diepoxypropyl ether of propylene glycol; diepoxypropyl ether of neopentyl glycol; such as ethylene glycol, propylene glycol or A polyepoxy propyl ether of a polyether polyol obtained by adding an aliphatic polyol of glycerin to one or more kinds of alkylene oxides (ethylene oxide and propylene oxide).

又，下述式(I)表示之單官能環氧化合物亦可舉出作為脂肪族環氧化合物。R1係可為分枝之碳數1至15的烷基。烷基的碳數較佳為6以上，更佳為6至10。其中較佳為分枝的烷基。作為式(I)表示之單官能環氧化合物，能夠舉出2-乙基己基環氧丙基醚。 Moreover, the monofunctional epoxy compound represented by the following formula (I) can also be mentioned as an aliphatic epoxy compound. The R 1 group may be a branched alkyl group having 1 to 15 carbon atoms. The carbon number of the alkyl group is preferably 6 or more, more preferably 6 to 10. Among them, a branched alkyl group is preferred. The monofunctional epoxy compound represented by the formula (I) is exemplified by 2-ethylhexylepoxypropyl ether.

脂環式環氧化合物係指在分子內具有至少1個與脂環式環的碳原子一起形成環氧乙烷環結構之化合物。在此，所謂「與脂環式環的碳原子一起形成環氧乙烷環結構」，係指下述式(II)表示的結構。式中的n為2至5的整數。 The alicyclic epoxy compound means a compound having at least one carbon atom in the molecule together with a carbon atom of an alicyclic ring to form an oxirane ring structure. Here, the phrase "the oxirane ring structure is formed together with the carbon atom of the alicyclic ring" means a structure represented by the following formula (II). n in the formula is an integer of 2 to 5.

將此式(II)之(CH2)n中的1個或複數個氫原子除去後的形式之基與其它化學結構之化合物鍵結成為脂環式環氧化合物。又，形成脂環式環之(CH2)n中的1個或複數個氫原子，亦可被如甲基和乙基的直鏈狀烷基取代。 The group of the form in which one or a plurality of hydrogen atoms in the (CH 2 )n of the formula (II) is removed is bonded to a compound having another chemical structure to form an alicyclic epoxy compound. Further, one or a plurality of hydrogen atoms in the (CH 2 )n of the alicyclic ring may be substituted with a linear alkyl group such as a methyl group and an ethyl group.

作為環氧化合物者，較佳為脂環式環氧化合物，從容易得到與偏光件的密著性更優異的保護層而 言，較佳為具有環氧環己烷(在上述式(II)，n=4者)、或環氧環庚烷(在上述式(II)，n=5者)之環氧化合物。 The epoxy compound is preferably an alicyclic epoxy compound, and preferably has an epoxycyclohexane (in the above formula (II) from a protective layer which is more excellent in adhesion to a polarizer. , n=4), or an epoxy compound of epoxycycloheptane (in the above formula (II), n=5).

本組成物中，環氧化合物可單獨使用1種，亦可併用2種以上。 In the present invention, the epoxy compound may be used singly or in combination of two or more.

(自由基聚合起始劑)  (radical polymerization initiator)  

本組成物含有上述自由基聚合性化合物時，較佳為進一步含有自由基聚合起始劑。自由基聚合起始劑係藉由照射活性能量線，而能夠使(甲基)丙烯酸系化合物等自由基聚合性化合物開始聚合者即可，能夠使用眾所周知者。 When the composition contains the above radical polymerizable compound, it is preferred to further contain a radical polymerization initiator. The radical polymerization initiator can be used to polymerize a radically polymerizable compound such as a (meth)acrylic compound by irradiation with an active energy ray, and a known one can be used.

作為自由基聚合起始劑者，可舉出：如苯乙酮、3-甲基苯乙酮、苄基二甲基縮酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、2-甲基-1-[4-(甲基硫基)苯基-2-嗎啉丙烷-1-酮及2-羥基-2-甲基-1-苯基丙烷-1-酮的苯乙酮系起始劑；如二苯基酮、4-氯二苯基酮及4,4’-二胺基二苯基酮的二苯基酮系起始劑；如苯偶姻丙基醚及苯偶姻***的苯偶姻醚系起始劑；如4-異丙基噻噸酮(thioxanthone)的噻噸酮(thioxanthone)系起始劑；以及酮、茀酮、樟腦醌、苯甲醛、蒽醌等。 As the radical polymerization initiator, there are mentioned, for example, acetophenone, 3-methylacetophenone, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy- 2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl-2-morpholinepropan-1-one and 2-hydroxy-2-methyl-1- Acetophenone-based initiator of phenylpropan-1-one; starting from diphenyl ketone of diphenyl ketone, 4-chlorodiphenyl ketone and 4,4'-diaminodiphenyl ketone a benzoin ether initiator such as benzoin propyl ether and benzoin ethyl ether; a thioxanthone initiator such as 4-thioxanthone; Ketone, fluorenone, camphorquinone, benzaldehyde, hydrazine and the like.

自由基聚合起始劑係能夠容易地取得市售品，例如可各自以商品名舉出BASF公司製的"IRGACURE(註冊商標)184"、"IRGACURE(註冊商標)907"、"DAROCUR(註冊商標)1173"、"Lucirin(註冊商標)TPO"等。 In the case of a free radical polymerization initiator, a commercially available product can be easily obtained. For example, "IRGACURE (registered trademark) 184", "IRGACURE (registered trademark) 907", "DAROCUR (registered trademark), manufactured by BASF Corporation, can be used. ) 1173", "Lucirin (registered trademark) TPO", etc.

在本組成物，自由基聚合起始劑係可單獨 使用1種，亦可併用2種以上。 In the present composition, the radical polymerization initiator may be used singly or in combination of two or more.

(陽離子聚合起始劑)  (cationic polymerization initiator)  

本組成物含有上述氧雜環丁烷化合物、上述環氧化合物等陽離子聚合性化合物時，較佳為進一步含有陽離子聚合起始劑。陽離子聚合起始劑係可藉由照射可見光線、紫外線、X射線、電子射線等活性能量線來產生陽離子種或路易斯酸，而開始陽離子聚合性化合物的聚合反應。作為陽離子聚合起始劑，可舉出芳香族重氮鎓鹽、芳香族碘鎓鹽、芳香族鋶鹽等鎓鹽、鐵-芳烴錯合物等。 When the composition contains a cationically polymerizable compound such as the above oxetane compound or the above epoxy compound, it is preferred to further contain a cationic polymerization initiator. The cationic polymerization initiator can start a polymerization reaction of a cationically polymerizable compound by irradiating an active energy ray such as visible light, ultraviolet rays, X-rays, or electron rays to generate a cationic species or a Lewis acid. Examples of the cationic polymerization initiator include an onium salt such as an aromatic diazonium salt, an aromatic iodonium salt, and an aromatic onium salt, and an iron-aromatic hydrocarbon complex.

作為芳香族重氮鎓鹽者，例如可舉出苯重氮鎓六氟銻酸鹽、苯重氮鎓六氟磷酸鹽、苯重氮鎓六氟硼酸鹽等。 Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

作為芳香族碘鎓鹽者，例如可舉出二苯基碘鎓肆(五氟苯基)硼酸鹽、二苯基碘鎓六氟磷酸鹽、二苯基碘鎓六氟銻酸鹽、二(4-壬苯基)碘鎓六氟磷酸鹽等。 Examples of the aromatic iodonium salt include diphenyliodonium (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and 4-indole phenyl) iodonium hexafluorophosphate.

作為芳香族鋶鹽者，例如可舉出三苯基鋶六氟磷酸鹽、三苯基鋶六氟銻酸鹽、三苯基鋶肆(五氟苯基)硼酸鹽、4,4’-雙[二苯基鋶基]二苯基硫醚雙六氟磷酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫醚雙六氟銻酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫醚雙六氟磷酸鹽、7-[二(對甲苯甲醯基)鋶基]-2-異丙基噻噸酮(thioxanthone)六氟銻酸鹽、7-[二(對甲苯甲醯基)鋶基]-2-異丙基噻噸酮(thioxanthone)肆(五氟苯基)硼酸鹽、4-苯基羰 基-4’-二苯基鋶基-二苯基硫醚六氟磷酸鹽、4-(對第三丁基苯基羰基)-4’-二苯基鋶基-二苯基硫醚六氟銻酸鹽、4-(對第三丁基苯基羰基)-4’-二(對甲苯甲醯基)鋶基-二苯基硫醚肆(五氟苯基)硼酸鹽等。 Examples of the aromatic onium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium (pentafluorophenyl) borate, and 4,4'-double. [diphenylindenyl]diphenyl sulfide dihexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexafluoroantimonate , 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexafluorophosphate, 7-[bis(p-tolylmethyl)indolyl]-2- Thioxanthone hexafluoroantimonate, 7-[bis(p-tolylmethyl)indolyl]-2-isopropylthioxanthone (thioxanthone) quinone (pentafluorophenyl) borate , 4-phenylcarbonyl-4'-diphenylindenyl-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylindenyl-diphenyl Thiophene hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-bis(p-tolylmethyl) fluorenyl-diphenyl sulfide quinone (pentafluorophenyl) borate Wait.

作為鐵-芳烴錯合物者，例如可舉出二甲苯-環戊二烯基鐵(II)六氟銻酸鹽、異丙苯-環戊二烯基鐵(II)六氟磷酸鹽、二甲苯-環戊二烯基鐵(II)參(三氟甲基磺醯基)甲基化物等。 Examples of the iron-aromatic hydrocarbon complex include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, and Toluene-cyclopentadienyl iron (II) ginseng (trifluoromethylsulfonyl) methide or the like.

該等陽離子聚合起始劑係能夠容易地取得市售品，例如可各自以商品名舉出由日本化藥股份有限公司販賣之"KAYARAD(註冊商標)PCI-220"及"KAYARAD(註冊商標)PCI-620"、由Dow Chemical公司販賣之"UVI-6990"、由DAICEL-CYTEC股份有限公司販賣之"UVACURE(註冊商標)1590"、由ADEKA股份有限公司販賣之"ADEKA OPTOMER(註冊商標)SP-150"及"ADEKA OPTOMER(註冊商標)SP-170"、由日本曹達股份有限公司販賣之"CI-5102"、"CIT-1370"、"CIT-1682"、"CIP-1866S"、"CIP-2048S"及"CIP-2064S"、由MIDORI化學股份有限公司販賣之"DPI-101"、"DPI-102"、"DPI-103"、"DPI-105"、"MPI-103"、"MPI-105"、"BBI-101"、"BBI-102"、"BBI-103"、"BBI-105"、"TPS-101"、"TPS-102"、"TPS-103"、"TPS-105"、"MDS-103"、"MDS-105"、"DTS-102"及"DTS-103"、由Rhodia公司販賣之"PI-2074"等。 For the above-mentioned cationic polymerization initiators, commercially available products can be easily obtained, for example, "KAYARAD (registered trademark) PCI-220" and "KAYARAD (registered trademark) sold by Nippon Kayaku Co., Ltd., respectively, under the trade name. PCI-620", "UVI-6990" sold by Dow Chemical Company, "UVACURE (registered trademark) 1590" sold by DAICEL-CYTEC Co., Ltd., "ADEKA OPTOMER (registered trademark) SP sold by ADEKA Co., Ltd. -150" and "ADEKA OPTOMER (registered trademark) SP-170", "CI-5102", "CIT-1370", "CIT-1682", "CIP-1866S", "CIP" sold by Japan Soda Co., Ltd. -2048S" and "CIP-2064S", "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-103", "MPI" sold by MIDORI Chemical Co., Ltd. -105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105" ", "MDS-103", "MDS-105", "DTS-102" and "DTS-103", "PI-2074" sold by Rhodia.

該等陽離子聚合起始劑之中，從能夠吸收 300nm以上波長之光線，具有優異的硬化性且能夠得到具有良好的機械強度和密著性之硬化物而言，較佳為芳香族鋶鹽。 Among the above-mentioned cationic polymerization initiators, an aromatic sulfonium salt is preferred from a light-absorbing material which is capable of absorbing light having a wavelength of 300 nm or more and having excellent curability and having good mechanical strength and adhesion.

陽離子聚合起始劑可單獨使用1種，亦可混合2種以上使用。 The cationic polymerization initiator may be used singly or in combination of two or more.

(其它添加劑)  (other additives)  

本組成物係除了上述的化合物以外，在不損害本發明效果的範圍，亦可含有光敏化劑、溶劑、調平劑、抗氧化劑、光安定劑、紫外線吸收劑等。 The composition may contain, in addition to the above-mentioned compound, a photosensitizer, a solvent, a leveling agent, an antioxidant, a photostabilizer, an ultraviolet absorber, or the like, insofar as the effects of the present invention are not impaired.

作為亦可使用在本實施形態的光敏化劑者，例如可舉出羰基化合物、有機硫化合物、過硫化物、氧化還原系化合物、偶氮化合物、重氮化合物、鹵化合物、光還原性色素等。 Examples of the photosensitizer to be used in the present embodiment include a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo compound, a diazo compound, a halogen compound, and a photoreducible dye. .

作為亦可使用在本實施形態的溶劑者，例如有如正己烷和環己烷的脂肪族烴類；如甲苯和二甲苯的芳香族烴類；如甲醇、乙醇、丙醇、異丙醇及正丁醇的醇類；如丙酮、甲基乙基酮、甲基異丁基酮及環己酮的酮類；如乙酸甲酯、乙酸乙酯及乙酸丁酯的酯類；如甲基賽路蘇、乙基賽路蘇及丁基賽路蘇的賽路蘇類；如二氯甲烷和氯仿的鹵化烴類等。 As the solvent which can be used in the present embodiment, for example, aliphatic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; such as methanol, ethanol, propanol, isopropanol and positive Alcohols of butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate and butyl acetate; Sue, Ethyl sulphate and butyl sulphate cyclazone; such as methylene chloride and chloroform halogenated hydrocarbons.

作為亦可使用在本實施形態的調平劑者，能夠使用聚矽氧系、氟系、聚醚系、丙烯酸共聚物系、鈦酸酯系等各種化合物。 As the leveling agent of the present embodiment, various compounds such as polyfluorene-based, fluorine-based, polyether-based, acrylic copolymer-based, and titanate-based compounds can be used.

作為亦可使用在本實施形態的抗氧化劑者，例如可舉出如酚系和胺系的一次抗氧化劑、硫系二次抗氧化劑等。 Examples of the antioxidant that can be used in the present embodiment include a phenol-based and amine-based primary antioxidant, and a sulfur-based secondary antioxidant.

作為亦可使用在本實施形態的光安定劑者，可舉出受阻胺系光安定劑(HALS)等。 As the light stabilizer which can be used in the present embodiment, a hindered amine light stabilizer (HALS) or the like can be given.

作為亦可使用在本實施形態的紫外線吸收劑，可舉出二苯基酮系、苯并***系、苯甲酸酯系等。 The ultraviolet absorber which can be used in the present embodiment may, for example, be a diphenylketone type, a benzotriazole type or a benzoate type.

[保護膜]  [protective film]  

第2圖係顯示本實施形態的積層膜的層結構的變形例之剖面示意圖。如第2圖所示，在積層膜2中，在偏光件層11之與樹脂層21所積層之側為相反之側，能夠進一步積層保護膜23。作為形成保護膜23之材料，能夠使用與形成上述樹脂層21之材料同樣的樹脂。形成樹脂層21之材料與形成保護膜23之材料，各自可相同亦可不同。 Fig. 2 is a schematic cross-sectional view showing a modification of the layer structure of the laminated film of the embodiment. As shown in FIG. 2, in the laminated film 2, the protective film 23 can be further laminated on the side opposite to the side where the layer of the polarizer layer 11 and the resin layer 21 are laminated. As the material for forming the protective film 23, the same resin as that of the material forming the resin layer 21 can be used. The material forming the resin layer 21 and the material forming the protective film 23 may be the same or different.

保護膜23係能夠透過接著劑層33積層在偏光件層11。 The protective film 23 can be laminated on the polarizer layer 11 through the adhesive layer 33.

作為接著劑層33者，可舉出水系接著劑、活性能量線硬化型接著劑，作為活性能量線硬化型接著劑，可舉出陽離子聚合系活性能量線硬化型接著劑、自由基聚合系活性能量線硬化型接著劑。又，亦可設置黏著劑(pressure-sensitive adhesive)層來代替接著劑層33。作為黏著劑層者，可舉出含有丙烯酸系樹脂之黏著劑。 Examples of the adhesive layer 33 include a water-based adhesive and an active energy ray-curable adhesive. Examples of the active energy ray-curable adhesive include a cationic polymerization-based active energy ray-curable adhesive and a radical polymerization activity. Energy line hardening type adhesive. Further, a pressure-sensitive adhesive layer may be provided instead of the adhesive layer 33. As an adhesive layer, the adhesive containing an acrylic resin is mentioned.

在偏光件層11之與樹脂層21所積層之面為 相反側、或保護膜之偏光件層11所積層之面為相反側，亦可設置黏著劑層(未圖示)。藉由設置黏著劑層，能夠將積層膜2貼合在顯示裝置的液晶胞。作為黏著劑層，可舉出含有丙烯酸系樹脂之黏著劑。本發明的積層膜較佳為配置在液晶胞(liquid crystal cell)的視認側。 An adhesive layer (not shown) may be provided on the opposite side of the surface of the polarizer layer 11 on which the resin layer 21 is laminated, or the surface on which the polarizer layer 11 of the protective film is laminated. By providing the adhesive layer, the laminated film 2 can be bonded to the liquid crystal cell of the display device. Examples of the adhesive layer include an adhesive containing an acrylic resin. The laminated film of the present invention is preferably disposed on the viewing side of the liquid crystal cell.

[積層膜的製造方法]  [Manufacturing method of laminated film]  

本實施形態的積層膜1係包含下列步驟：(i)在具有慢軸之樹脂層21的一面，形成包含在分子內具有至少1個(甲基)丙烯醯基之化合物的接著劑組成物層(以下有稱為「接著劑組成物層」之情形)之步驟；(ii)將偏光件層11與上述(i)形成有樹脂層21之接著劑組成物層，樹脂層21的慢軸對偏光件層11的吸收軸成為45±10°或135±10°的方式貼合，而得到依順序積層有偏光件層11、接著劑組成物層、樹脂層21的積層體之步驟；及(iii)對上述(ii)所得的積層體，照射活性能量線(例如紫外線、可見光、電子射線、X射線等)，使接著劑組成物層硬化而得到接著劑層31之步驟。以下，針對各步驟舉出具體例進行說明。 The laminated film 1 of the present embodiment includes the following steps: (i) forming an adhesive composition layer containing a compound having at least one (meth)acryl fluorenyl group in the molecule on one side of the resin layer 21 having a slow axis (hereinafter, a step called "adhesive composition layer"); (ii) a polarizer layer 11 and (i) an adhesive composition layer in which the resin layer 21 is formed, and a slow axis pair of the resin layer 21 a step of laminating the absorption axis of the polarizer layer 11 at 45±10° or 135±10°, and obtaining a laminate in which the polarizer layer 11, the adhesive composition layer, and the resin layer 21 are sequentially laminated; Iii) The layer obtained by the above (ii) is irradiated with an active energy ray (for example, ultraviolet rays, visible light, electron rays, X-rays, etc.) to cure the adhesive composition layer to obtain the adhesive layer 31. Hereinafter, specific examples will be described with respect to each step.

上述(i)顯示之步驟，首先，準備具有慢軸之樹脂層21。連續地製造偏光件層11時，係有長條狀偏光件層係有在流動方向具有吸收軸之情形。從能夠藉由卷至卷之方式製造積層體(積層膜)，而且從能夠以使該吸收軸與樹脂層21的慢軸所成之角度成為上述範圍之方式配 置兩者之觀點而言，樹脂層21較佳為斜向被延伸而製造者。 In the above step (i), first, a resin layer 21 having a slow axis is prepared. When the polarizer layer 11 is continuously produced, the strip-shaped polarizer layer is provided with an absorption axis in the flow direction. From the viewpoint of being able to form a laminate (layered film) by roll-to-roll, and to arrange both of them so that the angle between the absorption axis and the slow axis of the resin layer 21 is within the above range, the resin Layer 21 is preferably extended obliquely to the manufacturer.

作為在斜向延伸所使用之延伸機者，例如可舉出拉幅式延伸機。拉幅式延伸機係能夠對橫向或縱向或其雙方向，施行左右不同速度的進給力、拉伸力或牽引力。作為此種拉幅式延伸機者，可舉出橫單軸延伸機、同時雙軸延伸機等，只要能夠將樹脂膜連續地進行斜延伸，就能夠使用任意適當的延伸機。 As the extender used for the oblique extension, for example, a tenter type stretcher can be cited. The tenter type extension machine is capable of applying a feed force, a tensile force or a traction force at different speeds in the lateral direction or the longitudinal direction or in both directions. As such a tenter type extender, a horizontal uniaxial stretching machine, a simultaneous biaxial stretching machine, or the like can be used, and any suitable stretching machine can be used as long as the resin film can be obliquely extended continuously.

作為在樹脂層21的一面形成接著劑組成物層之方法，可舉出直接塗佈本組成物且依照所需進行乾燥之方法。又，作為另外的方法，可舉出將本組成物塗佈在透明基材膜且依照所需進行乾燥後，將該塗佈層轉印至偏光件層11之方法。後者的情況，係在上述(ii)顯示的步驟之前將基材膜除去。透明基材膜係能夠使用與上述同樣的樹脂。又，在透明基材膜，本組成物的塗佈面亦可預先施行剝離處理。 As a method of forming an adhesive composition layer on one surface of the resin layer 21, a method of directly applying the composition and drying it as needed may be mentioned. Further, as another method, a method in which the composition is applied to a transparent substrate film and dried as necessary, and then the coating layer is transferred to the polarizer layer 11 is exemplified. In the latter case, the substrate film is removed before the step (ii) shown above. The same resin as described above can be used for the transparent substrate film. Further, in the transparent base film, the coated surface of the composition may be subjected to a release treatment in advance.

作為本組成物的塗佈方法，能夠採用眾所周知的塗佈方法，例如可舉出刮刀片、繞線棒、模塗佈器、刮刀式塗佈器(comma coater)、凹版塗佈器等。 As a coating method of the present composition, a well-known coating method can be employed, and examples thereof include a doctor blade, a wire bar, a die coater, a comma coater, a gravure coater, and the like.

在上述(ii)顯示之步驟，係能夠將偏光件層11、與上述(i)形成有樹脂層21之接著劑組成物層貼合，而得到依序積層有偏光件層11、接著劑組成物層、樹脂層21之積層體。 In the step (ii), the polarizer layer 11 and the (i) adhesive layer 21 formed with the resin layer 21 can be bonded to each other to obtain a polarizing layer 11 and an adhesive composition. A layered body of the material layer and the resin layer 21.

在上述(iii)顯示之步驟，係藉由對上述(ii) 所得到的積層體，照射如可見光線、紫外線、X射線、或電子射線之活性能量線，使接著劑組成物層硬化成為接著劑層31來得到積層膜1。 In the step (iii), the laminate layer obtained by the above (ii) is irradiated with an active energy ray such as visible light, ultraviolet light, X-ray, or electron ray to harden the adhesive composition layer. The layer 31 is used to obtain the laminated film 1.

照射活性能量線所使用的光源係沒有特別限定，能夠利用在400nm以下的波長具有發光分布之光源。作為此種光源，例如可舉出低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、鹵化金屬燈等。 The light source used to illuminate the active energy ray is not particularly limited, and a light source having a light-emitting distribution at a wavelength of 400 nm or less can be used. Examples of such a light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a halogenated metal lamp, and the like.

活性能量線的照射強度，係依照進行硬化的接著劑組成物而不同，在對陽離子聚合起始劑的活性化有效的波長區域之照射強度，較佳係設定為10至2500mW/cm2的範圍。 The irradiation intensity of the active energy ray differs depending on the composition of the adhesive to be cured, and the irradiation intensity in the wavelength region effective for the activation of the cationic polymerization initiator is preferably set to a range of 10 to 2500 mW/cm 2 . .

活性能量線的照射時間，係依照進行硬化之接著劑組成物而不同，以照射強度與照射時間的乘積表示之累計光量，較佳係設定為10至2500mJ/cm2的範圍。 The irradiation time of the active energy ray differs depending on the composition of the adhesive to be cured, and the integrated light amount expressed by the product of the irradiation intensity and the irradiation time is preferably set to a range of 10 to 2,500 mJ/cm 2 .

此外，在上述的製造例，係將接著劑組成物層形成在樹脂層21的一面，但是亦可形成在偏光件層11的一面，亦可形成在雙方。如第2圖所示，在偏光件層11之與樹脂層21所貼合之側為相反的側，可積層保護膜23，亦可設置用以貼合於液晶胞之黏著劑層(未圖示)。 Further, in the above-described production example, the adhesive composition layer is formed on one surface of the resin layer 21, but may be formed on one surface of the polarizer layer 11, or may be formed on both sides. As shown in FIG. 2, on the side opposite to the side where the resin layer 21 is bonded to the polarizer layer 11, a protective film 23 may be laminated, and an adhesive layer for bonding to the liquid crystal cell may be provided (not shown). Show).

依照如上述構成之積層膜，即便在濕熱環境下亦能夠保持較高的偏光度。 According to the laminated film having the above configuration, a high degree of polarization can be maintained even in a humid heat environment.

<積層膜坯膜>  <Laminated film film>  

在本實施形態，偏光件層及樹脂層皆可為長條狀。本實施形態的積層膜坯膜(長條狀積層膜)係具有帶狀偏光膜坯膜(長條狀偏光件層)；帶狀樹脂膜坯膜(長條狀樹脂層)；及將偏光膜坯膜與樹脂膜坯膜接著之接著劑層。 In the present embodiment, both the polarizer layer and the resin layer may be elongated. The laminated film blank film (long laminated film) of the present embodiment has a strip-shaped polarizing film film (long polarizing layer), a strip-shaped resin film (long resin layer), and a polarizing film. The green film and the resin film are followed by an adhesive layer.

偏光膜坯膜係在將PVA系樹脂作為形成材料之帶狀膜，在膜的縱軸方向配向二色性色素而成者。PVA系樹脂及二色性色素係與上述相同。 The polarizing film blank film is a belt-shaped film in which a PVA-based resin is used as a forming material, and is a dichroic dye in the longitudinal direction of the film. The PVA-based resin and the dichroic dye are the same as described above.

樹脂膜坯膜，係將以熱可塑性樹脂與塑化劑作為形成材料之帶狀膜，在相對於該膜的縱軸方向為斜交之方向進行延伸而成者。藉此，在與偏光膜坯膜積層時能夠採用卷至卷工法且能夠將製造步驟簡略化。熱可塑性樹脂及塑化劑係與上述相同。 The resin film blank film is formed by extending a strip film having a thermoplastic resin and a plasticizer as a forming material in a direction oblique to the longitudinal axis of the film. Thereby, the roll-to-roll method can be employed in laminating with the polarizing film blank, and the manufacturing steps can be simplified. The thermoplastic resin and the plasticizer are the same as described above.

樹脂膜坯膜較佳為相位差膜坯膜。樹脂膜坯膜係相對於上述偏光膜坯膜的吸收軸於任意角度被賦予有慢軸。任意角度係例如相對於上述偏光膜坯膜的吸收軸，以45±10°或135±10°為佳。藉由使慢軸的角度為上述範圍，將本實施形態的積層膜坯膜應用在顯示裝置時，即便隔著偏光玻璃觀看時，亦能夠成為具有優異的視認性之構成。 The resin film blank film is preferably a phase difference film blank film. The resin film blank film is provided with a slow axis at an arbitrary angle with respect to the absorption axis of the above-mentioned polarizing film blank film. The arbitrary angle is preferably, for example, 45 ± 10 ° or 135 ± 10 ° with respect to the absorption axis of the above-mentioned polarizing film blank film. When the laminated film of the present embodiment is applied to a display device by using the angle of the slow axis in the above range, it is possible to have excellent visibility even when viewed through a polarizing glass.

接著劑層包含接著劑組成物的硬化物作為形成材料，接著劑組成物包含在分子內具有至少1個(甲基)丙烯醯基之化合物。在分子內具有至少1個(甲基)丙烯醯基之化合物係與上述相同。咸認在分子內具有至少1個(甲基)丙烯醯基之化合物，除了上述之與塑化劑的親和性低之 外，在聚合時際形成交聯結構，因此塑化劑不易侵入包含該化合物之組成物的硬化物。藉此，可推測於濕熱環境下(例如，室溫60℃、濕度95%的環境下)，即使塑化劑由樹脂膜坯膜往偏光膜坯膜遷移時，亦可抑制塑化劑侵入。 The subsequent layer contains a cured product of the adhesive composition as a forming material, and the adhesive composition contains a compound having at least one (meth)acryl fluorenyl group in the molecule. The compound having at least one (meth) acrylonitrile group in the molecule is the same as described above. A compound having at least one (meth) acrylonitrile group in the molecule, in addition to the above-mentioned affinity with a plasticizer, forms a crosslinked structure at the time of polymerization, so that the plasticizer does not easily intrude A cured product of the composition of the compound. Therefore, it is presumed that in a hot and humid environment (for example, an environment of room temperature of 60° C. and a humidity of 95%), even when the plasticizer migrates from the resin film to the polarizing film, the intrusion of the plasticizer can be suppressed.

使用如上述構成之積層膜坯膜時，即便在濕熱環境下亦能夠保持較高的偏光度。 When the laminated film formed as described above is used, a high degree of polarization can be maintained even in a hot and humid environment.

[實施例]  [Examples]  

以下，藉由實施例說明本發明，但是本發明係不被該等實施例限定。在本實施例所使用的未延伸膜，係指未經延伸的狀態之膜。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples. The unstretched film used in the present embodiment means a film in an unextended state.

[積層膜的耐濕熱性之評估]  [Evaluation of the heat and humidity resistance of laminated film]  

將實施例及比較例的積層膜在溫度65℃、相對濕度90%的環境放置250小時，比較放置前後的視感度修正偏光度。此時，將放置後的視感度修正偏光度減去放置前的視感度修正偏光度後之值的絕對值(△Py)為0.3以下者評定為○，將△Py大於0.3者判定為×。又，視感度修正偏光度係使用下述方法進行測定。將結果顯示在表1至3。 The laminated film of the examples and the comparative examples was allowed to stand in an environment of a temperature of 65 ° C and a relative humidity of 90% for 250 hours, and the degree of visibility correction before and after the placement was compared. At this time, the absolute value (ΔPy) of the value obtained by subtracting the visual sensitivity correction polarization degree after the placement from the placement is 0.3 or less, and is evaluated as ○, and the ΔPy is more than 0.3, and it is judged as ×. Further, the illuminance correction degree of polarization was measured by the following method. The results are shown in Tables 1 to 3.

(視感度修正偏光度的測定)  (Measurement of visual sensitivity corrected polarization)  

針對實施例及比較例的積層膜，使用附積分球的分光光度計(日本分光股份有限公司製、「V7100」)測定在波長380nm至780nm的範圍之MD穿透率及TD穿透率。其次，使用MD穿透率及TD穿透率且基於(T1)計算出在各波長之 偏光度。 For the laminated film of the examples and the comparative examples, the MD transmittance and the TD transmittance in the wavelength range of 380 nm to 780 nm were measured using a spectrophotometer ("V7100" manufactured by JASCO Corporation) equipped with an integrating sphere. Next, the MD transmittance and the TD transmittance are used and the degree of polarization at each wavelength is calculated based on (T1).

在此，所謂「MD穿透率」，係表示從格蘭-湯姆森(Glan-Thomson)稜鏡出來的偏光方向與積層膜試樣的穿透軸成為平行時之穿透率。又，所謂「TD穿透率」，係表示從格蘭-湯姆森稜鏡出來的偏光方向與積層膜試樣的穿透軸成為正交時之穿透率。 Here, the "MD penetration rate" means the transmittance when the polarization direction extracted from Glan-Thomson is parallel to the transmission axis of the laminated film sample. In addition, the "TD penetration rate" indicates the transmittance when the polarization direction from Glan Thomson and the transmission axis of the laminated film sample are orthogonal.

(評估試樣的透濕度的測定)  (Evaluation of the moisture permeability of the sample)  

評估試樣係以下述方式製作。首先，以使厚度為約2至3μm的方式，將接著劑組成物使用桿塗佈器塗佈於三乙酸纖維素膜上，形成接著劑組成物層。作為用以測定評估試樣的透濕度之三乙酸纖維素膜，係使用厚度為57.5μm、透濕度(藉由杯式法(JIS Z 0208、溫度40℃、濕度90%RH)所算出之值)為553g/m2‧24小時之Konica Minolta股份有限公司製之KC6UA。繼而，由接著劑組成物層側，使用Fusionv UV Systems公司製的"D Bulb"，以累計光量成為400mJ/cm2之方式照射紫外線，使接著劑組成物層硬化而作為評估試樣。藉由杯式法(JIS Z 0208、溫度40℃、濕度90%RH)測定所得之評估試樣的透濕度杯式法。 The evaluation sample was produced in the following manner. First, an adhesive composition was applied onto a cellulose triacetate film using a bar coater so as to have a thickness of about 2 to 3 μm to form an adhesive composition layer. As a cellulose triacetate film for measuring the moisture permeability of the evaluation sample, a thickness of 57.5 μm and a moisture permeability (value calculated by a cup method (JIS Z 0208, temperature 40° C., humidity 90% RH) are used. ) is KC6UA manufactured by Konica Minolta Co., Ltd. of 553 g/m 2 for ‧24 hours. Then, from the side of the adhesive composition layer, "D Bulb" manufactured by Fusionv UV Systems Co., Ltd. was used to irradiate ultraviolet rays so that the cumulative amount of light became 400 mJ/cm 2 , and the adhesive composition layer was cured to obtain an evaluation sample. The obtained moisture permeability cup method of the evaluation sample was measured by a cup method (JIS Z 0208, temperature 40 ° C, humidity 90% RH).

[製造例(接著劑組成物的調製)]  [Production Example (Modulation of Adhesive Composition)]  

依照表1至3顯示之調配量，分別調製實施例及比較例的接著劑組成物。但是調製所使用的化合物之名稱係有以簡稱表示之情形。 The adhesive compositions of the examples and the comparative examples were prepared according to the amounts shown in Tables 1 to 3. However, the names of the compounds used for the modulation are as indicated by the abbreviation.

又，陽離子聚合起始劑"ADEKA OPTOMER(註冊商標)SP-150"係使用丙烯碳酸酯溶液者，在表1表示其有效成分量。又，環氧系交聯劑"Sumirez Resin(註冊商標)650"係使用水溶液者，在表2表示其有效成分量。 Further, the cationic polymerization initiator "ADEKA OPTOMER (registered trademark) SP-150" is a propylene carbonate solution, and the amount of the active ingredient is shown in Table 1. In addition, the epoxy-based crosslinking agent "Sumirez Resin (registered trademark) 650" is an aqueous solution, and the amount of the active ingredient is shown in Table 2.

此外，針對接著劑組成物的各成分使用下述化合物。 Further, the following compounds were used for each component of the adhesive composition.

[活性能量線硬化性接著劑組成物]  [Active energy ray-curable adhesive composition]   (陽離子聚合性化合物)  (cationic polymerizable compound)  

"CELLOXIDE(註冊商標)2021P"：3,4-環氧基環己基甲基3,4-環氧基環己烷羧酸鹽，購自Daicel化學股份有限公司。 "CELLOXIDE (registered trademark) 2021P": 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, available from Daicel Chemical Co., Ltd.

"YX8000"：雙酚的二環氧丙基醚，購自三菱化學股份有限公司。 "YX8000": Di-epoxypropyl ether of bisphenol, purchased from Mitsubishi Chemical Corporation.

"ARON OXETANE(註冊商標)OXT-101"：3-乙基-3-羥甲基氧雜環丁烷，購自東亞合成股份有限公司。 "ARON OXETANE (registered trademark) OXT-101": 3-ethyl-3-hydroxymethyl oxetane, available from East Asia Synthetic Co., Ltd.

上述陽離子聚合性化合物之中，氧雜環丁烷化合物的構造如下式(IV)所示。 Among the above cationically polymerizable compounds, the structure of the oxetane compound is represented by the following formula (IV).

(自由基聚合性化合物)  (radical polymerizable compound)  

"DMAA"：二甲基丙烯醯胺基，購自KJ chemicals股份有限公司。 "DMAA": dimethyl methacrylamide, available from KJ Chemicals, Inc.

"4HBA"：4-羥基丁基丙烯酸酯，購自日本化成股份有限公司。 "4HBA": 4-hydroxybutyl acrylate, purchased from Nippon Kasei Co., Ltd.

"UV-3700B"：胺甲酸乙酯丙烯酸酯，購自日本合成化學工業股份有限公司。 "UV-3700B": Ethyl urethane acrylate, available from Japan Synthetic Chemical Industry Co., Ltd.

"CHDMMA"：1,4-環己烷二甲醇單丙烯酸酯，購自日本化成股份有限公司。 "CHDMMA": 1,4-cyclohexane dimethanol monoacrylate, purchased from Nippon Kasei Co., Ltd.

"A-DCP"：三環癸烷二甲醇二丙烯酸酯，購自新中村化學工業股份有限公司。 "A-DCP": Tricyclodecane dimethanol diacrylate, purchased from Xinzhongcun Chemical Industry Co., Ltd.

(陽離子聚合起始劑)  (cationic polymerization initiator)  

"ADEKA OPTOMER(註冊商標)SP-150"：4,4’-雙[二苯基鋶基]二苯基硫醚 雙六氟磷酸鹽系光陽離子聚合起始劑、以丙烯碳酸酯溶液的形式購自股份有限公司ADEKA。 "ADEKA OPTOMER (registered trademark) SP-150": 4,4'-bis[diphenylindenyl]diphenyl sulfide bishexafluorophosphate photocationic polymerization initiator, in the form of a propylene carbonate solution Purchased from ADEKA, a company.

(自由基聚合起始劑)  (radical polymerization initiator)  

"DAROCUR(註冊商標)1173"：2-羥基-2-甲基-1-苯基-丙烷-1-酮，購自BASF Japan股份有限公司。 "DAROCUR (registered trademark) 1173": 2-hydroxy-2-methyl-1-phenyl-propan-1-one, available from BASF Japan Co., Ltd.

"IRGACURE(註冊商標)907"：2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮，購自BASF JAPAN股份有限公司。 "IRGACURE (registered trademark) 907": 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, available from BASF JAPAN Co., Ltd.

[水系接著劑組成物]  [Water-based adhesive composition]   (聚乙烯醇)  (polyvinyl alcohol)  

"KURARAY POVAL(註冊商標)KL-318"：羧基改質聚乙烯醇，購自股份有限公司KURARAY。 "KURARAY POVAL (registered trademark) KL-318": carboxyl modified polyvinyl alcohol, available from KURARAY Co., Ltd.

(環氧系交聯劑)  (epoxy crosslinker)  

"Sumirez Resin(註冊商標)650"：水溶性聚醯胺環氧樹脂(固體成分濃度30%的水溶液)，購自住化CHEMTEX股份有限公司。 "Sumirez Resin (registered trademark) 650": a water-soluble polyamide resin (an aqueous solution having a solid concentration of 30%), purchased from Sumitomo CHEMTEX Co., Ltd.

[其它成分]  [Other ingredients]  

"SH710"：矽酮系調平劑，購自TORAY．DOW CORNING股份有限公司。 "SH710": Anthrone-based leveling agent, purchased from TORAY. DOW CORNING GmbH.

[實施例1至5、比較例1至6]  [Examples 1 to 5, Comparative Examples 1 to 6]   (a)偏光件層的製造  (a) Fabrication of a polarizer layer  

將平均聚合度約2400、皂化度99.9莫耳%以上且厚度30μm的聚乙烯醇膜，進行乾式單軸延伸成為約5倍，而且在保持緊張狀態的狀態下，浸漬在60℃的純水1分鐘後，在碘/碘化鉀/水的重量比為0.05/5/100的水溶液於28℃浸漬60秒。隨後，在碘化鉀/硼酸/水的重量比為 8.5/8.5/100的水溶液於72℃浸漬300秒。接著，於26℃的純水進行洗淨20秒後，於65℃進行乾燥而製造出在單軸延伸後的聚乙烯醇膜配向有碘之偏光件層。偏光件的厚度為12μm。 A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of 99.9 mol% or more and a thickness of 30 μm was subjected to dry uniaxial stretching to about 5 times, and immersed in pure water at 60 ° C while being kept in a state of tension. After a minute, the aqueous solution of iodine/potassium iodide/water in a weight ratio of 0.05/5/100 was immersed at 28 ° C for 60 seconds. Subsequently, the aqueous solution of potassium iodide/boric acid/water in a weight ratio of 8.5/8.5/100 was immersed at 72 ° C for 300 seconds. Subsequently, the film was washed in pure water at 26 ° C for 20 seconds, and then dried at 65 ° C to produce a polarizing material layer in which the polyvinyl alcohol film after uniaxial stretching was aligned with iodine. The thickness of the polarizer was 12 μm.

(b)樹脂層的準備  (b) Preparation of resin layer  

準備藉由斜向延伸而製造出的包含塑化劑之三乙酸纖維素膜作為樹脂層。該三乙酸纖維素膜的一面係形成有硬塗層。又，慢軸對樹脂層的縱軸方向之角度平均為約45°。 A cellulose triacetate film containing a plasticizer produced by oblique stretching was prepared as a resin layer. A side of the cellulose triacetate film is formed with a hard coat layer. Further, the angle of the slow axis to the longitudinal axis direction of the resin layer was about 45° on average.

作為藉由斜向延伸而製造出的三乙酸纖維素膜係使用下述材料。 As the cellulose triacetate film produced by oblique stretching, the following materials were used.

藉由斜向延伸而製造出的三乙酸纖維素膜：Konica Minolta股份有限公司製、KC4UGR-HC、厚度=44μm、Re(590)=106nm、Rth(590)=75nm、Rth(590)/Re(590)=0.71、Re(450)/Re(550)=0.96、Re(630)/Re(550)=1.02) A cellulose triacetate film produced by oblique stretching: Konica Minolta Co., Ltd., KC4UGR-HC, thickness = 44 μm, R e (590) = 106 nm, R th (590) = 75 nm, R th (590 ) /R e (590)=0.71, R e (450)/R e (550)=0.96, R e (630)/R e (550)=1.02)

此外，Re(590)、Re(450)、Re(550)、Re(630)係各自表示在測定波長590nm、450nm、550nm、630nm之面內相位差值，Rth(590)係表示在測定波長590nm之厚度方向相位差值。 Further, R e (590), R e (450), R e (550), and R e (630) each represent an in-plane retardation value at a measurement wavelength of 590 nm, 450 nm, 550 nm, and 630 nm, and R th (590) The phase difference value in the thickness direction at a measurement wavelength of 590 nm is shown.

(c)積層膜的製造  (c) Manufacture of laminated film  

接著，在上述(b)的樹脂層之未形成有硬塗層的面，塗佈製造例所得到的接著劑組成物，形成接著劑組成物層。具體而言，係將接著劑組成物使用桿塗佈器(第一理化股份 有限公司製)以硬化後的膜厚成為約2μm的方式進行塗佈。此外，對作為形成材料之厚度23μm的降莰烯系樹脂的未延伸膜[日本ZEON股份有限公司製的商品名"ZEONOR(註冊商標)"]的一面施行電暈放電處理。在該電暈放電處理面與樹脂層同樣地進行塗佈上述接著劑組成物，形成接著劑組成物層。此外，未延伸膜係積層膜中之保護膜的原材料。 Next, on the surface of the resin layer (b) where the hard coat layer was not formed, the adhesive composition obtained in the production example was applied to form an adhesive composition layer. Specifically, the adhesive composition was applied so that the film thickness after hardening became about 2 μm using a bar coater (manufactured by First Chemicals Co., Ltd.). In addition, a corona discharge treatment was performed on one side of an unstretched film (trade name "ZEONOR (registered trademark)") manufactured by Nippon Zeon Co., Ltd., which is a material having a thickness of 23 μm. The above-described adhesive composition was applied to the corona discharge treated surface in the same manner as the resin layer to form an adhesive composition layer. Further, the raw material of the protective film in the film-free laminated film is not stretched.

將上述(a)所製造的偏光件層的一面與樹脂層進行貼合，並且將偏光件層的另一面與形成有未延伸膜之接著劑組成物層貼合來製造積層物。貼合係使用貼附裝置(Fujipla股份有限公司製，「LPA3301」)。貼合時係使偏光件層的吸收軸與樹脂層的慢軸之構成角度成為45°。 One surface of the polarizer layer produced in the above (a) was bonded to the resin layer, and the other surface of the polarizer layer was bonded to the adhesive composition layer on which the unstretched film was formed to produce a laminate. For the bonding system, an attachment device ("LPA3301" manufactured by Fujipla Co., Ltd.) was used. In the bonding, the angle of formation of the absorption axis of the polarizer layer and the slow axis of the resin layer was 45°.

其次，使用附輸送帶的紫外線照射裝置[燈係使用Fusionv UV Systems公司製的"D Bulb"]，以累計光量成為250mJ/cm2之方式，從所得到的積層物之未延伸膜側照射紫外線來使接著劑組成物層硬化。如此進行而製造出包含保護膜/偏光件層/接著劑層/樹脂層/硬塗層之積層膜。 Next, an ultraviolet ray irradiation apparatus with a conveyor belt ["D Bulb" manufactured by Fusionv UV Systems Co., Ltd.) was used, and ultraviolet rays were irradiated from the unstretched film side of the obtained laminate so that the cumulative amount of light became 250 mJ/cm 2 . The adhesive composition layer is hardened. In this manner, a laminated film including a protective film/polarizer layer/adhesive layer/resin layer/hard coat layer was produced.

由各實施例及比較例所使用之接著劑組成物所得之評估試樣的透濕度，係如下述。 The moisture permeability of the evaluation sample obtained from the adhesive compositions used in the respective examples and comparative examples was as follows.

實施例3：297g/m2．24hr、實施例5：251g/m2．24hr、比較例1：447g/m2．24hr、比較例3：307g/m2．24hr、比較例4：428g/m2．24hr、比較例5：529g/m2．24hr Example 3: 297 g/m 2 . 24 hr, Example 5: 251 g/m 2 . 24 hr, Comparative Example 1: 447 g/m 2 . 24 hr, Comparative Example 3: 307 g/m 2 . 24 hr, Comparative Example 4: 428 g/m 2 . 24 hr, Comparative Example 5: 529 g/m 2 . 24hr

[比較例7]  [Comparative Example 7]  

(c)在積層膜的製造，除了進行下述操作以外，係與實施例1同樣地進行而製造比較例7的積層膜。 (c) The laminate film of Comparative Example 7 was produced in the same manner as in Example 1 except that the following operation was carried out.

將上述(b)所準備的樹脂層經由製造例所得到的水系接著劑組成物貼合在上述(a)所製造的偏光件層之一面。之後，在80℃進行乾燥5分鐘後，在40℃、23%RH進行熟化72小時來製造積層膜。 The resin layer prepared in the above (b) was bonded to one surface of the polarizer layer produced in the above (a) via the water-based adhesive composition obtained in the production example. Thereafter, the film was dried at 80 ° C for 5 minutes, and then aged at 72 ° C and 23% RH for 72 hours to produce a laminated film.

[參考例]  [Reference example]   (a-1)偏光件層的製造  (a-1) Fabrication of polarizer layer  

製造出在單軸延伸後的聚乙烯醇膜配向有碘之厚度30μm的偏光件層。 A polyvinyl alcohol film which was uniaxially stretched was bonded to a polarizer layer having a thickness of 30 μm.

(b-1)樹脂層的準備  (b-1) Preparation of resin layer  

準備對厚度43μm的三乙酸纖維素膜(KC4FR-1、Konica Minolta Opto股份有限公司製)施行有皂化處理者。該膜為延伸膜且含有塑化劑。 A saponification treatment was carried out on a cellulose triacetate film (KC4FR-1, manufactured by Konica Minolta Opto Co., Ltd.) having a thickness of 43 μm. The film is a stretched film and contains a plasticizer.

(b-2)保護膜的準備  (b-2) Preparation of protective film  

準備對附硬塗層的三乙酸纖維素膜施行有皂化處理者。該膜的厚度為83μm。 It is prepared to perform a saponification treatment on the hard-coated cellulose triacetate film. The film had a thickness of 83 μm.

(c-1)積層膜的製造  (c-1) Manufacture of laminated film  

藉由夾輥且透過上述製造例所得到的水系接著劑組成物將(b-1)準備的樹脂層貼合在上述(a-1)所製造的偏光件層之一面，而且透過相同接著劑組成物將(b-2)準備的保護膜貼合在另一面而製造出積層物。此時，係使樹脂層的慢軸與偏光件層的吸收軸成為大致平行。將(b-2)準備的保護膜貼合時係使無硬塗層的一側成為與偏光件層的貼合面。其次，在保持積層物的張力下使其通過乾燥爐，使接著劑乾燥而得到積層膜。 The resin layer prepared in (b-1) was bonded to one surface of the polarizer layer manufactured by the above (a-1) by a nip roll and passed through the water-based adhesive composition obtained in the above production example, and the same adhesive was passed through The composition was bonded to the other surface of the protective film prepared in (b-2) to produce a laminate. At this time, the slow axis of the resin layer and the absorption axis of the polarizer layer are made substantially parallel. When the protective film prepared in (b-2) is bonded, the side having no hard coat layer is a bonding surface with the polarizer layer. Next, the laminate was passed through a drying oven while maintaining the tension of the laminate, and the adhesive was dried to obtain a laminated film.

在樹脂層之與偏光件層的接著面為相反之側，設置儲存彈性模數約0.7MPa的黏著劑層(厚度15μm)。透過此黏著劑層，將積層膜貼合在玻璃且進行評估試樣。將該試樣，與上述耐濕熱性的評估相同地放置在溫度65℃、相對濕度90%的環境250小時，比較放置前後的視感度修正偏光度。其結果，視感度修正偏光度的變化量△Py為0.3%以下。 On the side opposite to the adhesion surface of the resin layer and the polarizer layer, an adhesive layer (thickness 15 μm) having an elastic modulus of about 0.7 MPa was stored. Through the adhesive layer, the laminated film was attached to the glass and the evaluation sample was evaluated. This sample was placed in an environment having a temperature of 65 ° C and a relative humidity of 90% for 250 hours in the same manner as the above evaluation of the heat and humidity resistance, and the degree of visibility correction polarization before and after the placement was compared. As a result, the amount of change ΔPy in the illuminance correction polarization degree is 0.3% or less.

從表1至3的結果顯示，使用包含在分子內具有至少1個(甲基)丙烯醯基之化合物的接著劑組成物時，即便△Py為0.3以下，在濕熱環境下亦能夠保持較高的偏光度。 The results from Tables 1 to 3 show that when an adhesive composition containing a compound having at least one (meth) acrylonitrile group in the molecule is used, even if ΔPy is 0.3 or less, it can be kept high in a moist heat environment. The degree of polarization.

綜上所述，能夠確認本發明為有用者。 As described above, it can be confirmed that the present invention is useful.

[產業上之可利用性]  [Industrial availability]  

本發明係能夠作為在液晶顯示裝置等顯示裝置之偏光的供給元件或偏光的檢測元件來利用。 The present invention can be utilized as a supply element for polarized light or a detection element for polarization of a display device such as a liquid crystal display device.

Claims (2)

一種積層膜，具有：偏光件層，係在聚乙烯醇系樹脂中配向有二色性色素；樹脂層，係將相對於前述偏光件層的吸收軸於斜交方向具有慢軸之樹脂膜作為形成材料者；及接著劑層，係將前述偏光件層與前述樹脂層接著者；其中，前述樹脂層包含塑化劑，前述接著劑層包含接著劑組成物的硬化物作為形成材料，前述接著劑組成物包含在分子內具有至少1個(甲基)丙烯醯基之化合物。  A laminated film comprising: a polarizer layer in which a dichroic dye is disposed in a polyvinyl alcohol resin; and a resin layer is a resin film having a slow axis in an oblique direction with respect to an absorption axis of the polarizer layer; And a binder layer, wherein the resin layer comprises a plasticizer, and the adhesive layer comprises a cured product of an adhesive composition as a forming material, and the The agent composition contains a compound having at least one (meth) acrylonitrile group in the molecule.   如申請專利範圍第1項所述之積層膜，其中，前述偏光件層及前述樹脂層皆為長條狀。  The laminated film according to claim 1, wherein the polarizer layer and the resin layer are elongated.  
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JP2016136171A (en) * 2015-01-23 2016-07-28 コニカミノルタ株式会社 Optical film, circularly polarizing plate, and organic electroluminescence display device

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TWI762500B (en) 2022-05-01
KR20190035847A (en) 2019-04-03

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