TW201831538A - Cured film formation composition, orientation material, and retardation material - Google Patents

Cured film formation composition, orientation material, and retardation material Download PDF

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TW201831538A
TW201831538A TW107101202A TW107101202A TW201831538A TW 201831538 A TW201831538 A TW 201831538A TW 107101202 A TW107101202 A TW 107101202A TW 107101202 A TW107101202 A TW 107101202A TW 201831538 A TW201831538 A TW 201831538A
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伊藤潤
菅野裕太
稲見佳代
畑中真
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日商日產化學工業股份有限公司
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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Abstract

To provide: an alignment material which has excellent vertical alignment properties and adhesiveness, and which is capable of vertically aligning polymerizable liquid crystals with high sensitivity even on a resin film; and a cured film forming composition for obtaining a retardation material that uses such an alignment material. A cured film forming composition which contains (A) a polymer that has a vertical alignment group and a polymerizable group containing a C=C double bond and (B) a radical polymerization initiator, and which is characterized in that the vertical alignment group is represented by formula (1). (In formula [1], each of Y1 and Y2 represents a single bond or the like; Y3 represents a single bond or an alkylene group having 1-15 carbon atoms; Y4 represents a single bond, a divalent cyclic group or the like; Y5 represents a divalent cyclic group selected from among a benzene ring, cyclohexane rings and heterocyclic rings; n represents an integer of 0-4, and in cases where n is 2 or more, the Y5 moieties may be the same as or different from each other; and Y6 represents a hydrogen atom, an alkyl group having 1-18 carbon atoms, or the like).

Description

硬化膜形成組成物、定向材料及相位差材料Hardened film forming composition, orientation material and retardation material

本發明係關於適合於使液晶分子垂直定向之垂直定向材料的硬化膜形成組成物。尤其本發明係關於用來改善填充有具有正介電各向異性之液晶(△ε＞0)之IPS液晶顯示裝置(In-plane Switching LCD；面內定向切換LCD)等之液晶顯示裝置(liquid crystal display；LCD)之可視角特性，或用來改善作為有機EL顯示器之防反射膜所使用之圓偏光板之可視角特性所使用之製作+C板(正C板)時有用之硬化膜形成組成物、定向材料及相位差材料。The present invention relates to a hardened film-forming composition of a vertical alignment material suitable for vertical alignment of liquid crystal molecules. In particular, the present invention relates to a liquid crystal display device (liquid) for improving an IPS liquid crystal display device (In-plane Switching LCD) filled with a liquid crystal (Δε> 0) having positive dielectric anisotropy. crystal display (LCD) viewing angle characteristics, or to improve the viewing angle characteristics of circular polarizers used as anti-reflection films for organic EL displays Composition, orientation material and retardation material.

IPS-LCD之特徵在於由於不會產生液晶分子垂直方向之傾斜，故因可視角不同所造成之亮度變化／色變化為少，但其弱點可例舉如不易提高對比與亮度、應答速度之點。例如專利文獻1所揭開，在提案初期之IPS-LCD中，未使用可視角之補償膜，如此之未使用可視角之補償膜之IPS-LCD中，在傾斜角之暗狀態下由於由於有相對較大之漏光，故有顯示低對比值之缺點。The characteristic of IPS-LCD is that it does not cause the tilt of the liquid crystal molecules in the vertical direction, so the brightness change / color change caused by different viewing angles is small, but its weaknesses can be exemplified by points that are not easy to improve contrast, brightness, and response speed. . For example, as disclosed in Patent Document 1, in the IPS-LCD at the early stage of the proposal, a viewing angle compensation film was not used. Thus, in an IPS-LCD without a viewing angle compensation film, in The relatively large light leakage has the disadvantage of showing a low contrast value.

專利文獻2揭示使用+C板與+A板(正A板)之IPS-LCD補償膜。本文獻中，關於該處記載之液晶顯示元件，揭示出以下之構成。 　　1)在藉由可對液晶層面施加平行電場之電極所供給之兩基板之間，夾著具有水平配向之液晶層。 　　2)兩偏光板中夾著有一枚以上之+A板與+C板。 　　3)+A板之主光軸係垂直於液晶層之主光軸。 　　4)液晶層之相位差值RLC 、+C板之相位差值R+C 、+A板之相位差值R+A ，係決定成滿足下式。 　　RLC ：R+C ：R+A ≒1：0.5：0.25 　　5)相對於+A板與+C板之相位差值而言，並未展現偏光板之保護薄膜在厚度方向之相位差值的關係(TAC、COP、PNB)。Patent Document 2 discloses an IPS-LCD compensation film using a + C plate and a + A plate (positive A plate). In this document, the following structure is disclosed about the liquid crystal display element described here. 1) A liquid crystal layer having a horizontal alignment is sandwiched between two substrates supplied by electrodes capable of applying a parallel electric field to the liquid crystal layer. 2) There is more than one + A plate and + C plate between the two polarizing plates. 3) The main optical axis of the + A plate is perpendicular to the main optical axis of the liquid crystal layer. 4) The liquid crystal layer retardation value R LC, + C plate retardation value of R + C, + A-plate retardation value of R + A, based decided to satisfy the following equation. R LC ： R + C ： R + A ≒ 1 ： 0.5 ： 0.25 5) Compared with the phase difference between the + A and + C plates, it does not show the phase difference in the thickness direction of the protective film of the polarizing plate. Relationship (TAC, COP, PNB).

又，已揭示以藉由將傾斜角之暗狀態之漏光予以最小化，而提供具有在正面及傾斜角之高對比特性、低色偏移(Color Shift)之IPS-LCD為目的之具有+A板與+C板之IPS-LCD(專利文獻3)。並且，為了改善作為有機EL顯示器之防反射膜所使用之圓偏光板之可視角特性，也提出使用+C板(專利文獻5)。 [先前技術文獻] [專利文獻]In addition, it has been revealed that by minimizing light leakage in the dark state of the tilt angle, and providing an IPS-LCD with high contrast characteristics on the front and tilt angle and low color shift, it has + A Panel and + C panel IPS-LCD (Patent Document 3). In addition, in order to improve the viewing angle characteristics of a circularly polarizing plate used as an anti-reflection film of an organic EL display, the use of a + C plate has also been proposed (Patent Document 5). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開平2-256023號公報 　　[專利文獻2]日本特開平11-133408號公報 　　[專利文獻3]日本特開2009-122715號公報 　　[專利文獻4]日本特開2001-281669號公報 　　[專利文獻5]日本特開2015-79256號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2-256023 [Patent Literature 2] Japanese Patent Application Laid-Open No. 11-133408 [Patent Literature 3] Japanese Patent Application Laid-Open No. 2009-122715 [Patent Literature 4] Japanese Patent Laid-Open No. 2001-281669 [Patent Document 5] Japanese Patent Laid-Open No. 2015-79256

[發明所欲解決之課題][Problems to be Solved by the Invention]

如過往所提案般，由於+C板能補償偏光板之在可視角大之處的漏光，故非常有用於當作作為IPS-LCD或有機EL顯示器之防反射膜所使用之圓偏光板之光學補償膜。但，藉由過往一般已知之延伸處理所成之方法，難以使垂直定向(正C板)性展現。As proposed in the past, the + C plate can compensate the light leakage of the polarizing plate in the place where the viewing angle is large, so it is very useful for the optical use of the circular polarizing plate used as the anti-reflection film of IPS-LCD or organic EL display. Compensation film. However, it is difficult to make the vertical orientation (positive C-plate) exhibit by a method generally known in the past.

又，使用過往已提案之聚醯亞胺之垂直定向膜在膜製作時則必須使用N-甲基-2-吡咯啶酮等之聚醯亞胺之溶劑。因此，雖然不會對玻璃基材時造成問題，但基材為膜時，則有在定向膜形成時導致對基材造成損傷之問題。另外，使用聚醯亞胺之垂直定向膜中，則變得必須在高溫下燒成，而仍有膜基材無法承受高溫之問題。 　　並且，也已提出藉由使用具有長鏈烷基之矽烷耦合劑等直接處理基材，而形成垂直定向膜之方法，但在基材表面不存在羥基時，則難以處理，且有基材受到限制的問題(專利文獻4)。In addition, in the case of a vertical alignment film using a previously proposed polyimide, a solvent of a polyimide such as N-methyl-2-pyrrolidone must be used in the production of the film. Therefore, although the glass substrate is not a problem, when the substrate is a film, there is a problem that the substrate is damaged when the alignment film is formed. In addition, in the vertical alignment film using polyimide, it becomes necessary to sinter at high temperature, and there is still a problem that the film substrate cannot withstand high temperature. In addition, a method for forming a vertical alignment film by directly treating a substrate using a silane coupling agent having a long-chain alkyl group has also been proposed. However, when there is no hydroxyl group on the surface of the substrate, it is difficult to handle and the substrate is subjected to The problem of limitation (Patent Document 4).

近年來因應降低製造成本之需求，而要求在TAC(三乙醯基纖維素)膜、COP(環烯烴聚合物)膜等之平價樹脂膜上，藉由所謂輥對輥(roll to roll)來進行生產。然而，上述般之從過往材料所形成之定向膜則難以在樹脂膜之上製造+C板。In recent years, in response to the need to reduce manufacturing costs, it has been required to use so-called roll-to-roll on affordable resin films such as TAC (triethylfluorenyl cellulose) films and COP (cycloolefin polymer) films. in production. However, it is difficult to manufacture a + C plate on a resin film with the orientation film formed from the previous materials.

因此，需求密著性優異且在TAC膜等之樹脂膜上仍可形成高信賴+C板之定向材料，與形成該種定向材料用之硬化膜形成組成物。Therefore, there is a need for an alignment material that is excellent in adhesion and can form a high-reliability + C plate on a resin film such as a TAC film, and a hardened film forming composition for forming such an alignment material.

本發明係基於以上之見解或研討結果所完成者，其所欲解決之課題在於提供一種用來提供定向材料之硬化膜形成組成物；該定向材料具有優異垂直定向性，且具備光學補償膜所要求之透明性或溶劑耐性，並且具備與基材及聚合性液晶層之密著性，即使在樹脂膜上在低溫短時間之燒成條件下仍能安定地使聚合性液晶垂直定向。The present invention is completed based on the above findings or research results. The problem to be solved is to provide a hardened film-forming composition for providing an alignment material. The alignment material has excellent vertical alignment and is provided with an optical compensation film. The required transparency or solvent resistance, as well as the adhesion to the substrate and the polymerizable liquid crystal layer, allow the polymerizable liquid crystal to be vertically oriented stably even under low-temperature and short-term firing conditions on the resin film.

且，本發明之另一目的在於提供定向材料與使用該定向材料所形成之有用於+C板之相位差材料；該定向材料係由上述硬化膜形成組成物所得，具備優異垂直定向性與密著性，且具備耐溶劑性，即使在樹脂膜上在低溫短時間之燒成條件下仍能安定地使聚合性液晶垂直定向。And, another object of the present invention is to provide an alignment material and a phase difference material for a + C plate formed by using the alignment material; the alignment material is obtained from the above-mentioned hardened film forming composition, and has excellent vertical orientation and denseness. Adhesiveness and solvent resistance, even under low temperature and short-term firing conditions on the resin film, the polymerizable liquid crystal can be vertically aligned stably.

從以下之記載即可明白本發明之其他目的及優點。 [用以解決課題之手段]Other objects and advantages of the present invention will be apparent from the following description. [Means to solve the problem]

本發明者等為了達成上述目的，經過精心重複研討之結果，發現藉由選擇將具有垂直定向性基與包含C=C雙鍵之聚合性基之聚合物作為基質之硬化膜形成材料，即可形成具有優異垂直定向性與密著性之硬化膜，進而完成本發明。In order to achieve the above-mentioned object, the present inventors have conducted careful and repeated research and found that by selecting a hardened film-forming material using a polymer having a vertical orientation group and a polymerizable group containing a C = C double bond as a matrix, A hardened film having excellent vertical orientation and adhesion is formed, and the present invention has been completed.

即，本發明中，第1觀點係關於一種硬化膜形成組成物，其特徵為含有 　　(A)具有垂直定向性基與包含C=C雙鍵之聚合性基之聚合物，以及 　　(B)自由基聚合起始劑， 　　且前述垂直定向性基為下述式(1)所示之基。(式[1]中， 　　Y1 表示單鍵或結合基， 　　Y2 表示單鍵、碳原子數1~15之伸烷基或 -CH2 -CH(OH)-CH2 -，或表示選自苯環、環己烷環或雜環之2價之環狀基，前述環狀基上之任意之氫原子可經碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代， 　　Y3 表示單鍵或碳原子數1~15之伸烷基， 　　Y4 表示單鍵，或表示選自苯環、環己烷環或雜環之2價之環狀基，或表示碳原子數17~30且具有類固醇骨架之2價之有機基，前述環狀基上之任意之氫原子可經羥基、碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代， 　　Y5 表示選自苯環、環己烷環或雜環之2價之環狀基，該等環狀基上之任意之氫原子可經羥基、碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代， 　　n表示0~4之整數，n為2以上時，Y5 彼此可為相同亦可為相異， 　　Y6 表示氫原子、碳原子數1~18之烷基、碳原子數1~18之含氟烷基、碳原子數1~18之烷氧基或碳原子數1~18之含氟烷氧基， 　　Y2 及Y3 中之伸烷基，以及，前述環狀基上之取代基及Y6 中之烷基、含氟烷基、烷氧基及含氟烷氧基可為直鏈狀、分枝狀或環狀之任一者或該等之組合， 　　又，Y2 及Y3 中之伸烷基，以及，Y6 中之烷基、含氟烷基、烷氧基及含氟烷氧基只要結合基彼此不相鄰，則可經1至3個結合基中斷， 　　並且，在Y2 、Y4 或Y5 表示2價之環狀基，或Y4 表示具有類固醇骨架之2價之有機基，或Y2 表示-CH2 -CH(OH)-CH2 -，或Y2 或Y3 表示伸烷基，或Y6 表示烷基或含氟烷基時，該2價之環狀基、該具有類固醇骨架之2價之有機基、該 -CH2 -CH(OH)-CH2 -、該伸烷基、該烷基及該含氟烷基與該等所鄰接之基可隔著結合基而結合， 　　且，上述結合基表示選自由-O-、-CH2 O-、-COO-、 -OCO-、-NHCO-、-NH-CO-O-及-NH-CO-NH-所成群之基， 　　但，Y2 至Y6 所分別表示之單鍵、碳原子數1~15之伸烷基、苯環、環己烷環、雜環、具有類固醇骨架之2價之有機基、-CH2 -CH(OH)-CH2 -、碳原子數1~18之烷基、碳原子數1~18之含氟烷基、碳原子數1~18之烷氧基及碳原子數1~18之含氟烷氧基之碳原子數之合計為6~30)。That is, in the present invention, the first aspect relates to a cured film-forming composition characterized by containing (A) a polymer having a vertically oriented group and a polymerizable group containing a C = C double bond, and (B) free Is a polymerization initiator, and the vertical alignment group is a group represented by the following formula (1). (In the formula [1], Y 1 represents a single bond or a bonding group, Y 2 represents a single bond, an alkylene group having 1 to 15 carbon atoms, or -CH 2 -CH (OH) -CH 2- , or it is selected from A bivalent cyclic group of a benzene ring, a cyclohexane ring or a heterocyclic ring. Any hydrogen atom on the aforementioned cyclic group may be an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. Fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine-containing alkoxy groups or fluorine atoms having 1 to 3 carbon atoms, Y 3 represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y 4 Represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, or a divalent organic group having 17 to 30 carbon atoms and a steroid skeleton, on the aforementioned cyclic group Any of the hydrogen atoms may be passed through a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or containing 1 to 3 carbon atoms. Fluoroalkoxy or fluorine atom is substituted, Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted by a hydroxyl group or a carbon atom. Alkyl group 1 to 3, alkoxy group 1 to 3 carbon atoms, fluorine containing 1 to 3 carbon atoms Group, the number of carbon atoms containing a fluorine atom or a fluoroalkyl group having 1 to 3 of the substituent, n-represents an integer of 0 to 4, n-2 or more, Y 5 may be different from each other, Y 6 represents hydrogen may be the same Atom, alkyl group with 1 to 18 carbon atoms, fluorine-containing alkyl group with 1 to 18 carbon atoms, alkoxy group with 1 to 18 carbon atoms or fluorine-containing alkoxy group with 1 to 18 carbon atoms, Y 2 And the alkylene group in Y 3 and the substituents on the aforementioned cyclic group and the alkyl group, fluorine-containing alkyl group, alkoxy group and fluorine-containing alkoxy group in Y 6 may be linear or branched Or any one or combination of cyclic groups, and the alkylene group in Y 2 and Y 3 and the alkyl group, fluorine-containing alkyl group, alkoxy group and fluorine-containing alkoxy group in Y 6 If the binding groups are not adjacent to each other, they can be interrupted by 1 to 3 binding groups, and Y 2 , Y 4, or Y 5 represents a divalent cyclic group, or Y 4 represents a divalent organic group having a steroid skeleton. , Or Y 2 represents -CH 2 -CH (OH) -CH 2- , or Y 2 or Y 3 represents an alkylene group, or Y 6 represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, The divalent organic group having a steroid skeleton, the -CH 2 -CH (OH) -CH 2- , the alkylene group, the The alkyl group and the fluorine-containing alkyl group and the adjacent groups may be bonded via a bonding group, and the bonding group is selected from the group consisting of -O-, -CH 2 O-, -COO-, -OCO-,- NHCO-, -NH-CO-O-, and -NH-CO-NH- groups, but single bonds represented by Y 2 to Y 6 , alkylene groups having 1 to 15 carbon atoms, benzene Ring, cyclohexane ring, heterocyclic ring, divalent organic group with steroid skeleton, -CH 2 -CH (OH) -CH 2- , alkyl group with 1 to 18 carbon atoms, and 1 to 18 carbon atoms The total number of carbon atoms of the fluorine-containing alkyl group, the alkoxy group having 1 to 18 carbon atoms and the fluorine-containing alkoxy group having 1 to 18 carbon atoms is 6 to 30).

第2觀點係關於如第1觀點之硬化膜形成組成物，其中(A)成分之聚合物中，包含C=C雙鍵之聚合性基為選自由丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基及馬來醯亞胺基所成群之至少一種。 　　第3觀點係關於如第1觀點或第2觀點之硬化膜形成組成物，其中更含有選自由(C)具有包含C=C雙鍵之聚合性基之單體及聚合物所成群之至少一種。 　　第4觀點係關於如第1觀點至第3觀點中任一項之硬化膜形成組成物，其係基於(A)成分100質量份而含有0.1質量份~50質量份之(B)成分。 　　第5觀點係關於第3觀點或第4觀點之硬化膜形成組成物，其係基於(A)成分100質量份而含有10質量份至1000質量份之(C)成分。The second aspect is the cured film-forming composition according to the first aspect, in which the polymerizable group containing a C = C double bond in the polymer of the component (A) is selected from the group consisting of acrylfluorenyl, methacrylfluorenyl, and ethylene At least one of the group consisting of an alkyl group, an allyl group, and a maleimidine group. The third aspect relates to the hardened film-forming composition according to the first or second aspect, and further contains at least one selected from the group consisting of (C) a monomer and a polymer having a polymerizable group containing a C = C double bond. One. A fourth aspect is the cured film-forming composition according to any one of the first aspect to the third aspect, which is based on 100 parts by mass of the component (A) and contains the component (B) in an amount of 0.1 to 50 parts by mass. A fifth aspect is a cured film-forming composition according to the third aspect or the fourth aspect, which is based on 100 parts by mass of the (A) component and contains the component (C) in an amount of 10 to 1,000 parts by mass.

第6觀點係關於一種定向材料，其特徵為使如第1觀點至第5觀點中任一項之硬化膜形成組成物硬化而得者。 　　第7觀點係關於一種相位差材料，其係使用硬化膜所形成者，該硬化膜係由如第1觀點至第5觀點中任一項之硬化膜形成組成物所得。 [發明之效果]A sixth aspect relates to an oriented material, which is obtained by hardening the cured film-forming composition according to any one of the first to fifth aspects. A seventh aspect relates to a retardation material, which is formed using a cured film obtained from the cured film-forming composition according to any one of the first to fifth aspects. [Effect of the invention]

根據本發明之第一態樣，提供一種有用於用來提供定向材料之硬化膜形成組成物，該定向材料具備優異垂直定向性，即使在樹脂膜上在低溫短時間之燒成條件下仍能安定地使聚合性液晶垂直定向。 　　根據本發明之第二態樣，提供一種定向材料，其係具有優異垂直定向性，且在低溫短時間之燒成條件下仍能安定地使聚合性液晶垂直定向。 　　根據本發明之第三態樣，提供相位差材料，其係即使在樹脂膜上仍能以高效率形成，且為高透明具有高溶劑耐性及與基板及液晶膜之密著性。According to a first aspect of the present invention, there is provided a hardened film-forming composition for providing an alignment material, which has excellent vertical orientation, and can be used even on a resin film under low-temperature and short-term firing conditions. Orient the polymerizable liquid crystal stably vertically. (2) According to a second aspect of the present invention, an alignment material is provided, which has excellent vertical alignment and can stably orient the polymerizable liquid crystal stably even under low temperature and short-term firing conditions. According to a third aspect of the present invention, a retardation material is provided, which can be formed with high efficiency even on a resin film, is highly transparent, has high solvent resistance, and adheres to a substrate and a liquid crystal film.

＜硬化膜形成組成物＞ 　　本發明之硬化膜形成組成物含有(A)成分即具有垂直定向性基與包含C=C雙鍵之聚合性基之聚合物，及(B)成分即自由基聚合起始劑。本發明之硬化膜形成組成物除了包含上述(A)成分及(B)成分，也可更含有(C)成分之選自由具有包含C=C雙鍵之聚合性基之單體及聚合物所成群之至少一種。且，在不損及本發明之效果範圍內，可含有其他添加劑。 　　以下，說明各成分之詳細內容。<Hard film-forming composition> The hard film-forming composition of the present invention contains (A) component, a polymer having a vertical alignment group and a polymerizable group containing a C = C double bond, and (B) component, which is a radical polymerization. Initiator. The hardened film forming composition of the present invention may further contain the component (C) in addition to the component (A) and the component (B), and is selected from monomers and polymers having a polymerizable group containing a C = C double bond. Groups of at least one. In addition, other additives may be contained within a range that does not impair the effect of the present invention. The details of each component are described below.

＜(A)成分＞ 　　本發明之硬化膜形成組成物所含有之(A)成分為具有垂直定向性基，與包含C=C雙鍵之聚合性基之聚合物。 　　本說明書中，垂直定向性基係例如包含碳原子數為6~30程度之烴基之基，具體而言係指後述之式[1]所示之基。 　　因此，作為垂直定向性基之單體，可舉出例如包含碳原子數6~30程度之烴基之單體。作為碳原子數6~30之烴基，可舉出如直鏈狀、分枝狀或環狀之包含碳原子數6~30之烷基或芳香族基之碳原子數6~30之烴基。因此作為包含碳原子數6~30之烴基之單體之具體例，可舉出如丙烯酸之烷基酯、甲基丙烯酸之烷基酯、烷基乙烯基醚、2-烷基苯乙烯、3-烷基苯乙烯、4-烷基苯乙烯、N-烷基馬來醯亞胺，且該烷基為碳原子數6~30者，亦或該等單體之烷基備取代成上述之包含碳原子數為6~30之芳香族基之碳原子數6~30之烴基者。<(A) component> (A) The component (A) contained in the hardened film forming composition of this invention is a polymer which has a vertical orientation group and a polymerizable group containing a C = C double bond. In this specification, the vertical alignment group is, for example, a group containing a hydrocarbon group having a carbon number of about 6 to 30, and specifically means a group represented by the formula [1] described later. Therefore, examples of the monomer having a vertical alignment group include a monomer containing a hydrocarbon group having about 6 to 30 carbon atoms. Examples of the hydrocarbon group having 6 to 30 carbon atoms include a linear, branched or cyclic hydrocarbon group having 6 to 30 carbon atoms or an aromatic group having 6 to 30 carbon atoms. Therefore, specific examples of the monomer containing a hydrocarbon group having 6 to 30 carbon atoms include alkyl esters of acrylic acid, alkyl esters of methacrylic acid, alkyl vinyl ethers, 2-alkylstyrene, 3 -Alkylstyrene, 4-alkylstyrene, N-alkylmaleimide, and the alkyl group is 6-30 carbon atoms, or the alkyl group of these monomers is substituted with the above A hydrocarbon group having 6 to 30 carbon atoms and an aromatic group having 6 to 30 carbon atoms.

垂直定向性基更具體而言為下述式[1]所示之基。式[1]中，Y1 表示單鍵或結合基。 　　式[1]中，Y2 表示單鍵、碳原子數1~15之伸烷基或 -CH2 -CH(OH)-CH2 -。 　　又作為Y2 ，可舉出如選自苯環、環己烷環或雜環之2價之環狀基，該等環狀基上之任意之氫原子可經碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代。The vertical alignment group is more specifically a group represented by the following formula [1]. In the formula [1], Y 1 represents a single bond or a bonding group. In the formula [1], Y 2 represents a single bond, an alkylene group having 1 to 15 carbon atoms, or -CH 2 -CH (OH) -CH 2- . As Y 2 , a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring may be mentioned. Any hydrogen atom on the cyclic group may pass through an alkane having 1 to 3 carbon atoms. Group, substituted with alkoxy group having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom.

作為上述雜環，可舉出如吡咯環、咪唑環、噁唑環、噻唑環、吡唑環、吡啶環、嘧啶環、喹啉環、砒唑林環、異喹啉環、咔唑環、嘌呤環、噻二唑環、嗒嗪環、砒唑林環、三嗪環、吡唑啶環、***環、吡嗪環、苯並咪唑環、噌啉環、啡啉環、吲哚環、喹喔啉環、苯並噻唑環、酚噻嗪環、噁二唑環、吖啶環等，較佳者為吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、砒唑林環、咔唑環、嗒嗪環、砒唑林環、三嗪環、吡唑啶環、***環、吡嗪環、苯並咪唑環。Examples of the heterocyclic ring include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an oxazoline ring, an isoquinoline ring, a carbazole ring, Purine ring, thiadiazole ring, pyrazine ring, oxazoline ring, triazine ring, pyrazidine ring, triazole ring, pyrazine ring, benzimidazole ring, perylene ring, morpholine ring, indole ring , Quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Preferred are pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, oxazoline ring , Carbazole ring, pyrazine ring, oxazoline ring, triazine ring, pyrazidine ring, triazole ring, pyrazine ring, benzimidazole ring.

作為舉出當作上述取代基之烷基，可舉出如甲基、乙基、n-丙基、異丙基、環丙基，作為上述烷氧基，可舉出如在作為前述烷基之具體例所例舉之基上鍵結有氧原子-O-之基。又作為上述含氟烷基、含氟烷氧基，可舉出如前述烷基及烷氧基當中任意之氫原子被氟原子取代之基。Examples of the alkyl group as the substituent include methyl, ethyl, n-propyl, isopropyl, and cyclopropyl. Examples of the alkoxy group include the alkyl group as described above. A specific example is a group in which an oxygen atom -O- is bonded to the base. Examples of the fluorine-containing alkyl group and fluorine-containing alkoxy group include a group in which any hydrogen atom among the alkyl group and the alkoxy group is substituted with a fluorine atom.

此等之中，從合成容易度之觀點，以Y2 為單鍵、碳原子數1~15之伸烷基，或選自苯環或環己烷環之2價之環狀基為佳。Among these, from the viewpoint of ease of synthesis, it is preferable that Y 2 is a single bond, an alkylene group having 1 to 15 carbon atoms, or a divalent cyclic group selected from a benzene ring or a cyclohexane ring.

上述式[1]中，Y3 表示單鍵或碳原子數1~15之伸烷基。 　　上述式[1]中，Y4 表示單鍵，或表示選自苯環、環己烷環或雜環之2價之環狀基，該等環狀基上之任意之氫原子可經羥基、碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代。In the above formula [1], Y 3 represents a single bond or an alkylene group having 1 to 15 carbon atoms. In the above formula [1], Y 4 represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring. Any hydrogen atom on these cyclic groups may pass through a hydroxyl group, Substituted by alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine-containing alkoxy groups having 1 to 3 carbon atoms or fluorine atoms .

作為上述雜環以及取代基所舉出之烷基等，可作成如同前述之Y2 中所例示者。Examples of the above-mentioned heterocyclic ring and the substituent include alkyl groups and the like as exemplified in Y 2 described above.

並且，作為Y4 ，可為碳原子數17~30且具有類固醇骨架之2價之有機基。其之較佳例為具有從選自膽固醇基、雄甾固醇基(androsteryl)、β-膽固醇基、上雄固醇基(epiandrosteryl)、麥角固醇基(eligosteryl)、雌固醇基(estryl)、11α-羥基甲基固醇基(11α-hydroxymethylstryl)、11α-孕甾素基(11α-progesteryl)、羊毛固醇基(lanosteryl)、美雌醇基(mestranyl)、甲基睪固酮基、降雄甾炔酮基(norethisteryl)、孕烯醇酮基(pregnenolonyl)、β-麥固醇基(β-sitosteryl)、豆固醇基(stigmasteryl)、睪固酮基(testosteryl)，及乙酸膽固醇酯等之構造去除2個氫原子而成之構造之2價之基。更具體而言，例如以下所示。(式中，＊表示結合位置。)In addition, Y 4 may be a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton. Preferred examples thereof include those selected from the group consisting of cholesterol group, androsteryl group, β-cholesteryl group, epidiandrosteryl group, eligosteryl group, and estradiol group ( estryl), 11α-hydroxymethylstryl, 11α-progesteryl, lanosteryl, mestranyl, methylsterone, Norethisteryl, pregnenolonyl, β-sitosteryl, stigmasteryl, testosteryl, and cholesterol acetate, etc. The structure is a bivalent base obtained by removing two hydrogen atoms. More specifically, it is as follows, for example. (In the formula, * indicates a coupling position.)

該等之中，從合成容易度之觀點，Y4 係以選自單鍵、苯環或環己烷環之2價之環狀基，或碳原子數17~30且具有類固醇骨架之2價之有機基為佳。Among these, Y 4 is a divalent cyclic group selected from a single bond, a benzene ring, or a cyclohexane ring, or a divalent valent group having 17 to 30 carbon atoms and having a steroid skeleton, from the viewpoint of ease of synthesis. Organic bases are preferred.

式[1]中，Y5 表示選自苯環、環己烷環或雜環之2價之環狀基，且該等環狀基上之任意之氫原子可經羥基、碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代。作為上述雜環以及取代基所舉出之烷基等，可作成如同前述之Y4 中所例示者。In Formula [1], Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, and any hydrogen atom on these cyclic groups may pass through a hydroxyl group and a carbon number of 1 to 3 is substituted by an alkyl group of 3, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms or a fluorine atom. Examples of the above-mentioned heterocyclic ring and substituents include the alkyl groups and the like as exemplified in Y 4 described above.

該等之中，Y5 係以選自苯環或環己烷環之2價之環狀基為佳。Among these, Y 5 is preferably a divalent cyclic group selected from a benzene ring or a cyclohexane ring.

又式[1]中，n表示0~4之整數，n為2以上時，Y5 彼此可為相同之基亦可為相異之基。其中從原料取得性或合成容易度之觀點，n係以0~3為佳。較佳為0~2。In formula [1], n represents an integer of 0 to 4, and when n is 2 or more, Y 5 may be the same base or different bases. Among them, n is preferably from 0 to 3 from the viewpoint of raw material availability or ease of synthesis. It is preferably 0 to 2.

式[1]中，Y6 表示氫原子、碳原子數1~18之烷基、碳原子數1~18之含氟烷基、碳原子數1~18之烷氧基或碳原子數1~18之含氟烷氧基。In the formula [1], Y 6 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or 1 to 18 carbon atoms. 18 of fluorine-containing alkoxy.

其中，Y6 係以碳原子數1~18之烷基、碳原子數1~10之含氟烷基、碳原子數1~18之烷氧基或碳原子數1~10之含氟烷氧基為佳。較佳係Y6 為碳原子數1~17之烷基或碳原子數1~17之烷氧基。特佳係Y6 為碳原子數1~16之烷基或碳原子數1~16之烷氧基。Among them, Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms Base is better. Preferably, Y 6 is an alkyl group having 1 to 17 carbon atoms or an alkoxy group having 1 to 17 carbon atoms. Particularly preferred Y 6 is an alkyl group having 1 to 16 carbon atoms or an alkoxy group having 1 to 16 carbon atoms.

尚且，Y4 為具有類固醇骨架之2價之有機基時，Y6 係以氫原子為佳。When Y 4 is a divalent organic group having a steroid skeleton, Y 6 is preferably a hydrogen atom.

上述式[1]中之定義中舉出之伸烷基、烷基、含氟烷基、烷氧基及含氟烷氧基可為直鏈狀、分枝狀或環狀之任一者或該等之組合。The alkylene group, alkyl group, fluorine-containing alkyl group, alkoxy group, and fluorine-containing alkoxy group listed in the definition in the above formula [1] may be any of linear, branched, or cyclic or A combination of these.

上述烷基可舉出例如，甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、1-甲基-n-丁基、2-甲基-n-丁基、3-甲基-n-丁基、1,1-二甲基-n-丙基、1,2-二甲基-n-丙基、2,2-二甲基-n-丙基、1-乙基-n-丙基、n-己基、1-甲基-n-戊基、2-甲基-n-戊基、3-甲基-n-戊基、4-甲基-n-戊基、1,1-二甲基-n-丁基、1,2-二甲基-n-丁基、1,3-二甲基-n-丁基、2,2-二甲基-n-丁基、2,3-二甲基-n-丁基、3,3-二甲基-n-丁基、1-乙基-n-丁基、2-乙基-n-丁基、1,1,2-三甲基-n-丙基、1,2,2-三甲基-n-丙基、1-乙基-1-甲基-n-丙基、1-乙基-2-甲基-n-丙基、n-庚基、1-甲基-n-己基、2-甲基-n-己基、3-甲基-n-己基、1,1-二甲基-n-戊基、1,2-二甲基-n-戊基、1,3-二甲基-n-戊基、2,2-二甲基-n-戊基、2,3-二甲基-n-戊基、3,3-二甲基-n-戊基、1-乙基-n-戊基、2-乙基-n-戊基、3-乙基-n-戊基、1-甲基-1-乙基-n-丁基、1-甲基-2-乙基-n-丁基、1-乙基-2-甲基-n-丁基、2-甲基-2-乙基-n-丁基、2-乙基-3-甲基-n-丁基、n-辛基、1-甲基-n-庚基、2-甲基-n-庚基、3-甲基-n-庚基、1,1-二甲基-n-己基、1,2-二甲基-n-己基、1,3-二甲基-n-己基、2,2-二甲基-n-己基、2,3-二甲基-n-己基、3,3-二甲基-n-己基、1-乙基-n-己基、2-乙基-n-己基、3-乙基-n-己基、1-甲基-1-乙基-n-戊基、1-甲基-2-乙基-n-戊基、1-甲基-3-乙基-n-戊基、2-甲基-2-乙基-n-戊基、2-甲基-3-乙基-n-戊基、3-甲基-3-乙基-n-戊基、n-壬基、n-癸基、n-十一基、n-十二基、n-十三基、n-十四基、n-十五基等。Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and 1-methyl. -N-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n- Propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3- Dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1- Ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1- Ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl , 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2 2,2-dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2- Ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2 -Ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n -Butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl , 1,2-dimethyl-n-hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3 , 3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n- Amyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2- Methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and the like.

作為上述伸烷基，可舉出如從前述烷基去除1個任意之氫原子之2價之基。 　　作為上述烷氧基，可舉出在作為前述烷基之具體例所例示之基上結合有氧原子-O-之基。 　　又作為上述含氟烷基、含氟烷氧基，可舉出如前述烷基及烷氧基當中任意之氫原子被氟原子取代之基。Examples of the alkylene group include a divalent group obtained by removing one arbitrary hydrogen atom from the alkyl group. As the alkoxy group, a group in which an oxygen atom -O- is bonded to the group exemplified as the specific example of the alkyl group is mentioned. As the above-mentioned fluorine-containing alkyl group and fluorine-containing alkoxy group, a group in which any hydrogen atom among the alkyl group and the alkoxy group is substituted with a fluorine atom is mentioned.

上述Y2 及Y3 中之伸烷基，以及，上述環狀基上之取代基及Y6 中之烷基、含氟烷基、烷氧基及含氟烷氧基可為直鏈狀、分枝狀或環狀之任一者或該等之組合。The alkylene groups in Y 2 and Y 3 described above, and the substituents on the cyclic group and the alkyl groups, fluorine-containing alkyl groups, alkoxy groups and fluorine-containing alkoxy groups in Y 6 may be linear, Either branched or cyclic or a combination of these.

又，Y2 及Y3 中之伸烷基，以及，Y6 中之烷基、含氟烷基、烷氧基及含氟烷氧基只要結合基彼此不相鄰，則能以1至3個結合基中斷。In addition, the alkylene group in Y 2 and Y 3 and the alkyl group, fluorine-containing alkyl group, alkoxy group, and fluorine-containing alkoxy group in Y 6 can be 1 to 3 as long as the bonding groups are not adjacent to each other. A binding base breaks.

並且，在Y2 、Y4 或Y5 表示2價之環狀基，或Y4 表示具有類固醇骨架之2價之有機基，或Y2 表示 -CH2 -CH(OH)-CH2 -，或Y2 或Y3 表示伸烷基，或Y6 表示烷基或含氟烷基時，該2價之環狀基、該具有類固醇骨架之2價之有機基、該-CH2 -CH(OH)-CH2 -、該伸烷基、該烷基及該含氟烷亦可與該等鄰接之基隔著結合基而結合。And Y 2 , Y 4 or Y 5 represents a divalent cyclic group, or Y 4 represents a divalent organic group having a steroid skeleton, or Y 2 represents -CH 2 -CH (OH) -CH 2- , When Y 2 or Y 3 represents an alkylene group, or Y 6 represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having a steroid skeleton, the -CH 2 -CH ( OH) -CH 2- , the alkylene group, the alkyl group, and the fluoroalkane may also be bonded to the adjacent groups via a bonding group.

又上述結合基表示選自由-O-、-CH2 O-、 -CO-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-CO-O-、 -O-CO-NH-及-NH-CO-NH-所成群之基。The above-mentioned binding group is selected from -O-, -CH 2 O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO- Groups formed by NH- and -NH-CO-NH-.

尚且，Y2 至Y6 所分別表示之單鍵、碳原子數1~15之伸烷基、苯環、環己烷環、雜環、具有類固醇骨架之2價之有機基、-CH2 -CH(OH)-CH2 -、碳原子數1~18之烷基、碳原子數1~18之含氟烷基、碳原子數1~18之烷氧基及碳原子數1~18之含氟烷氧基之碳原子數之合計為6~30，例如6~20。 　　該等之中，在考慮到垂直定向性與聚合性液晶之塗佈性時，垂直定向性基係以包含碳原子數7~18，尤其係8~16之烷基之基為佳。In addition, a single bond represented by Y 2 to Y 6 , an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, and -CH 2- CH (OH) -CH 2- , alkyl group having 1 to 18 carbon atoms, fluorine-containing alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and containing 1 to 18 carbon atoms The total number of carbon atoms of the fluoroalkoxy group is 6 to 30, for example, 6 to 20. Among these, in consideration of the vertical alignment property and the coatability of the polymerizable liquid crystal, the vertical alignment group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, especially an 8 to 16 alkyl group.

(A)成分之聚合物中，作為包含C=C雙鍵之聚合性基，可舉出如丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基及馬來醯亞胺基等。In the polymer of the component (A), examples of the polymerizable group containing a C = C double bond include acrylfluorenyl, methacrylfluorenyl, vinyl, allyl, and maleimide.

上述包含C=C雙鍵之聚合性基係能導入於聚合物之主骨架之側鏈，即，作為具有包含C=C雙鍵之聚合性基之特定側鏈，能導入至(A)成分之聚合物之側鏈。 　　(A)成分之聚合物中，上述具有包含C=C雙鍵之聚合性基之特定側鏈係以碳原子數為3~16且於末端具有不飽和鍵者為佳，以式(b2)所示之特定側鏈為特佳。The aforementioned polymerizable group containing a C = C double bond can be introduced into the side chain of the main skeleton of the polymer, that is, a specific side chain having a polymerizable group containing a C = C double bond can be introduced into the (A) component Polymer side chains. In the polymer of the component (A), the specific side chain having a polymerizable group containing a C = C double bond as described above is preferably one having 3 to 16 carbon atoms and having an unsaturated bond at the terminal. The formula (b2) The particular side chains shown are particularly preferred.

式(b2)中，R51 為碳原子數1~14之選自由脂肪族基、包含環式構造之脂肪族基及芳香族基所成群之2價之有機基，或，由選自該群之複數之2價之有機基之組合所構成之2價之有機基。R51 亦可包含酯鍵、醚鍵、醯胺鍵、 -CH2 CH(OH)CH2 -鍵或胺基甲酸酯鍵等。 　　式(b2)中，R52 為氫原子或甲基，以R52 為氫原子之特定側鏈為佳，較佳係末端為丙烯醯基、甲基丙烯醯基或苯乙烯基之特定側鏈。 In formula (b2), R 51 is a divalent organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or a group selected from the group consisting of: A divalent organic group composed of a combination of plural divalent organic groups of a group. R 51 may include an ester bond, an ether bond, a amide bond, a -CH 2 CH (OH) CH 2 -bond, a urethane bond, or the like. In formula (b2), R 52 is a hydrogen atom or a methyl group, and a specific side chain in which R 52 is a hydrogen atom is preferred, and a specific side chain whose terminal is acrylfluorenyl, methacrylfluorenyl, or styryl is preferred. .

取得本發明之(A)成分之聚合物之方法並無特別限定。例如，預先藉由自由基聚合等之聚合方法，生成具有垂直定向性基與特定官能基之聚合物。其次，藉由使具有特定官能基反應之基及包含C=C雙鍵之聚合性基之化合物(以下稱為特定化合物)反應，而可取得(A)成分之聚合物。The method of obtaining the polymer of (A) component of this invention is not specifically limited. For example, a polymer having a vertical alignment group and a specific functional group is produced in advance by a polymerization method such as radical polymerization. Next, by reacting a compound having a specific functional group and a polymerizable group containing a C = C double bond (hereinafter referred to as a specific compound), a polymer of the component (A) can be obtained.

作為其他方法，藉由對使具有與特定官能基反應之基及垂直定向性基之化合物、具有與特定官能基反應之基及包含C=C雙鍵之聚合性基之化合物，對具有特定官能基之聚合物進行反應，而可取得(A)成分之聚合物。As another method, a compound having a specific functional group and a vertically-alignable group, a compound having a reaction with a specific functional group, and a polymerizable group containing a C = C double bond can be used for a compound having a specific function The polymer of the base is reacted to obtain the polymer of the component (A).

在此，特定官能基係指羧基、環氧基、羥基、具有活性氫之胺基、酚性羥基或異氰酸酯基等之官能基，或，選自該等之複數種之官能基。Here, the specific functional group refers to a functional group such as a carboxyl group, an epoxy group, a hydroxyl group, an amine group having an active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or a functional group selected from a plurality of these.

與上述特定官能基之反應中，特定官能基，與特定化合物所具有之官能基且參與反應之基之較佳組合為，羧基與環氧基、羥基與異氰酸酯基、酚性羥基與環氧基、羧基與異氰酸酯基、胺基與異氰酸酯基，或，羥基與酸氯等。In the reaction with the above-mentioned specific functional group, the preferred combination of the specific functional group and the functional group possessed by the specific compound and the group participating in the reaction is a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, a phenolic hydroxyl group and an epoxy group , Carboxyl group and isocyanate group, amine group and isocyanate group, or hydroxyl group and acid chloride.

又，取得具有特定官能基之聚合物之方法並無特別限定。作為一例，可使具有與特定化合物反應用之官能基(特定官能基)之單體，即，具有羧基、環氧基、羥基、具有活性氫之胺基、酚性羥基或異氰酸酯基等之單體(亦稱為特定單體)進行聚合而得。在此，具有聚合使用之特定官能基之單體係可單獨使用，亦可併用複數種在聚合中不會反應之組合。The method for obtaining a polymer having a specific functional group is not particularly limited. As an example, a monomer having a functional group (specific functional group) for reacting with a specific compound, that is, a monomer having a carboxyl group, an epoxy group, a hydroxyl group, an amine group having an active hydrogen, a phenolic hydroxyl group, or an isocyanate group can be used. (Also known as a specific monomer) polymerized. Here, a single system having a specific functional group used in polymerization may be used alone, or a combination of plural types which do not react during polymerization may be used in combination.

以下，舉出取得上述之具有特定官能基之聚合物所必須之單體，即，特定單體之具體例。但，並非係到該等所限定者。Hereinafter, specific examples of the monomers necessary for obtaining the polymer having a specific functional group, that is, specific monomers will be given. However, it is not related to those defined.

作為具有羧基之單體，可舉出例如，丙烯酸、甲基丙烯酸、巴豆酸、單-(2-(丙烯醯氧基)乙基)鄰苯二甲酸酯、單-(2-(甲基丙烯醯氧基)乙基)鄰苯二甲酸酯、N-(羧基苯基)馬來醯亞胺、N-(羧基苯基)甲基丙烯醯胺及N-(羧基苯基)丙烯醯胺等。Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (propenyloxy) ethyl) phthalate, and mono- (2- (methyl Acrylic acid) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide and N- (carboxyphenyl) acrylic acid Amine, etc.

作為具有環氧基之單體，可舉出例如，環氧丙基甲基丙烯酸酯、環氧丙基丙烯酸酯、3,4-環氧基環己基甲基甲基丙烯酸酯、烯丙基環氧丙基醚、3-乙烯基-7-氧雜雙環[4.1.0]庚烷、1,2-環氧基-5-己烯及1,7-辛二烯單環氧化物等。Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethylmethacrylate, and allyl ring. Oxypropyl ether, 3-vinyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.

作為具有羥基之單體，可舉出例如，2-羥基乙基丙烯酸酯、2-羥基乙基甲基丙烯酸酯、2-羥基丙基丙烯酸酯、2-羥基丙基甲基丙烯酸酯、4-羥基丁基丙烯酸酯、4-羥基丁基甲基丙烯酸酯、2,3-二羥基丙基丙烯酸酯、2,3-二羥基丙基甲基丙烯酸酯、二乙二醇單丙烯酸酯、二乙二醇單甲基丙烯酸酯、己內酯2-(丙烯醯氧基)乙基酯、己內酯2-(甲基丙烯醯氧基)乙基酯、聚(乙二醇)乙基醚丙烯酸酯、聚(乙二醇)乙基醚甲基丙烯酸酯、5-丙烯醯氧基-6-羥基降莰烯-2-羧酸-6-內酯及5-甲基丙烯醯氧基-6-羥基降莰烯-2-羧酸-6-內酯等。Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4- Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol Monomethacrylate, caprolactone 2- (propenyloxy) ethyl ester, caprolactone 2- (methacryloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, Poly (ethylene glycol) ethyl ether methacrylate, 5-propenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, and 5-methacrylic acid-6-hydroxyl Norbornene-2-carboxylic acid-6-lactone and the like.

作為具有胺基之單體，可舉出例如，2-胺基乙基丙烯酸酯及2-胺基甲基甲基丙烯酸酯等。Examples of the monomer having an amine group include 2-aminoethyl acrylate and 2-aminomethylmethacrylate.

作為具有酚性羥基之單體，可舉出例如，羥基苯乙烯、N-(羥基苯基)丙烯醯胺、N-(羥基苯基)甲基丙烯醯胺及N-(羥基苯基)馬來醯亞胺等。Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamine, and N- (hydroxyphenyl) horse Laimide and so on.

作為具有異氰酸酯基之單體，可舉出例如，丙烯醯基乙基異氰酸酯、甲基丙烯醯基乙基異氰酸酯及m-四甲基茬異氰酸酯等。Examples of the monomer having an isocyanate group include acrylethyl ethyl isocyanate, methacryl ethyl ethyl isocyanate, and m-tetramethyl succinic isocyanate.

又，本發明中，在取得具有特定官能基之聚合物之際，除了特定單體以外，亦可併用能與該單體共聚合且不具有特定官能基之單體。 　　作為此種單體之具體例，可舉出如、具有與特定單體相異構造之丙烯酸酯化合物或甲基丙烯酸酯化合物、馬來醯亞胺化合物、丙烯醯胺化合物、丙烯腈、馬來酸酐、苯乙烯化合物及乙烯基化合物等。In addition, in the present invention, when obtaining a polymer having a specific functional group, in addition to the specific monomer, a monomer which can be copolymerized with the monomer and does not have a specific functional group may be used in combination. Specific examples of such a monomer include an acrylate compound or a methacrylate compound having a structure different from that of a specific monomer, a maleimide compound, an acrylamide compound, acrylonitrile, and malay. Acid anhydride, styrene compound and vinyl compound.

以下，舉出前述單體之具體例，但並非係受到該等所限定者。 　　作為前述具有與特定單體相異構造之丙烯酸酯化合物，可舉出例如，甲基丙烯酸酯、乙基丙烯酸酯、n-丙基丙烯酸酯、異丙基丙烯酸酯、n-丁基丙烯酸酯、異丁基丙烯酸酯、t-丁基丙烯酸酯、苄基丙烯酸酯、萘基丙烯酸酯、蒽基丙烯酸酯、蒽基甲基丙烯酸酯、苯基丙烯酸酯、2,2,2-三氟乙基丙烯酸酯、環己基丙烯酸酯、異莰基丙烯酸酯、2-甲氧基乙基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、2-乙氧基乙基丙烯酸酯、四氫糠基丙烯酸酯、3-甲氧基丁基丙烯酸酯、2-甲基-2-金剛烷基丙烯酸酯、2-丙基-2-金剛烷基丙烯酸酯、8-甲基-8-三環癸基丙烯酸酯，及，8-乙基-8-三環癸基丙烯酸酯等。Specific examples of the aforementioned monomers are given below, but they are not limited by these. Examples of the acrylate compound having a structure different from a specific monomer include methacrylate, ethacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and the like. Isobutyl acrylate, t-butyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, phenyl acrylate, 2,2,2-trifluoroethyl Acrylate, cyclohexyl acrylate, isofluorenyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate , 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate And, 8-ethyl-8-tricyclodecyl acrylate and the like.

作為前述具有與特定單體相異構造之甲基丙烯酸酯化合物，可舉出例如，甲基甲基丙烯酸酯、乙基甲基丙烯酸酯、n-丙基甲基丙烯酸酯、異丙基甲基丙烯酸酯、n-丁基甲基丙烯酸酯、異丁基甲基丙烯酸酯、t-丁基甲基丙烯酸酯、苄基甲基丙烯酸酯、萘基甲基丙烯酸酯、蒽基甲基丙烯酸酯、蒽基甲基甲基丙烯酸酯、苯基甲基丙烯酸酯、2,2,2-三氟乙基甲基丙烯酸酯、環己基甲基丙烯酸酯、異莰基甲基丙烯酸酯、2-甲氧基乙基甲基丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、2-乙氧基乙基甲基丙烯酸酯、四氫糠基甲基丙烯酸酯、3-甲氧基丁基甲基丙烯酸酯、2-甲基-2-金剛烷基甲基丙烯酸酯、γ-丁內酯甲基丙烯酸酯、2-丙基-2-金剛烷基甲基丙烯酸酯、8-甲基-8-三環癸基甲基丙烯酸酯，及，8-乙基-8-三環癸基甲基丙烯酸酯等。Examples of the methacrylate compound having a structure different from a specific monomer include methmethacrylate, ethylmethacrylate, n-propylmethacrylate, and isopropylmethyl Acrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methyl Acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isofluorenyl methacrylate, 2-methoxyethyl methacrylate Ester, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl- 2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate And, 8-ethyl-8-tricyclodecyl methacrylate and the like.

作為前述乙烯基化合物，可舉出例如，甲基乙烯基醚、苄基乙烯基醚、乙烯基萘、乙烯基咔唑、烯丙基環氧丙基醚、3-乙烯基-7-氧雜雙環[4.1.0]庚烷、1,2-環氧基-5-己烯、及、1,7-辛二烯單環氧化物等。Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl epoxypropyl ether, and 3-vinyl-7-oxa. Bicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide and the like.

作為前述苯乙烯化合物，可舉出例如，苯乙烯、甲基苯乙烯、氯苯乙烯、溴苯乙烯等。Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

作為前述馬來醯亞胺化合物，可舉出例如，馬來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、及N-環己基馬來醯亞胺等。Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide Wait.

又，上述具有特定官能基之聚合物係能適宜使用市售品。 　　作為於側鏈或末端具有1個以上環氧基之聚合物之市售品之具體例，作為雙酚A型環氧樹脂，可舉出如jER1001、同1002、同1003、同1004、同1055、同1007、同1009、同1010、同834、同828(以上，三菱化學(股)製)等，作為雙酚F型環氧樹脂，可舉出如jER806、同807(以上，三菱化學(股)製)等，作為苯酚酚醛型環氧樹脂，可舉出如jER152、同154(以上，三菱化學(股)製)、EPPN201、同202(以上，日本化藥(股)製)等，作為甲酚酚醛型環氧樹脂，可舉出如ECN-1299(旭化成(股)製)、EOCN-102、EOCN-103S、EOCN-104S、EOCN-1020、EOCN-1025、EOCN-1027(以上，日本化藥(股)製)、jER80S75(三菱化學(股)製)等，作為雙酚A酚醛型環氧樹脂，可舉出如jER157S70(三菱化學(股)製)等，作為聚醇之1,2-環氧基-4-(2-環氧乙烷基)環己烷加成物，可舉出如EHPE-3150((股)Daicel製)等。As the polymer having the specific functional group, a commercially available product can be suitably used. As a specific example of a commercially available product of a polymer having one or more epoxy groups at a side chain or at an end, examples of the bisphenol A epoxy resin include jER1001, the same as 1002, the same as 1003, the same as 1004, and the same as 1055. , Same as 1007, same as 1009, same as 1010, same as 834, same as 828 (above, manufactured by Mitsubishi Chemical Corporation), etc. As the bisphenol F-type epoxy resin, there can be mentioned jER806, same 807 (above, Mitsubishi Chemical ( As the phenol novolac epoxy resin, for example, jER152, Tong154 (above, manufactured by Mitsubishi Chemical Corporation), EPPN201, Tong 202 (above, manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of the cresol novolac epoxy resin include ECN-1299 (manufactured by Asahi Kasei Corporation), EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nihon Kayaku Co., Ltd.), jER80S75 (Mitsubishi Chemical Co., Ltd.) and the like. Examples of the bisphenol A phenolic epoxy resin include jER157S70 (Mitsubishi Chemical Co., Ltd.) and the like. Examples of the 2-epoxy-4- (2-oxiranyl) cyclohexane adduct include EHPE-3150 (made by Daicel).

作為於側鏈或末端具有1個羥基之聚合物之市售品之具體例，作為聚醚聚醇之具體例，可舉出如ADEKA製Adeka聚醚P系列、G系列、EDP系列、BPX系列、FC系列、CM系列、日油製Uniox(註冊商標)HC-40、HC-60、ST-30E、ST-40E、G-450、G-750、Uniol(註冊商標)TG-330、TG-1000、TG-3000、TG-4000、HS-1600D、DA-400、DA-700、DB-400、Nonion(註冊商標)LT-221、ST-221、OT-221等，作為聚酯聚醇之具體例，可舉出如DIC製Polylite(註冊商標)OD-X-286、OD-X-102、OD-X-355、OD-X-2330、OD-X-240、OD-X-668、OD-X-2108、OD-X-2376、OD-X-2044、OD-X-688、OD-X-2068、OD-X-2547、OD-X-2420、OD-X-2523、OD-X-2555、OD-X-2560、可樂麗製聚醇P-510、P-1010、P-2010、P-3010、P-4010、P-5010、P-6010、F-510、F-1010、F-2010、F-3010、P-1011、P-2011、P-2013、P-2030、N-2010、PNNA-2016、C-590、C-1050、C-2050、C-2090、C-3090等，作為聚己內酯聚醇之具體例，可舉出如DIC製Polylite(註冊商標)OD-X-2155、OD-X-640、OD-X-2568、戴爾化學製Plaxel(註冊商標)205、L205AL、205U、208、210、212、L212AL、220、230、240、303、305、308、312、320等。Specific examples of commercially available products of polymers having one hydroxyl group at the side chain or at the end, and specific examples of polyether polyols include Adeka polyether P series, G series, EDP series, and BPX series manufactured by ADEKA. , FC series, CM series, Uniox (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG- 1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, Nonion (registered trademark) LT-221, ST-221, OT-221, etc., as the polyester polyol Specific examples include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, manufactured by DIC, and others. OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD- X-2555, OD-X-2560, Kuraray Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010 , F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, C-590, C-1050, C-2050, C-2090, C -3090 and the like, and specific examples of polycaprolactone polyols include Polylite (registered trademark) OD-X-2155 made by DIC. OD-X-640, OD-X-2568, Plaxel (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc. .

(A)成分之聚合物之重量平均分子量係以1,000至200,000為佳，以2,000至150,000為較佳，以3,000至100,000為更佳。重量平均分子量若為超過200,000之過大者時，會有對溶劑之溶解性降低而操作性降低之情況，重量平均分子量若為未滿1,000之過小者時，會有在光硬化時變得硬化不足而溶劑耐性及耐熱性降低之情況。 　　尚且，本說明書中，重量平均分子量係藉由凝膠滲透層析(GPC)，使用聚苯乙烯作為標準試料所得之值。The weight average molecular weight of the component (A) polymer is preferably 1,000 to 200,000, more preferably 2,000 to 150,000, and even more preferably 3,000 to 100,000. If the weight average molecular weight is more than 200,000, the solubility in the solvent may be reduced, and the handleability may be reduced. If the weight average molecular weight is less than 1,000, it may be insufficiently hardened during photocuring. In addition, the solvent resistance and heat resistance may be reduced. In addition, in this specification, the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

(A)成分之聚合物中，垂直定向性基之存在比例，以該聚合物之全重複單位每100莫耳而言，以3莫耳%~50莫耳%為佳，以5莫耳%~45莫耳%為更佳。未滿3莫耳%時，會有垂直定向性變得不充足之情況，若多過50莫耳%時，會有對與液晶之密著性產生不良影響之情況。In the polymer of component (A), the proportion of the vertical alignment group exists. For every 100 mol of the polymer's total repeating unit, it is preferably 3 mol% to 50 mol%, and 5 mol%. ~ 45 mole% is better. When it is less than 3 mol%, the vertical alignment may become insufficient. When it exceeds 50 mol%, the adhesion to the liquid crystal may be adversely affected.

(A)成分之聚合物中，包含C=C雙鍵之聚合性基之存在比例，在以該聚合物之全重複單位每100莫耳而言，以20莫耳%~97莫耳%為佳，以25莫耳%~95莫耳%為更佳，在未滿20莫耳%時，會有硬化變得不充足之情況，若多過97莫耳%時，則有垂直定向性變得不充足之情況。(A) The proportion of the polymerizable group containing a C = C double bond in the polymer of component A is from 20 mol% to 97 mol% per 100 mol of the polymer's total repeating unit. It is better to use 25 mol% ~ 95 mol%. When it is less than 20 mol%, the hardening may become insufficient. If it exceeds 97 mol%, the vertical orientation will change. Inadequate situation.

＜(B)成分＞ 　　本發明之硬化膜形成組成物中之(B)成分為自由基聚合起始劑。 　　作為自由基聚合起始劑，能使用公知者，可舉出例如，烷基苯酮(Alkylphenone)類、二苯甲酮類、醯基膦氧化物類、米伽勒之苄醯基苯甲酸酯類、肟酯類、單硫化四甲基秋蘭姆類、噻噸酮類等。<Component (B)> (B) The component (B) in the cured film-forming composition of the present invention is a radical polymerization initiator. As a radical polymerization initiator, a known one can be used, and examples thereof include Alkylphenones, benzophenones, fluorenylphosphine oxides, and benzylfluorenyl benzoate of Miguel. Class, oxime esters, tetramethylthiuram monosulfide, thioxanthone, etc.

作為本發明所使用之自由基聚合起始劑，可舉出例如，二乙醯基等之α-二酮類；安息香等之酮醇類；安息香甲基醚、安息香乙基醚、安息香異丙基醚等之酮醇醚類；噻噸酮、2,4-二乙基噻噸酮、噻噸酮-4-磺酸、二苯甲酮、4,4’-雙(二甲基胺基)二苯甲酮、4,4’-雙(二乙基胺基)二苯甲酮等之二苯甲酮類；苯乙酮、p-二甲基胺基苯乙酮、α,α-二甲氧基-α-乙醯氧基苯乙酮、α,α-二甲氧基-α-苯基苯乙酮、p-甲氧基苯乙酮、1-[2-甲基-4-甲硫基苯基]-2-嗎啉基-1-丙酮、α,α-二甲氧基-α-嗎啉基-甲硫基苯基苯乙酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁-1-酮等之苯乙酮類；蒽醌、1,4-萘醌等之醌類；氯苯乙酮(Phenacyl chloride)、三溴甲基苯基碸、參(三氯甲基)-s-三嗪等之鹵素化合物；[1,2’-雙咪唑]-3,3’,4,4’-四苯基、[1,2’-雙咪唑]-1,2’-二氯苯基-3,3’,4,4’-四苯基等之雙咪唑類、二-tert-丁基過氧化物等之過酸化物；2,4,6-三甲基苄醯基二苯基膦氧化物等之醯基膦氧化物類等。 　　作為市售品，可舉出如以Irgacure 184、369、379EG、651、500、907、CGI369、CG24-61、OXE02、Lucirin LR8728、Lucirin TPO、Darocure 1116、1173(以上，BASF(股)製)、Evecryl P36(UCB(股)製)等之商品名所市售者。Examples of the radical polymerization initiator used in the present invention include α-diketones such as diethylfluorenyl; ketoalcohols such as benzoin; benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl Ketol ethers such as methyl ethers; thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino ) Benzophenones such as benzophenone, 4,4'-bis (diethylamino) benzophenone; acetophenone, p-dimethylaminoacetophenone, α, α- Dimethoxy-α-acetophenone, α, α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 1- [2-methyl-4 -Methylthiophenyl] -2-morpholinyl-1-acetone, α, α-dimethoxy-α-morpholinyl-methylthiophenylacetophenone, 2-benzyl-2-dione Acetophenones such as methylamino-1- (4-morpholinylphenyl) -butan-1-one; quinones such as anthraquinone, 1,4-naphthoquinone; and phenacyl chloride ), Tribromomethylphenylphosphonium, ginseng (trichloromethyl) -s-triazine and other halogen compounds; [1,2'-bisimidazole] -3,3 ', 4,4'-tetraphenyl [1,2'-bisimidazole] -1,2'-dichlorophenyl-3,3 ', 4,4'-tetraphenyl, etc. Type, per-acids of di-tert-butyl peroxide, etc .; fluorenyl phosphine oxides such as 2,4,6-trimethylbenzylfluorenyl diphenylphosphine oxide and the like. Examples of commercially available products include Irgacure 184, 369, 379EG, 651, 500, 907, CGI369, CG24-61, OXE02, Lucirin LR8728, Lucirin TPO, Darocure 1116, 1173 (above, made by BASF). , Evecryl P36 (UCB (stock) system) and other commercial names.

上述之中，以1-[2-甲基-4-甲硫基苯基]-2-嗎啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁-1-酮、α,α-二甲氧基-α-苯基苯乙酮等之苯乙酮類、氯苯乙酮、三溴甲基苯基碸、2,4,6-三甲基苄醯基二苯基膦氧化物、1,2’-雙咪唑類與4,4’-雙(二乙基胺基)二苯甲酮與巰基苯並噻唑之併用、Lucirin TPO(商品名)、Irgacure 651(商品名)、Irgacure 369(商品名)、Irgacure 907(商品名)、Irgacure OXE02(商品名)為佳。Among the above, 1- [2-methyl-4-methylthiophenyl] -2-morpholinyl-1-acetone and 2-benzyl-2-dimethylamino-1- (4- Morpholinylphenyl) -butan-1-one, acetophenones such as α, α-dimethoxy-α-phenylacetophenone, chloroacetophenone, tribromomethylphenylhydrazone, 2 Of 4,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide, 1,2'-bisimidazoles and 4,4'-bis (diethylamino) benzophenone with mercaptobenzothiazole In combination, Lucirin TPO (trade name), Irgacure 651 (trade name), Irgacure 369 (trade name), Irgacure 907 (trade name), and Irgacure OXE02 (trade name) are preferred.

上述自由基聚合起始劑係可單獨使用1種，亦可組合2種以上使用。 　　相對於(A)成分100質量份，上述自由基聚合起始劑係以使用0.1~50質量份為佳，較佳使用1~30質量份，特佳使用2~30質量份之量。自由基聚合起始劑之使用量在少於前述範圍時，容易受到因氧所導致之自由基之去活化之影響(感度降低)，在多於前述範圍時，有相溶性變差，保存安定性降低之傾向。These radical polymerization initiators may be used singly or in combination of two or more kinds. The above-mentioned radical polymerization initiator is preferably used in an amount of 0.1 to 50 parts by mass relative to 100 parts by mass of the component (A), more preferably 1 to 30 parts by mass, and particularly preferably 2 to 30 parts by mass. When the amount of the radical polymerization initiator is less than the foregoing range, it is susceptible to the deactivation of the free radical caused by oxygen (the sensitivity is reduced). When the amount of the radical polymerization initiator is more than the foregoing range, the compatibility is deteriorated and the storage stability Sexual decline.

＜(C)成分＞ 　　本發明之硬化膜形成組成物可含有選自由具有包含C=C雙鍵之聚合性基之單體及聚合物所成群之至少一種作為(C)成分。<(C) component> 硬化 The cured film-forming composition of the present invention may contain, as the (C) component, at least one selected from the group consisting of a monomer and a polymer having a polymerizable group containing a C = C double bond.

尚且，本說明書中(甲基)丙烯酸酯化合物係指丙烯酸酯化合物與甲基丙烯酸酯化合物之雙方。例如(甲基)丙烯酸係指丙烯酸與甲基丙烯酸。又，(甲基)丙烯醯基係表示CH2 =CHCO-與CH(CH3 )=CHCO-。In addition, in this specification, a (meth) acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth) acrylic refers to acrylic and methacrylic. The (meth) acrylfluorenyl group represents CH 2 = CHCO- and CH (CH 3 ) = CHCO-.

以下，作為本發明之(C)成分具有包含C=C雙鍵之聚合性基之單體及聚合物，從提高膜強度之觀點，以1分子中具有2個以上包含C=C雙鍵之聚合性基之單體及聚合物為佳。以下，例舉適宜化合物之一例，但(C)成分並非係受限於該等例示者。Hereinafter, as the monomer (C) of the present invention, a monomer and a polymer having a polymerizable group containing a C = C double bond, from the viewpoint of improving the strength of the film, two or more molecules containing a C = C double bond are contained in one molecule. Polymerizable group monomers and polymers are preferred. Hereinafter, an example of a suitable compound is given, but the component (C) is not limited to those exemplified.

作為具有2個(甲基)丙烯醯基之化合物，可舉出例如乙二醇二(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、丙二醇二(甲基)丙烯酸酯、新戊二醇二(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、1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-已二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、2-甲基-1,8-辛二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三環[5.2.1.02,6 ]癸烷二甲醇二(甲基)丙烯酸酯、二噁烷二醇二(甲基)丙烯酸酯、2-羥基-1-丙烯醯氧基-3-甲基丙烯醯氧基丙烷、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷、參羥基乙基異三聚氰酸酯二(甲基)丙烯酸酯、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀、十一烯氧基乙二醇二(甲基)丙烯酸酯、1,3-金剛烷二醇二(甲基)丙烯酸酯、1,3-金剛烷二甲醇二(甲基)丙烯酸酯、乙氧基化雙酚A二(甲基)丙烯酸酯等。Examples of the compound having two (meth) acrylfluorenyl groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, tricyclic [ 5.2.1.0 2,6 ] Decanedimethanol di (meth) acrylate, dioxanediol di (meth) acrylate, 2-hydroxy-1-propenyloxy-3-methacrylic acid Propane, 2-hydroxy-1,3-di (meth) acryloxypropane, p-hydroxyethyl isotricyanate di (meth) acrylate, 9,9-bis [4- (2 -(Meth) acryloxyethoxy) phenyl] fluorene, undecenyloxyethylene glycol di (meth) acrylate, 1,3-adamantane di Alcohol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, and the like.

作為具有2個以上(甲基)丙烯醯基之化合物係可適宜使用市售品，可舉出例如，輕丙烯酸酯3EG-A、輕丙烯酸酯4EG-A、輕丙烯酸酯9EG-A、輕丙烯酸酯14EG-A、輕丙烯酸酯PTMGA-250、輕丙烯酸酯NP-A、輕丙烯酸酯MPD-A、輕丙烯酸酯1.6HX-A、輕丙烯酸酯1.9ND-A、輕丙烯酸酯MOD-A、輕丙烯酸酯DCP-A、輕丙烯酸酯BP-4EAL、輕丙烯酸酯BP-4PA、輕丙烯酸酯HPP-A、輕酯G-201P、輕酯P-2M、輕酯EG、輕酯2EG、輕酯3EG、輕酯4EG、輕酯9EG、輕酯14EG、輕酯1.4BG、輕酯NP、輕酯1.6HX、輕酯1.9ND、輕酯G-101P、輕酯G-201P、輕酯BP-2EMK[以上，皆為共榮社化學(股)製]；NK酯701A、同A-200、同A-400、同A-600、同A-1000、同A-B1206PE、同ABE-300、同A-BPE-10、同A-BPE-20、同A-BPE-30、同A-BPE-4、同A-BPEF、同A-BPP-3、同A-DCP、同A-DOD-N、同A-HD-N、同A-NOD-N、同APG-100、同APG-200、同APG-400、同APG-700、同A-PTMG-65、同1G、同2G、同3G、同4G、同9G、同14G、同23G、同BPE-80N、同BPE-100、同BPE-200、同BPE-500、同BPE-900、同BPE-1300N、同DCP、同DCP-N、同HD-N、同NOD-N、同NPG、同1206PE、同701、同9PG[以上，皆為新中村化學工業(股)製]；FANCRYL　FA-124AS、同FA-129AS、同FA-222A、同FA-240A、同FA-P240A、同FA-P270A、同FA-321A、同FA-324A、同FA-PTG9A、同FA-121M、同FA-124M、同FA-125M、同FA-220M、同FA-240M、同FA-320M、同FA-321M、同FA-3218M、同FA-PTG9M[以上，皆為日立化成(股)製]；DPGDA、HODA、TPGDA、EBECRYL(註冊商標)145、同150、IRR214-K、PEG400DA-D、EBECRYL(註冊商標)11、HPDNA[DAICEL-ALLNEX(股)製]；Biscoat ＃195、同＃230、同＃260、同＃310HP、同＃335HP、同＃700HV、同＃540、同＃802、同＃295[以上，皆為日本合成化學工業(股)製]等。As the compound having two or more (meth) acrylfluorenyl groups, commercially available products can be suitably used, and examples thereof include light acrylate 3EG-A, light acrylate 4EG-A, light acrylate 9EG-A, and light acrylic acid. Ester 14EG-A, light acrylate PTMGA-250, light acrylate NP-A, light acrylate MPD-A, light acrylate 1.6HX-A, light acrylate 1.9ND-A, light acrylate MOD-A, light Acrylate DCP-A, Light Acrylate BP-4EAL, Light Acrylate BP-4PA, Light Acrylate HPP-A, Light Ester G-201P, Light Ester P-2M, Light Ester EG, Light Ester 2EG, Light Ester 3EG , Light Ester 4EG, Light Ester 9EG, Light Ester 14EG, Light Ester 1.4BG, Light Ester NP, Light Ester 1.6HX, Light Ester 1.9ND, Light Ester G-101P, Light Ester G-201P, Light Ester BP-2EMK [ The above are all Gongrongsha Chemical Co., Ltd.]; NK ester 701A, the same A-200, the same A-400, the same A-600, the same A-1000, the same A-B1206PE, the same ABE-300, the same A -BPE-10, same as A-BPE-20, same as A-BPE-30, same as A-BPE-4, same as A-BPEF, same as A-BPP-3, same as A-DCP, same as A-DOD-N, Same as A-HD-N, same as A-NOD-N, same as APG-100, same as APG-200, same as APG-400, same as APG-700, same as A-PTMG-65, same as 1G, same as 2G, same as 3G, Same as 4G, same as 9G, same as 14 G, same as 23G, same as BPE-80N, same as BPE-100, same as BPE-200, same as BPE-500, same as BPE-900, same as BPE-1300N, same as DCP, same as DCP-N, same as HD-N, and same as NOD -N, same as NPG, same as 1206PE, same as 701, and same as 9PG [above, all are made by Xinzhongcun Chemical Industry Co., Ltd.]; FANCRYL FA-124AS, same FA-129AS, same FA-222A, same FA-240A, same FA-P240A, same FA-P270A, same FA-321A, same FA-324A, same FA-PTG9A, same FA-121M, same FA-124M, same FA-125M, same FA-220M, same FA-240M, same FA-320M, same FA-321M, same FA-3218M, same FA-PTG9M [above, all are Hitachi Chemical Co., Ltd.]; DPGDA, HODA, TPGDA, EBECRYL (registered trademark) 145, same 150, IRR214-K PEG400DA-D, EBECRYL (registered trademark) 11, HPDNA [DAICEL-ALLNEX (share) system]; Biscoat # 195, same # 230, same # 260, same # 310HP, same # 335HP, same # 700HV, same # 540 , Same # 802, Same # 295 [above, all are made by Japan Synthetic Chemical Industry (stock)] and so on.

作為具有3個(甲基)丙烯醯基之化合物(3官能化合物)，可舉出例如，環氧乙烷變性1,1,1-三羥甲基乙烷三(甲基)丙烯酸酯[環氧乙烷加成莫耳數3~30]、環氧乙烷變性三羥甲基丙烷三(甲基)丙烯酸酯[環氧乙烷加成莫耳數3~30]、環氧丙烷變性三羥甲基丙烷三(甲基)丙烯酸酯[環氧丙烷加成莫耳數3~30]、環氧乙烷變性丙三醇三(甲基)丙烯酸酯[環氧乙烷加成莫耳數3~30]、環氧丙烷變性丙三醇三(甲基)丙烯酸酯[環氧丙烷加成莫耳數3~30]、參(2-(丙烯醯氧基)乙基)異三聚氰酸酯、ε-己內酯變性參(2-(丙烯醯氧基)乙基)異三聚氰酸酯[ε-己內酯加成莫耳數1~30]、1,1,1-三羥甲基乙烷三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、貳三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯等。Examples of the compound (trifunctional compound) having three (meth) acrylfluorenyl groups include, for example, ethylene oxide-denatured 1,1,1-trimethylolethane tri (meth) acrylate [cyclo Ethylene oxide addition mole number 3 ~ 30], ethylene oxide modified trimethylolpropane tri (meth) acrylate [ethylene oxide addition mole number 3 ~ 30], propylene oxide modified three Methylolpropane tri (meth) acrylate [propylene oxide addition mole number 3 to 30], ethylene oxide modified glycerol tri (meth) acrylate [ethylene oxide addition mole number 3 ~ 30], propylene oxide modified glycerol tri (meth) acrylate [propylene oxide addition mol number 3 ~ 30], ginseng (2- (propenyloxy) ethyl) isocyanuric acid Acid ester, ε-caprolactone denatured ginseng (2- (propenyloxy) ethyl) isocyanurate [ε-caprolactone addition mol number 1 to 30], 1,1,1- Trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Glycerol tri (meth) acrylate and the like.

上述3官能化合物係可適宜使用市售品，可舉出例如Biscoat ＃360[大阪有機化學工業(股)製]；NK酯A-GLY-9E、同A-GLY-20E、同AT-20E[以上，皆為新中村化學工業(股)製]；TMPEOTA、OTA480、EBECRYL(註冊商標)135[以上，皆為DAICEL-ALLNEX(股)製]、Biscoat ＃295、同＃300[以上，皆為大阪有機化學工業(股)製]；輕丙烯酸酯TMP-A、同PE-3A、輕酯TMP[以上，皆為共榮社化學(股)製]；NK酯A-9300、同A-9300-1CL、同A-TMM-3、同A-TMM-3L、同A-TMM-3LM-N、同A-TMPT、同TMPT[以上，皆為新中村化學工業(股)製]；PETIA、PETRA、TMPTA、EBECRYL(註冊商標)180[以上，皆為DAICEL-ALLNEX(股)製]等。As the trifunctional compound, commercially available products can be suitably used, and examples thereof include Biscoat # 360 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; NK ester A-GLY-9E, same as A-GLY-20E, and AT-20E [ The above are all made by Shin Nakamura Chemical Industry Co., Ltd .; TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [above, all are made by DAICEL-ALLNEX (share)], Biscoat # 295, same # 300 [above, all are Osaka Organic Chemical Industry Co., Ltd.]; light acrylate TMP-A, same as PE-3A, light ester TMP [above, all by Kyoeisha Chemical Co., Ltd.]; NK ester A-9300, same as A-9300 -1CL, the same A-TMM-3, the same A-TMM-3L, the same A-TMM-3LM-N, the same A-TMPT, the same TMPT [above, all are from the Nakamura Chemical Industry (stock) system]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [above, all are made by DAICEL-ALLNEX (shares)] and so on.

作為具有4個(甲基)丙烯醯基之化合物(4官能化合物)，可舉出例如，環氧乙烷變性貳三羥甲基丙烷四(甲基)丙烯酸酯[環氧乙烷加成莫耳數4~40]、環氧乙烷變性季戊四醇四(甲基)丙烯酸酯[環氧乙烷加成莫耳數4~40]、貳三羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等。Examples of the compound (four functional compounds) having four (meth) acrylfluorenyl groups include, for example, ethylene oxide denatured trimethylolpropane tetra (meth) acrylate [ethylene oxide addition molybdenum] Ear number 4 to 40], ethylene oxide denatured pentaerythritol tetra (meth) acrylate [ethylene oxide addition mole number 4 to 40], trimethylolpropane tetra (meth) acrylate, pentaerythritol Tetra (meth) acrylate and the like.

上述4官能化合物係可適宜使用市售品，可舉出例如NK酯ATM-4E、同ATM-35E[以上，皆為新中村化學工業(股)製]；EBECRYL(註冊商標)40[DAICEL-ALLNEX(股)製]等、Biscoat ＃300[大阪有機化學工業(股)製]；輕丙烯酸酯PE-4A[共榮社化學(股)製]；NK酯AD-TMP、同A-TMMT[以上，皆為新中村化學工業(股)製]；EBECRYL(註冊商標)140、同1142、同180[以上，皆為DAICEL-ALLNEX(股)製]等。Commercially available products of the above-mentioned tetrafunctional compounds are suitable, and examples thereof include NK ester ATM-4E and the same ATM-35E [above, all manufactured by Shin Nakamura Chemical Industry Co., Ltd.]; ALLNEX (stock) system], Biscoat # 300 [Osaka Organic Chemical Industry (stock) system]; light acrylate PE-4A [Kyoeisha Chemical (stock) system]; NK ester AD-TMP, same as A-TMMT [ The above are the new Nakamura Chemical Industry (share) system]; EBECRYL (registered trademark) 140, the same 1142, the same 180 [above, all are DAICEL-ALLNEX (share) system] and so on.

作為具有5個以上(甲基)丙烯醯基之化合物(5官能以上之化合物)，可舉出例如，環氧乙烷變性二季戊四醇六(甲基)丙烯酸酯[環氧乙烷加成莫耳數6~60]、環氧乙烷變性三季戊四醇八(甲基)丙烯酸酯[環氧乙烷加成莫耳數6~60]、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯等。Examples of the compound having five or more (meth) acrylfluorenyl groups (a compound having five or more functions) include, for example, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate [ethylene oxide addition mole Number 6 ~ 60], ethylene oxide denatured tripentaerythritol octa (meth) acrylate [ethylene oxide addition mole number 6 ~ 60], dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (methyl) Group) acrylate, tripentaerythritol octa (meth) acrylate, and the like.

上述5官能以上之化合物係可適宜使用市售品，可舉出例如，NK酯A-DPH-12E[新中村化學工業(股)製]、Biscoat ＃802[大阪有機化學工業(股)製]；輕丙烯酸酯DPE-6A[共榮社化學(股)製]；NK酯A-9550、同A-DPH[以上，皆為新中村化學工業(股)製]；DPHA[DAICEL-ALLNEX(股)製]等。Commercially available products of the above 5-functional compounds are suitable, and examples thereof include NK ester A-DPH-12E [manufactured by Shin Nakamura Chemical Industry Co., Ltd.], Biscoat # 802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.] ; Light acrylate DPE-6A [Kyoeisha Chemical Co., Ltd.]; NK ester A-9550, same as A-DPH [above, all are made by Shin Nakamura Chemical Industry Co., Ltd.]; DPHA [DAICEL-ALLNEX (shares ) System] and so on.

作為2官能胺基甲酸酯(甲基)丙烯酸酯，可舉出例如，苯基環氧丙基醚之(甲基)丙烯酸加成物與六亞甲基二異氰酸酯之胺基甲酸酯化物、苯基環氧丙基醚之(甲基)丙烯酸加成物與甲苯二異氰酸酯之胺基甲酸酯化物。Examples of the bifunctional urethane (meth) acrylate include (meth) acrylic acid adducts of phenylglycidyl ether and urethane products of hexamethylene diisocyanate. (Phenyl glycidyl ether) (meth) acrylic acid adduct and toluene diisocyanate urethane.

上述2官能胺基甲酸酯(甲基)丙烯酸酯係可適宜使用市售品，可舉出例如AH-600、AT-600[以上，皆為共榮社化學(股)製]；NK Oligo U-2PPA、同U-200PA、同UA-160TM、同UA-290TM、同UA-4200、同UA-4400、同UA-122P、同UA-W2A[以上，皆為新中村化學工業(股)製]；EBECRYL(註冊商標)210、同215、同230、同244、同245、同270、同280／15IB、同284、同285、同4858、同8307、同8402、同8411、同8804、同8807、同9227EA、同9270、KRM(註冊商標)7735[以上，皆為DAICEL-ALLNEX(股)製]；紫光(註冊商標)UV-6630B、同7000B、同7461TE、同2000B、同2750B、同3000、同3200B、同3210EA、同3300B、同3310B、同3500BA、同3520TL、同3700B、同6640B[以上，皆為日本合成化學工業(股)製]等。Commercially available commercially available bifunctional urethane (meth) acrylates are suitable, and examples include AH-600 and AT-600 [above, all manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-2PPA, same as U-200PA, same as UA-160TM, same as UA-290TM, same as UA-4200, same as UA-4400, same as UA-122P, and same as UA-W2A [above, all are Xinzhongcun Chemical Industry Co., Ltd. System]; EBECRYL (registered trademark) 210, same 215, same 230, same 244, same 245, same 270, same 280 / 15IB, same 284, same 285, same 4858, same 8307, same 8402, same 8411, and 8804 , The same 8807, the same 9227EA, the same 9270, the KRM (registered trademark) 7735 [above, all are made by DAICEL-ALLNEX (shares)]; Ziguang (registered trademark) UV-6630B, the same 7000B, the same 7461TE, the same 2000B, the same 2750B , The same 3000, the same 3200B, the same 3210EA, the same 3300B, the same 3310B, the same 3500BA, the same 3520TL, the same 3700B, and the same 6640B [above, all made by Japan Synthetic Chemical Industry (stock) system] and so on.

作為具有3個(甲基)丙烯醯基之多官能胺基甲酸酯(甲基)丙烯酸酯化合物之市售品之具體例，可舉出如NK Oligo UA-7100[新中村化學工業(股)製]；EBECRYL(註冊商標)204、同205、同264、同265、同294／25HD、同1259、同4820、同8311、同8465、同8701、同9260、KRM(註冊商標)8296、同8667[以上，皆為DAICEL-ALLNEX(股)製]；紫光(註冊商標)UV-7550B、同7000B、同7510B、同7461TE、同2750B[以上，皆為日本合成化學工業(股)製]等。As a specific example of a commercially available product of a polyfunctional urethane (meth) acrylate compound having three (meth) acrylfluorenyl groups, NK Oligo UA-7100 [Sinakamura Chemical Industry Co., Ltd. )]; EBECRYL (registered trademark) 204, the same 205, the same 264, the same 265, the same 294 / 25HD, the same 1259, the same 4820, the same 8111, the same 8465, the same 8701, the 9260, KRM (registered trademark) 8296, Same as 8667 [above, all made by DAICEL-ALLNEX (stock)]; Ziguang (registered trademark) UV-7550B, the same 7000B, the same 7510B, the same 7461TE, and the same 2750B [above, all made by Japan Synthetic Chemical Industry (stock)] Wait.

作為具有4個(甲基)丙烯醯基之多官能胺基甲酸酯(甲基)丙烯酸酯化合物之市售品之具體例，可舉出如EBECRYL(註冊商標)8210、同8405、KRM(註冊商標)8528[以上，皆為DAICEL-ALLNEX(股)製]；紫光(註冊商標)UV-7650B[日本合成化學工業(股)製]等。Specific examples of commercially available products of polyfunctional urethane (meth) acrylate compounds having four (meth) acrylfluorenyl groups include EBECRYL (registered trademark) 8210, the same as 8405, KRM ( (Registered trademark) 8528 [above, all made by DAICEL-ALLNEX (stock)]; Ziguang (registered trademark) UV-7650B [made by Japan Synthetic Chemical Industry (stock)] and so on.

作為具有5個以上(甲基)丙烯醯基之多官能胺基甲酸酯(甲基)丙烯酸酯化合物(5官能以上之胺基甲酸酯(甲基)丙烯酸酯)，可舉出例如，季戊四醇三(甲基)丙烯酸酯與六亞甲基二異氰酸酯之胺基甲酸酯化物、季戊四醇三(甲基)丙烯酸酯與甲苯二異氰酸酯之胺基甲酸酯化物、季戊四醇三(甲基)丙烯酸酯與異佛爾酮二異氰酸酯之胺基甲酸酯化物、二季戊四醇五(甲基)丙烯酸酯與六亞甲基二異氰酸酯之胺基甲酸酯化物等。Examples of the polyfunctional urethane (meth) acrylate compound having 5 or more (meth) acrylfluorenyl groups (5 or more functional urethane (meth) acrylate) include, for example, Carbamates of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate, carbamates of pentaerythritol tri (meth) acrylate and toluene diisocyanate, pentaerythritol tri (meth) acrylic acid Carbamates of esters and isophorone diisocyanates, carbamates of dipentaerythritol penta (meth) acrylate and hexamethylene diisocyanate, and the like.

上述5官能以上之胺基甲酸酯(甲基)丙烯酸酯係可適宜使用市售品，可舉出例如，UA-306H、UA-306T、UA-306I、UA-510H[以上，皆為共榮社化學(股)製]；NK Oligo U-6LPA、同U-10HA、同U-10PA、同U-1100H、同U-15HA、同UA-53H、同UA-33H[以上，皆為新中村化學工業(股)製]；EBECRYL(註冊商標)220、同1290、同5129、同8254、同8301R、KRM(註冊商標)8200、同8200AE、同8904、同8452[以上，皆為DAICEL-ALLNEX(股)製]；紫光(註冊商標)UV-1700B、同6300B、同7600B、同7605B、同7610B、同7620EA、同7630B、同7640B、同7650B[以上，皆為日本合成化學工業(股)製]等。Commercially available commercially available urethane (meth) acrylates of the above-mentioned five or more functions can be suitably used, and examples thereof include UA-306H, UA-306T, UA-306I, and UA-510H [above, all are common Rongshe Chemical Co., Ltd.]; NK Oligo U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA-33H [above, all new Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 220, same as 1290, same as 5129, same as 8254, same as 8301R, KRM (registered trademark) 8200, same as 8200AE, same as 8904, and 8452 [above, all are DAICEL- ALLNEX (share) system]; Ziguang (registered trademark) UV-1700B, same 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B [above, all are from Japan Synthetic Chemical Industry (stock ) System] and so on.

本發明之(C)成分可為、分子內具有1個以上末端為聚合性不飽和鍵之側鏈的高分子化合物。作為此種具有末端為聚合性不飽和鍵之側鏈的高分子化合物，較佳可舉出在分子內之2個以上之側鏈具有(甲基)丙烯醯基之高分子化合物。The component (C) of the present invention may be a polymer compound having at least one side chain having a polymerizable unsaturated bond at the end in the molecule. As such a polymer compound having a side chain having a polymerizable unsaturated bond at its terminal, a polymer compound having a (meth) acrylfluorenyl group in two or more side chains in the molecule is preferable.

作為上述高分子化合物，可舉出如胺基甲酸酯丙烯醯基系、環氧基丙烯醯基系、各種(甲基)丙烯酸酯系等之含有1個以上(甲基)丙烯醯基之高分子化合物。Examples of the above-mentioned polymer compounds include urethane acryl based systems, epoxy acryl based systems, various (meth) acrylic based systems containing one or more (meth) acryl based groups Polymer compounds.

(C)成分之高分子化合物之重量平均分子量係以1,000~200,000為佳，較佳為5,000~50,000。分子量未滿1,000時，有不會達成本發明之效果的情況。另一方面，分子量若為超過100,000之過大者時，有不溶解於組成物的情況。The weight average molecular weight of the polymer compound of the component (C) is preferably 1,000 to 200,000, and more preferably 5,000 to 50,000. When the molecular weight is less than 1,000, the effects of the present invention may not be achieved. On the other hand, when the molecular weight is too large exceeding 100,000, it may not be dissolved in the composition.

作為此種(C)成分之化合物，可舉出例如，Acrit 8BR-930M、同8UH-1006、同8KQ-2001、同8KX-078、同1SX-1055[以上，大成精細化工股份有限公司製]、SMP-250A、SMP-360A、SMP-550A[以上，共榮社化學股份有限公司製]等之聚合物。Examples of the compound of the component (C) include, for example, Acrit 8BR-930M, the same as 8UH-1006, the same as 8KQ-2001, the same as 8KX-078, and the same as 1SX-1055 [above, manufactured by Dacheng Fine Chemical Co., Ltd.] , SMP-250A, SMP-360A, SMP-550A [above, manufactured by Kyoeisha Chemical Co., Ltd.] and other polymers.

在含有(C)成分時之含量係基於(A)成分之100質量份為10質量份至1000質量份，以15質量份至500質量份為佳。The content when the component (C) is contained is based on 100 parts by mass of the component (A) and is preferably 10 parts by mass to 1,000 parts by mass, and preferably 15 parts by mass to 500 parts by mass.

＜溶劑＞ 　　本發明之硬化膜形成組成物主要係在溶解於溶劑之溶液狀態下使用。此時使用之溶劑只要係能溶解(A)成分、(B)成分、因應必要之(C)成分及／或後述之其他添加劑即可，其之種類及構造等並非係受到特別限定者。<Solvent> The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at this time is only required to be capable of dissolving the component (A), the component (B), the necessary component (C) and / or other additives described later, and the type and structure thereof are not particularly limited.

作為溶劑之具體例，可舉出例如，甲醇、乙醇、n-丙醇、異丙醇、n-丁醇、異丁醇、2-甲基-1-丁醇、n-戊醇、乙二醇單甲基醚、乙二醇單乙基醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚、丙二醇丙基醚、丙二醇丙基醚乙酸酯、甲苯、茬、甲基乙基酮、異丁基甲基酮、環戊酮、環己酮、2-丁酮、3-甲基-2-戊酮、2-戊酮、2-庚酮、γ-丁內酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、環戊基甲基醚、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、及N-甲基-2-吡咯啶酮等。Specific examples of the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, and ethylene glycol. Alcohol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, stubble, methyl ethyl ketone , Isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropionic acid Ethyl acetate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, lactic acid Ethyl ester, butyl lactate, cyclopentyl methyl ether, N, N-dimethylformamide, N, N-dimethylacetamidine And N- methyl-2-pyrrolidone, and the like.

在使用本發明之硬化膜形成組成物，於樹脂膜上形成硬化膜而製造定向材料時，在從對樹脂膜展現耐性之溶劑的觀點，以甲醇、乙醇、n-丙醇、異丙醇、n-丁醇、2-甲基-1-丁醇、2-庚酮、異丁基甲基酮、二乙二醇、丙二醇、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯等為佳。When the hardened film forming composition of the present invention is used to form a hardened film on a resin film to produce an oriented material, from the viewpoint of a solvent exhibiting resistance to the resin film, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferred.

此等溶劑係可單獨使用1種，或可使用2種以上之組合。These solvents may be used singly or in combination of two or more kinds.

＜其他添加劑＞ 　　並且，本發明之硬化膜形成組成物在不損及本發明之效果範圍內，因應必要亦可含有增感劑、密著向上劑、矽烷耦合劑、界面活性劑、流變調整劑、顏料、染料、保存安定劑、消泡劑、防氧化劑等。<Other additives> In addition, the hardened film-forming composition of the present invention may contain a sensitizer, an adhesion-upward agent, a silane coupling agent, a surfactant, and a rheological adjustment agent, if necessary, within a range that does not impair the effects of the present invention. Agents, pigments, dyes, storage stabilizers, defoamers, antioxidants, etc.

＜硬化膜形成組成物之調製＞ 　　本發明之硬化膜形成組成物為含有(A)成分之具有垂直定向性基與包含C=C雙鍵之聚合性基之聚合物、(B)成分之聚合起始劑，且含有 因應所需之(C)成分之選自由具有包含C=C雙鍵之聚合性基之單體及聚合物所成群之至少一種，並且在不損及本發明之效果範圍內，可含有其他添加劑之組成物。又通常係使用作為該等溶解於溶劑之溶液形態。<Preparation of hardened film-forming composition> 硬化 The hardened film-forming composition of the present invention is a polymer containing a vertical alignment group containing the component (A) and a polymerizable group containing a C = C double bond, and a polymerization of the component (B) An initiator and containing at least one component (C) as required, selected from the group consisting of monomers and polymers having a polymerizable group containing a C = C double bond, and without impairing the effect of the present invention Within the scope, a composition containing other additives may be included. It is usually used in the form of a solution dissolved in a solvent.

本發明之硬化膜形成組成物之較佳例係如以下所示。 　　[1]：含有(A)成分、基於(A)成分100質量份為0.1質量份~50質量份之(B)成分的硬化膜形成組成物。 　　[2]：(A)成分、基於(A)成分100質量份為0.1質量份~50質量份之(B)成分、基於(A)成分100質量份為10質量份~1000質量份之(C)成分，以及溶劑的硬化膜形成組成物。Preferred examples of the cured film-forming composition of the present invention are as follows. [1]: A hardened film forming composition containing the component (A) and containing the component (B) in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the component (A). [2]: (A) component, 0.1 to 50 parts by mass of (B) component based on 100 parts by mass of (A) component, (C) 10 to 1000 parts by mass based on 100 parts by mass of (A) component ) Components, and a solvent-cured film-forming composition.

在使用本發明之硬化膜形成組成物作為溶液時之調配比例、調製方法等係如以下所詳述。 　　本發明之硬化膜形成組成物中之固體成分之比例只要各成分均勻地溶解於溶劑，即並非係受到特別限定者，為1質量%~60質量%，以2質量%~50質量%為佳，較佳為2質量%~20質量%。在此，固體成分係指從硬化膜形成組成物之全部成分去除溶劑者。When using the cured film-forming composition of the present invention as a solution, the formulation ratio, preparation method, and the like are described in detail below. As long as the proportion of the solid component in the hardened film forming composition of the present invention is uniformly dissolved in the solvent, that is, it is not particularly limited, it is 1% to 60% by mass, and preferably 2% to 50% by mass. , Preferably from 2% by mass to 20% by mass. Here, the solid content means a solvent that is removed from all the components of the cured film-forming composition.

本發明之硬化膜形成組成物之調製方法並無特別限定。作為調製法，可舉出例如，對溶解於溶劑之(A)成分之溶液，以規定之比例混合(B)成分，以及(C)成分等而作成均勻溶液之方法，或，在該調製法之適當段階中，因應必要更添加其他添加劑進行混合之方法。The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method in which a solution of the component (A) dissolved in a solvent is mixed with a predetermined ratio of the component (B) and the component (C) to prepare a homogeneous solution. In the appropriate stage, if necessary, other additives are added for mixing.

又，經調製之硬化膜形成組成物之溶液係以使用孔徑0.2μm程度之過濾器等進行過濾後才使用為佳。The solution of the prepared hardened film-forming composition is preferably used after filtering with a filter having a pore size of about 0.2 μm or the like.

＜硬化膜、定向材料及相位差材料＞ 　　將本發明之硬化膜形成組成物之溶液在基板(例如，矽／二酸化矽被覆基板、氮化矽基板、經金屬例如，鋁、鉬、鉻等所被覆之基板、玻璃基板、石英基板、ITO基板等)或膜基板(例如，三乙醯基纖維素(TAC)膜、聚碳酸酯(PC)膜、環烯烴聚合物(COP)膜、環烯烴共聚物(COC)膜、聚對酞酸乙二酯(PET)膜、丙烯酸膜、聚乙烯膜等之樹脂膜)等之上，藉由棒塗佈、旋轉塗佈、流延塗佈、輥塗佈、狹縫塗佈、狹縫塗佈後接續旋轉塗佈、噴墨塗佈、印刷等進行塗佈來形成塗膜，其後藉由加熱板或烤箱等進行加熱乾燥，而可形成硬化膜。該硬化膜係可直接適用當作定向材料。<Hardened film, orientation material, and retardation material> The solution of the hardened film forming composition of the present invention is placed on a substrate (for example, a silicon / diacid-coated substrate, a silicon nitride substrate, or a metal such as aluminum, molybdenum, chromium, or the like). Covered substrate, glass substrate, quartz substrate, ITO substrate, etc.) or film substrate (for example, triethyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin Copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene film and other resin films), etc., by bar coating, spin coating, cast coating, roll Coating, slit coating, slit coating, followed by spin coating, inkjet coating, printing, etc. to form a coating film, and then heating and drying by a hot plate or oven to form a hardening membrane. This hardened film system can be directly used as an orientation material.

作為加熱乾燥之條件，在硬化膜(定向材料)之成分不會析出至塗佈於其上之聚合性液晶溶液之程度，使由交聯劑所成之交聯反應進行即可，可採用例如，從溫度60℃~200℃、時間0.4分鐘~60分鐘之範圍當中適宜選擇之加熱溫度及加熱時間。加熱溫度及加熱時間係以70℃~160℃，0.5分鐘~10分鐘為佳。As a condition for heating and drying, it is sufficient that the cross-linking reaction formed by the cross-linking agent proceeds so that the components of the cured film (orientation material) do not precipitate to the polymerizable liquid crystal solution applied thereon. , Suitable heating temperature and heating time from the range of temperature 60 ℃ ~ 200 ℃, time 0.4 minutes ~ 60 minutes. The heating temperature and heating time are preferably 70 ° C to 160 ° C, preferably 0.5 minutes to 10 minutes.

使用本發明之硬化性組成物所形成之硬化膜(定向材料)之膜厚為例如0.05μm~5μm，可考慮到使用之基板之階段差或光學性、電性質後適宜選擇。The film thickness of the cured film (orientation material) formed by using the curable composition of the present invention is, for example, 0.05 μm to 5 μm, and may be appropriately selected in consideration of the step difference of the substrate to be used, or optical and electrical properties.

由本發明之硬化膜組成物所形成之定向材料由於具有耐溶劑性及耐熱性，故在此定向材料上塗佈具有垂直定向性之聚合性液晶溶液等之相位差材料，可在定向材料上使其定向。且，藉由使已成為定向狀態之相位差材料直接硬化，即可形成相位差材料作為具有光學異方性之層。又，形成定向材料之基板為膜時，則變得能有用當作相位差膜。Since the alignment material formed of the hardened film composition of the present invention has solvent resistance and heat resistance, a phase difference material such as a polymerizable liquid crystal solution having vertical alignment is coated on the alignment material, and the alignment material can be applied to the alignment material. Its orientation. In addition, by directly hardening the phase difference material that has been oriented, a phase difference material can be formed as a layer having optical anisotropy. When the substrate on which the alignment material is formed is a film, it becomes useful as a retardation film.

又，也可使用具有如上述所形成之本發明之定向材料之2枚基板，隔著間隔器，使兩基板上之定向材料互相面對貼合後，在該等基板之間注入液晶，而作成液晶經定向之液晶顯示元件。 　　因此，本發明之硬化膜形成組成物係適宜使用於製造各種相位差材料(相位差膜)或液晶顯示元件等。 [實施例]Alternatively, two substrates having the alignment material of the present invention formed as described above may be used, and the alignment materials on the two substrates may be bonded to each other via a spacer, and then liquid crystal may be injected between the substrates, and A liquid crystal display device in which the liquid crystal is oriented. Therefore, the cured film-forming composition of the present invention is suitably used for manufacturing various retardation materials (phase retardation films), liquid crystal display devices, and the like. [Example]

以下，例舉本發明之實施例，具體地說明本發明，但本發明並非係受到該等所限定而解釋者。 [實施例使用之省略記號] 　　以下之實施例使用之省略記號之意義係如以下所示。Hereinafter, examples of the present invention are exemplified, and the present invention is specifically described, but the present invention is not limited by these explanations. [Omitted Symbols Used in Examples] 意义 The meaning of the omitted symbols used in the following examples is as follows.

＜A成分之原料＞ 　　LAA：月桂基丙烯酸酯 　　PAA：棕櫚基丙烯酸酯 　　HEMA：2-羥基乙基甲基丙烯酸酯 　　GMA：環氧丙基甲基丙烯酸酯 　　AOI：昭和電工(股)製Karenz AOI 　　AIBN：α,α’-偶氮二異丁腈 　　LA：月桂基酸 　　M100：3,4-環氧基環己基甲基甲基丙烯酸酯 　　5PCA：4-(4-戊基環己基)安息香酸<Raw materials of component A> LAA: Lauryl acrylate PAA: Palmyl acrylate HEMA: 2-hydroxyethyl methacrylate GMA: Glycidyl methacrylate AOI: Karenz AOI manufactured by Showa Denko Corporation AIBN : Α, α'-azobisisobutyronitrile LA: Lauryl acid M100: 3,4-epoxycyclohexyl methyl methacrylate 5PCA: 4- (4-pentylcyclohexyl) benzoic acid

＜B成分＞ 　　IRG：BASF公司製 IRGACURE 907 　　OXE：BASF公司製 IRGACURE OXE 02<Component B> IRG: IRGACURE 907 manufactured by BASF Corporation OXE: IRGACURE OXE 02 manufactured by BASF Corporation

＜C成分＞ 　　DPHA：DAICEL-ALLNEX(股)製 二季戊四醇六丙烯酸酯 　　SMP：共榮社化學(股)製 UV硬化型丙烯酸聚合物 SMP-550A<Component C> DPHA: DIPEL-ALLNEX (stock) dipentaerythritol hexaacrylate SMP: Kyoeisha Chemical Co., Ltd. UV-curable acrylic polymer SMP-550A

＜其他＞ 　　MAA：甲基丙烯酸 　　CYM303：六甲氧基甲基三聚氰胺 　　PTSA：p-甲苯磺酸・一水合物<Others> MAA: methacrylic acid CYM303: hexamethoxymethyl melamine PTSA: p-toluenesulfonic acid · monohydrate

＜溶劑＞ 　　實施例及比較例之各硬化膜形成組成物為含有溶劑，該溶劑係使用丙二醇單甲基醚(PM)、乙酸丁酯(BA)、乙酸乙酯(EA)。<Solvent> 硬化 Each of the cured film-forming compositions of Examples and Comparative Examples contains a solvent, and the solvent is propylene glycol monomethyl ether (PM), butyl acetate (BA), or ethyl acetate (EA).

＜聚合物之分子量之測量＞ 　　聚合例中之丙烯酸共聚物之分子量係使用(股)Shodex公司製常溫凝膠滲透層析(GPC)裝置(GPC-101)、Shodex公司製管柱(KD-803、KD-805)藉由如以下之操作來測量。 　　尚且，下述之數平均分子量(以下稱為Mn)及重量平均分子量(以下稱為、Mw)係以聚苯乙烯換算值來表示。 　　管柱溫度：50℃ 　　溶析液：N,N-二甲基甲醯胺(作為添加劑，溴化鋰-水合物(LiBr・H2 O)為30mmol／L，磷酸・無水結晶(o-磷酸)為30mmol／L，四氫呋喃(THF)為10mL／L) 　　流速：1.0mL／分 　　檢量線作成用標準試樣：東曹公司製TSK標準聚環氧乙烷(分子量約900,000、150,000、100,000、30,000)、及、聚合物實驗室公司製聚乙二醇(分子量約12,000、4,000、1,000)。<Measurement of the molecular weight of the polymer> The molecular weight of the acrylic copolymer in the polymerization example was obtained by using a normal temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Shodex Corporation and a column (KD-803) manufactured by Shodex Corporation. (KD-805) is measured by the following operation. The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene. Column temperature: 50 ℃ Eluent: N, N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr · H 2 O) is 30mmol / L, phosphoric acid · anhydrous crystal (o-phosphoric acid) is 30mmol / L, Tetrahydrofuran (THF) is 10mL / L) Flow rate: 1.0mL / Separation calibration line standard sample: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation Polyethylene glycol (molecular weight approximately 12,000, 4,000, 1,000) manufactured by Polymer Labs.

＜聚合例1＞ 　　使LAA 3.0g、GMA 12.0g、作為聚合觸媒之AIBN 0.3g溶解於PM 45.7g，藉由在80℃中使其反應20小時而取得丙烯酸共聚物溶液。使取得之丙烯酸共聚物溶液徐徐地滴入己烷500.0g中而使固體析出，藉由過濾及減壓乾燥而取得丙烯酸共聚物(P1)。取得之丙烯酸共聚物之Mn為14,000，Mw為38,000。<Polymerization Example 1> 3.0 g of LAA, 12.0 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in PM 45.7 g, and the acrylic copolymer solution was obtained by reacting at 80 ° C for 20 hours. The obtained acrylic copolymer solution was slowly dropped into 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P1) was obtained by filtration and drying under reduced pressure. The obtained acrylic copolymer had Mn of 14,000 and Mw of 38,000.

＜聚合例2＞ 　　使PAA 3.0g、GMA 12.0g、作為聚合觸媒之AIBN 0.3g溶解於PM 45.7g，藉由在80℃中使其反應20小時而取得丙烯酸共聚物溶液。使取得之丙烯酸共聚物溶液徐徐地滴入己烷500.0g中而使固體析出，藉由過濾及減壓乾燥而取得丙烯酸共聚物(P2)。取得之丙烯酸共聚物之Mn為12,000，Mw為30,000。<Polymerization Example 2> 3.0 g of PAA, 12.0 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM, and an acrylic copolymer solution was obtained by reacting at 80 ° C for 20 hours. The obtained acrylic copolymer solution was slowly dropped into 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P2) was obtained by filtration and drying under reduced pressure. The obtained acrylic copolymer had Mn of 12,000 and Mw of 30,000.

＜聚合例3＞ 　　使LAA 3.0g、HEMA 12.0g、作為聚合觸媒之AIBN 0.3g溶解於PM 45.7g，藉由在80℃中使其反應20小時而取得丙烯酸共聚物溶液。使取得之丙烯酸共聚物溶液徐徐地滴入己烷500.0g中而使固體析出，藉由過濾及減壓乾燥而取得丙烯酸共聚物(P3)。取得之丙烯酸共聚物之Mn為8,600，Mw為20,000。<Polymerization Example 3> 3.0 3.0 g of LAA, 12.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM, and an acrylic copolymer solution was obtained by reacting at 80 ° C for 20 hours. The obtained acrylic copolymer solution was slowly dropped into 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P3) was obtained by filtration and drying under reduced pressure. The obtained acrylic copolymer had a Mn of 8,600 and a Mw of 20,000.

＜聚合例4＞ 　　使LAA 1.5g、GMA 13.5g、作為聚合觸媒之AIBN 0.3g溶解於PM 45.7g，藉由在80℃中使其反應20小時而取得丙烯酸共聚物溶液。使取得之丙烯酸共聚物溶液徐徐地滴入己烷500.0g中而使固體析出，藉由過濾及減壓乾燥而取得丙烯酸共聚物(P4)。取得之丙烯酸共聚物之Mn為15,000，Mw為32,000。<Polymerization Example 4> 1.5 g of LAA, 13.5 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM, and an acrylic copolymer solution was obtained by reacting them at 80 ° C for 20 hours. The obtained acrylic copolymer solution was slowly dropped into 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P4) was obtained by filtration and drying under reduced pressure. The obtained acrylic copolymer had Mn of 15,000 and Mw of 32,000.

＜聚合例5＞ 　　使LAA 4.5g、GMA 10.5g、作為聚合觸媒之AIBN 0.3g溶解於PM 45.7g，藉由在80℃中使其反應20小時而取得丙烯酸共聚物溶液。使取得之丙烯酸共聚物溶液徐徐地滴入己烷500.0g中而使固體析出，藉由過濾及減壓乾燥而取得丙烯酸共聚物(P5)。取得之丙烯酸共聚物之Mn為14,000，Mw為31,000。<Polymerization Example 5> 4.5 g of LAA, 10.5 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM, and the acrylic copolymer solution was obtained by reacting at 80 ° C for 20 hours. The obtained acrylic copolymer solution was gradually dropped into 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P5) was obtained by filtration and drying under reduced pressure. The obtained acrylic copolymer had Mn of 14,000 and Mw of 31,000.

＜聚合例6＞ 　　使M100 10.0g、作為聚合觸媒之AIBN 0.4g溶解於PM 46.4g,藉由在80℃中使其反應20小時而取得丙烯酸共聚物溶液。使取得之丙烯酸共聚物溶液徐徐地滴入己烷500.0g中而使固體析出，藉由過濾及減壓乾燥而取得丙烯酸共聚物(P6)。取得之丙烯酸共聚物之Mn為18,000，Mw為38,000。<Polymerization Example 6> 10.0 g of M100 and 0.4 g of AIBN as a polymerization catalyst were dissolved in 46.4 g of PM, and an acrylic copolymer solution was obtained by reacting at 80 ° C for 20 hours. The obtained acrylic copolymer solution was slowly dropped into 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P6) was obtained by filtration and drying under reduced pressure. The obtained acrylic copolymer had Mn of 18,000 and Mw of 38,000.

＜聚合例7＞ 　　使MAA 13.8g、LAA 14.1g、HEMA 7.2g、作為聚合觸媒之AIBN 0.68g溶解於PM 107.0g，藉由在80℃中使其反應16小時而取得丙烯酸共聚物溶液(固體成分濃度25質量%)(P7)。取得之丙烯酸共聚物之Mn為13,300，Mw為27,800。<Polymerization Example 7> (13.8 g of MAA, 14.1 g of LAA, 7.2 g of HEMA, 0.68 g of AIBN as a polymerization catalyst were dissolved in 107.0 g of PM, and an acrylic copolymer solution was obtained by reacting it at 80 ° C for 16 hours ( (Solid content concentration: 25% by mass) (P7). The obtained acrylic copolymer had Mn of 13,300 and Mw of 27,800.

＜合成例1＞ 　　使聚合例1取得之丙烯酸共聚物(P1)7.5g、丙烯酸4.5g、二丁基羥基甲苯0.4g、作為反應觸媒之氯化苄基三乙基銨0.3g溶解於PM 30g，以110℃使其反應20小時。將此溶液徐徐滴入己烷500g而使固體析出，藉由過濾及減壓乾燥而取得具有丙烯醯基之丙烯酸共聚物(PA-1)。實施1 H-NMR分析，確認了丙烯酸共聚物(PA-1)具有丙烯醯基。<Synthesis Example 1> 7.5 g of acrylic copolymer (P1) obtained in Polymerization Example 1, 4.5 g of acrylic acid, 0.4 g of dibutylhydroxytoluene, and 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM 30 g was reacted at 110 ° C for 20 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, and the acrylic copolymer (PA-1) having a propylene fluorenyl group was obtained by filtration and drying under reduced pressure. The 1 H-NMR analysis was performed, and it was confirmed that the acrylic copolymer (PA-1) had a propylene fluorenyl group.

＜合成例2＞ 　　使聚合例2取得之丙烯酸共聚物(P2)7.5g、丙烯酸4.5g、二丁基羥基甲苯0.4g、作為反應觸媒之氯化苄基三乙基銨0.3g溶解於PM 30g，以110℃使其反應20小時。將此溶液徐徐滴入於己烷500g而使固體析出，藉由過濾及減壓乾燥而取得具有丙烯醯基之丙烯酸共聚物(PA-2)。實施1 H-NMR分析，確認了丙烯酸共聚物(PA-2)具有丙烯醯基。<Synthesis Example 2> 7.5 g of acrylic copolymer (P2) obtained in Polymerization Example 2, 4.5 g of acrylic acid, 0.4 g of dibutylhydroxytoluene, and 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM 30 g was reacted at 110 ° C for 20 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, and then filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-2) having an acrylic fluorenyl group. The 1 H-NMR analysis was performed, and it was confirmed that the acrylic copolymer (PA-2) had a propylene fluorenyl group.

＜合成例3＞ 　　使聚合例3取得之丙烯酸共聚物(P3)2.0g、2-丙烯醯氧基乙基異氰酸酯4.3g、二丁基羥基甲苯0.4g、作為反應觸媒之二丁基錫二月桂酸酯10mg溶解於四氫呋喃60g，以60℃使其反應5小時。將此溶液徐徐滴入己烷500g而使固體析出，藉由過濾及減壓乾燥而取得具有丙烯醯基之丙烯酸共聚物(PA-3)。實施1 H-NMR分析，確認了丙烯酸共聚物(PA-3)具有丙烯醯基。<Synthesis Example 3> 2.0 g of the acrylic copolymer (P3) obtained in Polymerization Example 3, 4.3 g of 2-propenyloxyethyl isocyanate, 0.4 g of dibutylhydroxytoluene, and dibutyltin dilaurate as a reaction catalyst 10 mg of the ester was dissolved in 60 g of tetrahydrofuran, and reacted at 60 ° C for 5 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, and the acrylic copolymer (PA-3) having a propylene fluorenyl group was obtained by filtration and drying under reduced pressure. The 1 H-NMR analysis was performed, and it was confirmed that the acrylic copolymer (PA-3) had a propylene fluorenyl group.

＜合成例4＞ 　　使聚合例4取得之丙烯酸共聚物(P4)6.8g、丙烯酸4.5g、二丁基羥基甲苯0.4g、作為反應觸媒之氯化苄基三乙基銨0.3g溶解於PM 30g，以110℃使其反應20小時。將此溶液徐徐滴入己烷500g而使固體析出，藉由過濾及減壓乾燥而取得具有丙烯醯基之丙烯酸共聚物(PA-4)。實施1 H-NMR分析，確認了丙烯酸共聚物(PA-4)具有丙烯醯基。<Synthesis Example 4> 6.8 g of acrylic copolymer (P4) obtained in Polymerization Example 4, 4.5 g of acrylic acid, 0.4 g of dibutylhydroxytoluene, and 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM. 30 g was reacted at 110 ° C for 20 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, and then filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-4) having an acrylic fluorenyl group. The 1 H-NMR analysis was performed, and it was confirmed that the acrylic copolymer (PA-4) had a propylene fluorenyl group.

＜合成例5＞ 　　使聚合例5取得之丙烯酸共聚物(P5)8.2g、丙烯酸4.5g、二丁基羥基甲苯0.4g、作為反應觸媒之氯化苄基三乙基銨0.3g溶解於PM 30g，以110℃使其反應20小時。將此溶液徐徐滴入己烷500g而使固體析出，藉由過濾及減壓乾燥而取得具有丙烯醯基之丙烯酸共聚物(PA-5)。實施1 H-NMR分析，確認了丙烯酸共聚物(PA-5)具有丙烯醯基。<Synthesis Example 5> 8.2 g of acrylic copolymer (P5) obtained in Polymerization Example 5, 4.5 g of acrylic acid, 0.4 g of dibutylhydroxytoluene, and 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM 30 g was reacted at 110 ° C for 20 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, and the acrylic copolymer (PA-5) having a propylene fluorenyl group was obtained by filtration and drying under reduced pressure. The 1 H-NMR analysis was performed, and it was confirmed that the acrylic copolymer (PA-5) had a propylene fluorenyl group.

＜合成例6＞ 　　使聚合例6取得之丙烯酸共聚物(P6)8.0g、丙烯酸2.4g、LA1.6g、二丁基羥基甲苯0.4g、作為反應觸媒之氯化苄基三乙基銨0.3g溶解於PM 50g，以110℃使其反應20小時。將此溶液徐徐滴入己烷500g而使固體析出，藉由過濾及減壓乾燥而取得具有丙烯醯基之丙烯酸共聚物(PA-6)。實施1 H-NMR分析，確認了丙烯酸共聚物(PA-6)具有丙烯醯基。<Synthesis Example 6> 8.0 g of acrylic copolymer (P6) obtained in Polymerization Example 6, 2.4 g of acrylic acid, LA 1.6 g, 0.4 g of dibutylhydroxytoluene, and benzyltriethylammonium chloride as a reaction catalyst 0.3 g was dissolved in 50 g of PM and reacted at 110 ° C for 20 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, and the acrylic copolymer (PA-6) having a propylene fluorenyl group was obtained by filtration and drying under reduced pressure. The 1 H-NMR analysis was performed, and it was confirmed that the acrylic copolymer (PA-6) had a propylene fluorenyl group.

＜合成例7＞ 　　使聚合例6取得之丙烯酸共聚物(P6)8.0g、丙烯酸1.8g、LA1.7g、二丁基羥基甲苯0.4g、作為反應觸媒之氯化苄基三乙基銨0.3g溶解於PM 50g，以110℃使其反應20小時。將此溶液徐徐滴入己烷500g而使固體析出，藉由過濾及減壓乾燥而取得具有丙烯醯基之丙烯酸共聚物(PA-7)。實施1 H-NMR分析，確認了丙烯酸共聚物(PA-7)具有丙烯醯基。<Synthesis Example 7> 8.0 g of acrylic copolymer (P6) obtained in Polymerization Example 6, 1.8 g of acrylic acid, LA 1.7 g, 0.4 g of dibutylhydroxytoluene, and benzyltriethylammonium chloride as a reaction catalyst 0.3 g was dissolved in 50 g of PM and reacted at 110 ° C for 20 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, and the acrylic copolymer (PA-7) having a propylene fluorenyl group was obtained by filtration and drying under reduced pressure. The 1 H-NMR analysis was performed, and it was confirmed that the acrylic copolymer (PA-7) had a propylene fluorenyl group.

＜合成例8＞ 　　使聚合例6取得之丙烯酸共聚物(P6)8.0g、丙烯酸3.2g、5PCA 2.2g、二丁基羥基甲苯0.4g、作為反應觸媒之氯化苄基三乙基銨0.3g溶解於PM 60g，以110℃使其反應20小時。將此溶液徐徐滴入己烷500g而使固體析出，藉由過濾及減壓乾燥而取得具有丙烯醯基之丙烯酸共聚物(PA-8)。實施1 H-NMR分析，確認了丙烯酸共聚物(PA-8)具有丙烯醯基。<Synthesis Example 8> 8.0 g of acrylic copolymer (P6) obtained in Polymerization Example 6, 3.2 g of acrylic acid, 2.2 g of 5 PCA, 0.4 g of dibutylhydroxytoluene, and benzyltriethylammonium chloride as a reaction catalyst 0.3 g was dissolved in 60 g of PM and reacted at 110 ° C for 20 hours. This solution was slowly dropped into 500 g of hexane to precipitate a solid, and the acrylic copolymer (PA-8) having a propylene fluorenyl group was obtained by filtration and drying under reduced pressure. The 1 H-NMR analysis was performed, and it was confirmed that the acrylic copolymer (PA-8) had a propylene fluorenyl group.

＜實施例＞ 　　以表1所示之組成調製出實施例之各硬化膜形成組成物。其次，使用各硬化膜形成組成物形成硬化膜，且對取得之硬化膜分別進行垂直定向性及密著性之評價。<Examples> (1) Each of the cured film-forming compositions of the examples was prepared with the composition shown in Table 1. Next, each cured film-forming composition is used to form a cured film, and the obtained cured film is evaluated for vertical orientation and adhesion, respectively.

＜比較例＞ 　　參考WO2015／019962號記載之方法，調製出表2所示之比較例之各硬化膜形成組成物。其次，使用各硬化膜形成組成物形成硬化膜，對取得之硬化膜分別進行垂直定向性及密著性之評價。<Comparative Example> With reference to the method described in WO2015 / 019962, each cured film-forming composition of the comparative example shown in Table 2 was prepared. Next, a cured film was formed using each cured film-forming composition, and the obtained cured film was evaluated for vertical orientation and adhesion, respectively.

[垂直定向性之評價] 　　在TAC膜上使用刮棒塗佈機將實施例之各硬化膜形成組成物塗佈成濕膜厚4μm。在熱循環式烤箱中，分別以溫度110℃進行60秒鐘加熱乾燥，其後，以1000mJ／cm2 曝光此塗膜，在TAC膜上分別形成硬化膜。 　　於此硬化膜上，使用刮棒塗佈機將Merck(股)製之垂直定向用聚合性液晶溶液RMS03-015塗布成濕膜厚6μm。以500mJ／cm2 曝光此塗膜而製作出相位差材料。 　　使用大塚電子(股)製相位差測量裝置RETS100，測量已製作之該等相位差材料之面內相位差之入射角度依存性。將入射角度0度下之面內相位差值為0，入射角度±50度下之面內相位差為38±5nm之範圍者判斷為已垂直定向。評價結果係整合表示於後述之表3中。[Evaluation of Vertical Orientation] Each of the cured film-forming compositions of the examples was applied to a TAC film using a bar coater to a wet film thickness of 4 μm. In a thermal cycle oven, each was heated and dried at a temperature of 110 ° C. for 60 seconds, and then the coating film was exposed at 1000 mJ / cm 2 to form a hardened film on each of the TAC films. On this cured film, a vertical liquid crystal polymer solution RMS03-015 made by Merck (strand) was applied using a bar coater to a wet film thickness of 6 μm. This coating film was exposed at 500 mJ / cm 2 to prepare a retardation material. The phase difference measuring device RTS100 made by Otsuka Electronics Co., Ltd. was used to measure the incident angle dependency of the in-plane phase difference of the phase difference materials that have been manufactured. The in-plane phase difference value at an incidence angle of 0 degrees is 0, and the in-plane phase difference value at an incidence angle of ± 50 degrees is in a range of 38 ± 5 nm. The evaluation results are collectively shown in Table 3 described later.

在TAC膜上使用刮棒塗佈機將比較例之各硬化膜形成組成物塗佈成濕膜厚4μm。在熱循環式烤箱中，分別以溫度110℃進行60秒鐘加熱乾燥，在TAC膜上分別形成硬化膜。 　　於此硬化膜上，使用刮棒塗佈機將Merck(股)製之垂直定向用聚合性液晶溶液RMS03-015塗布成濕膜厚6μm。以500mJ／cm2 曝光此塗膜而製作出相位差材料。 　　使用大塚電子(股)製相位差測量裝置RETS100，測量已製作之該等相位差材料之面內相位差之入射角度依存性。將入射角度0度下之面內相位差值為0，入射角度±50度下之面內相位差為38±5nm之範圍者判斷為已垂直定向。評價結果係整合表示於後述之表3中。Each cured film-forming composition of the comparative example was coated on a TAC film with a wet film thickness of 4 μm using a bar coater. In a thermal cycle type oven, heat drying was performed at a temperature of 110 ° C. for 60 seconds to form a hardened film on the TAC film. On this cured film, a vertical liquid crystal polymer solution RMS03-015 made by Merck (strand) was applied using a bar coater to a wet film thickness of 6 μm. This coating film was exposed at 500 mJ / cm 2 to prepare a retardation material. The phase difference measuring device RTS100 made by Otsuka Electronics Co., Ltd. was used to measure the incident angle dependency of the in-plane phase difference of the phase difference materials that have been manufactured. The in-plane phase difference value at an incidence angle of 0 degrees is 0, and the in-plane phase difference value at an incidence angle of ± 50 degrees is in a range of 38 ± 5 nm. The evaluation results are collectively shown in Table 3 described later.

[密著性之評價] 　　在TAC膜上使用刮棒塗佈機將實施例及比較例之各硬化膜形成組成物塗佈成濕膜厚4μm。在熱循環式烤箱中，分別以溫度110℃進行60秒鐘加熱乾燥，其後，以1000mJ／cm2 曝光此塗膜，在TAC膜上分別形成硬化膜。 　　於此硬化膜上，使用刮棒塗佈機將Merck(股)製之垂直定向用聚合性液晶溶液RMS03-015塗布成濕膜厚6μm。以500mJ／cm2 曝光此基板上之塗膜而製作出相位差材料。 　　對此相位差材料，使用切割刀以縱橫1mm之間隔切劃成5×5格。在此切痕上使用透明膠帶(Scotch tape)進行玻璃紙膠帶(cellophane tape)剝離試驗。評價係將25格全部未剝離而殘留者視為○，即使剝離1格者也視為×。評價結果係整合表示於後述之表3中。[Evaluation of Adhesion] Each of the cured film-forming compositions of Examples and Comparative Examples was applied to a TAC film using a bar coater to a wet film thickness of 4 μm. In a thermal cycle oven, each was heated and dried at a temperature of 110 ° C. for 60 seconds, and then the coating film was exposed at 1000 mJ / cm 2 to form a hardened film on each of the TAC films. On this cured film, a vertical liquid crystal polymer solution RMS03-015 made by Merck (strand) was applied using a bar coater to a wet film thickness of 6 μm. A coating film on this substrate was exposed at 500 mJ / cm 2 to prepare a retardation material. This retardation material was cut into 5 × 5 grids using a cutter at intervals of 1 mm in length and width. A cellophane tape peeling test was performed on this cut using a scotch tape. In the evaluation system, the 25 cells were not peeled off and the remaining ones were regarded as ○, and even the 1 cell peeling was regarded as ×. The evaluation results are collectively shown in Table 3 described later.

如表3所示，使用實施例之硬化膜形成組成物而得之定向材料與使用比較例之硬化膜形成組成物而得之定向材料相同地展現良好之垂直定向性。As shown in Table 3, the alignment material obtained by using the cured film-forming composition of the example exhibited good vertical alignment as the alignment material obtained by using the cured film-forming composition of the comparative example.

使用實施例之硬化膜形成組成物而得知硬化膜展現優異之密著性。相對於此，使用比較例之硬化膜形成組成物而得之硬化膜則難以取得密著性。 [產業上之可利用性】It was found that the cured film exhibits excellent adhesion using the cured film-forming composition of the examples. In contrast, in the cured film obtained using the cured film-forming composition of the comparative example, it was difficult to obtain adhesion. [Industrial availability]

本發明之硬化膜形成組成物係能非常地有用當作形成液晶顯示元件之液晶定向膜，或形成設置於液晶顯示元件之內部或外部之光學異方性膜用之定向材料用的材料，特別係適合當作作為IPS-LCD或有機EL顯示器之防反射膜所使用之圓偏光板之光學補償膜用材料。The hardened film-forming composition of the present invention can be very useful as a material for forming a liquid crystal alignment film for a liquid crystal display element, or an alignment material for forming an optical anisotropic film provided inside or outside the liquid crystal display element, and particularly, It is a material for optical compensation films of circular polarizing plates suitable as anti-reflection films for IPS-LCD or organic EL displays.

Claims (7)

一種硬化膜形成組成物，其特徵為含有 　　(A)具有垂直定向性基與包含C=C雙鍵之聚合性基之聚合物，以及 　　(B)自由基聚合起始劑，且 　　前述垂直定向性基為下述式(1)所示之基；式[1]中， 　　Y1 表示單鍵或結合基， 　　Y2 為單鍵、碳原子數1~15之伸烷基或 -CH2 -CH(OH)-CH2 -，或表示選自苯環、環己烷環或雜環之2價之環狀基，前述環狀基上之任意之氫原子可經碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代， 　　Y3 表示單鍵或碳原子數1~15之伸烷基， 　　Y4 表示單鍵，或表示選自苯環、環己烷環或雜環之2價之環狀基，或表示碳原子數17~30且具有類固醇骨架之2價之有機基，前述環狀基上之任意之氫原子可經羥基、碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代， 　　Y5 表示選自苯環、環己烷環或雜環之2價之環狀基，且該等之環狀基上之任意之氫原子可經羥基、碳原子數1~3之烷基、碳原子數1~3之烷氧基、碳原子數1~3之含氟烷基、碳原子數1~3之含氟烷氧基或氟原子所取代， 　　n表示0~4之整數，n為2以上時，Y5 彼此可為相同亦可為相異， 　　Y6 表示氫原子、碳原子數1~18之烷基、碳原子數1~18之含氟烷基、碳原子數1~18之烷氧基或碳原子數1~18之含氟烷氧基， 　　Y2 及Y3 中之伸烷基，以及，前述環狀基上之取代基及Y6 中之烷基、含氟烷基、烷氧基及含氟烷氧基可為直鏈狀、分枝狀或環狀之任一者或該等之組合， 　　又，Y2 及Y3 中之伸烷基，以及，Y6 中之烷基、含氟烷基、烷氧基及含氟烷氧基只要結合基彼此不相鄰，則可經1至3個結合基中斷， 　　並且，在Y2 、Y4 或Y5 表示2價之環狀基，或Y4 表示具有類固醇骨架之2價之有機基，或Y2 表示-CH2 -CH(OH)-CH2 -，或Y2 或Y3 表示伸烷基，或Y6 表示烷基或含氟烷基時，該2價之環狀基、該具有類固醇骨架之2價之有機基、該 -CH2 -CH(OH)-CH2 -、該伸烷基、該烷基及該含氟烷基亦可與該等鄰接之基隔著結合基而結合， 　　且上述結合基表示選自由-O-、-CH2 O-、-COO-、 -OCO-、-NHCO-、-NH-CO-O-及-NH-CO-NH-所成群之基， 　　但，Y2 至Y6 所分別表示之單鍵、碳原子數1~15之伸烷基、苯環、環己烷環、雜環、具有類固醇骨架之2價之有機基、-CH2 -CH(OH)-CH2 -、碳原子數1~18之烷基、碳原子數1~18之含氟烷基、碳原子數1~18之烷氧基及碳原子數1~18之含氟烷氧基之碳原子數之合計為6~30。A hardened film-forming composition comprising (A) a polymer having a vertical alignment group and a polymerizable group containing a C = C double bond, and (B) a radical polymerization initiator, and the vertical alignment The base is a base represented by the following formula (1); In the formula [1], Y 1 represents a single bond or a bonding group, Y 2 is a single bond, an alkylene group having 1 to 15 carbon atoms or -CH 2 -CH (OH) -CH 2- , or it is selected from benzene A bivalent cyclic group of a ring, a cyclohexane ring or a heterocyclic ring. Any hydrogen atom on the aforementioned cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, It is substituted by a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group or a fluorine atom having 1 to 3 carbon atoms, Y 3 represents a single bond or an alkylene group having 1 to 15 carbon atoms, and Y 4 represents A single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, or a divalent organic group having 17 to 30 carbon atoms and a steroid skeleton. Arbitrary hydrogen atoms can pass through a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and fluorine containing 1 to 3 carbon atoms. An alkoxy or fluorine atom is substituted, and Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted by a hydroxyl group, a carbon Alkyl group 1 to 3, alkoxy group 1 to 3 carbon atoms, fluorine containing 1 to 3 carbon atoms Alkyl, fluorine-containing alkoxy or fluorine atom having 1 to 3 carbon atoms, n represents an integer of 0 to 4, when n is 2 or more, Y 5 may be the same as or different from each other, and Y 6 represents Hydrogen atom, alkyl group with 1 to 18 carbon atoms, fluorine-containing alkyl group with 1 to 18 carbon atoms, alkoxy group with 1 to 18 carbon atoms or fluorine-containing alkoxy group with 1 to 18 carbon atoms, Y The alkylene groups in 2 and Y 3 , and the substituents on the aforementioned cyclic group and the alkyl groups, fluorine-containing alkyl groups, alkoxy groups, and fluorine-containing alkoxy groups in Y 6 may be linear and branched. Any one or a combination of cyclic or cyclic, and alkylene groups in Y 2 and Y 3 and alkyl groups, fluorine-containing alkyl groups, alkoxy groups, and fluorine-containing alkoxy groups in Y 6 As long as the binding groups are not adjacent to each other, they can be interrupted by 1 to 3 binding groups, and Y 2 , Y 4 or Y 5 represents a divalent cyclic group, or Y 4 represents a divalent organic group having a steroid skeleton. When Y 2 represents -CH 2 -CH (OH) -CH 2- , or Y 2 or Y 3 represents an alkylene group, or Y 6 represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group , of the divalent organic group having a steroid skeleton of the -CH 2 -CH (OH) -CH 2 -, the alkylene, The alkyl and fluorinated alkyl group may also be bound via the group adjacent to such groups incorporated, and said bonding group selected from the group consisting represents -O -, - CH 2 O - , - COO-, -OCO -, - NHCO -, -NH-CO-O- and -NH-CO-NH- groups, but single bonds represented by Y 2 to Y 6 , alkylene groups having 1 to 15 carbon atoms, and benzene rings , Cyclohexane ring, heterocyclic ring, divalent organic group having a steroid skeleton, -CH 2 -CH (OH) -CH 2- , alkyl group having 1 to 18 carbon atoms, containing 1 to 18 carbon atoms The total number of carbon atoms of the fluoroalkyl group, the alkoxy group having 1 to 18 carbon atoms, and the fluorine-containing alkoxy group having 1 to 18 carbon atoms is 6 to 30. 如請求項1之硬化膜形成組成物，其中(A)成分之聚合物中，包含C=C雙鍵之聚合性基為選自由丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基及馬來醯亞胺基所成群之至少一種。For example, the cured film-forming composition of claim 1, wherein the polymer of the component (A), the polymerizable group containing a C = C double bond is selected from the group consisting of acrylfluorenyl, methacrylfluorenyl, vinyl, and allyl And at least one group of maleimidine imine groups. 如請求項1或2之硬化膜形成組成物，其中更含有(C)選自由具有包含C=C雙鍵之聚合性基之單體及聚合物所成群之至少一種。The hardened film forming composition according to claim 1 or 2, further comprising (C) at least one selected from the group consisting of a monomer and a polymer having a polymerizable group containing a C = C double bond. 如請求項1至3中任一項之硬化膜形成組成物，其係基於(A)成分100質量份而含有0.1質量份~50質量份之(B)成分。The cured film-forming composition according to any one of claims 1 to 3, which contains the component (B) in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the component (A). 如請求項3或4之硬化膜形成組成物，其係基於(A)成分100質量份而含有10質量份至1000質量份之(C)成分。The cured film-forming composition according to claim 3 or 4, which contains the component (C) in an amount of 10 to 1000 parts by mass based on 100 parts by mass of the component (A). 一種定向材料，其特徵為使如請求項1至5中任一項之硬化膜形成組成物硬化而得者。An oriented material characterized by being obtained by hardening the hardened film-forming composition according to any one of claims 1 to 5. 一種相位差材料，其特徵為使用硬化膜而形成者，該硬化膜係由如請求項1至5中任一項之硬化膜形成組成物所得。A retardation material characterized by being formed using a cured film obtained from the cured film-forming composition according to any one of claims 1 to 5.
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