WO2014038260A1 - Procédé de fabrication de film à cristaux liquides alignés - Google Patents

Procédé de fabrication de film à cristaux liquides alignés Download PDF

Info

Publication number
WO2014038260A1
WO2014038260A1 PCT/JP2013/066002 JP2013066002W WO2014038260A1 WO 2014038260 A1 WO2014038260 A1 WO 2014038260A1 JP 2013066002 W JP2013066002 W JP 2013066002W WO 2014038260 A1 WO2014038260 A1 WO 2014038260A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
film
region
polymerization
Prior art date
Application number
PCT/JP2013/066002
Other languages
English (en)
Japanese (ja)
Inventor
宍戸　厚
アリ プリィマギ
恭平 久野
敦 工藤
吉弘 熊谷
吾郎 須崎
涼 西村
Original Assignee
Ｊｘ日鉱日石エネルギー株式会社
国立大学法人東京工業大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ｊｘ日鉱日石エネルギー株式会社, 国立大学法人東京工業大学 filed Critical Ｊｘ日鉱日石エネルギー株式会社
Priority to KR1020157008383A priority Critical patent/KR101993955B1/ko
Priority to JP2014534217A priority patent/JP5992047B2/ja
Publication of WO2014038260A1 publication Critical patent/WO2014038260A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Definitions

  • the present invention relates to a method for producing an oriented film.
  • a method for uniformly aligning a liquid crystal compound a method for aligning a compound using an external field such as an electric field or a magnetic field, a so-called rubbing method, oblique deposition method, microgroove method, LB film method, A method has been proposed in which anisotropy is imparted to the surface of the substrate in contact with the liquid crystalline compound by a photo-alignment method, etc., so that the substrate itself has an alignment regulating force, and this is used to align the liquid crystalline compound. .
  • a manufacturing method of a liquid crystal display element and an alignment film using a method for uniformly aligning such a liquid crystalline compound industrially, from the viewpoint of increasing area, processing time and processing cost. From the standpoint of superiority, a method using a rubbing method (for example, a method of rubbing an alignment film such as polyimide with a velvet cloth made of cotton, rayon or the like) has been generally used.
  • Non-patent Document 1 Photoinduced Opposite Diffusion of Nematic and Isotropic Monomers during Patterned Photopolymerization (Non-patent Document 1) described on pages 135 to 145 of Mater (Vol.10, No.1) Fills a cell containing two opposed glass slides that have been rubbed with a mixture containing two monomers and exposes a portion of the mixture layer using a grid-like photomask. A method for orienting a polymer in the exposed area is disclosed.
  • Non-Patent Document 1 a polymer is partially formed using a lattice-like photomask, and the obtained film has a narrow orientation region. That is, the method disclosed in Non-Patent Document 1 is merely a method for producing a partially oriented film, and a technical method for producing an oriented film in which orientation is continuously formed in a large area. The above idea was not described in Non-Patent Document 1 at all. Moreover, in the manufacturing method actually used in the said nonpatent literature 1, the board
  • This invention is made
  • the present inventors have found that when the first polymerizable compound is polymerized under the same conditions, the polymerization completion time is longer than that of the first polymerizable compound. And a film made of a polymerizable composition, wherein at least one of the first polymerizable compound, the second compound, and the compound obtained after polymerization is a compound exhibiting liquid crystallinity.
  • the method for producing an oriented film of the present invention contains a first polymerizable compound and a second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions. And using a film made of a polymerizable composition, wherein at least one of the first polymerizable compound, the second compound and the compound obtained after polymerization is a compound exhibiting liquid crystallinity, After the polymerization of the polymerizable composition is started from a partial region of the film, the boundary of the region is continuously moved toward the unpolymerized region at such a speed that the compound exhibiting liquid crystallinity is aligned. Thus, an orientation film is obtained.
  • the first polymerizable compound is a compound having one or more polymerizable functional groups, and the number of the polymerizable functional groups is that of the second compound. It is preferable that the number is 1 or more than the number of polymerizable functional groups.
  • the polymerizable composition is polymerized by photopolymerization, and the boundary is continuously moved toward the unpolymerized region. It is preferable to continuously move the boundary of the irradiated region toward the region not irradiated with light.
  • a photomask is used during the photopolymerization, and the photomask is continuously moved so that the boundary of the light irradiation region is not irradiated with light. It is preferable to move continuously toward the region.
  • a photomask is preferably a mask in which a plurality of substantially rectangular openings are formed such that the long sides of each opening are substantially parallel.
  • a prepolymerized film as the film made of the polymerizable composition.
  • the moving speed of the boundary is preferably 1 ⁇ 10 ⁇ 7 to 4 ⁇ 10 ⁇ 1 m / s.
  • the first polymerizable compound is at least one compound selected from the group consisting of the following compounds C11 to 15 and the second compound Is preferably at least one compound selected from the group consisting of the following compounds C21-24.
  • the combination of the first polymerizable compound and the second compound in the polymerizable composition includes at least one compound selected from the group consisting of the following compounds C11 to 15 and the following compound C21. A combination with at least one compound selected from the group consisting of ⁇ 24 is preferred.
  • the compounds C11 to C13 that can be selected as the first polymerizable compound are respectively represented by the following general formula (1): Z 1 pM 1 -L 1- (M 2 -L 2 ) qM 3 -Z 2 r (1)
  • Z 1 and Z 2 in the formula (1) may be the same or different, and each is a group represented by the formula: -L 3 -S 1 -F 1 , and F 1 is an acrylic group Any one of a group and a methacryl group, S 1 is either a single bond or a linear alkylene group having 1 to 12 carbon atoms, and L 3 is an ether group, an ester group or a carbonate group.
  • the compound C14 that can be selected as the first polymerizable compound is represented by the following general formula (2):
  • R 5 is either hydrogen or a methyl group, and x is 2 or 3.
  • a compound represented by The compound C15 that can be selected as the first polymerizable compound is represented by the following general formula (3):
  • R 5 is either hydrogen or a methyl group, and y is an integer of 2 to 12. It is a compound represented by these.
  • Z 1 in formula (1) is a group represented by the formula: -L 3 -S 1 -F 1 , F 1 is one of an acryl group and a methacryl group, and S 1 is A single bond, L 3 is a single bond, p is 1, M 1 is a 1,4-phenylene group, L 1 is a single bond, q is 0, M 3 is 1, 4-phenylene group, and Z 2 is selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms (more preferably Is a cyano group) and r is 1.
  • Z 1 in formula (1) is a group represented by the formula: -L 3 -S 1 -F 1 , F 1 is any one of an acryl group and a methacryl group, and S 1 is A straight-chain alkylene group having 1 to 12 carbon atoms, L 3 is an ether group, p is 1, M 1 is a 1,4-phenylene group, L 1 is a single bond, and q is 0 M 3 is a 1,4-phenylene group, and Z 2 is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • Z 1 in formula (1) is a group represented by the formula: -L 3 -S 1 -F 1 , F 1 is one of an acryl group and a methacryl group, and S 1 is A group represented by the formula: (CH 2 CH 2 O) z (z is 2 or 3), L 3 is a single bond, p is 1, and M 1 is a 1,4-phenylene group. L 1 is a single bond, q is 0, M 3 is a 1,4-phenylene group, Z 2 is a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a carbon number of 1 to 12.
  • Z 1 is a group represented by the formula: -L 3 -S 1 -F 1 , F 1 is any one of an acryl group and a methacryl group, and S 1 is a group having 1 to 12 carbon atoms
  • a linear alkylene group, L 3 is an ether group, p is 1, M 1 is a 1,4-phenylene group, L 1 is —COO—, q is 0, and M 3 Is a 1,4-phenylene group and Z 2 is selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (More preferably a cyano group) and r is 1.
  • FIG. 1 is a schematic longitudinal sectional view schematically showing a state before starting photopolymerization on a film made of a polymerizable composition.
  • 2 is a schematic longitudinal sectional view schematically showing a state in which polymerization is started from a partial region of the film by irradiating light from a light source, and FIG. 3 shows the boundary of the polymerization region in FIG.
  • FIG. 4 is a schematic longitudinal sectional view schematically showing a state after being moved toward an unpolymerized region, and FIG. 4 is a state after the boundary of the polymerized region in FIG. 3 is moved toward the unpolymerized region. It is a schematic longitudinal cross-sectional view which shows typically.
  • the dotted line S indicates the boundary of the overlapping region
  • the arrow A conceptually indicates the direction in which the boundary S of the overlapping region is moved
  • the arrow L conceptually indicates the light emitted from the light source.
  • A1 conceptually shows a region polymerized by irradiation with light L (polymerization region: exposed portion)
  • A2 shows an unpolymerized region not irradiated with light L (unpolymerized region: light shielding portion).
  • A3 conceptually indicates a region where orientation is formed.
  • the light source 11 and the light emitted from the light source 11 are transmitted.
  • the light source 11 is arranged on one of the two substrates 12 and the light from the light source 11 is irradiated only on a partial region of the film 13.
  • a photomask 14 that can shield a part of the film 13 is disposed therebetween.
  • the light source 11 is turned on and the light L is emitted from the light source 11.
  • the reaction does not proceed and remains unpolymerized in the light shielding portion A2, but the polymerization proceeds in the exposed portion A1 where the light is irradiated. In this way, a part of the region is exposed, and the polymerization of the polymerizable composition is started from a part of the film 13 (exposed portion) A1.
  • a compound flow (mainly the flow of the first polymerizable compound) is generated from the light shielding portion A2 to the exposure portion A1 which is the polymerization region.
  • At least one compound among the compounds obtained later is subjected to a kind of shear stress, and the compound exhibiting liquid crystallinity is in the vicinity of the boundary S between the polymerization region (exposed portion) A1 and the unpolymerized region (light-shielding portion) A2.
  • the alignment region A3 is formed (induced).
  • the direction in which the flow due to the movement of such a compound occurs is substantially perpendicular to the boundary S between the polymerization region (exposure portion) A1 and the non-polymerization region (light-shielding portion) A2.
  • the average orientation direction is usually a direction substantially perpendicular to the boundary S.
  • Non-patent Document 1 a case where the position of the boundary S is fixed by fixing the photomask 14 at the position shown in FIG.
  • the alignment region is limited to the region near the boundary, and approximately several tens to several hundreds ⁇ m in the direction perpendicular to the boundary of the light irradiation region Only an alignment region is formed in a certain region.
  • FIGS. 1 to 4 as shown in FIGS. 2 to 4, the boundary S between the superposed region (exposure portion) A1 and the unpolymerized region (light-shielding portion) A2 is used.
  • the boundary S is moved toward the unpolymerized region A2 by continuously moving the photomask 14. Then, after the polymerization of the polymerizable composition is started from a partial region of the film 13 (see FIG. 2), the boundary S of the polymerization region is continuously moved toward the unpolymerized region A2 (see FIG. 2). 2 to 4), the diffusion of the compound is induced at each time the boundary S moves (at a new position), and it is possible to continuously cause photopolymerization and orientation induced by diffusion.
  • the alignment region is continuously increased by continuously moving the boundary S of the polymerization region A1 toward the unpolymerized region at a speed at which the compound exhibiting liquid crystallinity is aligned. It is possible to make it.
  • the alignment region can be continuously increased. Therefore, it is possible to efficiently manufacture an orientation film having an alignment region formed in a large area.
  • the present invention moves the boundary S between the overlapping region (exposure part) A1 and the unpolymerized region (light-shielding part) A2 toward the unpolymerized region A2, so that the boundary S that moves is moved.
  • the principle of forming the alignment is described by taking as an example the case where a photopolymerizable compound is used as the first polymerizable compound or the second compound.
  • the diffusion phenomenon of the substance generated by moving the boundary S between the polymerization region (exposure portion) A1 and the unpolymerization region (light-shielding portion) A2 toward the unpolymerization region A2 is not limited to a photopolymerizable compound because it is a method that makes it possible to increase the alignment region by forming an alignment on the substrate.
  • a compound other than the photopolymerizable compound for example, a thermally polymerizable compound may be used.
  • the compound exhibiting liquid crystallinity is oriented using a compound that moves from an unpolymerized region to a polymerized region in the film after the polymerization is started. It is possible to control the direction of orientation in the direction in which the compound moves (direction approximately perpendicular to the boundary of the region). Therefore, for example, when polymerization is performed by photopolymerization, the orientation can be controlled in various directions according to the shape of the mask.
  • FIG. 5A shows the relationship before starting photopolymerization between the photomask 14 and the substrate 12 (before moving the boundary S of the light irradiation region) when viewed from the light source side (the optical axis direction of the light to be irradiated).
  • 5 (b) is a schematic plan view schematically showing the relationship between the photomask 14 and the substrate 12 after photopolymerization when viewed from the light source side (the boundary S of the light irradiation region). It is the schematic plan view which shows typically the state moved to the direction of arrow A).
  • the boundary S of the overlapping region A1 is perpendicular to the two sides of the substrate 12, and when the boundary S is moved as schematically shown in FIGS. 5 (a) to 5 (b).
  • the compound flows almost perpendicularly to the boundary S, and the alignment direction is controlled substantially perpendicular to the boundary S.
  • the edge of the mask 14 is inclined and the boundary S is moved so that the boundary S is in contact with the two sides of the substrate 12 at an angle other than perpendicular, the mask S 14 is moved with respect to the oblique boundary S.
  • FIG. 6 is a schematic plan view schematically showing the relationship between the photomask 14 and the substrate 12 when viewed from the light source side (the optical axis direction of light to be irradiated).
  • the photomask 14 shown in FIG. 6 is formed so that the edges are formed obliquely and the boundary S is in contact with the two sides of the substrate 12 at an angle other than perpendicular.
  • the compound flow is induced in a direction substantially perpendicular to the mask boundary S due to the diffusion induction of the compound (the arrow P in the figure conceptually indicates the direction perpendicular to the boundary S). It is assumed that the flow of the compound occurs in substantially the same direction as the arrow P and / or in the direction 180 ° opposite to that).
  • the orientation direction is controlled. As described above, when the moving speed of the boundary S is high, the vector of the moving direction of the boundary S (the direction indicated by the arrow A) and the vector perpendicular to the boundary S (the direction indicated by the arrow P) The orientation direction is controlled in the direction of the vector sum.
  • the boundary S is moved when the boundary S is moved as schematically shown in FIGS. 5A and 5B, and when the edge of the mask 14 is inclined as schematically shown in FIG.
  • the orientation direction is controlled in a different direction.
  • the present invention is a method that enables the orientation to be formed by utilizing the diffusion phenomenon of the substance while moving the boundary of the polymerization region, thereby increasing the orientation region.
  • the present inventors speculate that it is possible to efficiently produce an orientation film having a property and having an orientation region formed in a large area.
  • FIG. 1 It is a schematic longitudinal cross-sectional view which shows typically the state before starting photopolymerization with respect to the film
  • FIG. 5 (a) is a schematic plan view schematically showing a relationship before starting photopolymerization between the photomask and the substrate when viewed from the light source side (state before moving the boundary of the light irradiation region)
  • FIG. 5B is a schematic plan view schematically showing a relationship after starting photopolymerization between the photomask and the substrate (a state where the boundary of the light irradiation region is moved) when viewed from the light source side.
  • It is a schematic plan view which shows typically the relationship before the photopolymerization start of the photomask which formed the edge diagonally, and a board
  • POM polarizing microscope
  • the method for producing an oriented film of the present invention comprises a first polymerizable compound and a second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions, And using the film
  • polymerization is a compound which shows liquid crystallinity
  • a composition containing a first polymerizable compound and a second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions Use.
  • a first polymerizable compound and a second compound those having different polymerization completion times when polymerized under the same conditions are used.
  • the matters such as the long and short polymerization completion time are relatively required between the first polymerizable compound and the second compound, and here, “when polymerized under the same conditions” Is a condition that allows the first polymerizable compound to be polymerized (temperature condition in the case of thermal polymerization, light irradiation condition in the case of photopolymerization, etc.) as appropriate, and the same selected condition This is the case where polymerization is carried out.
  • the “polymerization completion time” is, for example, when the polymerizable composition is polymerized by photopolymerization, and is irradiated with light (for example, light of 366 nm) while being held at a constant temperature condition (for example, 85 ° C.).
  • each of the first polymerizable compound and the second compound is introduced into the cell and separately polymerized, and the time until the polymerization of each compound is completed is determined as the film is formed.
  • two soda glass substrates having a size of 25 mm square and a thickness of 1.1 mm are used, and these are bonded to each other with 100 ⁇ m-thick polyimide tape as spacers (two places on the left and right sides) to produce a glass cell with a cell thickness of 100 ⁇ m.
  • spacers are formed in two places on two parallel vertical sides (left and right) of the glass substrate so that the overlapping area of the planar portions of the upper and lower substrates is 15 mm long and 25 mm wide (spacer The glass substrate portions where the spacers are not formed are openings, and the internal size of the cell is 15 mm long, 10 mm wide, and 100 ⁇ m thick.
  • the photopolymerization initiator may be contained in a predetermined amount (for example, 1 mol%) with respect to the compound for measuring the polymerization completion time.
  • a mixed mixture is prepared, and then the mixture is poured into the glass cell while melting at 100 ° C. until the inside of the cell is filled by capillarity, and up to 85 ° C.
  • the film was held at 85 ° C. for 3 minutes to form a film of the polymerizable composition (film size: length 15 mm, width 10 mm, thickness 100 ⁇ m), and then the film was removed from the high pressure mercury lamp with a filter at 366 nm
  • the glass cell is coated with the film irradiated with light at an intensity of 1.9 mW / cm 2 for photopolymerization and irradiated with light every predetermined time (for example, 5 seconds, 15 seconds, 30 seconds, and 60 seconds). The time until the completion of polymerization may be measured by taking out the sample and washing the surface with chloroform and visually confirming whether or not a film is formed.
  • the first polymerizable compound and the second compound to be used are compared, and a compound having a shorter polymerization completion time is used as the first polymerizable compound.
  • a compound (including a non-polymerizable compound) in which polymerization does not proceed under the polymerization conditions of the first polymerizable compound and the polymerization completion time is infinite is used as the second compound.
  • the first polymerizable compound is a compound having one or more polymerizable functional groups, and the number of the polymerizable functional groups is the first number.
  • the first polymerizable compound is A compound having 1 or more (more preferably 2 or more, more preferably 2 to 4) polymerizable functional groups, and the second compound has 0 or 1 (more preferably 1) polymerizable functional groups.
  • it is a compound having By using compounds having different numbers of polymerizable functional groups in this way as the first polymerizable compound and the second compound, respectively, it is possible to increase the difference in polymerization rate between these compounds, and the polymerization region during polymerization In the vicinity of the boundary, the concentration of the compound can be generated more efficiently, and the diffusion of the compound can be caused more efficiently, and the alignment can be formed more efficiently near the boundary of the polymerization region.
  • the number of polymerizable functional groups of the first polymerizable compound is less than the lower limit, it does not polymerize or it becomes difficult to polymerize the first polymerizable compound at a sufficiently high speed, and the efficiency It tends to be difficult to enlarge the alignment region well.
  • the number of polymerizable functional groups of the first polymerizable compound exceeds the upper limit, the polymerization proceeds faster than the diffusion of the compound, so that it tends to be difficult to form an orientation associated with the diffusion. is there.
  • such a polymerizable functional group is not particularly limited, and known ones can be used as appropriate, for example, vinyl group, allyl group, vinyl ether group, acrylic group, methacryl group, oxetane group, epoxy group. , Cinnamoyl group, chalcone group, coumarin group and the like.
  • vinyl ether group, acrylic group, methacryl group, oxetane group, epoxy group, cinnamoyl group, chalcone group from the viewpoint of ease of synthesis of compound, handling property, etc. are preferable, and an acrylic group, a methacryl group, an oxetane group, and an epoxy group are more preferable.
  • the first polymerizable compound, the second compound and the compound obtained after polymerization is liquid crystalline. It is necessary to be a compound showing That is, at least one of the first polymerizable compound and the second compound needs to be a compound exhibiting liquid crystallinity before and / or after polymerization.
  • the “compound obtained after polymerization” refers to a compound obtained when the polymerizable composition is polymerized, for example, a homopolymer of a first polymerizable compound, a second compound A homopolymer and a copolymer of a first polymerizable compound and a second compound are included.
  • the compound exhibiting liquid crystallinity is preferably a compound exhibiting liquid crystallinity in a predetermined temperature range (so-called thermotropic liquid crystal compound).
  • thermotropic liquid crystal compound is an enantiotropic liquid crystal compound that exhibits liquid crystallinity in both the temperature rising process and the temperature lowering process when the behavior of the liquid crystal phase is confirmed when the temperature is raised and lowered.
  • it may be a monotropic liquid crystal compound exhibiting liquid crystallinity only in one of the temperature rising process and the temperature falling process.
  • at least one of the first polymerizable compound, the second compound, and the compound obtained after the polymerization is a compound exhibiting liquid crystallinity (a compound having liquid crystallinity).
  • the diffusion of the compound in the film is excited, and it becomes possible to apply shear stress (shear stress) to the compound exhibiting liquid crystallinity.
  • shear stress shear stress
  • Z 1 and Z 2 are each independently a hydrogen atom; a halogen atom (more preferably F, Cl, Br); CN; NO 2 ; OCF 3 ; a linear or branched group having 1 to 18 carbon atoms.
  • An alkyl group ⁇ wherein the alkyl group is an oxygen atom, —COO—, —OCO—, —OCOO—, —CONR 1 —, to which one or more carbons of the alkyl group are not continuously bonded.
  • —NR 1 CO—, —OCO—NR 1 —, or —NR 1 COO— may be substituted (wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). . ⁇ ; Alkoxy group having 1 to 18 carbon atoms; and the formula: -L 3 -S 1 -F 1 ⁇ In the formula: F 1 represents the following formulas (F-1) to (F-20):
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Any one of the groups represented by S 1 is a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms (in the alkylene group, one or a plurality of carbons in the alkylene group are not continuously bonded).
  • An oxygen atom, —COO—, —OCO—, —OCOO—, —CONR 3 —, —NR 3 CO—, —OCO—NR 3 —, or —NR 3 COO— may be substituted (wherein R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)).
  • L 1 and M 3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group,
  • p and r each independently represent 1, 2, or 3; q represents 0, 1, or 2; When there are a plurality of Z 1 and / or Z 2 , they may be the same or different. ]
  • the compound represented by these is preferable. In addition, you may utilize such a compound which shows liquid crystallinity individually by 1 type or in combination of 2 or more types.
  • a compound that can be used in addition to the compound exhibiting liquid crystallinity similarly to the compound exhibiting liquid crystallinity, vinyl group, allyl group, vinyl ether group, acrylic group, methacryl group, oxetane group, epoxy group, cinnamoyl group, chalcone group, A compound having a functional group such as a coumarin group can be used.
  • thermal polymerization compounds and photopolymerization compounds that can be used as compounds that can be used in addition to the compound exhibiting liquid crystallinity, and these can be used as appropriate.
  • Examples of the vinyl compound having a vinyl group include styrene, ⁇ -methylstyrene, vinyl acetate, N-vinylpyrrolidone, N-vinylcaprolactam and the like.
  • vinyl ether compounds having a vinyl ether group examples include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexane dimethanol monovinyl ether, Examples include cyclodecane vinyl ether, benzyl vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and dicyclopentadiene vinyl ether.
  • Examples of the (meth) acrylic compound having an acrylic group or a methacrylic group include, as monofunctional monomers, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl.
  • Alkyl (meth) acrylates such as (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxy-3-phenylpropyl acrylate; cyclohexyl ( Saturated or unsaturated alicyclic alkyl (meth) such as (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Acrylate; substituted aryl (meth) acrylates such as benzyl (meth) acrylate; alkoxy (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; unsaturated such as (meth) acryloylmorpholine Amide compounds; carboxyl
  • Examples of (meth) acrylic polyfunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate and the like can be mentioned.
  • Examples of the compound having an epoxy group include ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, diethylene glycol diglycidyl ether, and triethylene glycol.
  • Diglycidyl ether propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether Hydrogenated bisphenol A diglycidyl ether, 3 ', 4'-epoxy Cicyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, vinylcyclohexene monooxide, And 1,2: 8,9-diepoxy limonene.
  • Examples of the compound having an oxetane group include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylylenebisoxetane, 3-ethyl-3 (((3-ethyloxetane-3-yl) methoxy) methyl) Oxetane, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene, 3-ethyl-3- (phenoxymethyl) oxetane, bis (3-ethyl-3-oxetanylmethyl) ether, And 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane.
  • the first polymerizable compound and the second compound to be contained in the polymerizable composition it is easy to control the position of the boundary between the polymerized region and the unpolymerized region at the time of polymerization, and more efficiently as desired. It is preferable to use a photopolymerizable compound because it is possible to form a film having orientation and to further improve work efficiency. That is, in the present invention, it is preferable that at least one or both of the first polymerizable compound and the second compound is a photopolymerizable compound, and the polymerizable composition is polymerized by photopolymerization. It is more preferable to use a photopolymerizable compound as both the one polymerizable compound and the second compound.
  • the photopolymerizable compound mentioned here is a compound in which a functional group reacts due to the presence of a photoinitiator such as vinyl group, allyl group, vinyl ether group, acrylic group, methacryl group, oxetane group, and epoxy group.
  • a compound in which a functional group reacts with light without a photoinitiator may be used.
  • Examples of photopolymerizable compounds that react with functional groups without a photoinitiator include compounds having functional groups capable of photodimerization such as cinnamoyl groups, chalcone groups, and coumarin groups. it can.
  • the first polymerizable compound is a compound represented by the general formula (1) from the viewpoint of being a monomer capable of proceeding polymerization more efficiently
  • Z 1 in the formula And Z 2 are groups represented by -L 3 -S 1 -F 1 (Z 1 and Z 2 may be the same or different, and from the viewpoint of ease of synthesis, F 1 is an acrylic group or a methacryl group
  • S 1 is a single bond or a linear alkylene group having 1 to 12 carbon atoms
  • L 3 is an ether group (—O—).
  • each of Z 1 and Z 2 is a group represented by -L 3 -S 1 -F 1 (wherein Z 1 and Z 2 are They may be the same or different, and are preferably the same group from the viewpoint of ease of synthesis.), F 1 is an acrylic group or a methacryl group, and S 1 is a single bond or a carbon number.
  • L 3 is any one of an ether group, an ester group and a carbonate group (more preferably an ether group), p is 1, M 1 is 1,4- A phenylene group, L 1 is —COO—, M 2 is a 1,4-phenylene group, L 2 is —OCO—, q is 1, and M 3 is a 1,4-phenylene group.
  • each of Z 1 and Z 2 is a group represented by -L 3 -S 1 -F 1 (wherein Z 1 and Z 2 are They may be the same or different, and are preferably the same group from the viewpoint of ease of synthesis.), F 1 is an acrylic group or a methacryl group, and S 1 is represented by the formula: (CH 2 CH 2 O) z (z is 2 or 3), L 3 is a single bond, p is 1, M 1 is a 1,4-phenylene group, and L 1 Is a single bond or an ester group (more preferably a single bond), q is 0, M 3 is a 1,4-phenylene group, and r is 1, Compound C13, The following general formula (2):
  • R 5 is either hydrogen or a methyl group (in addition, a plurality of R 5 may be the same or different), and x is 2 or 3. .
  • Compound C14 represented by: The following general formula (3):
  • R 5 is any one of hydrogen and methyl group (in addition, a plurality of R 5 may be the same or different), and y is an integer of 2 to 12) .
  • Compound C15 represented by Is also preferable. These may be a polymerizable compound exhibiting liquid crystallinity at least before and after polymerization, or may not exhibit liquid crystallinity when a second compound described later exhibits liquid crystallinity.
  • Examples of the first polymerizable compound include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 4,4′-bis (8- (meth) acryloyloxy-3,6-dioxaoctyl-1-oxy) biphenyl, 4,4′-bis (9- (meth) acryloyloxy) nonyloxybiphenyl, 4, 4′-bis (6- (meth) acryloyloxy) hexyloxybiphenyl and 1,4-bis (6- (meth) acryloyloxyhexyloxy) methylhydroquinone are particularly preferred.
  • the second compound to be contained in the polymerizable composition is preferably a compound exhibiting liquid crystallinity at least before and after polymerization from the viewpoint of forming an orientation film more efficiently.
  • the first polymerizable compound exhibits liquid crystallinity, it is not necessarily a compound exhibiting liquid crystallinity.
  • an orientation film can be formed more efficiently by using a compound exhibiting liquid crystallinity as the second compound.
  • Z 1 is represented by -L 3 -S 1 -F 1
  • F 1 is an acryl group or a methacryl group
  • S 1 is a single bond
  • 3 is a single bond
  • p is 1
  • M 1 is a 1,4-phenylene group
  • L 1 is a single bond
  • q is 0,
  • M 3 is a 1,4-phenylene group
  • Z 2 is one selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (more preferably a cyano group).
  • a linear alkylene group of 1 to 12 L 3 is an ether group, p is 1, M 1 is a 1,4-phenylene group, L 1 is a single bond, q is 0 M 3 is a 1,4-phenylene group, and Z 2 is selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms
  • Z 1 is represented by -L 3 -S 1 -F 1 and F 1 is an acrylic group Is a methacryl group
  • S 1 is a linear alkylene group having 1 to 12 carbon atoms
  • L 3 is an ether group
  • p is 1
  • M 1 is a 1,4-phenylene group
  • q is 0, M 3 is a 1,4-phenylene group
  • Z 2 is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and a carbon atom.
  • Compound C24 which is one (more preferably a cyano group) selected from the alkoxy groups of formula 1 to 12, and r is 1, I
  • Such second compounds include 4- (6- (meth) acryloyloxyhexyloxy) -4′-cyanobiphenyl, 4- (9- (meth) acryloyloxynonyloxy) -4′-cyanobiphenyl, 4- (5- (meth) acryloyloxy-3-oxapentyl-1-oxy) -4′-cyanobiphenyl, 4- (8- (meth) acryloyloxy-3,6-dioxaoctyl-1-oxy) It is particularly preferable to use -4′-cyanobiphenyl, 4-cyanophenyl-4- (2-acryloyloxyethoxy) benzoate.
  • the content ratio of the first polymerizable compound and the second compound to be contained in the polymerizable composition is not particularly limited, but the first polymerizable compound and the second compound are not limited.
  • the molar ratio ([first polymerizable compound]: [second compound]) is preferably 0.1: 99.9 to 99.9: 0.1, and 2:98 to 98: 2 is more preferable, and 4:96 to 96: 4 is even more preferable.
  • the molar ratio of the first polymerizable compound to the second compound ([first polymerizable compound]: [second compound]) is 5:95 to 95: 5 is more preferable, and 10:90 to 80:20 is even more preferable.
  • the diffusion rate is slow, and therefore, the rate of moving the boundary tends to be slow.
  • the upper limit is exceeded, polymerization is performed rather than compound diffusion. Since it proceeds too fast, it tends to be difficult to form an orientation accompanying diffusion.
  • the total amount of the first polymerizable compound and the second compound in the polymerizable composition is 70 mol% in molar ratio. It is preferable that it is more (more preferably 80 mol% or more). When the total amount of the first polymerizable compound and the second compound is less than the lower limit, the liquid crystallinity is lowered and alignment tends to be difficult.
  • a photopolymerization initiator when the polymerizable composition is photopolymerized, it is preferable to use a photopolymerization initiator because the polymerization can proceed more efficiently.
  • a photopolymerization initiator is not particularly limited, and known ones can be used as appropriate, and commercially available products (for example, trade name “Irgacure 651” manufactured by BASF) may be used.
  • the amount used can be appropriately designed according to the type of compound in the polymerizable composition to be used, the light absorption wavelength, etc., for example, the polymerizable composition It may be 0.1 to 10 mol% based on all the compounds.
  • the form (size including thickness etc.) of such a polymerizable composition is not particularly limited, and the form can be appropriately changed according to the intended design. It may be 1 to 200 ⁇ m.
  • the film made of such a polymerizable composition may be a coating film obtained by applying the polymerizable composition on a substrate, and the polymerizable composition is introduced into a so-called cell.
  • the polymerizable composition may be in the form of a film by a cell, and there is no particular limitation on the method of forming the film and the presence or absence of use of the substrate at the time of production, and a known method can be used as appropriate. Etc.
  • membrane which consists of said polymeric composition on a board
  • membrane which consists of such polymeric composition from a viewpoint of forming an orientation film, maintaining the shape and uniformity of a film
  • a substrate for example, to arrange a film in a cell using a cell including two substrates
  • the other surface is a gas phase interface.
  • the material of such a substrate or cell is not particularly limited, and a known material (for example, glass or plastic) can be appropriately used.
  • the substrate in the case where the polymerization is performed by photopolymerization, in the case where the substrate is in contact with the light incident surface side of the film, it is necessary to make light incident through the substrate. It is preferable to be made of a material that can transmit at least light having a wavelength used for photopolymerization.
  • the polymerization of the polymerizable composition is started from a partial region of the film.
  • “initiating the polymerization of the polymerizable composition from a partial region of the film” referred to here is, for example, setting a part of the film from the beginning as a region for starting the polymerization, and polymerizing from the region. (For example, in the case of photopolymerization, a part of the film is previously present in a portion (exposed portion) irradiated with light from a light source, and the polymerizable composition is exposed from the exposed portion of the film.
  • the method for polymerizing the film made of the polymerizable composition from a part of the region is not particularly limited, and a known method can be appropriately employed.
  • a method for starting polymerization from a partial region of such a film for example, light (X-ray, electron beam, ultraviolet ray, visible light, infrared ray (heat ray), etc.) is irradiated on a partial region, Examples thereof include a photopolymerization method in which polymerization is started from an irradiation region and a thermal polymerization method in which heating is started from a partial region and polymerization is started from the heating region.
  • a polymerization method in part from the viewpoint of easier control of the region to be polymerized, ease of handling, ease of setting and management of irradiation intensity and irradiation energy of light to be irradiated. It is preferable to employ a photopolymerization method in which light is irradiated to the region.
  • photopolymerization when the film that is the object of photopolymerization is supported by a cell or the like, if the substrate on the light irradiation surface side is not transparent, photopolymerization is performed using an electron beam. And the use of electron beams is useful when the substrate is not transparent.
  • photopolymerization when photopolymerization is employed as a polymerization method of the polymerizable composition, it is possible to proceed the polymerization reaction more efficiently, and it is preferable to use ultraviolet rays or visible light.
  • a light source for irradiating such light is not particularly limited, and a known light source that can be used for photopolymerization can be used as appropriate.
  • a lamp or the like may be used.
  • the light irradiation wavelength used in such photopolymerization is not particularly limited, and may be determined in consideration of the absorption spectrum of the compound, the recommended use wavelength of the photoinitiator, and the like. Further, for example, in the case where polymerization is performed in a state where a film made of a polymerizable composition is formed on a substrate and one interface of the film is in contact with the surrounding atmospheric gas, a compound containing an acryl group or a methacryl group is used. When a radical reaction is used, polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen from the viewpoint that, when oxygen is present, it is difficult for the polymerization to proceed due to oxygen inhibition.
  • an inert gas such as nitrogen
  • the polymerization may be performed in a state where the film made of the polymerizable composition is in contact with the atmospheric gas (the state where the interface of the film is in contact with the gas phase), and the film made of the polymerizable composition
  • the polymerization may be carried out in such a state that does not come into contact with the atmospheric gas (where the film interface is in contact with the wall surface (solid phase) of the cell).
  • the heating temperature is determined depending on the type of polymerizable composition used, the type of polymerization reaction, the liquid crystal However, it is usually preferable to set the temperature to about room temperature (about 25 ° C.) to about 300 ° C., taking into consideration the properties, viscosity of the polymerizable composition, easiness of heating, and the like. If the heating temperature is lower than the lower limit, it may be difficult to efficiently advance the polymerization reaction or formation of the alignment film due to crystallization of the polymerizable composition or one of the components, or the polymerizable composition.
  • the photopolymerization it is preferable to irradiate light at an intensity of 0.1 ⁇ W / cm 2 ⁇ 30mW / cm 2, the light intensity of 0.5 ⁇ W / cm 2 ⁇ 10mW / cm 2 Irradiation is more preferable. If the illuminance of such light is less than the lower limit, the reaction rate is slow, so the transition speed of the boundary is slow, and the productivity tends to decrease. On the other hand, when the upper limit is exceeded, the polymerizable compound diffuses. When the polymerization reaction rate is too high, the compound is not sufficiently diffused and the oriented film tends to be not obtained.
  • a method for irradiating light to a part of the region is not particularly limited, and for example, using a light source that can irradiate only part of the region.
  • the photomask may be used to irradiate light from a part of the region, but it is preferable to use a photomask because the control of the polymerized region and the unpolymerized region becomes easier.
  • the compound exhibiting liquid crystallinity is aligned after the polymerization of the polymerizable composition is started from a partial region of the film made of the polymerizable composition.
  • the boundary of the region is continuously moved at a speed toward the unpolymerized region. In this way, by continuously moving the boundary between the polymerized region and the unpolymerized region toward the unpolymerized region, the polymerization is continuously performed, and in the region near the moving boundary, It becomes possible to cause the diffusion phenomenon sequentially and continuously, thereby increasing the orientation region continuously and obtaining an orientation film.
  • the polymerization conditions for continuously moving the boundary of the region toward the unpolymerized region in this way, the same conditions as the polymerization conditions at the start of the polymerization described above may be employed.
  • the speed at which the compound exhibiting liquid crystallinity is oriented which is the moving speed when moving the boundary, is formed by polymerization, the type of compound exhibiting liquid crystallinity, the type of compound that diffuses and moves, and polymerization.
  • Type of compound (polymerized product) first polymerizable compound, type of second compound, type of compound obtained after polymerization
  • polymerization conditions employed during polymerization for example, light irradiation when employing photopolymerization
  • the time required for aligning the liquid crystal compound in the film differs depending on the conditions, etc., and so on.
  • the diffusion movement (flow) of the compound in the polymerizable composition in the vicinity of the boundary between the polymerized region and the unpolymerized region due to the concentration gradient of the compound that occurs in the polymerized region and the unpolymerized region, the diffusion movement (flow) of the compound in the polymerizable composition in the vicinity of the boundary between the polymerized region and the unpolymerized region.
  • a kind of shear stress to the liquid crystal compound present in the polymerizable composition to align the liquid crystal compound in the vicinity of the boundary.
  • the “speed at which the compound is aligned” varies depending on the type of the compound exhibiting liquid crystallinity, the type of the compound that diffuses and moves, the type of the compound formed by polymerization (polymer), and the like.
  • the polymerization rate of the first polymerizable compound is very fast, and the concentration gradient of the compound suddenly occurs in the polymerized region and the unpolymerized region, In the case where the moving speed of the first polymerizable compound to the polymerization region is very high, even if the moving speed of the boundary is relatively high, the first polymerizable compound can move to the polymerization region.
  • the shear stress generated along with the movement can be sufficiently applied to the compound exhibiting liquid crystallinity existing in the polymerization region, and the compound exhibiting liquid crystallinity can be sufficiently aligned.
  • the polymerization rate of the polymerizable compound is In the case where the concentration gradient of the compound is gently generated in the polymerized region and the unpolymerized region, and the moving speed of the first polymerizable compound to the polymerized region is slow, the compound exhibiting liquid crystallinity is sufficiently displaced. Since it takes time to apply the stress, if the moving speed of the boundary is increased, it becomes difficult to align a compound exhibiting sufficient liquid crystallinity in the vicinity of the boundary.
  • the rate at which a compound exhibiting liquid crystallinity is aligned refers to the type of compound exhibiting liquid crystallinity, the type of compound that diffuses and moves, the type of compound formed by polymerization (polymer), What is necessary is just to determine so that orientation may arise suitably according to superposition
  • the speed at which such a compound exhibiting liquid crystallinity is aligned is preferably 1 ⁇ 10 ⁇ 7 to 4 ⁇ 10 ⁇ 1 m / s. More preferably, it is 10 ⁇ 6 to 4 ⁇ 10 ⁇ 2 m / s.
  • the polymerization reaction proceeds faster than the diffusion of the compound, so that the diffusion transfer of the compound is suppressed by increasing the viscosity, and the shear stress is sufficiently applied to the compound exhibiting liquid crystallinity.
  • the combination of the first polymerizable compound and the second compound is any one of the above-mentioned preferred combinations, and 0.1 ⁇ W / cm 2 to 30 mW / cm 2 in the polymerization of the polymerizable composition.
  • the speed at which the compound exhibiting liquid crystallinity is oriented (moving speed for moving the boundary) can efficiently form an oriented film. From this point of view, it is preferably set to 1 ⁇ 10 ⁇ 7 to 4 ⁇ 10 ⁇ 1 m / s.
  • the method of continuously moving the boundary of the region toward the unpolymerized region is not particularly limited.
  • the polymerization method is thermal polymerization
  • the heating region is continuously connected to the unpolymerized region. It is only necessary to adopt a method that can be moved in an appropriate manner, and when the polymerization method is photopolymerization, the light irradiation region can be continuously moved to an unirradiated region. Any possible method may be adopted as appropriate.
  • the moving speed of the boundary can be controlled more easily, and an alignment region can be formed more efficiently.
  • the boundary of the light irradiation region is directed to the unexposed region of light. It is preferable to adopt a method of continuously moving them.
  • the method of continuously moving the boundary of the light irradiation region toward the non-irradiated region is not particularly limited as long as it is a method capable of moving the boundary, and the polymerizable composition
  • a method of continuously moving the light source itself so that only a part of the region can be irradiated with light, or a film of the polymerizable composition is continuously moved while fixing the light source.
  • a photomask is used during the photopolymerization, and the photomask is continuously moved. It is preferable to employ a method of using a photomask during the photopolymerization and a method of continuously moving the film of the polymerizable composition while fixing the photomask. As described above, by adopting photopolymerization for the polymerization of the polymerizable composition and using a photomask, the boundary of the light irradiation region can be continuously moved toward the light non-irradiation region. Can be achieved more easily.
  • FIGS. 1 to 4 show preferred embodiments of the method for producing an oriented film of the present invention when the polymerizable composition is polymerized by photopolymerization and a photomask is used for the photopolymerization.
  • a photomask is used for the photopolymerization.
  • FIGS. 1 to 4 first, light is shielded between the film 13 and the light source 11 so that only a partial region of the film 13 is irradiated with light from the light source 11.
  • a possible photomask 14 FIG. 1
  • polymerization of the polymerizable composition is started from a partial region A1 of the film 13 by irradiating light from the light source 11 (see FIG. 2).
  • the boundary S of the polymerization region is directed toward the unpolymerized region A2 at a speed at which the compound exhibiting liquid crystallinity is aligned.
  • the film is moved continuously (in the direction of arrow A) (see FIGS. 3 to 4), thereby obtaining an oriented film.
  • the boundary S between the polymerized region and the unpolymerized region can be moved by a simple method such as a method of moving the photomask 14. This can be achieved, and the oriented film can be produced more efficiently.
  • the oriented film of the present invention when a photomask is used is described.
  • the embodiment of the manufacturing method is not limited to the above embodiment.
  • a method of moving the photomask 14 is adopted in order to move the boundary S between the superposed region and the non-polymerized region.
  • a method of moving the film 13 itself may be employed.
  • the polymerization of the polymerizable composition is started after the light is applied to a part of the region R 1 of the film 13.
  • the polymerization method that can be employed in the method for producing an oriented film is not limited to the method employed in the embodiment, and for example, the entire film is covered with a photomask, and the liquid crystal is started with the start of light irradiation.
  • the photomask or film is continuously moved at a speed at which the compound exhibiting the property is aligned, and the film is introduced into the light irradiation region (exposed portion) at the speed, thereby Polymerization is started from the region (partial region of the film) introduced into the irradiated region (exposed portion), and the boundary of the polymerized region is directed to the unpolymerized region at such a rate that the liquid crystalline compound is oriented as it is.
  • Move the orientation film The method may be employed so as to obtain a Lum.
  • the orientation direction can be easily controlled according to the edge shape of the photomask.
  • the control of the orientation according to the edge shape of the photomask will be briefly described with reference to the embodiments shown in FIGS.
  • a photomask 14 as shown in FIG. 5 is used as a photomask
  • the compound flows in a direction substantially perpendicular to the boundary S shown in FIG.
  • the orientation direction can be controlled.
  • the flow of the compound is basically in a direction substantially perpendicular to the boundary S shown in FIG. Occurs, when the boundary S is substantially perpendicular to the oblique boundary S, or when the movement speed of the boundary S is high, a vector in the direction of movement of the boundary S (arrow A) and a vector in the direction perpendicular to the boundary S (arrow P)
  • the orientation direction can be controlled in the direction of the vector sum. Therefore, when photopolymerization using a photomask is performed, the orientation direction can be easily controlled in a desired direction according to the edge shape of the photomask. Therefore, in order to form a desired alignment direction, it may be used while appropriately changing the edge shape of the photomask, which makes it possible to easily control the alignment direction.
  • FIG. 7 and 8 are schematic plan views schematically showing the relationship between the photomask 14 and the substrate 12 when viewed from the light source side (in the optical axis direction of the irradiated light).
  • the light source, the photomask 14 and the substrate 12 are disposed so that the film disposed on the substrate 12 can be photopolymerized by the light transmitted through the opening 14A.
  • Such a photomask 14 shown in FIGS. 7 and 8 has a plurality of substantially rectangular openings 14A.
  • the “substantially rectangular shape” means a shape corresponding to a rectangular shape such as the opening 14A shown in FIG. 7, four rectangular corners having an arc shape, or a long side or a short side of the rectangle. 8 is a parallelogram shape in which the angles of the four corners are not 90 degrees, such as the opening 14A shown in FIG. Includes arc-shaped ones and shapes in which a portion corresponding to a long side or a short side is an arc-shaped side).
  • the substantially rectangular opening is such that the side of the opening corresponding to the long side (which may be an arcuate side) corresponds to the short side (which may be an arcuate side) like a rectangle. It is an expression intended to be an elongated shape that is longer than the side.
  • Such a substantially rectangular shape (elongate shape) of the opening 14A is not particularly limited, and the long side length Y may be longer than the short side length X.
  • the ratio (Y / X) of the long side length Y to the short side length X is preferably 2.0 or more, more preferably 5.0 to 2.0 ⁇ 10 5. preferable. ).
  • the length X of the short side of the opening 14A differs depending on the substrate 12 used in the polymerization, the size of the film, and the like, and cannot be generally described, but is 1 ⁇ m to 10 mm.
  • the thickness is preferably 10 ⁇ m to 1 mm.
  • the long sides of each opening are arranged substantially in parallel.
  • the openings 14A are preferably formed periodically, and it is more preferable that the openings 14A having the same shape are formed periodically.
  • the pitch of the openings 14A is not particularly limited, but is preferably 1 ⁇ m to 10 mm, and more preferably 10 ⁇ m to 1 mm. .
  • the pitch of the openings 14A When the pitch of the openings 14A is less than the lower limit, the orientation tends to be difficult to occur. On the other hand, when the pitch exceeds the upper limit, a film having a uniform in-plane orientation tends to be hardly obtained.
  • the number of openings may be two or more and is not particularly limited, and the design may be changed as appropriate depending on the size of the mask and the substrate. it can.
  • an opening is formed in a film formed on the substrate while moving the substrate 12 in the same direction as the direction A.
  • the boundary S of the polymerization region is formed for each opening 14A, and each boundary S is continuously moved toward the unpolymerized region.
  • the mask is moved to the same length as the interval (distance) between adjacent openings, thereby aligning in a large area. A region can be formed, and an oriented film can be efficiently formed.
  • the orientation direction can be controlled according to the shape of the edge of the opening 14A.
  • the orientation direction can be controlled in a direction perpendicular to the long side of the opening 14A.
  • the edge of the opening 14 ⁇ / b> A has two sides of the substrate 12 when viewed from the light source side.
  • the compound flows in a direction substantially perpendicular to the long side of the opening 14A due to the polymerization, and is substantially perpendicular to the long side, or the moving speed of the substrate 12 Is fast, the orientation direction can be controlled in the direction of the vector sum of the vector in the moving direction (arrow A) and the vector in the direction substantially perpendicular to the long side (arrow P).
  • the photopolymerization methods that can be suitably employed in the present invention have been described with reference to FIGS. 7 to 8, the photopolymerization methods that can be employed in the present invention are limited to these methods. Is not to be done.
  • photopolymerization may be performed by appropriately adopting a method of fixing the substrate 12 and moving the mask and the light source.
  • the boundary between the regions is formed at such a speed that the compound exhibiting liquid crystallinity is aligned.
  • An oriented film is manufactured by continuously moving toward an unpolymerized region, but a prepolymerized film is used as a film made of a polymerizable composition used for manufacturing such an oriented film. May be.
  • preliminary polymerization means that the film of the polymerizable composition is slightly polymerized to such an extent that the flowability of the polymerizable composition is not impaired (for example, light is applied to both prepolymerization and main polymerization).
  • the film of the polymerizable composition is irradiated with light that is weaker than the main polymerization to slightly polymerize the components in the film to such an extent that fluidity is not impaired.
  • the present invention from the viewpoint of forming an oriented film in as short a time as possible by increasing the speed of continuously moving the boundary of the polymerization region toward the unpolymerized region, after pre-polymerization
  • a prepolymerization method is not particularly limited.
  • the preliminary polymerization is, for example, preliminary polymerization by photopolymerization using a photomask in which a plurality of substantially rectangular openings are formed so that the long sides of each opening are substantially parallel. There may be.
  • the light is irradiated with an intensity of 2 . If the illuminance of light is less than the lower limit, the reaction tends to be inadequate and the effect of prepolymerization tends to be difficult to obtain. On the other hand, when the upper limit is exceeded, polymerization of the polymerizable compound proceeds excessively, resulting in the polymerization.
  • the boundary of the region is continuously directed toward the unpolymerized region at such a rate that the compound exhibiting liquid crystallinity is oriented. Even if it is moved, the compound does not sufficiently diffuse and tends to be unable to obtain an oriented film.
  • the photopolymerization conditions are the same as the photopolymerization conditions described as the polymerization method of the polymerizable composition, except for the conditions relating to the illuminance of the light. The following conditions can be adopted.
  • the first polymerizable compound and the second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions, and A film composed of a polymerizable composition, wherein at least one of the first polymerizable compound, the second compound and the compound obtained after polymerization is a compound exhibiting liquid crystallinity.
  • the boundary of the region is continuously moved toward the unpolymerized region at a speed such that the compound exhibiting liquid crystallinity is aligned. It is possible to obtain a conductive film.
  • the compound exhibiting liquid crystallinity is obtained by utilizing a kind of shear stress generated by a compound that moves from an unpolymerized region to a polymerized region in the film after the start of polymerization. From the orientation, it is basically possible to control the orientation direction in the direction in which the compound moves (the direction perpendicular to the boundary of the region). Accordingly, it is possible to control the orientation in various directions according to the pattern orientation and change the orientation direction depending on the location.
  • the present invention is a method for forming an orientation by utilizing a substance diffusion phenomenon while moving the boundary of the polymerization region, and thereby increasing the orientation region.
  • the polymerization further proceeds in order to complete the polymerization reaction.
  • the film may be allowed to stand under temperature conditions.
  • a step of further proceeding the polymerization may be separately performed.
  • the orientation is formed by utilizing the diffusion phenomenon of the substance while moving the boundary of the polymerization region.
  • an oriented film having an oriented structure fixed may be obtained.
  • the conditions for such a post-polymerization step are not particularly limited, and may be carried out while appropriately changing according to the type of components in the polymerizable composition to be used.
  • a long oriented film can be produced by roll-to-roll by using a long substrate film or the like for the substrate.
  • the orientation film obtained by the method for producing an orientation film of the present invention can be a film in which the orientation of the compound exhibiting liquid crystallinity is formed in a large area, and therefore a polarizing plate or a liquid crystal It can be used as a retardation film for use in a display (LCD), a retardation film for use in an antireflection circularly polarizing plate of an organic EL display, or a 3D pattern retardation film.
  • LCD display
  • a retardation film for use in an antireflection circularly polarizing plate of an organic EL display or a 3D pattern retardation film.
  • the 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl thus obtained is a compound having a rigid cyanobiphenyl structure as a mesogen, as is clear from the above formula (4). Further, using a differential scanning calorimeter (DSC 6220 manufactured by DSC SII Nano Technology), the temperature was raised and lowered at a rate of 1 ° C./min to give 4- (6-acryloyloxyhexyloxy) -4′-cyanobiphenyl. As a result of confirming the behavior of the liquid crystal phase, the liquid crystal phase is not shown, and the phase transition from the crystal layer to the isotropic phase is 69 ° C. during the temperature rising process, and the phase is changed from isotropic phase to crystallinity at 53 ° C. during the temperature lowering process. Phase transition.
  • Irgacure 651 manufactured by BASF
  • a photopolymerization initiator was added at a ratio of 1 mol% with respect to all the compounds, and once dissolved in dichloromethane, the solvent was distilled off to obtain a polymerizable composition.
  • a product was prepared. As the solvent is distilled off, some components also evaporate, and the molar ratio of the first polymerizable compound and the second compound in the polymerizable composition ([first polymerizable compound]: The [second compound]) was 2:98.
  • the polymerization completion times of the first polymerizable compound and the second compound were measured as follows.
  • Two soda glass substrates with a size of 25 mm square and a thickness of 1.1 mm are made with a polyimide tape with a thickness of 100 ⁇ m as a spacer, and the overlapping area of the planar portions of the upper and lower substrates is 15 mm long and 25 mm wide (spacer A glass cell having a cell thickness of 100 ⁇ m was produced by bonding the parallel surfaces so that the sides parallel to the long side direction overlap each other by 15 mm (in this cell, the spacers were formed by two parallel vertical two sides (left and right) of the glass substrate).
  • the portions of the glass substrate that were formed at the locations and were not formed with spacers were openings, and the size inside the cell was 15 mm long, 10 mm wide, and 100 ⁇ m thick.
  • a mixture in which the photopolymerization initiator Irgacure 651 was mixed with the compound for measuring the polymerization completion time so as to have a content of 1 mol% was prepared.
  • the glass cell was placed on a hot stage (trade names “FP-90, FP-82HT” manufactured by METTLER TOLEDO), and then the glass mixture was melted at a temperature of 100 ° C. by capillary action while melting the mixture.
  • the first polymerizable compound (EGDMA) was confirmed to form a film with an irradiation time of 30 seconds, and the polymerization completion time was confirmed to be between 15 seconds and 30 seconds, and the second compound (A6CB). ), Film formation was confirmed at an irradiation time of 60 seconds, and polymerization completion time was confirmed to be between 30 seconds and 60 seconds or less.
  • soda glass substrates each having a size of 25 mm square and a thickness of 1.1 mm are mixed with epoxy adhesive mixed with silica particles having a diameter of 2 ⁇ m on the left and right ends (two parallel sides) of the glass substrate.
  • a glass cell having a cell thickness of 2 ⁇ m was applied by applying and adhering them with a length of 25 mm and a width of 2.5 mm (the adhesive also functions as a spacer. The portions not applied with the adhesive were used as openings). did.
  • the soda glass substrate used was subjected to UV ozone treatment after ultrasonic cleaning in the order of neutral detergent, ion-exchanged water, acetone and isopropanol.
  • the polymerizable composition was melted under a temperature condition of 100 ° C. After pouring the polymerizable composition into the glass cell from one opening by capillary action through the opening, the temperature was lowered to 85 ° C. at a rate of 0.5 ° C./min, and then held at 85 ° C. for 10 minutes. A film of the polymerizable composition (film size: length 20 mm, width 20 mm, thickness 2 ⁇ m) was obtained.
  • a photomask having a square shape with a length of 30 mm and a width of 30 mm was fixedly disposed so as to cover the entire film in the glass cell (so that the film enters the light shielding portion).
  • light irradiation is started from the light source, the glass cell is moved while irradiating light, and the film in the glass cell is moved toward the light irradiation region at 25 ⁇ m / s, so that the exposure unit Polymerization is started from a partial region of the introduced film, and the boundary between the light irradiation region and the light non-irradiation region is continuously moved toward the non-irradiation region at 25 ⁇ m / s under a temperature condition of 85 ° C.
  • the exposed portion A1 on the soda glass substrate 12 of the cell before moving the glass cell is a rectangle of 5 mm in length and 25 mm in width.
  • the region is a region of 5 mm vertically from the opening on the side where the polymerizable composition is not injected, and the film does not exist in the region.
  • the direction of movement of the cell is the direction perpendicular to the boundary S of the light irradiation area A1 (as shown in FIGS. 5A to 5B). Direction opposite to the direction indicated by arrow A).
  • FIG. 5A to 5B Direction opposite to the direction indicated by arrow A).
  • FIG. 5 is a schematic plan view schematically showing a state in which the substrate and the photomask are viewed from the light source side (the optical axis direction of light to be irradiated).
  • a high pressure mercury lamp (trade name “SX-UI501HQ” manufactured by Ushio Inc.) is used as a light source, and a colored glass filter (manufactured by AGC Techno Glass Co., IRA-265, UV-D54C, ND) is used. (90%) and ND (40%) were used in combination and irradiated with ultraviolet light having an illuminance of 16 ⁇ W / cm 2 (peak wavelength: 366 nm).
  • the glass cell was inserted between two orthogonally arranged polarizing plates and observed while rotating the glass cell. And it was confirmed that the obtained film was an orientation film oriented almost uniformly in an area of about 20 mm square. The dark field direction was parallel or perpendicular to the absorption axes of the two polarizing plates arranged orthogonally. Further, when the orientation state was confirmed using a polarizing microscope (trade name “BX50” manufactured by Olympus Corporation), the obtained film was uniformly oriented, and the orientation was confirmed even in a minute region.
  • a polarizing microscope trade name “BX50” manufactured by Olympus Corporation
  • an absorption spectrum (A ⁇ ) in a direction perpendicular to the mask edge of the photomask and an absorption spectrum in a direction parallel to the mask edge of the photomask ( A //) was measured.
  • an ultraviolet-visible spectrophotometer V-650ST manufactured by JASCO Corporation
  • the polarization direction was adjusted using a Grand Taylor prism.
  • FIG. 9 shows an absorption spectrum. As is clear from the results of the absorption spectrum shown in FIG. 9, the absorbance of the absorption spectrum (A ⁇ ) in the direction perpendicular to the mask edge of the photomask is greater than the absorption spectrum (A //) in the parallel direction. I understood.
  • the order parameter S showed a very large value of 0.39.
  • the order parameter S was obtained from the average value after obtaining the order parameter S for each wavelength from the absorbance (A) data in increments of 1 nm between the measurement wavelengths of 305 nm and 325 nm.
  • the compound having liquid crystallinity (polymer having a structural unit derived from A6CB) is against the mask edge (boundary S in FIG. 5) of the photomask. It was found to be oriented in the vertical direction. Further, when the retardation ⁇ nd was confirmed using a Belek compensator (U-CBE manufactured by Olympus), the ⁇ nd for light having a wavelength of 546 nm was 80 nm. In addition, when birefringence (DELTA) n was calculated and calculated
  • Example 2 The cell thickness was changed from 2 ⁇ m to 3 ⁇ m, the illuminance of ultraviolet light was changed from 16 ⁇ W / cm 2 to 50 ⁇ W / cm 2 (peak wavelength: 365 nm), and the cell moving speed was changed from 25 ⁇ m / s to 2.5 ⁇ m / s.
  • a film was obtained in the same manner as in Example 1.
  • Example 2 In order to confirm the characteristic of the film obtained in Example 2, when the said glass cell was inserted between two polarizing plates arrange
  • a polarizing microscope trade name “BX50” manufactured by Olympus Co., Ltd.
  • the compound having liquid crystallinity (polymer having a structural unit derived from A6CB) is against the mask edge (boundary S in FIG. 5) of the photomask. It was found to be oriented in the vertical direction. Further, when the retardation ⁇ nd was confirmed using a Belek compensator (U-CBE manufactured by Olympus), the ⁇ nd with respect to light having a wavelength of 546 nm was 465 nm. In addition, when birefringence (DELTA) n was calculated and calculated
  • 1-hexanediol dimethacrylate (HDDMA: manufactured by Tokyo Chemical Industry Co., Ltd .: bifunctional methacrylate) represented by the following formula:
  • the glass is prepared by utilizing the first polymerizable compound and the second compound so that the molar ratio of the two compounds ([first polymerizable compound]: [second compound]) is 4:96.
  • a film (transparent uncolored: thickness after curing: 1.8 ⁇ m) was obtained in the same manner as in Example 1 except that post-polymerization was performed to further advance the polymerization.
  • the moving direction of the boundary S is the same as that in the first embodiment.
  • the polymerization completion time of said 1st polymeric compound (HDDMA) was measured using the method similar to Example 1, said 1st polymeric compound (HDDMA) was a film in irradiation time 30 seconds.
  • the polymerization completion time was more than 15 seconds and not more than 30 seconds.
  • Example 1 In order to confirm the characteristic of the film obtained in Example 3, when the said glass cell was inserted between two polarizing plates arrange
  • a polarizing microscope trade name “BX50” manufactured by Olympus Co., Ltd.
  • the absorption spectrum (A ⁇ ) in the direction perpendicular to the mask edge of the photomask and the absorption spectrum in the parallel direction (A / /) was measured, and the order parameter S was obtained from the calculation formula (1).
  • the order parameter S showed a very large value of 0.37.
  • the compound having liquid crystallinity (a polymer having a structural unit derived from A6CB) is against the mask edge (boundary S in FIG. 5) of the photomask. It was found to be oriented in the vertical direction. Furthermore, when retardation ⁇ nd was confirmed using a Belek compensator (U-CBE manufactured by Olympus), ⁇ nd with respect to light having a wavelength of 546 nm was 150 nm. In addition, when birefringence (DELTA) n was calculated and calculated
  • Example 4 Before starting the photopolymerization, the prepolymerization step described below is performed on the film of the polymerizable composition to use the prepolymerized film for the photopolymerization, and the photomask for the photopolymerization is used.
  • a film was obtained in the same manner as in Example 3 except that the moving speed was changed from 20 ⁇ m / s to 2000 ⁇ m / s, and the conditions for post-polymerization (conditions for standing) were changed to 120 ° C. for 10 minutes. (Transparent uncolored: thickness after curing: 2 ⁇ m) was obtained.
  • film size: length 20 mm, width 20 mm, thickness 2 ⁇ m: film obtained by injecting the polymerizable composition into the glass cell from the opening by capillary action On the other hand, using a mask in which a plurality of substantially rectangular openings are formed so that the long sides of each opening are substantially parallel as shown in FIG. A preliminary polymerization step of irradiating with light was performed.
  • FIG. 7 shows the relationship between the mask used for such pre-polymerization and the substrate (soda glass substrate forming a glass cell on which the film of the polymerizable composition is formed) when viewed from the light source side.
  • the description will be given with reference.
  • FIG. 7 is a schematic plan view schematically showing the relationship between the mask 14 and the substrate 12 (soda glass substrate forming a glass cell on which the film of the polymerizable composition is formed) when viewed from the light source side. .
  • the edge (long side) of the opening 14A of the mask 14 and the two sides on the substrate 12 2 in contact with the long side).
  • the mask 14 was arranged so that the angle formed with the side) was 90 °.
  • the length X of the short side of each opening is 100 ⁇ m
  • the length Y of the long side of each opening is 40 mm
  • each opening has the same shape and is periodically arranged.
  • a so-called grating mask is used (in FIG. 7, the number of openings 14A is four, but in reality, many openings are formed at a pitch of 200 ⁇ m in a region longer than the length of the film having a length of 20 mm.
  • FIG. 10 A polarizing microscope (POM) photograph showing a part of the mask actually used is shown in FIG. 10).
  • the entire film of the polymerizable composition in the glass cell was covered with a mask (openings of a plurality of masks were formed on the film). Covered with a mask to be placed).
  • a light source is arranged on the film so that light is always irradiated through the opening of the mask (if the mask is not present, the light source is placed at a position where the entire surface of the film is irradiated with light. Arranged.) The film is irradiated only with light transmitted through the opening during the prepolymerization.
  • a prepolymerization step of polymerizing under a temperature condition of 120 ° C. without fixing and moving the mask was performed for 1 minute.
  • a high pressure mercury lamp (trade name “SX-UI501HQ” manufactured by Ushio Inc.) is used as a light source, and a colored glass filter (manufactured by AGC Techno Glass Co., IRA-265, UV-) is used.
  • Example 4 after carrying out the prepolymerization step as described above, a film was formed by performing photopolymerization on the film after the prepolymerization as described above.
  • the glass cell was inserted between two polarizing plates arranged orthogonally and observed while rotating the glass cell. Similar to the film obtained in 1 above, it was confirmed that the film obtained in Example 4 had a dark field and a bright field, and was an oriented film oriented almost uniformly in an area of about 20 mm square. It was.
  • the direction of the dark field was a direction parallel or perpendicular to the absorption axes of the two polarizing plates arranged orthogonally. Further, when the orientation state was confirmed using a polarizing microscope (trade name “BX50” manufactured by Olympus Co., Ltd.), the obtained film was uniformly oriented, and the orientation was confirmed even in a minute region.
  • a photomask used for photopolymerization is a mask formed by arranging a plurality of substantially rectangular openings such that the long sides of each opening are substantially parallel as shown in FIG.
  • the mask is the same as that used in Example 4), the moving speed of the photomask is changed from 20 ⁇ m / s to 2 ⁇ m / s, the moving time of the photomask is set to 50 seconds, and the photomask is used for photopolymerization.
  • the film transparent uncolored: thickness after curing: 1. thickness
  • FIG. 7 is a schematic plan view schematically showing the relationship between the mask 14 and the substrate 12 (soda glass substrate forming a glass cell on which the film of the polymerizable composition is formed) when viewed from the light source side.
  • the same mask so-called grating mask
  • the photomask 14 In the photopolymerization, when viewed from the light source side, the angle formed by the edge (long side) of the opening 14A of the mask 14 and the two sides (two sides in contact with the long side) on the substrate 12 is 90.
  • the mask 14 was arranged so as to be at an angle. Further, in such photopolymerization, as schematically shown in FIG.
  • the mask when viewed from the light source side, the entire film of the polymerizable composition in the glass cell is covered with a mask, A mask was disposed (the mask was disposed such that openings of a plurality of masks were disposed on the film). Furthermore, when arranging such a mask, when viewed from the light source side, the mask is arranged so that the end (outer edge) of the mask does not pass over the film during the movement of the mask (the mask is always on the film). The mask is placed so that the short side of the opening does not pass over the film during movement of the mask when viewed from the light source side (when viewed from the light source side).
  • the mask was arranged so that the short side of the opening 14A and the two sides on the substrate 12 in contact with the long side of the opening were parallel.
  • a light source is arranged on the film so that light is always emitted through the opening of the mask, and the mask, film, and light source are arranged so that the entire surface of the film is irradiated as a result of movement of the mask.
  • the light source was placed at a position where the entire surface of the film was irradiated with light if no mask was present.
  • the film is irradiated only with the light transmitted through the opening.
  • irradiation of light from the light source was started, and while irradiating light, the mask was moved at a speed of 2 ⁇ m / s for 50 seconds to irradiate the entire surface of the film.
  • the moving direction of the mask was a direction perpendicular to the long side of the opening 14A of the mask (the same direction as the direction A in FIG. 7).
  • a high pressure mercury lamp (trade name “SX-UI501HQ” manufactured by Ushio Inc.) is used as a light source, and a colored glass filter (manufactured by AGC Techno Glass Co., IRA-265, UV-) is used.
  • D54C, ND (90%), and ND (40%) were used in combination, and ultraviolet light with an illuminance of 1.0 ⁇ W / cm 2 (peak wavelength: 366 nm) was irradiated through the opening 14A.
  • Example 5 in order to confirm the characteristics of the film (Example 5) obtained by performing photopolymerization using a photomask having an opening (so-called grating mask), between two polarizing plates arranged orthogonally
  • the film obtained in Example 5 had a dark field and a bright field. It was confirmed that the film was oriented uniformly in a 20 mm square region.
  • the direction of the dark field was a direction parallel or perpendicular to the absorption axes of the two polarizing plates arranged orthogonally.
  • a polarizing microscope trade name “BX50” manufactured by Olympus Co., Ltd.
  • the compound having liquid crystallinity (polymer having a structural unit derived from A6CB) was exposed at the edge of the opening of the photomask (the length of the opening in FIG. 7). It was found that the film was oriented in a direction perpendicular to (side). Further, when the retardation ⁇ nd was confirmed using a Belek compensator (U-CBE manufactured by Olympus), the ⁇ nd with respect to light having a wavelength of 546 nm was 290 nm.
  • U-CBE Belek compensator
  • a photomask used for photopolymerization is a mask formed by arranging a plurality of substantially rectangular openings such that the long sides of each opening are substantially parallel as shown in FIG.
  • the mask is the same as that used in Example 4), the moving speed of the photomask is changed from 20 ⁇ m / s to 2 ⁇ m / s, the moving time of the photomask is set to 50 seconds, and the photomask is used for photopolymerization.
  • the film transparent uncolored: thickness after curing: 1. thickness
  • FIG. 11 is a schematic plan view schematically showing the relationship between the mask 14 and the substrate 12 (soda glass substrate forming a glass cell on which the film of the polymerizable composition is formed) when viewed from the light source side.
  • the photomask 14 is the same as the photomask used in Embodiment 4, and when the mask is viewed from the light source side as schematically shown in FIG. The angle formed by the long side of 14A and the two sides on the substrate in contact with the long side was 45 °.
  • the mask is covered so that the entire film of the polymerizable composition in the glass cell is covered with the mask.
  • the mask was arranged such that the openings of the plurality of masks were arranged on the film.
  • the mask when placed such a mask, when viewed from the light source side, the mask is arranged so that the end (outer edge) of the mask does not pass over the film during movement of the mask (the mask is always on the film). Further, the mask was arranged so that the short side of the opening did not pass over the film during the movement of the mask when viewed from the light source side.
  • a light source is arranged on the film so that light is always emitted through the opening of the mask, and the mask, film, and light source are arranged so that the entire surface of the film is irradiated as a result of movement of the mask.
  • the light source was placed at a position where the entire surface of the film was irradiated with light if no mask was present.
  • the film is irradiated only with the light transmitted through the opening.
  • light irradiation was started from a light source, and while irradiating light, the mask was moved at a speed of 2 ⁇ m / s for 50 seconds to irradiate the entire surface of the film. Note that the moving direction of the mask was the same as the direction indicated by the arrow A in FIG.
  • a high-pressure mercury lamp (trade name “SX-UI501HQ” manufactured by Ushio Inc.) is used as a light source, and a colored glass filter (manufactured by AGC Techno Glass Co., IRA-265, UV-) is used.
  • D54C, ND (90%), and ND (40%) were used in combination, and ultraviolet light with an illuminance of 1.0 ⁇ W / cm 2 (peak wavelength: 366 nm) was irradiated through the opening 14A.
  • Example 6 the photopolymerization performed in Example 6 is performed so that the angle of the region S is 45 ° with respect to the two sides of the substrate 12 (the long side of the opening is arranged at 45 ° obliquely).
  • photopolymerization was performed, and basically the same method as the photopolymerization employed in Example 5 was adopted except that the mask was rotated by 45 ° and arranged.
  • the characteristics of the film (Example 6) obtained by performing photopolymerization using a photomask (so-called grating mask) so that the edge of the opening 14A is obliquely arranged are confirmed. Therefore, when the glass cell was inserted between two orthogonally arranged polarizing plates and observed while rotating, the glass cell had a dark field and a bright field as in the film obtained in Example 1. And it was confirmed that the film obtained in Example 6 is an oriented film oriented almost uniformly in an area of about 20 mm square. The direction of the dark field was a direction parallel or perpendicular to the absorption axes of the two polarizing plates arranged orthogonally. Further, when the orientation state was confirmed using a polarizing microscope (trade name “BX50” manufactured by Olympus Co., Ltd.), the obtained film was uniformly oriented, and the orientation was confirmed even in a minute region.
  • a polarizing microscope trade name “BX50” manufactured by Olympus Co., Ltd.
  • the compound having liquid crystallinity (polymer having a structural unit derived from A6CB) is longer than the long side (mask edge) of the opening of the photomask. It was found that the film was oriented in a vertical direction (a direction inclined by 45 ° with respect to the end of the cell). Further, when the retardation ⁇ nd was confirmed using a Belek compensator (U-CBE manufactured by Olympus), the ⁇ nd with respect to light having a wavelength of 546 nm was 140 nm.
  • Example 7 The photomask used in the photopolymerization is changed to a mask having edges obliquely arranged as schematically shown in FIG. 12, and the moving speed of the photomask is changed from 20 ⁇ m / s to 2 ⁇ m / s.
  • a film transparent uncolored: as in Example 3) except that the photomask was placed and moved as follows during polymerization, and the post-polymerization conditions were changed to 120 ° C. and 10 minutes. Thickness after curing: 2 ⁇ m) was obtained.
  • FIG. 12 shows the relationship between the photomask used for photopolymerization and the substrate when viewed from the light source side (a soda glass substrate forming a glass cell on which the film of the polymerizable composition is formed). A brief description will be given with reference.
  • FIG. 12 is a schematic plan view schematically showing a relationship between the mask 14 and the substrate 12 (soda glass substrate forming a glass cell on which the film of the polymerizable composition is formed) when viewed from the light source side.
  • the photomask 14 is the same as the photomask used in Embodiment 3, and when the mask is viewed from the light source side, the boundary S that is an edge and the substrate that contacts the boundary S The angle between the upper two sides was 45 °.
  • the moving direction of the mask was the same as the direction indicated by the arrow A in FIG.
  • a high-pressure mercury lamp (trade name “SX-UI501HQ” manufactured by Ushio) is used as a light source, and a colored glass filter (manufactured by AGC Techno Glass, IRA-265, UV-) is used.
  • D54C, ND (90%), and ND (40%)) were used in combination and irradiated with ultraviolet light having an illuminance of 1.0 ⁇ W / cm 2 (peak wavelength: 366 nm).
  • the photopolymerization performed in Example 7 is performed such that the angle of the boundary S is 45 ° with respect to the two sides of the substrate 12.
  • a method similar to the photopolymerization employed in Example 3 was employed except that a mask having S of 45 ° was used.
  • Example 7 in order to confirm the characteristics of the film (Example 7) obtained by performing photopolymerization by using a photomask so that the edges of the mask are arranged obliquely, they were arranged orthogonally.
  • the glass cell was inserted between two polarizing plates and observed while rotating the glass cell, it had a dark field and a bright field as in the film obtained in Example 1, and was obtained in Example 7.
  • the obtained film was an oriented film which was oriented almost uniformly in an area of about 20 mm square.
  • the direction of the dark field was a direction inclined by 45 ° with respect to the absorption axes of the two polarizing plates arranged orthogonally.
  • the orientation state was confirmed using a polarizing microscope (trade name “BX50” manufactured by Olympus Co., Ltd.), the obtained film was uniformly oriented, and the orientation was confirmed even in a minute region.
  • the compound having liquid crystallinity (polymer having a structural unit derived from A6CB) was perpendicular to the photomask boundary S (mask edge). It was found that the film was oriented in a direction inclined by 45 ° with respect to the end of the cell. Furthermore, when retardation ⁇ nd was confirmed using a Belek compensator (U-CBE manufactured by Olympus), ⁇ nd with respect to light having a wavelength of 546 nm was 390 nm. In addition, when birefringence (DELTA) n was calculated and calculated
  • Example 7 As is clear from the results as described above, it was confirmed that in the films obtained in Examples 1 to 7, an oriented film uniformly oriented over almost the entire polymerization region was formed. According to the method for producing an oriented film of the present invention, it was found that an oriented film having a large area can be produced. In addition, from the result of Example 4, it was also confirmed in the present invention that an orientation film can be efficiently formed at a sufficient rate. In addition, the film obtained in Example 5 achieves uniform alignment over the entire film with a mask moving distance of 100 ⁇ m (for the distance between the openings).
  • Example 5 From these results (Example 5), it can be seen that by using a photomask having a plurality of openings, it is possible to more efficiently manufacture an alignment film having an alignment region formed in a large area. Further, in Examples 6 and 7, the photo-polymerization is performed with the mask edge inclined, so that the orientation is formed in a direction substantially perpendicular to the mask edge. It was found that the orientation direction can be sufficiently controlled by the shape.
  • the method for producing an orientation film according to the present invention is a particularly excellent method in that an orientation region can be formed in a large area.
  • the orientation film can be used for a polarizing plate or a liquid crystal display (LCD). It is useful as a method for producing an alignment film for use as a retardation film, a retardation film for use in an antireflection circularly polarizing plate for organic EL displays, a 3D pattern retardation film, and the like.
  • 11 light source
  • 12 substrate
  • 13 film made of polymerizable composition
  • 14 photomask
  • 14A opening
  • X length of short side of opening 14A
  • Y length of long side of opening 14A
  • S boundary of overlapping region
  • A arrow conceptually indicating a direction in which the boundary S of overlapping region is moved
  • P arrow conceptually indicating a direction perpendicular to the boundary S of overlapping region
  • L irradiation from a light source
  • A1 region irradiated with light (polymerized region: exposed portion)
  • A2 unpolymerized region not irradiated with light (unpolymerized region: light-shielding portion)
  • A3 orientation formed Area.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un film à cristaux liquides alignés (dans lequel les molécules de cristaux liquides sont alignées) à l'aide d'un film de départ comprenant une composition polymérisable qui comprend un premier composé polymérisable et un second composé qui présente un temps d'achèvement de polymérisation plus long que celui du premier composé polymérisable, les deux temps d'achèvement de polymérisation étant déterminés dans les mêmes conditions de polymérisation, et dans lequel le premier composé polymérisable, le second composé et/ou le composé obtenu après la polymérisation est un composé de cristaux liquides. Le procédé est caractérisé par l'amorçage de la polymérisation de la composition polymérisable dans une région partielle du film de départ, puis le déplacement de la limite de la région de façon continue vers une région non polymérisée à une vitesse de telle sorte que le composé de cristaux liquides peut être aligné, et l'obtention par là d'un film à cristaux liquides alignés.
PCT/JP2013/066002 2012-09-04 2013-06-10 Procédé de fabrication de film à cristaux liquides alignés WO2014038260A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020157008383A KR101993955B1 (ko) 2012-09-04 2013-06-10 배향성 필름의 제조 방법
JP2014534217A JP5992047B2 (ja) 2012-09-04 2013-06-10 配向性フィルムの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-194598 2012-09-04
JP2012194598 2012-09-04

Publications (1)

Publication Number Publication Date
WO2014038260A1 true WO2014038260A1 (fr) 2014-03-13

Family

ID=50236883

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/066002 WO2014038260A1 (fr) 2012-09-04 2013-06-10 Procédé de fabrication de film à cristaux liquides alignés

Country Status (4)

Country Link
JP (1) JP5992047B2 (fr)
KR (1) KR101993955B1 (fr)
TW (1) TW201414819A (fr)
WO (1) WO2014038260A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208236A1 (fr) * 2013-06-28 2014-12-31 国立大学法人東京工業大学 Procédé de production d'un film orienté
KR20170122644A (ko) 2016-04-27 2017-11-06 엘지디스플레이 주식회사 광학이방성 고분자막, 유기el표시장치 및 액정표시장치의 제조 방법
JP2018032010A (ja) * 2016-08-18 2018-03-01 富士フイルム株式会社 光学フィルムの製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107632727B (zh) * 2016-07-18 2024-04-12 京东方科技集团股份有限公司 触摸显示屏及其制备方法、显示装置和驱动方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003048903A (ja) * 2001-08-08 2003-02-21 Dainippon Ink & Chem Inc 光学異方体の製造方法
JP2005173547A (ja) * 2003-07-31 2005-06-30 Dainippon Ink & Chem Inc 光学異方体の製造方法
JP2009276652A (ja) * 2008-05-16 2009-11-26 Lintec Corp 光照射方法、光学フィルムの製造方法および光照射装置
WO2012014803A1 (fr) * 2010-07-30 2012-02-02 シャープ株式会社 Dispositif d'affichage à cristaux liquides et son procédé de production
JP2012137616A (ja) * 2010-12-27 2012-07-19 Dic Corp 立体画像表示装置用複屈折レンズ材料、及び、立体画像表示装置用複屈折レンズの製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007093785A (ja) * 2005-09-27 2007-04-12 Fujifilm Corp 表示装置用部材の製造方法、及び表示装置用部材並びに表示装置
JP2010032860A (ja) * 2008-07-30 2010-02-12 Sony Corp 配向膜及びその製造方法、配向基板及びその製造方法、並びに液晶表示素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003048903A (ja) * 2001-08-08 2003-02-21 Dainippon Ink & Chem Inc 光学異方体の製造方法
JP2005173547A (ja) * 2003-07-31 2005-06-30 Dainippon Ink & Chem Inc 光学異方体の製造方法
JP2009276652A (ja) * 2008-05-16 2009-11-26 Lintec Corp 光照射方法、光学フィルムの製造方法および光照射装置
WO2012014803A1 (fr) * 2010-07-30 2012-02-02 シャープ株式会社 Dispositif d'affichage à cristaux liquides et son procédé de production
JP2012137616A (ja) * 2010-12-27 2012-07-19 Dic Corp 立体画像表示装置用複屈折レンズ材料、及び、立体画像表示装置用複屈折レンズの製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208236A1 (fr) * 2013-06-28 2014-12-31 国立大学法人東京工業大学 Procédé de production d'un film orienté
JP2015011222A (ja) * 2013-06-28 2015-01-19 国立大学法人東京工業大学 配向性フィルムの製造方法
KR20170122644A (ko) 2016-04-27 2017-11-06 엘지디스플레이 주식회사 광학이방성 고분자막, 유기el표시장치 및 액정표시장치의 제조 방법
JP2018032010A (ja) * 2016-08-18 2018-03-01 富士フイルム株式会社 光学フィルムの製造方法

Also Published As

Publication number Publication date
JPWO2014038260A1 (ja) 2016-08-08
KR20150052203A (ko) 2015-05-13
KR101993955B1 (ko) 2019-06-27
TW201414819A (zh) 2014-04-16
JP5992047B2 (ja) 2016-09-14

Similar Documents

Publication Publication Date Title
KR101313044B1 (ko) 중합성 조성물
TWI419872B (zh) A polymerizable compound and a polymerizable composition
JP6192710B2 (ja) 表面ダイレクタ配向層及び該層を含む液晶デバイス
JP5055757B2 (ja) 液晶性多官能アクリレート誘導体およびその重合体
JP5310548B2 (ja) 重合性の液晶性化合物、液晶組成物および重合体
WO2005116165A1 (fr) Composition de cristaux liquides polymérisable et corps anisotrope optiquement
KR20120008425A (ko) 광학 필름, 이의 제조방법, 및 이를 포함하는 액정 표시 장치
KR20110003312A (ko) 3관능 (메타)아크릴레이트 화합물 및 상기 화합물을 함유하는 중합성 조성물
JP2012087286A (ja) 感光性化合物および該化合物からなる感光性ポリマー
JP5992047B2 (ja) 配向性フィルムの製造方法
JP5546093B2 (ja) 重合性化合物及び重合性組成物
JP4924865B2 (ja) 重合性液晶化合物、重合性液晶組成物及びこれの重合体
KR101648041B1 (ko) 중합성 화합물
TWI662075B (zh) 氰基二苯乙烯
JP4936930B2 (ja) 重合性化合物及び重合性組成物
JP2015529343A (ja) 光学フィルムおよびこれを含む表示素子
WO2015029596A1 (fr) Procédé de production de film polarisant
KR20070021258A (ko) 중합성 액정 조성물 및 광학 이방체
JP5694067B2 (ja) 重合性組成物
JP6012553B2 (ja) 配向性フィルムの製造方法
JP7088463B2 (ja) 液晶組成物、温度応答性調光素子およびその製造方法
JP6239082B2 (ja) 光学フィルム及びこれを含む表示素子
JP6388279B2 (ja) 周期構造を有する光学フィルムの製造方法
CN102040521B (zh) 聚合性化合物
JP2004168863A (ja) 光重合性液晶組成物およびそれを用いた光学素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13835517

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014534217

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20157008383

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 13835517

Country of ref document: EP

Kind code of ref document: A1