JP4955594B2 - Optical material patterned in optical axis direction and phase difference - Google Patents

Description

The present invention relates to an optical material including a patterned retardation layer in which an optical axis direction and a retardation amount are patterned, and a manufacturing method thereof.

An optical material having a pattern in which the optical axis direction and the phase difference amount are different from each other in a pattern can provide a complicated latent image as, for example, a forgery prevention seal, and is therefore considered to have a wide range of applications.
Patent Document 1 discloses a method for producing a retardation plate whose optical axis direction is patterned using a polymerizable liquid crystal. In this method, patterning in the optical axis direction is performed by providing a layer of birefringent material on an alignment layer provided with regions rubbed in different directions. However, this method cannot perform patterning of the phase difference amount.

Patent Document 2 discloses an optical component for security use which is formed by laminating a polarizer and a phase shifter and has regions having different optical axis directions. The phaser is made of a liquid crystal composition, and the optical axis is patterned using a photo-alignment film. This article is only subjected to optical axis patterning, not phase difference patterning, and has relatively low security.
Japanese Patent Laid-Open No. 11-84385 Special table 2001-525080

An object of the present invention is to provide an optical material in which an optical axis direction and a phase difference amount are patterned.

As a result of intensive studies for solving the above-mentioned problems, the present inventors have achieved patterning of the optical axis direction and the amount of retardation by combining orientation patterning of the alignment layer and pattern exposure of the retardation layer. Based on this finding, the present invention was completed.
That is, the present invention provides the following [1] to [ 11 ]: [1] A region having two or more regions having different optical axis directions on the support and having different phase differences. It is a manufacturing method of the optical material which has a patterning phase difference layer containing two or more, Comprising: The manufacturing method containing the following process (A) and following process (1)-(4):
(1) on a support and dried to a composition comprising a photo-alignment material is applied, by performing the pattern exposure of the irradiated polarized ultraviolet light polarized ultraviolet light of at least different polarization direction different regions, different Producing an alignment layer in which a region having an optical axis direction is formed ;
(2) A step of applying and drying a solution containing a liquid crystalline compound on the alignment layer obtained in step (1);
(A) After the step (2), the retardation layer containing the liquid crystal compound coated in the step (2) is immersed in the additive solution, or the additive solution is formed on the retardation layer. Applying and drying;
(3) the laminate obtained in the step (A), have a row pattern exposure in different exposure conditions to at least a different region to form a different phase difference amount step;
(4) The process of producing a patterning phase difference layer by baking the laminated body obtained at a process (3) at 50 to 400 degreeC.

[2] A method for producing an optical material including a patterning retardation layer that includes two or more regions having different optical axis directions and two or more regions having different retardation amounts on a support, Production method including the following step (1A) and the following steps (11) to (14):
(11) An alignment layer in which regions having different optical axis directions are formed by rubbing at least different regions in different directions through a mask on the composition for forming an alignment layer on a support. Producing step;
(12) A step of applying and drying a solution containing a liquid crystalline compound on the alignment layer obtained in step (11);
(1A) After the step (12), the retardation layer containing the liquid crystal compound coated in the step (12) is immersed in the additive solution, or the additive solution is formed on the retardation layer. Applying and drying;
(13) to the laminate obtained in the step (1A), have row pattern exposure in different exposure conditions to at least different areas, forming a different amount of phase difference;
(14) A step of baking the layered product obtained in step (13) at 50 ° C. or higher and 400 ° C. or lower to produce a patterning retardation layer.

[3] A method for producing an optical material including a patterning retardation layer including two or more regions having different optical axis directions and two or more regions having different retardation amounts on a support, Production method including the following step (2A) and the following steps (21) to (26):
(21) on a temporary support, dried compositions comprising an optical alignment material is applied, by performing the pattern exposure of the polarized ultraviolet light for irradiating polarized ultraviolet light of different polarization directions in at least different regions, together Producing an alignment layer in which regions having different optical axis directions are formed ;
(22) A step of applying and drying a solution containing a liquid crystalline compound on the alignment layer obtained in the step (21);
(2A) After the step (22), the retardation layer containing the liquid crystalline compound applied in the step (22) is immersed in the additive solution, or the additive solution is formed on the retardation layer. Applying and drying;
(23) A step of providing a transfer adhesive layer on the liquid crystalline compound obtained in the step ( 2A );
(24) A step of transferring the laminate obtained in step (23) onto a support;
(25) to the laminate obtained in the step (24), have a row pattern exposure in different exposure conditions to at least different areas, forming a different amount of phase difference;
(26) A step of baking the layered product obtained in the step (25) at 50 ° C. or more and 400 ° C. or less to produce a patterning retardation layer.

[4] A method for producing an optical material comprising a patterning retardation layer including two or more regions having different optical axis directions and two or more regions having different retardation amounts on a support, Manufacturing method including the following step (3A) and the following steps (31) to (36):
(31) An alignment layer in which regions having different optical axis directions are formed by rubbing at least different regions in different directions through a mask on the alignment layer forming composition on the temporary support. Producing step;
(32) A step of applying and drying a solution containing a liquid crystalline compound on the alignment layer obtained in the step (31);
(3A) After the step (32), the retardation layer containing the liquid crystalline compound applied in the step (32) is immersed in the additive solution, or the additive solution is formed on the retardation layer. Applying and drying;
(33) A step of providing a transfer adhesive layer on the liquid crystalline compound obtained in step ( 3A );
(34) A step of transferring the laminate obtained in the step (33) onto a support;
(35) to the laminate obtained in the step (34), have a row pattern exposure in different exposure conditions to at least different areas, forming a different amount of phase difference;
(36) A step of producing a patterning retardation layer by baking the laminate obtained in the step (35) at 50 ° C. or more and 400 ° C. or less.

[5] The production method according to any one of [1] to [4], wherein the additive is a polymerization initiator.
[6] Any of [1] to [5], including a step of irradiating the coated retardation layer with ultraviolet rays before the step of immersing in the additive solution or the step of applying the additive solution. The production method according to claim 1.
[7] The patterning retardation layer, the manufacturing method according to any one of you containing polymer having orientation group in the side chain [1] to [6].
[8] The liquid crystalline compound contained in the coating solution for the retardation layer formed on the alignment layer has a combination of a radical reactive group and a cationic reactive group, and the radical reactive group is acrylic. The production method according to any one of [1] to [7], which is a group or a methacryl group, and the cationic reactive group is a vinyl ether group, an oxetane group or an epoxy group.
[9] The manufacturing method according to any one of [1] to [8], wherein the coating liquid for the retardation layer formed on the alignment layer contains a horizontal alignment agent.
[10] The alignment layer is a layer formed from a composition comprising an optical isomerization material or photo-dimerization type material [1], [3], according to any one of [5] to [9] Manufacturing method .
[11] The [1] to optical materials ing been produced by the method according to any one of [10].
[ 12 ] The optical material according to [ 11 ], wherein the optical material is used as anti-counterfeiting means.
[13] The optical element comprising an optical material according to [11] or [12].

The present invention provides an optical material in which the optical axis direction and the phase difference amount are patterned.

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  In the present specification, “the same” for the angle means that the difference in angle is within a range of less than ± 5 °. This range is preferably less than ± 4 °, and more preferably less than ± 3 °. Therefore, for example, when “the direction of the shaft is the same”, it means that the difference in the direction of the shaft is within a range of less than ± 5 °, and when “the direction of the shaft is different”, It means that the difference in orientation is ± 5 ° or more.

  In this specification, retardation, retardation, or Re represents in-plane retardation. In-plane retardation (Re (λ)) is measured with KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments) by making light having a wavelength of λ nm incident in the normal direction of the film. Retardation or Re in this specification means those measured at wavelengths of 611 ± 5 nm, 545 ± 5 nm, and 435 ± 5 nm for R, G, and B, respectively. It means that measured at a wavelength of 5 nm or 590 ± 5 nm.

The optical material of the present invention includes a patterning retardation layer including two or more regions having different optical axis directions and two or more regions having different retardation amounts. That is, in the optical material of the present invention, the optical axis direction and the phase difference amount are patterned. The region where the optical axis direction is different from the region where the phase difference amount is different may be the same or different from each other. In other words, regions having the same optical axis direction may have the same phase difference amount, and regions having the same phase difference amount may have the same optical axis direction; There may be different parts, and / or there may be parts having different optical axis directions in a region having the same phase difference amount.
In this specification, the “optical axis” is a concept including a “slow axis”. “Axial direction” means an in-plane axial direction.

  In the present specification, “patterning” refers to producing two or more regions having different optical properties depending on the direction of the optical axis or the amount of phase difference in a film-like (layered) object, or Means having two or more of the same region. Here, the regions having the same optical properties do not need to be continuous with each other, and may be discontinuously distributed. In addition, it is assumed that two or more existing regions having different optical properties are gathered to form a continuous film-like object.

Hereinafter, materials, manufacturing methods, etc. will be described in detail for the patterned elliptically polarizing plate of the present invention. However, the present invention is not limited to this embodiment, and other embodiments can be carried out with reference to the following description and conventionally known methods, and the present invention is limited to the embodiments described below. It is not something.

(Retardation layer)
The patterning retardation layer can be formed by patterning the retardation layer. The retardation layer may be a layer having optical characteristics that are not isotropic, that is, at least one incident direction in which Re is not substantially zero when the retardation is measured. In the optical material of the present invention, the retardation layer is composed of a composition containing a polymer having an orientation group in the side chain. Since the orientation groups have the property of being easily aligned in a uniform direction, control of the axial direction is facilitated by using a polymer having an orientation group in the side chain.
The retardation layer preferably has a retardation disappearance temperature. The retardation disappearance temperature is preferably greater than 20 ° C. and 250 ° C. or less, more preferably 40 ° C. to 245 ° C., further preferably 50 ° C. to 245 ° C., and 80 ° C. to 240 ° C. Is most preferred. Further, as the retardation layer, it is also preferable to use a retardation layer whose retardation disappearing temperature is increased by performing exposure. In this specification, “retardation disappearance temperature” means that when the retardation layer is heated from a state of 20 ° C. at a rate of 20 ° C. per minute, the retardation of the retardation layer at the certain temperature is the retardation of the retardation layer. The temperature at which the retardation of the layer at 20 ° C. is 30% or less.

  As a result, there is a difference in the retardation disappearance temperature between the exposed area and the unexposed area, and the baking is performed at a temperature higher than the retardation disappearance temperature of the unexposed area and lower than the retardation disappearance temperature of the exposed area. Only the retardation of the exposed portion can be selectively lost. In this case, the increase in the retardation disappearance temperature due to exposure is preferably 5 ° C. or more in consideration of the efficiency of selective disappearance of only the retardation of the unexposed area and the robustness against temperature variations in the heating apparatus. More preferably, the temperature is at least 20 ° C, and particularly preferably at least 20 ° C. Further, it is preferable that the retardation disappearance temperature of the exposed portion is not in the temperature range of 250 ° C. or less because the retardation of the unexposed portion is easily lost.

(Polymer having orientation group)
The polymer having an orientation group is composed of a polymer main chain and a polymer side chain. Any component of the polymer main chain may be used, and examples thereof include polyacrylate, polymethacrylate, polysiloxane, and polyvinyl. The orientation group is contained in the polymer side chain. The alignment group has a partial structure (mesogen) imparting a function exhibiting liquid crystallinity.
Any structure may be used as the partial structure that provides the liquid crystallinity. For example, the “polymers” edited by the Liquid Crystal Handbook Editorial Committee, Liquid Crystal Handbook, Maruzen, Chapters 3 and 8 of 2000 What is described in "Liquid crystal" is mentioned.

The retardation layer preferably contains a liquid crystal compound, particularly a liquid crystal compound having at least one reactive group. The polymer having an orientation group in the side chain may be a liquid crystal compound. By forming the retardation layer from a composition containing a liquid crystal compound having at least one reactive group, control of the slow axis direction by an alignment layer described later and the like is facilitated. Such a retardation layer can be prepared by applying and drying a solution containing a liquid crystal compound having at least one reactive group to form a liquid crystal phase, and then polymerizing and fixing by irradiation with heat or ionizing radiation. . Such a manufacturing method will be described below.

[Liquid crystal compounds]
In general, liquid crystal compounds can be classified into a rod-shaped type and a disk-shaped type based on their shapes. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a disk-like liquid crystal compound is preferably used. Two or more kinds of rod-like liquid crystalline compounds, two or more kinds of disc-like liquid crystalline compounds, or a mixture of a rod-like liquid crystalline compound and a disk-like liquid crystalline compound may be used. It is more preferable to use a rod-like liquid crystal compound or a disk-like liquid crystal compound having a reactive group because temperature change and humidity change can be reduced, and at least one of the reactive groups in one liquid crystal molecule is 2 or more. More preferably it is. The liquid crystalline compound may be a mixture of two or more, and in that case, at least one preferably has two or more reactive groups.

It is also preferable that the liquid crystal compound has two or more reactive groups having different polymerization conditions. In this case, it is possible to produce a retardation layer containing a polymer having an unreacted reactive group by selecting conditions and polymerizing only a part of plural types of reactive groups. The polymerization conditions used may be the wavelength range of ionizing radiation used for polymerization immobilization, or the difference in polymerization mechanism used, but preferably a radical reaction group and a cationic reaction that can be controlled by the type of initiator used. A combination of groups is good. A combination in which the radical reactive group is an acrylic group and / or a methacryl group and the cationic group is a vinyl ether group, an oxetane group and / or an epoxy group is particularly preferable because the reactivity can be easily controlled.

Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used. The polymer liquid crystalline compound is a polymer compound obtained by polymerizing a rod-like liquid crystalline compound having a low molecular reactive group. The rod-like liquid crystal compound having a low-molecular reactive group that is particularly preferably used is a rod-like liquid crystal compound represented by the following general formula (I).
Formula (I): Q ¹ -L ¹ -A ¹ -L ³ -ML ⁴ -A ² -L ² -Q ²
In the formula, Q ¹ and Q ² are each independently a reactive group, and L ¹ , L ² , L ³ and L ⁴ each independently represent a single bond or a divalent linking group. A ¹ and A ² each independently represent a spacer group having 2 to 20 carbon atoms. M represents a mesogenic group.
Hereinafter, the rod-like liquid crystal compound having a reactive group represented by the general formula (I) will be described in more detail. In the formula, Q ¹ and Q ² are each independently a reactive group. The polymerization reaction of the reactive group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the reactive group is preferably a reactive group capable of addition polymerization reaction or condensation polymerization reaction. Examples of reactive groups are shown below.

Examples of the divalent linking group represented by L ¹ , L ² , L ³ and L ⁴ include —O—, —S—, —CO—, —NR ² —, —CO—O—, and —O—CO. —O—, —CO—NR ² —, —NR ² —CO—, —O—CO—, —O—CO—NR ² —, —NR ² —CO—O—, and NR ² —CO—NR ^2. A divalent linking group selected from the group consisting of-is preferred. R ² is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. In the formula (I), Q ¹ -L ¹ and Q ² -L ² -are CH ₂ ═CH—CO—O—, CH ₂ ═C (CH ₃ ) —CO—O—, and CH ₂ ═C ( Cl) -CO-O-CO- O- are _{preferable, CH 2 = CH-CO-} O- is most preferable.

A ¹ and A ² represent spacer groups having 2 to 20 carbon atoms. An alkylene group having 2 to 12 carbon atoms, an alkenylene group, and an alkynylene group are preferable, and an alkylene group is particularly preferable. The spacer group is preferably a chain and may contain oxygen atoms or sulfur atoms that are not adjacent to each other. The spacer group may have a substituent and may be substituted with a halogen atom (fluorine, chlorine, bromine), a cyano group, a methyl group, or an ethyl group.
Examples of the mesogenic group represented by M include all known mesogenic groups. In particular, a group represented by the following general formula (II) is preferable.
Formula (II): - (- W 1 -L 5) n -W 2 -
In the formula, W ¹ and W ² each independently represent a divalent cyclic alkylene group or a cyclic alkenylene group, a divalent aryl group or a divalent heterocyclic group, and L ⁵ represents a single bond or a linking group. Specific examples of the linking group include specific examples of groups represented by L ^{1 to} L ⁴ in the formula (I), —CH ₂ —O—, and —O—CH ₂ —. n represents 1, 2 or 3.

W ¹ and W ² include 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, pyridazine-3,6-diyl . In the case of 1,4-cyclohexanediyl, there are trans isomers and cis isomers, but either isomer may be used, and a mixture in any proportion may be used. More preferably, it is a trans form. W ¹ and W ² may each have a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, etc.), and an alkoxy group having 1 to 10 carbon atoms. (Methoxy group, ethoxy group, etc.), C1-10 acyl group (formyl group, acetyl group, etc.), C1-10 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), carbon atom Examples thereof include an acyloxy group having 1 to 10 (acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like.
Preferred examples of the basic skeleton of the mesogenic group represented by the general formula (II) are shown below. These may be substituted with the above substituents.

  Examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto. In addition, the compound represented by general formula (I) is compoundable by the method as described in Japanese National Patent Publication No. 11-513019 (WO97 / 00600).

  As another aspect of the present invention, there is an aspect in which a discotic liquid crystal is used for the retardation layer. The retardation layer is preferably a layer of a low molecular weight liquid crystal discotic compound such as a monomer or a polymer layer obtained by polymerization (curing) of a polymerizable liquid crystal discotic compound. Examples of the discotic (discotic) compound include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physicslett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, page 2655 (1994), and azacrown-based and phenylacetylene-based macrocycles. The above discotic (discotic) compounds generally have a discotic nucleus at the center of the molecule, and groups (L) such as linear alkyl groups, alkoxy groups, and substituted benzoyloxy groups are substituted in a radial pattern. In other words, it has liquid crystallinity and generally includes a so-called discotic liquid crystal. However, when such an aggregate of molecules is uniformly oriented, it exhibits negative uniaxiality, but is not limited to this description. Further, in the present invention, it is not necessary that the final product is formed from a discotic compound, for example, the low molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by reaction with heat, light or the like, resulting in high molecular weight and loss of liquid crystallinity.

In the present invention, it is preferable to use a discotic liquid crystalline compound represented by the following general formula (III).
Formula (III): D (-LP) _n
In the formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12.
In the formula (III), preferred specific examples of the discotic core (D), the divalent linking group (L) and the polymerizable group (P) are (D1) described in JP-A No. 2001-4837, respectively. To (D15), (L1) to (L25), (P1) to (P18), and the discotic core (D), divalent linking group (L) and polymerizable group ( The contents regarding P) can be preferably applied here.
Preferred examples of the discotic compound are shown below.

The retardation layer is formed by applying a composition containing a liquid crystalline compound (for example, a coating solution) to the surface of an alignment layer described later to obtain an alignment state exhibiting a desired liquid crystal phase, and then converting the alignment state to heat or ionizing radiation. It is preferable that it is a layer produced by fixing by irradiation.
When a discotic liquid crystalline compound having a reactive group is used as the liquid crystalline compound, it may be fixed in any alignment state of horizontal alignment, vertical alignment, tilt alignment, and twist alignment. In the present specification, “horizontal alignment” means that, in the case of a rod-like liquid crystal, the molecular long axis and the horizontal plane of the transparent support are parallel, and in the case of a disc-like liquid crystal, the circle of the core of the disc-like liquid crystal compound. The horizontal plane of the board and the transparent support is said to be parallel, but it is not required to be strictly parallel. In the present specification, an orientation with an inclination angle of less than 10 degrees with the horizontal plane is meant. And The inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.

  When two or more retardation layers composed of a composition containing a liquid crystalline compound are laminated, the combination of the liquid crystalline compounds is not particularly limited, and a laminate of all layers made of a discotic liquid crystalline compound, which is all rod-like liquid crystalline It may be a laminate of a layer made of a compound, a laminate of a layer made of a composition containing a discotic liquid crystalline compound and a layer made of a composition containing a rod-like liquid crystalline compound. Moreover, the combination of the alignment states of each layer is not particularly limited, and retardation layers having the same alignment state may be stacked, or retardation layers having different alignment states may be stacked.

  The retardation layer is preferably formed by applying a coating liquid containing a liquid crystalline compound and the following polymerization initiator and other additives onto a predetermined alignment layer described later. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Fixation of alignment state of liquid crystalline compounds]
The aligned liquid crystalline compound is preferably fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a reactive group introduced into the liquid crystal compound. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is more preferable. The photopolymerization reaction may be either radical polymerization or cationic polymerization. Examples of radical photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. An acyloin compound (described in US Pat. No. 2,722,512), a polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,212,970). Examples of the cationic photopolymerization initiator include organic sulfonium salt systems, iodonium salt systems, phosphonium salt systems, and the like. Organic sulfonium salt systems are preferable, and triphenylsulfonium salts are particularly preferable. As counter ions of these compounds, hexafluoroantimonate, hexafluorophosphate, and the like are preferably used.

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. Light irradiation for the polymerization of the liquid crystalline compound is preferably performed using ultraviolet rays. Irradiation energy is preferably ^{10mJ / cm 2 ~10J / cm 2} , further preferably 25~800mJ / cm ^2. Illuminance is preferably 10 to 1,000 / cm ^2, more preferably 20 to 500 mW / cm ^2, further preferably 40~350mW / cm ^2. The irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm. In order to accelerate the photopolymerization reaction, light irradiation may be performed under an inert gas atmosphere such as nitrogen or under heating conditions.

[Optical alignment by polarized irradiation]
The retardation layer may be a layer in which in-plane retardation is manifested or increased by photo-alignment by polarized light irradiation. This polarized irradiation may also serve as a photopolymerization process in the above-described orientation fixation, or may be further fixed by non-polarized irradiation after performing polarized irradiation first, or may be fixed first by non-polarized irradiation. The photo-alignment may be performed by irradiation with polarized light, but it is desirable to perform only the irradiation with polarized light or to further fix by non-polarized light irradiation after the irradiation with polarized light first. When polarized light irradiation also serves as a photopolymerization process in the above-described orientation fixation and a radical polymerization initiator is used as a polymerization initiator, polarized light irradiation should be performed in an inert gas atmosphere with an oxygen concentration of 0.5% or less. preferable. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. The illuminance is preferably 20 to 1000 mW / cm ^2, more preferably 50 to 500 mW / cm ^2, further preferably 100 to 350 mW / cm ^2. Although there is no restriction | limiting in particular about the kind of liquid crystalline compound hardened | cured by polarized light irradiation, The liquid crystalline compound which has an ethylenically unsaturated group as a reactive group is preferable. The irradiation wavelength preferably has a peak at 300 to 450 nm, and more preferably has a peak at 350 to 400 nm.

[Post-curing by UV irradiation after polarized irradiation]
The retardation layer may be further irradiated with polarized or non-polarized ultraviolet rays after the first irradiation with polarized light (irradiation for photo-alignment). By further irradiating polarized or non-polarized ultraviolet rays after the first irradiation with polarized light, the reaction rate of the reactive group is increased (post-curing), the adhesion and the like are improved, and production can be performed at a high transport speed. Post-curing may be polarized or non-polarized, but is preferably polarized. Moreover, it is preferable to carry out post-curing twice or more, and polarized light or non-polarized light may be combined with polarized light and non-polarized light. However, when combined, it is preferable to irradiate polarized light before non-polarized light. Irradiation with ultraviolet rays may or may not be replaced with an inert gas. However, particularly when a radical polymerization initiator is used as the polymerization initiator, it is preferably performed in an inert gas atmosphere having an oxygen concentration of 0.5% or less. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. The illuminance is preferably 20 to 1000 mW / cm ^2, more preferably 50 to 500 mW / cm ^2, further preferably 100 to 350 mW / cm ^2. In the case of polarized light irradiation, the irradiation wavelength preferably has a peak at 300 to 450 nm, and more preferably 350 to 400 nm. In the case of non-polarized light irradiation, it preferably has a peak at 200 to 450 nm, and more preferably has a peak at 250 to 400 nm.

[Fixing of alignment state of liquid crystal compound having radical reactive group and cationic reactive group]
As described above, it is also preferable that the liquid crystalline compound has two or more kinds of reactive groups having different polymerization conditions. In this case, it is possible to produce a retardation layer containing a polymer having an unreacted reactive group by selecting conditions and polymerizing only a part of a plurality of types of reactive groups. Polymerization particularly suitable when a liquid crystalline compound having a radical reactive group and a cationic reactive group (for example, the aforementioned I-22 to I-25) is used as such a liquid crystalline compound. The immobilization conditions will be described below.

  First, as the polymerization initiator, it is preferable to use only a photopolymerization initiator that acts on a reactive group intended to be polymerized. That is, it is preferable to use only a radical photopolymerization initiator when selectively polymerizing radical reactive groups and only a cationic photopolymerization initiator when selectively polymerizing cationic reactive groups. The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.1 to 8% by mass, and 0.5 to 4% by mass of the solid content of the coating solution. It is particularly preferred.

Next, it is preferable to use ultraviolet rays for light irradiation for polymerization. At this time, if the irradiation energy and / or illuminance is too strong, both the radical reactive group and the cationic reactive group may react non-selectively. Accordingly, the irradiation energy is preferably ^{5mJ / cm 2 ~500mJ / cm 2} , more preferably 10 to 400 mJ / cm ^2, and particularly preferably ^{20mJ / cm 2 ~200mJ / cm 2} . The illuminance is preferably 5 to 500 mW / cm ^2, more preferably 10 to 300 mW / cm ^2, and particularly preferably 20 to 100 mW / cm ^2. The irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm.

  Of the photopolymerization reactions, reactions using radical photopolymerization initiators are inhibited by oxygen, and reactions using cationic photopolymerization initiators are not inhibited by oxygen. Therefore, when a liquid crystal compound having a radical reactive group and a cationic reactive group is used as the liquid crystalline compound and one kind of the reactive group is selectively polymerized, the radical reactive group is selectively polymerized. In some cases, it is preferable to perform light irradiation in an inert gas atmosphere such as nitrogen, and in the case of selectively polymerizing a cationic reactive group, light irradiation is performed under an oxygen-containing atmosphere (for example, in the air). It is preferable.

[Horizontal alignment agent]
In the composition for forming the retardation layer, at least one of a fluorine-containing homopolymer or copolymer using a compound represented by the following general formulas (1) to (3) and a monomer represented by the general formula (4) is contained. Thus, the molecules of the liquid crystal compound can be substantially horizontally aligned.
Hereinafter, the following general formulas (1) to (4) will be described in order.

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and X ¹ , X ² and X ^{3 each} represent a single bond or a divalent linking group. The substituent represented by each of R ^{1 to} R ³ is preferably a substituted or unsubstituted alkyl group (more preferably an unsubstituted alkyl group or a fluorine-substituted alkyl group), an aryl group (particularly a fluorine-substituted alkyl). An aryl group having a group is preferred), a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, and a halogen atom. The divalent linking groups represented by X ¹ , X ² and X ³ are each an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, —NR ^a — ( R ^a is ^a divalent linking group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, —SO ₂ —, and combinations thereof. Preferably there is. The divalent linking group is selected from the group consisting of an alkylene group, a phenylene group, —CO—, —NR ^a —, —O—, —S—, and SO ₂ —, or the group. It is more preferably a divalent linking group in which at least two groups are combined. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms of the divalent aromatic group is preferably 6-10.

In the formula, R represents a substituent, and m represents an integer of 0 to 5. When m represents an integer greater than or equal to 2, several R may be same or different. Preferred substituents for R are the same as those listed as preferred ranges for the substituents represented by R ¹ , R ² , and R ³ . m preferably represents an integer of 1 to 3, particularly preferably 2 or 3.

In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent. The substituents represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably the substituents represented by R ¹ , R ² and R ³ in the general formula (1). It is listed as a thing. As the horizontal alignment agent used in the present invention, the compounds described in paragraph numbers [0092] to [0096] of JP-A-2005-99248 can be used, and the synthesis method of these compounds is also described in the specification. ing.

In the formula, R represents a hydrogen atom or a methyl group, X represents an oxygen atom or a sulfur atom, Z represents a hydrogen atom or a fluorine atom, m represents an integer of 1 to 6, and n represents an integer of 1 to 12. Represents. In addition to the fluorine-containing polymer containing the general formula (4), the compounds described in JP-A-2005-206638 and JP-A-2006-91205 can be used as the unevenness improving polymer in coating as a horizontal alignment agent. Are also described in the specification.
The addition amount of the horizontal alignment agent is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 1% by mass of the mass of the liquid crystal compound. In addition, the compounds represented by the general formulas (1) to (4) may be used alone or in combination of two or more.

[Post-processing of retardation layer]
Various post-treatments may be performed in order to modify the produced retardation layer. Examples of post-treatment include corona treatment for improving adhesion, addition of a plasticizer for improving flexibility, addition of a thermal polymerization inhibitor for improving storage stability, and a coupling treatment for improving reactivity. It is done. Further, when the polymer in the retardation layer has an unreacted reactive group, it is also an effective modifying means to add a polymerization initiator corresponding to the reactive group. Examples of the means for adding a plasticizer or a photopolymerization initiator include a means for immersing the retardation layer in a solution of the corresponding additive, and a means for applying and permeating the solution of the corresponding additive on the retardation layer. Etc. Further, possible to add an additive to the coating liquid of the layer when applying another layer on top of the retardation layer, a method of immersing the phase difference layer may be mentioned down.
In the present invention, after the step of applying and drying a solution containing a liquid crystal compound on the alignment layer, the retardation layer containing the liquid crystal compound coated in the step is immersed in the additive solution, Or it has the process of apply | coating the solution of an additive on this retardation layer, and drying.

[Alignment layer]
In this specification, the alignment layer may be referred to as an alignment film. Since the alignment layer functions to define the alignment direction of the liquid crystal compound provided thereon, the patterning retardation layer can be easily obtained by patterning the function of the alignment film. The alignment layer is generally provided on a support or temporary support described later or an undercoat layer coated on the support or temporary support. The alignment layer may be any layer as long as it can impart alignment to the retardation layer, and typical examples include a photo alignment layer and a rubbing alignment layer.

(Photo-alignment layer)
The photo-alignment layer can be made from a photo-alignment material. The photo-alignment material is not particularly limited, but a photoisomerization material that reversibly changes the alignment regulation force by changing only the molecular shape mainly by irradiating polarized light, and the molecule itself by irradiating polarized light. Photoreactive materials such as a photodimerization type material to be changed can be mentioned.
Hereinafter, examples of the photo-alignment material include examples of the photodimerization type material (P-1 to P-40) and the photoisomerization material (P-101 to P-104). It is not limited to.
In addition, x, y, z in a formula shows the mole percentage of each repeating unit. In the above formulas (P-101) to (P-104), n represents an integer of 1 or more.

(Rubbing alignment layer)
Preferred examples of the alignment layer include a rubbing treatment layer of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, and ω-tricosanoic acid, dioctadecylmethylammonium chloride and stearyl. Examples thereof include a cumulative film formed by Langmuir-Blodgett method (LB film) such as methyl acid, or a layer in which a dielectric is oriented by applying an electric field or a magnetic field.

  Examples of organic compounds for the alignment layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol, poly (N-methylolacrylamide), polyvinylpyrrolidone, styrene / vinyltoluene. Copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, polyethylene, polypropylene, polycarbonate, etc. And polymers such as silane coupling agents. Examples of preferable polymers include polyimide, polystyrene, polymers of styrene derivatives, gelatin, polyvinyl alcohol, and alkyl-modified polyvinyl alcohol having an alkyl group (preferably having 6 or more carbon atoms).

  A polymer is preferably used for forming the alignment layer. The type of polymer that can be used can be determined according to the orientation (particularly the average tilt angle) of the liquid crystal compound. For example, in order to align the liquid crystalline compound horizontally, a polymer that does not decrease the surface energy of the alignment layer (ordinary alignment polymer) is used. Specific types of polymers are described in various documents about liquid crystal cells or optical compensation sheets. For example, polyvinyl alcohol or modified polyvinyl alcohol, a copolymer with polyacrylic acid or polyacrylate, polyvinyl pyrrolidone, cellulose, or modified cellulose are preferably used. The alignment layer material may have a functional group capable of reacting with the reactive group of the liquid crystal compound. The reactive group can be introduced by introducing a repeating unit having a reactive group in the side chain or as a substituent of a cyclic group. It is more preferable to use an alignment layer that forms a chemical bond with the liquid crystal compound at the interface. Such an alignment layer is described in JP-A-9-152509, and acid chloride or Karenz MOI (manufactured by Showa Denko KK). The modified polyvinyl alcohol in which an acrylic group is introduced into the side chain by using The thickness of the alignment layer is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm. The alignment layer may have a function as an oxygen blocking film.

  A polyimide film (preferably fluorine atom-containing polyimide) widely used as an alignment layer for LCD is also preferable as the organic alignment layer. This is a polyamic acid (for example, LQ / LX series manufactured by Hitachi Chemical Co., Ltd., SE series manufactured by Nissan Chemical Co., Ltd., etc.) is applied to the support surface and baked at 100 to 300 ° C. for 0.5 to 1 hour. And then obtained by rubbing.

  Moreover, the rubbing process can utilize a processing method widely adopted as a liquid crystal alignment process of LCD. That is, a method of obtaining the orientation by rubbing the surface of the orientation layer in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.

Moreover, as a vapor deposition material for the inorganic oblique vapor deposition film, SiO ₂ is representative, and metal oxides such as TiO ₂ and ZnO ₂ , fluorides such as MgF ₂ , and metals such as Au and Al. The metal oxide can be used as an oblique deposition material as long as it has a high dielectric constant, and is not limited to the above. The inorganic oblique deposition film can be formed using a deposition apparatus. An inorganic oblique vapor deposition film can be formed by fixing the film (support) and performing vapor deposition, or moving the long film and performing continuous vapor deposition.

(Patterning method)
[Pattern exposure]
Pattern exposure can be performed for patterning of the retardation layer. Pattern exposure means performing exposure under different exposure conditions on two or more regions of the birefringence pattern builder. The “two or more regions” at this time may or may not have overlapping portions, but preferably does not have overlapping portions.
The pattern exposure may simply be pattern exposure that produces only unexposed portions and exposed portions. In this case, usually, an area where a phase difference is desired to be left is exposed. Further, the pattern exposure may be a pattern exposure including an exposed portion under one or more exposure conditions that are halftone between the unexposed portion and the exposed portion.
The pattern exposure may be performed by a single exposure or a plurality of exposures. For example, the exposure may be performed by one exposure using a mask having two or more regions showing different transmission spectra depending on the region, or the two may be combined.

The exposure conditions are not particularly limited, and examples include exposure peak wavelength, exposure illuminance, exposure time, exposure amount, temperature during exposure, atmosphere during exposure, and the like. Among these, from the viewpoint of ease of condition adjustment, the exposure peak wavelength, the exposure illuminance, the exposure time, and the exposure dose are preferable, and the exposure illuminance, the exposure time, and the exposure dose are more preferable. The areas exposed under different exposure conditions during pattern exposure then exhibit birefringence that is different through firing and controlled by the exposure conditions. In particular, different phase difference amounts are given. Note that the exposure conditions between two or more exposure regions exposed under different exposure conditions may be changed discontinuously or may be changed continuously.

[Mask exposure]
Exposure using an exposure mask is useful as a means for generating exposure regions with different exposure conditions. For example, after performing exposure using an exposure mask that exposes only one region, the temperature, atmosphere, exposure illuminance, exposure time, and exposure wavelength are changed to perform exposure using another mask or overall exposure. The exposure conditions for the previously exposed area and the later exposed area can be easily changed. Further, a mask having two or more regions showing different transmission spectra depending on the region is particularly useful as a mask for changing the exposure illuminance or the exposure wavelength. In this case, exposure with different exposure illuminances or exposure wavelengths can be performed on a plurality of regions by performing only one exposure. It goes without saying that different exposure amounts can be given by performing exposure for the same time under different exposure illuminances.
When scanning exposure using a laser or the like is used, it is possible to change the exposure condition for each region by a method such as changing the light source intensity or changing the scanning speed depending on the exposure region.

As a pattern exposure method, contact exposure using a mask, proxy exposure, projection exposure, or the like may be used, or direct drawing may be performed by focusing on a predetermined position without using a mask using a laser or an electron beam. The irradiation wavelength of the light source for the exposure preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm. In the case where a step is simultaneously formed by the photosensitive resin layer, it is also preferable to irradiate light in a wavelength region that can cure the resin layer (eg, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a blue laser, and the like can be given. Usually 3~2000mJ / cm ² about the preferred amount of exposure, and more preferably 5~1000mJ / cm ² or so, more preferably 10 to 500 mJ / cm ² or so, and most preferably at about 10 to 100 mJ / cm ² .

[Heating (baked)]
By baking the phase-exposed retardation layer at 50 ° C. or more and 400 ° C. or less, the retardation amount is patterned with a pattern according to the exposure conditions during the pattern exposure. When the retardation disappearance temperature before exposure of the used retardation layer is T1 [° C.] and the retardation disappearance temperature after exposure is T2 [° C.] (when the retardation disappearance temperature is not in the temperature range of 250 ° C. or lower). T2 = 250), and the baking temperature is preferably T1 ° C. or higher and T2 ° C. or lower, more preferably (T1 + 10) ° C. or higher and (T2-5) ° C. or lower, and (T1 + 20) ° C. or higher and (T2-10) ° C. or lower. Is most preferred.
When using a retardation layer in which the retardation disappearance temperature rises, the exposure reduces the retardation of the unexposed area in the layer by exposure, while the exposed area has little or no decrease in retardation. As a result, the retardation of the unexposed portion becomes smaller than the retardation of the exposed portion, and a pattern of the presence or absence of an axis or a phase difference amount is produced.

[Axial patterning]
The method of patterning in the axial direction is not particularly limited, but as described above, patterning in the direction of the optical axis (slow axis) of the retardation layer can be preferably performed using the alignment layer.
A layer containing a liquid crystal compound provided on the photo-alignment layer, preferably a layer containing a liquid crystal compound provided directly on the photo-alignment layer is a polarized light from which the photo-alignment layer was produced when irradiated with ultraviolet light. Liquid crystal molecules are aligned in the polarization direction of ultraviolet light. Similarly, a layer containing a liquid crystal compound provided on the rubbing alignment layer, preferably a layer containing a liquid crystal compound provided directly on the rubbing alignment layer, is liquid crystal in the rubbing direction when irradiated with ultraviolet light. The molecules are oriented.

Therefore, when providing the patterning retardation layer on the photo-alignment layer, the pattern exposure technique used when the patterning retardation layer is formed on the layer formed from the composition for forming the photo-alignment layer containing the alignment material; By a similar method, polarized ultraviolet light is pattern-irradiated and the photo-alignment property of this layer is patterned. A composition containing a liquid crystal compound is applied on the obtained photo-alignment layer, dried, and the like, and then irradiated with ultraviolet light to obtain a retardation layer whose axial direction is patterned. Similarly, when providing a patterning retardation layer on a rubbing alignment layer, the layer before rubbing formed from the rubbing alignment layer forming composition is rubbed through a mask or the like, and the rubbing direction of this layer is determined. Pattern. A composition containing a liquid crystal compound is applied onto the obtained rubbing alignment layer, dried, and the like, and then irradiated with ultraviolet light to obtain a retardation layer whose axial direction is patterned.

(Other layers)
[Support]
The optical material of the present invention may have a support. The support is not particularly limited and may be rigid or flexible.
The rigid support is not particularly limited, but is a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, a metal such as an aluminum plate, an iron plate, or a SUS plate. A board, a resin board, a ceramic board, a stone board, etc. are mentioned. There are no particular limitations on the flexible support, but cellulose esters (eg, cellulose acetate, cellulose propionate, cellulose butyrate), polyolefins (eg, norbornene polymers), poly (meth) acrylic acid esters (eg, polymethyl) Methacrylate), polycarbonate, polyester and polysulfone, and norbornene-based plastic films. In view of ease of handling, the thickness of the rigid support is preferably 100 to 3000 μm, and more preferably 300 to 1500 μm. As a film thickness of a flexible support body, 3-500 micrometers is preferable and 10-200 micrometers is more preferable.

(Production method using transfer material)
The optical material of the present invention may be produced using a transfer material. By using the transfer material, application using an organic solvent can be performed at a place different from the place where the patterning material is produced, and the work and equipment burden when using the patterning material are reduced.
The functional layer useful in the transfer material will be described below.

[Temporary support]
The transfer material preferably has a temporary support. The temporary support may be transparent or opaque and is not particularly limited. Examples of polymers constituting the temporary support include cellulose esters (eg, cellulose acetate, cellulose propionate, cellulose butyrate), polyolefins (eg, norbornene-based polymers), poly (meth) acrylic acid esters (eg, poly Methyl methacrylate), polycarbonate, polyester and polysulfone, norbornene-based polymers. For the purpose of inspecting optical properties in the production process, the transparent support is preferably a transparent and low birefringent material, and cellulose ester and norbornene are preferred from the viewpoint of low birefringence. As a commercially available norbornene-based polymer, Arton (manufactured by JSR Co., Ltd.), Zeonex, Zeonore (manufactured by Nippon Zeon Co., Ltd.), or the like can be used. Inexpensive polycarbonate, polyethylene terephthalate, and the like are also preferably used.

[Transfer adhesive layer]
The transfer material preferably has a transfer adhesive layer. The transfer adhesive layer is not particularly limited as long as it is transparent, uncolored, and has sufficient transferability. However, a photosensitive or heat-sensitive resin layer is desirable from the viewpoint of baking resistance required when used for a substrate for a liquid crystal display device.

[Adhesive layer]
As the pressure-sensitive adhesive, for example, a material that is excellent in optical transparency and exhibits appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties is preferable. Specific examples include pressure-sensitive adhesives that are appropriately prepared using a polymer such as an acrylic polymer, silicone polymer, polyester, polyurethane, polyether, and synthetic rubber as a base polymer. Control of the adhesive properties of the pressure-sensitive adhesive layer can be achieved by, for example, controlling the degree of crosslinking and molecular weight depending on the composition and molecular weight of the base polymer forming the pressure-sensitive adhesive layer, the crosslinking method, the content ratio of the crosslinkable functional group, the blending ratio of the crosslinking agent, etc. It can be suitably performed by a conventionally known method such as adjustment.

[Pressure-sensitive resin layer]
The pressure-sensitive resin layer is not particularly limited as long as adhesiveness is exhibited by applying pressure, and rubber-based, acrylic-based, vinyl ether-based, and silicone-based pressure-sensitive adhesives can be used as the pressure-sensitive adhesive. In the production stage and coating stage of adhesives, solvent-based adhesives, non-aqueous emulsion adhesives, water-based emulsion adhesives, water-soluble adhesives, hot melt adhesives, liquid curable adhesives, and delayed A tack-type adhesive can be used. The rubber-based pressure-sensitive adhesive is disclosed in New Polymer Library 13 “Adhesion Technology”, Kobunshi Publishing Co., Ltd. 41 (1987). The vinyl ether-based pressure-sensitive adhesive includes those having a main component of an alkyl vinyl ether polymer having 2 to 4 carbon atoms, vinyl chloride / vinyl acetate copolymer, vinyl acetate polymer, polyvinyl butyral and the like mixed with a plasticizer. As the silicone-based pressure-sensitive adhesive, a rubber-like siloxane can be used to give film formation and film condensing power, and a resin-like siloxane can be used to give stickiness and adhesion.

[Thermosensitive resin layer]
The heat-sensitive resin layer is not particularly limited as long as it exhibits adhesiveness by applying heat, and examples of the heat-sensitive adhesive include hot-melt compounds and thermoplastic resins. Examples of the heat-meltable compound include low molecular weight products of thermoplastic resins such as polystyrene resin, acrylic resin, styrene-acrylic resin, polyester resin, and polyurethane resin, carnauba wax, molasses, candelilla wax, rice wax, and Plant waxes such as aucuric wax, beeswax, insect wax, shellac, and animal waxes such as whale wax, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, ester wax, and oxidation Examples include various waxes such as petroleum waxes such as waxes, and mineral waxes such as montan wax, ozokerite, and ceresin wax. Further, rosin, hydrogenated rosin, polymerized rosin, rosin modified glycerin, rosin modified maleic resin, rosin modified polyester resin, rosin modified phenolic resin, rosin derivatives such as ester gum, phenol resin, terpene resin, ketone resin, cyclopentadiene Examples thereof include resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and alicyclic hydrocarbon resins.

  These heat-meltable compounds preferably have a molecular weight of usually 10,000 or less, particularly 5,000 or less and a melting point or softening point in the range of 50 to 150 ° C. These hot melt compounds may be used alone or in combination of two or more. Examples of the thermoplastic resin include ethylene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, and cellulose resins. Of these, ethylene copolymers and the like are particularly preferably used.

[Photosensitive resin layer]
The photosensitive resin layer is made of a photosensitive resin composition, and may be positive or negative and is not particularly limited. As the photosensitive resin layer, a commercially available resist material can also be used, and it is preferable to exhibit adhesiveness by light irradiation. The photosensitive resin layer is preferably formed from a resin composition containing at least (1) a polymer, (2) a monomer or oligomer, and (3) a photopolymerization initiator or a photopolymerization initiator system.

Hereinafter, the components (1) to (3) will be described.
(1) Polymer As the polymer (hereinafter sometimes simply referred to as “binder”), an alkali-soluble resin composed of a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. These binder polymers having polar groups may be used alone or in the form of a composition used in combination with ordinary film-forming polymers. The polymer content relative to the total solid content is generally 20 to 70% by mass, preferably 25 to 65% by mass, and more preferably 25 to 45% by mass.

(2) Monomer or oligomer The monomer or oligomer used in the photosensitive resin layer is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization by light irradiation. . Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexa Diol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the colored resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred.

(3) Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system used in the photosensitive resin layer, a vicinal poly disclosed in US Pat. No. 2,367,660 is used. Ketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. No. 3,046,127 And a polynuclear quinone compound described in U.S. Pat. No. 2,951,758, a combination of a triarylimidazole dimer described in U.S. Pat. No. 3,549,367 and a p-aminoketone, and a benzoin described in JP-B 51-48516. Thiazole compounds and trihalomethyl-s-triazine compounds, US Pat. No. 4,239,850 It may be mentioned triazine compounds, U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification or the like - trihalomethyl listed in. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.

These photopolymerization initiators or photopolymerization initiator systems may be used singly or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

The photosensitive resin layer preferably contains an appropriate surfactant from the viewpoint of effectively preventing unevenness. The surfactant can be used as long as it is mixed with the photosensitive resin composition. Preferred surfactants used in the present invention include JP2003-337424A [0090] to [0091], JP2003-177522A [0092] to [0093], and JP2003-177523A [0094]. ] To [0095], JP 2003-177521 A [0096] to [0097], JP 2003-177519 A [0098] to [0099], JP 2003-177520 A [0100] to [0101]. [0102] to [0103] of JP-A-11-133600 and surfactants disclosed as inventions of JP-A-6-16684 are preferred. In order to obtain a higher effect, a fluorosurfactant and / or a silicon surfactant (a fluorosurfactant or a silicon surfactant, a surfactant containing both a fluorine atom and a silicon atom) ) Or two or more types are preferable, and a fluorine-based surfactant is most preferable. When using a fluorosurfactant, the number of fluorine atoms in the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. If the number of fluorine atoms is too large, it is not preferable in that the solubility in an ordinary solvent not containing fluorine is lowered. When the number of fluorine atoms is too small, it is not preferable in that the effect of improving unevenness cannot be obtained.
As a particularly preferred surfactant, the following general formula (a) and a monomer represented by the general formula (b) are included, and the mass ratio of the general formula (a) / the general formula (b) is 20/80 to 60 / The thing containing 40 copolymers is mentioned.

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 18, and m represents an integer of 2 to 14. p and q represent integers of 0 to 18, but are not included when both p and q are simultaneously 0.

A particularly preferred surfactant represented by the general formula (a) is referred to as a monomer (a), and a monomer represented by the general formula (b) is referred to as a monomer (b). C _m F _{2m + 1} shown in the general formula (a) may be linear or branched. m shows the integer of 2-14, Preferably it is an integer of 4-12. The content of C _m F _{2m + 1} is preferably 20 to 70% by mass, particularly preferably 40 to 60% by mass, based on the monomer (a). R ¹ represents a hydrogen atom or a methyl group. Moreover, n shows 1-18, and 2-10 are preferable especially. R ² and R ³ shown in the general formula (b) each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each represent an integer of 0 to 18, but p and q do not include 0. p and q are preferably 2 to 8.

Moreover, as a particularly preferable monomer (a) contained in one molecule of the surfactant, those having the same structure or those having different structures within the above defined range may be used. The same applies to the monomer (b).
The weight average molecular weight Mw of the particularly preferable surfactant is preferably 1000 to 40000, and more preferably 5000 to 20000. The surfactant contains the monomers represented by the general formula (a) and the general formula (b), and the weight ratio of the general formula (a) / the general formula (b) is 20/80 to 60/40. It is characterized by containing a coalescence. Particularly preferred 100 parts by weight of the surfactant is preferably composed of 20 to 60 parts by weight of the monomer (a), 80 to 40 parts by weight of the monomer (b), and the remaining part by weight of other optional monomers. It is preferable that the monomer (a) is composed of 25 to 60 parts by mass, the monomer (b) is composed of 60 to 40 parts by mass, and other optional monomers are composed of the remaining part by mass.

Examples of the copolymerizable monomer other than the monomers (a) and (b) include styrene, vinyl toluene, α-methyl styrene, 2-methyl styrene, chlorostyrene, vinyl benzoic acid, vinyl benzene sulfonic acid soda, and amino styrene. Styrene and its derivatives, substituted products, dienes such as butadiene and isoprene, acrylonitrile, vinyl ethers, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, partially esterified maleic acid, styrene sulfonic acid maleic anhydride, silica And vinyl monomers such as cinnamate, vinyl chloride and vinyl acetate.
Particularly preferred surfactants are copolymers such as monomer (a) and monomer (b), but the monomer sequence is not particularly limited and may be random or regular, for example, block or graft. Furthermore, particularly preferable surfactants can be used by mixing two or more of those having different molecular structures and / or monomer compositions.
As content of the said surfactant, 0.01-10 mass% is preferable with respect to the layer total solid of a photosensitive resin layer, and 0.1-7 mass% is especially preferable. The surfactant contains a predetermined amount of a surfactant having a specific structure, an ethylene oxide group, and a polypropylene oxide group, and a liquid crystal provided with the photosensitive resin layer by containing it in a specific range in the photosensitive resin layer. Display unevenness of the display device is improved. If it is less than 0.01% by mass relative to the total solid content, the display unevenness is not improved, and if it exceeds 10% by mass, the effect of improving the display unevenness does not appear much. When the above-mentioned particularly preferable surfactant is contained in the photosensitive resin layer, it is preferable in that display unevenness is improved.

  Specific examples of preferable fluorine-based surfactants include compounds described in paragraph numbers [0054] to [0063] of JP-A No. 2004-163610. Moreover, the following commercially available surfactant can also be used as it is. Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176, F189, and R08. (Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants, or silicon-based surfactants. be able to. Polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicon surfactant. In the present invention, a compound described in paragraphs [0046] to [0052] of JP-A No. 2004-331812, which is a fluorine-based surfactant not containing the monomer represented by the general formula (a), is used. Is also preferable.

[Mechanical property control layer]
It is preferable to form a mechanical property control layer between the temporary support and the retardation layer of the transfer material in order to control the mechanical properties and the unevenness followability. As the mechanical property control layer, those exhibiting flexible elasticity, those softened by heat, those exhibiting fluidity by heat, and the like are preferable, and a thermoplastic resin layer is particularly preferable. As the component used for the thermoplastic resin layer, organic polymer materials described in JP-A-5-72724 are preferable. It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxy Chill nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

[Peeling layer]
The transfer material may have a release layer on the temporary support. The release layer controls the adhesion between the temporary support and the release layer, or between the release layer and the layer immediately above it, and has a role of assisting the release of the temporary support after transferring the retardation layer. In addition, the other functional layers described above, such as an alignment layer and a mechanical property control layer, may have a function as a release layer.
In the transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, an oxygen blocking film having an oxygen blocking function described in JP-A-5-72724 and an alignment layer for forming the optical anisotropy are preferably used. Among these, a layer formed by mixing polyvinyl alcohol or polyvinyl pyrrolidone and one or more of their modified products is particularly preferable. The thermoplastic resin layer, the oxygen barrier film, and the alignment layer can also be used.

[Surface protective layer]
A thin surface protective layer is preferably provided on the resin layer in order to protect it from contamination and damage during storage. The property of the surface protective layer is not particularly limited and may be made of the same or similar material as the temporary support, but it should be easily separated from the adjacent layer (for example, transfer adhesive layer). As a material for the surface protective layer, for example, silicon paper, polyolefin or polytetrafluoroethylene sheet is suitable.

  Each layer such as a retardation layer, a photosensitive resin layer, a transfer adhesive layer, an orientation layer, a thermoplastic resin layer, a mechanical property control layer and an intermediate layer is formed by a dip coating method, an air knife coating method, a spin coating method, a slit coating method, It can be formed by coating by a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

[Method of transferring transfer material onto transfer material]
The method for transferring the transfer material onto a transfer material such as a support (substrate) is not particularly limited, and the method is not particularly limited as long as the retardation layer can be transferred onto the substrate. For example, a transfer material formed in a film shape can be attached by pressing or thermocompression bonding with a roller or flat plate heated and / or pressurized using a laminator with the transfer adhesive layer surface side of the transfer material surface side. . Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575.
Examples of the material to be transferred include a support, a laminate including a support and another functional layer.

[Transfer process]
After transferring the transfer material onto the transfer material, the temporary support may or may not be peeled off. However, when it does not peel, it is preferable that the temporary support has transparency suitable for subsequent pattern exposure, heat resistance that can withstand baking, and the like. Further, there may be a step of removing an unnecessary layer transferred together with the retardation layer. For example, when a copolymer of polyvinyl alcohol and polyvinyl pyrrolidone is used as the alignment layer, the layer above the alignment layer can be removed by development with a weak alkaline aqueous developer. As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.
Further, after transfer, another layer may be formed on the surface after the temporary support is peeled off or the unnecessary layer is removed as necessary.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.
First, a preparation method and a production method of each material will be described.

(Preparation method of glass substrate)
A smoothing agent (COLOR MOSAIC CT-2000L manufactured by Fuji Film Electro Materials Co., Ltd.) is applied to a glass substrate by a spin coating method (1000 rpm, 30 seconds), and heated in an oven at 200 ° C. for 1 hour.
(Method for producing photo-alignment film H-1)
A 1% by mass cyclohexanone solution of the following compound P-16 (x = 0.9, y = 0.1) is prepared. This solution is applied onto the glass substrate by spin coating (3500 rpm, 20 seconds) so that the thickness after drying is about 0.05 to 0.15 μm, and dried at 100 ° C. for 2 minutes.

The film obtained as described above is irradiated with ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm in the air. At this time, a wire grid polarizer (manufactured by Moxtek, ProFlux PPL02) is set in direction 1, and exposure is further performed through a mask A (a quartz exposure mask having an image pattern). Thereafter, a wire grid polarizer is set in direction 2 and exposure is performed through the mask B. The distance between the exposure mask surface and the photo-alignment film is set to 200 μm. The illuminance of ultraviolet rays used at this time is 100 mW / cm ² in the UV-A region (integration of wavelengths 380 nm to 320 nm), and the irradiation amount is 1000 mJ / cm ² in the UV-A region.

Further, after applying a methanol solution of 1% by weight photoacid generator (Chiba, UVI-6974), ultraviolet rays were glass using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 160 W / cm under air. By irradiating the entire surface of the substrate, a photo-alignment film H-1 is produced. The illuminance of ultraviolet rays used at this time is 260 mW / cm ² in the UV-A region (integration of wavelengths 380 nm to 320 nm), and the irradiation amount is 2600 mJ / cm ² in the UV-A region.

(Method for producing photo-alignment film H-2)
A 1 mass% cyclohexanone solution of the following compound 3 synthesized according to the methods described in JP-A-2006-85099, JP-A-2000-226448, and Liquid Crystals, Vol. 31, page 233 (1975) Prepare. This solution is applied onto the glass substrate by spin coating (3500 rpm, 20 seconds) so that the thickness after drying is about 0.05 to 0.15 μm, and dried at 100 ° C. for 2 minutes.

The film obtained as described above is irradiated with ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm in the air. At this time, a wire grid polarizer (manufactured by Moxtek, ProFlux PPL02) is set in direction 1, and exposure is further performed through a mask A (a quartz exposure mask having an image pattern). Thereafter, a wire grid polarizer is set in direction 2 and exposure is performed through the mask B. The distance between the exposure mask surface and the photo-alignment film is set to 200 μm. The illuminance of ultraviolet rays used at this time is 100 mW / cm ² in the UV-A region (integration of wavelengths 380 nm to 320 nm), and the irradiation amount is 1000 mJ / cm ² in the UV-A region.

(Preparation method of rubbing alignment film H-3)
An alignment film coating solution RN-1199 (manufactured by Nissan Chemical Industries, Ltd.) is spin-coated on a glass substrate (3000 rpm / 30 seconds) and dried in an oven at 80 ° C. for 3 minutes. Then, it is further heated in a 220 ° C. clean oven for 60 minutes.
A mask of mask pattern A is placed on the substrate obtained by referring to the description of paragraph number “0181” of Japanese Patent Laid-Open No. 2006-221189, and rubbing is performed in direction 1 from the top. Thereafter, rubbing is performed in the direction 2 through the mask of the mask pattern B.

(Preparation method of coating liquid LC-1 for retardation layer)
After preparing the following composition, it is filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-1 for retardation layer.
LC-1-1 was synthesized based on the method described in JP-A No. 2004-123882. LC-1-1 is a liquid crystal compound having two reactive groups. One of the two reactive groups is an acrylic group which is a radical reactive group, and the other is an oxetane group which is a cationic reactive group. is there.
LC-1-2 is Tetrahedron Lett. Synthesized according to the method described in Journal, Vol. 43, page 6793 (2002).
───────────────────────────────────────
Coating composition for retardation layer (%)
───────────────────────────────────────
Rod-shaped liquid crystal (LC-1-1) 19.57
Horizontal alignment agent (LC-1-2) 0.01
Cationic photopolymerization initiator (Cyracure UVI 6974, manufactured by Dow Chemical) 0.40
Polymerization control agent (IRGANOX1076, manufactured by Ciba Specialty Chemicals Co., Ltd.)
0.02
Methyl ethyl ketone 80.0
───────────────────────────────────────

A coating liquid LC-1 for retardation layer is applied on the photo-alignment film H-1 or H-2 or the rubbing alignment film H-3, and dried at a film surface temperature of 105 ° C. for 2 minutes to obtain a liquid crystal phase state. After that, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under the air, ultraviolet rays are irradiated to fix the orientation state, and a retardation layer having a thickness of 2.4 μm is formed. A retardation layer sample is prepared. The illuminance of ultraviolet rays used at this time is 50 mW / cm ² in the UV-B region (integration of wavelengths 280 nm to 320 nm), and the irradiation amount is 35 mJ / cm ² in the UV-B region.

(Preparation method of polymerization initiator supply coating liquid AD-1)
After preparing the following composition, it is filtered through a polypropylene filter having a pore size of 0.2 μm and used as a polymerization initiator supply coating liquid AD-1.
───────────────────────────────────
Coating solution composition for transfer adhesive layer (% by mass)
───────────────────────────────────
Benzyl methacrylate / methacrylic acid / methyl methacrylate = 35.9 / 22.4 / 41.7 molar ratio random copolymer (weight average molecular weight 38,000) 8.05
KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 4.83
Radical photopolymerization initiator (2-trichloromethyl-5- (p-styrylstyryl)
1,3,4-oxadiazole) 0.12
Hydroquinone monomethyl ether 0.002
Megafuck F-176PF (Dainippon Ink Chemical Co., Ltd.) 0.05
Propylene glycol monomethyl ether acetate 34.80
Methyl ethyl ketone 50.538
Methanol 1.61
───────────────────────────────────

(Pattern exposure method)
The polymerization initiator supply layer solution AD-1 is applied on the retardation layer sample obtained above and dried to form a 1.0 μm polymerization initiator supply layer. Pattern exposure is performed at an exposure amount of 80 mJ / cm ² using a photomask having a pattern C made of chromium on an M-3L mask aligner and quartz glass. The halftone of pattern C uses a pattern that absorbs 15% of the light amount.

(Development method)
Next, baking is performed in a clean oven at 230 ° C. for 1 hour to prepare a retardation layer sample.
(Phase difference measurement)
The optical properties of the retardation layer sample are measured with the optical system shown in FIG. A halogen light source MHF-D100LR manufactured by Moritex is used as the halogen light source, and a fiber multichannel spectrometer USB2000 manufactured by Ocean Optics is used as the photodetector.
The optical system shown in FIG. 2 is a measurement position limiting mask, which can limit the measurement position and measure the optical characteristics of one mask. By changing the direction of the polarizing plate and the direction of the λ / 4 plate, the phase difference amount and the slow axis direction can be measured.

Using the glass substrate, alignment film, retardation layer coating solution, and polymerization initiator supply coating solution, optical materials (Examples 1 to 3) in which the axial direction and the retardation amount are patterned as shown in Table 1 are prepared. did. That is, an optical material (Examples 1 to 3) in which an alignment film patterned in the axial direction and a retardation layer patterned in the axial direction and the phase difference amount were sequentially laminated on the glass substrate.

The phase difference amount and the slow axis direction of the produced optical material were measured for each patterning site in FIG. The results are shown in Table 2. From Table 2, it can be seen that the axial direction and the phase difference amount are patterned in any of the examples.

(Example 4: Example using transfer material)
(Preparation of coating liquid CU-1 for thermoplastic resin layer)
The following composition is prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as a coating liquid CU-1 for a thermoplastic resin layer.
───────────────────────────────────────Coating solution composition for thermoplastic resin layer (%)
───────────────────────────────────────Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / Methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55/30/10/5, weight average molecular weight = 100,000, Tg≈70 ° C.)
5.89
Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, weight average molecular weight = 10,000, Tg≈100 ° C.)
13.74
BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.20
Megafuck F-780-F (manufactured by Dainippon Ink & Chemicals, Inc.) 0.55
Methanol 11.22
Propylene glycol monomethyl ether acetate 6.43
Methyl ethyl ketone 52.97
───────────────────────────────────────

(Preparation of coating liquid AL-1 for alignment layer)
The following composition is prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as the intermediate layer / orientation layer coating solution AL-1.
──────────────────────────────────――
Coating solution composition for intermediate layer / alignment layer (%)
──────────────────────────────────――
Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.) 3.21
Polyvinylpyrrolidone (Luvitec K30, manufactured by BASF) 1.48
Distilled water 52.1
Methanol 43.21
──────────────────────────────────――

(Preparation of retardation film transfer material T-1)
On the temporary support of a 100 μm-thick easy-adhesive polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.), in order using a wire bar, the coating solution CU-1 for the thermoplastic resin layer, for the alignment layer The coating liquid AL-1 was applied and dried. The dry film thicknesses are 14.6 μm and 1.6 μm, respectively.
(Preparation of photo-alignment film)
A 1% by mass cyclohexanone solution of Compound 3 is prepared. This solution is applied to the film using a wire bar so that the thickness after drying is about 0.05 to 0.15 μm, and dried at 100 ° C. for 2 minutes.

The film obtained as described above is irradiated with ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm in the air. At this time, a wire grid polarizer (manufactured by Moxtek, ProFlux PPL02) is set in direction 1, and exposure is further performed through a mask A (a quartz exposure mask having an image pattern). Thereafter, a wire grid polarizer is set in direction 2 and exposure is performed through the mask B. The distance between the exposure mask surface and the photo-alignment film is set to 200 μm. The illuminance of ultraviolet rays used at this time is 100 mW / cm ² in the UV-A region (integration of wavelengths 380 nm to 320 nm), and the irradiation amount is 1000 mJ / cm ² in the UV-A region.

(Application of coating liquid LC-1 for retardation layer)
Next, LC-1 was applied using a wire bar, dried at a film surface temperature of 105 ° C. for 2 minutes to form a liquid crystal phase, and then an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm under air. ) To irradiate ultraviolet rays having an illuminance of 240 mW / cm ² and an irradiation amount of 600 mJ / cm ² to fix the alignment state, and form a 3.5 μm-thick retardation layer. Finally, photosensitive transfer After the coating liquid AD-1 for adhesive layer is applied and dried to form a photosensitive resin layer having a thickness of 1.0 μm and dried, a protective film (12 μm thick polypropylene film) is further pressure-bonded to transfer a retardation film. T-1 is produced.

(Production of phase difference pattern)
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds with a shower and washed with pure water. This substrate is heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.
After peeling off the protective film of the transfer material T-1 for producing the birefringence pattern, a laminator (manufactured by Hitachi Industries (Lamic II type)) is used, and the substrate heated at 100 ° C. for 2 minutes is heated to a rubber roller temperature. Lamination is performed at 130 ° C., linear pressure of 100 N / cm, and conveyance speed of 1.4 m / min. After lamination, the temporary support is peeled off.

(Pattern exposure method)
The above material is subjected to pattern exposure at an exposure amount of 80 mJ / cm ² using an M-3L mask aligner manufactured by Mikasa and a photomask in which a pattern C is made of chromium on quartz glass.

  Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development is performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa, and the mechanical property control layer and the alignment layer are removed. Next, baking is performed for 1 hour in a clean oven at 230 ° C.

The optical material of Example 4 was produced by the above procedure.
The phase difference amount and the slow axis direction of the thus prepared retardation layer sample were measured for each patterning portion shown in FIG. The results are shown in Tables 4 and 5.
As described above, a retardation layer sample in which the axial direction and the amount of retardation were patterned using transfer could be produced.

It is a figure which shows the mask pattern used for preparation of the optical material of an Example, a rubbing direction, and a polarization direction. It is a figure which shows the optical system used for the phase difference measurement of the optical material produced in the Example. It is a figure which shows the pattern for demonstrating the optical axis direction and phase difference amount of the optical material produced in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Halogen light source 2 Pinhole 3 Lens 4 Polarizing plate and rotation holder 5 λ / 4 plate and rotation holder 6 Sample and XY stage 7 Measurement position limiting mask (square hole of 200 μm × 200 μm is opened)
8 Photodetector

Claims (13)

A manufacturing method of an optical material having a patterning retardation layer including two or more regions having different optical axis directions and two or more regions having different retardation amounts on a support, the following steps ( A) and a production method comprising the following steps (1) to (4):
(1) on a support and dried to a composition comprising a photo-alignment material is applied, by performing the pattern exposure of the irradiated polarized ultraviolet light polarized ultraviolet light of at least different polarization direction different regions, different Producing an alignment layer in which a region having an optical axis direction is formed ;
(2) A step of applying and drying a solution containing a liquid crystalline compound on the alignment layer obtained in step (1);
(A) After the step (2), the retardation layer containing the liquid crystal compound coated in the step (2) is immersed in the additive solution, or the additive solution is formed on the retardation layer. Applying and drying;
(3) the laminate obtained in the step (A), have a row pattern exposure in different exposure conditions to at least a different region to form a different phase difference amount step;
(4) The process of producing a patterning phase difference layer by baking the laminated body obtained at a process (3) at 50 to 400 degreeC. A method for producing an optical material including a patterning retardation layer including two or more regions having different optical axis directions and two or more regions having different retardation amounts on a support, the following steps ( 1A) and a production method comprising the following steps (11) to (14):
(11) An alignment layer in which regions having different optical axis directions are formed by rubbing at least different regions in different directions through a mask on the composition for forming an alignment layer on a support. Producing step;
(12) A step of applying and drying a solution containing a liquid crystalline compound on the alignment layer obtained in step (11);
(1A) After the step (12), the retardation layer containing the liquid crystal compound coated in the step (12) is immersed in the additive solution, or the additive solution is formed on the retardation layer. Applying and drying;
(13) to the laminate obtained in the step (1A), have row pattern exposure in different exposure conditions to at least different areas, forming a different amount of phase difference;
(14) A step of baking the layered product obtained in step (13) at 50 ° C. or higher and 400 ° C. or lower to produce a patterning retardation layer. A method for producing an optical material including a patterning retardation layer including two or more regions having different optical axis directions and two or more regions having different retardation amounts on a support, the following steps ( 2A) and a production method comprising the following steps (21) to (26):
(21) on a temporary support, dried compositions comprising an optical alignment material is applied, by performing the pattern exposure of the polarized ultraviolet light for irradiating polarized ultraviolet light of different polarization directions in at least different regions, together Producing an alignment layer in which regions having different optical axis directions are formed ;
(22) A step of applying and drying a solution containing a liquid crystalline compound on the alignment layer obtained in the step (21);
(2A) After the step (22), the retardation layer containing the liquid crystalline compound applied in the step (22) is immersed in the additive solution, or the additive solution is formed on the retardation layer. Applying and drying;
(23) A step of providing a transfer adhesive layer on the liquid crystalline compound obtained in the step ( 2A );
(24) A step of transferring the laminate obtained in step (23) onto a support;
(25) to the laminate obtained in the step (24), have a row pattern exposure in different exposure conditions to at least different areas, forming a different amount of phase difference;
(26) A step of baking the layered product obtained in the step (25) at 50 ° C. or more and 400 ° C. or less to produce a patterning retardation layer. A method for producing an optical material including a patterning retardation layer including two or more regions having different optical axis directions and two or more regions having different retardation amounts on a support, the following steps ( 3A) and a production method comprising the following steps (31) to (36):
(31) An alignment layer in which regions having different optical axis directions are formed by rubbing at least different regions in different directions through a mask on the alignment layer forming composition on the temporary support. Producing step;
(32) A step of applying and drying a solution containing a liquid crystalline compound on the alignment layer obtained in the step (31);
(3A) After the step (32), the retardation layer containing the liquid crystalline compound applied in the step (32) is immersed in the additive solution, or the additive solution is formed on the retardation layer. Applying and drying;
(33) A step of providing a transfer adhesive layer on the liquid crystalline compound obtained in step ( 3A );
(34) A step of transferring the laminate obtained in the step (33) onto a support;
(35) to the laminate obtained in the step (34), have a row pattern exposure in different exposure conditions to at least different areas, forming a different amount of phase difference;
(36) A step of producing a patterning retardation layer by baking the laminate obtained in the step (35) at 50 ° C. or more and 400 ° C. or less. The manufacturing method according to any one of claims 1 to 4, wherein the additive is a polymerization initiator. 6. The method according to claim 1, further comprising a step of irradiating the coated retardation layer with ultraviolet rays before the step of immersing in the additive solution or the step of applying the additive solution. Manufacturing method. The patterned retardation layer, the manufacturing method according to any one of 請 Motomeko 1-6 you containing polymer having orientation group in the side chain. The liquid crystalline compound contained in the coating solution for the retardation layer formed on the alignment layer has a combination of a radical reactive group and a cationic reactive group, and the radical reactive group is an acryl group or methacrylic group. The production method according to claim 1, wherein the cationic reactive group is a vinyl ether group, an oxetane group or an epoxy group. The manufacturing method of any one of Claims 1-8 which contains a horizontal aligning agent in the coating liquid of the phase difference layer formed on the said orientation layer. The manufacturing method according to claim 1 , wherein the alignment layer is a layer formed from a composition containing a photoisomerization material or a photodimerization type material . Optical materials ing been produced by the production method according to any one of claims 1-10. The optical material according to claim 11 , wherein the optical material is used as a forgery preventing means. An optical element comprising the optical material according to claim 11 .

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