JP2010243850A - Multilayer birefringence pattern builder and method for producing article having multilayer birefringence pattern - Google Patents

Abstract

Provided is a multilayer birefringence pattern builder having a plurality of optically anisotropic layers, which can efficiently form different birefringence patterns for each layer. Furthermore, the present invention provides a method for producing an article having a multilayer birefringence pattern having a plurality of optically anisotropic layers having different birefringence patterns for each layer, which has excellent anti-counterfeiting properties and design properties, with a smaller number of steps. provide.
A multilayer birefringence pattern builder comprising at least two optically anisotropic layers (12F) and (12S) which are capable of forming different birefringence patterns, comprising a polymer compound having a reactive group.
[Selection] Figure 1

Description

  The present invention relates to a multilayer birefringence pattern builder and a method for producing an article having a multilayer birefringence pattern.

Techniques that use optical anisotropy to affect the visual state of the image and the state of the image itself include changes in visibility due to relaxation of the orientation of the stretched film (for example, Patent Document 1), and molecules that exhibit optical anisotropy. There are known ones that control the orientation direction (for example, Patent Document 2) and those that use selective reflection of cholesteric liquid crystals (for example, Patent Document 3).
An image obtained using the technique of Patent Document 1 or Patent Document 2 is not perceptible or difficult to perceive in a normal state, and can be perceived by overlaying a predetermined polarizer on the image (in this normal state). In the following, images that are unperceivable or difficult to perceive are referred to as latent images). An image obtained by using the technique of Patent Document 3 shows a predetermined change in an image perceived in a normal state by a predetermined operation (such as overlaying or tilting filters). Such special images using optical anisotropy are used as, for example, securities, credit cards, documents, etc. as a medium for authenticity identification. In these applications, further improvements in anti-counterfeiting and design properties are desired.

JP-A-9-68927 Special table 2001-525080 gazette Japanese Patent Laid-Open No. 11-42875

On the other hand, in an article having a multilayer birefringence pattern, it is conceivable to provide a plurality of optically anisotropic layers having different birefringence patterns for each layer. However, laminating such optically anisotropic layers one by one causes a problem that the number of processes increases and the production becomes complicated. For example, when the procedure of applying an optically anisotropic layer, exposing, and baking is performed a plurality of times, the baking process requires time and energy, and is not efficient.
An object of the present invention is to provide a multilayer birefringence pattern builder having a plurality of optically anisotropic layers, which can efficiently form different birefringence patterns for each layer. Furthermore, the present invention provides a method for producing an article having a multi-layer birefringence pattern having a plurality of optically anisotropic layers having different anti-counterfeiting properties and design properties and having different birefringence patterns for each layer with a smaller number of steps. The issue is to provide.

The above object has been achieved by the following invention.
(1) A multilayer birefringence pattern builder comprising at least two optically anisotropic layers which are capable of forming different birefringence patterns, comprising a polymer compound having a reactive group.
(2) The multilayer birefringence pattern builder according to (1), wherein the birefringence pattern formation reaction conditions differ in at least two of the optically anisotropic layers.
(3) The multilayer birefringence pattern builder according to (2), wherein the reaction conditions for forming the birefringence pattern are different in the spectral absorption peak wavelength.
(4) The multilayer birefringence pattern builder according to (3), wherein the birefringence pattern formation reaction conditions are different in the absorption spectrum of the photopolymerization initiator.
(5) The multilayer birefringence pattern builder according to (2), wherein the birefringence pattern formation reaction conditions are different in polarization absorption characteristics.
(6) The multi-layer birefringence pattern builder according to (5), wherein the polarization absorption characteristic is that the orientation direction of the dichroic photopolymerization initiator is different.

(7) The optically anisotropic layer is formed by applying and drying a solution containing a liquid crystalline compound having at least two reactive groups to form a liquid crystal phase, and then polymerizing and fixing by irradiation with heat or ionizing radiation. The multilayer birefringence pattern builder according to any one of (1) to (6).
(8) The multilayer birefringence pattern builder according to (7), wherein the liquid crystalline compound has two or more reactive groups having different polymerization conditions.
(9) The multilayer birefringence pattern builder according to (8), wherein the liquid crystalline compound has at least a radical reactive group and a cationic reactive group.
(10) The multilayer birefringence pattern builder according to any one of (7) to (9), which is modified after the optically anisotropic layer is polymerized and fixed.
(11) The modification is performed in such a manner that the additive in the functional layer diffuses into the optically anisotropic layer in the step of forming another functional layer on the optically anisotropic layer. The multilayer birefringence pattern builder as described.
(12) The multilayer birefringence pattern builder according to any one of (1) to (6), wherein the optically anisotropic layer is made of a stretched film.
(13) The multilayer birefringence pattern according to any one of (1) to (12), which is manufactured by a manufacturing method including transferring a transfer material including an optically anisotropic layer onto a transfer material. material.
(14) The transfer material according to (13), wherein at least the [A] optical anisotropic layer and the [B] transfer adhesive layer are laminated in this order on a temporary support. Multilayer birefringence pattern builder.

(15) A method for producing an article having a multilayer birefringence pattern, including at least the following steps [1] to [3] in this order:
[1] A step of producing a multilayer birefringence pattern builder comprising at least two optically anisotropic layers capable of forming different birefringence patterns, comprising a polymer compound having a reactive group;
[2] A step of exposing at least one of the optically anisotropic layers of the multilayer birefringence pattern builder so as to give a latent image of an arbitrary pattern independently of the other optically anisotropic layers. ;
[3] A step of baking the laminate obtained after the step [2] at 50 ° C. or higher and 400 ° C. or lower.
(16) A method for producing an article having a multilayer birefringence pattern, including at least the following steps [11] to [13] in this order:
[11] A step of producing a multilayer birefringence pattern builder comprising at least two optically anisotropic layers capable of forming different birefringence patterns, comprising a polymer compound having a reactive group;
[12] A step of performing partial heating of an arbitrary pattern independently of other optically anisotropic layers on at least one of the optically anisotropic layers of the multilayer birefringence pattern builder;
[13] A step of reacting the multilayer birefringence pattern builder with an unreacted reactive group in the optically anisotropic layer to increase durability of the optically anisotropic layer.
(17) The manufacturing method according to (16), wherein the step [13] is performed by whole surface exposure.
(18) The production according to (16), wherein the step [13] is performed by a heat treatment at a temperature lower than a temperature reached by the optically anisotropic layer of the heated portion in the step [12]. Method.
(19) Any one of (15) to (18), wherein the step [2] or the step [12] is performed using a difference in spectral absorption peak wavelength of each optical anisotropic layer. The production method according to item.
(20) The method according to (19), wherein at least two of the optically anisotropic layers have photopolymerization initiators having different absorption spectra.
(21) Any one of (15) to (18), wherein the step [2] or the step [12] is performed using a difference in polarization absorption characteristics of each optically anisotropic layer. The manufacturing method as described in.
(22) The method according to (21), wherein at least two of the optically anisotropic layers have a dichroic photopolymerization initiator.
(23) In any one of (15) to (18), the step [2] or the step [12] is performed using a difference in vertical position of each optically anisotropic layer. The manufacturing method as described.
(24) The manufacturing method according to (23), wherein the step [2] is performed using a condensing optical system having a variable focal length.

(25) An article used as a forgery prevention means obtained by the production method according to any one of (15) to (24).
(26) An optical element obtained by the production method according to any one of (15) to (24).

The multilayer birefringence pattern builder according to the present invention has a plurality of optically anisotropic layers capable of forming different birefringence patterns for each layer, and can be efficiently manufactured.
According to the manufacturing method of the present invention, an article having a multilayer birefringence pattern, which has a high anti-counterfeit effect and a high visual effect, can be manufactured with a small number of steps. Articles manufactured by the manufacturing method of the present invention are useful as anti-counterfeiting means and optical elements.

It is a schematic sectional drawing which shows the example of the multilayer birefringence pattern preparation material of this invention. It is a schematic sectional drawing of the example of the article | item which has a multilayer birefringence pattern obtained by the manufacturing method of this invention. It is a figure which shows each shape of three photomasks MB1, MG1, and MR1 used in Example 1. It is a figure which shows the area | region which has a different retardation in the sample produced using the photomask in Example 1. FIG. It is a figure which shows each shape of the three photomasks MB2, MG2, and MR2 used in Example 2. It is a figure which shows the area | region which has a different retardation in the sample produced using the photomask in Example 2. FIG. It is a figure which shows each shape of the two photomasks MG3 and MR3 used in Example 3. It is a figure which shows the pattern observed when a polarizing plate is piled up on the sample produced using the photomask in Example 4, (a) arrange | positions so that the absorption axis of a polarizing plate may become a 45 degree direction. In this case, (b) shows a case where the polarizing plate is arranged so that the absorption axis is approximately 90 °. It is a figure which shows each shape of three photomasks MD1 and MD2 used in Example 4. FIG. It is a figure which shows the area | region which has a different retardation in the sample produced using the photomask in Example 4. FIG.

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, retardation or Re represents in-plane retardation. In-plane retardation (Re (λ)) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (trade name, manufactured by Oji Scientific Instruments). 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.

  In this specification, “substantially” for the angle means that the error from the exact angle is within a range of less than ± 5 °. Furthermore, the error from the exact angle is preferably less than 4 °, more preferably less than 3 °. With regard to retardation, “substantially” means that the retardation is within ± 5%. Furthermore, Re is not substantially 0 means that Re is 5 nm or more. In addition, the measurement wavelength of the refractive index indicates an arbitrary wavelength in the visible light region unless otherwise specified. In the present specification, “visible light” refers to light having a wavelength of 400 to 700 nm.

[Multilayer birefringence pattern builder]
FIG. 1 is a schematic cross-sectional view of several examples of a multilayer birefringence pattern builder according to the present invention. The multilayer birefringence pattern builder is a material for producing a multilayer birefringence pattern, and is a material capable of producing an article having a multilayer birefringence pattern through a predetermined process. The multilayer birefringence pattern builder shown in FIG. 1A is an example having a first optically anisotropic layer 12F and a second optically anisotropic layer 12S on a support (substrate) 11. The multilayer birefringence pattern builder shown in FIG. 1B is an example having alignment layers 13A and 13B. The alignment layers 13A and 13B are formed by applying and drying a solution containing a liquid crystalline compound as the optically anisotropic layers 12F and 12S to form a liquid crystal phase, and then polymerizing and fixing by irradiation with heat or ionizing radiation. It functions as a layer for assisting the alignment of the liquid crystal compound.

  The multilayer birefringence pattern builder shown in FIG. 1C is an example having transfer adhesive layers 14A and 14B because it is made using a transfer material. The multilayer birefringence pattern builder shown in FIG. 1D is an example in which a reflective layer 35 is further provided on the support 11. The multilayer birefringence pattern builder shown in FIG. 1E is an example having a reflective layer 35 under the support 11. The multilayer birefringence pattern builder shown in FIG. 1 (f) is an example having a back adhesive layer 16 and a release layer 17 under the support 11 for further pasting on another article after the multilayer birefringence pattern is produced. .

[Multilayer birefringence pattern builder used as transfer material]
The multilayer birefringence pattern builder can be used as a transfer material. By using a multilayer birefringence pattern builder as a transfer material, a multilayer birefringence pattern builder having a plurality of optically anisotropic layers on a desired support or an article having a plurality of layers having a birefringence pattern can be produced. It can be done easily.

[Article having multilayer birefringence pattern]
In this specification, “an article having a multilayer birefringence pattern” means two or more optically anisotropic layers, and at least one of the optically anisotropic layers has two regions having different birefringence. Means an article having the above. More preferably, at least one of the optically anisotropic layers of the article having a multilayer birefringence pattern has three or more regions having different birefringence. Individual regions having the same birefringence may be continuous or discontinuous.
FIG. 2 is a schematic cross-sectional view of several examples of articles having a multilayer birefringence pattern obtained by a production method using a multilayer birefringence pattern builder. An article having a multilayer birefringence pattern obtained by the method of the present invention has two or more optically anisotropic layers, and at least one of the optically anisotropic layers is a patterned optically anisotropic layer. In the present specification, the “patterned optically anisotropic layer” means “an optically anisotropic layer having regions having different birefringence in a pattern”.
The article having the multilayer birefringence pattern shown in FIG. 2 can be produced by subjecting the multilayer birefringence pattern builder according to the present invention to a predetermined treatment (for example, pattern exposure or partial heating as described later).

  The article having a multilayer birefringence pattern shown in FIG. 2A is an example composed of two patterned optically anisotropic layers 112F and 112S. An article having a multilayer birefringence pattern produced by the production method of the present invention has at least two or more optically anisotropic layers, and at least one of them (two layers in FIG. 2 (a)) is It has two or more regions having different birefringence (in the first patterned optically anisotropic layer, the first layer first region 112F-A and the first layer second region 112F-B, In the isotropic layer, the second layer first region 112S-A and the second layer second region 112S-B). The article having the multilayer birefringence pattern shown in FIG. 2B has a plurality of regions having different birefringence (first layer first region 112F-A and second region 112F-B, second layer first region 112S-). In addition to A and the second region 112S-B), each of the patterned optically anisotropic layers has isotropic regions 112F-N and 112S-N, respectively. The article having the multilayer birefringence pattern shown in FIG. 2 (c) has patterned optically anisotropic layers 112F (112F-A and 112F-B) and 112S (112S-A and 112S-B) on the support 11, respectively. This is an example having alignment layers 13A and 13B.

  The article having the multilayer birefringence pattern shown in FIG. 2D is an example having transfer adhesive layers 14A and 14B because it is made of a transfer material. As in this case, at least one layer of the optically anisotropic layer may be the patterned optically anisotropic layer (112S), and a uniform (solid) optically anisotropic layer (other than the other) having no pattern ( 113F) may be included. The article having the multilayer birefringence pattern shown in FIG. 2E is formed on the support 11 in order from the support side, the reflective layer 35, the transfer adhesive layer 14A, the patterned optical anisotropic layer 112F, the transfer adhesive layer 14B, and the patterned optics. In this example, the anisotropic layer 112S is provided, and two optically anisotropic layers are provided with mutually independent patterns.

  Hereinafter, a multilayer birefringence pattern builder, a method for producing an article having the multilayer birefringence pattern using the multilayer birefringence pattern, a material for the article having the multilayer birefringence pattern, a production method, and the like will be described in detail. 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.

[Optically anisotropic layer]
The optically anisotropic layer in the multilayer birefringence pattern builder has a single incident direction where Re is not substantially 0 when the phase difference is measured, that is, a layer having optical properties that are not isotropic.

The optically anisotropic layer in the multilayer birefringence pattern builder includes a polymer compound. By including the polymer compound, different kinds of requirements such as birefringence, transparency, solvent resistance, toughness and flexibility can be satisfied. The polymer compound in the optically anisotropic layer has an unreacted reactive group. The retardation of the optically anisotropic layer is changed by heating (especially, when it has a retardation disappearing temperature, it shows a significant decrease in retardation). Thus, it becomes possible to control the degree of change in retardation during heating, and further, the change in retardation can be controlled in a pattern by performing pattern exposure.
On the other hand, by heating a part of the area first, the heating part and the non-heating part have a temporary retardation difference, and then the unreacted reactive group is reacted by a process such as exposure. A technique that fixes the difference in retardation is also possible.
As described above, by appropriately combining exposure and heating processes, the optically anisotropic layer in the multilayer birefringence pattern builder according to the present invention can efficiently draw an optically anisotropic pattern.
The polymer compound in the optically anisotropic layer of the multilayer birefringence pattern builder according to the present invention refers to a macromolecule formed by bonding a large number of atoms, for example, a compound having a molecular weight of 3000 or more. Specific examples include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyethers, and copolymers thereof. Various monomers may be copolymerized in these polymers. Examples of such monomers include carboxylic acid-terminated acrylic monomers and liquid crystalline acrylic monomers. Examples of the (unreacted) reactive group include a vinyl group, an acrylic group, a methacryl group, an epoxy group, and an oxetanyl group. The content of the polymer compound in the optically anisotropic layer is preferably 5 to 99% by mass, more preferably 10 to 95% by mass.

The optically anisotropic layer is preferably solid at 20 ° C., more preferably at 30 ° C., and even more preferably at 40 ° C. This is because if it is solid at 20 ° C., it is easy to apply other functional layers, and to transfer and paste onto a support.
In order to apply other functional layers, the optically anisotropic layer in the present invention preferably has solvent resistance. In this specification, “having solvent resistance” means that the retardation after immersion for 2 minutes in the target solvent is in the range of 30% to 170% of the retardation before immersion, more preferably 50% to 150%. %, Most preferably in the range of 80% to 120%. The target solvent is water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, hexane, chloroform, ethyl acetate, preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol. Among monomethyl ether acetate and N-methylpyrrolidone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, or a mixed solvent thereof is most preferable.

  The optically anisotropic layer may have a retardation of 5 nm or more at 20 ° C., preferably 10 nm or more and 10,000 nm or less, and most preferably 20 nm or more and 2000 nm or less. If the retardation is 5 nm or less, it may be difficult to form a birefringence pattern. If the retardation exceeds 10,000 nm, the error may increase and it may be difficult to achieve practical accuracy.

The method for producing the optically anisotropic layer is not particularly limited, but after applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, polymerization is performed by irradiation with heat or ionizing radiation. Method of immobilizing and preparing; Method of stretching a layer in which a monomer having at least two reactive groups is polymerized and immobilizing; Stretching after introducing a reactive group into a polymer layer using a coupling agent A method; or a method of introducing a reactive group using a coupling agent after stretching a layer made of a polymer.
As will be described later, the optically anisotropic layer of the present invention may be formed by transfer.
The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm.

[Optically anisotropic layer formed by polymerizing and fixing a composition containing a liquid crystalline compound]
When preparing a liquid crystal phase by applying a solution containing a liquid crystalline compound having at least one reactive group as a method for producing an optically anisotropic layer to form a liquid crystal phase, and then fixing by polymerization by irradiation with heat or ionizing radiation Is described below. In this production method, it is easy to obtain an optically anisotropic layer having a thin film thickness and an equivalent retardation as compared with a production method of obtaining an optically anisotropic layer by stretching a polymer described later.

[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 an optically anisotropic layer including 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 may be different in the polymerization mechanism used, but preferably controllable by the type of initiator used, a radical reactive group and a cationic reaction 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. In this specification, Et represents an ethyl group, and Pr represents a propyl group.

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 translations of PCT 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 optically anisotropic layer. The optically anisotropic 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 optically anisotropic layer is formed by applying a composition containing a liquid crystal 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, A layer prepared by fixing by irradiation with ionizing radiation is preferred. At this time, the liquid crystal compound preferably has at least two reactive groups, more preferably has two or more reactive groups having different polymerization conditions, and has a radical reactive group and a cationic reactive group. Is more preferable.
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 optically anisotropic layers comprising 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, all having rod-like properties. It may be a laminate of a layer made of a liquid crystal compound, a laminate of a layer made of a composition containing a discotic liquid crystal compound and a layer made of a composition containing a rod-like liquid crystal compound. The combination of the alignment states of the layers is not particularly limited, and optically anisotropic layers having the same alignment state may be stacked, or optically anisotropic layers having different alignment states may be stacked.

  The optically anisotropic 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. Aciloin compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of 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 optically anisotropic layer may be a layer that exhibits or increases in-plane retardation by photo-alignment by polarized light irradiation. This polarized light irradiation may serve as the photopolymerization process in the above-described orientation fixation, or may be further fixed by non-polarized light irradiation after first polarized light irradiation, or may be fixed first by non-polarized light irradiation. The photo-alignment may be carried out by irradiation with polarized light, but it is desirable to carry out only the irradiation with polarized light or to perform further immobilization with non-polarized light after performing polarized light irradiation 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 optically anisotropic 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 adhesiveness and the like are improved, and production can be carried out 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 an optically anisotropic layer including a polymer having an unreacted reactive group by selecting conditions and polymerizing only a part of plural 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 optically anisotropic 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): By containing, 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 — (Ra Is a divalent linking group selected from the group consisting of alkyl groups having 1 to 5 carbon atoms or hydrogen atoms), —O—, —S—, —SO—, —SO ₂ — and combinations thereof. Is preferred. Divalent linking group is an alkylene group, a phenylene group, -CO -, - NRa -, - O -, - S- and SO ₂ - divalent linking group or a group selected from said group of selected from the group consisting of More preferably, it is a divalent linking group in which at least two 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 ¹⁰ represents a substituent, and m1 represents an integer of 0 to 5. When m1 represents an integer of 2 or more, the plurality of R ¹⁰ may be the same or different. Preferred substituents for R ¹⁰ are the same as those listed as preferred ranges for the substituents represented by R ¹ , R ² , and R ³ . m1 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 paragraphs [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, m2 is an integer of 1 to 6 and n2 is 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.

[Optically anisotropic layer produced by stretching]
The optically anisotropic layer may be prepared by stretching a polymer. The optically anisotropic layer preferably has at least one unreacted reactive group, but when preparing such a polymer, the polymer having a reactive group may be stretched in advance, A reactive group may be introduced into the subsequent optically anisotropic layer using a coupling agent or the like. Features of the optically anisotropic layer obtained by the stretching method include low cost and self-supporting property (no support is required for forming and maintaining the optically anisotropic layer).

[Post-processing of optical anisotropy]
Various post-treatments may be performed to modify the produced optically anisotropic 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. In addition, when the polymer in the optically anisotropic layer has an unreacted reactive group, it is also an effective modifying means to add a polymerization initiator corresponding to the reactive group. For example, adding a radical photopolymerization initiator to an optically anisotropic layer obtained by polymerizing and fixing a liquid crystalline compound having a cationic reactive group and a radical reactive group using a cationic photopolymerization initiator Thus, the reaction of an unreacted radical reactive group when pattern exposure is performed later can be promoted. Examples of the means for adding the plasticizer and the photopolymerization initiator include a means for immersing the optically anisotropic layer in a solution of the corresponding additive and a solution of the corresponding additive on the optically anisotropic layer. And means for infiltration. Moreover, when another layer is applied on the optically anisotropic layer, an additive may be added to the coating solution of the layer and the optically anisotropic layer may be immersed (diffused). In the present invention, depending on the type and amount of the additive to be immersed in this case, particularly the photopolymerization initiator, the exposure amount to each region at the time of pattern exposure to the birefringence pattern material described later and each finally obtained By adjusting the relationship with the retardation of the region, it is possible to approximate the desired material properties.

[Multilayer birefringence pattern builder]
The multilayer birefringence pattern builder is a material for producing a multilayer birefringence pattern, and is a material that can obtain a multilayer birefringence pattern through a predetermined process. The multilayer birefringence pattern builder may be usually a film or a sheet. In addition to the optically anisotropic layer described above, the multilayer birefringence pattern builder may have a functional layer capable of imparting various secondary functions. Examples of the functional layer include a support, an alignment layer, a reflective layer, and a back adhesive layer. In addition, a multi-layer birefringence pattern builder used as a transfer material or a multi-layer birefringence pattern builder made using a transfer material has a temporary support, a transfer adhesive layer, or a mechanical property control layer. May be.

[Support]
The multilayer birefringence pattern builder may have a support for the purpose of maintaining mechanical stability. The support used for the multilayer birefringence pattern builder 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, polyimide, polyester and polysulfone, norbornene-based plastic films, paper, aluminum foil, cloth, and the like. 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. The support preferably has heat resistance sufficient not to be colored or deformed by baking to be described later. It is also preferable that the support itself has a reflecting function instead of the reflecting layer described later.

[Alignment layer]
As described above, an alignment layer may be used for forming the optically anisotropic layer. The alignment layer is generally provided on a support or temporary support or an undercoat layer coated on the support or temporary support. The alignment layer functions so as to define the alignment direction of the liquid crystal compound provided thereon. The orientation layer may be any layer as long as it can impart orientation to the optically anisotropic layer. Preferred examples of the alignment layer include a rubbing-treated layer of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, 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 (trade name, Showa Denko ( A modified polyvinyl alcohol in which an acrylic group is introduced into a side chain using a product manufactured by KK) is particularly preferred. 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 done by applying polyamic acid (for example, LQ / LX series manufactured by Hitachi Chemical Co., Ltd., SE series manufactured by Nissan Chemical Co., Ltd., etc., both trade names) to the support surface, and at 0. After baking for 5 to 1 hour, it is 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.

[Support that also serves as an alignment layer]
In order to align the liquid crystal layer, a method of forming an alignment layer on a support and rubbing the surface is generally used. However, depending on the combination of the coating solution and the support, it is possible to align the liquid crystal layer by directly rubbing the support. Examples of such a support include a support mainly composed of an organic compound, particularly a polymer, preferably used in an alignment layer described later. Examples of such a support include a PET film and a polyimide film.

[Uneven alignment layer]
As the alignment layer of the liquid crystal, not only a film subjected to rubbing or ionizing line alignment but also a film having small irregularities can be used.
Various structures can be employed for the recess forming region. For example, a structure in which a plurality of grooves are arranged in parallel in the width direction at equal intervals can be employed in the recess forming region.

  These grooves may not be parallel to each other, but the longer the grooves are, the easier the long axes of the liquid crystal molecules or their mesogenic groups are aligned. The angle formed by these grooves is, for example, 5 ° or less, and typically 3 ° or less.

  These grooves may be arranged vertically and horizontally. The lengths of the grooves may be equal to each other or different from each other. Further, the distance between adjacent grooves in the length direction may be uniform or non-uniform. Furthermore, the distance between the grooves adjacent in the width direction may be uniform or non-uniform. Further, grooves having the same length may be arranged vertically and horizontally in each of the recess forming regions. Or you may arrange the groove | channel of various length at random.

  By making the grooves substantially parallel and appropriately setting the pitch, the diffraction grating can be constituted by these grooves.

The recess forming layer (uneven alignment layer) can be formed, for example, by a method of recording a hologram pattern using a two-beam interference method on a photosensitive resin material or a method of drawing a pattern by an electron beam. Alternatively, as is done in the manufacture of surface relief holograms, it can be formed by pressing a mold provided with fine linear projections onto the resin. For example, the concave portion forming layer is obtained by a method of pressing a master having a linear convex portion against a thermoplastic resin layer formed on a substrate while applying heat, that is, a hot embossing method. .
Alternatively, the recess forming layer is formed by applying an ultraviolet curable resin on the substrate, irradiating the substrate with ultraviolet rays while curing the ultraviolet curable resin while pressing the original, and then removing the original. It is also possible.

  According to these methods, it is possible to form a plurality of recess formation regions having different groove length directions in one plane. In addition, according to these methods, a plurality of recess formation regions having different groove depths, widths, and / or grooves can be formed in one plane.

  The original plate can be obtained, for example, by performing electroforming of a mother die obtained by a method of recording a hologram pattern using a two-beam interference method, a method of drawing a pattern by an electron beam, or a method of cutting by a cutting tool. It is done. When the above-described diversity is not given to the recess forming layer, the groove may be formed by rubbing.

  The depth of these grooves is, for example, in the range of 0.05 μm to 1 μm. The length of the groove is, for example, 0.5 μm or more. The pitch of the grooves is, for example, 0.1 μm or more, and typically 0.75 μm or more. The pitch of the grooves is, for example, 10 μm or less, and typically 2 μm or less. In order to align the liquid crystal molecules or their mesogenic groups with a high degree of order, it is advantageous that the pitch of the grooves is small.

[Reflective layer]
The multilayer birefringence pattern builder may have a reflective layer in order to produce a multilayer birefringence pattern that can be more easily identified. Although it does not specifically limit as a reflection layer, For example, metal layers, such as aluminum and silver, are mentioned.

[Rear adhesive layer]
The multilayer birefringence pattern builder may have a post-adhesive layer for attaching an article having a multilayer birefringence pattern prepared after pattern exposure and baking described below to another article. The material of the post-adhesion layer is not particularly limited, but is preferably a material having adhesiveness even after undergoing a baking step for producing a multilayer birefringence pattern.

[Two or more optically anisotropic layers]
The multilayer birefringence pattern builder according to the present invention has two or more optically anisotropic layers. Two or more optically anisotropic layers may be adjacent to each other in the normal direction, or another functional layer may be sandwiched therebetween. Two or more optically anisotropic layers may have almost the same retardation or different retardations. Further, the slow axis directions may be in substantially the same direction, or may be in different directions.

[Production method of multilayer birefringence pattern builder]
The method for producing the multilayer birefringence pattern builder is not particularly limited. For example, the optically anisotropic layer may be applied directly on the support or formed by coating another layer on the support material. Transfer the prepared optically anisotropic layer, form as a self-supporting optically anisotropic layer, form another functional layer on the self-supporting optically anisotropic layer, self-supporting And a method such as bonding the optically anisotropic layer to a support. Among these, from the point of not limiting the physical properties of the optically anisotropic layer, the optically anisotropic layer is transferred onto the support using a method of directly forming the optically anisotropic layer on the support and a transfer material. A method is preferable, and a method of transferring an optically anisotropic layer onto a support using a transfer material is more preferable because there are few restrictions on the support.

As a method for producing a multilayer birefringence pattern builder comprising two or more optically anisotropic layers as in the present invention, the method described above may be repeated a plurality of times (for example, an alignment layer → an optically different layer). Isotropic layer → orientation layer → optically anisotropic layer and repeated coating, transfer to the substrate as many times as necessary, etc.) may be combined (after orientation layer → optically anisotropic layer is applied) Transcription, etc.). Since the degree of freedom of the layer configuration is high, a method of transferring the optically anisotropic layer prepared as a transfer material on the substrate a plurality of times is more preferable.
Below, the transfer material for transferring an optically anisotropic layer is demonstrated. Such a transfer material is referred to as a “transfer material for producing a birefringence pattern” in Examples and the like described later.

[Temporary support]
The birefringence pattern builder used as a 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 from the viewpoint of low birefringence, cellulose ester and norbornene are preferred. As a commercially available norbornene-based polymer, Arton (trade name, manufactured by JSR Corporation), Zeonex, Zeonore (all of which are trade names, manufactured by Nippon Zeon Co., Ltd.) and 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, and includes an adhesive layer made of an adhesive, a pressure-sensitive resin layer, a heat-sensitive resin layer, a photosensitive resin layer, and the like. 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.

  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.

  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.

  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. Furthermore, rosin derivatives such as rosin, hydrogenated rosin, polymerized rosin, rosin modified glycerin, rosin modified maleic resin, rosin modified polyester resin, rosin modified phenolic resin and 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.

  The photosensitive resin layer is made of a photosensitive resin composition, and may be positive type or negative type, and is not particularly limited, and a commercially available resist material can also be used. When used as a transfer adhesive layer, it is preferable to exhibit adhesiveness by light irradiation. In view of environmental and explosion-proof problems in the manufacturing process of articles such as substrates for liquid crystal display devices, aqueous development with an organic solvent of 5% or less is preferred, and alkaline development is particularly preferred. 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. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in 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 a polar group may be used alone or in the form of a composition used in combination with a normal film-forming polymer. 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 such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and methacrylates.
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 and a p-aminoketone described in U.S. Pat. No. 3,549,367, 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 as a mixture 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 JP 2003-337424 A [0090] to [0091], JP 2003-177522 A [0092] to [0093], and JP 2003-177523 A [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 fluorosurfactant 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 ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group, and R ¹⁴ 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 different structures within the above defined range may be used. The same applies to the monomer (b).
The particularly preferable surfactant has a mass average molecular weight Mw of preferably 1000 to 40000, and more preferably 5000 to 20000. The surfactant contains the monomer 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 such that the monomer (a) is 20 to 60 parts by weight, the monomer (b) is 80 to 40 parts by weight, and other optional monomers are the remaining parts by weight. 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. When the content is less than 0.01% by mass with respect to the total solid content, display unevenness is not improved. When the above-described particularly preferable surfactant is contained in the photosensitive resin layer to produce a color filter, 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 (trade name, manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171 and F173. , F176, F189, R08 (trade name, manufactured by Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (trade name, manufactured by Asahi Glass Co., Ltd.) An activator or a silicon-based surfactant can be mentioned. Polysiloxane polymer KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (trade name, 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 optically anisotropic layer of the transfer material in order to control the mechanical properties and the uneven 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 substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). 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 birefringence pattern builder used as 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 the release layer, and serves to assist the release of the temporary support after transferring the optically anisotropic 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, it is preferable to use an oxygen barrier film having an oxygen barrier function described in JP-A-5-72724 as an “isolation layer” or the alignment layer for forming the optical anisotropy. Among these, a layer formed by mixing polyvinyl alcohol or polyvinyl pyrrolidone and one or more of the modified products thereof 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 optically anisotropic layer, photosensitive resin layer, transfer adhesive layer and orientation layer, thermoplastic resin layer, mechanical property control layer and intermediate layer formed as desired is formed by dip coating, air knife coating, spin It can be formed by coating by a coating method, a slit coating method, 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 method of simultaneous application is 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).
In addition, when applying a layer (for example, a transfer adhesive layer) to be applied on the optically anisotropic layer, by adding a plasticizer or a photopolymerization initiator to the coating solution, the optical effect by immersing those additives is added. The anisotropic layer may be modified at the same time.

[Method of Transferring Transfer Material onto Transferred 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 optically anisotropic 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 the support and another functional layer, or a (multilayer) birefringence pattern builder.

[Transfer process]
After transferring the birefringence pattern 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 unnecessary layers transferred together with the optically anisotropic 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. Alternatively, the transfer material may be transferred to the surface after the temporary support is removed or the unnecessary layer is removed as necessary. The transfer material used at this time may be the same as or different from the transfer material previously transferred. Further, the slow axis of the optically anisotropic layer of the transfer material previously transferred and the optically anisotropic layer and slow axis of the newly transferred transfer material may be in the same direction or in different directions. As described above, transferring a plurality of optically anisotropic layers means that a birefringence pattern having a large retardation and a slow axis having a large retardation formed by laminating a plurality of optically anisotropic layers having the same slow axis direction. This is useful for producing a special birefringence pattern in which a plurality of layers having different directions are laminated.

[Production of an article having a multilayer birefringence pattern]
After producing the multilayer birefringence pattern builder as described above (step [1]), at least the following steps [2] and [3] are performed in this order to produce an article having a multilayer birefringence pattern. can do.
[2] Exposure that gives a latent image of an arbitrary pattern independently of other optical anisotropic layers (pattern exposure) on at least one of the optical anisotropic layers of the multilayer birefringence pattern builder )
[3] A step of baking the laminate obtained after the step [2] at 50 ° C. or higher and 400 ° C. or lower.
Alternatively, an article having a multilayer birefringence pattern can also be produced by manufacturing a multilayer birefringence pattern builder (step [11]) and then performing at least the following steps [12] and [13] in this order. .
[12] A step of performing partial heating of an arbitrary pattern independently of other optically anisotropic layers on at least one of the optically anisotropic layers of the multilayer birefringence pattern builder;
[13] A step of reacting the multilayer birefringence pattern builder with an unreacted reactive group in the optically anisotropic layer to increase durability of the optically anisotropic layer.
Details of each method will be described below.

[Multilayer birefringence pattern manufacturing method using pattern exposure]
In this method, pattern exposure is performed on a part or all of the multilayer birefringence pattern builder to cure the corresponding region to increase heat resistance, and then heating (baking) is performed to determine whether each region has an exposure amount. Alternatively, it is a method for producing an article having a pattern by reducing the optical anisotropy according to the size (the region where the exposure amount is smaller has a larger reduction width), and generating an optical anisotropy discrepancy.

[Pattern exposure]
In this specification, the pattern exposure means exposure performed so that only a partial region of the multilayer birefringence pattern builder is exposed. 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. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a blue laser, and the like can be given. A preferable exposure amount is usually about 3 to 2000 mJ / cm ² , more preferably about 5 to 1000 mJ / cm ² , and most preferably about 10 to 500 mJ / cm ² .

[Exposure conditions for pattern exposure]
In the production method of the present invention, depending on the configuration of the multilayer birefringence pattern builder used for multilayer birefringence pattern fabrication, the birefringence of the multilayer birefringence pattern builder generated after baking according to the exposure conditions during pattern exposure (for example, letter May be different. In such a case, the exposure condition may be controlled according to the birefringence desired to be obtained after baking by using the property. Further, in order to obtain a plurality of regions having different birefringence, the exposure conditions may be different depending on the regions.

  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 amount are preferable, and the exposure illuminance, the exposure time, and the exposure amount are more preferable. Regions exposed under different exposure conditions during pattern exposure then exhibit birefringence that is different through firing and controlled by the exposure conditions. Give different retardation values. That is, by adjusting the exposure conditions for each region during pattern exposure, it is possible to produce a birefringence pattern having a desired retardation that is different for each region after firing. 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.

[Exposure such that at least one optically anisotropic layer gives a latent image of an arbitrary pattern independently of other optically anisotropic layers]
In the production method of the present invention, exposure is performed so as to give a latent image of an arbitrary pattern independently of other optically anisotropic layers to at least one optically anisotropic layer of the multilayer birefringence pattern builder. A step of performing. That is, the multilayer birefringence pattern builder according to the present invention has different birefringence pattern formation reaction conditions in at least two of the optically anisotropic layers. One of the different birefringence pattern formation reaction conditions is, for example, a spectral peak wavelength, which can be realized by using a photopolymerization initiator having a different absorption spectrum. Further, for example, it can be realized by using a dichroic photopolymerization initiator which has a polarization absorption characteristic and is oriented in different directions. Note that “the spectral peak wavelengths are different” means that the spectral peak wavelengths between the two layers are preferably different by 15 nm or more, more preferably by 30 nm or more. “Different polarization absorption characteristics” means that the absorption maximum direction between two layers is preferably different by 30 ° or more, more preferably 60 ° or more.
As a specific method of the above-mentioned process, for example, the photosensitive wavelength of the optically anisotropic layer in which the photosensitive wavelength of the optically anisotropic layer is different for each layer and exposure is performed with light having a wavelength corresponding to the desired layer. Examples include a method in which absorption anisotropy is imparted to the characteristics and exposure is performed with linearly polarized light in a direction corresponding to a desired layer with different absorption maximum directions for each layer.

[Method for making the photosensitive wavelength of the optically anisotropic layer different for each layer]
By making the photosensitive wavelength of the optically anisotropic layer different for each layer, it is possible to give the conditions for forming a birefringence pattern having a different spectral peak wavelength for each layer. As this method, for example, a method in which the photopolymerization initiator contained in the optically anisotropic layer (or immersed in the post-treatment) is different for each layer can be mentioned. As the photopolymerization initiator used in this case, in addition to the photopolymerization initiator that reacts mainly with ultraviolet light as described above, a photopolymerization initiator that reacts with visible light or infrared light is used. The degree can be increased. As a photoinitiator which reacts with visible light or infrared light, the combination of the organic boron compound shown to the following A-1 to A-10 and the organic pigment | dye shown to 1-1 to 1-18 can be mention | raise | lifted, for example. In addition, compounds such as those disclosed in JP-A Nos. 2000-171974 and 2002-82431 can also be used.

[Method of making absorption anisotropy of optically anisotropic layer different for each layer]
By making the absorption anisotropy of the optically anisotropic layer different for each layer, birefringence pattern formation reaction conditions having different polarization absorption characteristics can be given for each layer. As this method, for example, a method of containing / immersing a dichroic photopolymerization initiator in the optically anisotropic layer can be mentioned. As the dichroic photopolymerization initiator used in this method, a liquid crystalline dichroic photopolymerization initiator having a property of being aligned with the polymerizable liquid crystal is preferable. In this case, in order to align in an orderly manner, it is preferable that a dichroic photopolymerization initiator is contained in the optically anisotropic layer from the beginning.
Specifically, a method described in European Patent No. 1389199A1 can be used.

[How to use the difference in vertical position of each layer]
In addition, when using a scanning optical system for exposure, the optical system is configured so that the depth of focus becomes extremely shallow, and the difference in vertical position of each layer of the optically anisotropic layer is utilized to apply only to the target layer. There is also a method of collecting and reacting.

[Heating (Bake)]
A multilayer birefringence pattern can be produced by heating the pattern-exposed multilayer birefringence pattern builder to 50 ° C. or more and 400 ° C. or less, preferably 80 ° C. or more and 400 ° C. or less.

[Post-treatment (bleaching organic dyes)]
When an organic dye is used in the optically anisotropic layer, the color of the organic dye may remain, and this can be bleached by post-treatment as necessary. For example, a boron compound can be excessively added in advance, radicals can be generated from the boron compound by overall exposure, and the pigment can be decomposed and bleached. This method is more effective when performed while heating. When the wavelength used for bleaching and the wavelength used for the pattern exposure wavelength are close, this treatment is preferably performed after baking.

[Multilayer birefringence pattern manufacturing method using partial heating]
In this method, a partial region of the multilayer birefringence pattern builder is partially heated to reduce the optical anisotropy of the region, and then react with an unreacted reactive group in the optical anisotropic layer. This is a method for producing an article having a multilayer birefringence pattern by performing a treatment for increasing the durability of the anisotropic layer.

[Partial heating]
The method of heating a part of the multilayer birefringence pattern builder is not particularly limited. And a method of partially heating the multilayer birefringence pattern builder using heat mode exposure. In order to perform partial heating of an arbitrary pattern independently for each of two or more optically anisotropic layers, a method of partially heating a multilayer birefringence pattern builder using heat mode exposure is more preferable.

[Heating using heat mode exposure]
Heat mode exposure can also be used as heating of a partial region. The heat mode exposure that can be performed in the present invention will be described below. Hans-Joachim Time, IS & Ts NIP 15: 1999 International Conference on Digital Printing Technologies, p209, photoexciting a light-absorbing substance (for example, a dye) in a photosensitive material, and undergoing chemical or physical change. It is known that there are roughly two modes in the process from photoexcitation of the light-absorbing substance that forms an image to chemical or physical change. One is that the photo-excited light-absorbing substance is deactivated by some photochemical interaction (for example, energy transfer, electron transfer) with other reactants in the photosensitive material, and as a result, the activated reactant is The so-called photon mode causes the chemical or physical change necessary for the above-mentioned image formation. The other is a photo-excited light-absorbing material that generates heat and deactivates, and the reaction material is converted into the above-described using the heat. This is a so-called heat mode that causes a chemical or physical change necessary for image formation.

The exposure process using each of the above modes is called photon mode exposure and heat mode exposure. The technical difference between photon mode exposure and heat mode exposure is whether or not the energy amount of several photons to be exposed can be added to the target reaction energy amount. For example, consider that a certain reaction is caused by using n photons. In photon mode exposure, photochemical interaction is used, so that one-photon energy cannot be added together due to the requirement of quantum energy and momentum conservation laws. That is, in order to cause some kind of reaction, a relationship of “one photon energy amount ≧ reaction energy amount” is necessary. On the other hand, in heat mode exposure, heat is generated after light excitation, and light energy is converted into heat and used, so that the amount of energy can be added. Therefore, it is sufficient if there is a relationship of “energy amount of n photons ≧ energy amount of reaction”. However, this energy amount addition is restricted by thermal diffusion. That is, if the next photoexcitation-deactivation process occurs and the heat is generated before the heat escapes from the exposed portion (reaction point) of interest now, due to thermal diffusion, the heat is surely accumulated and added, and the temperature of that portion increases. Leads to. However, when the next heat generation is slow, the heat escapes and does not accumulate. In other words, in the heat mode exposure, even when the same total exposure energy amount is used, the result is different between the case where the high energy amount light is irradiated for a short time and the case where the low energy amount light is irradiated for a long time. It becomes advantageous for accumulation. Thus the heat mode exposure requires exposure power density at the plate surface of the photosensitive material is 5000 W / cm ² or more, preferably it is necessary to 10000 W / cm ² or more.

[Light source for heat mode exposure]
Examples of the light source for the heat mode exposure include a halogen lamp and a laser. However, as described above, since high-density exposure is required, it is preferable to scan and use a solid laser, a gas laser, or a semiconductor laser. Although the peak of the irradiation wavelength of a light source is not specifically limited, What corresponds to the absorption wavelength of the below-mentioned photothermal conversion agent is preferable. The exposure amount is usually 50~1000mJ / cm ^2, more preferably about 80~500mJ / cm ² or so, and most preferably about 100~250mJ / cm ^2.

[Photothermal conversion agent]
In partial heating using heat mode exposure, it is desirable that a photothermal conversion agent that absorbs light of a predetermined wavelength and converts it into heat is present in the optically anisotropic layer. Any photothermal conversion agent may be used as long as it has a function of converting absorbed light into heat, but a product having an absorption peak in the irradiation wavelength range of a light source used for heat mode exposure is preferable. Examples of the photothermal conversion agent include dyes and pigments as shown below.

  As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.

  Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A Nos. 58-173696, 58-181690, 58-194595, JP-A-58-112793, JP-A-58-224793, JP-A Naphthoquinone dyes described in JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., and JP-A-58-112792 Examples thereof include squarylium dyes described in publications and the like, and cyanine dyes described in British Patent 434,875.

  In addition, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also suitable. ) Pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363 59-84248, 59-84249, 59-146063, and 59-146061, the pyrylium compounds described in JP-A-59-216146, cyanine dyes described in US Pat. The pentamethine thiopyrylium salt described in Japanese Patent No. 4,283,475, etc., and Japanese Patent Publication Nos. 5-13514 and 5-19702 are disclosed. And pyrylium compounds are also preferably used.

  Another example of a preferable dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993.

  Examples of pigments include commercially available pigment and color index (CI) manuals, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (published by CMC, published in 1986), “Printing” The pigments described in "Ink Technology", published by CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used.

[Step of performing partial heating of any pattern on at least one optically anisotropic layer independently of other optically anisotropic layers]
The manufacturing method of the present invention includes a step of performing partial heating of an arbitrary pattern independently of other optical anisotropic layers on at least one optical anisotropic layer of a multilayer birefringence pattern builder. is there. As a specific method of such a process, for example, a wavelength corresponding to a desired layer after the photothermal conversion agent contained in (or immersed in) the optically anisotropic layer has a different absorption wavelength for each layer. The method of performing heat mode exposure with the light of this is mentioned. Also, when using a scanning optical system as a light source for heat mode exposure, the optical system is configured so that the focal depth becomes extremely shallow, and the difference in the vertical position of each layer of the optically anisotropic layer is used to achieve the purpose. There is also a method of drawing by condensing and generating heat only on the layer.

[Treatment of increasing the durability of the optically anisotropic layer by reacting unreacted reactive groups in the optically anisotropic layer]
In the optically anisotropic layer that has been subjected to the patterned heat treatment, the region where the heat treatment has not been performed has an unreacted reactive group while having retardation, and is still in an unstable state. In order to react or deactivate the unreacted reactive group remaining in the untreated region, it is preferable to perform a heat treatment on the entire surface or a reaction treatment by a whole surface exposure.

  The reaction treatment by the overall heat treatment is a temperature lower than the retardation disappearance temperature of the optically anisotropic layer of the multilayer birefringence pattern builder used, and the temperature at which the reaction or deactivation of the unreacted reactive group proceeds efficiently. It is preferable. Generally, heating at about 120 to 180 ° C. may be performed, 130 to 170 ° C. is more preferable, and 140 to 160 ° C. is more preferable, but the required birefringence (retardation) and the optically anisotropic layer to be used The suitable temperature differs depending on the thermosetting reactivity. The heat treatment time is not particularly limited, but is preferably 1 minute to 5 hours, more preferably 3 minutes to 3 hours, and particularly preferably 5 minutes to 2 hours.

The reaction treatment can be performed by whole surface exposure instead of the whole surface heat treatment. In this case, the irradiation wavelength of the light source 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 approximately as preferred exposure amount, more preferably 5~1000mJ / cm ² or so, still more preferably 10 to 500 mJ / cm ² or so, and most preferably at about 10 to 300 mJ / cm ² .

[Finish heat treatment]
If you want to further improve the stability of the birefringence pattern created in the previous steps, you can further react with unreacted reactive groups remaining after immobilization to increase durability, Finishing heat treatment may be performed for the purpose of removing unnecessary components by vaporizing or burning them. This is particularly effective when a birefringence pattern is produced by pattern exposure and heating overall exposure, or pattern-like heat treatment and overall exposure. The finishing heat treatment may be performed at a temperature of about 180 to 300 ° C, more preferably 190 to 260 ° C, and even more preferably 200 to 240 ° C. The heat treatment time is not particularly limited, but is preferably 1 minute to 5 hours, more preferably 3 minutes to 3 hours, and particularly preferably 5 minutes to 2 hours.

[Functional layer laminated on birefringence pattern]
The birefringence pattern builder may be exposed and baked as described above to produce a birefringent pattern, and then a functional layer having various functions may be further laminated to form an article having a multilayer birefringence pattern. . Although it does not specifically limit as a functional layer, For example, the hard-coat layer which prevents the damage | wound of a surface, the reflection layer which makes easy the visual recognition of a birefringence pattern etc. are mention | raise | lifted. In order to facilitate identification, it is particularly preferable to have a reflective layer under the birefringence pattern.

[Article having multilayer birefringence pattern]
Articles obtained by exposing and baking a multilayer birefringence pattern builder as described above are usually almost colorless and transparent. On the other hand, when sandwiched between two polarizing plates, or between a reflective layer and a polarizing plate, When sandwiched, it shows a characteristic light or darkness or color and can be easily recognized visually. Taking advantage of this property, an article having a multilayer birefringence pattern obtained by the above manufacturing method can be used, for example, as a forgery preventing means. That is, an article having a multilayer birefringence pattern produced by the production method of the present invention, in particular, an article having a multilayer birefringence pattern including a reflective layer is usually almost invisible visually, but can be easily obtained through a polarizing plate. Multicolor images can be identified. When the birefringence pattern is copied without passing through the polarizing plate, nothing is reflected. Conversely, when the birefringence pattern is copied through the polarizing plate, it remains as a permanent pattern, that is, a visible pattern without the polarizing plate. Therefore, it is difficult to duplicate a birefringence pattern. Since a method for producing such a birefringence pattern is not widespread and the material is also special, it is considered suitable for use as a forgery prevention means. In particular, in the present invention, since two or more optically anisotropic layers have different birefringence patterns (or patterns and solids), the anti-counterfeiting property and the design property are excellent.

[Optical element]
Further, an article having a multilayer birefringence pattern obtained by the above manufacturing method can be used for an optical element. For example, when an article having a multilayer birefringence pattern obtained by the above manufacturing method is used as a structural optical element, it is possible to produce a special optical element that has an effect only on specific polarized light. As an example, the diffraction grating produced by the refractive index pattern of the present invention functions as a polarization separation element that strongly diffracts specific polarized light, and can be applied to the projector and optical communication fields.

  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.

(Example 1: Material for producing multi-layer birefringence pattern with different photosensitive wavelength and production of article having multi-axis multi-layer birefringence pattern using the same)

(Preparation of coating liquid CU-1 for mechanical property control layer)
The following composition was prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as a coating liquid CU-1 for a mechanical property control layer.

───────────────────────────────────
Coating composition for mechanical property control layer (%)
───────────────────────────────────
Methyl methacrylate / 2-ethylhexyl acrylate /
Benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55/30/10/5, mass average molecular weight = 100,000,
Tg≈70 ° C.) 5.89
Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, mass average molecular weight = 10,000, Tg≈100 ° C.)
13.74
Ethoxylated bisphenol A dimethacrylate (BPE-500, trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.20
Fluorosurfactant (Megafac F-780-F, trade name, 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 was prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as an alignment layer coating liquid AL-1.
───────────────────────────────────
Coating liquid composition for alignment layer (%)
───────────────────────────────────
Polyvinyl alcohol (PVA205, trade name, manufactured by Kuraray Co., Ltd.) 3.21
Polyvinylpyrrolidone (Luvitec K30, trade name, manufactured by BASF)
1.48
Distilled water 52.10
Methanol 43.21
───────────────────────────────────

(Preparation of coating liquid LC-1 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-1 for an optically anisotropic layer. 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 a discotic compound added for the purpose of orientation control. LC-1-2 is Tetrahedron Lett. It was synthesized according to the method described in Journal, Vol. 43, page 6793 (2002).

───────────────────────────────────
Coating composition for optically anisotropic layer (%)
───────────────────────────────────
Rod-like liquid crystal (LC-1-1) 32.92
Horizontal alignment agent (LC-1-2) 0.02
Cationic photopolymerization initiator (CPI100-P, trade name, manufactured by San Apro Co., Ltd.) 0.33
Polymerization control agent (IRGANOX1076, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.)
0.07
Methyl ethyl ketone 66.66
───────────────────────────────────

(Preparation of coating solution ADR-1 for red photosensitive layer adjacent transfer adhesive layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution ADR-1 for a red photosensitive layer adjacent transfer adhesive layer. Boron compound B-1 has radical generating ability and works as a photo radical generator when used in combination with an organic dye. The red photosensitive dye D-1 is an organic dye having a property of absorbing red light centered around 660 nm.

───────────────────────────────────
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 (mass average molecular weight 38,000) 7.73
Acrylic polyfunctional monomer (KAYARAD DPHA, trade name, manufactured by Nippon Kayaku Co., Ltd.) 4.63
Boron compound (B-1) 0.39
Red photosensitive dye (D-1) 0.13
Radical polymerization initiator (2-trichloromethyl-5- (p-styrylstyryl)
1,3,4-oxadiazole) 0.12
Hydroquinone monomethyl ether 0.002
Fluorosurfactant (Megafac F-176PF, trade name, manufactured by Dainippon Ink & Chemicals, Inc.)
0.05
Propylene glycol monomethyl ether acetate 34.80
Methyl ethyl ketone 50.538
Methanol 1.61
───────────────────────────────────

(Preparation of coating solution ADG-1 for green photosensitive layer adjacent transfer adhesive layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution ADG-1 for the green photosensitive layer adjacent transfer adhesive layer. The green photosensitive dye D-2 is an organic dye having a property of absorbing green light centered around 530 nm.

───────────────────────────────────
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 (mass average molecular weight 38,000) 7.73
Acrylic polyfunctional monomer (KAYARAD DPHA, trade name, manufactured by Nippon Kayaku Co., Ltd.) 4.63
Boron compound (B-1) 0.39
Green photosensitive dye (D-2) 0.13
Radical polymerization initiator (2-trichloromethyl-5- (p-styrylstyryl)
1,3,4-oxadiazole) 0.12
Hydroquinone monomethyl ether 0.002
Fluorosurfactant (Megafac F-176PF, trade name, manufactured by Dainippon Ink & Chemicals, Inc.)
0.05
Propylene glycol monomethyl ether acetate 34.80
Methyl ethyl ketone 50.538
Methanol 1.61
───────────────────────────────────

(Preparation of coating solution ADB-1 for blue photosensitive layer adjacent transfer adhesive layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution ADB-1 for the blue photosensitive layer adjacent transfer adhesive layer. Blue photosensitive dye D-3 is an organic dye having a property of absorbing blue light centered around 470 nm.

───────────────────────────────────
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 (mass average molecular weight 38,000) 8.05
Acrylate polyfunctional monomer (KAYARAD DPHA, trade name, manufactured by Nippon Kayaku Co., Ltd.) 4.83
Boron compound (B-1) 0.39
Green photosensitive dye (D-3) 0.13
Radical polymerization initiator (2-trichloromethyl-5- (p-styrylstyryl)
1,3,4-oxadiazole) 0.12
Hydroquinone monomethyl ether 0.002
Fluorosurfactant (Megafac F-176PF, trade name, manufactured by Dainippon Ink & Chemicals, Inc.)
0.05
Propylene glycol monomethyl ether acetate 34.80
Methyl ethyl ketone 50.538
Methanol 1.61
───────────────────────────────────

(Preparation of transfer material TRR-1 for preparing red photosensitive birefringence pattern)
On a temporary support of a 100 μm-thick easy-adhesive polyethylene terephthalate film (COSMO SHINE A4100, trade name, manufactured by Toyobo Co., Ltd.) The alignment layer coating liquid AL-1 was applied and dried. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, the coating liquid LC-1 for optically anisotropic layer 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 air-cooled metal halide having an output of 160 W / cm under air. An optically anisotropic layer having a thickness of 1.7 μm was formed by fixing the alignment state by irradiating ultraviolet rays using a lamp (manufactured by Eye Graphics Co., Ltd.). The illuminance of ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths from 320 nm to 400 nm), and the irradiation amount was 80 mJ / cm ² in the UV-A region. The optically anisotropic layer of the sample was a polymer solid at 20 ° C. having uniaxial positive optical anisotropy, and exhibited MEK (methyl ethyl ketone) resistance.
Finally, a coating solution ADR-1 for red photosensitive layer adjacent transfer adhesive layer is applied on the optically anisotropic layer and dried to form a 1.2 μm transfer adhesive layer, and then a protective film (polypropylene film having a thickness of 12 μm). ) Was pressure-bonded to prepare a transfer material TRR-1 for preparing a red photosensitive birefringence pattern. In this step, the optically anisotropic layer is appropriately modified by the radical polymerization initiator contained in ADR-1. Also in the subsequent application of another coating solution for the transfer adhesive layer, the optically anisotropic layer is modified into a shape suitable for the subsequent process according to the coating solution.

(Preparation of green photosensitive birefringence pattern transfer material TRG-1)
For producing a green photosensitive birefringence pattern in the same manner as TRR-1, except that the coating liquid ADG-1 for green photosensitive layer adjacent transfer adhesive layer is used instead of the coating liquid ADR-1 for red photosensitive layer adjacent transfer adhesive layer A transfer material TRG-1 was prepared.

(Preparation of blue photosensitive birefringence pattern transfer material TRB-1)
For producing blue photosensitive birefringence pattern in the same manner as TRR-1, except that coating liquid ADB-1 for blue photosensitive layer adjacent transfer adhesive layer is used instead of coating liquid ADR-1 for red photosensitive layer adjacent transfer adhesive layer A transfer material TRB-1 was produced.

(Preparation of multilayer birefringence pattern builder BPM-1)
The alkali-free glass was immersed in pure water and then subjected to an ultrasonic cleaner for 5 minutes. This glass was preheated at 105 ° C. for 15 seconds with a substrate preheating apparatus.

  The glass heated at 105 ° C. for 15 seconds using a laminator (trade name: Lamic II) manufactured by Hitachi Industries, Ltd. after peeling off the protective film TRB-1 for transferring the blue photosensitive birefringence pattern. The laminate was laminated at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min. At this time, lamination was performed so that the slow axis of the optically anisotropic layer in TRG-1 was approximately 0 °. (The slow axis direction is shown clockwise from the traveling direction of the substrate during lamination. The same applies hereinafter)

  After lamination, the transfer material TRG-1 for green photosensitive birefringence pattern preparation was again laminated on the substrate after the temporary support was peeled off by the same method. At this time, the optically anisotropic layer in TRG-1 was laminated so that the slow axis direction was approximately 45 °.

  After the second lamination, a red photosensitive birefringence pattern transfer material TRR-1 was further laminated on the substrate after the temporary support was peeled off by the same method. At this time, the optically anisotropic layer in TRR-1 was laminated so that the slow axis direction was approximately 90 °. After lamination, the temporary support was peeled off to produce a multilayer birefringence pattern builder BPM-1. Table 1 summarizes the transfer materials used for the production of BPM-1, the respective central photosensitive wavelengths, and the slow axis directions of the optically anisotropic layers possessed by each.

Table 1
──────────── ――――――――――
Transfer material used Slow axis direction
────────────────── ――――
TRB-1 0 °
TRG-1 45 °
TRR-1 90 °
────────────────── ――――

(Preparation of multilayer birefringence pattern BP-1)
BPM-1 was subjected to mask exposure three times while changing the exposure center wavelength and the photomask. Table 2 shows the mask number, exposure center wavelength, and exposure amount used, and FIG. 3 shows the mask used. A xenon lamp was used as the light source, and a bandpass filter corresponding to the exposure center wavelength to be obtained was used in combination.

Table 2
──────────── ――――――――――――――――――――
Mask number Exposure center wavelength / nm Exposure amount / mJ / cm ²
────────────────── ――――――――――――――
Mask MB1 470 50
Mask MG1 530 50
Mask MR1 660 50
────────────────── ――――――――――――――

  The exposed substrate is baked in a clean oven at 200 ° C. for 1 hour, and finally, bleaching exposure is performed for 30 seconds under an illuminance of 38000 lux using a white fluorescent lamp, and the multilayer birefringence pattern BP shown in FIG. -1 was produced.

  In BP-1, the region that was never exposed during the process (referred to as region N) had almost no optical anisotropy, whereas the region exposed through the mask had uniaxial optical anisotropy. Had. Regions corresponding to the masks MB1, MG1, and MR1 are defined as a region B1, a region G1, and a region R1, respectively. The front retardation and the slow axis direction of each region were measured by a parallel Nicol method using a fiber spectrometer. The results are shown in Table 3.

Table 3
──────────── ―――――――――――――――― ─
Region Retardation / nm Slow axis direction / °
────────────────────── ――――
Region B1 138.3 0.2
Region G1 141.5 44.5
Region R1 137.9 90.8
────────────────────── ―――― ─

  From the comparison between Table 1 and Table 3, the following can be said. The portion of the region B1 exposed with blue light through the mask MB1 is TRB-1, which has a central photosensitive wavelength in blue light among TRB-1, TRG-1, and TRR-1 used for manufacturing BPM-1. As a result, only the optically anisotropic layer of TRB-1 has a slow axis in the 0 ° direction because only the optically anisotropic layer of TRB-1 remains optically anisotropic after baking. Similarly, only the optically anisotropic layer TRG-1 is exposed in the region G1 exposed with green light, and only the optically anisotropic layer TRR-1 is exposed in the region R1 exposed with red light. As a result, the region G1 has a slow axis in the 45 ° direction and the region R1 has a slow axis in the 90 ° direction. That is, an optically anisotropic layer derived from TRB-1 by blue light exposure, an optically anisotropic layer derived from TRG-1 by green light exposure, an optically anisotropic layer derived from TRR-1 by red light exposure, Independent patterns can be produced. By changing the direction of the slow axis of each optically anisotropic layer as in this example, a multilayer birefringence pattern in which optically anisotropic layers having different slow axes and different patterns are stacked can be easily formed. Obtainable.

(Example 2: Material for producing multi-layer birefringence pattern with different photosensitive wavelength and production of article having multi-layer birefringence pattern with different phase difference using the same)

(Preparation of red photosensitive birefringence pattern transfer material TRR-2)
A transfer material TRR-2 for producing a red photosensitive birefringence pattern was produced in the same manner as TRR-1, except that the thickness of the optically anisotropic layer was changed to 4.0 μm.

(Preparation of green photosensitive birefringence pattern transfer material TRG-2)
A transfer material TRG-2 for producing a green photosensitive birefringence pattern was produced in the same manner as TRG-1, except that the thickness of the optically anisotropic layer was 3.2 μm.

(Preparation of phase difference measurement sample)
The alkali-free glass was immersed in pure water and then subjected to an ultrasonic cleaner for 5 minutes. This glass was preheated at 105 ° C. for 15 seconds with a substrate preheating apparatus.

  After peeling off the protective film of the transfer material TRB-1 for producing blue photosensitive birefringence pattern, laminator (manufactured by Hitachi Industries, Ltd. (trade name: Lamic II type)) was used for the glass heated at 105 ° C. for 15 seconds. Lamination was performed at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min. At this time, lamination was performed so that the slow axis of the optically anisotropic layer in TRB-1 was approximately 0 °. After lamination, the temporary support was peeled off to obtain a phase difference measurement sample TRB-1R. Similarly, samples TRG-2R and TRR-2R for phase difference measurement corresponding to TRG-2 and TRR-2 were produced. Table 4 shows the front retardation of the prepared retardation measurement sample.

Table 4
──────────── ――――――――――――――
Sample for measurement Frontal retardation / nm
────────────────── ――――――――
TRB-1R 138.7
TRG-2R 277.6
TRR-2R 362.1
────────────────── ――――――――

(Preparation of multilayer birefringence pattern builder BPM-2)
The alkali-free glass was immersed in pure water and then subjected to an ultrasonic cleaner for 5 minutes. This glass was preheated at 105 ° C. for 15 seconds with a substrate preheating apparatus.

The substrate heated at 105 ° C. for 15 seconds using a laminator (trade name: Lamic II type) after peeling off the protective film of the blue photosensitive birefringence pattern transfer material TRB-1 The laminate was laminated at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min. At this time, lamination was performed so that the slow axis of the optically anisotropic layer in TRB-1 was approximately 0 °.
After lamination, the transfer material TRG-2 for green photosensitive birefringence pattern preparation was again laminated on the substrate after the temporary support was peeled off by the same method. At this time, lamination was performed so that the slow axis of the optically anisotropic layer in TRG-2 was approximately 0 °.

  After the second lamination, the transfer material TRR-2 for birefringence pattern preparation was further laminated on the substrate after the temporary support was peeled off by the same method. Also in this case, lamination was performed so that the slow axis of the optically anisotropic layer in TRR-2 was approximately 0 °. After the lamination, the temporary support was peeled off to prepare a multilayer birefringence pattern builder BPM-2 of the present invention in which a plurality of optically anisotropic layers of Example 2 were laminated.

(Production of three-color birefringence pattern BP-2 by sequential exposure)
BPM-2 was subjected to mask exposure three times while changing the exposure center wavelength and the photomask. Table 5 shows the number of the mask used, the exposure center wavelength, and the exposure amount, and FIG. 5 shows a diagram of the mask used. A xenon lamp was used as the light source, and a band-pass filter corresponding to the desired exposure center wavelength was also used.

Table 5
──────────── ――――――――――――――――――――
Mask number Exposure center wavelength / nm Exposure amount / mJ / cm ²
────────────────── ――――――――――――――
Mask MB2 470 10
Mask MG2 530 10
Mask MR2 660 10
────────────────── ――――――――――――――

  The exposed substrate is baked in a clean oven at 200 ° C. for 1 hour, and finally, bleaching exposure is performed for 30 seconds under an illuminance of 38000 lux using a white fluorescent lamp, and the multilayer birefringence pattern BP− shown in FIG. 2 was produced. Table 6 shows the results of measuring the front retardation in the sample regions B2, G2, and R2 corresponding to the masks MB2, MG2, and MR2.

Table 6
──────────── ――――――――――
Area Retardation / nm
─────────────────────
Region B2 141.5
Region G2 279.6
Region R2 364.9
―――― ─────────────────

  By comparing Table 4 and Table 6, the following can be understood. That is, each of the regions B2, G2, and R2 has an optically anisotropic layer derived from TRB-1, TRG-2, and TRR-2 in order, having a photosensitive wavelength corresponding to the wavelength used when the region is exposed. The corresponding retardation is shown. That is, by changing the retardation of each optically anisotropic layer as in this example, it is possible to easily obtain a multilayer birefringence pattern in which optically anisotropic layers having different retardations and different patterns are laminated. Can do.

(Example 3: Fabrication of photosensitive wavelength-separated multi-layer birefringence pattern material and article having a bivariate birefringence pattern using the same)

(Preparation of bilayer birefringence pattern builder BPM-3 of the present invention)
The aluminum vapor-deposited glass was immersed in pure water and subjected to an ultrasonic cleaner for 5 minutes. This glass was preheated at 105 ° C. for 15 seconds with a substrate preheating apparatus.

A substrate heated at 105 ° C. for 15 seconds using a laminator (trade name: Lamic II) manufactured by Hitachi Industries, Ltd. after peeling off the protective film TRG-1 for producing the green photosensitive birefringence pattern. The laminate was laminated at a roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min. At this time, lamination was performed so that the slow axis of the optically anisotropic layer in TRG-1 was in the 0 ° direction.
After lamination, the transfer material TRR-1 for producing a red photosensitive birefringence pattern was laminated on the substrate after peeling the temporary support by the same method as before. At this time, lamination was performed so that the slow axis of the optically anisotropic layer in TRR-1 was approximately 45 °. After lamination, the temporary support was peeled off to produce the multilayer birefringence pattern builder BPM-3 of the present invention.

(Preparation of birefringence birefringence pattern BP-3)
BPM-3 was subjected to two mask exposures while changing the exposure center wavelength and the photomask. Table 7 shows the mask number, exposure center wavelength, and exposure amount used, and FIG. 7 shows a diagram of the mask used. A xenon lamp was used as the light source, and a band-pass filter corresponding to the desired exposure center wavelength was also used.

Table 7
──────────── ――――――――――――――――――――
Mask number Exposure center wavelength / nm Exposure amount / mJ / cm ²
────────────────── ――――――――――――――
Mask MG3 530 10
Mask MR3 660 10
────────────────── ――――――――――――――

The exposed substrate is baked in a clean oven at 200 ° C. for 1 hour, and finally subjected to bleaching exposure for 3 seconds under an illuminance of 38000 lux using a white fluorescent lamp. -3 was produced. The pattern observed when a polarizing plate is overlaid on BP-3 is shown in FIG. At this time, the polarizing plate was arranged so that the absorption axis of the polarizing plate was approximately 45 °. In the figure, the gray portion is a silver-colored portion and the black portion is a blue-purple portion, and a pattern composed of both can be easily read only under the polarizing plate. As can be seen from the figure, in this arrangement, a pattern according to the pattern of the mask MG3 was observed.
By rotating the polarizing plate (only) from the state of FIG. 8A, BP-1 reveals a different pattern. FIG. 8B shows a pattern that is observed when the polarizing plate is disposed so that the absorption axis is approximately 90 °. As can be seen from the figure, in this arrangement, a pattern according to the pattern of the mask MR3 was observed.
The pattern of FIG. 8A and the pattern of FIG. 8B are alternately switched and observed by turning the polarizing plate and changing the angle with BP-3. Such a switching pattern is realized by a laminated structure of patterned optically anisotropic layers having slow axes in directions different by 45 °. As described above, by using the multilayer birefringence pattern manufacturing method of the present invention, it is possible to easily make a two-type birefringence pattern excellent in forgery prevention and design.

(Example 4: Material for producing a multilayer birefringence pattern with different absorption directions and an article having a multi-axis birefringence pattern using the same)

(Preparation of coating liquid LC-2 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-2 for an optically anisotropic layer. LC-1-3 is a dichroic photopolymerization initiator having an absorption axis in the major axis direction of the molecule.

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Coating composition for optically anisotropic layer (%)
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Rod-like liquid crystal (LC-1-1) 32.24
Horizontal alignment agent (LC-1-2) 0.03
Cationic photopolymerization initiator (CPI100-P, trade name, manufactured by San Apro Co., Ltd.) 0.33
Radical dichroic photopolymerization initiator (LC-1-3) 0.67
Polymerization control agent (IRGANOX1076, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.)
0.07
Methyl ethyl ketone 66.66
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(Preparation of coating solution AD-1 for transfer adhesive layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution AD-1 for transfer adhesive layer.

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Coating solution composition for transfer adhesive layer (% by mass)
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Benzyl methacrylate / methacrylic acid / methyl methacrylate = 35.9 / 22.4 / 41.7 molar ratio random copolymer (mass average molecular weight 38,000) 8.05
Acrylate polyfunctional monomer (KAYARAD DPHA, trade name, manufactured by Nippon Kayaku Co., Ltd.) 4.83
Radical photopolymerization initiator (2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine)
0.12
Hydroquinone monomethyl ether 0.002
Fluorosurfactant (Megafac F-176PF, trade name, manufactured by Dainippon Ink & Chemicals, Inc.)
0.05
Propylene glycol monomethyl ether acetate 34.80
Methyl ethyl ketone 50.538
Methanol 1.61
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(Preparation of transfer material TRD-1 for preparing a dichroic birefringence pattern)
On a temporary support of a 100 μm-thick easy-adhesive polyethylene terephthalate film (COSMO SHINE A4100, trade name, manufactured by Toyobo Co., Ltd.) The alignment layer coating liquid AL-1 was applied and dried. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, coating liquid LC-2 for optically anisotropic layer 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 air-cooled metal halide having an output of 160 W / cm under air An optically anisotropic layer having a thickness of 1.2 μm was formed by fixing the alignment state by irradiating ultraviolet rays using a lamp (made by Eye Graphics Co., Ltd.). The illuminance of ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths from 320 nm to 400 nm), and the irradiation amount was 80 mJ / cm ² in the UV-A region. The optically anisotropic layer of the sample was a polymer solid at 20 ° C. having uniaxial positive optical anisotropy, and exhibited MEK (methyl ethyl ketone) resistance.
Finally, the transfer adhesive layer coating solution AD-1 is applied on the optically anisotropic layer and dried to form a 1.2 μm transfer adhesive layer, and then a protective film (polypropylene film having a thickness of 12 μm) is pressure-bonded. A transfer material TRD-1 for preparing a dichroic birefringence pattern was prepared.

(Preparation of multilayer birefringence pattern builder BPM-4)
The alkali-free glass was immersed in pure water and then subjected to an ultrasonic cleaner for 5 minutes. This glass was preheated at 105 ° C. for 15 seconds with a substrate preheating apparatus.

  After peeling off the protective film of the transfer material TRD-1 for producing the dichroic birefringence pattern, it was heated at 105 ° C. for 15 seconds using a laminator (manufactured by Hitachi Industries, Ltd. (trade name, Lamic II type)). The glass was laminated at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min. At this time, lamination was performed so that the slow axis of the optically anisotropic layer in TRD-1 was approximately 0 °.

  After lamination, the transfer material TRD-1 for preparing a dichroic birefringence pattern was again laminated on the substrate after the temporary support was peeled off by the same method. At this time, TRD-1 laminated for the second time was laminated so that the slow axis direction of the optically anisotropic layer therein was approximately 90 °. After lamination, the temporary support was peeled off to produce a multilayer birefringence pattern builder BPM-4.

(Preparation of multilayer birefringence pattern BP-4)
BPM-4 was exposed twice using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) having an output of 160 W / cm and a photomask. In the exposure, exposure was performed using linearly polarized light using a wire grid polarizing filter (ProFlux PPL02 (high transmittance type), trade name, manufactured by Moxtek) and polarized light in different directions at the first time and the second time. The exposure was performed in a nitrogen atmosphere with an oxygen concentration of 0.3% or less, and the exposure illuminance was 20 mW / cm ² in the UV-B region. Table 8 shows the mask number, polarization direction, and exposure amount used, and FIG. 9 shows the mask used.

Table 8
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Mask number Polarization direction / ° Exposure / mJ / cm ²
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Mask MD1 0 50
Mask MD2 90 50
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  The exposed substrate was baked in a clean oven at 200 ° C. for 1 hour to produce a multilayer birefringence pattern BP-4 shown in FIG.

  In BP-4, the region that was never exposed during the process had almost no optical anisotropy, whereas the region exposed through the mask had uniaxial optical anisotropy. Regions corresponding to the masks MD1 and MD2 are defined as a region D1 and a region D2, respectively. The front retardation and the slow axis direction of each region were measured by a parallel Nicol method using a fiber spectrometer. The results are shown in Table 9.

Table 9
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Region Retardation / nm Slow axis direction / °
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Region D1 102.5 0.5
Region D2 99.2 89.2
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  From the comparison between Table 8 and Table 9, the following can be said. That is, only the optically anisotropic layer having the dichroic initiator oriented in the 0 ° direction is cured in response to the exposure in the region D1 exposed through the mask MD1 with the linearly polarized light in the 0 ° direction. After baking, only the optical anisotropy having a slow axis in the 0 ° direction remained. On the other hand, only the optically anisotropic layer having a dichroic initiator oriented in the 90 ° direction is cured in response to the exposure in the portion of the region D2 exposed with the linearly polarized light in the 90 ° direction through the mask MD2. Only an optical anisotropy having a slow axis in the 90 ° direction remained after baking. That is, the optical anisotropy pattern having the slow axis in the corresponding direction could be drawn independently due to the difference in the polarization direction during exposure.

11 Support or Substrate 12F First Optical Anisotropic Layer 12S Second Optical Anisotropic Layer 13A First Alignment Layer 13B Second Alignment Layer 14A First Transfer Adhesive Layer 14B Second Transfer Adhesive Layer 16 Rear Adhesive Layer 17 Release Layer 35 reflective layer 112F first patterned optical anisotropic layer 112F-A patterned first optical anisotropic layer (first layer first region)
112F-B Patterned first optically anisotropic layer (first layer second region)
112F-N Patterned first optically anisotropic layer (first layer isotropic region)
112S Second patterned optically anisotropic layer 112S-A Patterned second optically anisotropic layer (second layer first region)
112S-B Patterned second optically anisotropic layer (second layer second region)
112S-N Patterned second optically anisotropic layer (second layer isotropic region)
113F First optical anisotropic layer (solid)

Claims (26)

  A multilayer birefringence pattern builder comprising at least two optically anisotropic layers comprising a polymer compound having a reactive group and capable of forming different birefringence patterns.   2. The multilayer birefringence pattern builder according to claim 1, wherein the birefringence pattern formation reaction conditions differ in at least two of the optically anisotropic layers.   3. The multilayer birefringence pattern builder according to claim 2, wherein the birefringence pattern formation reaction conditions are different at a spectral absorption peak wavelength.   The multilayer birefringence pattern builder according to claim 3, wherein the birefringence pattern formation reaction conditions are different in the absorption spectrum of the photopolymerization initiator.   The multilayer birefringence pattern builder according to claim 2, wherein the birefringence pattern formation reaction conditions differ in polarization absorption characteristics.   6. The multi-layer birefringence pattern builder according to claim 5, wherein the polarization absorption characteristic is that the orientation direction of the dichroic photopolymerization initiator is different.   The optically anisotropic layer is formed by applying and drying a solution containing a liquid crystalline compound having at least two reactive groups to form a liquid crystal phase, and then polymerizing and fixing by irradiation with heat or ionizing radiation. The multilayer birefringence pattern builder according to any one of 1 to 6.   The multilayer birefringence pattern builder according to claim 7, wherein the liquid crystal compound has two or more kinds of reactive groups having different polymerization conditions.   The multilayer birefringence pattern builder according to claim 8, wherein the liquid crystalline compound has at least a radical reactive group and a cationic reactive group.   The multilayer birefringence pattern builder according to any one of claims 7 to 9, wherein the optically anisotropic layer is modified after being polymerized and fixed.   The multilayer according to claim 10, wherein the modification is performed in such a manner that an additive in the functional layer diffuses into the optically anisotropic layer in the step of forming another functional layer on the optically anisotropic layer. Birefringence pattern builder.   The multilayer birefringence pattern builder according to any one of claims 1 to 6, wherein the optically anisotropic layer is made of a stretched film.   The multilayer birefringence pattern builder according to any one of claims 1 to 12, which is produced by a production method including transferring a transfer material including an optically anisotropic layer onto a transfer material.   14. The multilayer composite according to claim 13, wherein the transfer material is obtained by laminating at least an [A] optical anisotropic layer and a [B] transfer adhesive layer in this order on a temporary support. Refractive pattern builder. A method for producing an article having a multilayer birefringence pattern, including at least the following steps [1] to [3] in this order:
[1] A step of producing a multilayer birefringence pattern builder comprising at least two optically anisotropic layers capable of forming different birefringence patterns, comprising a polymer compound having a reactive group;
[2] A step of exposing at least one of the optically anisotropic layers of the multilayer birefringence pattern builder so as to give a latent image of an arbitrary pattern independently of the other optically anisotropic layers. ;
[3] A step of baking the laminate obtained after the step [2] at 50 ° C. or higher and 400 ° C. or lower. A method for producing an article having a multilayer birefringence pattern, including at least the following steps [11] to [13] in this order:
[11] A step of producing a multilayer birefringence pattern builder comprising at least two optically anisotropic layers capable of forming different birefringence patterns, comprising a polymer compound having a reactive group;
[12] A step of performing partial heating of an arbitrary pattern independently of other optically anisotropic layers on at least one of the optically anisotropic layers of the multilayer birefringence pattern builder;
[13] A step of reacting the multilayer birefringence pattern builder with an unreacted reactive group in the optically anisotropic layer to increase durability of the optically anisotropic layer.   The manufacturing method according to claim 16, wherein the step [13] is performed by whole surface exposure.   The manufacturing method according to claim 16, wherein the step [13] is performed by a heat treatment at a temperature lower than a temperature reached by the optically anisotropic layer of the heated portion in the step [12].   The production according to any one of claims 15 to 18, wherein the step [2] or the step [12] is performed using a difference in spectral absorption peak wavelength of each optically anisotropic layer. Method.   The production method according to claim 19, wherein at least two of the optically anisotropic layers have photopolymerization initiators having different absorption spectra.   The method according to any one of claims 15 to 18, wherein the step [2] or the step [12] is performed using a difference in polarization absorption characteristics of each optically anisotropic layer. .   The production method according to claim 21, wherein at least two of the optically anisotropic layers have a dichroic photopolymerization initiator.   The manufacturing method according to any one of claims 15 to 18, wherein the step [2] or the step [12] is performed using a difference in vertical position of each optically anisotropic layer.   The manufacturing method according to claim 23, wherein the step [2] is performed using a condensing optical system having a variable focal length.   An article used as a forgery prevention means obtained by the production method according to any one of claims 15 to 24.   The optical element obtained by the manufacturing method of any one of Claims 15-24.

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