JP2016200664A - Latent image forming body, latent image forming body set, method for manufacturing latent image forming body, image display method and decorative laminate - Google Patents

Latent image forming body, latent image forming body set, method for manufacturing latent image forming body, image display method and decorative laminate Download PDF

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JP2016200664A
JP2016200664A JP2015079262A JP2015079262A JP2016200664A JP 2016200664 A JP2016200664 A JP 2016200664A JP 2015079262 A JP2015079262 A JP 2015079262A JP 2015079262 A JP2015079262 A JP 2015079262A JP 2016200664 A JP2016200664 A JP 2016200664A
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latent image
polymer
image forming
group
forming body
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幸志 樫下
Koshi Kashishita
幸志 樫下
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Jsr株式会社
Jsr Corp
Jsr株式会社
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Abstract

A latent image forming body capable of easily expressing a variety of designs is provided. A latent image forming body 10 has a latent image formed on at least one surface of a substrate 11, and the latent image is visualized by being disposed between a pair of crossed Nicols polarizing plates. The latent image forming body 10 is a polymer having at least one selected from the group consisting of a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane, and having a photoalignment group [ An alignment layer 12 formed on a substrate 11 using a polymer composition containing P], and a liquid crystal layer 13 formed by applying and curing a polymerizable liquid crystal on the alignment layer 12. [Selection] Figure 1

Description

  The present invention relates to a latent image forming body, a latent image forming body set, a method for manufacturing a latent image forming body, an image display method, and a decorative laminate.

  Conventionally, an image, color, and the like on a substrate are changed using characteristics of a polarizing plate (see, for example, Patent Documents 1 to 3). In Patent Document 1, a polarizing plate and a strip-shaped polarizing sheet are arranged on the side surfaces of a plurality of rectangular members constituting the bellows-like assembly, and the color is changed by shifting the assembly from a folded state to a developed state. It is disclosed to change. Patent Document 2 discloses that a polymer liquid crystal layer is provided on a polarizing film, and a sheet on which the polarizing film is further laminated is heated to form an image on the polymer liquid crystal layer.

  In Patent Document 3, as a film useful for preventing counterfeiting, a reflective layer, a polarization conversion rotating layer containing liquid crystal molecules laminated on the reflective layer and fixed to have a twisted nematic alignment structure, A latent image forming film is disclosed. The polarization conversion rotating layer of Patent Document 3 is produced by applying a solution containing a liquid crystal material on an alignment substrate and twisting nematic alignment in a liquid crystal state, and then fixing the alignment structure of liquid crystal molecules. When this latent image forming film is observed under natural light, the presence of the latent image cannot be confirmed, but the image is identified by arranging a plurality of polarizing plates on the latent image forming film.

Japanese Patent No. 4187388 Japanese Patent Laid-Open No. 5-88633 JP 2008-116839 A

  If it is possible to form a variety of latent images of characters and pictures on the base material, it is useful as a decorative laminate to give various articles such as window glass, curtains, toys, stationery, etc. is there. However, as in Patent Document 2, when an image is formed on a polymer liquid crystal layer by heat, if an attempt is made to form a complicated pattern, a clear image cannot be obtained, and the patterns that can be expressed are limited.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a latent image forming body capable of easily expressing various designs.

  The present invention employs the following means in order to solve the above problems.

  The first configuration relates to a latent image forming body in which a latent image is formed on at least one surface of a substrate, and is selected from the group consisting of a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane. An alignment layer formed on a substrate using a polymer composition containing at least one polymer having a photo-alignment group [P], and applying and curing a polymerizable liquid crystal on the alignment layer And a liquid crystal layer formed.

  2nd structure is related with the manufacturing method of the latent image formation body in which the latent image was formed in at least one surface of a base material, The group consisting of the polymer of the monomer which has a polymerizable carbon-carbon unsaturated bond, and polyorganosiloxane A step of applying a polymer composition comprising at least one polymer selected from the above and having a polymer [P] having a photo-alignment group on a substrate to form a coating film, and a mask having a predetermined pattern And a step of irradiating the coating film with polarized radiation, and a step of applying and curing a polymerizable liquid crystal on the coating film after the irradiation of the polarized radiation to form a liquid crystal layer.

  According to the latent image forming body including the alignment layer and the liquid crystal layer, it is possible to express a design corresponding to the alignment direction of the liquid crystal molecules in each region of the base material surface. In particular, in the first configuration and the second configuration, since the alignment layer is formed of a polymer composition containing a specific polymer [P], the sensitivity to radiation is high, and each region on the substrate surface The orientation orientation of the liquid crystal molecules in can be precisely controlled by radiation irradiation. Therefore, it is possible to form a latent image with high discrimination. Moreover, since the coating film formed using the polymer composition containing the polymer [P] has high sensitivity to radiation, for example, use a mask on which a desired pattern is printed on a transparent resin plate. Can do. In other words, a mask can be produced simply by printing a desired pattern on a transparent substrate, and thus various patterns of latent images can be easily expressed.

  In the present specification, “radiation” includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like. The “latent image” means an image formed so as to be invisible or difficult to see only by visual observation, and is visualized by some condition (here, crossed Nicol arrangement). “Image” means not only an object such as a person or an object but also a figure, a pattern, a character, and the like.

  In the above structure, the photoalignable group is preferably a group containing a cinnamic acid structure. In this case, the coating film formed using the polymer composition containing the polymer [P] can be further improved in sensitivity to radiation, and can be easily expressed as a latent image with high discrimination. is there.

A third configuration relates to a latent image forming body set, and includes the latent image forming body according to any one of the first to fourth configurations and a pair of polarizing plates.
The fourth configuration comprises a polymer [P] having at least one selected from the group consisting of a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane and having a photo-alignment group. A latent image forming polymer composition.
A fifth configuration is an image display method including a step of visualizing a latent image by arranging the latent image forming body of the first configuration between a pair of polarizing plates arranged in a crossed Nicols manner.
The sixth configuration relates to a decorative laminate, which is at least one selected from the group consisting of a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane, and has a photoalignment group. An alignment layer formed on a substrate using a polymer composition containing a polymer [P], and a liquid crystal layer formed by applying and curing a polymerizable liquid crystal on the alignment layer And

Sectional drawing which shows typically schematic structure of a latent image formation body. The schematic diagram which shows the manufacturing method of a latent image formation body. The figure which shows typically schematic structure of a latent image formation body set. The figure which shows the example of application of the laminated body for a decoration typically.

≪Latent image forming body≫
Hereinafter, embodiments will be described in detail. As shown in FIG. 1, a latent image forming body 10 of the present embodiment includes a base material 11, an alignment layer 12 formed on the base material 11, and a liquid crystal layer 13 formed on the alignment layer 12 and containing liquid crystal molecules. With.

  The alignment layer 12 is an organic thin film containing a polymer and has a function of controlling the alignment direction of liquid crystal molecules in the liquid crystal layer 13. The alignment layer 12 of the present embodiment comprises a polymer [P] having at least one selected from the group consisting of a polymer of a compound having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane and having a photoalignment group. It is formed using the polymer composition to contain. The liquid crystal layer 13 is formed using a polymer liquid crystal. The polymerizable liquid crystal used here is preferably a liquid crystal compound or a liquid crystal composition that is polymerized by at least one treatment of heating and light irradiation.

<Latent image forming polymer composition>
Next, the polymer composition used for forming the alignment layer 12 will be described in detail.
<Polymer [P]>
The photo-alignment group of the polymer [P] is a functional group that imparts anisotropy to the film by a photoisomerization reaction, a photodimerization reaction, or a photolysis reaction by light irradiation. Specific examples of the photo-alignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a cinnamic acid structure-containing group containing a cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton, a chalcone or a derivative thereof. Examples include a chalcone-containing group containing as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a polyimide-containing structure containing a polyimide or a derivative thereof as a basic skeleton, etc. . Among these, the photo-alignment group possessed by the polymer [P] is preferably a group containing a cinnamic acid structure in that it has a high orientation ability and can be easily introduced into the polymer.

Examples of the group having a cinnamic acid structure include a monovalent group obtained by removing a hydrogen atom of a carboxyl group of cinnamic acid, or a group in which a substituent is introduced into the benzene ring of the monovalent group ( Hereinafter, these are also referred to as “order cinnamate groups”), a monovalent group in which a carboxyl group of cinnamic acid is esterified, and a divalent organic group is bonded to a benzene ring, or the monovalent group And a group in which a substituent is introduced into the benzene ring of the group (hereinafter also referred to as “reverse cinnamate group”). The forward cinnamate group can be represented by, for example, the following formula (cn-1), and the reverse cinnamate group can be represented, for example, by the following formula (cn-2).
(In formula (cn-1), R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. R 2 is a phenylene group or biphenylene. Group, terphenylene group or cyclohexylene group, or at least a part of hydrogen atoms of these groups is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or hydrogen of the alkoxy group A group substituted by a monovalent group in which at least a part of the atoms is substituted with a halogen atom or a cyano group, A 1 is a single bond, an oxygen atom, a sulfur atom, an alkanediyl group having 1 to 3 carbon atoms, -CH = CH -, - NH - , * 1 -COO -, * 1 -OCO -, * 1 -NH-CO -, * 1 -CO-NH -, * 1 -CH 2 -O- or * 1 - O-CH 2 - ( " * 1 ".R 3 is a bond showing a.) And R 2 is a halogen atom, an alkyl group having 1 to 3 carbon atoms, a is .a alkoxy group or a cyano group having 1 to 3 carbon atoms 0 Or, b is an integer of 0 to 4. However, when b is 2 or more, a plurality of R 3 may be the same or different, and “*” indicates a bond.
In formula (cn-2), R 4 is an alkyl group having 1 to 3 carbon atoms. R 5 is a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. A 2 represents an oxygen atom, * 1 —COO—, * 1 —OCO—, * 1 —NH—CO—, or * 1 —CO—NH— (“* 1 ” represents a bond to R 6 ). It is. R 6 is an alkanediyl group having 1 to 6 carbon atoms. c is 0 or 1, and d is an integer of 0-4. However, when d is 2 or more, the plurality of R 5 may be the same or different. “*” Indicates a bond. )

Specific examples of the group represented by the above formula (cn-1) include, for example, the following formula
(In the above formula, “*” indicates a bond.)
A group represented by each of
Specific examples of the group represented by the above formula (cn-2) include, for example, the following formula
(In the above formula, “*” indicates a bond.)
Groups represented by each of the above; and the like.

(Photo-alignable polyorganosiloxane)
When the polymer [P] is a polyorganosiloxane, the polyorganosiloxane (hereinafter also referred to as “photo-alignable polyorganosiloxane”) is obtained by, for example, hydrolyzing and condensing a hydrolyzable silane compound. Can be obtained. Specific examples include [1a] or [2a] below.
[1a] An epoxy group-containing polyorganosiloxane is synthesized by hydrolytic condensation of a hydrolyzable silane compound (ms-1) having an epoxy group or a mixture of the silane compound (ms-1) and another silane compound. Then, the resulting epoxy group-containing polyorganosiloxane is reacted with a carboxylic acid having a photo-alignment group (hereinafter also referred to as “specific carboxylic acid”).
[2a] A method of hydrolyzing and condensing a hydrolyzable silane compound (ms-2) having a photoalignable group or a mixture of the silane compound (ms-2) and another silane compound.
Among these, the method [1a] is preferable because it is simple and can increase the introduction ratio of the photoalignable group in the polymer [P].

  Specific examples of the silane compound (ms-1) include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyl. Methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, etc. Can be mentioned. As the silane compound (ms-1), one of these can be used alone, or two or more can be used in combination.

Other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds. For example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Alkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane;
3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3-cyclohexylamino) propyltri Nitrogen / sulfur-containing alkoxysilanes such as methoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane;
3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, alkoxysilanes containing unsaturated bonds such as p-styryltrimethoxysilane; in addition to trimethoxysilylpropyl succinic anhydride Can be mentioned. Other silane compounds can be used alone or in combination of two or more.

The hydrolysis / condensation reaction of the silane compound is carried out by reacting one or more of the above silane compounds with water, preferably in the presence of an appropriate catalyst and an organic solvent.
In the method of [1a], from the viewpoint of suppressing side reactions caused by an excessive amount of epoxy groups while allowing the partial structure (b) to be sufficiently introduced into the polymer, The epoxy equivalent of the polysiloxane is preferably 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol. Therefore, in synthesizing the epoxy group-containing polysiloxane, it is preferable to adjust the usage ratio of the silane compound (ms-1) so that the epoxy equivalent of the obtained polysiloxane is in the above range. In the hydrolysis / condensation reaction, the proportion of water used is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, per 1 mol of the silane compound (total amount).

Examples of the catalyst used in the hydrolysis / condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds and the like. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, and should be set as appropriate. For example, it is preferably 0.01 to 3 times the total amount of the silane compound. More preferably, it is 0.05-1 times mole.
Examples of the organic solvent used in the above hydrolysis / condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent is preferably 10 to 10,000 parts by weight, and more preferably 50 to 1,000 parts by weight with respect to a total of 100 parts by weight of the silane compounds used in the reaction.

  The hydrolysis / condensation reaction is preferably carried out by heating with, for example, an oil bath. In the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C. The heating time is preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux. Moreover, after completion | finish of reaction, it is preferable to wash | clean the organic-solvent layer fractionated from the reaction liquid with water. In this washing, washing with water containing a small amount of salt (for example, an aqueous ammonium nitrate solution of about 0.2% by weight) is preferable in that the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed to remove the solvent. The polysiloxane can be obtained. The method for synthesizing the polyorganosiloxane is not limited to the hydrolysis / condensation reaction described above, and may be performed by, for example, a method in which a hydrolyzable silane compound is reacted in the presence of oxalic acid and alcohol.

  In the method [1a], the epoxy group-containing polyorganosiloxane obtained by the above reaction is then reacted with a specific carboxylic acid. As a result, the epoxy group of the epoxy group-containing polyorganosiloxane reacts with the carboxylic acid to obtain a polyorganosiloxane having a photoalignment group. The specific carboxylic acid is not particularly limited as long as it has a photoreactive group, but is preferably a carboxylic acid having a group containing a cinnamic acid structure as a photoalignable group. Examples of such specific carboxylic acid include carboxylic acid in which a hydrogen atom is bonded to the bond portion in the group represented by each of formula (cn-1) and formula (cn-2). it can. More specifically, for example, each group given as a specific example of the group represented by the above formula (cn-1) and each example given as a specific example of the group represented by the above formula (cn-2). Examples thereof include carboxylic acids in which a hydrogen atom is bonded to the bond in the group. Specific carboxylic acid can be used individually by 1 type or in combination of 2 or more types.

  Note that the synthesis method of the compound in which a hydrogen atom is bonded to the bond of the group represented by each of the formula (cn-1) and the formula (cn-2) is not particularly limited, and a conventionally known method is used. They can be combined. As a typical synthesis method, for example, a method of reacting a compound having a benzene ring skeleton substituted with a halogen atom and (meth) acrylic acid or a derivative thereof in the presence of a transition metal catalyst under basic conditions; For example, a method in which cinnamic acid in which a hydrogen atom of a benzene ring is substituted with a halogen atom and a compound having a benzene ring skeleton substituted with a halogen atom are reacted in the presence of a transition metal catalyst.

  In the reaction between the epoxy group-containing polyorganosiloxane and the specific carboxylic acid, a carboxylic acid having no photo-alignment group (other carboxylic acid) may be used. The other carboxylic acid to be used is not particularly limited, but a carboxylic acid having a group containing a polymerizable carbon-carbon unsaturated bond (hereinafter, also referred to as “unsaturated bond-containing carboxylic acid”) can be preferably used. By using an unsaturated bond-containing carboxylic acid in combination, a polyorganosiloxane having a group containing a polymerizable carbon-carbon unsaturated bond and a photoalignment group is obtained. In addition, the use of such a polyorganosiloxane as at least a part of the polymer component of the polymer composition is preferable in that the adhesion of the film to the substrate and the stability over time of the film can be improved.

  Specific examples of the unsaturated bond-containing carboxylic acid include, for example, (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and phthalic acid monohydroxy Unsaturated carboxylic acid such as ethyl (meth) acrylate; unsaturated polycarboxylic acid anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride; Etc. The carboxylic acid having a polymerizable carbon-carbon unsaturated bond can be used alone or in combination of two or more.

  In synthesizing the photoalignable polyorganosiloxane, as the other carboxylic acid, a compound other than the unsaturated bond-containing carboxylic acid can be used as necessary. Examples of such other carboxylic acids include propionic acid, benzoic acid, methylbenzoic acid, and carboxylic acid having a group capable of imparting liquid crystal alignment ability (liquid crystal alignment group) to the coating film without being irradiated with light. Can be mentioned. Here, examples of the liquid crystal aligning group include a group having a C 4-20 alkyl group, a C 4-20 fluoroalkyl group, a C 4-20 alkoxy group, and a C 17-51 steroid skeleton. Examples thereof include a group having a structure (polycyclic structure) in which two or more rings are linked directly or via a linking group. In addition, other carboxylic acid can be used individually by 1 type or in combination of 2 or more types.

  In the reaction of the epoxy group-containing polyorganosiloxane with the specific carboxylic acid, the use ratio of the specific carboxylic acid (the total amount when two or more types are used) develops an appropriate pretilt angle imparting characteristic to the coating film. From a viewpoint, it is preferable to set it as 0.001-1.5 mol with respect to the total 1 mol of the epoxy group which polyorganosiloxane has, It is more preferable to set it as 0.01-1.0 mol, More preferably, it is made into -0.8 mol. Moreover, it is preferable that the usage-amount of unsaturated bond containing carboxylic acid shall be 0.001-1.0 mol with respect to the total 1 mol of the epoxy group which polyorganosiloxane has, 0.01-0.8 mol It is more preferable to set it as 0.05 to 0.5 mol.

  The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. As said catalyst, a well-known compound etc. can be used as what is called a hardening accelerator which accelerates | stimulates reaction of an organic base and an epoxy compound, for example. Of these, tertiary organic amines or quaternary organic amines are preferred. The ratio of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing polyorganosiloxane.

  Examples of the organic solvent used in the above reaction include hydrocarbons, ethers, esters, ketones, amides, alcohols and the like. Among these, from the viewpoint of solubility of raw materials and products, and ease of purification of products, it is preferable to use at least one selected from the group consisting of ethers, esters and ketones, and specific examples of particularly preferred solvents Examples thereof include 2-butanone, 2-hexanone, methyl isobutyl ketone, and butyl acetate. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight.

The reaction temperature in the above reaction is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water.
Thus, a solution containing the photoalignable polyorganosiloxane as the polymer [P] can be obtained. This reaction solution may be used for the preparation of the polymer composition as it is, may be used for the preparation of the polymer composition after isolating the photoalignable polyorganosiloxane contained in the reaction solution, or simply. You may use for the preparation of a polymer composition, after refine | purifying the photo-alignment polyorganosiloxane which isolate | separated. Isolation and purification of the photoalignable group polyorganosiloxane can be performed according to a known method.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably in the range of 100 to 50,000, and in the range of 200 to 10,000 for the photoalignable polyorganosiloxane. More preferably. When the weight-average molecular weight of the photoalignable polyorganosiloxane is in the above range, it is easy to handle when producing a latent image forming body, and the obtained latent image forming body has sufficient material strength and characteristics. By using photo-alignable polyorganosiloxane as the polymer [P], the heating temperature when forming the alignment layer 12 can be set to a relatively low temperature (for example, 150 ° C. or lower), and the substrate that can be used is limited. This is preferable in terms of a small amount of energy and energy saving.

(Photo-alignable unsaturated polymer)
In the case where the polymer [P] is a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as “photo-alignable unsaturated polymer”), the polymerizable carbon-carbon unsaturated polymer. Examples of the monomer having a saturated bond include (meth) acrylic compounds, aromatic vinyl compounds, conjugated diene compounds, maleimide group-containing compounds, and the like. The photoalignable unsaturated polymer is preferably a monomer polymer containing a (meth) acrylic compound from the viewpoint of transparency and material strength.

  A photo-alignment unsaturated polymer is, for example, an epoxy group-containing (meth) acrylic compound (ma-1), or the (meth) acrylic compound (ma-1) and other epoxy-free compounds. After polymerizing a mixture with the monomer (ma-2) in the presence of a polymerization initiator, the obtained polymer (hereinafter also referred to as “epoxy group-containing unsaturated polymer”), a specific carboxylic acid, Can be obtained by a method of reacting.

  Examples of the (meth) acrylic monomer (ma-1) include unsaturated carboxylic acid esters having an epoxy group. Specific examples thereof include, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate. Α-ethyl acrylate 3,4-epoxybutyl, (meth) acrylate 3,4-epoxycyclohexylmethyl, (meth) acrylate 6,7-epoxyheptyl, α-ethyl acrylate 6,7-epoxyheptyl, Examples include 4-hydroxybutyl glycidyl ether of acrylic acid, (meth) acrylic acid (3-ethyloxetane-3-yl) methyl, and the like. In addition, a (meth) acrylic-type monomer (ma-1) can be used individually by 1 type in the above or in combination of 2 or more types.

Other monomers are not particularly limited as long as they have a polymerizable carbon-carbon unsaturated bond. Specific examples thereof include, for example, (meth) acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, vinyl benzoic acid and other unsaturated carboxylic acids: methyl (meth) acrylate, (meth) Ethyl acrylate, propyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, (meth) acrylate lauryl, ( (Meth) acrylic acid trimethoxysilylpropyl, (meth) acrylic acid methoxyethyl, (meth) acrylic acid-N, N-dimethylaminoethyl, (meth) acrylic acid methoxypolyethylene glycol, (meth) acrylic acid tetrahydrofurfuryl, ( (Meth) acrylic compounds such as 2-hydroxyethyl methacrylate ;
Aromatic vinyl compounds such as styrene, methylstyrene, divinylbenzene;
Conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene;
And maleimide group-containing compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide. Other monomers can be used alone or in combination of two or more.

In the synthesis of the epoxy group-containing unsaturated polymer, the total amount (number of moles) of epoxy groups per 1 g of the polymer is preferably 5.0 × 10 −5 or more, and 1.0 × 10 −4 to 1 It is more preferably 0.0 × 10 −2 mol / g, and further preferably 5.0 × 10 −4 to 5.0 × 10 −3 mol / g. Therefore, the use ratio of the (meth) acrylic monomer (ma-1) is preferably adjusted so that the total number of moles of epoxy groups per gram of the epoxy group-containing unsaturated polymer is within the above range. .
In the above synthesis, the proportion of monomers other than the (meth) acrylic compound (aromatic vinyl compound, etc.) is 30 moles relative to the total amount of monomers used for the synthesis of the epoxy group-containing unsaturated polymer. % Or less, and more preferably 20 mol% or less.

  The polymerization reaction of the monomer having a polymerizable carbon-carbon unsaturated bond is preferably performed by radical polymerization. Examples of the polymerization initiator used in the reaction include initiators usually used in radical polymerization. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4- Azo compounds such as dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis (t Organic peroxides such as -butylperoxy) cyclohexane; hydrogen peroxide; redox type initiators composed of these peroxides and reducing agents. Among these, an azo compound can be preferably used. As a polymerization initiator, these can be used alone or in combination of two or more. The use ratio of the polymerization initiator is preferably 0.01 to 50 parts by weight and more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the total amount of monomers used in the reaction. .

  The polymerization reaction is preferably performed in an organic solvent. Examples of the organic solvent used for the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, and the like. Among these, it is preferable to use at least one selected from the group consisting of alcohols and ethers, and it is more preferable to use partial ethers of polyhydric alcohols. Preferred examples thereof include diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate. In addition, as an organic solvent, these 1 type can be used individually or in combination of 2 or more types.

  The reaction temperature in the polymerization reaction is preferably 30 to 120 ° C, more preferably 60 to 110 ° C. The reaction time is preferably 1 to 36 hours, and more preferably 2 to 24 hours. The amount of organic solvent used (a) is such that the total amount (y) of monomers used in the reaction is 0.1 to 50% by weight with respect to the total amount (x + y) of the reaction solution. An amount is preferred.

  The epoxy group-containing unsaturated polymer obtained by the above reaction is then reacted with a specific carboxylic acid. As specific carboxylic acid to be used, the illustration of specific carboxylic acid used by the synthesis | combination of photo-alignment polyorganosiloxane is applicable. In the reaction, the specific carboxylic acid may be used alone, or other carboxylic acid other than the specific carboxylic acid may be used in combination. The description of the photo-alignment polyorganosiloxane can be applied to specific examples of other carboxylic acids that may be used and preferable exemplary descriptions.

  In the reaction of the epoxy group-containing unsaturated polymer with the specific carboxylic acid, the use ratio of the specific carboxylic acid (the total amount when using two or more types) expresses a suitable pretilt angle imparting characteristic to the coating film. From the viewpoint of making it, it is preferably 0.001 to 1.5 mol, more preferably 0.01 to 1.0 mol, based on a total of 1 mol of epoxy groups of the unsaturated polymer, 0 More preferably, it is 1 to 0.8 mol. Moreover, it is preferable that the usage-amount of unsaturated bond containing carboxylic acid shall be 0.001-1.0 mol with respect to a total of 1 mol of the epoxy group which an unsaturated polymer has, 0.01-0.8 More preferably, the molar amount is 0.05 to 0.5 mol.

  The reaction between the epoxy group-containing unsaturated polymer and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. Here, as a catalyst used for reaction, the catalyst etc. which were illustrated by the description of the synthesis | combination of photo-alignment polyorganosiloxane are mentioned. Of these, quaternary ammonium salts can be preferably used. The amount of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 80 parts by weight or less, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing unsaturated polymer. is there.

  As the organic solvent used in the reaction, examples of the organic solvent that can be used in the polymerization of the (meth) acrylic monomer can be applied, and among them, an ester is preferable. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight. The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

  In this way, a solution containing the photo-alignable unsaturated polymer as the polymer [P] can be obtained. This reaction solution may be used for the preparation of the polymer composition as it is, may be used for the preparation of the polymer composition after isolating the photoalignable unsaturated polymer contained in the reaction solution, or You may use for the preparation of a polymer composition, after refine | purifying the isolated photo-alignment unsaturated polymer. Isolation and purification of the photoalignable unsaturated polymer can be performed according to a known method.

  In addition, the synthesis method of a photo-alignment unsaturated polymer is not limited to said method. For example, a monomer having a photoalignable group and a polymerizable carbon-carbon unsaturated bond, or a mixture of a monomer having a photoalignable group and a polymerizable carbon-carbon unsaturated bond and another monomer Can also be obtained by a method of polymerizing in the presence of a polymerization initiator.

  For the photo-alignable unsaturated polymer, the polystyrene-equivalent number average molecular weight (Mn) measured by GPC improves the liquid crystal alignment of the formed film and ensures the stability of the liquid crystal alignment over time. In view of the above, it is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

<Other ingredients>
The polymer composition contains the polymer [P], but may contain other components as necessary. Examples of the other components include polymers other than the polymer [P], metal chelate compounds, curing accelerators, surfactants, and the like.

[Other polymers]
The other polymer is not particularly limited and can be appropriately selected according to the purpose. For example, the polymer is a monomer polymer having a polymerizable carbon-carbon unsaturated bond and has a photo-alignment group. Polymer not having (hereinafter also referred to as “polymer [Q]”), polyorganosiloxane having no photo-alignment group, polyamic acid, polyamic acid ester, polyimide, cellulose derivative, polyacetal, polystyrene derivative, poly (Styrene-phenylmaleimide) derivatives and the like.

  When the polymer [P] contained in the polymer composition is a photoalignable polyorganosiloxane, the composition preferably further contains a polymer [Q]. By using the polymer [Q] in combination, a coating film having sufficiently high latent image forming ability and adhesion to the substrate can be obtained even if the amount of the polymer [P] used is reduced. Moreover, a new function by the polymer [Q] can be added. Specifically, it is possible to improve adhesion durability, lower the firing temperature during production, shorten the firing time, and reduce the process load.

  The polymer [Q] can be obtained by polymerization using a monomer having no photo-alignment group and having a polymerizable carbon-carbon unsaturated bond. Examples of the monomer include (meth) acrylic compounds, aromatic vinyl compounds, conjugated diene compounds, maleimide group-containing compounds, etc., and specific examples thereof are used for the synthesis of photoalignable unsaturated polymers. Examples of monomers that may be used are applicable. From the viewpoint of transparency and material strength, the polymer [Q] is preferably a monomer polymer containing a (meth) acrylic compound.

  In the synthesis of the polymer [Q], it is preferable to use a (meth) acrylic compound (ma-1) having an epoxy group from the viewpoint of improving the adhesion of the film to the substrate. In this case, the proportion of the compound (ma-1) used is preferably 1 to 95 mol%, and preferably 3 to 85 mol%, based on the total amount of monomers used for the synthesis of the polymer [Q]. More preferably, it is more preferably 5 to 70 mol%. In addition, about reaction conditions at the time of obtaining polymer [Q], the description of a photo-alignment unsaturated polymer is applicable.

When other polymers are blended into the polymer composition, the blending ratio (the total amount when blending two or more) is based on 100 parts by weight of the total polymer contained in the polymer composition. 60 parts by weight or less, preferably 0.1 to 50 parts by weight, more preferably 0.1 to 40 parts by weight.
Moreover, in the polymer composition containing the photoalignable polyorganosiloxane and the polymer [Q], the blending ratio of the polymer [Q] is based on the total of the photoalignable polyorganosiloxane and the polymer [Q]. It is preferably 98% by weight or less, more preferably 1 to 95% by weight, and still more preferably 5 to 90% by weight.

[Metal chelate compounds]
The metal chelate compound is a component having a catalytic action for a crosslinking reaction between epoxy structures, and is contained in the polymer composition for the purpose of promoting the crosslinking reaction.
As the metal chelate compound, an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium, and zirconium is preferable. Specifically, as an aluminum chelate compound, for example, diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris ( Ethyl acetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum, etc .; titanium chelate compounds such as diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (Acetylacetonate) titanium, etc .; as a chelate compound of zirconium, for example, tri-n-butoxyethylacetate Cetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetonate) zirconium, tetrakis (ethylacetoacetate) ) Zirconium and the like can be mentioned respectively. As a metal chelate compound, 1 type selected from these can be used individually or in combination of 2 or more types.

Among these, it is preferable to use an aluminum chelate compound as the metal chelate compound, which is selected from the group consisting of diisopropoxyethyl acetoacetate aluminum, tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum. It is more preferable to use one or more types.
The use ratio of the metal chelate compound is preferably 60 parts by weight or less, more preferably 0.1 to 50 parts by weight, and still more preferably with respect to 100 parts by weight of the total polymer components in the polymer composition. 1 to 40 parts by weight.

[Curing accelerator]
The curing accelerator is contained in the polymer composition for the purpose of enhancing the catalytic action of the curing catalyst and promoting the crosslinking reaction between the epoxy structures.
As a hardening accelerator, the compound which has a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group etc. can be used, for example. Of these, compounds having a phenol group, silanol group or carboxyl group are preferred, and compounds having a phenol group or silanol group are more preferred.
Specific examples thereof include a curing accelerator having a phenol group such as cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, bis (4-hydroxyphenyl) sulfone, bis (hydroxynaphthyl) sulfone, (3- Hydroxyphenyl) (4-hydroxyphenyl) sulfone, phenyl (4-hydroxyphenyl) sulfone, (methoxyphenyl) (4-hydroxyphenyl) sulfone, 4-benzylphenol, 2,2-bis (4-hydroxyphenyl) propane, etc. ;
Examples of the curing accelerator having a silanol group include trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene, and triphenylsilanol. , Tri (p-tolyl) silanol, tri (m-trifluoromethylphenyl) silanol, tri (o-trifluoromethylphenyl) silanol, tri (m-fluorophenyl) silanol, tri (o-fluorophenyl) silanol, diphenyl Examples thereof include silane diol and di (o-tolyl) silane diol. In addition, as a hardening accelerator, 1 type selected from these can be used individually or in combination of 2 or more types.

  As the curing accelerator, it is particularly preferable to use a compound having a silanol group. The use ratio of the curing accelerator is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total polymer components in the polymer composition, and 0.5 More preferably, it is made into -20 weight part.

[Surfactant]
The surfactant can be contained in the polymer composition for the purpose of improving the applicability of the polymer composition to the substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. be able to. In addition, as surfactant, 1 type selected from these can be used individually or in combination of 2 or more types.
The proportion of the surfactant used is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less, with respect to 100 parts by weight of the total polymer components in the polymer composition.

  In addition, the polymer composition may contain components other than the above within the range which does not prevent the objective and effect of this invention. Examples of such components include compounds having at least one epoxy group in the molecule, functional silane compounds, silica particles, fillers, antifoaming agents, photosensitizers, dispersants, antioxidants, adhesion assistants, Examples thereof include an antistatic agent, an antibacterial agent, and an ultraviolet absorber. In addition, these mixing | blending ratios can be suitably set in the range which does not prevent the effect of this invention according to each compound to mix | blend.

[solvent]
The polymer composition is prepared as a liquid composition in which the above polymer [P] and other optional components are preferably dispersed or dissolved in an appropriate solvent.
The solvent to be used is preferably an organic solvent. For example, alcohol, ether, ketone, amide, ester, hydrocarbon and the like can be suitably used. Especially, it is preferable to use 1 or more types selected from the partial ester of polyhydric alcohol, ether, a ketone, and ester. Specifically, the partial ester of polyhydric alcohol is propylene glycol monomethyl ether; the ether is diethylene glycol ethyl methyl ether; the ketone is one or more selected from methyl ethyl ketone, cyclopentanone and cyclohexanone; As the ester, one or more selected from ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, ethyl acetoacetate and propylene glycol monomethyl ether acetate can be preferably used.

  The proportion of the solvent used is determined from the viewpoint of making the coating composition of the polymer composition and the film thickness of the formed coating film appropriate, and the solid content concentration of the polymer composition (all components other than the solvent in the polymer composition). Of the total weight of the polymer composition) is preferably 0.2 to 10% by weight, and more preferably 3 to 10% by weight.

<Method for producing latent image forming body>
Next, a method for producing the latent image forming body 10 using the polymer composition will be described. The latent image forming body 10 can be manufactured by a method including the following steps [1] to [3].
Step [1]: A step of applying a polymer composition containing the polymer [P] onto a substrate to form a coating film (alignment layer 12).
Step [2]: A step of irradiating the coating film obtained in Step [1] with polarized radiation through a mask having a predetermined pattern.
Step [3]: A step of forming a liquid crystal layer 13 by applying and curing a polymerizable liquid crystal on the coating film after irradiation with polarized radiation.
A method for producing a latent image forming body will be described with reference to FIG.

<Step [1]; Formation of coating film>
First, the polymer composition is applied to at least a part of the substrate 11 to form a coating film (FIG. 2A). The substrate 11 is made of synthetic resin such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate, or the like; transparent glass made of float glass, soda glass, or the like. A substrate can be preferably used. Among these, TAC is generally used as a protective layer of a polarizing film, for example. In addition, polymethyl methacrylate is preferable in terms of low hygroscopicity of the solvent, good optical characteristics, and low cost. In addition, conventionally well-known pre-processing may be given to the surface which forms a coating film in order to make the adhesiveness of a base-material surface and a coating film further favorable with respect to the base material 11 to be used. The region where the polymer composition is applied to the substrate 11 may be appropriately set according to the region where the latent image is formed, and may be applied to a part of the substrate surface, or may be applied to the entire surface of the substrate surface. It may be applied. Moreover, a polymer composition may be apply | coated to only one surface of the base material 11, and a polymer composition may be apply | coated to a some surface (for example, both surfaces of the base material 11).

  Application | coating of the polymer composition on the base material 11 can be based on a suitable coating method. For example, roll coater method, spinner method, printing method, ink jet method, bar coater method, extrusion die method, direct gravure coater method, chamber doctor coater method, offset gravure coater method, single roll kiss coater method, small diameter gravure method Reverse kiss coater method using roll, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air doctor coater method, forward rotation roll coater method, blade coater method, knife coater method, impregnation coater method, An MB coater method, an MB reverse coater method, or the like can be employed.

  After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40 to 150 ° C, more preferably 80 to 140 ° C. The heating time is preferably 0.1 to 15 minutes, and more preferably 1 to 10 minutes. The film thickness of the coating film (alignment layer 12) formed on the base material 11 is preferably 0.001 to 1 μm, more preferably 0.05 to 0.5 μm.

<Step [2]; irradiation of polarized radiation>
Next, the coating film formed on the substrate 11 as described above is irradiated with polarized radiation (FIG. 2C). Examples of the polarized radiation to be irradiated include ultraviolet rays or visible rays including light having a wavelength of 150 to 800 nm. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As the polarized light, it is preferable to use light including linearly polarized light. The light irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof.
Examples of the light source used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and a mercury-xenon lamp (Hg-Xe lamp). Polarized light can be obtained by means of using these light sources in combination with, for example, a filter or a diffraction grating. The dose of light is preferably in a 0.1~1,000mJ / cm 2, more preferably to 1 to 500 mJ / cm 2, and even more preferably from 2~200mJ / cm 2.

  Irradiation with polarized radiation is performed through a mask 14 on which a desired pattern is formed. The material of the mask 14 is not particularly limited, and various materials can be applied. Specifically, for example, metal masks such as stainless steel, nickel, nickel-iron alloy, nickel-cobalt alloy; polytetrafluoroethylene (PTFE), polyether ether ketone (PEEK), polyether sulfone (PES), polyphenylene ether ( PPE), resin masks such as polyester and polyethylene terephthalate; and glass masks such as quartz. In particular, the coating film formed using the polymer composition containing the polymer [P] has high sensitivity to radiation, and for example, when an arbitrary pattern printed on a transparent plate such as an OHF film is used as a mask. Also, an identifiable latent image can be formed. Moreover, a mask can be produced simply by printing on an OHF film or the like, and various patterns of latent images can be easily formed. Examples of the pattern printing method for the transparent plate include an inkjet method and a laser method.

  The design of the mask 14 can be appropriately selected according to the use of the latent image forming body, and various types such as a person, an object, a figure, a pattern, and a character can be adopted. The mask 14 may have a symbol portion as a light shielding portion, or may have a symbol portion as a transmission portion and a portion other than the symbol as a light shielding portion. The thickness of the mask 14 is not particularly limited, but is preferably 0.001 to 2 mm, and more preferably 0.01 to 1 mm.

Irradiation of the polarized radiation to the coating film may be performed only once from a predetermined polarization direction through the mask 14, but radiation having a different polarization direction (incident direction) may be irradiated to the coating film a plurality of times. . According to the aspect in which the radiation having different polarization directions is irradiated a plurality of times, the orientation direction of the liquid crystal can be rewritten, and a plurality of regions having different orientation directions can be formed on the light irradiation surface of the coating film. Specifically, a production method including the following step (2-1) is preferable.
(2-1) A step of irradiating the coating film with polarized radiation having a polarization direction different from that at the time of radiation irradiation through the mask 14 before irradiating the coating film with the polarizing radiation through the mask 14.

The description of the above step [2] can be applied to the description of the type, wavelength, light source, irradiation amount, and the like of the polarized radiation irradiated in the step (2-1). When rewriting the orientation direction, first, radiation is applied to the entire surface of the coating film without passing through the mask in the step (2-1) (see FIG. 2B), and then through the mask 14 in the step [2]. Irradiation is performed (see FIG. 2C). That is, the latent image forming body 10 is preferably manufactured by a method including the following steps (2-A) and (2-B) as a radiation irradiation step.
(2-A) A step of irradiating the coating film with polarized radiation of the first polarization direction L1 to impart the liquid crystal alignment ability of the first alignment direction C1.
(2-B) The coating film is irradiated with the polarized radiation of the second polarization direction L2 different from the first polarization direction L1 through the mask 14, and the orientation direction of a part of the coating film is set to the second orientation. The process of rewriting to direction C2.
According to such irradiation, the orientation direction of the non-mask area can be easily rewritten. In addition, the orientation is aligned by performing the first irradiation on the entire surface of the coating film, and in that state, the second irradiation is performed only on a part of the coating film, thereby eliminating the mask region. It is considered that the difference in orientation direction from the mask region becomes clear.

  The second polarization direction L2 in the step (2-B) is not particularly limited as long as it is different from the first polarization direction L1 of the polarized radiation irradiated in the step (2-A), but the first polarization direction L1. The rotation direction from is preferably 70 to 110 °. Thus, the alignment layer 12 having a plurality of regions 12a and 12b having different alignment directions is obtained (FIG. 2D).

<Step [3]; Formation of Liquid Crystal Layer 13>
Next, a polymerizable liquid crystal is applied on the alignment layer 12 to form a coating film containing the polymerizable liquid crystal. A conventionally well-known thing can be used as a polymeric liquid crystal. Specific examples include nematic liquid crystal compounds described in Non-Patent Document 1 (“UV curable liquid crystal and its application”, liquid crystal, Vol. 3, No. 1, (1999), pp 34-42). . Further, cholesteric liquid crystal; discotic liquid crystal; twisted nematic alignment type liquid crystal to which a chiral agent is added may be used. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds, or may be a composition containing a known polymerization initiator, an appropriate solvent, and the like. In order to apply the polymerizable liquid crystal on the formed alignment layer 12, an appropriate application method such as a bar coater method, a roll coater method, a spinner method, a printing method, an ink jet method, or the like can be employed.

  Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to at least one treatment selected from heating and light irradiation to cure the coating film and form the liquid crystal layer 13 ( (Refer FIG.2 (e)). It is preferable to perform these treatments in a superimposed manner because good alignment can be obtained. The heating temperature of the coating film should be appropriately selected depending on the type of polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80 ° C. The heating time is preferably 0.5 to 5 minutes.

As irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation dose of light, preferably in the 50~10,000mJ / cm 2, and more preferably a 100~5,000mJ / cm 2. The thickness of the liquid crystal layer 13 to be formed is appropriately set depending on the desired optical characteristics, the optical characteristics of the polymerizable liquid crystal to be used, and the like, but is set in the range of 0.1 to 1.5 μm, for example.

≪Latent image forming body set and image display method≫
The latent image forming body 10 obtained in this way is used in combination with a pair of polarizing plates (polarizing film), whereby the latent image is visualized. As shown in FIG. 3, the latent image forming body set 20 of the present embodiment includes the above-described latent image forming body 10, and a first polarizing plate 14 and a second polarizing plate 15 as a pair of polarizing plates.

  The first polarizing plate 14 and the second polarizing plate 15 are not particularly limited as long as they have a function as a polarizer. For example, the first polarizing plate 14 and the second polarizing plate 15 are referred to as “H films” that absorb iodine while stretching and aligning polyvinyl alcohol. A polarizing plate comprising a polarizing film sandwiched between cellulose acetate protective films, or a polarizing plate made of an H film itself. The orientations of the transmission axes of the first polarizing plate 14 and the second polarizing plate 15 are not particularly limited as long as the orientations of the transmission axes can be different from each other when the polarizing plates 14 and 15 are arranged to face each other.

  In order to visualize the latent image formed on the latent image forming body 10, the latent image forming body 10 is arranged between the first polarizing plate 14 and the second polarizing plate 15 that are arranged in crossed Nicols. That is, in the latent image forming body 10 of this embodiment, in the state as it is, the latent image corresponding to the pattern of the mask used at the time of radiation irradiation is not observed. On the other hand, when the latent image forming body 10 is placed under crossed Nicols, a pattern corresponding to the mask appears on at least one surface of the latent image forming body 10. Visualization of the latent image is performed in a state where the light source is arranged on the side opposite to the observation side, if necessary. The light source to be arranged is not particularly limited, and examples thereof include natural light sources such as the sun and artificial light sources such as incandescent bulbs and fluorescent lamps.

  In the latent image forming body set 20, the pair of polarizing plates 14 and 15 may be integrated with the latent image forming body 10 through, for example, an adhesive layer, or may be integrated. It may be configured as a separate part. The adhesive layer when integrating the pair of polarizing plates 14 and 15 and the latent image forming body 10 is formed using, for example, an aqueous adhesive in which polyvinyl alcohol is dissolved in water, an adhesive having a polar group, or the like. Can do.

≪Decoration Laminate≫
The latent image forming body 10 can be effectively applied to decorative laminates for the design of various articles such as toys, stationery, and household items, buildings, and vehicles. Especially, it is useful for window decoration uses, such as a window glass, a curtain, the shutter for windows, a roll screen, a blind, etc. by the point with high decoration property and a weather resistance.

  There is no particular limitation on the usage mode when the latent image forming body 10 is used as a laminated body for window decoration. For example, as shown in FIG. 4, a polarizing plate integrated latent image forming body 16 in which the latent image forming body 10 and the first polarizing plate 14 are integrated with respect to a window glass 17 (multilayer glass in FIG. 4). It arrange | positions indoors and the 2nd polarizing plate 15 is arrange | positioned in the position which opposes the 1st polarizing plate 14 on both sides of the latent image formation body 10 on the indoor side. The 2nd polarizing plate 15 is affixed on the indoor side surface of the window glass 17, for example. In such an embodiment, by using the polarizing plate-integrated latent image forming body 16 as a curtain, a roll screen, or a blind, the latent image can be visualized according to opening and closing of the curtain or the like. Moreover, a light shielding effect can be expressed by arranging a pair of polarizing plates in crossed Nicols, and privacy can be ensured while providing design properties.

  In addition, about the polarizing plate integrated latent image formation body 16, it is good also as a structure which affixes and uses for the window glass 10 instead of the structure used as a curtain. In this case, the latent image forming body 10 may be disposed between the polarizing plates 14 and 15. For example, the polarizing plate integrated latent image forming body 16 is attached to the same surface as the surface on which the second polarizing plate 15 is attached. . Moreover, it replaces with the structure arrange | positioned in the indoor side of the window glass 17 about the 2nd polarizing plate 15, and may be arrange | positioned between the two glass in a multilayer glass, or the surface of the outdoor side of the window glass 17 It may be pasted on.

<< Other Embodiments >>
The present invention is not limited to the above embodiment, and may be configured as follows, for example.

  In the said embodiment, although the base material 11 and the polarizing plate (1st polarizing plate 14) were used as separate components, you may use a polarizing plate as the base material 11. FIG. When laminating the latent image forming body 10 and the polarizing plate, it is necessary to precisely control the angle of the polarizing plate with respect to the polarization axis in a specific direction so that the desired optical characteristics can be exhibited. In consideration of these points, a coating film is formed on the base material as a polarizing plate using the polymer composition, and then an alignment layer having a liquid crystal alignment ability in a predetermined angle direction using a photo-alignment method. By setting it to 12, the step of bonding the latent image forming body 10 onto the polarizing plate while controlling the angle thereof can be omitted.

  The alignment layer 12 and the liquid crystal layer 13 may be formed on the glass substrate as the base material 11 and may be used as the latent image forming body 10. Such a latent image forming body 10 can be applied to a window glass as it is. Moreover, in this structure, the latent image of a window glass can be visualized by arrange | positioning a polarizing plate to the outdoor side and indoor side of a window glass, respectively. For example, by using a roll-up curtain or a blind as the polarizing plate on the indoor side, it is possible to switch between latent image / visualization according to the operation of the resident.

  In the latent image forming body 10, a protective layer may be disposed on the liquid crystal layer 13 in order to maintain durability and mechanical characteristics. The protective layer is preferably a transparent substrate, and examples thereof include films made of triacetyl cellulose (TAC), cyclic olefin resin, polyethylene terephthalate, polycarbonate, acrylic resin, acrylic / styrene copolymer resin, polyolefin resin, and the like. In the latent image forming body 10, a dye may be contained in the protective layer to impart a color feeling.

  The use of the latent image forming body 10 is not limited to decoration. For example, you may apply to a security use. Specifically, forgery prevention of objects such as cards, identification cards, passports, examination cards, banknotes, gift certificates, stock certificates, securities, cash vouchers, pass tickets, tickets, admission tickets, public competition voting tickets, etc. It can be applied to the purpose of identifying the object. According to the latent image forming body of the present invention, the latent image can be visualized simply by being placed under crossed Nicols, and the authenticity / incorrectness of the object can be easily determined visually. Moreover, the coating film formed with the polymer composition containing the polymer [P] has high sensitivity to radiation, and thus the recognized image is clear.

  The latent image forming body of the present invention can also be applied to various advertisements such as store advertisements and in-car advertisements such as trains and buses. According to the latent image forming body of the present invention, it is possible to switch the latent image / visualization of the pattern according to the arrangement of the polarizing plates 14 and 15, and to have an excellent aesthetics and design when applied to advertising purposes. It can be played.

  The number of polarizing plates used when the latent image of the latent image forming body 10 is visualized is not limited to two (a pair), and may be three or more. Moreover, the polarizing plate in the latent image forming body set may be at least a pair, and may include three or more polarizing plates.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

  In the following examples, the weight average molecular weight Mw, the number average molecular weight Mn and the epoxy equivalent of the polymer, and the solution viscosity of the polymer solution were measured by the following methods. The required amounts of raw material compounds and polymers used in the following examples were ensured by repeating the synthesis on the synthesis scale shown in the following synthesis examples as necessary.

[Weight average molecular weight Mw and number average molecular weight Mn of the polymer]
Mw and Mn are polystyrene equivalent values measured by GPC under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm 2
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.
[Solution viscosity of polymer solution]
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.

<Synthesis of polyorganosiloxane having epoxy group>
[Synthesis Example 1]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 70.5 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 14.9 g of tetraethoxysilane, 85.4 g of ethanol and triethylamine 8.8 g was charged and mixed at room temperature. Subsequently, 70.5 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 2 hours while stirring under reflux. The operation of concentrating the reaction solution and diluting with butyl acetate was repeated twice to distill off triethylamine and water to obtain a polymer solution containing polyorganosiloxane (SEp-1). As a result of 1 H-NMR analysis, it was confirmed that no side reaction of the epoxy group occurred during the reaction. Mw of this polyorganosiloxane (SEp-1) was 11,000, and the epoxy equivalent was 182 g / mol.

<Synthesis of cinnamic acid derivatives>
The synthesis reaction of cinnamic acid derivatives was carried out in an inert atmosphere.
[Synthesis Example 2]
In a 500 mL three-necked flask equipped with a condenser, 19.2 g of 1-bromo-4-cyclohexylbenzene, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetamide are mixed. did. 7 g of acrylic acid was added to this mixed solution with a syringe and stirred. Further, the mixed solution was stirred while heating at 120 ° C. for 3 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution to collect the precipitate. The recovered precipitate is recrystallized with a 1: 1 (weight ratio) solution of ethyl acetate and hexane, thereby converting the compound represented by the following formula (M-1) (cinnamate derivative (M-1)) to 10 0.2 g was obtained.

<Synthesis of photoalignable polyorganosiloxane>
[Synthesis Example 3]
In a 100 mL three-necked flask, 11.3 g of the polyorganosiloxane (SEp-1) having an epoxy group obtained in Synthesis Example 1, 13.3 g of butyl acetate, cinnamic acid derivative (M-1) obtained in Synthesis Example 2 7 g, 0.54 g of acryloyl group-containing carboxylic acid (Aronix M-5300, manufactured by Toa Gosei Co., Ltd.) and 0.10 g of a quaternary amine salt (Sun Apro, UCAT18X) were charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, an additional 20 g of butyl acetate was added, and this solution was washed with water three times. Then, an additional 20 g of butyl acetate was added, and the solvent was distilled off so that the solid concentration was 10% by weight. As a result, a butyl acetate solution having a solid content concentration of 10% by weight containing the polymer (S-1) which is a photoalignable polyorganosiloxane was obtained. The weight average molecular weight Mw of the polymer (S-1) was 18,000.

[Synthesis Example 4]
In a 100 mL three-necked flask, 11.3 g of the polyorganosiloxane (SEp-1) having an epoxy group obtained in Synthesis Example 1, 13.3 g of butyl acetate, cinnamic acid derivative (M-1) obtained in Synthesis Example 2 7 g and quaternary amine salt (Sun Apro, UCAT18X) 0.10 g were charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, an additional 20 g of butyl acetate was added, and this solution was washed with water three times. Then, an additional 20 g of butyl acetate was added, and the solvent was distilled off so that the solid concentration was 10% by weight. As a result, a butyl acetate solution having a solid content concentration of 10% by weight containing the polymer (S-2) which is a photoalignable polyorganosiloxane was obtained. The weight average molecular weight Mw of the polymer (S-2) was 17,000.

<Synthesis of other polymers>
[Synthesis Example 5]
A flask equipped with a condenser and a stirrer was charged with 1 part by weight of 2,2′-azobis (isobutyronitrile) as a polymerization initiator and 180 parts by weight of diethylene glycol methyl ethyl ether as a solvent. Subsequently, 70 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate and 30 parts by weight of 3-methyl-3-oxetanylmethyl methacrylate were added, and after the atmosphere was replaced with nitrogen, stirring was started gently. The solution temperature was raised to 80 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (PAc-1) which is an epoxy group-containing poly (meth) acrylate. The resulting polymer solution had a solid content concentration of 32.8% by weight. Mn of the obtained polymer was 16,000.
[Synthesis Example 6]
100 parts by weight of the epoxy group-containing poly (meth) acrylate (PAc-1) obtained in Synthesis Example 5, 20 parts by weight of acryloyl group-containing carboxylic acid (Aronix M-5300, manufactured by Toagosei Co., Ltd.), tetrabutyl as a catalyst 10 parts by weight of ammonium bromide and 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent were charged and stirred at 90 ° C. for 12 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was diluted with 100 parts by weight of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting with butyl acetate was repeated twice to obtain a polymer solution containing a polymer (PAc-2) which is an acryloyl group-containing poly (meth) acrylate. Mn of the obtained polymer was 20,000. In addition, propylene glycol monomethyl ether acetate content of the obtained polymer solution was 20% by weight.

[Example 1]
<Preparation of polymer composition for forming latent image>
As a polymer component, the butyl acetate solution containing the polymer (S-1) obtained in Synthesis Example 3 is converted into the polymer (S-1) in an amount corresponding to 70 parts by weight, and in Synthesis Example 6 An amount corresponding to 30 parts by weight of the solution containing the obtained polymer (PAc-2) in terms of the polymer (PAc-2), tris (acetylacetonate) aluminum (aluminum chelate A (W) as a catalyst , Produced by Kawaken Fine Chemical Co., Ltd.) and 40 parts by weight of tri (p-tolyl) silanol as a curing accelerator were mixed, and n-butyl acetate (BA), methyl ethyl ketone (MEK) and propylene glycol were used as solvents. Monomethyl ether acetate (PGMEA) was added, and the solid content concentration was adjusted to 5% by weight and the weight ratio of each solvent was adjusted to BA: MEK: PGMEA = 50: 40: 10. Subsequently, this obtained solution was filtered with a filter having a pore diameter of 1 μm to prepare a polymer composition (A-1).

<Manufacture of latent image forming body (decorative film)>
The polymer composition (A-1) prepared above was applied to one side of a TAC film as a substrate using a bar coater, and baked in an oven at 120 ° C. for 2 minutes to have a film thickness of 0.1 μm. The coating film was formed. Next, using a Hg-Xe lamp and a Grand Taylor prism, the surface of the coating film was irradiated with polarized ultraviolet light 10 mJ / cm 2 containing a 313 nm emission line perpendicularly from the normal of the substrate surface (hereinafter, this polarized ultraviolet irradiation was performed). Also called “polarized ultraviolet irradiation A”) to form a coating film. Next, on this coating film, using a commercially available OHP sheet printed with a laser printer as a mask, with the polarization direction rotated 45 ° horizontally from the previously irradiated “polarized ultraviolet irradiation A”, The orientation azimuth was rewritten by irradiating with polarized ultraviolet light 15 mJ / cm 2 containing a 313 nm emission line using a Hg-Xe lamp and a Grand Taylor prism (hereinafter, this polarized ultraviolet irradiation is also referred to as “polarized ultraviolet irradiation B”). .
Next, a polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was used, and this was filtered through a filter having a pore size of 0.2 μm. Then, the polymerizable liquid crystal was applied onto the film using a bar coater, and the oven set at 50 ° C. After being baked for 1 minute, using a Hg-Xe lamp, the polymerizable liquid crystal is cured by irradiating a non-polarized ultraviolet ray containing a bright line of 365 nm at 1,000 mJ / cm 2 to form a latent image forming body (decoration). Film).

<Evaluation of decorative film>
[Decoration performance]
The decorative film obtained above was placed between polarizing plates arranged in crossed Nicols, and transmitted light was irradiated from the opposite direction to the observation side and observed visually. If a latent image is formed on the decorative film, when the decorative film is placed between the polarizing plates, the part masked at the time of exposure to “polarized UV irradiation B” (the part of the pattern printed on the OHP sheet) Is observed white and the other parts are observed black. In addition, the better the decorative performance of the decorative film, the greater the contrast ratio between the mask portion and other portions. When the contrast ratio between the mask portion and other portions is 500 or more, the decoration performance is “good (A)”, when the contrast ratio is 50 or more and less than 500, the decoration performance is “good (B)”, and the contrast ratio is 50. When the decorative performance was evaluated as “bad (C)”, the decorative performance of this decorative film was “good (A)”. The contrast ratio was measured using a spectral radiance meter “CS-2000A” manufactured by Konica Minolta.

[Adhesion]
Using an equally spaced spacer with a guide, the decorative film obtained above was cut with a cutter knife at 1 mm intervals to form 10 × 10 lattice patterns. Next, after the cellophane tape was brought into close contact with the lattice pattern, the cellophane tape was peeled off from the lattice pattern. The notches in the lattice pattern after the cellophane tape was peeled off were observed to evaluate the adhesion to the substrate. Adhesion “good (A)” when no separation was observed along the cut line or at the intersection of the lattice pattern, and although the separation was observed, the number of lattice eyes where separation occurred was the entire lattice pattern Adhesiveness “Yes (B)” when the number is less than 10% with respect to the number of dots, and adhesion when the number of grid eyes where peeling occurs is 10% or more with respect to the total number of grating patterns. The adhesiveness of this decorative film was “good (A)” as a result of evaluating the property “bad (C)”.

[Evaluation of heat and humidity resistance]
The decorative film obtained above was exposed to an environment of 60 ° C. and 45% RH for 24 hours. Thereafter, in the same manner as the above “adhesion”, the wet heat stability was evaluated by observing the notches in the lattice pattern after the lattice pattern was formed on the decorative film and the cellophane tape was peeled off. At this time, when no delamination is confirmed, the heat-and-moisture resistance is “good (A)”, and when the number of grids with peeling is less than 10% of the total number of grid patterns, When the stability “good (B)” was 10% or more and the heat stability was evaluated as “bad (C)”, the moisture and heat resistance of this decorative film was “good (A)”. .

[Examples 2 to 5 and Comparative Example 1]
<Preparation of polymer composition for forming latent image>
Except having used each component of the kind and compounding quantity which are shown in following Table 1, it operates similarly to preparation of a polymer composition (A-1), and each polymer composition (A-2)-(A-5). ) Was prepared.

In addition, the numerical value of the compounding quantity in Table 1 shows the compounding ratio (parts by weight) of each compound with respect to a total of 100 parts by weight of the polymer components used for the preparation of the polymer composition. In the polymer compositions (A-1) to (A-3) and (A-5), two types of polymers were used as the polymer component. In Table 1, abbreviations are as follows.
B-1: Tris (acetylacetonate) aluminum (aluminum chelate A (W), manufactured by Kawaken Fine Chemicals)
K-1: Tri (p-tolyl) silanol BA: n-butyl acetate IBA: isobutyl acetate MEK: methyl ethyl ketone PGMEA: propylene glycol monomethyl ether acetate EA: ethyl acetate EAA: ethyl acetoacetate EDM: diethylene glycol ethyl methyl ether CHN: cyclohexanone CPN : Cyclopentanone PGME: Propylene glycol monomethyl ether

<Manufacture and evaluation of decorative film>
A decorative film was produced in the same manner as in Example 1 using the latent image forming polymer composition shown in Table 2 below, and the decorative film was evaluated in the same manner as in Example 1. The results are shown in Table 2. In Example 5, the same polymer composition as in Example 1 was used, and a polymethyl methacrylate film was used as the substrate.

  As shown in Table 2, in Examples 1 to 5, the evaluation of the decoration performance, the adhesion to the base material, and the resistance to moist heat was all “A” or “B”. On the other hand, in the comparative example, the decorative performance and wet heat resistance stability evaluation was “C”, which was inferior to that of the example.

  DESCRIPTION OF SYMBOLS 10 ... Latent image formation body, 11 ... Base material, 12 ... Orientation layer, 13 ... Liquid crystal layer, 14 ... 1st polarizing plate, 15 ... 2nd polarizing plate, 16 ... Polarizing plate integrated latent image formation body, 17 ... Window Glass, 20 ... latent image forming body set

Claims (10)

  1. A latent image forming body in which a latent image is formed on at least one surface of a substrate,
    A polymer composition comprising a polymer [P] having at least one selected from the group consisting of a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane and having a photoalignment group A latent image forming body comprising: an alignment layer formed on the substrate by use; and a liquid crystal layer formed by applying and curing a polymerizable liquid crystal on the alignment layer.
  2.   The latent image forming body according to claim 1, wherein the photo-alignment group is a group containing a cinnamic acid structure.
  3.   The latent image forming body according to claim 1, wherein the polymer [P] is a polyorganosiloxane having a group containing a polymerizable carbon-carbon unsaturated bond and the photoalignable group.
  4. The polymer [P] is a polyorganosiloxane having the photo-alignment group,
    The said polymer composition contains polymer [Q] which is a polymer of the monomer which has a polymerizable carbon-carbon unsaturated bond, and does not have a photo-alignment group further. The latent image forming body according to any one of the above.
  5.   A latent image forming body set comprising the latent image forming body according to any one of claims 1 to 4 and a pair of polarizing plates.
  6. A method for producing a latent image forming body in which a latent image is formed on at least one surface of a substrate,
    A polymer composition comprising a polymer [P] having at least one selected from the group consisting of a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane and having a photoalignment group Applying on the substrate to form a coating film, irradiating the coating film with polarized radiation through a mask having a predetermined pattern, and polymerizing on the coating film after irradiation with the polarized radiation And a step of forming a liquid crystal layer by applying and curing a liquid crystal.
  7.   The latent image forming body according to claim 6, further comprising a step of irradiating the coating film with polarized radiation having a polarization direction different from that of the polarized radiation before the coating film is irradiated with the polarized radiation through the mask. Manufacturing method.
  8.   For forming a latent image, comprising a polymer [P] having at least one selected from the group consisting of a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane and having a photo-alignment group Polymer composition.
  9.   An image display method comprising a step of visualizing a latent image by arranging the latent image forming body according to any one of claims 1 to 4 between a pair of polarizing plates arranged in crossed Nicols.
  10.   A polymer composition comprising a polymer [P] having at least one selected from the group consisting of a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond and a polyorganosiloxane and having a photoalignment group A decorative laminate comprising: an alignment layer formed on a substrate using; and a liquid crystal layer formed by applying and curing a polymerizable liquid crystal on the alignment layer.
JP2015079262A 2015-04-08 2015-04-08 Latent image forming body, latent image forming body set, method for manufacturing latent image forming body, image display method and decorative laminate Pending JP2016200664A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998052077A1 (en) * 1997-05-09 1998-11-19 Rolic Ag Optical element
JP2009223001A (en) * 2008-03-17 2009-10-01 Fujifilm Corp Optical material patterned with optical axis direction and phase difference amount
JP2010221650A (en) * 2009-03-25 2010-10-07 Fujifilm Corp Anti-falsifying medium
JP2014026261A (en) * 2012-06-21 2014-02-06 Jsr Corp Liquid crystal aligning agent, liquid crystal aligned layer, retardation film, method for manufacturing retardation film, liquid crystal display element, and polymer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998052077A1 (en) * 1997-05-09 1998-11-19 Rolic Ag Optical element
JP2001525080A (en) * 1997-05-09 2001-12-04 ロリク アーゲー Optical element
JP2009223001A (en) * 2008-03-17 2009-10-01 Fujifilm Corp Optical material patterned with optical axis direction and phase difference amount
JP2010221650A (en) * 2009-03-25 2010-10-07 Fujifilm Corp Anti-falsifying medium
JP2014026261A (en) * 2012-06-21 2014-02-06 Jsr Corp Liquid crystal aligning agent, liquid crystal aligned layer, retardation film, method for manufacturing retardation film, liquid crystal display element, and polymer

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