JP2006231791A - Pattern forming method and recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new pattern forming method, by which a three-dimensional pattern with arbitrary size can be formed on a recording material having a recording layer including a diazonium salt compound, and the recording layer used for it. <P>SOLUTION: This pattern forming method is employed for forming bump-like matters in an exposed region of the recording material having the recording layer including the diazonium salt compound on a support through a pattern-wise irradiation with laser light or with a light-emitting diode. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a pattern forming method and a recording material used therefor. More specifically, the present invention relates to a novel pattern forming method capable of forming a three-dimensional pattern with an arbitrary size on a recording material having a recording layer containing a diazonium salt compound, and a recording material used therefor.

The diazonium salt compound generates nitrogen gas by photolysis or thermal decomposition. A culver system is one that utilizes such properties of diazonium salt compounds.
The Culver system is a method for forming a fine bubble image by expanding a nitrogen gas generated by heating a film in which a photosensitive diazonium salt compound is dispersed in a resin binder after exposure.
A bubble photo to which a culver system is applied was developed by Kalver and is known under the name “Kalver Film”. The culver system is disclosed in various documents (for example, see Non-Patent Document 1 and Patent Documents 1 to 6).
Such a bubble photograph uses a phenomenon in which the fine bubbles generated in the resin binder scatter light to change the permeability of the film, but the film is expanded by the generated bubbles to form protrusions. It won't swell.
Japanese Patent Laid-Open No. 50-11017 JP-A-53-16622 Japanese Patent Laid-Open No. 53-110519 JP-A-53-112730 JP 54-37724 A Japanese Patent Laid-Open No. 57-42041 (Japan) Photographic Society, “Basics of Photographic Engineering (Non-Silver Photography)”, Corona, 1982, p. 470-p. 476

  An object of the present invention is to provide a novel pattern forming method capable of forming a three-dimensional pattern with an arbitrary size on a recording material having a recording layer containing a diazonium salt compound, and a recording material used therefor.

In the course of studying a recording material provided with a recording layer containing a diazonium salt compound, the present inventors exposed the recording layer with a light source having a high illuminance such as a laser beam. I discovered the phenomenon that a shape was formed. The method for generating the protrusion-shaped object in this way is not performed in conventional bubble photography, and it is completely unknown that the size of the protrusion-shaped object can be arbitrarily changed according to the exposure amount. Thus, the present inventors have completed the present invention.
That is, the means for solving the problems are as follows.

  <1> A pattern characterized in that a recording material having a recording layer containing a diazonium salt compound on a support is irradiated with laser light or a light emitting diode in a pattern to form a protrusion-shaped object in an exposed region It is a forming method.

<2> energy intensity of the light irradiation, a pattern forming method according to <1>, wherein the range of ^{1J / cm 2 ~100J / cm 2} .

<3> The pattern forming method according to <1> or <2>, wherein the recording layer has an oxygen permeability coefficient of 10 ml · 25 μm / m ² · 24 h · atm or less.

<4> The above <1>, further comprising a gas barrier layer as an upper layer and / or a lower layer of the recording layer, wherein the gas barrier layer has an oxygen permeability coefficient of 5 ml · 25 μm / m ² · 24 h · atm or less. It is a pattern formation method of any one of>-<3>.

  <5> The recording layer according to any one of <1> to <4>, wherein the recording layer further contains a photothermal conversion substance, and the maximum absorption wavelength of the photothermal conversion substance is in a range of 330 nm to 1300 nm. It is a pattern formation method of description.

  <6> The pattern forming method according to any one of <1> to <5>, wherein the diazonium salt compound is encapsulated in a microcapsule.

<7> A recording material having a recording layer containing a diazonium salt compound on a support, wherein the recording layer has an oxygen transmission coefficient of 10 ml · 25 μm / m ² · 24 h · atm or less. .

<8> The above-mentioned <7, wherein a gas barrier layer is further provided as an upper layer and / or a lower layer of the recording layer, and the oxygen permeability coefficient of the gas barrier layer is 5 ml · 25 μm / m ² · 24 h · atm or less. >.

  <9> The recording material according to <7> or <8>, wherein the recording layer further contains a photothermal conversion substance, and the maximum absorption wavelength of the photothermal conversion substance is in the range of 330 nm to 1300 nm. is there.

  <10> The recording material according to any one of <7> to <9>, wherein the diazonium salt compound is encapsulated in a microcapsule.

<11> A recording layer containing a diazonium salt compound is provided on a support, and the recording layer has an oxygen transmission coefficient of 10 ml · 25 μm / m ² · 24 h · atm or less, and is patterned by a laser beam or a light emitting diode. The recording material is characterized in that a projection-shaped object is formed in the exposed region by irradiating light.

  Here, in the present invention, the “projection shape object” means a raised portion formed in the exposure region.

In the present invention, as described in detail later, a recording layer containing a diazonium salt compound is irradiated with a laser beam or a light source with a high illuminance of a light-emitting diode and irradiated with a narrow beam to instantaneously heat the recording layer. It is necessary to generate nitrogen gas, and nitrogen gas is rapidly generated by such light irradiation, resulting in the formation of a protrusion-shaped object. That is, in the present invention, in order to form a protrusion-shaped object, light and heat need to act instantaneously.
On the other hand, the Culver system (bubble photo) performs light irradiation and then heat development. Also, the applied light source need not have high illuminance. Further, in the culver system, only the inside of the recording layer becomes cloudy due to bubbles, and the surface of the recording material is planar, and a three-dimensional pattern is not formed.
It can be said that the pattern forming method of the present invention is greatly different from the culver system from the above points.

  Further, the recording material of the present invention has a gas permeability (for example, oxygen permeability) range of a recording layer containing a diazonium salt and a gas barrier layer provided as necessary, so that laser light or light emission can be obtained. A protrusion-shaped object can be formed by high-illuminance exposure using a diode. In this respect, it can be said that the recording material of the present invention is greatly different in configuration from the above-described culver film.

According to the pattern forming method of the present invention, a recording material provided with a recording layer containing a diazonium salt compound on a support is irradiated with a laser beam or a light emitting diode with high illuminance in a pattern. A three-dimensional pattern in which a protrusion-shaped object having an arbitrary size is formed in the exposure region can be formed.
In addition, according to the recording material of the present invention, it is possible to provide a pann forming material capable of forming a protrusion-shaped object having an arbitrary size by exposure with high illuminance using a laser beam or a light emitting diode.

Hereinafter, the present invention will be described in detail.
In the pattern forming method of the present invention, a recording material having a recording layer containing a diazonium salt compound on a support (recording material of the present invention) is irradiated with a laser beam or a light emitting diode in a pattern to form an exposure area. A protrusion-shaped object is formed.
The first aspect of the recording material of the present invention has a recording layer containing a diazonium salt compound on a support, and the oxygen permeability coefficient of the recording layer is 10 ml · 25 μm / m ² · 24 h · atm or less. It is characterized by that.
The second aspect of the recording material of the present invention has a recording layer containing a diazonium salt compound on a support, and the oxygen permeability coefficient of the recording layer is 10 ml · 25 μm / m ² · 24 h · atm or less. A projection-shaped object is formed in the exposure region by irradiating light in a pattern with a laser beam or a light emitting diode.

[Recording material]
The recording material of the present invention will be described.
The recording material in the present invention preferably has a recording layer containing a diazonium salt compound on a support, and further has a gas barrier layer as an upper layer and / or a lower layer of the recording layer. Moreover, you may have other layers, such as a backcoat layer, as needed.

  The recording layer in the present invention needs to contain a diazonium salt compound. The recording layer preferably further contains a photothermal conversion substance, and may contain other components as necessary. Hereinafter, each component constituting the recording layer will be described.

<Diazonium salt compound>
The diazonium salt compound in the present invention is preferably a compound represented by the following general formula (I).

In the general formula (I), Ar represents a substitutable aromatic ring, and X ⁻ represents a counter anion.
Ar may have a substituent Y, and as Y, various electron donating groups and electron withdrawing groups are preferable. Ar may have a plurality of substituents Y, and the substituents Y in this case may be the same or different.

Specifically, the substituent Y possessed by Ar is preferably, for example, a substituted amino group, an alkylthio group, an arylthio group, an alkoxy group, or an aryloxy group.
When Y represents a substituted amino group, the substituted amino group includes an alkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, an arylamino group having 6 to 10 carbon atoms, and a carbon number. A 7-20 N-alkyl-N-arylamino group and a C2-C20 acylamino group are preferable, and these groups may further have one or more substituents. Moreover, substituents, such as the said alkyl group, may couple | bond together and a cyclic amino group may be formed.
When Y represents an alkylthio group, an alkylthio group having 1 to 18 carbon atoms is preferable. When Y represents an arylthio group, an arylthio group having 6 to 10 carbon atoms is preferable, and when it represents an alkoxy group, an alkoxy group having 1 to 18 carbon atoms is preferable. When a group is preferable and represents an aryloxy group, an aryloxy group having 6 to 10 carbon atoms is preferable, and these groups may further have one or more substituents.

  Examples of the alkyl group and aryl group in the substituted amino group, alkylthio group, arylthio group, alkoxy group, or aryloxy group represented by Y include the following groups.

Furthermore, as said Y, a hydrogen atom, a C1-C8 alkyl group, a chlorine atom, a fluorine atom, a C1-C15 alkoxy group, a C1-C12 alkylsulfonyl group, a C6-C18 An arylsulfonyl group, an acyl group having 1 to 18 carbon atoms, an alkoxycarbonyl group having 1 to 18 carbon atoms, a sulfonamide group having 1 to 12 carbon atoms, a carbonamido group having 2 to 13 carbon atoms, a nitro group, and a cyano group. preferable.
The alkyl group and alkylsulfonyl group may be branched and may be substituted with a halogen atom, an alkoxy group, an aryloxy group, a phenyl group, an alkoxycarbonyl group, an acyloxy group, or a carbamoyl group.
The arylsulfonyl group may be substituted with a halogen atom, an alkyl group, or an alkoxy group.

  Specific examples of Y include those shown below.

  When Y represents a substituted amino group, examples of the cyclic amino group formed by bonding the substituents include the following.

In the general formula (I), as the counter anion represented by X ⁻ , for example, a perfluoroalkylcarboxylic acid having 1 to 20 carbon atoms (for example, perfluorooctanoic acid, perfluorodecanoic acid, perfluorododecanoic acid), C1-C20 perfluoroalkylsulfonic acid (for example, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, perfluorohexadecanesulfonic acid), C7-50 aromatic carboxylic acid (for example, 4,4- Di-t-butylsalicylic acid, 4-t-octyloxybenzoic acid, 2-n-octyloxybenzoic acid, 4-t-hexadecylbenzoic acid, 2,4-bis-n-octadecyloxybenzoic acid, 4-n- Decylnaphthoic acid), aromatic sulfonic acids having 6 to 50 carbon atoms (for example, 1,5-naphthalenedisulfonic acid, 4-t Octyloxy benzenesulfonic acid, 4-n-dodecylbenzenesulfonic acid), 4,5-di -t- butyl-2-naphthoic acid, Tetorafu' boric acid, tetraphenyl borate, etc. hexafluorophosphate and the like. Among them, perfluoroalkylcarboxylic acids having 6 to 16 carbon atoms, aromatic carboxylic acids having 10 to 40 carbon atoms, aromatic sulfonic acids having 10 to 40 carbon atoms, tetrafluoroboric acid, tetraphenylboric acid, hexafluorophosphoric acid Etc. are preferable.

  Specific examples [(1) to (34)] of the diazonium salt compound suitably used in the present invention are listed below, but the present invention is not limited thereto.

The coating amount of the diazonium salt compound in the recording layer is preferably from ^{0.05mmol / m 2 ~10mmol / m 2} , 0.1mmol / m 2 ~3mmol / m 2 is particularly preferred.

  The diazonium salt compound preferably has a maximum absorption wavelength in the range of 330 to 1300 nm when the recording layer does not contain a dye described later.

-Microencapsulation-
In the present invention, it is preferable to encapsulate the diazonium salt compound in a microcapsule for the purpose of improving the preservability before use of the recording material. The method for forming the microcapsules can be appropriately selected from known methods.
The polymer substance forming the capsule wall of the microcapsule has a glass transition temperature of 60 to 200 ° C. in particular because it is necessary to have a property of being impermeable at normal temperature and permeable when heated. Are preferable, and examples thereof include polyurethane, polyurea, polyamide, polyester, urea / formaldehyde resin, melamine resin, polystyrene, styrene / methacrylate copolymer, styrene / acrylate copolymer, and a mixed system thereof.

  Specifically, an interfacial polymerization method or an internal polymerization method is suitable as the microcapsule formation method. Details of the capsule forming method and specific examples of the reactant are described in the specifications of US Pat. Nos. 3,726,804 and 3,796,669. For example, when polyurea or polyurethane is used as the capsule wall material, polyisocyanate and a second substance that reacts therewith to form a capsule wall (for example, polyol or polyamine) are mixed in an aqueous medium or an oily medium to be encapsulated. Then, these are emulsified and dispersed in water and then heated to cause a polymer formation reaction at the oil droplet interface to form a microcapsule wall. Polyurea can also be produced when the addition of the second substance is omitted.

  In the present invention, it is preferable that the polymer material forming the capsule wall of the microcapsule contains polyurethane and / or polyurea as components because of excellent manufacturing suitability and thermal response sensitivity.

Next, a method for producing a diazonium salt compound-encapsulating microcapsule (polyurea / polyurethane wall) will be described.
First, the diazonium salt compound is dissolved or dispersed in a hydrophobic organic solvent that becomes the core of the capsule to prepare an oil phase that becomes the core of the microcapsule. At this time, polyisocyanate is further added as a wall material.

  In the preparation of the oil phase, the hydrophobic organic solvent used for forming the core of the microcapsule by dissolving and dispersing the diazonium salt compound is preferably an organic solvent having a boiling point of 100 to 300 ° C., for example, alkylnaphthalene, alkyldiphenyl. Ethane, alkyldiphenylmethane, alkylbiphenyl, alkylterphenyl, chlorinated paraffin, phosphate ester, maleate ester, adipate ester, phthalate ester, benzoate ester, carbonate ester, ether, sulfate ester And sulfonic acid esters. You may use these in mixture of 2 or more types.

When the solubility of the diazonium salt compound to be encapsulated in the organic solvent is inferior, a low-boiling solvent having a high solubility of the diazonium salt compound to be used can be supplementarily used together. For example, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride, tetrahydrofuran, acetonitrile, acetone and the like can be mentioned.
For this reason, the diazonium salt compound preferably has an appropriate solubility in a high-boiling hydrophobic organic solvent and a low-boiling solvent, and specifically has a solubility of 5% or more in the solvent. Is preferred. The solubility in water is preferably 1% or less.

On the other hand, an aqueous solution in which a water-soluble polymer is dissolved is used for the aqueous phase to be used, and after the oil phase is added thereto, emulsification and dispersion are performed by means of a homogenizer or the like. It facilitates and acts as a dispersion medium for stabilizing the emulsified and dispersed aqueous solution. Here, in order to more uniformly emulsify and disperse and stabilize, a surfactant may be added to at least one of the oil phase and the aqueous phase. As the surfactant, a known emulsifying surfactant can be used.
As addition amount in the case of adding surfactant, 0.1-5 mass% is preferable with respect to the oil phase mass, and 0.5-2 mass% is more preferable.

  The water-soluble polymer used in the water-soluble polymer aqueous solution in which the prepared oil phase is dispersed is preferably a water-soluble polymer having a solubility in water of 5% or more at the temperature to be emulsified, such as polyvinyl alcohol and its modification. , Polyacrylamide and derivatives thereof, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyvinylpyrrolidone, ethylene- Acrylic acid copolymer, vinyl acetate-acrylic acid copolymer, carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivative, arabic gum, sodium alginate and the like can be mentioned.

  It is preferable that the water-soluble polymer has no or low reactivity with an isocyanate compound. For example, a polymer having a reactive amino group in a molecular chain such as gelatin reacts by being modified in advance. It is preferable to eliminate the property.

The polyvalent isocyanate compound is preferably a compound having a trifunctional or higher functional isocyanate group, but may be a bifunctional isocyanate compound. Specifically, xylene diisocyanate and hydrogenated products thereof, hexamethylene diisocyanate, tolylene diisocyanate and hydrogenated products thereof, and diisocyanates such as isophorone diisocyanate are used as main raw materials, and these dimers or trimers (burette or isocyanate). Nurate), other polyfunctional adducts such as trimethylolpropane polyols and bifunctional isocyanates such as xylylene diisocyanate, adducts of trimethylolpropane polyols and xylylene diisocyanate and other bifunctional isocyanates Examples thereof include a compound in which a high molecular weight compound such as polyether having active hydrogen such as polyethylene oxide is introduced, and a formalin condensate of benzene isocyanate.
The compounds described in JP-A-62-212190, JP-A-4-26189, JP-A-5-317694, and Japanese Patent Application No. 8-268721 are preferable.

The amount of the polyvalent isocyanate used is determined so that the average particle size of the microcapsules is 0.3 to 12 μm and the wall thickness is 0.01 to 0.3 μm. The dispersed particle diameter is generally about 0.2 to 10 μm.
In an emulsified dispersion in which an oil phase is added to an aqueous phase, a polyisocyanate polymerization reaction occurs at the interface between the oil phase and the aqueous phase to form a polyurea wall.

If a polyol and / or polyamine is further added to the hydrophobic solvent in the aqueous phase or the oil phase, it can react with the polyvalent isocyanate and be used as one of the components of the microcapsule wall. In the above reaction, it is preferable to keep the reaction temperature high or to add an appropriate polymerization catalyst from the viewpoint of increasing the reaction rate.
Specific examples of these polyols or polyamines include propylene glycol, glycerin, trimethylolpropane, triethanolamine, sorbitol, hexamethylenediamine and the like. When a polyol is added, a polyurethane wall is formed.
The polyisocyanate, polyol, reaction catalyst, polyamine for forming a part of the wall agent, etc. are well-known in the book (Keiji Iwata, Polyurethane Handbook, Nikkan Kogyo Shimbun (1987)).

  The emulsification can be carried out by appropriately selecting from known emulsifiers such as a homogenizer, a manton gorey, an ultrasonic disperser, a dissolver, and a kedy mill. After emulsification, the emulsion is heated to 30 to 70 ° C. in order to promote the capsule wall formation reaction. Further, during the reaction, in order to prevent the capsules from aggregating, it is necessary to add water to reduce the collision probability between the capsules or to perform sufficient stirring.

  Further, a dispersion for preventing aggregation may be added again during the reaction. As the polymerization reaction proceeds, the generation of carbon dioxide gas is observed, and its end can be regarded as the approximate end point of the capsule wall formation reaction. Usually, the target diazonium salt compound-containing microcapsules can be obtained by reacting for several hours.

<Photothermal conversion material>
In the present invention, a photothermal conversion substance may be used. As the photothermal conversion substance, any substance can be used as long as it can absorb ultraviolet light, visible light, infrared light, white light, and the like and convert it into heat. For example, carbon black, carbon graphite, organic pigment, iron powder, Examples thereof include graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide. Particularly preferred in the present invention are dyes, pigments or metal fine particles having a maximum absorption wavelength in the range of 330 nm to 1300 nm.

As the dye, commercially available dyes and known dyes described in literature (for example, “Dye Handbook” edited by Organic Synthetic Chemical Society, published in 1970) can be used. Specific examples include azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, and metal thiolate complexes.
Examples of preferable dyes include cyanine dyes described in, for example, 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-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58- Naphthoquinone dyes described in JP-A-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc. Examples include squarylium dyes described in JP-A-58-112792, and cyanine dyes described in British Patent 434,875.

  Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used. Further, substituted arylbenzo (thio) pyrylium salts described in US Pat. No. 3,881,924, and trimethine salt described in JP-A-57-142645 (US Pat. No. 4,327,169). Apyrylium salt, JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, JP-A-59-84248, JP-A-59-84249, JP-A-59-146063, JP-A-59- Pyryllium compounds described in Japanese Patent No. 146061, cyanine dyes described in JP-A-59-216146, pentamethine thiopyrylium salt described in US Pat. No. 4,283,475, etc. The pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. Examples of other preferable dyes include near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

  Examples of pigments that can be used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by the Japan Pigment Technical Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, 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 , Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Among these pigments, carbon black is preferable.

  These photothermal conversion substances are 0.01 to 50% by mass, preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 10% by mass, particularly preferably pigments, in the case of dyes. Can be used in a proportion of 3.1 to 10% by mass. If the amount of the photothermal conversion substance added is less than 0.01% by mass, the sensitivity may be low, and if it exceeds 50% by mass, the film strength of the photothermal conversion substance-containing layer may be weak. Moreover, the photothermal conversion substance may be used alone or in combination of two or more.

The photothermal conversion substance in the present invention is preferably an infrared absorbing substance from the viewpoint of efficiently causing photothermal conversion. The infrared absorbing substance is not particularly limited as long as it is a substance that absorbs infrared rays, and may be an inorganic compound or an organic compound.
Among the inorganic compounds that are infrared absorbing materials, carbon black is preferable.
Among the organic compounds that are infrared absorbing substances, infrared absorbing dyed pigments are preferable. Here, some infrared absorbing dyes form aggregates and insolubles and are used as pigments, and others are used as dyes by being dissolved in an appropriate solvent. Any of these forms can be used, and hereinafter, such dyes are collectively referred to as infrared absorbing dye pigments.
The infrared absorbing dye / pigment can be used without particular limitation, and among them, the cationic dye / pigment, complex salt-forming dye / pigment, and quinone neutral dye / pigment described in detail below are preferable.

  The infrared absorbing dye / pigment may be added to any of the binder, the microcapsule oil, and the microcapsule wall. When it is added to the binder, it is preferable to use a water-soluble one, and when it is added to the binder, it is preferable to use an oil-soluble one.

  The coating amount of the infrared absorbing dye / pigment is determined by the absorbance of the wavelength having the highest absorbance in the infrared region in the recording material produced. As this light absorbency, the range of 0.1-4.0 is preferable and the range of 0.2-2.5 is more preferable.

Below, the infrared absorption dyeing pigment which can be used in this invention is demonstrated in detail.
(1) Cationic dye / pigment Cationic dye / pigment is a dye represented by the following general formula (2).
D ₁ ⁺ [X ₁ ^{-1 / m} ] _m General formula (2)
However, the D ₁ ⁺ is a cationic dye mother nucleus, X ₁ ^- a counter anion, m represents an integer of 1-4.

As D ₁ ⁺ which is a cationic dye mother nucleus in the general formula (2), polymethine (including cyanine), azurenium, pyrylium, thiopyrylium, squarylium, triarylmethane, immonium, diimmonium and the like are preferable. X ₁ ^{-1 / m} is not particularly limited as long as it can form a counter anion.
Examples of the cationic dye include the following specific dyes.

(2) Complex salt-forming dye / pigment The complex salt-forming dye / pigment is preferably a thiol nickel complex salt, a phthalocyanine dye or a naphthalocyanine dye, and specific dyes can be mentioned as follows.

(3) Quinone-based neutral dye / pigment As the quinone-based neutral dye / pigment, naphthoquinone dyes and anthraquinone dyes are preferable, and specific dyes such as the following can be exemplified.

Of the infrared absorbing dyes and pigments used in the present invention, those having an active group that reacts with the microcapsule wall material when the microcapsules are formed are also effective.
Specific examples of the active group include an isocyanate group, a hydroxy group, a mercapto group, and an amino group. Particularly, an isocyanate group and a hydroxy group are preferable, and a cationic dye / pigment having an active group as described below, Complex salt-forming dyes and quinone neutral dyes are preferred.
(1) -1 Cationic dye / pigment Cationic dye / pigment is a dye represented by the following general formula (2).
D ₁ ⁺ [X ₁ ^{-1 / m} ] _m (2)
However, the D ₁ ⁺ is a cationic dye mother nucleus, X ₁ ^- a counter anion, m represents an integer of 1-4.

As D ₁ ⁺ which is a cationic dye mother nucleus in the general formula (2), polymethine (including cyanine), azurenium, pyrylium, thiopyrylium, squarylium, triarylmethane, immonium, diimmonium and the like are preferable. X ₁ ^{-1 / m} is not particularly limited as long as it can form a counter anion, and the active group that reacts with the microcapsule wall may be either D ₁ ⁺ or X ₁ ^{-1 / m} .

  Examples of the cationic dye having an active group include the following specific dyes.

(2) -1 Complex salt-forming dye / pigment As the complex salt-forming dye / pigment having an active group, a thiol nickel complex salt, a phthalocyanine dye, and a naphthalocyanine dye are preferable, and the following specific dyes can be exemplified.

(3) -1 Quinone-based neutral dye / pigment Examples of the quinone-based neutral dye / pigment having an active group are preferably naphthoquinone dyes and anthraquinone dyes, and specific dyes such as the following can be exemplified.

<Others>
In the present invention, it is preferable to further contain nitrocellulose in the recording layer for the purpose of improving the photothermal conversion effect. Nitrocellulose is decomposed by the heat generated when the photothermal conversion substance absorbs near-infrared laser light, efficiently decomposes the diazonium salt, or contributes to the formation of protrusions by generating gas from the nitrocellulose itself. be able to.

  The nitrocellulose is produced by converting a natural cellulose purified by a conventional method into a nitrate with a mixed acid, and introducing some or all of the nitro groups into the three hydroxyl groups present in the glucopyranose ring, which is a constituent unit of cellulose. Obtainable. The nitrification degree of the nitrocellulose is preferably 2 to 13, more preferably 3 to 8, and still more preferably 5 to 6. Here, the nitrification degree represents mass% of nitrogen atoms in nitrocellulose. If the degree of nitrification is extremely high, the effect of promoting ablation is enhanced, so that a protrusion-shaped object cannot be formed. Also, nitrocellulose becomes explosive, and there is a danger in handling nitrocellulose when producing a recording material. When the degree of nitrification is extremely low, the effect of promoting the formation of protrusion-shaped objects cannot be obtained sufficiently.

In addition, the degree of polymerization of nitrocellulose is preferably 100 to 1000, more preferably 150 to 1000, from the viewpoint of the formation of protrusions (that is, ablation is difficult to occur).
The content of nitrocellulose in the recording layer is preferably 0 to 80% by mass and more preferably 5 to 20% by mass with respect to the total solid component of the recording layer.

  In addition to the above-described diazonium salt compound and photothermal conversion substance, the recording layer can contain other components as required.

  For the recording layer, for example, a microcapsule containing a diazonium salt compound and a coating solution containing other components added as necessary are prepared, and the coating solution is coated on a support such as paper or a synthetic resin film. It can be applied by drying.

The coating method can be appropriately selected from known coating methods, and examples thereof include bar coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, and curtain coating.
The dry coating amount of the recording layer after coating and drying is preferably 2.5 to 30 g / m ² .
The film thickness of the recording layer is preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm.

The recording layer needs to have a gas barrier property from the viewpoint of the formation of the protrusion-shaped product. Specifically, the oxygen permeability coefficient is preferably 10 ml · 25 μm / m ² · 24 h · atm or less, and particularly preferably 5 ml · 25 μm / m ² · 24 h · atm or less. The lower limit of the oxygen transmission coefficient of the recording layer is not particularly limited, but is about 2.5 × 10 ⁻⁶ ml · 25 μm / m ² · 24 h · atm.

In the present invention, the gas barrier property in the recording layer and the gas barrier layer described later refers to a property of suppressing permeation of nitrogen gas generated when the diazonium salt compound is decomposed. Therefore, the gas barrier property is expressed by the permeability coefficient of nitrogen gas, but since the molecular size is almost the same, it is expressed here by the oxygen permeability coefficient.
The oxygen permeability coefficient in the present invention refers to a measured value obtained under the following conditions, and the oxygen permeability coefficient in the present specification is obtained by this measurement method.
The measurement was performed after the recording layer or gas barrier layer coating liquid was applied on a PET support with a bar coater, and the film peeled after drying was conditioned for 24 hours. The oxygen transmission coefficient per 25 μm is obtained.
-Measurement conditions-
Test method: JIS K7126 B method (isobaric method)
Testing machine: Mocon oxygen permeability testing machine OX-TRAN2 / 10 type Testing temperature: 23 ° C
Test humidity: 60% RH
Test gas: 100% oxygen,
Transmission area: 50 cm ²

In the present invention, it is preferable to further have a gas barrier layer as an upper layer and / or a lower layer of the recording layer.
When a gas barrier layer is provided as an upper layer and / or a lower layer of the recording layer, the oxygen permeability coefficient of the gas barrier layer is preferably 5 ml · 25 μm / m ² · 24 h · atm or less, particularly 1 ml · 25 μm / m. It is preferably ² · 24 h · atm or less. The lower limit of the oxygen permeability coefficient of the gas barrier layer is not particularly limited, but is about 2.5 × 10 ⁻⁶ ml · 25 μm / m ² · 24 h · atm. The thickness of the gas barrier layer is preferably 0.2 μm to 5 μm, particularly preferably 0.5 μm to 3 μm.
As a coating method, the same method as that for the recording layer can be applied.

In order for the recording layer and the gas barrier layer to satisfy the oxygen permeability coefficient as described above, polyvinyl alcohol (including modified products), ethylene vinyl alcohol copolymer, polyvinylidene chloride, mica-containing gelatin, and the like are preferably included. . From the viewpoint of handleability, it is particularly preferable to include polyvinyl alcohol. When both the recording layer and the gas barrier layer are provided, these may be included in both layers, or may be included in only one layer (for example, only the gas barrier layer).
The gas barrier layer provided as the upper layer and / or lower layer of the recording layer preferably contains an ethylene vinyl alcohol copolymer (EVOH) and mica-containing gelatin.

In addition to the above components, a binder, a pigment, or the like may be mixed in the recording layer or cas barrier layer.
The binder can be appropriately selected from known water-soluble polymer compounds and latexes.
Examples of the water-soluble polymer compound include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, starch derivatives, casein, gum arabic, gelatin, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, Examples thereof include polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, epichlorohydrin-modified polyamide, isobutylene-maleic salicylic anhydride copolymer, polyacrylic acid, polyacrylic acid amide and the like, and modified products thereof.

Examples of the latex include styrene-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion.
Of these, hydroxyethyl cellulose, starch derivatives, gelatin, polyvinyl alcohol derivatives, polyacrylic acid amide derivatives and the like are preferable.

  Examples of the pigment include any organic and inorganic pigments such as kaolin, calcined kaolin, talc, wax stone, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, lithopone, amorphous. Silica, colloidal silica, calcined stone, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, microballoon, urea-formalin filler, polyester particles, cellulose filler and the like.

  As the support that can be used in the present invention, any of the paper supports used for ordinary pressure-sensitive paper, thermal paper, dry or wet diazo copy paper, etc. can be used, acidic paper, neutral paper, Coated paper, plastic film laminated paper, synthetic paper, plastic films such as polyethylene terephthalate and polyethylene naphthalate, and glass substrates can be used.

  On the support, a back coat layer may be provided for the purpose of correcting the curl balance or improving the chemical resistance from the back surface. The back coat layer can be provided in the same manner as the protective layer.

[Pattern formation]
The pattern formation by the pattern formation method of this invention is demonstrated. In the present invention, a three-dimensional pattern is formed by irradiating the above-described recording material with a laser beam or a light emitting diode in a pattern to form a protrusion-shaped object in the exposure region.

The mechanism of pattern formation in the present invention will be described in detail by taking as an example the case where a recording material containing a diazonium salt compound and an infrared absorbing substance is used for the recording layer.
Pattern formation in the recording layer containing the diazonium salt compound and the infrared absorbing material is performed by irradiating the infrared absorbing material in an image-like manner with a laser beam or the like that excites the infrared absorbing material. The infrared absorbing material absorbs laser light, and the light energy is converted into thermal energy.
Due to this thermal energy, the field where the diazonium salt and the diazonium salt are present is rapidly heated. The heated diazonium salt undergoes normal thermal decomposition and releases nitrogen gas. At the same time, the heated film becomes soft and expands with the generated nitrogen gas.
As a result, a projecting bubble pattern (projection-shaped object) is formed. The conditions for forming the protruding bubble pattern are not clear, but the upper and lower films (gas barrier layer, etc.) of the recording layer and the hardness (viscoelasticity) of the support are involved and soft (viscous) It is considered that a nitrogen gas escapes in the direction of greater elasticity, thereby forming a protruding bubble pattern.

When the recording layer contains a photothermal conversion material other than the infrared absorbing material, a visible light laser, a UV laser, or a light emitting diode corresponding to the material can be used. When no photothermal conversion substance is used, a laser or light emitting diode corresponding to the wavelength of the diazonium salt can be used.
The oscillation wavelength of the laser light is preferably in the infrared region of 700 nm to 1300 nm. Specific examples include a helium-neon laser, an argon laser, a carbon dioxide gas laser, a YAG laser, a semiconductor laser, and those obtained by converting them into a half wavelength by SHG.

In the present invention, from the viewpoint of pattern formability, the energy intensity at the time of light irradiation is preferably in the range of ^{1J / cm 2 ~100J / cm 2} , in ^{particular, 1J / cm 2 ~30J / cm} 2 It is preferable that it is the range of these.

The size and shape of the protrusion-shaped object formed in the present invention can be arbitrarily controlled by adjusting the energy intensity of irradiated light, the beam diameter at the time of irradiation, and the like. Usually, the thing about 0.1-20 micrometers in height can be formed.
Also, the shape of the protrusion-shaped object can be any shape according to the purpose, such as a dot shape, a linear shape (such as a saddle shape), a planar shape, or the like.
The protrusion-shaped object formed by the present invention can be easily confirmed by observing the surface or cross section of the recording material with a microscope.

The recording material used in the present invention can be fixed. Fixing means that the diazonium salt is photodecomposed and loses its ability to generate nitrogen gas. At the time of fixing, it is necessary to perform light irradiation while suppressing the exposure energy per unit area so that the nitrogen gas generated by the decomposition of the diazonium salt does not form a protrusion-shaped object.
As a light source used for fixing, a fluorescent lamp, a high-pressure mercury lamp, a xenon lamp, and a light emitting diode are preferable. The energy intensity at the time of light irradiation of these light sources is preferably less than 1 J / cm ² , and particularly preferably less than 300 mJ / cm ² .

  Examples are shown below, but the present invention is not limited thereto. The following “parts” or “%” mean “parts by mass” or “% by mass”, respectively, unless otherwise specified.

[Example 1]
<Preparation of phthalated gelatin solution>
Phthalated gelatin (trade name: MGP gelatin, manufactured by Nippi Collagen Co., Ltd.) 32 parts, 1,2-benzothiazolin-3-one (3.5% methanol solution, manufactured by Daito Chemical Industry Co., Ltd.) 0.9143 Part and 367.1 parts of ion-exchanged water were mixed and dissolved at 40 ° C. to obtain a phthalated gelatin aqueous solution.

<Preparation of alkali-treated gelatin solution>
25.5 parts of alkali-treated low ion gelatin (trade name; # 750 gelatin, manufactured by Nitta Gelatin Co., Ltd.), 1,2-benzothiazolin-3-one (3.5% methanol solution, Daito Chemical Industry Co., Ltd.) )) 0.7286 parts, calcium hydroxide 0.153 parts, and ion-exchanged water 143.6 parts were mixed and dissolved at 50 ° C. to obtain an aqueous gelatin solution for preparing an emulsion.

(1) Preparation of recording layer coating solution <Preparation of diazonium salt compound-encapsulated microcapsule solution (c)>
To 16.1 parts of ethyl acetate, 4.4 parts of a diazonium salt compound (Exemplary Compound (17)), 4.8 parts of monoisopropylbiphenyl, and 4.8 parts of diphenyl phthalate are added and heated to 40 ° C. uniformly. Dissolved. A mixture of xylylene diisocyanate / trimethylolpropane adduct and xylylene diisocyanate / bisphenol A adduct as a capsule wall material (trade name; Takenate D119N (50 mass% ethyl acetate solution), Takeda Pharmaceutical Co., Ltd.) 8.6 parts was added and stirred uniformly to obtain a mixture (I).

  Separately, 16.3 parts of ion-exchanged water and 0.34 part of Scarph AG-8 (50% by mass) manufactured by Nippon Seika Co., Ltd. were added to 58.6 parts of the phthalated gelatin aqueous solution to obtain a mixture (II). It was.

The mixed solution (I) was added to the mixed solution (II), and the mixture was emulsified and dispersed at 40 ° C. using a homogenizer (manufactured by Nippon Seiki Seisakusho). After adding 20 parts of water to the obtained emulsion and homogenizing it, the mixture was stirred at 40 ° C. for 3 hours while removing ethyl acetate. Thereafter, 4.1 parts of ion exchange resin Amberlite IRA68 (manufactured by Organo Corp.) and 8.2 parts of Amberlite IRC50 (manufactured by Organo Corp.) were added and further stirred for 1 hour. Thereafter, the ion exchange resin was removed by filtration, and the concentration was adjusted so that the solid content concentration of the capsule liquid was 20.0% to obtain a diazonium salt compound-encapsulating microcapsule liquid (c). The obtained microcapsules had a median diameter of 0.36 μm as a result of particle size measurement (measured by LA-700, manufactured by Horiba, Ltd.).
In the obtained microcapsule liquid (c), 90 parts of the above alkali-treated gelatin aqueous solution, 120 parts of 10% aqueous solution of silica-modified polyvinyl alcohol (trade name: R-1130, manufactured by Kuraray Co., Ltd., saponification degree 98%), ions 107.3 parts of exchanged water and 3.5 parts of the infrared absorbing dye (exemplary compound DYE-10) were mixed to obtain a recording layer coating solution.

(2) Preparation of coating solution for gas barrier layer 1000 parts of 10% aqueous solution of silica-modified polyvinyl alcohol (trade name: R-1130, manufactured by Kuraray Co., Ltd., saponification degree 98%), (4-nonylphenoxytrioxyethylene) 50 parts of sodium butyl sulfonate (manufactured by Sankyo Chemical Co., Ltd., 2.0 mass% aqueous solution) was mixed to obtain a coating solution for a gas barrier layer provided as an upper layer of the recording layer.

(3) Production of support with undercoat layer <Preparation of coating solution for undercoat layer>
40 parts of enzyme-degraded gelatin (average molecular weight: 10000, PAGI viscosity: 1.5 mPa · s, PAGI jelly strength: 20 g) is added to 60 parts of ion-exchanged water and dissolved by stirring at 40 ° C. Prepared.

  Separately, 8 parts of water-swelling synthetic mica (aspect ratio: 1000, trade name: Somasif ME100, manufactured by Corp Chemical Co.) and 92 parts of water were mixed, and then wet-dispersed with Viscomill, and the average particle size was 2.0 μm. A mica dispersion was obtained. Water was added to the mica dispersion so that the mica concentration was 5% by mass and mixed uniformly to prepare a desired mica dispersion.

  To 100 parts of the 40% by weight gelatin aqueous solution at 40 ° C., 120 parts of water and 556 parts of methanol are added and mixed with sufficient stirring. Then, 208 parts of 5% by weight of the mica dispersion is added and mixed with sufficient stirring. 9.8 parts of 66 mass% polyethylene oxide type surfactant were added. The liquid temperature was kept at 35 to 40 ° C., and 7.3 parts of an epoxy compound gelatin hardener was added to prepare an undercoat layer coating solution (5.7% by mass) to obtain an undercoat layer coating solution. .

<Preparation of support with undercoat layer>
Wood pulp consisting of 50 parts of LBPS and 50 parts of LBPK is beaten to 300 ml of Canadian freeness with a disk refiner, 0.5 parts of epoxidized behenamide, 1.0 part of anionic polyacrylamide, 1.0 part of aluminum sulfate, polyamide polyamine epichlorohydrin 0.1 parts and 0.5 parts of cationic polyacrylamide were added at an absolutely dry mass ratio with respect to the pulp, and a base paper having a basis weight of 114 g / m ² was made with a long paper machine and adjusted to a thickness of 100 μm by a calendar process.

Next, after corona discharge treatment was performed on both sides of the base paper, polyethylene was coated to a resin thickness of 36 μm using a melt extruder to form a matte surface resin layer (this surface is called the back surface). . Next, using a melt extruder on the side opposite to the surface on which the resin layer is formed, 10 mass% of anatase-type titanium dioxide and a polyethylene containing a small amount of ultramarine are coated so that the resin thickness is 50 μm. A resin layer was formed (this surface is called a front surface). After the corona discharge treatment is applied to the polyethylene resin-coated surface of the back surface, aluminum oxide (trade name; alumina sol 100, manufactured by Nissan Chemical Industries, Ltd.) / Silicon dioxide (trade name; Snowtex O, Nissan Chemical Industries ( Co., Ltd.) = 1/2 (mass ratio) was dispersed in water and applied in an amount of 0.2 g / m ² after drying. Next, the front surface of the polyethylene resin-coated surface was subjected to corona discharge treatment, and then the undercoat liquid was applied so that the amount of mica applied was 0.26 g / m ² to obtain a support with an undercoat layer.

<Coating of recording layer>
On the support with an undercoat layer, two recording layers and a gas barrier layer are successively applied from the bottom in the order, and dried under the conditions of 30 ° C. humidity 30% and 40 ° C. humidity 30%, respectively. Obtained material. At this time, the coating amount of the recording layer is such that the diazonium salt compound (Exemplary Compound (17)) has a solid coating amount of 0.16 g / m ^2, and the gas barrier layer has a thickness of 2.3 μm. Application was performed.
The oxygen permeability coefficient of the recording layer was determined by the above measurement method and found to be 7.6 ml · 25 μm / m ² · 24 h · atm. The oxygen permeability coefficient of the gas barrier layer was 0.039 ml · 25 μm / m ² · 24 h · atm.
The recording material in Example 1 was produced as described above.

<Image recording (projection pattern formation)>
The obtained recording material was exposed at 150 mW and a linear velocity of 0.25 m / sec using a semiconductor laser (manufactured by Sanyo, DL-8032-001) having an oscillation wavelength of 830 nm.
The beam diameter of the laser beam was 5.5 μm.
After the laser beam irradiation, the entire surface of the recording layer was irradiated with a fluorescent lamp lamp (365 nm), and the diazonium salt was completely photolyzed and fixed.
As described above, a protrusion pattern (protrusion shape) was formed.

<Confirmation of protruding pattern>
As for the recording material for image recording, the formation state of the protruding pattern was confirmed by an electron microscope and a surface roughness meter. As a result, a protrusion having a radius of 16.5 μm and a height of 4.02 μm with respect to the beam center of the laser beam was exposed at the exposed portion. It was confirmed that a pattern was formed.
Further, when laser exposure was performed while changing the energy per unit length, it was found that the protrusion pattern increased in proportion to the irradiation energy. Table 1 below shows the change in irradiation energy and the change in the height of the pattern on the protrusion formed thereby.

[Example 2]
A recording material was prepared in the same manner as in Example 1 except that 4.4 parts of the diazonium salt compound (Exemplary Compound (17)) in Example 1 were replaced with 4.1 parts of the Diazonium Salt Compound (Exemplary Compound (23)). A projection-like pattern was formed by image recording and fixing.
Regarding the recording material for image recording, the formation state of the protruding pattern was confirmed in the same manner as in Example 1. As a result, the exposed portion had a protruding shape with a radius of 16.1 μm and a height of 3.99 μm with respect to the center of the laser beam. It was confirmed that a pattern was formed.
Further, in the same manner as in Example 1, a change in irradiation energy and a change in the height of the protruding pattern formed thereby were confirmed. The results are also shown in Table 1.

[Example 3]
Other than changing the solid content coating amount 0.16 g / m ² of the diazonium salt compound (Exemplary Compound (17)) in Example 1 to 0.40 g / m ² and changing the gas barrier layer thickness 2.3 μm to 5.1 μm In the same manner as in Example 1, a recording material was prepared, and a protruding pattern was formed by image recording and fixing.
The oxygen permeability coefficient of the recording layer was determined by the above measuring method and found to be 3.1 ml · 25 μm / m ² · 24 h · atm. The oxygen permeability coefficient of the gas barrier layer was 0.018 ml · 25 μm / m ² · 24 h · atm.
Regarding the recording material for image recording, the formation state of the protruding pattern was confirmed in the same manner as in Example 1. As a result, the exposed portion had a protruding shape with a radius of 22.5 μm and a height of 5.88 μm with respect to the center of the laser beam. It was confirmed that a pattern was formed.
Further, in the same manner as in Example 1, a change in irradiation energy and a change in the height of the protruding pattern formed thereby were confirmed. The results are also shown in Table 1.

[Example 4]
A recording material was produced in the same manner as in Example 1 except that 3.5 parts of the infrared absorbing dye (Exemplary Compound DYE-10) in Example 1 were replaced with 3.8 parts of Infrared Absorbing Dye (Exemplary Compound DYE-15). Then, a protruding pattern was formed by image recording and fixing.
Regarding the recording material for image recording, the formation state of the protruding pattern was confirmed in the same manner as in Example 1. As a result, the exposed portion had a protruding shape with a radius of 16.3 μm and a height of 4.00 μm with respect to the center of the laser beam. It was confirmed that a pattern was formed.
Further, in the same manner as in Example 1, a change in irradiation energy and a change in the height of the protruding pattern formed thereby were confirmed. The results are also shown in Table 1.

[Example 5]
A recording material was prepared in the same manner as in Example 1 except that 3.5 parts of the infrared absorbing dye (Exemplary Compound DYE-10) in Example 1 was replaced with 3.6 parts of the infrared absorbing dye (Exemplary Compound DYE-23). Then, a protruding pattern was formed by image recording and fixing.
Regarding the recording material for image recording, the formation state of the protruding pattern was confirmed in the same manner as in Example 1. As a result, the exposed portion had a protruding shape with a radius of 16.5 μm and a height of 4.03 μm with respect to the center of the laser beam. It was confirmed that a pattern was formed.
Further, in the same manner as in Example 1, a change in irradiation energy and a change in the height of the protruding pattern formed thereby were confirmed. The results are also shown in Table 1.

[Comparative Example 1]
In Example 1, the recording material in Comparative Example 1 was prepared in the same manner as in Example 1 except that the diazonium salt compound (Exemplary Compound (17)) was not used when preparing the diazonium salt compound-encapsulating microcapsule solution. did.
Image recording (projection pattern formation) was performed on the obtained sample of the recording material in the same manner as in Example 1, but almost no projection pattern was observed.

[Comparative Example 2]
The recording material of Example 1 was fixed on the entire surface with a fluorescent lamp lamp (365 nm) without irradiating the semiconductor laser light, but almost no protruding pattern was observed.

  The present invention can be applied to a pattern forming method for forming a three-dimensional projection pattern combining a recording energy intensity and a beam system, and a recording material used therefor. For example, application development to high-density optical recording materials is possible.

Claims (11)

  A pattern forming method comprising: irradiating a recording material having a recording layer containing a diazonium salt compound on a support with light irradiation in a pattern by a laser beam or a light emitting diode to form a protrusion-shaped object in an exposed region. The pattern forming method according to claim 1, the energy intensity of the light irradiation, characterized in that it is in the range of ^{1J / cm 2 ~100J / cm 2} . 3. The pattern forming method according to claim 1, wherein the recording layer has an oxygen transmission coefficient of 10 ml · 25 μm / m ² · 24 h · atm or less. The gas barrier layer is further provided as an upper layer and / or a lower layer of the recording layer, and the oxygen permeability coefficient of the gas barrier layer is 5 ml · 25 μm / m ² · 24 h · atm or less. The pattern formation method of any one of Claims 1.   The pattern forming method according to claim 1, wherein the recording layer further contains a photothermal conversion substance, and the maximum absorption wavelength of the photothermal conversion substance is in the range of 330 nm to 1300 nm.   The pattern forming method according to claim 1, wherein the diazonium salt compound is encapsulated in a microcapsule. A recording material comprising a recording layer containing a diazonium salt compound on a support, wherein the oxygen permeability coefficient of the recording layer is 10 ml · 25 μm / m ² · 24 h · atm or less. 8. The gas barrier layer according to claim 7, further comprising a gas barrier layer as an upper layer and / or a lower layer of the recording layer, wherein an oxygen permeability coefficient of the gas barrier layer is 5 ml · 25 μm / m ² · 24 h · atm or less. Recording material.   9. The recording material according to claim 7, wherein the recording layer further contains a photothermal conversion substance, and the maximum absorption wavelength of the photothermal conversion substance is in the range of 330 nm to 1300 nm.   The recording material according to claim 7, wherein the diazonium salt compound is encapsulated in a microcapsule. It has a recording layer containing a diazonium salt compound on the support, the oxygen transmission coefficient of the recording layer is 10 ml · 25 μm / m ² · 24 h · atm or less, and light irradiation in a pattern with a laser beam or a light emitting diode A recording material in which a protrusion-shaped object is formed in the exposed region by performing the above.