JPH07306527A - Image forming material and image forming method - Google Patents

Abstract

PURPOSE:To provide an image forming material which has a good preservable property and is capable of forming images with a high sensitivity and high resolution and an excellent image forming method using this image forming material. CONSTITUTION:This image forming material has a layer 1 contg. a primary amine or a precursor capable of releasing ammonia and/or the primary amine and a layer 2 contg. a compd. which is decolored or colored by the ammonia and/or the primary amine on at least one surface on a base material 3. A layer 4 selected from a layer contg. a polymerizable compd. and a polymn. initiator, a layer contg. a depolymerizable compd. and a barrier layer is disposed between the two layers 1 and 2 of the image forming material described above.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material capable of forming an image with high sensitivity and high resolution, and further to an excellent image forming method using the image forming material.

[0002]

2. Description of the Related Art Conventionally, many compounds that change color when reacted with ammonia and / or amines have been known, and an image forming method utilizing this reaction has been proposed. As such an image forming method, for example, diazo-
A method of forming a dye by reacting an amine with a dye precursor containing a coupler system as a color former, a method of forming a dye by reacting phthalaldehyde or ninhydrin with an amine or ammonia, and a certain cyanine dye , A styryl dye, a rhodamine dye, an azo dye, a pyrylium dye, and a method of changing the spectral absorption of the original dye by reacting with an amine or ammonia have been proposed.

However, in these image forming methods for forming dyes or changing the spectral absorption of dyes, it is necessary to separate ammonia and / or amines from the compounds that react with them in a normal state, Attempts have been made to functionally separate layers, but sufficient functional separation has not yet been achieved.

In order to solve this problem, Japanese Patent Publication No. 54-2
No. 091, No. 54-10856, No. 54-10857 and the like propose image forming materials using a cobalt (III) complex having ammonia as a ligand.

This method is not problematic for separation from a compound which changes color by reacting with ammonia as long as the ligand is not released, but it forms an image at low energy because of its low molar extinction coefficient. In some cases, the storage stability of the cobalt (III) complex itself and the stability of the photoreducing agent used in combination are still insufficient, so that the storage stability of the image cannot be ensured in some cases.

In order to solve these problems, Japanese Patent Publication No. 1-53453 discloses a material having a layer containing a cobalt (III) complex and a compound which changes color by reacting with ammonia. It has been proposed that an image is formed by facing and heating a material provided with a layer containing a.

However, with this method, it is difficult to form an image with high sensitivity as in the above method, and
Since there is an air layer between the facing materials, ammonia diffuses along the air layer, making it difficult to obtain sufficient resolution. Further, there is a drawback that waste materials are produced in addition to the image-formed image forming material.

[0008]

The present invention has been made based on the above circumstances. That is, the object of the present invention is to
An object of the present invention is to provide an image forming material having good storability, capable of forming an image with high sensitivity and high resolution, and further to provide an excellent image forming method using the image forming material.

[0009]

DISCLOSURE OF THE INVENTION As a result of intensive investigations by the present inventors, a layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine, and an ammonia and / or primary amine. In the image-forming material having a layer containing a compound that discolors or develops color, a layer containing a polymerizable compound and a polymerization initiator, a layer containing a depolymerizable compound or a barrier layer is provided between the two layers. It has been found that the above problems can be solved by the image forming material. Further, as a result of investigating an image forming method suitable for the image forming material, the following constitution of the present invention has been reached. That is, (1) a layer containing a primary amine or a precursor containing a precursor capable of releasing ammonia and / or a primary amine on at least one side of a substrate, and decoloring or coloring with ammonia and / or a primary amine An image forming material having a layer containing a compound, wherein a layer containing a polymerizable compound and a polymerization initiator is provided between the two layers.

(2) The image forming material according to (1), wherein the polymerization initiator is a photopolymerization initiator.

(3) A layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine on at least one surface of a substrate, and decoloring or coloring with ammonia and / or a primary amine The image-forming material having a layer containing the compound, wherein the layer containing the depolymerizable compound is provided between the two layers.

(4) In the layer containing the depolymerizable compound,
The image-forming material as described in (3), which further contains a photodepolymerization initiator.

(5) A layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine on at least one surface of a substrate, and decoloring or coloring with ammonia and / or a primary amine An image-forming material having a layer containing the compound, wherein a barrier layer is provided between the two layers.

(6) The barrier layer is a vapor deposition layer (5)
The image forming material described.

(7) In the image forming material provided with the vapor deposition layer,
The image forming material according to (6), further comprising a layer containing a photothermal conversion compound in contact with the vapor-deposited layer.

(8) The photothermal conversion compound is 600 to 1100 nm
The image-forming material as described in (7), which is a dye or a dye having a maximum absorption wavelength.

(9) The barrier layer comprises a resin and 600 to 1100n
The image forming material according to (5), which is a layer containing a dye or a dye having an absorption maximum wavelength in m.

(10) The image-forming material as described in (1) to (9), wherein the compound that develops color with ammonia and / or a primary amine is a compound represented by the following general formula (1).

[0019]

[Chemical 3]

In the formula, Q represents an atomic group necessary for constituting an aromatic ring or a 5- or 6-membered heterocycle, and the aromatic ring or heterocycle may have a substituent.

(11) The compound that is decolorized by the ammonia and / or primary amine is a pyrylium dye (1) to
The image forming material described in (9).

(12) The image forming material as described in (1) to (9), wherein the precursor capable of releasing ammonia and / or primary amine is a compound represented by the following general formula (2).

[0023]

[Chemical 4]

In the formula, L ₁ represents ammonia and / or a primary amine ligand which forms a complex with a cobalt cation,
L ₂ represents a coordination compound other than ammonia and / or a primary amine which forms a complex with a cobalt cation. k is 1
An integer of 3, m is an integer of 1 to 6, n is an integer of 0 to 5, and when m and n are 2 or more, a plurality of L ₁ and L ₂ may be the same or different. X ⁻ represents a counter anion.

(13) A layer containing a precursor capable of releasing ammonia and / or a primary amine and a layer containing a compound capable of decoloring or developing with ammonia or a primary amine are formed on at least one surface of a substrate. An image forming material having a layer containing a polymerizable compound and a polymerization initiator, a layer containing a depolymerizable compound, or a barrier layer between the two layers is used, and energy is supplied in accordance with an image signal. An image forming method of forming an image by applying a heat treatment and then heating.

(14) The image forming method according to (13), wherein the energy given according to the image signal is light energy.

(15) A layer containing a precursor capable of releasing ammonia and / or a primary amine and a layer containing a compound capable of decoloring or developing with ammonia or a primary amine are formed on at least one surface of a substrate. An image-forming material having a layer containing a polymerizable compound and a polymerization initiator, a layer containing a depolymerizable compound, or a barrier layer between the two layers, and using the image-forming material according to an image signal. An image forming method of forming an image by applying 1 energy and then adding a second energy for releasing ammonia and / or a primary amine from a precursor and then heating.

(16) First provided according to the image signal
16. The image forming method according to claim 15, wherein the energy is light energy, and the second energy for releasing ammonia and / or primary amine from the precursor is light energy having a wavelength different from that of the first energy.

The image forming material and the image forming method of the present invention will be sequentially described in detail below.

<Image-forming material> The image-forming material of the present invention comprises a layer containing a primary amine, or a layer containing a precursor capable of releasing ammonia and / or a primary amine on at least one side of a substrate, and an ammonia and / or Or a layer containing a compound that is decolorized or colored by a primary amine,
It is characterized in that a certain layer is further provided between the layers (hereinafter, it may be referred to as an image forming composition layer in a form including all of these layers). The precursor here means that ammonia and / or
Alternatively, it refers to a compound that releases a primary amine, or a compound that releases ammonia and / or a primary amine by the action of active species generated by giving a certain energy.

As the above-mentioned substrate, paper, synthetic paper (for example, synthetic paper containing polypropylene as a main component, synthetic paper having a pigment coating layer having a porous structure on one or both sides); acrylic acid ester, methacrylic acid Acrylic resin such as ester; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate; Polyolefin resin such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyethylene, polypropylene and polystyrene Polyamide resins such as nylon and aromatic polyamide; polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, polyparabanic acid, phenoxy resin, epoxy resin, urethane resin , Melamine resin, alkyd resin,
Films or sheets of various resins such as phenolic resins, fluororesins, silicone resins; plastic films or sheets made by laminating two or more layers of the above resins; various polymeric materials, metals, ceramics; or wood pulp or cellulose Examples thereof include a film or sheet in which the resin layer is laminated on paper or the like made from pulp, sulfite pulp, or the like.

In the present invention, the substrate made of a resin is preferably a sheet or film stretched and heat-set from the viewpoint of dimensional stability, whether it has no internal microvoids or has microvoids. It can be appropriately selected according to. The base material is
When transparency is required, such as for transparent originals such as OHP or mask materials, or for sticking on glass, it is preferable that the required transparency is not impaired, and in the case of a reflection image, it is formed. In order to improve the sharpness of the formed image, it is preferable to add a white pigment such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay or calcium carbonate.

The thickness of the substrate is usually 10 to 1000 μm, preferably 25 to 800 μm, and is appropriately selected from such a range.

The layer containing a primary amine or a precursor capable of releasing ammonia and / or primary amine is composed of a binder resin and various additives in addition to the essential components.

As the primary amine, those represented by the following general formula (3) and having a boiling point of 100 ° C. or higher are preferable from the viewpoint of storage stability, and among them, those of 150 ° C. or higher are more preferable.

General formula (3) R-NH ₂ Here, each R represents a substituted or unsubstituted alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group or heterocyclic group. Representative compound examples are shown below.

[0037]

[Chemical 5]

[0038]

[Chemical 6]

[0039]

[Chemical 7]

[0040]

[Chemical 8]

[0041]

[Chemical 9]

The precursor capable of releasing ammonia and / or primary amine is classified into those which are released by heat energy or light energy.

Examples of the compound that releases ammonia and / or primary amine by heat include, for example, azodicarbonamide, aminoguanidine or its hydrochloride, N-ethyl-N'-.
Examples thereof include phenylurea, ammonium carbamate, biuret, hydrazobenzene, a salt of an aniline derivative and an alkyl halide, and metal complexes described in US Pat. No. 3,224,878.

As the compound that releases ammonia and / or primary amine by light, for example, carbamic acid derivative such as ethyl carbanylate, ammonia and / or primary amine represented by the general formula (2) can be used. Examples include cobalt (III) complexes having a ligand.

Of these, when the dimensional stability of the image-forming material is required against heat, compounds which release ammonia and / or primary amine by light are preferable, and among them, the compound represented by the general formula (2) The cobalt (III) complex represented by the formula (1) is more preferable because it can release a plurality of ammonia and / or primary amines.

Next, the cobalt (III) complex represented by the general formula (2) will be described in detail.

[0047] L ₁ represents an ammonia and / or primary amine to form a cobalt cations and complex, their L ₁
The following compounds may be mentioned as specific examples.

L1-1: NH ₃ L1-2: H ₂ NCH ₂ CH ₂ NH ₂ L1-3: H ₂ NCH ₂ CH (CH ₃ ) NH ₂ L1-4: H ₂ NCH ₂ CH ₂ NHCH ₃ L1- _{5: H 2 CH 2 CH 2} N (CH 3) 2 L1-6: H 2 NCH 2 CH (NH 2) CH 2 NH 2 L1-7: N (CH 2 CH 2 NH 2) 3 L1-8: H ₂ N (CH ₂ ) ₃ NH ₂ L1-9: H ₂ NCH ₂ CH (NH ₂ ) CH ₂ NH ₂ L1-10: H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ L1-11: H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ L1-12: H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ L1-13: (H ₂ NH ₂ CH ₂ ) ₂ NCH ₂ CH ₂ N (CH ₂ CH ₂ NH ₂ ) ₂ L1-14: H ₂ NCH ₂ CONH ₂ L1-15: C ₃ H ₇ NHCH ₂ CONH ₂ L1-16: H ₂ NCH ₂ CONHC ₃ H ₇ L1-17 : H ₂ NCSNH ₂ L1-18: 2,2'- diaminodiphenyl L1-19: 2- carbamoylpyridin-L1-20: 6- amino-2,2'-bi (pyridine) L1-21: H ₂ NCH ₂ COO ^- L ₂ each represents a coordination compound other than ammonia and / or primary amine to form a cobalt cation complexes, following reduction specific examples thereof L ₂ There is a mixture.

[0049]

[Chemical 10]

[0050]

[Chemical 11]

[0051] _{L2-22: H 2 O L2-23: CO} L2-24: CH 2 = CH 2 L2-25: CH≡CH L2-26: F - L2-27: Cl - L2-28: Br - L2 ^{-29: I - L2-30: OH -} L2-31: H - L2-32: NO 2 - L2-33: SCN - L2-34: N 3 - L2-35: CN - L2-36: CH 3 COO ^- L2-37: CO ₃ ^2- Moreover, the cobalt (III) a pair of complex anions X represented by general formula (2) ^- include those as follows.

[0052] ^{F -, Cl -, Br -} , I -, ClI 2 -, ClBr 2 -, B
_{^{r 3 -, IBr 2 -,}} BrI 2 -, I 3 -, FSO 3 -, N 3 -, CN -, NCO -, NCS
_{^{-, NCSe -, ClO 4 -}} , BF 4 -, PF 6 -, SbF 6 -, AsF 6 -, CO 3 2-,
_{^{NO 3 -, SO 4 2-,}} PO 4 3-

[0053]

[Chemical 12]

R ^{1 to} R ⁶ may be the same or different and each is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, an aryl group, an aralkyl group, an alkenyl group or an alkynyl group. Or represents a heterocyclic group. Further, two or more of R ^{1 to} R ⁶ may combine with each other to form a ring.

R represents a substituted or unsubstituted alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group or heterocyclic group.

R ⁶ , R ⁷ and R ⁸ each represent a substituted or unsubstituted alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group or heterocyclic group.

Further, a cobalt (III) complex having a boron anion represented by the following general color (4) as a counter anion can also be preferably used since it has excellent solubility in an organic solvent.

[0058]

[Chemical 13]

Some of the above-mentioned boron anions act as a photoreducing agent and can release ammonia and / or a primary amine without using a photoreducing agent described later. be able to.

The boron anion acting as such a photoreducing agent is represented by the general formula (4), in which R ₁ , R ₂ ,
R ₃ and R ₄ are each a substituted or unsubstituted alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group,
It represents a heterocyclic group or a cyano group. This R ₁ ~ R ₄
May be the same or different, and two or more may combine with each other to form a ring. In addition, r represents the integer of 1-3.

The alkyl group includes straight chain and branched alkyl, and examples thereof include methyl, ethyl, butyl, i-butyl, hexyl, octyl and stearyl. The alkenyl group preferably has 2 to 20 carbon atoms. The alkynyl group preferably has 2 to 20 carbon atoms. The cycloalkyl group is preferably a 5- to 7-membered ring. A benzyl group is preferred as the aralkyl group. The heterocyclic group is preferably a heterocyclic group having aromaticity, and examples thereof include a thiophene group. The aryl group is preferably a phenyl group or a naphthyl group.

These groups may be further substituted,
As the substituent, a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a hydroxyl group, an amino group (including an alkyl-substituted amino group), an alkoxy group, a carbamoyl group, -COOR ', OCOR' (R 'is an alkyl group). Group, an organic group such as an aryl group).

Specific examples of these boron anions include the following.

[0064]

[Chemical 14]

[0065]

[Chemical 15]

[0066]

[Chemical 16]

[0067]

[Chemical 17]

The content of the above-mentioned primary amine or the precursor capable of releasing ammonia and / or primary amine is usually 2 to 70% by weight, more preferably 5 to 50% by weight based on the total amount of the composition forming the layer. %.

In a layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine, a binder resin may be contained for the purpose of improving the film formation of the layer and the uniformity of the layer. The binder resin is preferably a cellulose-based compound such as a cellulose addition compound, cellulose ester or cellulose ether; a polyvinyl acetal-based resin such as polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal or polyvinyl butyral; polystyrene or styrene-acrylonitrile copolymer. Acrylic resins such as poly (meth) acrylic acid ester and (meth) acrylic acid copolymers; polyvinylpyrrolidone, polyvinyl acetate, polyacrylamide, rubber resins, ionomer resins, olefin resins, poly Examples thereof include ester resins, gelatin, casein and the like.

One of these various binder resins may be used alone, or two or more thereof may be used in combination. The amount of the binder resin used is usually 30 to 98% by weight of the total amount of the layer forming composition, more preferably 50 to 95%.
% By weight.

Cobalt (III) represented by the general formula (4)
The complex is itself photoreduced, but a photoreducing agent may be added for the purpose of changing the photosensitive wavelength range or aiming at higher sensitivity.

The term "photoreducing agent" as used herein means a state in which the compound undergoes photolysis or transfer to reduce the cobalt (III) complex to a cobalt (II) complex and easily release ammonia and / or primary amine. Or a substance capable of producing a reducing agent precursor that can be converted into such a reducing agent. Examples of the photoreducing agent include quinones,
Disulfides, diazoanthrones, diazophenanthrones, carbazides, diazosulfonates, diazonium salts, aromatic azides, benzimidazoles, aziridines, and the like.Specific compounds include October 1974. Research Disclosure 12617
For example, those described in Table 1 on pages 13 to 14 and 14 to 17 can be used.

Furthermore, a complex represented by the following general formula (5), which is composed of a cationic dye and a borate anion, can be used in the present invention because the wavelength at which decomposition is caused can be controlled by selecting the cationic dye. You can

[0074]

[Chemical 18]

In the formula, Dye ⁺ represents a cationic dye,
R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a group having the same meaning as described in the general formula (4). However, at least one of R _{1 to} R ₄ is an alkyl group. Two or more of R _{1 to} R ₄ may combine with each other to form a ring.

As the cationic dye represented by Dye ⁺ , a cyanine dye and a polymethine dye are preferable. Specific examples of the cationic dye include JP-A-62-143044 and 63-208036.
No. 64-84245, 64-88444, JP-A 1-152108,
Those described in JP-A-3-202609 can be used.

When a photoreducing agent is added, it is preferably 0.01 to 20% by weight, more preferably 0.1 to 20% by weight based on the total amount of the layer forming composition.
~ 10% by weight.

When ammonia and / or primary amine is released by light energy, a sensitizer or a ligand exchange agent may be added to the composition layer in order to improve the image forming efficiency.

Examples of the sensitizer include triazine compounds described in JP-A-64-13140, aromatic onium salts and aromatic halonium salts described in JP-A-64-13141, and JP-A-64-13143. Organic peroxides described in JP-B-45-37377 and U.S. Pat.
Examples thereof include the bisimidazole compound described in 3,652,275. Further, the borate represented by the following general formula (6) can also be preferably used as the sensitizer.

[0080]

[Chemical 19]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as defined in the general formula (4), and Y ⁺ is a counter cation (eg, alkali metal, ammonium, phosphonium, etc.). Group 5A onium compounds, 6A group onium compounds such as sulfonium and tellurium). Specific examples of the compound are described in JP-A-64-13142,
Japanese Unexamined Patent Publication No. 2-4804, U.S. Patents 3,754,921, 3,716,366
Nos. 4,297,441 and 4,307182.

The sensitizer is used in the entire amount of the image forming composition layer.
The amount is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.

As the ligand exchange agent, JP-A-59-95529 is known.
The compounds and imide compounds described on page 10 can be added. Examples of the imide compound include compounds represented by the following general formula (7).

[0084]

[Chemical 20]

[0085] In the formula, each independently R ₅ and R ₆ are alkyl groups (e.g. methyl, ethyl, propyl) represents a, R ₅
And R ₆ may combine with each other to form a saturated or unsaturated carbocycle or heterocycle. These rings may further have a substituent (for example, an alkyl group, an alkoxy group, a nitro group, a halogen atom, etc.). R ₇ is a hydrogen atom or a group capable of splitting off upon heating (eg, —Si (R ₅ ) ₃ , —CONHR ₅ , —COR
₅ ) is represented. W represents a single bond or a divalent linking group, but -C
O- or -CS- is preferred. Z represents an oxygen atom or a sulfur atom.

Specifically, succinimide, phthalimide, 2-methylsuccinimide, dithiouracil, 5-methyl-5-pentylhydantoin, phthalimide, nitrophthalimide, 2,3,4,5-tetrachlorophthalimide, 5,
5'-dimethyloxazolone, diphenylhydantoin,
Melenimide, glutarimide, pyromellitic imide,
N- (trimethylsilyl) phthalimide, hydantoin, 3-
Examples thereof include compounds such as methylphthalimide and 4-octylphthalimide.

The addition amount of the ligand exchange agent and the imide compound varies depending on the constitution and purpose of the image forming material, but is preferably 0.1 to 40 mol% with respect to the addition amount of the cobalt complex of the present invention.

In addition to the above-mentioned precursor capable of releasing primary amine or ammonia and / or primary amine, binder resin, photoreducing agent, sensitizer and ligand exchange agent, the effects of the present invention are impaired. Other additives such as fillers (inorganic fine particles, organic resin particles), pigments, antistatic agents, plasticizers, thermal solvents, oxygen quenchers may be added within the range not specified.

Examples of the filler include inorganic fine particles and organic resin particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina, etc., and organic fine particles include resin particles such as fluorine resin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. And so on.

Examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay and acid clay.

As the antistatic agent, in addition to cationic surfactants, anionic surfactants, nonionic surfactants, polymeric antistatic agents, conductive fine particles and the like, "11290 chemical products", Chemical Industry Daily Compounds described on pages 875 to 876 of the same company can also be preferably used.

Examples of the plasticizer include phthalic acid esters, trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, oxalic acid esters, epoxidized soybean oil, and epoxies such as epoxystearic acid. In addition to orthophosphoric acid esters, phosphorous acid esters, glycol esters, etc., the compounds described in "Chemical products of 11290", Kagaku Kogyo Nippo Co., Ltd., pages 843 to 857, etc. can also be preferably used.

Further, the hot solvent is solid at room temperature,
A compound that reversibly becomes a liquid when heated is used. Specifically, alcohols such as terpineol and menthol; amides such as acetamide and benzamide; esters such as coumarin and benzyl cinnamate; ethers such as diphenyl ether and crown ether; camphor, p-
Ketones such as methylacetophenone; aldehydes such as vanillin and dimethoxybenzaldehyde; hydrocarbons such as p-benzylbiphevir and stilbene; higher alcohols such as eicosanol; higher fatty acid esters such as cetyl palmitate; higher fatty acids such as stearamide. Fatty acid amides; monomolecular compounds represented by higher amines such as behenylamine; beeswax, candelilla wax, paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax, and other waxes; Rosin derivatives such as ester gum, rosin maleic acid resin, and rosin phenol resin; phenol resin, ketone resin, diallyl phthalate resin, terpene hydrocarbon resin, cyclopentadiene resin, porosity Olefin resins, polycaprolactone resins, polyethylene glycol, high molecular compounds typified by polyether such as polypropylene glycol.

In the present invention, the hot solvent having a melting point or softening point of 10 to 150 ° C. is preferable.

As the oxygen quencher, N, N-dialkylaniline derivatives are preferable, for example, US Pat. No. 4,772,541.
Compounds described in column 11, line 58 to column 12, line 35 of No.

In the present invention, it is usually preferable to select the total amount of additives to be added within the range of 0.1 to 30% by weight based on the total amount of the layer-forming composition.

The layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine is prepared by dispersing or dissolving the above composition in a solvent to prepare a coating liquid,
A coating method in which a layer such as a substrate is coated and dried to form a layer, or after the above layer is formed on a peelable sheet, the layer is faced with the layer to be laminated and heated and / or applied. It can be formed by a transfer method or the like in which pressure treatment is performed for transfer.

As the solvent used in the above coating liquid,
Water, alcohols (eg ethanol, propanol); cellosolves (eg methyl cellosolve, ethyl cellosolve); aromatics (eg toluene, xylene,
Chlorobenzene); Ketones (eg acetone, methyl ethyl ketone); Ester-based solvents (eg ethyl acetate,
Butyl acetate and the like); ethers (eg tetrahydrofuran, dioxane); chlorine-based solvents (eg chloroform, trichloroethylene); amide-based solvents (eg dimethylformamide, N-methylpyrrolidone); dimethyl sulfoxide and the like. For the coating, conventionally known gravure roll coating method, extrusion coating method, wire bar coating method, roll coating method and the like can be adopted.

The layer containing the primary amine or the precursor capable of releasing ammonia and / or the primary amine may be a single layer, and if necessary, the composition and the like may be the same or different. You may provide as a multilayer structure of two or more layers.

The thickness of the layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine is usually 0.5 to 50 μm, preferably 2 to 30 μm. It is appropriately selected according to.

In the present invention, in addition to the above-mentioned layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine, a compound decoloring or developing with ammonia or a primary amine is contained. The layers are laminated onto the substrate.

Examples of compounds that develop with ammonia or primary amines include o-phthalaldehyde and ninhydrin, while examples of compounds that decolorize with ammonia or primary amines include certain cyanine dyes and styryl dyes. , Rhodamine dyes, azo dyes, pyrylium dyes, and the like.

Among these, the compound represented by the above general formula (1) is particularly preferable because a polymer dye is formed during color development and image stability is improved.

Examples of the 5- or 6-membered heterocycle in the general formula (1) include heterocycles such as imidazole, furan, thiophene, pyrazole, triazole, pyridine, pyrimidine, benzothiazole, indole and quinoline.

The following compounds may be mentioned as specific examples of the general formula (1).

[0106]

[Chemical 21]

[0107]

[Chemical formula 22]

[0108]

[Chemical formula 23]

[0109]

[Chemical formula 24]

[0110]

[Chemical 25]

These compounds are known as Chem. Ber. (Hemische Berichte) 88, 1276 (1955), 89, 1574 (1956), 9
0,2646 (1957), 99.634 (1966), J.Org.Chem. (Journal of Organic Chemistry) 24,372 (195
9), 29, 3048 (1964), Z. Chem. (Zeit Schrift
Hule Chemie) 11,175 (1971), 11,17 (1971), and the method described in JP-A-2-184678, etc.

The amount of the compound represented by the general formula (1) added is usually 2 to 100% by weight based on the total amount of the layer-forming composition,
It is more preferably 5 to 80% by weight.

As the compound that is decolorized with ammonia or a primary amine, it is preferable that the compound has no absorption in the visible region or has as little absorption as possible when decolorized. A pyrylium dye is particularly preferable as such a compound. preferable. The following compounds may be mentioned as specific examples of these compounds.

7-1: 2,6-diphenyl-4- (3-methoxyphenyl) pyrylium perchlorate 7-2: 4-phenyl-2,6-diethylpyrylium perchlorate 7-3: 4- (4 -Morpholinophenyl) -2,6-diphenylpyrylium perchlorate 7-4: 2,6-bis (p-methoxyphenyl) -4-phenylpyrylium tetrafluoroborate 7-5: 2,4-diphenyl-6- (β-Methyl-3,4-diethoxytyryl) pyrylium tetrafluoroborate 7-6: 4- (4-dimethylaminovinyl) -2,6-diphenylpyrylium perchlorate 7-7: 2- (2-naphthyl) -4,6-diphenylpyrylium perchlorate 7-8: 2,6-diphenyl-4- [2- (10-methylphenothiazyl)] pyrylium perchlorate 7-9: 2-butyl-3- [β -(2-Hydroxy-1-naphthyl) vinyl] -naphtho [2,1-b] pyrylium perchlorate 7-10: 4- (2-hydroxybenzylidene) -1,2,3,4-tetra Droxyxanthylium perchlorate 7-11: 4- (4-methylmercaptophenyl) -2,6-diphenylpyrylium perchlorate 7-12: 9-phenyldibenzo [aj] xanthylium perchlorate 7-13 : 2,6-diphenyl-4- (4-methoxycarbonylphenyl) pyrylium perchlorate 7-14: 5,6-dihydro-2,4-diphenylnaphtho [1,2-b] pyrylium tetrafluoroborate 7- 15: 8- (benzo [b] -3H-1,2-dithiol-3-yridine)-
9,10,11,12-Tetrahydro-8H-cyclohepta [e] naphtho
[2,1-b] Pyrylium perchlorate The addition amount of the pyrylium dye is usually 1 to 70% by weight, and more preferably 3 to 50% by weight based on the total amount of the layer forming composition.

The layer containing a compound that discolors or develops color with ammonia or a primary amine contains a binder resin in addition to the above-described compound that discolors or develops color for the purpose of improving the uniformity of the layer. Preferably.

As the binder resin, the resin used for the layer containing the above-mentioned primary amine or the precursor capable of releasing ammonia and / or primary amine can be appropriately selected and used. One kind of the various binder resins may be used alone, or two or more kinds thereof may be used in combination.

The binder resin is usually 0 to 99% by weight, more preferably 20 to 97% by weight, based on the total amount of the layer forming composition.
Used.

In addition to the above-described decolorizable or color-developing compound and binder resin, fillers (inorganic fine particles, organic resin particles), pigments, antistatic agents, plasticizers, thermal solvents, in addition to the compounds which do not impair the effects of the present invention, Other additives such as an oxygen quencher may be added, and specific examples thereof include those used in the layer containing the above-mentioned primary amine or a precursor capable of releasing ammonia and / or primary amine. It is possible to appropriately select and use various kinds of additives to be added.

The total addition amount of these additives is usually preferably selected in the range of 0.1 to 30% by weight based on the total amount of the layer forming composition.

The layer containing the compound capable of decoloring or developing a color may be a single layer, or may be provided as a multi-layer structure of two or more layers having the same composition or different compositions, if necessary.

In the present invention, the thickness of the layer containing the compound that decolorizes or develops color is usually 0.5 to 100 μm, preferably 2 to 50 μm, and is appropriately selected according to the purpose.

The layer containing a compound capable of decoloring or developing a color can be formed in the same manner as the layer containing a primary amine or a precursor capable of releasing ammonia and / or primary amine.

In the present invention, a layer containing the above-mentioned primary amine or a precursor capable of releasing ammonia and / or a primary amine, and a compound capable of erasing or developing a color by ammonia and / or a primary amine are contained. It is characterized in that a certain layer is further provided between the layers.

Here, the specific layer means a precursor capable of releasing a primary amine or ammonia and / or a primary amine when heated, a primary amine, or an ammonia and / or an ammonia in the image forming method described later. Alternatively, a compound which is decolorized or colored by a primary amine changes its thermophysical properties so that it is mixed with each other depending on the image, or the layer disappears due to the energy for image formation. Examples of such a layer include a layer containing a polymerizable compound and a polymerization initiator, a layer containing a depolymerizable compound, and a barrier layer. Hereinafter, each layer will be described in detail.

The layer containing the polymerizable compound and the polymerization initiator is image-wise polymerized by the image forming method described later, and the unpolymerized portion of the layer is treated with ammonia or a primary amine when heated. However, it mixes with a compound that decolorizes or develops color, and decolorizes or develops color, and on the contrary, does not mix in a polymerized part, so that an image is formed on the image forming material.

Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond and a compound having an epoxy group. In the present invention, a compound having an ethylenically unsaturated bond is preferable.

The polymerization initiator is not particularly limited as long as the energy (for example, light energy, heat energy, electric energy, etc.) at which the initiator acts on the active species, but the energy application area is required to obtain high resolution. Light energy that can be narrowed down is preferable, and a photopolymerization initiator that can generate active species with this light energy is preferable.

As the polymerizable compound having an ethylenically unsaturated bond, a known monomer capable of addition polymerization or cross-linking polymerization can be used without particular limitation. Specific monomers include, for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, monofunctional acrylic acid esters such as 2-hydroxypropyl acrylate and their derivatives, or these acrylates replaced with methacrylate, itaconate, crotonate, maleate, etc. Compounds; bifunctional acrylic acid esters such as polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A diacrylate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, and derivatives thereof,
Alternatively, compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, etc .; or trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate,
Polyfunctional acrylic acid esters such as dipentaerythritol hexaacrylate and pyrogallol triacrylate and their derivatives, or compounds in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, etc .; A so-called prepolymer having methacrylic acid introduced therein and imparted with photopolymerizability can also be suitably used. In addition to these, JP-A-58-212994, 61-6649, and
62-46688, 62-48589, 62-173295, 62-1870
No. 92, No. 63-67189, JP-A No. 1-244891, and the like, and compounds described in “Chemical products of 11290”, Kagaku Kogyo Nippo, pages 286 to 294, “UV. EB
The compounds described in "Curing Handbook (Raw Materials)", Kobunshi Kogakukai, pages 11 to 65, and the like can also be preferably used.

Among these, compounds having two or more acryl or methacryl groups in the molecule are preferable, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferable. Further, in the present invention, one kind or a mixture of two or more kinds of these monomers or prepolymers can be used.

Effective photopolymerization initiators for polymerizable compounds having an ethylenically unsaturated bond include benzoin compounds such as benzoin and benzoin methyl ether; carbonyl compounds such as benzophenone and Michler's ketone; azobisisobutyronitrile. And azo compounds such as azodibenzoyl; sulfur compounds such as dibenzothiazolyl sulfide and tetraethylthiuram sulfide; halides such as carbon tetrabromide and tribromophenyl sulfone; di-t
-Peroxides such as butyl peroxide and benzoyl peroxide; metal carbonyls and European Patents 0,126,712 and 0,1
Examples include various metal complexes such as iron arene complexes described in No. 52,377, and the above-mentioned general formula (5) used when photoreducing a precursor capable of releasing ammonia and / or primary amine. A complex consisting of the cationic dye and borate anion is also preferably used.

Such a photopolymerization initiator can be selected and used in various manners depending on the wavelength of light capable of activating the initiator, but in any case, due to problems of color turbidity and coloring, a colorless one is used from the beginning. Alternatively, those which are decolorized after exposure, in other words, those which have extremely low or no absorption in the visible region (400 to 800 nm) are preferable.

The above-mentioned polymerizable compound is usually 10 to 90% by weight, preferably 20 to 80% by weight, based on the total amount of the layer forming composition,
The polymerization initiator is preferably added and mixed in an amount of usually 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the polymerizable compound.

A binder resin is preferably added to the layer containing the polymerizable compound and the polymerization initiator in order to ensure layer separation and to improve storage stability. As the binder resin, a polyvinyl acetal resin, Examples thereof include cellulose resins, olefin resins, vinyl chloride resins, (meth) acrylic resins, styrene resins, polycarbonates, polysulfones, polycaprolactone resins, polyacrylonitrile resins, urea resins, phenoxy resins, rubber resins and the like. Further, a resin having an unsaturated bond in the resin (for example, diallyl phthalate resin and its derivative, chlorinated polypropylene, etc.) can be polymerized with the above-mentioned polymerizable compound, and therefore can be suitably used according to the application. .

As the binder resin, one kind or a combination of two or more kinds of the above-mentioned resins can be used. The binder resin is 10 to 10% of the total amount of the layer forming composition.
It is preferable to add and mix 90% by weight, more preferably 20 to 80% by weight.

In addition to the above-mentioned polymerizable compound, polymerization initiator and binder resin, fillers (inorganic fine particles, organic resin particles), pigments, antistatic agents, plasticizers, Other additives such as a hot solvent and an oxygen quencher may be added, and specific examples thereof include the above-mentioned primary amine or a layer containing a precursor capable of releasing ammonia and / or primary amine. Various additives to be used can be appropriately selected and used. Generally, the total amount of additives added is preferably selected in the range of 0.1 to 30% by weight based on the total amount of the layer-forming composition.

In the present invention, the thickness of the layer containing the polymerizable compound and the polymerization initiator is usually 0.05 to 20 μm, preferably
The thickness is 0.5 to 10 μm and is appropriately selected according to the purpose.

The layer containing the polymerizable compound and the polymerization initiator can be formed in the same manner as the layer containing the primary amine or the precursor capable of releasing ammonia and / or the primary amine.

The layer containing the depolymerizable compound is image-wise depolymerized by the image forming method described later, and the depolymerized portion of this layer is treated with ammonia or 1% when heated.
An image is formed on the image-forming material, because the primary amine mixes with the compound that decolorizes or develops color, and decolorizes or develops the color, and on the contrary, does not mix in the part that does not depolymerize. The depolymerizable compound referred to herein is a compound in which the main chain or side chain causes depolymerization by giving itself a certain kind of energy (for example, electromagnetic wave, thermal energy, electric energy, etc.), or depolymerization. A compound in which the main chain or side chain causes depolymerization due to the action of a polymerization initiator.

In the layer containing the depolymerizable compound, it is preferable to further add a depolymerization initiator in order to accelerate depolymerization of the depolymerizable compound. Such a depolymerization initiator is
The energy is not particularly limited as long as the initiator can be an active species, but an electromagnetic wave capable of narrowing the energy application area is preferable for obtaining high resolution.
A photodepolymerization initiator capable of generating active species with light energy having a wavelength of 0 to 1000 nm is preferable.

Examples of the compound which itself causes depolymerization include polymethylmethacrylate, polyhexafluorobutylmethacrylate, polydimethyltetrafluoropropylmethacrylate, and poly (trifluoroethyl-
α-chloro acrylate), polymethyl vinyl ketone, poly (methyl isopropenyl ketone), poly (methyl isopropenyl-t-butyl ketone), methyl methacrylate.
Phenyl isopropenyl ketone copolymer, methyl methacrylate / 3-methacryloxyimino-2-butanone copolymer, methyl methacrylate / indanone copolymer, polyglutarimide (eg glutarimide-modified acrylic acid or methacrylic acid), poly ( (Olefin sulfone)
(For example, alternating copolymer of 1-butene and sulfur dioxide, 2-
Alternating copolymer of methyl-1-pentene and sulfur dioxide, 5-
Alternating copolymer of hexene-2-one and sulfur dioxide, alternating copolymer of acetylene and sulfur dioxide, etc.), polyacetylene, nitrocellulose, polymethacrylonitrile,
Examples thereof include polycarbonate synthesized from a certain kind of active carbonyloxy compound and bisphenol A.

Further, as the compound which causes depolymerization by the action of the depolymerization initiator, the above-mentioned compound which itself causes depolymerization, and further poly (p-formyloxystyrene), poly (p-pivaloyl) Oxystyrene), poly (pt-butoxycarbonylstyrene), polyphthalaldehyde and the like. In addition, since polyphthalaldehyde becomes phthalaldehyde by depolymerization, it can be used as a compound which itself reacts with ammonia and / or a primary amine to develop a color.

As the above-mentioned depolymerizable compound, commercially available products can be used as they are, or poly (olefin sulfone)
Is a polycarbonate synthesized from an active carbonyloxy compound and bisphenol A by the method described in J. Electrochem. Soc. (Journal of Electrochemical Society) 128, 1304 (1981) and the like. , Ch
em.Commun. (Journal of Chemical Society, Chemical Communication) 1514 (1985), J. Im
aging Sci. (Journal of Imaging Science) 30 (2), 59 (1986), Polym.J. (Polymer Journal) 19 (1), 31 (1987), ACS Symp.Ser. (ACS Symposium)・ Series) 346, 162 (1987) etc., poly (p-formyloxystyrene) is a macromoleculer
(Macromolecular) 18,317 (1985), ACS Symp.Ser.
(Id.) By the method described in 266, 269 (1985) and the like, and polyphthalaldehyde can be obtained from J. Polym. Sci. (Journal of Polymer Science) A-1 (7), 497 (1969), Polym. En
g.Sci. (Polymer Engineering Science) 2
It can also be synthesized by referring to the method described in 3,1012 (1983) and the like.

Examples of the photodepolymerization initiator include pyridine-N-oxide and compounds that generate a protonic acid in the layer upon receiving light. As the compound that generates a protonic acid in the layer, an onium salt is preferable, Among them, onium salts of Group VIa elements are particularly preferable.

Examples of such onium salts include dibutylphenacylsulfonium tetrafluoroborate, dibutyl (4-hydroxyphenyl) sulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexahydrate. Fluorophosphate, tris (4-thiomethoxyphenyl) sulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylselenonium tetrafluoroborate, triphenyltelluronium tetrafluoroborate and the like,
Further, U.S. Pat. No. 4,258,128, J.Polym.Sci.Polym.Chem.E
d. (Journal of Polymer Science Polymer Chemistry Edition) 17,977 (1979), 1
8,2677 (1980), 18,2697 (1980), Adv.Polym.Sci. (Advances in Polymer Science) 62,1 (1984)
The compounds described in etc. can also be preferably used.

Since the above-mentioned onium salt has absorption only at 350 nm or less, it is preferable to perform wavelength sensitization with a photosensitizer when light does not reach the depolymerizable compound-containing layer sufficiently. , Such sensitizers include phenothiazine, anthracene, perylene, thioxanthone,
Fluorenone, naphthoquinone, anthraquinone, phenanthrenequinone, etc., and Prog.Org.Coatings.
(Progress in Organic Coating) 1
The compounds described in 3,35 (1985) and the like can also be preferably used.

Such a depolymerizable compound is usually used in an amount of 50 to 99.9% by weight, preferably 70 to 99% by weight, based on the total amount of the layer-forming composition.
Further, the photodepolymerization initiator and the photosensitizer are usually added in an amount of 0.1 to 100 parts by weight, more preferably 0.5 to 40 parts by weight, based on 100 parts by weight of the depolymerizable compound. Is preferably used.

Further, in the present invention, in addition to the above-mentioned depolymerizable compound and depolymerization initiator, a binder resin or an additive may be added within a range that does not impair the effects of the present invention. For example, the binder resin and various additives used in the layer containing the above-mentioned primary amine, or a precursor capable of releasing ammonia and / or primary amine can be appropriately selected and used. The amount of the binder resin and various additives added is usually the total amount of the layer-forming composition.
It is preferable to select in the range of 0 to 30% by weight.

The thickness of the layer containing the polymerizable compound and the polymerization initiator is usually 0.05 to 20 μm, preferably 0.5 to 10 μm, and is appropriately selected according to the purpose.

The layer containing the depolymerizable compound and the depolymerization initiator can be formed in the same manner as the layer containing the primary amine or the precursor capable of releasing ammonia and / or the primary amine. .

The barrier layer imparts imagewise energy (for example, electromagnetic wave, thermal energy, electric energy, etc.) by the image forming method described later to perforate or crack the layer, and perforate or crack the layer. In the portion, ammonia or a primary amine mixes with a compound that decolorizes or develops color when heated, and decolorizes or develops the color. On the contrary, it does not mix in the unchanged barrier layer part. An image is formed on.

In the normal state, the barrier layer does not mix with the compound in which ammonia or the primary amine decolorizes or develops, and if the layer is perforated or cracked when energy is applied,
Although it may have any composition, it is preferably formed by a vapor deposition layer in order to ensure sufficient barrier properties.

Further, in order to obtain high resolution, it is preferable to use light energy capable of narrowing the energy application area. As such a barrier layer, resin and 600 to 1100 n are used.
It is preferably formed of a layer containing a dye or dye having an absorption maximum wavelength in m.

When the barrier layer is formed as a vapor deposition layer, for example, aluminum, zinc, antimony, indium, selenium, tin, tantalum, chromium, lead, gold, silver, platinum, nickel, niobium, germanium, silicon, molybdenum, manganese. , A metal such as tungsten or palladium, or a metal oxide thereof can be used. These vapor-deposited layers are formed of the above-mentioned metal or metal oxide.
It can be formed by using one kind or a combination of two or more kinds, and as a vapor deposition method, a vacuum vapor deposition method, an ion plating method,
By a known method such as a sputtering method, a metal vapor-deposited thin film can be provided as a single crystal or a polycrystal of a metal or a metal oxide.

The thickness of this vapor-deposited layer is usually 0.0005 to 0.5 μm, preferably 0.001 to 0.1 μm.

As with the layer containing the polymerizable compound and the polymerization initiator described above, in order to obtain high resolution, it is preferable to use light energy capable of narrowing down the energy application area, and the light energy of 600 to 1100 nm is preferable. Light energy having a wavelength is preferable because it can be more efficiently converted into heat energy.

When this light energy is used, it is preferable to further provide a layer containing a photothermal conversion compound in contact with the vapor deposition layer in order to efficiently perforate or crack the vapor deposition layer.

As the photothermal conversion compound, 600 used
Particularly preferably a dye or dye having an absorption maximum wavelength in the range of ~ 1100 nm, as such dyes or dyes, for example, cyanine dyes, rhodacyanine dyes, oxonol dyes, carbocyanine dyes, dicarbocyanine dyes, tricarbocyanine dyes, Tetracarbocyanine dyes, pentacarbocyanine dyes, styryl dyes, pyrylium dyes, phthalocyanine dyes, metal-containing dyes, and the like, specifically, Chem. Rev. (Chemical Reviews) 92, 1197 (199
The compounds described in 2) and the like can be used.

These photothermal conversion compounds are used in the layer forming composition 10
It is preferable to add and mix in an amount of 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, relative to 0 parts by weight.

The layer containing the photothermal conversion compound is preferably added with a binder resin for holding the compound in addition to the photothermal conversion compound. As such a binder resin, the above-mentioned primary amine can be used. Alternatively, a resin used in forming a layer containing a precursor capable of releasing ammonia and / or a primary amine can be appropriately selected and used, and the amount is 10 to 90% by weight of the total amount of the layer forming composition, It is preferable to use by adding and mixing in the range of 20 to 80% by weight.

Further, various additives other than the photothermal conversion substance and the binder resin may be added within the range not impairing the effects of the present invention. Specific examples thereof include primary amine, ammonia and / or Various additives used in the layer containing the precursor capable of releasing the primary amine can be appropriately selected and used.

The total amount of the additives to be added is usually preferably selected in the range of 0 to 30% by weight based on the total amount of the layer forming composition.

The thickness of the photothermal conversion layer is usually 0.05 to 3 μm, preferably 0.1 to 1 μm. The photothermal conversion layer can be formed by the same method as that for the layer containing a primary amine, or a precursor capable of releasing ammonia and / or a primary amine.

Also, the barrier layer is made of a resin and 600 to 1100 nm.
In the case of forming a layer containing a dye or a dye having an absorption maximum wavelength, it can be formed with the same composition as the layer containing the photothermal conversion compound described above, but the thickness of the layer than the layer containing the photothermal conversion compound It is also preferable to make it thicker, usually 0.1
˜10 μm, preferably 0.5 to 5 μm.

In the present invention, 1 is provided on at least one surface of the substrate.
Polymerization between a layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine, a layer containing a compound capable of decoloring or coloring by ammonia and / or a primary amine, and the two layers The image-forming material is provided with a layer containing a polymerizable compound and a polymerization initiator, a layer containing a depolymerizable compound or a barrier layer, and various image-forming materials can be used within this range.

A typical image forming material is shown in FIG. 1, but the present invention is not particularly limited to these constitutions, and depending on the use of the image forming material, as shown in FIGS.
A protective layer made of a resin for ensuring the durability of the image forming material, ammonia or 1 for improving the fixing of the image.
A fixing layer containing a compound that inactivates a primary amine, and an intermediate layer formed of a resin having a cushioning property for uniform heating may be provided. A conventional two-layer separation type image forming material is shown in FIG.

The protective layer may be formed by a known method such as using the resin film used as the base material of the image-forming material as it is and laminating it through an adhesive layer, or it is molded into the resin film. The resin can also be formed by a method similar to that for the layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine. A compound such as an ultraviolet absorber and / or a light stabilizer which improves image durability may be added to the protective layer.

Examples of the ultraviolet absorber and / or light stabilizer include those disclosed in JP-A-59-158287, JP-A-63-74686, and JP-A-63-145089.
No. 59-196292, No. 62-229594, No. 63-122596,
61-283595, JP-A 1-204788, 5-92670, `` 11
290 chemical products ”, compounds described in Kagaku Kogyo Nippo Co., Ltd., pages 869 to 875, and the like, and known compounds that improve the image durability of other image recording materials can be mentioned.

When a protective layer is provided, it is usually 0.5-100 μm.
m, preferably 2 to 50 μm.

The fixing layer is not particularly limited as long as it can inactivate ammonia or a primary amine and improve image fixing, and specifically, it can be inactivated by a compound that reacts with ammonia or a primary amine. Examples of such compounds include Braenste, such as oxalic acid and polyacrylic acid.
d Acids; epoxy group-containing compounds such as styrene oxide and aliphatic polyglycidyl ethers; acyl halides such as cinnamoyl chloride; aromatic acid anhydrides such as phthalic anhydride; halogenated alkyls such as stearyl bromide; phenacyl sulfonyl chloride Or a precursor capable of releasing these compounds, for example, tetrabutylammonium hydrogen sulfite, etc., and these compounds are contained in the range of 5 to 50% by weight based on the total amount of the fixing layer forming composition. It is preferable to select.

The fixing layer can be composed of the same binder resin as the layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine and various additives, but is fixed after image formation. Therefore, it is preferable to determine the composition of the fixing layer so that a compound that reacts with ammonia or a primary amine can move at a temperature higher than the heating temperature during image formation.

When a fixing layer is provided, it is usually 1 to 100 μm,
It is preferably 5 to 50 μm.

The cushioning resin used for the intermediate layer is not particularly limited as long as it is a resin that can be deformed when heated and / or pressed, and examples thereof include polyester resin, styrene resin, vinyl chloride resin, and acrylic resin. Examples thereof include resins, olefin resins, rubber resins, and the like, and a resin layer having a porous interior is also suitably used.

When an intermediate layer is provided, it is usually 2 to 50 μm, preferably 5 to 30 μm.

In the present invention, a layer containing a base material and a compound capable of decoloring or developing a color, or a layer containing a base material and a primary amine or a precursor capable of releasing ammonia and / or primary amine, etc. When the adhesive strength between the base material and the layer to be laminated is insufficient (for example, when the difference in the wetting angle (contact angle) between the resins to be laminated is large, particularly when it is 5 deg or more), before the layer to be laminated is provided. It is preferable that the surface to be laminated is subjected to a treatment. As the method of this surface treatment, corona discharge treatment, flame treatment, ozone treatment,
UV treatment, radiation treatment, roughening treatment, chemical treatment,
Known resin surface modification techniques such as plasma treatment, low temperature plasma treatment, primer treatment, and grafting treatment can be applied as they are. Specifically, "Basics and applications of polymer surfaces (below)" Kagaku Dojin, Chapter 2, "Handbook of New Polymer Materials" Maruzen,
The methods described in Chapter 8 and the like can be referred to, and one kind or two or more kinds thereof can be used in combination.

<Image Forming Method> -Image Forming Method 1-In the present invention, an image is formed by applying imagewise energy to the image forming material in accordance with an image signal and then applying heat and pressure. In this case, the precursor capable of releasing ammonia and / or primary amine is subjected to imagewise energy and / or heating to release ammonia and / or primary amine from the precursor.

The image forming material having a layer containing a polymerizable compound and a polymerization initiator, a layer containing a depolymerizable compound or a barrier layer will be described in detail below.

In an image-forming material provided with a layer containing a polymerizable compound and a polymerization initiator, the layer is polymerized by energy applied to the imagewise, and the polymerized portion is a primary amine, or ammonia and / or 1 A layer containing a precursor capable of releasing a primary amine, and ammonia and / or 1
A strong resin layer is formed between the primary amine and the layer containing the compound that is decolorized or colored. If the energy to which the precursor is added can release the ammonia and / or the primary amine, ammonia and / or the primary amine is produced from the precursor when the energy is added. Further, in the precursor which does not release ammonia and / or primary amine with the energy applied to the precursor but can be released by heating, ammonia and / or primary amine is produced by the heat treatment in the next step. It Further, in the case of a precursor capable of releasing ammonia and / or a primary amine by either the applied energy or the heat treatment in the next step, the ammonia and / or the primary amine is more efficiently generated than the above-mentioned precursor. Is generated.

Then, by heating the image-forming material, ammonia and / or primary amine released from the primary amine or precursor through the unpolymerized part of the layer containing the polymerizable compound and the polymerization initiator. Amine, ammonia and /
Alternatively, compounds that are decolorized or colored by the primary amine are mixed and decolorized or colored to form an imagewise image on the image forming material according to an image signal.

[0179] In this case, the mixture means that the compound that moves, decolorizes or develops to a layer containing a compound that decolorizes or develops ammonia or a primary amine is a primary amine, or ammonia and / or a primary amine. Is transferred to a layer containing a precursor capable of releasing, and ammonia or a primary amine and a compound that decolorizes or develops color are freely transferred to each other,
These differ depending on the composition of each layer, the heat treatment method, and the image forming material.

Further, in the image-forming material provided with the layer containing the depolymerizable compound, the layer is depolymerized by the energy applied to the imagewise. In the depolymerized portion, the thermal properties of the layer itself are deteriorated by the decomposition of the depolymerizable compound, or voids are formed in the layer containing the depolymerizable compound by the gas generated by the decomposition. Then, by heat treatment, the primary amine or ammonia and / or the primary amine released from the precursor through the depolymerized portion is mixed with the decolorizing or color-developing compound, and the image is decolorized or colored. An image is imagewise formed on the forming material according to the image signal.

On the other hand, in the image-forming material provided with the barrier layer, the layer is perforated or cracked by the energy applied to the imagewise, and then the layer is heat-treated to give a primary amine through the depolymerized portion, Or ammonia and / or a primary amine released from the precursor,
Compounds that decolorize or develop color are mixed and decolorized or developed to form an image in an imagewise manner on the image forming material according to an image signal. The term "perforation" as used herein does not mean that the barrier layer-forming substance scatters and disappears and does not end, but a break in a certain area based on the vicinity of the center of the area where the substance is applied to the adjacent layers. All are scattered and enter, or it refers to melting and spreading around without interruption in a certain area based on the vicinity of the center of the area to which energy is applied.In addition, a crack is an area to which energy is applied. It means that the above-mentioned splashing or melting partially occurs at some sites.

The image-wise energy corresponding to the image signal applied to the image-forming material is not particularly limited as long as it is energy sufficient to activate the polymerization initiator or depolymerizable compound and perforate or crack the barrier layer. Can be used without.

Such energy includes electromagnetic waves,
Although heat, electricity, ultrasonic waves, etc. can be mentioned, in order to obtain high resolution, electromagnetic waves capable of narrowing the energy application area, particularly ultraviolet rays having a wavelength of 1 nm to 1 mm, visible rays, and infrared rays are preferable. Examples of the light source to which energy can be applied include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a quartz mercury lamp and a high pressure mercury lamp.
The energy applied at this time can be appropriately selected and used by adjusting the exposure distance, time and intensity depending on the type of the image forming material.

In case of collectively exposing the above energy,
A mask material having a negative pattern of a desired exposure image formed of a light-shielding material may be superposed and exposed. When using an array type light source such as a light emitting diode array, or when controlling the exposure of a halogen lamp, metal halide lamp, tungsten lamp, or other light source with an optical shutter material such as liquid crystal or PLZT, a digital signal corresponding to the image signal is used. It is possible to expose. In this case, direct writing can be performed without using a mask material.

In the case of a laser, it can be appropriately selected according to the wavelength range of the image forming material used.
Further, since it is possible to focus light into a beam and perform scanning exposure according to image data, it is suitable for direct writing without using a mask material. When a laser is used as a light source, the exposure area can be easily narrowed down to a minute size, and high-resolution image formation becomes possible.

The laser light source used in the present invention is a well-known solid laser such as ruby laser, YAG laser, glass laser; He-Ne laser, Ar ion laser, Kr ion laser, CO ₂ laser, Gas laser such as CO laser, He-Cd laser, N ₂ laser, excimer laser; semiconductor laser such as InGaP laser, AlGaAs laser, GaAsP laser, InGaAs laser, InAsP laser, CdSnP ₂ laser, GaSb laser; chemical laser, dye laser Etc. can be mentioned. .

The exposure direction of light energy is such that when the substrate contains a white pigment and hardly transmits light (for example, white P
Light energy is applied to the ET film) from the image forming composition layer side. When the base material is transparent, it may be supplied from the base material side or the opposite direction as long as the energy is sufficient, but in view of energy efficiency, the surface contains the polymerizable compound and the polymerization initiator. It is preferable to perform the exposure from the direction in which the absorption of the wavelength of the light energy applied to the layer, the layer containing the depolymerizable compound or the barrier layer is small.

In the image forming method of the present invention, an image is formed by heating the image forming material after applying energy. The heat treatment in this case can be used without particular limitation as long as it is uniformly and sufficiently heated.

As the heat treatment means, an oven, a thermal head, a heat roll, a hot stamp, a hot pen or the like that applies only heat or a means that applies heat and applies pressure at the same time can be selected and used at appropriate times. In order to efficiently mix the ammonia and / or primary amine with the compound that decolorizes or develops color, it is more preferable to apply pressure simultaneously with heating.

When an oven is used, the heating temperature is usually
The temperature is 60 to 200 ° C., preferably 80 to 180 ° C., the heating time is usually 0.1 to 300 seconds, preferably 0.5 to 100 seconds, and the thermal head is used for usual melt transfer, sublimation transfer, etc. Can be used as is. The heating temperature when using a heat roll is usually 60 to 200 ° C,
It is preferably in the range of 80 to 180 ° C, and the pressure is usually 0.1 to
20 kg / cm, preferably 0.5-10 kg / cm, and the transport speed is usually 0.1-100 mm / sec, preferably 0.5-50 mm /
Seconds. Further, when using a hot stamp, the heating temperature is usually 60 to 200 ° C., preferably 80 to 150 ° C., and the pressure is usually 0.05 to 10 kg / cm ² , preferably 0.5 to 5
The heating time is usually 0.1 to 300 seconds, preferably 0.5 to 100 seconds, in kg / cm ² .

If it is desired to apply more pressure only to the heat treatment in the oven or the like, the heat and pressure treatment can be carried out, for example, by treating with a pressure roll in the oven.

In the image forming material having a barrier layer, when the photothermal conversion layer is provided adjacent to the vapor deposition layer, the photothermal conversion layer converts light energy into thermal energy, and the thermal energy is converted into thermal energy. Perforate or crack. The same applies to the case where the barrier layer is formed by the layer containing the resin and the light-heat converting compound, and the light energy is converted into heat energy by the light-heat converting compound.
This thermal energy causes the layer to perforate or crack.

When a fixing layer is further provided, the compound capable of deactivating ammonia or the primary amine in the fixing layer is treated as a primary compound by treating the fixing layer at a higher condition than the above heat treatment. It can be inactivated and fixed by thermal diffusion or heat transfer to a layer containing amine, ammonia or primary amine.

In the image forming material provided with the layer containing the polymerizable compound and the polymerization initiator, the same effect as that of the fixing layer can be obtained by completely polymerizing the unpolymerized portion after image formation.

Image Forming Method 2-In the present invention, the image forming material is imagewisely given a first energy and then a second energy is applied to release ammonia and / or a primary amine from the precursor. Then, an image is formed by heating after that.

The above-mentioned first energy is the same as the energy for activating the polymerization initiator or depolymerizable compound and perforating or cracking the barrier layer described in the above-mentioned image forming method 1, and the second energy. Refers to an energy different from the first energy sufficient to release ammonia and / or primary amine from the precursor.

In the present invention, the layer containing the polymerizable compound and the polymerization initiator is polymerized, the depolymerizable compound is depolymerized, and the barrier layer is perforated or cracked by applying the first energy to the image forming material. However, in a layer containing a precursor capable of releasing ammonia and / or primary amines, the precursor remains unchanged or only very little ammonia and / or primary amines are released. To that end, a second energy different from the first energy sufficient to release the ammonia and / or primary amine from the precursor is applied to convert the precursor to ammonia and / or primary amine. Then, by heating and pressurizing, the ammonia and / or primary amine was mixed with the compound that is decolored or colored by the ammonia and / or primary amine, and the image forming material was decolorized or colored according to the image signal. An image is formed.

The first energy is preferably light energy in that the energy application area can be narrowed down in order to obtain high resolution, and the second energy is the first energy which does not affect the heat treatment described later. The light energy having a wavelength different from the light energy added as is particularly preferable.

Examples of such a combination of the first energy / second energy include near-infrared / ultraviolet rays, visible light / ultraviolet rays, ultraviolet rays / visible light, and the like. , The barrier layer, and the precursor capable of releasing ammonia and / or primary amine can be appropriately selected and used.

Specific examples of the first energy applying means, the second energy applying means and the heat treatment means used in the image forming method 2 include the same means as those described in the image forming method 1.

[0201]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" means "parts by weight as active ingredients" unless otherwise specified.

(Preparation of image-forming material) The substrate and surface treatment, intermediate layer, barrier layer, fixing layer, and
In addition to the protective layer, each functional layer was combined to prepare an image forming material of the present invention and a comparative image. Table 1 shows the layer composition and layer composition.
And summarized in Table 2.

Substrate (a) 100 μm stretched transparent polyethylene terephthalate (PE
T) Film (T100) (manufactured by DIAFOIL Hoechst) (b) 100 μm stretched white PET film (W410, manufactured by DIAFOIL Hoechst).

Surface treatment (a) Corona discharge treatment on surface (b) Polyester resin (manufactured by Unitika Ltd .: Elitel UE
Methyl ethyl ketone / toluene (1/1) solution in which 5 parts by weight of 3600) is dissolved is applied on the substrate by wire bar coating and dried to form a primer layer having a thickness of 0.05 μm.

Intermediate layer (a) ethylene-vinyl acetate copolymer (vinyl acetate content 1
0%, melt index 20g / 10min) is sufficiently melt-kneaded and extruded to form an intermediate layer with a thickness of 20μm on the substrate.

(B) An ethylene-vinyl acetate copolymer (Evaflex EV-40Y manufactured by Mitsui DuPont Polychemical Co., Ltd.) was used.
30 parts by weight of the dissolved toluene solution is applied to the base material by wire bar coating and dried to form an intermediate layer with a thickness of 10 μm.

Primary amine, ammonia and / or primary amine
Precursor-containing layer capable of releasing min (a) A primary amine-containing layer forming coating solution having the following composition is applied by wire bar coating and dried to form a 5.0-μm-thick primary amine-containing layer.

Dodecyl bromide 4.0 parts Polyvinyl acetoacetal 16.0 parts (Sekisui Chemical Co., Ltd .: S-REC KS-1) Methyl ethyl ketone 60 parts (b) In the same manner as in (a) except that dodecyl bromide was changed to tetramethylene diamine. Form primary amine-containing layer.

(C) A primary amine-containing layer was formed in the same manner as in (a) except that glycine was used instead of dodecyl bromide.

(D) An ammonia-releasing precursor-containing layer forming coating solution having the following composition is applied by wire bar coating and dried to form an ammonia-releasing precursor-containing layer having a thickness of 10 μm.

[0211] ^{_{[Co 3+ (NH 3) 6}} ] (CF 3 COO -) 3 3.6 parts 2-i-propoxy-1,4-0.6 parts succinimide 1.0 parts of polyvinyl formal 13.4 parts naphthoquinone (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha: Denka Formal # 20) p-Benzylbiphenyl 1.5 parts Acetone 20 parts Methyl ethyl ketone 60 parts (e) 2-i-propoxy-1,4-naphthoquinone 0.6 parts (compound-1) except (d) and (d)) Similarly, a precursor-containing layer capable of releasing ammonia is formed.

(F) 2-i-propoxy-1,4-naphthoquinone 0.6
A precursor-containing layer capable of releasing ammonia was formed in the same manner as in (d) except that 1.0 part was used for (compound-2).

(G) A primary amine-releasing precursor-containing layer forming coating solution having the following composition is applied by wire bar coating and dried to form a primary amine-releasing precursor-containing layer having a thickness of 15 μm. .

[Co ³⁺ (H ₂ NCH ₂ CH ₂ NH ₂ ) ₃ ] (B ^- Ph ₄ ) ₃ 4.6 parts Phthalimide 1.5 parts Ethylcellulose (T-10) manufactured by Hercules Co. 14.4 parts Acetone 20 parts Methylethylketone 60 parts ( h) A coating solution for forming a precursor-containing layer capable of releasing ammonia and primary amine having the following composition is applied and dried by wire bar coating to form a precursor-containing layer capable of releasing ammonia and primary amine having a thickness of 15 μm. .

[Co ³⁺ (NH ₃ ) ₆ ] (B ^- Ph ₄ ) ₃ 2.3 parts [Co ³⁺ (H ₂ NCOCH ₂ NH ₂ ) ₃ ] (B ^- Ph ₄ ) ₃ 2.3 parts Diphenylhydantoin 1.5 parts Polyvinyl Butyral 14.4 parts (Sekisui Chemical Co., Ltd., S-REC BL-1) Acetone 20 parts Methyl ethyl ketone 60 parts (i) (h) ammonia- and primary amine-releasing precursor-containing layer forming coating liquid, and further (compound- A precursor-containing layer capable of releasing ammonia and a primary amine was formed in the same manner as in (h) except that 0.8 part of 1) was added.

(J) (h) Ammonia and a primary amine-releasing precursor-containing layer forming coating solution, and further (Compound-2)
A precursor-containing layer capable of releasing ammonia and a primary amine was formed in the same manner as in (h) except that 1.0 part of was added.

[0217]

[Chemical formula 26]

Polymerizable Compound- and Polymerization Initiator-Containing Layer (a) A polymerizable compound and a polymerization initiator-containing layer forming coating solution having the following compositions are applied and dried by wire bar coating to give a polymerizable compound having a thickness of 1.0 μm. And a layer containing a polymerization initiator.

Polymethylmethacrylate 10.0 parts (Mitsubishi Rayon Co., Ltd .: Dianal BR-83) Dipentaerythritol hexaacrylate 37.0 parts (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) Bis (2-o-chlorophenyl-4,5-diphenylimidazole) ) 2.25 parts 2-mercaptobenzothiazole 0.75 parts methyl ethyl ketone 50 parts (b) except that bis (2-o-chlorophenyl-4,5-diphenylimidazole) was replaced with 2,2'-dihydroxy-4-methoxybenzophenone ( A layer containing a polymerizable compound and a polymerization initiator is formed in the same manner as in a).

(C) A coating liquid for forming a polymerizable compound- and polymerization initiator-containing layer having the following composition was applied by wire bar coating and dried to form a 1.0 μm-thick polymerizable compound and polymerization initiator-containing layer.

Styrene-ethylene propylene rubber-acrylonitrile copolymer 10.0 parts (JSR AES117 manufactured by Japan Synthetic Rubber Co., Ltd.) 18.0 parts trimethylolpropane triacrylate (ARONIX M-309 manufactured by Toagosei Chemical Industry Co., Ltd.) Dipentaerythritol hexaacrylate 20.0 parts (KAYARAD DPHA: above) 3,3'-carbonylbis (7-diethylaminocoumarin) 2.5 parts Diphenyl / phenacylsulfonium tetrafluoroborate 2.5 parts Toluene 200 parts Methyl ethyl ketone 200 parts (d) 3,3'-Carbonylbis (7-diethylaminocoumarin), diphenyl phenacyl sulfonium tetrafluoroborate, instead of tris (2,2'-dipyridyl) ruthenium bis (hexafluorophosphate), diphenyliodonium hexafluorophosphate, respectively (c) and Polymerizable compound in the same manner A layer containing a substance and a polymerization initiator is formed.

(E) A coating liquid for forming a polymerizable compound- and polymerization initiator-containing layer having the following composition is applied by wire bar coating and dried to form a 1.0 μm-thick polymerizable compound and polymerization initiator-containing layer.

Polymethylmethacrylate (Dianal BR-83: supra) 10.0 parts Dipentaerythritol hexaacrylate 25.0 parts (KAYARAD DPHA: supra) EO-modified tetrabromobisphenol A dimethacrylate 10.0 parts (Daiichi Kogyo Seiyaku Co., Ltd .: New Frontier BR-42M) Compound-3 (photopolymerization initiator) 0.80 parts Tetrabutylammonium tetraphenylborate 2.60 parts 1-Phenyl-5-mercaptotetrazole 0.80 parts N, N, 2,4,6-pentamethylaniline 0.80 parts Methyl ethyl ketone 50 parts (f) Compound-3 and tetrabutylammonium tetraphenylborate were replaced by compound-4 (photopolymerization initiator) and lithium tetraphenylborate, respectively, except that the polymerization was carried out in the same manner as in (e). A layer containing a compound and a polymerization initiator is formed.

[0224]

[Chemical 27]

Depolymerizable compound-containing layer (a) A depolymerizable compound-containing layer-forming coating solution having the following composition is applied by wire bar coating and dried to give a thickness of 1.5.
Form a layer containing μm depolymerizable compound.

Poly (p-formyloxystyrene) 10 parts Dibutyl / phenacylsulfonium hexafluoroantimonate 1.0 part 2-i-propoxy-1,4-anthraquinone 0.5 part Methyl ethyl ketone 85.5 parts (b) Depolymerizable compound having the following composition The coating liquid for forming the contained layer is applied and dried by wire bar coating to a thickness of 2.5.
Form a layer containing μm depolymerizable compound.

Poly (1-butene sulfone) (manufactured by Chisso Corporation: PBS) 9.0 parts Pyridine-N-oxide 1.0 part Methyl cellosolve acetate 80 parts Cyclohexanone 10 parts (c) Depolymerizable compound-containing layer forming coating composition having the following composition Is applied by wire bar coating and dried to a thickness of 2.0
Form a layer containing μm depolymerizable compound.

Polyphthalaldehyde 10 parts Triphenylsulfonium hexafluoroantimonate 1.0 part Perylene 0.5 part Dimethylformamide 88.5 parts (d) A depolymerizable compound-containing layer forming coating solution having the following composition is applied and dried by wire bar coating. , Thickness 1.5
Form a layer containing μm depolymerizable compound.

Compound-5 (depolymerized compound) 9.0 parts Triphenylsulfonium trifluoroacetate 1.0 part Anthracene 0.5 part Tetrahydrofuran 90 parts Barrier layer (a) A barrier layer forming coating solution having the following composition is applied and dried by wire bar coating. Then, a barrier layer with a thickness of 1.0 μm is formed.

Compound-6 (photothermal conversion compound, λmax 740 nm / MeOH) 1.0 part Gelatin 9.0 parts Distilled water 90 parts (b) A barrier layer-forming coating solution having the following composition is applied and dried by wire bar coating to a thickness. Formed a barrier layer of 1.5 μm.

Compound-7 (photothermal conversion compound, λmax 787 nm / CH ₂ Cl ₂ ) 1.0 part Nitrocellulose 9.0 parts Methyl ethyl ketone 90 parts (c) A 100 Å-thick aluminum metal thin film was formed by a vacuum deposition method.

(D) A thin metal film of tin having a thickness of 50 Å is formed by a sputtering method, and a photothermal conversion compound-containing layer forming coating solution having the following composition is applied and dried by wire bar coating to a thickness of 0.5. Form a photothermal conversion layer of μm.

Compound-8 (photothermal conversion compound, λmax 814 nm / MeOH) 0.5 part Polyethylene wax (Microflat CE-150) 4.5 parts Toluene 60 parts Ethyl acetate 15 parts Acetone 20 parts

[0234]

[Chemical 28]

Decoloring or coloring with ammonia or primary amine
Compound-containing layer (a) A coating liquid for forming a compound-containing layer that develops color with the following ammonia or primary amine is applied by wire bar coating and dried to form a color forming layer having a thickness of 15 μm.

Aldehyde (1-31) 4.0 parts Polyvinyl butyral (ESREC BL-1: supra) 16 parts Methyl ethyl ketone 80 parts (b) Except that the aldehyde (1-31) was replaced with (1-32), (a) ) And the color forming layer is formed.

(C) A color forming layer was formed in the same manner as in (a) except that the aldehyde was replaced with (1-9).

(D) A color-forming layer was formed in the same manner as in a) except that the aldehyde was replaced with (1-1).

(E) The following compound-containing layer forming coating solution which is decolorized with ammonia or primary amine is applied by wire bar coating and dried to form a decolorizing layer having a thickness of 20 μm.

8- (benzo (b) -3H-1,2-dithiol-3-yridin) -9,10,11,12-2.0 parts tetrahydro-8H-cyclohepta (e) naphtho (2,1-b) Pyrylium perchlorate Styrenic resin (Kresin KR01 manufactured by Nippon Steel Chemical Co., Ltd.) 17 parts p-Benzylbiphenyl 1.0 part Acetone 20 parts Methyl ethyl ketone 60 parts The pyrylium dye used in (f) (e) is 2,4-diphenyl- 6-
An image forming composition layer was formed in the same manner as in (e) except that (β-methyl-3,4-diethoxystyryl) pyrylium fluoroborate was used instead.

(G) An image-forming composition similar to (e) except that the pyrylium dye used in (e) was replaced with 2,6-diphenyl-4- (4-methoxycarbonylphenyl) pyrylium perchlorate. Forming a physical layer.

(H) Instead of the pyrylium dye used in (e), 8- (benzo (b) -3H-1,2-dithiol-3-yridine)-
9,10,11,12-Tetrahydro-8H-cyclohepta (e) naphtho (2,1-b) pyrylium perchlorate 0.7 parts, 2,4-diphenyl-6- (β-methyl-3,4-diethoxy 0.65 parts of styryl) pyrylium fluoroborate and 2,6-diphenyl-4- (4-methoxycarbonylphenyl) pyrylium perchlorate
An image forming composition layer was formed in the same manner as in (e) except that 0.65 part was used.

Fixing layer (a) A fixing layer forming coating solution having the following composition was applied by wire bar coating and dried to form a fixing layer having a thickness of 5.0 μm.

Epoxy resin (manufactured by Tohto Kasei Co., Ltd .: Epotote YH-300) 4.0 parts Polycarbonate (manufactured by Mitsubishi Gas Chemical Co., Inc .: Iupilon Z-200) 20 parts Toluene 60 parts Methyl ethyl ketone 16 parts b) Fixing layer forming coating solution having the following composition Is applied by wire bar coating and dried to form a fixing layer with a thickness of 5.0 μm.

Phenacyl sulfonyl chloride 3.0 parts Polyarylate (U-Polymer U-100 manufactured by Unitika Ltd.) 20 parts Tetrahydrofuran 67 parts Protective layer (a) A protective layer forming coating solution having the following composition is applied and dried by wire bar coating. Then, a 3.0 μm thick protective layer is formed.

Polymethylmethacrylate (Dianal BR- 88 : Id.) 5.0 parts Titanium oxide (Idemitsu Kosan Co., Ltd .: Idemitsu Titania IT-UD) 3.0 parts Methyl ethyl ketone 92 parts (b) 25 μm transparent stretched PET film (Dia foil Hoechst) Product: S) is treated on one side with corona discharge, and the treated layer is coated with an adhesive layer forming coating solution having the following composition by wire bar coating and dried to form a film with an adhesive layer having a thickness of 1.0 μm. A protective layer is formed by bonding with a pressure roll.

Polyester resin (manufactured by Toyobo Co., Ltd .: Byron 300) 10 parts Methyl ethyl ketone 90 parts

[0248]

[Table 1]

[0249]

[Table 2]

(Formation of Image) Using 64 types of image forming materials shown in Tables 1 and 2, images were formed by the following methods (a to l).

(A) A filter for cutting light of 400 nm or more is applied, and a wedge pattern is adhered to the image forming composition layer side of the image forming material (15 × 15 cm). : P-627-HA) to form a latent image by batch exposure (exposure energy of 500 mJ / cm ² ), and then heat and pressure treatment of the image forming material with a heat roll to form an image.

The sensitivity, reproduced resolution and image fog of the image forming material were evaluated according to the following criteria. The evaluation results and the processing conditions (temperature, pressure, time) are shown in Tables 3 and 4.

<< Sensitivity >> An image is formed by exposing and heating by applying a mask having a wedge gradation such that the density difference between adjacent steps is 0.10 and the density difference between adjacent steps is 0.10, and the formed image density Exposure energy (E: unit mJ) that gives a density of +0.10 (-0.10 for pyrylium dye)
/ Cm ² ) was evaluated in four levels.

◎… E ≦ 20 ○… 20 <E ≦ 50 △… 50 <E ≦ 100 ×… 100 <E << Resolution >> Plate control wedge (manufactured by UGRA)
Was used to observe the reproducibility of 150-dot / inch halftone dots of 2 to 98% with a microscope, and the reproduced halftone dot area (Z: unit%) was observed.

∘: 2 ≦ Z ≦ 98 ○: 5 ≦ Z ≦ 95 Δ: 10 ≦ Z ≦ 90 ×: 15 ≦ Z ≦ 85 << Image Fogging >> Concentration of image-forming material before image formation and heat-treated image The difference (D) from the density of the part which was not decolorized or developed after the formation was measured.

A: D ≦ 0.10 O: 0.10 ≦ D <0.25 Δ: 0.25 ≦ D <0.50 ×: 0.50 <D (b) After heating and pressurizing at (a), the temperature is further raised by 20 ° C. and the same. An image fixing process was performed by heating and pressurizing under the conditions.

The sensitivity, resolution and image fog were evaluated according to the same criteria as in (a). The evaluation results are shown in Tables 3 and 4.

(C) A xenon flash lamp (Xenofax FX manufactured by Ideal Science Co., Ltd. is used instead of the printer for the bright room light-sensitive material.
180 is used, exposure time is 1 ms, exposure energy is 100 mJ
/ Cm ² , the number of exposure was 5), and an image was formed and evaluated in the same manner as in (a).

The sensitivity and resolution were evaluated according to the same criteria as in (a). The results and processing conditions are shown in Tables 3 and 4.

After the heating / pressurizing treatment in (d) and (c), the temperature was further raised by 20 ° C. and the heating / pressurizing treatment was carried out under the same conditions to carry out the image fixing treatment.

The sensitivity, resolution and image fog were evaluated according to the same criteria as in (a). The results are shown in Tables 3 and 4.

(E) Argon ion laser (American Laser 60C, output 30 mW, wavelength 514.5 nm, beam diameter 0.
65mm), the aperture is focused to 20μm, the latent image is formed by scanning exposure (scanning pitch 20μm), and the image forming material (15 × 15cm) is heated / pressurized with a heat roll. To form an image.

The sensitivity of the image forming material (minimum average exposure amount required for image formation) and image fog were evaluated according to the following criteria.
The results and treatment conditions (temperature, pressure, time) are shown in Table 5.

<Sensitivity> The average exposure dose (E) on the surface of the image forming material (the minimum required average exposure dose, unit: mJ / cm ² ) is shown.

A: E ≦ 50 O: 50 <E ≦ 100 Δ: 100 <E ≦ 250 × ... 250 <E << Image Fogging >> Concentration of image forming material before image formation and heat treatment to form an image. The difference (D) from the density of the part where the subsequent decolorization or color development was not performed was measured.

A: D ≦ 0.10 O: 0.10 ≦ D <0.25 Δ: 0.25 ≦ D <0.50 ×: 0.50 <D (f) After heating under pressure (e), the temperature is further raised by 20 ° C. and the same. An image fixing process was performed by heating and pressurizing under the conditions. The sensitivity and image fog were evaluated according to the same criteria as (e).
The results are shown in Table 5.

(G) Using an argon ion laser (manufactured by American Laser Co .: aforesaid), the aperture was focused to 20 μm and scanning exposure was performed (scanning pitch 20 μm), then 400
After applying a filter that cuts light of nm or more and exposing the entire surface (exposure energy 200 mJ / cm ² ) with a bright room light-sensitive material printer (P-627-HA: described above), the image forming material (15 x 15 cm) was used. An image was formed by heating with a heat roll.

The sensitivity, resolution and image fog were evaluated according to the same criteria as in (e). Results and processing conditions (temperature, pressure, time)
Is shown in Table 5.

After the heating / pressurizing treatment in (h) and (g), the temperature was further raised by 20 ° C. and the heating / pressurizing treatment was carried out under the same conditions to carry out the image fixing treatment.

The sensitivity and image fog were evaluated according to the same criteria as in (e). The results are shown in Table 3.

(I) Semiconductor laser (LT090M manufactured by Sharp Corporation)
D, output 100mW, main wavelength 830nm), after focusing, scan exposure (beam diameter 8μm, scan pitch 5μm) to form a latent image, image forming material (5x5cm) is heated by hot stamping Processed to form an image.

The sensitivity of the image forming material (minimum average exposure amount required for image formation), the reproduced resolution, and the image fog were evaluated according to the following criteria. The results and processing conditions (temperature, pressure, time) are shown in Table 6.

<Sensitivity> The average exposure dose (E) of the surface of the image forming material (the minimum required average exposure dose, unit: mJ / cm ² ) is shown.

A: E ≦ 50 O: 50 <E ≦ 100 Δ: 100 <E ≦ 500 × ... 500 <E << Resolution >> Resolvable per 1 mm when an image is formed with the minimum required average exposure amount. The number of lines (N) was evaluated.

◎ ... 120 ≦ N ○ ... 80 ≦ N <120 Δ ... 40 ≦ N <80 × ... N <40 << Image Fogging >> The density of the image forming material before image formation and the image formation by heat treatment. The difference (D) from the density of the part where the subsequent decolorization or color development was not performed was measured.

A: D ≦ 0.10 O: 0.10 ≦ D <0.25 Δ: 0.25 ≦ D <0.50 ×: 0.50 <D (j) After heating and pressurizing, the temperature is further raised by 20 ° C. and the same. An image fixing process was performed by heating and pressurizing under the conditions.

The sensitivity, resolution and image fog were evaluated according to the same criteria as (i). The results are shown in Table 6.

(K) A semiconductor laser (LT090MD: described above) was used to perform focus and scanning exposure (beam diameter 8 μm, scanning pitch 5 μm), and then a filter for cutting light of 400 nm or more was applied, and a bright room light-sensitive material After full exposure (exposure energy 200 mJ / cm ² ) with a printer (P-627-HA: above),
The image forming material (15 × 15 cm) was heat-treated with a heat roll to form an image.

The sensitivity, resolution and image fog were evaluated according to the same criteria as in (e). The results and processing conditions (temperature, pressure, time) are shown in Table 6.

After the heating / pressurizing treatment in (l) (k), the temperature was further raised by 20 ° C. and the heating / pressurizing treatment was carried out under the same conditions to carry out the image fixing treatment.

The sensitivity, resolution and image fog were evaluated according to the same criteria as in (k). The results are shown in Table 6.

Separately, unused samples of the image-forming materials of the present invention and the comparative example were stored in the dark under the following conditions, and increased by 0.10 or more (decolored) from the density before the storage or the density not developed. In the case of the pyrylium dye, the storability in the dark of the image-forming material was evaluated by the number of days (T) until the decrease was 0.10 or more. The results are shown in Tables 7 and 8.

<< Heat resistant storage (DT storage); 55 ° C, humidity 20
%, "Heat and humidity resistant storage (HDT storage): 50 ° C, humidity 8
0% >>, the following four-level evaluation was performed.

◎ ... 7 ≦ T ○ ... 4 ≦ T <7 Δ ... 2 ≦ T <4 × ... T <2 << Room temperature storage (RT storage); 25 ° C. >>, << Low temperature storage (LT
Storability); −5 ° C.) is the following four-stage evaluation.

A: 30 ≦ T ○: 20 ≦ T <30 Δ: 10 ≦ T <20 × ... T <10 Furthermore, each image forming material on which the above-mentioned image formation was performed was exposed at 40 ° C. with a xenon weather meter. Image lightfastness was evaluated by the number of days (T) from the density of the part that was exposed to light and was not decolored or before being exposed to increase (0.10 or more was decreased in the case of a decolorizable pyrylium dye). The results are shown in Tables 7 and 8.

<< Image lightfastness storage stability >> A ... 7 ≦ T O ... 4 ≦ T <7 Δ ... 2 ≦ T <4 x ... T <2

[0287]

[Table 3]

[0288]

[Table 4]

[0289]

[Table 5]

[0290]

[Table 6]

[0291]

[Table 7]

[0292]

[Table 8]

[0293]

As is clear from the results of Tables 3 to 8,
The image forming material of the present invention has good sensitivity, resolution, reduction of fog, and storability, and also has excellent light resistance of the formed image.

[Brief description of drawings]

FIG. 1 is a cross-sectional view (a, b) showing a structural example of an image forming material of the present invention.

FIG. 2 is a sectional view (c to h) showing another structural example of the image forming material of the present invention.

FIG. 3 is a cross-sectional view (in) showing another configuration example of the image forming material of the present invention.

FIG. 4 is a cross-sectional view (o) showing a configuration example of a conventional image forming material.
~ S).

[Explanation of symbols]

1 layer containing a primary amine, or a precursor capable of releasing ammonia and / or primary amine 2 layer containing a compound that is decolored or colored by ammonia and / or primary amine 3 base material 4 polymerizable compound Layer containing polymerization initiator, layer containing depolymerizable compound, barrier layer 5 Protective layer 6 Fixing layer 7 Intermediate layer

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B41M 5/26 G03C 1/67 5/08 351 G03F 7/027 502 7/028 7/11 7/26 521

Claims (16)

[Claims] 1. A layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine on at least one surface of a substrate, and a color erasing or coloring by the ammonia and / or the primary amine. An image forming material having a layer containing a compound, wherein a layer containing a polymerizable compound and a polymerization initiator is provided between the two layers. 2. The image forming material according to claim 1, wherein the polymerization initiator is a photopolymerization initiator. 3. A layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine on at least one side of a substrate, and a color erasing or coloring by the ammonia and / or the primary amine. An image forming material having a layer containing a compound, wherein a layer containing a depolymerizable compound is provided between the two layers. 4. The photodepolymerization initiator is further contained in the layer containing the depolymerizable compound.
The image forming material described. 5. A layer containing a primary amine or a precursor capable of releasing ammonia and / or a primary amine on at least one surface of a substrate and a color erasable or colored by the ammonia and / or the primary amine. An image forming material having a layer containing a compound, wherein a barrier layer is provided between the two layers. 6. The image forming material according to claim 5, wherein the barrier layer is a vapor deposition layer. 7. The image forming material according to claim 6, wherein the image forming material provided with the vapor deposition layer is further provided with a layer containing a photothermal conversion compound in contact with the vapor deposition layer. 8. The image forming material according to claim 7, wherein the photothermal conversion compound is a dye or a dye having an absorption maximum wavelength at 600 to 1100 nm. 9. The barrier layer comprises a resin and 600 to 1100 nm
The image forming material according to claim 5, wherein the image forming material is a layer containing a dye or a dye having an absorption maximum wavelength. 10. The image forming material according to claim 1, wherein the compound that develops color with ammonia and / or a primary amine is a compound represented by the following general formula (1). [Chemical 1] [In the formula, Q represents an atomic group necessary for forming an aromatic ring or a 5- or 6-membered heterocycle, and the aromatic ring or heterocycle may have a substituent. ] 11. The image forming material according to claim 1, wherein the compound that is decolorized with ammonia and / or a primary amine is a pyrylium dye. 12. The image forming material according to claim 1, wherein the precursor capable of releasing ammonia and / or primary amine is a compound represented by the following general formula (2). [Chemical 2] [In the formula, L ₁ represents ammonia and / or a primary amine ligand forming a complex with a cobalt cation, and L ₂ represents ammonia and / or 1 forming a complex with a cobalt cation.
Represents a coordination compound other than a primary amine. k is an integer from 1 to 3,
m represents an integer of 1 to 6, n represents an integer of 0 to 5, and when m and n are 2 or more, a plurality of L ₁ and L ₂ may be the same or different. X ⁻ represents a counter anion. ] 13. A substrate having a layer containing a precursor capable of releasing ammonia and / or a primary amine and a layer containing a compound capable of decoloring or developing with ammonia or a primary amine on at least one surface of a substrate. Then, an image forming material provided with a layer containing a polymerizable compound and a polymerization initiator, a layer containing a depolymerizable compound, or a barrier layer between the two layers is used to generate energy according to an image signal. An image forming method comprising forming an image by applying and then heating. 14. The energy provided according to the image signal is light energy.
13. The image forming method described in 13. 15. A substrate containing a precursor containing a precursor capable of releasing ammonia and / or a primary amine and a layer containing a compound capable of decoloring or developing with ammonia or a primary amine, on at least one side of a substrate. Then, an image forming material having a layer containing a polymerizable compound and a polymerization initiator, a layer containing a depolymerizable compound, or a barrier layer between the two layers is used, and the first An image forming method comprising forming an image by applying energy and then adding second energy for releasing ammonia and / or a primary amine from a precursor and then heating. 16. A first applied according to the image signal
16. The image forming method according to claim 15, wherein the energy is light energy, and the second energy for releasing ammonia and / or primary amine from the precursor is light energy having a wavelength different from that of the first energy.