JPH06118640A - Recording material - Google Patents

Abstract

PURPOSE:To improve light resistance before use by using microcapsules containing a specified electron donative colorless dye, an aniline compound, and a hindered phenol compound. CONSTITUTION:The recording material comprises the microcapsules containing the electron donative colorless dye represented by formula I, the aniline compound represented by formula II, and the hindered phenol represented by formula III or IV, and an electron acceptor. In formulae I-IV, each of R<1>-R<4> is, independently, alkyl or aryl, or each of (R<1> and R<2>) and (R<3> and R<4>) may combine with each other to form a 5-to 8-membered hetero ring comprising the adjacent N atom and optional other hetero atom, or R<1> and/or R<2> may combine with the C atom situated at the o-position to the -N(R<1>)(R<2>) group and R<3> and/or R<4> may combine with the C atom situated at the o-position to the -N(R<3>)(R<4>) group to form an N-containing hetero ring; R<9> is H or substituted amino; and m is an integer of 1-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material utilizing a color-forming reaction between an electron-donating colorless dye and an electron-accepting compound, and more particularly to a recording material having improved light resistance before use.

[0002]

2. Description of the Related Art Recording materials using an electron-donating colorless dye and an electron-accepting compound are pressure-sensitive paper, thermal paper, photosensitive pressure-sensitive paper,
It is already well known as an electrically conductive recording paper and a thermal transfer paper. For example, British Patent No. 2140449, US Patent Nos. 4480052, 4436920, and 48.
No. 00149, Japanese Patent Publication No. 60-23992, and Japanese Patent Laid-Open No. 60
For details, see No. 123,556 and No. 60,123,557.

As a recording material, research has been earnestly conducted for improvement of properties such as color density and color sensitivity, and fastness before use and color image. In recent years, recording materials using an electron-donating colorless dye and an electron-accepting compound have come to be used for proofreading copy materials and printing materials, and to prevent coloring of the background of such recording materials by light irradiation. Research is also being carried out. The electron-donating colorless dye represented by the general formula (1) described above has a good color developability, but has a problem of poor light resistance before use.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material using an electron-donating colorless dye and an electron-accepting compound and having good light resistance before use.

[0005]

Means for Solving the Problems The present invention includes an electron-donating colorless dye represented by the following general formula (1), an aniline compound represented by the following general formula (2), and the following general formula (3) or the following general formula. A recording material comprising a microcapsule containing a hindered phenol compound represented by formula (4) and an electron-accepting compound.

[0006]

[Chemical 5]

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group or an aryl group, and R ¹ and R ² or R ³ and R ⁴ are bonded to each other, R ¹ and / or R ¹ and / or may form a ring which may include a 5-membered to 8-membered heteroatom including the nitrogen atom to which they are attached.
Or R ² is bonded to a carbon atom in the ortho position with respect to the bonding position of —NR ¹ R ² , and R ³ and / or R ⁴ is —NR ³ R
^It may be bonded to a carbon atom in the ortho position with respect to the bonding position of ⁴ to form a nitrogen-containing heterocycle, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group, R ⁹ is a hydrogen atom,
It represents an alkyl group, an alkoxy group, a halogen atom or a substituted amino group, and m represents an integer of 1 to 4. )

[0008]

[Chemical 6]

(In the formula, R ¹⁰ represents an alkyl group or an aryl group, R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an aryl group,
Represents an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted amino group, an alkylthio group or an arylthio group, and k and n are each independently 1
Represents an integer of 5; )

[0010]

[Chemical 7]

(In the formula, R ¹³ represents a secondary or tertiary alkyl group, R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group, R ¹⁷ represents a hydrogen atom, It represents a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group or an alkoxycarbonylalkyl group.)

[0012]

[Chemical 8]

(In the formula, R ¹⁸ represents a secondary or tertiary alkyl group, R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group, and R ²² represents an ester or an ether. Or a hydrocarbon group which may have an amide bond,
Alternatively, it represents a sulfur atom, and p represents an integer of 2 to 4. )

The alkyl group and aryl group in each of the above formulas further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a halogen atom, a nitro group, a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group,
It may have a substituent such as a substituted amino group, a substituted oxycarbonyl group, a substituted oxysulfonyl group, an alkylthio group and an arylsulfonyl group.

The electron-donating colorless dye used in the present invention is a compound represented by the above general formula (1). In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are
An alkyl group having 1 to 18 carbon atoms or 6 to 1 carbon atoms
2 aryl groups are preferred. Further R ¹ and R
² , or R ³ and R ⁴ are bonded to each other and may contain a 5-membered to 8-membered heteroatom including the nitrogen atom to which they are bonded, for example, pyrrolidine, piperidine, morpholine, thiol It may form a morpholine, piperazine or caprolactam ring. In addition, R ¹ and / or R
² is bonded to a carbon atom in an ortho position with respect to the bonding position of -NR ¹ R ² , or R ³ and / or R ⁴ is -NR ³ R
Bonding to the carbon atom in the ortho position with respect to the bonding position of ⁴ ,
Tetrahydroquinoline, indoline, julolidine ring and the like may be formed.

Examples of the group represented by -NR ¹ R ² or -NR ³ R ⁴ include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, dioctylamino group. Group, diphenylamino group, ditolylamino group, dibenzylamino group, N-methyl-N-ethylamino group, N-methyl-N-butylamino group, N-ethyl-N-butylamino group, N-ethyl-N- β-methoxyethylamino group, N-ethyl-N-β-ethoxyethylamino group, N
-Ethyl-N-β-phenoxyethylamino group, N-methyl-N-β-cyanoethylamino group, N-methyl-N
-Β-chloroethylamino group, N-ethyl-N-cyclohexylamino group, N-ethyl-N-pentylamino group, N-ethyl-N-tetrahydrofurfurylamino group, N-ethyl-N-tolylamino group, N -Ethyl-N
-Methoxyphenylamino group, N-ethyl-N-benzylamino group, N-ethyl-N-chlorobenzylamino group, pyrrolidino group, piperidino group, morpholino group, and piperazino group.

R ⁵ and R ⁶ are a hydrogen atom or a carbon atom of 1
It is preferably an alkyl group, an alkoxy group or a halogen atom of -18. Specific preferred examples of R ⁵ and R ⁶ include a hydrogen atom, a methyl group, an ethyl group, a propyl group,
Butyl group, octyl group, phenyl group, tolyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, propoxy group, butoxy group, octyloxy group, benzyloxy group, phenoxyethoxy group, chlorine atom, bromine atom, fluorine atom Etc. The substitution position of R ⁵ and R ⁶ is −
A meta position is preferable with respect to the substitution position of NR ¹ R ² and —NR ³ R ⁴ .

R ⁷ and R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁷ and R
Specific preferred examples of ⁸ include a hydrogen atom, a methyl group, an ethyl group, a propyl group and a butyl group, and a hydrogen atom is particularly preferred.

R ⁹ is preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a halogen atom, a dialkylamino group having 2 to 24 carbon atoms, an alkylarylamino group or a diarylamino group. . R
Preferred specific examples of ⁹ are hydrogen atom, methyl group, ethyl group, propyl group, butyl group, octyl group, phenyl group, tolyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, propoxy group, butoxy group, Octyloxy group, benzyloxy group, phenoxyethoxy group,
Chlorine atom, bromine atom, fluorine atom, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, dioctylamino group, diphenylamino group, ditolylamino group, dibenzylamino group, N -Methyl-N-ethylamino group, N-methyl-N-butylamino group, N-ethyl-
N-butylamino group, N-ethyl-N-β-methoxyethylamino group, N-ethyl-N-β-ethoxyethylamino group, N-ethyl-N-β-phenoxyethylamino group, N-methyl-N -Β-cyanoethylamino group, N-
Methyl-N-β-chloroethylamino group, N-ethyl-
N-cyclohexylamino group, N-ethyl-N-pentylamino group, N-ethyl-N-tetrahydrofurfurylamino group, N-ethyl-N-tolylamino group, N-ethyl-N-methoxyphenylamino group, N- Ethyl-N-
Benzylamino group, N-ethyl-N-chlorobenzylamino group, pyrrolidino group, piperidino group, morpholino group,
Examples thereof include a piperazino group.

Specific examples of the electron-donating colorless dye represented by the general formula (1) are shown below, but the invention is not limited thereto.

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

The aniline compound used in the present invention is a compound represented by the above general formula (2). In the general formula (2), R ¹⁰ is preferably an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 12 carbon atoms. Preferred specific examples of R ¹⁰ include methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl group, phenyl group, tolyl group, methoxyphenyl group, methoxytolyl group, methylthio group, etc. Can be mentioned.

R ¹¹ and R ¹² are a hydrogen atom or a carbon atom of 1
~ 18 alkyl groups, alkoxy groups, alkylthio groups,
Alkoxycarbonyl group, halogen atom, 6 carbon atoms
~ 12 aryl group, aryloxy group, aryloxycarbonyl group, arylthio group, C2-24
Are preferably a dialkylamino group, an alkylarylamino group or a diarylamino group, and particularly preferably an alkoxy group or an alkyl group. Specific preferred examples of R ¹¹ and R ¹² include, in addition to those enumerated above as preferred specific examples of R ⁹ , a methylthio group, an ethylthio group, an octylthio group, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a phenyl group. , Tolyl group,
Examples thereof include a methoxyphenyl group, a phenoxycarbonyl group and a phenylthio group.

Specific examples of the aniline compound represented by the above general formula (2) are shown below, but the invention is not limited thereto.

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

In the present invention, the amount of the aniline compound used is preferably 10 to 2000% by weight, and particularly preferably 50 to 1000% by weight of the electron-donating colorless dye used.

The hindered phenol compound used in the present invention is a compound represented by the above general formula (3) or a compound represented by the above general formula (4).

In the above general formula (3), R ¹³ is preferably a secondary or tertiary alkyl group having 3 to 18 carbon atoms. Preferred examples of R ¹³ are iso-propyl group, t-butyl group, t-pentyl group, t-hexyl group, t-octyl group, t-decyl group, t-dodecyl group and the like.

R ¹⁴ , R ¹⁵ and R ¹⁶ are preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group such as secondary and tertiary alkyl groups. Specific preferred examples of R ¹⁴ , R ¹⁵ and R ¹⁶ are:
Hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group,
The dodecyl group, and those enumerated above as preferred specific examples of R ¹³ can be mentioned.

R ¹⁷ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group or an alkoxycarbonylalkyl group having 3 to 24 carbon atoms. preferable. Specific preferred examples of R ¹⁷ include hydroxyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, methoxy group, ethoxy group, propoxy group, butoxy group. , Octyloxy group, benzyloxy group, ethoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, 2-octadecyloxycarbonylethyl group, butoxycarbonylmethyl group, phenoxycarbonylethyl group and the like.

In the above general formula (4), R ¹⁸ is preferably a secondary or tertiary alkyl group having 3 to ¹⁸ carbon atoms. Preferred specific examples of R ¹⁸ are iso-propyl group, t-butyl group, t-pentyl group, t-hexyl group, t-octyl group, t-decyl group, t-dodecyl group and the like.

R ¹⁹ , R ²⁰ and R ²¹ are preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group such as secondary and tertiary alkyl groups. Specific preferred examples of R ¹⁹ , R ²⁰ and R ²¹ are:
Hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group,
The dodecyl group, and those enumerated above as preferred specific examples of R ¹⁸ can be mentioned.

R ²² is preferably a hydrocarbon group having a total of 1 to 30 carbon atoms, which may have an ester, ether or amide bond, or a sulfur atom. Ester contained in the hydrocarbon group represented by R ^22, the number of ether or amide bond is preferably the same or higher number and value of at p in the general formula (4), with R ²² The hydrocarbon group represented may contain a carbocycle, a heterocycle or a side chain.

Next, the above general formula (3) or general formula (4)
Specific examples of the hindered phenol compound represented by are shown below, but the invention is not limited thereto.

[0042]

[Chemical 18]

[0043]

[Chemical 19]

[0044]

[Chemical 20]

In the present invention, the amount of the hindered phenol compound used is 5 to 2 of the electron-donating colorless dye used.
00 wt% is preferable, and 20 to 100 wt% is particularly preferable.

In the recording material of the present invention, if necessary, the well-known triphenylmethanephthalide compound, fluoran, together with the electron-donating colorless dye represented by the general formula (1) is used. Compounds, phenothiazine compounds, indolylphthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, fluorene compounds, etc. The electron-donating colorless dye represented by formula (1) may be used in an amount of 100% by weight or less.

Of these, specific examples of phthalides are, for example, US Reissue Patent No. 23,024 and US Patent No. 3,024.
491,111, 3,491,112, 3,491,116 and 3,509,174.
And specific examples of fluoran compounds are disclosed in US Pat. No. 3,624,1.
No. 07, No. 3,627,787, No. 3,641,
011; 3,462,828; 3,68
No. 1,390, No. 3,920,510, No. 3,9
59,571, specific examples of spirodipyrans are U.S. Pat. No. 3,971,808, and pyridine-based and pyrazine-based compounds are U.S. Pat. Nos. 3,775,424;
853,869, 4,246,318, and specific examples of fluorene compounds are described in European Patent 278,614 and the like.

In the recording material of the present invention, the aforementioned electron-donating colorless dye, aniline compound and hindered phenol compound are contained in microcapsules. The recording material of the present invention is the same as the recording material using the conventional electron-donating colorless dye, except that the specific aniline compound and the hindered phenol compound are contained in the microcapsules as described above. The above-described microcapsules according to the present invention can be manufactured by utilizing a method for manufacturing microcapsules known per se.

As a method for producing capsules, for example, US Pat. Nos. 2,800,457 and 2,800,45 are cited.
Method utilizing coacervation of hydrophilic colloid sol described in No. 8, British Patent Nos. 867,797, 950,443, 989,264, 1,
091,076 and the like, the method described in US Pat. No. 3,103,404 and the like. As the capsule wall material, a synthetic resin wall material is preferable, and for example, polyurethane and / or polyurea type and melamine resin type are preferable.

The electron-accepting compound used in the recording material of the present invention to be colored by contacting with the colorless dye is
Conventional compounds conventionally used for recording materials containing an electron-donating colorless dye and an electron-accepting compound, for example, phenol derivatives, phenol derivatives containing a polymerizable group, salicylic acid derivatives, benzoic acid derivatives, aromatic carboxylic acids, and Examples thereof include metal salts, acid clay, bentonite, novolac resins, metal-treated novolac resins, metal complexes, and mixtures of two or more of these. Examples of these electron-accepting compounds are, for example, Japanese Patent Publication No. 40-93.
09, JP-B-45-14039, JP-A-52-14
0483, JP-A-48-51510, JP-A-57-
210886, JP-A-58-87089, JP-A-5
9-112286, JP-A-60-176795, JP-A-61-95988, JP-A-4-226455, U.S. Pat. Nos. 3,767,449 and 4,219,21.
9, No. 4,269,893, No. 4,374,6
No. 71, No. 4,687,869 and the like. In particular, a combination of a salicylic acid derivative and a phenol derivative is preferable. When these are applied to recording materials, it is preferable to use them as fine dispersions or fine droplets or in the form of a film.

Further, in this case, various additives well known in the fields of recording materials and polymer resins, such as pigments, waxes, antistatic agents, ultraviolet absorbers, defoamers,
Additives such as conductive agents, fluorescent dyes, and surfactants can be used.

In the recording material of the present invention, a general coloring method using an electron-accepting compound and an electron-donating colorless dye in a microcapsule is to destroy the microcapsule or
It is utilized that the electron-donating colorless dye and the electron-accepting compound are brought into contact with each other to cause a coloring reaction by controlling the permeability of the microcapsule wall by heat.

In the recording material of the present invention, a dispersion of microcapsules containing the above-mentioned electron-donating colorless dye, aniline compound and hindered phenol is coated on a support to form a layer containing the microcapsules. Alternatively, a dispersion containing an electron-accepting compound may be applied onto the same support to form a layer containing an electron-accepting compound, and a dispersion containing the microcapsules and the electron-accepting compound together may be formed. It may be coated on a support to form a layer containing the microcapsules and the electron-accepting compound together. Further, a layer containing this microcapsule is formed on one support,
A recording material may be formed by forming a layer containing an electron-accepting compound on another support and combining both the supports.

Further, a layer containing microcapsules containing an electron-donating colorless dye having another color-developing hue may be formed as a separate layer on the same support. A plurality of microcapsules having different wavelengths may be contained in the same layer.

When used for pressure-sensitive paper, US Pat.
No. 505,470, No. 2,505,471, No. 2,505,489, No. 2,548,366, No. 2,712,507, No. 2,730,456,
No. 2,730,457, No. 3,103,404
No. 3,418,250, No. 4,010,03
It can take various forms as described in patents such as No. 8. The most common form consists of at least a pair of sheets having an electron-donating colorless dye and an electron-accepting compound provided on separate supports.

When it is used for thermal paper, it is disclosed in JP-A-1-10.
The method described in No. 5782, No. 1-237189, etc. can be followed.

When used in a light- and heat-sensitive recording material, a latent image is formed on the photopolymerizable composition upon exposure, and a component relating to color development or decolorization upon heating moves in the recording material in accordance with the latent image to form a color image. An image is formed, and in this system, at least one kind of components relating to coloring or decoloring is encapsulated in microcapsules, and in the photopolymerizable composition,
It is preferable to contain an ethylenically unsaturated compound and a photopolymerization initiator. Further, it is preferable that the components relating to color development or decolorization include an electron donating colorless dye and an electron accepting compound.

One preferable constitution is a layer comprising a microcapsule containing an electron-donating colorless dye and a photocurable composition containing an electron-accepting compound having a polymerizable ethylene group and a photopolymerization initiator on a support. It is the configuration provided in.

Another preferred structure supports a layer comprising a microcapsule containing an electron-donating colorless dye, an electron-accepting compound, a compound having a polymerizable ethylene group and a photopolymerizable composition containing a photopolymerization initiator. It is a configuration provided on the body.

Another preferred structure is a structure in which a layer comprising a microcapsule containing an electron-donating colorless dye, a compound having a polymerizable ethylene group and a photopolymerization initiator, and an electron-accepting compound is provided on a support. Is.

For details, see JP-A-3-72358 and JP-A-3-72358.
-87827, JP-A-4-226455, JP-A-6
3-184738, 58-88739, 62-
The method described in, for example, 143044 can be followed.

[0062]

EXAMPLES Examples will be shown below, but the present invention is not limited thereto. Unless otherwise specified,% means% by weight.

Example 1 1) Preparation of Microcapsule Sheet Containing Electron-Donating Colorless Dye As the electron-donating colorless dye, the compound 7.5 of the specific example (1) is used.
g, the compound of the specific example (22) as an aniline compound 7.
5 g and a specific example as a hindered phenol compound (4
3 g of the compound of 2) was added to 100 g of diisopropyl naphthalene.
To prepare an oily liquid. To this oily solution, 10 g of carbodiimide-modified diphenylmethane diisocyanate, 5 g of hexamethylene diisocyanate isocyanurate, and 3 g of ethylenediamine butylene oxide adduct (addition mole number of butylene oxide to ethylenediamine 16.8 mol, molecular weight 1267) 3 g were dissolved to obtain a primary solution. Was prepared.

Next, 10 g of polyvinyl alcohol and 5 g of carboxymethyl cellulose were dissolved in 140 g of water to prepare a secondary solution. While vigorously stirring the secondary solution, the above primary solution was poured into this to form an oil-in-water emulsion. When the size of the oil droplet reached 5.0 μm, the stirring was weakened, and then 100 g of water at 20 ° C. and tetraethylenepentamine 1.
After adding 6 g, the temperature of the system was gradually raised to 75 ° C. and kept at this temperature for 90 minutes to prepare a capsule liquid.

In the thus obtained capsule liquid, 80 g of a 15% aqueous solution of polyvinyl alcohol, 30 g of carboxy-modified styrene-butadiene rubber (SBR) latex in solid content, and starch particles (average particle size 5 μm) 6
0 g was added. Next, water was further added to adjust the solid content concentration to 20% to obtain a coating liquid. This coating solution was applied to 40 g / m ² base paper so as to have a dry weight of 4 g / m ² by an air knife coating machine and dried to produce an electron-donating colorless dye-containing microcapsule sheet.

Example 2 As an electron-donating colorless dye, the compound of Specific Example (5) was used in the same amount instead of the compound of Specific Example (1), and the compound of Specific Example (22) was used as the aniline compound. An electron donating colorless dye-containing microcapsule sheet was produced in the same manner as in Example 1 except that the same amount of the compound shown in Specific Example (23) was used.

Example 3 As the electron-donating colorless dye, the same amount of the compound shown in the specific example (5) was used in place of the compound of the specific example (1), and the aniline compound was used in place of the compound of the specific example (22). An electron donating colorless dye-containing microcapsule sheet was produced in the same manner as in Example 1 except that the same amount of the compound shown in Specific Example (27) was used.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the compound of the specific example (22) which was an aniline compound and the compound of the specific example (42) which was a hindered phenol compound were not added. Thus, a microcapsule sheet containing an electron-donating colorless dye was obtained.

2) Preparation of electron-accepting compound sheet 10 g of 3,5-bis-α-methylbenzylsalicylic acid zinc salt (electron-accepting compound) was added to 20 g of 1-isopropylphenyl-2-phenylethane and dissolved. The obtained solution was mixed with 50 g of a 2% aqueous solution of polyvinyl alcohol and 0.1 g of a 10% aqueous solution of dodecylbenzenesulfonic acid triethanolamine salt, and emulsified to have an average particle size of 3 μm to prepare an emulsion.

Next, 80 g of calcium carbonate and 2 of zinc oxide
0 g, 1 g of sodium hexametaphosphate and 200 g of water were mixed with the above emulsion, and then the resulting mixture was further mixed with 100 g of a 10% polyvinyl alcohol (PVA) aqueous solution and carboxy-modified S as a binder.
BR latex (10 g (as solid content)) was added and water was added so that the solid content concentration became 20% to obtain a coating liquid (A).

Next, 10 g of the electron-accepting compound, 20 g of Shilton clay, 60 g of calcium carbonate, and zinc oxide 2
0g and sodium hexametaphosphate 1g and water 200g
The dispersion liquid consisting of and was dispersed by a sand grinder so that the average particle diameter was 3 μm to prepare a dispersion liquid. To this dispersion, 116 g of 10% PVA aqueous solution and 10 g of carboxy-modified SBR latex (as solid content) were added, and water was added so that the solid content concentration became 20% to obtain a coating liquid (B).

[0072] coating solution (A) and coating solution and (B) were mixed in a 1: 1 weight ratio with an electron-accepting compound in terms, the base paper of 50 g / m ^2, a solid of 5.0 g / m ² min Was coated with an air knife coater so as to be coated, and dried to prepare an electron-accepting compound sheet.

3) Light resistance test before use The microcapsule sheets containing the electron-donating colorless dye prepared in Examples 1 to 3 and Comparative Example 1 were mixed with a xenon fade meter [FAL-25AX-HC type (manufactured by Suga Test Instruments Co., Ltd.). )] For 4 hours, then superimpose it on an electron-accepting compound sheet, continuously press-print the letter m of the lowercase alphabet with an IBM 6747 type electronic typewriter to develop a color, and then to obtain a density D after 24 hours have elapsed. ¹ was measured using a Macbeth reflection densitometer (Macbeth RD918).

Separately, the electron-donating colorless dye-containing microcapsule sheets of Examples 1 to 3 and Comparative Example 1 which were not irradiated with light were superposed on the electron-accepting compound sheet, and the letters m in the lowercase alphabet were continuously formed using an IBM 6747 type electronic typewriter. The density D ² after pressure printing was performed, the color was developed, and 24 hours after the color was developed, was measured by a Macbeth reflection densitometer (Macbeth RD91
It was measured in 8). Light resistance value as an index of light resistance before use =
D ¹ / D ² was calculated and shown in Table 1. As is clear from the results in Table 1, the recording material of the present invention has good light resistance before use.

[0075]

[Table 1]

Example 4 1) Preparation of an electron-donating colorless dye capsule liquid As the electron-donating colorless dye, the compound 12 of Specific Example (5) was used.
g, the compound 20 of the specific example (30) as an aniline compound
g and specific examples of hindered phenol compounds (4
3 g of the compound of 3) was dissolved in 10.4 g of ethyl acetate, and further 12.4 g of dicyclohexyl phthalate, 27 g of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) and Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) 3
A solution was prepared by adding g. This solution was added to a mixed solution of 4.6 g of polyvinyl alcohol and 74 g of water,
The emulsion was dispersed at 0 ° C. to obtain an emulsion having an average particle size of 2.5 μm.
100 g of water was added to the obtained emulsion and stirred with stirring 60
The mixture was heated to 0 ° C, and after 2 hours, an electron-donating colorless dye capsule solution was prepared.

2) Preparation of emulsion of photocurable composition 0.12 g of 2-o-chlorophenyl-4,5-diphenylimidazole dimer and 0.12 g of 7-diethylamino-4-methylcoumarin to accelerate polymerization. As an auxiliary agent for the purpose, 0.06 g of N-phenylglycine ethyl ester was added to a solution of 8 g of ethyl acetate in the following electron-accepting compound (EA
1) 7 g and the following electron-accepting compound (EA2) 3 g were added.

[0078]

[Chemical 21]

The obtained solution was added to a mixed solution of 9.6 g of 7.5% PVA aqueous solution, 0.8 g of 2% sodium nonylphenoxybutanesulfonate aqueous solution and 0.8 g of 2% sodium dodecanesulfonate aqueous solution. A homogenizer (manufactured by Nippon Seiki Co., Ltd.) emulsified at 10,000 rpm for 5 minutes to obtain an emulsion of the photocurable composition.

3) Preparation of coating liquid for light- and heat-sensitive layer 4 g of the electron-donating colorless dye capsule liquid prepared in 1) and 12 g of the photocurable composition emulsion prepared in 2) and 15%
12 g of an aqueous PVA solution was mixed to prepare a coating liquid for the photosensitive / heat-sensitive layer.

4) Preparation of coating liquid for protective layer 4.5 g of 10% gelatin aqueous solution, 1.5 g of distilled water and 2%
Nonylphenoxybutane sulfonate aqueous solution of sodium 0.5
and 1.5 g of a 1% aqueous solution of 2,4-dichloro-6-hydroxy-s-triazine sodium salt and Syloid 7
2 (FUJI-DEVISON CHEMICHAL
LTD. The coating liquid for the protective layer was prepared by mixing the amount of the product (made by Mitsui Chemical Co., Ltd.) and the coating amount of 50 mg / m ² with 1 g of Snowtex N.

5) Preparation of photosensitive / thermosensitive recording material and image formation Application of the coating liquid for photosensitive / thermosensitive layer onto a 100 μm polyethylene terephthalate film using a coating bar so that the dry weight of the coating layer was 8 g / m ^2. And 30 ℃
And dried for 10 minutes to form a photosensitive / thermosensitive layer. Exposure
The protective layer coating solution was applied onto the heat-sensitive layer using a coating bar so that the dry weight of the coated layer was 5 g / m ² .
A photosensitive / thermosensitive recording material was prepared by forming a protective layer by drying at 30 ° C. for 10 minutes.

The resulting light- and heat-sensitive recording material was exposed to ultraviolet light from a 1000 W high-pressure mercury lamp (Oak Jet Light) for 60 seconds through a lith film on which an image was developed. Then, when heated with a hot plate of 120 ° C. for 5 seconds, a clear cyan color image was obtained. The image density was 2.0 and the density of the non-image area was 0.08.

Example 5 As the electron-donating colorless dye, the same amount of the compound shown in the specific example (7) was used instead of the compound of the specific example (5), and the aniline compound was used instead of the compound of the specific example (30). A light- and heat-sensitive recording material was produced in the same manner as in Example 4 except that the same amount of the compound shown in Specific Example (31) was used.

Example 6 Instead of the compound of Example (5) as the electron-donating colorless dye, the same amount of the compound of Example (11) was used, and as the hindered phenol compound, the compound of Example (43) was used. Instead of using the same amount of the compound shown in Specific Example (46), the same procedure as in Example 4 was carried out.
A thermal recording material was prepared.

Example 7 As the electron-donating colorless dye, the compound of the specific example (10) was used in the same amount instead of the compound of the specific example (5), and the compound of the specific example (43) was used as the hindered phenol compound. Instead of using the same amount of the compound shown in Specific Example (49), the same procedure as in Example 4 was carried out.
A thermal recording material was prepared.

Example 8 Example 8 was repeated except that the same amount of the compound shown in Example (54) was used as the hindered phenol compound instead of the compound shown in Example (43). Exposure
A thermal recording material was prepared.

Comparative Example 2 The same procedure as in Example 4 was carried out except that the compound of specific example (30) which was an aniline compound and the compound of specific example (43) which was a hindered phenol compound were not added. A light and heat sensitive recording sheet was obtained.

6) Light resistance test before use The light and heat sensitive recording materials of Examples 4 to 8 and Comparative Example 2 before image formation were treated with a xenon fade meter [FAL-25A.
X-HC type (manufactured by Suga Test Instruments Co., Ltd.)] was used to measure the color density when irradiated with light for 2 hours using a Macbeth reflection densitometer. The results are shown in Table 2. As is clear from Table 2, the recording material of the present invention is excellent in less light coloring before use.

[0090]

[Table 2]

[0091]

The recording material of the present invention is a recording material containing microcapsules containing an electron-donating colorless dye and an electron-accepting compound, wherein the electron-donating colorless dye represented by the general formula (1) By using a microcapsule containing the aniline compound represented by the general formula (2) and the hindered phenol compound represented by the general formula (3) or the general formula (4), the light resistance before use is said to be good. Produce an effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B41M 5/30 6956-2H B41M 5/18 104 6956-2H 108

Claims (1)

[Claims] 1. An electron donating colorless dye represented by the following general formula (1), an aniline compound represented by the following general formula (2), and a hinder represented by the following general formula (3) or the following general formula (4). A microcapsule containing a dephenol compound, and a recording material containing an electron-accepting compound. [Chemical 1] (In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently
Represents an alkyl group or an aryl group, R ¹ and R ² , or R
³ and R ⁴ may be bonded to each other to form a ring which may include a 5-membered to 8-membered hetero atom including the nitrogen atom to which they are bonded, and R ¹ and / or R ² is −
R ³ and / or R ⁴ are bonded to a carbon atom in the ortho position with respect to the bonding position of NR ¹ R ² and R ³ and / or R ⁴ are bonded to a carbon atom in the ortho position with respect to the bonding position of —NR ³ R ^4. A nitrogen heterocycle may be formed, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group. R ⁹ is a hydrogen atom, an alkyl group,
Represents an alkoxy group, a halogen atom or a substituted amino group,
m represents an integer of 1 to 4. ) [Chemical 2] (In the formula, R ¹⁰ represents an alkyl group or an aryl group, and R ¹¹
And R ¹² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted amino group, an alkylthio group or an arylthio group, and k and n represents the integer of 1-5 each independently. ) [Chemical 3] (In the formula, R ¹³ represents a secondary or tertiary alkyl group, and R ^13
14 , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group, and R ¹⁷ represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group or an alkoxycarbonylalkyl group. Represent ) [Chemical 4] (In the formula, R ¹⁸ represents a secondary or tertiary alkyl group, and R ^18
19 , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group, R ²² represents a hydrocarbon group which may have an ester, ether or amide bond, or a sulfur atom, and p is 2 Represents an integer of 4; )