JPS5833240A - Heat developable type diazo copying material - Google Patents

Abstract

PURPOSE:To obtain a heat developable type diazo copying material also usable for a recording material, capable of forming a high-density image and superior in raw storage stability in spite of lowering the developing temp. in order to reduce a manufacturing cost of a copying machine. CONSTITUTION:Lowering of developing temp. is executed by using a heat-meltable substance of 50-150 deg.C m.p. as a color developing adjuvant for a photosensitive layer consisting essentially of a diazo compound, a coupling component, and a color developing adjuvant, and drop of raw storage stability resulting from the use of this adjuvant is prevented by using a specified acrylic graft copolymer as the outer shell, and encapsulating the coupling component. Besides, a diazo compound advantageous for forming a high-density image can be used as a result of lowering of the developing temp.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-developable diazo copying material which can also be used as a recording material.

Heat-developable diazo copying materials generally have a photosensitive layer containing a diazo compound, a coupling component, and a coloring aid as main components on a support such as paper or film.The coloring aids include urea and sodium trichloroacetate. etc. are used. All of the diazo copying materials in this building are developed by heating at 150 to 200 DEG C., and the developing mechanism utilizes alkali (ammonia gas, caustic soda) that is decomposed and generated by heating. Also, low temperature development (cIO ~ 130℃)
In an attempt to do this, a higher fatty acid amide is used as a color development aid, but the developing machine costs only $11! This method utilizes the activation of a diazo compound and a coupling component by heating and melting.

However, in these conventional heat-developable diazo copying materials, the former has a high development temperature as mentioned above, so diazo compounds with high heat resistance are selected and used, which is disadvantageous for forming high-density images. . For this reason, this type of diazo copying material generally has the disadvantage that it is not possible to obtain high-density images compared to dry diazo copying materials developed with ammonia gas. Furthermore, it requires a heating device with a high temperature and high N degree (if the temperature is not controlled within ±10°C, there will be insufficient development or changes in color tone), which increases the cost of the transfer machine. There is also. Furthermore, although low-temperature development is possible with the latter, there is a drawback that the storage stability of the copying material itself (hereinafter referred to as raw storage stability) is reduced.

Because of these drawbacks, methods using heat-developable diazo copying materials result in dry copies. Although it has advantages such as the ability to make a copying machine compact because the developing section is simple, it has not yet become mainstream in the diazo copying process.

The purpose of the present invention is to provide a heat-developable diazo copying material that can obtain high-density images through low-temperature development at about 90 to 130°C, has excellent storage stability, and is low in cost, even though the cost of copying machines is reduced. It also provides recording materials.

That is, according to the present invention, in a heat-developable diazo copying material in which a photosensitive layer containing a diazo compound, a coupling component, and a coloring aid as main components is provided on a support, the coloring aid has a melting point of 5.
It is a thermofusible substance at 0 to 150°C, and the coupling component is encapsulated with a graft copolymer obtained by graft polymerizing monomers from Group B below and monomers from Group C below to resin from Group A below. A heat-developable diazo copying material is provided.

A copolymer consisting of the monomer represented by the general formula (1) and the monomer represented by the general formula (2) of the resin of group A General formula (1) General formula (2) (However, R is -HC0H3X is 10000ylH2n+1 + 0OnH2n++
t (5≦n≦20)) Group B monomer General formula (3) represented by general formula (3) (However, R represents -Hfu〇H30, and the resin of Group A When Fi contains a glycidyl methacrylate component, it is acrylic acid or (and) methacrylic acid; when it contains acrylic acid or Fi (and) a methacrylic acid component, it is glycidyl methacrylate) Group 0 Shichitsumani general formula (4) Monomer general formula (4) represented by
gO (represents 3001H2n++ (1≦n≦6)9) According to the present invention, low-temperature development can be achieved by using a thermofusible substance with a melting point of 50 to 150°C as a coloring aid, and for this purpose, The resulting loss of shelf life can be prevented by encapsulation of the coupling components with special graft copolymers. Furthermore, because of low-temperature development, it is possible to use a diazo compound which is advantageous for forming high-density images. Furthermore, in the case of the present invention, by using a special graft copolymer as the capsule wall material, the encapsulated product of a general copolymer, such as a vinyl acetate/methacrylic acid varnish coupling component, has excellent dispersion stability during coating. Because it has excellent properties and does not cause aggregation,
Diazo compound and coupling component used in the present invention have the advantage that the production stability of the photosensitive liquid is very good, and it also has excellent adhesion to the support, making it difficult to cause lab-off phenomenon (peeling phenomenon).5 Diazo compound and coupling component used in the present invention As such, those conventionally used in the field of two-component diazo copying materials can be used as they are.

That is, as a diazo compound, for example, 4-diazo-1
-dimethylaminebenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-dipropylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-thiazo-1-dibenzylaminobenzene, 4-
Cia/-1-ethylhydroxyethylaminobenzene, 4-diazo-1-diethylamine-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4-diazo-1-benzoylamino-295-
Jetoxybenzene, 4-thiazo-1-morpholinobenzene, 4-diazo-1-morpholino-2-5-jethoxybenzene, 4-diazo-1-morpholino-2v5-dibutoxybenzene.

4-sia7”-1-anilinobenzene, 4-diazo-1
-dimethylamino-3-carboxybenzene, 4-diazo-1-tolylmercapto-295-jethoxybenzene% 4-diazo-1t4-methoxypenzoylamino-2+5-jethoxybenzene 9-metal chloride of diazo compounds such as zene Double salts with halides (e.g. zinc chloride, cadmium chloride, tin chloride, etc.)
and salts of strong acids such as sulfuric acid, boron tetrafluoride, and hexafluorophosphoric acid of the diazo compounds, but are not limited to these, of course.

As cup and ring components, all those for general two-component diazo copying materials can be used. For example, resorcinol, 7
0roglucin, 2ν5-dimethyl-4-morpholinomethylphenol, 3-hydroxycyanoacetanilide,
parasulfoacetanilide, l-benzoylamino-8
-hydroxynaphthalene-3?6-disulfonamide,
2?2-dihydroxynaphthalene, 2phage hydroxynaphthalene-3 dirodisulfonic acid sodium, 2゜3-
Dihydroxy-6-sulfone tlj17-ta, 2
r5-dihydroxynaphthalene-6-sodium sulfonate, 1-hydroxynaphthalene-4-sodium sulfonate,
]-Amino-3-hydroxynaphthalene-316-disulfonamide, naphthol As1-1〇- naphthol As-D, 2-hydroxynaphthalene-3-
Biguanide, 2-hydroxynaphthoic acid morpholinopropylamide, 2-hydroxynaphthoic acid ethanolamide, 2-hydroxynaphthoic acid-N-dimethylamine propylamide hydrochloride, 2t492'94'-tetrahydroxydiphenyl, 214ν2'*4'-tetra Examples include hydroxydiphenyl sulfoxide.

The thermofusible material in the present invention is a thermofusible substance that is hydrophobic (insoluble in water) and has a melting point of 50 to 150°C, and that dissolves the diazo compound and the coupling component well when melted. Any material can be used, but preferred examples include the following.

(1) Fatty acid amide represented by the general formula A-1 ROOMH, (A-1) (wherein R represents a saturated or unsaturated alkyl group having 5 to 24 carbon atoms). Specific examples of this include the following.

Caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, araxic acid amide, behenic acid amide, palmitoleic acid amide, oleic acid amide, eicosenoic acid amide, erucic acid amide, elaidic acid amide, trans-1νl-eicosenoic acid amide 1-linoleic acid amide, lyrinic acid amide, ricinoleic acid amide.

(2) General formula A-2 and A-2'R'0ONHR2 (A-2) Also U R"NHOOR'
(A-2') (In the above formula, R1 and R3 have 5 to 5 carbon atoms.
24 saturated or unsaturated alkyl groups, R2 and R4 each represent an alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group). Specific examples of this include the following.

That is, specific examples of general formula A-2 include, for example, N-methylpalmitic acid amide, N-methylstearic acid amide, N-propyl stearic acid amide%N-butyl stearic acid amide, stearic acid anilide, N-methylbehenyl Acid amide, N-eterbe heptacid amide *N-':j
7' phosphoric acid amide, N-butyllauric acid amide, capric acid 〇-methoxyanilide, N- Specific examples of the general formula ^-21 include hexyl stearic acid amide, N-octadecyl acetamide, N=niophtadecyl butyramide N-ophtadecyl propionamide, N-oleylacetamide, N-oleyl Benzamide, N-laurylbutyramide, N-laurylbenzamide, N-behenylacetamide, N-
Behenylpropionamide, N-behenylbenzamide, N-myristylbenzamide, N-stearylbenzamide, N-stearylacetamide, N-stearylcyclohexylamide, N-stearyl-13-O-chlorobenzamide% N-halmitylhenzamide, N -Palmitylacetamide.

(3) General formula A-3 (wherein R1 and R2 are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R3 is a hydrogen atom or an alkyl or alkenyl group having 1 to 5 carbon atoms, and n is 1 or 2). A specific example of such a thing is a first-order one.

Mono(or di)benzamide, NνN-dimethyl mono(
or di)benzamide, NUN-butyl mono(or di)benzamide, N5N-methyl-ethyl-mono(or di)benzamide.

4-methylbenzmono(or di)benzamide, 4-butylbenzmono(or di)benzamide.

(4) General formula A-4 14- R'0CONHR2 (A-4) (wherein R' and R2 are a chain or cyclic alkyl group or alkenyl group (having 1 to 30 carbon atoms), an aryl group, or an alkenyl group. It is an alkyl group, and its substituents include halogen, oxygen-containing groups (hydroxyl, carboxyl, alkoxy, etc.), nitrogen-containing groups (amine, nitro, etc.), ionic groups (mercapto, sulfide, etc.) ), etc.). As a concrete example of this, for example,
These include:

N-phenylcyclohexyl salbamate, N-phenyldecahydronaphthyl carbamate, N-naphthyl hydronaphthyl carbamate, N-phenylcyclohexyl carbamate, N-phenylbutyl carbamate,
N-naphthylpropylcarbamate, N-phenyl-(
methoxy-propyl-phenyl)carbame)tN-
Hexyl-1-phenylethylcarbamate, N-hexyl-1-benzylethylcarbamate, N-naphthyldichloropropylcarbamate, N-naphthylpropylcarbamatetN-phenyl-(furopyrudryl)carbamate, N-phenylmethylcyclohexylcarbamate, N- Naphthyl linobutyl carbamate, N-phenylxylyl carbamate, N-naphthyl-t-butyl carbamate, N-phenyl-1s2s3>4-tetrahydronaphthyl carbamate, N-naphthyl-1-phenylethyl carbamate, N-phenyl-1-benzyl -1so-propylcarbamate, N-phenyldimethylcyclohexy, lucarpamate, N-phenylmethylcyclohexylcarbamate, N-phenyl-3-
Oxo-n-butyl carbamate, N-phenyldimethylcyclohexyl carbamate, N-phenyl-2-naphthylethyl carbamate, N-phenyltolyl carbamate, N-phenyl (1-phenyl-1so-furobyl) carbamate, N-phenyldecenyl Carbamate, N-phenyl (l-carboxyl-is.

-butyl) carbamate, N-naphthylpropyl carbamate, N-phenylheptyl carbamate.

(5) General formula A-5 R'OOR" (A-5) (
In the formula, al and R''H are chain or cyclic alkyl groups or alkenyl groups having 6 to 30 carbon atoms.

It is an aryl group or an aralkyl group, and these substituents further include other substituents, such as oxygen-containing groups such as a hydroxyl group, an oxo group, a carboxyl group, and an alkoxyl group;
(May have nitrogen-containing groups such as amine groups and nitro groups, sulfur-containing groups such as mercapto groups and sulfide groups)
A ketone compound represented by Specific examples of this include one such as the fifth order.

Didecyl ketone, decyl undecyl ketone, diundecyl ketone, undecyl dodecyl ketone, didodecyl ketone, dodecyl tridecanyl ketone, ditridecanyl ketone, tridecanyl 17-ketone decanyl ketone, ditridecanyl ketone, tetradecanyl pentadecanyl Ketone, dipentadecanyl ketone, pentadecanyl hexadecanyl keto/, ditridecanyl ketone, hexadecanyl hexadecanyl ketone, dihebutatecanyl-ketone, heptadecanyl octadecanyl keto/, dioctadecanyl ketone, octadecanyl ketone Nylnonadecanyl ketone, dinonadecanylketone, cyclohexyldecyl ketone, cyclohexyl undecyl ketone,
Cyclohexyl dodecyl ketone, cyclohexyl undecyl ketone, cyclohexyl tetradecanyl ketone, cyclohexyl pentatecanyl ketone, cyclohexyl hexadecanyl ketone, cyclohexyl hebutadecanyl ketone, cyclohexyl octadecanyl ketone, cyclohexyl undecyl ketone, phenyldecyl ketone , phenyl undecyl ketone, phenyl dodecyl ketone, phenyl tridecanyl ketone, phenyl tetradecanyl ketone, phenyl pentadecanyl ketone, 18-phenyl hexatelyketone, phenyl heptadecanyl ketone, phenyl octadecanyl ketone, phenyl nona Decanylketone, benzopheno/, thioxybenzoin, chalcone, 4v4I-cyn-7'robi-penzophenone, 4!4I-di-n-octylbenzophenone, 4-n-ocf-4'-n-nonyl Benzophenone, 4+4' n f sylbenzophenone.

(6) Polyalkylene glycol Polyalkylene glycol has a molecular weight of 6,000 to
200,000 is preferable, and specific examples of this include ethylene oxide, propylene oxide,
polymers of alkylene oxides such as butylene oxide,
Examples include polyethylene glycol, polypropylene glycol, and copolymers thereof, such as polyoxyethylene-oxypropylene block polymers.

(7) General formula A-7 (In the formula, R1νR3 represents an alkyl, aralkyl, or aryl group having 2 to 12 carbon atoms, and R2tR'ij carbon number 2
~12 alkyl, aryl group) The above general formula (
Specific examples of A-7) include the following.

NUN'-diphenyl-NsN'-diethylurea, NU
N'-diphenyl-NtN'-di-n-clobylurea,
N9N'-diphenyl-NUN〆-di-isopropyl 1
liR element, NνN'-diphenyl-dilopethylurea, NtN'-diphenyl-NUN'-ci-5ec-butylurea, NνN'-diphenyl-NsN'-dite
rt-butyl urea, NtN'-diphenyl-NtN +
-C n -Henf Ruurea * NνN'-Diphenyl-NtN"/'-n-Hekynlurea, N9N'-Diphenyl-N+N'-Di〇-Hephthyl W Element * N +
N'-diphenyl-N'-n-octylurea, N'-diphenyl-N.

N'-di-n-nonylurias, NνN'-diphenyl-N
UN'-di-n-decyl urea, N-di-n-diphenyl-
N 9N'-diphenyl-N'-di-n-padecyl urea, N + N'-di(4-methylphenyl)-
NνN'-di-n-propylurea, NtuN/-di(4-
ethylphenyl) -N'-di-n-butyl urea,
NνN'-di(4-methoxyphenyl)-NνN/
, ) yl-hexylurea, NUN'-di(4-ethoxyphenyl)-N'-di-n-propylurea, N
νN'-di(4-)methylphenyl) N9N'-di-n-hexylurea, N gN〆-di(4-hexylphenyl)-N+N'-di-n-behenylurea, NtN
'-Diallyl-NνN'-di-n-hexylurea, NNF-diallyl-NνN'-di-n-octylurea, N
tN'-diaryk Nt'N'-di-n-decyl urea %NvN'-diallyl-NvN'-di-n-dodecyl urea, NtN'-diphenyl-NtN'-diallylurea, etc.

(8) General formula A-8 21- A guanidine derivative represented by

In the general formula, R1 and R2 each have 5 to 24 carbon atoms.
Preferably ij I represents an alkyl or alkenyl group of 0 to 20, a substituted or unsubstituted phenyl group, a substituted or unsubstituted cyclohexyl group, or a substituted or unsubstituted morpholino group. In this case, examples of substituents that may be bonded to the phenyl N group, cyclohexyl group and morpholino group include lower alkyl groups, preferably methyl groups, and the number of substituents is usually 1 to 2. be. Examples of such guanidine derivatives include 1+3 N-cyhentatecylguanidine, 1?3-N-dihexadecylguanidine, 1t3-N-diheptadecylguanidine,
1t3N-octadecylguanidine, 1s3N-dinonandecylguanidine, 1ν3-N-dieicosylguanidine, lν3-N-cytodecenylguanidine, 1*3
N-dihexadecenylguanidine, 1t3N-dieicosenylguanidine, 1t3
N-diphenylguanidine, 113-N-ditolylguanidine, 1+3 N-dixylguanidine, 1s
Examples include 3N-dicyclohexylguanidine, 1t3N-di(methylcyclohexyl)guanidine/, 1v3-N-dimorpholinoguanidine, 1v3-N-di(methylmorpholino)guanidine, and 1+3N-di(dimethylmorpholino)guanidine.

(9) General formula A-9 Ar(-000-Y)n (A9) (wherein, Ar is an aromatic group such as a phenyl group or a naphthyl group, and this aromatic group is an alkyl group or an aralkyl group. , alkoxy group, aryloxy group, acyl group, aroyl group,)
(Y is an alkyl group or a phenyl group, and these alkyl groups or phenyl groups can also have various substituents as described above). Aroyloxy compound. Specific examples of this compound include those having the structures shown below.

25- All of the above compounds used in the present invention are hydrophobic, and
It is sparingly soluble or insoluble in water and is used in the form of fine particles with a particle size of 0.1 to 10 μm.

In the present invention, the coupling component is encapsulated in a graft copolymer. This encapsulation is carried out using known encapsulation methods (for example, U.S. Pat. No. 2,800
457 and 2800458).

The particle size of the obtained capsules is suitably 1 to 50 microns.

Structure of the graft copolymer used in the present invention - Ethylhexyl methacrylate, 2-ethylhexyl acrylate, stearyl methacrylate, hinylstearyl ether Examples of general formula (2) of A moiety: acrylic acid, methacrylic acid, glycidyl Acrylate, glycidyl methacrylate 26 Examples of part B Niacrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate Examples of part C: styrene, vinyltoluene, chlorostyrene, methyl acrylate, methyl methacrylate, ethyl acrylate, isobutyl methacrylate , n-butyl methacrylate, n-butyl acrylate In the present invention, the ratio of the above-mentioned coupling component to the graft copolymer is 1:(0.5-10) (by weight)
is appropriate.

In the present invention, in addition to the above-mentioned materials, it is also possible to use in combination a substance that is generated into dialkali upon heating, which is used in ordinary heat-developable diazo copying materials, and various additives used in ordinary diazo copying materials. can. That is, as a preservability improving agent, sodium naphthalene monosulfonate, sodium naphthalene disulfonate, sodium naphthalene trisulfonate, sulfosalicylic acid, cadmium sulfate, magnesium sulfate, cadmium chloride, zinc chloride, etc. f: Can be used for convenience. Antioxidants such as thiourea and urea coating; solubilizing agents such as caffeine and theophylline; acid stabilizers such as citric acid, tartaric acid, sulfuric acid, oxalic acid, boric acid, phosphoric acid,
Birophosphoric acid or the like can be used, and a small amount of saponin can also be added. (Polymer substances such as starch, casein, polyvinyl acetate, polyacrylic acid derivatives, and polyvinyl alcohol can be used as inders.) Inorganic or organic materials such as silica, starch, clay, and resins have been used as image density improvers. Fine particles can be used.

To make the diazo copying material of the present invention, a diazo compound, a coupling component, a color development aid (however, the coupling component is encapsulated), and an aqueous liquid in which other additives are dissolved or dispersed are mixed with a support such as paper or film. It is preferable to apply the photosensitive layer on the body by a conventional coating method and dry it to have an adhesion amount of 2.5 to 159/m<2>. Another method is to use a coupling component, a color development aid (however, the coupling component is encapsulated), and a portion of the additive (9% includes an image density improver and an image density improver).
An aqueous liquid in which (inder) is dissolved or dispersed is coated and dried on a support to form a precoat layer with a coating weight of 2 to 10 tons (7 m), and on top of that, an aqueous liquid in which a diazo compound and other additives are dissolved or dispersed. Apply the liquid and dry it, the amount of adhesion is 0.5
A laminated type may be provided by providing a photosensitive layer of ~5 f/m'. In any case, the ratio of the diazo compound to the coloring aid of the coupling component (based on non-encapsulated components) is 1:
(o, 1-IO): (0, 1-20) (weight) is suitable.

There are two methods for forming an image on the heat-developable diazo copying material of the present invention. First, like general diazo copying materials, this heat-developable diazo copying material is image-wise exposed using a fluorescent lamp or mercury lamp, and then exposed to infrared rays, a heated roller, high frequency, etc.
There is a method of heating to about 0 to 130°C, and the other method is to heat the heat-developable diazo copying material to the above temperature in an imagewise manner using a thermal pen, thermal head, etc., similar to general heat-sensitive recording materials. method, or a method of imagewise exposure and heating with infrared light. In either method, the unreacted diazo compound in the non-image area can be decomposed and fixed by irradiating the entire surface with ultraviolet rays from a fluorescent lamp or a mercury lamp, as with general diazo copying materials.

Next, the present invention will be explained in more detail with reference to Examples. In addition, examples of synthesis of the graft copolymer used in the present invention will also be shown below.

Synthesis Example 1 Take 30 (l) of Isopar H (manufactured by Esso Standard) in a container equipped with a stirrer, thermometer, and reflux condenser and heat to around 90°C. Lauryl methacrylate 19 (1, glycidyl methacrylate 102, benzoyl peroxide 2 t) A mixed solution of lauryl dimethylamine 1f, acrylic acid 52,
0.1f of hydroquinone was added and reacted at 90°C for 15 hours. Add Isopar H3O0f to this reaction mixture,
At 90°C, a solution of 5 methyl methacrylate (1, P-aminostyrene 5?, 2 v azobisisobutylnitrile)
The mixture was added dropwise over an hour and stirred for an additional hour to obtain a white dispersed polymerization product. The product was a stable latex with a solids content of 28%.

30- Synthesis Example 2 Take kerosene 3BOf in a reactor similar to Synthesis Example 1 and add 90
Heat to 220 °C and 2-ethylhexyl methacrylate
t, glycidyl methacrylate) 8F.

A mixed solution of benzoyl peroxide 1f was added dropwise over 2 hours, then stirred at 90°C for 40 minutes to complete the reaction, and lauryl dimethylamine 19, methacrylic acid 5f, and hydroquinone 0.12 were added and allowed to react at 90°C for 18 hours. Ta.

Kerosene 2209 was added to this reaction mixture, and a solution of 3 styrene (1, 52 methacrylic acid, 2 vol of azobisisobutylnitrile) was added dropwise at 90°C over 1 hour, and the mixture was further stirred for 2 hours to obtain a highly stable dispersed polymer. Ta.

Synthesis Example 3 Isopar H1000f was brought to 90 to 100 tl in a container equipped with a stirrer, a thermometer, and a cooler, and a mixed solution of lauryl methacrylate (5BOf), 26 t of acrylic acid, and 5 t of benzoyl peroxide was added dropwise over 3 hours. Then heat and stir for 2 hours.

Lauryldimethylamine 32. Glycidyl methacrylate 259% and tcrt-butylcatechol 0.22% were added, and after reacting at 90°C for 2 hours, Isopar 117002 was added.

A solution of SalItCyE Nyltoluene 17 (1, P-Nitrostine Of *Azobisinbuterium) 1F 51F was added dropwise over 2 hours, and the mixture was stirred for an additional 3 hours to obtain a syrup-like dispersed polymer liquid. The solids content was 29.1%.

Synthesis Example 4 A dispersed polymer was obtained in the same manner as in Synthesis Example 1 using dimethylamine ethyl methacrylate 52 instead of P-aminostyrene.

Synthesis Example 5 300f of isooctane is placed in a reactor similar to Synthesis Example 1 and heated to 90°C. In this, 195 t of 2-ethylhexyl methacrylate, 52 t of glycidyl methacrylate,
A mixed solution of benzoyl peroxide 21 was added dropwise and stirred for 2 hours. The solids content of this copolymer was 38.7%. Furthermore, this copolymer contains 12. lauryl dimethylamine and 32. acrylic acid. Add hydroquinone 0.05 f and 20
The reaction was carried out at 80-90°C for a period of time. Acid value after reaction is 3.2
Met. Add Isopar H30 (l) to this reaction mixture and keep it at 90°C (methyl methacrylate) 120? , a solution of azobisisobutylnitrile 42 is added dropwise and stirred for 2 hours to obtain a dispersed polymer product. This polymer was a stable dispersion with a solids content of 33.7%.

Synthesis Example 6 A dispersed polymer was obtained in the same manner as in Synthesis Example 5 using methyl acrylate (12Of) instead of methyl methacrylate. Solid content (d): 33.9%, milky white.

Synthesis Example 7 A dispersed polymer was obtained in the same manner as in Synthesis Example 5 using stearyl methacrylate 195f instead of 2-ethylhexyl methacrylate. The solid content was 32.6%.

Synthesis Example 8 A dispersed polymer was obtained in the same manner as in Synthesis Example 5 using vinyl stearyl ether 33-195f instead of 2-ethylhexyl methacrylate. Solid content is 31
．． It was 8%.

Synthesis Example 9 Using vinyl acetate 80f instead of methyl methacrylate in Synthesis Example 1, a milky white dispersed polymer was obtained. The solids content was 3o, 5%.

Synthesis Example 1゜ Hydroxyethyl methacrylate 52 was used instead of P~ruaminostyrene in Synthesis Example 1 to obtain a dispersed polymer.

Synthesis Example 11 A stable dispersion similar to Synthesis Example 1 was obtained by using 4-vinylpyridine 10f instead of P-aminostyrene in Synthesis Example 1.

Example 1 Graft copolymer 202 obtained in Synthesis Example 1 was dissolved in 100 CC of cyclohexane, and after dissolving, naphthol ASI
(1) is well dispersed. The solution is strongly stirred in 2'00 CC of a 10% aqueous solution of polyvinyl alcohol to emulsify it. Further, under strong stirring, the cyclohexane is removed by distillation at a reduced pressure of -34~. is kept below 50°C. After the cyclohexane is completely removed, the capsules are filtered and washed with water. After washing with water, the capsules are vacuum dried to obtain particles with a particle size of 10-30μ and a coupler content of 25.
18.7 t of encapsulated coupler (1) in weight % was obtained.

In addition, the graft copolymer 2of and naphthol A3
Encapsulated coupler 15.62 with a particle size of 10 to 30 μm and a coupler content of 25% by weight could also be obtained by atomizing and drying a cyclohexane solution containing 10F by a spray drying method and removing cyclohexane.

Next, the encapsulated coupler (1)
sr silica fine particles (particle size l~5μ)
39 10% aqueous solution of polyvinyl alcohol
1 (1 stearic acid amide (particle size 1-10μ)
39 water
A mixture of more than 100 cc was dispersed with a homogenizer to obtain a pre-coat liquid, and this was applied onto the surface of the base paper for diazo copying paper using a wire bar and dried to form a pre-coat layer with a coating weight of 32/m2. Furthermore, thiourea 12 isopropyl alcohol 3 CC citric acid 12 saponin
1.12 water
A heat-developable diazo copying material was prepared by applying and drying 100 cc of a photosensitive liquid using a glass doctor to form a photosensitive layer with a coating weight of 19/m<2>. (
Sample A) 1 On the other hand, for comparison, the same procedure was carried out except that the graft copolymer 201 obtained in Synthesis Example 1 was replaced with vinyl acetate-lauryl methacrylate copolymer 20F at the stage of preparing the encapsulated coupler. A heat-developable diazo copying material (Sample B) was prepared.

Next, an original was placed on top of each sample and exposed to ultraviolet light, and then heated using an infrared heater at 110° C. for 3 seconds to form a blue image, and its density was measured. In addition, in order to test the raw storage stability, each sample was forced to deteriorate by leaving it in a desiccator at 50°C and 50% RH for 24 hours, then taken out, and the entire surface was irradiated with a fluorescent lamp to remove the diazozoic acid in the photosensitive layer. All the compounds were decomposed, the skin concentration was measured, and this was compared with the skin concentration measured after the same treatment without forced deterioration.

Note that the image density and background density are based on a Macbeth densitometer. The results are shown in Table-1.

Table 1 As can be seen from this table, the products of the present invention are excellent in both image density and shelf life.

In addition, in order to examine the cohesiveness of the precoat liquid when preparing sample AIB, the viscosity was measured using a B-type viscometer at 37° C. (20° C.). The measurement results are shown in Table-2.

Table 2 * Difficult to apply with wire parser Also, in order to investigate the lab-off properties of samples A and B,
When a laboratory test was conducted using a commercially available laboratory tester, sample A according to the present invention showed no peeling force, whereas sample B had peeling of the encapsulated coupler, making it difficult to put it into practical use. .

Example 2 Graft copolymer 152 obtained in Synthesis Example 2 was heated and dissolved in 100 CC of naphtha (boiling point 80-100°C).

While increasing the temperature to 50-55°C, 2-hydroxy-
Disperse 3-naphthoic acid morpholinopropylamide 538-f. The solution is strongly stirred and emulsified in 200 cc of a 10% gelatin aqueous solution heated to 50 to 55°C. Further, naphtha is removed by distillation under reduced pressure while stirring vigorously. After the naphtha is completely removed, the capsules are filtered and
Wash with water. After washing with water, vacuum dry the capsules to obtain a particle size of 10~
9.2 t of encapsulated coupler (11) with a diameter of 30μ and a coupler content of 25% by weight was obtained.

The same encapsulation method was followed except that the same amount of 3-hydroxycyanoacetanilide was used as a coupler.
9.5 tons of encapsulated coupler (1) having a diameter of 0 to 30μ and a coupler content of 25% by weight were obtained.

In this example, when removing naphtha by vacuum distillation, if the naphtha is completely removed by heating to 50 to 60°C, the encapsulated coupler will be dispersed in the gelatin/aqueous solution. A liquid is obtained, the filtration and water washing steps can be omitted, and it can be used as it is as a precoat liquid in the next step.

Then the encapsulated coupler (II)
6 f encapsulation coupler (n+)
-i y Starch fine particles (particle size 5-20μ)
2f Hydroxy engineered cellulose No. 1
0% aqueous solution] or behenic acid anilide (particle size 1-10μ)
4v water 1
A mixture consisting of 00CC is dispersed with a homogenizer to obtain a precoat liquid, which is coated onto a base paper for diazo copying paper using a wire bar and dried to form a precoat layer with an adhesion amount of 3 f/m2. .

Zinc chloride 2f tartaric acid
12 saponins
0.1f water
A photosensitive liquid consisting of 100CC was applied and dried using a glass doctor to form a photosensitive layer with a coating thickness of 0.897 m''.

Next, the original was superimposed on the heat-developable diazo copying material obtained in this manner, exposed to ultraviolet light, and heated to 100°C using an infrared heater.
When heated for 5 seconds, a high density black image was formed. Note that the raw storage stability of this material was excellent as in Example 1. Note that the precoat liquid used in preparing this copying material did not aggregate and was very stable. Furthermore, no ψ-off phenomenon was observed in this copying material.

When this diazo copying material was brought into contact with a recorder equipped with a 110 DEG C. thermal pen, a high-density black image was immediately formed on a yellow background. Then, when the entire surface was irradiated with a fluorescent lamp for 3 seconds, the yellow background turned white and was completely fixed.

Example 3 Graft copolymer 109 obtained in Synthesis Example 3 was dissolved in ligroin 100CC, and after dissolving, phloroglucin 5f
Disperse well. The solution is strongly stirred into 200 cc of a 10% aqueous solution of polyvinyl alcohol to emulsify it.

Further, under strong stirring, ligroin was completely removed by distillation under reduced pressure to obtain an aqueous dispersion of encapsulated coupler 4l- (Ill) 8.91F having a particle size of 10 to 30 μm and a coupler content of 30%. next.

Encapsulated coupler (P/) dispersion
202 Urea 2f Sulfuric acid 0.22 Gelatin 1f Polystyrene fine powder (particle size 1~5μ) 10t Stearylbenzamide 5v Saponin
0.1? water
A mixture consisting of 100CC was dispersed with a homogenizer to form a photosensitive liquid, which was applied to base paper for diazo copying paper and dried to give an adhesion amount of 39/? A photosensitive layer of F1'' was provided.

Next, an original was placed on the heat-developable diazo copying material thus obtained, exposed to ultraviolet light, and then instantaneously heated with a xenon flash lamp, resulting in the formation of a high-density black image.

Note that the raw storage stability of this material was excellent as in Example 1.

In addition, no aggregation was observed in the photosensitive solution used to prepare this material, but it remained stable over time, and no lab-off phenomenon was observed in this material.

Patent applicant Ricoh Co., Ltd. Agent Patent Attorney Toshiaki Ikeura 43-

Claims (1)

[Claims] (1) In a heat-developable diazo copying material in which a photosensitive layer mainly composed of a diazo compound, a coupling component, and a coloring aid is provided on a support, the coloring aid is a heat-fusible substance with a melting point of 50 to 150°C. and the coupling component is the following A
A heat-developable diazo copying material characterized in that it is encapsulated with a graft copolymer obtained by graft-polymerizing a monomer of group B and a monomer of group e0 below to a resin of group B. A copolymer consisting of a monomer represented by the general formula (1) and a monomer represented by the general formula (2). General formula (1) General formula (2) (However, R is -Hs 0Hs X is -0000n H2n+1 + 0OnH2n +
11 (representing 5≦n≦20)) When the monomer general formula (3) of the group B monomer is represented by the general formula (3) % formula % and the glycidyl methacrylate component is contained in the resin of the group A is acrylic acid or (and) methacrylic acid, acrylic acid or (and)
When a methacrylic acid component is included, it is glycidyl methacrylate) Monomer general formula (4) represented by monomer general formula (4) of group 0 (where, R is -H* 0Hs Z is 10000 nHzn+t (1≦n≦4) )ν”0
0001H2y1+1 (represents 1≦n≦6)9)