JPS60187586A - Diazo-fixed thermal recording material with excellent image storage properties - Google Patents

Abstract

PURPOSE:To obtain a diazo fixable type thermal recording material having high sensitivity, excellent preservability and excellent light fastness of images, by using a compound of general formula 1 as a yellow color forming coupler. CONSTITUTION:At least one compound of general formula 1 is used as a yellow color forming coupler compound, in a diazo fixable type thermal recording material provided with a photosensitive thermal recording layer comprising a diazonium salt, a coupler compound, a particulate dispersed material of a hydrophobic organic basic compound showing a basic atmosphere when being melted by heating (color developer) and a water-soluble binder as main constituents on a base. In general formula 1, each of R1 and R2 is H or 1-6C alkyl, or they together form an alicyclic ring, which may be substituted by halogen or alkyl, and each of R3 and R4 is H, halogen, -18C alkyl, alkoxy or cycloalkyl. The coupler compound is incorporated in the thermal recording layer in the form of a particulate dispersed material having a particle diameter of not larger than 10mum, by using a dispersing means such as a ball mill.

Description

[Detailed Description of the Invention] Kimi Ri 1 is heat-sensitive 1i 12 green to Shang Yibo, and the meat squad l is disgusting to the original, and the diazo gradual type feeling is differentiated between sexes, and Tsuji d (in the book ly)

In the last 4 years, in response to the demands of society, the development of the aforementioned printers, facsimile machines, etc. took place at a rapid pace. Heavy speed grinder, +iu of facsimile <
Therefore, electrophotography, static recording, discharge recording, ink printing, heat-sensitive self-edging, and the like are known as methods for forming an image on a recording medium. Among these methods, the thermal recording method has become rapidly popular in recent years because it is comparatively simple to direct the equipment and the recording paper is 4B in size.

As one method of the heat-sensitive recording method, a heat-sensitive self-edge sheet made of a combination of a color-forming substance such as crystal violet lactone and a phenolic compound such as bisphenol is used. 9 kakosho 4
It is described in Japanese Patent No. 5-14.039 and is already known. These +1 & thermal recording sheets are widely used as recording paper for office work, various recorders, electrocardiographs, IL desks, computer terminals, facsimiles, etc.

However, with the conventional method described above, if the printed material is heated by mistake, the color may develop and the printed text may not be printed properly, or it may be tampered with after printing. 9, and its improvement is strongly desired1.

The book 9 opening etc. was intended to provide a heat-sensitive recording material for fixed eyebrows that solved the problem of 0, and was made with 1υ, and first, a basic substance that promotes the reaction between the diazonium salt and the Gler ratio compound was used. By using a guanidine derivative having a specific general formula as a substance, a constant M 0J' with high sensitivity and excellent storage stability can be obtained.
We have already proposed the idea of providing a complete thermal recorder. (% Kaisho 57-45094, Showa 57-125
09'l Publication).

As a result of further development, Fuda Kaisha et al. found that at least one chemical substance selected from the chemical compound group represented by the following general formula <1) was added to bamboo as a yellow color-forming Kagura compound with a particle size of 0.
．． By using it as a 5 to 10 micron imitative particulate separation, it has a sensitivity of 1.5 μm and a long shelf life, while also being resistant to light by 1.1 times! There are 14 diazo thermograms with excellent markings.

General formula (1) (However, l(+,, l(+2 is hydrogen, an alkyl group having 1 to 6 carbon atoms or l(,, R2 jointly forms a cycloalkyl ring. Also, the cycloalkyl ring is a halogen , may be substituted with an alkyl group.

Further, R3 and ■ represent hydrogen, halogen, an alkyl group having 18 or less carbon atoms, an alkoxy group, or a cycloalkyl group.

) The effect of improving image storage stability due to the use of the Kabra compound represented by the general formula (1) was observed not only when the hydrophobic guanidine m4 compound was used, but also when it was used as a general color developer of the widely known Aiso-based compound. However, guanidine derivatives of general formula (11) and general formula (ill) have been developed in Europe as autobasic compounds suitable for beaks, and have high sensitivity and excellent storage stability, as well as excellent preservation properties. A diazo type thermosensitive recording material is obtained.

General formula (old general formula (till ■t1゜ [in the formula, 1t5, 6, 7, ') and 1t9 are hydrogen, alkyl having 18 or less carbon atoms, cyclic alkyl, ali/L/.

Represents aralkyl, amino, algylamino, acylamino, carbamoylamino, pseudocyclic residue, l:Llo
B 1m kJjt, 7 Lukylene, Phenylene,
naphthylene or -0-0- (in the formula,
Also included are those containing direct radicals derived from alkoxy, nitro, acylamino, alkylamino, and halogen. ] The diazonium salt used in the present invention can be arbitrarily used in the compounds* used in conventionally known diazo-type tawara printing materials, but examples include the following -1itu formula (IV),
The metals represented by (V) and (Vl) can be particularly preferably used.

(IV) Ym In the formula, i(, , and 几, 2 is alkyl having 1 to 5 carbon atoms, or haalcoquine, or oxyalkyl, benzyl,
+tm benzyl, benzoyl, it-substituted pennoyl, phenyl group, hydrogen atom, etc. are all shown, Y and Z are halogen atoms, alkyl having 1 to 5 carbon atoms, carboxyl, carbon X number 1
-5 alkoxyl, nitro, acetoxy groups, etc., rn and n ri O or a positive integer of 4 or less. Also, XdCl-113r-1S04-1NO, PF-1C
In addition to anions such as 1O, 13F4-, etc., ions such as ZnC42, CdC12tpi, or 5nCt4 are added to these anions.

Specific examples include 4-N,N-dimethylaminobenzenediazonium chloride, 3-chloro-4-N,N-dimethylaminobenzenediazonium chloride, 4-N,N-
Diethylaminobenzenediazonium chloride, 2.5
-Jethoxy-4-N, N-diethylaminobenzenediazonium chloride, 4-N-ethyl-hydroxyethylaminobenzenediazonium chloride, 4-N.

Hageethoxyamine benzenediazonium chloride, 4-phenylaminobenzenediazonium chloride,
4. -N-(P-methoxyphenyl)-aminobenzenediazonium chloride and the like.

(V) Y+□ Zn In the formula, J3 is -C1 (2CH20CH2C:H2- or -C
I-i20CH2CIL2-, -C)12(,H2CH
2CH2-, etc.

X, 'Y, Z, In and n are the general formula (IV) (7) and times, s, -! Specific compound examples include 4-morpholinobenzenediazonium chloride, 2,5-jethoxy-4-morpholinobenzenediazonium chloride, 4-oxazolidinobenzenediazonium chloride, 3-methyl-4-
Examples include piperidinobenzenediazonium chloride.

Zn In the formula, 几, 4Vi argyl group and aryl group are all shown.

Further, X, YXZXm and n have the same meanings as in general formula (IV).

Specific compound examples include 4-ethylkab)-2,5-
Examples include jetoxybenzenediazonium chloride, 4-tolylmercapto-2,5-shedquin benzenediazonium chloride, and 4-benzylmercapto-2,5-dimethoxybenzenediazonium chloride.

Furthermore, to prevent doweling and pre-coupling of the diazonium salt, gold oxide can of course be used during the VC photosensitive and thermal process, but this is different from the organic, ageless, and organic materials used in conventionally known diazo type copying materials. Oxidized compounds can be used in a variety of ways; specific examples include Shiraishi Ichiha, citric acid, boric acid,
Lactic acid, gluconic acid, 1 phosphorus, triku I goro 1 i cleft,
Dichloromethane, dichloromethane, malo/acid, maleic acid, etc. are all suitably used.

If I Kumi” Bikino, 1. These 1st class compounds are +Ji: , i3. ', 1.0% to 30% in ratio
It is preferable to use it within the range of lli□, more preferably within the range of 5 to 15%.

As a specific example of what corresponds to general formula (1), ν11
Now you can scramble for the next thing.

General formula (1) These coupler compounds can be reduced to a particle size of lOμ using a t-ball mill, a -9-doped grinder, an atomizer, etc.
It can be contained in the light and heat sensitive layer as the following fine particulate dispersion.

The coupler compound may be a combination of one or more compounds selected from the above general formula (1), or a yellow coupler having an active methylene group, a phenolic coupler, a coupler having a pyrazolone ring, a β-naphthol derivative, etc. In combination with compounds of general formula (1), dyes exhibiting desired spectral absorption properties may be produced.

Further, at the time of dispersion, the coupler compound may be dispersed alone, but it is also possible to co-disperse only the +T'' machine basic compound and others with machining if necessary.

If the organic basic compound used as a color developer is mixed with the water used as a solvent when applying to the support rod, the pH of the coating solution will increase, causing capri of the scalp and deterioration of storage stability. Therefore, it is desirable that it exists as a discontinuous fine particulate dispersion in the coating layer, and if the solubility in water at 20°C is less than i, oy7, it will also have good humidity and heat resistance. Heterocyclic compounds such as aliphatic imigzoline derivatives and piperidine derivatives can also be suitably used, but in particular, compounds of the following general formula (
When the hydrophobic guanidine derivatives (n) and (Ill) are used as total color developers, they are diazo-fixing type thermosensitive materials that have excellent storage stability under high temperature and high humidity conditions and develop colors with high sensitivity. You can read the entire record. Further, as the color developer, one having a melting point in the range of 100 to 170°C can be particularly preferably used.

The blood tinting agent may be dispersed alone using a dispersion means such as a ball mill, a sand grinder, an attritor, or the like, but it may also be co-dispersed with a coupler compound and other additives as necessary.

General formula (II) 几9 Or, general formula (in the town 1 几10 C formula) ts 1, IL, R8 and ■mo are hydrogen,
Alkyl, cyclic alkyl, aryl having 18 or less carbon atoms,
aralkyl, amino, alkylamino, acylamino,
Carbamoylamino, heterocyclic residue, 1L+old
-0-0 for low i alkylene, phenylene, and naphthylene
-(In the formula, 1st grade alkylene, SO2, S2, S, 0
, -N14- or a single bond), and the aryl group in the formula ζ/u lower alkyl, alkoxy, nitro, °
Those having a 1a substituent selected from an acylamino group, an alkylamino group, and a halogen are also mentioned.] Typical examples thereof are shown in Table 2, which represent hexyl groups.

Table-2 (1) H (2) N)l (4) CH.

CH3 H3 (22) (23) (25) (26) C:H,C0-Nu (29) kJ (34n (35) to H-4;-NH,.

(36) (37) (38) (39) (40) ' (41) (42) (43) These guanidine derivatives e shown above can be easily synthesized by known methods or methods similar thereto. I can do it.

The photosensitive/thermosensitive layer of the present invention contains a diazonium salt, a coupler compound, a color developer, a water-soluble binder, etc. as main components, and these may be provided as a single layer on a support as a photosensitive/thermosensitive layer. The layer may be divided into two layers or multiple layers and provided on the support.

Binder materials for forming the photosensitive and thermosensitive layer of the present invention include corn starch, gum arabic, glue, gelatin, casein, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxyl methyl cellulose, polyacrylamide, carpoxymethyl dengue, and dialdehyde. Starch or its modified products such as starch, polyvinyl alfur or its modified products 9 and 4, polypeel pyrrolidone, isobutylene-maleic anhydride, polyacrylate, styrene-maleic anhydride. It copolymer, polyvinyl chloride, polyvinylidene carbide, polystyrene, stencil methacrylate rubber (=SDR3 methacrylate phtadiene rubber (=H4131 also), nitrile butadiene rubber (=NBR), polymethyl methacrylate, Examples include synthetic resin emulsions such as polypropylene, polyacrylonitrile, and acrylic esters, and these binders can be used alone or in combination.

Since the coupling reaction of di'rzonium salts is promoted in a permissive solvent such as water, the storage stability of the bamboo fixed heat-sensitive recording material using diazonium foundation under high temperature and humidity is low. By selecting a binder 4A material having a high ratio of 4A to 4A, it is also possible to improve the performance of ordinary water-temperature-prone molecular binders such as formalin, glyoxal, chromium alum, geltaraldehyde, melamine, /formalin resin, urea/formalin filler, etc. The storage stability can also be completely improved by using a waterproofing agent used in the material.

Specific examples of pigments used in the photosensitive and heat-sensitive layer of the present invention include kaolin, calcined kaolin, talc, waxite, diatomaceous earth, styrene resin particles, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, r"R titanium, barium carbonate, urea-formalin filler, cellulose filler, aluminum oxide, etc. can be removed, but from the viewpoint of thermal head matching properties such as scum and sticking, JP-A-53-118059.54-2
5845.54-118846.54-L18847 It is preferable to use an oil-absorbing pigment with an oil absorption of 80 to 500 d/100 F in the standard method specified in JIS K5101, and directly contact the heat-\throat in %. In the layer, it is desirable to use an oil-absorbing skin material such as calcined kaolin, urea-formalin fins, etc. that exhibits the above-mentioned oil absorption amount.

Other auxiliary ingredients include zinc chloride, zinc sulfate, sodium citrate, and thiourea sulfate to suppress or assist color development.
Sugars such as y-guanidine, calcium gluconate, sorbitol, and sucrose are used, and if necessary, anti-foaming agents and anti-foaming agents are added, and wax is used to improve sticking and color sensitivity. It is possible to use metal soaps and metal soaps.

Specifically, waxes include paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax, as well as higher fats (eg, stearinamide, stearamide, laurylamide, myristylamide, hardened bovine IM amide, palmitin amide), etc. Amide, oleinated amide, acetamide, coconut fat + ft amide, or methylolated products of these 1111 fatty acid amides, methylene bisstearoamide, ethylene bisstearoamide, and υi class; can be lost.

Examples of metal soaps include polyvalent metal salts of higher fatty acids, ie, zinc stearate, aluminum stearate, calcium stearate, olein v, l1li lead, and the like.

Also, as a sensitizer that improves color development sensitivity, it has a melting point of 90℃~
It is also possible to use a substance that has a temperature of 150° C. and has good compatibility with organic basic compounds, coupler compounds, etc. when heated.

As these substances, any substance can be used as long as it has good compatibility during heating, but in particular - benzene rings,
A substance having a naphthalene ring tray and also having a polar group such as an ether bond or a carbonyl group (ketone group, ester group) can be suitably used. Specifically, dimethyl terephthalate, dibenzyl tere7thaleate, l-methoxynaphthalene, 1,4-jethoxynaphthalene, O-benzyl ether of P-hydroxybenzo n-benzyl ester,
etc.

Although these can be used alone as dispersed, they can also be used as co-dispersed with organic basic compounds, coupler compounds, etc.

In addition to paper, synthetic resin films, laminated papers, etc. can also be used as a support for one-time use.Also, when using one-time use as a whole support, diazonium salts can be easily coated directly onto the support. Since a large amount of diazonium salt is required to penetrate into the voids of the paper base and be fully immersed into the interior, the ltB IA of photofixing by flashlight after thermal printing may decrease, and this drawback can be prevented. Therefore, if necessary, the paper substrate may be coated with a void photonic agent such as silica sol, alumina, modified titanium, or kaolin, or a highly concentrated agent such as starch, casein, polyvinyl alcohol, or polyvinyl acetate emulsion in combination with these agents.
It may be precoated in combination with a molecular material and then applied with a photosensitive layer (K heat Lm).

Next, we will explain the entire history of the present invention in detail with examples and comparative examples.

夷) JIM Shio 1ll Prepare a light and heat sensitive layer with the formulation described in F, and after drying, the coating amount on the support is 9.5'tAr? A fixing type heat-sensitive recording material is prepared by coating and drying it so that it becomes Ic.

The unit is the vehicle amount i/small.

Incidentally, liquid A and B'4VL were prepared by grinding the following formulation in a ball mill for 48 hours.

Example 2 In Example 1, the compound *(6) in Table 1 was used in Solution A (,
A diazo-fixed heat-sensitive recording material was prepared in the same manner as in the example except that: 11° was used.

Example 3 A diazo-fixed thermosensitive recording material was prepared in the same manner as in Example 1, except that in Example 1vc, compound (6) of Table 1 was used in combination with A(fi).

Comparative Example 1 A fixed heat-sensitive self-adhesive body was entirely prepared in the same manner as in Example 1, except that acetoacetanilide was used in place of A'e in Table 1 and (6) sound in Table 1. did.

Example 4 Prepared with a composition containing a diazonium salt and completely lacking a photosensitive layer,
The amount of mineral IT after drying on the support is 2. OY/n? Apply it so that it looks like this.

A heat-sensitive layer containing a color developer prepared in the following formulation was coated on the photosensitive layer, and the coating amount after drying was 8.0 v/n? The entire diazo-fixed heat-sensitive recording material is prepared by applying the resin so as to give the following properties.

The AM and B solutions were prepared by grinding the following formulations in a ball mill for 48 hours.

Solution B Example 5 A diazo complete skin thermosensitive recording material was prepared in the same manner as in Example 4 except that compound (17) in Table 1 (compound m(14) in Table 1) was used in Solution A in Example 4. Created.

Example 6 A diazo-fixed 4P heat-sensitive recording material was produced in the same manner as in Example 4 except that the compound shown in Table 1 (instead of using 1 force (compound (15) in Table 1) was used in Solution A. Created.

Ratio 1 Bite Example 2 In Example 1 Sori 4, Compound (17) of Table 1 was used in Solution A
Except for using O-chloroacetanilide instead of using
Create a border and fc.

Like this! Smooth diazo-fixed thermal recording material'
1: 1 It was heated at 50° C. for 5 seconds to develop color in a L1 heat block, and the diazonium salt was decomposed and fixed by full-field ultraviolet exposure.

One color image obtained in this way was measured using a xenon fade meter (manufactured by Suga Test Instruments, FAL-25X-HCl, 1
[I1lt1. jl # Ax 1 jf 60 w/vrl at 4 (' If 6 (1 prefecture) when irradiated for 24 hours under φ conditions, the initial image 1 density and image 1 image survival rate are shown in Table 3.

The measurement results were measured using a Macbeth f4 degree meter (1(I)-5141) using a Kodak filter ÷106 for black pigments and a Kodak filter ÷94 for yellow wood.

Table-3

Claims (1)

[Claims] 1. Diazonium salt, coupler compound, and color developing film
A diazo-concentration film comprising a light-sensitive and heat-sensitive layer on a support, which contains imitative particulate fractions of a hydrophobic organic basic compound that exhibits a J1-based atmosphere when bath-melted by heat as l, and a water-bathable binder as a main component of gold. In the thermosensitive recording material, the yellow color-forming thread Kagura compound is at least one other compound selected from the group of compounds represented by the general formula CI Fixed-layer thermographic H type.General formula (1) (However, It1 and JL2 are hydrogen, an alkyl group having 1 to 6 carbon atoms, or R1 and It2 jointly form a cycloalkyl ring.Also, a cycloalkyl ring may be substituted with a halogen or an alkyl group. Also, JL,, It. ゛ represents hydrogen, a halogen, an argyl group, an alkoxy group, or a cycloalkyl group having 18 or less carbon atoms.) 2. Hydrophobic organic A diazo-fixed heat-sensitive recording material with excellent image storage stability according to claim 1, wherein the basic compound is a hydrophobic guanidine derivative represented by the general formula (II) or (Ill). And. General formula (II) ltl. [In the formula, 1 and 5, "6.1'L7, I and 1t" are hydrogen, alkyl having 18 or less carbon atoms, cyclic alkyl, aryl, aralkyl, amino, algylamino, Coating acylamino, carbamoylamino, and enomoto ring residues,
. is +Jk a 'y alkylene phenylene, naphthylene or -0-0- (in the formula X (!yo lower alkylene, S
O2, S2, S,,0. -NJ-1-'jtake-z(j
The aryl group in the human body may have a substituent selected from lower alkyl, alkoxy group, nitro, acylamino, alkylamino group, upper, mouth, etc. ]