JPS5863934A - Thermodevelopable type diazo copying material - Google Patents

Abstract

PURPOSE:To obtain a copying material capable of forming a high density image even through low temp. development, and improved in shell life of unexposed products, by adding a specified substance capable of melting a coupling component together to a diazo compd. and this coupling component. CONSTITUTION:A thermodevelopable type diazo copying material is prepared by forming on a support a layer contg. a diazo compd., and a coupling component for developing color in contact with this diazo comd., and at least one of a substance for melting the coupling component together with itself having general formulaIin which A is methylene or 3-4 alkylidene; X is H or halogen; (m) is 2-4; (n) and (n') are 1-5: or formula II in which R is 10-30C straight chain alkyl; (m) is 2-4; and, (n) and (n') are 1-5: or formula III, thus permitting a high contrast image to be obtained even by low temp. development, a shell life of this unexposed product to be greatly improved as compared with the conventional color developing adjuvant of aliphatic amide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-formable diazo copying material, and more particularly to a heat-formable diazo copying material containing a diazo compound, a coupling component, and a specific substance for eutectic dissolution of the coupling component.
Relating to W diazo copying material.

In general, a heat-developable diazo copying material is one in which a photosensitive layer containing a diazo compound, a coupling component, and a coloring aid as main components is provided on a support such as paper or film, and has a photosensitive layer of +11
Urea, sodium trichloroacetate, etc. are used as coloring aids. All of this type of diazo copying material is
Developing is performed by heating at ~200°C, and the mechanism uses an alkali (ammonia gas, caustic soda, etc.) that decomposes upon heating. Also, (2
) Low-temperature development (about 90 to 130°C) As an attempt at 1f1, it has been proposed to use higher fatty acid amide compounds as coloring aids, but the development mechanism of this is that the higher fatty acid amide compounds are heated and melted. This method utilizes the activation of a diazo compound and a coupling component.

However, in these conventional diazo copying materials for close-up images, the developing temperature is high in the case of +1).
As the diazo compound, a material with high heat resistance is selected and used, which is disadvantageous to the formation of high concentrations. Therefore, this diazo copying material has a relatively slow development speed and a high density 1iki.
It has the disadvantage that it is difficult to obtain a high-quality image, and furthermore, it requires a high-temperature and highly accurate heating device (the heating temperature may be insufficient or the color tone may change), so the cost of the copying machine itself is unavoidable. It also has the disadvantage of being expensive. On the other hand, in the heat-developable diazo copying material mentioned in (2) above, although low-temperature development is possible, the shelf life of the nude photographic material itself (hereinafter sometimes referred to as "raw shelf life") is said to be reduced. There are drawbacks.

However, in order to improve these drawbacks, it has been proposed to use a mixture of a diazo compound, a coupling component, or a basic substance and a wax having a melting point of 50 to 250°C, which are thoroughly mixed and ground. (Unexamined Japanese Patent Publication No. 55-11: (4
However, the thermal sensitivity is still slow and it is difficult to obtain high art colored images. Furthermore, a method of encapsulating a diazo compound or a coupling component with a wax has also been proposed (U8P32025101, but this method cannot be said to be as satisfactory as the above).

The purpose of the present invention is to eliminate the drawbacks described so far, to obtain a high-density colored image with a small amount of thermal energy without impairing storage stability, and to provide a heat-generated image with excellent storage stability. An object of the present invention is to provide an immersion am diazo copying material.

As a result of various studies and studies aimed at producing such a diazo copying material, the present inventors have discovered that this can be achieved by using a specific thermal eutectic melting agent. The present invention was completed based on such knowledge.

That is, the heat-developable diazo copying material of the present invention is prepared by contacting a diazo compound and a skeleton diazo compound on a support (1).
,,) [However, A is a methylene group or an alkylidene group having 3 to 4 carbon atoms, X is hydrogen or) 10 gen, m is an integer of 2 to 4, n and n' are 1 to 5
is an integer. ] 0 (OmH1mO←H [However, R is a linear alkyl group having 10 to 30 carbon atoms, m
is an integer of 2 to 4, and n and n' are integers of 1 to 5.

] 0 = 0-0 (It is characterized by being provided with a layer containing at least one type of thermal eutectic melting agent represented by OH, OH, and 0+H.

The present invention will be explained in more detail below. The thermal eutectic dissolving agents used in the Perspective*m diazo copying material according to the present invention are all known substances.

The method for producing the compound represented by the general formula (1) is disclosed in, for example, Japanese Patent Publication No. 44-27570, Japanese Patent Publication No. 4B-23134, and Japanese Patent Application Laid-open No. 150-105638, and in particular, , A is a methylene group, and m is 2 or 3. Compounds in which A is a methylene group and m is 2 or 3 are suitable for use because they are easily available and inexpensive.

The compound represented by the general formula (seal) is synthesized by adding alkylene oxide/ to the linear glycol of the above general formula. That is, it is synthesized by adding sodium hydroxide as a catalyst to a linear glycol, heating the mixture to 150 to 180° C., and bubbling, for example, ethylene oxide into the liquid while stirring vigorously.

The compound represented by the structural formula (sulfuric acid) is usually obtained by adding 2 moles of ethylene oxide to 1 mole of terephthalic acid.

In the present invention, by using at least one compound represented by the above general formula or structural formula (1) (1) (*) as a thermal eutectic dissolving agent, the product (contemplative type) It has now become possible to simultaneously achieve low-temperature development and improvement of raw storage properties of diazo copying materials.

This thermal eutectic solubilizer is water-insoluble and solid at room temperature, and is used in the form of fine particles with a particle size of 0.1 to 10 Pm, and the coupling component is eutecticly melted by heating to dissolve the coupling component and the diazo compound. It is extremely effective in promoting the coupling reaction of It is thought that by having such an effect, low-temperature development could be achieved without impairing storage stability. Furthermore, since this thermal eutectic solubilizing agent eutecticizes only the coupling component, it is believed to contribute to improving the shelf life.

The amount of at least one compound (thermal eutectic solubilizer) represented by the general formula or structural formula (〇) (mark) (*) used is:
A suitable amount is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 1 part by weight of the diazo compound. 8. The thermal eutectic dissolving agent used in the present invention can be used in combination with fatty acid amides, which are generally used as thermally fusible substances, and others.

As the diazo compound and coupling component used in the present invention, 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
-dimethylannobenzene, 4-diazo-1-dimethylannobenzene, 4-diazo-1-dipro♂lua2no4
-
4-Diazo-1-ethylhydrooxyethylaznobenzene, 4-diazo-1-diethylamino-3-methoxy(benzene), 4-diazo-1-dimethylannor-2-methylbenzene, 4-diazo-1-benzoylamino-2 ，
5-Jethoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-jethoxybenzene, 4-diazo-1-morpholino-2.
5-Jethoxybenzene, 4-diazo-1-anilinobenzene, 4-dimethyl 1-dimethyl minnow 3-cal I
xybenzene, 4-diazo-1-tolylmercapto-
Chlorides of diazo compounds such as 2,5-jethoxybenzene, 4-diazo-1,4-methoxybenzoylannor-2,5-jethoxybenzene and metal halides (e.g. zinc chloride, cadium chloride, tin chloride, etc.) and salts of the diazo compounds with strong acids such as sulfuric acid, boron tetrafluoride, and bexafluorophosphoric acid, but are not limited to these, of course.

As coupling components, all those for general two-component disk diazo copying materials can be used, such as resorcinol, phloroglucin, 2,5-dimethyl-4-morpholinomethylphenol, 3-hydroxycyanoacetanilide, and sulfoacetanilide. , 1-benzoylamino-8
-hydroxynaphthalene-3,6-cisulfonade,
2.2-dihydroxynaphthalene, 2.7-dihydroxynaphthalene-3.6-sodium disulfonate, 2.3-
Sodium dihydroxy-6-sulfonate, 2, B--)
Sodium hydroxynaphthalene-6-sulfonate, sodium 1-hydroxynaphthalene-4-sulfonate, 1-7ono-3-hydrosinapthalene-3,6-cisulfonate, naphthol A8, naphthol A8-D, 2-hydroxynaphthalene- 3-Pigrinide, 2-hydrocacinaphthoic acid morpholinopropylamide, 2-hydroxynaphthoic acid ethanolamide, 2-hydroxynaphthoic acid-N-dimethylaminopropyl agide hydrochloride, 2,4
．． 2', etetrahydroxydiphenyl, z, 4. r
, (-tetrahydroxydiphenyl sulfoxide group).

In addition to the above-mentioned materials, various additives used in ordinary diazo copying materials can be used in combination with the photosensitive layer of the contemplation-type diazo copying material of the present invention. That is, as a preservability improver, sodium monosulfonate, sodium naphthalene-disulfonate, sodium naphthalene-trisulfonate, sodium sulfosalicyl, cadmium sulfate, magnesium sulfate, cadmium chloride, and sodium chloride are used. You can use a magnifying glass, etc. In addition, thiourea, urea, etc. are used as antioxidants, caffeine, theophylline, etc. are used as solubilizers, and citric acid, tartaric acid, sulfuric acid, cidic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. are used as acid stabilizers. In addition, a small amount of Cy2) can be added. As the material/goo, polymeric substances such as starch, casein, ♂yl acetate, and lyacrylic acid derivatives can be used. Furthermore, inorganic or organic fine particles such as silica, starch, clay, and resin can be used as image density improvers.

In practice, in order to prepare the contemplative diazo copying material of the present invention, a diazo compound, a kabulifug component (c-coupling component can be encapsulated if necessary), a thermal eutectic solubilizing agent, and other additives are added. Dissolved or dispersed aqueous liquid on paper,
A photosensitive layer with a coating weight of 2.5 to 15 f/- may be provided by coating and drying on a support such as a film by a conventional coating method.

Alternatively, the coupling component (the coupling component can be encapsulated if necessary), the thermal eutectic dissolving agent, and some of the additives (particularly the image density improver and the noider) can be dissolved or dispersed. A precoat layer with a coating weight of 2 to 10 f/- is provided by applying and drying the aqueous liquid on the support, and then an aqueous liquid in which the diazo compound and other additives are dissolved or dispersed is applied and dried to adhere to the pre-coat layer. Amount 0.5-5
A laminated type may be provided by providing an f/d photosensitive layer.

In any case, the ratio (weight ratio) of the diazo compound, coupling component, and thermal eutectic dissolving agent is 1:(0,1 to 10
): (o, 1-20) is suitable.

There are two methods for forming an imprint on the contemplative diazo copying material of the present invention. First, like general diazo copying materials, this close-up one-wrinkle diazo copying material is exposed to ms-shaped light using a fluorescent lamp or mercury lamp, and then heated to approximately 90 to 130°C using infrared rays, a heat roller, high frequency, etc. The other method is to heat the diazo copy material imagewise to the above temperature using a thermal pen or a thermal head, similar to general heat-sensitive recording materials, or to heat the diazo copying material to the above temperature in an imagewise manner using infrared light. In both methods, the unreacted diazo compound in the non-image area is removed by irradiating the entire surface with ultraviolet rays using a fluorescent lamp or mercury lamp, as with general diazo copying materials. can be decomposed and fixed.

As described above, the contemplation type diazo copying material of the present invention uses a specific substance as a thermal eutectic dissolving agent, so that it is possible to obtain a high density 1III even in low-temperature development.
Moreover, the shelf life of the products of the present invention is significantly improved compared to fatty acid oxides, which are conventional coloring aids.

Next, examples will be shown.

Example 1 Naphthol A8 417 repulsion fine particles (particle size 1-5P) 3f 1096 aqueous solution of polyvinyl alcohol 10f thermal eutectic solubilizer (1) 3 fK! Uniol DA-350F manufactured by L (average number of added moles of ethylene oxide 2.6)) Water 1
A mixture consisting of 000C was dispersed with a homogenizer to obtain a precoat liquid, and this was applied to the surface of diazo copying base paper using a lζ wire par and dried to form a precoat layer with a coating weight of about 4f/-. Furthermore, 4-diazo-2,5-dibutoxyphenylmorpholine chloride e'/2 ZnO111,5tthiourea
1f inzorobil alcohol
35C citric acid
1t Sainino 1.1 water 100
A photosensitive liquid made of CC was applied and dried using a glass doctor, and the amount of adhesion was about 1 t/w? A thermal imaging diazo copying material was prepared by providing a photosensitive layer (Sample 1).

A contemplative diazo copying material (sample 2) was prepared in exactly the same manner.

Next, a manuscript was placed over each of the above samples and exposed to ultraviolet light.
Then, it was heated at 110° C. for 3 seconds using an infrared heater to form a blue image, and its density was measured. In addition, to test the raw shelf life, each sample was heated to 50% I'L at 50°C.
After leaving it in a H desiccator for 24 hours for forced deterioration, it was taken out, and the entire surface was irradiated with a fluorescent lamp to decompose all the diazotized metals in the photosensitive layer, and the background concentration was measured. It was compared with the skin density measured after the same treatment without deterioration. The image contrast and background density ' are based on the Macbeth density needle.

The results are shown in Table 1. The heat-developable diazo copying material of the present invention has significantly improved shelf life compared to the conventional material (Sample 2) without impairing its low-temperature properties. I can't be sure that it is.

Table-1! ! Example 2 Phthol As-D 49 Silica fine particles (particle size 1 to 5p) 3t hydroxymethylcellulose 554 water fljfK 20
f Thermal eutectic solubilizer (厘) 41 Compound water to which 2 moles of ethylene dioxide have been added 10
A mixture consisting of 00C was dispersed using a homogenizer, a pre-coat liquid was prepared, and this was applied onto the surface of a base paper for diazo copying paper using a wire and dried to obtain a coating amount of about 417W?
After forming a precoat layer of 4-diazo-1-tolylmercapto 1.5f-2
, 5-jethoxybenzene PF.

Thiourea 1f isopropyl alcohol 3cc citric acid
1t Sarnin
1.1 f water
A photosensitive liquid consisting of 100CC was applied and dried using a glass doctor, and a photosensitive layer with a coating weight of about 1 f/- was provided to prepare a close-up type diazo copying material (Sample 3).
.

For comparison, the thermal eutectic solubilizer (Iris) 3 in the precoat liquid
A diazo copying material (Su/Sol 4) was prepared in exactly the same manner except that F was replaced with rumitic acid amide 4t.

Next, one or more of each sample is overlaid with an original and exposed to ultraviolet light.
Then, it was heated at 110° C. for 3 seconds using an infrared heater to form a back-colored image, and its density was measured. In addition, in order to test the raw storage stability, each sample was heated at 50℃ and 509gRH.
After leaving it in a desiccator for 24 hours for forced deterioration, it was taken out, and the entire surface was irradiated with a fluorescent lamp to separate all the diazo compounds in the photosensitive layer, and the background concentration was measured. It was compared with the skin density measured after similar processing. It should be noted that the front concentration and skin concentration here are also based on the Macbeth densitometer.

The results were as shown in Table-2.

Table 2 Example 3 After forming the same precoat layer as in Example 2 on the surface of diazo copying base paper, 4-diazo-2,5-dizolo4xy 1.32-phenylmorpholine BP4 thiourea was further added thereon. 1f3-hydroxycyanoacetanilide 0.82 methanol
5CC machine sulfuric acid 0
．． 1 f malic acid 1 f saponin
0.1 water
A heat-developable diazo copying material was prepared by applying and drying a photosensitive solution consisting of 100CC using a glass doctor to form a photosensitive layer having a coating weight of about 0.8f or more (Sample 5).

When this diazo copying material (Sample 5) was brought into contact with a recording needle equipped with a 110° C. hot pen to make a recording, a high density black image was formed on a yellow background immediately after contact. Then, when the entire surface was irradiated with a fluorescent lamp for 3 seconds, the yellow background turned white and was completely fixed. In addition, it was observed that the fresh storage property of this sample 5 was excellent like that of sample 1.

Example 4 Chlorinated arm rough-in (point 60-62°C at 111) 20f
was dissolved in 100 cc of cyclohexane, and after dissolving, phloroglucin 10F was well dispersed. The solution was strongly stirred and emulsified in 200 cc of a 10% aqueous solution of ♂Nyl alcohol. Furthermore, cyclohexane is removed by distillation under reduced pressure while stirring vigorously. At that time, the heating temperature is kept below 50°C.

The capsules from which cyclohexane has been completely removed are filtered and washed with water. After washing with water, vacuum dry the capsules to obtain a particle size of l.
An encapsulated coupler 142f having a coupling component of 30% by weight was obtained. Next, encapsulated coupler 14.2f thiourea 2f sulfuric acid
0.2f gelati 7 iF4 Listile/fine powder (particle size 1-5 ps) 10f thermal eutectic dissolving agent (seal) 5f (terephthal [1
A compound obtained by adding 972 moles of ethyl oxide to a mole) Sibenzene sulfate Sunin 0.1 f water
A mixture consisting of 100 cc was dispersed with a homogenizer to remove the photosensitive liquid, and this was applied to base paper for diazo copying paper and dried to obtain an adhesion amount of approximately 3.
A photosensitive layer of f/'- was provided.

Next, when a manuscript was placed on top of the thus-obtained Kujuro Ringo diazo copying material (sample 6) and heated for 2 to 3 seconds at the same time as the exposure using an infrared lamp, the high-density black side gIC image density was 1.14. ) was formed. Incidentally, it was observed that the raw storage stability of Sample 6 was as excellent as that of Sample 1.

Claims (1)

[Claims] 1. The following general formula or structural formula (1) in which a diazo compound, a coupling component that can develop a color upon contact with the diazo compound, and a cough coupling component are eutectically dissolved on a support.
(1) A heat-transfer type digital photocopying material, characterized in that it is provided with a layer containing at least one type of thermal eutectic melting agent represented by (1). (+) [However, A is a methylene group or an alkylidene group having 3 to 4 carbon atoms, X is hydrogen or halogen, m is an integer of 2 to 4, nm
and n' are integers from 1 to 5. ] [However, R is a linear alkyl group having 10 to 30 carbon atoms, m
is an integer of 2 to 4, and a and n' are integers of 1 to Is. ]