JPH01947A - diazo copying material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a diazo copying material that utilizes a coupling reaction (color-forming reaction) between a diazo compound and a coupler.

C. Prior Art] Phenol derivatives and naphthol derivatives have been known as coupling components for photosensitive paper used in the diazo copying method. This method has disadvantages in that the image may become yellowed or the formed azo dye may not be stable, resulting in loss of image sharpness over time.

In recent years, as copies have become higher contrast and deeper colors, β-
Research has been carried out on coupling components mainly based on naphthoic acid, and among these, naphthol AS derivatives are well known. Azo dyes that use naphthol AS-based coupling components have excellent resistance to photo-oxidation effects caused by moisture and ultraviolet rays.

When used as a copy, there are a number of drawbacks such as yellowing of the coupler due to alkaline agents, poor coupling ability, and solubility in aqueous solvents. In addition, a photooxidation prevention method when a β-naphthoic acid coupler is used as a coupling component (JP-A-56-33642, JP-A-56-33643)
However, the photooxidation prevention effect of acrylic vinyl chloride resin is unsatisfactory.

Furthermore, the addition of an antioxidant, as reported in JP-A No. 56-66884, is not practical due to oxidative coloring of the antioxidant, and research on the photobleaching mechanism of azo dyes has recently revealed that - heavy ring oxygen Measures to prevent various organometallic salts (quenchers) from photo-oxidation due to The photooxidant of the azo dye had almost no effect at all.

Therefore, JP-A-49-6936, JP-A-50-754
No. 35.

JP-A-54-35723 and JP-A-54-35724 describe methods for stabilizing azo dyes formed by these coupling components and diazo components by chelating them; Azo dyes formed using phenolic and naphthol derivatives as coupling components are difficult to chelate, and even if chelated, the chelate bond is likely to break off due to changes in pH or environmental conditions (humidity) and is unstable. be. It is also inferior in light fastness.

Furthermore, photosensitive paper using a phenylhydrazine-based coupling component as a coupling component is also known, but in this case, the solution becomes cloudy when preparing the photosensitive solution, making it practically unusable. Couplers with a ring can greatly improve the above-mentioned drawbacks, but generally, couplers with a pyrone ring have problems with the chelation rate, require high energy for chelation, and are subject to many practical constraints (environmental, pH1 development conditions, etc.), making it difficult to put it into practical use as a photosensitive paper.

The present inventors previously proposed a diazo copying material using the coupler represented by the above general formula and an allyl-modified polyvinyl alcohol resin as a binder for the precoat layer.

Although this product is excellent in terms of light fastness and prevention of deterioration in non-image areas, it has disadvantages in that it is inferior in storage stability and V water resistance.

〔the purpose〕

An object of the present invention is to provide a diazo copying material that exhibits excellent light fastness that does not cause copy deterioration even when exposed to NOx gas in the atmosphere or sunlight for a long period of time, and has excellent water resistance and shelf life. shall be.

〔composition〕

According to the present invention, in a diazo copying material in which a photosensitive layer containing at least a coupler is provided on a support via a precoat layer, an allyl-modified polyvinyl alcohol resin and an amino resin are used as binders for the precoat layer, and the coupler is There is provided a diazo copying material characterized in that a compound represented by the following general formula (1) or 1 and a compound represented by the following general formula (n) are used as .

(In the formula, .: Integer R of 1 to 3: hydroxyl group, alkoxy group having 1 to 3 carbon atoms, 1 morpholino group, dimethylamino group, diethylamino group) The diazo copying material of the present invention can be used as a coupler.

It is characterized by using a compound represented by the above general formula CI) or/and general formula (II), and these couplers have a fast coupling rate with the diazo compound described later, and also have a high coupling rate during development. It has excellent color development speed, and the color image obtained by such a coupling reaction also has excellent light fastness.
For example, there is no image deterioration even when exposed to NOx in the atmosphere or sunlight for a long time, and it provides a clear sky blue color tone.

When the coupler represented by the general formula (1) used in the present invention is used as an azo dye, the spectral absorption of the dye is 2-
Unlike hydroxy-3-naphthoic acid couplers, it has a narrow absorption range and provides a clear color tone.

Specific examples of the compound represented by the general formula (1) used in the present invention include the following compounds.

2-hydroxynaphthoic acid morpholinopropylamide, 2-hydroxynaphthoic acid ethanolamide, 2-hydroxynaphthoic acid-N-dimethylaminopropylamide, 2-hydroxynaphthoic acid hydroxypropylamide.

2-Hydroxynaphthoic acid morpholinoethylamide 2-hydroxynaphthoic acid-N-diethylaminopropylamide.

Specific examples of the compound represented by the general formula (II) used in the present invention include the following compounds.

2-Hydroxy-naphthalene-3-carboyl-3'-
Pyridylamide.

2-Hydroxy-naphthalene-3-carboyl-3'-
Pyridylamide hydrochloride.

2-Hydroxy-naphthalene-3-carboyl-2'-
Pyridylamide.

2-Hydroxy-naphthalene-3-carboyl-2'-
Pyridylamide hydrochloride.

2-Hydroxy-naphthalene-3-carboyl-4'-
Pyridylamide, 2-hydroxy-naphthalene-3-carboyl-4'-
Pyridylamide hydrochloride The above couplers used in the present invention are soluble not only in aqueous systems but also in non-aqueous systems. It can be applied to any synthetic paper base that has a high prevalence.

The present invention requires the use of an allyl-modified polyvinyl alcohol resin and an amino resin as a binder for the precoat layer.

When a binder made of allyl-modified polyvinyl alcohol resin is used in the precoat layer, the coupler component is prevented from oxidizing and fading due to NOx in the atmosphere, sunlight, etc., and deterioration of the non-image area of the copy is greatly improved. Although the reason for this is not clear, it is thought to be due to physicochemical interactions such as the reducibility and gas permeability of functional groups in these resins.

In the present invention, the allyl-modified polyvinyl alcohol resin used for the precoat layer has a saponification degree of 30-85■o1%.
is preferred. In addition, the degree of modification is 0.02 to 0.60.
■o1% is appropriate.

In addition, the degree of polymerization should be in the range of 100 to 1000 without causing any problem to the viscosity, and the thickness of the precoat layer should be 0.3 to 50 μ■
is preferable; if it is less than 0.3 μm, its effects will not be fully exhibited, while if it exceeds 50 μm, the paper quality will be lost.

In addition, amino resins also reduce atmospheric NOx as a coupler component.
It suppresses oxidative discoloration reactions caused by sunlight and sunlight, suppresses the deterioration characteristics of non-image areas of copies, and improves storage stability under high humidity and water resistance.

Although the reason for this is not clear, it is thought to be due to a crosslinking reaction with the hydroxyl group of the allyl-modified polyvinyl alcohol, which is used in combination with physicochemical interactions such as reducing properties and gas permeability of functional groups in the resin.

Polyacrylic acid-based resin, known as conventional pre-coated resin,
When materials such as polymethacrylic acid, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, polyalkyd, polystyrene, polysulfone, methylcellulose, hydroxycellulose, etc. are applied to the precoat layer using the coupler of the present invention, the present invention The purpose of TL cannot be achieved.

The amino resin used in the precoat layer of the present invention is an aminoacrylic oligomer with a molecular weight of 20,000 to 5,000.
0 and a glass transition temperature (τG) of 10 to 30°C.

Regarding the weight ratio of the amino resin and the allyl-modified polyvinyl alcohol resin used in the present invention, it is appropriate to use 1-9 parts by weight of the allyl-modified polyvinyl alcohol to 1-9 parts by weight of the amino-based resin.

Further, it is preferable that the precoat layer of the diazo copying material of the present invention contains silane.

In this case, the purpose of the silica is to increase the density of the azo dye formed and obtain a high-density image.

Any material can be used as long as it can provide a high-density image, but it is desirable to use one with an average particle size of 10 μm or less.

It is appropriate that the thickness of the precoat layer is such that the amount of adhesion after drying is 1 to 5 g/i.

As the diazo compound used in the present invention, those conventionally used in the field of diazo copying materials can be used as they are.

Therefore, as a diazo compound, 1, for example, 4-diazo-
1-dimethylaminobenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-dipropylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-diazo-1-dibenzylaminobenzene, 4
-Diazo-1-ethylhydroxyethylaminobenzene, 4-diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4-diazo-1-benzoylamino-2,5 −
Jetoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-jethoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1 -anilinobenzene, 4-diazo-1-dimethylamino-3-carboxybenzene, 4-diazo-1-tolylmercapto-2,5
-Double salts of diazo compounds such as jetoxybenzene, 4-diazo-1,4-methoxybenzoylamino-2,5-jethoxybenzene and chloride metal halides (zinc chloride, cadmium chloride, tin chloride, etc.); , salts of the diazo compounds with strong acids such as sulfuric acid, boron tetrafluoride, hexafluorophosphoric acid, etc., but are not limited to these, of course.

In the present invention, in addition to the one or more materials, various additives commonly used in diazo copying materials can be used, such as ethylene glycol, triethylene glycol, etc. as a development accelerator; naphthalene as a preservability improver. - Sodium monosulfonate, sodium naphthalene-disulfonate, sodium naphthalene-trisulfonate, sulfosalicylic acid, cadmium sulfate, magnesium sulfate.

Cadmium chloride, zinc chloride, etc.; antioxidants such as thiourea, urea; solubilizers such as caffeine, theophylline; acid stabilizers such as citric acid, tartaric acid, sulfuric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. In addition, a small amount of saponin can be added.

Further, as an image density improver, a suitable amount of silica or other fillers such as inorganic and organic fine particles such as starch, clay, and resin can be added to the photosensitive layer.

One paper is used to prepare the diazo copying material of the present invention.

The above-mentioned precoat layer is provided on a support such as a film, and a coating solution consisting of a diazo compound, the above-mentioned coupling component, and other auxiliary agents as required is applied and dried to form a photosensitive layer. good.

〔effect〕

Since the diazo copying material of the present invention has the above-mentioned structure, it has excellent light fastness, which means that copying does not deteriorate even when exposed to NOx gas in the atmosphere or sunlight for a long period of time, and has good water resistance and storage stability. is also excellent.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 The following precoat layer coating solution was applied onto a support of diazo copying base paper (basis weight 62 g/rrr) so that the coating weight after drying was 3 g/-, and dried with hot air at 80 to 120°C. A precoat layer was provided. (Moisture in paper 5%) [Precoat layer liquid A] Silica 35g (lim
IT gun content: 4b%) After adding water to the above materials and stirring, further water was added to make the total amount IQ.

Next, a diazo copying material was prepared by coating the following photosensitive liquid A on the precoat layer so that the coating amount after drying was 0.63 g/rrf.

[Photosensitive liquid A]

Citric acid 10g Thiourea 10g Zinc chloride
After mixing, dissolving and dispersing 10g or more of ingredients, water is added to make the total amount IQ.

Example 2 A diazo copying material was prepared in the same manner as in Example 1, except that precoat layer coating solution A was replaced with precoat layer coating solution B below, and photosensitive solution A was replaced with photosensitive solution B. .

[Precoat layer coating liquid B]

Silica 40g Add water to the above ingredients and stir, then add more water to make the total amount IQ.

[Photosensitive liquid B]

Citric acid 10g Thiourea 10g 2-hydroxy-3-naphthoic acid Ethanol 5g Amidozinc chloride 10g After adding water to the above materials and stirring, water was further added to make the total amount IQ.

Comparative Example 1 A comparative diazo copying material was prepared in the same manner as in Example 1 except that precoat layer coating liquid A was replaced with precoat layer coating liquid C described below.

[Precoat layer coating liquid C]

Silica 35g After adding water to the above ingredients and stirring, further water was added to make the total amount IQ.

Comparative Example 2 A diazo copying material of Comparative Example 2 was prepared in the same manner as in Example 2, except that precoat layer coating liquid A was replaced with the following precoat layer coating liquid.

[Precoat layer coating liquid D]

Silica 40g Add water to the above ingredients and stir, then add more water to make the total amount IQ.

Comparative Example 3 A diazo copying material of Comparative Example 3 was produced in the same manner as in Example 1, except that the precoat layer coating solution A was replaced with the following precoat layer coating solution E, and the photoreceptor A was replaced with the following photoreceptor C. It was created.

[Precoat layer coating liquid E]

Silica 40g After adding water to the above ingredients and stirring, further water was added to make the total amount iQ.

[Photosensitive liquid C]

Citric acid: 10 g Thiourea: 10 g
What was said.

A light fastness test, a water resistance test, and a fresh storage test were conducted on the samples of Examples 1 to 2 and Comparative Examples 1 to 3 obtained above. The results are shown in Tables 1 to 5. Note that Table 5 shows the overall evaluation. In addition, the test method was as follows.

[Light fastness test]

The above sample was transferred to a diazo copying machine (Recopy Super Dry, 5
D580 (manufactured by Ricoh) and developed with Shimadzu 11 (KK)
Xenon fade meter (environmental conditions: 30℃, 80%
) for 12 hours, and the density changes in the image and non-image areas before and after the test were observed.

[Water resistance test]

Samples developed in the same manner as in the light fastness test were immersed in water at 20° C. for 2 hours, and changes in the density of the image area before and after the test were observed.

[Raw storage test]

Each sample obtained above was left in a dark place at 50° C. and 65% atmosphere for 24 hours, and then completely exposed and developed using a diazo copying machine (Ricobee Super Dry 5D-580, manufactured by Ricoh Co., Ltd.). The density of the non-image area was measured.

On the other hand, samples stored at low temperature and low humidity were also developed in the same way.

The density of the non-image area was measured (before the test) and changes in density were observed in both areas.

The density of the image area and non-image area in each test was measured using a photovoltmeter (green filter).

Table-1 Light fastness test results (image section) Table-2 Light fastness test results (non-image area) Table-3 Water resistance test results Table-4 Raw preservation test results (non-image area) Table-5 Comprehensive evaluation table ×: Inferior Patent applicant Rico Co., Ltd.

Claims (1)

[Claims] (1) In a diazo copying material in which a photosensitive layer containing at least a coupler is provided on a support via a precoat layer, an allyl-modified polyvinyl alcohol resin and an amino resin are used as binders for the precoat layer, and the couplers listed below are commonly used. A diazo copying material characterized by using a compound represented by formula (I) or 1 and a compound represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, n: an integer of 1 to 3 R: hydroxyl group, alkoxy group having 1 to 3 carbon atoms, morpholino group, dimethylamino group, diethylamino group)