JPS6027007B2 - diazo developer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-amine diazo developer used for developing diazo photosensitive materials.

Generally, a wet method, a dry method, or a thermal method is employed as a developing method for diazo photosensitive materials.

The wet method is a method in which a one-component type photosensitive paper coated with a photosensitive solution containing a diazo compound on a paper support is exposed and then treated with an alkaline aqueous solution of a coupler to develop color. This is a developing method in which a two-component photosensitive paper coated with a photosensitive solution containing a diazo compound and a coupler is exposed and then treated with ammonia gas to develop color.Thermal method is a method in which a diazo compound, coupler and alkali are generated on the paper support. This is a developing method in which a two-component type diazo photosensitive paper coated with a photosensitive agent is exposed and then heated to generate alkali to develop color. However, with the wet method, the copies are taken out wet, crystals precipitate due to evaporation of water in the developer, and the developer gets colored over time, staining the background of the copy.
The disadvantage is that you cannot always get a good quality copy. In addition, the dry method uses ammonia as a developer, and therefore has the disadvantage that it has a strong odor and is a problem in terms of environmental hygiene, and that the developing device is large and expensive. Furthermore, the thermal method has the disadvantage that the photosensitive paper has poor storage stability because it contains an alkali generator that generates alkali when heated. In order to improve these shortcomings, in recent years a developing method has been developed in which, for example, an alkaline agent is used as an organic amine, and a developer is dissolved in a diluent such as ethylene glycol, and then a developing agent is applied onto exposed two-component diazo photosensitive paper using a rubber roller or the like. has been proposed (Japanese Patent Publication No. 45-23515). This method can overcome the drawbacks of the above-mentioned developing methods, but since the developer generally contains organic amines that are susceptible to air oxidation, the developed copies may be significantly discolored or gutter-colored, for example, the background of the copies may be Undesirable phenomena such as yellowing and the developer itself becoming brown due to long-term use occur. Furthermore, although not as bad as ammonia, t-organic amines also have a characteristic odor, which has the disadvantage of deteriorating the working environment. The present invention provides a semi-dry diazo developer which always provides good quality copies and is free from coloration and odor by using a non-amine type alkaline agent.

Such a developer contains 20 to 5% by weight of an alkali metal salt and/or alkali metal salt of an amino acid, 10 to 6% by weight of a polyhydric alcohol, and a general formula Rm.
, 01 (CQC day 20) n (R, is C3 to C2.

alkyl or alkylphenol group, n is 1 to 20)
, m is 1 to 3, X is H or] 0.01 to 1% by weight of a surfactant represented by
It consists of 1% by weight and the remainder of water.

By the way, the present inventors have previously proposed in Samurai Application No. 81223/1986 to improve the conventional semi-dry type developer, in which an alkali IJ metal salt of an amino acid or an alkali is added to a diluent such as a polyhydric alcohol ether as an alkaline agent. A solution containing metal salts was proposed, but it was unsatisfactory in terms of odor. Therefore, as a diazo developing method that does not have any odor or curl immediately after copying, 20 to 5% by weight of an alkali metal salt and/or an alkali metal salt is added to the alkaline agent.
At the same time as this application, we proposed a method in which a developing solution consisting of 10 to 6% by weight of polyhydric alcohol as a diluent and the remainder of water was applied to photosensitive paper below the gunwale and developed. During copying, the surface of the developing rubber roller tended to be contaminated by adhesion of dyes in the photosensitive paper. In contrast, according to the present invention, there is little solvent odor, yellowing or curling of the background of copies, and therefore the stockability of copies is good, and there is no contamination of the surface of the developing roller.

If the surfactant of the above general formula is used alone, contamination of the developing roller can be prevented, but new problems arise such as foaming of the developer and deterioration of the uniform developability of copies due to the foaming. However, it has been confirmed that this problem can be solved by using a water-based silicoso antifoaming agent. The alkali metal salts and/or alkali metal salts of amino acids used in the present invention dissociate in water to exhibit alkali, and therefore have coloring properties equivalent to organic amines, and unlike amines, they are odorless substances.

Furthermore, these substances are highly hygroscopic and have extremely high solubility in polyhydric alcohols and water, so they have features such as not crystallizing even when water evaporates. Such alkali metal salts or alkaline earth metal salts of amino acids include L
-Q-alanine, DL-Q-alanine, 8-alanine,
L-alloisoleucine, L-Q-amino acid, D-B-aminobutyric acid, DL-8-amino/butyric acid, y-aminobutyric acid,
DL-q-ami/butyric acid, L-asparagine, 0-asparagine, L-aspartic acid, DL-aspartic acid, L-asterbine, L-canavanine, L-citrulline, creatine, creatinine, L-cysteine, L
Cystine, D-cystine, L-glutamic acid, D-
Glutamic acid, OL-glutamic acid, L-glutamine, glycine, L-histidine, L-Q-hydroxyproline, L-B-hydroxyproline, L-isoleucine, DL-isoleucine, L-leucine, DL-leucine, L-lysine, L-methionine, DL-methionine,
L-norleucine, D-norleucine, L1/luvaline, ○1/luvaline, DL-norvaline, L-octopine, DL-ornithine, L-ornithine, L-phenylalanine, 3-phenylalanine, DL-phenylalanine, ○ - Sodium such as phenylalanine, L-proline, sarcosine, L-serine, DL-serine, taurine, L-threonine, L-tryptophan, L-tyrosine, DL-tyrosine, L-Q-valine, DL-valine, DL-valine and 3-valine, Salts such as potassium, lithium, magnesium, calcium and barium alone or in combination
Used as a mixture of more than one species. If it is less than 20%, developability will be poor, and if it is more than 50%, yellowing of the background will become severe after copying, which is not preferable. Polyhydric alcohols can be used as

Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dibropylene glycol, tripropylene glycol, polypropylene glycol, glycerin, trimethylene glycol, tetramethylene glycol, butanediol, Examples include 1,5-bentanediol, hexylene glycol, and octylene glycol, which may be used alone or in combination of two or more. The amount used is in the range of 10 to 6% by weight; if it is less than 10%, curling will become large, and if it is more than 60%, the odor will be strong, so it is not preferable. In addition to polyhydric alcohol, water is used as a diluent.

Water increases the solubility of the alkaline agent and also improves color development. The amount is the amount excluding the total amount of the alkali agent, polyhydric alcohol, surfactant, and silicone component of the antifoaming agent.
The surfactant is used to prevent dye staining on the developing roller and is represented by the above general formula.

As a specific example, when x is day, R is an alkyl ether or alkylphenol ether of polyoxyethylene such as octyl, nonyl, decyl, furyl, myristyl, cetyl, palmityl, stearyl, oleyl, etc., and when X is are respectively polyoxyethylene alkyl ethers or alkylphenol phosphate esters, and Rm.X is the respective mono-, di- or triester.

The amount of these surfactants used is 0.001 to 1% by weight.
A range of is preferred. However, at 0.001%, there is no effect of preventing contamination, and at 10% or more, the barrier of the developer drops and adversely affects the color development of copies. Further, as the water-based silicone antifoaming agent, a syrup made by adding a special filler to silicone oil or an emulsion of silicone oil is used.

Examples of the silicone oil in this) include compounds of the following general formula. (However, R=C3-C2o alkyl or alkylphenol group, n=50-1000, a=2-3
, m=1 to 20> These water-based silicone antifoaming agents are used in a silicone concentration range of 0.001 to 1% by weight.

If it is less than 0.001%, there will be no antifoaming effect, and if it is more than 1%, the solubility will be poor.

The developer of the present invention can be applied to a semi-dry diazo development method (for example, a method in which the developer is applied in small amounts using a developing rubber roller as described above).

In this case, it is appropriate that the amount of developer applied (adhesive amount) be less than 100 ml on the ship's side; if the amount is more than that, a dry copy will not be obtained. This developer can be applied to any two-component type diazo photosensitive paper that is generally commercially available, but the diazo photosensitive paper that provides particularly good color development and high density images uses 4-diazo-2,5-jet as a diazo compound. Toximorpholinobenzene chloride, 4-diazo-2,5-dibutoxymorpholinobenzene chloride, 4-diazodipropylaniline chloride, 4-diazo-2,5-diethoxy4-(4'-methoxy)penzoyl Zinc chloride double salt such as aminobenzene chloride is used, and 2,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene-6-sulfonic acid sodium, 2-hydroxy-3-naphthoic acid 8-amino/ethylamide, 2-hydrohydride is used as a coupling component. . xy-3-naphthoic acid ethanolamide, 2-hydro. xy-3-naphthoic acid morpholinoethylamide, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 1-biguanidino-7-naphthol, resorcinol, Q-resorcinic acid ethanolamide, ethylenediamine-N,N-bisacetoacetamide, diresorcinol, etc. Examples include two-component pears. As described above, the developer of the present invention is odorless and does not change over time, so that good quality copies can always be obtained, and there is no generation of bubbles or staining of the developing rubber roller with dye.

Further, when applied in a semi-dry manner, there are advantages such as copies can be obtained in a dry state and no curling occurs. Examples are shown below.

Example water 8o super ethylene glycol 30' inpropyl alcohol 30' citric acid
2 female thiourea
3cough 2-hydroxy-3naphthoic acid ethanolamide
15g caffeine 1 female 4-diazo-2,5-dibutoxymorpholinobenzene chloride (zinc chloride Enoki salt) 1 female sabonin
Add water to 1 g of the solution to prepare a photosensitive solution with a total amount of IZ, and add 9
A two-component type diazo photosensitive paper was prepared by coating and drying it on white base paper for photosensitive paper.

Next, a suitable original was placed on the photosensitive paper and exposed with a crab light lamp, and then a developer (No. 1, 4, 7) having the composition shown in the table below was added.
, 15 and 16 are comparative examples, and the others are examples) were applied using a rubber roller, and roller staining, antifoaming properties, and image density were measured. Note) *1: Tested on 10 sheets of unexposed photosensitive paper.

○ indicates no roller stains, × indicates there is. *2: The generation of bubbles caused by the rotation of the rubber roller during development, ○ indicates no bubbles, △ indicates bubbles are present, and × indicates a large amount of bubbles.

*3: Measure the image density of the copy 30 seconds after development using a photovolt densitometer OA coloring solution: Grinkarium 20
wt%, propylene glycol 40wt%, female Shigetaka Yuo
B phenomenon solution: L-glutamic acid socalywam 30wt%,
Contains 40 wt% ethylene glycol and balance water.

Emulgen 105: Bolioxyethylene lawaryl Able CI 2 days 250 (CH2CH20) nH Emulgen 4
20: Borioxyethylene oleyl Able C, 8 days 3
50 and other 2m20 wind emulgen 810: polyoxyethylene alkyl ether, octerphenol, and ester phenol 920: polyoxyethylene alkyl ether mono-, di-, or triline A mixture of acid esters.

Claims (1)

[Claims] 1. 20 to 50% by weight of an alkali metal salt and/or alkaline earth metal salt of an amino acid, and 10 to 60% by weight of a polyhydric alcohol.
Weight % and the general formula Rm・X [where R is R_1O-(C
H_2CH_2O)n (R_1 is a C_3 to C_2_0 alkyl or alkylphenol group, n is 1 to 20),
m is 1 to 3, X is H or ▲ There are mathematical formulas, chemical formulas, tables, etc.
A diazo developer consisting of 1% by weight and the remainder of water.