JP3526259B2 - Diazo photosensitive paper - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diazo photosensitive paper, more specifically, a diazo photosensitive layer is provided on a base paper having a neutral paper as a support through a precoat layer, and a back layer is provided on the opposite surface. Diazo photosensitive paper.

[0002]

2. Description of the Related Art Diazo photosensitive paper is generally composed of a photosensitive layer containing a diazo compound, a coupling component and various auxiliaries on a support of acid paper having a pH of 2 to 5 which is sized with a rosin sizing agent. Has been done.

However, in recent years, the mainstream of high-quality paper and copy printing paper used as a support for diazo photosensitive paper has a pH of 6 to 9 sized by a neutral sizing agent such as alkyl ketene dimer and alkenyl succinic anhydride. Most of them are made of functional paper, and conventional acid paper is made into a special paper, which increases the cost and makes it difficult to obtain the paper. Now, the trend of the neutral paper market with calcium carbonate as a filler cannot be ignored.

As a result, in the future, there is no choice but to use neutral paper for diazo photosensitive paper, but when these neutral papers are used as a support for diazo photosensitive paper, they are stored. It is said that the pre-coupling gradually progresses, unfavorable coloring occurs, and the uniformity, smoothness, and denseness (hereinafter referred to as texture) of the image area are deteriorated, so that it cannot be put to practical use. The reason is that these neutral papers generally contain calcium carbonate, kaolin, talc, titanium oxide, etc. in the paper as a filler, and due to their alkaline nature, precoupling gradually progresses during storage. .

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and includes calcium carbonate, kaolin,
An object of the present invention is to provide a diazo photosensitive paper in which pre-coupling during storage, which is a disadvantage thereof, is prevented even when a neutral paper containing talc, titanium oxide or the like is used as a support for the diazo photosensitive paper.

[0006]

According to the present invention, firstly, in a diazo photosensitive paper support comprising a neutral paper having a paper surface pH of 6 or more, at least as a surface sizing agent for the support. There is provided a support for diazo photosensitive paper, which is characterized by using a soluble processed starch. Second, the paper pH
Is a neutral paper of 6.0 to 7.5, does not contain a filler of an alkaline salt, and contains a filler selected from kaolinite and talc, which is a surface sizing agent. There is provided a support for diazo photosensitive paper, characterized in that at least soluble starch is used as. Thirdly, there is provided a support for diazo photosensitive paper as described in the above first or second, characterized in that the support contains 50% or more of recycled pulp made from waste paper. Fourthly, the support for diazo photosensitive paper according to any one of the above first to third, characterized in that it further contains at least one or more calcium, aluminum, zinc sulfate or chloride as a surface sizing agent. The body is provided. Fifth, there is provided the support for diazo photosensitive paper as described in any one of the above first to third, which contains soluble starch and amorphous porous silica as the surface sizing agent. Sixth, as a surface sizing agent, soluble starch, sulfates or chlorides of calcium, aluminum, zinc, and amorphous porous silica are contained, and any one of the above first to third is provided. A support for diazo photosensitive paper is provided. .

Further, according to the present invention, seventhly, there is provided a diazo photosensitive paper having the support for the diazo photosensitive paper described in any one of the first to sixth above as a support. Eighth, there is provided the diazo photosensitive paper described in the seventh, wherein the photosensitive layer of the photosensitive paper contains at least one of zinc chloride and an acid. Ninth, the side opposite to the photosensitive layer surface of the photosensitive paper (back layer)
The above-mentioned seventh diazo photosensitive paper is provided which contains at least one of boric acid and an acid. Tenth,
The seventh aspect, wherein the photosensitive layer of the photosensitive paper contains one or more zinc chloride and an acid, and the diazo photosensitive paper contains one or more boric acid and one or more acids on the side opposite to the photosensitive layer surface (back layer). A diazo photosensitive paper is provided.

The invention will be described in detail below. As mentioned above, the present invention, by using soluble starch as the surface size of the neutral paper, acts as a water and alkali resistant barrier layer to block the effects of calcium carbonate in the support and It is believed that the drawbacks of using a neutral base paper are eliminated in order to reduce the diffusion and penetration of the coated diazo copy layer into the support. Further, by incorporating a metal salt and an acid in the photosensitive layer and the back layer, the influence of the alkalinity permeated and diffused from the support is reduced, so that it is considered that the drawbacks when the neutral paper base paper is used are eliminated.

The neutral paper used in the present invention is LBKP, N
Papermaking is carried out by a conventional method, mainly consisting of chemical pulp typified by BKP, sizing agents, and fillers, and other papermaking auxiliaries as needed. The pulp material used may be mechanical pulp or waste paper pulp in combination, or may be mainly composed of these. The neutral paper thus obtained has a paper surface pH of 6 or more (the pH of the neutral paper when extracted with cold water or the like is 7 to 9).

As the raw material of the waste paper pulp referred to in the present invention, the top white, ruled white, cream white, card,
Special white, medium white, imitation, fair white, Kent, white art, special cut,
Examples include separate papers, newspapers and magazines. Further specific examples include printer paper such as non-coated computer paper, thermal paper, and pressure-sensitive paper (registered trademark) that are information-related paper, and P paper.
OA waste paper such as PC paper, art paper, coated paper, lightly coated paper, coated paper such as matte paper, high-quality paper, high-quality paper, notebook, notepaper, wrapping paper, fancy paper, medium-quality paper, newsprint, Recycled paper, supermarket wrapping paper, imitation paper, pure white roll paper, uncoated paper such as milk carton, and waste paper such as paperboard, such as chemical pulp paper and high-yield pulp-containing paper are used. It is not particularly limited whether it is printed or not.

The soluble starch used in the present invention includes corn starch, tapioca starch, potato starch,
In addition to raw starch such as wheat starch, using these as raw materials, enzymatic decomposition, oxidation, etherification, cationization, esterification,
Aldehydes and modified ones such as α-form and soluble ones can be used.

As the hydrophobic resin emulsion used in the present invention, polyvinyl acetate, polyacrylic acid ester resin emulsion, styrene-acrylic acid ester copolymer, vinyl chloride-acrylic acid ester copolymer emulsion are used. it can. If the copolymer resin contains the above-mentioned components, it can be used even if the copolymer resin further contains the third component.

The acid used in the present invention may be any water-soluble and non-volatile acid. Representative examples of the inorganic acid include sulfuric acid and boric acid. On the other hand, examples of the organic acid include citric acid, tartaric acid, malic acid and the like. The acid contained in the back layer is 0.1 to 5.0 g / m ^2.
Applied in the range of 0.2 to 2.0 g / m ²
Is.

The diazo photosensitive paper of the present invention is a precoat layer composed of a fine particle powder and a binder for the purpose of improving image density, photosensitivity, and writing property on a support made of a neutral base paper. And a back layer can be provided on the side opposite to the photosensitive layer.

The diazo compound used in the present invention is a diazonium salt represented by the following general formula.

[0016]

[Chemical 1] (In the formula, Ar represents a substituted or unsubstituted aromatic moiety, ArN ²⁺ represents a diazonium cation, and X ⁻ represents an acid anion.)

Specific examples of the diazo compound include, for example,
4-diazo-N, N-dimethylaniline, 4-diazo-
N, N-diethylaniline, 4-diazo-N, N-methylhydroxyethylaniline, 4-diazophenylmorpholine, 4-diazo-N, N-dibutylaniline, 4
-Diazo-2,5-dimethoxyphenylmorpholine, 4
-Diazo-2,5-diethoxyphenylmorpholine, 4
-Diazo-2,5-dipropoxyphenylmorpholine,
4-diazo-2,5-dibutoxyphenylmorpholine,
4-diazo-2,5-dibutoxy-N-benzyl-N-
Ethylaniline, 4-diazo-2,5-dibutoxy-
N, N-dibutylaniline, 4-diazo-2,5-dibutoxy-N-benzyl-N-oxyethylaniline, 4
-Diazo-2,5-dibutoxyphenylpiperazine, 4
-Diazo-2,5-diethoxyphenylpyrrolidine, 4
-Diazo-2,5-dipropoxyphenylpiperidine,
4-diazo-2,5-diethoxy-N, N-dimethylaniline, 4-diazo-1-benzoylamino-2,5-
Dibutoxybenzene, 4-diazo-1- (4′-methoxybenzoylamino) -2,5-dimethoxybenzene,
4-diazo-1- (4'-methoxybenzoylamino)
-2,5-diethoxybenzene, 4-diazo-1-
(4'-Methyldibenzoylamino) -2,5-dipropoxybenzene, 4-diazo-1- (3'-chlorobenzoylamino) -2,5-diethoxybenzene, 4-diazo-1- (3 ' -Methoxybenzoylamino) -2,
5-dibutoxybenzene, 4-diazo-1- (3'-methyldibenzoylamino) -2,5-dimethoxybenzene, 4-diazo-1-phenylmercapto-2,5-dipropoxybenzene, 4-diazo- 1- (4'-toluylmercapto) -2,5-diethoxybenzene, 4-diazo-1- (4'-methoxyphenylmercapto)-
2,5-dibutoxybenzene, 4-diazo-1- (4 '
-Chlorophenylmercapto) -2,5-dimethoxybenzene, 4-diazo-1- (3'-toluylmercapto) -2,5-diethoxybenzene, 4-diazo-1-
(3'-Methoxyphenylmercapto) -2,5-dipropoxybenzene, 4-diazo-1- (2'-toluylmercapto) -2,5-dibutoxybenzene, 4-diazo-1-phenoxy-2,5 -Dibutoxybenzene, 4
-Diazo-1- (4'-methoxyphenoxy) -2,5
-A double salt of chloride such as diethoxybenzene, zinc chloride, cadmium chloride, tin chloride, etc., and sulfuric acid of diazo,
Examples thereof include salts of inorganic acids such as hexafluorophosphoric acid and tetrafluoroboric acid.

Next, the coupler used in the present invention is a coupler which forms a dye by coupling with a diazo compound.
There are so-called active methylene compounds having a methylene group next to a carbonyl group, phenol derivatives, naphthol derivatives and the like. For example, resorcin, phloroglucin,
Sodium 2,3-dihydroxynaphthalene-6-sulfonate, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid-N, N
-Dimethylaminomorpholinopropylamide, 2-hydroxy-3-naphthoic acid octylamide, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5
-Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfonylnaphthalene, sodium 2,7-dihydroxynaphthalene-3,6-disulfonate, 2,3-dihydroxynaphthalene-6-sulfonic acid, 1 -Hydroxynaphthalene-4-
Sodium sulfonate, 2-hydroxy-3-naphthoic acid anilide, benzoylacetanilide, 3-hydroxycyanoacetanilide, parasulfoacetanilide,
1-phenyl-3-methyl-5-pyrazolone, 1-
(2,4,6-Trichlorophenyl) -3-anilino-
Examples thereof include 5-pyrazolone, 2,4-bis- (benzoylacetamino) toluene, and 1,3-bis- (pivaloylacetaminomethyl) benzene, but are not limited to these. These couplers can be used alone or in combination of two or more, and any hue can be obtained if necessary.

In the diazo photosensitive paper of the present invention, in addition to the above-mentioned color-forming components, various additives that are applied to ordinary diazo photosensitive paper, and naphthalene-sodium monosulfonate and sodium naphthalene-disulfonate as a storage stability improver. ,
Aromatic sulfonates such as sodium naphthalene-trisulfonate, sulfone salicylic acid, cadmium sulfate, magnesium sulfate, cadmium chloride, zinc chloride, zinc sulfate,
Metal salts such as aluminum sulfate can be used.

As the image density reinforcing agent, colloidal silica, amorphous silica fine powder and the like can be used.

Further, polyhydric alcohols such as glycols and glycol ethers and their derivatives can be used as the development accelerator.

Furthermore, caffeine, thioferin, alcohols such as ethanol and isopropanol, etc. as solubilizers, citric acid, tartaric acid, sulfuric acid, etc. as acid stabilizers.
Oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. can be used, and in addition, a small amount of saponin can be added.

When a back coat layer is provided on the surface of the support for the purpose of controlling the curl of the diazo copying material, any conventionally known material can be applied. The diazo copying material of the present invention thus produced is a dry developing method using ammonia gas or a semi-dry developing method using an alkaline organic solvent (the coating amount on the diazo copying material is 5 g / m ² or less. It is visualized by a slight amount of developing method).

[0024]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited thereto. All parts and percentages below are by weight. The neutral paper used in Examples and Comparative Examples is made by a known method,
The surface size is a base paper which has been treated by a known method such as a conventional size press or a gate roll size press.

[Example 1] A base paper for diazo photosensitive paper was obtained by performing size press on a neutral paper composed of 100% LBKP and having a pH of 6.8 on the paper surface with a surface sizing solution at an adhesion amount of 1.7 g / m ^2. It was (Size press solution composition) Oxidized starch) Petrocoat ZP-2 manufactured by Nichino Kagaku Co., Ltd. 3 parts Polyvinyl alcohol aqueous solution (20%) 2 parts Water 95 parts A precoat layer having the following composition on the diazo photosensitive paper base paper. The solution was applied with an air knife and dried to obtain a precoat layer having an adhesion amount of 1.2 g / m ² .

(Precoat layer liquid composition) Styrene-acrylic acid ester copolymer emulsion (Mitsui Chemicals 45%) 5 parts Polyvinyl alcohol aqueous solution (20%) 5 parts Fine silica 3 parts Water 90 parts On this precoat layer: A diazo photosensitive layer solution having the composition of (1) was applied and dried with an air knife, and the amount of adhesion was 0.6 g.
A photosensitive layer of / m ² was formed to prepare a diazo photosensitive paper of the present invention.

(Photosensitive layer liquid composition) 4-diazo-2,5-dibutoxyphenylmorpholine chloride / 1/2 zinc chloride 1 part 2-hydroxy-3-naphthoic acid morpholinopropylamide 1 part Tartaric acid 1.5 parts Cafe In 0.5 part Methyl alcohol 1 part Saponin 0.1 part Water 97 parts A back layer liquid having the following composition was applied to the base paper on the opposite side of the precoat-coated photosensitive layer by an air-knife, dried, and attached. A back layer having an amount of 1.0 g / m ² was formed to prepare the diazo photosensitive paper of the present invention.

[0028] (Back layer composition)     Ethylene glycol 3 parts     97 parts of water

Example 2 As a support, LBKP30
%, Imitation waste paper pulp 70%, and a neutral pH paper having a composition of pH 6.4, a diazo photosensitive paper was prepared by the same liquid and manufacturing method as in Example 1.

[Example 3] A diazo photosensitive paper was prepared in the same manner as in Example 2 except that 4 parts of zinc chloride was added to the photosensitive layer of Example 2.

[Example 4] A diazo photosensitive paper was prepared in the same manner as in Example 2 except that the back layer in Example 2 was changed to the following composition. (Back layer composition) Boric acid 3 parts Malic acid 2 parts Water 95 parts

Example 5 A diazo photosensitive paper was prepared in the same manner as in Example 3, except that the back liquid in Example 3 was changed to the following composition. (Back layer composition) Boric acid 3 parts Sulfuric acid 1 part Water 96 parts

Comparative Example 1 A diazo photosensitive paper was prepared in the same manner as in Example 1, except that the oxidized starch having the surface size in Example 1 was removed.

The original image was superposed on the diazo photosensitive paper thus prepared and exposed by a diazo copying machine (SD-730 manufactured by Ricoh),
When developed, a blue image was obtained. The obtained image density was evaluated by a reflection densitometer (Macbeth densitometer RD914 type).
It was measured at. Further, in order to test the raw storability, each sample was allowed to stand at 50 ° C. for 5 days to be forcibly deteriorated, then taken out, exposed on the entire surface by the above copying machine, and the density of the background portion was measured by a reflection densitometer. The results are shown in Table 1.

[0035]

[Table 1]

From Table 1, the diazo photosensitive paper of the present invention of the present invention has a good raw storability, whereas the comparative examples based on the prior art show a markedly poor storability of the background part. (Large fog)
As described above, the diazo photosensitive paper in which the diazo copying material layer of the present invention is provided on the neutral paper having a paper surface pH of 6.0 or more has excellent raw storability even though the neutral paper support is used. ing.

[0037]

As is apparent from the detailed and specific description above, after kaolin and talc are used as the filler of the support, a diazo copying material layer is provided on the diazo photosensitive paper base paper having a specific surface size treatment. By using the diazo photosensitive paper according to the present invention, which has the following properties, it has excellent raw storability, high color development and low background density, and high image uniformity and smoothness even though a neutral paper support is used. An extremely excellent effect is obtained in which an image with a high texture (texture) is obtained and the discoloration of the background after image formation is small.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kazunori Umehara 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Tsutomu Matsuda 1-3-6 Nakamagome, Ota-ku, Tokyo In stock company Ricoh (72) Inventor Mitsumasa Omura 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh company (56) Reference JP-A-10-333275 (JP, A) JP-A-4- 218040 (JP, A) JP-A-4-303834 (JP, A) JP-A-3-44631 (JP, A) JP-A-2-950 (JP, A) JP-A-5-297516 (JP, A) JP-A-6-67343 (JP, A) JP-A-6-89007 (JP, A) JP-A-6-35113 (JP, A) JP-A-6-148801 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/775 501 G03C 1/61 G03C 1/76 352

Claims (3)

(57) [Claims] 1. A photosensitive layer on a support and a photosensitive layer on the support.
It is a diazo photosensitive paper with a back layer on the side opposite the layer.
The support is neutral paper having a paper surface pH of 6 or more, and
At least a soluble modified starch as the surface sizing agent for the support.
Powder is used, and the back layer contains boric acid and one or more acids.
A diazo photosensitive paper characterized by being contained in the above. 2. The photosensitive layer contains at least one of zinc chloride and an acid.
The object according to claim 1, characterized in that
Azo photosensitive paper. 3. The diazo photosensitive paper according to claim 1, wherein the support contains 50% or more of recycled pulp made from waste paper .