JPS6085995A - Blank planographic printing plate - Google Patents

Abstract

PURPOSE:To contrive perfect compatibility of hydrophilic nature and water resistance, by a method wherein an image-receiving layer comprising as a main constituent a reaction product of a reaction between a copolymeric resin comprising maleic acid anhydride as a copolymeric component and a cross-linking agent consisting of a polyisocyanate compound is provided on a base. CONSTITUTION:A solution of a maleic acid anhydride copolymer in an organic solvent having no active hydrogen which solution further contains a polyisocyanate compound added thereto is applied to the base. After drying, the coated layer is heated to effect a cross-linking reaction. An image-receiving layer of a blank printing plate thus obtained is excellent in adhesion to the base, and since only a non-image part is treated to be hydrophilic after forming an image, the adhesion to an image-forming material (e.g., an oil base ink or a toner) is favorable, and delamination or flaking-off of the image part hardly occurs. In addition, the blank printing plate shows a high water resistance.

Description

[Detailed Description of the Invention] Technical Field The present invention relates to a lithographic printing original plate (), and more particularly, the amount of image that increases by 1q when the surface changes from hydrophobic to hydrophilic]! r! F
t was established (Zuta Gaki ■! Concerning the original plate for lithographic printing.

Conventional technology Conventionally, planographic printing original plates used in office printing have a grain size of 4kl to 100g of support such as temporary aluminum.9 ρ642
Ken) [Sun! -G) Body] [h 2- 'ri 9th edition.

■ A printing original plate for electrophotographic engraving in which a photoconductive layer using 111i 11 or the like is provided on a conductive support.

■ A drawing-type printing original plate that has a hydrophilic image-receiving layer on a support such as water-resistant paper.

1, among others, the above ■
The drawing-type printing original plate can easily form an image by handwriting with oil-based ink, by printing with a tie, or by electrophotographic copying ('c+・) - forming a single image. Therefore, it is better than the other original printing plates mentioned above (1) and (2).

In recent years, with the spread of electrophotographic copying machines, the if of this 1.F.
Demand for printing master plates with zero drawing pattern is increasing.

However, the both image-receiving layers in the 111 printing 15:1 plate of this drawing type (C1) are similar to other types of lithographic printing master plates,
It is necessary to retain a thin film of water on the surface of the non-image area after plate making to repel 1 x 1 oil + 1 ink, and for this purpose it must be highly hydrophilic. Also, during printing, the material is always wet and comes into contact with the inking roller and blanket and is repeatedly subjected to mechanical forces, so it must have sufficient water resistance and strength to withstand this.

In conventional white-line lithographic printing plates, in order to increase both hydrophilicity and water resistance by 1, additives such as polyvinylalnylene, diradine, casein, gum arabic, starch, and silver are added. 1-su derivative (carboxymethyl L
Glyoxal, melamine, urea, amine resins (urea-formaldehyde resin, melamine-formaldehyde resin), etc. as crosslinking agents for water-soluble resins such as lulose, hydroyacethyl cellulose, polyacrylic acid sorta, poly-1-ethylene A xide, and polyacrylamide. An image-receiving layer is used in which an inorganic pigment such as zinc oxide is added to this.

However, these image-receiving layers cannot be said to be sufficient in terms of achieving both hydrophilicity and water resistance.For example, if you look at water resistance as a car and increase the amount of crosslinking agent, the hydrophilicity will be impaired. If hydrophilicity is emphasized, the water resistance will be insufficient and the printing durability will be poor.

Therefore, this kind of direct! 'The printing durability of the i-type lithographic printing plate is several 100 sheets/4 sheets! An object of the present invention is to completely balance the hydrophilicity and water resistance of the image-receiving layer, and to achieve a 11-100% improvement in the image-receiving layer. An object of the present invention is to provide an original plate for drawing-type lithographic printing that allows for the production of high-quality printed matter and has a high printing durability.

The lithographic printing original plate of the present invention has a structure in which maleic anhydride is added as a polymerization component, a resin is combined with a polyisomer, i) a compound is crosslinked with a compound J: C of 1) indicates that an image-receiving layer containing a reactant as one component is provided.

The image-receiving layer of this invention is different from the conventional one using a hydrophilic resin, and originally the surface of the hydrophobic layer 1 is on the right side.
After image formation, it is a layer that can be changed to a hydrophilic surface by simple processing.

In order to form this layer, a resin having an acid anhydride group, such as a copolymer containing maleic anhydride as one copolymer component (hereinafter referred to as maleic anhydride copolymer), and a crosslinking agent are used. A reaction product with a polyisocyanate compound is used.

Examples of the maleic anhydride copolymer used in the present invention include methyl vinyl ether, ]-delvinyl ether,
2-chloro[1 vinyl ethyl ether, propyl vinyl 1
Co-HQ aggregates of lower alkyl vinyl ethers such as vinyl ether, isobutyl vinyl needle, and 2-methoxyedyl vinyl ether and phosphoric anhydride Copolymers of maleic anhydride such as styrene, copolymers of maleic anhydride such as ethylene, etc. , a copolymer of vinyl acetate and maleic anhydride, etc.

Furthermore, these maleic anhydride co-Xn combinations in which a portion of the acid anhydride ring is opened can also be used.

Examples of positive isocyanate compounds used as crosslinking agents include 1-toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, and naphthylene-1,5-diisocyanate.
Diisocyanate-1, 3,3'-dimedylbiphenyl-
4,4'-diisocyanate, 1-rephenylmethane-4,4-,4''-1-diisocyanate, tris(
1)-isocyanehphenyl)diaphenyl),
Aromatic polyisocyanes such as polymethylene polyphenyl isocyanate 1~ and xylylene diisocyanate 1~
Alternatively, aliphatic polyisocyanes such as hexylylene diisocyanate, ]-rimedyl hexylylene diisocyanate, and isophorone diisocyanate 1- or Iζ include dimers, trimers, and the like.

The printing original plate of the present invention basically has a form in which an image-receiving layer is provided on a support. The support used here is:
(a) Paper, (b) Paper coated or impregnated with resin on both sides of one side S1, (C) Plastic membrane, <(1
) Synthetic paper or the like is used, and it is particularly preferable that it is water resistant.

In order to produce the printing original plate of the present invention, first, the above-mentioned MA-L-twinic acid anhydride copolymer is coated with an active hydrogen-containing compound such as te-1-rahydro-cofuran, diochirin, dimethylbormamide, etc. on a suitable support. Apply a solution containing a polyisocyanate compound dissolved in an organic solvent.

After drying, heat treatment is performed to cause a crosslinking reaction between the maleic anhydride copolymer and the polyisocyanate compound. The temperature and time of this heat treatment vary depending on the combination of the maleic anhydride copolymer and the polyincyanate compound used, but can be selected within the range of approximately 80 to 20°C and several minutes to several hours.

When forming this image-receiving layer, in order to promote the cross-linking reaction between maleic anhydride and the polyisocyanate compound, catalysts such as dibdeltin dilaurate, dibdeltin diacetate, lead 2-1-dylhexylate, titanate ~ Rub 1 ~ Oxide, Al] ~ 2 LM soot, Sividel suth (2-ethylhexane-1), Potassium phosphate, Andimontrik [1] Metal compounds such as light, or triethylamine, 1- An appropriate amount of amine such as ethylenediamine can be added.

Picture II of the original printing plate of the present invention! ! The receiving layer IJ, for example, is a crosslinking reaction product of a maleic anhydride copolymer and a polyisocyanate compound, but the strength of the layer is modified (V), Ill (7) jBI. l
1tt/: Polyester resin, polyimide resin, polycarbonate resin, acrylic resin, borisdylene resin, vinyl aretal resin or vinyl acetate resin can be added.

However, in this case, it is desirable that the ratio of 14I to 15 resin in one layer be less than 50% by weight. The rate of hydrophilization is slow and the hydrophilicity is insufficient, resulting in background stains on printed matter.

Receive images of this complaint! The layer has adhesion to the image forming material (e.g., oil-based ink, 1 to 100% ink), writeability, or 1 to 1 in the case of image formation using an electrophotographic copying machine.
- In order to improve the transfer characteristics, etc., the surface is
: Matte 1~ compounding agent or containing a pine 1~ compounding agent in the layer V
But J, yes. As matting agents, inorganic N6 such as tadoepo, zinc oxide, titane oxide, barium sulfate, aluminum oxide, calcium carbonate, quartz dioxide, clay, glass particles, polymethacrylate, boristyrene, phenolic resin. There are polymer particles such as.

The plate making of the lithographic printing original plate of the present invention is carried out by the image (τ) forming process and the parent wood forming process.
Similar to the original printing plate for drawing A plate, for example, oil-based in 1-,
An image is formed on the JT layer using a typewriter or the like, or by electrophotographic copying using a dry toner or a wet toner. 1. Form and cover an image by transferring a toner image and applying it to a fixed volume.

The original plate on which the image has been formed is immersed in a parent wood treatment solution to change the surface of the image-receiving layer from hydrophobic to hydrophilic in the non-image area. The hydrophilic treatment liquid used here is, for example, an alkaline solution in the case of an image-receiving layer made of a crosslinking reaction product of maleic anhydride and a polyisocyanate compound. In this case, the surface of the image-receiving layer, 15, and the acid anhydride groups near the surface are ring-opened by hydrolysis with an alkaline solution to generate OOL1 groups at -1--, thereby changing from a hydrophobic surface to a hydrophilic surface. There is something to do. Specific examples of the alkaline solution used include, for example, silicic acid 1-
Lium, phosphate 11, hydroxide, Lium,
Aqueous solutions of inorganic salts with potassium hydroxide'cK, non-seventynia water or Aqueous solution containing organic amines such as panolamine, butanolamine, and dylenediamine 4
1 and 11 organic solvents such as ethanol, benzyl alcohol, ]-dylene glycol, and glycerin, and a culm surface activator are added as necessary.

The covering time required for hydrophilization varies depending on the composition of the image-receiving layer, the degree of crosslinking, the prescription of the mother wood treatment solution, etc., but it may vary depending on the appropriate patterning and selection of the strip 1'1. Second Pi! You can make it hydrophilic with Maro.

After hydrophilic treatment, water (if necessary) 511, and drying, a good Y lithographic printing plate 4q is formed from a lipophilic (ink-philic) image area and a hydrophilic non-image area. The non-image area of the printing plate, that is, the surface of the hydrophilized image-receiving layer exhibits desirable hydrophilicity. This hydrophilicity can be confirmed, for example, by measuring the contact angle with water. However, the contact angle with water on the surface of the image-receiving layer before hydrophilic treatment is 60° or more, but after hydrophilic treatment it is approximately 10°.
The hydrophilicity decreases to ~15°, and there is a surface that can be measured well in water. , is sufficient to provide high quality printed matter without background smudges.

In addition, the image-receiving layer, whose surface has been treated with hydrophilic treatment, swells almost even when immersed in water! f Shows high water resistance. Lithograph printing at the time of printing) & 1 in a wet state, and moreover, 4 by Branfoot, -7-1-ng [''-ler! i! Although the printing plate is subjected to mechanical pressure 4, the hydrophilized layer of the printing plate according to the present invention is not destroyed under such conditions.

In the present invention, the image-receiving layer is a plus 1 ivy film,
Excellent contact between synthetic paper and support 'C11,3
After image formation, only the surface of the non-image (resistance 2 part) is covered by the parent tree. Compared to the case in which an image was formed in case), the adhesion to the image forming material (oil-based ink, 1-)-) was better, and peeling and chipping of the image area were less likely to occur.

Due to the above advantages, the lithographic printing original plate of the present invention has the following advantages:
0 provides lithographic printing plates that have high printing durability and produce high quality printed matter.

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

Example 1 [Image-receiving Seriyumi coating liquid] Medyl vinyl ether-maleic anhydride copolymer (Aldo 1) Tsuhi Chemical Company ￥A) 1 part by weight Toluene - 0.17 parts by weight of 2,4-diisocyanate Dibutyltin dilaurate 0.02￥Xff1 part Te1
- Lahydrofuran 19 parts The image-receiving layer coating solution having the above composition was coated on a 100 μm thick polyester film-L, and 10 parts
After drying at 0°C for 5 minutes, heat treatment was performed at 150°G for 2 hours to form an image-receiving layer of about 3 μm, and the lithographic printing original plate of the present invention was prepared. ? Ta.

A good toner image was formed on this original printing plate-1 by applying a dry developer (Al(11)) to this original printing plate-1. Next, a good toner image was formed.
σ) The original plate was diluted with 1% by weight sl-lium silicate aqueous solution/) 1
The surface of the image-receiving layer in the non-image area of -C was made hydrophilic by immersing it in a hydrophilic treatment solution consisting of -C for 10 seconds. Water); View, *2 After drying,
In order to confirm the hydrophilicity, the contact angle of the non-1itii base with water was measured and found to be approximately 10° (65° before hydrophilic treatment).

This J: The lithographic printing plate made by sea urchin ()) -
Made in A7t? Print +fflΔ+) 13HIJl'l
"L Kono" January (Wasuko L K ink, d3A,
When I diluted Tutsi solution 5 times with water C and used my hair as dampening water, I printed it, and the result was a bright print with no missing images on a D11 background! i +1
, (1 (10 Sawara) 200 years ago.

Example 2 [Image receiving Pi coating solution] Methyl vinyl ether-maleic anhydride copolymer (manufactured by Rudrich Kumino J.L. Company) 1 part by weight diphenylmethane-4,4-1 diisocyanate 1-0.15 Detrahydrofuran for heavy lifting 19 Double part The image-receiving layer coating solution having the above composition was coated on a polyester film with a thickness of 100 μm.
After drying at 150 DEG C. for 5 minutes, an image-receiving layer having a thickness of 3 .mu.m was formed by heat treatment at 150 DEG C. for 2 hours, and the lithographic printing original plate of the present invention was prepared.

A good dot was formed on this printing original plate in the same manner as in Example 1.
After the image was formed, the surface of the non-image area was immersed for 15 seconds in a 1% helium aqueous solution of 1% helium, washed with water, and dried.

When the lithographic printing plates prepared in this manner were printed in the same manner as in Example 1, more than 50,000 clear prints without background stains or missing images were obtained.

Example 3 [Image-receiving layer coating liquid] Styrene-maleic anhydride tlJU polymer (7' Rudrich Chemical Company Y! 1) 1 inch weight Toluene-2,4-diisocyanate-1.0.09 thousand parts 1.4- Dioxane 19. Image receiving coating liquid with the above composition. After drying 100 μm poly varnish 7 film for 5 minutes, 1! i (Heat-treated at 1° C. for 211 minutes to form an image-receiving layer with a thickness of about 3 μm, and prepare the original plate for reprint printing of the present invention.

Handwritten with oil-based magic ink C on this original printing plate.
jQi 1% was formed. Next, in order to make the surface of the non-image area of this one-claw plate hydrophilic, it was immersed in an aqueous solution of 1% silicic acid and rum for 20 seconds, washed with water, and dried.

When the lithographic printing plate thus prepared was printed in the same manner as in Example 1, clear prints with no background stains or missing images were printed at 1°, +100 or more.

Effects According to the present invention, it is possible to obtain high-quality printed matter that is completely compatible with book-like hydrophilicity and water resistance (1), and has minimal background stains.

Patent applicant: Kanri Co., Ltd. 21- Agent Patent Attorney Gaku Komatsu Tan Agent Patent Attorney Hiroshi Asahi

Claims (1)

[Claims] (1) An image-receiving layer whose main component is a reaction product of a copolymer resin containing maleic anhydride and a crosslinking agent made of a polyisocyanate compound is provided on the support. Original plate for lithographic printing.