JPS5988732A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain an image forming material developable with water and giving an image with superior resistance to water, acid and solvent by emulsion- polymerizing a vinyl monomer having a photosensitive group with other monomers including a monomer having two or more polymerizable vinyl groups in the molecule. CONSTITUTION:When a vinyl monomer having a photosensitive group is emulsion-polymerized with other vinyl monomers, a monomer having >=2 polymerizable vinyl groups in the molecule is used by >=1wt% of the amount of other vinyl monomers. By blending the resulting resin emulsion composition, a photosensitive resin composition is obtd. Said vinyl monomer having a photosensitive group is a water insoluble liq. monomer such as the ester of carboxylic acid having an azido group with a vinyl monomer having a hydroxyl group or the adduct of an isocyanate compound having an azido group to a vinyl monomer having a hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an image developed in water, and the resulting image is water resistant.
This invention relates to an image forming material that has excellent properties such as acid resistance and solvent resistance.

The photosensitive material for plate making is developed so that the photosensitive film in the areas corresponding to either the unexposed area or the exposed area is removed, and the resulting image is used as a photosensitive material for metal corrosion or printing.
It is used as a. The most preferable form of performance required for such a photosensitive material is that development can be done with tap water, and if the 1:1 developed image has good lipophilicity and good solvent resistance and abrasion resistance, it can be used for lithographic printing. It can be used as a printing plate, and if it has good acid resistance, it can be used as a photorenost for metal 1 grade, and if it has good water resistance, it can be used as various image forming materials.

Although various materials have been developed and put into use as such photosensitive materials for plate making, none of these materials meet the conditions described below. For example, azo resin, which is known as a photosensitive material that can be developed with water, has poor abrasion resistance and requires reinforcement with a lunker in order to be used as a printing plate5. The silicate ester of polyvinyl alcohol is
Although it has good acid resistance, it has the disadvantage of being developed in a solvent.

In order to develop a photosensitive material that improves the drawbacks of such conventional photosensitive materials, the present inventors have developed a method of combining a vinyl monomer having an anddo group, another vinyl momer, water + 1 emulsion of a self-photosensitive polymer which is 21i+ via tJ. When used, it can be developed with water, and the image is lipophilic, so it has good ink acceptance, 1) 1, abrasion resistance, and good I1. It was discovered that a printing plate with the highest quality could be obtained. : Unlike conventional photosensitive materials, Nochino can be developed with water, and (θ・j
Although it is a material whose abrasion resistance and acid resistance are uncertain, in order to perform photocrosslinking between the polymer and Ihr that form the emulsion in image formation, image reproduction 1) Conventional uniform solution system in 1- 1, which was found to have a drawback that it was inferior to the photosensitive materials of 1. That is, since the image is formed at the connection between the ladle and the comrades, a sharp outline could not be obtained at the periphery of the image. 5: The cross-linking between 1' and 1' progresses, or the light transmission within the polymer 1' is insufficient, resulting in insufficient photo-crosslinking of the polymer R, 1', which has unfavorable results in terms of solvent resistance. 'I
In order to improve the drawbacks noted in 1-, the inventors of the present invention made extensive research into u611 and completed the present invention. That is, when emulsion polymerizing vinyl 3-77-mer having photosensitive J1 (177-) and vinyl 3-77-mer of another kind or one divine tool 1, at least 1% by weight of the vinyl monomer in the 1-1- 2 in 1 nitrate;
1) Using Moamer with polymerizable vinyl group of J juice
It has been found that by using a photosensitive resin composition containing a resin emulsion paste composition, the disadvantage described in item 1 can be overcome. in this way! By adding a polyfunctional vinyl moamer during L-polymerization, the water dispersibility of a densely cross-linked microgel can be obtained, resulting in finer particles than ordinary latex, which improves the image quality obtained from a homogeneous solvent system. , resulting in an image with sharp outlines.

Furthermore, since the individual particles are tightly cross-linked, a photosensitive material with excellent solvent resistance and durability can be obtained.

Vinyl molymer having a photosensitive group in the present invention (hereinafter referred to as
Photosensitive moamers (referred to as photosensitive moamers) are liquids that do not dissolve in water, such as carboxylic acids with azide groups (atbenzoic acid, azidobenzenesulfonic acid, derivatives thereof, etc.) and vinyl moamers with hydroxyl groups (hydroxyl moamers). esterified product with ethyl acrylate, hydroxyethyl methacrylate = 4-, or
Examples include 1-1 adducts of isonane 1 compounds (and7I nylisonanate, derivatives thereof, etc.) and vinylmore 7- having a 1-hyfuroxyl group; 2-Methacryloyloxyethyl anthate, ・1-and-amp, 2-7-ammonyl 6-acid, ・1-at-amp, 1-menal--2-methacryloyloxyethyl anthate, ・1- Examples include 2-methacryloyloxyethyl azidobenzenesulfonate and 2-methacryloyloxyethyl .'1-azidophenylcarbamate. Examples of photosensitive monomers include esters of acrylic acid or methacrylic acid having benzoin or benzophenone in the side chain. Examples include benzoin acrylate), hengeine methacrylate, 1-acryloyloxybe/zo7-7, 1-
Examples include methacrylyloxybenzophenone and vinylbenzophenone. , these 14ΦJ or 2 sacred tools-
1- is put to use.

In the present invention, examples of the vinylmore 7- (hereinafter referred to as polyfunctional vinyl 77-i) having two or more -I- polymerizable vinyl molecules in the molecule include divinylbenzene, ethylene glycol ( meth)acrylate (indicates both ethylene glycol no acrylate and ethylene glycol no methacrylate-1, the same shall apply hereinafter), neopentyl glycol acrylate, methylene bisacrylamide, trimethylol propane) (meth) acrylate -)., tetramethylolmethanetetra(meth)acrylate, etc. are mentioned as examples. Kagaru multifunctional +1
All common vinyl monomers can be used for vinyl monomers and (W). For example, styrene, vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid, etc. can be mentioned.

One or more types of vinyl photosensitive moamer and pond
The ratio in the 2L polymerization of mer is photosensitive 177-3~
70% by weight, preferably 5 to 60% by weight and 7% by weight of other vinyl moles 7-30-, preferably t or 4().-
05 weight part is 1%. If you use the photosensitive + r1 moamer beyond the lower limit of the range, it will be difficult to add the photosensitive Vl or image formation, and if you use it beyond the 10 limit, the film will lack durability and Bi1. The above-mentioned starved vinyl mower 7 - at least 1 ton, % or more, preferably 3
11'i' fri bamboo vinyl resin/mer is used in a heavy F of 11% or more. If the darkening vinyl monomer is used in an amount less than the lower limit, the solvent resistance, 1f1, and image development properties of the film will be poor.

Emulsion polymerization may be carried out in the usual manner and illegally, for example in an inert gas atmosphere, with the presence of conventional protective colloids, 7L-forming agents I, and U-reaction initiation. I11
While dropping the monomer at ζ, the temperature is 6 (,1-8,”
) C. for 2 to 5 hours. 1-2 protection 5
(Water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, alkyl celluloses, polyacrylamide, polymethacrylamide, etc. can be used as the roller. In the present invention, when The process may be carried out without using such a protective colloid, or it may be used by adding it after emulsion polymerization.

”2, 7L-forming agents and reaction initiators can be used in general manner. That is, any of cationic, anionic, and nonionic agents can be used as the IL agent. Examples of the reaction initiator include persulfates and hydrogen sulfites.

In the present invention, it is also possible to add pond material to the resin emulsion composition obtained as described above.

An example of such a material is a material that can be heated to -11°C or lower for 1 (month) at normal pressure in order to improve film strength and improve adhesion to the base material.
It is a polymerizable ethylenically unsaturated compound with a boiling point of .

Specific examples include (meth)acrylamide,
N, N'-methylenebis(meth)acrylamide, N-
Methylol (meth)acrylamide, triacryl formal, 11-butoxymethyl (meth)acrylamide, Nt-methyl (meth)acrylamide, sodium (meth)acrylate, calcium (meth)acrylate, zinc (meth)acrylate, aluminum (meth)acrylate, polyethylene glyfur di(meth)acrylate, 2-hydroxyethyl (meth)acryle 8
- monoto, 2-hydroxyethyl (meth)acrylic r--1,
Alternatively, it is an acrylic olicomer derived from epoxy or urethane. , Nige), 1, Una 1 Publication/
The addition of l/l ethylene-based saturated compounds can be applied to photosensitive compounds such as vinyl chloride containing
This is particularly effective when an emulsion is used. The amount of addition of the darning material is preferably 3 to 10% by weight based on the solid content of the emulsion paste composition described above.

The composition of the present invention, which has the following constitution (11), contains highly crosslinked polymer particles dispersed in water due to the addition of polyfunctional vinyl 77-77 during the 1.7L polymerization. Therefore, it has good storage stability as a photosensitive solution, and the storage stability of the film obtained by coating and drying the composition on a substrate is also good, making it very useful as a presensitized image forming material. It is something. In addition, the polymer particles themselves are abrasive and highly crosslinked, causing them to become dull. .

Images obtained by crosslinking between 1 and 2 have excellent water resistance, solvent resistance,
Has acid resistance, wear resistance, etc. It also has the feature that excellent images with distinct differences can be obtained even after water development.

. When the composition of the present invention is applied to a substrate-1-, dried, and then irradiated with ultraviolet rays through a negative film, the exposed areas harden to become a so-called negative-type photosensitive material that becomes Xlξ-soluble in water. The hardened film has excellent acid resistance, so 7-Otrenost Mako for metal processing can be used as a refill for screen printing, and mainly in the presence of water, it accepts oil-based inks and has excellent abrasion and solvent resistance. Since it has good properties, it can also be used as an offset 1S plate for lithography which requires printing durability.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples.

Example 1 Into a fourth flask equipped with a stirrer, a thermometer, a nitrogen injection tube, and a reflux condenser, add 1:+ +:+ parts by weight of water and 2 parts by weight of sodium lauryl sulfate: ((
) The air was replaced with nitrogen over a period of 1 minute. Then, the temperature was raised to 710°C, and then 1 part by weight of 2-methacryloyloxyethyl 4-andoamine, Q, 6-acid, and 8 parts of tyrene/hinylbenyan 11 parts by weight were added. , Add 10 ton (11)% of the mixed Moa 7-mixture and stir for 30 minutes (91 reaction start, 64 parts of 0.2 ton of potassium persulfate and 64 parts of hydrogen sulfite).
).

an aqueous solution in which 2 parts by weight were each dissolved in SIjHt parts of water,
How about adding % of 1jY to 10 times of 1 da? L! Akiko;
? (After 1 minute, it becomes 6 (, 1”
Slowly drop the Moamar mixture solution and the reaction initiator aqueous solution.
15 drops 1.゛The humidity was kept at 7 (1 = 75 °C, and after the end of the drop 1 After doing this, the crystallinity of the product was reduced to 1.

7L-1 compound thus obtained] il f1
A 7% by weight polyvinyl alcohol aqueous solution 1 was added to the Φ15' portion to obtain a photosensitive U (fatty phosphorescent product).

The second composition was applied to a sand aluminum plate using a whirler and dried. - After leaving it overnight, the film was vacuum-adhered and exposed with a chemical lamp: (Exposed for one minute, developed by rubbing with a cotton ball under running tap water until the temperature reached 11. The image area was stained to make the image easier to see. When the second image was observed using an engineering microscope, the ring 1- around the image periphery was sharp. After that, when oil-based offset ink was rubbed on the printing plate in the presence of water, the ink was deposited only on the image area.When this was printed using an offset printing machine, a clear printed image was obtained.

In addition, after storing the material coated on a grained aluminum plate for 6 hours in a CO'C oven, there will be no continuous tone density change (Kodak Photo Ink Step Tablet) No. 2
When it was vacuum-adhered and processed in the same manner as exposure and water development,
There was no change in the number of remaining steps of the stencil between the plates before and after storage at 60°C.

Further, the photosensitive resin composition in the emulsion state thus obtained was stored in a dark place for 6 months, and the appearance of the liquid was J-, with no change.
An image was created on aluminum plate-1 by processing in the same manner as described above, and it was identical to the image taken 6 months earlier.

Comparative Example 1 The pond was treated in the same manner as in Example 1, except that 1 part by weight of vinylbenzene was not used in Example 1 to obtain photosensitive T84.
A fat composition was prepared (Ij), 2) This composition was coated on a sand 11 aluminum plate using a whitewasher, and dried.4.
The 7' film was vacuum-adhered, exposed for 5 minutes using a chemical lamp, and developed by rubbing it with a cotton pad under running tap water. When this image was observed under a microscope in the same manner as in Example 1, it was found that the outline of the peripheral part of the image was not sharp and had irregularities.

Furthermore, after storing the material coated on the Sand 11 aluminum plate for 6 hours in a G (1"C oven), the Fugunku 7 Photographic Step Tablet No. 2 was made into a plate.
The plate before storage had residual steps (the number of steps had increased by 4 to 5), making it difficult to develop.

Furthermore, when the thus obtained photosensitive resin composition in the form of an emulsion was stored at an Ifi facility, the emulsion turned yellow after two months, and after one month, the emulsion broke and a precipitate was generated.

Example 2 4-at-an Q, 2-7 chloroyloxyethyl kanoate]
The excretion was treated in the same manner as in Example 1 using 1 part by weight, 7 parts by weight of styrene, and 2.5 parts by weight of dihinylbenzene. Sand [1] was applied to an aluminum plate, and the plate was stored in an oven for 7 hours and the unheated plate was exposed to a chemical lamp for 3 minutes, and then exposed to water under running tap water. After development was carried out by wiping with cotton, the image area was dyed with an aqueous solution of crystal violet.

, Ninora's both had a step number of steps, and there was no difference. The outline of the image periphery was sharp, and when this plate was used for printing, a bright printed image was obtained.

When this photosensitive resin composition in an emulsion state was stored in a dark place for 6 months, there was no change in the appearance of the liquid, and when images were made using this liquid, they were the same as the images made 6 months ago. ·there were.

Example: Polymerization of (in Example 2, using benzoin acrylate + 1o polymerization part in place of 1-acyanF-anQ and 10 parts by weight of 2-acryloyloxyethyl cyanoate, and the other parts are as in Example)) A similar treatment was carried out according to the method to obtain an emulsion polymer.In this way, 7L was added to 10fl of the 7L compound obtained in 1
Polyhinyl alfur aqueous solution 1,11F% concentration (1
(Amount of 71 ζ, 1 ton of acrylamide, N,
One part of N'-methylenebisacrylamide was mixed to obtain Photosensitive 1-1 (composite button product).

This composition was applied to sand 11 aluminum roots 1- using a whirler and dried. - After leaving it overnight, I vacuum-adhered the film and developed it with a chemical lamp for 11 minutes with the dew point turned off for 11 minutes and then running tap water for 1 minute. Indicated. Furthermore, gol this thing,
After drawing, when I rubbed the O7 Seno F oil-based ink on the printing plate with water, the ink was inked only in the image area.

This item is off-seller 1. When the paper was printed on a full press, a very bright printed image was obtained, and there was no change even after 150,000 copies were printed.

Examples 1 to 11 Emulsion polymerization was carried out using the same method (i) as in Example 1 using 1 moa 7- as shown in Table 1 to produce a resin emulsion compact. of each example! As a result of conducting the same tests as in Example 1, it was found that the water developer 1, 15- was superior to the composition of Example 1 in terms of image sharpness, ink receptivity, and preservability. Similar effects were observed.

16- *Moamer A: 4-azidobenzoic acid 2-methacryloyloxyethyl monomer B: , =1-andbenzoic acid 1-methyl-2-methacryloyloxyethyl monomer C: ・1-andophenylcarbamic acid 2-
Methacryloyloxyethylmo/mer D: 4-acryloyloxybenzophenone** Treated according to Example 3.

Patent applicant: Nippon Paint Co., Ltd. Representative Patent Attorney Aoyama Aoyama 1 other person 19-

Claims (1)

[Scope of Claims] 1. A photosensitive resin composition comprising a resin emulsion composition obtained by emulsion polymerization of a vinyl monomer having a photosensitive group and one or two types of vinyl monomers. and at least 1% by weight of the vinyl monomer in the pond
- Inside the brace: A composition characterized in that it is a monomer having 22 or more polymerizable vinyl groups. 2. The composition according to item 1 above, which is a vinyl monomer having a photosensitive group or an esterified product of a carboxylic acid having an anddo group and a vinyl monomer having a hydroxyl group. 3. The composition according to item 1 above, which is a vinyl monomer having a photosensitive group or an adduct of an isocyanate compound having an azide group and a vinyl monomer having a hydroxyl group. 4. The photosensitive group-containing vinyl monomer is an acrylic acid ester or a vinyl compound having benzoin or penzophene as a side chain.
"Above, Iik's tU product. 2 or more 1- polymerization layers 1' vinyl J1 (in the 0 molecule)
1-distribution 1n in which the monomer having is vinylbenzene
The composition according to I. 6, % light) 7: Vinyl monomer having 7:
- 3-70 ton 11)% of the total 1- power distribution composition; 7. The photosensitive resin composition has a boiling point of 1-1' fl
+1 '0 to 4- polymerizable ethylenically unsaturated compound to the solid content of the resin emulsion composition;) -100
1-The composition of the ffN term in the range of width %.