JPS61120142A - Photosensitive resin plate forming method - Google Patents

Abstract

PURPOSE:To remove a viscosity of a surface of a cured material composed of a relief forming photosensitive resin by incorporating a specific alcohol, an acid, or an amide of a satd. or an unsatd. long chain hydrocarbon to a photosensitive resin composition and then by making the plate. CONSTITUTION:The photosensitive resin composition comprises a prepolymer. A compound shown by the formula R1-X (wherein X is -CH2OR2, -COOH, -CONH2, R1 is CnH2n+1, CnH2n-1, (n) is 11-21, R2 is H, -CO-R3-S-R3-COOH2-R1, R3 is a hydrocarbon residue, is incorporated to the obtd. composition. The obtd. composition is exposured in an aqueous solution contg. >=0.01wt% an alkaline metal of a sulfurous acid, and the photosensitive resin is cured. A compd. shown by the formula R1-X comprises erucic acidamide and myristic acid. The compd. shown by the formula R1-X is incorporated to the titled plate, thereby removing a tacky adhesion of the titled plate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a photosensitive resin plate having a relief image without surface tackiness.

(Prior art and problems) The creation of relief images using photosensitive resin basically involves the following steps:
The image forming exposure process is carried out by the current factory.

In addition, the mechanical strength of the relief image is improved after the development process,
A re-exposure step is usually added to reduce surface tack. If development is done with a liquid developer,
Drying takes place.

However, photosensitive resins that are polymerized by actinic rays,
If only the m4 step is carried out, the surface tackiness of the obtained cured product becomes large and becomes a problem for practical use. The surface tackiness of the cured product is caused by the fact that the top of the relief image is located on the surface layer of the photosensitive resin plate during image formation, so polymerization is inhibited by oxygen in the air, and depending on the resin composition, it may be noticeable. Shows stickiness. Also, the sides and bottom of the relief image exhibit stickiness due to incomplete polymerization. In particular, when using a developer whose developer composition includes water or more, semi-cured portions tend to remain on the sides and bottom, resulting in significant stickiness. Recently, in order to treat waste liquid and improve the working environment, methods of developing with an aqueous surfactant solution, an aqueous alkaline solution, or water alone have been mainly practiced, but the tackiness remains high.

The surface tackiness of such cured products is 1 in 9. When handling the cured product, it may stick to the hands of the worker, deterioration of workability due to adhesion of the cured products to each other, and quality deterioration due to the adhesion of chisels. Problems such as this arise. Furthermore, when using the cured product as a printing plate, in addition to the above-mentioned drawbacks, the plate's li! ii) During printing, dirt or paper dust adheres to the surface of the middle surface of the inner part, causing stains on the printed matter, making it necessary to stop the printing machine and wiping the plate during printing, or when the substrate is In the case of paper, paper smudges may occur, resulting in a decrease in workability and a decrease in printing yield.

Various methods have been attempted to solve these problems.

There are known methods for surface modification through chemical and physical treatments, such as treatment with chemicals such as oxidizing agents and reducing agents, and ■) coating the relief surface with various coating agents after creating the relief.・ ■゛) For the method, please refer to the special public Sho 5G.
-389,64 1% Method for preventing oxygen inhibition during post-exposure with wax or reducing substances, as shown in the methods described in the specifications of Publications No. 50-31487 and JP-A No. 58-97043. etc. are known. However, these methods did not have a sufficient adhesive removal effect as described below.

In addition, although method I) has an initial effect, there are problems with the increase in complicated steps and the lack of sustainability of the effect.

(Means for Solving the Problem) In order to solve the problem caused by the surface tackiness of the cured product as described above, the present inventor took into consideration the problems of existing tack removal methods, and developed a photosensitive material for relief formation. As a result of intensive studies to eliminate the surface tackiness of the cured resin product, we found that the general formula R, -X (where X
10H! OR wealth.

-Coon or -CONHs s R1 is Cn H2
,. □ or CnH -valent hydrocarbon group, 凰 is 11 or more 2
An integer of 1 or less n-1, R is Hl or -Co-Rs 8 Rm
-COOCHs-R1, Rs is a divalent hydrocarbon group having 1 to 6 carbon atoms) By post-exposure in an aqueous solution containing 0.01% by weight or more of salt, we have completed a method for producing photosensitive resin plates that stably stick to the surface immediately after plate making and have no adhesive properties.

In the photosensitive resin composition of the present invention, the main photosensitive resin composition, that is, the composition before containing compound (2), has the property of being insolubilized by actinic light, and a typical example is ethyl V. A prepolymer having a polymerizable unsaturated group and optionally a diethylenically unsaturated monomer,
Examples include compositions comprising a photopolymerization sensitizer and a thermal polymerization inhibitor.

Examples of prepolymers include unsaturated polyesters, unsaturated polyurethanes, unsaturated polyamides, unsaturated (meth)acrylates, modified versions of these, and various male compounds having carbon-carbon double bonds. can do. To explain in more detail, examples of unsaturated polyesters include unsaturated acids such as maleic acid, fumaric acid, and itaconic acid, or their acid anhydrides, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, and triethylene glycol. Polyesters with polyhydric alcohols such as methylolzolonone, or polyesters in which part of the acid component is replaced with saturated polybasic acids such as succinic acid, adipic acid, phthalic acid, isophthalic acid, phthalic anhydride, and trimellitic acid. There are many examples. Unsaturated Bo.

Refletane is one in which an addition-polymerizable unsaturated group is introduced using the terminal isocyanate group or hydroxyl group of a compound linked via a urethane group derived from a polyol and polyisocyanate having a terminal hydroxyl group of 2g1A or more, such as those mentioned above. 1,4-polybutadiene, hydrogenated or non-hydrogenated 1,2-polybutadiene, tutadiene-styrene copolymer, butadiene-acrylonitrile Copolymer, toluylene diisocyanate, diphenylmethane-4
, 42-diisocyanate, hexamethylene diisocyanate, and other polyisocyanates into which an unsaturated group is introduced using the terminal incyanate of polyurethane or the reactivity of the hydroxyl group, that is, the above-mentioned unsaturated Cal I
hydroxyl group, Cal I xyl group,
Compounds into which an unsaturated group is introduced by reacting a compound having active hydrogen such as an amino group with incyanate, or a compound into which an unsaturated group is introduced by reacting a car-xyl group with a hydroxyl group, or the unsaturated group mentioned above. Examples include compounds in which polyesters are linked with polyisocyanate (Japanese Patent Publication No. 51-37320, Japanese Patent Publication No. 7761-1982, Japanese Patent Publication No. 36444-1988, Japanese Patent Publication No. 7363-1973, Japanese Patent Publication No. 34930-1985) Specifications of each publication photosensitive resin compositions described in the book). In addition, JP-A No. 56-120718, JP-A No. 4
Examples include photosensitive resin compositions described in No. g-43126. The number average molecular weight of these prepolymers is generally SOO or higher, but the double bond 1
When the molecular weight of each double bond exceeds i, o o o, the surface tackiness often becomes large. In particular, when the molecular weight of one double bond exceeds s, ooo, the tackiness becomes significant, and the urethane prepolymer In the case of a type in which a double bond is introduced at the end, the molecular weight between the double bonds is large, so the surface tackiness is further increased, and the effect of the present invention is extremely effective.

As prepolymers other than those mentioned above, it is also possible to use compounds that do not contain double bonds and are photopolymerized by a mechanism other than the addition of ethylenic double bonds.

Various known compounds can be used as the ethylenically unsaturated monomer, and examples of such compounds include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, or esters thereof, such as alkyl-, Cycloal medium roux,
Halog/alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl-, tetrahydrofurfuryl-, allyl-, glycidyl-, benzyl-, phenoxy-acrylate and methacrylate, alkylenegly, coal, I-lyoxyalkylene! Recall mono- or diacrylates and methacrylates, trimethylo-luprono/triacrylates and methacrylates, pentaerythritol tetraacrylates and methacrylates, acrylamide, methacrylamide or derivatives thereof, such as alkyl, hydroxyalkyl N
Allyl compounds, such as allyl alcohol, allyl isocyanate, allyl heptatarate,
triallyl cyanurate, maleic acid, maleic anhydride, fumaric acid or its esters, e.g. t-alkyl,
Other unsaturated compounds such as mono- or dimaleates and fumarates of alkyl halides, alkoxyalkyl, such as styrene, vinyltoluene, divinylbenzene,
Examples include N-vinylcarbazole and N-vinylpyrrolidone. Also, a part of these monomers may be added to an azide compound such as 4.41-diazidostilbene, p-7
22lene-pisaziF, 4,4'-diazidobenzopheno, 4-4'-diazidostilbene, 4,4'-diazidochalcone, 2,6(4'-azidobenzal)-cyclohequinanone, 4 a 4' -Diazidostilbene-α
-, /7/L/men[,4#4'-diazide diphenyl, 4,4'-diazidostilpey-2,2'-sodium disulfonate, etc. K placement! A frog and a tortoise can be made.

These monomers are used in an amount of 0 per 100 parts by weight of the prepolymer.
It may be added in a range of 200 parts by weight.

Compound Q used in the present invention is represented by the following general formula.

General formula R7-X (where X is 10H, OR, -CO
OH or -CON) II, R, is a zn+i -valent hydrocarbon group of CnI (t or Cn H2n++, n is an integer of 11 to 21, R3 is [or -Co-R3~S -Rs C00CH snow-
R1m (R1 is a divalent hydrocarbon group having 1 to 6 carbon atoms) Compound (1) has an effect on the composition of the photosensitive resin in terms of solubility in the base photosensitive resin and tack removal effect depending on the amount added. It is preferable to select one based on the number of carbon atoms.Those with a small number of carbon atoms are generally easy to dissolve, but the effect of removing surface tackiness is small.As the number of carbon atoms increases, the effect of removing tackiness is large, but the resin becomes cloudy and image reproduction becomes difficult. In terms of the balance between solubility and adhesive removal effect, R in the formula
1 preferably has a carbon number in the range of 11 to 21, and in particular, a compound in which X is a hydroxyl group, a syl group, an amide group, or a thiodiester represented by -CH1OC-R1S Rm C-0CHIRI is effective in removing stickiness. is highly suitable. Further, when X is a hydroxyl group or a car-xyl group, R1''CIl~Cl is also an amide group, R1-
C11 saturated hydrocarbons and ctyllms unsaturated hydrocarbons, and in the case of thiodiesters at-ctt
~C1? , R1-rich C3 compounds are particularly effective in removing tack and have high solubility in resins. These compounds (1) can be used alone or in combination.

Examples of variants of compound ■ are lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, lauric acid, myristic acid, normitic acid, stearic acid, and stearic acid: 2! L Lauric acid amide, myristic acid amide, normitin amide, stearic acid amide, erucic acid amide, diracryl thiodillobionate, simiristyl thiodipropionate, distearyl thiodipropionate, oleyl alcohol, erucyl alcohol, olein acids, erucic acid, oleic acid amide, erucic acid amide, and the like.

When compound (1) is added alone or in combination to a photosensitive resin composition, if the total amount added is less than 0.1% by weight based on the base of the composition, it will not be substantially effective in removing surface tackiness; %], the surface tack removal effect is sufficiently exhibited, but the solubility of the composition in the substrate decreases and the resin becomes cloudy, resulting in a decrease in iiigR reproducibility and furthermore, the mechanical strength of the cured product decreases. The optimum amount to be added must be determined for each resin since the solubility varies depending on the structure of the base composition, but 0.1 to 6% by weight is suitable, especially for surface tackiness. From the viewpoint of the removal effect and the mechanical strength of the cured product, a range of 0.5 to 4% by weight is preferred.

Methods for incorporating the compound (4) into the photosensitive resin composition include a method in which the compound (4) is mixed in advance into a prepolymer and then mixed with an ethylenically unsaturated monomer, a polymerization initiator, etc.; A method of mixing it with a prepolymer, a polymerization initiator, etc. after mixing, a method of adding it to a photosensitive resin composition and mixing it, etc. are adopted, but the effect of adding it is not known no matter which method is used.

In addition, various commonly used photosensitizers, ie, photopolymerization sensitizers, may be used. Examples of such substances include benzoin, benzoin alkyl ethers such as benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, dimethoxyphenylacetophenone, benzophenone, henosyl, diacetyl, diphenyl sulfide, and niosin. ,
Thionine, thioxanthone, etc. can be used in an amount of 0.001 to 10% by weight of the composition.

As a thermal polymerization inhibitor, hydroquinone, Mineno-tert-butylhydroquinone, benzoquinone, 2,5-diphenyl-p-benzoquinone, hyfurific acid, di-p-fluorophenylamine, P-/toxyphenol, 2,6-
Examples include di-tert-butyl-p-cresol. It is desirable that these thermal polymerization inhibitors only prevent thermal polymerization reactions (dark reactions) without suppressing photoreactions. Therefore, the amount of thermal polymerization inhibitor added is
For the total IK of prepoly i- and crosslinking agent, o, oos ~ &
It is desirable to set it within a moderate range.

The alkali metal ring or alkaline earth metal salt of sulfite used in the present invention is specifically sodium sulfite,
Examples include ILr1/L potassium and calcium sulfite.

The concentration of the aqueous solution used in post-exposure should be at least 0.01% by weight; if it is less than that, it will not be effective in removing the adhesive force immediately after plate making. In addition, since there is a difference in the sticky layer removal effect νζ depending on the noodle content of compound (1) in the photosensitive resin composition, o,
More preferably, it is osxt% or more. The upper limit is particularly limited to lk<, suspension is effective, but since the post-exposure step also serves as the purpose of imparting physical properties, suspension delays the exposure time, prolonging the working time, and from the economic point of view. Just set an upper limit.

To prepare the photosensitive resin plate of the present invention, first, a photosensitive resin plate having a relief image is prepared according to a standard method. When a negative film is exposed to light using a light source such as a metal halide lamp, a xenon lamp, or sunlight, the exposed areas of the image harden. jl The non-image area that is not exposed to light is removed by blowing air, or a liquid that dissolves or disperses the uncured photosensitive resin composition, such as water, an acid-alkali aqueous solution, an aqueous solution of a surfactant, or an organic solvent. Dissolve or disperse in an aqueous solution containing

Then, the relief image of this resin plate is formed#
Immerse the surface in an aqueous solution of an alkali metal salt of sulfite or an alkaline earth metal salt, and then apply a carbon arc lamp, ultra-high pressure mercury lamp, high-pressure mercury lamp, ultraviolet fluorescent lamp, metal halide lamp, xenon lamp, germicidal lamp, or sunlight. Irradiate the image side using a light source such as The irradiation time may be set to be the same as the time for post-exposure for the purpose of improving physical properties. After irradiation, drying is performed.

(Function) Evaluation of non-adhesion after exposure and curing is performed using K as follows. In Fig. 1, a sample piece 1, that is, a cured plate with a thickness of 3H, is dried and then placed on a horizontal pedestal 2 with the resin side facing upward at a temperature of 20°C. The aluminum ring 3 with a width of 13 m was brought into contact with the parrot, and a load of Ksoo II was applied to the aluminum ring 3 and left for 4 seconds. Then, the aluminum ring 3 was pulled up at a constant speed of 30 meters per minute, and the aluminum ring 3 was removed from the sample piece 1. Read the adhesion force when it is separated using Pushinible Gauge 4.

The lower the adhesive force, the better the non-adhesive property. The indicated value by the above measurement method is so! If it exceeds i, when the adhesive surfaces of the cured product overlap each other during handling, a solid layer is formed that is difficult to peel off. In addition, even when various films, foils, and plate materials are used as supports and relief images are formed on them,
If cured products are piled up, the adhesive surface and the support will stick together, making it difficult to separate them. Therefore, the adhesive force needs to be 5oIi or less. In addition, especially when used as a printing plate, paper dust may adhere to the adhesive surface and cause stains on the printed matter. The phenomenon of baldness occurs. To prevent this,
It is preferable that the adhesive strength is 3011 or less.

Many ordinary photosensitive resins give cured products with adhesive strength of ioo, g or more, and photosensitive resin compositions that give cured products with particularly low hardness have high adhesive strength (many of them exceed 300 g). Ta.

Furthermore, when using a photosensitive resin composition containing compound (4) without using an aqueous solution of an alkali metal salt or alkaline earth metal salt of sulfite, the adhesive strength was 301! As shown below, it exceeded 30 II immediately after plate making.

However, in the present invention, by using post-exposure in an alkali metal salt or alkaline earth metal salt of sulfite, a plate with no tackiness can be obtained immediately after plate making.

(Example) Next, Examples and Comparative Examples will be described. In principle, the number of parts in k means parts by weight.

Example 1-I Lipropylene glycol (number average molecular weight [hereinafter referred to as Mn
(abbreviated as )200G), 1 part of propylene glycol adipate diol (Mn=2000), and both ends incyanate type polycrethane were obtained. Polypropylene glycol monomethacrylate) (MIS-380)
was reacted to obtain a polyurethane pre-I remer (Mn-16500) modified at both ends with methacrylate.To 100 parts of this prepolymer, 25 parts of polypropylene glycol monomethacrylate (Mn=380), 15 parts of lauryl methacrylate, and tetraethylene glycol di 10 parts of methacrylate, 1.5 parts of 2,2-dimethoxyphenylacetophenone, and 0.2 parts of 2,6-di-t-butyl-p-cresol were added, and 1.5 parts of erucic acid amide was added and mixed. A photosensitive resin composition (4) was obtained. Next, a propylene film with a thickness of 20μ was placed on the negative film as a cover film, a spacer with a thickness of 3t was provided on top of the film, RKm product (■) was poured into the spacer, and a 4-layer film with a thickness of Zooμ was placed on top of the film as a support. It was covered with a film and exposed to light using a chemical lamp. Next, the cover film was peeled off, and the sample was washed with warm water at 40°C containing 20% of nonionic surfactant, and then the developer was washed away with running water, and the sample was immersed in an aqueous solution of sodium sulfite using a chemical lamp. A post-exposure was performed. A cured plate was obtained by drying for one minute in a SaC dryer. The surface adhesive strength immediately after drying was oI.

Example 2 The same procedure as in Example I was carried out except that myristic acid was used instead of erucic acid amide in the photosensitive resin composition, and a cured plate with a surface adhesion of oy was obtained immediately after drying. .

Example 3 Example 1! /c, in place of erucic acid amide in the photosensitive resin composition, cimilistyl thiodipropionate was added to 0.
．． After exposure and development, post-exposure was carried out using a 2 i placement area and an oleylamide 1 overlay area, changing the concentration of the sodium sulfite aqueous solution. Germicidal lamp with a center wavelength of 254 nm (Toshiba G
C-15 type) and chemical lamp (center wavelength 370 nm)
) was used to simultaneously irradiate a distance of about 15 lines for about 10 minutes. The adhesive strength was examined 30 minutes after drying.

Spicy 1 Measured values when left at room temperature for 30 minutes after drying Examples 4 and 5 5-fold The results of the same operation as in Example 1 except that the compounds shown in the table were used instead of sodium tptE acid were shown. .

Table 2 Types and adhesion of post-exposure aqueous solutions 11% by weight aqueous solution 2 Comparative examples 1, 2 and 3 of stagnation values after drying and leaving at room temperature for 30 minutes Compounds (removal of either or both of sodium sulfite during re-exposure) The surface adhesion of this method was shown.

Comparative Examples 4 and 5 (Sulfite) An example was shown in which reducing sodium thiosulfate and glucose were used in place of IJium. There was almost no adhesive force removal effect.

Claims (1)

[Claims] When creating a photosensitive resin plate, the general formula R_1-X (where X is -CH_2OR_2, -COOH or -CO
NH_2, R_1 is CnH_2_n_+_1 or Cn
H_2_n_-_1 monovalent hydrocarbon group, n is 11 or more 2
An integer less than or equal to 1, R_3 is H or -CO-R_3-S-
Using a photosensitive resin composition containing a compound represented by R_3-COOCH_2-R_1 and R_2 are divalent hydrocarbon groups having 1 to 6 carbon atoms, an alkali metal salt or alkaline earth metal salt of sulfite A method for creating a photosensitive resin layer, characterized by post-exposure in an aqueous solution containing 0.01% by weight or more of