JPS62950A - Material for photosensitive resin plate - Google Patents

Abstract

PURPOSE:To shorten the exposure time and to improve the work efficiency by using a prescribed acrylic ester as at least part of a polymerizable monomer in a photosensitive layer contg. a polymer, the polymerizable monomer and a photopolymn. initiator as essential components. CONSTITUTION:A photosensitive layer contg. a polymer, a polymerizable mono mer and a photopolymn. initiator as essential components is formed to obtain a material for a photosensitive resin plate. At this time, an acrylic ester represented by chemical formula I is used as at least part of the polymerizable monomer. In the formula I, R<1> is H or methyl, each of R<2> and R<3> is H, -A'-OH, -(A''O)nH or -A-OOC-R<1>C=CH2, R<2> and R<3> are not simultaneously H or -A- OOC-R<1>C=CH2, each of A, A' and A'' is lower alkylene having optionally hy droxyl, and n is an integer of 1-20. The acrylic ester represented by the formu la I has satisfactory solubility in water and shows high sensitivity in case where each of R<2> and R<3> is alkyl or polyoxyalkylene having no hydroxyl.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive resin plate material, particularly a photosensitive resin plate material that uses a specific acrylic ester as a polymerizable monomer and has good sensitivity to light. .

(Prior Art) In general, a photosensitive resin plate material contains as essential components a polymerizable polymer and a photopolymerization initiator in addition to a polymer as a binder. When using such a resin plate material to form an image and develop it, exposure takes a long time due to the influence of oxygen in the atmosphere. Therefore, in order to improve workability,
Although it is necessary to remove oxygen from the system, replacing oxygen by introducing an inert gas such as carbon dioxide gas or nitrogen gas is not only expensive, but also does not lead to a reduction in work efficiency. For this reason, in reality, the oxygen in the system is consumed by exposing the resin plate material for a short time (pre-exposure), and then it is exposed through an image film (main exposure) to form an image and harden the plate material. It is carried out. Although this method of combining pre-exposure and main exposure is extremely economical, there is a limit to the improvement in workability as long as certain polymerizable monomers and photopolymerization initiators are used. For this reason, there is a demand for resin plate materials with higher photosensitivity, and research and development is continuing on new materials and combinations of polymerizable monomers and photopolymerization initiators.

One of the recent trends in research and development is to chemically combine a polymerizable double bond-containing compound, which has traditionally been used as a mixture, with an organic amine as a polymerization accelerator within the same molecule. There is a movement to synthesize compounds with polymerizable double bonds and basic nitrogen atoms and use them as polymerizable monomers (for example, Japanese Patent Publication No. 48-41
No. 708, Special Publication No. 57-18173, Special Publication No. 59-59
No. 0051, JP-A-57-114139, JP-A-58
-30748, JP-A-59-48760, JP-A-5
1-102228, JP 59-170835, JP 51-171949, JP 59-172644
No., JP-A-59-187025, etc.).

(Problems to be Solved by the Invention) In general, the above-mentioned compounds having a polymerizable double bond and a basic nitrogen atom in the same molecule are more effective than conventional mixtures of polymerizable double bond-containing compounds and organic amines. Although it has excellent sensitivity in the atmosphere, its sensitivity is still not fully satisfactory.

(Means for Solving the Problems) As a result of conducting research in search of polymerizable monomers with even higher sensitivity, the present inventors discovered the fact that the compound represented by the general formula below meets such objectives. Based on this finding, we have completed the present invention: CH2=CR'-Coo-A-N (I) (
In the formula, R1 is hydrogen or methyl, R2 and R3 are each hydrogen, -A'-OH, -(A″0)nH or -A
-00OR' C= CHt (However, R' and R3 are both hydrogen or -A -00C-R' C= CH2
It is never. ), A, A' and A'' are each lower alkylene which may have a hydroxyl group, and n is an integer having 1 to 20 carbon atoms. In a photosensitive resin plate material having a photosensitive layer containing as an essential component, at least a part of the polymerizable monomer is represented by formula (1).
A highly sensitive resin plate material characterized by using an acrylic ester represented by:

When using the photosensitive resin plate material of the present invention, it is not always possible to omit pre-exposure, but regardless of whether or not pre-exposure is omitted, when conventional commercially available photosensitive resin plate materials are used, In comparison, the exposure time can generally be reduced to about half, so work efficiency is significantly improved.

(Function) The photosensitive resin plate material of the present invention contains a polymer, a polymerizable monomer, and a photopolymerization initiator for the polymerizable monomer as essential components, and at least a part of the polymerizable monomer is the acrylic ester (I). It is.

As the polymer, polymers conventionally used as binders in photosensitive resin plate materials can be used. Specific examples of such polymers include partially saponified polyvinyl acetate, cellulose derivatives, polyethylene oxide, sodium polyacrylate, polyamide, etc. Particularly, partially saponified polyvinyl acetate (particularly with a degree of saponification of 60 to 99 mol%) Preference is given to using water-soluble polymers such as

Various compounds having a polymerizable double bond in the molecule can be used as the polymerizable monomer, and specific examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, β-hydroxyedyl acrylate, and β- Hydroxypropyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate,
Methoxypolyethylene glycol monoacrylate, ethoxypolyethylene glycol monoacrylate, glycerol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate,
Tetramethylolmethanetetraacrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, β-hydroxyethyl methacrylate,
β-hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, methoxypolyethylene glycol monomethacrylate, ethoxypolyethylene glycol monomethacrylate, glycerol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, acrylamide, N-methylol acrylamide, n-butoxymethylacrylamide, isobutoxyacrylamide, n-t-butylacrylamide, methylenebis(acrylamide), ethylenebis(acrylamide), propylenebis(acrylamide), methacrylamide, N-methylolmethacrylamide, n-
Examples include butoxymethylmethacrylamide, isobutoxymethacrylamide, nt-butylacrylamide, methylenebis(methacrylamide), ethylenebis(methacrylamide), propylenebis(methacrylamide), and the like.

In the present invention, it is necessary to use an acrylic acid ester represented by formula (1) as all or a part of the above polymerizable monomer. The chemical structure of acrylic ester (I) is that at least one of R2 and R3 is an alkyl group or polyoxyalkylene group having a hydroxyl group, and R2 and R3 are a corresponding alkyl group or polyoxyalkylene group not having a hydroxyl group. It exhibits significantly higher sensitivity than when it is an oxyalkylene group. Lower alkyl or lower alkylene represented by each symbol in formula (r) preferably has no more than 5 carbon atoms, especially 1 to 3 carbon atoms.
It is desirable that it be within the range of . It is usually preferred that both nt and R3 are not hydrogen. Specific examples of the acrylic ester (1) include the following compounds.

CHt = CHC00CI(tCI((OH)C
I(t-N(CHzCHtOH)t (CH*=CHC00CH*CH(OH)CHz) -
N CHt CHt OH (CH* Two=CHC00CH1CHCO Summer ()CHt
)z -N CHt CI-I (OH) CH5(C
Hy=CHCOOCHtCH(OH)CHt)t-N(
CHtCHtO)sH CHt = C(CH3)COOC14t CH(O
H)-Ctl t N (CHt CH* OH)! (
CHz=C(CHt)COOCHtCH(OH)-CH
t ) t N CHt CH! OH(CH*MiC(
CI-13)CooCHtCH(OH)-CHy)zN
cHtc)Summer (OH)CH.

CH2= C(CH3) COOCHt CH(OH)
-CI-IJtN (CHtCr-(to)3H, etc.).

These acrylic esters (1) generally exhibit good solubility in water. Therefore, it is suitable for producing a water-developable resin plate material. In addition, when using this acrylic acid ester (1) in combination with other polymerizable monomers as described above, it goes without saying that a water-soluble monomer should be selected for the latter, but a water-insoluble monomer should also be selected for the latter. If the proportion used is relatively small, the resulting resin plate material can be made water-developable.

The above-mentioned acrylic ester (1) is, for example, an epoxide represented by the formula (wherein B is lower alkylene and R+ has the same meaning as above) and the formula: %formula%() (wherein R2 and R3 are It can be produced by reacting an amine represented by (same meaning as above) by a conventional method. For example, both may be mixed in the presence of an appropriate inert solvent if necessary, and maintained at a temperature of about 0 to 100°C for several minutes to several hours. In this case, if necessary, a catalyst (eg, hydrochloric acid, perchloric acid, aluminum chloride, tin chloride) may be used to promote the reaction.

A specific polymerizable monomer may be selected by considering compatibility depending on the type of polymer used. If necessary, an appropriate solvent,
For example, high-boiling alcohols (e.g. ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, butanediol, trimethylolpropane, tetramedyloethane, glycerol,
jetanol) may be blended.

When acrylic ester (1) and other compounds having polymerizable double bonds are used together as polymerizable monomers, there is no particular restriction on the amount of the compound having polymerizable double bonds; As the amount increases, the sensitivity of the photosensitive resin composition itself tends to decrease, so the amount of the compound having a polymerizable double bond is usually 95% by weight or less based on the weight of the total polymerizable monomer. It is preferably adjusted to 80% by weight or less, more preferably 50% by weight or less.

Although there are no particular restrictions on the type of photopolymerization initiator, aromatic ketones or a combination thereof with amines are usually used. Compounds having an aromatic ring and a ketone group in the molecule are used as aromatic ketones, and specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α
-Methylbenzoin, 2-methylanthraquinone, 9-
Fluorenone, benzyl, acetophenone, 2゜2゛-
Examples include dimethoxy-2-phenylacetophenone, benzophenone, phenyl-2-thenylketone, p-dimethylaminobenzophenone, p,p'-tetramethyldiaminobenzophenone, and the like. These compounds may optionally have a substituent such as a cyano group, nitro group, methoxy group, or sulfonic acid group. As the amine, common amines such as dimethatolamine, jetanolamine, and triethylamine can be used, but part or all of them can be replaced with the acrylic ester (r). That is, the acrylic ester (1) itself used as a polymerizable monomer may also serve as a photopolymerization initiator component. Rather, if deterioration of physical properties such as surface properties is expected due to the amine remaining in the resin composition after curing, it is preferable not to use an ordinary amine.

The photosensitive resin composition of the present invention may contain a polymer as an essential component depending on its intended use.

For example, when used as a coating material, it is common not to add a polymer,11 whereas when used as a printing plate material, a polymer is usually added.

As the polymer, partially saponified polyvinyl acetate, cellulose derivatives, polyethylene oxide, sodium polyacrylate, polyamide, etc. may be used.

The ratio of these essential components used is usually polymerizable motsuma-1
0.01 to 10 parts by weight of the photopolymerization initiator (aromatic ketone + amine) and 50 to 300 parts by weight of the polymer, and the ratio of the aromatic ketone and amine used as the photopolymerization initiator is molar. The ratio l=1 to 30, and part or all of the polymerizable monomer and/or the amine may be replaced with the acrylic ester (I).

When the acrylic acid ester (1) is used as a photopolymerization initiator component as well as a polymerizable monomer component, and when an ordinary amine is not used as an essential component of the photopolymerization initiator, the proportion of the essential component used is 0 to 500 parts by weight, preferably 50 to 15 parts by weight of polymerizable monomer per 100 parts by weight of polymerization initiator (aromatic ketone + acrylic ester (I))
0 parts by weight, 50-800 parts by weight of polymer, preferably 1
00 to 400 parts by weight, and the molar ratio of aromatic ketone and acrylic ester (1) used as a photopolymerization initiator is usually l:5 to 500, preferably 1:l 5 to 1.
May be 00.

In addition to the above essential ingredients, polymerization inhibitors (e.g. 2,6-di[-butyl-p-cresol, hydroquinone, p-methoxyphenol), dyes (e.g. rose bengal, eosin, methylene blue, malachite green), etc. may be added as necessary. May be blended.

The above-mentioned essential components and optional components are mixed by adding an appropriate liquid such as water or an organic solvent as necessary to obtain a photopolymerizable resin composition. However, since the acrylic acid ester (1) generally exhibits a liquid state with low viscosity, it is possible to formulate a liquid form of light that is easy to handle by blending a polymer, a photopolymerization initiator, and other appropriate optional components without necessarily using a solvent. It is also possible to prepare polymerizable resin compositions.

A highly sensitive resin plate material can be obtained by coating the photopolymerizable resin composition obtained here on a suitable support and drying to form a photosensitive film. Supports are usually metals (e.g. aluminum, zinc, iron), plastics (
For example, polyethylene terephthalate, polystyrene,
Polymethyl methacrylate, nylon, cellulose acetate, polyethylene, polypropylene, polycarbonate, polyacrylonitrile, polyvinyl chloride), glass, etc. are used. If necessary, the surface of these supports may be subjected to a pretreatment such as etching, electrolytic oxidation, or corona discharge, or a thin layer such as an adhesive layer or an antihalation layer may be provided.

In order to form an image using the highly sensitive resin plate material of the present invention, a conventional method may be employed.

For example, an image film (negative film or positive film) is brought into close contact with the surface of the high-sensitivity resin plate via an appropriate film or coating layer as required, and exposed. After exposure, an image can be formed by dissolving and removing the unexposed portions with a suitable developer.

Various active light sources can be used for exposure, such as medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, and ultraviolet fluorescent lamps. In addition, tungsten lamps, white fluorescent lamps, visible light lasers, etc. may be used.As the developer, depending on the type of photosensitive composition, water; acid;
Alkali, organic solvents, etc. may be used, but the use of water is particularly advantageous. As mentioned above, the acrylic ester (1) used in the present invention is water-soluble, so by selecting water-soluble components such as polymers and polymerizable monomers, water-developable photosensitivity can be achieved. It is possible to easily obtain a resin plate material of.

(Example) The present invention will be explained in more detail by giving examples below. However, the ``Department'' refers to the Heavy Equipment Department.

Reference example 1 Formula: (CHt=C(CH3)COOC)1tCH(OH
) -CHt)tNCHtCHtOH Preparation of acrylic ester (1) 2 moles of glycidyl methacrylate, 1 mole of ethanolamine and 2 moles of ethanol were mixed and stirred at 50°C. After reacting for about 8 hours, ethanol is removed under reduced pressure to obtain the title compound.

Reference example 2 Formula +(CH,=C(CH3)C00CH,Cl-1(O
H)-CH2)2N CHtCH(OH)CH3 Preparation of acrylic acid ester (1) 2 mol of glycidyl methacrylate, 1 mol of isopropanolamine and 2 mol of isopropanol are mixed, 60
The mixture was maintained at ℃ and stirred. After reacting for about IO hours, the isopropanol is removed under reduced pressure to yield the title compound.

Reference example 3 Formula: (CHt=C(CH3)COOCHtCH(OH)
-CH2), 100 parts of acrylic ester (I) represented by NCH, CH, OH and 3 parts of benzoin ethyl ether
A photosensitive resin composition was obtained by mixing the two parts.

This photosensitive resin composition was applied onto a tin plate using an applicator to form a coating film with a thickness of 500 μm. This coating film was irradiated with light from a 3KW high-pressure mercury lamp in the atmosphere from a distance of 70 cm, and the number of seconds until the coating film lost its tackiness was taken as a measure of curability. Curing time was 5 seconds.

Reference Example 4 As acrylic ester (1), the formula: (CH,=C-(
CHJC00CI(ICH(OH)CHt)tN C
The same operation as in Reference Example 3 was performed except that the compound represented by Ht-CH(Of-1)CH3 was used. The resulting photosensitive resin composition had a curability of 5 seconds.

Reference Example 5 The same procedure as in Reference Example 3 was carried out except that a compound represented by the formula: %Formula% CI-LCH(OH)CH3 was used as the acrylic ester (1). The resulting photosensitive resin composition had a curability of 5 seconds.

Reference Example 6 The same operation as in Reference Example 3 was performed except that a compound represented by the formula: %Formula%)) and N(CH,CH20)3H was used as the acrylic ester (1). The resulting photosensitive resin composition had a curability of 6 seconds.

Example! 100 parts of partially saponified polyvinyl acetate (average degree of polymerization 500, degree of saponification 80, 1 mol%) and 80 parts of pure water are mixed and dissolved in Nigu at a temperature of 90 to 95°C for 30 minutes.

After dissolving, the temperature in the tank was lowered to 60°C, and 0.06 part of p-methoxyphenol and 2°6-ditertiary-butyl-
0.14 parts of p-cresol, 3 parts of benzoin isopropyl ether and the formula +(CH2=C(CHs)COO
CHtCH(OH)-CI-12), NCH, CHmO
A mixture of 80 parts of acrylic ester (1) represented by H is added dropwise to the mixture over 40 minutes. The mixture obtained by degassing under reduced pressure was poured onto a treated iron plate with a thickness of 0.3 μm coated with an antihalation agent, a coin PVC sheet with a thickness of 0.5 mm was placed on the top surface, and the gap was filled in advance with the resin layer. It is passed through two rolls set to have a thickness of 0.7 mm and formed into a sheet. After cooling, the coin vinyl chloride sheet on the top surface is peeled off and dried for 40 minutes in a drying oven at 60° C. to obtain a photosensitive resin plate material.

A test negative film (150 lines, 3%, 5%, 10%, 20% halftone dots,
(diameter 100μ, 200μ independent point, width 40μ, 60μ thin line part) are vacuum-adhered, and a 3KW high-pressure mercury lamp is heated to 70cI.
Irradiated from a distance of I. The irradiation time was 1 second for surface exposure and 20 seconds for main exposure. The exposed plate material was developed by spraying neutral water at a temperature of 40° C. from a spray developing device at a pressure of 3 kg/cm 2 for 1 minute and 30 seconds. The unexposed area (uncured area) was eluted into water, and a relief was obtained. 3%
Good image reproducibility was observed with no dropout of fine parts such as halftone dots, independent points with a diameter of 100 μm, and thin lines with a width of 40 μm.

Example 2 The same procedure as in Example 1 was carried out except that 80 parts of acrylic acid ester (1) having the formula: %N(CH2C1-LOH) was used as the polymerizable monomer. The resulting relief has 3% halftone dots, diameter 10
Good image reproducibility was observed, with no dropout of minute parts such as 0μ independent points and 40μ thin lines.

Example 3 As a polymerizable monomer, the formula: (CHt = C(CHs) COOCH2CH(0
1()-CHe ) t N C) I t CH(OH
) The same procedure as in Example 1 was carried out except that 80 parts of acrylic ester (I) represented by CH3 was used. The obtained relief showed good image reproducibility, with no dropout of minute parts such as 3% halftone dots, independent dots with a diameter of 100 μm, and thin lines with a width of 40 μm.

Comparative Example 1 The same procedure as in Example 1 was carried out, except that 80 parts of a compound represented by the formula: CHJ t N CH * CHt CI-1s was used as the polymerizable monomer. The relief obtained has 10% halftone dots, diameter 2
It was observed that parts finer than 00μ independent points, 60μ thin lines, etc. fell off.

Comparative Example 2 The same operation as in Example 1 was carried out except that 80 parts of a compound represented by the formula: %Formula%()OCOC(CH3)=CHt)t was used as the polymerizable monomer. In the relief obtained, it was observed that parts finer than 10% halftone dots, independent dots with a diameter of 20 μm, and thin lines with a width of 60 μm were removed.

Comparative Example 3 60 parts of 2-hydroxyethyl methacrylate (trimethylolpropane trimethacrylate) as polymerizable monomers
The same procedure as in Example 1 was carried out except that 10 parts of trimethylolpropane triacrylate were used. In the obtained relief, drop-off was observed in areas finer than 20% halftone dots, independent dots with a diameter of 200 μm, and thin lines with a width of 60 μm.

(Effects of the Invention) As is clear from the above, the present invention is characterized in that acrylic ester (I) is used as at least a part of the polymerizable monomer component in the highly sensitive resin plate material. As a result, sensitivity to light in the atmosphere is significantly increased, and curing can be completed in a relatively short period of time. That is, by using the highly sensitive resin plate material of the present invention, it is possible to significantly improve the workability during image formation.

Claims (1)

[Claims] 1. In a photosensitive resin plate material having a photosensitive layer containing a polymer, a polymerizable monomer, and a photopolymerization initiator as essential components, at least a portion of the polymerizable monomer has the formula: ▲Mathematical formula, chemical formula , tables, etc. ▼ (In the formula, R^1 is hydrogen or methyl, R^2 and R^
3 are hydrogen, -A'-OH, -(A″O)_nH, respectively
or -A-OOC-R^1C=CH_2 (but R^
2 and R^3 are both hydrogen or -A-OO-C-R^1
It is never the case that C=CH_2. ), A, A' and A
" is a lower alkylene that may have a hydroxyl group, and n is an integer having 1 to 20 carbon atoms." A highly sensitive resin plate material characterized by using an acrylic ester represented by the following formulas. 2, R^2 and R^3 are not hydrogen. 3. The resin plate material according to claim 1, wherein the polymer is a water-soluble polymer. 4. The resin plate material according to claim 1, wherein the polymer is a water-soluble polymer. The resin plate material according to claim 3, which is partially saponified polyvinyl acetate. 5. The weight ratio of the polymer and the polymerizable monomer is 100:20.
200. The resin plate material according to claim 1, which has a particle size of 200 to 200. 6. The molar ratio of polymerizable monomer and photopolymerization initiator is 100:
The resin plate material according to claim 1, which has a molecular weight of 0.01 to 10.