JP2003302756A - Photosensitive resin composition, photosensitive resin printing plate precursor using the same, and printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition using an epoxy monomer or an epoxy ester monomer as a photopolymerizable monomer, giving a sharp relief image and substantially free from chlorine. <P>SOLUTION: The photosensitive resin composition comprises (A) a soluble polymer, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, wherein one or more (B1) epoxy monomers or (B2) epoxy ester monomers are contained as the photopolymerizable monomer (B) and the organic chlorine concentration (AOX) of the composition is ≤20 ppm. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition,
Regarding a photosensitive resin original plate and a printing plate using the same, more specifically, a photosensitive resin composition for producing a relief plate for printing,
The present invention relates to a photosensitive resin original plate and a relief plate for printing using the same. In particular, it relates to a photosensitive resin original plate that can be developed with water or alcohol.

[0002]

2. Description of the Related Art A photosensitive resin composition used for a relief plate for printing generally contains a soluble polymer, a photopolymerizable monomer and a photopolymerization initiator as essential components, and if necessary, a stabilizer and a plasticizer. Additives such as

These photosensitive resin compositions are irradiated with an actinic ray through a negative film (or a positive film) having a transparent image area to cure the photosensitive layer in the exposed area, and then the photosensitive layer in the unexposed area is appropriately exposed. By dissolving and removing with a solvent,
It is widely known to make relief or flexographic plates for printing.

As a photopolymerizable monomer which is one component of the photosensitive resin composition, for example, an epoxy monomer having an epoxy ring such as glycidyl (meth) acrylate, an epoxy compound and a carboxylic acid such as (meth) acrylic acid. It is well known to use so-called epoxy ester monomers in which and are ring-opened.

Epoxy monomers and epoxy ester monomers have good compatibility with soluble polymers used as binders for developing water or alcohol development, and can suppress turbidity of the photosensitive resin composition to a low level.
You can get a sharp image.

Most of such epoxy monomers and epoxy ester monomers are synthesized by using epichlorohydrin as a starting material. For example, the synthetic reaction of glycidyl methacrylate is a two-step reaction in which the carboxyl group of methacrylic acid is ring-opened and added to the epoxy ring of epichlorohydrin, hydrogen chloride is eliminated and the ring is closed, and the epoxy ring is formed again. In this synthetic method, a product in which the reaction has not progressed to the second stage, that is, a monomer in which chlorine has not been eliminated is mixed in a considerable proportion, and it is also difficult to completely isolate it by distillation. Further, the epoxy ester monomer obtained by ring-opening addition of a carboxylic acid and an epoxy compound having an epoxy ring often uses epichlorohydrin as a raw material of the epoxy compound,
It has the same problems as the epoxy monomer.

If the photosensitive resin composition contains bound chlorine, chlorine will be contained in chips and used relief plates produced in the process of manufacturing the printing plate precursor. When incinerating chlorine-containing substances, it is necessary to completely combust at high temperature in order to suppress the generation of Dioshikin, and the chlorine gas concentration generated at that time is also regulated by law (according to the Air Pollution Control Law Enforcement Regulation
0mg / m ³ = 10ppm, according to the Minister stipulated values based on the specific chemical substances obstruction prevention regulations 3 mg / m ³ =
1 ppm).

Similarly, the developing waste liquid produced when the relief plate is produced also contains chlorine. There is currently no regulation in Japan for chlorine concentration in wastewater, but in Heisei 2
In order to suppress the generation of dioxins in the bleached kraft pulp and dissolving pulp manufacturing process,
It has established a voluntary target value to reduce the concentration of organic chlorine (AOX) in factory wastewater to 1.5 kg / pulp ton or less. In addition, Germany, which is an environmentally advanced country, is subject to laws and regulations (organic chlorine concentration is 1 ppm or less), and there is a possibility that Japan will also be subject to regulations.

The photosensitive resin composition having a low chlorine content contains an epoxy monomer or an epoxy ester monomer and has a chlorine content of 0.2% by weight (2000 pp).
m) The following photosensitive resin compositions have been proposed (for example, refer to Patent Document 1-2). However, with these values, the chlorine concentration of the waste liquid containing 5% of the photosensitive resin composition is 1 at maximum.
The value is 00 ppm, which is far below the German regulation value of 1 ppm.

[0010]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-194781 (page 1-2)

[0011]

[Patent Document 2] Japanese Patent Laid-Open No. 2002-182382 (page 1-2)

[0012]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above problems, and an object thereof is to provide a photosensitive resin composition using an epoxy monomer or an epoxy ester monomer as a photopolymerizable monomer. Thus, a sharp relief image is obtained, and a photosensitive resin composition that is substantially chlorine-free is provided.

[0013]

The photosensitive resin composition of the present invention mainly has the following constitution in order to solve the above problems. That is, “(A) a soluble polymer, (B) a photopolymerizable monomer and (C) a photopolymerization initiator-containing photosensitive resin composition, wherein (B) the photopolymerizable monomer is 1
A photosensitive resin composition containing at least one kind of (B1) epoxy monomer or (B2) epoxy ester monomer and having an organic chlorine concentration (AOX) of 20 ppm or less.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

The present invention is characterized in that the photosensitive resin composition has an organic chlorine concentration (AOX) of 20 ppm or less. In this case, the developing waste liquid containing 5% of the photosensitive resin composition has an AOX of 1 ppm or less. In order to suppress the AOX of the photosensitive resin composition to 20 ppm, AO as a simple substance
A component having a low X, preferably 40 ppm or less, is used.
Add only trace amounts of high AOX components.

The organic chlorine concentration (AOX) referred to in the present invention means the concentration of chlorine to which a chlorine atom is covalently bound, such as polyvinyl chloride, and does not include ionic free chlorine such as sodium chloride. What is AOX? Absorbable Organic
It is an abbreviation for Halogen and is also referred to as an adsorptive organic halogen, but in the present invention, it is used as an organic chlorine concentration. Other chlorine concentrations include total chlorine concentration and free chlorine concentration, and each concentration satisfies the following equation (1). The free chlorine concentration is an ionic bond chlorine concentration, and for example, chlorine in an inorganic halogen compound is applicable. (Total chlorine concentration) = (AOX) + (free chlorine concentration) (1) The total chlorine concentration is measured by the combustion method / coulometric titration method.
The total chlorine concentration is measured by subjecting a sample to thermal decomposition in an argon stream and hydrogen chloride produced by burning in an oxygen stream in an electrolyte solution by coulometric titration. As a commercially available measuring instrument, a trace chlorine measuring device "TS-300CL type" (Co., Ltd.)
(Dia Instruments), chlorine / sulfur analyzer "T
OX-100 type "(manufactured by Dia Instruments Co., Ltd.)
Is mentioned. Generally, silver is often used as the titrant, and the titration is performed according to the following reaction formula (2). HCl + Ag ⁺ → H ⁺ + AgCl ↓ (2) AOX is measured by a combustion method / coulometric titration method using activated carbon. First, the sample is adsorbed on activated carbon and then immersed in a nitrate solution to remove free chlorine. AOX is measured by burning the adsorbed activated carbon and similarly performing coulometric titration. As a commercially available measuring instrument, there is a chlorine / sulfur analyzer “TOX-100” (manufactured by Dia Instruments Co., Ltd.) in which an adsorption device “TXA-03 type” is combined.

Usually, AOX requires a sample whose main component is water such as river water or lake water, and cannot be measured in a solid state. Since the photosensitive resin composition is usually a sheet-like solid or a liquid with high viscosity and contains almost no water, the AOX of the photosensitive resin composition in the present invention is measured by the indirect method described below. It That is, the photosensitive resin composition is dissolved or swollen in water to prepare a developing waste liquid containing 5% of the composition, and the value is calculated back from the AOX measurement value of the developing waste liquid. For example, if the AOX of the developing waste liquid is 1 ppm, the AOX of the photosensitive resin composition is calculated to be 20 ppm. Monomeric AOX is also indirectly measured.

Although the free chlorine concentration can be measured by an ion chromatogram, the total chlorine concentration and the A
It can also be calculated from the difference in OX.

Since the total chlorine concentration requires less labor than that of AOX and the value of AOX or more is obtained from the above formula (1), the total chlorine concentration may be used as the chlorine concentration measurement object. When the total chlorine concentration of the photosensitive resin composition is 20 ppm or less, the AOX of the photosensitive resin composition is necessarily 20.
It is because it becomes below ppm.

Each component of the photosensitive resin composition of the present invention will be described.

In the present invention, the (A) soluble polymer is a polymer soluble in any solvent such as water, an aqueous acid solution, a lower aliphatic alcohol or a mixture thereof, and examples thereof include soluble polyamide and polyvinyl alcohols. To be

Soluble polyamide refers to JP-A-48-72.
Polyamide containing sulfonic acid group or sulfonate group obtained by copolymerizing sodium 3,5-dicarboxybenzene sulfonate as shown in JP-A-250, shown in JP-A-49-43465. A polyamide having an ether bond, which is obtained by copolymerizing any one of a dicarboxylic acid having an ether bond in the molecule, a diamine, or a cyclic amide, as disclosed in JP-A-50-7605. Such as N, N′-di (γ-aminopropyl) piperazine and the like, and a basic nitrogen-containing polyamide obtained by copolymerization, and a polyamide obtained by quaternizing these polyamides with acrylic acid or the like. 55-74537, a copolymer containing a polyether segment having a molecular weight of 150 to 1500 If polyamides, and alpha-(N,
Examples thereof include polyamides obtained by ring-opening copolymerization of N-dialkylamino) -ε-caprolactam.

The vinyl alcohols include fully saponified polyvinyl acetate, partially saponified polyvinyl alcohol, and unsaturated groups at the hydroxyl groups of completely saponified polyvinyl acetate and partially saponified polyvinyl acetate as disclosed in JP-A-3-274558. Denatured polyvinyl alcohol to which a compound having a compound is added, a hydroxyl group of completely saponified polyvinyl acetate or partially saponified polyvinyl acetate as shown in JP-A-4-283749 is reacted with an acid anhydride to add a carboxyl group to a side chain. Modified polyvinyl alcohol. The polyvinyl acetate used as a starting material for the polyvinyl acetate and the modified polyvinyl alcohol preferably has a saponification degree of 60% to 100% from the viewpoint of developability.

The content of the (A) soluble polymer in the photosensitive resin composition is preferably 30 to 80% by weight, more preferably 50 to 70% by weight. If the content is less than 30% by weight, the composition tends to cold flow, and the physical properties of the image may deteriorate. On the contrary, 80% by weight
If it exceeds the range, the sensitivity may be lowered or the developing time may be prolonged. Further, the cross-linking density may be low, and the water resistance and solvent resistance of the image may be lowered.

In the present invention, the (B) photopolymerizable monomer is a monomer containing at least one photopolymerizable unsaturated group in the molecule, and is at least one or more (B1) epoxy monomer or (B2). ) It is necessary to include an epoxy ester monomer in the photosensitive resin composition. The (B1) epoxy monomer and the (B2) epoxy ester monomer have good compatibility with the (A) soluble polymer, the transparency of the photosensitive resin composition is high, and a sharp image can be obtained. (B1) epoxy monomer and (B
2) Epoxy ester monomer has an organic chlorine concentration of 40 pp
It is preferable to use those having a size of m or less. When the organic chlorine concentration of the photopolymerizable monomer is more than 40 ppm, the organic chlorine concentration of the entire photosensitive resin composition is 2 depending on the amount of addition.
This is because there are many cases where it exceeds 0 ppm.

The (B1) epoxy monomer referred to in the present invention is a monomer having an epoxy ring in its structure, and for example, glycidyl acrylate (acrylic acid glycidyl ester), glycidyl methacrylate (methacrylic acid glycidyl ester), maleic acid glycidyl ester, malein. Examples thereof include acid diglycidyl ester, fumaric acid glycidyl ester, and fumaric acid diglycidyl ester.

(B1) As a method for producing an epoxy monomer, a method in which a carboxylic acid monomer such as (meth) acrylic acid and an epichlorohydrin are subjected to an addition reaction is generally used, and a commercially available product "Blenmer G" (manufactured by NOF Corporation) , Glycidyl methacrylate). The epoxy ester produced by this production method contains a large amount of by-products having in its structure organic chlorine due to epichlorohydrin as a raw material, and the organic chlorine concentration in most cases exceeds 1000 ppm. On the other hand, the esterification product obtained from the carboxylic acid monomer and glycidol does not use chlorine-containing epichlorohydrin as a starting material, and therefore chlorine is not included in the structure of the product, and a substantially chlorine-free monomer is obtained. As a commercially available product of the epoxy monomer produced by this method, "Blenmer GS" (manufactured by NOF CORPORATION, glycidyl methacrylate, total chlorine concentration: 10 ppm or less) can be mentioned. Another method is to modify the ethylenic double bond into an epoxy ring by the peracetic acid method. In the present invention, as the (B1) epoxy monomer, it is preferable to use the above substantially chlorine-free epoxy monomer.

The (B2) epoxy ester monomer referred to in the present invention is a structure obtained by ring-opening addition of a carboxylic acid and the above-mentioned (B1) epoxy monomer, or a ring-opening addition of a carboxylic acid monomer and a glycidyl ether (or ester). It is a monomer having a different structure, and there is no epoxy ring in the structure, and a hydroxyl group is newly generated. Examples include (meth) acrylic acid adducts of glycidyl (meth) acrylate, succinic acid adducts of glycidyl (meth) acrylate, (meth) acrylic acid adducts of glycidyl phthalate esters, and (poly) ethylene glycol diglycidyl ester Examples thereof include (meth) acrylic acid adducts, (poly) ethylene glycol diglycidyl ether (meth) acrylic acid adducts, and bisphenol A diglycidyl ether (meth) acrylic acid adducts.

In the production of the (B2) epoxy ester monomer, it is preferable to use glycidol as the raw material of the reaction product epoxy monomer, glycidyl ether, or glycidyl ester, without using epichlorohydrin. For example, glycerin dimethacrylate is obtained by an addition reaction of the above-mentioned "Blenmer GS" (total chlorine concentration: 10 ppm or less) and methacrylic acid, and a commercially available product of the production method is "Blenmer GMR-R" (NOF Corporation).
Manufactured, total chlorine concentration: 10 ppm or less). Further, esterification of methacrylic acid and glycerin gives a product having a similar structure and containing substantially no bound chlorine.

Starting from epichlorohydrin (B
1) An epoxy monomer is a two-step reaction in which the production reaction is a ring-opening addition and a ring-closing elimination, and a large amount of chlorine-containing by-products is contained. The same applies to the (B2) epoxy ester monomer produced based on (B1). Generally, when a chlorine atom is introduced into a compound, it has a property that the refractive index of the compound increases. When substances having different refractive indices are mixed, light scattering is likely to occur, and when such a photosensitive resin composition is photocured, it becomes difficult for actinic rays to go straight, and the resulting image relief becomes less sharp. The previous studies have revealed that the presence of a chlorine-containing by-product has a great influence on the sharpness of the image relief formed. The (B1) epoxy monomer and the (B2) epoxy ester monomer starting from glycidol do not contain chlorine-containing by-products like the monomer starting from epichlorohydrin, and have almost a single structure. Is obtained. By using the monomer of such a production method, light scattering in the photosensitive resin composition can be reduced, and the relief printing plate can obtain a sharp image.

Either one of (B1) epoxy monomer and (B2) epoxy ester monomer may be used, or both may be mixed and used. The total content of (B1) and (B2) with respect to the entire photopolymerizable monomer (B) is preferably 5% by weight to 100% by weight.
When the total of (B1) and (B2) is 5% by weight with respect to (B), the compatibility with the (A) soluble polymer is exhibited.

The content of these (B) photopolymerizable monomers in the photosensitive resin composition is preferably 5 to 60% by weight, more preferably 15 to 40% by weight. The content is 5
When the content is 60% by weight, a good image can be obtained because the curing rate by photopolymerization is sufficient. On the contrary, when the content is 60% by weight or less, the curing shrinkage ratio does not increase and the physical properties of the image do not deteriorate. . Further, the AOX of the photosensitive resin composition is 20.
It does not exceed ppm.

In the present invention, as the photopolymerization initiator (C), conventionally known ones can be used, and examples thereof include benzophenones, acetophenones, benzyls, benzoin alkyl ethers, benzyl alkyl ketals, and anthraquinone. And thioxanthones. Specific examples include benzophenone, benzoin, acetophenone, benzoin methyl ether, benzyl dimethyl ketal, anthraquinone and the like. In the present invention, when the photopolymerization initiator is a chlorine-containing compound (for example, 2-chloroanthraquinone), it should be avoided that at least the amount thereof is used.

The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.05 to 5% by weight, more preferably 0.1 to 2% by weight. The content is 0.05% by weight
When it is above, photopolymerization is likely to start, and conversely, when it is 5% by weight or less, photopolymerization in the thickness direction of the photosensitive layer using the composition is not deteriorated, and the exposed photosensitive area is easily chipped. There is no.

In the photosensitive resin composition of the present invention, 0.001 of hydroquinone, hydroquinone monomethyl ether, 2,6-t-butyl-p-cresol and the like are used as stabilizers.
You may contain 1-5weight%. Further, as a plasticizer, a low molecular weight plasticizer such as ester or amide, an oligomer such as polyesters, polyethers or liquid rubbers is contained,
It is also possible to change the physical properties of the photocured product. Further, known dyes and pigments are added to color the photosensitive resin composition,
The exposed image area can be made clear.

The photosensitive resin composition of the present invention is prepared by dissolving (A) a soluble polymer in a suitable solvent, adding (B) a photopolymerizable monomer and (C) a photopolymerization initiator, and stirring the mixture sufficiently. To obtain a solution of the composition and remove the solvent from the solution.

The photosensitive resin composition of the present invention can be obtained by a known method such as hot pressing, casting, melt extrusion, solution casting, or the like, which is a sheet-shaped photosensitive resin printing plate precursor having a desired thickness. Can be Further, the sheet-like material may be laminated on a support with or without a known adhesive to form a photosensitive layer. As the support, any material such as steel, aluminum, glass, a plastic film such as a polyester film, and a metal-deposited film can be used.

In the case of a photosensitive resin printing plate precursor (raw plate) comprising a photosensitive layer and a support, a protective layer is laminated on the photosensitive layer. In the protective layer, a film-shaped plastic, for example, a polyester film having a thickness of 100 μm, on which a film having a thickness of 1 to 3 μm, which is transparent and has no adhesion and is dispersible or soluble in a developer, is formed. Is used.
By laminating the film having this thin coating on the photosensitive resin printing plate precursor such that the coating contacts the photosensitive layer, even when the surface adhesion of the photosensitive layer is strong,
The plastic film can be easily peeled from the photosensitive resin printing plate precursor before the exposure operation.

In the photosensitive resin printing plate precursor of the present invention, a negative film or a positive film having a transparent image portion is closely adhered on the photosensitive layer, and an actinic ray is irradiated from above to perform exposure. , The exposed part is hardened and becomes insoluble. A light source such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp or the like having a wavelength of 300 to 400 nm as the center is usually used as the actinic ray.

After the exposure, a suitable solvent, preferably water, particularly neutral water is used as a solvent to dissolve and remove the non-exposed portion, whereby rapid development is carried out in a short time, and a printing plate (relief plate) is obtained. can get. As a developing system, it is preferable to use a spray developing device, a brush developing device, or the like.

[0041]

EXAMPLES The present invention will be described in more detail below with reference to examples. Parts in the examples mean weight.

For the measurement of the total chlorine concentration in the photopolymerizable monomer and the photosensitive resin composition, 20 mg of a sample was prepared and the above-mentioned "TOX-100 type" was used as a measuring device.
(Manufactured by Dia Instruments Co., Ltd.).

The developing waste liquid containing 5% of the photosensitive resin composition is about 10 g of the photosensitive resin composition and 19
Double the weight of RO water
C-2200 type "(manufactured by Toray Industries, Inc.) was added to a flask and stirred well to obtain. If the dissolution or dispersion was insufficient, a photosensitive resin composition with a spatula was used. While crushing, the mixture was stirred.

The AOX measurement is carried out by the adsorption device "TXA-0".
Activated carbon for AOX measurement using 3 "(manufactured by Mitsubishi Chemical Corporation)
20m at approximately 3.3m / min to the column packed with
After passing 1 time to adsorb the organochlorine compound, a nitrate solution was passed through to remove the inorganic halogen compound by flowing out to prepare a sample, which was analyzed using "TOX-100 type". The AOX of the developing waste liquid containing 5% of the photosensitive resin composition is calculated from the measured AOX value of the waste liquid based on the measured AO value of the RO water used for the waste liquid.
It was determined by subtracting the X value. AOX of photopolymerizable monomer
Was determined by subtracting the measured AOX value of RO water from the measured AOX value of the 5% RO aqueous solution or the RO dispersion, and multiplying it by 20. The AOX of the photosensitive resin composition was determined by multiplying the AOX value of the developing waste solution containing 5% of the above composition by 20 times.

<Example 1> 62 parts of ε-caprolactam,
38 parts of nylon salt of N- (2-aminoethyl) piperazine and adipic acid and 100 parts of water were put into a stainless steel autoclave, and the air inside was replaced with nitrogen gas 5 times, and then heated at 180 ° C. for 1 hour. . Then, the reaction temperature was raised to 240 ° C. for 45 minutes to gradually remove the distilled water, and the mixture was further heated for 2 hours while flowing nitrogen gas at a flow rate of 20 ml / min to obtain polyamide-1.

A flask containing 106 parts of diethylene glycol, 182 parts of glyidol and 20 parts of 50% sulfuric acid was reacted for 3 hours while heating at 150 ° C., and 2% NaOH was added.
Neutralized with. The reaction product was purified by distillation under reduced pressure to obtain diethylene glycol diglycidyl ether-1.

Polyamide-1: 55.0 parts, N-ethyltoluenesulfonic acid amide: 7.7 parts, 1,4-naphthoquinone: 0.02 parts, 2,4-diaminoazobenzene:
0.03 parts, methanol: 50.0 parts and RO water: 1
0 part was mixed at 60 ° C. for 2 hours in a heating disintegrator with stirring to completely dissolve the polymer, and then an acrylic acid adduct of diethylene glycol diglycidyl ether-1: 30.
1 part (total chlorine concentration: 10 ppm or less), methacrylic acid:
3.1 parts, itaconic acid: 0.1 part, hydroquinone monomethyl ether: 0.1 part, ammonium sulfite: 13
Parts and benzyl dimethyl ketal: 1.0 part were added and dissolved for 30 minutes. Next, the temperature was gradually raised to distill off methanol and water, and the mixture was concentrated until the temperature inside the kettle reached 110 ° C. At this stage, a viscous photosensitive resin composition having fluidity was obtained. The total chlorine concentration and AOX of the composition are 5 p
It was pm or less.

Copolyester (Vylon RV-30
A 180 μm-thick polyester film having a 15 μm-thick coating film made of a reaction product of 0SS, Toyobo Co., Ltd., polyfunctional isocyanate (Coronate L, Nippon Polyurethane Co., Ltd.) and a brown dye. Then, the above-mentioned photosensitive resin composition was cast on the film-formed surface of the support to form a photosensitive layer. A 125 μm-thick polyester film having a 2 μm-thick polyvinyl alcohol (AH-24, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) film was exposed to light using a laminator so that the film side was in contact with the photosensitive layer. The layers were laminated on each other to obtain a sheet-shaped laminate having a total thickness of 1080 μm. This laminate solidified into a rigid plate at room temperature. After 24 hours, this laminate was heated at 103 ° C. for 3 minutes to obtain a photosensitive resin printing plate precursor (raw plate).

After storing this raw plate for 7 days or more, 125
The polyester film of μm was peeled off, a test negative film (a gray scale negative film for sensitivity measurement and a negative film of an image for image reproducibility evaluation) was brought into vacuum contact, and exposed for 40 seconds with an ultra-high pressure mercury lamp. Then, using tap water as a developing solution and using a brush type washer (100 μmφ nylon brush, JW-A2-PD type manufactured by JEOL Ltd.) for 2 minutes at 23 ° C., a relief image could be obtained. . After further drying with warm air at 60 ° C. for 5 minutes, the relief plate exposed for 30 seconds with an ultra-high pressure mercury lamp was evaluated.
Gray scale is 16 steps, image area is 3% halftone dot, 100μ
m independent points and 30 μm thin lines were reproduced. Also, 30
The relief depth of 0 μm slit width was 81 μm.
It was confirmed that the sensitivity was high and the image reproducibility was excellent.
As a result of a printing test using this relief plate, a sharp printed matter without thickening of the image was obtained, and no damage to the relief was observed even after printing 20,000 copies. The photosensitive resin composition and its relief could be sent to incineration. A developer waste solution containing 5% of the composition is AOX.
Was less than 1 ppm, and the wastewater did not require any special treatment.

Comparative Example 1 In Example 1, instead of the acrylic acid adduct of diethylene glycol diglycidyl ether-1, "Denacol EX-850" (manufactured by Nagase Chemical Industry Co., Ltd.), epichlorohydrin was used as a starting material. Diethylene glycol diglycidyl ether)
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the acrylic acid adduct (AOX: 3200 ppm) was used (AOX: 980 ppm). Then, a photosensitive resin printing plate precursor was prepared in the same manner as in Example 1. 300
The image reproducibility was the same as in Example 1 except that the relief depth of the μm slit width was 70 μm, which was slightly low.
OX is high and the AOX of the developing waste liquid containing 5% of the photosensitive resin composition is 49 ppm (that is, the AOX of the composition is 9
It was 80 ppm), and draining it as it was was not preferable in terms of environmental hygiene.

<Example 2> ε-caprolactam 55.0
Parts, N, N'-bis (γ-aminopropyl) piperazine adipate 40.0 parts, 1,3-bisaminomethylcyclohexane adipate 7.5 parts and water 100 parts were placed in a reactor and subjected to sufficient nitrogen substitution. After that, it was sealed and gradually heated. From the time when the internal pressure reached 10 kg / cm 2, water in the reactor was gradually distilled off and returned to normal pressure in 1 hour, and then the reaction was carried out at normal pressure for 0.5 hour. The maximum polymerization temperature was 210 ° C. A transparent pale yellow polyamide-2 having a melting point of 140 ° C. and a specific viscosity of 1.83 was obtained.

After stirring 111 parts of glydidol and 11 parts of 98% concentrated sulfuric acid in a flask equipped with a reflux condenser for several minutes, 74 parts of phthalic anhydride was added, and the mixture was reacted at 105 ° C. to 110 ° C. for 6 hours while stirring. , The oil layer was separated, and unreacted glycidol was removed. Wash the remaining liquid with water,
The solution was neutralized with a 2% aqueous solution of NaOH and purified by distillation under reduced pressure to obtain phthalic acid diglycidyl ester-1.

Polyamide-2: 55.0 parts, N-ethyltoluenesulfonic acid amide: 5.0 parts, 1,4-naphthoquinone: 0.03 parts, methanol: 50.0 parts and R
O water: 10 parts was mixed at 60 ° C. for 2 hours in a heating disintegrator with stirring to completely dissolve the polymer, and then acrylic acid adduct of phthalic acid diglycidyl ester-1: 34.7 parts (total: Chlorine concentration: 5 ppm or less, AOX: 5 ppm or less), methacrylic acid: 2.9 parts, "Blenmer GS"
(Glycidyl methacrylate starting from glycidol, manufactured by NOF CORPORATION, total chlorine concentration: 10 ppm or less): 1.0
Part, hydroquinone monomethyl ether: 0.1 part, ammonium sulfite: 0.3 part, oxalic acid: 0.1 part and benzyl dimethyl ketal: 1.0 part, and added 30
Dissolved for minutes. Next, the temperature was gradually raised to distill off methanol and water, and the mixture was concentrated until the temperature inside the kettle reached 110 ° C. At this stage, a viscous photosensitive resin composition having fluidity was obtained. The total chlorine concentration and AOX were 10 ppm or less.

Copolyester (Vylon RV-30
A 180 μm-thick polyester film having a 15 μm-thick coating film made of a reaction product of 0SS, Toyobo Co., Ltd., polyfunctional isocyanate (Coronate L, Nippon Polyurethane Co., Ltd.) and a brown dye. Then, the above-mentioned photosensitive resin composition was cast on the film-formed surface of the support to form a photosensitive layer. A 125 μm-thick polyester film having a 2 μm-thick polyvinyl alcohol (AH-24, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) film was exposed to light using a laminator so that the film side was in contact with the photosensitive layer. The layers were laminated on each other to obtain a sheet-shaped laminate having a total thickness of 1080 μm. This laminate solidified into a rigid plate at room temperature. After 24 hours, this laminate was heated at 103 ° C. for 3 minutes to obtain a photosensitive resin printing plate precursor (raw plate).

A test negative film similar to that used in Example 1 was irradiated with a chemical lamp for 3 minutes to obtain a relief plate in the same manner as in Example 1. This relief plate was
As a result of the same evaluation as in Example 1, the gray scale was 15
2% halftone dots, 100 μm independent dots, and 30 μm fine lines were reproduced in the step and image areas. The relief depth of the 300 μm slit width was 86 μm. It was confirmed that the sensitivity was high and the image reproducibility was excellent. As a result of a printing test using this relief plate, a sharp printed matter without an image thickening was obtained, and no damage to the relief was observed even after printing 50,000 copies. The photosensitive resin composition and its relief could be sent to incineration. Further, the developing waste liquid containing 5% of the composition has an AOX of less than 1 ppm,
The wastewater did not require any special treatment.

Comparative Example 2 74 parts of phthalic anhydride, 129 parts of epichlorohydrin, and 2 parts of trimethylammonium chloride were reacted in a flask equipped with a reflux condenser at 80 ° C. to 90 ° C. for 6 hours with stirring to give an oil layer. Then, unreacted epichlorohydrin was removed. The residual liquid was washed several times with water, neutralized with a 2% NaOH aqueous solution, and purified by distillation under reduced pressure to obtain phthalic acid diglycidyl ester-2.

In Example 2, instead of the acrylic acid adduct of phthalic acid diglycidyl ester-1, the acrylic acid adduct of phthalic acid diglycidyl ester-2 (AO
X: 3700 ppm) instead of "Blemmer GS", "Blenmer G" (glycidyl methacrylate starting from epichlorohydrin, manufactured by NOF CORPORATION, AOX: 54)
A photosensitive resin composition was obtained in the same manner as in Example 2 except that it was used (AOX: 1300p).
pm). Then, a photosensitive resin printing plate precursor was prepared in the same manner as in Example 1. The image reproducibility was the same as in Example 2 except that the relief depth of the 300 μ slit width was 82 μm, which was rather low, but the AOX of the developing waste liquid containing 5% of the photosensitive resin composition was high, and the AOX was 65 ppm ( That is, the AOX of the composition is 1300 ppm),
It was unfavorable to drain the water as it was in terms of environmental hygiene.

Example 3 In Example 2, instead of the acrylic acid adduct of phthalic acid diglycidyl ester-1, "Blemmer GMR-R" (methacrylic acid adduct of glycidyl methacrylate starting from glycidol, NOF ( AOX: 10 ppm or less) manufactured by K.K.) was used to obtain a photosensitive resin composition by the same method as in Example 2 (AOX: 10 ppm or less).

Then, in the same manner as in Example 1, a photosensitive resin printing plate precursor was obtained. The same test negative film as in Example 1 was used to irradiate with a chemical lamp for 3 minutes to obtain a relief plate in the same manner as in Example 1. The relief plate was evaluated in the same manner as in Example 1 to obtain a gray scale. , 16%, 2% halftone dots, 100 μm independent points, and 30 μm fine lines were reproduced in the image area. Also, 300 μm
The relief depth of the slit width was 76 μm. It was confirmed that the sensitivity was high and the image reproducibility was excellent. As a result of a printing test using this relief plate, a sharp printed matter without an image thickening was obtained, and no damage to the relief was observed even after printing 50,000 copies. The photosensitive resin composition and its relief could be sent to incineration.
Further, the developing waste liquid containing 5% of the photosensitive resin composition is AO.
X was less than 1 ppm, and the wastewater did not require any special treatment.

Comparative Example 3 In Comparative Example 2, instead of the acrylic acid adduct of phthalic acid diglycidyl ester-1, "Blenmer GMR" (methacrylic acid adduct of glycidyl methacrylate starting from epichlorohydrin, NOF Corporation). Manufactured by AOX: 4200 ppm) was used to obtain a photosensitive resin composition by the same method as in Example 2 (AOX: 1460 ppm). Then Example 1
A photosensitive resin printing plate precursor was prepared in the same manner as in. Thirty
The image reproducibility was similar to that of Example 3, except that the relief depth of the 0 μm slit width was 72 μm, which was rather low.
The AOX of the developing waste liquid containing a high AOX and 5% of the photosensitive resin composition was 73 ppm (that is, the AOX of the composition was 1460 ppm), and draining as it was was not environmentally friendly.

<Example 4> Acrylonitrile was added to both ends of polyethylene glycol having a number average molecular weight of 600, and the resulting mixture was reduced with hydrogen to obtain an equimolar salt of α, ω-diaminopolyoxyethylene and diadipic acid: 60 Parts by weight,
ε-caprolactam: 20 parts by weight and equimolar salt of hexamethylenediamine and adipic acid: 20 parts by weight are melt-polymerized to obtain a relative viscosity (1 g of the polymer is chloral hydrate 1).
Viscosity measured at 25 ° C.): 2.50
Polyamide-3 was obtained.

Polyamide-3: 50 parts by weight, water: 34 parts by weight and ethanol: 22 parts by weight were placed in a three-necked flask equipped with a stirring spatula and a cooling tube, and heated at 90 ° C. for 2 hours while stirring. Then, polyamide-3 was dissolved. After cooling to 70 ° C., 1.5 parts by weight of “Blenmer GS” (glycidyl methacrylate starting from glycidol, manufactured by NOF CORPORATION, total chlorine concentration: 10 ppm or less) was added and stirred for 30 minutes. Furthermore, "Blenmer GMR-R" (methacrylic acid adduct of glycidyl methacrylate starting from glycidol, manufactured by NOF CORPORATION, total chlorine concentration: 10 ppm or less): 8 parts by weight, 2-acryloyloxyethyl-2-hydroxyethyl Phthalic acid "HOA-
MPE "(manufactured by Kyoeisha Chemical Co., Ltd., total chlorine concentration: 1500
ppm, AOX: 10 ppm or less, total chlorine concentration is derived from chloride ion): 24 parts by weight, polyethylene glycol "PEG # 400" (manufactured by Lion Corporation): 5 parts by weight,
N, N, N ', N'-tetra (2-hydroxy-3-metaacloyloxypropyl) -m-xylenediamine: 5 parts by weight, tetramethylolmethane triacrylate "NK ester A-TMM-3" (new Nakamura Chemical Co., Ltd.
Made, total chlorine concentration: 1200ppm, AOX: 10ppm
Hereinafter, the origin of the total chlorine concentration is chloride ion): 4 parts by weight,
"Irgacure 651" (benzyl dimethyl ketal,
1.3 parts by weight of Ciba-Geigy Co., Ltd. and 0.01 parts by weight of hydroquinone monomethyl ether were added and stirred for 30 minutes to obtain a photosensitive resin composition having fluidity.

"Vylon 31SS" (toluene solution of polyester resin, manufactured by Toyobo Co., Ltd.): 240 parts by weight are heated at 70 ° C. for 3 hours and then cooled to 30 ° C., ethylene glycol diglycidyl ether dimethacrylate: 5 parts by weight. And "UVA-933LP" (ethyl acetate solution of acrylic acid ester-based copolymer, produced by Yushisha Kogyo Co., Ltd.)
Manufactured): 29 parts by weight were added and mixed for 2 hours. further,
"Coronate 3015E" (ethyl acetate solution of polyvalent isocyanate resin, manufactured by Nippon Polyurethane Industry Co., Ltd.): 2
0 part by weight was added to obtain a first adhesive layer A coating liquid.

1,3,5-triacroyl-hexahydro-1,3,5-triazine: 3 parts by weight, 4-tert
-Butylcatechol: 0.05 parts by weight and "Ultramid 1C" (polyamide copolymer, manufactured by BASF Japan Ltd.): 51 parts by weight, methanol: 150 parts by weight,
"Solmix H-11" (alcohol mixture, manufactured by Nippon Alcohol Co., Ltd.): dissolved in a mixed solvent of 60 parts by weight and water: 23 parts by weight at 70 ° C. for 5 hours, and then triphenylphosphine: 1 part by weight , "AS-A" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): 0.02 parts by weight, "Nopco NX-Z"
(Manufactured by San Nopco Ltd.): 0.04 parts by weight, N, N,
N ', N'-tetra (2-hydroxy-3-metaacloyloxypropyl) metaxylene diamine: 42 parts by weight and "Irgacure 651" (benzyl dimethyl ketal, manufactured by Ciba Geigy): 4 parts by weight The mixture was added and mixed for 3 hours to obtain a second adhesive layer B coating liquid.

A coating liquid for the first adhesive layer A was applied onto a "Lumirror T60" (polyester film, manufactured by Toray Industries, Inc.) having a thickness of 250 μm by a bar coater so that the film thickness after drying was 20 μm, and the temperature was 180 ° C. In the oven for 3 minutes to remove the solvent, and then the second adhesive layer B coating liquid is applied on the first adhesive layer A by a bar coater so that the dry film thickness is 10 μm.
Dry in an oven at 0 ° C for 1 minute, then "Lumira" / first
Substrate-1 in which adhesive layer A / second adhesive layer B were laminated was obtained.

After exposing the substrate-1 from the second adhesive layer B side to 100 mJ / cm ² with an ultrahigh pressure mercury lamp, the photosensitive resin composition is cast on the second adhesive layer B side of the substrate-1 at 60 ° C. And dried in an oven for 4 hours to obtain a photosensitive resin sheet having a thickness of 950 μm in which “Lumirror” / first adhesive layer A / second adhesive layer B / photosensitive resin layer were sequentially laminated. The thickness of the photosensitive resin sheet was controlled by setting a spesser having a predetermined thickness on the substrate and scraping off the portion of the photosensitive resin composition protruding from the spesser with a horizontal metal scale or the like.

[Gausenol KL-05] (polyvinyl alcohol having a saponification degree of 78.5% to 82%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) on a 125 μm-thick “Lumirror S10” (polyester film, manufactured by Toray Industries, Inc.) A) water / ethanol mixed solvent (weight ratio: 4/6) solution) was applied by a bar coater to a dry film thickness of 1 μm, and the solution was placed in an oven at 120 ° C. for 30 seconds to remove the solvent. Polyamide-3 and "Gothenol KH-17" (polyvinyl alcohol having a saponification degree of 78.5% to 81.5%,
Mixture of Nippon Synthetic Chemical Industry Co., Ltd. (weight ratio: 8 /
The water / ethanol mixed solvent solution (weight ratio: 4/6) of 2) was applied by a bar coater so that the dry film thickness was 1 μm, and the solution was placed in an oven at 120 ° C. for 30 seconds to remove the solvent and form two layers. Cover film in which the polymer layer of
Got 1.

A water / ethanol mixed solvent (weight ratio: 7/3) was applied on the photosensitive resin layer of the photosensitive resin sheet with a bar coater # 20 to swell the photosensitive resin layer, and then a cover film- Roller pressure was applied so that the polymer layer of 1 and the photosensitive resin layer were in contact with each other to obtain a photosensitive resin printing plate precursor.

The same test negative film as in Example 1 was used to irradiate with a chemical lamp for 3 minutes to obtain a relief plate in the same manner as in Example 1.
As a result of the same evaluation as in Example 1, the gray scale was 16
2% halftone dots, 100 μm independent dots, and 30 μm fine lines were reproduced in the step and image areas. The relief depth of the 300 μm slit width was 105 μm. It was confirmed that the sensitivity was high and the image reproducibility was excellent. As a result of a printing test using this relief plate, a sharp printed matter without an image thickening was obtained, and no damage to the relief was observed even after printing 50,000 copies. The photosensitive resin composition and its relief could be sent to incineration. Further, the development waste liquid containing 5% of the photosensitive resin composition has AOX of 1 ppm.
(That is, the AOX of the composition was less than 20 ppm), and the wastewater did not require any special treatment.

Comparative Example 4 In Example 4, instead of "Blenmer GS" (glycidyl methacrylate starting from glycidol, total chlorine concentration: 10 ppm or less), "Blenmer G" (glycidyl methacrylate starting from epichlorohydrin, NOF Corporation). Made, total chlorine concentration: 5400
ppm) instead of "Blenmer GMR-R" (methacrylic acid adduct of glycidyl methacrylate starting from glycidol, total chlorine concentration: 10 ppm or less), "Blenmer GMR" (methacrylic acid adduct of glycidyl methacrylate starting from epichlorohydrin, NOF (stock)
A photosensitive resin printing plate precursor was obtained in the same manner except that the production and total chlorine concentration: 4200 pm) were used. The image reproducibility was the same as that of Example 4 except that the blank depth of the 300 μm slit width was 97 μm, which was slightly low, but the AOX of the developing waste liquid containing 5% of the photosensitive resin composition was measured and found to be 2
6 ppm (that is, AOX of the photosensitive resin composition is 52
It was as high as 0 ppm), and draining it as it was was not environmentally friendly.

Example 5 ε-caprolactam: 10 parts by weight, N- (2-aminoethyl) piperazine and adipic acid nylon salt: 90 parts by weight, and water: 100 parts by weight were put into a stainless steel autoclave, and After replacing the air with nitrogen gas, the mixture was heated at 180 ° C. for 1 hour, and then water was removed to obtain polyamide-4.

In a flask equipped with a cooling tube, partially saponified polyvinyl alcohol "Gothenol KL-05" (saponification degree: 78.5% to 82.0%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Manufactured): 50 parts by weight, succinic anhydride: 2 parts by weight and acetone: 10 parts by weight, and after heating at 60 ° C. for 6 hours,
The condenser was removed and the acetone was volatilized. Then 100
After carrying out two purification steps for eluting unreacted succinic anhydride with 1 part by weight of acetone, vacuum drying was carried out at 60 ° C. for 5 hours, and modified polyvinyl alcohol-1 in which succinic acid was ester-bonded to a part of hydroxyl groups. Got

In a three-necked flask equipped with a stirring spatula and a condenser tube, "Blenmer GS" (glycidyl methacrylate starting from glycidol): 130 parts by weight, acrylic acid: 80 parts by weight, hydroquinone monomethyl ether:
Add 0.1 parts by weight, 0.1 parts by weight of triethanolamine and 100 parts by weight of methanol, and add 60 parts at 60 ° C.
Heated for minutes. Thereafter, the cooling tube was removed to volatilize the methanol, and the resultant was washed twice with 100 parts by weight of acetone and then vacuum dried to obtain an acrylic acid adduct monomer-1 of glycidyl methacrylate (total chlorine concentration: 10 ppm or less).

In a three-necked flask equipped with a stirring spatula and a cooling tube, polyamide-4: 7.5 parts by weight, modified polyvinyl alcohol-1: 47.5 parts by weight, diethylene glycol: 11 parts by weight, water: 38 parts by weight. Parts and ethanol: 44 parts by weight were added, and the mixture was heated with stirring at 110 ° C. for 30 minutes and then at 70 ° C. for 90 minutes to dissolve the polymer. Next, 3 parts by weight of "Blenmer GS" (glycidyl methacrylate starting from glycidol, manufactured by NOF CORPORATION, total chlorine concentration: 10 ppm or less):
Stir for 0 minutes. Further, "Blenmer GMR-R" (methacrylic acid adduct of glycidyl methacrylate starting from glycidol, total chlorine concentration: 10 ppm or less): 12 parts by weight, acrylic acid adduct of glycidyl methacrylate-1
(Total chlorine concentration: 10 ppm or less): 5 parts by weight, acrylic acid adduct of diethylene glycol diglycidyl ether-1 (total chlorine concentration: 10 ppm or less): 6 parts by weight, "N"
K ester A-200 "(acrylic acid ester product of polyethylene glycol having an average molecular weight of 200 at both ends, manufactured by Shin-Nakamura Chemical Co., Ltd., total chlorine concentration: 19 ppm): 5 parts by weight," Irgacure 651 "(benzyl dimethyl ketal, Ciba Geigy Co., Ltd.): 0.1 parts by weight, “Irgacure 184” (α-hydroxyketone, Ciba Geigy Co., Ltd.): 1.5 parts by weight and hydroquinone monomethyl ether: 0.01 parts by weight. The mixture was added and stirred for 30 minutes to obtain a photosensitive resin composition having fluidity.

"Byron 31SS" (toluene solution of polyester resin, manufactured by Toyobo Co., Ltd.): 260 parts by weight and "PS-8A" (benzoin ethyl ether, manufactured by Wako Pure Chemical Industries, Ltd.): 2 parts by weight Mix at 70 ° C for 2
After heating for an hour, the mixture was cooled to 30 ° C., and ethylene glycol diglycidyl ether dimethacrylate (7 parts by weight) was added to obtain 2
Mixed for hours. Furthermore, "Coronate 3015E" (ethyl acetate solution of polyvalent isocyanate resin, manufactured by Nippon Polyurethane Industry Co., Ltd.): 25 parts by weight and "EC-136"
8 "(industrial adhesive, manufactured by Sumitomo 3M Limited): 14
Parts by weight were added to obtain a first adhesive layer C coating liquid.

"Gothenol KH-17" (saponification degree 7
8.5% to 81.5% polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: 50 parts by weight of "Solmix H"
-11 "(alcohol mixture, Nippon Alcohol Co., Ltd.
(Manufactured by Japan): 200 parts by weight and water: 200 parts by weight, and dissolved in a mixed solvent at 70 ° C. for 2 hours, and then “Blenmer G” (glycidyl methacrylate, manufactured by NOF CORPORATION): 1.5
Parts by weight were added and mixed for 1 hour, and further, (dimethylaminoethyl methacrylate) / (2-hydroxyethyl methacrylate) / (methacrylic acid) copolymer (manufactured by Kyoeisha Chemical Co., Ltd.): 3 parts by weight, "Irgacure 651""(Benzyl dimethyl ketal, manufactured by Ciba Geigy):
5 parts by weight, "epoxy ester 70PA" (acrylic acid adduct of propylene glycol diglycidyl ether,
Kyoeisha Chemical Co., Ltd .: 21 parts by weight and ethylene glycol diglycidyl ether dimethacrylate: 20 parts by weight were added, mixed for 90 minutes, cooled to 50 ° C., and then “Florard TM FC-430” (Sumitomo 3M Limited).
(Manufactured): 0.1 part by weight was added and mixed for 30 minutes to obtain a second adhesive layer D coating liquid.

A coating liquid for the first adhesive layer C was applied onto a "Lumirror T60" (polyester film, manufactured by Toray Industries, Inc.) having a thickness of 250 μm by a bar coater so that the film thickness after drying was 40 μm, and the temperature was 180 ° C. In the oven for 3 minutes to remove the solvent, and then the second adhesive layer D coating liquid is applied on the first adhesive layer C by a bar coater so that the dry film thickness is 30 μm.
Dry in an oven at 0 ° C for 3 minutes, then "Lumira" / first
Substrate-2 in which adhesive layer C / second adhesive layer D was laminated was obtained.

After exposing the substrate-2 from the side of the second adhesive layer D to 100 mJ / cm ² with an ultra-high pressure mercury lamp, the photosensitive resin composition was cast on the side of the second adhesive layer D of the substrate-2 at 60 ° C. And dried in an oven for 5 hours to obtain a photosensitive resin sheet having a thickness of 950 μm, in which “Lumirror” / first adhesive layer C / second adhesive layer D / photosensitive resin layer were sequentially laminated. The thickness of the photosensitive resin sheet was controlled by setting a spesser having a predetermined thickness on the substrate and scraping off the portion of the photosensitive resin composition protruding from the spesser with a horizontal metal scale or the like.

[Gausenol AL-06] (polyvinyl alcohol having a saponification degree of 91% to 94%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) on "Lumilar S10" (polyester film, manufactured by Toray Industries, Inc.) having a thickness of 125 μm. ) Solution of water / ethanol mixed solvent (weight ratio: 6/4) is applied by a bar coater so that the dry film thickness is 1 μm, and the solution is placed in an oven at 120 ° C. for 30 seconds to remove the solvent, A cover film-2 having a polymer layer laminated thereon was obtained.

A water / ethanol mixed solvent (weight ratio: 5/5) was applied on the photosensitive resin layer of the photosensitive resin sheet with a bar coater # 20 to swell the photosensitive resin layer, and then a cover film- Roller pressure was applied so that the polymer layer of 2 and the photosensitive resin layer were in contact with each other to obtain a photosensitive resin printing plate precursor.

A test negative film similar to that used in Example 1 was irradiated with a chemical lamp for 3 minutes to obtain a relief plate in the same manner as in Example 1. This relief plate was
As a result of the same evaluation as in Example 1, the gray scale was 15
2% halftone dots, 150 μm independent points, and 30 μm fine lines were reproduced in the step and image part. The relief depth of the 300 μm slit width was 170 μm. It was confirmed that the sensitivity was high and the image reproducibility was excellent. As a result of a printing test using this relief plate, a sharp printed matter without an image thickening was obtained, and no damage to the relief was observed even after printing 50,000 copies. The photosensitive resin composition and its relief could be sent to incineration. Further, the development waste liquid containing 5% of the photosensitive resin composition has AOX of 1 ppm.
(That is, the AOX of the composition was less than 20 ppm), and the wastewater did not require any special treatment.

Comparative Example 5 In Example 5, instead of “Blenmer GS” (glycidyl methacrylate starting from glycidol, total chlorine concentration: 10 ppm or less), “Blenmer G” (glycidyl methacrylate starting from epichlorohydrin, total chlorine concentration: 5400 ppm). ), "Blenmer GMR-R" (methacrylic acid adduct of glycidyl methacrylate starting from glycidol, total chlorine concentration: 10
instead of "Blenmer GMR" (methacrylic acid adduct of glycidyl methacrylate starting from epichlorohydrin, total chlorine concentration: 4200 ppm), acrylic acid adduct of glycidyl methacrylate-1 (starting from glycidol, total chlorine concentration: 10 ppm or less) Instead of "light ester G201P" (same structural formula compound starting from epichlorohydrin, Kyoeisha Chemical Co., Ltd., total chlorine concentration: 7500 ppm), acrylic acid adduct of diethylene glycol diglycidyl ether-1 (starting from glycidol, total chlorine) Instead of "concentration: 10 ppm or less", "epoxy ester 70PA" (acrylic acid adduct of propylene glycol diglycidyl ether starting from epichlorohydrin, manufactured by Kyoeisha Chemical Co., Ltd., total chlorine concentration: 10,000 p
A photosensitive resin printing plate precursor was obtained in the same manner except that (a pm or more) was used.

The blank depth of the 300 μm slit width is 152
The image reproducibility was the same as that of Example 5 except that it was slightly lower than μm, but when the AOX of the developing waste liquid containing 5% of the photosensitive resin composition was measured, it was 76 ppm (that is, the photosensitive resin composition). AOX is 1520 ppm), and it is not preferable to drain the water as it is in terms of environmental hygiene.

[0084]

As is clear from the above description, the photosensitive resin composition of the present invention can provide a relief plate having sharp image reproducibility. In addition, since the chlorine content is as low as 20 ppm or less, scraps generated during the manufacturing process and products that are out of specification, waste developer that appears when the user creates relief plates, and relief plates that have been used for printing are discarded. In that case, it can be incinerated, which is also environmentally friendly, and does not require the labor and cost of separating waste.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AB02 AC01 AD01 BC32 BC42                       BC74 BC83 CB07 CB24 FA03                       FA17                 2H096 AA03 BA05 BA20 EA02 GA08                       LA16

Claims (7)

[Claims] 1. A photosensitive resin composition containing (A) a soluble polymer, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, wherein one or more kinds of (B) photopolymerizable monomers are used. A photosensitive resin composition comprising (B1) an epoxy monomer or (B2) an epoxy ester monomer and having an organic chlorine concentration (AOX) of 20 ppm or less. 2. A photosensitive resin composition containing (A) a soluble polymer, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, wherein one or more kinds of (B) photopolymerizable monomers are used. A photosensitive resin composition comprising (B1) an epoxy monomer or (B2) an epoxy ester monomer and having a total chlorine concentration of 20 ppm or less. 3. A (B1) epoxy monomer or (B)
2) The photosensitive resin composition according to claim 1, wherein the epoxy ester monomer is a reaction product of glycidol (or a derivative thereof) and (meth) acrylic acid. 4. The (B2) epoxy ester monomer comprises:
The photosensitive resin composition according to claim 1 or 2, which is a reaction product of glycerin and (meth) acrylic acid. 5. A photosensitive resin printing plate precursor comprising a support and a photosensitive layer formed of the photosensitive resin composition according to claim 1 formed on the support. 6. A printing plate comprising the photosensitive resin printing plate precursor according to claim 5 exposed and then developed. 7. The printing plate according to claim 6, which is a relief plate.