JPS5990845A - Photosensitive polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a titled photosensitive composition having improved water developing characteristics by blending water-soluble polyamide, specified polyether and an unsaturated compd. having an ethylenic double bond. CONSTITUTION:(A) 100pts.wt. water-soluble (or water-dispersible) polyamide (preferably a polyamide copolymer having 30-70wt% structural unit consisting of polyoxyethylene with a terminal amino group whose polyether segment part has 150-1,500mol.wt. and of an aliphatic dicarboxylic acid), (B) 0.5-50pts.wt. polyoxyethylene (polyoxypropylene may also be used) having 200-5,000mol.wt. and (C) 20-200pts.wt. unsaturated compd. having an ethylenic double bond such as 2-hydroxyethyl (meth)acrylate, are dissolved in a mixed solvent of alcohol and water under heating.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyamide photosensitive resin composition with improved water developability.

Soluble polyamide, photopolymerizable unsaturated compound and necessary (
Photosensitive polyamide resin compositions which are insolubilized by light and which include a photopolymerizable initiator are used as printing plate materials such as letterpress materials, lithographic materials, intaglio materials, and stencil materials, and as photoresists. Within these.

For example, in the case of a letterpress printing plate material, a film having a transparent image area of positive or positive is closely attached to the surface of the photosensitive resin layer of an original plate, which is made by providing a layer of a photosensitive resin composition on a support, and the film is exposed through the film. After performing a photopolymerization reaction on the photosensitive layer in the light irradiated area to make it insolubilized, a relief image is obtained on the support by dissolving and removing the unexposed area with a suitable bath agent. Traditionally, alcohol or a mixed bath of alcohol and water have been used as developing solvents to dissolve and remove unexposed areas, but recently polyamide photosensitive resins that can be developed with neutral water have been developed. There is.

There are several known examples of water-developable polyamide photosensitive resin compositions. First, JP-A-48-7225
No. 0 proposes a system in which a photopolymerizable unsaturated compound is blended into a polyamide having sulfonic acid or its salt groups. In JP-A-49-4365, a system was proposed in which a photopolymerizable unsaturated compound was blended into polyamide containing an ether bond, and in JP-A-50-7605, a system in which a photopolymerizable unsaturated compound was blended into polyamide containing basic nitrogen was proposed. A system that combines the following has been proposed. 1. JP-A-55-74537 proposes a system using a polyamide containing 9 polyether segments of constant molecular weight.

The polyamides proposed in these known examples are:

It is not completely soluble in neutral water, but a portion of the polymer is dispersible in water to varying degrees. Therefore, there was a drawback that the time required for the development step of completely dissolving and removing the unexposed areas with neutral water was too long. In order to improve such drawbacks, fi with basic nitrogen
In systems using l-polyamide, it has been proposed to quaternize basic nitrogen by adding a quaternizing agent such as acrylic acid (Japanese Patent Laid-Open No. 5'5-66555). Although this method has a remarkable effect on improving water developability, the quaternizing agent is eluted into the developer, making the developing water acidic, causing irritation to the skin of developing workers and pollution caused by wastewater. There are concerns that this may occur.

The present inventors have conducted intensive studies on a method for improving the water developability of a printing plate material made of a polyamide photosensitive resin composition without making the developing water acidic.

We have arrived at the present invention.

The present invention relates to a photosensitive resin composition with improved water-developability, characterized in that it comprises at least the following components (a) to (c).

(a) Water-soluble or water-dispersible polyamide 100
Part by weight (b) Polyoxyethylene or polyoxypropylene having a molecular weight in the range of 200 to 5,000.

At least one polyether selected from the group consisting of poly(oxyethylene/oxypropylene)
0.5-50 parts by weight (C) Unsaturated compound having a polymerizable ethylenic double bond 20-2
Each component of the present invention will be explained in detail below.

Component (a) of the present invention is a water-soluble or water-dispersible polyamide. What does water-soluble mean here?

For example, when a polyamide formed into a film is immersed in warm water and rubbed with a brush, all or a portion of the polyamide is eluted and the film loses weight or collapses.

Furthermore, water dispersibility refers to the case where when a polyamide film is soaked in water or warm water and rubbed with a brush, the polyamide swells and disperses, and the film loses weight or collapses as it is dispersed in water.

The water-soluble or water-dispersible polyamide that is the component (a) of the present invention includes all conventionally proposed polyamides. For example, a polyamide containing a sulfonic acid group or a surnet group obtained by copolymerizing L-unaro, sodium 5-dicarboxybenzenesulfonate, etc., as shown in JP-A No. 48-72250; A polyamide having an ether bond obtained by copolymerizing one of a dicarboxylic acid, an amine, or a cyclic amide having an ether bond in the molecule as shown in No. 11, No. 49-43565.

Yorina N shown in Japanese Patent Application Laid-Open No. 50-7605.

Polyamides containing basic nitrogen obtained by copolymerizing N'-cy(γ-aminopropyl)pipera/Nnatowo and polyamides obtained by quaternizing these polyamides with acrylic acid etc. A copolyamide containing a polyether segment having a molecular weight of 150 to 1,500.

and a (N, N/-Sialkylia))-ε
- ring-opening polymerization of caglolactam or (1-(N, +v'
Examples include polyamides obtained by ring-opening copolymerization of -dialkylamino)-ε-cabrobuctam and ε-caglolactam.

Among these polyamides, 3 structural units consisting of polyoxyethylene and aliphatic dicarboxylic acid or diamine having an amino group or carboxyl group at the end and a polyether segment portion having a molecular weight of 150 to 150 units are used.
A copolyamide containing 0 to 70% by weight is most preferably used. This polyamide has very good compatibility with the polyether component (b) due to the effect of the ether bonds contained in the molecule, so water developability can be greatly improved with almost no deterioration in performance due to the addition of polyether. It can be improved.

(a) Component polyamide is prepared by reacting the amino groups and carboxyl groups at the ends of the water-soluble or water-dispersible polyamide with the epoxy groups of an unsaturated epoxy compound such as glycidyl methacrylate to form unsaturated bonds at the ends. It is also possible to use what has been introduced.

In addition, as the polyamide of component (a), two of the above polymers may be used.
It is also possible to use a mixture of more than one type.

Since the polyether component (b) itself has good water solubility, when used in combination with the polyamide component (a), it exhibits the effect of improving the water developability of the entire photosensitive resin composition. I can do it. Therefore, the chemical groove a of the polyether is also limited to those having good water solubility. Among various polyethers, polyoxyethylene, polyoxypropylene, and poly(oxyethylene/oxypropylene) copolymers can be used because they have good water solubility. Other polyethers, such as polyoxy/methylene (ri, since low molecular weight polymers are thermally unstable)
Usually, a high molecular weight polymer having a molecular weight of ioooo or more is used, but it does not have any water solubility. Those with an alkylene group of 4 or more carbon atoms, such as polyoxybutylene (does not have sufficient water bathability because the number of ether groups in one molecular chain is small. For the above reasons, component (b) The polyether used must be selected from polyoxyethylene, polyoxypropylene, poly(oxyethylene/oxypropylene) copolymers. Of these, polyoxyethylene has the best water solubility and (a
) is particularly preferably used because it has good compatibility with the polyamide component.

If the molecular weight of the polyether component (b) is less than 200, it will be included in the polyamide component (a) and only be expected to function as a one-step plasticizing process, and the effect of improving water developability will be low. unacceptable. On the other hand, if the molecular weight exceeds 5,000, the compatibility with the polyamide of component (a) decreases significantly, resulting in phase separation in the photosensitive layer. Indeed, when the molecular weight of the polyether exceeds 5000 f, a decrease in the water solubility of the polyether itself is observed. For the above reasons, the molecular weight of the polyether needs to be between 200 and 5,000, preferably between 300 and 3,000.

If the amount of component (b) used is less than 0.5 parts by weight per 100 parts by weight of the polyamide component (a), the effect of improving water developability will not be exhibited. On the other hand, if the amount of component (b) exceeds 50 parts by weight based on 100 parts of polyamide (a), phase separation often occurs even if the i1+11 composition of the polyamide is selected. For the above reasons, the amount of component (b) used must be in the range of 0.5 to 50 parts by weight, preferably 5 to 40 parts by weight.

(C) Unsaturated compound i having an ethylenic double bond as component
d. Any material can be used as long as it is compatible with the polyamide of component (a). Specific examples include the following: 2-hydroquinethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
Monofunctional vinyl monomers with hydroxyl groups such as Ro-chloro-2-hydroxypropyl (meth)acrylate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl phthalate, ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether. The double bond and hydroxyl group obtained by reacting (meth)acrylic acid with a divalent to pentavalent glycidyl ether such as
A polyfunctional vinyl monomer having 5 polyfunctional vinyl monomers, a reaction product of an unsaturated carboxylic acid such as (meth)acrylic acid and glycidyl (meth)acrylate, a reaction product of a divalent to pentavalent saturated carboxylic acid such as acetic acid and glycidyl (meth)acrylate reactant of.

Polyfunctional vinyl monomers having a hydroxyl group and two or more unsaturated groups such as a reaction product of a primary or secondary amine such as xylylene diamine and glycidyl (meth)acrylate, acrylamide, N-methylolacrylamide, methylenebisacrylamide, etc. Contains acrylamide and bisacrylamide.

(C) Component usage amount U, (a) component polyamide 100
It is necessary that the weight line be in the range of 20 to 200 with respect to the overlapping part. Zunawaji, the unsaturated compound of component (C) is 2
If the amount is less than 0 parts by weight, the density of the frame structure formed by photopolymerization of these unsaturated hydrogen compounds will be very low. Therefore, part of the photopolymerized portion dissolves into water during development, making it impossible to obtain sufficient image reproducibility. On the other hand, if the amount of the unsaturated compound (C) exceeds 200 parts by weight, the density of the crosslinked structure formed by photopolymerization becomes excessive, and the resulting relief becomes extremely brittle.

Problems such as cracks appearing in reliefs occur during printing. For these reasons, the amount fl of component (C) used is 20 to 200 parts by weight, preferably 50 to 15 parts by weight, per 100 parts by weight of the polyamide component (a).
It is 0 parts by weight.

A photoinitiator may be added to the photosensitive resin composition of the present invention in order to rapidly carry out photopolymerization. All known photoinitiators f4 can be used. For example, benzoins, benzophenones, atraquinones,
Examples include pencils, acetophenone cheeks, and diacetyls. The amount of photoinitiator used is preferably in the range of 0.001 to 10% by weight based on the total photosensitive resin composition.

In order to increase the thermal stability of the photosensitive resin composition of the present invention, all known thermal polymerization inhibitors can be used. Preferred thermal polymerization inhibitors include phenols, hydroquinones, and catechols. In addition, it is also possible to use phosphorus compounds such as triphenylphosphine, L-ascorbic acid, etc. as a heat stabilizer.These thermal polymerization inhibitors and heat stabilizers It is preferable to use it in the range of 0.001 to 5% by weight based on the total amount of the substance.Dye, pigment, surfactant.

It is also possible to add deodorants, ultraviolet absorbers, etc.

The usual production of the composition of the present invention involves heating the polyamide component (a) in a mixed solvent of alcohol/water in a heating bath.
Subsequently, component (1) polyether, component (C) unsaturated compound, a photoinitiator, a thermal polymerization inhibitor, etc. are added and thoroughly stirred and dissolved. In this way, photosensitive j! A J resin solution is obtained.

To form a photosensitive layer from the above photosensitive resin solution,
After distilling off the solvent and drying, the granulated product can be molded onto a support by heating and pressing with a press or the like. Alternatively, it is also possible to make a photosensitive sheet by a dry film forming method and adhere this sheet onto a support to form a photosensitive layer.

The photosensitive layer can also be formed by drying directly on the support (film formation or melt film formation.Supports include iron and stainless steel.

Metal plates such as aluminum and copper, synthetic resin sheets such as polyester film, and synthetic rubber sheets such as styrene-butadiene copolymer are used.

The photosensitive layer is preferably formed to have a thickness of 0.1 to 10 mm.

Forming a relief image for printing using a photosensitive plate material made of the photosensitive resin composition of the present invention A negative or positive original film is closely adhered to the photosensitive layer prepared in the same manner as in the previous method. 1 Ultra-high-pressure mercury lamps that typically emit wavelengths of 30D to 400μm.

High-pressure mercury lamps, metal halide lamps, and xenon lamps.

Irradiates ultraviolet light from carbon arc lamps and chemical lamps,
An insolubilization reaction is carried out by photopolymerization. Next, a relief is formed on the support by dissolving the unexposed areas into water using a spray type developer or a brush type developer using neutral water.

The photosensitive resin composition of the present invention has both improved water developability and good image reproducibility. This allows for the good image reproduction of component (b) to be achieved without deteriorating the inherent good image reproduction of the polyamide photosensitive resin consisting of polyamide as component (a) and unsaturated compound as component (C). This is due to the fact that it has excellent water solubility. That is, (a
The water-soluble or water-dispersible polyamides (component ) generally do not have sufficient water solubility and therefore have the disadvantage of requiring a long water development time. In particular, a spray type developing device is different from a brush type developing device in which M is forcibly thawed or dispersed by applying external force.

Since water is simply sprayed at a pressure of about 2 to 4 kg/a++', 1.
A long development time of 0 minutes or more is often required.

However, since the polyether, which is the component (1) of the present invention, is a completely water-soluble polymer, by using it together, the water developability of the entire photosensitive resin is dramatically improved, and the spray type developing device However, for a photosensitive layer with a thickness of 700 μm, it is possible to completely remove the unexposed portions within 6 minutes.

The photosensitive resin composition of the present invention exhibits its effects most when used as a letterpress material, but it is also used as a planographic material.

It can also be used as an intaglio material, stencil material, and photoresist.

The present invention will be explained in more detail in Examples below.

Example 1 α obtained by adding acrylonitrile to both ends of polyoxyethylene with a number average molecular weight of 600 and reducing it with hydrogen,
Relative viscosity ( 1g of polymer was dissolved in 100πt of chloral hydrate and heated to 25'C.
A polyamide with a constant (hereinafter the same) of 240 was obtained.

100 parts by weight of the polyamide thus obtained was mixed with 150 parts by weight of a mixed solvent of ethanol/water-50,750 (weight ratio).
Parts by weight were dissolved by heating at 80'C. Next, 2 parts by weight of glycidyl methacrylate was added and reacted at 80°C for 1 hour to add the epoxy group of glycidyl methacrylate to the amine group and carboxyl group at the end of the polyamide to form a meta-2IJ loyl group at the end of the polymer. Introduced. after that.

20 parts by weight of polyoxyethylene having a number average molecular weight of 1000 as a polyether, and 20 parts by weight of an addition reaction product of propylene glycol diglycidyl ether and acrylic acid as a photopolymerizable unsaturated compound.

Adduct of xylylene diamine and glycidyl methacrylate: 45 parts by weight, 10 parts by weight of trimethylolpropane triacrylate, 6 parts by weight of dimethylbenzyl ketal as a photoinitiator, 0.1 parts by weight of hydroquinone as a thermal polymerization inhibitor.
Parts by weight were added and thoroughly stirred.

The photosensitive resin composition thus obtained.

The substrate was cast onto a 250 μm thick steel substrate coated with an epoxy adhesive and cured so that the thickness after drying was 950 μm. Next, the film was placed in an oven at 60° C. for 4 hours to completely remove the solvent, thereby forming a photosensitive layer with a substrate.

A test negative film (133 to 9.3, 5%, 10-inch halftone dots, diameter 200 μm) was placed on this photosensitive layer.

Eight independent points (with widths of 50 μm and 70 μm) were vacuum-adhered and exposed for 2 minutes using a high-pressure mercury exposure device. Then, by using a spray-type cleaning device containing 30'C of neutral water and developing for 4 minutes at a pressure of 3 kg/an'', the unexposed areas were completely dissolved and removed, and a relief image was formed on the substrate. .

When this relief was examined, it was confirmed that fine parts 1 such as 6 halftone dots, 200μ independent dots, and 50μ thin lines were sufficiently reproduced. A printing test was conducted using this plate material, and good printed matter was obtained.

Comparative Example 1 In Example 1. A photosensitive plate material was obtained in exactly the same manner except that polyoxyethylene with a number average molecular weight of BLOO was not used and the amount of polyamide was increased from 100 parts by weight to 120 parts by weight.

The same test negative film as in Example 1 was vacuum-adhered to this photosensitive layer, and exposed for 2 minutes using a high-pressure mercury lamp exposure device.
When developed using a spray type washing device containing neutral water at ℃, it was found that Example 1 was used to completely dissolve and remove the unexposed areas.
It took 12 minutes, three times as long as the previous four minutes.

When the resulting relief was examined, the fine lines with a width of 50 μm were significantly bent due to swelling with water due to the long development time, and the thin wires with a width of 70 μm were also slightly bent.

Example 2 A obtained by adding acrylonitrile to both ends of polyoxyethylene having a number average molecular weight of 400 and reducing it with hydrogen,
50 parts by weight of equimolar width of ω-diaminopolyoxyethylene and adipic acid, 25 parts by weight of ε-caglolactam HfτB
, and salts of hexamethylene diamine and adipic acid 25
Eight parts by weight were polymerized under normal conditions to obtain a polyamide with a relative viscosity of 230.

The relative viscosity I A polyamide of 2.50 was obtained.

90 parts by weight of polyamide copolymerized with the polyoxyethylene component thus obtained, 10 parts by weight of ring-opening copolyamide of α-(N,N-dimethylamino)-ε-caprolactam and ε-caprolactam, and alcohol. /water=
60,740 (weight ratio) in 120 parts by weight of mixed bath agent
゛C is a common understanding of heating. Next, 5 parts by weight of polyoxyethylene having a number average molecular weight of 600 as a polyether, 60 parts by weight of an addition reaction product of ethylene glycol diglyndyl ether and methacrylic acid as a photopolymerizable unsaturated compound, p
-Hydroxyethyl-β-acryloyl oxyneethyl phthalate total 36 parts by weight, 2 parts by weight of benzoin methyl ether as a photoinitiator *2 parts by weight of triphenylphosphine as a thermal stabilizer fIL t- as a thermal polymerization inhibitor
1 part by weight of butylcatechol was added and thoroughly stirred and dissolved.

The photosensitive resin composition thus obtained.

200μ thick polyester film substrate coated with polyester adhesive, including the thick substrate after drying)
It was cast so that the thickness was 970μ.

This was placed in an open oven at 60°C for 5 hours to completely remove the solvent.

Alcohol/water = 60740 on the surface of the photosensitive layer with this substrate
After applying a thin layer of (weight ratio) solvent.

A 100 μm thick polyester film that had been matted by chemical etching was laminated thereon. In this way, a plate material with a cover film could be obtained.

When this plate material was stored in a dark place for one week and the cover film was peeled off, the matte shape of the film was transferred to the surface of the photosensitive layer to obtain a matted surface of the photosensitive layer.

Next, when the same test negative film as in Example 1 was vacuum-adhered to the photosensitive layer, uniform adhesion could be achieved very easily due to the matte shape of the surface of the photosensitive layer.

B. Ultraviolet rays from a chemical lamp were irradiated through the film for 5 minutes. Thereafter, when it was developed using the same spray type washing machine as in Example 1, the unexposed areas were completely dissolved and removed in 5 minutes.

When I examined the obtained relief, I found that it had 6 halftone dots.

It was confirmed that 200μ independent points, 50μ thin lines, etc. were reproduced without problems.

Comparative Example 2 A photosensitive plate material was produced in exactly the same manner as in Example 2, except that the polyether with a number average molecular weight of 600 was not added and the total amount of the addition reaction product of ethylene glycol diglycidyl ether and methacrylic acid was increased to 65 parts by weight. Created.

When this plate material was exposed in the same manner as in Example 2 and 'fA imaged, it took 7 minutes and 30 seconds to dissolve and remove the unexposed portions in water. This development time was 2.5 times that of Example 2. When I examined the obtained relief, it was found that 2 widths were 50μ.
It was confirmed that bending occurred in the thin wire.

Example 6 α obtained by adding acrylonitrile to both ends of polyoxyethylene with a number average molecular weight of 1000 and reducing it with hydrogen.
, 65 parts by weight of an equimolar salt of ω-diaminopolyoxyethylene adivic acid and 35 parts by weight of ε-caprolactam were melt-polymerized under normal conditions to obtain a polyamide with a relative viscosity of 2,800.

100 parts by weight of this polyamide was mixed with ethanol/water, = 70 parts by weight.
It was dissolved in a mixed solvent of 750 (weight ratio) by heating at 80°C. Then, several thousand equal parts 7-y1c+o as polyether
, 40 parts by weight of polyoxyethylene of o, 70 parts by weight of an addition reaction product of propylene glycol diglycidyl ether and acrylic acid, and 5Di of an addition reaction product of glycidyl methacrylate and methacrylic acid as photopolymerizable unsaturated compounds.
5 parts by weight of benzophenone as a photoinitiator and 7 parts by weight of hydroquinone monomethyl as a thermal polymerization inhibitor.
02 parts by weight was added and sufficiently stirred to dissolve.

This photosensitive resin composition was placed on a 300 μm thick aluminum substrate coated with an epoxy adhesive and cured.

The film was cast to a thickness of 700 μm (including the substrate) after drying. Then, it was placed in a 6D'a oven for 6 hours to completely remove the solvent.

The photosensitive plate material lined with the aluminum substrate thus obtained was exposed in the same manner as in Example 1, and the water temperature was 25°C.
Using a spray type washing machine at ℃, pressure 4 kg, /a
The unexposed areas were completely dissolved and removed within 6 minutes of development time.

When I examined the obtained relief, I found that there were 6 halftone dots.

It was confirmed that fine parts such as 200μ independent points and 50μ thin lines were reproduced without problems.

Example 4 In Example 1, the average molecular weight of the polyether was 110
A photosensitive resin plate material was prepared in exactly the same manner except that polyoxypropylene having a molecular weight of 9 and 400 was used in place of the 0D polyoxyethylene.

This plate material was exposed and developed in exactly the same manner as in Example 1.

It took 6 minutes to completely remove the unexposed areas. This development time was 15 times longer than that of Comparative Example 2 when polyoxyethylene was added in Example 1.

It was confirmed that the obtained relief was reproduced without any problems down to the minute details.

Example 5 A photosensitive resin was prepared in exactly the same manner as in Example 1, except that poly(oxyethylene/oxypropylene) having a molecular weight of 400 and a polyoxyethylene content of 60 mol was added instead of polyoxyethylene as the polyether. A plate material was produced.

When this plate material was exposed and developed using the same method as in Example 1, the development time was 5 minutes and 30 seconds, which was 1 minute and 50 seconds longer than in Example 1 when polyoxyethylene was added, but The time was 30 seconds shorter than when adding oxypropylene. It was confirmed that the relief obtained could be reproduced without any problem using a fine partial agent.

Claims (1)

[Claims] (1) Lower Fte A photosensitive polyamide resin composition comprising at least the components (a) to (C). (a) Water-soluble or water-dispersible polyamide 1DO
Part by weight (b) Polyoxyethylene or polyoxypropylene having a molecular weight in the range of 200 to 5,000. At least one polyether selected from the group consisting of poly(oxyethylene/oxypropylene)
05 to 50 parts by weight (C) Unsaturated compound having a polymerizable ethylenic double bond 20 to 200 parts by weight (2) Water-soluble or water-dispersible polyamide. The molecular weight of the polyether segment part is 150 to 150
0, and is a copolymerized polyamide containing 60 to 70 units by weight of polyoxyethylene having an amine group or carboxyl group at the end and an aliphatic dicarboxylic acid or an amine. Photosensitive polyamide resin composition. (3) The polyether of component (b) has a molecular weight of 200~
The photosensitive polyamide resin composition according to claim 1, which is a polyoxyethylene of 5000.