JPS6063533A - Manufacture of printing plate material - Google Patents

Abstract

PURPOSE:To obtain a printing plate material having a photosensitive resin uniform in film thickness and soluble in water or an org. solvent rationally with good productivity by using a concentration means as a means for removing a solvent out of a photosensitive resin compsn. CONSTITUTION:A photosensitive resin compsn. composed essentiall of a polymer soluble in water or in an org. solvent and a photosensitive monomer is concentrated to the concn. of >=70wt% of the total weight by evaporating a solvent, and it is laminated on a support 8 in a uniform film thickness. As an embodiment of such a process, the low concd. composn. mixed and prepd. with a preparation means 1 is delivered in a constant feed rate with a pump 2 to a concentration means 3, such as a vent-provided extruder to evaporate the solvent here, and the concd. compsn. is laminated on a metallic plate or a film with a constant feed rate means 6. The monomer can be added after the concn. means 3 so as to control to the min. the time length of the resin compsn. to be subjected to heating in order to avoid polymer. Such a process permits continuous concn. of the resin compsn. even poor in heat stability to a high concn. without impariging heat stability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing a printing plate material having a photosensitive resin layer soluble in water or an organic solvent.

[Prior art and its problems]

Printing plate material (hereinafter referred to as printing plate material) having a uniform thickness layer (hereinafter referred to as photosensitive resin layer) of a photosensitive resin composition soluble in water or an organic solvent (hereinafter referred to as solvent) The key point of the manufacturing method is that the main components are a solvent-soluble polymer (hereinafter referred to as "polymer") and a photosensitive monomer (hereinafter referred to as "monomer"), and a photosensitive resin composition (hereinafter referred to as "resin composition") containing a solvent. The problem lies in how to avoid the fact that the thermal stability of substances (hereinafter referred to as substances) is usually insufficient.

That is, even though the resin composition contains a large amount of monomer, in order to maintain the photosensitive properties of the resin composition and obtain a good printing plate material, the thermal polymerization inhibitor in the resin composition is Since the amount added is suppressed to a small amount, thermal polymerization tends to occur during the manufacturing process.

Therefore, the conventional technology is 2, for example,
As in the publication, the resin composition is prepared, discharged, and roll-molded at a low temperature of 80° C. or lower using a large amount of solvent, thereby preventing the resin composition from being thermally polymerized during the manufacturing process. However, in order to obtain a good printing plate material, it is necessary to suppress the amount of solvent in the photosensitive resin layer to a relatively small amount.

Therefore, the biggest problem with the prior art is that it is necessary to dry the solvent from the photosensitive resin layer, but this drying process takes an extremely long time. For this reason, drying becomes rate-limiting in the manufacturing process, and there is a limit to productivity improvement.

Since the drying equipment is expensive, the manufacturing cost is high, and it is not necessarily a rational manufacturing method.

[Object of the present invention]

The purpose of the present invention is to eliminate the above-mentioned conventional drawbacks and to produce a printing plate material having a photosensitive resin layer soluble in water or an organic solvent with a uniform film thickness in a rational manner and with high productivity.

Moreover, it is an object of the present invention to provide a method of manufacturing at low cost.

[Configuration of the present invention]

The present invention has the following configuration to achieve the above object.

That is, a water or organic solvent solution of the photosensitive resin composition whose main components are a water or organic solvent-soluble polymer and a photosensitive monomer accounts for 70% or more by weight of the whole is discharged. .

The present invention is characterized by a method for manufacturing a printing plate material, which is laminated onto a support and formed into a uniform film thickness.

Polymers used in the printing plate material of the present invention include:

For example, polyvinyl alcohol type, cellulose derivative type,
Examples of the monomer include polyvinyl acetate, polyvinyl acecool, and polyamide. Examples of the monomer include acrylic ester, methacrylic ester, ethylene glycol diglycidyl ether derivatives, and propylene glycol diglycidyl ether derivatives.

Water, lower alcohol, etc. are used as the solvent for these main components, and a metal plate or film is used as the support for the printing plate material.

A cover film is also laminated if necessary.

The present invention will be explained in more detail based on the drawings.

FIG. 1 is a schematic diagram showing an example of a method for manufacturing a printing plate material according to the present invention. The apparatus shown in FIG.

Means for dissolving, mixing and preparing a low concentration resin composition (hereinafter referred to as
Preparation means)1. Pump for quantitatively transporting a low concentration resin composition 2. Concentration means for obtaining a high concentration resin composition by evaporating the solvent from the low concentration resin composition and concentrating it (hereinafter abbreviated as concentration means)3. Vacuum pump 4. Means for quantitatively discharging a high concentration resin composition (hereinafter abbreviated as discharge means)
5. Means for dispensing a fixed amount (hereinafter abbreviated as discharging means) 6. A means for laminating the diamond, high concentration resin composition 8, a support 9 such as a metal plate or a film, and a cover film 10 if necessary (described below).

(abbreviated as molding means)11. Conveyors 12 with rubber or steel belts are constructed so as to be arranged one after the other in the running direction.

Further, a short-time drying device 13 may be provided between the diamond and the molding means 11 if necessary.

Here, the preparation means 1 is a stirring tank, a kneader, etc., the concentration means 3 is a batch type stirring tank, kneader, etc., or the continuous type is a thin film evaporator, a vent extruder, etc., and the discharge means 5 is a screw.

As the discharging means 6 such as a gear pump, an extruder or a gear pump can be used, and as the molding means 11, a cast ink method, a calender method, etc. can be used.

In addition, when performing continuous concentration using a vent extruder, examples of models include a multi-screw extruder 1, which can sufficiently mix the resin composition by shearing as it has multiple screws and its rotation speed is high, such as a twin-screw extruder. However, it has a large concentration ability and there is no vent-up of the resin composition.

Particularly preferred.

A feature of the manufacturing method according to the present invention having the above configuration is that a concentrating means 3 is provided instead of drying as a means for removing the solvent from the photosensitive resin layer.

The concentration means 3 may be of a batch type in the case of a resin composition with relatively good thermal stability, but a continuous type is preferable in the case of a resin composition with insufficient thermal stability.

In other words, by continuously evaporating the solvent in an extremely short period of time, such as one minute or less, and continuously discharging the resulting high-concentration resin composition, it is possible to evaporate the solvent at high temperatures close to the boiling point of the solvent that results from the high concentration. By minimizing the thermal history time, thermal polymerization can be avoided.

In addition, if the amount of solvent in the resin composition is less than 30% by weight, it may be left as is without drying, or the solvent may be reduced to an appropriate amount by drying for a short time of 30 minutes or less6-, thereby reducing the burden of drying. is small, but if the amount of solvent exceeds that amount, drying will take a long time, and the advantage of high concentration will be lost.

FIG. 2 is a schematic diagram showing another example of the method for manufacturing a printing plate material according to the present invention. The apparatus shown in FIG.

means for dissolving the polymer (hereinafter abbreviated as dissolving means) 14;
Pump 2 for quantitatively transporting the low concentration polymer solution. Concentration means for obtaining a high concentration polymer solution by evaporating the solvent from the low concentration polymer solution and concentrating it. 3. Vacuum pump 4. A pump for quantitatively transporting the monomer in the monomer tank 15 2. Mixing means (hereinafter abbreviated as mixing means) for mixing the high concentration polymer solution and the monomer to obtain the high concentration resin composition 8 16. Means for dispensing a fixed amount6. A means 11 for laminating and molding the diamond, high concentration resin composition 8, a support 9 such as a metal plate or film, and a cover film 10 if necessary.
A conveyor 12 with a rubber or steel belt,
The configuration is such that they are arranged sequentially along the running direction.

Here, the dissolving means 14 includes a stirring tank, a kneader, etc.
The mixing means 16 is a two-dose stirring tank.

A kneader, etc., or a fluid mixer in a continuous type.

An extruder etc. can be used.

A feature of the manufacturing method according to the present invention having the above configuration is that a means 3 for concentrating the polymer solution in advance instead of drying is provided as a means for removing the solvent from the photosensitive resin layer, and then a high concentration polymer solution is added. Means 16 for mixing the monomers is provided.

That is, the reason why the thermal stability of the resin composition is insufficient is that it contains a large amount of monomer.

By delaying the addition of the monomer as much as possible, it is possible to minimize the period of heat history at high temperatures that occurs due to the high concentration of the resin composition, and to avoid thermal polymerization.

In this case, since the polymer solution alone has good thermal stability, the concentration means 3 can be freely selected from either a batch type or a continuous type.

Further, the mixing means 16 may be of a batch type in the case of a resin composition having relatively good thermal stability.

In the case of resin compositions with insufficient thermal stability, continuous formula % formula If the compatibility is insufficient and the viscosity ratio is large, the above-mentioned multi-screw extruder with a high shear rate may be used as the mixing means 16, since this may affect the photosensitive properties.
It is preferable to use it as

In this case, if a multi-screw extruder is also used as the concentration means 6, concentration and mixing can be performed in an integrated device, which is more preferable as a rational manufacturing method.

FIG. 6 is a schematic view showing still another example of the method for manufacturing a printing plate material according to the present invention. The apparatus shown in FIG. 6 includes a polymer feeder 17. Pump 2 for quantitatively transporting the solvent and plasticizer in the melting aid tank 19; a melting means (hereinafter abbreviated as melting means -t) for plasticizing, heating, and melting the polymer with a small amount of melting aid 20. A pump for quantitatively transporting the monomer in the monomer tank 15 2. A mixing means 16 for mixing a high concentration polymer melt and a monomer to obtain a high concentration resin composition 8, a means 6° for discharging a fixed amount of the high concentration resin composition 8, Support 9 such as a plate or film
and a means 11 for laminating the cover film 10 as required.A conveyor 12 having a belt made of rubber or steel is arranged sequentially along the traveling direction.

Here, as the melting means 20 and the mixing means 16, a kneader 1 extruder or the like can be used.

The manufacturing method according to the present invention having the above configuration is characterized by a means 20 for removing the solvent from the photosensitive resin layer by melting the polymer at a high concentration by adding only a small amount of solvent from the beginning without the need for drying. ,after that.

A means 16 for mixing the high concentration polymer melt and the monomer is provided.

In other words, only a small amount of solvent is used.

There is no need for concentration or drying, and there is no need for melting means 20.
By using the same device as the mixing means 16, and preferably using the above-mentioned multi-screw extruder, continuous melting and mixing can be achieved, resulting in an extremely simplified manufacturing method. Furthermore, since the resin composition is continuously discharged, the heat history time at high temperatures caused by increasing the concentration of the resin composition is minimized, and thermal polymerization can be avoided.

[Effects of the present invention]

The present invention has the above-mentioned configuration, and therefore exhibits excellent effects as shown in the first order.

First of all, not only a resin composition with good thermal stability,
Even for resin compositions with insufficient thermal stability, continuous concentration or continuous mixing of polymer liquid and monomer can extremely shorten the thermal history time of the resin composition at high temperatures, improving thermal stability. can be retained and highly concentrated.

In addition, it is possible to discharge the resin composition at a high concentration.

The photosensitive resin layer can be molded without drying or with only a short drying time. Therefore, a large amount of drying equipment is not required,
2. Rational printing plate material with a photosensitive resin layer soluble in water or organic solvent with uniform thickness.

The initial objective of manufacturing at low cost with high productivity can be achieved. The provision of inexpensive printing plates is highly desirable in terms of the long-awaited use of resin plates for printing plate materials from the viewpoint of workability and the like.

Furthermore, since the resin composition is highly concentrated, a high viscosity can be obtained, and therefore, ordinary high temperature molding techniques such as casting method, calender method, extrusion method, etc. can be applied. Therefore, the resin composition can be easily molded into a uniform film thickness, and a printing plate material with good thickness accuracy can be obtained.

Example 1 A printing plate was manufactured using the apparatus shown in FIG.

100 parts by weight of a copolyamide containing 50 parts by weight of polyether segments, 40 parts by weight of N-butylbenzene sulfonamide, 20 parts by weight of ethanol, and 60 parts by weight of water were added to a stirring tank, and the mixture was heated at 75°C under stirring. The polyamide was dissolved over a period of 3 hours.

After dissolving, 55 parts by weight of β-hydroxy ethyl β'-acryloyloxy ethyl phthalate and 2 parts by weight of α-methoxy benzoin methyl ether.

2 parts by weight of hydroquinone monomethyl ether 000 was added and mixed at 75°C for 30 minutes.

After mixing, the mixture is concentrated under 8CMo and a vacuum degree of 400 Torr for 30 minutes to evaporate 20.6 parts by weight of the mixed solvent of ethanol and water. Next, the highly concentrated resin composition obtained by concentration was transported to a secondary extruder by a pump, defoamed in the extruder, temperature controlled, and discharged in a fixed amount from a die onto a support film.

After discharging, 75 parts by weight of the mixed solvent of ethanol and water was dried by hot air drying at 60°C for 10 minutes, and the cover film was laminated and the film thickness was laminated using a pair of press rolls heated to 90°C and a nip pressure of 201 cg/an. A printing plate having a photosensitive resin layer was obtained with only a short drying time.

Example 2 A printing plate was manufactured using the apparatus shown in FIG.

Copolyamide of ε-caprolactam and N,N'-bis(aminopropyl)piperazine (copolymerization ratio 35:6
5 parts by weight) 100 parts by weight, 54 parts by weight of methanol, 5 parts by weight of water
4 parts by weight were added to a stirring tank, and the polyamide was dissolved in the same manner as in Example 1.

After dissolving, ethylene glycol, diglycidyl ether,
Adding 60 parts by weight of diacrylate, 2 parts by weight of Penzofe 13-non, and 0.1 part by weight of hydroquinone,
Mixing was performed at 75°C for 30 minutes.

After mixing, it was transported to a thin film evaporator using a pump and heated to 90°C.

Continuous concentration was performed for 1 minute at a vacuum degree of 400 Torr to evaporate 794 parts by weight of a mixed solvent of methanol and water.

Next, the high-concentration resin composition obtained by concentration was dispensed in a fixed amount in the same manner as in Example 1, except that in this case, the support film and cover film were directly laminated without drying, and the film thickness was adjusted. A printing plate having a resin layer was obtained.

Example 6 A printing plate was manufactured using the apparatus shown in FIG.

100 parts by weight of N-methoxy methylated 6-bolyamide, N
- Adding 60 parts by weight of ethyltoluene sulfonamide, 80 parts by weight of ethanol, and 53.3 parts by weight of water to a stirring tank,
Polyamide is dissolved in the same manner as in Example 1.

Concentration was carried out for 60 minutes at a solubility of 90° C. and a vacuum of 400 Torr, and 100.7 parts by weight of the mixed solvent of ethanol and water was evaporated to obtain a highly concentrated polymer solution.

14- Next, a mixture of this highly concentrated polymer solution, 38 parts by weight of β-hydroxy ethyl β'-acryloyl oxyethyl phthalate, 2 parts by weight of α-methoxy benzoin methyl ether, and 0.02 parts by weight of hydroquinone was added to each. A high concentration resin composition was obtained by transporting a fixed amount using a pump and continuously mixing at 90°C using a fluid mixer.

Thereafter, it was molded in the same manner as in Example 2 to obtain a printing plate having a photosensitive resin layer.

Example 4 A printing plate was manufactured using the apparatus shown in FIG.

Polyvinyl alcohol (saponification degree 82 moles).

100 parts by weight (degree of polymerization: 5QO) and 186.8 parts by weight of water were added to Nigu and dissolved in the same manner as in Example 1.

After melting, 100°C, vacuum level 300 Torr, 6
It was concentrated for Q minutes, and 125.6 parts by weight of water was evaporated to obtain a highly concentrated polymer solution.

Next, this highly concentrated polymer solution and β-hydroxyethyl
A mixture of 240 parts by weight of methacrylate, 6.9 parts by weight of benzoin, and 0.01 part by weight of hydroquinone was transported quantitatively using a pump, and continuously mixed and defoamed at 98°C using a twin-screw pusher to form a highly concentrated resin. A composition was obtained.

Thereafter, it was molded in the same manner as in Example 2 to obtain a printing plate having a t-photosensitive resin layer.

Example 5 A printing plate was manufactured using the apparatus shown in FIG.

Polyvinyl alcohol (saponification degree 80 mol).

Polymerization degree 500) 100 parts by weight, diethylene glycol 30 parts by weight, ethanol 32.6 parts by weight, water 75.4 parts by weight
Parts by weight were added to a stirring tank and dissolved in the same manner as in Example 1.

After dissolving, it is continuously concentrated at 100°0 using a twin-screw extrusion machine,
Evaporate 77.8 parts by weight of a mixed solvent of ethanol and water,
A highly concentrated polymer solution was obtained.

Next, propylene glycol diglycidyl ether
A mixture of 68 parts by weight of diacrylate, α-methoxy, and 2 parts by weight of benzoin methyl ether was quantitatively transported to the middle of the twin-screw extruder using a pump, and heated to 98°C by the high concentration polymer solution and the twin-screw extruder. The mixture was continuously mixed and defoamed to obtain a highly concentrated resin composition.

Thereafter, it was molded in the same manner as in Example 2 to obtain a printing plate having a photosensitive resin layer.

Example 6 A printing plate was manufactured using the apparatus shown in FIG.

Polyvinyl alcohol (saponified & 80 molt.

100 parts by weight (degree of polymerization: 500) and 33.9 parts by weight of water were supplied to a twin-screw extruder, the polymer was plasticized with water, and heated to 100°C to melt.

After melting the polymer, N-methylol and
A mixture of 60 parts by weight of acrylamide and diethylene glycol bisether, 60 parts by weight of dia-7ton acrylamide, and 2 parts by weight of α-methoxy benzoin methyl ether was quantitatively transported and continuously heated at 98°C using a twin-screw extrusion machine. mixed.

Defoaming was performed to obtain a highly concentrated resin composition.

Thereafter, it was molded in the same manner as in Example 2 to obtain a printing plate having a photosensitive resin layer.

Example 7 A printing plate was manufactured using the apparatus shown in FIG.

Polyvinyl 0 alcohol (saponification degree 80 mol).

100 parts by weight of polymerization degree 500), 30 parts by weight of diethylene glycol, and 299 parts by weight of water were fed to a twin-screw extrusion machine,
Plasticize the polymer with water and diethylene glycol,
It was heated to 100°C and melted.

After melting the polymer, 68 parts by weight of propylene glycol diglycidyl ether diacrylate and α-methoxy benzoin were placed in the middle of the twin-screw extruder.

A quantitative amount of a mixture of 2 parts by weight of methyl ether was transported.

The mixture was continuously mixed and defoamed at 98° C. using a twin-screw extrusion machine to obtain a highly concentrated resin composition.

Thereafter, it was molded in the same manner as in Example 2 to obtain a printing plate having a photosensitive resin layer.

Example 8 A printing plate was manufactured using the apparatus shown in FIG.

ε-caprolactam and N,7-bis(amino.

Copolymerized polyamide (copolymerization ratio 6) of piperazine (propyl)
5 to 65 parts by weight) 100 parts by weight, 28.6 parts by weight of water to 2
The polymer was supplied to a shaft extrusion machine, plasticized with water, and heated to 100°C to melt it.

After melting the polymer, 60 parts by weight of ethylene glycol diglycidyl ether diacrylate was placed in the middle of the twin-screw extrusion machine.
A mixture of 2 parts by weight of benzophenone and 0.1 part by weight of nohydroquinone was quantitatively transported, and continuously mixed and defoamed at 90°C using a twin-screw pusher.

A highly concentrated resin composition was obtained.

Thereafter, it was molded in the same manner as in Example 2 to obtain a printing plate having a photosensitive resin layer.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of a method of manufacturing a container according to the present invention. FIGS. 2 and 3 are schematic diagrams showing other examples of two methods of manufacturing a container according to the present invention. 1: Preparation means for low concentration resin composition 2: Pump 3: Concentration means 4: Vacuum pump 5: Discharge means 6: Discharge means 7: Gui 8: High concentration resin composition 9: Support 10: Cover film 11: Molding Means 12: Conveyor 13: Drying device 14: Polymer melting means 15: Monomer tank 16: Mixing means 17: Polymer feeder 18: Polymer supply amount control mechanism 19; Melting aid tank 20: Polymer melting means Patent applicant Azuma Shi Co., Ltd. Formula Company Fig. 1 Fig. 2 ryJ 3rd rgJ

Claims (1)

[Claims] Discharging a water or organic solvent solution of a photosensitive resin composition containing a water or organic solvent-soluble polymer and a photosensitive monomer as main components in a proportion of 70% or more by weight of the whole; A method for producing a printing plate material, which comprises laminating it onto a support and forming it into a uniform film thickness.