JPH0369099B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a photosensitive resin composition. More specifically, the present invention provides a photosensitive resin composition that has excellent sensitivity, water resistance, water developability, smoothness, and resolution and is useful for producing screen printing plates, second originals, television fluorescent surfaces, etc. It is about things. Prior Art A photosensitive resin composition comprising saponified polyvinyl acetate and a styrylpyridinium salt compound or a styrylquinolinium salt compound is known.
The photoreaction of this photosensitive resin is a photocrosslinking reaction by photodimerization of a styrylpyridinium salt compound or a styrylquinolinium salt compound grafted onto saponified polyvinyl acetate. Therefore, there is no change in the amount of hydroxyl groups contained in the saponified polyvinyl acetate in the photosensitive layer before and after light irradiation. For this reason, the water resistance of the portion cured by light irradiation does not improve, and it swells significantly during water development, resulting in a drawback that high resolution cannot be obtained. Furthermore, JP-A No. 58-25304 discloses an acylated or acetalized saponified polyvinyl acetate,
A method for producing a photosensitive resin containing a styrylpyridinium salt compound or a styrylquinolinium salt compound has been proposed. However, this photosensitive resin cannot be developed with water due to its high hydrophobicity, and therefore an organic solvent must be used as a developer. However, this photosensitive resin has the disadvantage that high resolution cannot be obtained because it swells significantly in organic solvents. Furthermore, this highly hydrophobic photosensitive resin is also recognized to have a drawback of extremely low photosensitivity. Based on the above knowledge, if the photosensitive resin is made appropriately hydrophobic in advance, the image area after photocuring will exhibit high hydrophobicity, and water swelling will be prevented during water development, resulting in higher resolution. was expected. However, due to the above-mentioned hydrophobicization, the non-exposed areas also show high hydrophobicity, so the time required for water development becomes longer, and as a result, the degree of water swelling in the exposed areas increases, resulting in high resolution. There was also concern that the photosensitivity would decrease. Therefore, it has been considered extremely difficult to obtain a highly sensitive photosensitive resin that has appropriate hydrophobicity and high resolution, but is water developable. Problems to be solved by the invention Although water development is possible, it has moderate hydrophobicity,
To obtain a photosensitive resin composition having excellent resolution, water resistance, smoothness, and sharpness at the end of an image. Means for Solving the Problems The photosensitive resin composition of the present invention is a resin composition containing a photosensitive resin component containing at least one derivative of saponified polyvinyl acetate, and a resin emulsion. In the saponified polyvinyl acetate derivative of the photosensitive resin component, a portion of the vinyl alcohol units in the main chain of the saponified polyvinyl acetate are replaced by at least one photosensitive unit and at least one hydrophobic unit. and the photosensitive unit has the general formula (): [However, in the above formula (),

[Formula] represents a vinyl alcohol unit residue in the main chain of the saponified polyvinyl acetate derivative, and Y is the following general formula () and ():

【formula】

[Formula] represents one member selected from the group, m represents an integer of 1 to 6, n represents 0 or 1, and in the above formulas () and (), R ₁ is a hydrogen atom, a substituted alkyl groups and aralkyl groups that are not
and one member selected from an aralkyl group and an alkyl group having at least one member selected from a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond, and R ₂ is a hydrogen atom and a lower alkyl group. represents one member of
X ^- represents an anion], and
The above-mentioned gynophobic units have the general formulas (), () and (): and [However, in the above formulas (), () and (),

[Formula] is the same as above, and R ₃ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, an aminophenyl group, a nitrophenyl group, a tolyl group, a carboxyphenyl group, and a sulfoxy represents one member selected from a phenyl group, and R ₄ , R ₅ and R ₆ each independently represent an alkyl group having 1 to 9 carbon atoms, or
Including the case where only one of R ₄ , R ₅ , R ₆ is a hydrogen atom, R ₇ is an alkyl group having 2 to 9 carbon atoms,
represents one member selected from phenyl group, benzyl group, benzoyl group and propionyl group]
The resin emulsion may include vinyl acetate polymer, vinyl acetate-ethylene copolymer, vinyl acetate acrylate copolymer, acrylate ester polymer, styrene-acrylate copolymer, vinyl acetate-methacrylate copolymer. containing at least one resin selected from styrene-butadiene copolymer and acrylonitrile-butadiene copolymer, and the solid weight of the resin in the emulsion component and the weight of the solid resin in the photosensitive resin component. It is characterized by a ratio of 99:1 to 10:90. As mentioned above, the photosensitive resin composition of the present invention has
It comprises a photosensitive resin component and an emulsion component, and the ratio of the weight of the resin solids in the emulsion component to the weight of the resin solids in the photosensitive resin component is 99:1 to 10:90. It is within the range but 95:5
It is more preferable that the ratio is within the range of ~30:70. The photosensitive resin component contains one or more saponified polyvinyl acetate derivatives, and the saponified polyvinyl acetate derivative has at least one type of vinyl alcohol unit in the main chain of the saponified polyvinyl acetate. photosensitive unit and at least one hydrophobic unit. The above photosensitive unit is formed by substituting a part of the vinyl alcohol unit in the main chain of saponified polyvinyl acetate, and has the general formula ()
It is expressed as In the above formula (), Y is represented by the formula () and () are pyridinium salt residues and quinolinium salt residues, respectively, and are generally included in quaternary ammonium salt residues. It is something that will be done. In the general formulas () and (), R ₁ is a hydrogen atom, an unsubstituted alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, such as methyl , ethyl, propyl, butyl, pentyl, and hexyl groups, and unsubstituted aralkyl groups, such as benzyl, phenylethyl, methylbenzyl, and naphthylmethyl groups, as well as hydroxy groups, carbamoyl groups, ether bonds, and unsaturation. It is selected from alkyl groups and aralkyl groups having at least one member selected from bonds (eg, double bonds). Also, in the general formulas () and (),
R ₂ is a hydrogen atom, and a lower alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, such as methyl, ethyl,
selected from propyl, butyl, pentyl and hexyl groups, and X ^- is an anion, such as chloride, bromide, sulfate, phosphate, perchlorate, methoxysulfate, methanesulfonate, p -Represents toluenesulfonic acid ion, hydrogen borofluoride ion, etc. In addition, hydrophobic units substituting a portion of the vinyl alcohol unit in the main chain of saponified polyvinyl acetate have the general formulas (), () and ().
It is expressed as In the general formula (), R ₃ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, an aminophenyl group, a nitrophenyl group, a tolyl group, a carboxyphenyl group, and a sulfoxyphenyl group. To be elected. In the general formula (), R ₄ , R ₅ , and R ₆ are each independently an alkyl group having 1 to 9 carbon atoms, or only one of R ₄ , R ₅ , and R ₆ is a hydrogen atom. selected from alkyl groups including In the general formula (), R ₇ has 2 to 2 carbon atoms.
9 alkyl group, phenyl group, benzyl group, benzoyl group, and propionyl group. In the photosensitive saponified polyvinyl acetate derivative of the present invention, the saponified polyvinyl acetate has a content of 50 to
It is preferable to have a degree of saponification of 100% and a degree of polymerization of 300 to 4000. Further, it is preferable that 0.1 to 60 mol% of the vinyl alcohol units contained in the main chain of the saponified polyvinyl acetate are substituted with the photosensitive unit, and this substitution rate is within the range of 0.5 to 40 mol%. It is more preferable. Furthermore, 0.1 to 19 of the vinyl alcohol units contained in the main chain of saponified polyvinyl acetate
It is preferable that mol % is substituted by the hydrophobic unit, and this substitution rate is 0.4 to 10 mol %.
It is more preferable that it is within the range of . If the amount of the photosensitive unit is less than the above 0.1 mol%, the photosensitivity may be insufficient;
If the temperature exceeds that level, there will be no particular improvement in photosensitivity, and on the contrary, the viscosity of the aqueous resin solution will increase significantly, and it may become unusable. Also, the amount of hydrophobic units is
If it is less than 0.1 mol%, the resulting cured resin will have insufficient water resistance, and if it is more than 19 mol%,
Water development of the resulting photosensitive resin composition becomes difficult, and resolution becomes insufficient. The photosensitive polyvinyl acetate saponide compound derivative used in the present invention is prepared by combining (1) a polyvinyl acetate saponide compound, and (2) the lower general formulas () and () in an aqueous solvent in the presence of an acidic catalyst. [However, in the above formulas () and (),
Y, m, and n are the same as defined above, and t represents 0 or 1] at least one quaternary ammonium salt compound (styrylpyridium salt compound and styrylquinolium salt compound); and (3) a condensation reaction of at least one aldehyde compound, such as butyraldehyde, octylaldehyde, heptylaldehyde, nonylaldehyde, benzaldehyde, naphthylaldehyde, aminobenzaldehyde, nitrobenzaldehyde, carboxybenzaldehyde, or sulfoxybenzaldehyde ( The compound of formula () and the aldehyde compound (3) are produced by dehydration condensation reaction, and the compound of formula () is produced by dealcoholization condensation reaction). Alternatively, the photosensitive polyvinyl acetate saponide compound derivative used in the present invention can be obtained by acylating a saponified polyvinyl acetate with an acylating agent in advance, and then combining this acylated product with a quaternary ammonium salt compound of the general formulas () and () above. It can also be produced by a method of causing a condensation reaction with at least one of the following. As the acylating agent in this method, chlorides such as acetyl chloride, propionyl chloride, benzoyl chloride, etc., or acid anhydrides such as acetic anhydride, benzoic anhydride, etc. can be used. As quaternary ammonium salt compounds of general formulas () and (), 1-methyl-4-{2-[4
-2,2-dimethoxyethoxy)phenyl]ethyl}-pyridinium methosulfate, N-methyl-4
styrylpyridinium salt compounds such as -(p-formylstyryl)-pyridinium methosulfate and N-methyl-2-(p-formylstyryl)-pyridinium hydrochloride, and 1-methyl-4-{2 -[4-(2,2-dimethoxyethoxy)phenyl]ethyl}-quinolinium methosulfate, N-methyl-4-(p-formylstyryl)-
Quinolinium methosulfate and N-methyl-
Examples include styrylquinolium salt compounds such as 2-(p-formylstyryl)-quinolinium hydrochloride. The above condensation reaction between the quaternary ammonium salt compound, saponified polyvinyl acetate, and aldehyde compound is carried out in an aqueous solvent in the presence of an acidic solvent, generally at a pH of 1 to 3 and at an appropriate temperature, for example, 30 to 60 C. for an appropriate period of time, for example 3 to 6 hours, and then stirred or allowed to stand at room temperature for 1 day. The emulsion component used in the present invention contains at least one kind of resin, and examples of such resin include vinyl acetate polymer, vinyl acetate-ethylene copolymer, and vinyl acetate-acrylic acid ester copolymer. , acrylic ester polymer, styrene-acrylic ester copolymer, vinyl acetate-methacrylic ester copolymer, styrene-
Examples include butadiene copolymer, acrylonitrile-butadiene copolymer, and the like. Emulsions of these resins contain nonionic emulsifiers. The photosensitive resin composition of the present invention is prepared by uniformly mixing a photosensitive resin component and an emulsion component in a desired ratio. In the composition of the present invention, the emulsion component is effective for improving the water resistance and resolution of the cured image area after exposure. Furthermore, a hydrophobic component in the photosensitive resin component is also effective in improving the water resistance and resolution of the image area cured by exposure. Function In the photosensitive resin composition of the present invention, an emulsion component is used in combination, and in the photosensitive resin component, a photosensitive unit of the general formula () bonded to a main chain of saponified polyvinyl acetate,
The hydrophobic unit of general formula (), () and/or () significantly improves the water resistance and resolution of the exposed and hardened image area. EXAMPLES The present invention will be further illustrated by the following examples. In the examples, the water resistance of the exposed image area, the resolution, the number of remaining stages using Kodatsu Step Tablet No. 2,
The smoothness of the image area was measured or evaluated by the following method. (1) Water resistance of exposed image area The obtained photosensitive plate was washed with shower water (water pressure 2
Kg/cm ² ) Washing was performed 20 times. After that, the photosensitive plate was dried, and the degree of destruction of the plate image area by shower water and the adhesion state between the image area and the nylon mesh were observed using a stereoscopic microscope [AFX-model manufactured by Nikon Corporation].
The images were observed using a 160x magnification. Items where part of the image area is destroyed or where a void is formed between the image area and the nylon mesh are evaluated as "poor water resistance", and those with destruction and no void are evaluated as "water resistance". It was rated as "good quality". (2) Resolution A silver salt negative film (width 30, 40, 50, 60, 70,
80, 90, 100, 125, 150, 175, 200, 250 and
Negative film (for high-resolution observation that can form a 300 μm slit) was stacked, placed in a sealed light irradiation device, degassed with a vacuum pump, and then exposed to the camera from a height of 1 m using a 2 kW ultra-high pressure mercury lamp. Irradiated for minutes. Thereafter, this photosensitive plate was washed 6 times with shower water (water pressure 2 kg/cm ² ) using a fully automatic plate making, developing and washing machine SW type manufactured by Kyowa Kiko Co., Ltd., and then developed. After drying, observe the photosensitive plate. For example, the resolution of a photosensitive plate with slits with a width of 40 μm or more is written as 40 μm, or the resolution of a photosensitive plate with slits with a width of 100 μm or more is written as 40 μm. image quality
It was written as 100 μm. The smaller the displayed slit width, the higher the resolution of the photosensitive plate. (3) Remaining plate number using Step Tablet No. 2 manufactured by Kodak Co. On the obtained photosensitive plate, Step Tablet No. 2 manufactured by Kodak Co. was superimposed, exposed, and developed. After drying, the photosensitive plate was observed, and the number of developed platens remaining was indicated. Generally, the higher the number of remaining stages, the higher the sensitivity. (4) Image smoothness The photosensitive plate after development was examined under a stereoscopic microscope [manufactured by Nikon Co., Ltd.]
AFX-type] for observation at 160x magnification. Particularly, the upper part of the image edge portion was observed, and those with a small difference in height were evaluated as having good smoothness, and those with an extreme difference in height were evaluated as having poor smoothness. Example 1 100 g of saponified polyvinyl acetate (degree of polymerization 1800, degree of saponification 78 mol%), 10 g of N-methyl-4-(p-formylstyryl)pyridinium methosulfate, and n
-Dissolve 8 g of butyraldehyde in 900 g of water,
Adjust the pH to 2.5 with phosphoric acid, stir at 40°C for 4 hours,
The mixture was further stirred at room temperature all day and night. After the condensation reaction, the reaction solution is PHed using an anion exchange resin and a cation exchange resin.
After adjusting to 6 to 7, the exchange resin was removed to prepare a photosensitive resin component (A). 60 g of this photosensitive resin component (A) and 18 g of an aqueous polyvinyl acetate emulsion (solid content concentration 50%) were mixed to prepare a photosensitive resin composition. This composition was printed on a screen printing plate (nylon 200 mesh).
A film thickness of 15 μm was applied on top and dried. Overlay the negative film on the resulting photosensitive plate,
Light was irradiated for 4 minutes from a height of 1 m using a 2 kW ultra-high pressure mercury lamp. When the photosensitive plate was then developed with water, the exposed areas remained and the unexposed areas were washed away, forming an image. Regarding the above photosensitive plate and the obtained printing plate, water resistance of exposed areas, resolution, number of remaining plates using Kodaku Step Tablet No. 2, gloss of image areas, etc. were measured. The results are shown in Table 1. Example 2 Saponified vinyl acetate-2,2-dibutylhexylate vinyl ester copolymer (polymerization degree 1800, saponification degree 85 mol%, 2,2-dibutylhexylate vinyl ester content 6 mol%) 100 g and N -Methyl-4-(p-formylstyryl)pyridinium methosulfate (10 g) was dissolved in 900 g of water, and the following Example 1 was prepared.
Photosensitive resin component (B) was prepared in the same manner as above. A composition similar to that in Example 1 was prepared using this photosensitive resin component (B), and a photosensitive plate similar to that in Example 1 was prepared using this composition, and an exposure test was conducted. The results are shown in Table 1. Example 3 Saponified polyvinyl acetate containing 1.2 mol% of N-methyl-4-(p-formylstyryl)quinolinium group (degree of polymerization 1800, degree of saponification 88 mol%)
Suspend 100g in pyridine from step 2, add 10g of benzoyl chloride, stir at 40-50℃ for 1 hour, continue stirring at room temperature for 5 hours, take out the solid, and wash with methanol. and dried. A photosensitive resin composition (C) was prepared by dissolving 100 g of this resin in 900 g of water. Prepared photosensitive resin component
The same operation as in Example 1 was performed using 60 g of (C). The results are shown in Table 1. Comparative Example 1 100 g of saponified polyvinyl acetate (degree of polymerization 1800, degree of saponification 78 mol%) and 10 g of N-methyl-4-(p-formylstyryl) pyridinium methosulfate were added to water.
A comparative photosensitive resin component (Aa) was prepared by dissolving 900 g of the sample and subjecting it to the same operations as in Example 1. Using this comparative component (Aa), the same operation as in Example 1 was performed. The results are shown in Table 1. Comparative Example 2 100 g of saponified polyvinyl acetate (degree of polymerization 1800, degree of saponification 85 mol%) and 10 g of N-methyl-4-(p-formylstyryl) pyridium methosulfate were added to water.
A comparative photosensitive resin component (Ba) was prepared by dissolving 900 g of the sample and subjecting it to the same operations as in Example 1. Using this comparative component (Ba), the same operation as in Example 1 was performed. The results are shown in Table 1. Comparative Example 3 The same operation as in Example 1 was carried out using only the photosensitive resin component (C) prepared in Example 3 and without the aqueous emulsion. The results are shown in Table 1. Comparative Example 4 The same operation as in Example 1 was carried out using only the photosensitive resin component (A) prepared in Example 1 and without the aqueous emulsion. The results are shown in Table 1. Example 4 60 g of the photosensitive resin component (A) prepared in Example 1 and 18 g of an aqueous emulsion of vinyl acetate-ethylene copolymer (solid content concentration 50%, polymerization component ratio of vinyl acetate and ethylene 1 mol/1 mol) were mixed to prepare a photosensitive resin composition. Using this composition,
A photosensitive plate similar to that in Example 1 was prepared and an exposure test was conducted. The results are shown in Table 1. Example 5 Aqueous emulsion of 60 g of the photosensitive resin component (A) prepared in Example 1 and vinyl acetate-butyl acrylate copolymer (solid content concentration 50%, polymerization component ratio of vinyl acetate and butyl acrylate 1) 18 g (mol/1 mol) were mixed to prepare a photosensitive resin composition. Using this composition, a photosensitive plate similar to that in Example 1 was prepared and an exposure test was conducted. The results are shown in Table 1. Example 6 60 g of the photosensitive resin component (A) prepared in Example 1 and 18 g of an aqueous emulsion (solid content concentration 50%) of neopentyl glycol diacrylate polymer were mixed to prepare a photosensitive resin composition. Using this composition, a photosensitive plate similar to that in Example 1 was prepared and an exposure test was conducted. The results are shown in Table 1. Example 7 An aqueous emulsion (solid content concentration 50%,
A photosensitive resin composition was prepared by mixing 18 g of vinyl acetate and ethylene glycol dimethacrylate (polymerization component ratio 1 mol/1 mol). Using this composition, a photosensitive plate similar to that in Example 1 was prepared and an exposure test was conducted. The results are shown in Table 1. Example 8 60 g of the photosensitive resin component (A) prepared in Example 1 and 18 g of an aqueous emulsion of styrene acetate-butadiene copolymer (solid content concentration 50%, polymerization component ratio of styrene and butadiene 1 mol/1 mol) mix,
A photosensitive resin composition was prepared. Using this composition, a photosensitive plate similar to that in Example 1 was prepared and an exposure test was conducted. The results are shown in Table 1. Example 9 60 g of the photosensitive resin component (A) prepared in Example 1 and 18 g of an aqueous emulsion of acrylonitrile acetate-butadiene copolymer (solid content concentration 50%, polymerization component ratio of acrylonitrile acetate and butadiene 1 mol/1 mol) were mixed to prepare a photosensitive resin composition. Using this composition, a photosensitive plate similar to that in Example 1 was prepared and an exposure test was conducted. The results are shown in Table 1.

【table】

[Table] In Comparative Examples 1, 2, and 3, the remaining number of stages is the same as in Example 1.
When the exposure amount was increased to 6 to 7, which is about the same as the number of remaining stages shown in Comparative Example 1,
The resolution of 2 and 3 was even worse than that of 100-125 μm. Further, in the case of Comparative Examples 1, 2, and 3, the water resistance of the exposed image area remained poor even when the exposure amount was increased. Effects of the Invention The photosensitive resin composition of the present invention has become slightly hydrophobic by appropriately sealing the hydroxyl groups contained in a large amount in the saponified polyvinyl acetate with hydrophobic groups in advance. Nevertheless, the speed of water development is practically sufficient. In addition, the water resistance of the exposed area, ie, the image area, is improved and swelling by water is significantly reduced, so the resulting image exhibits excellent water resistant resolution, smoothness, and adhesion to the substrate. Further, by using an emulsion resin in combination, it becomes more excellent in water resistance, resolution, smoothness, and adhesion to the base plate.

Claims (1)

[Scope of Claims] 1. A photosensitive resin component comprising at least one derivative of saponified polyvinyl acetate, a resin emulsion, and a resin composition comprising the saponified polyvinyl acetate derivative of the photosensitive resin component. is one in which a part of the vinyl alcohol unit in the main chain of saponified polyvinyl acetate is replaced by at least one kind of photosensitive unit and at least one kind of hydrophobic unit, and the photosensitive unit is , general formula (): [However, in the above formula (), [formula] represents a vinyl alcohol unit residue in the main chain of the saponified polyvinyl acetate derivative, and Y represents the following general formulas () and (): [formula] [formula] m represents an integer of 1 to 6, n represents 0 or 1, and in the above formulas () and (), R ₁ is a hydrogen atom, unsubstituted Alkyl groups and aralkyl groups,
and one member selected from an aralkyl group and an alkyl group having at least one member selected from a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond, and R ₂ is a hydrogen atom and a lower alkyl group. represents one member of
X ^- represents an anion], and
The hydrophobic unit has the general formulas (), () and (): and [However, in the above formulas (), () and (),
[Formula] is the same as above, and R ₃ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, an aminophenyl group, a nitrophenyl group, a tolyl group, a carboxyphenyl group, and a sulfoxy Represents one member selected from phenyl groups, R ₄ , R ₅ and R ₆ each independently represent an alkyl group having 1 to 9 carbon atoms, or R ₄ , R ₅ and R ₆ each independently represent an alkyl group having 1 to 9 carbon atoms; R ₇ represents a member selected from an alkyl group having 2 to 9 carbon atoms, a phenyl group, a benzyl group, a benzoyl group, and a propionyl group, including the case where only one of them is a hydrogen atom. selected from the group
The resin emulsion includes a vinyl acetate polymer, a vinyl acetate-ethylene copolymer, a vinyl acetate acrylate copolymer,
Containing at least one resin selected from acrylic ester polymer, styrene-acrylic ester copolymer, vinyl acetate-methacrylic ester copolymer, styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer, and the resin solid weight in the emulsion component,
The ratio to the resin solid content weight in the photosensitive resin component is
A photosensitive resin composition, characterized in that the ratio is within the range of 99:1 to 10:90. 2 The degree of saponification of the saponified polyvinyl acetate is 50
The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is within the range of 100%. 3. The photosensitive resin composition according to claim 1, wherein 0.1 to 60 mol% of the vinyl alcohol units contained in the main chain of the saponified polyvinyl acetate are substituted with the photosensitive unit. 4. The photosensitive resin composition according to claim 1, wherein 0.1 to 19 mol% of the vinyl alcohol units contained in the main chain of the saponified polyvinyl acetate are substituted with the hydrophobic unit.