JPS6036504A - Production of photo-sensitive resin - Google Patents

Abstract

PURPOSE:The titled resin that is obtained by reaction of a specific chalcone derivative with a homo- or copolymer bearing alcoholic hydroxyls in the presence of an effective amount of 2,4,6-trinitrochlorobenzene, thus giving chemically stable photo-sensitive membranes. CONSTITUTION:The objective resin having groups of formula II is obtained by reaction between (A) a chalcone derivative of formula I [one of R1 or R2 is oxomethylene bone and the other is a single bond; R3 is H, alkyl, cyano, nitro, alkoxy, alkoxycarbonyl, halogen], e.g., 4-carboxychalcone and (B) a homo- or copolymer bearing alcoholic hydroxyls such as polyvinyl alcohol in the presence of an effective amount of 2,4,6-trinitrochlorobenzene, preferably the ratio of A:C is 1/1-1/1.5. USE:Photoresists, PS plate for printing.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a photosensitive resin. More specifically, the present invention relates to a method for producing a photosensitive resin having a chalcone group or a derivative group thereof as a photocrosslinkable group.

Hitherto, known methods for synthesizing photosensitive resins having chalcone or derivative groups thereof include a method in which polybenzalacetophenone is reacted with an aldehyde, and a method in which polystyrene is reacted with cinnamic acid chloride in a Friedel-Crafts reaction. With these methods, it is not possible to obtain a photosensitive resin with a high substitution rate of photocrosslinkable groups, and as a result, the sensitivity is low. However, conventional synthesis methods require long reaction times.

There are problems such as gelation.

The present inventors aimed to overcome the drawbacks of the conventional photosensitive resin manufacturing method (as a result of extensive research, the general formula (1
) or its derivatives represented by 2.4.6
-We succeeded in directly reacting a polymer or copolymer having an alcoholic hydroxyl group in the presence of trinitrochlorobenzene, resulting in the completion of the present invention.

In other words, this invention specifies the general formula (RI, R2, and Rs in the formula have the same meanings as above) for a polymer or copolymer having an alcoholic hydroxyl group.
It is characterized in that the chalcone derivative represented by is reacted in the presence of an effective amount of 2,4°6-trinitrochlorobenzene.

The present invention provides a method for producing a photosensitive resin having a group represented by the general formula (R, , R2, and Rs in the formula have the same meanings as above).

Polymers or copolymers with alcoholic hydroxyl groups used in the present invention include vorivinyl alcohol, polyhydroxyethyl acrylate, hydroxyethyl acrylate-styrene copolymer, hydroxyethyl methacrylate-methyl methacrylate copolymer, and polyvinyl alcohol. -2-Hydroxypropyl methacrylate, copolymer of polyethylene and polyvinyl alcohol, etc. can be reduced. In addition, the chalcone derivatives represented by the general formula (1) include 4-carboxychalcone, 4-carboxychalcone,
4-cyano-4=carboxychalcone, 4-n propyl-3-carboxychalcone, 4'-chloro-2-h sulfoxychalcone, 4-nitro-4-carboxychalcone,
3-Methyl-2-carboxychalcone.

4-Mej-xychalcone, 3-methoxycarbonyl-4
- Carboxychalcone, etc. can be mentioned. Examples of the organic base used in the present invention include pyridine, triethylamine, 4-dimethylaminopyridine, and 1,4-diazabicyclo(2,2,2)octane.

Examples of reaction solvents include N,N-dimethylacetamide,
Examples include N,N-dimethylformamide, dimethylsulfogide, hexamethylphosphoric triamide, and the like. The reaction temperature is preferably in the range of 20°C to 100°C, but is not limited thereto. In this case, the molar ratio of the chalcone derivative and 2.4.6-)linitrochlorochlorobenzene is selected in the range of 1:1 to 1=1.5. However, it is not limited to this. In addition, the molar ratio of the organic base and chalcone derivative used as necessary is 2.
:1 to 5:1 is desirable, but other values are also possible.

The reaction product is obtained by pouring the reaction mixture into water.

The photosensitive resin provided by the present invention can be prepared by dissolving this effective amount in an organic solvent to form a solution, which can be applied to aluminum plates, copper plates, etc.
It can be applied onto the surface of a support such as a zinc plate or a copper-clad laminate by means such as casting, spraying, or coating, and then dried to form a film.

The photosensitive film thus obtained inherits the physical properties of the polymer used as the base, is strong, and has good adhesion to the support. When the coating film thus obtained is irradiated with light through a negative lens and the unexposed areas are removed with a solvent, a negative image is obtained. Furthermore, since it has extremely high sensitivity, is chemically stable, and does not cause so-called dark reactions, it is easy to maintain quality in the solution state and film forming state. Therefore, it is suitable for applications such as photoresist, printing PSJk, and metal etching mask.

Next, the present invention will be explained in detail using examples.

Example 1 - 1 g of polyvinyl alcohol with a m content of 14oo and a saponification degree of 85% was dissolved in 80 ml of dimethylacetamide, and 7.44 g of 4-carboxychalcone and 2.4.6-
Add 7.30 g of trinitrochlorobenzene, further add 12 g of pyridine, and react at 80° C. for 4 hours.

Next, the resulting reaction mixture is poured into a large excess of water to isolate the desired photosensitive resin. After washing with ethanol.

Dry. Yield was 2.71g. When we investigated the ultraviolet absorption spectrum of this substance, the absorption maximum was 3101m.
From this, we investigated the introduction rate of chalcone groups and found that 6
It was 0%. Furthermore, when the infrared absorption spectrum was examined, absorption based on chalcone groups was observed at 15Q5cm-'+ and 1665cm''-'.

Example 2 Degree of polymerization 1700. 0.44 g of polyvinyl alcohol with a degree of saponification of 85% was dissolved in 40 ml of dimethylacetamide, and 3.
82 g and 2.4.6-dolinitrochlorobenzene 3.2
1 g of pyridine was added thereto, and further 5.1 g of pyridine was added, followed by reaction at 85° C. for 2 hours. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried. Yield was 2.12g. When the ultraviolet absorption spectrum of this product was examined, the absorption maximum was found to be 3 Q 5 nm, and when the introduction rate of chalcone groups was examined from this, it was found to be 6796. Further investigation of the infrared absorption spectrum revealed that the absorption based on chalcone groups was 1600 Cm-' and 1650 Cm-'
was recognized and received.

Example 3 Degree of polymerization: 2000. Dissolve 044 g of polyvinyl alcohol with a degree of saponification of 85% in 40 ml of dimethylacetamide, and add 3.72 g of 4-chloro-4-carboxychalcone to this solution.
2.4.6-1 Add 3.21 g of linitrochlorobenzene, add 51 g of pyridine, and heat at 80°C for 23 hours.
Time reaction. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin.

After washing with ethanol, it was dried. Yield was 2.55g. When the ultraviolet absorption spectrum of this product was examined, the absorption maximum was found to be 315 nm, and when the introduction rate of chalcone groups was examined from this, it was found to be 76%. Furthermore, when the infrared absorption spectrum was examined, absorption based on chalcone groups was observed at 1600 cm-'r and 1665 cm-'.

Example 4 Degree of polymerization 1700. 0.25 g of polyvinyl alcohol with a degree of saponification of 90% was mixed with dimethylacetamide 2 Q Tll
1 and 1.97 g of 45 methyl-3-carboxychalcone and 2.4.6-)linitrochlorobenzene 1
．． Add 83g and further add 3.2g of pyridine to make 85
Stir the reaction at ℃ for 4 hours. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried twice. Yield is 0.92
It was g. When the ultraviolet absorption spectrum of this product was examined, the absorption maximum was 316 nm, and when the introduction rate of chalcone groups was examined from this, it was 59%. Furthermore, when the infrared absorption spectrum was examined, absorption based on chalcone groups was observed at 1605 cm-' and 16600 m-'.

Example 5 Degree of polymerization: 500. 0.25 g of polyvinyl alcohol with a degree of saponification of 85% was dissolved in 20 ml of dimethyl sulfoxide, 219 g of 3-nitro-3-carboxycarbonate and 183 g of 2,4,6-trinitrochlorobenzene were added thereto, and 3.4 g of pyridine was added. and incubate for 25' at 70°C.
J6' Ijt+reaction occurs.

Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin.

After washing with ethanol, it was dried. Yield was 1.35g. When the ultraviolet absorption spectrum of this material was examined, the maximum absorption was found to be 320 nm.

The introduction rate of chalcone groups was investigated and found to be 70%. Further investigation of the infrared absorption spectrum revealed that the absorption based on chalcone groups was 1600 cm-' and 168 cm-'.
5 Cm-'K was observed.

Example 6 Degree of polymerization 2100. 0.25 g of polyvinyl alcohol with a degree of saponification of 87% was dissolved in 20 ml of dimethylformamide, and 2.19 g of 2'-nitro-4-carboxychalcone was added to the solution.
g and 2.4.6-) linitrochlorobenzene 1.83 g
and then 3.2 g of pyridine and heated at 80°C for 24 hours.
Allow time to react. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin.

After washing with ethanol, it was dried. Yield was 1.28g. When the ultraviolet absorption spectrum of this product was examined, the absorption maximum was found to be 319 nm, and when the introduction rate of chalcone groups was examined from this, it was 68%. Further examination of the infrared absorption spectrum revealed absorption based on chalcone groups at 1600 cm-'+ and 1585 cm-'. In addition, the absorption based on nitro group is 1560 Cm'',
"1350 cm-" Ni? b Rare f, :,.

Example 7 1.15 g of polyhydroxyethyl acrylate with a molecular weight of 45,000 was dissolved in 80 ml of dimethylpolamide, and 2.52 g of 4-carboxychalcone and 2.4.6-
) Add 2.53 g of linitrochlorobenzene, further add 4.2 g of pyridine, and react at 40° C. for 24 hours.

Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried. Yield was 3.24g. When I investigated the ultraviolet absorption spectrum of this substance, the absorption maximum was 310.
nm, and when the chalcone group introduction rate was investigated from this, it was 87%. Further investigation of the infrared absorption spectrum revealed that the absorption based on chalcone groups was 1605 crn.
-'.

and 1665 Cm-'.

Patent applicant Hirobe Kawada, Director of the Agency of Industrial Science and Technology

Claims (1)

[Claims] A polymer or copolymer having an alcoholic hydroxyl group has the general formula (in the formula, one of R1 and R2 is an oxomethylene bond, the other is a simple bond, R3 is a hydrogen atom, an alkyl group, cyano group, nitro group, alkoxy group, alkoxycarbonyl group, or halogen atom) in the presence of an effective amount of 2,4゜6-trinitrochlorobenzene. . A method for producing a photosensitive resin having a group represented by the general formula (R, , R2, and Rs in the formula have the same meanings as above).