JPS6036503A - Photosensitive resin - Google Patents

Abstract

PURPOSE:The titled resin that is obtained by reaction of a specific chalcone derivative with a polymer or copolymer bearing alcoholic hydroxyls, thus giving photosensitive membranes of high toughness, high adhesion, high sensitivity and high chemical stability, having specific groups, by forming the polymer into films on a support. CONSTITUTION:The objective resin having at least one of the group of formula IIis obtained by reaction between a chalcone derivative of formula I (one of R1 and R2 is oxo-methylene bond and the other is single bond; R3 is H, alkyl, cyano, nitro, alkoxy, alkoxycarbonyl, halogen) such as 4-carboxychalcone and a polymer or copolymer bearing alcoholic hydroxyls such as polyvinyl alcohol, preferably in a solvent such as dimethylformamide in the presence of 2,4,6-trinitrotoluene and an organic base such as pyridine. USE:Photoresists, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photosensitive resins. More specifically, the present invention relates to a photosensitive 1/1-4A1 resin having a chalcone group or a derivative group thereof as a photocrosslinkable group.

Until now, many photosensitive resins having chalcone or its derivative groups have been known, such as those obtained by reacting polybenyarutophenone with aldehyde and those obtained by subjecting polystyrene to a Friedel-Crafts reaction of cinnamic acid chloride. It is being In these methods, photosensitive disease JIi7 with a high substitution rate of photocrosslinkable groups
cannot be obtained, resulting in low sensitivity. Furthermore, conventional synthesis methods require a long reaction time and have the problem of preventing kelization.

The present inventors have conducted intensive research to overcome the drawbacks of conventional photosensitive resins.

The present invention succeeded in directly reacting the chalcone represented by the general formula (1) or a derivative thereof with a polymer or copolymer having an alcoholic hydroxyl group in the presence of 2.4.6-)linitrochlorobenzene. I came to do this. That is, the present invention is produced by reacting a chalcone derivative represented by the general formula (in the formula, R, R, R3 have the same meanings as above) with a polymer or copolymer having an alcoholic hydroxyl group. The present invention provides a photosensitive resin having a group represented by the general formula (in the formula, 1.Rz and Rs have the same meanings as in Section 7iij).

Alcoholic hydroxyl μ used in the present invention.

Polyvinyl alcohol, polyhydroxyethyl acrylate, hydroxyethyl acrylate-styrene copolymer, hydroxyethyl methacrylate-1-methyl methacrylate copolymer,
Examples include poly-2-hydroxypropyl methacrylate-1-, a copolymer of polyethylene and polyvinyl alcohol, and the like. Further, as the chalcone derivatives represented by the general formula (1), 4-carboxychalcone, 4'-carboxychalcone, 4'-cyano-4-carboxychalcone + 4'-11propyl-3-carboxychalcone,
4'-chloro-2-carboxychalcone, 4'-nitro-4-carboxychalcone, 3'-methyl-2-carboxychalcone, 4'-methoxychalcone, 3-methoxychalcone-4-carboxychalcone, etc. can be mentioned.

Further, the reaction between a polymer or copolymer having an alcoholic hydroxyl group and a chalcone derivative represented by the general formula (1) is carried out in a solvent such as dimethylbormamide, dimethyl sulfoxide, ethyl cellosolve, or ethylene glycol monomethyl ether.

2.4.6-) It is possible to ladle linitrotoluene and an organic base together. Specific bases include pyridine, triethylamine, 4-dimethylaminopyridine, 1.4-
Examples include diazabicyclo[2°2.2]octane. Reaction l,',1'1 degree is 100 degrees from 20℃
A range of 0.degree. C. is preferred, but is not limited thereto.

In this case, the chalco" derivative is selected from the range of 2.4.6 trinitrochlorochlorobenzene. However, it is not limited to this. Also, if necessary, the organic base used and the mole of the chalcone derivative are selected. The ratio preferably ranges from 2:1 to 5:1, but may be other than that.The reaction product is obtained by pouring the reaction mixture into water or alcohol.

The photosensitive resin provided by the present invention has this effective ffi
is dissolved in a plywood solvent to form a solution, applied to the surface of a support such as an aluminum plate, copper plate, zinc plate, or copper-clad laminate by means such as casting, spraying, or coating, and dried to produce a product. It can be membraned.

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. In this way, a negative image is obtained by irradiating light through the negative coating film and removing the unexposed areas with a solvent. Furthermore, since it has extremely high sensitivity and is chemically stable, so-called dark reactions do not occur, quality can be maintained in the solution state and in the film forming state. For the sake of A
It is suitable for applications such as resists, printing PS plates, metal etching masks, etc.

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

Reference Example 1 1 g of polyvinyl alcohol with a degree of polymerization of 1400 and a degree of saponification of 85 L/FO was mixed with dimethylacetamide ε30
m1 and 4-carboxychalcone 7,44
g and 2.4.6-trinitrochlorobenzene 7.30
Then, 12 g of pyridine was added and the mixture was reacted at 80° C. for 4 hours. Next, the obtained reaction mixture was added to a large excess of ice to obtain the desired photosensitivity '3xJ II! Isolate 'i'. After washing with ethanol.

Dry. The amount of absorption (was 2.71 g).When I examined the ultraviolet absorption spectrum of this product, the amount of absorption was 310.
nn], and when the incorporation rate of chalcone groups was investigated from this, it was 60%. Furthermore, we investigated the infrared absorption spectrum and found that it was based on Calcomp and Shini (absorption power: 605
cm-', and 1665 (nl"-1 with 5 min.
3. Reference Example 2 II Combined/fJf ] 70
01 η 11 molten angle j', 4-11 times this, J pill 4-force sulfoxychalcone 3.82 g and 2.4.6-)
Add 3.21 g of linitrochlorobenzene to 1 liter of linitrochlorobenzene, add 51 g of pyridine, and react at 85°C for 2 hours. The resulting reaction mixture was then added to a large excess of ethanol to obtain [j
Dissect the target photosensitive resin. After washing with ethanol,
Dry. Yield i+ was 2.12 g. When we plotted the ultraviolet absorption spectrum of this substance in y and v, the absorption maximum was 3
0G old 11, and from now on the introduction rate of chalcone group, □
ill'J overall score was 67%. Further investigation of the infrared absorption spectrum revealed that the absorption caused by the chalcone group was 1600 Cm'-' and 165 (, l cm
−' was recognized.

Reference example 3 Degree of polymerization: 2000. 0.44 g of polyvinyl alcohol with a degree of saponification of 85% was dissolved in 40 ynl of dimethylacetamide, and 37 g of 47-chloro-4-carboxychalcone was added to the solution.
2B and 2.4.6-) 2;・[1 Chlorobenzene 3.
Add 21g of pyridine, further add 5.1g of pyridine,
231 in C. , j. The resulting reaction mixture was then added to a large excess of -1-tanol to obtain a photosensitive reaction. After washing with ethanol, it was washed with Akira:*rNy. Yi-h: is 2
．． It was 55g. When the ultraviolet absorption spectrum of this product was examined, the maximum absorption was found to be 315 nm, and when the proportion of chalcone groups was examined from the first stage, it was 76%.

Furthermore, in the infrared absorption spectrum, absorptions at 160Qcm-' and 1665C111-' were observed in the L(jbej,-- and chalcone groups).

Reference example 4 Degree of polymerization 1,700. Dissolve 0.25 g of polyvinyl alcohol with degree of Kelization 9]0% in 2 Q ml of dimethylacetamide, and add 1 ml of 47-methyl-3-carboxychalcone to this solution.
．． ．． 97 g and 2. 4. 6-Dolinylochlorobenzene 1.83 g Fully processed, Salanipyridine 3.2
g and reacted at 85°C for 4 n4-times. then i
II. Add a large excess of ethanol to the first reaction mixture to make it 1! Buy Shikosho TBL IIFi as a single purchase. After washing with ethanol, it was dried. , yield is 0,92
It was g. When the ultraviolet absorption spectrum of this product was examined, the absorption maximum was 316 null, and when the proportion of chalcone groups was examined from Koi 1, it was 59%. Further investigation of the infrared absorption spectrum revealed that the absorption based on chalcone groups was 1605 cnl-' and 1660 cnl-'.
It was measured in cm-'.

Reference Example 5 = 0.25 g of polyvinyl alcohol with a degree of Φ polymerization of 00 and a degree of saponification of 85% was added to dimethyl sulfoxo + X2O11]
1 and added 2.19 g of 3-nitro-3-carne tosychalcone and 1.83 g of 2.4.6-1-linitone, and further 3.4 g of pyridine.
was added and reacted at 270°C for 25 hours.

Next, P and others added anti-J, 'L Hakama jIL compound to a large excess of upper ethanol to make it FI-like.
lli'i is simply f'il・-4. , washed with ethanol and dried. The yield was 1; 35 g. When I investigated the ultraviolet absorption spectrum of this substance, the absorption maximum was 3.
2 Q nn1.

From this, we investigated the introduction rate of chalcone groups and found that it was 7 (1%).Furthermore, we analyzed the infrared absorption spectra of al: and 1. Based on the chalcone groups (absorption or
', and 1685011-1 were recognized.

Example 1 1 g of 1 illir obtained in Reference Example 1 was dissolved in t'lQ ml of dimethylacetamide, and the solution was cast onto an aluminum plate and dried. Pass the negative through this at 50C
Light from a 500W xenon lamp was irradiated for 1 second from a distance of 11 seconds. When the unexposed areas were removed with dimethylacetamide, a clear relief image was obtained.

Example 2 1 g of the resin prepared in Reference Example 2 was dissolved in 20 ml of dimethylformamide, and this was applied to an aluminum plate using a spin coater. Pass the negative through the obtained coating 5
When light from a 500W xenon lamp was irradiated for 1 second from a distance of Q cm and the unexposed areas were removed with dimethylformamide, a clear relief image was obtained.

Example 3 1 g of the resin obtained in Reference Example 3 was dissolved in dimethylformamide 2
Dissolve in 0ml, cast onto an aluminum plate, and dry. This was irradiated with light from a 500W xenon lamp for 1 second from a distance of 50CTnpiI through the negative.

When the unexposed areas were removed with dimethylacetamide,
A clear relief image was obtained.

Example 4 1.5 g of the resin obtained in Reference Example 4 was dissolved in 25 ml of methyl ethyl ketone, and the solution was cast onto a silicon wafer and dried. Light from a 500 W xenon lamp was shined through this through a negative for 2 seconds from a distance of 50 cm.

When the unexposed areas were removed with methyl ethyl ketone, a clear relief image was obtained.

Example 5 1 g of the resin obtained in Reference Example 5 was mixed with 2 dimethylacetamide.
Dissolve it in 0ml and cast it on a copper plate.

dry. Light from a 500W xenon lamp was illuminated for 2 seconds through this through a negative lens from a 50 cm pH1i beam distance. When the unexposed areas were removed with a solvent, a clear relief image was obtained. I got hit 4 times.

Claims (1)

[Claims] A polymer or copolymer having an alcoholic hydroxyl group has the general formula (in the formula, one of R+ and R2 is an oxomethylene bond, the other is a simple bond + R3 is a hydrogen atom or an alkyl group) , cyanobacterium, nitro group, alkoxy group, alkoxycarbonyl group, halogen atom) obtained by the general formula (R, , R2, R in the formula have the same meanings as above). A photosensitive resin having a small number of (all 1) units represented by