JPH0332779B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photosensitive composition comprising a photosensitive diaryliodonium salt and a polymer containing an alkenyloxyalkyloxy group as a constituent unit. vinyl monomers, oxirane ring compounds, cyclic ethers, cyclic sulfides, cyclic amines, cyclic silicon compounds with high electron density in the double bond and by liberating Lewis acid catalysts when exposed to radiant energy. A composition comprising both components of a photosensitive aromatic onium salt in an effective amount capable of inducing polymerization of an organic substance is disclosed in JP-A-50-151976 and JP-A-Sho.
It is disclosed in Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14279, Japanese Patent Publication No. 53-25686, and is publicly known.
Also known are photosensitive compositions comprising a photosensitive aromatic diazonium salt, an epoxy resin, and the like. However, although the use of diazonium provides compositions that harden quickly, hardening and gelation can occur even when stored in the dark. Furthermore, diazonium salts are generally thermally unstable, and it is not preferable to heat a coating film formed from the composition.
Therefore, there are limitations in practical use. Diaryliodonium salts also do not have the disadvantages associated with compositions made of aromatic diazonium salts, but do not provide as fast a cure as diazonium salts. Furthermore, the above-mentioned photosensitive compositions have poor dry etching resistance against so-called dry etching, which is a photosensitive resin processing technology that has recently attracted attention. The present inventors conducted extensive research in order to improve these prior art techniques, and came up with the present invention. That is, the present invention provides at least general formula (A) and general formula (B) in the same molecule.

[expression] and

[Formula] (R ₁ in the formula represents a divalent organic group) A polymer having a molecular structure connected by repeating units represented by the formula and an effective amount of the general formula (R ₂ and R ₃ in the formula are hydrogen atoms, alkyl groups, nitro groups, alkoxy groups, M is boron atoms, phosphorus,
The present invention provides a photosensitive composition comprising a diaryliodonium salt represented by: arsenic or antimony, and X represents a halogen atom. The polymer compound represented by the general formula (A) used as a core component in the present invention may be of any type as long as it has a phenolic hydroxyl group. Examples include homopolymers of 2,3 or 4-hydroxystyrene, 4-hydroxy-3-nitrostyrene, and combinations of these monomers with acrylonitrile, styrene, α-methylstyrene, vinyl acetate, alkyl acrylates, and methacrylic acid. Examples include copolymers with linear polymerizable monomers such as alkyl esters and maleic anhydride. The molecular weight of these hydroxyl group-containing polymer compounds is preferably about 2,000 to 200,000. General formula (B)
The unit represented by the formula (A) is obtained by adding a haloalkyl vinyl ether represented by the general formula XR ₂ OCH=CH ₂ (X is a halogen atom, R ₂ is a divalent organic group) to the polymer represented by the general formula (A). It is obtained by reacting in the presence of a condensing agent. In addition, as a photosensitive diaryliodonium salt, Macromolecules Vol.10, No.6, pp.1307
~1315 (1977), diphenyliodonium tetrafluoroborate, 4-methoxydiphenyliodonium tetrafluoroborate, 4,4'-dimethyldiphenyliodonium tetrafluoroborate, 4 tetrafluoroborate , 4′-isopropyldiphenyliodonium,
4,4'-t-butyldiphenyliodonium tetrafluoroborate, 4,4'-t-butyldiphenyl iodonium tetrafluoroborate,
General formula of 4'-dichlorodiphenyliodonium, 3,3'-dinitrodiphenyliodonium tetrafluoroborate, etc. (R ₃ and R ₄ in the formula are hydrogen atoms, alkyl groups, nitro groups, alkoxy groups, M is boron atoms, phosphorus,
arsenic, antimony, and x represents a halogen atom). In order to produce the photosensitive composition of the present invention, an effective amount of the polymer having a molecular structure connected by at least repeating units represented by general formula (A) and general formula (B) in the same molecule is added. Diaryliodonium salt may be dissolved in an organic solvent and mixed. Any organic solvent may be used as long as it dissolves the above-mentioned polymer and diaryliodonium salt. Examples include N,N-dimethylformamide, N,N
-Dimethylacetamide, dioxane, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, isobutyl ketone and the like. The content of the polymer is selected depending on the application so as to provide the required viscosity. The proportion of diaryliodonium salt to the polymer can also be varied within a wide range, but effective results are achieved when using 1 to 20% diaryliodonium salt, based on the weight of the polymer. However, these amounts may be selected outside the above range depending on the properties of the polymer, the intensity of actinic light, etc. The composition thus obtained can be applied to metals, rubber, plastics, paper, wood, etc. by conventional methods.
It can be applied to a substrate such as glass, and by irradiating the applied material with actinic light, it can be crosslinked and cured in several seconds to several minutes. Application fields of the photosensitive composition of the present invention include plate-making materials, photocurable paints, photocurable printing inks, resist films for chemical milling of printed circuits, etc., and photoresists for microfabrication of semiconductors and integrated circuits. is possible. In particular, the diaryliodonium salt that is a component of the photosensitive composition of the present invention has an ultraviolet absorption spectrum of 200 to
Since it exhibits strong absorption in the 300 nm region, it is extremely promising as a photoresist for deep ultraviolet microfabrication. Next, the present invention will be explained in more detail with reference to Reference Examples and Examples. Reference example 1 A reaction vessel into which nitrogen was introduced was washed with hexane.
4.8 g (0.1 mol) 50% sodium hydrogen, dry N,
20 g of N-dimethylacetamide was charged, and a solution of 12 g of poly-4-vinylphenol (weight average molecular weight 21,000) dissolved in 70 g of dry N,N-dimethylacetamide was added to this solution while stirring, and stirring was continued for about 2 hours. Ta. Next, 30 g of 2-chloroethyl vinyl ether, 1.5 g of anhydrous sodium carbonate, and 0.05 g of triethylbenzylammonium chloride were added to this, and after reacting at 80°C for 24 hours, most of the reaction mixture was distilled under reduced pressure at 80°C. N,N-dimethylacetamide and unreacted 2-chloroethyl vinyl ether were removed, and diethyl ether was added to the residue to dissolve it. This solution is washed several times with a saturated aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to remove liquid components. The residue is again dissolved in diethyl ether containing a small amount of methylene chloride and poured into a large amount of hexane with stirring. In this way, a vinyloxyethyl etherified polymer was obtained. Absorption based on vinyl groups was confirmed from the infrared absorption spectrum. Absorption based on double bonds was confirmed at δ = 4.08, 4.22, and 6.45 using proton nuclear magnetic resonance absorption spectroscopy. The presence of phenolic hydroxyl groups was also confirmed from infrared absorption spectra and ultraviolet absorption spectra. This confirmed that the obtained polymer had a molecular structure connected by repeating units consisting of phenolic hydroxyl groups and vinyloxyalkyl groups. Reference Example 2 Similar to Reference Example 1, using poly-4-vinylphenol with a weight average molecular weight of 3450 as a starting material,
A vinyloxyethyl etherified polymer was obtained. It was confirmed that the polymer obtained by the same method as in Reference Example 1 had a molecular structure connected by repeating units consisting of phenolic hydroxyl groups and vinyloxyalkyl groups. Example 1 Poly-4-vinylphenyl vinyloxyethyl ether obtained from poly-4-vinylphenol having a weight average molecular weight of 21,000 by the method of Reference Example 1.
A photosensitive composition was prepared by dissolving 15 g of diphenyliodonium tetrafluoroborate and 1.5 g of diphenyliodonium tetrafluoroborate in 85 g of N,N-dimethylformamide. This was applied to a thickness of approximately 10μm on a glass plate, and 230nm light separated from a 2KW xenon lamp was irradiated, and methyl isobutyl ketone-butanol (50/50 volume ratio)
Developed with mixed solution and measured residual film rate
More than 90% of the remaining film was obtained by exposure at 20 mJ/cm ² .
Furthermore, when exposed through a quartz negative and removing the unexposed areas with a solvent, a clear pattern was obtained, with a minimum line width of 2 μm or less. Example 2 The same treatment as in Example 1 was carried out using diphenyliodonium hexafluorophosphate in place of the diphenyliodonium tetrafluoroborate salt in the composition of Example 1. The residual film rate was 90% or more at an exposure dose of lOmJ/cm ² . Also, those exposed through a mask showed a clear pattern. Example 3 The same treatment as in Example 1 was carried out using 4,4'-t-butyldiphenyliodonium tetrafluoroborate instead of diphenyliodonium tetrafluoroborate in the composition of Example 1. ,
A residual film yield of 90% or more was shown at an exposure dose of 20 mJ/cm ² . Example 4 14 g of the polymer obtained in Reference Example 2 and 1 g of diphenyliodonium hexafluoroborate were mixed with 70 ml of N,N
- It was dissolved in dimethylacetamide and exposed using the same procedure as in Example 1. Exposure of 25 mJ/cm ² was sufficient to obtain a residual film rate of 90% or more.
In addition, a clear negative image was obtained by exposing through the negative and removing the unexposed portion.

Claims (1)

[Claims] 1 At least repeating units in the same molecule represented by general formula (A) general formula (B) [formula] and [formula] (R ₁ in the formula represents a divalent organic group) Polymer with linked molecular structure and effective amount of general formula (R ₂ and R ₃ in the formula are hydrogen atoms, alkyl groups, nitro groups, alkoxy groups, M is boron atoms, phosphorus,
arsenic or antimony, and X represents a halogen atom) A photosensitive composition comprising a diaryliodonium salt represented by: