JPS58143338A - Photoresist composition - Google Patents

Abstract

PURPOSE:To enhance adhesion with a base, and sensitivity, by adding a specified water-soluble silane compd. to a specified photosensitive compsn. CONSTITUTION:A water-soluble polyazamide type silane compd. having the shown formula, such as a compd. (R<1> is methylene, R<2> is ethylene, R<3> is propylene, and x=y=2), is added to a photosensitive compsn. composed of a water- soluble bisazide compd., such as 4,4'-diazidostilbene-2,2'-disulfonic acid, a water- soluble diazo compd., such as benzidinetetrazonium chloride, and a water-soluble polymer, such as PVA. As a result, a photoresist compsn. enhanced in adhesion with a base and high in sensitivity is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a photoresist composition, and more particularly to a photoresist composition with high sensitivity and improved adhesion to a substrate.

[Technical background of the invention and its problems]

Conventionally, photoresist compositions have been widely used for plate making or photoetching, and generally have the following properties depending on their intended use.

It is necessary to be prepared. In other words, ■It has excellent resolution, ■It has high sensitivity, ■It has good storage stability, and ■The hardened photoresist film is tough and corrosion resistant.
(1) It has excellent abrasion resistance, (2) It has good adhesion to the substrate and has a large development latitude, and (2) The photoresist and developer used do not pose a risk of pollution.2.

Conventionally, dichromate-based photoresists, which are a mixture of monochromic acid salts and water-soluble polymers such as glue, gelatin, egg white, and polyvinyl alcohol, have been widely used as water-soluble photoresists used for these purposes. Ta. This is because this photoresist is inexpensive and meets the above conditions.
This is because the performance was almost satisfactory regarding ■■■.

However, even in the dark, this glazed photoresist gradually deteriorates due to a natural reaction called dark reaction and becomes unusable, and it also causes pollution due to the disposal of chromium used as a photocrosslinking agent. It had drawbacks such as:

In order to eliminate these drawbacks, attempts have been made to produce photoshift cysts by introducing photosensitive groups into the polymer material itself or by mixing an organic photosensitizer with the polymer.

As one such attempt, a method is known in which a photoresist is constructed by mixing an organic photocrosslinking agent with a water bathing polymer instead of dichromates.

For example, 4,4'-bisazidostilbene-2,2
Water-soluble bisazide compounds with hydrophilic groups such as '-disulfonic acid and its salts and polyacrylamide.

There is a photoresist composition comprising polyvinylpyrrolidone and a water-soluble polymer such as gelatin. This bisazide photoresist has various performances depending on the properties of the water-bathable polymer to which it is combined, and among the above-mentioned strings and bonds, it exhibits almost satisfactory performance with respect to α) ■■■. However, this type of photoresist generally has poor adhesion to the substrate, and if the developing conditions are too strong, part or all of the cured photoresist film may peel off from the substrate, while if the developing conditions are too weak, the unhardened photoresist film may peel off from the substrate. It has the disadvantage that some parts remain and do not provide sufficient resolution. or.

Since it has a so-called reciprocity law failure characteristic in which sufficient pattern formation cannot be performed unless the light is strong above a certain level, there is a limit in pattern printing.

In general, bisazide-based photoresists have poorer adhesion to a substrate than dichromate-based photoresists. Although the reason for this is not clear, it is thought that in dichromate-based photoresists, chromium ions have the effect of bonding the substrate and polymer, whereas in bisazide-based photoresists, they have no such effect.

Therefore, in order to eliminate such drawbacks, bisazide photoresists include γ-aminopropyltrimethoxysilane, N-, (β-aminoethyl)γ-aminopropylmethyldimethoxysilane, and N-(β-aminoethyl)r Attempts have also been made to improve the adhesion between the photoresist and the substrate by adding at least one silane compound such as -aminopropyltrimethoxysilane as an adhesion promoter (see Japanese Patent Publication No. 19982/1982). however,
Even when these silane compounds were added, bisazide photoresists did not provide sufficient adhesion to the substrate.

[Purpose of the Invention J The present invention provides a novel method that does not cause pollution during handling, has good resolution and storage stability, has high sensitivity, exhibits sufficient adhesion to a substrate, and can form a tough coating film. The present invention provides a photoresist composition.

[Summary of the invention]

The photoresist composition of the present invention is a photoresist composition of the above-mentioned prior art (Japanese Patent Publication No. 19982/1982) which is made from a photosensitive composition containing a water-soluble polymer, a bisazide-based primary crosslinking agent, and the listed adhesion promoter. However, the photosensitive composition further contains a water-soluble diazo compound and a water-bathable polyazamide-based silane compound that contributes to further adhesion as an adhesion promoter to form a bond with the entire substrate. This has the same adhesion between the two as described above, and also increases the sensitivity.

That is, the photoresist composition of the present invention is characterized in that 3 St (OR')s (wherein R1, R2, and R3 are each carbon Numbers 1 to 10
The alkylene group x and y each represent an integer of 1 or more and 10 or less. ) It is characterized by containing a water-soluble polyazamide-based silane compound shown in the following.

The water-bathable bisazide compound used in the present invention includes known compounds such as 4,4'-diazidostilbene-2,2'-disulfonic acid, 4,4', which is described in Japanese Patent Publication No. 51-48946. -Diazidobenzalacetophenone-2-sulfonic acid, 4,4'-diazidostilbene-α-carboxylic acid, and salts thereof.

In addition, as a component of the photosensitive composition according to the present invention, the water-soluble diazo compound newly contained is a compound of known f, such as Japanese Patent Publication No. 52-3267, Japanese Patent Publication No. 56-6
530, namely benzidine tetrazonium chloride, 3,3'-dimethylbenzidine tetrazonium chloride, 3,3'-dimethoxybenzidine tetrazonium chloride, 4,4'
Examples include tetrazonium chloride of -diaminodiphenylamine, tetrazonium sulfate of 3,3'-diethylbenzidine, formalin condensate of diazodiphenylamine, and double salts thereof.

These water-soluble diazo compounds are thought to have the function of also increasing the adhesion of the photosensitive composition itself to the substrate.

Next, examples of water-bathable polymers include known synthetic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyvinyl methyl ether, polyvinyl acetal, and polyacrylic acid; gelatin, shellac, gum arabic, and casein. Copolymers such as methyl vinyl ether and maleic acid, acrylamide and diaseptone acrylamide, acrylamide and vinyl alcohol; acrylonitrile-grafted polyvinyl alcohol, glycidyl methacrylate-grafted polyvinyl alcohol, β-oxyethyl methacrylate-grafted polyvinyl Examples include grafted polymers such as alcohol; semi-synthetic polymers such as carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, and BoIJ-L-glutamic acid (Na salt). At least one of these water-soluble polymers needs to be crosslinked with the above-mentioned water-soluble bisazide compound or aqueous azide flj by the action of ultraviolet light.

A particularly effective water-soluble polymer that can be applied to the present invention is a combination of polyvinylpyrrolidone and polyvinyl alcohol.

In this case, the proportion of polyvinylpyrrolidone to polyvinyl alcohol is 0.1 to 8.0 by weight,
Preferably, tL< is in the range of 0.5 to 3.0.

If it is less than 0.5, a clear pattern cannot be obtained.

This is because if it exceeds 3.0, the adhesion will decrease.

When using a water-soluble polymer comprising polyvinylpyrrolidone and polyvinyl alcohol under the above conditions, the blending ratio of the aqueous bisazide f arsenate to the water-soluble diazo compound is 1.0 to 10, preferably 3.0 in weight ratio. ~7.
If the blending ratio is less than 3.0, the photosensitivity of the resulting photosensitive composition will decrease;
, exceeds 0, the overall adhesion strength decreases.

In the photosensitive composition according to the present invention, a small amount of a surfactant, such as polyethylene glycol, alkyl phenoxy polyethylene oxide phosphate, sodium hexametaphosphate, etc., or a small amount of an alcohol, such as , ethyl alcohol, glycerin, ethylene glycol, sorbitol, ter-methyl alcohol, etc. are effective because they enhance the antifoaming properties, photosensitive film forming properties, etc. of the photosensitive composition.

The photoresist composition of the present invention comprises the lf&f detailed above.
t=M compound, general formula: H-eNHRINHR2C
O-)-3 S i (OR' )a each represents an alkylene group having 1 to 10 carbon atoms, and X and y each represent an integer of 1 to 10. ) is composed of a water-soluble polyazamide-based silane f arsenic material as an adhesion promoter.

As the polyazamide-based silane compound according to the present invention,
For example, %5PI (Saiety of Plastics)
1L compound described in Industry) Volume 30, Edition 22, 6 ('197.5), specifically K.

Examples include water-soluble polyazamide-based silane compounds in which RI=methylene group, R2: ethylene group, R'': furopylene' JM: x=172.

In the photoresist composition of the present invention, the amount of the water-bathable polyazamide silane metal material added is 0.01 to 20 parts per 100 parts of the water-bathable polymer;
If the amount is preferably 0.1 to 10 parts by weight, the adhesion to the entire substrate can be sufficiently increased.

The polyazamide-based silane compound according to the present invention has two or more different functional groups in the molecule, one of which is a hydroxyl group present on the surface of a substrate (for example, a glass plate, a metal plate, a ceramic plate) or an adsorbed group. It is thought that the adhesion to the substrate is increased by reacting with the water contained therein, and the other functional group exhibits an affinity for the water bathing polymer, resulting in strong adhesion or integrity as a whole. In addition, the water-soluble silane compound does not cause any pollution problems, so it can be said to be preferable from the viewpoint of safety in handling. Furthermore, the photoresist composition of the present invention can be obtained by using a water-soluble polymer in combination with a water-bathable bisazide compound and a water-bathable diazo compound as a crosslinking agent. It also has extremely sensitive sensitivity characteristics that cannot be obtained with other cameras.

[Embodiments of the invention]

Examples 1 to 3 Polyvinylpyrrolidone: Ni-90 (GAF, trade name)
50 parts by weight, polyvinyl alcohol EG-40 (Nippon Gosei ■, trade name) 50 parts by weight, 4,4'-bisazidostilbene-2,2'-cisulfonic acid sodium salt 6
．． 0 parts by weight and 1.2 parts by weight of a phosphate of a formalin condensate of diazodiphenylamine were dissolved in 8000 parts by weight of water, and water-soluble polyazamide silane of type 3a shown in Table 1 was added as an adhesion promoter. A photoresist solution was prepared by blending 6 parts by weight of each of the compounds. Next, these photoresist solutions were applied to glass substrates (100 x 100 m).
) and let it dry, then apply a mask (diameter 0.35
(a two-dimensional array of circles of 0.6 m at a pitch of 0.6 m) were placed in close contact with each other and exposed to light for 1 minute using a 500 W ultra-high pressure mercury lamp. Thereafter, in order to compare the adhesion strength, development was carried out under the following conditions.

Water pressure 2.0 h/j liquid
Temperature 40~41C Nozzle panel distance 300 words Nozzle diameter
1.0 Dust image time: 20 seconds At this time, the number of missing dots in the cured photoresist was observed, and the results are shown in Table 1 in correspondence with the adhesion promoter used.

Table 1 (IIl: Polyazamide-based silane compound (trade name) manufactured by Union Carbide Co., Ltd.) In addition, the above photoresist compositions all have a good resolution of about 20 μm, and the formed coating film has good corrosion resistance and The abrasion resistance was also sufficiently satisfactory for practical use.Furthermore, these photoresist compositions also had excellent storage stability, with almost no deterioration in quality even if left in a dark place at room temperature for one month. There wasn't.

Example 4 A water-soluble photoresist having the composition shown in Table 2 was prepared, and its properties were investigated by applying it to a process of coating a color picture tube with a non-original absorbing substance. Note that the materials used are the same as in Examples 1 to 3.

Table 2 Table 3 shows the results of examining the photosensitivity to ultraviolet rays. Here, sensitivity refers to a 20' black stripe color picture tube with a shadow mask diameter of 0.2 words and a color of 0.19.
(2) Exposure time (illuminance: 30,000 A?ux) required to obtain a pattern size of (center part).

Comparative Examples 1 to 3 The adhesion promoters shown in Table 4 were used instead of the adhesion promoters used in Examples 1 to 3, and the photoresist solution was polyvinylpyro')7K-90 (GAF Co., Ltd., Parts name) 100 parts by weight, 4,4'-bisazidostilbene-2
, 10 parts by weight of sodium salt of 2'-disulfonic acid, 3
000' parts of water was used. Table 4 shows the results of comparing the adhesion forces in the same manner as Examples 1 to 3.

Table 4 [Effects of the Invention] As is clear from the above description, the photoresist composition of the present invention has the following properties: (1) high adhesion to the substrate, (2) high sensitivity, (2) high resolution, (4) corrosion resistance, It has the advantages of being able to form a coating film with excellent abrasion resistance, ■ excellent storage stability, and ■ no risk of pollution problems, and is suitable for industrial applications such as plate making or photo etching. The value is extremely great.

Claims (1)

[Claims] A photosensitive composition comprising a water-soluble bisazide compound, a water-soluble diazo compound (b compound), and a water-soluble polymer. ~1
The alkylene group 0, X, and y each represent an integer of 1 or more and 10 or less. ) A photoresist composition containing a water-bathable polyazamide-based silane compound.