DE2303671B2 - Photohardenable photoresist layer - Google Patents

Description

The invention relates to a light-curable photoresist layer, containing a water-soluble polymer, a water-soluble bisazide compound and an alkoxysilane.

Heretofore, photohardenable photoresist layers have been widely used for the manufacture of printing forms or used for photo-etching purposes. The materials that can be used for these purposes must be general have the following properties:

1. high resolution,

2. excellent storage capacity,

3. high toughness and strength as well as excellent corrosion and abrasion resistance in the hardened state,

4. Adequate adhesion to the substrate and high latitude for development, and finally should

5. The light-curable photoresist layers and the developers used for them are free from any danger be an environmental pollution.

Photoresist layers are known which contain a water-soluble bisazide compound having hydrophilic groups such as 4,4'-bisazido-stilbene-2,2'-disulfonic acid or a salt thereof and a water-soluble polymer such as Polyacrylamide, polyvinylpyrrolidone or gelatin. For example, refer to DT-PS 7 52 852 and 8 32 546. These bisazide type photo-curable layers are essentially the same as those mentioned above Conditions 1, 2, 3, and 5, although the properties vary according to the properties of the particular The polymers used are variable.

However, this type of photohardenable layer generally has poor adherence to the surface Underlay and furthermore has the defect that part or all of the hardened photoresist layer is deposited in the case of extremely severe development conditions \ on the backing stands out, while in the case of extraordinarily tired development conditions unhardened portions of the photoresist layer remain, so that the resolution is insufficient will.

From US-PS 35 20 683 it is known the adhesive strength of photoresist layers with alkoxysilanes to improve. However, this known prior art is not based on any aqueous system. In contrast are from DT-OS 21 35 482 light-crosslinkable layers made of a water-soluble polymer, a Bisazide and an alkoxysilane known. However, these known layers have not yet been fully satisfactory either.

The object of the invention is to provide a bisazide type photoresist layer with improved adhesiveness on the pad.

According to the invention, this object is achieved by a light-curable photoresist layer which is water-soluble Polymer, contains a water-soluble bisazide compound and an alkoxysilane, which is characterized is that they as alkoxysiian y-aminopropyi-! riäthoxysilan, N - (/? - Aminoäthyl) -y-aminopropylmethyidimethoxysilan or N - (/? - Aminoäthyi) -y-aminopropyltrimethoxysilane contains.

With the photoresist layer according to the invention, good adhesion to the substrate is also achieved during development achieved.

It is assumed that the improvement of the bond strength through a chemical reaction of the Alkoxysilane achieved with the glass substrate on the one hand and a high affinity for the water-soluble polymer will.

The reaction of alkoxysilane with (SiOH) groups on the glass substrate is illustrated schematically by the following Equation reproduced:

R-Si (OR) + - SiOH

- R — Si — O — Si— + ROH

The amount of the alkoxysilane to be used in the photoresist layer according to the invention is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight per 100 parts by weight of the water-soluble poly kidneys.

The effective amount of the functional alkoxysilane can therefore be varied within an extremely wide range. For example, when the alkoxysilane is added in the above-mentioned amount, one is obtained Photoresist layer of much improved adhesiveness. In addition, the alkoxysilane has no influence whatsoever the photosensitivity of the photoresist layer.

As a water-soluble bisazide compound and a water-soluble one Polymers are different compounds for functionally alkoxysilane-containing photoresist layers useful, but even if the kinds of the water-soluble bisazide compounds and the water-soluble polymers, there will be no

significant change in the action of the functional alkoxysilane as an adhesion promoting agent was observed. The useful amount of the water-soluble bisazide compound is natural depending on the kind of the compound and of the water-soluble polymer used, variable; however, it is usually 1 to 30 parts by weight per 100 parts by weight of the water-soluble polymer.

Examples of water-soluble bisazide compounds used in accordance with the invention include 4,4'-bisazido-stilbene-2,2'-disulfonic acid or pure its salts, 4,4'-bisazido-benzalacetophenone-2-sulfonic acid or one of its salts or 4,4'-bisazido-stilbene - / - curbonic acid or one of its salts.

Examples of the water-soluble polymers to be used in accordance with the invention include. Polyacrylamide, Hydroxymethyl cellulose, polyvinylpyrrolidone, poly-L-glutamic acid and its salts, gelatin, Polyvinyl alcohol, water-soluble polyvinyl butyral, acrylamide-vinyl alcohol copolymers or polyvinyl alcohol with grafted acrylonitrile.

The present invention is explained in more detail below with reference to examples in which all Parts are by weight.

example 1

1 part of polyacrylamide and 0.02 part of the sodium salt of 4,4'-bisazido-stilbene-2,2'-disulfonic acid were dissolved in 100 parts of water to prepare a photoresist solution. This photoresist solution was mixed with 0.01 part of each of the 4 alkoxysilanes listed below in Table 1 as adhesion promoters. The photoresist solution was then uniformly applied to a glass base measuring 50 × 50 mm and dried to form a photoresist layer. This photoresist layer was then brought into close contact with a mask (produced by two-dimensionally arranged disks 0.35 mm in diameter at a distance of 0.6 mm) and exposed to the light of an 800-lux lamp for 5 minutes, the light source being a Mercury ultra high pressure lamp was used; it was then developed by spraying water (with a water pressure of 0.5 kg / cm ² ).

A nozzle was used to check the adhesiveness of the dots of the cured photoresist layer water flow from 1 mm diameter under a water pressure corresponding to 40 mm Hg vertically directed at the 160 mm spaced material for 2 minutes and the peeling state of the cured photoresist dots checked. The results obtained are in the following Table 1 summarized.

Table t

From the results shown in Table 1 it clearly follows that that the alkoxysilanes used according to the invention have an excellent adhesion promoting effect own.

B e i s ρ i e 1 2

A photoresist solution containing 100 parts polyvinylpyrrolidone, 60 parts of polyacrylamide, 32 parts of the sodium salt of 4,4'-bisazido-stilbene-2,2'-disulfonic acid

ίο and 1000 parts of water was with 1.6 parts of N - (/ i-Aminüäthyl) -y-aminopropyl-trimethoxysilane offset as an adhesion promoter.

In the same manner as in Example 1, a Photoresist layer formed from the photoresist solution, which then affects the adhesiveness of the dots was checked, and it was found that these did not stand out. On the other side was that Number of points (that stood out) for one in the same way as above, but without liability promotion funds produced photoresist layer at 18.

Example 3

In the same manner as in Example 1, photoresist solutions were made with 1 part of polyacrylamide, 0.02 part of the sodium salt of 4,4'-bisazido-stilbene-2,2'-disulfonic acid and 100 parts of water and 0, 0.001, 0.003, 0.005, 0.01 or 0.05 parts of N - (/ 3-aminoethyl) -y-aminopropyl-trimethoxysilane photoresist layers formed as an adhesion promoter, which were then checked for the adhesiveness of the dots, the by exposing the photoresist layers to light of 8000 lux for 5 seconds was. The results obtained are shown in Table 2.

Table 2

Alkoxysilane

number of
peeled off
Points

Vinyl tris (/ 3-methoxyethoxy) silane

y-aminopropyl-triethoxysilane

N - (/ 3-aminoethyl) -y-aminopropylmethyl

dimethoxysilane

N - (/? - Aminoethyl) -y-aminopropyl-tri-

methoxvsilane

16
9
2
0

Applied amount number of Adhesion promoters lifted (Parts per 100 parts of the Points Polymers)

0.1

0.3
0.5
1
5

15th
4th
0
0
0
0

From Table 2 it follows that when adding the alkoxysilane in proportions of 0.1 to 5 parts per 100 parts of the water-soluble polymer give excellent results.

Example 4

A photoresist solution of the same composition as in Example 2 was applied to a zinc plate using polished surface and then dried to form a photoresist layer, which with regard to the Adhesion of dots was checked in the same manner as in Example 1 to be found could that no points were peeled off. On the other hand, the number of points was the same In the same way as above, but without the photoresist layer (which were lifted off), at 12.

Claims (5)

Patent claims: 1. Light-curable Photorcsislschichl containing a water-soluble polymer, a water-soluble bisazide compound and an alkoxysilane, thereby marked as Alkoxysiliin y-aminopropyhriethoxysilane. (N - /> Amiiioälhyl) -5'-aniinopropylmcth> Idiiielhox> SiIan or N - (/ i-AniiiH> iIthyl) -} '- aminopropyIirimethoxy- n> contains silane. 2. Photoresist layer according to claim 1, characterized characterized in that the amount of the alkoxysilane is from 0.01 to 10 parts by weight per 100 parts by weight of the water-soluble polymer. 3. photoresist layer according to claim 1, characterized in that the amount of water-soluble Bisaridverbiniiun »at 1 to 30 parts by weight per 100 parts by weight of the water-soluble polymer. 4. photoresist layer according to claim 1, characterized in that the water-soluble bisazide compound 4,4'-bisazido-sülbcn-2,2'-disulfonic acid or one of its salts; 4,4'-bisazido-benzalacetophenone-2-sulfonic acid or one of its salts or 4,4'-bisazido-stilbene-y-carboxylic acid or one of its Salts is. 5. Pholoresistseliicht according to claim 1, characterized characterized in that the water-soluble polymer polyacrylamide, polyvinylpyrrolidone, gelatin, hydroxymethyl cellulose, Poly-L-glutamic acid or its salts, water-soluble polyvinyl butyral, polyvinyl alcohol, Acrylamide-vinyl alcohol copolymers or polyvinyl alcohol with grafted acrylonitrile is.