DE2303671A1 - PHOTO RESIN LAYER - Google Patents

Description

PatontanwBK · DIpL-Inc *. R. BEETZ
DIpMn-. V ... LAM? »?; EIGHT

Divlw-. .. '. · . :: - ϊ: ~: f Z Jr.
β Mönohen 22, Sl-oinsdoifetf. 1β

81-20.084P January 25, 1973

HITACHI, LTD., Tokyo (Japan)

Photoresin layer

The invention also relates to a photosensitive Resin layer or photo ice layer, which is a water-soluble Polymer and a water-soluble bisazide compound as Photocrosslinking agents contain a particular object of the invention is such a composition with improved adhesiveness on the pad.

Heretofore, photosensitive resins have been used (This abbreviation for photosensitive resin compositions will be used extensively in the following description) on a broad basis for the production of reproduction plates or printing forms or used for photo-etching purposes * The materials that can be used for these purposes must be generally have the following properties;

81- (P0ü 29636) IToHe

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1} hoiies resolution!

2} excellent storage capacity;

3) increase toughness or strength as well as excellent corrosion and abrasion resistance, etc. in the hardened condition?

4) Adequate adhesion to the substrate and high Development leeway and ultimately should

5) ^ iS photosensitive resins and those used for them Developers free from any risk of environmental pollution aein.

As aqueous usable for the above purposes pMot © @ sensitive resin compositions have been largely Photoresists of the bichromate type applied, which by adding bichromate as a crosslinking agent to water-soluble Polymers such as glue, gelatin, albumin or polyvinyl alcohol These photosensitive resins or photorssists are formed Not only are they cheap, but they are essentially the same as conditions 1, 3, and 4 above. They are However, if there are some defects in such a way that even when stored in the dark there is a gradual change, which the composition as a result of a "Bunkel-2? eaktion" designated thermochemical reaction is unusable, another disadvantage is that it acts as a crosslinking agent Chromium compounds used in waste disposal pose problems of water pollution a.

In an effort to remedy these shortcomings, numerous attempts have been made to prepare a} bofosensl ⁴ - - ^ resin composition by introducing a {1. toempfiiidli ^ en group in the high polymer itself or durcii / ermiaeheii d * -? Polymers with an organic öensibilisac

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For example, a process has been proposed in which an organic Photocrosslinking agent used instead of bichromate and mixed with the water-soluble polymer to form a photosensitive layer.

Photoreaist layers are an example of such layers to mention the a water-soluble bisazide compound with 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 exhibit. These bisazide type photosensitive layers essentially comply with the aforementioned conditions 1, 2, 3 and 5 »although the properties will vary depending on the properties of the particular polymer used.

This type of photosensitive resin composition however, it generally has poor adhesiveness to the substrate and, moreover, has the defect that a hurry or the entire cured photoresist layer in the palle extraordinarily severe development conditions from the substrate stands out, nourishing in the Ealle of extraordinarily mild development Under the conditions, uncured portions of the photoresist layer remain, so that the resolution becomes insufficient.

In general, photoresist layers are made with bisazide compounds as the crosslinking agent in terms of adhesion to the substrate, the photosensitive ones obtained using bichromate Underlay layers. The reason for this has not yet been clarified, but it can be assumed that the chromium ions in the latter case mediate a bond of the polymer to the substrate, while in the former case no such ions are available with a corresponding effect. Accordingly

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were layers of photoresist firmly bonded to the substrate must be such as photoresist layers for the production of ParbfernBeh picture tubes exclusively using manufactured by Biehromat as a crosslinking agent, while the photoresist layers with water-soluble bisazide compounds have not yet been used.

The aim of the invention is therefore to provide a photoresist • of the bisazide type with improved adhesion to the substrate, those free from the aforementioned deficiencies of the conventional photoresist layers is of the bisazide type.

This object is achieved according to the invention in that a water-soluble alkoxysilane is used as the adhesion promoting agent Agent is added to a mixture comprising a water-soluble polymer and a water-soluble photocrosslinking agent of the bisazide type; this mixture is then applied to a substrate to form a photoresist layer.

The functional alkoxysilane used as an adhesion promoting agent according to the invention has at least two different ones functional groups in the molecule. One of the functional groups has an effect with regard to the Increase in the adhesion of the photoresist to the substrate such as ZoB. Glass or metal by reaction with on the substrate surface hydroxyl groups present or with water adsorbed on the substrate surface, while the other functional group has an affinity for different water-soluble polymers.

In other words, when the functional alkoxysilane corresponding to the formula B-Si- (OH ') or E-Si- (OR ¹ ) ~ is reacted with silanol-

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groups (SiOH), R 'of the functional alkoxysilane is bonded to the OH of the silanol with the formation of E ¹ OH. It follows that the Si in the functional alkoxysilane is bonded to the Si of the silanol via 0, as is illustrated by the equation given below containing functional alkoxysilanes sufficiently adhere to the glass substrate. The reaction of alkoxysilane with (SiOH) groups is shown schematically by the following equation!

R-Si- (OR ') + -SiOH ► E-Si-O-Si- + R ¹ OH

I t If

To achieve the goal of the invention, a large number of functional alkoxyailanes are used) favorable results are especially given with those mentioned below Get connections!

Vinyl tris (δ-methoxyethoxy) silane GH ₂ -GH-Si (OCSH ₂ -CH ₂ -OCH ₃ ) ₃

f -aminopropyl-triethoxysilane

N- (ß-Aminoethyl) -y-aminopropyl-methyl-dimethoxysilane H2N- (CH ₂ ) ₂ -! JH- (CH _a ) ₃ Si (OCH ₃ ) ₂

GH ₅

N- (β-aminoethyl) ~} f-aminopropyl-trimethoxysilane H ₂ N- (CHg) ₂ -NH- (CHg) ₃ Si (OCH ₅ ) ₃

The amount of the in the l-hotoreaist occurs according to the lir-

3 0; Ρ " 7 f] D 8 6

f Inciting functional alkoxysilane to be used is from 0 _T 01 to 10 weight parts, preferably 0.1 to 5 Grew.-share of the water-soluble polymer per 100 parts by weight.

As water-soluble biaazide compounds and water-soluble polymers, different compounds can be used for functional alkoxysilane-containing egg resist layers, but even if the types of water-soluble bisazide compounds and water-soluble polymers change, no significant change is observed in the effect of the functional alfcoxyeilane as an adhesion-promoting agent. The useful amount of water soluble Bisazidverbindu is, of course, dependent on the type of said compound and from feenutzten water-soluble polymers, variable \ jeäaeh it is usually from 1 to 30 parts by weight per 100 parts by weight teiie of water soluble polymers.

Examples of water-soluble bisazide compounds used in accordance with the invention include 4,4 * -Bisaeid9-stilbene-2,2 ^L -disulfonic acid and its salts? 4,4'-bisazido-benzalacetophenone-2-aulphonic acid and its salts; and 4 _? 4 ^l -Bi8azidQ-stilbene-jf-carboxylic acid and its salts.

Examples of the water-soluble polymers to be used according to the invention include polyacrylamide, hydroxymethyl cellulose, Polyvinylpyrrolidone, roly-L-glutamic acid and their salts, gelatin, polyvinyl alcohol, water-soluble Polyvinyl butyral, acrylamide-vinyl alcohol copolymers and polyvinyl alcohol with grafted-on acrylonitrile.

The present invention is subsequently based on v. ,. Äeiapielen explained in more detail, in which all iles are related to the - · ■ - weight.

BATH ORIGINAL example 1

A! Eil polyacrylamide ( "Orfioc N-1", a product of Organo Co., Ltd.) and 0.02 part of 4,4 Έ atriumsal ζ ^ -bis-azido-stilbene-2,2-disulfonic acid were dissolved in ^f 100 liters of water dissolved to make a photoresist solution. This photoresist solution was mixed with 0.01 part each of the 4 functional alkoxyeilanes given in the table below as adhesion promoters. The photoresist solution was then applied evenly to a glass base measuring 50 mm 50 mm in size and dried to form a photoresist layer 0.6 mm) brought into close contact and exposed to the light of an 800 lux lamp for 5 minutes, a Queek wedge ultra-high pressure lamp being used as the light source, followed by development by spraying on water (with a water pressure of 0.5 kg / cm).

To check the adhesiveness of the points of the hardened Photoresist layer was made from a diameter of 1 mm diameter exiting water flow below a 40 mrnHg corresponding water pressure vertically for 2 minutes on the 160 mm spaced substrate and the peeling state of the cured photoresist dots checked. the The results obtained are summarized in Table 1 below.

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Table 1

functional alkoxysilane Number of ab
flipped points Vinyl tris (ß-methoxyethoxy) silane
jf-aminopropyl-triethoxysilane
N- (ß-aminoethyl) -tf-aminopropyl-
methyldimethoxysilane
N- (ß-aminoethyl) -tf-aminopropyl-
trimethoxysilane 16
9
2
O
O

From the results shown in Table 1 it follows clearly that that the functional alkoxysilanes have an excellent adhesion promoting effect.

Example 2

A photoresist solution with 100 parts of polyvinylpyrrolidone K-90 (a product of BASF Co.) »60 parts of polyacrylamide (« Kurifloc PE-HI ¹ S a product of Kurita Industrial Co., Ltd.) »32 parts of the sodium salt of 4, V-bisazido -stilbene ^, 2'-disulfonic acid and 1,000 parts of water would be mixed with 1.6 parts of N- (ß-aminoethyl) - ^ - aminopropyl-trimethoxysilane as an adhesion promoter.

In the same way as in Example 1, a photoresist layer was formed formed from the photoresist solution, which then has been checked with regard to the adhesiveness of the points,

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it was found that these did not stand out. On the other hand, the number of points (the stood out) with a photoresist made in the same way as above, but without adhesion promoters at 18.

Example 3

In the same way as in Example 1, photoresist solutions with one part of polyacrylamide (Kurifloc PH-141), 0.02 part of the sodium salt of 4.4 ^f -bisazido-stilbene-2.2 ^l -disulfonic acid and 100 ropes of water and 0; 0.001; 0.003} 0.005 1 0.01 or 0.05 ropes of N- (ß-Aminoäthyl) -tf-aminopropyltrimethoxysilane formed as an adhesion promoter photoresist layers, which were then checked for the adhesiveness of the dots, the 5 seconds long exposure of the photoresist layers with a light of 3000 lux had been formed. The results obtained are shown in Table 2.

Table 2

applied amount of adhesion promoting agent Number of from (file per 100 parts of polymer) raised points O 15th 0.1 4th 0.3 0 0.5 0 1 0 5 0

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From! Table 2 it follows that when adding the functional Alkoxyeilans in proportions of 0.1 to 5 parts per 100 ropes of the water-soluble polymer excellent results can be obtained.

The effective amount of the functional alkoxy silane is variable within an extremely wide range "If the functional alkoxy silane is, for example, added in an amount of O ₁ Qt to 10 parts per 100 parts of the water-soluble polymer, to obtain a photoresist layer of greatly improved adherence" Further, influences the functional alkoxysilane in no way affects the photosensitivity of the photoresist layer.

Example 4

A photoresist solution of the same composition as Example 2 was applied to a zinc plate with a polished surface and then applied to form a photoresist layer dried, which was checked for the adhesiveness of dots in the same way as in Example 1, whereby it was found that no dots were peeled off · On the other hand, the number of dots was in photoresist layer produced in the same way as above but without adhesion promoter (which was lifted off) at 12.

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Claims (7)

Claims Containing photosensitive resin layer
a water-soluble polymer, a water-soluble biaazide compound and a functional alkoxysilane. 2. Photosensitive resin layer according to claim 1, characterized in that the amount of the functional alkoxy silanes is 0.01 to 10 parts by weight per 100 parts by weight of the water-soluble polymer. 3. Photosensitive resin layer according to claim 1, characterized in that the amount of the water-soluble bisazide compound is 1 to 30 parts by weight per 100 parts by weight of the water-soluble polymer. 4. Photosensitive resin layer according to claim 1, characterized in that the water-soluble bisazide compound by a member from the group consisting of 4,4 ^l -bisazido-stilbene-2,2 ^f -aisulfonic acid and salts thereof; 4,4'-bisazido-benzalacetophenone-2-sulfonic acid and its salts and 4,4'-bisazido-stilbene - / - carboxylic acid and its salts is formed. 5. Photosensitive resin layer according to claim 1, characterized characterized in that the water-soluble polymer by a representative from the group polyacrylamide, polyvinylpyrrolidone, Gelatin, hydroxymethyl cellulose, poly-L-glutaic acid and their salts, water-soluble polyvinyl butyral, polyvinyl alcohol, acrylamide-vinyl alcohol copolymers and polyvinyl alcohol is formed with grafted acrylonitrile. 309832/1086 7. Photosensitive resin layer according to claim 1, characterized in that ; that the functional alkoxysilane by a representative from the group vinyl-tris- (ß-methoxyethoxy) -silane, ^ -aminopropyl-triethoxysilane, H- (ß-aminoethyl) - ^ - aminopropyl-methyldimethoxysilane and N- (ß ~ aminoethyl) - V-aminopropyl- trimethoxysilane is formed. 309832/1086