DD211415A1 - POSITIVE PHOTO COPYLIGHT WITH IMPROVED PROPERTIES - Google Patents

Abstract

This invention relates to positive photocopying varnishes having improved properties which contain a novolac binder. The aim of the invention is the production of positive photocopy coatings which have constant properties with constant or improved application properties in different batches. This is achieved by using novolaks with a narrow molecular distribution spectrum and largely regular molecular structure, which are characterized by flow temperatures of 95 to 180 degrees C and. Inconsistency between 1.5 and 2.2 are marked. The photocopying varnishes produced with these novolaks have constant properties in various batches and, surprisingly, an increased practical photosensitivity with good application behavior (viscosity, developability, relief structure).

Description

Inventor : Berlin, 07. 02, 1983

Dr. Ho / Gö

W. Siebert>

E. Hintzmann /

W. Baumbacii

J. Barnikov.

Dr. Ch. Rabe 9 / 7QQO ^

Ξ. Brandt ^ AI Ό 3 Z j

G. Bahr D, Hoffmann M. Stoltze

Positive photocopy coatings with improved properties

Field of application of the invention

The invention relates to positive photocopy coatings having improved properties which contain a lovolak as a binder.

Characteristic of the known technical solutions

Positive photocopying lacquers are light-sensitive lacquers which are prepared by exposure and removal of the exposed areas with so-called developers (usually alkaline).

10 aqueous solutions) provide a relief image

Relief images can be used to make printing plates, printed circuits and the like. Ä. Serve. In a particularly widespread embodiment, these positive photocopying lacquers consist of at least one photosensitive component, preferably a 1-0s: o-2-diazoarene (quinone diazide) or an aryl diazonium salt, high polymer binders, especially at least one novolak, d. H. an unbranched, partially soluble, generally not postcurable phenol-formaldehyde resin, as well as organic solvents and optionally excipients, such as dyes 0. ä. Positive photocopying varnishes of this type are u. a. in DD-PS 59 24O, 69 262, 109 093 »DE-PS 893 748, 11 34 887, US-PS 3,046,120, 3,061,430, 3,130,047, 3,130,048, 3,188,210

c cr-π a Q a Q * π ί -i si 4 fs

247992 1 ²

and numerous other patents.

The as described above. However, positive photocopy coatings have significant variations in many application properties such as adhesion to certain substrates, elasticity of the enamel layers, e-image contrast of the eel images, practical photosensitivity, and melting behavior. These variations are essentially caused by the fact that the novolaks used are non-uniform, i. H. the different batches of Hovolaks have different properties, because in their preparation by acid condensation of phenols with! formaldehyde products of different molecular size, the use of several different phenols with different sequences of phenolic building blocks that are represented in different batches in different proportions. In the technical use of

However, 20 positive photocopy coatings are essential

necessary that they have consistent properties, because otherwise different technological parameters would have to be determined empirically for each batch of paint · To take this into account, similar to the technical use of natural products, the novolaks before their use for the production of positive-Fot © copier lacquers on tested their application properties and reused only suitable batches. However, this process is very cumbersome and labor-intensive, and nevertheless different batches of positive varnishes exhibit variations in their properties which are attributable to the novolaks used for their preparation. "

247 99 2 1 3

Aim of the invention ;

The aim of the invention is therefore the production of positive EoTouchierlacken that are reproducible at least constant, but improved if possible application properties in different batches with constant properties ·

Presentation of the Invention of the Invention

The invention is therefore based on the object novolake find that have good photochemical properties due to their structure and production and are largely reproducible, so that when used as a binder in photocopying high quality coatings with constant properties are obtained. This abandonment could be solved by the use of ÜTovolaken, which are produced in a homogeneous and oriented ongoing condensation reaction, as described in the patent application DD-Az. G 08 G / 245 572/6 is described. These novolaks show a narrow molecular distribution spectrum and a largely regular molecular structure, which is, inter alia. in a narrow range and in heterogeneity figures (definition and determination, see: Foundations of the macromolecular Ghemie / Philipp, B; Eeinisch, G. - 2nd edition Berlin 19? 6 p. 35) between 0.5 and 3.0 ( compared to 6 to 8 in the previously used Hovolaken) expresses. If these novolaks contain two different phenolic building blocks, they are arranged alternately in the molecule. If three different phenolic building blocks are present, one is arranged regularly according to the conditions of production, while the other two are distributed statistically in the molecule. This structure is referred to below as semialternating.

99

The novolaks characterized above, when used as binders in positive photocopy coatings, are expected to permit the production of photocopying varnishes whose properties are reliably reproducible while keeping the other production conditions constant Exposure to produce a developable relief image) as photocopying varnishes produced with the conventional Jtfovolaks. In addition, they have the following favorable application properties:

uniform viscosity of their solutions, so that

during coating, uniform layers of defined thickness are obtained,

uniform solubility during development,

good tempering properties, so that the fine structure of the relief image produced is precisely

20 can be kept ·

Apart from the use of the novel instead of the previously used novolaks, the preparation of the photocopying lacquers according to the invention is carried out in known manner in a quiet manner by dissolving the components (binder, photosensitive component and optionally additives) in at least one organic solvent. Although in principle all 1-0zo-2-diazoarenes (quinone diazides) and aryl diazonium salts used in photocopy production can be used, the use in

30 combination with 1-0xo-2-diazonaphthene-4- or

-5-sulfonsäurearylestern found to be particularly useful because the solubility of this compound when using the novel novolaks in contrast to the binders previously used

247992

is not ela limits, so that their high photochemical activity can be particularly well exploited. Because of the higher practical photosensitivity due to the use of the novel novolaks, it is possible either to shorten the exposure times compared to the previous paints au (or * weaker light sources to use) or the amount of photosensitive component used (i-Os: o-2-diazoarene or Aryl diazonium salt) essential to

10 ring.

Optionally, the Fotokopierlacken more binders, for. As organic solvents, suitable non-polar or weakly polar solvents or mixtures thereof may be used. Preferred is a mixture of ethyl glycol acetate, n-butyl acetate and xylene.

Table 1 lists some novolaks which are particularly suitable for the preparation of the photocopying lacquers according to the invention, without the claim of protection being restricted to them.

Table 1

Novolacs with defined and semi-defined phenol body sequences for use as binders in positive photoprints -

Substr. designation

S e

u e η final group

Confluence

setting range O ₀

alternating o-cresol p-cresol novolak resin

alternating m-cresol ~ p-cresol novolak resin

OH

or ¹ "

CH,

-CHJ -

129-135

1: 1

135-145

Substr. designation

Sequence completion group

Composition

tfließgereich

alternating Dian-p-tert-butylphenol »Movolak resin

alternating Dian ~ p-cresol-Hovolak resin

OH

OH

-CM,-

-CH ₁ -

CU t

HJC-C CHj

Oh

OH

t CH

1: 1

145-150

120-134

( j

Substrate

sequence

ABSOLUTE GROUP

composition

Flow range ⁰ C

alternately

(p ~ cresol) ~ Hovolak resin

jn

1: 1

* semi-annual

o-cresol-P-Kr esole-bistp-cresol) «- Novolac resin +)

OH

1 C-Wj

CN,

04

120-125

The phenolic bodies enclosed in dashed angle brackets are randomly distributed in the molecule, i. in the formula interchangeable »

Sut> str · designation

S β g u e η ζ termination group

composition

Flow range ⁰ O

semialternating m-cresol-p-cresolbis-Cp-cresol) Movolak resin

CH,

sea-promoting o-cresol ra-cresol-p-cresol-uovolac resin

"CH ₁ -

CW,

on

3: 2ϊ1

1s2i1

125-135

125-135 130-140

Substr * designation

S e g u θ η ζ Termination group

composition

Flow range ⁰ O

semialternating o-cresol p-tert. butyl-pheno1 novolak resin

semialternating o-cresol ~ BV-Kr eso 1-p-tert-butylpheno! * "Novolac resin

\ "Ν

a)

b)

118-128 120-125

128-135 130-140

_Bezeiclmuns

S equ θ η ζ termination-flow- ^grouping range

_? H

semitransforming m ~ cresol ~ p ~ cresol ~ p-tert, -butylphenol-uovolac resin

135-14-5

* M,

/ Aa ι ι 12

Examples of export Example 1:

1 g of 2,3. ^ Rihydro: xybenzophenone tris (i-oxo-diazonaphthen-5-sulfonic acid) ester and

5 2.5 g ITovolak Hr. 1

be.in 8 ml of a solvent mixture of 70 vol .-% Bthylglykolacetet, 15 vol .-% n-butyl acetate and 15 YoI .-% Z ^ len at room temperature with stirring and then to 0.2, filtered to particle-free. The positive photocopy paint solution thus produced is applied by spin-coating using a centrifuge on an oxidized silicon wafer, followed by drying the layer at 90 ⁰ G. The resulting lacquer layer has a thickness of 1.5 / μm. After Eontakt exposure behind a Cr mask (Hg-Heocksrucklampe HBO 200, manufacturer: YSB Optical Works Rathenow, exposure time 12 s) are developing with the aqueous solution of a phosphate buffer with pH 13 , 4 perfect relief images at room temperature. In Yergleich to be obtained with commercially available paints, which were produced using Uovolaken with random distribution of the blocks, only at much longer exposure times flawless relief images

(for example, with the varnish offered by the 3'a * Shipley Inc., GB under the name AZ 1370 H after 20 s). Ablations on the unexposed layer parts did not occur in the paint according to the invention under the above conditions.

30 Example 2:

1 g of tris- (1'-osD-.2'-diazonaphthene-sulfone) 7OO 2 -50-

methyl benzoate and 2.5S Hovolak JSr. 2

7 ay ι ι ¹³

are dissolved as in Example 1 in 8 ml Lösungsgemiscli and applied to oxidized silicon wafers. Exposure takes place with the aid of the MHIR irojection exposure system from Carl Zeiss Jena, DDS. In order to obtain perfect relief images under the development conditions mentioned in Example 1, a setting to 2,000 Skt. Is required during the exposure. Compared to this, with a commercial varnish (AZ 1370 H of the company, Shipley Inc., Coventry, GB) produced using a statistically constructed Hovolak, perfectly developable relief images were obtained only at 3,500 Skt.

Example 3:

1 g CDris-C 1 * -0x0-2 * -diazonaphthen-sulfonylosy - ^ *) benzoic acid methyl ester and

1.5 § Hovolak Hr. 10

are dissolved as in Example 1 in 8 ml of solvent mixture and applied to oxidized silicon wafers. Exposure takes place with the aid of the Eo-ejection exposure system lAHJS of the Pa. Carl Zeiss Jena, GDR.

In order to obtain flawless relief images under the development conditions mentioned, a setting of 2,000 Skt. Is required during the exposure.

Example 3a:

Thus, a positive type photocopying varnish according to Example 3 is prepared and processed; However, Hovolak No. 10 from a batch is not used, but a mixture of approximately equal parts of three different batches. While using batch mixtures of novolacs with statistical distribution of the blocks in laboratory experiments even with only slight fluctuations in the average molecular weight we-

ι a

significant deteriorations in photosensitivity and copy contrast have not been observed in the present case

3 Example 4:

20 g of the precipitate of p-diazodiethyl aniline and phenolic sulfonic acids (prepared according to DE-OS 17 97 282), 50 g Hovolak Hp · 7, 10 1 g methyl violet,

100 g of methyl glycol, 100 g of ethyl glycol and 100 g of acetone

are combined, stirred at room temperature until complete homogenization and filtered particle-free to 0.2yum. The positive-Potokopierlack solution thus produced is applied by spin on a centrifuge on an oxidized silicon wafer, the disc is then dried at 90 ⁰ G, exposed as in Example 1 and developed with the aqueous solution of a phosphate buffer with pH 13.2. The necessary to achieve perfect relief images exposure time was 10 s.

Claims (4)

Invention; sansprüche 1. positive photocopying with improved properties, in particular with increased photosensitivity with high eeproduction and good application behavior, consisting of at least one novolak, at least one photosensitive component and organic solvents and optionally excipients, such as dyes, inter alia, characterized in that novolacs with narrow molecular distribution spectrum and largely regular molecular structure L, which by flow temperatures of 95 to 180 ⁰ O and s Uniformity between 0.5 and 390 are characterized. 2 · Po sit iv-3? Otokopierlacke according to item 1, characterized in that the hovolaks used contain two to three different phenolic bricks ' and that in two phenolic building blocks these are arranged alternately in the molecule, while in three phenolic each one regularly and the other two . statistically distributed in the molecule. 3 »Positive-Potokopierlack according to item 1 and 2, characterized in that they are phenol, preferably phenol, o-, m- and / or p-cresol, 3,4- and / or 3,5-xylenol, p-tert-butylphenol, 2 , 2-bis (4 - * - h7drox7phenyl) -propane and resorcinol. 4. Positive -] otokopierlack according to item 1 to 3, characterized in that are used as photosensitive components 1-020-2-diazoarene and / or aryl diazonium salts. 47992 Positive IPotokopierlack according to item 1 "to 4-, characterized in that is used as the photosensitive component, in particular an i-Qxo-2-diazonaphthen ~ 4 or · -5-sulfonsäurearylester.