DE2202360B2 - Photographic recording material for the production of intermediate originals and methods for the production of intermediate originals and light masks - Google Patents

Description

The use of photohardenable recording materials has become common practice in both graphic art and electronic technology because they are easy to produce, are very uniform, are inexpensive and also have other known advantages. During the production often have copies he made ^r, which require the use of so-called light masks. These masks are copied from an original. For example, one procedure involves making a copy of the original on flat silver halide printing film. This process is commonly used during printed circuit board manufacture. The silver halide film must then be bleached to reduce the image density so that the processor can see through the image to align the copy while operating under safety light. The safety light used here is the one that leaves out the UV component to which a photopolymerizable resist composition is sensitive.

Usually yellow light is used as a safety light. Under this light, the black, developed silver prevents the processor from seeing through the image in order to align the copy. However, the bleaching process produces a brown color that he can easily see through while making additional copies. This transparency is very important, since the processor often has to superimpose different copies of images so that they fit.
The disadvantages inherent in this procedure are obvious. Various operations such as exposure, development, bleaching and washing are required to make the mask. They must all be carried out under safety light for silver halide, which is due to the photographic

Bophic silver halide system inherent in the safety light for the photopolymerizable system differs. In addition, holes are common damage to the silver halide system, with a subsequent passage of ultraviolet light

h5 undesired exposure through these holes in the photopolymer copy causes. This damage pattern is z. B. not portable for printed circuits. Therefore Often many masks have to be made just to

a single win that in every relationship satisfied. In addition, the bleaching becomes excess Removes silver that is either lost or must be recovered from the treatment solution. Finally, after several exposures, the bleached image turns into a heavily blackened one State back that prevents the processor from ensuring a fitting cover, which is why the mask must then be discarded. The use of masks of this type is therefore only for a short time possible.

Another way of working uses so-called light masks for the production of, for example, integrated circuits with the aid of photolithographic methods. These masks are copied from the original using the photoreduction process as described by Madien et al. In "Integrated Circuit Engineering-Basic Technology", Chapter 3, 4th Edition (1966), published by Boston Technical Publishers, Inc. This is referred to as the master copy. m designated original drawing is prepared and in a 200 to lOOOfachen magnification of actual size because of the high manufacturing cost carefully protected copies of the original are generally prepared, for example, optically clear photogra- 2 ^r> phical glass plates which are coated with a fine grain silver halide emulsion of high resolution . Because of the very delicate and fragile nature of these masks, only a limited number of copies can be made. In addition, these masks also suffer from the damage caused by holes, as mentioned above.

Another type of mask commonly used for this method is that of George and Seaman described in "Photo-Methods for Industry", October 1967, pp. 66/67. These are masks from "Metal-on-glass type," which are usually thin deposits a nickel-chromium-iron alloy or chromium on a glass base. It will then A layer of photoresist is applied over the deposit and the original master copy is made known, described in the literature methods imaged on a photoresist layer. Of the unhardened remaining area of the photopolymerizable layer is made by solvent development and washed out the metal down to the glass in these areas with special etching solutions, such as inorganic Acids, etched away. What remains of the cured photoresist is then removed and the metal image Thoroughly cleaned with the delivery of a suitable light mask. The metal mask is far from the emulsion mask superior, due to their hardness and their ability to reproduce the original largely faithfully. However, these metal masks are very expensive to manufacture, as are those required to manufacture them many procedural steps prevent their application in those technical areas in which the costs represent a major factor. These metal masks also suffer from damage from holes and are also relatively opaque to visible light, which is why proper registration is difficult is.

It is also known to use light-sensitive diazotype materials to produce intermediate originals, see for example DE-OS e.5 17 72 329. Although the use of silver salts can be dispensed with in this way, other disadvantages and limitations have to be accepted . The instability of the diazotype materials working on the basis of diazonium compounds is generally known, which gives rise to considerable difficulties in practical use. It is also known that photomasks show a comparatively small difference between D "," and Dm "on this basis. In practice, the optical density in the non-image areas is therefore relatively high, while it is comparatively too low in the image areas. This in turn gives rise to difficulties when using such light masks.

Finally, multilayer photographic recording materials based on photopolymerizable materials are known Layers, which consist of a support of a photopolymerizable, photohardenable layer and consist of a cover sheet, with between the support and the photopolymerizable light-curable layer a polymeric intermediate layer can also be provided, see for example NL-PS 67 14 36] and DE-AS 12 85 876. The use of dyes in the photopolymerizable layer or in the polymeric intermediate layer has been proposed, with the use of UV light absorbing Photographic recording materials with a targeted structure for dyes is known the production of intermediate originals based on such photopolymerizable systems are, however not yet proposed.

The invention is based on the object of eliminating the disadvantages indicated for the prior art and to provide a photohardenable material that is easy to use and requires only a few operations and costly method to intermediate originals and light masks for making copies can be processed.

Accordingly, in a first embodiment, the invention relates to a photographic one Recording material for the production of intermediate originals from a support, one on top applied layer of a macromolecular organic polymer and at least one colorant, a photoresist-forming layer and a peelable top layer, which is characterized is that the layer containing the macromolecular polymer has at least one essentially for UV light contains impermeable, but transparent to visible light colorant and that the adhesive strength of the The top layer on the photoresist-forming layer is lower than the adhesive strength for UV light impermeable layer on it that the UV light impermeable layer is soluble in solvents and that the support is transparent.

The term "colorant" used here includes both dyes and pigments that are capable of are, the offset layer of the macromolecular polymer against the action of UV light to make impermeable.

The photographic recording material of the invention thus corresponds to the following structure:

Top layer A
photoresist-forming layer (a)
UV light absorbing polymer layer (b)
Layer support B

The multilayer recording material is essentially for actinic light in the visible range

of the spectrum is transparent, but because of the in the ultraviolet dye or pigment present in the UV light absorbing layer (b) is an optical one Density of at least 0.5 or higher, for example up to about 5.0, for that region of the spectrum which is used to get the photohardening going. This is the area between 200 and 500 mu. The photoresist-forming layer and the UV light absorbing layer should be strong enough tack together to avoid breaking or tearing when the top layer A or the Layer support B can be peeled off the adjacent surface.

A mask suitable for lithographic work under transparency is available if the Layer support B adheres more firmly to the UV light absorbing layer (b) than the top layer A to the photoresist forming layer (a). You then expose the photoresist-forming layer through the top layer A and pulls A through before the subsequent development Wash off to form a suitable mask on the substrate B.

A good light mask can also be obtained with reverse bond strength ratios; H. if the substrate B adheres less firmly to the UV light absorbing layer (b) than the cover layer A. on the photoresist forming layer (a). After peeling off B, the remaining three layers can be applied a dimensionally stable and rigid support can be laminated, for example on optical glass. To Lamination and exposure remove the top layer A and the solvent development of the layer (a) then provides the light mask under the resist.

In both cases there are masks that in every respect of the fidelity and sharpness of the image masks obtained correspond to current methods.

The intermediate originals or masks obtained on the basis of the invention have the great advantage that their Substantially lower cost to manufacture and significantly less operator labor required. aside from that For example, the materials of the invention are transparent to visible light so that it can be operated is to ensure a correct registration when reproducing copies of these masks. The low cost associated with the low manual labor permits a greater one Room for maneuver if accidental errors or misunderstandings arise. Another advantage is that Intermediate originals and masks are made available that are relatively free of holes and other layer damage, such as that with the application of silver halide emulsions or metal masks go hand in hand, not have. The masks are also much more resistant to cracking like they are can occur with normal further treatment. In the same way, the masks are resistant to each other a fading and accordingly have a longer lifespan than those based on Masks made using silver halide systems. Moreover, the system of the invention is with others photopolymerizable systems compatible, and you can work in a relatively bright safety light. This Preference is important to processors. The new materials can also be under the same Safety light that was used earlier can be applied.

In a preferred embodiment, the photographic recording material of the invention contains

(a) a photohardenable layer in intimate contact with

(b) a layer of a solvent-soluble resin, for example polyvinyl acetate, with a UV light absorbing compound in a concentration that has an absorption of at least 99% of the actinic light in the range of the spectrum from 200 to 500 πιμ ensures, while the layer mixture for actinic light present in the form of a thin coating is an optical one Density of 0.5 or more, and preferably 1.0 or more.

The layers can be applied or laminated together by methods known in the art will.

Both layers (a) and (b) are arranged between the layer support B and the cover layer A, the consist of polyethylene terephthalate or polyethylene. The support and the top layer serve to to wear or to wear both the ultraviolet light absorbing layer and the photohardenable layer protection. The materials described above can be used as a transparent lithographic mask are by exposing through the top layer, removing the top layer, developing the image obtained and the polymeric layer below the image washes out, leaving the mask on the Layer support that rests against the UV light absorbing layer. In the same way one can use the above Apply the materials described as a light mask by first removing the substrate from the UV light absorbing layer peel off the remaining three layers on a rigid or stronger one dimensionally stable support, the UV light absorbing layer being the support should be applied. The photoresist-forming layer is then exposed to actinic light and the top layer is removed on the photoresist layer and developed as described above, leaving a Light mask on the rigid support.

The polymeric, solvent-soluble, UV light absorbing layers are used as binders macromolecular organic polymers that form solid films. Examples: polystyrene, copolymers of vinylidene chloride and acrylonitrile, polyacrylates and polymethacrylates, polyamides, polyvinyl esters. These polymers can have molecular weights in the range of 500 to 150,000 and are said to be in solvents or Soluble developing solutions generally used for developing photoresists. Examples: Methyl chloroform, trichlorethylene, mixed solvents such as those of methyl isobutyl ketone and isopropanol as well as other substances known to the person skilled in the art. The invention is not necessarily limited to that Solvents that are useful for developing photoresists are limited, but are allowed to Attack and solvents useful for removing the polymeric, UV light absorbing layer in no case be able to dissolve the polymerized areas of the adjacent photohardened image. Particularly useful materials are those using the same solvent can to develop the photoresist image and at the same time the dye absorbing the UV light or to dissolve pigment-containing polymer layer, which saves operator work.

The solvent-soluble polymeric binders can be used to produce the mask

all ultraviolet light absorbing substances are mixed or dispersed. Usable substances are: 2,3-Dihydroxybenzophenon _unc | 2,2'-dihydroxy-4-methoxy-benzophenone.

Since some light-curable image-providing layers also against actinic light just below the UV range of the spectrum are sensitive and since most UV dyes have sharper cutoff points, it is It is also useful to incorporate yellow or orange dyes into the UV light absorbing layers, such as Oil Yellow 3G (Color Index No. 29) and Luxol Fast Yellow T (C.I. No. 47). Alternatively, you can also do one use only dye that absorbs in both the yellow and ultraviolet regions of the spectrum. It is valuable for the UV light absorbing layer if the optical density of the Mixture of ultraviolet absorbent, dye and binder consisting of a layer in the actinic Area has an optical density of at least 1.5 to 5.0 and a subsequent passage of the prevents actinic light in that spectral range that is used to cause the photopolymerization initiate, namely the range from about 200 to 500 πιμ. The photo-curable, photosensitive masses and materials that can be used for the Production of the layer placed over the UV light absorbing substance of the type described suitable with delivery of a combination that creates the image to be used as a mask. To these crowds include uniformly crosslinkable, photohardenable materials according to US Pat. No. 3,525,504 and the photopolymerizable compositions according to US Pat. No. 3,469,982. As in US Pat. No. 3,526,504 described, the photoresist compositions crosslink when exposed to actinic, ultraviolet radiation Light are exposed, and form a hard, polymeric surface in these exposed areas. Other Resist or resist-like layers are described by J. K o sar in "Light-Sensitive Systems", 1965, published by John Wiley and Sons. The so-called cinnamates belong here (cf. I.e., p. 14ff.). dichromated colloids (see I.e., Chapter 2), and Diazo type process (cf. l.c, Chapter 6) as well as many other customary resist materials that are commercially available and are known to those skilled in the art. These layers can be applied individually and then on separate supports are laminated together or sequentially stacked or extruded, whereafter they are drawn or laminated onto the base films. Other methods are also available for this Purpose possible. By applying adhesive layers to the substrate or the top layer, you can give either the support or the top layer the property of being stronger on the adjacent one Layer to adhere than the other.

Examples of binders that are suitable for the UV light absorbing layer are as follows:

Chemical composition molecular
weight Viscosity (centipoise in ang
given solution at 25 ° C) Enamel
Point ( ⁰ C) Polystyrene resin 1500 800 (46% in toluene) 100 Polystyrene resin 300-400 6000 (80% in toluene) 75 Mixed polymer of vinylidene chloride
and acrylonitrile - 80 (20% methyl ethyl ketone) - Polyvinyl chloride - 40 (20% in acetone) - Polyamide (melt index of 10 ° at 225 ° C) - - -15 to -10 Polyvinyl formal 26-34,000 - - Polyvinyl butyral 45-55,000 - - Cellulose acetate butyrate - 98 (15% in benzene) - 90 mole percent methyl methacrylate λ
10 mol% methacrylic acid 1 30,000 2-ethoxyethanol - Linear γ-methylstyrene resin - 10,000 at 149 ^° C
(60% in toluene) - Mixed polymer of 89.5-91.5%
Vinyl chloride and vinyl acetate as the remainder - - - Mixed polymer of 85-88% polyvinyl - 70 (15% in toluene) -

Chloride, 0.8-1.2% maleic acid,
10% vinyl acetate

Mixed polymer of methyl methacrylate and
Methacrylic acid (pH = 8)

Chlorinated rubber with 30% chlorine

Copolymer of vinyl pyrollids and

Styrene

Polymethyl methacrylate

Polyvinyl alcohol (99-100% hydrolyzed)

Mixed polymer of vinyl pyrollidone and

Vinyl acetate

30,000,500 (29.5 to 31.5% in water) -

17-25 (25% in benzene)
1000 (melt viscosity)

70-1400 (37.5% in toluene)
55-65 (4% in water at 20 ⁰ C)
25,000 (melt viscosity)

Below are examples of ultraviolet dyes, ultraviolet absorbers and other dyes, which can be dispersed in or mixed with the binders described above:

^r >

2,2'-dihydroxy-4-methoxy-benzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone,
Hydroxyphenylbenzotriazole,

2 (2'-Hydroxy-5'-methoxyphenyl) -benzotriazole, io

Resorcinol monobenzoate,
2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-benzopheno! I-5-sulfonic acid 15

(also its sodium salt),
Ethyl ^ -cyano ^ -diphenyl acrylate,
2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, Luxol Fast Orange

(GRL Color Index No 25) (Solvent Orange) 20

(GS Color Index No. 24) (Solvent Orange)

(R Color Index No. 20) (Solvent Orange) Plasto Orange

(M Color Index No. 21) (Solvent Orange) Oil-Orange 2 ^r >

(Color Index No. 12 055)

(Solvent Yellow No. 14)
Sudan Orange RA

(Color Index No. 12 055)

(Solvent Yellow No. 14) jo

Latyl Orange 3R

(Color Index No. 26) (Disperse Orange) Capracyl-Orange R

(Color Index No. 60) (Acid Orange) Luxol Fast Yellow j5

(G Color Index No. 45) (Solvent Yellow)

(TColor Index # 47) (Solvent Yellow) Plasto Yellow

(GRColor Index No. 39) (Solvent Yellow)

(MGS Color Index No. 40) (Solvent Yellow) 40

Oil-Yellow

(3G Color Index No. 29) (Solvent Yellow)

(N Color Index No. 2) (Solvent Yellow) Sudan Yellow

(Color Index No. 30) (Solvent Yellow) 45

Latyl-Yellow

(3G Color Index No. 54) (Disperse Yellow) Latyl Orange

(NSTColor Index No. 25) (Disperse Orange) Capracyl-Yellow 50

(N Color Index No. 113) (Acid Yellow) Latyl-Yellow

"(YWL Color Index No. 42) (Disperse Yellow) Capracyl-Yellow

(NW Color Index No. 113) (Acid Yellow) 55

Capracyl Orange

(R Color Index No. 60) (Acid Orange) Bakcar-Yellow

(CY Color Index No. 75) (Disperse Orange) Yellow 60

(2G Color Index No. 3) (Disperse Yellow) Primrose Yellow

(Color Index No. 77 603) (pigment) Chrome-Yellow light

(Color Index No. 77 603) (pigment) ₆ 5

Chrome-Yellow Medium

(Color Index No. 77 600) (pigment) Dispersed manganese dioxide

Toluidine Yellow

(GWCo1orIndex No. 71 680) (pigment)
Molybdate Orange

(Color Index No. 77 605) (pigment)
Dalamar Yellow

(Colorlndex No.il 741) (pigment)
Green gold

(Color Index No. 12 775) (pigment)
Graphtol Yellow

(Color Index No. Pigment Yellow No. 61)
Graphtol orange

(Color Index No. Pigment Orange No. 13)
Victoria Pure Blue

(BO Color Index No. 42 595)

The invention is illustrated by the following examples:

example 1

The following two solutions A and B were prepared:

Solution a

(for use in making the
UV light absorbing layer)

g 15% acrylic hydrosol in water which is a terpolymer made from 55% methyl methacrylate, 40% ethyl acrylate and 5% acrylic acid, solids content: 30% by weight with a particle size of 0.01 to 0.05 microns
95 g Capracyl-Yellow NW, Color Index No. 113
95 g Capracyl-Orange R, Color Index No. 60
35 g Bakcar-Yellow CY, Color Index No. 75
50 g Yellow 2G, Color Index No. 3
g of water.

This mixture was stirred for 1 hour and then the following ingredients were added:

20 grams of trimethylol propane triacrylate
5 g conc. Sodium lauryl sulfate

(10% in water)
10% aqueous solution of a fluorinated hydrocarbon with the following chemical structure:

^ C ₈ F ₁₇ -SO ₂ -N CH ₂ CO j K "

Solution b

(for use in manufacturing
the photoresist layer)

g copolymer of methyl methacrylate (90

Mol%) and methacrylic acid (10 mol%)
24g dimers of o-chlorophenyl-4,5-bis- (m-methoxyphenyl) -imidazole

12 grams of 4,4'-bis (dimethylamino) benzophenone
72 g mixed esters of triethylene glycol dicaproate and dicaprylate

g trimethylol propane triacrylate
g 2- {2-ethoxy) ethanol
g trichlorethylene

Viscosity: 16 cps at 25 "C.

Solution A was applied by machine to a 0.18 mm thick clear film support made of polyethylene terephthalate applied, which had an adhesive layer made of a resin on one side and according to the specifications of the Example IV of US Pat. No. 2,779,684

had been. Solution A was coated on the side provided with the adhesive layer under Use of an air brush known to those skilled in the art. After heating and drying, the Layer A applied the solution B and the then present product in the same way with a 0.019 mm thick, clear, biaxially oriented polyethylene terephthalate film which has been made dimensionally stable in the heat laminated to form a material corresponding to the structure described above. Included A is the biaxially oriented and dimensionally stable polyethylene terephthalate, (a) is a photopolymerizable, layer produced with solution B, 0.0025 mm thick when dry, (b) is the UV light absorbing Layer of solution A, which is also 0.0025 mm thick in the dry state, while B has the polyethylene terephthalate film provided with an adhesive layer. The product was 2 min. With a Carbon arc exposure device exposed. Distance: 45.7 cm. Was exposed through a test image that made consisted of a pencil drawing that recreated a printed circuit board. After stripping the Cover layer A, the photoresist image formed on (a) was developed in the following solution:

60 ml 2- (2-butoxy) ethanol
2 ml octylphenoxyethoxyethanol
66.5 g sodium silicate solution (60% solids in water) Remainder: 1 liter of water.

This solution not only developed the photoresist image on the photopolymer, but also dissolved that polymeric, UV light absorbing layer in the identical areas below the image on below Creation of a yellow-colored, exact, clean intermediate original, which is used for the production of further Copies was usable.

Example 2

The following solutions A and B were prepared: Solution A

1000 g of polyvinyl acetate with a viscosity of 13 to 18 cps in the form of an 8.6% solution in benzene at 20 ° C

60 g of a terpolymer, produced by reacting 1200 g of methyl methacrylate, 50 g of methacrylic acid nitrile and 500 g of methacryloxypropyltrimethoxysilane with a molecular weight of 15,700 (analysis: 1.03% N and 3.15% SiO ₂ )

100 g trimethylolpropane trimethacrylate
100 g of 2,2'-dihydroxy-4-methoxybenzophenone
100 g Luxol Fast Yeitow-T, Color Index No 47
100 g of ethyl alcohol
14,500 g trichlorethylene.

This solution contained 7% solids and had a viscosity of 17 cps at 25 ° C

Solution b

578 grams of polymethyl methacrylate;

Molecular weight 30,000
220 grams of polymethyl methacrylate;

Molecular weight 60,000
95 g terpolymer according to "A"
835 grams of trimethylol propane trimethacrylate
135 g triethylene glycol diacetate

24 g of o-chloropheryl-4,5-bis (n-methoxy-

phenyl) imidazole dimer
9 grams of 7-diet nylamino-4-methylcoumarin
9 g of 2-mercaptobenzothiazole
• \ 1000 g methyl alcohol
7975 grams of methylene chloride.

This solution contained approximately 17.5% solids.

Solution A was applied to a clear, 0.023 mm thick, biaxially oriented, heat set, polyethylene terephthalate support upset.

Coating was carried out using a doctor blade. After drying, the film was with 0.025 mm thick polyethylene laminated to protect the UV light absorbing layer obtained, which had a dry thickness of 0.010 mm and showed the following optical densities (measured on a Cary optical spectrophotometer):

450 πιμ = 1.73
400 Γημ = 2.59
350 πιμ = 3.32
300 ιημ = 2.25.

This UV light absorbing layer was then placed on a covering glass slide of the size 7.62 cm 10.16 cm transferred by scrubbing thoroughly cleaned with solvents. The layer was transferred by removing the Polyethylene top layer and lamination of the UV

jo light-absorbing layer on the glass plate with the aid of ^{rollers heated to 100 to 120 °} C. at a speed of 1.83 m / min.

The solution B was oriented in the same way on a 0.019 mm thick, clear, biaxially oriented and in the Heat-solidified layer support made of polyethylene terephthalate applied after drying lay then a 0.010 mm thick layer of photoresist laminated with a polypropylene top layer to protect the image-bearing layer during further processing.

The polyethylene terephthalate support was then exposed to the UV light which was firmly laminated onto the glass peeled off absorbent layer, after which the polypropylene cover layer is removed from the photoresist layer and laminating the two layers together as described above. It came into being a laminated photopolymerizable material corresponding to the structure described above, where A consisted of polyethylene terephthalate, (a) the photopolymerizable layer and (b) the UV light is absorbent layer, while B was made of glass.

The photopolymerizable layer (a) was then 10 seconds at a distance of 40.6 cm with a 1000 watt quartz iodine lamp iliiich exposed a negative that a Standard test sample showed. This consisted of a simulated electronic printed circuit. The polyethylene terephthalate top layer A was removed by peeling it off and the image obtained through Immersion in a solution made up of a mixture of 90% by weight methyl isobutyl ketone and 10 % By weight isopropanol. It was then sprayed with water and the present yellow image through Inflation of compressed air dried. The solvent used here dissolved both the uncured Areas of the photoresist layer as well as then the colored polymeric underlayer leaving behind a suitable positive mask on a rigid glass support suitable for the application of

Images on photoresists with a light sensitivity between 300 and 450 ιημ.

Example 3

The solutions described in Example 2 were prepared as indicated and based on their corresponding Documents applied. After stripping the polyethylene cover layer from the UV light absorbing Layer corresponding to solution A, the material was applied to one piece using the technique described clear polymethyl methacrylate laminated on. The photoresist layer was then absorbent with the UV light Layer on the polymethyl methacrylate as described with formation of a recording material combined from the structure described, where A is polyethylene terephthalate, (a) photoresist, (b) UV light absorbent layer and B polymethyl methacrylate. A negative test image was applied through layer A to the Layer (a) exposed for 6 seconds with a 1000 watt quartz iodine lamp at a distance of 40.64 cm. Then became Layer A removed and the photoresist image developed by spraying (30 sec.) With methyl chloroform, subsequent second spraying with 2-methoxyethanol and longer spraying with water. That on the Solid polymethyl methacrylate base produced a positive yellow image, which is suitable for use as a Suitable for a light mask, it was then dried with compressed air.

Example 4

30th

Solution A for use as an ultraviolet light absorbing layer was made as follows manufactured:

2000 g of the acrylic acid hydrosol described in Example 1

50% solution of sodium lauryl sulfate in water

30 g of fluorinated hydrocarbon as a 10% aqueous solution according to Example 1.

This solution was heated to 35 ° C and a mixture of the following substances was slowly added:

40 g Latyl Yellow 3G, Color Index No. 54

35 g Luxol Fast Orange GS, Color Index No. 24

20 g of 2,2'-dihydroxy-4-methoxybenzophenone.

45

This solution was applied to a 0.18 mm thick clear polyethylene terephthalate support coated with an adhesive layer, the procedure being carried out as in Example 4 of US Pat. No. 2,779,684, using a doctor blade and forming a dry, 0.005 mm thick layer. Again, this cover was laminated to a thin sheet of polyethylene to prevent surface damage during storage and transfer. After removing the cover layer, the photoresist material of Example 2 was laminated onto the UV light absorbing layer which was on the polyester provided with a resin adhesive layer, to obtain a laminated, photopolymerizable material having the structure A described above, polyethylene terephthalate is, (a) photoresist, (b) UV light absorbing layer and B polyethylene terephthalate coated with a resin adhesive layer. A negative test image was placed over A for 10 seconds with a 1000 watt quartz iodine lamp at a distance of 40.64 cm exposed A was then peeled off and the photoresist image on (a) developed by spraying with methyl chloroform for 35 seconds, spraying again for 15 seconds with 2- (2-butoxy) ethanol and spraying with water for 1 minute. This development process also dissolved the UV light absorbing layer in the same area below the image. The orange-yellow image obtained was dried with compressed air. A photopolymerizable material was then prepared with the following composition:

525 g polymethyl methacrylate,

Molecular weight: 30,000
300 g polymethyl methacrylate,

Molecular weight: 60,000
525 grams of trimethylol propane triacrylate
128 g of triethylene glycol diacetal

9 g of 4,4'-bis (diethylamino) benzophenone
42.3 g of o-chlorophenyI-4,5-bis (n-methoxy-

phenyl) imidazole dimer
2.1 g tri- (4-diethylamino-3-methyl) -

phenylmethane
500 g of methyl alcohol
7970 grams of methylene chloride
Viscosity: 17 cps at 25 ° C.

This material was oriented to a clear, biaxially oriented, 0.019 mm thick and dimensionally stable in the heat made polyethylene terephthalate support coated to form a dry thickness of 0.008 mm, after which it was laminated with a top layer of polypropylene. The photopolymerizable Layer had a photosensitivity in the range of 300 to 400 µm. After removal of the polypropylene top layer this photoresist was made on a film with the aid of hot rollers according to Example 2 laminated with anodized aluminum. The as described produced light mask was then placed over the polyethylene terephthalate cover layer and 5 sec. exposed at a distance of 16 inches using the 1000 watt quartz iodine light source Peeling off the polyethylene terephthalate support, the photoresist image was developed for 30 seconds. Spray with methyl chloroform and 1 min. Spray with water. The anodized aluminum was in those Areas where the photoresist layer had been removed by immersion in a 10% aqueous solution Sodium hydroxide solution etched leaving an exact replica of the light mask that stuck on the aluminum plate was etched.

Example 5

For use as a UV light absorbing layer, a solution A was prepared as follows:

100g5% solution of polyvinyl acetate in water

(Viscosity: 55 to 65 cps at 20 ⁰ C)
1 g Oil Yellow 3G, Color Index No. 29
1 g Luxol Fast Yellow T, Color Index No. 47
1 g of 2 £ '-dihydroxy-4-methoxybenzophenone

50 ml EthanoL

After thorough stirring, this mixture was coated onto a clear polyethylene terephthalate support which had been prepared in accordance with the information in US Pat. No. 3,443,950 and coated with an adhesive layer and also covered with a thin adhesive layer of gelatin (0.5 mg / dm ² ). After drying, the UV light absorbing layer had a thickness of

0.05 mm. The photoresist material of Example 2 was used laminated to the top of the dried, UV light absorbing layer to form a photopolymerizable one Recording material, of the structure described above, wherein A is polyethylene terephthalate is (a) photoresist (b) UV light absorbing layer and 3 polyethylene terephthalate equipped with a gel adhesive layer A test image was placed on A for 30 seconds with a xenon arc lamp at a distance exposed from 40.64 cm. Layer A was then peeled off and the photoresist image was sprayed on of methyl chloroform (25 sec.) and spraying of hot water (25 sec.) and cold water (15 sec.) developed. The obtained image with a colored replica underlayer gave an excellent one Light mask.

Example 6

For the UV light absorbing layer, solution A was prepared as follows:

2000 g of 15% acrylic acid hydrosol (described in Example 1)

35 g Dalamar Yellow (Color Index No. 11,741) 0.5 g sodium lauryl sulfate
0.05gVictoria Pure Blue BO (Color Index No.

42 595)

1.5 grams of 2,2'-dihydroxy-4-methoxybenzophenone
5 grams of trimethylol propane triacrylate

This solution was stirred for 2 hours and applied to a 0.18 mm thick, adhesive resin layer equipped polyethylene terephthalate, which is described in Example 3, with the formation of a Stacked pitch thickness of 0.05 mm. The material had an optical density of 5-7 between 300 and 500 mu. A photoresist coating mixture was then applied with the following composition:

5g

Ig
3g

Polymethyl methacrylate,

Molecular weight: 30,000

Triethylene glycol diacetate

Trimethylol propane triacrylate
0.1 g benzophenone
0.1 g 4,4'-bis (dimethylamino) -

benzophenone
1 g of ethanol
Remainder: methylene chloride to 50 g.

This mixture was applied to a 0.019 mra thick Poiyäthylenterephthalatschichtträger and then laminated onto the UV light absorbing layer as described above photopolymerizable recording material, wherein according to the structure A Polyethylene terephthalate, (a) the photoresist (b) the UV light absorbing layer and B that with a Adhesive Resin Coated Polyethylene Terephthalate This recording material was treated with a A solar device operating at 1000 watts at a distance of 40.64 cm through a photographic silver halide negative test image exposed, which had been placed on top of layer A. Layer A was peeled off and the photoresist image through 10 sec. Spray developed with chloroform. By spraying with 2-ethoxyethanol for a further 25 seconds and then 1 min. Water wash, development was completed and each area of the Removed UV light absorbing layer from underneath the unexposed area of the already dissolved Photoresists lay. After drying, the green-colored positive was used to create the following photosensitive ones Exposing materials:

1) One described in US Pat. No. 3,458,311 The photopolymer printing plate was passed through this mask for 45 seconds at a distance of 91.44 cm exposed under the upright carbon arc device. Line and halftone patterns were exposed with the Developed developer described in US Pat. No. 3,458,311 and a suitable one Preserved printing form.

2) The following "sticky" photopolymer system was made:

40.2% polymethyl methacrylate

Molecular weight: 30,000
50.2% polyoxyethylated trimethylolpropane triacrylate

5.6% polyoxyethylene lauryl ether
0.16% 2-mercaptobenzothiazoI
0.16% 7-diethylamino-4-methylcoumarin
1.6% o-chlorophenyl-4,5-bis (m-methoxy-

phenyl) imidazole dimer
25% solids in trichlorethylene.

40

45

50

55

60

b5 This material was coated onto a polyethylene terephthalate support coated with an adhesive resin layer to form a dry thickness of 0.010 mm, and overlaid by lamination with a 0.019 mm thick polyethylene terephthalate film. The light mask was imaged on this material by exposure to a xenon arc device (exposure time: 15 seconds; distance: 45.7 cm). The image formed by curing the tacky polymer in the exposed area was developed after removal of the polyethylene terephthalate cover film by dusting with a dry, colored dye which adhered to those tacky areas. This material is described in US Pat. No. 3,3 07,943. The colored image obtained was transferred to a coated starting paper by lamination at 110 ° C., after which an excellent positive copy of the light mask was retained.

3) A relatively less sensitive orthosensitive one Silver halide film consisting mainly of chlorobromide with small amounts of iodide was ten seconds with the same Light mask using a 100 watt and 20 volt standard incandescent lamp spaced apart 134.6 cm through a 0.6 neutral density filter and a No. 47 Wratten filter exposed. The image was made in a standard developer suitable for many processes (Metol-Hydroquinone) developed, after which the fixing in a usual photographic Fixative took place. After washing and drying carried out in the customary manner, was get a very high resolution black and white image.

Example 7

For use as a UV light absorbing layer, a mixture was prepared by the following Ingredients were placed in a ball mill:

909 531/143

500 μl 5% acrylic acid hydrosol (in example 1 described)

50 g of 10% aqueous saponin solution
30 g Latyl Yellow YWL, Color Index No. 42
8 g Latyl Orange NST, Color Index No. 25
10 grams of trimethylol propane triacrylate
25 g of a urea formaldehyde

Mixed polymers
5 g of 2 £ '-dihydΓoxy-4-methoxybenzophenone.

After 16 hours of milling, the mixture was filtered through a felt and formed into a Coated dry thickness of 0.05 mm on a polyethylene layer carrier, which is an underlayer according to Example 4 carried. The support was then heated to cause the polymer to flow together bring, after which a transparent, orange-colored layer was obtained, which has the following optical Densities showed:

wavelength (ηιμ)

Optical density

500
400
350
300

> 4.52
> 4.52
> 2
> 2

Solution b
(for making the photoresist layer)

The above solutions correspond to percentages for a 20% solids solution in a mixture of 3 parts of methyl ethyl ketone and 1 part of isopropanol.

Solution A was applied to a 0.18 mm thick polyethylene terephthalate support as described in Example 1 and dried. Solution B was then layered over A to form a layer weight of 87 mg solids / dm ^J and dried. This layer was then treated with a 3% strength. aqueous solution of PoIw in \ laIkuhol (medium viscosity; 99% saponified).

10

15th

20th

25th

30th

The photoresist material described in Example 2 was then laminated onto this layer and the exposure development was carried out in the same manner as described in this example. This Mask material was useful for applying images to photoresist covered copper plates for printed circuits.

Example 8
The following two solutions were made:

Solution a

(for making the UV light
absorbent layer)

The same as described in Example 1.

Mixed polymer of 90 moles of methyl 53.80 / 0 50 methacrylate and 10 moles of methacrylic acid Pentaerythritol triacrylate, containing 0.4% p-methoxyphenol 44.1% as a thermal inhibitor 2.0% Tertiary butyl anthraquinone 55 Ethyl violet 0.1% (C. 1. Basic Violet 4) dye

containing 2% of a polyoxyethylene surfactant, as described in US Pat. No. 3,458,311, Example 1, overlaid. The top coat weight of the dried polyvinyl alcohol layer was 12 mg / dm ² . The multi-coated material was then exposed for 3 seconds with an upright carbon arc exposure device through a test image which simulated an integrated electrical circuit (exposure distance: 43.18 cm). The photoresist image obtained was developed with a developer having the following composition:

Isopropyl alcohol (99%)

Sodium hydroxide

water

10VoL- ° / c

0.1 vol- '

89.9 vol. - ¹

40

45

bo The recording material was covered with the developer and left to soak for 30 seconds. The entire top layer as well as the unexposed areas of the photopolymerizable layer and the colored polymeric layer below the corresponding areas were removed by treatment with a slurry Use as a mask.

It is not essential that the layers of material be between a support and a Cover layer are arranged horizontally. Other embodiments are possible, for example by the UV light absorbing layer (b) produces a sufficient thickness so that a portion of this layer can be thermally cured to serve as a support for the material. In addition, the Removal of the top layer may be of practical importance. The described and illustrated embodiments however, they are preferred.

Example 9

Solution A (the UV light absorbing layer) was prepared as described in Example 1 and applied applied a 0.18 mm thick polyethylene terephthalate support. A crosslinkable isoprene resist, compiled by W. L Hunter and P. N. Crabtree and described in U.S. Pat "Photographic Science and Engineering", Vol. 13, No. 5, p. 271 (1969) was about the dried, UV light absorbent layer layered using a doctor blade held 0.05 mm apart. the The resist layer was dried for 2 minutes at 38 ° C. and then as described in Example 1 with a test image exposed, after which the product obtained was developed in a xylene-based developer by it was immersed in the developer for 10 minutes at room temperature. The recording material was then with a mixture of 50 parts of ethanol and 50 parts of water. The mask obtained was suitable for Making other copies.

Example 10

Solution A of Example 1 was prepared for the UV light absorbing layer and as in Example 9 described piled up and dried. Then the following mixture was made using an im Distance of 0.05 mm held squeegee applied over this layer:

10 g gelatin for photographic use 90 g of distilled water

5 g potassium dichromate

5 g of 10% aqueous saponin solution.

The gelatin was dissolved in the water by immersion and soaking at 38 ^° C., after which potassium dichromate and saponin were slowly added with stirring. After this mixture had been applied to the UV light absorbing layer of the type described above, the coating was dried with warm air and the recording material obtained was exposed for 5 minutes through the test image, using the same exposure conditions and the same light source as in Example 1 The exposed recording material was then developed by immersion (30 seconds) in the following solution:

9.6 g sodium borate decahydrate

2.0 g of 10% solution of octylphenoxyethanol

in water

180.0 g 2- (2-butoxyethanol) Remainder: 1 liter of water.

The developed image was rinsed with cold water and dried. A yellow copy remained of the original, which was impermeable to light with a wavelength between 200 to 500 ΐημ and is suitable for the Use as a mask of the original.

Example 11

30th

As described in Example 9, a solution A for the UV light absorbing layer was prepared and upset. Then a crosslinkable photosensitive composition was prepared by dissolving 0.5 g of (1,4-butanediol) dibenzoate 4,4'-bis (diazonium zinc chloride) in 25 ml of acetone, containing: 2.5 g of polymethyl methacrylate / hydroxyethyl methacrylate / lat (molecular weight: about 30,000; 90 mol% Methyl methacrylate), 0.5 g of p-toluenesulfonic acid, 1.0 g of triethylene glycol diacetate, 2 ml of ethanol and 1 ml of water. This mixture was applied to the dried UV light absorbing layer. A test image was then applied to the dried, light-sensitive layer and exposed for 2 min. At a distance of 61 cm with a carbon arc exposure device (2500 watts; 14 amperes). This was followed by treatment with ammonia vapors developed, and then washed out the exposed areas with 1,1,1-trichloroethane. The one for washing out the exposed areas of the photosensitive Mixture of applied solvents also removed the same areas from the UV light absorbing Layer, leaving behind a negative image of the original, which turns out to be a light mask for application of images on subsequent copies.

Example 12

Solution A for the UV light absorbing layer was prepared as indicated in Example 9, then coated and dried according to the specifications of US Pat. No. 3,376,139 Diallyl isophthalate prepolymer prepared. This photosensitive prepolymer was then dissolved in methyl isobutyl ketone while maintaining a solvent to prepolymer ratio! from 5: 1. The resulting solution was then sensitized by adding 4,4'-bis (dimethylamine) benzophenone (0.01 g of the sensitizing agent per 63 g of solution) was applied to the UV light absorbing layer by spraying and dried the thickness of the dried layer: 0.003 mm. The test image was then applied to the above as described in Example 1 Material placed, exposed and the product obtained by immersion in 1,1,1-trichloroethane for 30 seconds A colored copy of the original was obtained, which can be used to make further copies suited.

Example 13 The following solution was made:

Mixed polymer of Ethyl acrylate (about 88%) and Acrylic acid (about 12%) ') 100 g NH ₄ OH solution

(saturated, approx. 58% NH ₃ ) 12g

distilled water 888 g

*) This copolymer is a thermoplastic acrylic acid polymer with a molecular weight of approx 260000 which contains a number of carboxylic acid groups The ammonium salt formed in the above solution had a tensile strength of 4100 PST.

50 g of this solution were mixed with 50 g of the acrylic acid hydrosol described in Example 1 plus 5 g of a 25% strength aqueous solution of a fluorinated hydrocarbon, the chemical structure given in Example 1. Then 10 g of solid potassium permanganate were added and the mixture was stirred for 2 hours until the evolution of gas ceased. 10 ml of 2- (2-ethoxyethanol) were added and the solution was applied to a 0.18 mm thick polyethylene terephthalate film according to Example 1 using a doctor blade held at a distance of 0.05 mm to give a dry weight of 50 mg / dm ² . This multilayer material was then overlaid with the photosensitive resist composition of Example 1 (solution B) and laminated as indicated in the same example, exposed to a test image and developed. The brown «. MnO2 copy of the original image strongly absorbed between 200-500 ηιμ and was a useful intermediate original.

Claims (6)

Patent claims: 1. Photographic recording material for the production of intermediate originals from a Layer support, a layer made of a macromolecular organic polymer applied to it and * at least one colorant, a photoresist-forming one Layer and a removable cover layer, characterized in that the the layer containing macromolecular polymers is at least one essentially for UV light contains impermeable, but transparent to visible light colorant and that the adhesive strength of the The top layer on the photoresist-forming layer is lower than the adhesive strength for UV light impermeable layer on her that the layer impermeable to UV light is soluble in solvents and that the support is transparent 2. Photographic recording material according to claim 1, characterized in that the for ultraviolet light opaque layer has an optical density of 1.5 to 5 for the area has between 200 and 500 ηιμ. 3. Photographic recording material according to claim 1 and 2, characterized in that the photoresist-forming layer is addition polymerizable or photo-crosslinkable. 4. Photographic recording material according to one of Claims 1 to 3, characterized in that that the substrate adheres less firmly to the layer impermeable to UV light than that Top layer on the photoresist-forming layer. 5. A method for producing intermediate originals using a recording material from a layer support, a layer applied on top of a macromolecular organic Polymers and at least one colorant, a photoresist-forming layer and one removable cover layer, characterized in that the macromolecular polymer containing Layer at least one substantially impermeable to UV light but to visible light Contains permeable colorant and that the adhesion of the top layer to the photoresist-forming Layer is lower than the adhesive strength of the layer which is impermeable to UV light to it the layer which is impermeable to UV light is soluble in solvents and the layer support is transparent and that by imagewise exposure through the adhered to the photoresist-forming layer Cover layer through, peeling off the cover layer and then developing a photoresist image produces and thereby the uncured areas of the photoresist-forming layer and those below them washes out lying parts of the layer impermeable to UV light. 6. Process for the production of light masks using a recording material from a layer support, a layer applied on top of a macromolecular organic Polymers and at least one colorant, a photoresist-forming layer and a top layer, characterized in that the layer containing the macromolecular polymer at least one substantially impermeable to UV light but permeable to visible light Contains colorants and that the adhesive strength of the The top layer on the photoresist-forming layer is lower than the adhesive strength for UV light impermeable layer on her that the layer impermeable to UV light is soluble in solvents and that the adhesive strength of the support to the layer which is impermeable to UV light is lower than the adhesive strength of the top layer to the photoresist-forming layer that one is the support removed, the remaining photographic recording material with the opaque to UV light Layer laminated onto a rigid transparent support and that one darch imagewise exposure, peeling off the cover layer and subsequent development of a photoresist image produces and thereby the uncured areas of the photoresist-forming layer and those below them washes out lying parts of the layer impermeable to UV light