US 4,740,450 AGrant
Method of Making Image Reproducing Material Having Scratch Improvment
Issue Date:1988-04-26
•1 Claims
Abstract
An image reproducing material which comprises a support and at least a photosensitive resin layer and scratch resistance layer borne on the support, said scratch resistance layer containing a compound represented by AmBn, wherein A is mono- or divalent, straight or branched C.sub.11-20 aliphatic hydrocarbon; B is hydrogen, hydroxyl, amino, nitrile, aldehyde, carboxyl, or alkylamide, alkylester, ammonium salt or a periodic table group I-IV metal salt of a carboxylic acid; m is an integer of 1 to 3; and n is 1 or 2. A process for preparing the image reproducing material as well as a process for preparing an image reproduced material by using the image reproducing material are also described.
Metadata
Assignee
- Toyo Boseki Kabushiki Kaisha
Inventors
- Nobuyuki Tamaoki
- Yoshio Katoh
- Akitada Osako
- Toshihiko Kajima
- Shinichi Tanaka
Application Information
Application Number:US 0012858
Filing Date:1987-01-08
Priority Date:1983-09-13
Art Unit:156
Classifications
IPC:
G03C 168
Field of Search:
430522273;281;950;961;52316;26
Patent Drawings
This patent does not have any drawings.
Description
The following examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.
EXAMPLE 1
A polyeseter film (thickness: 100 .mu.m) was coated with a composition having the following formulation by a reverse roll coater and dried to prepare a polyester film having an undercoat layer (thickness: 0.5 .mu.m).
Next, various photosensitive compositions were prepared by mixing and dispersing the ingredients in the following formulation and then each of them was coated on the above-prepared polyester film having the undercoat layer by a reverse roll coater to form a photosensitive resin layer (thickness: 3 .mu.m) thereon.
Further, a protective overcoat layer composition of the following formulation was coated on each resulting film to prepare a photosensitive film having a protective overcoat layer (thickness of the protective layer: 1 .mu.m).
A test negative film composed of a combination of a step guide with 21 steps (manufactured by Dainihon Screen Co.) and a dot image (150 l/in, halftone dot area ratio: 50%) was put on each resulting photosensitive film and it was exposed to a light for predetermined period of time by using a bright room printer(manufactured by ORC Co.) to form an image. After the protective overcoat layer was removed by washing with water, the film was dipped in (A) 0.75% aqueous Na.sub.2 CO.sub.3 solution or (B) 5% aqueous Na.sub.5 P.sub.3 O.sub.10 solution adjusted to 30.degree. C. for 10 seconds according to the kind of the film, rubbed with sponge while washing with water to develop the image and then dried to obtain a reversed image. It was found that hardening was completed by 5th step of the step guide and the dots reproduced the negative copy well.
Next, a reproduced dot image prepared in the same manner as described above was treated by dipping in 5% aqueous hydroquinone solution adjusted to 30.degree. C. for 15 seconds, washing with water and drying.
The sample thus obtained was subjected to a loaded scratch test by using a surface properties tester Model Heidon-14 (manufactured by Shintokagaku KK) with a sapphire needle (0.1 mm in diameter) at a rate of 100 mm/min. The results are shown in Table 1. As is seen from Table 1, it was found that surface scratch resistance property of the image was remarkably improved by using the method of the present invention.
Example 2
A surface of a polyester film (thickness: 100 .mu.m) was washed and dried and then aluminum was deposited thereon in 500 .ANG. thickness under vacuum of 10.sup.-5 Torr order with a resistance heating type vacuum metallizer.
Then, each photosensitive composition shown in Table 2 was prepared and coated on the above aluminum deposited polyester film by a reverse coater to form a photosensitive coating layer in 3 .mu.m thickness thereon.
Further, on this film was coated a protective overcoat layer composition of the following formulation according to the same manner as described above to prepare a photosensitive film having a protective overcoat layer of 1 .mu.m thick.
A test negative film composed of a combination of a step guide with 21 steps (manufactured by Dainihon Screen Co.) and a dot image (150 l/in, halftone dot area ratio: 50%) was put on each resulting photosensitive film and it was exposed to a light for predetermined period of time by using a bright room printer (manufactured by ORC Co.). Then, after the protective overcoat layer was removed by washing with water, the film was dipped in (A) 0.75% aqueous Na.sub.2 CO.sub.3 solution adjusted to 30.degree. C. for 10 seconds and rubbed with a sponge while washing with water to develop and to remove the unexposure part of the photosensitive resin layer. The film thus treated was further dipped in a second developer, aqueous saturated calcium hydroxide solution (30.degree. C.) for 3 minutes, washed with water, dipped in 5% aqueous hydroquinone solution (30.degree. C.) for 15 seconds, washed with water and dried to obtain a sample for measuring scratch resistance.
The sample thus obtained was subjected to a loaded scratch test according to the same manner as in Example 1. The results are shown in Table 2. As is seen from Table 2, it was found that surface scratch resistance properties of the image was remarkably improved by using the method of the present invention.
Example 3
A photosensitive layer (thickness: 3 .mu.m) was prepared on the polyester film having the undercoat layer of Example 1 by coating a composition which is the composition No. 5 in Example 1 containing the compound shown in Table 3 with a reverse roller coater and drying. Further, a protective overcoat layer in 1 .mu.m thickness was formed on this film according to the same manner as in Example 1. A sample for scratch resistance testing was prepared in the same manner as in Example 1 except that the developer (A) is used and its scratch hardness was determined. The results are shown in Table 3. As is seen from Table 3, all the scratch resistance improvers tested are effective.
Example 4
Four kinds of image reproducing materials, A, B, C and D were prepared according to the following manner:
Image reproducing material A
A composition having the following formulation was coated on a polyester film (thickness: 100 .mu.M) by a reverse roller coater and dried to prepare a polyester film with an undercoat layer of 0.5 .mu.m thick.
Then, a photosensitive composition was prepared by mixing and dispersing the ingredients of the following formulation and was coated on the above polyester film with an undercoat layer by a reverse roller coater to form a photosensitive resin layer in 3 .mu.m thickness.
Likewise, a protective overcoat composition of the following formulation was coated on the resulting film to prepare a photosensitive film A with the protective overcoat layer in 1 .mu.m thickness.
A test negative film composed of a combination of a step guide with 21 steps (manufactured by Dainihon Screen Co.) and a dot image (150 l/in, halftone dot area ratio: 50%) was put on each resulting photosensitive film and it was exposed to a light for a predetermined period of time by using a bright room printer (manufactured by ORC Co.). Then, after the the protective overcoat layer was removed by washing with water, the film was dipped in 0.75% aqueous Na.sub.2 CO.sub.3 solution adjusted to 30.degree. C. for 10 seconds and rubbed with a sponge while washing with water to develop the film and dried to obtain a reversed image. It was found the the film was hardened by 5th step of the step guide and the negative image was well reproduced by dots.
A reproducing halftone dot image prepared in the same manner as described above was dipped in 5% aqueous hydroquinone solution and washed with water, dried to obtain the image reproducing material A.
Image reproducing material B
The surface of a polyester film (thickness: 100 .mu.m) was washed with water, dried and then aluminum was deposite thereon in a thickness of 500 .ANG. under vacuum of 10.sup.-6 order by a resistance heat type vacuum metallizer.
Next, a photosensitive composition of the following formulation was prepared and coated on the above polyester film having a deposit of aluminum by a reverse roll coater to prepare a photosensitive layer coating in 3 .mu.m thickness.
Further, a protective overcoat layer was provided on this film in the same manner as in the above image reproducing material A to obtain a photosensitive film B.
According to the same manner as in preparation of the image reproducing material A, the film was exposed to light for 5 seconds. Then, after removal of a protective overcoat layer by washing with water, the film was dipped in 0.75% aqueous solution of Na.sub.2 CO.sub.3 at 30.degree. C. for 10 seconds and an image was developed by rubbing with a sponge while washing with water and the unexposed part of the photosensitive resin layer was removed. Then, it was dipped in the second developer aqueous saturated solution of calcium hydroxide (30.degree. C.) for 3 minutes and washed with water, and again, dipped in 5% aqueous solution of hydroquinone (30.degree. C.) for 15 seconds, washed with water and dried to obtain an image reproducing material B. It was hardened by 5th step of the step guide and the halftone dots reproduced the negatives precisely.
Image reproducing material C
Polyester (100 parts by weight) obtained by condensation polymerization of 2-methyl-2-(N,N-diethylamino)methyl-1,3-propanediol and terephthalic acid in the molecular ratio of 1.1:1 according to a conventional method and diphenylmethane diisocyanate (1, 3, 5 or 7 parts, respectively) were dissolved in benzene (525 parts) and the mixture was stirred at 30.degree. C. for 40 minutes. Then, tribromomethylphenylsulfone (61 parts) was dissolved in the mixture, which was coated on the polyester film with an undercoat layer used for preparing the image reproducing material A, to obtain a photosensitive film C with a photosensitive layer in 5 .mu.m thickness. This film was exposed to light for 20 seconds in the same manner as in preparation of the image reproducing material A.
This film was dipped in the developer which was prepared by dissolving bromophenol blue (0.0066 parts) in a mixture of water and methanol (water/methanol=4/6 by volume) at 20.degree. C. for 180 seconds to develop an image and dried to obtain an image reproducing material C which was colored in enough density by the 4th step and the halftone dots well reproduced the negatives.
Image reproducing material D
Fuji lithocontact film (Trade mark, Fuji film KK) was used as a photosensitive film D. The film was exposed to light for 5 seconds according to the same manner as in preparation of the image reproducing material A. Then, an image was developed with High lithodol, a standard developer for Fuji lithofilm, for 2 minutes at 20.degree. C. with continuous stirring and then dipped in 3% aqueous solution of acetic acid (20.degree. C.) for 20 seconds to quench the reaction. Then, by using acidic hard film fixer Fuji fix (Trade mark, Fuji film KK), fixing was carried out at 20.degree. C. for 3 minutes and then the film was dipped in 2% aqueous solution of sodium nitrite which acted as a washing promotor, washed by running water for 5 minutes and dried at 50.degree. C. by warm air for 30 seconds to prepare image reproducing material D. The step guide was developed by the 3rd to 4th steps and halftone dots well reproduced the negative.
In order to test the effect of the present invention, the treatment solution shown in Table 4 was prepared.
The above-obtained image reproducing materials A-D were treated with these treatment solution according to the following two methods (E) and (F). (the method applied is shown in Table 4)
(E) The surface of the image was wiped 5 times with Webril Litho-Pads (Trade Mark of 100% cotton pad manufactured by Kendal Co.) previously dipped in the treatment solution and well wrung and it was air-dried.
(F) The image reproducing material was air-dried after being dipped in the treatment solution at 20.degree. C. for 30 seconds.
The image reproducing material thus treated was subjected to a loaded scratch test as described above. The results were shown in Table 5.
As is seen from Table 5, it was found that surface scratch resistance property of the image was remarkably improved by using the treatment solution of the scratch resistance improver and employing the method of the present invention.
Example 5
The photosensitive film A of Example 4 was exposed to light to form an image according to the same manner as in Example 1 and the protective overcoat layer was removed by washing with water. Then, it was dipped in 0.75% aqueous solution of Na.sub.2 Co.sub.3 containing 0.5% of sodium lauryl sulfate for 10 seconds and developed by rubbing with a sponge while washing with water and dried to obtain the reversed image. The step guide was hardened by the 5th step and the halftone dots well reproduced the negatives. When this image reproducing material was subjected to the loaded scratch resistance test in the same manner as in Example 1, the scratch strength was 150 g. In comparison with the scratch strength of the image reproducing material A developed with the developer containing no sodium lauryl sulfate (8 g), it is apparent that the scratch resistance property was remarkably improved.
Claims
What is claimed is:
1. A process for preparing an image reproducing material for a lithofilm said process comprising (a) forming a coating composition by admixing scratch resistance improver, photosensitive layer ingredients and coating solvent, said scratch resistance improver being present in an amount ranging from about 0.35 to 10% by weight of the photosensitive layer ingredients, said scratch resistance improver having the formula AmBn wherein A is mono- or divalent, straight or branched C.sub.11-20 aliphatic hydrocarbon; B is hydroxyl, amino, nitrile, aldehyde, carboxyl, alkylamide, ester of carboxylic acid with C.sub.1-3 monohydric or polyhydric alcohol, or ammonium salt or a periodic table group I-IV metal salt of a carboxylic acid, m is an integer of 1 to 3; and n is 1 or 2, said photosensitive layer ingredients being such as to provide a photosensitive layer in step (c) with a fluidizing point not higher than 95.degree. C. and comprising monomer containing one or more photopolymerizable double bonds, a photopolymerization initiating amount of photoinitiator, a functional amount of binder which is a solid organic polymeric material at a temperature lower than 50.degree. which has film forming properties in the photosensitive layer formed in step (c), and actinic light absorber to provide an absorbance of 1.5 to 4 in the photosensitive layer formed in step (c); (b) coating said composition onto a transparent support in amount and thickness to provide a photosensitive layer of thickness of 1 to 6 microns in step (c); (c) drying coating provided by step (b) so that it contains less than 100 ppm coating solvent to obtain photosensitive layer with scratch resistance improver therein of thickness of 1 to 6 microns and fluidizing point not higher than 95.degree., whereupon, because of said dried state and because of said fluidizing point, said scratch resistance improver migrates to the surface of the photosensitive layer removed from said support to provide scratch resistance properties thereto.