CN1027838C - Non-diazotate blueprinting and blueprint film - Google Patents

Abstract

The present invention relates to a novel non-diazotate heavy nitrogen resin solarizing film. Photosensitiser is composed of photosensitizer (heavy nitrogen resin 1, 2, 4 type or 2, 1, 5 type), adhesive (metacresol formaldehyde resin, novolac resin and deflective and offset hepatitis resin), a sensitizing agent (diphenyl ketone, rice-ketone, etc.), a plasticizing agent (santicizer 218a, etc.) and an ultraviolet absorbent (gylcol ether and acetate). Compared with the existing heavy diazonium salt film, the film has the advantages of high photosensitizing speed, large density, good fastness, self immersion for defilming, good wear resistance, high stability and long retention period of a raw film. In addition, the advantages of the present invention are superior to or are not inferior to those of the existing heavy diazonium salt film.

Description

Non-diazotate blueprinting and blueprint film

In the prior art, diazo salt all is a positivity as morpholinyl or sulfydryl, promptly makees base map with positive and shines the copy (duplicate) that prints off positive.But, make the film that photosensitizer is made with diazo salt, its sensitization becomes the mechanism of phase to determine the bonding film that has layer transparent.The components such as phenolic compound that contain trace in the transparent bonding film of this layer, oxidation becomes dark bonding film lentamente with the passage of time.Make non-lines position become more and more heavier by background color is very for a short time, influence is used and is continued the copying blueprint.The raw cook of diazonium salt film (being unexposed film) particularly, its storage life was counted from the day of the coating of production producer, only had 6 months to 1 year, also was a deficiency.

China's utility model patent 86207979.9, though overcome two crucial disadvantages of diazonium salt film, its sepia can shine the good blueprint of quality, does three base map difficulties.Because the density value of this film does not reach 3.0.

The objective of the invention is to develop diazo resin sun a kind of non-diazo salt, novel and shine positive film.This sensitive film had both overcome the raw cook storage life weak point of diazonium salt film, and the deficiency of transparent bonding film is arranged, and had improved the diazo resin sun again and had shone positive film, had big, the anti-advantage of fading, preventing fragility of density.Its raw cook duration of insurance reached more than 7 years, and sepia, three base maps were deposited in indoor indefinite duration.

Photosensitizer of the present invention is adjacent folded naphthoquinones photosensitive material.It is 1,2,4 type emulsion, and chemical full name is 1-diazonium, 2-naphthoquinones, 4-sulfonic acid polyphenol ester, or is called 1,2,4 adjacent nitrine naphthoquinone sulfonic acid esters.Also can select 2,1,5 type emulsion for use, chemical full name is 2-diazonium, 1-naphthoquinones, 5-sulfonic acid polyphenol ester, or is called 2,1,5 adjacent nitrine naphthoquinone sulfonic acid esters.1,2,4 types, 2,1,5 type emulsion, both are nonionic, salify not, so have no water wettability, hydrolysis can not take place in stable high to moisture in malaria.Their photosensitive group is that nitrogen-atoms connects and composes azido by three keys, the same with the diazo of diazo salt, ultraviolet ray is auxilliary just decomposes when penetrating immediately when being subjected to, emit nitrogen, molecule rearranges, and generates the compound contain five yuan of carboxylic acid structures, demonstrate acidity and the alkali-soluble that has by flush away, the sheet base is transparent, does not have mucous membrane.The resinous coat of sensitization does not still keep original insoluble to light alkaline developer, is retained and gets off to become the figure phase, and promptly Figure of description is seen at the line markings position for details.

The embodiment 5 of BrP GB1463717 provides the example of going up coating at polyester film base (POLYESTER FILM).But its color only is green to light yellow.

Film color of the present invention is six kinds of chromatograms such as black, dark green black, redness, rufous, blueness, orange colour.These six kinds of films possess identical performance.

Photosensitizer of the present invention, it is rational adding about 2.6% to 16.8% by weight.

The bonding agent that non-diazo salt sun shines positive film can be selected the macromolecular compounds such as linear phenolic resin, epoxy resin or vinylidene chloride-acrylonitrile copolymer resin of m-cresol formaldehyde resin, modification for use.Use by about 2.8% weight to about 12.4% weight.

In order to improve light sensitivity, reduce the time shutter, improve blueprint efficient, in prescription, add about by weight 0.3% to about 9.9% sensitizer, for example benzophenone, cyclohexanone, Michler's keton etc. are desirable.

Plastifier can be used in the sensitization component, for example, and diethyl phthalate, dibutyl phthalate, triethylene glycol acid esters, glycerine triethyl and similar compounds.These plastifier are according to the general assembly (TW) of sensitization composition, and weight by about 0.2% or 4.2% part by weight use.

Employed coloring compound is dyestuff and pigment in being coated with the positive film of manufacture-illegal diazo salt sun solarization.The example of this component is the black WRLH of card magnetic dragon, nigrosine, nigrosine, spirit black, the red as fire B of pure molten sun-proof, the bright red 2GL of kation, methylene blue, sodium alizarinsulfonate, ultra-fine carbon black, the black iron of oxidation and similar dyestuff and pigment.Usually the concentration of dyestuff or pigment is present in sun with about concentration of 0.9% to 10% by weight and shines in the positive film.

In sensitization formula of liquid of the present invention, also has ultraviolet light absorber, for example phenol, ethyl cinnamate, benzotriazole, gaultherolin, 2,4-two basic benzophenone (UV-0), 2-hydroxyl-4-methoxy benzophenone, dihydroxy-4-n-octyloxy-benzophenone and similar chemical reagent.The amount that it is fit to approximately is 0.2% to 6.4%, adds by weight.

The sensitization liquid component that contains above-mentioned batching dissolves in the solvent that is fit to, and is coated on polyester film base (PET) support.No matter the sheet base is two-sided light, and still one side hair one side light, light sensitive layer of the present invention are to be coated on the light face of polyester film base.The solvent that is fit to is ethylene glycol monomethyl ether, ethylene glycol ethyl ether or same kind solvent, and butyl acetate, ethyl acetate or same kind solvent.The part by weight of glycol ethers solvent and acetates solvent is about 80%-60%: 20%-40%.

Specific embodiment is as follows:

Example 1:

1,2,4 type emulsion (or 2,1,5 type emulsion) 8.6%

Metacresol formaldehyde resin 3.7%

Linear phenolic resin 0.8%

The black WRLH(of card magnetic dragon or nigrosine or nigrosine) 6.3%

Bright red 2GL(of kation or the red as fire B of pure molten sun-proof) 0.6%

Ethylene glycol monomethyl ether 60%

Butyl acetate 20%

Example 2:

1,2,4 type emulsion (or 2,1,5 type emulsion) 5.5%

Metacresol formaldehyde resin 3.2%

Linear phenol-aldehyde resin 4.4%

Phenol 4.3%

The red as fire B2.6% of the molten sun-proof of alcohol

Ethylene glycol monomethyl ether 45%

Butyl acetate (or butyl acetate) 35%

Example 3:

1,2,4 type emulsion (or 2,1,5 type emulsion) 7.2%

Metacresol formaldehyde resin 2.8%

Epoxy resin (6101) 3.4%

Vinylidene chloride-acrylonitrile copolymer resin 1.5%

Black WRLH(of card magnetic dragon or nigrosine, nigrosine) 5.8%

Benzophenone 1.6%

The red as fire B2.7% of the molten sun-proof of alcohol

Ethylene glycol monomethyl ether 45%

Butyl acetate 30%

Example 4:

1,2,4 type emulsion (or 2,1,5 type emulsion) 4.0%

Metacresol urea formaldehyde 2.8%

Vinylidene chloride-acrylonitrile copolymer resin 4.6%

2-hydroxyl-4-methoxy benzophenone 3.2%

Diethyl phthalate 0.8%

Methylene blue 4.6%

Ethylene glycol monomethyl ether 40%

Ethyl acetate 40%

Example 5:

1,2,4 type emulsion (or 2,1,5 type emulsion) 3.8%

Metacresol formaldehyde resin 4.2%

Vinylidene chloride-acrylonitrile copolymer resin 6%

Triethylene glycol acid esters 2.5%

Alizarin yellow 5.5%

The red as fire B3% of the molten sun-proof of alcohol

Ethylene glycol monomethyl ether 45%

Butyl acetate 30%

In the Large Scale and Continuous coating machine, make 1.0 meters-1.2 meters wide films.The two-sided light of its sheet base state, or one side hair one side light.The one side hair is immersion coating or machinery fluffing, thick 0.10 millimeter to 0.13 millimeter of sheet base.Film color is six kinds of chromatograms such as black, blackish green, red, rufous, blueness, orange colour.

Quartz burner is desirable light source, and the main peak value of the spectrum that it is launched is at 365-421 nanometer (nm).

Can just adopt and shine (the former figure of the polyester back side contacts with the film coat side), or anti-solarization the (the former figure of polyester is positive to be contacted with the film coat side).

Developer formula is as follows:

1000 milliliters in tap water (below 25 ℃)

NaOH (chemical pure) 10-30 gram

Tri-sodium phosphate (chemical pure) 10-30 gram

Potassium chloride (chemical pure) 5-15 gram

Add stirring and dissolving successively.With stock alcohol thermometer or mercury temperature instrumentation liquid temperature.20-25 ℃ liquid temperature, development effect are good.

Wash, thoroughly wash down the remaining alkali lye on sepia or three base map two sides.

Photographic fixing, the lactic acid photographic fixing with 20 ‰.The acid-base neutralization reaction generates soluble-salt and water.

Wash, thoroughly wash down the remaining acid solution on sepia or three base map two sides.

Drying, in the oven dry of the sheet base hothouse below 40 ℃, or natural draining drying.

Figure of description is explained:

I-film II-exposure III-development IV-one-tenth phase

1.-light sensitive layer 2.-polyester film base 3.-sheet base hair side

A-ultraviolet B-developer solution

Claims (2)

1, diazo resin sun a kind of non-diazo salt, that be made of light sensitive layer and sheet base shines positive film, described light sensitive layer is to be formed by applying on polyester film base of sensitization liquid, and described sensitization liquid comprises emulsion 2,1,5 adjacent nitrine naphthoquinone sulfonic acid esters, bonding agent m-cresol formaldehyde resin, sensitizer Michler's keton, plastifier glycerine triethyl, the colorant nigrosine, the organic solvent ethylene glycol monomethyl ether is characterized in that described sensitization liquid also comprises the bonding agent vinylidene chloride-acrylonitrile copolymer resin, colorant nigrosine.

2, sun according to claim 1 shines positive film, it is characterized in that various component concentrations by the weight of this component and its scope of number percent of sensitization liquid general assembly (TW) are in the described sensitization liquid: described emulsion about 2.6% to 16.8%, described bonding agent about 2.8% to 12.4%, described sensitizer about 0.3% to 9.9%, described plastifier about 0.2% to 4.2%, described colorant is about 0.9% to 10%, and all the other are described organic solvent.