CN1031300C - Photographic element with novel subbing layer - Google Patents
Photographic element with novel subbing layer Download PDFInfo
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- CN1031300C CN1031300C CN88104681A CN88104681A CN1031300C CN 1031300 C CN1031300 C CN 1031300C CN 88104681 A CN88104681 A CN 88104681A CN 88104681 A CN88104681 A CN 88104681A CN 1031300 C CN1031300 C CN 1031300C
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
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Abstract
The use of a gelled network of inorganic oxide particles on the polymeric surface of a substrate provides a subbing layer having the potential for antistatic properties, antihalation properties, and good coatability.
Description
The present invention relates to be coated on on-chip photosensitive emulsion with glue-line or bottom.
Preparation fontanelization silver photosensitive material has become the integrated technology of multidisciplinary and many technology.The subject that these are different as polymer chemistry, crystallography, physics, electrostatics, dyestuff chemistry, coating or the like, must concentrate one's energy to produce and a kind ofly can carry out the photosensitive material that fast speed is taken pictures.
Say on the traditional sense, two challenges that relate to sensitization industry be photosensitive emulsion to selected base material (promptly, polymer matrix film, for example polyester, polyolefin, cellulose ester-based and polymer-coated paper substrate, for example paper of Chinese white filled polyolefin or polyvinylidene chloride coating) sticking problem.Another problem is, specifically, produces static or fricting static charge on film in the film of the hi-vision storage of machinery production, causes image blurring.
Proposed the method for the processing of many different constituents, composite bed and substrate, effectively improved the adhesion between emulsion layer and substrate, this can obtain proof a large amount of patent in the present technique field.The sampling of these patents comprises, United States Patent (USP) 3,271,345,2,943,937,4,424,273,3,791,831 or the like.In photographic science, a large amount of work is also at eliminate static charge on sensitive film.Different types of working example of being done in this area comprises United States Patent (USP) 4,582,782,3,884,699,3,573,049, or the like.
Various pending problems (for example, the adhesion of interlayer) can utilize the particle matting agent in photosensitive material backing layer or the top layer to solve, and same, photosensitive effect (for example, light scattering) can utilize the particle-containing layer in the photosensitive material to realize.The purposes of these particle-containing layers is shown in United States Patent (USP) 4,343, in 873,4,144,064,3,507,678,4,022,622 or the like.
Typical case's sensitization carrier is included in the base material that scribbles glue-line at least one surface, and this glue-line helps gel layer (comprising emulsion layer) to adhere on the base.Traditional glue-line is described in United States Patent (USP) 3,343, in 840,3,495,984,3,495,985 and 3,788,856.
The present invention relates on base, have the photosensitive material (element) of at least a fontanel silver emulsion layer, wherein base has at least one polymeric surface, adheres to one deck inorganic particle thereon and preferably contains a kind of gel of difunctional silane inorganic oxide particles or the net of hydrolysis.
The present invention relates to photosensitive material.This material comprises the base that has at least a fontanel silver emulsion layer in its surface.Surface with emulsion hereinafter refers to the main surface of base.The fontanel silver emulsion generally includes the fontanelization silver particle (being also referred to as crystal or particle) in the adhesive medium of the water permeable that is stated from a kind of hydrophilic colloid.Recent findings, utilize inorganic particle preferably net gelation or hydrolysis of oxide as one deck coating on the polymer surfaces, gluing (or being coated with primer) substrate (U.S. Patent application application on April 21st, 40930,1987) that can provide a kind of very good being used to take pictures emulsion.Have been found that, the stratum granulosum of this gelation can provide one or more superperformances, give photosensitive material many performances, and being not limited to antistatic property, they comprise the easy coating performance of stratum granulosum, sense small pot with a handle and a spout for boiling water or herbal medicine inertia (to photosensitive emulsion and its inorganic evil of performance), adhesiveness is (wet and dried, adhesion substrate and emulsion layer), reduce direct reflection (that is anti-dizzy performance).Determined that wet adhesion can weaken in developing process.Suppose that the bonding force between gelation net and gelatin is a kind of acid/alkali bonding force.Under the PH rising condition, this bonding force is fully weakened in development, thus other material in the emulsion will with gelatin competitive reaction on the sol-gel coating position.This can weaken bonding force between gelatin layer and gelation mesh layer, can produce the bubbling or the separation of interlayer.
Find according to practice of the present invention, add difunctional silane in the gelation net and will between inorganic particle and gelatin, produce a kind of extensive chemical bonding force.
The difunctional silane of term is meant that this compound has the silane of easy reaction at an end of molecule, with can with gelatin hardener reaction or the different reactive materials that directly reacts with gelatin.This second functionality can make compound and inorganic particle reaction (passing through silylation), also can react (with the gelatin hardener reaction of energy and gelatin reaction) with gelatin.Preferred second functional group is nitrogen base and epoxy (for example, glycidyl) on the compound.Second functionality can partly exist or exist with some these class groups by single functional group.
Be used for representing the molecular formula of the difunctional silane of the present invention to be
(Q)
n-R-Si(OR′)
3
Wherein R ' is an alkyl or aryl,
R is a kind of organic group, has (n+1) external bond or valency,
N is 0,1 or 2, and
Q is a kind of the reaction with the photosensitive hardening agent or part (for example, a-amino acid) direct and the gelatin reaction.
Preferred R
1Be the alkyl of 1～10 carbon atom, be preferably the alkyl of 1～4 carbon atom.Preferred R is a kind of aliphatic series or aromatics abutment, and for example alkylidene, arlydene, alkane are for arlydene or fragrant for alkylidene, and they can be by ehter bond (oxygen or thioether), nitrogen key or other key interval than inertia.R is the alkylidene of 1～2 carbon atom, and the best is the alkylidene of 2～8 carbon atoms, and n equals 1.Preferably epoxy, or amino, uncle or secondary amino group, the best is a primary amino radical.
The previous second pointed functional group can multiple this class group and exist, and refers to (Q)
n-R-part can for example comprise
NH
2-(CH
2)
2-NH-(CH
2)
2-NH-(CH
2)
3-
NH
2-(CH
2)-
3
(NH
2)
2-CH-CH
2--
Or the like.
Substrate of the present invention can comprise having any material of a preparation as the polymeric surface of substrate first type surface at least.
Except gelatin; the gelatin that also comprises acroleic acid esterification in the present invention as the fontanelization silver photosensitive emulsion of protective colloid; the gelatin of the gelatin of phthalate and malonic acid esterification for example; but the also plain compound of fibre-bearing; for example hydroxyethyl cellulose and carboxymethyl cellulose, soluble starch, for example dextrin; the hydrophilic polymer class, for example polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyacrylamide, the plastifier class that is used for stable dimensions, latex polymer class and matting agent also can add.Finished emulsion is coated on the appropriate carriers.
Spendable carrier comprises the synthetic polymer film, for example polyalkyl acrylate or polyalkyl methacrylate, polystyrene, Polyvinylchloride, part formal polyvinyl alcohol (PVA), polycarbonate, polyesters, for example polyethylene terephthalate, polyamide-based, cellulose derivative film, NC Nitroncellulose for example, cellulose acetate, Triafol T, cellulose acetate butyrate, the paper of coating alpha-olefine polymers class or gelatin (natural polymer), for example synthetic paper made of polystyrene; Just can use any transparent or opaque carrier that is generally used for photosensitive material.The polymer matrix film that is coated with primer is also very useful, and they are coated in polyvinylidene chloride on the polyester including, but not limited to the polymkeric substance (for example, gelatin is coated on the polyethylene terephthalate) of gelatin linging.Other primer, for example aziridine, acrylates and melamino-for maldehyde also are well-known.This primer comprises polymeric material, wherein adds pigment and particle, and titania for example improving the white background of image, and provides anti-dizzy effect or other photosensitive effect.
Substrate of the present invention can use the sensitization fontanel silver of any kind, and be not limited to silver chloride, also comprise silver bromide, chlorine silver bromide, iodine chlorine silver bromide, bromo-iodide and chlorosulfonylation silver particle, they can be many any in crystal form or the crystalline form of obtaining, but be not limited to cube, comprise tetrahedron, stratiform, flat tablet, orthorhombic particle or the like.
Soluble silver salt and solubility fontanelle compound can in addition, can adopt the method (so-called contrary mixing method) that forms fontanelization silver particle in the presence of excessive silver ion by such as one-jet technology.Also can adopt so-called control dual-jet technology, wherein the PAg of liquid phase (forming fontanel silver) keeps constant.Zhi Bei two or more fontanel silver emulsions respectively, use also can mutually combine.
After forming precipitation or physics slaking, the fontanel silver emulsion generally from the fontanel silver emulsion, removes soluble-salt.For this purpose, can use a kind of emulsion bar (noodle) method for washing, wherein remove the solubility salt by gel emulsion.Also can use flucculation process, utilize the inorganic salts that contains multivalent anions, anionic surfactant, anionic polymer or gelatine derivative.
Though so-called former emulsion is not chemical sensitization, and can be used as the fontanel silver emulsion, the normally chemical sensitization of fontanel silver emulsion.For example, this chemical sensitization can pass through following document (H.Frieser ed., Die Grundlagen der photogra phischen prozessemit Silverhalogeniden, Akademische Verlagsgesell Schaft, pp.675-734 (1968)) method described in is carried out.
Promptly, utilization can with the sulfocompound of active gelatin and silver reaction (for example, thiosulfate, thiocarbamide, sulfhydryl compound class and rhodanine class) method for sensitizing, utilize reducing substances (for example, tin salt class, amine, hydrazine derivate class, formamidine sulfinic acid, silane compound class) the reduction method for sensitizing, (for example use precious metal chemical complex, the VIII family metal metal complex salts of platinum, rhodium, iridium, palladium for example in gold complex salt, the periodic table,) the noble metal method for sensitizing, or the like all can use or the use that also can mutually combine separately.
The sulphur sensitization method is specified in for example United States Patent (USP) 1,574,944,2,419,974 and 4,054,458; The noble metal method for sensitizing is specified in United States Patent (USP) 2,399, and 083,2,448,060 and BrP 618,061.
Can add all cpds in the employed in the present invention photosensitive emulsion, in production, storage or photo-process, produce mist in order to prevent photochromics, perhaps the sense of stability optical property.Just can add many compounds that are referred to as antifogging agent or stabilizing agent, azole (benzotriazole salt for example for example, nitro glyoxaline, the nitrobenzimidazole class, the chloro benzimidazole class, bromobenzene and imidazoles, the dimercaptothiodiazole class, the mercaptobenzothiazoler class, the mercaptobenzimidazole class, the dimercaptothiodiazole class, the aminotriazole(ATA) class, the Phenyltriazole class, nitrobenzene triazole type and mercapto-tetrazole class, (particularly 1-phenyl-5-mercapto-tetrazole), sulfhydryl miazines, the mercapto-triazine class, the thione compounds class (for example, the oxazoline thioketones), a word used for translation indenes class (for example, three a word used for translation indenes classes, (the particularly 4-hydroxyl-replacement-(1 of four a word used for translation indenes classes, 3,3a, 7) four a word used for translation indenes classes), and five a word used for translation indenes class), the phenyl thiosulfuric acid, phenyl sulfinic acid, and benzenesulfonamide.
For example, the typical example of this compounds and use their method to be specified in United States Patent (USP) 3,954,474,3,982,947 and Japanese patent laid-open publication gazette 28660/77.
Photochromics photosensitive emulsion layer of the present invention (for example can contain poly-alkyl epoxy or its derivant class, ethers, ester class and amine), sulfide compound class, thiomorpholine class quarternary ammonium salt compound class urethane ester derivant class, urea derivative class, imdazole derivatives class, 3-pyrazolidine ketone, p-dihydroxy-benzene or its derivant, or the like, be used to improve sensitization degree or contrast, or quicken to develop.For example, can use at United States Patent (USP) 2,400,532,2,423,549,2,716,062,3,617,280,3,722,021,3,808,003, and BrP 1,488, the compound described in 991.
With regard to regard to employed bonding agent or protecting colloid in the emulsion layer of photochromics of the present invention and the middle dielectric layer, preferably use the gelatin class.In addition, other hydrophilic colloid also can use.For example, can use protein-based, the derivant class of gelatin for example, the graft polymer class of gelatin and other polymer class, albumin, and casein, the sugar derivatives class, cellulose derivative class (hydroxyethyl cellulose for example for example, carboxymethyl cellulose, and sulfate cellulose), mosanom, and starch derivative class, with various synthesis hydrophilic polymeric materials, homopolymer or multipolymer, for example, polyvinyl alcohol (PVA), polyvinyl alcohol (PVA) part acetal, poly-(N-vinyl) pyrrolidine, polyacrylic acid, polymethylacrylic acid, the polybutylene acid amides, polyvinyl imidazol, and polyvinyl pyrazoles.
As a kind of black and white reflection photochromics, this material must rapid processing especially effectively for photochromics of the present invention.In addition, it can be used as a kind of X line record photochromics, ray machine process photochromics, is used for the photochromics of fasystem, or the like, say that further can be used as multilayer, many colors light-sensitive material has at least two kinds of different spectral sensitization degree.
Multilayer, many colors photosensitive material generally include a kind of carrier, and the sense of one deck at least red milk liquid layer on this carrier, the green emulsion layer of one deck sense at least, and the blue emulsion layer of one deck sense at least.Above-mentioned glue-line ordering can suitably be selected.Usually sense red milk liquid layer contains the cyano group dyestuff that forms coupling agent, feels green emulsion layer and contains the rosaniline dyes that forms coupling agent, feels blue emulsion layer and contains the yellow dye that forms coupling agent.Under some situation, can use other combination.Even under many colors of multilayer photosensitive material situation, reflection photochromics of the present invention also demonstrates very significant effect.
The spectral sensitization dyestuff can be used in one or more fontanel silver emulsions, and is very useful to coating substrate of the present invention.In the art, these sensitizing dyestufves are used for improving fontanel silver to various electromagnetic spectrums as everyone knows, for example ultraviolet, blue, green, yellow, orange, red, near infrared and infrared susceptibility.These dyestuffs can be used for sensitized emulsion separately or with other dyestuff combination.
The supported coating of the present invention is made up of a kind of gelation net of continuous inorganic, metal oxide particle, and this net contains a kind of difunctional silane.The average primary particle diameter of particle is preferably lower than about 500 or 200 .Term used herein " continuously " refers to, in the place of gelation net coating, discontinuous point or gap that in fact the covering surfaces of base does not exist straight line to run through.Yet this layer may be and porous normally, wherein not have tangible straight line hole or gap.Term " gelation net " means a kind of aggregation that interconnects, forms the colloidal particles of porous three-dimensional net.Usually whole or main bonding be between the particulate material and with silane generation bonding, but also can have some bonding agents, for example about gelatin metal oxide below 5%.Term " porous " means between the inorganic, metal oxide of being piled up generation by metal oxide particle and has the space.Term " initial size " means the average grain of not assembling single particle of inorganic, metal oxide.Term " particle " comprises sphere, non-sphere, microfilament shape grain pattern.If difunctional silane is added to before coating in a kind of water-soluble metal oxide sol, silane will hydrolysis on the position of aforesaid (OR ') so, and hydroxyl replaces (OR ') base.For example, three ethoxy silane will become ortho-siliformic acid.In containing the burning particle solution, the hydrolysising silane molecule is the bonding of " oxirane " usually, with reversible manner combine with metal oxide particle (
)。When solution is dried to coating layer, expect that most hydrolysising silane molecule will combine with metal oxide by the bonding of " oxirane ", so that metal oxide particle can not be washed out coating by simple washing.The existence of silane molecule does not hinder the gel-based particle net and obtains bond strength, although the bond strength required time may increase.
Coating layer should be thicker than monolayer of particles.The thickness of preferred coatings should be equal to or greater than three average particulate diameters, and the best is equal to or greater than four particle diameters.
Goods of the present invention comprise substrate, for visible light, it can be transparent, translucent or opaque, has a polymeric surface at least, forms the coating that one deck has the continuous gel net of the inorganic oxide particles form of the difunctional silane that promotes the adhesion effective dose on it.When gluing is coated on transparent substrate with the raising light transmission, coated article is compared with uncoated substrate, be at least in 400～900nm in the wavelength width scope, the transmissivity overall average of its common incident light has increased at least 2%～10% or higher, and this depends on the substrate of coating.When using the coating substrate, detect by an unaided eye usually, 2% or the increase of more rays impingement rate be significantly, and the increase that is enough to produce a kind of measurable energy transmission rate.Wavelength optical transmission rate in the light part scope of spectrum also increases.
The gelation net is a kind of porous coating, has the space between the inorganic oxide particles of coating.If porosity is too little, antireflective property then can reduce so.If porosity is too big, coating then is crisp, and the adhesion of substrate is reduced.Usually, obtain the gel net by colloidal solution, this colloidal solution can provide about 25～70% (volume) porosity when dry, 30～60% (volumes) in the preferred range.Colloidal solution by dry q.s produces sample and uses " Quantasorb " surface area analyser (by Quantachrome company so that a kind of about 50 milligrams～100 milligrams drying to be provided, Syosett, NY. produce) analytic sample, can determine porosity.
The hole of porous coating provides a kind of various secondary wavelength gap between inorganic particle, and wherein refraction index sports the coating refraction index from the refraction index of air.The gap of these secondary wavelength is present among the whole coating, provides a kind of porosity according to coating to calculate refraction index (RI) and has been about 1.15～1.40, is preferably 1.20～1.30 coating.When the voidage of coating is high, for example, about 70% (volume) or higher, then the RI value is lower.When the porosity of coating is low, 25% (volume) or when lower, then the RI value is higher for example.
The average primary particle diameter of colloid unit machine metal oxide particle is preferably lower than about 200 .Average primary particle diameter the best of colloid unit machine metal oxide particle is lower than about 70 .When original mean grain size was too big, obtaining the dry coating surface was the poor efficiency antireflecting coating.
Preferred dry coating average thickness is about 300～10, and 000 more preferably is 800～5000 , and the best is 900～2000 .The coating antistatic property that can provide like this.When coating was too thick, the bonding force of coating and pliability reduced, and peel off easily or form powder under the effect of mechanical stress.
The goods of clear sheet or membraneous material can be coated with at single or double, and to improve light transmission, double spread can reach and improve transmissivity to greatest extent.
The technology of coating superficial layer of the present invention comprises with colloid inorganic, metal oxide particle (at this; be preferably silane) the solution coat substrate; solution preferably contains at least 0.2 or 0.5～15% (weight) particle; the average primary particle diameter of particle preferably is about and is lower than 500 or 200 ; be preferably lower than about 70 ; the temperature of dry coating must not surpass the substrate degradation temperature, is preferably lower than about 200 ℃, and optimum range is 80～120 ℃.Coating can make substrate decreased average direct reflection at least 20% in wavelength coverage is 400～900nm.
Can adopt standard coating technique method to be coated with, for example rod is coated with, cutter is coated with, shield be coated with, rotate that notch board is coated with, spraying and dip-coating.Before coating, can adopt such as technical finesse substrates such as corona discharge, flame treatment and electron beams to obtain uniform coating.In general, do not need pre-service.Before coating, can add difunctional silane in the coating process or after the coating.Before being recommended in coating silane is joined in the coating compound.If be coated with and dry back adding silane at " gel net ", then the latter should add from aqueous solution, and silane will occur with the form of its hydrolysis like this.
Colloid inorganic oxide solution (as the hydrosol or organogel) is coated in the substrate of goods to be coated and under suitable low temperature less than about 200 ℃, be preferably in 80～120 ℃ of dryings to remove moisture content or organic liquid medium.Coating also can be at room temperature dry, but should be enough to make the coating bone dry drying time.Baking temperature should be lower than the substrate decomposition temperature.The coating of gained is hygroscopic, so just can absorb water and/or make the water generation rehydrated, and for example according to room temperature and damp condition, suction (or rehydrated) amount is up to about 15～20% (weight).
Be used for the finely-divided solid inorganic, metal oxide that colloid inorganic oxide solution of the present invention comprises liquid.Terminology used here " solution " is included in the dispersion liquid or the suspending liquid of the superminiature finely divided particulate in the liquid medium.Be used to implement on the solution appearance of the present invention from transparent to muddiness.Being specially adapted to inorganic, metal oxide of the present invention is that those metal oxide particles are negative charge, and they comprise tin oxide (SnO
2), titania, antimony oxide (Sb
2O
5), silicon dioxide and be coated with the silicon dioxide of aluminium oxide and other inorganic, metal oxide of period of element Table III family and IV family and composition thereof.The selection inorganic, metal oxide depends on required last equilibrium response.Inorganics also is effective when for example silicon nitride, silit and magnesium fluoride provide with gel form.
Colloidal coating liquid preferably contains 0.2～15% (weight) of having an appointment, and contains the colloid inorganic, metal oxide particle of 0.5～8% (weight) of having an appointment better.Be about at granule content under the situation of 5% (weight), the thickness of gained coating is reduced equably, thus, the adhesive effect that demonstrates substrate surface descends.Be higher than in concentration under the situation of 15% (weight), may be faced with to obtaining the difficulty that enough thin coating (improve transmittance and reduce reflectivity to reach) is being met.Be lower than in concentration under the situation of 0.2% (weight), cause worker's process efficiency poor owing to must remove a large amount of liquid, and may reduce anti-reflective.
The thickness of the wet coating solution that is coated with depends on the concentration of the inorganic, metal oxide particle that is coated with in the feed liquid and required dry coating thickness, the dry coating thickness that wet coating solution thickness preferably makes gained is between about 80～500nm, and preferably about 90～200nm is thick.
As required, be coated with and also optionally in the feed liquid contain a kind of surfactant,, can reduce the tack of coating substrate but comprise excessive surfactant to improve solution in on-chip wetting ability.The example of suitable surfactant comprises " Tergitol " TMN-6 (Union CarbideCorp.) and " Triton " X-100 (Rohm and Haas Corp.).In general, spendable surfactant, its consumption account for below about 0.5% (weight) of solution.
As required, be coated with feed liquid and can select and contain a kind of very small amount of polymer adhesive, particularly hydrophilic polymer bonding agent, with improve scratch resistance or be reduced in after use the particle dust that forms in the process of coating substrate.Useful polymer adhesive comprises polyvinyl alcohol (PVA), polyvinyl acetate (PVA), gelatin, polyesters, polyamide-based, polyvinyl pyrrolidone, copolyesters class, the multipolymer of acrylic acid and/or methacrylic acid and cinnamic multipolymer.In the weight of inorganic, metal oxide particle, be coated with feed liquid and can contain the following polymer adhesive of 5% (weight) of having an appointment.The effective dose of polymer adhesive is generally between about 0.1～5% (weight), to reduce particle dust.If use these bonding agents in a large number, then may reduce some useful performances (as antistatic behaviour) of coating, therefore, they are not recommended most.
The content of difunctional silane is generally gel particle layer solid content and is at least 0.1% (weight), is preferably 1～20% (weight) of gel particle layer solid content, more preferably 0.2～10% of gel particle layer solid content (weight).
Adopt following operation to prepare the used whole samples of following embodiment.
Embodiment
Experimental technique: by prepare described each sample of subordinate list with the below.
Water will obtain the solid particle that colloidal sol is diluted to required number percent from production firm.Then, the coupling agent with regulation adds in the dilute solution.Weight percent of pressing metal oxide solid particle calculates the coupling agent consumption.After adding coupling agent, potpourri split suddenly shook 30 seconds so that the coupling agent dissolving.Then, add the auxiliary agent of the Triton X-100 surfactant of 0.05～1% (weight) as coating.This potpourri is applied on the suitable substrate membrane in the following manner: 1) 10cm * 10cm thin-film sheet is placed on the plane; 2) a potpourri spherolite is extracted sheet material end face (about 1 milliliter); 3) #4 stainless steel coiling rod makes potpourri expand along sheet material; 4) with coated sheet in 100 ℃ baking oven dry 2 minutes.The dry coated sheet of order at room temperature left standstill one day or a couple of days (before using).
Then, preparation standard X-ray photosensitive emulsion and be applied on the above-mentioned sheet material: 1) temperature of emulsion mixture is transferred to about 40 ℃ by following manner; 2) an emulsion spherolite (about 2ml) is extracted the sheet material end face that has been coated with colloidal sol; 3) with #24 stainless steel coiling rod emulsion is expanded along sheet material; 4) sheet material that will be coated with emulsion descended dry about 2 hours at 50 ℃.
Adhesion test method: adopt following method to detect the test specimen that all is used for the emulsion tack.According to following test,, provide grade each sample between 0～10 according to the approximate percent of remaining emulsion on sample.So if emulsion residue 50%, then grade is " 5 "; If all emulsion retains, then grade is " 10 ".
Test method is as follows: 1) at room temperature, (the above-mentioned X-ray emulsion material that has been coated with of 5cm * 10cm) immerses X-ray developer, lasts two minutes with one; From developer, take out this material, still use developer moistening simultaneously, rule with the cross hatch pattern, and enclose with steady pressure annular movement 24 with the finger tip of rubber sheet gloves with the slasher rib; 3) this sample is washed also drying in cold water; 4) (the 3M#610 adhesive tape of 2.5cm * 5cm) is attached on the cross hatch zone of test material and peels off with strength with one; 5) this sample is defined the level by above-mentioned emulsion tack test method.
The substrate membrane that is used for embodiment is the PET with 4 mil thick of about 0.04 micron poly-(1,2-dichloroethene) linging that contains terpolymer.
Triton-X-100/H with 0.50 gram 10% (weight)
2The solution of O joins in each collosol intermixture to help coating.
Embodiment 1
According to the method described above, adopt following silica/silicon alkane coupling agent to be coated with four samples of feed liquid preparation:
APS is 3-aminopropyl three ethoxy silane
A. 17.2 restrain the Nalco2326 cataloids, 82.6 gram water, 0.25 gram APS (2.5% silicon dioxide)
B. 17.2 restrain the Nalco2326 cataloids, 82.7 gram water, 0.125 gram APS
C. 27.6 restrain the Nalco2326 cataloids, 72.0 gram water, 0.4APS (4.0% silicon dioxide)
D. 55.2 restrain the Nalco2326 cataloids, 44.0 gram water, 0.8APS (9.0% silicon dioxide)
According to described method each sample that has prepared is fully carried out adhesion test.Adhesion test result, A, B and D are " 10 " levels (not breaking), and B is " 9.5 " level.
Embodiment 2
Three samples of Sample A, B, C and the D of preparation similar embodiment 1, different is not add silane coupling agent (APS).
A. 17.2 restrain the Nalco2326 cataloids, 82.8 gram water
B. 27.6 restrain the Nalco2326 cataloids, 72.4 gram water
C. 55.2 restrain the Nalco2326 cataloids, 44.8 gram water
Adhesion test result, A, B and C are " 0 " level (breaking fully)
Embodiment 3
In order to measure dissimilar silane coupling agents, prepare three samples in addition.The prescription of these samples is as follows:
A. 27.6 restrain the Nalco2326 cataloids, 72.0 gram water, 0.4 gram r-diglycidyl oxygen propyl group trimethoxy silane
B. 27.6 restrain the Nalco2326 cataloids, 72.0 gram water, 0.40 gram methylpropenyl oxygen propyl group dimethoxy silane
C. 27.0 restrain the Nalco2326 cataloids, 72.0 gram water, 0.40 chloro propyl group, three ethoxy silane attaches power test findings are as follows: Sample A is " 10 " level, and sample B is " 0 " level, and sample C is " 0 " level.This functional group of these results and expectation and gelatin reactive consistent.
Embodiment 4
In order to measure the validity of organic titanate coupling agent, prepare two samples.
A. 27.6 restrain the Nalco2326 cataloids, 72.0 gram water, 0.4 gram isopropyl three (positive ethylamino ethylamino) titanate
B. 27.6 restrain the Nalco2326 cataloids, 72.0 gram water, 0.40 gram two (the dioctylphyrophosphoric acid root closes) ethylidene titanate
Adhesion test result, Sample A are " 3 " level, and sample B is " 0 " level.
Embodiment 5
Different size or dissimilar silicon dioxide are used in explanation for example, prepare three samples:
A. 16.7 restrain the Nalco1060 cataloids, 94.8 gram water, 0.25 gram APS
C. 8.33 restrain the Nalco1034 cataloids, 91.5 gram water, 0.25 gram APS
Adhesion test result, Sample A, B and C are " 10 " level.
Embodiment 6
The sample of three similar embodiment 5 of preparation, different is not use APS.The adhesion test result is " 0 " level.
Embodiment 7
Prepare 12 samples with the colloidal metal oxide except that silicon dioxide:
GPS is a r-glycidyl oxygen propyl trimethoxy silicane.
A. 21.4 restrain Nalco TX-2588 colloidal titania, 78.4 gram water, 0.25 gram APS
B. 8.33 restrain Nalco ISJ-612 cataloid/aluminium oxide, 91.5 gram water, 0.25 gram APS
C. 11.4 restrain Nalco ISJ-613 colloidal aluminas, 88.4 gram water, 0.25 gram APS
D. 25.0 restrain Nalco ISJ-614 colloidal aluminas, 74.8 gram water, 0.25 gram APS
E. 10.0 restrain Nalco ISN-20 colloid tin oxide, 89.8 gram water, 0.25 gram APS
F. 17.9 restrain NYacol colloid yttria, 81.9 gram water, 0.25 gram APS
G. 10.4 restrain NYacol colloidal iron oxide silicate, 89.4 gram water, 0.25 gram APS
H. 12.5 restrain NYacol colloidal zirconia acetate, 87.3 gram water, 0.25 gram APS
I. 11.6 restrain NYacol colloid cerous nitrates, 88.2 gram water, 0.25 gram APS
J. 8.33 restrain Nalco IS T612-cataloid/aluminium oxide, 91.5 gram water, 0.25 gram GPS
The adhesion test result is as follows: Sample A and E are " 10 " level, and degree sample B, C, D, F, G, H, I and J are " 0 " level.Notice that in Sample A and E, colloidal solid is an anionic, and in all other sample, particle is cationic.
Embodiment 9
Adopt coating compound 2B and above-mentioned preparation method to prepare a sample that is coated with silicon dioxide.This sample is immersed the solution of a kind of 0.10% APS in ethanol, and the time is 15 seconds, and is air-dry then.By above-mentioned operation this sample is carried out emulsion and be coated with the redoubling detection.The adhesion test result is " 10 " level.
Embodiment 10 adopts coating compound 2B and above-mentioned preparation method to prepare 4 samples that are coated with silicon dioxide.With these samples with the following X-ray emulsion coating that has improved:
A. 100 restrain the X-ray emulsions, 0.05 gram APS
B. 100 restrain the X-ray emulsions, 0.20 gram APS
C. 100 restrain the X-ray emulsions, 0.40 gram APS
The adhesion test result is as follows: sample C and D are " 10 " level, and sample B is " 3 " level, and Sample A is " 2 " level.
Embodiment 11
Adopt sample that is coated with silicon dioxide of coating compound 1C preparation, that different is dissolving 0.56 gram K﹠amp in potpourri; The K#312 gelatin.According to above-mentioned operation this sample is carried out emulsion coating and detection.The adhesion test result is " 10 " level.In addition, be coated with the electric conductivity of sample of silicon dioxide and optical property and with the coating of potpourri 1C preparation the sample of silicon dioxide compare.Term gel and gelation when they are used for being illustrated in the inorganic dispersion liquid that uses particle in the stratification, are known in the present technique field.Aforementioned gel comprises the sclerosis dispersion of the colloid in the liquid, promptly aforesaid gel net.Gelation is the method for hardening gel.This gelation is usually finished by discharged liquid.Opposite with thermal decomposition, gelation not necessarily needs to add heat, and this is because gelation is taken place.These temperature and humidities may be removed the liquid of q.s, and it is harder that gel particle is become.Certainly can adopt heat to quicken the liquid discharge process, because air-flow possibility direct projection or flat fire are to gel coat.
Available multiple different physical term is described the gel coating that this liquid discharged, and (it generally contains the liquid of some significant quantities, arrive up to 10% or 15% as at least 0.1% (weight), or content is higher in some cases), and this gel coating is to be different from other grain pattern, for example sintering is adhered or the heat fusing particle.Particle is combined into a kind of continuous gel net in the gel rubber system, and it is well-known in the art, and particle has formed a kind of inorganic polymer net, or a kind of inorganic salt system to refer in particle network the gel of silicon dioxide (as have).Adhesion (as Van der Waals force and hydrogen chain) can form a pith of particle bonding mechanism.The feature of gel combination obviously is different from the use polymer adhesive, and the latter has formed bonding medium, with keep particle mutually continuously and its particle itself do not apply direct adhesion mutually.
As previously mentioned, the size of colloidal solid is very important in the gel.Ball milling particle method is made generally in and is lower than about 1 micron particle.Unless adopt chemical method to form the littler particle (it is gathered into bulky grain effectively, and ball milling is smashed this agglomerate to pieces then) of particle diameter, may be true otherwise be about 1 micron by the particle diameter limit that the physics method obtains.
In order only to form a whole layer, in the gel component, can not use bulky grain with gel method.This bulky grain does not have enough bond strengths, is unable to bear any great abrasion.
Claims (13)
1. the thin polymer film of a radiosensitive photosensitive material has photosensitive emulsion and the continuous gel stratum reticulare that contains the inorganic particle of a kind of difunctional silane that promotes bonding amount on its at least one surface.
2. the film of claim 1, wherein said inorganic particle is an inorganic oxide particles.
3. the film of claim 2, the gel net of wherein said inorganic oxide particles comprises the thin layer of average thickness between 300-10,000 .
4. the film of claim 2, the gel net of wherein said inorganic oxide particles comprises the thin layer of average thickness between 800-5,000 .
5. the film of claim 2, the gel net of wherein said inorganic oxide particles comprises the thin layer of average thickness between 900-2,000 .
6. claim 1,2,3,4 or 5 film, wherein said inorganic oxide particles are selected from silicon dioxide, titania, tin ash and their potpourri class.
7. the film of claim 2, wherein said difunctional silane is represented with following formula:
(Q)
n—R—Si(OR
1)
3
R wherein
1Be alkyl or aryl, R is a kind of organic group with the outside valency of n+1, and n is 1 or 2, and Q is the part of reacting with gelatin hardener or gelatin.
8. the film of claim 5, wherein said difunctional silane is represented with following formula:
(Q)
n—R—Si(OR
1)
3
R wherein
1Be alkyl or aryl, R is a kind of organic group with the outside valency of n+1, and n is 1 or 2, and Q is and gelatin hardener or gelatin reactive moieties.
9. the film of claim 7, wherein R
1Be C
1-4Alkyl, R are a kind of bridging part that is selected from the inferior aralkyl of alkylidene, arlydene, alkarylene and at least 10 carbon atoms, and n is 1, and Q is amino or epoxy radicals.
10. the film of claim 8, wherein R
1Be C
1-4Alkyl, R are a kind of alkylidene, arlydene, alkarylene and bridging part of the inferior aralkyl of 10 carbon atoms at the most of being selected from, and n is 1, and Q is amino or epoxy radicals.
11. the film of claim 9, wherein R is an alkylidene, and Q is a primary amino radical.
12. the film of claim 1,3 or 7, wherein said substrate are a kind of polymer films that is selected from the polyester of polyester and linging.
13. the film of claim 5, wherein said substrate are a kind of polymer films that is selected from the polyester of polyester and linging.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7968787A | 1987-07-30 | 1987-07-30 | |
| US079,687 | 1987-07-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030984A CN1030984A (en) | 1989-02-08 |
| CN1031300C true CN1031300C (en) | 1996-03-13 |
Family
ID=22152154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88104681A Expired - Lifetime CN1031300C (en) | 1987-07-30 | 1988-07-29 | Photographic element with novel subbing layer |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0301827B1 (en) |
| JP (1) | JP2823207B2 (en) |
| KR (1) | KR970007784B1 (en) |
| CN (1) | CN1031300C (en) |
| AR (1) | AR243687A1 (en) |
| AU (1) | AU603908B2 (en) |
| BR (1) | BR8803780A (en) |
| CA (1) | CA1338180C (en) |
| DE (1) | DE3882178T2 (en) |
| MX (1) | MX12346A (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2002449C (en) * | 1988-12-05 | 2001-05-08 | Mark A. Strobel | Pressure-sensitive article with priming layer |
| US5422189A (en) * | 1992-10-01 | 1995-06-06 | Minnesota Mining And Manufacturing Company | Flexible optically uniform sign face substrate |
| US5344751A (en) * | 1993-05-28 | 1994-09-06 | Minnesota Mining And Manufacturing Company | Antistatic coatings |
| US5236818A (en) * | 1992-11-02 | 1993-08-17 | Minnesota Mining And Manufacturing Company | Antistatic coatings |
| US5445866A (en) * | 1993-10-19 | 1995-08-29 | Minnesota Mining And Manufacturing Company | Water-based transparent image recording sheet |
| US5464900A (en) * | 1993-10-19 | 1995-11-07 | Minnesota Mining And Manufacturing Company | Water soluble organosiloxane compounds |
| US5460918A (en) * | 1994-10-11 | 1995-10-24 | Minnesota Mining And Manufacturing Company | Thermal transfer donor and receptor with silicated surface for lithographic printing applications |
| US5484694A (en) | 1994-11-21 | 1996-01-16 | Eastman Kodak Company | Imaging element comprising an electrically-conductive layer containing antimony-doped tin oxide particles |
| US5771764A (en) * | 1995-11-13 | 1998-06-30 | Eastman Kodak Company | Use of cutting tools for photographic manufacturing operations |
| US5576162A (en) | 1996-01-18 | 1996-11-19 | Eastman Kodak Company | Imaging element having an electrically-conductive layer |
| DE69700632T2 (en) | 1996-02-15 | 2000-05-31 | Minnesota Mining And Mfg. Co., Saint Paul | Laser-induced recording process with thermal transfer by heat |
| US5674654A (en) * | 1996-09-19 | 1997-10-07 | Eastman Kodak Company | Imaging element containing an electrically-conductive polymer blend |
| US5981126A (en) * | 1997-09-29 | 1999-11-09 | Eastman Kodak Company | Clay containing electrically-conductive layer for imaging elements |
| US5827630A (en) * | 1997-11-13 | 1998-10-27 | Eastman Kodak Company | Imaging element comprising an electrically-conductive layer containing metal antimonate and non-conductive metal-containing colloidal particles and a transparent magnetic recording layer |
| US5866287A (en) * | 1997-11-13 | 1999-02-02 | Eastman Kodak Company | Imaging element comprising and electrically-conductive layer containing metal antimonate and non-conductive metal-containing colloidal particles |
| US5869227A (en) * | 1997-12-18 | 1999-02-09 | Eastman Kodak Company | Antistatic layer with smectite clay and an interpolymer containing vinylidene halide |
| US6124083A (en) * | 1998-10-15 | 2000-09-26 | Eastman Kodak Company | Antistatic layer with electrically conducting polymer for imaging element |
| US6190846B1 (en) | 1998-10-15 | 2001-02-20 | Eastman Kodak Company | Abrasion resistant antistatic with electrically conducting polymer for imaging element |
| US6168911B1 (en) | 1998-12-18 | 2001-01-02 | Eastman Kodak Company | Formulations for preparing metal oxide-based pigment-binder transparent electrically conductive layers |
| US6077655A (en) * | 1999-03-25 | 2000-06-20 | Eastman Kodak Company | Antistatic layer for imaging element containing electrically conductive polymer and modified gelatin |
| IT1309912B1 (en) | 1999-05-07 | 2002-02-05 | Imation Corp | PHOTOGRAPHIC ELEMENT WITH A LAYER THAT IMPROVES MEMBERSHIP TO THE SUPPORT |
| KR101587300B1 (en) | 2008-03-14 | 2016-01-20 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Stretch releasable adhesive tape |
| EP3240847B1 (en) | 2014-12-30 | 2020-04-29 | 3M Innovative Properties Company | Water-based pressure-sensitive adhesive compositions |
| EP3240811B1 (en) | 2014-12-30 | 2018-11-28 | 3M Innovative Properties Company | Water-based pressure-sensitive adhesive compositions |
| KR20170104142A (en) | 2014-12-30 | 2017-09-14 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Aqueous pressure-sensitive adhesive composition |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3169865A (en) * | 1960-07-29 | 1965-02-16 | Eastman Kodak Co | Zirconia subbed photographic paper |
| US3615538A (en) * | 1968-08-02 | 1971-10-26 | Printing Dev Inc | Photosensitive printing plates |
| GB1286467A (en) * | 1968-11-18 | 1972-08-23 | Agfa Gevaert | Proteinaceous colloid compositions and their adherence to glass supports |
| UST873009I4 (en) * | 1969-11-07 | 1970-04-14 | Defensive publication | |
| JPS5119982B2 (en) * | 1972-01-26 | 1976-06-22 | ||
| GB1437185A (en) * | 1972-10-10 | 1976-05-26 | Agfa Gevaert | Non-stocking achroring layers for polyester film |
| US4048357A (en) * | 1972-10-10 | 1977-09-13 | Agfa-Gevaert N.V. | Method of coating multi-layer graphic film |
| CA1109589A (en) * | 1977-03-28 | 1981-09-22 | Larry A. Lien | Ultraviolet radiation protective, abrasion resistant, bloom resistant coatings |
| JPS5583042A (en) * | 1978-12-18 | 1980-06-23 | Fuji Photo Film Co Ltd | Photographic material |
| US4374898A (en) * | 1981-06-25 | 1983-02-22 | E. I. Du Pont De Nemours And Company | Elastomeric film |
| JPS6061259A (en) * | 1983-09-14 | 1985-04-09 | ダイアホイルヘキスト株式会社 | Polyester film |
| JPS6067938A (en) * | 1983-09-24 | 1985-04-18 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
| JPS6095433A (en) * | 1983-10-29 | 1985-05-28 | Daikin Ind Ltd | Formation of polymer film |
| JP2502275B2 (en) * | 1984-07-02 | 1996-05-29 | キヤノン株式会社 | Information signal reproducing device |
| JPS61213841A (en) * | 1985-03-20 | 1986-09-22 | Ricoh Co Ltd | Diazo copying material |
| EP0250154A3 (en) * | 1986-06-18 | 1989-07-12 | Minnesota Mining And Manufacturing Company | Photographic element on a polymeric substrate with novel subbing layer |
| US5204219A (en) | 1987-07-30 | 1993-04-20 | Minnesota Mining And Manufacturing Company | Photographic element with novel subbing layer |
-
1988
- 1988-07-12 AU AU18957/88A patent/AU603908B2/en not_active Expired
- 1988-07-20 MX MX1234688A patent/MX12346A/en unknown
- 1988-07-27 CA CA000573120A patent/CA1338180C/en not_active Expired - Fee Related
- 1988-07-27 EP EP88306918A patent/EP0301827B1/en not_active Expired - Lifetime
- 1988-07-27 DE DE88306918T patent/DE3882178T2/en not_active Expired - Lifetime
- 1988-07-29 JP JP63190519A patent/JP2823207B2/en not_active Expired - Lifetime
- 1988-07-29 CN CN88104681A patent/CN1031300C/en not_active Expired - Lifetime
- 1988-07-29 AR AR88311557A patent/AR243687A1/en active
- 1988-07-29 BR BR8803780A patent/BR8803780A/en not_active IP Right Cessation
- 1988-07-29 KR KR1019880009608A patent/KR970007784B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| MX12346A (en) | 1993-12-01 |
| JPS6449040A (en) | 1989-02-23 |
| DE3882178T2 (en) | 1994-02-03 |
| EP0301827A2 (en) | 1989-02-01 |
| KR890002707A (en) | 1989-04-11 |
| DE3882178D1 (en) | 1993-08-12 |
| CN1030984A (en) | 1989-02-08 |
| BR8803780A (en) | 1989-02-21 |
| EP0301827A3 (en) | 1989-07-12 |
| AU603908B2 (en) | 1990-11-29 |
| CA1338180C (en) | 1996-03-26 |
| JP2823207B2 (en) | 1998-11-11 |
| AU1895788A (en) | 1989-02-02 |
| EP0301827B1 (en) | 1993-07-07 |
| KR970007784B1 (en) | 1997-05-16 |
| AR243687A1 (en) | 1993-08-31 |
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