Metal-based silver halide photosensitive material

Abstract

The invention belongs to the field of photoelectric display, and particularly relates to a metal-based silver halide photosensitive material which is characterized in that a high-adhesion bottom layer, a silver halide photosensitive layer and a functional protective layer are sequentially coated on a metal base material. The problems that an existing metal-based photosensitive material is low in precision, and the contrast between a pattern area and a non-pattern area is low are solved.

Description

Technical Field

[0001] The invention belongs to the field of optoelectronic display, and in particular relates to a metal-based silver halide photosensitive material. Background Art

[0002] With the rapid development of industrial production technology, the degree of intelligence in all walks of life is getting higher and higher. Almost all automation equipment requires the conversion of photoelectric signals. The conversion and automation control of photoelectric signals require high-precision calibration objects, such as calibration plates used in robotic arms and photoelectric encoders used in variable frequency motors. Due to the characteristics of good stability and long service life of metal substrates, the demand for metal-based calibration plates and photoelectric encoders is gradually increasing.

[0003] Patents CN116430682A and CN113753846A disclose that the production of metal code disks is achieved by combining magnetron sputtering chrome (chromium oxide) plating with photolithography. Utility model CN2205017Y discloses a production idea for a metal photosensitive plate, but does not disclose the specific structure of the photosensitive layer and the photosensitive principle. The precision of metal photosensitive plates produced by existing processes is limited. In addition, since the pattern formed by chrome plating is silver-gray and the chromium oxide plating is bluish, the reflectivity of the pattern area is low, resulting in a low contrast between the black area and the blank area of ​​the pattern formed by metal chromium or chromium oxide. The calibration plate or code disk produced by chrome plating or chromium oxide plating process cannot meet the recognition requirements of ultra-high precision and sensitivity. Therefore, there are still some problems that need to be solved in the existing metal-based photosensitive materials used for high-precision photoelectric recognition. Summary of the invention

[0004] The present application provides a metal-based silver halide photosensitive material, which solves the problems of low precision and low contrast between pattern areas and non-pattern areas of existing metal-based photosensitive materials.

[0005] In order to achieve the above technical purpose, the technical solution adopted by the present application is: a metal-based silver halide photosensitive material, a high-adhesion bottom layer and a silver halide photosensitive layer are sequentially coated on a metal substrate;

[0006] The high adhesion bottom layer comprises the following materials in parts by weight:

[0007]

[0008] The water latex is one or a combination of multiple types of water-based polyurethane, water-based acrylate or water-based epoxy resin emulsion in any weight ratio;

[0009] The silver halide photosensitive layer comprises the following substances in parts by weight:

[0010]

[0011] As an improved technical solution of the present application, a functional protective layer is also included, and the functional protective layer contains the following substances in parts by weight:

[0012]

[0013] As an improved technical solution of the present application, the dry thickness of the high-adhesion bottom layer is a coating of 50-900nm.

[0014] As an improved technical solution of the present application, the dry thickness of the silver halide photosensitive layer is a coating of 2-3 μm.

[0015] As an improved technical solution of the present application, the dry thickness of the functional protective layer is 0.5-1.5 μm.

[0016] As an improved technical solution of the present application, the metal substrate is stainless steel, aluminum, aluminum alloy, titanium, titanium alloy, chromium or metal alloy.

[0017] As an improved technical solution of the present application, the thickness of the metal substrate is 0.05-10 mm.

[0018] As an improved technical solution of the present application, the silver halide particles include silver chloride, silver bromide, silver iodobromide, silver iodochloride, silver iodobromochloride, silver bromochloride or silver chlorobromide.

[0019] As an improved technical solution of the present application, the particle size of the silver halide particles is 50-300nm.

[0020] As an improved technical solution of the present application, the matting agent is PMMA microspheres, PI microspheres, silicon dioxide, titanium dioxide, magnesium oxide, aluminum oxide, barium sulfate or calcium carbonate particles.

[0021] Beneficial Effects

[0022] Compared with the prior art, the present invention achieves the purpose of improving the processing accuracy of metal-based photosensitive materials and improving the contrast between black pattern areas and non-pattern areas by using metal-based photosensitive materials prepared with silver halide, taking advantage of the high precision and high black-white contrast of silver halide photosensitive technology, as well as the simple processing process of silver halide photosensitive materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Compare the reflectivity of the silver pattern area of ​​the sample (380nm-700nm);

[0024] Figure 2 Comparison sample silver plate pattern area reflectivity (700nm-1040nm);

[0025] Figure 3Example 6 sample black pattern real domain reflectivity (380nm-700nm);

[0026] Figure 4 Reflectivity of the black pattern area of ​​the sample in Example 6 (700nm-1040nm). DETAILED DESCRIPTION

[0027] A metal-based silver halide photosensitive material is provided, wherein a high-adhesion bottom layer and a silver halide photosensitive layer are coated in sequence on a metal substrate.

[0028] Wherein, the metal substrate is stainless steel, aluminum, aluminum alloy, titanium, titanium alloy, chromium or metal alloy; the thickness of the metal substrate is 0.05-10mm.

[0029] The high adhesion bottom layer comprises the following materials in parts by weight:

[0030]

[0031] The water latex in the high-adhesion bottom layer is one of water-based polyurethane, water-based acrylate or water-based epoxy resin emulsion or a combination of multiple ones in any weight ratio; the water-based polyurethane, water-based acrylate or water-based epoxy resin emulsion used in the bottom layer contains 0.01-5% by weight of active groups such as hydroxyl, amino or carboxyl.

[0032] Among them, the bridging agent used in the high-adhesion bottom layer is mainly blocked polyisocyanate, such as Mitsui Chemical's blocked water-based isocyanate bridging agent XWD-U380S or Lanxess' blocked isocyanate curing agent BI 200. The isocyanate (-NCO) groups released by this series of curing agents during heat treatment react with hydroxyl, carboxyl, amino and other groups on the water-based resin molecular chain to form a cross-linked structure. At the same time, the isocyanate (-NCO) groups in the curing agent structure can also react with the amino or carboxyl groups of gelatin in the silver halide photosensitive layer coated on the bottom layer, ensuring that the gelatin coating has good adhesion to the bottom layer.

[0033] The adhesion promoter in the high adhesion base layer is one or more of an organic silane adhesion promoter, an organic titanium adhesion promoter, a zirconium oxide aluminate adhesion promoter and an alkyl phosphate adhesion promoter in any weight ratio. More preferably, the adhesion promoter is aminopropyl triethoxysilane, DuPont 371 organic titanium adhesion promoter or 404 water-based phosphate adhesion promoter from Zhenglin Reagent.

[0034] Among them, the leveling agent in the high-adhesion bottom layer refers to a modified polysiloxane leveling agent, an acrylate leveling agent or a fluorocarbon leveling agent. Further preferably, the leveling agent is Deqian 455 modified polysiloxane leveling agent, BYK-381 water-based polyacrylate leveling agent or American 3M FC-4430 fluorocarbon leveling agent. The leveling agent can reduce the surface tension of the coating, improve its leveling and uniformity, and promote the coating to form a flat, smooth and uniform film layer during the drying and film-forming process.

[0035] Among them, the defoamer in the high-adhesion bottom layer is a silicone defoamer, a polyether defoamer or an alcohol defoamer. Further preferably, the defoamer is BYK-028 silicone defoamer, Hengxin Chemical X-288 polyether defoamer, isopropanol, n-butanol or polyethylene glycol-propylene glycol-ethylene glycol block copolymer. The function of the defoamer is to inhibit the generation of foam or eliminate the generated foam, so as to avoid the foam in the coating from having an adverse effect on the coating appearance.

[0036] The dry thickness of the high-adhesive bottom layer is a coating of 50-900 nm. The purpose is to form a bottom layer with a receiving function on the metal substrate to facilitate the coating of the silver halide photosensitive layer.

[0037] The silver halide photosensitive layer comprises the following substances in parts by weight:

[0038]

[0039] The dry thickness of the silver halide photosensitive layer is a coating of 2-3 μm.

[0040] Among them, the crosslinking agent in the silver halide photosensitive layer is one or more of cyanuric chloride and its derivatives, dichloropyrimidine and its derivatives, bifunctional epoxy compounds, diolefin compounds and dialdehyde compounds in any weight ratio. Further preferably, the crosslinking agent is 2,4-dichloro-6-hydroxy-s-triazine sodium salt, N,N-di(2,3-epoxypropyl)cyclohexylamine, 1,3-bis(vinylsulfone)methane or 1,3-bis(vinylsulfone)-2-propanol. The use of the crosslinking agent can cause the gelatin molecules to undergo crosslinking reactions, thereby improving the mechanical strength and chemical resistance of the coating.

[0041] Wherein, the particle size of the silver halide in the silver halide emulsion is 50-300nm. Further, in order to improve the imaging accuracy of the silver halide photosensitive material, the particle size of the silver halide is 50-180nm.

[0042] The anti-halation dye in the silver halide emulsion can be indoline imidazoline carbocyanine, quinoline cyanine, myrocyanine, pentamethine cyanine dye, or other polymethine cyanine dyes such as heptamethine cyanine dye. The anti-halation dye is added to the silver halide photosensitive layer to eliminate the light scattering caused by the interface between the silver halide particles and the photosensitive layer after the light enters the photosensitive layer during exposure, and the light reflected back to the photosensitive layer by the metal substrate, thereby improving the resolution and clarity of the photosensitive material.

[0043] The leveling agent in the silver halide photosensitive layer refers to a modified polysiloxane leveling agent, an acrylate leveling agent or a fluorocarbon leveling agent. Further preferably, the leveling agent is Deqian 455 modified polysiloxane leveling agent, BYK-381 water-based polyacrylate leveling agent or American 3M FC-4430 fluorocarbon leveling agent. The leveling agent can reduce the surface tension of the coating, improve its leveling and uniformity, and promote the coating to form a flat, smooth and uniform film layer during the drying and film-forming process.

[0044] Wherein, the defoamer in the silver halide photosensitive layer is an organosilicon defoamer, a polyether defoamer or an alcohol defoamer. Further preferably, the defoamer is BYK-028 organosilicon defoamer, Hengxin Chemical X-288 polyether defoamer, isopropyl alcohol, n-butanol or polyethylene glycol-propylene glycol-ethylene glycol block copolymer. The function of the defoamer is to inhibit the generation of foam or eliminate the generated foam, so as to avoid the foam in the coating from having an adverse effect on the coating appearance. The alcohol defoamer is isopropyl alcohol, n-butanol or polyethylene glycol-propylene glycol-ethylene glycol block copolymer. The function of the defoamer is to inhibit the generation of foam or eliminate the generated foam, so as to avoid the foam in the coating from having an adverse effect on the coating appearance.

[0045] Among them, the thickener in the silver halide photosensitive layer is sodium polyacrylate, sodium polystyrene sulfonate, polyvinyl pyrrolidone, or sodium carboxymethyl cellulose, etc. The function of the thickener is to adjust the viscosity of the silver halide photosensitive layer coating solution and improve the coating suitability of the coating solution.

[0046] Among them, the preservative in the silver halide photosensitive layer is phenol or kason, etc. The addition of preservatives can prevent gelatin from rotting due to bacterial invasion and affecting the photosensitive properties.

[0047] As an improved technical solution of the present application, a functional protective layer is also included, and the functional protective layer contains the following substances in parts by weight:

[0048]

[0049] Among them, the crosslinking agent in the functional protective layer is one or more of cyanuric chloride and its derivatives, dichloropyrimidine and its derivatives, bifunctional epoxy compounds, diolefin compounds and dialdehyde compounds in any weight ratio. Further preferably, the crosslinking agent is 2,4-dichloro-6-hydroxy-s-triazine sodium salt, N,N-di(2,3-epoxypropyl)cyclohexylamine, 1,3-bis(vinylsulfone)methane or 1,3-bis(vinylsulfone)-2-propanol. The use of the crosslinking agent can cause the gelatin molecules to undergo crosslinking reactions, thereby improving the mechanical strength and chemical resistance of the coating.

[0050] Among them, the matting agent used in the functional protective layer is PMMA microspheres, PI microspheres, silicon dioxide, titanium dioxide, magnesium oxide, aluminum oxide, barium sulfate or calcium carbonate particles. The matting agent used in the functional protective layer is selected from any one of the above, or a combination of multiple agents in any weight ratio. The matting agent used in the functional protective layer has good dispersion stability and will not aggregate and settle during the static standing of the coating liquid. The particle size distribution is uniform and does not affect the photosensitivity and resolution of the silver halide coating.

[0051] The leveling agent in the functional protective layer refers to a modified polysiloxane leveling agent, an acrylate leveling agent or a fluorocarbon leveling agent. Further preferably, the leveling agent is Deqian 455 modified polysiloxane leveling agent, BYK-381 water-based polyacrylate leveling agent or American 3M FC-4430 fluorocarbon leveling agent. The leveling agent can reduce the surface tension of the coating, improve its leveling and uniformity, and promote the coating to form a flat, smooth and uniform film layer during the drying and film-forming process.

[0052] The defoamer in the functional protective layer is a silicone defoamer, a polyether defoamer or an alcohol defoamer. Further preferably, the defoamer is isopropanol, n-butanol or a polyethylene glycol-propylene glycol-ethylene glycol block copolymer. The function of the defoamer is to inhibit the generation of foam or eliminate the generated foam, so as to avoid the foam in the coating from having an adverse effect on the coating appearance.

[0053] The thickener in the functional protective layer is sodium polyacrylate, sodium polystyrene sulfonate, polyvinyl pyrrolidone, or sodium carboxymethyl cellulose, etc. The thickener is used to adjust the viscosity of the functional protective layer coating solution and improve the coating suitability of the coating solution.

[0054] The preservative in the functional protective layer is phenol or kason, etc. The addition of the preservative can prevent gelatin from being rotten due to bacterial invasion and thus affecting the photosensitivity.

[0055] As an improved technical solution of the present application, the dry thickness of the functional protective layer is 0.5-1.5 μm.

[0056] The production process of the above-mentioned high-precision metal-based silver halide photosensitive material mainly involves coating technology. The production process is simple and pollution-free, and is suitable for rapid and large-scale production.

[0057] Example 1 According to the attached Figure 1 The structure shown is to coat a high-adhesion base layer, a silver halide photosensitive layer and a functional protective layer on a metal substrate in sequence. The specific operation is as follows:

[0058] (1) A stainless steel plate with a thickness of 1 mm was selected as the substrate, and both sides of the stainless steel were polished;

[0059] (2) Apply a high-adhesion primer layer on the stainless steel plate at a coating amount of 18 mL / m 2 After drying, a high-adhesion bottom layer with a thickness of 70 nm is obtained. The weight parts of each component are as follows:

[0060]

[0061] (3) A silver halide photosensitive layer is coated on the bottom layer, and the coating amount of the silver halide photosensitive layer is 68 mL / m 2 After drying, a 4 μm silver halide photosensitive layer is obtained. The weight proportions of the components in the formula are as follows:

[0062]

[0063]

[0064] (4) A functional protective layer is coated on the silver halide photosensitive layer with a coating amount of 27 mL / m 2 After drying, a 1.5 μm matte protective layer is obtained. The protective layer formula structure is as follows, and the percentages are all parts by weight:

[0065]

[0066] Embodiment 2 According to the attached Figure 2 The structure shown is coated with a high-adhesion primer layer, a silver halide photosensitive layer and a functional protective layer on both sides of the metal substrate in sequence. The formula and coating parameters of each coating are exactly the same as those of Example 1. The difference is that after completing the operation of Example 1, the operating steps of Example 1 are repeated on the other side of the metal substrate.

[0067] Example 3: A 2 mm thick aluminum alloy plate with both sides polished was selected as the substrate, and a high adhesion base layer, a silver halide photosensitive layer and a functional protective layer were coated in sequence. The specific operation is as follows:

[0068] (1) Apply a high-adhesion primer layer on the aluminum alloy plate with a coating amount of 10 mL / m 2 After drying, a high-adhesion bottom layer with a thickness of 420 nm is obtained. The weight parts of each component are as follows:

[0069]

[0070] (2) The formulation and coating parameters of the silver halide photosensitive layer and the functional protective layer are exactly the same as those in Example 1.

[0071] Example 4

[0072] A 2mm thick aluminum alloy plate with polished double sides was selected as the substrate, and a high-adhesion base layer, a silver halide photosensitive layer and a functional protective layer were coated in sequence. The specific operation is as follows:

[0073] (1) coating a high-adhesion primer layer on a stainless steel plate, wherein the formula and coating method of the high-adhesion primer layer are exactly the same as those in Example 3;

[0074] (2) A silver halide photosensitive layer is coated on the bottom layer, and the coating amount of the silver halide photosensitive layer is 75 mL / m 2 After drying, a 2 μm photosensitive layer is obtained. The photosensitive layer formula structure is as follows, and the percentages are all parts by weight:

[0075]

[0076] (3) A functional protective layer is coated on the silver halide photosensitive layer. The formulation and coating method of the functional protective layer are exactly the same as those in Example 1.

[0077] Example 5: A 2 mm thick aluminum alloy plate with both sides polished is used as the substrate, and a high-adhesion base layer, a silver halide photosensitive layer and a functional protective layer are coated in sequence. The specific operation is as follows:

[0078] (1) coating a high-adhesion primer layer on a stainless steel plate, wherein the formula and coating method of the high-adhesion primer layer are exactly the same as those in Example 3;

[0079] (2) coating a silver halide photosensitive layer on the bottom layer, wherein the formula and coating parameters of the silver halide photosensitive layer are exactly the same as those in Example 1;

[0080] (5) Coat a functional protective layer on the silver halide photosensitive layer with a coating amount of 30 mL / m 2 After drying, a 0.6 μm matte protective layer is obtained. The protective layer formula structure is as follows, and the percentages are all parts by weight:

[0081]

[0082]

[0083] Embodiment 6 According to the attached Figure 1 The structure shown is to coat a high-adhesion base layer, a silver halide photosensitive layer and a functional protective layer on a metal substrate in sequence. The specific operation is as follows:

[0084] (1) A stainless steel plate with a thickness of 1.2 mm was selected as the substrate, and both sides of the stainless steel were polished;

[0085] (2) Apply a high-adhesion primer layer on the stainless steel plate at a coating amount of 15 mL / m 2 After drying, a high-adhesion bottom layer with a thickness of 100 nm is obtained. The weight parts of each component are as follows:

[0086]

[0087] (3) A silver halide photosensitive layer is coated on the bottom layer, and the coating amount of the silver halide photosensitive layer is 65 mL / m 2 After drying, a 2.9 μm silver halide photosensitive layer is obtained. The weight proportions of the components in the formula are as follows:

[0088]

[0089] (6) A functional protective layer is coated on the silver halide photosensitive layer with a coating amount of 24 mL / m 2 After drying, a 1 μm matte protective layer is obtained. The protective layer formula structure is as follows, and the percentages are all parts by weight:

[0090]

[0091] The conditions of the substrate, high adhesion bottom layer and functional protective layer of Example 7 are exactly the same as those of Example 6. The difference from Example 6 is that no anti-halation dye is used in the formula of the silver halide photosensitive layer. The other conditions are exactly the same as those of Example 6.

[0092] Example 8: A high-precision transparent glass film with 5 μm, 15 μm, 25 μm, 35 μm and 45 μm line width patterns was used as a master. Figure 3 The method shown is covered on the photosensitive coating of the metal-based photosensitive plate made in Example 1, Example 3, Example 4, Example 5, Example 6 and Example 7, and processed according to the processes of exposure, development, fixing, water washing and drying, so as to form black patterns with different line widths and line spacings on the metal photosensitive plate. According to the method disclosed in patents CN116430682A and CN113753846A, a stainless steel plate exactly the same as that in Example 6 is used as a substrate, and chrome film plating, exposure, development, wet etching and photoresist removal are carried out on it to make samples with silver patterns of 5μm, 15μm, 25μm, 35μm and 45μm line widths as comparison samples.

[0093] The line width data was measured using a high-precision imaging tester, and the measurement results are shown in Tables 1 to 7;

[0094] The reflectivity of the black image area of ​​Example 6 and the comparison sample was measured using an Ocean Optics spectrometer. The test results are as follows: Figure 1-Figure 4 shown.

[0095] Table 1 Comparison of sample line data and comparative sample data in Example 1

[0096]

[0097] Table 2 Comparison of sample line data and master data in Example 3

[0098]

[0099] Table 3 Comparison of sample line data and master data in Example 4

[0100]

[0101] Table 4 Comparison of sample line data and master data in Example 5

[0102]

[0103] Table 5 Comparison of sample line data and master data in Example 6

[0104]

[0105] Table 6 Comparison of sample line data and master data in Example 7

[0106]

[0107]

[0108] It can be seen from Tables 1 to 5 that the precision of the metal photosensitive material prepared by the present invention for line widths of 15 μm and above can reach ±1 μm. However, the precision of the metal photosensitive material prepared by the present invention for line widths of 35 μm and above can only reach ±1 μm. The precision of the metal photosensitive material prepared by the present invention is significantly better than that of the comparative sample.

[0109] From the comparison of the data in Tables 1 to 5 and Table 6, it can be seen that without adding anti-halation dyes to the silver halide photosensitive layer, the accuracy of line widths of 45 μm and above can reach ±1 μm, indicating that adding anti-halation dyes to the silver halide photosensitive layer in the present invention has a significant effect on improving the photosensitivity accuracy.

[0110] Depend on Figure 1 - Figure 4By comparison, it can be seen that the reflectivity of the silver pattern area of ​​the comparison sample in most bands within the range of 380nm-1040nm exceeds 5%, and the reflectivity in the short-wave band <420nm and the long-wave band >840 exceeds 10%, and even exceeds 15%; while the reflectivity of the black pattern of the sample of the present application is ≤5% in the range of 380nm-1040nm, and the reflectivity of the pattern area is reduced, which is beneficial to improve the contrast between the pattern area and the non-pattern area, and is beneficial to improve the recognition sensitivity of the optical signal to the pattern area and the non-pattern area.

[0111] The above is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principles of the present invention, which do not affect the essence of the present invention. In the absence of conflict, the embodiments of the present application and the features in the embodiments can be combined with each other at will.

Claims

1. A metal-based silver halide photosensitive material, characterized in that: A high-adhesion primer layer and a silver halide photosensitive layer are sequentially coated on the metal substrate; The high adhesion bottom layer comprises the following materials in parts by weight: The water latex is one or a combination of multiple types of water-based polyurethane, water-based acrylate or water-based epoxy resin emulsion in any weight ratio; The silver halide photosensitive layer comprises the following substances in parts by weight:

2. A metal-based silver halide photosensitive material according to claim 1, characterized in that: It also includes a functional protective layer, which contains the following substances in parts by weight:

3. A metal-based silver halide photosensitive material according to claim 1, characterized in that: The dry thickness of the high-adhesion bottom layer is a coating of 50-900nm.

4. A metal-based silver halide photosensitive material according to claim 1, characterized in that: The dry thickness of the silver halide photosensitive layer is a coating of 2-4 μm.

5. The metal-based silver halide photosensitive material according to claim 1, characterized in that: The dry thickness of the functional protective layer is 0.5-1.5 μm.

6. The metal-based silver halide photosensitive material according to claim 1, characterized in that: The metal substrate is stainless steel, aluminum, aluminum alloy, titanium, titanium alloy, chromium or metal alloy.

7. A metal-based silver halide photosensitive material according to claim 6, characterized in that: The thickness of the metal substrate is 0.05-10mm.

8. The metal-based silver halide photosensitive material according to claim 1, characterized in that: The silver halide grains include silver chloride, silver bromide, silver iodobromide, silver iodochloride, silver iodobromochloride, silver bromochloride or silver chlorobromide.

9. The metal-based silver halide photosensitive material according to claim 1, characterized in that: The particle size of the silver halide is 50-300nm.

10. The metal-based silver halide photosensitive material according to claim 1, characterized in that: The matting agent is PMMA microspheres, PI microspheres, silicon dioxide, titanium dioxide, magnesium oxide, aluminum oxide, barium sulfate or calcium carbonate particles.

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