阅读说明：本技术 一种光刻胶保护材料以及使用其形成金属网格的方法 (Photoresist protective material and method for forming metal grid by using same ) 是由 李阳 王钧 江建国 于 2021-10-18 设计创作，主要内容包括：本发明提供了一种光刻胶保护材料以及使用其形成金属网格的方法,所述光刻胶保护材料包含以下组分：(A)消泡剂；(B)表面活性剂；(C)流平剂；(D)聚烯醇；(E)高化学惰性透明聚合物颗粒；(F)去离子水。本发明的光刻胶保护材料具有极好的防粘黏特性,可以减少在接触式曝光过程中对光罩表面的污染,在进行接触式掩膜UV曝光过程中不会对光罩产生粘黏；在涂布后曝光的过程中,也不会因为引入的颗粒而对UV光固化层固化效果产生影响。(The invention provides a photoresist protective material and a method for forming a metal grid by using the same, wherein the photoresist protective material comprises the following components: (A) defoaming agents; (B) a surfactant; (C) leveling agent; (D) a polyalkenol; (E) highly chemically inert transparent polymer particles; (F) deionized water. The photoresist protective material has excellent anti-sticking property, can reduce the pollution to the surface of the photomask in the contact exposure process, and can not stick to the photomask in the contact mask UV exposure process; in the process of exposure after coating, the curing effect of the UV light curing layer is not influenced by the introduced particles.)

1. A photoresist protective material, comprising the following components:

(A) defoaming agents;

(B) a surfactant;

(C) leveling agent;

(D) a polyalkenol;

(E) highly chemically inert transparent polymer particles; and

(F) deionized water.

2. The photoresist protective material of claim 1, wherein the photoresist protective material comprises the following components:

(A)0.01-3 wt% of a defoamer;

(B)0.01-6 wt% of a surfactant;

(C)0.01-6 wt% of flatting agent;

(D)5-50 wt% of a polyalkenol;

(E)0.01 to 10 wt% of highly chemically inert transparent polymer particles; and

(F) sufficient water is supplemented.

3. The resist protection material according to claim 1 or 2, wherein the defoaming agent is a polyacrylic defoaming agent or a silicone defoaming agent.

4. The resist protection material of claim 1 or 2, wherein the surfactant is one or more of a cationic surfactant, an anionic surfactant, and a nonionic surfactant,

wherein the cationic surfactant is selected from one or more of cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride and dodecyl pyridine ammonium chloride;

wherein the anionic surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate, sodium methyl stearate ethoxylate sulfonate, sodium alpha-alkenyl sulfonate, secondary alkyl sulfonate, sodium fatty alcohol-polyoxyethylene ether carboxylate, isooctyl alcohol phosphate, lauryl alcohol ether phosphate, Dowfax 2A1, DOWFAX 3B2, DOWFAX 8390, DOWFAX C6L, DOWFAX C10L and DOWFAX 30599; and is

The nonionic surfactant is selected from one or more of fatty alcohol-polyoxyethylene ether, octyl phenol-polyoxyethylene ether-10, dodecyl phenol-polyoxyethylene ether and fatty acid-polyoxyethylene ether.

5. The photoresist protective material according to claim 1 or 2, wherein the leveling agent is a non-ionic wetting agent selected from fatty alcohol polyoxyethylene ether HIC2008, branched alcohol alkoxylate ECOSURF^TMLFE-635Surfactant, Surfynol 82, Surfynol 104, Surfynol AD01, Surfynol SE-F, Surfynol SE, octyl pyrrolidone Surfadone^TMLP-100、Surfadone^TMOne or more of LP-300, BYK-320, BYK-307, BYK344, BYK323, BYK333, BYK349 and BYK 370.

6. The photoresist protective material of claim 1 or 2, wherein the highly chemically inert transparent polymer particles are selected from one or more of polypropylene, polyvinyl chloride, polytetrafluoroethylene, and styrenic thermoplastic elastomers.

7. The photoresist protective material of claim 1 or 2, wherein the highly chemically inert transparent polymer particles are selected from at least two of polypropylene, polyvinyl chloride, polytetrafluoroethylene, polyurethane thermoplastic elastomers, and styrenic thermoplastic elastomers.

8. A method for forming a metal grid on a flexible substrate, wherein the method comprises the steps of:

(1) sequentially coating a UV curable material, a Pd material, and the photoresist protective material according to any one of claims 1-7 on one surface of the flexible substrate;

(2) exposing and developing the coated flexible substrate to sequentially form a UV curable layer and a catalytic layer on a surface of the flexible substrate according to a desired pattern; and

(3) plating copper on the pattern to form the metal grid.

9. The method of claim 8, wherein the coating is a wet coating.

10. The method of claim 8, wherein the exposure is a contact exposure.

11. A metal grid touch sensor, characterized in that the metal grid of the metal grid touch sensor is formed by a method according to any of claims 8-10.

Technical Field

The invention belongs to the field of electroless copper plating, and particularly relates to a photoresist protective material and a method for forming a metal grid by using the same.

Background

The preparation process of the metal grid touch sensor mainly comprises coating, exposure, development, copper plating, blackening and the like. In particular, roll-coated structures on flexible substrates are currently typically made of a UV-curable base layer, an intermediate layer containing colloidal palladium nanoparticles and a top protective layer. And then, carrying out mask UV exposure on the coated coil, carrying out wet development to obtain a composite structure formed by an ultraviolet light curing base layer and the palladium nano particles on the top, and finally carrying out chemical copper plating by taking the palladium nano particles deposited on the ultraviolet light curing base layer as a catalyst to form a metal grid.

In order to ensure the uniformity and line width of the metal grid lines, a contact mask exposure is usually used. However, during contact mask UV exposure, the web tends to stick to the mask to varying degrees of severity. In severe cases, the coiled material and the mask are stuck to cause shutdown, even stripping can occur to pollute the mask, which not only affects the production efficiency, but also increases the risk in the production process. Therefore, in the contact mask uv curing process, it is necessary to prevent the photoresist protective coating from sticking to the mask to ensure the production is performed properly and to reduce the cleaning time.

Therefore, it is necessary to develop a resist protective coating that prevents the adhesion of the web to the mask (reticle) and is free from contamination for development.

Disclosure of Invention

The invention aims to overcome the defects that the storage time of a coated coil is short, the adhesion between the coil and a mask is easy to occur in contact exposure and the like in the prior art, and provides a photoresist protective coating material which can prevent the coil from being adhered to the mask (photomask) and has no pollution to development.

In order to achieve the above object, in one aspect, the present invention provides a photoresist protective material characterized in that the photoresist protective material comprises the following components:

(A) defoaming agents;

(B) a surfactant;

(C) leveling agent;

(D) a polyalkenol;

(E) highly chemically inert transparent polymer particles; and

(F) deionized water.

In a preferred embodiment of the present invention, the photoresist protection material comprises the following components:

(A)0.01-3 wt% of a defoamer;

(B)0.01-6 wt% of a surfactant;

(C)0.01-6 wt% of flatting agent;

(D)5-50 wt% of a polyalkenol;

(E)0.01 to 10 wt% of highly chemically inert transparent polymer particles; and

(F) sufficient water is supplemented.

In a preferred embodiment of the present invention, the defoaming agent is a polyacrylic defoaming agent or a silicone-based defoaming agent.

In a preferred embodiment of the present invention, the surfactant is one or more of a cationic surfactant, an anionic surfactant and a nonionic surfactant, wherein the cationic surfactant is selected from one or more of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride and dodecylpyridinium chloride; wherein the anionic surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate, sodium methyl stearate ethoxylate sulfonate, sodium alpha-alkenyl sulfonate, secondary alkyl sulfonate, sodium fatty alcohol-polyoxyethylene ether carboxylate, isooctyl alcohol phosphate, lauryl alcohol ether phosphate, Dowfax 2A1, DOWFAX 3B2, DOWFAX 8390, DOWFAX C6L, DOWFAX C10L and DOWFAX 30599; and the nonionic surfactant is selected from one or more of fatty alcohol-polyoxyethylene ether, octyl phenol-polyoxyethylene ether-10, dodecyl phenol polyoxyethylene ether and fatty acid polyoxyethylene ether. More preferably, the surfactant is sodium dodecyl diphenyl oxide disulfonate.

In a preferred embodiment of the present invention, the leveling agent is a nonionic wetting agent selected from fatty alcohol polyoxyethylene ether HIC2008, branched alcohol alkoxylate ecosourf^TMLFE-635Surfactant、Surfynol 82、Surfynol 104、SurfynolAD01, Surfynol SE-F, Surfynol SE, octyl pyrrolidone Surfadone^TMLP-100、Surfadone^TMOne or more of LP-300, BYK-320, BYK-307, BYK344, BYK323, BYK333, BYK349 and BYK 370.

In a preferred embodiment of the present invention, the highly chemically inert transparent polymer particles are selected from one or more of polypropylene, polyvinyl chloride, polytetrafluoroethylene and styrenic thermoplastic elastomers.

In a preferred embodiment of the present invention, the highly chemically inert transparent polymer particles are selected from at least two of polypropylene, polyvinyl chloride, polytetrafluoroethylene and styrenic thermoplastic elastomers.

In another aspect, the present invention also provides a method for forming a metal grid on a flexible substrate, wherein the method comprises the steps of:

(1) coating a UV curable material, a Pd material, and a photoresist protective material as described above on one surface of the flexible substrate in this order;

(2) exposing and developing the coated flexible substrate to sequentially form a UV curable layer and a catalytic layer on a surface of the flexible substrate according to a desired pattern; and

(3) plating copper on the pattern to form the metal grid.

In a preferred embodiment of the invention, the coating is a wet coating.

In a preferred embodiment of the present invention, the exposure is a contact exposure.

In another aspect, the present invention also provides a metal grid touch sensor, wherein the metal grid of the metal grid touch sensor is formed by the method as described above.

Compared with the prior art, the technical scheme of the invention at least comprises the following advantages:

one or more high chemical inertia transparent polymer particles (strong chemical inertia particles) are introduced into the photoresist protective material provided by the invention, so that oxygen and moisture can be effectively isolated to prevent the photocuring reaction from being influenced in the exposure process, the coated coil can be protected, and the storage time of the coated coil can be effectively prolonged. In addition, a coating formed by the photoresist protective material has excellent anti-adhesion property, can reduce the pollution to the surface of the photomask in the contact exposure process, and cannot generate adhesion to the photomask in the contact mask UV exposure process; in the process of exposure after coating, the curing effect of the UV light curing layer is not influenced by the introduced particles. Meanwhile, the formed coating has no influence on development and copper plating, and is suitable for preparing metal grids, so that the production efficiency is improved, and the risk in the production process is reduced.

Detailed Description

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 shows a flow diagram of an exemplary method of forming a metal grid in accordance with an embodiment of the present invention;

FIG. 2 shows a schematic representation of a sample prepared using a photoresist protective material of the invention before and after contact with a reticle according to an embodiment of the invention;

FIG. 3 shows a schematic of the change before and after a sample without a photoresist protective material is in contact with a reticle; and

FIG. 4 shows a schematic of the change before and after a sample without highly chemically inert transparent polymer particles in the photoresist protective material is contacted with a reticle.

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

Unless defined otherwise, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

In one aspect, the present invention provides a photoresist protective material, wherein the photoresist protective material comprises the following components:

(A) defoaming agents;

(B) a surfactant;

(C) leveling agent;

(D) a polyalkenol;

(E) highly chemically inert transparent polymer particles; and

(F) deionized water.

As used herein, the term "defoamer" refers to a chemical additive that can reduce and/or retard foam formation. The type of defoaming agent in the present invention is not particularly limited, and may be of the type commonly used in the art. More preferably, the defoaming agent may be a polyacrylic defoaming agent or a silicone defoaming agent, but is not limited thereto.

As used herein, the term "surfactant" refers to a substance that is capable of causing a significant reduction in the surface tension of a target solution. The surfactant of the present invention may use an anionic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof, without limitation. More preferably, the surfactant may be selected from one or more of cationic surfactant, anionic surfactant and nonionic surfactant, wherein the cationic surfactant may be selected from one or more of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride and dodecylpyridinium ammonium chloride; wherein the anionic surfactant may be selected from one or more of sodium dodecylbenzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate, sodium methyl stearate ethoxylate sulfonate, sodium alpha-alkenyl sulfonate, sodium secondary alkyl sulfonate, sodium fatty alcohol-polyoxyethylene ether carboxylate, isooctyl alcohol phosphate, lauryl alcohol ether phosphate, Dowfax 2a1, Dowfax 3B2, Dowfax 8390, Dowfax C6L, Dowfax C10L, and Dowfax 30599; and the nonionic surfactant can be one or more selected from fatty alcohol polyoxyethylene ether, octyl phenol polyoxyethylene ether-10, dodecyl phenol polyoxyethylene ether and fatty acid polyoxyethylene ether. Further preferably, the surfactant may be sodium dodecyl diphenyl oxide disulfonate.

As used herein, the term "leveling agent" refers to a class of materials that are effective in reducing the surface tension of a coating, increasing its leveling and uniformity. Examples of leveling agents may include, but are not limited to, nonionic wetting agents, specifically selected from fatty alcohol polyoxyethylene ether HIC2008, branched alcohol alkoxylates ecosourf^TMLFE-635Surfactant, Surfynol 82, Surfynol 104, Surfynol AD01, Surfynol SE-F, Surfynol SE, octyl pyrrolidone Surfadone^TMLP-100、Surfadone^TMOne or more of LP-300, BYK-320, BYK-307, BYK344, BYK323, BYK333, BYK349 and BYK370, and the like.

As used herein, the term "polyalkenol" refers to a homopolymer or copolymer polymerized from the same or different alkenols, and may in particular be polyvinyl alcohol or polyallyl alcohol or the like.

As used herein, the term "highly chemically inert transparent polymer particles" refers to a class of particles that have high transparency and are particularly strongly chemically inert. The components of the high-chemical-inertia transparent polymer particles are the key points of the photoresist protective material, can effectively isolate oxygen and water vapor to prevent the photocuring reaction from being influenced in the exposure process, can provide protection for a coated coil, and effectively prolong the storage time of the coated coil; and has excellent anti-sticking properties, and can reduce contamination of the photomask surface during contact exposure. Preferably, the highly chemically inert transparent polymer particles may be selected from one or more of polypropylene, polyvinyl chloride, polytetrafluoroethylene and styrenic thermoplastic elastomers. More preferably, the highly chemically inert transparent polymer particles may be selected from at least two of polypropylene, polyvinyl chloride, polytetrafluoroethylene, polyurethane thermoplastic elastomer, and styrenic thermoplastic elastomer.

In addition, the amounts of the components in the resist protective material of the present invention can be adjusted according to experience and practical needs of those skilled in the art. For example, in a preferred embodiment of the present invention, the photoresist protective material may comprise the following components:

(A)0.01-3 wt% of a defoaming agent, such as 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, or 3 wt% and the like;

(B)0.01-6 wt% surfactant, e.g., 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or 6 wt% surfactant, etc.;

(C)0.01 to 6 wt% of a leveling agent, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or 6 wt% of a leveling agent;

(D)5-50 wt% of a polyalkenol, e.g., 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt% of a polyalkenol, etc.;

(E)0.01 to 10 wt% of highly chemically inert transparent polymer particles, e.g., 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 3 wt%, 5 wt%, or 10 wt% of highly chemically inert transparent polymer particles, etc.; and

(F) make up sufficient water (which may be deionized water), i.e., to make up 100 wt%.

In another aspect, the present invention also provides a method for forming a metal grid on a flexible substrate, wherein the method comprises the steps of:

(1) coating a UV curable material, a Pd material, and a photoresist protective material as described above on one surface of the flexible substrate in this order;

(2) exposing and developing the coated flexible substrate to sequentially form a UV curable layer and a catalytic layer on a surface of the flexible substrate according to a desired pattern; and

(3) and plating copper on the pattern to form the metal grid on the flexible substrate.

With respect to step (1), fig. 1 shows a flowchart of an exemplary method of forming a metal mesh according to an embodiment of the present invention, in which a UV curable layer, a Pd nanoparticle layer, and a water-soluble protective layer are sequentially formed on one surface of a substrate by sequentially coating a UV curable material, a Pd material, and a photoresist protective material as described above on the surface of the substrate.

For the UV curable material as the first layer (or referred to as the base layer), the UV curable material may be a positive photoresist or a negative photoresist. In one embodiment, the positive photoresist may preferably include a resin material soluble in a developing solution after exposure, and the negative photoresist may preferably include a resin material insoluble in a developing solution after exposure. The developer is usually an aqueous solution containing an alkali compound and a surfactant, the alkali compound may be an inorganic or organic alkali compound, and these inorganic and organic alkali compounds may be used alone or in combination of two or more; as the surfactant, at least one selected from the group consisting of nonionic surfactants, anionic surfactants and cationic surfactants may be used, and these surfactants may be used alone or in combination of two or more.

In addition, a photoinitiator may be further included in the UV curable material, for example, in one embodiment of the present invention, the photoinitiator may be at least one selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, thioxanthone-based compounds, and oxime-based compounds. Specific examples of the acetophenone-based compound may include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like. Specific examples of the benzophenone-based compound may include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4' -methyl diphenyl sulfide, 2,4, 6-trimethylbenzophenone, and the like. Specific examples of the triazine-based compound may include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6-2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine and the like. Specific examples of the thioxanthone-based compound may include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. Specific examples of the oxime ester compounds may include o-ethoxycarbonyl- α -oxyimino-1-phenylpropan-1-one, 1, 2-octanedione, 1- (4-phenylthio) phenyl, 2- (o-benzoyloxime), and the like.

The Pd nanoparticle layer as the second layer is mainly used as a catalyst in electroless copper plating. The palladium nano-particles have the advantages of high catalytic activity, strong selectivity, convenient preparation and the like, and are widely used in the field of chemical copper plating. Common methods for preparing palladium nanoparticles include gas phase chemical reaction, precipitation, liquid phase reduction, spray pyrolysis, sol-gel, and the like. The liquid phase reduction method can be simply classified into an organic solvent synthesis method and an aqueous solution synthesis method according to the difference of solvents. The nano-particles prepared by the organic solvent synthesis method have the advantages of good crystallinity, good monodispersity, easy control of morphology and the like. The method for preparing palladium nano particles in the prior art is an organic solvent synthesis method.

The protective layer material as the third layer is mainly used for protection in the exposure stage, and is washed away by the developing solution in the developing stage. Since the components, contents, etc. of the photoresist protective material of the present invention have been described in detail in the foregoing section, the features of the photoresist protective material will not be described in detail in this section to avoid unnecessary redundancy.

According to the present invention, the three coating materials may be preferably applied by wet coating, i.e., a UV curable material, a Pd material, and a photoresist protective material in the form of a liquid or a solution may be sequentially coated on one surface of the substrate.

With respect to the step (2), the substrate coated with the UV curable material, the Pd material, and the photoresist protective material in this order is exposed to ultraviolet rays with a mask having a desired pattern disposed therebetween, thereby forming a desired pattern on the substrate. Based on the characteristics of the photoresist protective material, the photoresist protective material has the advantage of protecting and preventing the coiled material and the mask from being adhered during contact exposure. Thus, in a preferred embodiment of the present invention, the exposure may be a contact exposure.

Specifically, fig. 2 shows a schematic diagram of a sample prepared using the photoresist protective material of the present invention before and after contact with a reticle, in which no sticking and stripping phenomenon occurs, according to an embodiment of the present invention. Fig. 3 shows a schematic representation of the change before and after contact of a sample without photoresist protection material with a reticle, wherein the film side of the sample has been demolded after contact with the reticle. FIG. 4 shows a schematic representation of the change before and after contact with a reticle for a sample without highly chemically inert transparent polymer particles in the photoresist protective material, wherein the sample sticks to the reticle after contact and causes de-molding.

Subsequently, in the developing process, as described above, the UV curable material, the Pd material, and the photoresist protective material, which are not cured, may be removed in the developing process.

For step (3), since the protective layer material is removed, and the palladium nanoparticle layer is at the uppermost layer, it can be used as a catalyst for copper plating, so this step only needs to perform copper plating, for example, electroless copper plating, on the pattern, thereby forming the required metal grid.

In another aspect, the present invention also provides a metal grid touch sensor, the metal grid of which is formed by the method of forming a metal grid as described above.

In conclusion, the photoresist protective material has excellent anti-adhesion property, can reduce the pollution to the surface of the photomask in the contact exposure process, and cannot generate adhesion to the photomask in the contact mask UV exposure process; in the process of exposure after coating, the curing effect of the UV light curing layer is not influenced by the introduced particles.

Examples

Example 1

Preparation of protective Material with 3 wt% Aquaflon DF: weighing 75 wt% of pure water and 15 wt% of polyvinyl alcohol, mixing and dispersing uniformly, then adding 3 wt% of PTFE particle Aquaflon DF, 1 wt% of defoaming agent Agitan 290, 2 wt% of surfactant Dowfax 2A1 and 4 wt% of leveling agent Surfadone^TMLP-100 is mixed and stirred for 1 hour to obtain the photoresist protective material.

Coating a negative photoresist coating containing Irgacure 907 on one surface of a flexible substrate by using a coating wire rod, and then drying the coating in an oven at the temperature of 70 ℃ for 120 seconds to obtain a coating with the thickness of 800 nm; coating a palladium nanoparticle catalyst coating on the top of the photoresist film, then coating a photoresist protective material prepared as above to protect the two coatings, and then exposing by using ultraviolet light with a peak wave of 314 nm; after exposure, the substrate is washed by alkaline developing solution to remove the water-soluble protective coating and the uncured negative photoresist coating, the obtained sample is immersed in chemical copper plating solution to grow copper grids, and the palladium-containing nanoparticle catalyst plays a role in catalyzing copper plating reaction in the process.

Example 2

Copper plating was performed in a similar manner to example 1, except that the photoresist protective material was prepared as 1 wt% AquaFLON 50: 77 wt% of pure water and 15 wt% of polyvinyl alcohol are weighed, mixed and dispersed evenly, and then 1 wt% of PTFE particles Aquaflon 50, 1 wt% of defoaming agent Agitan 290, 2 wt% of surfactant Dowfax 2A1 and 4 wt% of leveling agent Surfadone are added^TMLP-100 is mixed and stirred for 1 hour to obtain the photoresist protective material.

Example 3

Copper plating was performed in a similar manner to example 1, except that the photoresist protective material was prepared as 2 wt% AquaFLON 50: weighing76 wt% of pure water and 15 wt% of polyvinyl alcohol are mixed and dispersed evenly, then 2 wt% of PTFE particles Aquaflon 50, 1 wt% of defoaming agent Agitan 290, 2 wt% of surfactant Dowfax 2A1 and 4 wt% of leveling agent Surfadone are added^TMLP-100 is mixed and stirred for 1 hour to obtain the photoresist protective material.

Example 4

Copper plating was performed in a similar manner to example 1, except that the photoresist protective material was prepared as 1 wt% AquaFLON DF +1 wt% AquaFLON 50: weighing 76 wt% of pure water and 15 wt% of polyvinyl alcohol, mixing and dispersing uniformly, then adding 1 wt% of PTFE particle Aquaflon DF, 1 wt% of PTFE particle Aquaflon 50, 1 wt% of defoaming agent Agitan 290, 2 wt% of surfactant Dowfax 2A1 and 4 wt% of leveling agent Surfadone^TMLP-100 is mixed and stirred for 1 hour to obtain the photoresist protective material.

Comparative example 1

Copper plating was performed in a similar manner to example 1, except that the photoresist protective material contained highly chemically inert transparent polymer particles.

Test example 1

The single-coated samples of examples 1 to 5 and comparative example 1 obtained according to the test as above were cut to a size of 5 inches, and then the samples were placed on a 5-inch reticle exposure jig, evacuated for 30 seconds and exposed. And after exposure is finished, closing the vacuum pump, opening the back surface of the jig, observing and calculating the adhering area of the coating surface and the photomask, tearing off the sample, observing whether foreign matters are left on the surface of the photomask after the sample is separated from the photomask, and calculating the residual area. The sticking and the residue on the mask surface after separation of the coated samples are shown in Table 1 below.

TABLE 1

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.