JP2000089456A - Corrosion-resistant resin composition, etching-resistant resin layer using the composition and production of shadow mask - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent distortion or twist in a metal thin plate during secondary etching with respect to a long-hole type (aperture grill type) shadow mask. SOLUTION: The corrosion-resistant resin compsn. is prepared from reactive unsatd. oligomers and monomers having acryloyl groups or methacryloyl groups in the molecular ends or side chains of the molecular structure, a photopolymn. initiator selected from benzoin alkylethers, benzophenones and acetophenones, and an ester plasticizer selected from trimellitic acids, adipic acid and maleic acid. The obtd. compsn. is applied and dried on the face of the metal thin plate 1 where a small aperture pattern 5 is formed after primary etching so as to form an etching-resistant resin layer 7, and then the metal plate is subjected to secondary etching and peeling treatment to obtain a shadow mask.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a shadow mask by a photo-etching method using a long strip-shaped metal thin plate, and more particularly, to a method for forming an etching-resistant resin layer used for manufacturing a shadow mask. The present invention relates to a resin composition and a method for producing a shadow mask.

[0002]

2. Description of the Related Art A general color display tube comprises an electron gun, a shadow mask, and phosphor screens of three colors of red, green and blue. The shadow mask is a thin iron-based material attached in front of the phosphor screen, and has a large number of regularly arranged holes through which electron beams pass. One hole corresponds to a set of three red, green, and blue phosphor dots, and plays a role of guiding three electron beams emitted from the electron gun to the respective phosphor dots.

In a general method of manufacturing a shadow mask, first, a photosensitive resin (photoresist) is applied to both surfaces of a thin metal plate made of iron or an iron alloy and dried to form a photosensitive layer. Next, an exposure mask having a predetermined light-shielding pattern (in many cases, two masks on the front and back sides) is aligned and brought into close contact with each other, pattern exposure is performed on the photosensitive layer with a predetermined exposure amount, and development and hardening are performed with a predetermined chemical solution. By performing a film treatment or the like, a resist pattern having a predetermined shape is formed on both surfaces of the metal thin plate.

Next, primary etching (half-etching) is performed on both surfaces of the metal sheet on which the resist pattern is formed using a ferric chloride solution or the like, and small holes and large holes of a predetermined shape are formed on both surfaces of the metal sheet. An opening pattern is formed.

[0005] Next, a predetermined resin solution is applied to one side of the metal sheet on which the small-hole opening pattern is formed by using a method such as roller coating, gravure coating, or spray coating, and dried to form an etching-resistant resin layer. I do.

Next, the large hole opening pattern on the other surface of the metal thin plate is subjected to secondary etching using a ferric chloride solution or the like until the metal thin plate penetrates to form a large hole opening pattern.

Next, the etching resistant resin layer and the resist pattern on the metal thin plate are peeled off using an alkaline aqueous solution to form a shadow mask having an opening pattern of a predetermined shape.

Here, for the purpose of improving the productivity, the etching time is shortened by increasing the specific gravity, the temperature, and the spray pressure of the secondary etching. At that time, especially in the case of the shadow mask of the long hole type (aperture grill type), the metal sheet becomes distorted or twisted during etching, and the slit pattern (blind pattern)
Deformation defects such as bending and bending occur, and in some cases, deterioration such as cracking and peeling occurs in the etching-resistant resin layer, and there is a problem that etching proceeds excessively and a predetermined hole size and shape cannot be obtained.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and has been described in connection with a shadow mask of an elongated hole type (aperture grill type). An object of the present invention is to provide a corrosion-resistant resin layer that does not cause corrosion, a corrosion-resistant resin composition forming the same, and a method of manufacturing a shadow mask using the same.

[0010]

In order to solve the above-mentioned problems in the present invention, first, in claim 1, a desired resist pattern is formed on both surfaces of a metal thin plate, and the metal thin plate is firstly formed from both surfaces. After etching (half-etching) to form a small hole opening pattern and a large hole opening pattern on both surfaces of the metal thin plate, an etching corrosion resistant resin layer is formed on one surface of the metal thin plate on the small hole opening pattern side, In the method for manufacturing a shadow mask, the second pattern of the large hole opening on the other surface of the thin metal plate is penetrated by secondary etching, and then the etching corrosion-resistant resin layer and the resist pattern are peeled off to produce a shadow mask. The corrosion-resistant resin composition forming the corrosion-resistant resin layer has an acryloyl group or a methacryloyl group at a terminal or a side chain in a molecular structure. Reactive unsaturated oligomers and monomers, benzoin alkyl ethers, photopolymerization initiators selected from the group consisting of benzophenones and acetophenones, and trimellitic acid, adipic acid and maleic acid selected from the group consisting of And an ester plasticizer.

According to a second aspect of the present invention, there is provided a corrosion-resistant resin composition having a viscosity at 25 ° C. of 5,000 cps or less.

According to a third aspect of the present invention, a corrosion-resistant resin layer is formed on the thin metal plate on the side of the small hole opening pattern using the corrosion-resistant resin composition according to the first or second aspect. It is a resin layer.

Further, in a fourth aspect of the present invention, there is provided a method of manufacturing a shadow mask, comprising forming the etching corrosion-resistant resin layer by using the corrosion-resistant resin composition according to the first or second aspect and performing secondary etching. It was done.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a corrosion-resistant resin composition forming an etching-corrosion-resistant resin layer in a shadow mask manufacturing process has an acryloyl group or a methacryloyl group at a terminal or a side chain in a molecular structure. Reactive unsaturated oligomers and monomers, benzoin alkyl ethers,
It is characterized by comprising a photopolymerization initiator selected from the group consisting of benzophenones and acetophenones, and an ester plasticizer selected from the group consisting of trimellitic acid, adipic acid and maleic acid.

The etching and corrosion resistant resin layer formed of the above corrosion resistant resin composition has a predetermined film strength, and has excellent properties of flexibility and flexibility (flexibility). In the case of an aperture grill type shadow mask, no distortion or twisting occurs in the metal sheet during secondary etching, the slit pattern is not deformed, and the etching time can be reduced and the quality of the shadow mask can be improved. It is.

Hereinafter, the corrosion resistant resin composition of the present invention will be described. First, a reactive unsaturated oligomer or monomer having an acryloyl group or a methacryloyl group at a terminal or a side chain in a molecular structure is used as a resin body. It is characterized in that the curing is hardly inhibited by oxygen and the curing speed by ultraviolet rays is high, and that the properties and physical properties of the cured product can be selected from a wide range by combining a large number of monomers and oligomers.

For example, polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligoacrylate, alkyd acrylate, polyol acrylate and the like are preferable.
Specific examples include polyether acrylate having etching resistance and curability, and polyol acrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, propylene glycol diacrylate, and neo Pentyl glycol acrylate, 1,4-butanediol acrylate, 1,6-
Hexanediol diacrylate, pentaerythritol diacrylate, trimethylpropane triacrylate and the like can be mentioned. In addition, in order to impart alkali releasability, phthalic acid containing a carboxyl group, adipic acid,
Polybasic acids such as maleic acid, itaconic acid, succinic acid and terephthalic acid, and ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, pentaerythritol ,
Polyester acrylate combined with a polyhydric alcohol such as dipentaerythritol and the like can be mentioned.

In order to increase the etching resistance of the corrosion-resistant resin layer, there is a method of increasing the molecular weight of the resin of the corrosion-resistant resin composition or increasing the density of cross-linking between the resin molecules. In that case, the viscosity of the corrosion-resistant resin composition at 25 ° C. is 5000 cp at 25 ° C. in view of suitability for coating when forming the etching corrosion-resistant resin layer because the molecular weight is large and the viscosity is easily increased.
It is preferably at most s. Further, the glass transition temperature (Tg) may be at least the temperature of the etchant used in the etching step, and is particularly preferably at least 60 ° C.

Next, the action of the photopolymerization initiator is that when it is irradiated with ultraviolet rays, electron beams, or the like, it is excited to generate radicals, which excite the double bonds of the reactive unsaturated oligomers and monomers, and radical polymerization proceeds. The chains grow one after another, and a resin coating having a three-dimensional network structure is obtained. As the photopolymerization initiator, benzoin alkyl ethers, benzophenones and acetophenones are preferable, and examples thereof include 2,2-dimethoxy-1,2-diphenylethanone and 1-hydroxycyclohexylphenyl ketone. The photopolymerization initiator is preferably used in an amount of 1 to 10% by weight of the total amount of the entirety.

Here, in particular, in the case of a long hole type (aperture grill type) shadow mask, a distortion or a twisting phenomenon was observed in the metal thin plate at the time of the second etching, and a deformation defect of the slit pattern occurred. This is because the etching and corrosion resistant resin is hard and brittle, and has low flexibility (flexibility), and is considered to have insufficient physical strength with respect to the etching solution.

It is known that the acrylic resin has a large volume shrinkage after curing, about 17 to 18% for ethyl methacrylate and about 20 to 21% for methyl methacrylate. After forming the coating film, it exists as a residual stress while accumulating internal stress, and the thermal and mechanical stresses of the subsequent etching solution etc. are repeatedly applied, the residual stress increases and exceeds the cohesive force of the coating film When this occurs, cracks occur, causing phenomena such as peeling and warping. It was concluded that it is possible to reduce the shrinkage strain by adding a plasticizer as a method of alleviating the shrinkage strain.

The addition of a plasticizer to the corrosion-resistant resin composition has the effect of penetrating into the molecules of the etching-corrosion-resistant resin layer and weakening van der Waals bonds that cause the hard network structure of the resin. It is believed that hard and flexible coating properties are obtained over a range. Also,
The addition of the plasticizer also improves the etching resistance, probably because the crosslinkability is increased at the same time. However, if a plasticizer with a low plasticizing efficiency is used, the solidification point will be reached earlier and the shrinkage strain will be excessively large, resulting in a bad result. There is.

Among them, it is effective to use trimellitic acid-based, adipic acid-based and maleic acid-based ester plasticizers, and the trimellitic acid ester plasticizer has the highest plasticizing effect. is there. As a specific ingredient,
Tributyl trimellitate (TBTM), tri-n-
Hexyl trimellitate (NHTM), tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate (TnOTM), tri-isooctyl trimellitate (TIOTM), tri-isodecyl trimellitate (TIDTM), Tori Alphano
lC _7-9 trimellitate, birds · AlfolC _6-10 trimellitate, and the like. Plasticizer is 1 to 1
5% by weight is preferred. At 5% by weight or more, Tg decreases,
Physical properties such as etching resistance were adversely affected, which was not preferable.

In order to prepare a corrosion resistant resin composition from the above resin, photopolymerization initiator and plasticizer, the reactive unsaturated oligomer or monomer having the acryloyl group or methacryloyl group, benzoin alkyl ethers, benzophenones And a photopolymerization initiator selected from the group consisting of acetophenones and trimellitic acid, adipic acid and an ester plasticizer selected from the group consisting of maleic acid under a constant heating, bulk polymerization and It may be mixed by a method such as solution polymerization or suspension polymerization.

Further, the viscosity of the corrosion-resistant resin composition at 25 ° C. is determined to be 5,000 cp from the suitability for coating and the coating property after coating.
It is preferably at most s.

Hereinafter, a method of manufacturing a shadow mask by forming an etching and corrosion resistant resin layer using the above-described corrosion resistant resin composition to form a shadow mask will be described with reference to FIG. First, a long strip-shaped metal sheet 1 made of iron or iron alloy
A photosensitive resin solution containing polyvinyl alcohol, casein or the like as a main component is applied to both surfaces and dried to form a photosensitive layer 2 (see FIG. 1A).

Next, an exposure mask having a predetermined light-shielding pattern is positioned on the photosensitive layers 2 on both surfaces of the metal thin plate 1 and pattern exposure is performed in close contact therewith. Next, develop with a predetermined chemical solution,
After hardening, resist patterns 2a and 2b having a small hole pattern 3 and a large hole pattern 4 on both surfaces of the metal sheet 1
Is formed (see FIG. 1B).

Next, primary etching (half-etching) is performed on both surfaces of the metal sheet 1 on which the resist patterns 2a and 2b are formed using an etching solution composed of ferric chloride.
To form a small hole opening pattern 5 and a large hole opening pattern 6 on both surfaces of the metal thin plate 1 (see FIG. 1C).

Next, a resin solution comprising the above-described corrosion-resistant resin composition is applied by a method such as roller coating or spray coating, and then dried and cured to form an etching-resistant corrosion-resistant resin layer 7 on the small hole opening pattern 5 side of the thin metal plate 1. It is formed (see FIG. 1D).

Next, the large hole opening pattern 6a on the other surface of the metal thin plate 1 is subjected to secondary etching using an etching solution made of ferric chloride until the metal thin plate 1 penetrates. Is formed (see FIG. 1E).

Next, the etching and corrosion-resistant resin layer 7 and the resist patterns 2a and 2b are stripped using an alkali stripping agent to form a shadow mask in which the small-hole opening pattern 5 and the large-hole opening pattern 6a are formed on the thin metal plate 1. (See FIG. 1 (f)).

Here, when the etching and corrosion resistant resin layer 7 formed of the above corrosion resistant resin composition is used, the etching resistance is improved as compared with the conventional one, and a material having excellent flexibility (flexibility) is obtained. It is possible to set etching conditions (higher specific gravity, higher temperature, higher spray pressure, etc. of the etching solution) for time etching, and productivity and workability are greatly improved.

[0033]

The present invention will be described below in detail with reference to examples.

First, a photosensitive resin solution containing polyvinyl alcohol and ammonium dichromate was coated on both surfaces of a thin metal plate 1 made of an Fe—Ni alloy having a thickness of 0.1 mm to form a photosensitive layer 2.

Next, the photosensitive layer 2 is exposed in close contact with an exposure mask having a predetermined pattern, developed and hardened, and a resist pattern 2a having a small hole pattern 3 and a large hole pattern 4 on both sides of the thin metal plate 1 is formed. 2b was formed.

Next, the resist pattern 2a and 2b spray etching (1 at a pressure of 3 kg / cm ² by using an etching solution composed of heated ferric chloride from both surfaces of the metal thin plate 1 formed 60 ° C. Next Etching) was performed to form a small hole opening pattern 5 and a large hole opening pattern 6 on both surfaces of the metal thin plate 1.

Next, the following corrosion-resistant resin composition A was applied to the small hole opening pattern 5 side of the thin metal plate 1 by using a roll coater, dried and cured to form an etched corrosion-resistant resin layer 7 having a thickness of 30 μm.

Composition of Corrosion Resistant Resin Composition A Polypropylene glycol diacrylate 40% by weight Pentaerythritol triacrylate 25% by weight Tetrahydrophthalic acid-1 6-hexanediol acrylate 30% by weight 1-hydroxycyclohexyl phenyl ketone 3% by weight tri-2-ethylhexyl trimellitate 2% by weight

[0039] Next, the spray etching (second etching) at a pressure of 3 kg / cm ² by using an etching solution comprising ferric chloride which is heated from the large hole opening pattern 6 side 60 ° C. of the sheet metal 1 The large hole opening pattern 6a was formed.

Next, the etching corrosion-resistant resin layer 7 and the resist patterns 2a and 2b are peeled off using an alkaline aqueous solution to produce a shadow mask in which the small hole opening pattern 5 and the large hole opening pattern 6a are formed on the metal sheet 1. did.

<Comparative Example> In the same process as in the embodiment, resist patterns 2a and 2b having a small hole pattern 3 and a large hole pattern 4 are formed on both surfaces of the thin metal plate 1, and primary etching is performed to perform opening of the small hole. The pattern 5, the large hole opening pattern 6, and the resist patterns 2a and 2b were formed.

Next, the following corrosion-resistant resin composition B was applied to the small hole opening pattern 5 side of the metal thin plate 1 using a roll coater, dried and cured to form an etched corrosion-resistant resin layer 7 having a thickness of 30 μm.

Composition of Corrosion Resistant Resin Composition B Polypropylene Glycol Diacrylate 42% by weight Pentaerythritol triacrylate 25% by weight Tetrahydrophthalic acid-1 6 hexanediol acrylate 30% by weight 1-hydroxycyclohexyl phenyl ketone 3% by weight

Next, secondary etching was performed in the same steps as in the example, and a release treatment was performed using an alkali release agent to produce a shadow mask.

The following evaluations were performed on the etched corrosion-resistant resin layers and shadow masks obtained in the above Examples and Comparative Examples. Adhesion test: A sample in the process of forming the etching and corrosion resistant resin layer obtained in Examples and Comparative Examples was immersed in an etching solution comprising a ferric chloride solution at 70 ° C. for 20 minutes. A 1 mm square block, a total of 100 pieces, was cross-cut with a knife, and then the particles were peeled off with an adhesive tape, and the number of blocks of the etched corrosion-resistant resin layer was visually observed and observed with an optical microscope to check the adhesion. . 90 ° bending test: A sample in the process of forming the etching and corrosion resistant resin layers obtained in Examples and Comparative Examples was immersed in an etching solution composed of a ferric chloride solution at 70 ° C. for 20 minutes, and then bent at 90 ° to perform etching and corrosion resistance. The number of cracks generated on the surface of the resin layer was observed with an optical microscope to examine the flexibility. Shadow mask evaluation: Observing the long hole type shadow masks obtained in the examples and comparative examples visually and with an optical microscope to determine whether there is any alkali corrosion or discoloration, based on the appearance inspection specification, and determine whether the product is good or defective. Judged. Table 1 shows the results of the evaluation.

[0046]

[Table 1]

As can be seen from the results shown in Table 1, the etched corrosion-resistant resin layer of the embodiment formed of the corrosion-resistant resin composition A of the present invention has a predetermined film strength, flexibility and flexibility (flexibility). When a shadow mask is made,
As a result, a shadow mask having improved etching resistance and free from defective hole diameter and hole shape was obtained.

[0048]

According to the present invention, the corrosion-resistant resin composition of the present invention is used to form an etching-corrosion-resistant resin layer, and a shadow mask is manufactured. Also, cracks and peeling do not occur in the etching and corrosion resistant resin layer, so that more non-defective shadow masks can be obtained than in the past. Therefore, the etching time in the shadow mask manufacturing process can be shortened, the production stability can be measured, and the quality of the shadow mask can be improved, thereby exhibiting excellent practical effects.

[Brief description of the drawings]

1 (a) to 1 (f) are partial cross-sectional views showing the steps of manufacturing a shadow mask using an etching and corrosion resistant resin layer of the present invention in the order of steps.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Metal thin plate 2 ... Photosensitive layer 2a, 2b ... Resist pattern 3 ... Small hole pattern 4 ... Large hole pattern 5 ... Small hole opening pattern 6 ... Large hole opening pattern 6a ... After secondary etching Large hole opening pattern 7: Etching corrosion resistant resin layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 290/06 C08F 290/06 F term (Reference) 2H025 AA00 AB17 AC01 AD01 BC14 BC34 BC43 BC53 BJ06 CA02 CA03 CA04 CC05 DA18 DA20 EA04 FA07 FA40 FA48 2H096 AA27 BA05 CA12 EA02 HA13 HA17 JA01 4J011 QB03 QB13 QB16 QB24 SA01 SA21 SA31 TA05 TA10 VA01 WA01 WA02 4J027 AB03 AB06 AB08 AB10 AB15 AB17 AB18 AB19 AB23 AB24 AB25 AC03 BA04 BA06 A CB10 CC05 CC06 CD10

Claims (4)

[Claims] 1. A desired resist pattern is formed on both sides of a thin metal plate, and primary etching (half etching) is performed on both sides of the thin metal plate to form a small hole opening pattern and a large hole opening pattern on both surfaces of the thin metal plate. After the formation, an etching and corrosion resistant resin layer is formed on one surface of the thin metal plate on the side of the small hole opening pattern, and the large hole opening pattern on the other surface of the thin metal plate is secondarily etched and penetrated. A method of manufacturing a shadow mask, wherein an etching corrosion-resistant resin layer and the resist pattern are peeled to form a shadow mask, wherein the corrosion-resistant resin composition forming the etching corrosion-resistant resin layer has acryloyl at a terminal or a side chain in a molecular structure. Unsaturated oligomers and monomers having a methacryloyl group or a benzoin alkyl ether, A corrosion-resistant resin comprising a photopolymerization initiator selected from the group consisting of nonones and acetophenones, and an ester plasticizer selected from the group consisting of trimellitic acid, adipic acid, and maleic acid. Composition. 2. The corrosion-resistant resin composition according to claim 1, wherein the viscosity at 25 ° C. is 5000 cps or less. 3. An etching and corrosion resistant resin layer, wherein a corrosion resistant resin layer is formed on the thin metal plate on the side of the small hole opening pattern using the corrosion resistant resin composition according to claim 1. 4. A method of manufacturing a shadow mask, comprising forming the etching corrosion-resistant resin layer using the corrosion-resistant resin composition according to claim 1 and performing secondary etching.