TWI492998B - A method for using protective film compound in etching process - Google Patents

Description

Method for using protective film composition in etching process

The present invention relates to a method of using a protective film composition in an etching process, and more particularly to an anti-corrosion protective film composition.

With the rapid development of the electronics industry, the manufacture of electronic products has gradually entered a trend of high performance. At present, the glass used on the touch panel is cut and polished, and defects are generated on the edge of the glass. Therefore, the edge of the glass is etched with hydrofluoric acid to level the edge of the glass to achieve the effect of strengthening the glass (such as Taiwan Patent No. 201121911, Japanese Patent Laid-Open No. 2011-231010, or US Patent No. 2012/0083401.

Furthermore, before the etching process, the portion of the glass that is not to be etched is covered with an anti-etching ink layer for protection, and after the etching process, the ink layer is removed by a stripping ink or a solvent (No. 20110092670) Korean Patent or Korean Patent No. 20110086475). However, in the process of stripping the ink, it is easy to cause corrosion of the surface of the glass due to alkali or solvent, resulting in a decrease in yield.

In another conventional etching process, a protective film is adhered to the portion of the glass that does not need to be etched, and after the etching process, the protective film is removed. However, it is necessary to use a filming device for the bonding operation to avoid air bubbles, so that the filming device needs to be purchased, thereby increasing the process cost, and the protective film is composed of a protective film, a layer of adhesive and a release film (or paper). The three-layer structure, so the material cost is higher than the ink, thus increasing the process cost. In addition, for different shapes and sizes of glass, the protective film needs to be cut, thereby increasing the process cost.

Therefore, 遂 developed a method of using coating printing liquid protective glue In order to form the required shape and size, the cutting operation is omitted, so that the process can be simplified to reduce the process cost. The main component of the liquid protective glue is a polyvinyl chloride resin or an acrylic resin, so as to withstand the external force of the glass cutting and polishing process to protect the glass from collision damage, but the material is not resistant to the etching of hydrofluoric acid. After the hydrofluoric acid etching process, the protective adhesive is easily peeled off, causing the glass to be eroded.

Therefore, how to overcome the various problems of the above-mentioned prior art has become a problem that is currently being solved.

In view of the above-mentioned various deficiencies of the prior art, the present invention provides a method for using a protective film formed by colloidal curing in an etching process, so as to protect a substance covering the protective film from hydrofluoric acid during the etching process. erosion.

The method for using the protective film composition in the etching process of the present invention comprises: dispersing the protective film composition in a printed manner on the surface of the object to be subjected to the etching process, wherein the protective film composition comprises an ultraviolet curing resin, a photosensitive oligomer (oligomer) and a reactive monomer; a fluorinated resin, wherein the fluorinated resin is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the ultraviolet curable resin; and a photoinitiator Wherein the photoinitiator is in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the ultraviolet curable resin; curing the protective film composition to form a protective film; and subjecting the article to the etching process .

The method of using the protective film composition in the etching process of the present invention achieves the purpose of resisting hydrofluoric acidity by curing the fluorinated resin. Furthermore, the method of using the protective film composition in the etching process of the present invention is for protecting a panel. However, it is not limited to the plane, but also protects the surface of the irregular shape. Further, the protective film composition can be applied to panels of various materials, such as a touch panel, and is not particularly limited.

The protective film composition has an overall viscosity of 500 to 100,000 cps, preferably 10,000 to 80,000 cps, more preferably 20,000 to 50,000 cps. If the overall viscosity of the protective film composition is too high, it may cause difficulty in coating and printing on the surface, such as the conductive film of the touch panel or the surface of the conductive glass; if the overall viscosity of the protective film composition is too low, the flow is likely to be caused. gum.

In the ultraviolet curable resin, the photosensitive oligomer may be an oligomer containing an unsaturated double bond, for example, may be selected from a urethane (meth) acrylate oligomer, epoxy ( Methyl) acrylate oligomer, pure (meth) acrylate oligomer, amino (meth) acrylate oligomer, organic fluorene (meth) acrylate oligomer, and polyester (methyl) At least one of the acrylate oligomers, the photosensitive oligomer may comprise a single oligomer composition or two or more oligomers, and the type of the oligomer component is not limited.

The reactive single system contains an unsaturated double bond and, depending on the functional group, produces a monofunctional reactive monomer and a polyfunctional reactive monomer. Wherein the monofunctional reactive single system is, for example, lauryl acrylate, stearyl acrylate or benzyl acrylate; the polyfunctional reactive single system For example, ethylene glycol dimethacrylate, ethoxylated bisphenol-A diacrylate, 1,4-butanediol diacrylate Propoxyglycerol triacrylate (propoxylated glyceryl triacrylate), pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate or dipentaerytjritol hexaacrylate. Further, the above various monomers may be used singly or in combination of two or more.

The fluorinated resin is obtained by polymerizing a fluorinated structural monomer, and the material thereof is a single type of monomer polymerization or at least two kinds of monomers, and the material type thereof is, for example, tetrafluoroethylene (tetrafluoroethylene). Ethylene), vinylidene fluoride, hexafluoropropylene, and perfluoromethyl vinylether, and the polymerization method may be emulsion polymerization or overall polymerization.

Further, the fluorinated resin is a powder having a particle diameter of 0.1 um to 100 um. If the particle diameter is less than 0.1 um, the oil absorption amount is high and workability is poor; if the particle diameter is larger than 100 um, the surface of the printed film formation is too rough. Further, the source of the fluorinated resin powder (finished product) is, for example, DU PONT Zonyl ^® MP-1200, MP1300 series PTFE POWDER, Minnesota Mining (3M) Dyneon TF9207, TF9205 series PTFE POWDER, or KITAMURA KTL -4N and KTL-8N PTFE POWDER.

Further, the content of the fluorinated resin is preferably from 10 to 150 parts by weight based on 100 parts by weight of the ultraviolet curable resin. If the content of the fluorinated resin is too high, the fluorinated resin is easily dispersed unevenly, and the film surface is pinhole, and the viscosity is high, resulting in poor workability; if the content of the fluorinated resin is too If it is low, the anti-hydrofluoric acidity of the protective film is not good, and the desired effect cannot be achieved.

The photoinitiator is a photopolymerization initiator which generates a radical by ultraviolet irradiation, for example, chloroacetophenone, a-amino acetophenone, and diphenylene. Benzoatephenone, methyl-2-benzoyl benzoate, benzyl dimethyl ketal, hydroxyl acetophenone, diethoxybenzene Diethoxy acetophenone, thioxanthone and benzyl dimethyl ketal or benzoin ether.

In addition, the content of the photoinitiator is preferably controlled within a range in which the protective film can maintain a curing rate and a strength, and therefore, the photoinitiator is 100 parts by weight relative to the ultraviolet curable resin. The content is preferably from 1 to 10 parts by weight, more preferably from 2 to 8 parts by weight.

The other embodiments of the present invention will be readily understood by those skilled in the art from this disclosure. It is to be understood that the structure, the proportions, the size, and the like of the present invention are intended to be used in conjunction with the disclosure of the specification, and are not intended to limit the invention. The conditions are limited, so it is not technically meaningful. Any modification of the structure, change of the proportional relationship or adjustment of the size should not fall under the influence of the invention and the purpose that can be achieved. It is within the scope of the technical contents disclosed in the present invention.

The method for preparing the protective film composition of the present invention is to first mix and mix the components, or grind and mix them into a gel, and then uniformly disperse them on the surface to be protected (such as a touch panel) by printing, and after solidifying into a film, The desired protective film can be obtained. Here, the printing method is, for example, screen printing, roller coating, spray coating, transfer printing, or impregnation coating, but is not limited thereto.

Further, the protective film composition of the present invention is formed on the surface to be protected to have a thickness of 5 to 200 μm, preferably 15 to 120 μm, more preferably 30 to 80 μm. If the film thickness is too thin, the film formation is resistant to hydrogen fluoride, and the effect of protection and direct stripping cannot be achieved; if the film thickness is too thick, it is not economical.

Further, the curing process causes the protective film composition to be cured by ultraviolet light to form a film.

In addition, after the surface to be protected is subjected to an etching process, if the cured protective film is to be removed, the protective film may be peeled off with a tape, without leaving the resin on the surface to be protected; or may be left on the surface to be protected. And don't have to tear it up.

Please refer to Table 1 for the examples and comparative examples of the materials. The examples are shown in "real" and the comparative examples are shown as "ratio".

In Table 1:

The photosensitive oligomer 1 is an aliphatic urethane (meth) acrylate (6131 from Changxing Chemical).

The photosensitive oligomer 2 is a urethane (meth) acrylate (Doublemer 850, derived from double bond chemistry).

Photosensitive oligomer 3 is epoxy (meth) acrylate (6233 from Changxing Chemical).

The reactive monomer 1 is a stearyl acrylate.

The reactive monomer 2 is ethylene glycol dimethacrylate.

The reactive monomer 3 is pentaerythritol triacrylate.

The fluorinated resin powder 1 is MP-1200 (from DuPont).

Fluorinated resin powder 2 is TF9205 (from Minnesota Mining).

In this experiment, the photoinitiator used was benzoatephenone.

Please refer to Table 2 for the evaluation test of film formation. Among them, the film thickness in the test state is 70 to 80 um, and the environmental drying condition is 1000 mj/cm ² . The test items are as follows:

Anti-hydrofluoric acid: The touch panel coated with the protective film is immersed in a solution of hydrofluoric acid concentration of 10% (wt%) for 1 hour at room temperature (15 to 30 ° C), if the protective film does not fall off, and The side etching depth is less than 300 um, which is good, and is indicated by "○". If the protective film is peeled off and the side etching depth is more than 300 um, it is bad, and it is represented by "x". Among them, the type of inspection instrument used is: Golden Image Microscope HM-2000; its magnification is 100 times.

Adhesion: The tensile force (g/cm) of the protective film peeled off from the conductive film of the touch panel.

Tear strength: The tensile force value (g/cm) at which the protective film was torn was tested. Among them, the manufacturer of the test rally scale used is: the large field meter manufacturer.

As shown in Fig. 1, it is a schematic diagram of steps (a) to (e) of the adhesion and tear strength test. The protective film 1 is elongated as shown in steps (a) to (c); when pulled to the limit, the protective film 1 is broken as shown in steps (d) to (e). Here, the size of the protective film 1 for testing is not limited to that shown in the step (a).

It can be seen from Table 2 that Examples 1 to 5 are added with a fluorinated resin, so the protective film will not corrode and degrade under the hydrofluoric acid etching test, and the side etching depth will not exceed 300 um, so the conductive film under the protective film (or glass) will not be eroded.

On the other hand, in Comparative Examples 1 to 3, the fluorinated resin was not added, so that the protective film was peeled off due to corrosion deterioration by the hydrofluoric acid etching test, and the conductive film (or glass) under the protective film was eroded.

In addition, in the protective film composition of the present invention, an additive such as an adhesion promoter, a rocking agent, a heat stabilizer, a filler, a pigment or a dye may be appropriately added, and the content of the additive may be adjusted according to the characteristic requirements, and Special restrictions.

The above embodiments are intended to illustrate the principles of the invention and its effects, and are not intended to limit the invention. Any of the above-described embodiments may be modified by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention should be as set forth in the appended claims.

1‧‧‧Protective film

Figure 1 is a diagram showing the adhesion and tear of the protective film composition of the present invention. A schematic diagram of steps (a) to (e) of the degree test.

1‧‧‧Protective film

Claims (14)

A method for using a protective film composition in an etching process, comprising: dispersing a protective film composition on a surface of an object to be subjected to an etching process, wherein the protective film composition comprises an ultraviolet curing resin, and comprises a photosensitive film And a reactive monomer; a fluorinated resin, wherein the fluorinated resin is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the ultraviolet curable resin; and a photoinitiator, wherein The photoinitiator is contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the ultraviolet curable resin; the protective film composition is cured to form a protective film; and the article is subjected to the etching process. The method for using a protective film composition in an etching process according to the first aspect of the invention, wherein the photosensitive oligomer is selected from the group consisting of a urethane (meth) acrylate oligomer and an epoxy (meth) acrylate. Ester oligomer, pure (meth) acrylate oligomer, amino (meth) acrylate oligomer, organic fluorene (meth) acrylate oligomer and polyester (meth) acrylate oligomer At least one of the group of objects. The method for using a protective film composition in an etching process according to claim 1, wherein the reactive single system is selected from the group consisting of a monofunctional reactive monomer and a polyfunctional reactive monomer. At least one of them. The method for using a protective film composition in an etching process according to the first aspect of the invention, wherein the fluorinated resin is obtained by polymerizing a fluorine-containing structural monomer. The method for using the protective film composition in the etching process according to claim 1, wherein the material of the fluorinated resin is a single type of monomer polymerization or a copolymerization of at least two types of monomers. A method of using a protective film composition in an etching process as described in claim 1, wherein the fluorinated resin is a powder. The method for using a protective film composition in an etching process as described in claim 6, wherein the powder has a particle size ranging from 0.1 um to 100 um. The method for using a protective film composition in an etching process according to the first aspect of the invention, wherein the photoinitiator is a photopolymerization initiator which generates a radical by ultraviolet irradiation. The method for using the protective film composition in the etching process as described in claim 1 is further included in the etching process, and the protective film is peeled off by using a tape. The method of using a protective film composition in an etching process as described in claim 1, wherein the etching process comprises etching using hydrofluoric acid. The method of using a protective film composition in an etching process as described in claim 1, wherein the printing method is screen printing, roller coating, spray coating, transfer printing or impregnation coating. The method of using a protective film composition in an etching process as described in claim 1, wherein the surface of the object touches a surface of the conductive film of the panel or a surface of the conductive glass. The composition of the protective film in the etching process as described in the first application of the patent scope The method of using the object, wherein the curing is ultraviolet light irradiation. The method of using a protective film composition in an etching process according to the first aspect of the invention, wherein the protective film composition is formed on the surface of the article to have a thickness of 5 to 200 μm.