TWI485524B - Photosensitive resin composition and use thereof - Google Patents

Description

Photosensitive resin composition and use thereof

The present invention relates to a photosensitive resin composition and use thereof, and more particularly to a photosensitive resin composition suitable for use in the touch panel industry and its use.

With the rapid development and application of semiconductor technology, in order to achieve portability, light weight and ease of operation, many electronic products have been converted from traditional keyboard or mouse input devices to touch panels. Input device.

The traditional add-on touch panel is designed as a two-layer structure of a protective glass and a touch-sensitive glass. In recent years, due to the demand for lightweight, manufacturers have begun to develop single-glass glass touch panels. In general, when manufacturing a single-glass (One Glass Solution, OGS) touch panel, the manufacturer usually sets the various sensing devices of the touch panel on the surface of a tempered glass master, and then cuts the stress. The method cuts the tempered glass master into the size required for the device for the back end process. However, the edge of the glass cut in this way will have weak stress Like, it is vulnerable to external forces and broken. Although this problem can be improved by using a laser cutting method, the manufacturing cost is too high and it is not advantageous for mass production. Therefore, there is a need to provide a low-cost process for cutting the touch panel glass, and the glass after the cutting does not have the problem of weakening the stress.

The main object of the present invention is to achieve a low-cost mass-free edge-free stress in a touch panel process by applying a novel negative photosensitive resin composition which is resistant to hydrofluoric acid etching and easy to strip. The purpose of the touch panel glass to weaken the problem.

In order to achieve the above object, an aspect of the present invention provides a photosensitive resin composition comprising: (A) 30% by weight to 50% by weight of an alkali-soluble resin; (B) 10% by weight to 20% by weight of a single (C) 5 to 15 weight percent of the photopolymerization initiator; (D) 2 to 5 weight percent of the polyfunctional mercapto compound, which may be a chain compound or a cyclic compound, and The polyfunctional mercapto compound comprises at least 2 mercaptopropionate groups; (E) from 2 weight percent to 10 weight percent of the decane compound; and (F) the balance solvent.

In the photosensitive resin composition of the present invention, any kind of polyfunctional mercapto compound can be used as long as the adhesion of the photosensitive resin composition can be reduced while ensuring its resistance to hydrofluoric acid etching. Special restrictions. For example, in one aspect of the present invention, the mercaptopropionate group contained in the polyfunctional mercapto compound may be substituted or unsubstituted with at least one substituent, and the substituent may be a C _1-4 alkane. base. In detail, in one embodiment of the present invention, the mercaptopropionate group contained in the polyfunctional mercapto compound may be a 3-mercaptopropionate group. Further, more specifically, the polyfunctional mercapto compound may contain 3 to 6 mercaptopropionate groups. However, the invention is not limited to this.

In the above photosensitive resin composition of the present invention, specific examples of the polyfunctional mercapto compound may include, but are not limited to, trimethylolpropane tris (3-mercaptopropionate), TMMP, formula 1), pentaerythritol tetrakis (3-mercaptopropionate), PEMP, formula 2), dipentaerythritol hexakis (3-mercaptopropionate) , DPMP, formula 3), 3-mercaptopropionic acid-[2,4,6-trioxo-1,3,5-triazine-1,3,5(2H,4H,6H)-subunit] -2,1-ethylene glycol ester (tris(thiopropionoylethyl)isocyanurate, TEMPIC, formula 4), pentaerythritol tetrakis (3-mercaptobutylate, PE 1, formula 5), ethoxylate Pentaerythritol tetrakis(3-mercaptopropionate) (formula 6), ethoxytrimethylolpropane tris(3-mercaptopropionate) (formula 7), pentaerythritol bis(3-mercaptopropionate) di(2) - mercaptoacetate) (Formula 8) or a combination thereof.

Equation 2

In the photosensitive resin composition of the present invention, the alkali-soluble resin may be an alkali-soluble acrylic resin. In detail, in one aspect of the present invention, the alkali-soluble acrylic resin may include an acrylic resin, an acrylic-epoxy resin, an acrylic-styrene resin, an acrylic-melamine resin, or a combination thereof.

In the above photosensitive resin composition of the present invention, the monomer may be a polyfunctional acrylate monomer. For example, the monomer can include At least two acrylates; preferably, the monomer may include from 2 to 6 acrylates; preferably, the monomer may also include from 2 to 4 acrylates, but the invention is not limited thereto. In detail, the polyfunctional acrylate monomer may be a water-insoluble monomer, a water-soluble monomer, or a combination thereof. For example, examples of the water-insoluble monomer may include, but are not limited to, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethyl ether propane trimethacrylate (trimethylolpropane trimethacrylate), tris(2-hydroxyethyl)isocyanurate triacrylate, di-trimethylolpropane tetraacrylate, pentaacrylate ester ), pentaerythritol tetraacrylate, dihexaerythritol hexaacrylate, dipentaerythritol hexaacrylate; examples of the water-soluble monomer may include, but are not limited to: Polyoxyethylene monomer: 2 (2-ethoxyethoxy)ethyl acrylate, 15 ethoxylated (15) trimethylolpropane triacrylate, 30 ethoxylated (30) bisphenol A diacrylate, 20 polyoxyethylene Ethoxylated (20) trimethylolpropane triacrylate, methoxypolyethylene glycol (350) monomethacrylate, methoxypolyethylene glycol (550) monoacrylate (methoxypolyethylene glycol (550) monomethacrylate), polyethylene glycol (200) diacrylate (polyethylene glycol (200) diacrylate), poly Polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, polypropylene glycol monomethacrylate . However, it should be understood that the above-exemplified monomer examples are for illustrative purposes only and the invention is not limited thereto.

In the above-mentioned photosensitive resin composition of the present invention, any conventional photopolymerization initiator can be used as long as it can be used to induce photopolymerization, and the present invention is not limited thereto. For example, in one aspect of the invention, the photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a diimidazole-based compound, an anthraquinone-based compound, or a combination thereof. Further, the photopolymerization initiator may be selected from any of the conventional commercially available products or combinations thereof, such as Irgacure ^® 149, Irgacure ^® 184, Irgacure ^® 369, Irgacure ^® 500, Irgacure ^® 651 manufactured by Ciba Specialty Chemicals. Irgacure ^® 784, Irgacure ^® 819, Irgacure ^® 907, Irgacure ^® 1700, Irgacure ^® 1800, Irgacure ^® 1850, Irgacure ^® 2959, Darocur ^® 1173, or Darocur ^® 4265, or Lucirin ^® TPO manufactured by Basf, but the invention is not only Limited to this.

In the photosensitive resin composition of the present invention, any type of solvent can be used as long as the composition of the photosensitive resin composition of the present invention can be appropriately dispersed and the desired effect can be attained, and the present invention is not particularly limited. Specifically, specific examples of the solvent which can be used as the photosensitive resin composition of the present invention include, but are not limited to, ethylene glycol propyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol methyl ether, and B. Glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether acetate, propylene glycol Ethyl acetate, propylene glycol propyl ether acetate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol propyl ether, 2-methoxy Ethyl acetate, ethyl 2-ethoxyacetate, methyl diethylene glycol acetate, ethyl diethylene glycol, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, methanol, ethanol, propanol, isopropanol, 2-methoxy Ethanol, 2-ethoxyethanol, diethylene glycol methyl ether, diethylene glycol diethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, or a combination thereof. However, it should be understood that the above-exemplified solvent examples are for illustrative purposes only, and the invention is not limited thereto.

In the photosensitive resin composition of the present invention, in order to improve the adhesion and hardness of the photosensitive resin composition to facilitate mass production process, the photosensitive resin composition of the present invention may include any type of decane compound. For example, in one aspect of the present invention, the decane compound may be an epoxy decane, but the invention is not limited thereto. Further, the decane compound may be selected from any of the conventional commercially available products or combinations thereof, such as Silquest Y-9936, Silquest A-1100, Silquest A-1101, Silquest A-1102, Silquest A- manufactured by Momentive. 1108, Silquest A-1110, Silquest A-1120, Silquest A-1122, Silquest A-1123, Silquest A-1126, Silquest A-1128, Silquest A-1130, Silquest A-1160, Silquest A-1170, Silquest A- 1230, Silquest A-137, Silquest A-162, Silquest A-174, Silquest A-186, Silquest A-187, Silquest A-189, Silquest A-1891, Silquest A-2120, Silquest FR-522, or Silquest FR -693, etc., but the invention is not limited herein.

Further, in the photosensitive resin composition of the present invention, the photosensitive resin composition may further comprise 0.1% by weight to 5% by weight of an adhesion promoter, thereby improving the adhesion of the photosensitive resin composition to glass. Further, the present invention does not particularly limit the kind of the adhesion promoter as long as the adhesion of the photosensitive resin composition of the present invention to glass can be improved. For example, in one aspect of the invention, the adhesion promoter can be melamine.

Further, in the photosensitive resin composition of the present invention, the photosensitive resin composition may be appropriately added with additives of other components without affecting the efficacy thereof depending on the needs of the actual application. For example, in one aspect of the present invention, the additive may be a colorant, a thermal crosslinking accelerator, a leveling agent, or a combination thereof, but the invention is not limited thereto.

According to the above, the photosensitive resin composition of the present invention can be used to prepare a photosensitive resin composition which is resistant to hydrofluoric acid etching and easy to remove.

Another object of the present invention is to provide a photosensitive resin composition which is resistant to hydrofluoric acid etching and easy to be peeled off through the photosensitive resin composition, and can be applied to a touch panel. In the glass cutting process.

In order to achieve the above object, another aspect of the present invention provides the use of the above photosensitive resin composition, which is used in a glass cutting process to form a photoresist having a cutting path. membrane. For example, the photosensitive resin composition can be applied to a touch A photoresist film having a cutting path is formed on the glass master of the panel by any conventional exposure and development process. Next, the glass master is immersed in a hydrofluoric acid solution so that hydrofluoric acid can cut the glass master along the cutting path. Finally, the photoresist film on the cut touch panel glass is stripped to complete the touch panel glass cutting process.

In the use of the photosensitive resin composition of the present invention described above, the photosensitive resin composition of the present invention has a reduced adhesion to a protective layer overcoat (OC) and a black photoresist (Black Matrix, BM). At the same time, it has the characteristics of resistance to hydrofluoric acid etching, and the photosensitive resin composition of the present invention is quite suitable for use in an element such as an inductive device for protecting a touch panel glass when the touch panel glass is cut with hydrofluoric acid.

Accordingly, by using the photosensitive resin composition prepared by the present invention to form a photoresist film having a cutting path on a touch panel glass master to be cut, mass production can be performed by low-cost hydrofluoric acid etching. A touch panel having the disadvantage of no edge stress weakening is prepared. In more detail, the photosensitive resin composition of the present invention is quite suitable for use in the manufacture of a single-glass type touch panel.

1‧‧‧Glass master

1'‧‧‧Touch glass

2‧‧‧Touch panel module

21‧‧‧Line area

22‧‧‧Black photoresist

3‧‧‧ photoresist layer

4‧‧‧ cutting path

1A to 1D are schematic views showing the flow of a process for cutting a glass master of a touch panel according to Embodiment 10 of the present invention.

Preparation example

Take 2,2'-azobisisoheptanenitrile (2,2'-Azobis-2,4-dimethylvaleronitrile, ADVN) 1.25 g, 20 g of methacrylic acid, 65 g of methyl methacrylate, and 2-ethyl 10 g of hexyl acrylate was slowly stirred in 144 g of propylene glycol methyl ether acetate, and a polymerization reaction was carried out at 75 ° C under a nitrogen atmosphere. After 4 hours, the above reaction was cooled to room temperature. The acrylic resin was confirmed by gel permeation chromatography to have a weight average molecular weight of about 30,000.

Examples 1 to 9

Please refer to Table 1 for the composition of the alkali-soluble resin, monomer, photopolymerization initiator, polyfunctional sulfhydryl compound, adhesion promoter, decane compound, leveling agent, colorant, and solvent according to Table 1. The formulation is prepared as the photosensitive resin composition of Examples 1 to 9, wherein the alkali-soluble resin used is the alkali-soluble acrylic resin prepared in the above Preparation Example, and the monomer is M-510 (manufactured by Toagosei Co., Ltd.). The photopolymerization initiators are Irgacure ^® 184 (manufactured by Ciba Specialty Chemicals) and Lucirin ^® TPO (manufactured by Basf), the adhesion promoter is melamine, and the decane compound is Silquest A-186 (CAS: 52682-88-9, manufactured by Momentive). The leveling agent is F-554 (manufactured by DIC), the coloring agent is Blue 7 (CAS: 2390-690-5), and the solvent is propylene glycol methyl ether acetate, and the polyfunctional fluorenyl compound used in each of the examples and the same The content is shown in Table 1.

Table 1

Comparative Examples 1 to 4

Referring to Table 2, the photosensitive resin compositions of Comparative Examples 1 to 4 were prepared in accordance with the composition formula shown in Table 2, substantially similar to the preparation method of the examples. As shown in Table 2, Comparative Example 1 differs mainly from the above-described Examples 1 to 9 in that no polyfunctional fluorenyl compound is used, and Comparative Example 2 differs mainly in the content of the polyfunctional fluorenyl compound, and Comparative Examples 3 and 4 The difference is that the linear thiol compound is used in place of the polyfunctional fluorenyl compound used in the examples.

Table 2

Test examples 1 to 13

First, a glass substrate was prepared and the surface of the glass substrate was cleaned with deionized water and acetone. Next, the photosensitive resin compositions prepared in the above Examples 1 to 9 and Comparative Examples 1 to 4 were uniformly applied onto the glass substrate by spin coating. Subsequently, the mixture was soft baked at 90 ° C for 10 minutes, and the photosensitive resin composition applied to the surface of the glass substrate was directly exposed with an ultrahigh pressure mercury lamp (exposure energy: 300 mJ/cm ² ) using a photomask. Next, development was carried out for 180 seconds with a 0.04% potassium hydroxide developer. Hard roasting was carried out for 30 minutes at 140 °C. Finally, the glass substrate and the photoresist layer were washed with secondary water at 25 ° C to obtain a desired sample.

<Corrosion resistance>

The samples prepared in the above Test Examples 1 to 13 were each immersed in 6% hydrofluoric acid for 4 hours for corrosion resistance test. The test results are shown in Table 3.

<stripping>

The samples prepared in the above Test Examples 1 to 13 were each immersed in a sodium hydroxide solution at 40 ° C for 10 minutes for peeling test. The test results are shown in Table 3.

<Storage Stability>

The samples prepared in the above Test Examples 1 to 13 were each stored at 25 ° C for 3 days. The criterion for storage stability is whether the sample forms a colloidal state after 3 days of storage, and if it is formed into a colloidal state, it is determined that it cannot be stored for 3 days. The test results are shown in Table 3.

As shown in Table 3, the polyfunctional mercapto compound contained in the photosensitive resin composition prepared by the composition of the present invention is a branched compound (such as Examples 1 to 6) or a cyclic compound (such as Examples 7 and 8). , the feeling of the invention The optical resin composition has excellent corrosion resistance, easy peelability, and storage stability. On the other hand, as a result of Comparative Example 1, when the photosensitive resin composition does not contain the polyfunctional fluorenyl compound, it is possible to maintain the resistance to hydrofluoric acid etching and storage stability, but it is difficult to form the photoresist layer from the glass. Strip on the substrate. As shown by the results of Comparative Example 2, when the content of the polyfunctional fluorenyl compound was higher than that of the present invention, although the peeling property was improved, the storage stability was lowered. Further, as shown by the results of Comparative Examples 3 and 4, although the linear mercapto compound which is used in place of the polyfunctional mercapto compound also contains a mercapto group, it is not easily peeled off from the glass substrate.

From the above results, it was found that the photosensitive resin compositions prepared in Examples 1 to 9 of the present invention did have excellent corrosion resistance, peelability, and storage stability as compared with Comparative Examples 1 to 4.

Example 10

In Example 10, the photosensitive resin composition prepared in Example 1 was applied to a touch panel glass master cutting process. Please refer to FIG. 1A to FIG. 1D , which are schematic diagrams of the process of cutting the glass master wafer of the touch panel of the embodiment 10. First, as shown in FIG. 1A, a glass master 1 of a touch panel is provided. The glass master 1 is formed with a plurality of touch panel modules 2, and the touch panel module 2 includes a line region 21 And a black photoresist 22. Next, as shown in FIG. 1B, the photosensitive resin composition prepared in the above Example 1 is applied onto the glass mother substrate 1, and the photosensitive resin composition is dried and subjected to an exposure and development process to form a cut-containing film. The photoresist layer 3 of the path 4. Please continue to refer to FIG. 1C, which is to form the photoresist having the cutting path 4 described above. The glass master 1 of layer 3 is immersed in a 6% hydrofluoric acid solution to form a touch glass 1' comprising a touch panel module 2. Finally, as shown in FIG. 1D, the touch glass 1' containing a touch panel module 2 is immersed in a 5% sodium hydroxide solution to strip the photoresist layer 3 overlying it, thereby completing the Touch panel glass master cutting process.

The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

1‧‧‧Glass master

3‧‧‧ photoresist layer

4‧‧‧ cutting path

Claims (7)

A use of a photosensitive resin composition for use in a glass cutting process using hydrofluoric acid to form a photoresist film having a cutting path, the photosensitive resin composition comprising: (A) 30% by weight to 50% by weight of alkali soluble resin; (B) 10% by weight to 20% by weight of monomer; (C) 5 to 15% by weight of photopolymerization initiator; (D) 2 to 5 weight percent a polyfunctional mercapto compound which is a chain compound or a cyclic compound, and the polyfunctional mercapto compound comprises at least 2 mercaptopropionate groups; and (E) 2 to 10% by weight of decane Compound (F) balance solvent. The use according to claim 1, wherein the mercaptopropionate group is substituted or unsubstituted with at least one substituent, and the substituent is a C _1-4 alkyl group. The use according to claim 2, wherein the mercaptopropionate group is a 3-mercaptopropionate group. The use of claim 1, wherein the polyfunctional mercapto compound comprises from 3 to 6 mercaptopropionate groups. The use of the first aspect of the invention, wherein the polyfunctional mercapto compound is trimethylolpropane tris (3-mercaptopropionate, TMMP), pentaerythritol IV (trimethylolpropane tris (3-mercaptopropionate), TMMP) 3-mercaptopropionate (PEMP), dipentaerythritol (3-巯) Dipentaerythritol hexakis (3-mercaptopropionate, DPMP), 3-mercaptopropionic acid-[2,4,6-trioxo-1,3,5-triazine-1,3,5(2H , 4H, 6H)-sub-]tris (thiopropionoylethyl) isocyanurate (TEMPIC), pentaerythritol tetrakis (3-mercaptobutvlate), or combination. The use according to claim 1, wherein the alkali-soluble resin is an alkali-soluble acrylic resin. The use of claim 1, wherein the single system is a polyfunctional acrylate monomer.