TWI503628B - Negative-type photosensitive resin composition - Google Patents

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition, and more particularly to a negative photosensitive resin composition suitable for a high temperature process.

In the preparation process of the display panel and the touch panel, various photosensitive resin compositions such as positive or negative are used as materials, and the photosensitive properties are used to pattern and harden the resin compositions to form a passivation layer and protect them. A member such as a layer or an insulating layer.

In view of the fact that a transparent conductive layer (such as indium tin oxide, ITO) as a panel member is required to have high transparency and high conductivity, the temperature at which ITO is sputtered is also required to be higher and higher. The injection temperature has reached 280 ° C, and the components used as a protective layer or a passivation layer also need to withstand high temperatures during the process. However, it is conventionally known that a photosensitive resin composition mainly composed of an acrylic resin or a decane resin causes a severe yellowing phenomenon in a high-temperature process, and causes a shrinkage of a volume of the resin composition, thereby causing a display panel or a touch panel. Problems such as poor adhesion. In addition, the etching resistance of the ITO etching solution or the like of the member such as the protective layer or the passivation layer must be improved to ensure the adhesion of the ITO layer or the metal alignment, so that it cannot be applied to the ITO having high transparency and high conductivity. Display panel or touch panel system In the process.

Therefore, there is an urgent need for a novel negative photosensitive resin composition which has excellent properties such as high heat resistance, high transparency, high chemical resistance, and high moisture resistance, and is applied to have high transparency and high electrical conductivity. ITO high temperature process.

The main object of the present invention is to provide a negative photosensitive resin composition which can be applied to a high temperature process by transmitting high heat resistance, high transparency, high chemical resistance, and high moisture resistance of the composition. The utility model provides a component such as a passivation layer, a protective layer or an insulating layer in a display panel or a touch panel.

In order to achieve the above object, the negative photosensitive resin composition provided by the present invention may comprise: (A) 5 to 25 weight percent of a polyoxyalkylene compound obtained by polymerizing a plurality of monomers, wherein The monomers may include at least: a oxoxane monomer as shown in formula (a-1), and a oxoxane monomer having an anhydride group;

Wherein R ₁ is each independently a C _1-6 alkyl group; (B) 0.1 to 20 weight percent of a citrate oligomer, as shown in formula (b-1);

Wherein R ₂ is each independently a C _1-6 alkyl group; and n is an integer from 2 to 10; (C) 0.1 to 10% by weight of a photoacid generator; and (D) a balance solvent.

In the negative photosensitive resin composition provided by the present invention, (A) the polyoxyalkylene compound is used as a main component of the resin composition, and is used for polymerizing (A) the monomer of the polyoxyalkylene compound. Wherein the monooxane single system represented by the formula (a-1) includes four alkoxy groups bonded to a halogen atom, which can provide a crosslinking point for condensation polymerization with each other, and the oxygen group containing the acid anhydride group Among the alkyl monomers, the anhydride groups thereof enhance the development solubility. Further, by exposing (C) the acid generated by the photoacid generator, (A) the polyoxyalkylene compound can be further subjected to a condensation reaction to increase the crosslinking density of the resin composition, thereby improving the heat resistance thereof. . Further, in order to increase the chemical resistance of the negative photosensitive resin composition of the present invention (e.g., the etching resistance to an ITO etching solution), the present invention provides (B) the phthalate oligomerization in the resin composition. As the crosslinking agent, the acid generated by exposure of (C) the photoacid generator is further crosslinked with (A) the polyoxyalkylene compound to achieve a greater crosslinking density.

In the (A) polyoxyalkylene compound of the above-mentioned negative photosensitive resin composition of the present invention, the anhydride group-containing oxirane monomer may be as shown in the formula (a-2): Wherein R ₃ may be selected from the group consisting of a direct bond, a C _1-6 alkyl group, and a C _1-6 alkoxy group; R ₄ is a C _1-6 alkoxy group; and an R ₅ system Each is independently a C _1-6 alkyl group or a C _1-6 alkoxy group.

In the negative photosensitive resin composition described above, in the alkoxysilane monomer represented by the formula (a-1), R _{1 is} preferably a C _1-3 alkyl group, and most preferably a tetraethoxy group. Decane. Further, in the anhydride group-containing oxirane monomer represented by the formula (a-2), R _{3 is} preferably a C _2-4 alkyl group, wherein a C ₃ alkyl group is preferred. R ₄ and R _{5 are} preferably a C _1-3 alkoxy group, wherein the anhydride group-containing oxirane single system represented by the formula (a-2) is preferably dihydro-3- [3-(Triethoxymethyl)propyl]furan-2,5-dione.

Further, based on the total weight ratio of the monomers to (A) the polyoxyalkylene compound, the oxoxane monomer represented by the formula (a-1) may account for 5 to 60%; and the acid anhydride group-containing group The siloxane monomer can be from 0.1 to 40%.

In the negative photosensitive resin composition as described above, (A) the polyoxyalkylene compound may further include at least one siloxane monomer represented by the formula (a-3).

Wherein, R ₆ hydrogen or C _1-20 Department of non-hydrolyzable organic group, C _1-20 of the non-hydrolyzable organic group may be for example a straight chain alkyl group of C _1-20 or branched chains, C _{1 a} linear or branched alkenyl group of _-20 , an aryl group of C _1-20 , or a similar substituent thereof, and the like, and the non-hydrolyzable organic group described above may be substituted or unsubstituted, for example, a substituent such as a halogen, an epoxy group, an amine group, a methacryl group, a cyano group, a fluorene group or a vinyl group, but R ₆ is not limited thereto; and the R ₇ groups are each independently selected from a C _1-6 alkane a group consisting of an oxy group and an aryloxy group. For example, the monomer represented by the formula (a-3) may be methyltrimethoxydecane, methyltriethoxydecane, methyltriisopropoxydecane, methyltri-n-butoxydecane, Ethyltrimethoxydecane, ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, n-propyltrimethoxydecane, n-propyltriethoxydecane, n-Butyltrimethoxydecane, n-butyltriethoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, phenyltrimethoxydecane, or phenyltriethoxydecane.

Wherein (A) the polyoxyalkylene compound is a oxoxane monomer represented by the formula (a-1), the anhydride group-containing oxirane monomer, at least as in the formula (a-3) a naphthenic monomer monomer represented by the formula (a-1) based on the total weight ratio of the polyoxyalkylene compound (A) 10 to 60%, the anhydride group-containing heoxane single system accounts for 0.5 to 40%, and at least one of the oxane single system as shown in the formula (a-3) accounts for 0 to 80%.

Further, in the oxoxane monomer represented by the formula (a-3), R _{6 is} preferably a C _1-3 alkyl group or a phenyl group; and R _{7 is} preferably each independently selected from the group consisting of C _1-3 alkane. The oxy group, wherein the oxoxane monomer represented by the formula (a-3) is more preferably at least one selected from the group consisting of phenyltrimethoxydecane, phenyltrimethoxysilane, and methyltrimethoxydecane. And a group consisting of ethyltriethoxydecane.

Further, the above (A) polyoxyalkylene compound may have a molecular weight of from 1,000 to 6,000 g/mole, preferably from 1,500 to 4,500 g/mole.

Furthermore, according to the resin composition provided in the present invention, in the silicate oligomer represented by the formula (b-1), R _{2 is} preferably a C _1-3 alkyl group, and wherein The methyl silicate is more preferred, and the methyl citrate is as follows: . .

Further, according to the resin composition provided in the present invention, (C) the photoacid generator may be subjected to protons after exposure, for example, trichloromethyl-s-triazine or diaryliodonium. a salt, a triarylsulfonium salt or the like, and among them, a triphenylsulfonium salt is preferred, and among the triphenylsulfonium salts, it is preferably any one of the formulae (c-1) to (c-3). One of the triphenylsulfonium salts shown:

The negative photosensitive resin composition provided by the invention can be used as a new generation of insulating layer transparent photoresist, which has transparency after high temperature resistance, good adhesion of metal substrate, low exposure energy, easy development and moisture resistance and corrosion resistance. Good characteristics such as engraving can be applied to ITO high temperature processes with high transparency and high conductivity.

Preparation Example 1 - Preparation of Polyoxane Compound A-1

83.2 g of tetraethoxynonane, 40.92 g of methyltrimethoxydecane, 30.44 g of dihydro-3-[3-(triethoxyindolyl)propyl]furan-2,5-dione, and 39.66 The phenyl trimethoxy decane was stirred in 172 g of solvent diacetone alcohol (DAA), and slowly dropped into 54 g of an aqueous phosphoric acid solution (0.0092 g of H ₃ PO ₄ dissolved in 54 g of water), and then heated to 110 ° C. A condensation polymerization reaction with a reaction time of 2 hours. After completion of the reaction, the alcohol and water were removed by distillation, and the obtained polyoxymethane compound A-1 had a solid content of 45% and a molecular weight of 3,800 g/mole.

Preparation Example 2 Preparation of Polyoxane Compound A-2

52.0 g of tetraethoxynonane, 13.64 g of methyltrimethoxydecane, 15.22 g of dihydro-3-[3-(triethoxyindolyl)propyl]furan-2,5-dione, and 118.98 The phenyl trimethoxy decane was stirred in 172 g of solvent diacetone alcohol (DAA), and slowly dropped into 54 g of an aqueous phosphoric acid solution (0.0092 g of H ₃ PO ₄ dissolved in 54 g of water), and then heated to 110 ° C. A condensation polymerization reaction with a reaction time of 2 hours. After completion of the reaction, the alcohol and water were removed by distillation, and the obtained polyoxymethane compound A-2 had a solid content of 45% and a molecular weight of 2000 g/mole.

Preparation Example 3 Preparation of Polyoxanane Compound A-3

This preparation example is roughly the same as the above-mentioned Preparation Example 2 except that tetraethoxy decane is not used as a monomer in the synthesis, but 47.66 g of methyltrimethoxydecane, 15.22 g is used. Dihydro-3-[3-(triethoxyindolyl)propyl]furan-2,5-dione, and 118.98 g of phenyltrimethoxydecane were stirred in 172 g of solvent PGMEA, slowly dropping After 54 g of an aqueous phosphoric acid solution (0.0092 g of H ₃ PO ₄ dissolved in 54 g of water), the mixture was heated to 110 ° C to carry out a condensation polymerization reaction for 2 hours. After completion of the reaction, the alcohol and water were removed by distillation, and the obtained polyoxyalkylene compound A-3 had a solid content of 45% and a molecular weight of 2,500 g/mole.

Example 1-6

Referring to Table 1, the polyoxyalkylene compound, the phthalate oligomer, the photoacid generator, and the solvent are disposed according to the composition formula shown in Table 1 as the photosensitive resin compositions of Examples 1 to 6, wherein The polyoxyalkylene compound used was the polyoxyalkylene compounds A-1 and A-2 prepared in the above Preparation Example 1-2. The silicate oligomer used is methyl phthalate. The photoacid generators used are Omnicat 432, Irgacure 290, and TR-PAG-201, and all of the photoacid generators are triphenylsulfonium salts, and the corresponding chemical formulas are as follows:

Comparative Example 1-6

Referring to Table 2, a polyoxyalkylene compound, a phthalate oligomer, a photoacid generator, a solvent, and the like were disposed according to the composition formula shown in Table 2 as the photosensitive resin compositions of Comparative Examples 1 to 6, wherein The polyoxyalkylene compound used was the polyoxyalkylene compounds A-1 to A-3 prepared in the above Preparation Example 2-3. In the comparative example, other cross-linking agent species are used in place of the phthalate oligomer used in the present invention, wherein the cross-linking agent used is tris(3-(trimethoxyindenyl)propyl) Tris(3-(trimethoxysilyl)propyl)isocyanurate, A-Link 597), Bis(triethoxysilyl)ethane, SIB 1817), PSI-021 (Poly (diethyoxysiloxane) 20.5-21.5% Si, 40-42% SiO ₂ ), and PSI-023 (Poly (diethyoxysiloxane) 23.0-23.5% Si, 48-52% SiO ₂ ).

Comparative Example 7

In this comparative example, Yongguang Chemical EOC 210 is used as a photosensitive resin composition, which is obtained by polymerization and condensation of an acrylic monomer such as styrene, methacrylic acid, benzyl methacrylate or tricyclodecyl ester. Acrylic resin.

Test case

First, a substrate was prepared and the surface of the substrate was cleaned with deionized water and acetone. Next, the negative photosensitive resin compositions prepared in the above Examples 1 to 6 and Comparative Examples 1 to 7 were uniformly applied onto the substrate by spin coating. Then, it was soft baked at 90 ° C for 5 minutes, and the negative photosensitive resin composition coated on the surface of the substrate was directly exposed by an ultrahigh pressure mercury lamp (exposure energy: 200 mJ/cm ² ) using a photomask. . Next, development was carried out with ENPD 80 developer for 60 seconds. Hard roasting was carried out at 230 ° C for 30 minutes. Finally, the substrate and the photoresist layer were washed with secondary water at 25 ° C to obtain a desired sample.

<hardness>

The samples prepared in the above test examples were pencil hardnesses of the samples obtained in accordance with the 8.4.1 pencil drawing hardness test of JIS K-5400-1990. The hardness was measured in units of pencil hardness, and the results are shown in Table 3.

<Penetration after heat resistance>

The samples prepared in the above test examples were heated at 280 ° C for 1 hour, and after heat treatment, the samples were tested for penetration at a wavelength of 400 nm using Photal MCPD-3000 (Dayu Technology). The results are shown in Table 3.

<Water wash test>

The samples prepared in the above test examples were shaken for 30 minutes in an ultrasonic bath at 25 °C. The evaluation results of the water wash resistance test are shown in Table 3, wherein the evaluation of the water wash resistance test is: excellent 4B>3B>2B>1B>0B.

<etching resistance test>

The sample prepared in the above test example was immersed in FeCl ₃ at 40 ° C for 120 seconds. The evaluation results of the etching resistance test are shown in Table 3. Among them, the evaluation of the etching resistance test is: excellent 4B>3B>2B>1B>0B is inferior.

<heat-resistant film shrinkage and yellowing>

In the above test examples, the samples prepared in Example 1 and Comparative Example 7 were heat-treated at 280 ° C for 1 hour, and the heat shrinkage rate thereof was calculated, wherein the heat shrinkage film ratio = (film thickness before heat resistance test - heat resistance) Film thickness after test) / film thickness before heat test × 100%. And, the evaluation criteria for visual yellowing are: transparent 5>4>3>2>1 yellow. The test results are shown in Table 4.

From the results of Table 4, it was confirmed that the negative photosensitive resin composition provided by the present invention has a high heat resistance property, and can remarkably improve the heat resistance characteristics of the insulating layer or the protective layer which is conventionally used as a panel.

From the above test results, it can be clearly understood that the negative photosensitive resin composition provided by the present invention can be used as a new generation insulating layer transparent photoresist, for example, can be applied to a touch panel insulating layer (OC1) and Protective layer (OC2), this product has good properties such as high temperature resistance, good adhesion to metal substrate, low exposure energy, easy development, moisture resistance, and etching resistance.

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.

Claims (11)

A negative photosensitive resin composition comprising: (A) 5 to 25 weight percent of a polyoxyalkylene compound, which is polymerized from a plurality of monomers, wherein the single systems include at least: a oxoxane monomer represented by the formula (a-1), and a oxosiloxane monomer having an acid anhydride group; Wherein R ₁ is each independently a C _1-6 alkyl group; (B) 0.1 to 20 weight percent of a silicate oligomer, as shown in formula (b-1); Wherein R ₂ is each independently a C _1-6 alkyl group; and n is an integer from 2 to 10; (C) 0.1 to 10% by weight of a photoacid generator; and (D) a balance solvent. The resin composition according to claim 1, wherein in the (A) the polyoxyalkylene compound, the monooxyalkylene group system containing the acid anhydride group is as shown in the formula (a-2): Wherein R ₃ is selected from the group consisting of a direct bond, a C _1-6 alkyl group, and a C _1-6 alkoxy group; R ₄ is a C _1-6 alkoxy group; and an R ₅ system Each is independently a C _1-6 alkyl group or a C _1-6 alkoxy group. The resin composition according to claim 1, wherein (A) the polyoxyalkylene compound is a siloxane monomer represented by the formula (a-1), and the acid anhydride group-containing group The oxirane monomer is polymerized, and the oxirane single system represented by the formula (a-1) accounts for 5 to 60% based on the total weight ratio of the monomer (A) to the polyoxy siloxane compound. And the anhydride group-containing heoxane single system accounts for 0.1 to 40%. The resin composition according to claim 1, wherein, in (A) the polyoxyalkylene compound, the monomers further comprise at least one siloxane monomer as shown in formula (a-3). : Wherein R ₆ is a non-hydrolyzable organic group of C _1-20 ; and R ₇ are each independently selected from the group consisting of a C _1-6 alkoxy group and an aryloxy group. The resin composition according to claim 4, wherein (A) the polyoxyalkylene compound is a oxirane monomer represented by the formula (a-1), and the anhydride group-containing group An oxyalkylene monomer obtained by polymerizing at least one oxoxane monomer represented by the formula (a-3), wherein the total weight ratio of the polyoxyalkylene compound (A) is based on the monomer The alkane single system shown in (a-1) accounts for 10 to 60%, and the anhydride is contained. The monooxyalkylene mono-system of the group accounts for 0.5 to 40%, and at least one monooxane system of the formula (a-3) accounts for 0 to 80%. The resin composition according to claim 1, wherein (A) the polyoxyalkylene compound is a siloxane monooxytetramethane as shown in (a-1). The resin composition according to claim 2, wherein the anhydride group-containing oxime group monohydrogen-3-[3-(triethoxy) represented by the formula (a-2) Mercapto)propyl]furan-2,5-dione. The resin composition according to claim 1, wherein the silicate oligomer represented by the formula (b-1) is a methyl silicate, which is represented by the following formula: The resin composition according to claim 1, wherein (C) the photoacid generator is a triphenylsulfonium salt. The resin composition according to claim 8, wherein the (C) triphenylsulfonium salt is a triphenylsulfonium salt represented by any one of the formulae (c-1) to (c-3). : The resin composition according to claim 1, wherein (A) the polyoxymethane compound has a molecular weight of 1000 to 6000 g/mole.