TW201816516A - Negative-type photosensitive resin composition and use thereof - Google Patents

Abstract

A negative-type photosensitive resin composition is disclosed, which comprises: (A) 10-50 wt% of a polysiloxane compound; (B) 0.1-30 wt% of a silicate oligomer; (C) 0.1-10 wt% of a photo acid generator, in which an anion of the photo acid generator is HB(C6F5)4<SP>-</SP>; and (D) residual solvent. In addition, a use of the above negative-type photosensitive resin composition is also disclosed.

Description

Negative photosensitive resin composition and use thereof

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

In the production process of display panels and touch panels, various types of photosensitive resin compositions such as positive or negative are used as materials, and their photosensitive properties are used to pattern and harden these resin compositions to form passivation layers and protect Layers, or insulating layers.

Transparent conductive layers (such as indium tin oxide, ITO) as panel components are required to achieve high transparency and high conductivity; and is different from plug-in touch panels, thinner and thinner in-cell touch technology (On -Cell), must be operated at a lower solidification temperature (for example, 120 ℃). However, at present, it is known that a photosensitive resin composition mainly composed of an acrylic resin or a siloxane resin has a hardness of ≦ H and a significant decrease in reliability to 0B after a baking temperature of 120 ° C; therefore, the acrylic resin material is at a low temperature. After the process, the hardness, etching resistance and other conditions have not met the current requirements.

In view of this, there is an urgent need for a novel negative photosensitive resin composition, which can be completely cured at low temperature, and the formed film has excellent characteristics such as high transparency, high chemical resistance, and high hardness, etc. It is used in semiconductor processes with high transparency and high conductivity, such as in-cell touch panel processes.

The main purpose of this disclosure is to provide a negative photosensitive resin composition, which is particularly suitable for low temperature solid baking, and the formed film has the characteristics of chemical resistance and high hardness.

The negative photosensitive resin composition disclosed in this disclosure may include: (A) 10 to 50 weight percent of a polysiloxane compound, which is polymerized from a plurality of monomers, wherein these single systems include the following Siloxane monomers represented by formulae (a-1) and (a-2); (a-1) (a-2) wherein R ₁ is each independently C _1-6 alkyl; R ₂ is C _6-20 cycloalkyl or C _6-20 aryl; and R ₃ are each independently selected from C _1-6 A group consisting of an alkoxy group and an aryloxy group; (B) 0.1 to 30% by weight of a silicate oligomer; (C) 0.1 to 10% by weight of a photoacid generator, wherein The anionic part of the photoacid generator is composed of pentafluorophenyl borate; and (D) the remaining solvent.

In the above-mentioned negative photosensitive resin composition provided in this disclosure, (A) the polysiloxane compound is used as a main component of the resin composition, and is used to polymerize (A) the polysiloxane compound monomer In addition, at least the monomers represented by formulas (a-1) and (a-2) must be included. In particular, the polysiloxane compound does not include a siloxane monomer containing an acid anhydride group. Among them, the single system shown by formula (a-1) includes four alkoxy groups connected to silicon atoms, which can provide cross-linking points for condensation polymerization with each other, and improve film-forming hardness and chemical resistance; and formula ( In addition to the monomers represented by a-2), in addition to being crosslinkable with the monomers represented by formula (a-1), the transparency of the formed film can be improved. In addition, by exposing (C) the acid generated by the photoacid generator, (A) the polysiloxane compound can be further subjected to a condensation reaction to increase the crosslinking density of the resin composition, thereby improving film reliability. Bad question. Furthermore, in order to increase the chemical resistance of the negative photosensitive resin composition disclosed in the present disclosure (such as etching resistance to ITO etchant), the present invention provides (B) the silicate oligomer in the resin composition. As a cross-linking agent, the acid generated when the (C) photoacid generator is exposed is further cross-linked with (A) the polysiloxane compound to achieve a larger cross-linking density.

In the negative photosensitive resin composition of the present disclosure, in the siloxane monomer represented by the formula (a-1), R ₁ may be each independently a C _1-6 alkyl group, and R _{1 is} preferably each independently C _1-3 alkyl. In a specific embodiment of the present disclosure, the siloxane single system tetraethoxysilane is represented by formula (a-1).

In the negative photosensitive resin composition disclosed in this disclosure, in the siloxane monomer represented by formula (a-2), R ₂ may be a C _6-20 cycloalkyl group or a C _6-20 aryl group, preferably C _6-12 cycloalkyl or C _6-12 aryl, more preferably cyclohexane or phenyl, and most preferably phenyl. In addition, R ₃ may be each independently selected from the group consisting of C _1-6 alkoxy and C _6-20 aryloxy, and is preferably each independently selected from C _1-3 alkoxy and C _{6- A} group of ₁₂ aryloxy groups, and more preferably, each is independently a C _1-3 alkoxy group. In a specific embodiment of the present disclosure, the siloxane monosystem phenyltrimethoxysilane is represented by formula (a-2).

In addition, in the negative photosensitive resin composition of the present disclosure, (A) the polysiloxane compound is polymerized from a siloxane monomer represented by formulas (a-1) and (a-2), and to make. Among them, the proportion of the siloxane monomer represented by the formulae (a-1) and (a-2) is not particularly limited. For example, based on the total weight ratio of these monomers to (A) the polysiloxane compound, the siloxane monomer represented by formula (a-1) may account for 30 to 70%, and the formula (a-2) The shown siloxane monomer may account for 30 to 70%; preferably, the siloxane monomer shown in formula (a-1) accounts for 40 to 60%, and the siloxane shown in formula (a-2) The single system accounts for 40 to 60%.

Furthermore, in the negative photosensitive resin composition disclosed in this disclosure, (A) the molecular weight of the polysiloxane compound may be 1000 to 8000 g / mole, preferably 1000 to 6000 g / mole, and more It is preferably 1500 to 4500 g / mol.

In the negative photosensitive resin composition disclosed in this disclosure, (B) the type of the silicate oligomer is not particularly limited, and can be represented by the following formula (b-1): (b-1) wherein R ₄ is each independently a C _1-6 alkyl group; and n is an integer from 2 to 10.

In a specific embodiment of the present disclosure, the silicate oligomer represented by formula (b-1) is methyl silicate, which is represented by the following formula: .

In addition, in the negative photosensitive resin composition of the present disclosure, (C) the type of the photoacid generator is not particularly limited as long as it is a pentafluorophenylborate anion portion containing a strong acid; for example, it may be Is a pentafluorophenyl borate as shown in any one of formulae (c-1) to (c-2): (c-1) (c-2).

In the negative photosensitive resin composition disclosed herein, the content of the solvent is the remaining amount of other components in the negative photosensitive resin composition, and the remaining amount is calculated based on the total amount of the negative photosensitive resin composition The remaining content after the content of other ingredients.

In addition, the present disclosure further provides an application of the foregoing negative photosensitive resin composition, which is used in a low-temperature solid-baking process, where the low temperature means 150 ° C or lower. Preferably, the temperature is 60 to 150 ° C; more preferably, the temperature is 80 to 150 ° C.

After the conventional acrylic resin is cured at a low temperature, the reaction is insufficient, resulting in poor hardness and reliability. Therefore, the present disclosure provides a negative-type photosensitive resin composition, which can be used as a new-generation insulating layer transparent photoresist, and is particularly suitable for low-temperature processes. In particular, the negative-type photosensitive resin composition of the present disclosure is cured at a low temperature. After baking, the formed film has a high crosslinking density, and the formed film has excellent transparency, good chemical resistance and UV resistance, and high hardness, and can be applied to semiconductors with high transparency and high conductivity. Process. For example, when applied to a touch panel, the film formed with the negative photosensitive resin composition disclosed herein has good chemical resistance, and has good reliability for chemicals such as ITO etchant; The film has excellent transparency and can be used on a transparent insulating layer for a touch panel.

The following is a description of the implementation of the disclosure through specific embodiments. Those skilled in the art can easily understand other advantages and effects of the disclosure from the content disclosed in the description. This disclosure can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified and changed for different viewpoints and applications without departing from the spirit of this creation.

Synthesis example - Polysiloxane Compound

In this synthesis example, polysiloxane compounds A-1 to A-5 were prepared according to the composition formula shown in Table 1 below. Among them, the preparation method is roughly described as follows.

Take the siloxane monomer and propylene glycol monomethyl ether acetate (PGMEA) at room temperature and slowly drop in 54 g of phosphoric acid aqueous solution (0.216 g of H ₃ PO ₄ in 54 g of water), and raise the temperature to 110 ° A condensation polymerization reaction was performed, and the reaction time was 2 hours. After the reaction is completed, the alcohol and water are removed by distillation. The weight average molecular weight (MW) and polydispersity index (PDI) after synthesis are shown in Table 1.

Table 1 TEOS: Tetraethyl orthosilicate, C ₈ H ₂₀ O ₄ Si, CAS NO .: 78-10-4 PTMS: Phenyltrimethoxysilane, C ₉ H ₁₄ O ₃ Si, CAS NO .: 2996-92-1 MTMS: Methyltrimethoxysilane, C ₄ H ₁₂ O ₃ Si, CAS NO .: 1185-55-3 IBTMS: Isobutyl (trimethoxy) ) silane), C ₇ H ₁₈ O ₃ Si, CAS.No .: 18395-30-7 STES: dihydro-3- [3- (triethoxysilyl) propyl] furan-2,5-di Ketone ((3-Triethoxysilylpropyl) succinic anhydride), C ₁₃ H ₂₄ O ₆ Si, CAS NO .: 93642-68-3

Examples and Comparative Examples - Negative sensitivity Resin composition

In the examples and comparative examples disclosed herein, the negative photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were prepared according to the composition formula shown in Table 2 below. Among them, the preparation method is roughly described as follows.

A polysiloxane compound, a silicate oligomer, a photoacid generator, and a solvent were formulated into the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 5 according to the composition formula shown in Table 2. The polysiloxane compounds used are the polysiloxane compounds A-1 to A-5 prepared in the above synthesis examples. The silicate oligomer used is tetramethyl silicate (B-1). The photoacid generators used are Irgacure 290 (C-1), TR-PAG-21608 (C-2), Omniat 432 (C-3) and Irgacure PAG 121 (C-4). Among them, the corresponding chemical formulas of methyl silicate 53A and the photoacid generator used are as follows: methyl silicate 53A (MS-53A): C ₁₀ H ₃₀ O ₁₃ Si ₄ , CAS NO .: 12002 -26-5 Photoacid generator Irgacure 290: CAS NO .: 1203809-92-0 Photoacid generator TR-PAG-21608 Photonic acid generator Omnicat 432: CAS NO .: 104558-95-4 Photoacid generator Irgacure PAG 121

Test case

First, a substrate is prepared, and the surface of the substrate is cleaned with deionized water and acetone. Next, the negative-type photosensitive resin compositions prepared in the above-mentioned Examples 1 to 4 and Comparative Examples 1 to 5 were each uniformly coated on the substrate by spin coating. Next, soft-bake at 90 ° C for 5 minutes, and use a mask to directly apply the above-mentioned negative photosensitive resin composition coated on the substrate surface with an ultra-high pressure mercury lamp (exposure energy: 230 mJ / cm ² ) exposure. Then, development was performed with a 2.38% TMAH developer for 60 seconds. Bake for 30 minutes at 120˚C. Finally, the substrate and the photoresist layer were washed with secondary water at 25 ° C to obtain the required sample, and the thickness of the sample was 1.5 μm.

< hardness ＞

The sample prepared in the above test example is a pencil hardness of the sample measured in accordance with JIS K-5400-1990 8.4.1 pencil scratch hardness test. The hardness is measured in pencil hardness, and the results are shown in Table 2.

< Etching resistance test ＞

The sample prepared in the above test example was immersed in aqua regia at 40 ° C for 160 seconds; then, it was immersed in stripping solution N-300 (ethanolamine Ethanolamine 30% + diethylene glycol monobutyl ether) at 60 ° C. Diethylene glycol monobutyl ether 70%) in 135 seconds. The evaluation results of the etching resistance test are shown in Table 2. Among them, the evaluation of the etching resistance test was: excellent ◎, good ○, and poor X.

Table 2 (Unit: grams)

As shown in the results of Examples 1 to 4 and Comparative Examples 4 to 5, when a negative-type photosensitive resin composition (Examples 1 to 4) was prepared using a polysiloxane compound containing TEOS and PTMS, the formed films were simultaneously Has better hardness and acid resistance. In addition, as shown in the results of Examples 1 to 4 and Comparative Examples 1 to 3, when a photoacid generator (Examples 1 to 4) whose anion portion is composed of pentafluorophenyl borate is used, the formed films are simultaneously Has better hardness and acid resistance.

From the above test results, it can be clearly understood that when a polysiloxane compound formed from a specific siloxane monomer and a photoacid generator composed of pentafluorophenyl borate are used to prepare the negative-type photosensitive of the present disclosure In the case of a solid resin composition, when the baking is performed at a low temperature (150 ° C. or lower), the formed film not only has transparency, but also has high hardness and high chemical resistance. Therefore, the negative-type photosensitive resin composition provided in this disclosure can be used as a new-generation insulating layer transparent photoresist. For example, it can be applied to touch panel insulating layer (OC1) and protective layer (OC2). It has good properties such as transparency after high temperature resistance, good adhesion to metal substrates, low exposure energy, easy development, moisture resistance, and etching resistance.

The above embodiments are merely examples for the convenience of description. The scope of the rights claimed in this disclosure should be based on the scope of the patent application, rather than being limited to the above embodiments.

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Claims (11)

A negative photosensitive resin composition includes: (A) 10 to 50 weight percent of a polysiloxane compound, which is polymerized from a plurality of monomers, wherein the single systems include the following formula (a -1) and the siloxane monomer shown in (a-2); (a-1) (a-2) wherein R ₁ is each independently C _1-6 alkyl; R ₂ is C _6-20 cycloalkyl or C _6-20 aryl; and R ₃ is each independently selected from C _1-6 A group consisting of an alkoxy group and an aryloxy group; (B) 0.1 to 30% by weight of a silicate oligomer; (C) 0.1 to 10% by weight of a photoacid generator, wherein The anionic part of the photoacid generator is composed of pentafluorophenyl borate; and (D) the remaining solvent. The resin composition according to item 1 of the scope of patent application, wherein (B) the silicate oligomer is represented by the following formula (b-1): (b-1) wherein R ₄ is each independently a C _1-6 alkyl group; and n is an integer from 2 to 10. The resin composition according to item 1 of the scope of patent application, wherein (A) the polysiloxane compound is polymerized from a siloxane monomer represented by formulas (a-1) and (a-2) , Wherein, based on the total weight ratio of these monomers to (A) the polysiloxane compound, the siloxane single system represented by formula (a-1) accounts for 30 to 70%, and the formula (a- 2) The siloxane single system shown accounts for 30 to 70%. The resin composition according to item 1 of the scope of patent application, wherein (A) the polysiloxane compound is polymerized from a siloxane monomer represented by formulas (a-1) and (a-2) , Wherein, based on the total weight ratio of these monomers to (A) the polysiloxane compound, the siloxane single system represented by formula (a-1) accounts for 40 to 60%, and the formula (a- 2) The siloxane single system shown accounts for 40 to 60%. The resin composition according to item 1 of the scope of the patent application, wherein (A) the polysiloxane compound is a siloxane single system tetraethoxy silane represented by the formula (a-1). The resin composition according to item 1 of the scope of the patent application, wherein (A) the polysiloxane compound is a siloxane triphenylsiloxane group represented by formula (a-2). The resin composition according to item 2 of the scope of patent application, wherein the silicate oligomer represented by formula (b-1) is methyl silicate 53A (methyl silicate), which is represented by the following formula : . The resin composition according to item 1 of the scope of the patent application, wherein (C) the photoacid generator is a pentafluorophenyl borate represented by any one of formulas (c-1) to (c-2) : (c-1) (c-2). The resin composition according to item 1 of the scope of patent application, wherein (A) the molecular weight of the polysiloxane compound is 1000-8000 g / mole. The use of the negative photosensitive resin composition according to any one of claims 1 to 9 of the scope of patent application, which is used for the low-temperature solid-baking process, wherein the low temperature means below 150 ° C. The use as described in item 10 of the patent application range, wherein the temperature is 80 to 150 ° C.