阅读说明：本技术 负型感光性树脂组合物及其用途 (Negative photosensitive resin composition and use thereof ) 是由 吴宜骏 徐慧桓 蓝大钧 张志毅 于 2019-01-16 设计创作，主要内容包括：一种负型感光性树脂组合物,包括：(A)5重量百分比至20重量百分比的聚硅氧烷化合物,其由多种单体所聚合而成,其中,这些单体包括如下式(a-1)、(a-2)及(a-3)所示的硅氧烷单体；(B)6重量百分比至20重量百分比的硅酸酯寡聚物,包括一低烷氧基硅酸酯寡聚物,其中该低烷氧基硅酸酯寡聚物的含量占该硅酸酯寡聚物总重量的60％至100％；(C)0.1重量百分比至10重量百分比的光酸产生剂；以及(D)余量溶剂；<Image he="153" wi="700" file="DDA0001947234670000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,R<Sub>1</Sub>至R<Sub>6</Sub>如说明书中所定义。此外,本发明还涉及一种前述负型感光性树脂组合物的用途。(A negative photosensitive resin composition comprising: (A)5 to 20 weight percent of a polysiloxane compound polymerized from a plurality of monomers, wherein the monomers comprise siloxane monomers represented by the following formulas (a-1), (a-2) and (a-3); (B)6 to 20 weight percent silicate oligomers comprising a low alkoxy silicate oligomer, wherein the low alkoxy silicate oligomer is present in an amount of 60 to 100 percent based on the total weight of the silicate oligomers; (C)0.1 to 10 weight percent of a photoacid generator; and (D) the balance solvent; wherein R is 1 To R 6 As defined in the specification. In addition, the invention also relates to a front coverThe use of the negative photosensitive resin composition.)

1. A negative photosensitive resin composition comprising:

(A)5 to 20 weight percent of a polysiloxane compound polymerized from a plurality of monomers, wherein the plurality of monomers comprise siloxane monomers represented by the following formulas (a-1), (a-2) and (a-3);

wherein R is₁Each independently is C_1-6An alkyl group;

R₂is C_6-20Cycloalkyl or C_6-20An aryl group;

R₃each independently selected from the group consisting of C_1-6Alkoxy and aryloxy groups;

R₄selected from the group consisting of a direct bond, C_1-6Alkyl and C_1-6Alkoxy groups;

R₅is C_1-6An alkoxy group; and

R₆each independently is C_1-6Alkyl or C_1-6An alkoxy group;

(B)6 to 20 weight percent silicate oligomers comprising a low alkoxy silicate oligomer, wherein the low alkoxy silicate oligomer is present in an amount of 60 to 100 percent based on the total weight of the silicate oligomers, and wherein the number of alkoxy groups attached to silicon atoms in the low alkoxy silicate oligomer is 20 to 50 percent based on the total number of substituents attached to silicon atoms;

(C)0.1 to 10 weight percent of a photoacid generator; and

(D) the balance being solvent.

2. The negative photosensitive resin composition of claim 1, wherein the silicate oligomer further comprises a high alkoxy silicate oligomer, the high alkoxy silicate oligomer is represented by the following formula (b-2):

wherein R is₉Each independently is C_1-6An alkyl group; and

m is an integer of 2 to 10.

3. The negative photosensitive resin composition of claim 2, wherein the high alkoxy silicate oligomer represented by formula (b-2) is represented by the following formula (b-2'):

4. the negative photosensitive resin composition according to claim 1, wherein the polysiloxane compound is polymerized from siloxane monomers represented by formulae (a-1), (a-2), and (a-3), the siloxane monomer represented by formula (a-1) accounts for 10 mol% to 70 mol% of the total moles of the polysiloxane compound, the siloxane monomer represented by formula (a-2) accounts for 10 mol% to 70 mol% of the total moles of the polysiloxane compound, and the siloxane monomer represented by formula (a-3) accounts for 0.5 mol% to 40 mol% of the total moles of the polysiloxane compound.

5. The negative-type photosensitive resin composition according to claim 1, wherein the polysiloxane compound is polymerized from siloxane monomers represented by formulae (a-1), (a-2), and (a-3), the siloxane monomer represented by formula (a-1) accounts for 30 mol% to 60 mol% of the total moles of the polysiloxane compound, the siloxane monomer represented by formula (a-2) accounts for 30 mol% to 60 mol% of the total moles of the polysiloxane compound, and the siloxane monomer represented by formula (a-3) accounts for 1 mol% to 20 mol% of the total moles of the polysiloxane compound.

6. The negative photosensitive resin composition according to claim 1, wherein the siloxane monomer represented by formula (a-1) is tetraethoxysilane.

7. The negative photosensitive resin composition of claim 1, wherein the siloxane monomer represented by formula (a-2) is phenyltrimethoxysilane.

8. The negative photosensitive resin composition according to claim 1, wherein the siloxane monomer represented by formula (a-3) is 3- (triethoxysilyl) propylsuccinic anhydride.

9. The negative photosensitive resin composition of claim 1, wherein the photoacid generator is an ionic photoacid generator.

10. The negative photosensitive resin composition according to claim 1, wherein the photoacid generator is represented by any one of the following formulae (c-1) to (c-4):

11. use of the negative photosensitive resin composition according to any one of claims 1 to 10, for a low-temperature curing process, wherein low temperature means 120 ℃ or less.

12. Use according to claim 11, wherein the temperature is from 80 ℃ to 120 ℃.

13. Use of the negative photosensitive resin composition according to any one of claims 1 to 10 for producing a resist film developed with an alkaline developer.

14. Use according to claim 13, wherein the alkaline developer is a KOH-containing developer.

Technical Field

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

Background

In the manufacturing process of display panels and touch panels, various photosensitive resin compositions, such as positive type or negative type, have been conventionally used as materials, and these resin compositions are patterned and cured by using their photosensitive properties to form members, such as passivation layers, protective layers, or insulating layers.

Nowadays, flexible display panels and touch panels are receiving great attention, and flexible substrates are used as substrates. Among them, the flexible substrate is mostly made of materials such as polyethylene terephthalate (PET) or polycycloolefin polymer (COP) that do not resist high temperature, so the post-stage process temperature is greatly reduced, for example, to 85 ℃ in order to match the characteristics of the flexible substrate. However, the conventional silicone resin material can maintain its transparency even after a low-temperature process, but is likely to crack after being bent, and thus cannot be applied to a flexible display panel or a touch panel.

In view of the above, there is a need for a novel negative photosensitive resin composition that can be fully cured at low temperature and can be applied to a flexible display panel or touch panel, wherein the formed film has excellent flexibility.

Disclosure of Invention

The main object of the present invention is to provide a negative photosensitive resin composition which is particularly suitable for low-temperature curing and in which a film having flexible properties is formed.

The negative photosensitive resin composition of the present invention may include: (A)5 to 20 weight percent of a polysiloxane compound polymerized from a plurality of monomers, wherein the monomers comprise siloxane monomers represented by the following formulas (a-1), (a-2) and (a-3);

wherein R is₁Each independently is C_1-6An alkyl group; r₂Is C_6-20Cycloalkyl or C_6-20An aryl group; r₃Each independently selected from the group consisting of C_1-6Alkoxy and aryloxy groups; r₄Selected from the group consisting of a direct bond, C_1-6Alkyl and C_1-6Alkoxy group(s)Group (d); r₅Is C_1-6An alkoxy group; and R₆Each independently is C_1-6Alkyl or C_1-6An alkoxy group;

(B)6 to 20 weight percent silicate oligomers comprising a low alkoxy silicate oligomer, wherein the low alkoxy silicate oligomer is present in an amount of 60 to 100 percent based on the total weight of the silicate oligomers, and wherein the number of alkoxy groups attached to silicon atoms in the low alkoxy silicate oligomer is 20 to 50 percent based on the total number of substituents attached to silicon atoms;

(C)0.1 to 10 weight percent of a photoacid generator; and

(D) the balance being solvent.

In the negative photosensitive resin composition provided by the present invention, the polysiloxane compound (a) is used as a main component of the resin composition, and the monomers used for polymerizing the polysiloxane compound (a) must include at least monomers represented by the formulae (a-1), (a-2) and (a-3). Wherein the monomer represented by the formula (a-1) comprises four alkoxy groups bonded to silicon atoms, and provides crosslinking points for condensation polymerization with each other; the monomer shown in the formula (a-2) can be crosslinked with other monomers, and can improve the transparency of a formed film; the monomer represented by the formula (a-3) is a siloxane monomer including an acid anhydride group. Since the polymeric polysiloxane compound (A) of the present invention comprises the monomer represented by formula (a-3), when a resist film is formed from the negative photosensitive resin composition of the present invention, the resist film can be developed using an alkaline developer (e.g., a developer containing KOH). In addition, the polysiloxane compound (a) can be further subjected to a condensation reaction by exposure to an acid generated by the photoacid generator (C). In the present invention, the silicate oligomer (B) is added to the resin composition as a crosslinking agent, and the resin composition is further crosslinked with the polysiloxane compound (A) by an acid generated by exposure to the photoacid generator (C). In particular, the silicate oligomer (B) as a cross-linking agent of the present invention comprises a low alkoxy silicate oligomer, and the cross-linking density of the polymeric polysiloxane compound (a) can be controlled by using the low alkoxy silicate oligomer, so that the film formed by the negative photosensitive resin composition of the present invention has a flexible characteristic, and can be applied to a flexible substrate to form an insulating film or a protective film having a flexible characteristic.

In the negative photosensitive resin composition of the present invention, the low alkoxy silicate oligomer may be represented by the following formula (b-1):

wherein R is₇Each independently is C_1-6Alkyl radical, C_1-6Alkoxy radical, C_6-20Aryl or C_3-6Epoxy groups, preferably, each independently C_1-6Alkyl or C_1-6Alkoxy, more preferably, each independently is C_1-3Alkyl or C_1-3An alkoxy group; r₈Is C_1-6An alkyl group; and n is an integer of 4 to 10.

In the negative photosensitive resin composition of the present invention, the silicate oligomer (B) may further optionally include a high alkoxy silicate oligomer represented by the following formula (B-2):

wherein R is₉Each independently is C_1-6An alkyl group; and m is an integer of 2 to 10. Further, in the silicate oligomer (B), the content of low alkoxy silicate oligomer (e.g., as shown in the formula (B-1)) is required to be larger than that of high alkoxy silicate oligomer as shown in the formula (B-2). For example, the high alkoxy silicate oligomer as shown in formula (B-2) may be contained in an amount of 0% to 40% by weight based on the total weight of silicate oligomer (B).

In an embodiment of the present invention, when the negative photosensitive resin composition does not include the high alkoxy silicate oligomer represented by the formula (B-2) but includes only the low alkoxy silicate oligomer (e.g., represented by the formula (B-1)), the content of the low alkoxy silicate oligomer is 100% of the total weight of the silicate oligomer (B). In another embodiment of the present invention, when the negative photosensitive resin composition comprises both low alkoxy silicate oligomers (e.g., as shown in formula (B-1)) and high alkoxy silicate oligomers as shown in formula (B-2), the content of the low alkoxy silicate oligomers is 60% to 99.9% of the total weight of the silicate oligomers (B), and the content of the high alkoxy silicate oligomers as shown in formula (B-2) is 0.1% to 40% of the total weight of the silicate oligomers (B).

In the negative photosensitive resin composition of the present invention, R is represented by the formula (a-1) in the siloxane monomer₁May each independently be C_1-6Alkyl, and preferably, R₁Each independently is C_1-3An alkyl group. In one embodiment of the present invention, the siloxane monomer represented by formula (a-1) is tetraethoxysilane.

In the negative photosensitive resin composition of the present invention, R is the siloxane monomer represented by the formula (a-2)₂Can be C_6-20Cycloalkyl or C_6-20Aryl, preferably C_6-12Cycloalkyl or C_6-12Aryl, more preferably cyclohexane or phenyl, and most preferably phenyl. Furthermore, R₃Can be independently selected from C_1-6Alkoxy and C_6-20Aryloxy, preferably each independently selected from the group consisting of C_1-3Alkoxy and C_6-12Aryloxy group, and more preferably, each independently C_1-3An alkoxy group. In one embodiment of the present invention, the siloxane monomer of formula (a-2) is phenyltrimethoxysilane.

In the negative photosensitive resin composition of the present invention, R is the siloxane monomer represented by the formula (a-3)₄Can be selected from a direct bond, C_1-6Alkyl and C_1-6Alkoxy, preferably C_1-6Alkyl, more preferably C_2-4An alkyl group. Furthermore, R₅Can be C_1-6Alkoxy, and preferably C_1-3An alkoxy group. Further, R₆May each independently be C_1-6Alkyl or C_1-6Alkoxy, preferably, each independently of the other, is C_1-6Alkoxy and more preferably, each is independently C_1-3An alkoxy group. In one embodiment of the present invention, the siloxane monomer represented by formula (a-3) is 3- (triethoxy)Silyl) propyl succinic anhydride.

In the negative photosensitive resin composition of the present invention, the polysiloxane compound (A) is polymerized from siloxane monomers represented by the formulae (a-1), (a-2) and (a-3). Wherein the proportion of the siloxane monomers represented by the formulae (a-1), (a-2) and (a-3) is not particularly limited. In one embodiment of the present invention, the siloxane monomer represented by formula (a-1) accounts for 10 mol% to 70 mol% of the total moles of the polysiloxane compound (A), the siloxane monomer represented by formula (a-2) accounts for 10 mol% to 70 mol% of the total moles of the polysiloxane compound (A), and the siloxane monomer represented by formula (a-3) accounts for 0.5 mol% to 40 mol% of the total moles of the polysiloxane compound (A). In another embodiment of the present invention, the siloxane monomer represented by formula (a-1) accounts for 30 to 60 mol% of the total number of moles of the polysiloxane compound (A), the siloxane monomer represented by formula (a-2) accounts for 30 to 60 mol% of the total number of moles of the polysiloxane compound (A), and the siloxane monomer represented by formula (a-3) accounts for 1 to 20 mol% of the total number of moles of the polysiloxane compound (A).

In the present invention, the phrase "siloxane monomer accounts for a mol% to Bmol% of the total number of moles of the polysiloxane compound", and more specifically, means that the siloxane monomer is contained in an amount of a mol% to B mol% based on 100 mol% of the total number of moles of the polysiloxane compound.

In the negative photosensitive resin composition of the present invention, the molecular weight of the polysiloxane compound (a) may be 1000 g/mol to 8000 g/mol, preferably 1000 g/mol to 6000 g/mol, and more preferably 1500 g/mol to 4500 g/mol.

In the negative photosensitive resin composition of the present invention, R is a low alkoxy silicate oligomer represented by the formula (b-1)₇May each independently be C_1-6Alkyl radical, C_1-6Alkoxy radical, C_6-20Aryl or C_3-6An epoxy group; preferably, each is independently C_1-6Alkyl or C_1-6Alkoxy, more preferably, each independently is C_1-3Alkyl or C_1-3An alkoxy group.

In the negative photosensitive resin composition of the present invention, a compound represented by the formula (b-1)In the low alkoxy silicate oligomer shown, R₈Can be C_1-6An alkyl group; and is preferably C_1-3An alkyl group.

In the negative photosensitive resin composition of the present invention, R is a low alkoxy silicate oligomer represented by the formula (b-1)₇And R₈The number of carbons of (a) may be the same or different. In one embodiment of the present invention, R₇May each independently be C_1-6Alkyl radical, C_1-6Alkoxy radical, C_6-20Aryl or C_3-6Epoxy group, and R₈May be a methyl group. In another embodiment of the present invention, R₇May each independently be methyl or methoxy, and R₈May be a methyl group.

In the negative photosensitive resin composition of the present invention, in the low alkoxy silicate oligomer represented by the formula (b-1), the number of alkoxy groups bonded to silicon atoms may be 20% to 50% of the total number of substituents bonded to silicon atoms. In other words, the low alkoxy silicate oligomer represented by the formula (b-1) may conform to the following formula (I):

20％≤[(R₇is the number of alkoxy groups + R₈Number of (c)/(R)₇Total number of (2) + R₈Number of (2)]x 100％≤50％ (I)。

In the negative photosensitive resin composition of the present invention, R is a high alkoxy silicate oligomer represented by the formula (b-2)₉May each independently be C_1-6Alkyl, and preferably, each is independently C_1-3An alkyl group. Further, m may be an integer of 2 to 10, preferably an integer of 5 to 10. In one embodiment of the present invention, the high alkoxy silicate oligomer represented by the formula (b-2) is methyl silicate, which is represented by the following formula (b-2'):

in the negative photosensitive resin composition of the present invention, the kind of the photoacid generator (C) is not particularly limited, and may be an ionic photoacid generator. For example, the photoacid generator (C) may be represented by any one of the following formulas (C-1) to (C-4):

in the negative photosensitive resin composition of the present invention, the content of the solvent is the residual amount of other components in the negative photosensitive resin composition, and the residual amount is the residual amount obtained by subtracting the content of other components from the total amount of the negative photosensitive resin composition. In the present invention, the kind of the solvent is not particularly limited. Specific examples of solvents include, but are not limited to, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Diethylene Glycol Monoethyl Ether Acetate (DGMEA); and the aforementioned solvents may be used alone or in combination.

In addition, the invention also provides application of the negative photosensitive resin composition in a low-temperature curing process, wherein the low temperature is below 120 ℃. Preferably at a temperature of 60 ℃ to 120 ℃; more preferably, the temperature is from 80 ℃ to 120 ℃.

Furthermore, the invention also provides the application of the negative photosensitive resin composition to the preparation of a photoresist film developed by an alkaline developer. The alkaline developer may be a developer containing KOH.

The known silicone resins do not exhibit the desired flexibility characteristics of the films formed after low temperature curing reactions. The invention provides a negative photosensitive resin composition, which is a transparent photoresist and is particularly suitable for low-temperature processes; in particular, the negative photosensitive resin composition of the present invention has excellent transparency and flexibility after being cured at low temperature, and can be applied to semiconductor processes. For example, when applied to a display panel or a touch panel, a film formed from the negative photosensitive resin composition of the present invention has excellent transparency, and can be used on a transparent insulating layer or a transparent protective layer of the display panel or the touch panel; the film formed by the negative photosensitive resin composition has excellent flexibility, and can be applied to an insulating layer or a protective layer of a flexible display panel or a touch panel.

Detailed Description

The following embodiments of the present invention are described by way of examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present invention.

As used in this specification and the appended claims, the singular forms "a", "an", and "the" may include one or more of the plural forms unless the context clearly dictates otherwise.

As used in the specification and the appended claims, the term "or" is generally employed in its sense including "and/or" unless the context clearly dictates otherwise.

The present invention will be more specifically described by way of examples, which are not intended to limit the scope of the present invention. In the following preparations, examples and comparative examples, temperatures are given in degrees centigrade and parts and percentages are by weight, unless otherwise indicated. Parts by weight relate to parts by volume as kilograms relate to liters.

PREPARATION EXAMPLE-polysiloxane Compound

In a three-necked flask having a volume of 500 ml, 93.6 g of tetraethoxysilane (TEOS, C) was charged₈H₂₀O₄Si, CAS No.: 78-10-4, as shown in the following formula (a-1-1), 89.2 g of Phenyltrimethoxysilane (PTMS, C)₉H₁₄O₃Si, CAS No.: 2996-92-1, represented by the following formula (a-2-1)) and 3- (triethoxysilyl) propylsuccinic anhydride (3- (triethoxysilyl) propylsuccinic anhydride, CAS: 93642-68-3, represented by the following formula (a-3-1), 30.44 g, 172 g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) as a solvent were added with an aqueous phosphoric acid solution at room temperature over 20 minutes while stirring. Next, the flask was immersed in an oil bath at 40 ℃ and stirred for 30 minutes, then the oil bath was heated to 110 ℃ within 30 minutes, kept at 110 ℃ for 90 minutes under reflux, distilled at 110 ℃ for 3 hours under reaction with nitrogen gas at 110 ℃ for 3 hoursThus, the polysiloxane compound A can be obtained.