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 张桂嘉 许若蓓 林凡森 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)10重量百分比至50重量百分比的聚硅氧烷化合物,其由多种单体聚合而成,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,且(a-3)所示的硅氧烷单体占聚硅氧烷化合物的总摩尔数的10mol％至50mol％；(B)0.1重量百分比至30重量百分比的硅酸酯寡聚物；(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="143" wi="700" file="DDA0001947364120000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,R<Sub>1</Sub>、R<Sub>2</Sub>、R<Sub>3</Sub>、R<Sub>4</Sub>及R<Sub>5</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)10 to 50 weight percent of polysiloxane compound, which is polymerized by a plurality of monomers, wherein the monomers comprise siloxane monomers shown in the following formulas (a-1), (a-2) and (a-3), and the siloxane monomer shown in (a-3) accounts for 10 to 50mol percent of the total mole number of the polysiloxane compound; (B)0.1 to 30 weight percent silicate oligomer; (C)0.1 to 10 weight percent of a photoacid generator; and (D) the balance solvent; wherein R is 1 、R 2 、R 3 、R 4 And R 5 As defined in the specification. In addition, the invention also relates to application of the negative photosensitive resin composition.)

1. A negative photosensitive resin composition comprising:

(A)10 to 50 weight percent of polysiloxane compound, which is polymerized by a plurality of monomers, wherein the plurality of monomers comprise siloxane monomers shown in the following formulas (a-1), (a-2) and (a-3), and the siloxane monomer shown in (a-3) accounts for 10 to 50mol percent of the total mole number of the polysiloxane compound;

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;

R₄each independently is C_1-6An alkyl group; and

R₅is C_6-20An alkyl group;

(B)0.1 to 30 weight percent silicate oligomer;

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

(D) the balance being solvent.

2. The negative photosensitive resin composition according to claim 1, wherein R is₅Is straight chain C_6-20An alkyl group.

3. The negative photosensitive resin composition according to claim 1, wherein the silicate oligomer is represented by the following formula (b-1):

wherein R is₆Each independently is C_1-6An alkyl group; and

n is an integer of 2 to 10.

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 60 mol% of the total moles of the polysiloxane compound, and the siloxane monomer represented by formula (a-2) accounts for 30 mol% to 70 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 25 mol% to 40 mol% of the total moles of the polysiloxane compound, the siloxane monomer represented by formula (a-2) accounts for 45 mol% to 55 mol% of the total moles of the polysiloxane compound, and the siloxane monomer represented by formula (a-3) accounts for 10 mol% to 25 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 of claim 1, wherein the siloxane monomer represented by formula (a-3) is decyltrimethoxysilane or hexyltrimethoxysilane.

9. The negative photosensitive resin composition according to claim 3, wherein the silicate oligomer represented by formula (b-1) is represented by the following formula (b-2):

10. the negative photosensitive resin composition of claim 1, wherein the photoacid generator is an ionic photoacid generator or a non-ionic photoacid generator.

11. 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):

12. the negative photosensitive resin composition according to claim 1, wherein the polysiloxane compound has a molecular weight of 1000 g/mol to 8000 g/mol.

13. Use of the negative photosensitive resin composition according to any one of claims 1 to 12, for a low-temperature curing process, wherein low temperature means 120 ℃ or less.

14. Use according to claim 13, wherein the temperature is from 80 ℃ to 120 ℃.

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)10 to 50 weight percent of polysiloxane compound, which is polymerized by a plurality of monomers, wherein the monomers comprise siloxane monomers shown in the following formulas (a-1), (a-2) and (a-3), and the siloxane monomer shown in (a-3) accounts for 10 to 50mol percent of the total mole number of the polysiloxane compound;

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; r₄Each independently is C_1-6An alkyl group; and R₅Is C_6-20An alkyl group;

(B)0.1 to 30 weight percent silicate oligomer (silicate oligomer);

(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). In particular, the polysiloxane compound does not include siloxane monomers containing anhydride groups. 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) can be crosslinked with other monomers, and can improve the flexibility of the formed film. 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 addition, the silicate oligomer (B) in the resin composition of the present invention can be used as a crosslinking agent, and can be further crosslinked with the polysiloxane compound (A) by an acid generated upon exposure to the photoacid generator (C). In particular, when the polymeric polysiloxane compound (a) contains the monomer represented by the formula (a-3) and the silicate oligomer (B) is used as a crosslinking agent, the negative photosensitive resin composition of the present invention can be applied to a flexible substrate to form an insulating film or a protective film having flexible characteristics.

The negative photosensitivity of the present inventionResin composition, siloxane monomer represented by the formula (a-1), R₁May 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)₄May each independently be C_1-6Alkyl, and preferably, R₄Each independently is C_1-3An alkyl group. Furthermore, R₅Can be C_6-20Alkyl, preferably straight-chain C_6-20Alkyl, more preferably C_6-10Alkyl, and most preferably straight chain C_6-10An alkyl group. In one embodiment of the present invention, the siloxane monomer of formula (a-3) is decyltrimethoxysilane, hexyltrimethoxysilane, or a combination thereof. In another embodiment of the present invention, the siloxane monomer of formula (a-3) is decyltrimethoxysilane. In yet another embodiment of the present invention, the siloxane monomer of formula (a-3) is hexyltrimethoxysilane.

In the negative photosensitive resin composition of the present invention, the polysiloxane compound (a) is polymerized from a siloxane monomer represented by the formulae (a-1), (a-2) and (a-3). Wherein the proportion of the siloxane monomer represented by the formulae (a-1) and (a-2) is not particularly limited. In one embodiment of the present invention, the siloxane monomer represented by formula (a-1) may account for 10 mol% to 60 mol% of the total moles of the polysiloxane compound, the siloxane monomer represented by formula (a-2) may account for 30 mol% to 70 mol% of the total moles of the polysiloxane compound, and the siloxane monomer represented by formula (a-3) may account for 10 mol% to 50 mol% of the total moles of the polysiloxane compound. In another embodiment of the present invention, the siloxane monomer represented by formula (a-1) may account for 25 to 40 mol% of the total moles of the polysiloxane compound, the siloxane monomer represented by formula (a-2) may account for 45 to 55 mol% of the total moles of the polysiloxane compound, and the siloxane monomer represented by formula (a-3) may account for 10 to 25 mol% of the total moles of the polysiloxane compound.

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.

Further, 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, the silicate oligomer (B) may be represented by the following formula (B-1):

wherein R is₆Each independently is C_1-6An alkyl group; and n is an integer of 2 to 10.

In the negative photosensitive resin composition of the present invention, R is a silicate oligomer represented by the formula (b-1)₆May each independently be C_1-6Alkyl, and preferably, R₆Each independently is C_1-3An alkyl group. Further, n may be an integer of 2 to 10, and n is preferably an integer of 5 to 10. In one embodiment of the present invention, the silicate oligomer represented by the formula (b-1) is methyl silicateate) 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 or a nonionic 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, the temperature is 60 ℃ to 120 ℃; more preferably, the temperature is 80 ℃ to 120 ℃.

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), 99 g of Phenyltrimethoxysilane (PTMS), 13 g of decyltrimethoxysilane (KBM-3103), and 172 g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) as a solvent were charged, and an aqueous phosphoric acid solution was added over 20 minutes at room temperature with stirring. Then, 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, and then heated at 110 ℃ for 90 minutes under constant temperature, and then distilled at 110 ℃ under constant temperature and reacted with nitrogen for 3 hours to obtain polysiloxane compound A-1.

Polysiloxane compounds A-2 to A-7 were prepared in accordance with the compositional formula of Table 1 below, using the same procedure. The weight average Molecular Weight (MW) and the polydispersity index (PDI) of the synthesized polysiloxane compound are shown in table 1 below. Wherein "mol%" refers to the percentage of siloxane monomers based on the total moles of polysiloxane compound.

TABLE 1

TEOS: tetraethoxysilane (tetraethoxysilane), C₈H₂₀O₄Si, CAS No.: 78-10-4, as shown in the following formula (a-1-1);

PTMS: phenyltrimethoxysilane (Phenyltrimethoxysilane), C₉H₁₄O₃Si, CAS No.: 2996-92-1, represented by the following formula (a-2-1);

KBM-3103: decyltrimethoxysilane, CAS No.: 5575-48-4, represented by the following formula (a-3-1);

KBM-3063: hexyltrimethoxysilane, CAS No.: 3069-19-0, as shown in the following formula (a-3-2);