TWI739360B - Negative photosensitive resin composition and use thereof - Google Patents

Abstract

A negative photosensitive resin composition is disclosed, which comprises: (A) 0.1 to 10 wt% of acrylic monomer or oligomer; (B) 0.2 to 30 wt% of acrylic resin; (C) 0.1 to 5 wt% of photo initiator; (D) 0.01 to 1 wt% of thermal initiator; (E) 0.1 to 5 wt% of epoxy monomer; and (F) organic solvent. Herein, a content of the acrylic monomer or oligomer is 25% to 45% of a total weight of the acrylic monomer or oligomer and the acrylic resin. Furthermore, the present disclosure also relates to a use of the aforesaid negative photosensitive resin composition in a roll to roll process.

Description

Negative photosensitive resin composition and its use

The present disclosure relates to a negative photosensitive resin composition and its application, in particular to a negative photosensitive resin composition used in a roll-to-roll manufacturing process and its application.

Old electronic devices (for example, display devices, touch devices or touch display devices, etc.) use glass as a substrate, which is not flexible, and is not suitable for electronic devices with curved designs or folding functions. Therefore, the industry has tried to replace glass with flexible substrates (for example, thin films). However, the conventional photoresist materials used in the glass process have the following shortcomings.

First, flexible substrates (for example, films) are often unable to withstand high-temperature processes, and the upper limit of the temperature must be below 140°C. However, when using photoresist materials traditionally used in the glass process, if the curing temperature is lowered below 140°C, the reaction temperature is insufficient, which will lead to poor reliability.

In addition, when a flexible substrate (for example, a film) is used and a roll-to-roll process is used, the cost of mass production can be significantly reduced. However, when using currently known photoresist materials that can be cured at low temperatures, although they can react below 140°C and meet the reliability requirements, they have sticking problems after soft baking and cannot be rewinded. They are not suitable for reeling. Volume process.

In view of this, there is an urgent need to develop a photosensitive resin composition that can improve the aforementioned problems and be applied to the roll-to-roll process.

The main purpose of the present disclosure is to provide a negative photosensitive resin composition, the formed film has non-stick properties, and can be applied to a roll-to-roll process.

The negative photosensitive resin composition of the present disclosure includes: (A) 0.1 to 10 weight percent of acrylic monomer or oligomer; (B) 0.2 to 30 weight percent of acrylic resin; (C) 0.1 to 5 weight percent (D) 0.01 to 1 weight percent of hot acid initiator; (E) 0.1 to 5 weight percent of epoxy monomer; and (F) the remaining organic solvent; among them, acrylic monomer Or the content of oligomer is 25% to 45% of the total weight of acrylic monomer or oligomer and acrylic resin.

In the negative photosensitive resin composition of the present disclosure, by controlling the ratio of the acrylic monomer or oligomer content to the total weight of the acrylic monomer or oligomer and the acrylic resin, the film formed will not only retain the In addition to the development characteristics, it also has non-stick characteristics. Therefore, when the negative photosensitive resin composition of the present disclosure is coated on a flexible substrate, it can be applied to a roll-to-roll process to prepare flexible electronic devices (for example, display devices, touch devices, touch devices). Display device, etc.) insulating layer or protective layer.

In the negative photosensitive resin composition of the present disclosure, the content of acrylic monomer or oligomer is 25% to 45% of the total weight of acrylic monomer or oligomer and acrylic resin, that is, 25%≦(A )/(A)+(B)≦45%. When the ratio is too low, there will be problems of inability to develop or poor development; when the ratio is too high, there will be problems of sticking after soft baking or easy to peel off after developing. In an embodiment of the present disclosure, the content of the acrylic monomer or oligomer is 25% to 33% of the total weight of the acrylic monomer or oligomer and the acrylic resin, that is, 25%≦(A)/(A) +(B)≦33%.

In the negative photosensitive resin composition of the present disclosure, (A) acrylic monomer or oligomer may be acrylic monomer, acrylic oligomer or a combination thereof. Among them, the acrylic oligomer may contain 2 to 10 acrylic monomers.

In the negative photosensitive resin composition of the present disclosure, (B) the acrylic resin may include an epoxy group-containing monomer. In an embodiment of the present disclosure, the acrylic resin can be made of methacrylic acid tricyclo[5,2,1,02,6]dec-8-yl ester (TCDMA), methacrylic acid (MAA), styrene (Styrene) , Methacrylic acid, 7-oxabicyclo[4.1.0]heptan-3-yl methyl ester (CYCLOMER M-100) and tetrahydrofuran methyl methacrylate (THFMA). More specifically, the acrylic resin can be made of methacrylic acid tricyclo[5,2,1,02,6]dec-8-yl ester, methacrylic acid, styrene, CYCLOMER M-100 and tetrahydrofuran methyl methacrylate. Aggregated. In addition, the molecular weight of the acrylic resin may be between 10,000 g/mole and 20,000 g/mole.

In the negative photosensitive resin composition of the present disclosure, (D) the thermal acid initiator is an initiator that can generate acid after heating. Wherein, the reaction temperature of the hot acid initiator can be 50°C to 150°C or 80°C to 150°C. In the present disclosure, the thermal acid initiator can be a cationic thermal acid initiator. In addition, the acid dissociation constant (pKa) of the acid formed after the hot acid initiator is heated can be less than or equal to -20 and greater than or equal to -30, that is, -30≦pKa≦-20; or less than -20 and greater than or equal to- 30, that is, -30≦pKa<-20. In an embodiment of the present disclosure, the acid radical of the thermal acid initiator is SbF6 ^- or B(C ₆ F ₅ ) ^- ; but the present disclosure is not limited to this.

In the negative photosensitive resin composition of the present disclosure, the type of (E) epoxy monomer is not particularly limited, as long as it is an epoxy group-containing monomer. In an embodiment of the present disclosure, the epoxy monomer may include bis(3,4-epoxycyclohexylmethyl)adipate (Bis(3,4-epoxycyclohexylmethyl)adipate), 3-epoxycyclohexylmethyl 3-Glycidoxypropyltrimethoxysilane (3-Glycidoxypropyltrimethoxysilane) or a combination thereof; but the present disclosure is not limited to this.

In addition to the aforementioned negative photosensitive resin composition, the present disclosure further provides the use of the aforementioned negative photosensitive resin composition, which is used in a roll-to-roll manufacturing process. In particular, the negative photosensitive resin composition of the present disclosure can be coated on a flexible substrate and cured at low temperature to form an insulating layer or protective layer. Since the negative photosensitive resin composition disclosed in the present disclosure has the characteristics of non-sticking on the surface after being cured at low temperature, it can be used in a roll-to-roll manufacturing process and can be wound and stored.

In the present disclosure, the flexible substrate can be a flexible substrate or a thin film. In addition, the material of the flexible substrate may include polycarbonate (PC), polyimide (PI), polypropylene (PP), polyethylene terephthalate (PET) ), or other plastic or polymer materials; but this disclosure is not limited to this. Furthermore, in the present disclosure, the low temperature may be below 140°C, for example: 80°C to 140°C or 120°C to 140°C.

The following is a specific embodiment to illustrate the implementation of the present disclosure. Those who are familiar with this technique can easily understand the other advantages and effects of the present disclosure from the content disclosed in this specification. The present disclosure can also be implemented or applied by other different specific embodiments, and various details in this specification can also be modified and changed according to different viewpoints and applications without departing from the spirit of the creation.

In this article, unless otherwise specified, the so-called feature A "or" or "and/or" feature B refers to the presence of nails alone, B alone, or both A and B; the so-called feature A "and" or "and" or "and" feature B is that the nail exists at the same time as B; the so-called "include", "include", "have", and "contain" refer to including but not limited to this.

In addition, if a value is between a first value and a second value, the value may be the first value, the second value, or another value between the first value and the second value.

Furthermore, in this article, a value "about" refers to a range including ±10% of the value, especially a range of ±5% of the value. The quantity given here is an approximate quantity, which means that the meaning of "covenant" can still be implied in the absence of a specific description of "covenant".

The present disclosure will be described in more detail through embodiments, but these embodiments are not used to limit the scope of the present disclosure. Unless otherwise specified, in the following preparation examples, examples and comparative examples, the temperature is Celsius, and the parts and percentages are by weight. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters.

Examples and Comparative Examples

In the following examples and comparative examples of this disclosure, the acrylic monomer or oligomer used is M-400 (CAS NO.: 29570-58-9), and its structure is shown in the following formula (A-1):

In the following examples and comparative examples of the present disclosure, the synthetic method of the acrylic resin (B-1) used is as follows.

In a flask equipped with a condenser and a stirrer, 4 parts by weight of the thermal radical initiator 2,2'-azobisisobutyl (AIBN) and 282 parts by weight of the solvent methyl ethyl diethylene glycol (Methyl Ethyl Di Glycol, MEDG), then add 46 parts by weight of tricyclodecanyl methacrylate (TCDMA), 21 parts by weight of methacrylic acid (MAA), 3 parts by weight of styrene (Styrene), 40 parts by weight of methacrylic acid, 7-oxabicyclo[4.1.0]hept-3-ylmethyl ester (Methacrylic acid, 7-oxabicyclo[4.1.0]hept-3 -ylmethyl ester, CYCLOMER M-100, manufactured by Daicel Chemical Industries, Ltd), 12 parts by weight of Tetrahydrofurfuryl methacrylate (THFMA), replaced with nitrogen, and then rapidly stirred to maintain the temperature at 65°C After 3 and a half hours, the temperature was increased to 75°C for 2 and a half hours to obtain a resin copolymer solution (B-1) with a solid content of 31.8% by weight and an average molecular weight (Mw) of 11,000.

In the following examples and comparative examples of the present disclosure, the photoinitiator used is: I-907 (CAS NO.: 71686-10-5), the structure of which is shown in the following formula (C-1); and ITX (CAS NO.: 5495-84-1), its structure is shown in the following formula (C-2):

In the following embodiments and comparative examples of the present disclosure, the structure of the thermal acid initiator used, the acid formed and the dissociation constant (pKa) of the acid radical are shown in Table 1 below.

Table 1

In the following examples and comparative examples of the present disclosure, the epoxy monomer used is: Bis(3,4-epoxycyclohexylmethyl)adipate (Bis(3,4-epoxycyclohexylmethyl)adipate) ( DM 4128E, CAS NO.: 3130-19-6), its structure is shown in the following formula (E-1); and 3-Glycidoxypropyltrimethoxysilane (A-187, CAS NO.: 2530-83-8), its structure is shown in the following formula (E-2):

In the following examples and comparative examples of this disclosure, the organic solvent (F-1) used is 1-Methoxy-2-propyl acetate (PGMEA) (CAS NO.: 108-65-6).

The aforementioned acrylic monomers or oligomers, acrylic resins, photoinitiators, thermal acid initiators, epoxy monomers and organic solvents were formulated into Examples 1 to 9 according to the composition formula shown in Table 4 below And the negative photosensitive resin composition of Comparative Examples 1 to 5.

Test case

First, prepare a substrate, which is a thin film with ITO formed on the surface, and clean the surface of the substrate with deionized water and acetone. Next, the negative photosensitive resin compositions prepared in the foregoing Examples 1 to 9 and Comparative Examples 1 to 5 were uniformly coated on the substrate by spin coating. Next, soft bake at 80°C for 5 minutes, and use a photomask to directly expose the negative photosensitive resin composition coated on the surface of the substrate ^{with a high-pressure mercury lamp (exposure energy: 100mJ/cm 2 ).} Next, development was performed with 1% ENPD 23 for 100 seconds. Hard bake for 30 minutes at 140°C. Finally, the required sample is obtained, and the thickness of the sample is 1.5~2.0μm.

Stickiness test

The sample obtained after soft baking is tested for stickiness. The scoring criteria are shown in Table 2 below.

Table 2

Etching resistance test

The sample prepared according to the manufacturing process is treated with aqua regia or aluminate (40℃, 160 seconds), the test piece is washed with ultrapure water and dried, and then treated with stripper N-300 (60℃, 135 seconds), Then rinse the test piece with ultrapure water and blow-dry it for a hundred grid test. The etch resistance test evaluation criteria are shown in Table 3 below.

table 3

Table 4

As shown in the results in Table 4, when the content of acrylic monomer or oligomer accounts for the ratio of the total weight of acrylic monomer or oligomer and acrylic resin (ie, (A)/(A)+(B)) At 20% (Comparative Example 1), the developability of the negative photosensitive resin composition is poor. When the ratio exceeds 45% (Comparative Examples 2 to 5), the formed film may be sticky. However, when this ratio is controlled within the range of 25% to 45% (implementation Examples 1 to 9), the negative photosensitive resin composition not only maintains good developability, but also has excellent anti-sticking properties. Therefore, the negative photosensitive resin composition of the present disclosure can be effectively applied to a roll-to-roll manufacturing process.

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

Claims (10)

A negative photosensitive resin composition, comprising: (A) 0.1 to 10 weight percent of acrylic monomer or oligomer; (B) 0.2 to 30 weight percent of acrylic resin; (C) 0.1 to 5 weight percent of light Initiator; (D) 0.01 to 1 weight percent of thermal acid initiator; (E) 0.1 to 5 weight percent of epoxy monomer; and (F) the balance of organic solvent; wherein, the acrylic monomer or The content of the oligomer is 25% to 33% of the total weight of the acrylic monomer or oligomer and the acrylic resin. The negative photosensitive resin composition according to claim 1, wherein the thermal acid initiator is a cationic thermal acid initiator. The negative photosensitive resin composition according to claim 1, wherein the acid dissociation constant of the acid formed after the thermal acid initiator is heated is less than or equal to -20 and greater than or equal to -30. The negative photosensitive resin composition according to claim 3, wherein the acid dissociation constant of the acid formed after the thermal acid initiator is heated is less than -20 and greater than or equal to -30. The negative photosensitive resin composition according to claim 1, wherein the acid radical of the thermal acid initiator is SbF ₆ ^- or B(C ₆ F ₅ ) ^- . The negative photosensitive resin composition according to claim 1, wherein the molecular weight of the acrylic resin is between 10,000 g/mole and 20,000 g/mole. The negative photosensitive resin composition according to claim 1, wherein the acrylic resin includes an epoxy group-containing monomer. The negative photosensitive resin composition according to claim 1, wherein the acrylic resin is composed of tricyclo[5,2,1,02,6]dec-8-yl methacrylate (TCDMA), methacrylic acid (MAA), styrene (Styrene), methacrylic acid, 7-oxabicyclo[4.1.0]heptan-3-yl methyl ester (CYCLOMER M-100) and tetrahydrofuran methyl methacrylate (THFMA) form. The negative photosensitive resin composition according to claim 1, wherein the epoxy monomer includes bis(3,4-epoxycyclohexanemethyl)adipic acid, 3-glycidoxypropyltrimethoxy Silane or a combination thereof. A use of the negative photosensitive resin composition according to any one of claims 1 to 9 in a roll-to-roll manufacturing process.