TWI618753B - Color photoresist composition - Google Patents

Abstract

A color photoresist composition and a method for detecting a dielectric constant loss rate thereof. The color photoresist composition includes a red material, a resin material, a photopolymerizable monomer, and a photoinitiator. The resin material is a first copolymer or a second copolymer. The first copolymer includes tricyclodecyl methacrylate (TCDMA), benzene, and acrylic acid (AA). The second copolymer includes epoxy dicyclopentenyl acrylate (EDCPA). ), Dicyclopentenyl acrylate (DCPA), vinyl toluene (VT), and acrylic acid (AA). The weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is 30% by weight or more. Photoinitiators include an oxime photoinitiator.

Description

Color photoresist composition

The disclosure relates to a color photoresist composition and a method for detecting a dielectric constant loss rate thereof, and more particularly to a color photoresist composition for a color filter layer and a method for detecting a dielectric constant loss rate thereof.

The color liquid crystal display device uses a color filter layer to present a color display screen, and the optical characteristics of the color filter layer have a key influence on the optical display effect of the color liquid crystal display device. The color filter layer includes photoresist layers of different colors.

When the operating frequency of the display device is changed, the photoresist layer material may be disintegrated due to the change of the operating frequency based on its own characteristics, so that the dielectric constant will decrease with the change of the operating frequency, which will have an impact on the electrical characteristics of the display device. Adverse effects.

This disclosure relates to a color photoresist composition and a method for detecting its dielectric constant loss rate. The color photoresist compositions according to the embodiments of the present disclosure all have better dielectric constant stability, so that the photoresist layer manufactured can have better electrical characteristics.

According to an embodiment of the present disclosure, a color photoresist composition is provided. The color photoresist composition includes a red material, a resin material, a photopolymerizable monomer, and a photoinitiator. The resin material is a first copolymer or a second copolymer. The first copolymer includes tricyclodecyl methacrylate (TCDMA) and acrylic acid (AA), and the second copolymer includes epoxy dicyclopentenyl acrylate (EDCPA), dicyclopentyl Dicyclopentenyl acrylate (DCPA), vinyl toluene (VT) and acrylic acid (AA). The weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is 30% by weight or more. Photoinitiators include an oxime photoinitiator.

According to another embodiment of the present disclosure, a color photoresist composition is provided. The color photoresist composition includes a color material, a resin material, a photopolymerizable monomer, and an oxime photoinitiator. The color material includes a C.I. Pigment Green 58 and a C.I. Pigment Yellow 138. The resin material includes a first copolymer or a second copolymer. The first copolymer includes tricyclodecyl methacrylate (TCDMA) and acrylic acid (AA), and the second copolymer includes epoxy dicyclopentene methacrylate (EDCPA), dicyclopentene methacrylate Esters (DCPA), vinyltoluene (VT) and acrylic acid (AA).

According to another embodiment of the present disclosure, a method for detecting a dielectric constant loss rate of a color photoresist composition is provided. The method for detecting the dielectric constant loss rate of the color photoresist composition includes: providing a color photoresist composition; measuring the color photoresist composition at a first operating frequency to obtain a first dielectric constant E1; And measuring the color photoresist composition at a second operating frequency to obtain a second dielectric constant E2, the dielectric constant loss rate of the color photoresist composition is | E1-E2 | / E1.

In order to have a better understanding of the above and other aspects of the present invention, preferred embodiments are described below in detail with the accompanying drawings, as follows:

S1 ~ S2‧‧‧ Curve

FIG. 1 illustrates the dielectric constant loss rate and the dielectric constant loss of the red photoresist composition according to the examples and comparative examples of the present disclosure.

FIG. 2 illustrates the dielectric constant loss rate and the dielectric constant loss of the green photoresist composition according to the examples and comparative examples according to the disclosure.

The color photoresist compositions according to the embodiments of the present disclosure all have better dielectric constant stability, so that the photoresist layer manufactured can have better electrical characteristics. The composition proposed in the embodiment is for illustrative purposes, and is not intended to limit the scope of the disclosure to be protected. Those with ordinary knowledge should modify or change these components according to the needs of actual implementation.

The "dielectric constant loss rate" described in this article represents the ratio of the two dielectric constant values measured at different operating frequencies. For example, the "dielectric constant loss rate (20 ~ 1000Hz)" is calculated as: ( (Dielectric constant (1000Hz)-Dielectric constant (20Hz)) / Dielectric constant (1000Hz), where the dielectric constant (1000Hz) represents the dielectric constant measured by these materials when the operating frequency is 1000Hz. The constant (20Hz) represents the dielectric constant of these materials measured at an operating frequency of 20Hz. The "dielectric constant loss rate" represents the change in the dielectric constant of these materials when the operating frequency changes. Shape can be used to show the stability of the electrical characteristics of these materials with respect to different operating frequencies.

According to some embodiments of the present disclosure, a method for detecting a dielectric constant loss rate of a color photoresist composition is proposed. The method for detecting the dielectric constant loss rate of the color photoresist composition includes: providing a color photoresist composition; measuring the color photoresist composition at a first operating frequency to obtain a first dielectric constant E1; And measuring the color photoresist composition at a second operating frequency to obtain a second dielectric constant E2, where the first dielectric constant E1 is greater than the second dielectric constant E2, the dielectric of the color photoresist composition The constant loss rate is | E1-E2 | / E1.

In some embodiments, the first operating frequency is, for example, 1000 Hz, and the second operating frequency is, for example, 20 Hz.

According to some embodiments of the present disclosure, a color photoresist composition is provided. In some embodiments, the color photoresist composition may include a red material, a resin material, a photopolymerizable monomer, and a photoinitiator. The resin material is a first copolymer or a second copolymer. The first copolymer includes tricyclodecyl methacrylate (TCDMA) and acrylic acid (AA), and uses benzene as a solvent, that is, the first copolymer is mainly composed of tricyclodecyl methacrylate Ester (TCDMA) and acrylic acid are copolymerized. The second copolymer includes epoxy dicyclopentenyl acrylate (EDCPA), dicyclopentenyl acrylate (DCPA), vinyl toluene (VT), and acrylic acid (AA) ), That is, the second copolymer is mainly copolymerized by epoxy dicyclopentene methacrylate (EDCPA), dicyclopentene methacrylate (DCPA), vinyl toluene (VT), and acrylic acid. Made. The weight of the resin material relative to the sum of the resin material and the photopolymerizable monomer The ratio is, for example, 30% by weight or more. Photoinitiators include an oxime photoinitiator.

The tricyclic decyl methyl acrylate (TCDMA) is represented by the chemical formula as follows:

Dicyclopentene methacrylate (DCPA) is represented by the chemical formula as follows:

The epoxy dicyclopentene methacrylate (EDCPA) is represented by the chemical formula as follows:

In the examples, the photopolymerizable single system is any suitable monomer having an unsaturated double bond and capable of performing a photopolymerization crosslinking reaction.

According to the embodiment of the present disclosure, the color photoresist composition can be used to make a color photoresist layer of a color filter layer, for example.

In some embodiments, the red material includes a C.I. Pigment Red 254 and a red dye. The color photoresist composition is, for example, a red photoresist composition, and can be used to make a red photoresist layer.

In some embodiments, the weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is, for example, less than 72% by weight. In some embodiments, the weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is, for example, 60 to 68% by weight.

In one embodiment, the photoinitiator in the red photoresist composition is an oxime photoinitiator, and the resin material is a first copolymer as described above, and the resin material is polymerized with respect to the resin material and the photopolymer. The weight ratio of the sum of the sexual monomers is, for example, 55 wt% or more.

In one embodiment, the resin material in the red photoresist composition is the aforementioned second copolymer, and the weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is, for example, 56% by weight or more.

In one embodiment, the photoinitiator in the red photoresist composition is an oxime photoinitiator, and the resin material is a second copolymer.

In some embodiments, the red dye in the red photoresist composition is an xanthene dye.

In some embodiments, for example, the photopolymerizable monomer may be a compound represented by the following chemical formula:

Wherein R is hydrogen or acryl.

The red photoresist compositions according to the embodiments of the present disclosure all have better dielectric constant stability, so that the red photoresist layer manufactured can have better electrical characteristics. Under the condition that the operating frequency is 20 Hz to 1000 Hz, the dielectric constant loss ratios of the red photoresist compositions in the examples are all 3.5% or less. In some embodiments, the dielectric constant loss rates are all 3% or less, preferably 2.5% or less.

According to some embodiments of the present disclosure, the color photoresist composition may include a color material, a resin material, a photopolymerizable monomer, and an oxime photoinitiator. The color material includes a C.I. Pigment Green 58 and a C.I. Pigment Yellow 138. The resin material may include a first copolymer as described above or a second copolymer as described above. In some embodiments, the color material includes C.I. Pigment Green 58 and C.I. Pigment Yellow 138. The color photoresist composition is, for example, a green photoresist composition, and can be used to make a green photoresist layer.

In one embodiment, the resin material in the green photoresist composition is the aforementioned first copolymer, and the photopolymerizable monomer may be, for example, a compound represented by the following chemical formula:

Wherein R is hydrogen or acryl.

In some embodiments, the resin material in the green photoresist composition includes the aforementioned first copolymer and a third copolymer, and the third copolymer includes tricyclodecyl methaerylate (TCDMA), diacid anhydride ( succinic anhydride (SA) and glycidyl methacrylate (GMA), that is, the third copolymer is mainly composed of methyl tricyclodecyl acrylate (TCDMA), dianhydride (SA) and methyl Glycidyl acrylate (GMA) is copolymerized.

In one embodiment, the resin material in the green photoresist composition includes the aforementioned first copolymer and the aforementioned third copolymer, and the weight ratio of the first copolymer to the sum of the resin material and the photopolymerizable monomer is, for example, It is 30% by weight or more.

In one embodiment, the resin material in the green photoresist composition includes the aforementioned first copolymer and the aforementioned third copolymer, and a weight ratio of the first copolymer to the resin material is, for example, 60% by weight or more.

The green photoresist compositions according to the embodiments of the present disclosure all have better dielectric constant stability, so that the green photoresist layer manufactured can have better electrical characteristics. Under the condition that the operating frequency is 20 Hz to 1000 Hz, the dielectric constant loss rates of the green photoresist composition of the examples are all 5% or less. Some implementation In the examples, the dielectric constant loss rates are all 4% or less.

In some embodiments of the present disclosure, the oxime photoinitiator may include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzene Peroxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-phenylhydrazine), 1,2-butanedione-1- [4 -(Phenylthio) phenyl] -2- (O-acetamidooxime), 1,2-octanedione-1- [4- (methylthio) phenyl] -2- (O- Phenylhydrazine), 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoxime)). An oxime photoinitiator may be included in an oxime ester compound, for example, 1- [9-ethyl-6- (2-methylphenylhydrazone) -9H-carbazol-3-yl] -ethyl Alkan-1-one oxime-O-acetate, ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxyphenylhydrazone) -9H-carbazole-3- Yl] -1- (O-ethenyloxime), ethyl ketone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxo Heteropentyl) methoxyphenylfluorene} -9H-carbazol-3-yl] -1- (O-ethylfluorenyloxime) and the like. In the examples, the sensitivity of the oxime ester compound is very high, and even at a low exposure amount, a pattern without edge defects and undercuts can be formed. In the examples, the oxime ester compounds can be used alone or in combination of two or more.

The embodiments are further described below. The measurement results of the red photoresist composition and the green photoresist composition and the dielectric constant loss rate of the examples and comparative examples are listed below to illustrate the characteristics of the color photoresist composition prepared by applying the present disclosure. However, the following embodiments are for illustrative purposes only and should not be construed as limitations on the implementation of the disclosure. The composition of each of the following examples and comparative examples is described in Tables 1-2, and the types of each component used are described below.

(1) Copolymer (1): TCDMA (1 to 30 parts by weight) / AA (1 to 40 parts by weight) copolymer / benzene (50 to 80 parts by weight) (solvent), copolymer (1) The molecular weight is 10,000 ~ 20,000.

(2) Copolymer (2): EDCPA (50 to 90 parts by weight) / AA (10 to 30 parts by weight) Amount) / VT (1 ~ 30) / DCPA (1 ~ 10 parts by weight) copolymer, the molecular weight of the copolymer (2) is 10,000 ~ 20,000.

(3) Copolymer (3): TCDMA (1 to 40 parts by weight) / SA (10 to 50 parts by weight) / GMA copolymer (20 to 40 parts by weight), and the molecular weight of the copolymer (3) is 5000 to 15,000.

(4) Copolymer (4): EDCPA (5 to 50 parts by weight) / AA (1 to 40 parts by weight) / N-cyclohexylmaleimide (CHMI) (40 to 90 parts by weight) / Hydroxyethyl methacrylate (HEMA) copolymer (1 to 40 parts by weight), and the molecular weight of the copolymer (4) is 5000 to 15,000.

(5) Photopolymerizable monomer (5): The chemical formula is as follows:

Wherein R is hydrogen or acryl.

(6) Photopolymerizable monomer (6): The chemical formula is as follows:

(7) Photopolymerizable monomer (7): The chemical formula is as follows:

(8) Oxime: Oxime photoinitiator.

(9) Photo initiator (DETX-S): 2,4-diethylthiazolone (2 4-dimethyl 9h-thioxanthen-9-one).

(10) Red pigment (R254): C.I. Pigment Red 254.

(11) Red dye (xanthene): xanthene dye.

(12) Green pigment (G58): C.I. Pigment Green 58.

(13) Yellow pigment (Y138): C.I. Pigment Yellow 138.

FIG. 1 shows the dielectric constant loss rate and the dielectric constant loss of the red photoresist composition of Examples E1-1 to E1-3 and Comparative Examples C1-1 to C1-4 according to the present disclosure. The dielectric constant loss rate and the dielectric constant loss of the green photoresist composition of Examples E2-1 to E2-9 and Comparative Example C2 according to the disclosure are shown. In Figures 1-2, the dielectric constant loss rate (20 ~ 1000Hz) of the left Y axis is calculated as: ((dielectric constant (1000Hz)-dielectric constant (20Hz)) / dielectric constant (1000Hz) It is represented by a bar graph; the dielectric constant loss (30Hz) on the right Y-axis is the dielectric constant loss measured at an operating frequency of 30Hz, and is represented by dashed curves S1 and S2.

First, referring to FIG. 1, the dielectric constants of all the embodiments can be seen. The number of loss rates are all below 3.5%. In detail, in Examples E1-1 and E1-2, when only the first copolymer (copolymer (1)) is used as the resin material and the first copolymer accounts for more than 55 wt% of the resin material, the dielectric constant loss rate Both are lower than 3%, and even the dielectric constant loss rate of Example E1-2 may be lower than 2.5%. In addition, in Example E1-3, when the resin material only uses the second copolymer (copolymer (2)) and the second copolymer accounts for 56 wt% or more of the resin material, the dielectric constant loss rate may be lower than 3.5%.

Please refer to Comparative Examples C1-1 and C1-2. When the resin material uses a copolymer other than the first copolymer or the second copolymer, the dielectric constant loss rate is higher than 3.5%. Please refer to Example E1-3 and Comparative Example C1-3 at the same time. Even if the resin material is a second copolymer, when the weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is greater than 72% by weight, the dielectric constant The loss rate will increase sharply, and the difference between the dielectric constant loss rates of Example E1-3 and Comparative Example C1-3 is as high as nearly 3%. In addition, please refer to Comparative Example C1-4. When a photoinitiator other than an oxime photoinitiator is used, the dielectric constant loss rate may also increase.

Furthermore, referring to FIG. 2, it can be seen that the dielectric constant loss rate of all the embodiments is lower than 5%. In detail, each of Examples E2-1 to E2-5 and E2-7 to E2-9 includes the first copolymer (copolymer (1)) and the photopolymerizable monomers each use the photopolymerizable monomer (5) And Example E2-6 includes the second copolymer ((copolymer (2)) and the photopolymerizable monomer also uses the photopolymerizable monomer (5), and the dielectric constant loss ratios thereof are all less than 5%. In Examples E2-3 to E2-5 and E2-7 to E2-9, the weight ratio of the first copolymer (copolymer (1)) to the sum of the resin material and the photopolymerizable monomer is 30 wt. Or more %, And their dielectric constant loss ratios are all approximately equal to or lower than 4%. Moreover, in Examples E2-5 and E2-9, even if the resin material further uses other copolymers, the first copolymer (copolymer (1 )) The weight ratio to the resin material is 60 or more wt%, and their dielectric constant loss rates are all about 4% or less.

In comparison, please refer to Comparative Example C2, in which the photopolymerizable monomer is not a photopolymerizable monomer (5), and the dielectric constant loss rate is greatly increased to nearly 6%.

In summary, although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope of the attached patent application.

S1‧‧‧ curve

Claims (10)

A color photoresist composition includes: 100 parts by weight of a red material, including a CI pigment red 254 and a xanthene red dye; 60-68 parts by weight of a resin material, wherein the resin material is It is a first copolymer or a second copolymer. The first copolymer includes tricyclodecyl methacrylate (TCDMA) and acrylic acid (AA). The weight of tricyclodecyl methacrylate and acrylic acid is The proportion is 1 ~ 30: 1 ~ 40. The second copolymer includes epoxy dicyclopentenyl acrylate (EDCPA), dicyclopentenyl acrylate (DCPA). , Vinyl toluene (VT) and acrylic acid (AA), wherein the weight ratio of epoxy dicyclopentene methacrylate, dicyclopentene methacrylate, vinyl toluene and acrylic acid is 50 to 90: 1 to 10: 1 to 30: 10 to 30; 32 to 40 parts by weight of a photopolymerizable monomer, wherein the weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is greater than or Equal to 30wt%, and the photopolymerizable single system is The chemical formula is as follows: Wherein R is hydrogen or acryloyl; and 100 parts by weight of a photoinitiator, including an oxime photoinitiator. The color photoresist composition according to item 1 of the scope of the patent application, wherein the weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is 60 to 68 wt%. The color photoresist composition according to item 1 of the scope of patent application, wherein the resin material is the first copolymer, and the weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is 55wt% or more. The color photoresist composition according to item 1 of the patent application range, wherein a dielectric constant loss rate of the color photoresist composition is less than 3.5%, and the color photoresist composition is at a first operating frequency. The measurement is performed to obtain a first dielectric constant E1, and the color photoresist composition is measured to obtain a second dielectric constant E2 at a second operating frequency. The first dielectric constant E1 is greater than the first dielectric constant E1. Two dielectric constants E2, and the dielectric constant loss rate of the color photoresist composition is | E1-E2 | / E1. The color photoresist composition according to item 1 of the patent application scope, wherein the resin material is the second copolymer. The color photoresist composition according to item 5 of the scope of the patent application, wherein the weight ratio of the resin material to the sum of the resin material and the photopolymerizable monomer is less than 72% by weight. A color photoresist composition includes: 100 parts by weight of a color material, including a CI Pigment Green 58 and a CI Pigment Yellow 138; and 30 to 70 parts by weight of a resin material, wherein the resin material includes a first copolymer Or a second copolymer, the first copolymer includes methyl tricyclodecyl acrylate (TCDMA) and acrylic acid (AA), wherein the weight ratio of methyl tricyclodecyl acrylate and acrylic acid is 1 to 30: 1 ~ 40, the second copolymer includes epoxy dicyclopentene methacrylate (EDCPA), dicyclopentene methacrylate (DCPA), vinyl toluene (VT), and acrylic acid (AA), of which epoxy two The proportion by weight of cyclopentene methacrylate, dicyclopentene methacrylate, vinyl toluene, and acrylic acid is 50 to 90: 1 to 10: 1 to 30: 10 to 30; 70 to 30 parts by weight of one A photopolymerizable monomer, and the photopolymerizable single system is represented by a chemical formula as follows: Wherein R is hydrogen or acrylyl; and 100 parts by weight of an oxime photoinitiator. The color photoresist composition according to item 7 of the patent application scope, wherein the resin material further includes a third copolymer, and the third copolymer includes tricyclodecyl methacrylate (TCDMA) and methyl Glycidyl methacrylate (GMA). The color photoresist composition according to item 7 in the scope of the patent application, wherein the weight ratio of the first copolymer to the sum of the resin material and the photopolymerizable monomer is 30% by weight or more, and / or The weight ratio of the first copolymer to the resin material is 60% by weight or more. The color photoresist composition according to item 7 of the patent application range, wherein a dielectric constant loss rate of the color photoresist composition is less than 5%, and the color photoresist composition is at a first operating frequency. The measurement is performed to obtain a first dielectric constant E1, and the color photoresist composition is measured to obtain a second dielectric constant E2 at a second operating frequency. The first dielectric constant E1 is greater than the first dielectric constant E1. Two dielectric constants E2, and the dielectric constant loss rate of the color photoresist composition is | E1-E2 | / E1.