TWI614575B - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition. The photosensitive resin composition includes a colorant, a resin material, and a monomer. The colorant and the monomer are mixed in a resin material. The resin material includes a first resin and a second resin. The average molecular weight of the first resin is greater than or equal to 20,000, and the weight ratio of the first resin to the resin material is greater than 0 wt% to less than or equal to 100 wt%. The weight ratio of the resin material to the sum of the resin material and the monomer is 50% by weight or more.

Description

Photosensitive resin composition

The present disclosure relates to a photosensitive resin composition, particularly a photosensitive resin composition for a color filter layer.

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, for example, including a red photoresist layer, a green photoresist layer, and a blue photoresist layer. Usually, photoresist layers of different colors need to be separately manufactured during the manufacturing process.

This disclosure relates to a photosensitive resin composition. In the photosensitive resin composition of the embodiment, the average molecular weight of the first resin of the resin material is greater than or equal to 20,000, and the weight ratio of the first resin to the resin material is greater than 0 wt% to less than or equal to 100 wt%, and the resin The weight ratio of the material to the sum of the resin material and the monomer is 50% by weight or more, so that the coating uniformity of the photosensitive resin composition can be improved, and the film of the photoresist color layer produced by the coating can be improved. Thick uniformity, which in turn provides better optical characteristics.

According to an embodiment of the present disclosure, a photosensitive tree is provided. Lipid composition. The photosensitive resin composition includes a colorant, a resin material, and a monomer. The colorant and the monomer are mixed in a resin material. The resin material includes a first resin and a second resin. The average molecular weight of the first resin is greater than or equal to 20,000, and the weight ratio of the first resin to the resin material is greater than 0 wt% to less than or equal to 100 wt%. The weight ratio of the resin material to the sum of the resin material and the monomer is 50% by weight or more.

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:

10‧‧‧ color filter

100‧‧‧ glass substrate

100B, 100G, 100R‧‧‧Photoresistive color layer

110‧‧‧retaining wall

120‧‧‧ Coating

130‧‧‧area

2B-2B ’, 3B-B’, 4B-4B’‧‧‧ hatching

BM‧‧‧Black Matrix

S1, S2‧‧‧ curves

FIG. 1 is a schematic cross-sectional view of a color filter layer.

FIG. 2A to FIG. 4B illustrate test methods for coatings made by the photosensitive resin compositions according to the examples and comparative examples of the present disclosure.

FIG. 5 is a schematic diagram of a film thickness of a coating layer made of the photosensitive resin composition according to the examples and comparative examples of the present disclosure.

In the photosensitive resin composition of the embodiment of the disclosure, the average molecular weight of the first resin of the resin material is greater than or equal to 20,000, and the weight ratio of the first resin to the resin material is greater than 0 wt% to less than or equal to 100 wt. %, And the weight ratio of the resin material to the sum of the resin material and the monomer is 50% by weight or more, so that the coating uniformity of the photosensitive resin composition can be improved, and the photoresist made by the coating can be improved. Uniformity of the thickness of the color layer Better optical 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.

According to an embodiment of the present disclosure, a photosensitive resin composition is provided. The photosensitive resin composition includes a colorant, a resin material, and a monomer. The colorant and the monomer are mixed in a resin material. The resin material includes a first resin and a second resin. The average molecular weight of the first resin is greater than or equal to 20,000, and the weight ratio of the first resin to the resin material is greater than 0 wt% to less than or equal to 100 wt%. The weight ratio of the resin material to the sum of the resin material and the monomer is 50% by weight or more.

According to the embodiment of the disclosure, the photosensitive resin composition may be, for example, a color photoresist layer of a color filter layer. In some embodiments, the photosensitive resin composition may be, for example, a blue photosensitive resin composition or a red photosensitive material. A resin composition or a green photosensitive resin composition.

FIG. 1 is a schematic cross-sectional view of a color filter layer. As shown in FIG. 1, for example, the manufacturing method of the color filter layer 10 is to fabricate three photoresistive color layers 100R, 100G, and 100R on the glass substrate 100 by a process of coating, exposing, developing, and baking. 100B, the photoresist color layers 100R, 100G and 100B are separated by a black matrix BM. In detail, after the two photoresist color layers 100R and 100G are manufactured, the material of the third photoresist color layer 100B is coated with a conventional photosensitive resin on the glass between the two photoresist color layers 100R and 100G. When it is on the substrate 100, it is easy to cause unevenness of the upper surface of the coated third photoresist color layer 100B due to the height difference between the two photoresist color layers 100R and 100G and the glass substrate 100, making the completed The upper surface of the third photoresist color layer 100B has Shown is a bowl-shaped concave shape.

However, according to the embodiment of the present disclosure, since the average molecular weight of the first resin of the resin material is greater than or equal to 20,000, the weight ratio of the first resin to the resin material is greater than 0% by weight to 100% by weight, and The weight ratio of the resin material to the sum of the resin material and the monomer is 50% by weight or more, so that the coating uniformity of the photosensitive resin composition can be improved, and the completion of the coating is not easily affected by the unevenness of the coating surface. The flatness of the upper surface of the photoresist color layer can improve the uniformity of the film thickness of the photoresist color layer. In other words, the photoresist color layer produced by using the photosensitive resin composition of the embodiment of the present disclosure can have a uniform film thickness and a flat upper surface, so it can present a more uniform optical color, and has better Optical characteristics.

According to some embodiments, the colorant may include a pigment, such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, and the like. pigment. Alternatively, the colorant may include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like.

The pigment may be used alone or in a combination of two or more of them to increase color purity.

According to some embodiments, the colorant may include a dye. In the present invention, when the colorant is a dye, a colored composition having a state in which the dye is uniformly dissolved in the composition can be obtained. The dye is not particularly limited and a known dye hitherto used for a color filter may be used.

For the chemical structure of the dye, for example, pyrazoleazo series dyes, anilinoazo series dyes, triphenyl Methane series dyes, anthraquinone series dyes, anthrapyridone series dyes, benzylidene series dyes, oxonol series dyes, pyrazolotriazol series dyes, Pyridoneazo series dyes, cyanine series dyes, phenothiazine series dyes, pyrrolopyrazoleazomethine series dyes, xanthene series dyes , Phthalocyanine series dyes, benzopyran series dyes, indigo or pyrromethene series dyes. Multimers of these dyes can also be used.

In addition, as the colorant, an acid dye and / or a derivative thereof is preferably used in some cases. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azo dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be effectively used.

Specific examples of the acid dye are described below, but the present invention is not limited thereto. For example, Acid Alizarin Violet N; Acid Black 1, Acid Black 2, Acid Black 24, and Acid Black 48; Acid Blue 1, Acid Blue 7, Acid Blue 9, acid blue 15, acid blue 18, acid blue 23, acid blue 25, acid blue 27, acid blue 29, acid blue 40, acid blue 41, acid blue 42, acid blue 43, acid blue 44, acid blue 45, Acid blue 62, acid blue 70, acid blue 74, acid blue 80, acid blue 83, acid blue 86, acid blue 87, acid blue 90, acid blue 92, acid blue 103, acid blue 112, acid blue 113, acid blue 120, acid blue 129, acid blue 138, acid blue 147, acid blue 158, acid blue 171, acid blue 182, acid blue 192, acid blue 243, and acid blue 324: 1; Acid Chrome Violet K; Acid fuchsin Fuchsin); Acid Green 1, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 16, Acid Green 25, Acid Green 27, and Acid Green 50; Acid Orange 6, Acid Orange 7 , Acid orange 8, acid orange 10, acid orange 12, acid orange 50, acid orange 51, acid orange 52, acid orange 56, acid orange 63, acid orange 74 and acid orange 95; acid red 1, acid Red 4, Acid Red 8, Acid Red 14, Acid Red 17, Acid Red 18, Acid Red 26, Acid Red 27, Acid Red 29, Acid Red 31, Acid Red 34, Acid Red 35, Acid Red 37, Acid Red 42 , Acid red 44, acid red 50, acid red 51, acid red 52, acid red 57, acid red 66, acid red 73, acid red 80, acid red 87, acid red 88, acid red 91, acid red 92, acid Red 94, Acid Red 97, Acid Red 103, Acid Red 111, Acid Red 114, Acid Red 129, Acid Red 133, Acid Red 134, Acid Red 138, Acid Red 143, Acid Red 145, Acid Red 150, Acid Red 151 , Acid red 158, acid red 176, acid red 183, acid red 198, acid red 211, acid red 215, acid red 216, acid red 217, Sex Red 249, Acid Red 252, Acid Red 257, Acid Red 260, Acid Red 266, and Acid Red 274; Acid Violet 6B, Acid Violet 7, Acid Violet 9, Acid Violet 17, and Acid Violet 19; Acid Yellow (Acid Yellow) 1, Acid Yellow 3, Acid Yellow 7, Acid Yellow 9, Acid Yellow 11, Acid Yellow 17, Acid Yellow 23, Acid Yellow 25, Acid Yellow 29, Acid Yellow 34, Acid Yellow 36, Acid Yellow 42, Acid Yellow 54, Acid Yellow 72, Acid Yellow 73, Acid Yellow 76, Acid Yellow 79, Acid Yellow 98, Acid Yellow 99, Acid Yellow 111, Acid Yellow 112, Acid Yellow 114, Acid Yellow 116, Acid Yellow 184, and Acid Yellow 243; Food Yellow 3; and derivatives of these dyes.

In addition, azo-series acid dyes, dibenzopiperan-series acid dyes, and phthalocyanine-series acid dyes are also preferable and it is also preferable to use, for example, C.I. Solvent Blue (C.I.Solvent Blue) 44 and 38; C.I. Solvent Orange 45; Rhodamine B and Rhodamine 110; acid dyes and derivatives of these dyes.

Among them, the colorant is preferably made of triallymethane series, anthraquinone series, azomethine series, benzylidene series, oxamidine series, cyanine series, phenothiazine series, pyrrole Benzopyrazoleimine series, dibenzopiperan series, phthalocyanine series, benzopiperan series, indigo series, pyrazole azo series, aniline azo series, pyrazolotriazole azo series, pyridine Ketone azo series, anthrapyridone series and pyrrole methylene series selected colorants.

In the embodiment, the average molecular weight of the first resin is, for example, 20,000 to 40,000.

In the embodiment, the average molecular weight of the second resin is, for example, less than 20,000. For example, in some embodiments, the average molecular weight of the second resin is, for example, 6000 to less than 20,000.

In some embodiments, the first resin is, for example, an acrylic resin. In some embodiments, the first resin is, for example, a photosensitive resin having a reactive functional group, and the reactive functional group refers to a functional group capable of performing a polymerization reaction with other monomers, for example, having an unsaturated double bond. Functional group or epoxy group.

In an embodiment, the first resin may include a material selected from the group consisting of tricyclodecyl methacrylate (TCDMA), glycidyl methacrylate (GMA), and methacrylate acid (MAA). Polymerization units of at least one or two of the group consisting of benzyl methyacrylate (BzMA).

In an embodiment, the weight ratio of the first resin to the resin material is, for example, greater than 15 wt% to less than or equal to 70 wt%.

In an embodiment, the weight ratio of the first resin to the resin material is, for example, greater than 27 wt% to less than or equal to 70 wt%.

In an embodiment, the second resin may include a material selected from the group consisting of tricyclodecyl methacrylate (TCDMA), glycidyl methacrylate (GMA), acrylic acid (Aa), 2 -Ethylhexanoic acid (2-Ethylhexyl Acrylate, 2EHA) is a polymerized unit of at least one or two of the groups.

In the embodiment, the single system is any suitable monomer having an unsaturated double bond and capable of undergoing a polymerization cross-linking reaction, and may be, for example, a trifunctional to hexafunctional monomer.

In an embodiment, the monomer may include more than one acrylic-based polyfunctional monomer.

In the embodiment, the weight ratio of the resin material to the sum of the resin material and the monomer is, for example, 50 to 55 wt%.

The embodiments are further described below. The composition of the examples and comparative examples, and the test methods and test results of their coatings are listed below to illustrate the characteristics of the photosensitive resin composition prepared by applying this disclosure. However, the following embodiments are for illustrative purposes only and should not be construed as limitations on the implementation of the disclosure.

First, FIG. 2A to FIG. 4B illustrate a test method for a coating made by the photosensitive resin composition according to the examples and comparative examples of the present disclosure.

Please refer to Figs. 2A to 2B, wherein Fig. 2A is a top view, and Fig. 2B is a cross-sectional view according to the section line 2B-2B 'of Fig. 2A. Like 2A ~ 2B As shown, a glass substrate 100 is provided.

Next, please refer to FIGS. 3A to 3B, where FIG. 3A is a top view, and FIG. 3B is a cross-sectional view according to the section line 3B-3B 'of FIG. 3A. As shown in FIGS. 3A to 3B, a plurality of retaining walls 110 are formed on the glass substrate 100. The blocking wall 110 formed here may have a height of about 3 millimeters (mm), for example, to simulate a case where two kinds of color photoresist layers are formed first.

Next, please refer to FIGS. 4A to 4B, where FIG. 4A is a top view, and FIG. 4B is a cross-sectional view according to the section line 4B-4B 'of FIG. 4A. As shown in FIGS. 4A to 4B, the photosensitive resin composition of the example or the comparative example is coated on the glass substrate 100 and the retaining wall 110 to form a coating layer 120 on the glass substrate 100 and the retaining wall. 110 on.

Please refer to FIG. 5. FIG. 5 is a schematic diagram of a film thickness of a coating layer made of a photosensitive resin composition according to the examples and comparative examples of the present disclosure. In detail, FIG. 5 can be regarded as an enlarged view of the area 130 in FIG. 4B, where the X axis of FIG. 5 indicates that the two retaining walls 110 are crossed along the direction of the section line 4B-4B ′ of FIG. 4A. The Y-axis represents the height of the coating 120 with the top surface of the retaining wall 110 as 0 Angstrom (Å).

As shown in FIG. 5, the curve S1 is the cross-sectional profile of the coating of the comparative example, and the curve S2 is the cross-sectional profile of the coating of the embodiment. The composition of the photosensitive resin composition used in the coating of the comparative example is as shown in comparative column 1 shown in Tables 1 to 2 in the later paragraphs of this document, and the group of the photosensitive resin composition used in the coating of the example is Become: as shown in Implementation Example 2 listed in Tables 1-2 in the later paragraphs of this article.

As shown in FIG. 5, a comparative example (curve) formed above the retaining wall 110 The coating portion of S1) has an inverted V-shaped upper surface (the area of the X axis is about 100 to 150 microns and the area of about 230 to 270 microns), and the coating of the embodiment (curve S2) formed above the retaining wall 110 The layer portion has a relatively flat upper surface. In addition, as shown in FIG. 5, the coating portion of the comparative example (curve S1) formed between the two retaining walls 110 has a bowl-shaped concave surface (the length of the X-axis is about 160 to 220 μm). Area), and the coating portion of the embodiment (curve S2) formed between the two retaining walls 110 has a relatively flat surface. In other words, the coating made of the photosensitive resin composition of the embodiment has a flatter surface and a more uniform film thickness, so the photoresist color layer made with this coating can have better optical characteristics.

Several related experimental contents and test results are further listed below to illustrate the characteristics of the photosensitive resin composition prepared by applying the present disclosure. The composition and test results of the following examples and comparative examples are described in Tables 1-2, and the types of each component used are described below.

(1) Blue pigment: B15: 6, product of Nippon Pigment.

(2) Purple pigment: V23, product of C & A Industries.

(3) The first resin: a mixed resin of tricyclodecyl methyl acrylate (TCDMA) and propylene methacrylate (GMA), a product of Showa Japan.

(4) The second resin: the material may be selected from the materials disclosed in the foregoing description of the invention, a product of Showa Japan.

(5) Monomer: The material can be selected from the materials disclosed in the foregoing description of the invention, products of Xinzhongcun Company.

As shown in Table 2, the symbol "◎" indicates excellent, that is, the scan shape of the film thickness is inverted, and the symbol "○" indicates good, that is, the scan shape of the film thickness is inverted (also (The top shape is longer than the bottom shape), the symbol "△" indicates that it is acceptable, that is, the scanning appearance of the film thickness is U-shaped The symbol “×” indicates poor, that is, the scanning appearance of the film thickness is V-shaped.

As shown in Table 2, it can be seen that when the weight ratio of the resin material to the sum of the resin material and the monomer is 50% by weight or more, and the weight of the first resin relative to the resin material has an average molecular weight of 20,000 or more When the ratio is greater than 0% by weight and less than or equal to 100% by weight, the photosensitive resin composition has good coating characteristics, and can form a coating having a uniform film thickness and a flat upper surface, and is applied to a photoresist color layer. Can have good optical characteristics.

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, S2‧‧‧ curves

Claims (9)

A photosensitive resin composition includes: a colorant; a resin material mixed with the resin material, wherein the resin material includes a first resin and a second resin, and the first resin is unsaturated Unsaturated double bond functional group or epoxy group photosensitive resin, the second resin includes a member selected from the group consisting of tricyclodecyl methacrylate (TCDMA), methacrylic acid ring At least one or two polymerized units of the group consisting of glycidyl methacrylate (GMA), acrylic acid (Aa), and 2-Ethylhexyl Acrylate (2EHA). An average molecular weight of a resin is greater than or equal to 20,000, and a weight ratio of the first resin to the resin material is greater than 0 wt% to less than 100 wt%; and a monomer mixed in the resin material, the monomer It is a trifunctional to hexafunctional monomer having an unsaturated double bond. The weight ratio of the resin material to the sum of the resin material and the monomer is 50 or more. wt%. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the colorant comprises at least one pigment or a dye, and is mixed in the resin material. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the average molecular weight of the first resin is 20,000 to 40,000, and / or the first resin The average molecular weight of the two resins is less than 20,000. The photosensitive resin composition according to item 3 of the scope of patent application, wherein the average molecular weight of the second resin is from 6000 to less than 20,000. The photosensitive resin composition according to item 1 of the patent application scope, wherein the first resin is an acrylic resin. The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the first resin comprises a material selected from the group consisting of tricyclodecyl methacrylate (TCDMA), glycidyl methacrylate (GMA), methacrylate acid (MAA), and benzyl methyacrylate (BzMA) in at least one or two of the polymerization units. The photosensitive resin composition according to item 1 of the patent application range, wherein a weight ratio of the first resin to the resin material is greater than 15 wt% to less than or equal to 70 wt%. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the monomer includes a polyfunctional monomer having more than one acrylic group. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the weight ratio of the resin material to the sum of the resin material and the monomer is For example, it is 50 ~ 55wt%.