Photosensitive resin composition, color filters and display devices

Abstract

This invention discloses a photosensitive resin composition, a color filter, and a display device. The photosensitive resin composition has the characteristic of curing after irradiation by an exposure machine. The photosensitive resin composition includes: a colorant, a resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator has a λ value, which conforms to the following formula: 0.3 ≤ [(A*B) + (C*D)]*E ≤ 2.5. In the above formula, A represents the light intensity I at a wavelength of 340 nm from the exposure machine. 340 With 365nm light intensity I 365 The ratio (I) 340 / I 365 B represents the percentage of light absorption intensity of the photopolymerization initiator at a wavelength of 340 nm; C represents 1; D represents the percentage of light absorption intensity of the photopolymerization initiator at a wavelength of 365 nm; and E represents the weight of the photopolymerization initiator / weight of the photosensitive resin composition.

Description

Technical Field

[0001] This invention relates to a resin composition, a color filter, and a display device, and particularly to a photosensitive resin composition, a color filter, and a display device. Background Technology

[0002] Display devices are widely used in daily life, including various portable or non-portable electronic products, workplace equipment, smart home appliances, transportation, and public uses, to provide relevant information and / or interactive modes, enhancing the convenience and enjoyment of users' lives and work. Photoresist plays a crucial role in display devices. Taking color LCD displays as an example, color filters are one means of achieving full-color display and thus increasing its added value. Color filters consist of photoresist of different colors, using filtering to generate red (R), green (G), and blue (B) primary colors of light, which are then mixed in different intensities to present various colors. Color photosensitive resin is the main raw material for the photoresist in color filters. The photoresist in color filters is formed by curing red, green, and blue (RGB) color photosensitive resin compositions.

[0003] Although the photosensitive resin compositions currently used to form photoresists are generally suitable in terms of formation methods, they do not fully meet all the requirements, and various attempts and adjustments are still being made to form photosensitive resin compositions for photoresists. Summary of the Invention

[0004] Some embodiments of the present invention disclose a photosensitive resin composition having the characteristic of curing after exposure to an exposure machine. The photosensitive resin composition may include a colorant, a resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. The photopolymerization initiator in the photosensitive resin composition may have a λ value, the λ value conforming to the following formula:

[0005] 0.3≦[(A*B)+(C*D)]*E≦2.5;

[0006] Where A represents the light intensity I at a wavelength of 340nm for the exposure machine. 340 With 365nm light intensity I 365 The ratio (I) 340 / I 365 );

[0007] B represents the absorption intensity of the photopolymerization initiator at a wavelength of 340 nm (in percentage).

[0008] C represents 1;

[0009] D represents the absorption intensity of the photopolymerization initiator at a wavelength of 365 nm (in percentage); while

[0010] E represents the weight of the photopolymerization initiator divided by the weight of the photosensitive resin composition.

[0011] Some embodiments of the present invention disclose a color filter that may include a photoresist formed by curing a photosensitive resin composition as described above.

[0012] Some embodiments of the present invention disclose a display device that may include the color filter described above. Detailed Implementation

[0013] Color filters are formed by coating a color photosensitive resin composition onto a substrate and then baking it at high temperature or irradiating it with an exposure machine to cure the color photosensitive resin composition into a photoresist. If the cross-linking of the components in the color photosensitive resin composition is insufficient, the cured photoresist will have disadvantages such as a loose internal structure, a small number of supports, or easy electron movement, resulting in poor volume impedance or electrical performance of the photoresist. Improving the volume impedance or electrical performance of the photoresist by selecting, adjusting, or changing the components and their proportions in the photosensitive resin composition to obtain a photoresist with a tight internal structure, a large number of supports, or less electron movement is also a focus of industry efforts.

[0014] It will be further understood that when the terms “comprises,” “comprising,” “includes,” and / or “including” are used in this specification, they specifically refer to the presence of the stated feature, integer, step, operation, element, component, and / or group thereof, but do not exclude the presence or addition of one or more other feature, integer, step, operation, element, component, and / or group thereof. When the singular forms “a” and “an” are used in this specification, they are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0015] In addition, unless otherwise explicitly stated, numerical values ​​relating to a particular component should be interpreted as including tolerance ranges in the component interpretation.

[0016] In this invention, the expression “ab” used to represent a specific numerical range is defined as “≥a and ≤b”.

[0017] The "C1-C" in this invention 20 Alkyl group and unsubstituted C1-C 20 Alkyl groups can be used interchangeably. "C1-C" 20 Alkyl / Unsubstituted C1-C20 "Alkyl" refers to a straight-chain or branched aliphatic hydrocarbon monovalent group in which all hydrogen atoms are unsubstituted and the main carbon chain has 1 to 20 carbon atoms. "Substituted C1-C..." 20 "Alkyl" refers to C1-C 20 At least one hydrogen atom on the alkyl group is occupied by a hydroxyl group, oxygen, or a substituted or unsubstituted C1-C atom. 20 Alkyl-substituted monovalent groups. Unsubstituted C1-C 20 Non-limiting examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, decaalkyl, dodecyl, pentadecyl, or eicosyl. The "C1-C" used in this invention... 20 "Lynyl" refers to compounds related to C1-C2. 20 Alkyl groups have the same structure as divalent groups.

[0018] The "C5-C" in this invention 20 "Cycloalkyl" and "Unsubstituted C5-C" 20 "Cycloalkyl" can be used interchangeably. "C5-C 20 Cycloalkyl / Unsubstituted C5-C 20 "Cycloalkyl" refers to a cyclic aliphatic hydrocarbon monovalent group in which all hydrogen atoms are unsubstituted and the hydrocarbon has 5 to 20 carbon atoms. "Substituted C5-C..." 20 "Cycloalkyl" refers to C5-C64 alkyl groups. 20 At least one hydrogen atom on the cycloalkyl group is occupied by a hydroxyl group, an oxygen atom, or a substituted or unsubstituted C1-C atom. 20 Alkyl-substituted monovalent groups. Unsubstituted C5-C 20 Non-limiting examples of cycloalkyl groups include, but are not limited to, cyclohexyl, dicycloheptyl, dicyclooctane, or tricyclodecyl.

[0019] In this invention, "acrylate group" and "unsubstituted acrylate group" can be used interchangeably. "Substituted acrylate group" refers to an acrylate group in which at least one hydrogen atom is replaced by a hydroxyl group, an oxygen group, or a substituted or unsubstituted C1-C atom. 20 Alkyl groups are substituted with monovalent groups. In some embodiments, the acrylic groups of the present invention have a structure Monovalent groups.

[0020] The "C1-C" in this invention 20 "Alkoxyphenyl" and "unsubstituted C1-C" 20 "Alkoxyphenyl" can be used interchangeably. "C1-C 20 Alkoxyphenyl / C1-C 20 "Alkoxyphenyl" refers to a phenyl group in which all hydrogen atoms are unsubstituted and it has a "C1-C" structure. 20 The monovalent group of "alkyl-O-phenyl". "Substituted C1-C..."20 "Alkoxyphenyl" refers to C1-C 20 C1-C in alkoxyphenyl 20 At least one hydrogen atom on the alkyl group is occupied by a hydroxyl group, oxygen, or a substituted or unsubstituted C1-C atom. 20 Alkyl groups are monovalent groups that are replaced by alkyl groups.

[0021] In this invention, "C1-C" 20 "alkylnitroso" refers to a group whose hydrogen atoms are not substituted and which has a "C1-C" structure. 20 The monovalent group is "alkyl-NO". In this invention, "isocyanate group" refers to a monovalent group with the structure "-CNO". In this invention, "nitro group" is a monovalent group with the structure "-NO2".

[0022] In this invention, "percentage value" refers to the value before the percentage symbol "%". For example, the percentage value of light absorption intensity a% refers to "a".

[0023] The following detailed description provides various embodiments. These embodiments are merely illustrative and do not limit the scope of protection intended for this invention. Other features, elements, methods, and parameters can still be used to implement this invention. The embodiments are presented only to illustrate the technical features of this invention and are not intended to limit the scope of protection of this invention. Those skilled in the art will be able to make equivalent modifications and variations based on the following description without departing from the spirit of this invention.

[0024] This invention relates to a photosensitive resin composition that cures upon exposure to an exposure machine. The photosensitive resin composition comprises: a colorant, a resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator has a λ value that conforms to the following formula:

[0025] 0.3≦[(A*B)+(C*D)]*E≦2.5.

[0026] Where A represents the light intensity I at a wavelength of 340nm for the exposure machine. 340 With 365nm light intensity I 365 The ratio (I) 340 / I 365 B represents the percentage of light absorption intensity of the photopolymerization initiator at a wavelength of 340 nm; C represents 1; D represents the percentage of light absorption intensity of the photopolymerization initiator at a wavelength of 365 nm; and E represents the weight of the photopolymerization initiator divided by the weight of the photosensitive resin composition. In one embodiment, the photosensitive resin composition has the property of curing after being irradiated with light at wavelengths of 340 nm and 365 nm using an exposure machine.

[0027] The exposure machine in the above formula refers to a UV exposure machine, for example, an exposure machine of model TME-150RSK manufactured by Topcon Corporation, but the present invention is not limited thereto. The light intensity at a wavelength of 340nm refers to the light energy intensity measured by an optical spectrum analyzer (Ocean Optic USB 2000+) when the UV exposure machine emits light at a wavelength of 340nm; while the light intensity at a wavelength of 365nm refers to the light energy intensity measured by an optical spectrum analyzer (Ocean Optic USB 2000+) when the UV exposure machine emits light at a wavelength of 365nm. In some embodiments, the light intensity at a wavelength of 365nm is greater than the light intensity at a wavelength of 340nm. For example, with the light intensity at a wavelength of 365nm as 100% as a baseline, the light intensity at a wavelength of 340nm is 7%. In this embodiment, the light intensity at a wavelength of 340nm is I... 340 With 365nm light intensity I 365 The ratio (I) 340 / I 365 It can be 0.07.

[0028] The photopolymerization initiator can be any compound capable of generating active free radicals, acids, etc., through the action of light, thereby initiating the photopolymerization reaction. In the photosensitive resin composition of the present invention, the photopolymerization initiator is not specifically limited, as long as its absorption intensity for light at a wavelength of 340 nm and for light at a wavelength of 365 nm conforms to the above formula. In some embodiments, the photopolymerization initiator may have an absorption intensity of approximately 40%-70% for light at a wavelength of 340 nm, and an absorption intensity of approximately 6%-80% for light at a wavelength of 365 nm.

[0029] In some embodiments, the photopolymerization initiator in the photosensitive resin composition of the present invention has a structure represented by the following formula II:

[0030]

[0031] Among them, R 2 Indicates NR 7 or CR 5 R 6 , where R 7 Indicates C1-C 20 alkyl nitroso or isocyanate group, R 5 and R 6 Each independently represents substituted or unsubstituted C1-C 20 Alkoxyphenyl; R 3 Indicates C1-C 20 Alkyl or nitro group; R 4 express Where R8 and R 9 Each independently represents substituted or unsubstituted C1-C 20 Alkyl; n and m each independently represent integers from 1 to 4, and when n or m is greater than 2, R 3 Or R 4 These may be the same as or different from each other; and * indicates the connection position with other parts in Formula II. In some embodiments, based on 100 parts by weight of the photosensitive resin composition, the content of the photopolymerization initiator may be 0.25-8.0 parts by weight, 0.5-7.0 parts by weight, or 0.75-5.0 parts by weight. In other words, in some embodiments, the value of the weight of the photopolymerization initiator / weight of the photosensitive resin composition may be 0.0025-0.08, 0.005-0.07, or 0.0075-0.05.

[0032] In the photosensitive resin composition of the present invention, the resin may comprise a photocurable resin, a thermosetting resin, a polymeric resin, or a combination thereof. In some embodiments, the resin may be a polymeric resin comprising the constituent units represented by the following formula I:

[0033]

[0034] Among them, R 1 Indicates hydrogen, C1-C 20 Alkyl, substituted or unsubstituted C5-C 20 cycloalkyl, or substituted or unsubstituted C1-C 20 Alkyl acrylic acid C1-C 20 Alkyl group. In some embodiments, R 1 Indicates hydrogen, Where * indicates the connection position with other parts in Formula I. In some embodiments, the weight average molecular weight of the resin is between 6,000 and 40,000. In some embodiments, based on a weight percentage of 100 parts by weight of the photosensitive resin composition, the resin content may be 1-20 parts by weight, 3-15 parts by weight, or 5-12 parts by weight.

[0035] In the photosensitive resin composition of the present invention, the purpose of the solvent is primarily to maintain the soluble state of the resin composition to achieve better coating results in future applications. Therefore, as long as the above-mentioned effect is achieved, there are no specific limitations on the use of the solvent. The solvent may include organic solvents, inorganic solvents, or combinations thereof. Examples of inorganic solvents include, but are not limited to, water. Examples of organic solvents include, but are not limited to, ester solvents, ether solvents, ketone solvents, alcohol solvents, alcohol-ether solvents, hydrocarbon solvents, pinene solvents, or any combination thereof. Examples of ketone solvents include, but are not limited to, acetone, butanone, or any combination thereof. Examples of ether solvents include, but are not limited to, diethyl ether. Examples of alcohol solvents include, but are not limited to, methanol, ethanol, n-butanol, or any combination thereof. Alcohol-ether solvents refer to solvent molecules that simultaneously possess both alcohol and ether functional groups; examples include, but are not limited to, ethylene glycol monoethyl ether. Examples of hydrocarbon solvents include, but are not limited to, toluene, xylene, or any combination thereof. Pine resin solvents are cyclic compounds obtained by distillation of natural pine resins, and examples may include, but are not limited to, turpentine, dipentene, pine oil, or any combination thereof. Ester solvents may include, but are not limited to, ethyl acetate (EAC), n-butyl acetate (BAC), propylene glycol monomethyl ether acetate, or any combination thereof. In some embodiments, the solvent may be an ester solvent. In some embodiments, the solvent may contain propylene glycol monomethyl ether acetate. In some embodiments, based on 100 parts by weight of the photosensitive resin composition, the solvent content may be 30-60 parts by weight, 30-55 parts by weight, 35-60 parts by weight, or 35-55 parts by weight.

[0036] In the photosensitive resin composition of the present invention, the colorant may include dyes, pigments, or combinations thereof. Examples of dyes may include, but are not limited to, oxanthracene dyes, cyanide dyes, triphenylmethane dyes, or any combination thereof. Examples of pigments may include, but are not limited to, CI Pigment Red R9, R97, R105, R122, R123, R144, R149, R166, R168, R175, R176, R177, R180, R192, R209, R215, R216, R224, R242, R254, R255, R264, R265, and R187. , R269, R291; CI Pigment Yellow Y3, Y12, Y13, Y14, Y15, Y16, Y17, Y20, Y24, Y31, Y53, Y83, Y86 , Y93, Y94, Y109, Y110, Y117, Y125, Y128, Y137, Y138, Y139, Y147, Y148, Y150, Y15 3. Y154, Y166, Y173, Y194, Y214, Y185; CI Pigment Blue B15, B15:3, B15:4, B15:6, B60, B80, B16; CI Pigment Orange O13, O31, O36, O38, O40, O42, O43, O51, O55, O59, O61, O64, O65, O71, O 73; CI pigment violet P1, P19, P23, P29, P32, P36, P38; CI pigment green G1, G2, G4, G7, G8, G10, G13, G14, G15, G17, G18, G19, G26, G36, G45, G48, G50, G51, G54, G55, G58, G59, G63; or any combination thereof. In some embodiments, based on 100 parts by weight of the photosensitive resin composition, the content of the colorant may be 15-55 parts by weight, 20-55 parts by weight, preferably 30-55 parts by weight, and more preferably 35-55 parts by weight.

[0037] In the photosensitive resin composition of the present invention, there is no specific limitation on the photopolymerizable monomer, and examples may include, but are not limited to, polymerizable compounds having one vinyl unsaturated bond, such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone; polymerizable compounds having two vinyl unsaturated bonds, such as 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate; and trimethylolpropane tri(meth)acrylate, ... Polymers containing three vinyl unsaturated bonds include pentaerythritol acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. In some embodiments, the photopolymerizable monomer is, for example, a compound having vinyl unsaturated double bonds. In some embodiments, the photopolymerizable monomer is, for example, a polymerizable compound having three vinyl unsaturated double bonds. In some embodiments, based on 100 parts by weight of the photosensitive resin composition, the content of the photopolymerizable monomer may be 1-10 parts by weight, preferably 2-8 parts by weight, and more preferably 3-6 parts by weight.

[0038] In some embodiments, the photosensitive resin composition may further include other additives such as leveling agents, fillers, antioxidants, light stabilizers, and chain movers, but is not limited thereto.

[0039] Another aspect of the present invention relates to a color filter, which may include a photoresist formed from the photosensitive resin composition of any of the foregoing embodiments.

[0040] Another aspect of the present invention relates to a display device that may include the aforementioned color filter.

[0041] The present invention will now provide several examples to illustrate more specifically the advantages of photosensitive resin compositions according to embodiments of the present invention.

[0042] Resin preparation

[0043] Resin-1

[0044] 213.6 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was then stirred while replacing the gas with nitrogen, and the temperature was raised to 90°C. 4.0 g of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture consisting of 20.0 g (0.20 mol) of methyl methacrylate, 88.0 g (0.40 mol) of tricyclodecyl methacrylate, and 34.4 g (0.4 mol) of methacrylic acid to form a mixture. This mixture was then added dropwise to the aforementioned flask using a dropping funnel. After the addition was complete, the mixture was stirred at 95°C for 3 hours to carry out a copolymerization reaction to produce a copolymer. Next, after replacing the air in the aforementioned flask, 42.6 g (0.3 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of hydroquinone (polymerization inhibitor) were added, and a ring-opening addition reaction was carried out at 120°C for 6 hours to produce a copolymer. Then, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution with a solids concentration of 30% by mass (solids acid value 30 mg KOH / g, weight average molecular weight 37,100). The resulting copolymer is resin-1, which has the constituent units shown in the following chemical formula:

[0045]

[0046] Resin-2

[0047] Resin B2-1

[0048] A nitrogen atmosphere was created by circulating an appropriate amount of nitrogen in a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and 100 g of propylene glycol monomethyl ether acetate was added. The mixture was then heated to 85°C while stirring. Using a drop pump, a solution was added dropwise over approximately 5 hours to the flask containing a mixture of 19 g of methacrylic acid (to form the building blocks on the lower left) and 171 g of 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate (in a molar ratio of 50:50) (trade name "E-DCPA", manufactured by Daicel Inc.). The solution was dissolved in 40 g of propylene glycol monomethyl ether acetate. On the other hand, using another drop pump, a solution formed by dissolving 26 g of the polymerization initiator 2,2'-azobis(2,4-dimethylpentanonitrile) in 120 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over approximately 5 hours. After the addition of the polymerization initiator was completed, the same temperature was maintained for approximately 3 hours, followed by cooling to room temperature to obtain a copolymer (resin B2-1) solution with a solid content of 43.5%. The resulting copolymer is resin B2-1, with a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and a solid acid value of 53 mg KOH / g. Resin B2-1 has the following constituent units as shown in the chemical formula:

[0049]

[0050] Resin B2-2

[0051] In a flask equipped with a reflux condenser, dropping funnel, and stirrer, a nitrogen atmosphere was introduced, and 280 g of propylene glycol monomethyl ether acetate was added. The mixture was then heated to 80°C while stirring. Over 5 hours, a mixed solution comprising 38 g of acrylic acid, 289 g of 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02]6)decane-9-yl acrylate (containing a molar ratio of 1:1), and 125 g of propylene glycol monomethyl ether acetate was added dropwise. Simultaneously, over 6 hours, a solution containing 33 g of 2,2-azobis(2,4-dimethylpentanones) dissolved in 235 g of propylene glycol monomethyl ether acetate was added dropwise. After the addition was complete, the mixture was kept at 80°C for 4 hours, then cooled to room temperature to obtain a copolymer (resin B2-2) solution with a solid content of 35.1% and a viscosity of 125 mPas measured by a type B viscometer (23°C). The obtained copolymer is resin B2-2, with a weight-average molecular weight (Mw) of 9.2 × 10⁻⁶. 3 The molecular weight distribution (Mw / Mn) is 2.08, and the acid value (converted from solid content) is 77 mgKOH / g. Resin B2-2 has the following constituent units represented by the chemical formulas:

[0052]

[0053] Resin B2-1 and Resin B2-2 are mixed in a weight ratio of 4:6 to obtain Resin-2.

[0054] Preparation of photopolymerization initiators

[0055] Photopolymerization initiator A

[0056] Step A-1: ​​Preparation of intermediate A1

[0057] 8.8 g of diphenyl sulfide, 8.4 g of 4-bromobenzophenone, 8.9 g of sodium tripentoxy, 1.3 g of bis(triphenylphosphine)palladium, and 150 mL of toluene were mixed to form a suspension. The suspension was stirred at 100 °C for 5 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, 2.0 g of silica gel was added and stirred for 30 minutes. The mixture was filtered, and the solvent was removed by distillation at 40 °C, yielding intermediate A1 as a brown solid.

[0058] Step A-2: Preparation of intermediate A2

[0059] 12.0 g of intermediate A1 was mixed with 150 mL of nitromethane, followed by the addition of 6.15 g of acetyl chloride and 8.5 g of aluminum chloride to obtain a mixture. The mixture was stirred at room temperature for 6.5 hours. Then, 10.4 g of acetyl chloride and 15.1 g of aluminum chloride were added to the mixture, and the mixture was stirred at room temperature for 2 hours to obtain a reaction solution. The reaction solution was poured into an ice bath for cooling, and extraction was performed using ethyl acetate. After washing the organic layer with dilute hydrochloric acid and removing the solvent by distillation at 40 °C, crystallization was performed to obtain intermediate A2 as a cream-colored solid.

[0060] Step A-3: Preparation of intermediate A3

[0061] 8.5 g of intermediate A2 was mixed with 56 mL of ethanol to obtain a solution. 3.23 g of hydroxylamine hydrochloride, 4.07 g of 1-chloropropane, and 50 mL of water were added to this solution, and the mixture was stirred under reflux for 4 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, it was extracted with ethyl acetate. The organic layer was washed with saturated brine, and the solvent was removed by distillation at 40 °C to obtain intermediate A3.

[0062] Step A-4:

[0063] 12.6 g of intermediate A3 was mixed with 50 mL of chloroform to obtain a solution. 5.18 g of triethylamine and 3.83 g of 2-chloroethanol were added to this solution under ice bath cooling. The solution was stirred overnight at room temperature to obtain a reaction solution. Water was added to the reaction solution under ice bath cooling, and oil-water separation was performed. The organic layer was washed with water, and the solvent was removed by distillation at 40 °C to obtain a yellow amorphous photopolymerization initiator A. Photopolymerization initiator A has the structure shown below:

[0064]

[0065] Photopolymerization initiator B

[0066] Step B-1: Preparation of intermediate B1

[0067] 7.76 g of diphenyl sulfide, 8.4 g of 4-bromobenzophenone, 7.79 g of sodium tripentoxy, 0.6 g of bis(triphenylphosphine)palladium, and 100 mL of toluene were mixed to form a suspension. The suspension was stirred at 100 °C for 5 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, 2.0 g of silica gel was added and stirred for 30 minutes. The mixture was then filtered, and the solvent was removed by distillation at 40 °C to obtain intermediate B1 as a brown solid.

[0068] Step B-2: Preparation of intermediate B2

[0069] 13.0 g of intermediate B1 was mixed with 150 mL of nitromethane to form a solution. 6.51 g of acetyl chloride and 8.5 g of aluminum chloride were added to this solution, and the mixture was stirred at this temperature for 6.5 hours. Then, 10.4 g of acetyl chloride and 18.1 g of aluminum chloride were added to the solution, and the mixture was stirred at room temperature for 2 hours to obtain a reaction solution. The reaction solution was poured into an ice bath for cooling, and extracted with ethyl acetate. After washing the organic layer with dilute hydrochloric acid and removing the solvent by distillation at 40 °C, crystallization was performed to obtain intermediate B2, a cream-colored solid.

[0070] Step B-3: Preparation of intermediate B3

[0071] 7.6 g of intermediate B2 was mixed with 56 mL of ethanol to form a solution. 2.93 g of hydroxylamine hydrochloride, 3.17 g of fulminate, and 40 mL of water were added to this solution, and the mixture was stirred under reflux for 4 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, it was extracted with ethyl acetate. The organic layer was washed with saturated brine, and the solvent was removed by distillation at 40 °C to obtain intermediate B3.

[0072] Step B-4:

[0073] 12.6 g of intermediate B3 was mixed with 50 mL of chloroform to form a solution. 5.28 g of triethylamine and 4.23 g of 1-chloropentane were added to this solution under ice bath cooling, and the mixture was stirred overnight at room temperature to obtain a reaction solution. The reaction solution was cooled in an ice bath, water was added, and oil-water separation was performed. The organic layer was washed with water, and the solvent was removed by distillation at 40 °C to obtain a yellow amorphous photopolymerization initiator B. Photopolymerization initiator B has the following structure:

[0074]

[0075] Photopolymerization initiator C

[0076] Step C-1: Preparation of intermediate C1

[0077] A suspension was prepared by mixing 8.76 g of diphenyl sulfide, 10.4 g of 4-bromobenzophenone, 8.79 g of sodium tripentoxy, and 0.9 g of bis(triphenylphosphine)palladium with 150 mL of toluene. The suspension was stirred at 100 °C for 5 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, 2.0 g of silica gel was added and the mixture was stirred for 30 minutes. The solution was then filtered, and the solvent was removed by distillation at 40 °C, yielding intermediate C1 as a brown solid.

[0078] Step C-2: Preparation of intermediate C2

[0079] 15.0 g of intermediate C1 was mixed with 150 mL of nitromethane to form a solution. 6.19 g of acetyl chloride and 10.5 g of aluminum chloride were added to this solution, and the mixture was stirred at room temperature for 6.5 hours. Then, 12.4 g of acetyl chloride and 20.1 g of aluminum chloride were added to the solution, and the mixture was stirred at room temperature for 2 hours to obtain a reaction solution. The reaction solution was poured into an ice bath for cooling, and extracted with ethyl acetate. After washing the organic layer with dilute hydrochloric acid and removing the solvent by distillation at 40 °C, crystallization was performed to obtain intermediate C2 as a cream-colored solid.

[0080] Step C-3: Preparation of intermediate C3

[0081] 8.0 g of intermediate C2 was mixed with 56 mL of ethanol to form a solution. 2.53 g of hydroxylamine hydrochloride, 9.57 g of chloroethane, and 30 mL of water were added to this solution, and the mixture was stirred under reflux for 4 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, it was extracted with ethyl acetate. The organic layer was washed with saturated brine, and the solvent was removed by distillation at 40 °C to obtain intermediate C3.

[0082] Step C-4:

[0083] 11.6 g of intermediate C3 was mixed with 50 mL of chloroform to form a solution. 4.78 g of triethylamine and 3.53 g of 1-chlorodecane were added to this solution under ice bath cooling. The solution was stirred overnight at room temperature to obtain a reaction solution. The reaction solution was cooled in an ice bath, water was added, and oil-water separation was performed. The organic layer was washed with water, and the solvent was removed by distillation at 40 °C to obtain a yellow amorphous photopolymerization initiator C. Photopolymerization initiator C has the following structure:

[0084]

[0085] Photopolymerization initiator D

[0086] Step D-1: Preparation of intermediate D1

[0087] 9.5 g of phenylnaphthylamine, 12 g of 4-bromobenzophenone, 8 g of sodium tripentoxy, and 1.2 g of bis(triphenylphosphine)palladium were mixed with 200 mL of toluene to form a suspension. The suspension was stirred at 100 °C for 5 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, 2.0 g of silica gel was added and stirred for 30 minutes. The mixture was then filtered, and the solvent was removed by distillation at 40 °C to obtain intermediate D1 as a brown solid.

[0088] Step D-2: Preparation of intermediate D2

[0089] 10.3 g of intermediate D1 was mixed with 150 mL of nitromethane to form a solution. 5.5 g of acetyl chloride and 11 g of aluminum chloride were added to this solution, and the solution was stirred at room temperature for 6 hours. Then, 13 g of acetyl chloride and 28 g of aluminum chloride were added to the solution to obtain a reaction mixture. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into an ice bath for cooling, and extracted with ethyl acetate. After washing the organic layer with dilute hydrochloric acid and removing the solvent by distillation at 40 °C, crystallization was performed to obtain intermediate D2 as a cream-colored solid.

[0090] Step D-3: Preparation of intermediate D3

[0091] 4.9 g of intermediate D2 was mixed with 75 mL of ethanol to form a solution. 1.8 g of hydroxylamine hydrochloride, 3.1 g of 4-oximevaleric acid, and 30 mL of water were added to this solution, and the mixture was stirred under reflux for 4 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, it was extracted with ethyl acetate. The organic layer was washed with saturated brine, and the solvent was removed by distillation at 40 °C to obtain intermediate D3.

[0092] Step D-4:

[0093] 3.5 g of intermediate D3 was mixed with 100 mL of chloroform to form a solution. 3.1 g of 6-chlorohexanol and 2.2 g of acetyl chloride were added to this solution under ice bath cooling, and the solution was stirred overnight at room temperature to obtain a reaction solution. The reaction solution was cooled in an ice bath, water was added, and oil-water separation was performed. The organic layer was washed with water, and the solvent was removed by distillation at 40 °C to obtain a yellow amorphous photopolymerization initiator D. Photopolymerization initiator D has the following structure:

[0094]

[0095] Photopolymerization initiator E

[0096] Step E-1: Preparation of intermediate E1

[0097] A suspension was formed by mixing 9.3 g of phenylnaphthylamine, 10.5 g of 4-bromobenzophenone, 9.3 g of sodium tripentoxyl, and 1.5 g of bis(triphenylphosphine)palladium with 250 mL of toluene. The suspension was stirred at 100 °C for 3.5 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, 2.3 g of silica gel was added and the mixture was stirred for 30 minutes. The solution was then filtered, and the solvent was removed by distillation at 40 °C to obtain a brown solid intermediate, E1.

[0098] Step E-2: Preparation of intermediate E2

[0099] An intermediate E1 of 8.3 g was mixed with 150 mL of nitromethane to form a solution. 6.5 g of acetyl chloride and 10 g of aluminum chloride were added to this solution, and the solution was stirred at room temperature for 6 hours. Then, 10 g of acetyl chloride and 25 g of aluminum chloride were added to the solution to obtain a reaction mixture. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into an ice bath for cooling, and extracted with ethyl acetate. After washing the organic layer with dilute hydrochloric acid and removing the solvent by distillation at 40 °C, crystallization was performed to obtain intermediate E2 as a cream-colored solid.

[0100] Step E-3: Preparation of intermediate E3

[0101] A solution was prepared by mixing 4.1 g of intermediate E2 with 100 mL of ethanol. 2.2 g of hydroxylamine hydrochloride, 3.7 g of sodium acetate, and 50 mL of water were added to this solution, and the mixture was stirred under reflux for 4 hours. After cooling the solution to room temperature, it was extracted with ethyl acetate. The organic layer was washed with saturated brine, and the solvent was removed by distillation at 40 °C to obtain intermediate E3.

[0102] Step E-4:

[0103] 3.3 g of intermediate E3 was mixed with 70 mL of chloroform to form a solution. 3.0 g of triethylamine and 3.0 g of acetyl chloride were added to this solution under ice bath cooling, and the solution was stirred overnight at room temperature to obtain a reaction solution. The reaction solution was cooled in an ice bath, water was added, and oil-water separation was performed. The organic layer was washed with water, and the solvent was removed by distillation at 40 °C to obtain a yellow amorphous photopolymerization initiator E. Photopolymerization initiator E has the structure shown below:

[0104]

[0105] Photopolymerization initiator F

[0106] Take a 100 mL double-necked flask and add 350.4 mg (1 mol) of 4,4'-(9-Fluorenylidene)diphenol, 190.8 mg (1 mol) of 1-chloroundecane, and 122.6 mg (1 mol) of 5-chloropentan-1-ol, each in one equivalent. Then add a 50 mL solution of tetrahydrofuran (THF). Stir and heat to 70 °C under reflux. After reacting for 1 day, cool to room temperature to obtain a reaction solution. Concentrate the reaction solution under reduced pressure to remove the tetrahydrofuran solution. Then dissolve it in dichloromethane and filter with diatomaceous earth to remove salts. After extraction with water and dichloromethane, dry the organic layer with anhydrous magnesium sulfate, filter, concentrate the filtrate under reduced pressure, and purify by column chromatography to obtain the white photopolymerization initiator F of the target compound. The photopolymerization initiator F has the following structure:

[0107]

[0108] Property evaluation of photopolymerization initiators

[0109] The absorption intensity of the photopolymerization initiator AF was measured using a UV-Vis spectrometer (Lambda 850), and the absorption intensity of the photopolymerization initiator AF for light at a wavelength of 340 nm and a wavelength of 365 nm is shown in Table 1 below.

[0110] Table 1

[0111]

[0112]

[0113] Preparation and evaluation of photosensitive resin compositions

[0114] The above-mentioned raw materials were mixed in the proportions shown in Tables 2 to 5 to prepare photosensitive resin compositions for Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-4, and 4-1 to 4-4, and Comparative Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-3, and 4-1 to 4-3, respectively, using spin coating. The above-mentioned photosensitive resin compositions were each spin-coated onto a conductive substrate to form sample films approximately 2-3 μm thick. The sample films were exposed and developed using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) with light at wavelengths of 340 nm and 365 nm, and then baked in an oven at 230°C to form photoresist by patterning the photosensitive resin compositions. Finally, gold electrodes (6 mm in diameter) were fabricated using a gold plating machine to obtain test pieces of Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-4, and 4-1 to 4-4, and Comparative Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-3, and 4-1 to 4-3.

[0115] The λ value of each photosensitive resin component was calculated based on the photopolymerization initiator used and the light intensity of the exposure machine.

[0116] λ=[(A*B)+(C*D)]*E

[0117] Where A represents the light intensity I at a wavelength of 340nm for the exposure machine. 340 With 365nm light intensity I 365 The ratio (I) 340 / I 365 B represents the percentage of light absorption intensity of the photopolymerization initiator at a wavelength of 340 nm; C represents 1; D represents the percentage of light absorption intensity of the photopolymerization initiator at a wavelength of 365 nm; and E represents the weight of the photopolymerization initiator / weight of the photosensitive resin composition.

[0118] The cross-sectional area of ​​the specimens in Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-4, and 4-1 to 4-4, and Comparative Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-3, and 4-1 to 4-3, is the area of ​​a circle with a diameter of 1 cm (radius * radius * π cm). 2The capacitance and dielectric loss values ​​of the specimens of Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-4, and 4-1 to 4-4, and Comparative Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-3, and 4-1 to 4-3, were measured using an impedance analyzer (Agilent Technologies E4990A), and their volume impedance values ​​were calculated. The thickness (unit: μm) of the specimens of Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-4, and 4-1 to 4-4, and Comparative Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-3, and 4-1 to 4-3, were measured using a contact scanning / stylus surface shape measuring instrument.

[0119] Volume impedance (R) formula: R=ρ*d / A (ρ: resistivity; A: cross-sectional area; d: thickness).

[0120] Based on the obtained volume impedance, it was determined whether the photoresists formed by curing the photosensitive resin compositions of Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-4, and 4-1 to 4-4, and Comparative Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-3, and 4-1 to 4-3, possess acceptable electrical properties. When the volume impedance is less than 2.00E+08, it indicates poor electrical performance, which is indicated by X in Tables 2 to 5. The above information is shown in Tables 2 to 5 below. The content of each component in Tables 2 to 5 is expressed as parts by weight of each component based on 100 parts by weight of the photosensitive resin composition.

[0121] Table 2

[0122]

[0123] Table 3

[0124]

[0125]

[0126] Table 4

[0127]

[0128]

[0129] Table 5

[0130]

[0131] The results in Tables 2 to 5 show that photosensitive resin compositions with a λ value less than 0.3 exhibit low volume impedance after curing, indicating poor electrical performance. Photosensitive resin compositions with a λ value greater than 2.5 result in photoresist surfaces that are uneven and unmeasurable after curing.

[0132] In summary, it can be concluded that when the photopolymerization initiator included in the photosensitive resin composition has a λ value that conforms to the above formula, the photoresist formed by the cured photosensitive resin composition will have higher volume impedance and better electrical properties. Therefore, color filters including such components and display devices including such color filters will also have better electrical properties.

[0133] The foregoing outlines the features of several embodiments of the present invention to facilitate a better understanding of the embodiments by those skilled in the art. Those skilled in the art should understand that they can design or modify other processes and structures based on the embodiments of the present invention to achieve the same objectives and / or advantages as the embodiments described herein. They should also understand that such equivalent processes and structures do not depart from the spirit and scope of the present invention, and that various changes, substitutions, and replacements can be made without departing from the spirit and scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition has the property of curing after being exposed to an exposure machine, and the photosensitive resin composition includes: One colorant; One resin; One photopolymer monomer; A photopolymerization initiator; and One solvent; The photopolymerization initiator has a value λ, which conforms to the following formula: 0.3≦[(A*B)+(C*D)]*E≦2.5; Where A represents the light intensity (I) of the exposure machine at a wavelength of 340 nm. 340 With a light intensity of 365 nm I 365 The ratio (I) 340 / I 365 ); B represents the percentage of light absorption intensity at a wavelength of 340 nm by the photopolymerization initiator; C represents 1; D represents the percentage of light absorption intensity at a wavelength of 365 nm by the photopolymerization initiator; while E represents the value of the weight of the photopolymerization initiator divided by the weight of the photosensitive resin composition. The photopolymerization initiator exhibits an absorption rate of 51.7%-70% for light at a wavelength of 340 nm, and 6%-45.5% for light at a wavelength of 365 nm. Furthermore, the irradiation intensity I at a wavelength of 340 nm using the exposure machine... 340 With a light intensity of 365 nm I 365 The ratio (I) 340 / I 365 The value is 0.07; This photopolymerization initiator has a structure represented by the following formula II: Formula II; Among them, R 2 Indicates NR 7 or CR 5 R 6 , where R 7 Indicates C1-C 20 alkyl nitroso or isocyanate group, R 5 and R 6 Each independently represents substituted or unsubstituted C1-C 20 Alkoxyphenyl; R 3 Indicates C1-C 20 Alkyl or nitro groups; R 4 express or , where R 8 and R 9 Each independently represents substituted or unsubstituted C1-C 20 alkyl; n and m each independently represent integers from 1 to 4. When n or m is greater than 2, R 3 Or R 4 They may be the same as or different from each other; and * indicates the connection point with other parts in Equation II.

2. The photosensitive resin composition according to claim 1, characterized in that, The resin is a polymer resin comprising the constituent units represented by the following formula I: Formula I; Among them, R 1 Indicates hydrogen, C1-C 20 Alkyl, substituted or unsubstituted C5-C 20 Cycloalkyl, or substituted or unsubstituted acrylic groups.

3. The photosensitive resin composition according to claim 2, characterized in that, R 1 Indicates hydrogen, , , ,or , where * indicates the connection position with other parts in Equation I.

4. The photosensitive resin composition according to claim 1, characterized in that, The resin has a weight-average molecular weight between 6,000 and 40,000; and / or the resin content is 1-20 parts by weight, based on 100 parts by weight of the photosensitive resin composition.

5. The photosensitive resin composition according to claim 1, characterized in that, Based on a weight of 100 parts by weight of the photosensitive resin composition, the content of the photopolymerization initiator is 0.25-8.0 parts by weight.

6. The photosensitive resin composition according to claim 1, characterized in that, Based on 100 parts by weight of the photosensitive resin composition, the solvent content is 30-60 parts by weight; and / or based on 100 parts by weight of the photosensitive resin composition, the colorant content is 15-55 parts by weight; and / or based on 100 parts by weight of the photosensitive resin composition, the photopolymerizable monomer content is 1-10 parts by weight.

7. A color filter, characterized in that, It includes a photoresist formed by curing a photosensitive resin composition according to any one of claims 1 to 6.

8. A display device, characterized in that, It includes the color filter according to claim 7.

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