TWI293959B - Resin compound containing benzoquinone-cyclopentadiene adduct and photoresist composition containing the same - Google Patents

Description

1293959 IX. Description of the Invention: [Technical Field] The present invention relates to a resin compound containing a benzoquinone-cyclopentadiene adduct, and a photoresist containing the resin compound Composition. The photoresist composition of the present invention has high resolution and can be developed in an alkaline aqueous solution, and is suitable for pattern conversion, and thus can be applied to a flat panel display and an electro-optical lithography process. [Prior Art] The liquid crystal display has the advantages of small size, light weight, low voltage driving, low power consumption, easy portability, and no space occupation, and its product application range is very wide, ranging from the ordinary life field to the high-level application in industry. The ever-changing, including clockchain, computer, television, communication products, medical equipment, air transportation, industrial equipment, military special purposes, etc., make high-quality liquid crystal displays gradually replace the traditional color image tube. The color filter is one of the key components in the thin film transistor (TFT) panel module, accounting for 16.6/ of the total production cost of the entire transistor transistor panel module. about. In addition to the glass substrate, the photoresist material accounts for a considerable proportion of the material cost, and the gap control material (Ph〇t〇-Spacer) is one of the main photoresist materials. The gap control material is mainly used to control the gap between the two glass panels of the LCD panel, and the gap uniformity between the panels is determined by the size of the gate gap control material and the distribution position of the panel. The gap control materials used in the transmission and the first use are oxygen-cut or meta-ceramic materials. The main disadvantages include: Body ball 1_ easy to expose, resulting in lower panel contrast value; 102921.doc 1293959 2. Insufficient mechanical strength results in panel strength Insufficient; and - 3 · Easy free flow or agglomeration, resulting in unevenness of the gap. Undesirable color change of the panel. In order to improve the above disadvantages, a photosensitive gap control material has been developed which has excellent mechanical properties, thermal stability, and chemical resistance in addition to stable formability. The photosensitive gap control material is mainly composed of a thermosetting resin, a photoinitiator, a photosensitive polyfunctional monomer, a solvent, and other additives, and the processing flow is similar to that of the pigment dispersion type photoresist. The polymer resin is used in the gap control material to provide properties such as adhesion of the color calender sheet or the glass substrate, heat resistance, and sufficient mechanical strength. In design, the monomer typically includes a functional group that can interact with the photoreceptor, with specific functional groups increasing its adhesion to the glass. The basic requirements of the polymer resin are high light transmittance, good heat resistance, high hardness, and good elastic recovery. The commonly used molecular resin is a phenolic resin or an acrylic polymer resin. Over the past decade or so, lithography has played a pivotal role in semiconductor manufacturing processes. Its main purpose is to draw the designed micro-circuit pattern on the substrate. The process is based on the principle of photoresist imaging. # Apply the photoresist to the substrate to form a thin film, and then it will contain the circuit diagram-4 light. The cover is placed over the film and then exposed to light or a source of radiation of a selected wavelength. After exposure, the exposed areas of the film undergo a chemical change which causes the exposed areas and the non-exposed areas to have different solubilities in the developer, so that after development, the photoresist film is formed into the desired circuit pattern. The photoresist is then applied to the substrate via the (4) circuit pattern (4). Negative photoresists are sometimes attached to the substrate as a permanent material. 102921.doc 1293959, in micro-shirt technology, the length of the wavelength of the exposure source or radiation source determines the line width of the circuit that can be installed. In the process of cross-linking (e:r〇SS_linking), the negative photoresist will adsorb the swellHng phenomenon, so that the line width is often larger than the line width of the mask, so the negative photoresist is more common. It is used in processes with low resolution requirements, and because of the cross-linking properties of negative photoresists, it can form hardness: ·" heat resistance|± good, good chemical resistance, so it can be applied to flat panel display Among them, for example, a pigment dispersion type color photoresist, a black matrix, and a photosensitive gap material. Currently]: _line (wavelength is 36511111) is the exposure source of the most common process for flat panel displays. In the lithography process, the photoresist back used is different depending on the wavelength of the exposure source. In other words, the chemical composition of the photoresist must be adjusted with the exposure light source. This is due to the different absorbance and sensitivity of the photoresist composition for different wavelengths of light. In general, a positive photoresist composition, containing >valley; tree sorghum, photoacid generator and other additives, and a negative photoresist composition containing a solvent, a resin, a photoinitiator, and a reaction Thinners and other additives. As is known in the art, the photoresist composition is a resin-based component and the photoresist composition is required to have a good lithographic effect, and the resin contained therein must have a low absorbance to light. In addition to the above-mentioned low light absorption, the resin used in a good photoresist must meet several other requirements, for example, it can adhere to and form a film on a substrate, can resist dumplings, has thermal stability, and is suitable. It has a molecular weight, is compatible with other photoresist components, is insoluble in an alkaline aqueous solution, can be stored for a long time, and has a low cost. Negative photoresists are required to have high hardness, good heat resistance and good chemical resistance. 102921.doc 1293959 A variety of resins have been disclosed in the prior art for use in photoresists. For example, University of Texas, Willson et al., Journal of Photopolymer Science and Technology, Vol. 11, pp. 465-474 (1998), reveals the use of four rings [4·4·0·12,5·17,12 The dodeca-3-ene-5-carboxylate is copolymerized with cis-butane dianhydride to synthesize a resin. Hyundai Electronics Industries Co., Ltd., Jung et al., DE 19758244 A1 and Journal of Photopolymer Science and Technology, Vol. 11, pp. 481-488 (1998), discloses the use of alcohols, esters and acid groups. The norbornene is copolymerized with cis-butyl diacid as a resin. U.S. Patent No. 5,843,624 and Proceedings of SPIE No. 2724, pp. 355-364 (1996) disclose the use of norbornene, maleic anhydride, and methacrylic acid or their derivatives. The copolymer is copolymerized into a resin. ITRI, et al., Proceedings of SPIE, Vol. 3999, pp. 919-925 (2000), discloses the copolymerization of ester- and acid-based raw borneol and cyclic aliphatic acrylates into resins. . Eternal Xie Yucai disclosed in the Republic of China Patent Publication No. 574,612 discloses a benzoquinone-cyclopentadiene adduct modified resin to improve the adhesion and resistance of the photoresist. Since the gap control material has a relatively high hardness requirement, although the above resin can provide certain physical properties, it does not fully satisfy the requirements for the resin for the gap control material application. In order to obtain a resin which can be effectively applied to a gap control material, the inventors of the present invention have extensively studied and found that a resin containing a functional group derived from a benzoquinone-cyclopentadiene adduct can achieve the above-mentioned object 102921 of the present invention. Doc 1293959. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a resin compound containing a diene monomer derived from a benzoquinone-cyclopentadiene adduct. Another object of the present invention is to provide a photoresist composition comprising the resin compound. [Embodiment] The resin compound of the present invention is obtained by polymerizing a biguanide monomer containing a benzoquinone-cyclopentadiene adduct with other monomers such as a styrene monomer, an acrylic monomer, and a maleic anhydride monomer. The resin compound of the present invention has the structure of the following formula (1):

R!, R2, R3 and Rs are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, and a solvent having 3 to 15 carbon atoms. a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 15 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 5 carbon atoms a group wherein the aryl group is preferably a phenyl group, a pyridyl group, a phenylthio group or a furyl group; and R4 is =0, -OR, -R or a group of the following formula (2): 102921.doc 1293959

Wherein R is selected from the group consisting of hydrogen, a substituted or unsubstituted linear or branched alkyl group having from 1 to 15 carbon atoms, a substituted or unsubstituted straight chain having from 1 to 15 carbon atoms or Branched heteroalkyl, substituted or unsubstituted cycloalkyl having 1 to 15 carbon atoms, substituted or unsubstituted heterocycloalkyl having 1 to 15 carbon atoms, containing 6 to a group of substituted or unsubstituted aryl groups of 15 carbon atoms and substituted or unsubstituted heteroaryl groups having 6 to 15 carbon atoms, wherein heteroalkyl, heterocycloalkyl and hetero The hetero atom in the aryl group is selected from the group consisting of 〇, N and S, preferably 0 or N; and 11 is 丨 to 丨❻; a is a value from 0 to 30; b is a value from 0 to 30; c is a value from 0 to 30; d is a value from 0 to 30; e is a value from 0 to 30; f is a value from 0 to 20; and g is a value from 0 to 1 〇. The diene monomer containing the benzene Icyclopentadiene adduct for synthesizing the resin compound of the present invention has the structure of the following formula (3):

Wherein R4 is as defined above. 102921.doc Formula (3) 1293959 The functional group of the diene monomer derived from the above benzoquinone-cyclopentadiene adduct contained in the resin compound of the present invention is used as a crosslinking group in the resin compound. The molecular weight of the resin is increased, and since the monofunctional group has a polar and saturated hydrocarbon hydrogen ring structure, the adhesion of the resin to the substrate and the ability of the resin to resist compression and damage can be increased. The acid anhydride group formed by the polymerization of other monomers such as maleic anhydride monomers which are polymerized with the diene monomer can be used as a crosslinking group in the hard baking process to increase the photoresist strength. According to a specific embodiment of the present invention, Ri, R2, R3 and R5 in the resin compound of the present invention are respectively selected from: hydrogen;

Ci-i5 alkyl; -C(R')(R')(R'), wherein each R' is independently a cl6 alkyl group, F or cf3; a group of the formula:

or

(In the above formula, n is an integer from 1 to 4, melon is an integer, R is an alkyl group, F or CF3, and R" is η, Cu alkyl, F or CF3); unsubstituted or one or two a &lt;:3.6 cycloalkyl group substituted with a substituent selected from Cw alkyl, F&amp;CFs; and unsubstituted or substituted by one, two or three selected from CM alkyl, F&CF3 102921.doc a group consisting of a phenyl group substituted by a group 1293959. According to a preferred embodiment of the invention, 1, 112, 113 and 115 are each hydrogen or an alkyl group; and 1 is = 〇, -〇H Or a group of the formula (2) wherein R is hydrogen or a Ci-6 alkyl group. The present invention further provides a photoresist composition comprising the following composition: (1) one or more resins having the structure of the above formula (1) a compound; (7) an initiator; and (3) a solvent. The initiator used in the photoresist composition of the present invention may be known in the art, and may, for example, be p-dimethylamine acetophenone. α,α,dimethoxyoxyazobenzophenone, 2,2'-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-mercapto[[methylthio) Benji]-2- 福福淋代_丙-1_同同,2,2,·双(o-chlorobenzene ^)-4,4',5,5,-tetraphenyldiimidazole, 252,_bis(o-fluorophenyl)_4,4,5,5,_tetraphenyldiimidazole, 2,2, _bis(o-methoxyphenyl)-4,4,5,5,-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4,5,5 ,-Tetraphenyldiimidazole, 2, bis(2,2',4,4,tetramethoxyphenyl)_4,4,5,5, tetraphenyldiimidazole and Irgacure® 369 (2 times Benzyl-2-N,N_:methylamino-1-(4-fofolin phenylbubutanone, manufactured by Chiba Specialty Chemicals). The solvent used in the photoresist composition of the present invention is in the art. It is known to be used in photoresist compositions|, and may be used singly or in combination of two or more, such as benzene, tetrahydroethylene, benzene, methanol, ethanol, ethylene glycol oxime (ethylene glyc oxime) 1 m〇n〇pr〇pyl ethe〇, ethylene glycol ether (4) coffee plus glycol m_ethyl ether), ethylene glycol scales (10) coffee plus coffee (3)! monomethyl ether), diglyme (diethylene milk (five) (1) 102921.doc -12- 1293959 ether), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (d Iethylene glycol monoethyl ether), diethylene glycol monobutyl ether, propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol The propylene glycol propyl ether acetate, the lactic acid ethyl acetate or the methyl-3-methoxypropionate is preferably diethylene glycol dioxime ether or propylene glycol ether acetate. In one embodiment of the photoresist composition of the present invention, the resin compound is contained in an amount of from about 9% to about 50%, preferably from about 9% to about 30%, based on the total weight of the composition of the photoresist; The agent is from about 0.1% to about 10%, preferably from about 0.8% to about 3%, based on the total weight of the resin compound, and the solvent is from about 45% to about 90% by weight based on the total weight of the photoresist composition. It is from about 65% to about 85%. The photoresist composition of the present invention may also contain additives conventionally used in the art, such as a crosslinker or a polyfunctional reactive diluent or a mixture thereof, and a preferred crosslinking agent may be, for example, a six (A). Hexyls (methoxymethyl) melamine, the crosslinking agent is used in an amount of from about 0.1% to about 10% by weight based on the total weight of the photoresist composition; preferably a polyfunctional reactive dilution The agent may be, for example, dipentaerythritol hexaacrylate, and the polyfunctional reactive diluent is used in an amount of from about 0.1% to about 30% by weight based on the total weight of the photoresist composition. The following examples are intended to further illustrate the invention, but are not intended to limit the scope of the invention. Modifications and modifications readily achievable by anyone skilled in the art are included within the scope of the disclosure of the present specification and the scope of the appended patent application 102921.doc • 13- 1293959. EXAMPLES Terminology: LAH ··'s lithium aluminum hydride BQDCPOH: l,4,4a,5,8,8a,9,9a,10,10a-+lL-l,4:5,8 -:T bridge 蒽9,10_ diol ("l,4,4a,5,8,8a,9,9a,10,10a-decahydro-l,4 : 5,8-dimethanoanthracene-9,10-diol Preparation of benzoquinone-cyclopentadiene adduct: (1) Freshly prepared cyclopentadiene (2.6 g, 0.4 mol) added p-benzoquinone (21.6 g, 0.2 mol) In a solution of ethanol (200 mol), the mixture was stirred for half an hour. The obtained colorless solid was filtered and washed with cold ethanol to obtain an almost completely reacted dicyclopentadiene-benzoquinone adduct (BQDCP). The above product (24 g, 10 mol) was added to a solution of <RTI ID=0.0>#</RTI> </RTI> <RTIgt; </RTI> <RTIgt; </RTI> <RTIgt; </RTI> <RTIgt; (3) Add 6 g of sodium hydride and 200 ml of diethyl ether to a 500 ml round bottom reaction flask equipped with a condenser, and slowly add a solution of the above product BQDCPOH (24 g) in tetrahydrofuran (1 ml) to reflux. 20 small reactions Further, adding butyl bromoacetate (0.2 mol), refluxing for 8 hours, and then concentrating to obtain a double-branched product. General synthesis procedure of the copolymer: Synthesis of copolymer 1214B: 2000 ml of a condenser tube In the round bottom reaction flask, Dicyclopentanyl Methacrylate (99 g), methyl propyl 102921.doc -14·1293959 enoic acid (51.6 g), methacrylonitrile (20.1) were added. g), isooctyl acrylate (27.6 g), a free radical initiator, namely azobisisobutyronitrile (AIBN, 7.38 g) and propylene glycol oxime ether acetate (PGMEA, 195 + 500 ml), with nitrogen And the reaction was carried out at 80 ° C for 24 hours to obtain the product. Mw = 12706. Synthesis of the copolymer 0112B: In a 2000 ml round bottom reaction flask equipped with a condenser, a solution of methyl dicyclopentanyl acrylate (82.5 g), Methacrylic acid (45.1 g), acrylic acid (5.4 g), allyl methacrylate (allyl methacrylate, 9_5 g), methacrylonitrile (15·1 g), styrene (7.8 g), acrylic acid Octyl ester (27.6 g), free radical initiator (ΑΙΒΝ, 7.3 8 ) And PGMEA (100 + 600 mL), and the nitrogen introduced into the reaction at 80 ° C 24 h to obtain the product .Mw = 20634. Synthesis of Copolymer 0202A: In a 2000 ml round bottom reaction flask equipped with a condenser, a solution of decyl decyl acrylate (99 g), methacrylic acid (5 1.6 g), methacrylonitrile (19.1 g) was added. ), isooctyl acrylate (27.6 g), BQDCP (3·45 g), free radical initiator (ΑΙΒΝ, 4.92 g) and PGMEA (195+500 ml), passed through nitrogen and at 80 ° C The product was reacted for 24 hours. Mw = 18832. Preparation of Reactive Copolymer · In the 1000 ml round bottom reaction flask equipped with a condenser, the above copolymer solution (300 g), catalyst (triethylamine, 0.5 g), glycidyl methacrylate ( Glycidyl methacrylate (28.8 g) and methyl hydroquinone (0.1 g) were reacted with nitrogen and reacted at 80 °C for 24 hours to give a reactive functional group product. This reactive copolymer was subjected to an alkylation reaction of the above copolymers 1214B, 0112B and 0202A to be applied to the following light 102921.doc -15-1293959 resist composition. Formulation of photoresist composition: The formulation of the photoresist composition used for the following evaluation procedures is shown in Table 1. Table 1 Photoresist composition Resin initiator (1) Reactive diluent (2) PGMEA A 1214B 10 gram · 1 gram 2 _ 7 gram 1 gram B 1214B 10 gram 0.15 gram 2.7 gram 1 gram C 0112B 10 gram 0.15 gram 2.7 gram 1 · 5 gram D 0202A10 gram 0 · 15 gram 2.7 gram 1.5 gram (1) starter Irgacure® 369 (manufactured by Chiba Specialty Chemicals). (2) The reactive diluent is dipentaerythritol hexyl acrylate. The evaluation process and conditions are as follows: The glass surface is first washed and baked, and then spin-coated (Spin Coating: 700 to 900 rpm/30 seconds) for soft baking (Soft Baking: 95 ° C / 120 seconds) to shift In addition to the solvent, the film thickness is 4 to 5 microns (μπι), followed by exposure to a close-up (Gap = 100pm) exposure machine (Εο=150 mJ/cm ^2, mj/cm 2 ), after exposure to light The developer (Changxing 彳bgong CD705) is developed for 40 to 80 seconds, then hard baked (HB: 220QC/30 minutes) to obtain a photoresist image, and finally the image is analyzed by an electronic scanning microscope. The results of the hardness tester (SHIMADZU DUH-W201S) are shown in Table 2 below: Table 2 Exposure energy of photoresist composition (mJ/cm2) Elastic recovery (10 mN) Compressive failure strength (milliton) Resolution (micron) A 150 96% 501 10.15 B 150 82% 616 10.10 C 150 80% 414 10.24 D 150 88% 640 10.00 102921.doc • 16- 1293959 It can be seen from Table 2 that the present invention contains a benzoquinone containing ring The photoresist composition of the resin compound of the pentadiene adduct has better compressive strength and solution Degree of analysis.

102921.doc 17-

Claims (1)

129393⁄4^27605 Patent Application - f text f Please replace the patent scope (April, April)|】Wang/10, the scope of application for patent: 1. A resin compound with the structure of (1) f. Repair (more) replacement page Ri, R2, R3 and R5 are each selected from the group consisting of: a Cm5 alkyl group; -C(R)(R)(R')' wherein R' is independently an alkyl group; a group of the formula: (In the above formula, η is an integer of 1 to 4, ^! is an integer from i to 6, R is Cw alkyl, F or CF3, and R" is Η, Cw alkyl, i^CF3); unsubstituted Or a C3-6 cycloalkyl group substituted by one or two substituents selected from the group consisting of Cw alkyl, F and CF3; and unsubstituted or one, two or three selected from the group consisting of Cu alkyl, F and CF3 a group consisting of a phenyl group substituted by a substituent; R4 is =0, -OR, -R or a group of the following formula (2): 102921-960417.doc J293959 Formula (2) wherein R is selected from hydrogen, including A substituted or unsubstituted linear or branched alkyl group of 1 to 15 carbon atoms, a substituted or unsubstituted linear or branched heteroalkane having 1 to 15 carbon atoms. a substituted or unsubstituted cycloalkyl group having 1 to 15 carbon atoms, a substituted or unidentified φ-substituted heterocycloalkyl group having 1 to 15 carbon atoms, and 6 to 15 a group consisting of a substituted or unsubstituted aryl group of a carbon atom, and a substituted or unsubstituted heteroaryl group having 6 to 15 carbon atoms, wherein a heteroalkyl group, a heterocycloalkyl group, and a heteroaryl group The hetero atom in the group is selected from the group consisting of Ο, N and S; and n is 1 to 10; a is a value from 0 to 30; b is a value from 0 to 30; e is a value from 0 to 30; d is a value from 〇 to 30; • 6 is a value from 〇 to 3〇; f is 0 to The value of 20; and g is a value of 0 to 10. 2. The resin compound of claim 1, wherein R1, R2, R3&amp; R5 are respectively hydrogen or C..6 alkyl; and R4 is =〇, - 〇H or a group of the formula (2) wherein R is hydrogen or Gw alkyl. 3. A photoresist composition comprising the following components: (1) 9% to 5 based on the total weight of the photoresist composition树脂% of the resin compound of the formula (1) as claimed in claim i; 102921-960417.doc 1293959 (2) an initiator of 1·1% to 10% by weight based on the total weight of the resin compound; and (3) The solvent of the total weight of the photoresist composition is from 45% to 90%. 4. The composition of claim 3, wherein the initiator is selected from the group consisting of p-dimethylamine acetophenone, α,α'-dimethoxy Azo acetophenone, 2,2,-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenol]2-福福林代_1-propion_, 2,2,-bis(o-chlorophenyl)_4,4,5,5,_tetraphenyldiimidazole, 2' double ( _fluorophenyl)-4,4',5,5'·tetraphenyl dimium sulphate, 2,2,_bis (o-oxo_base)_4,4',5,5,_tetraphenyl Base two flavor saliva, 2,2,_bis(p-methoxyphenyl)_4,4,5,5'-tetraphenyldiimidazole, 2,2,_bis (2,2,,4,4, _tetramethoxyphenyl)_4,4',5,5,-tetraphenyldiimidazole and 2_benzyl·2_Ν,Ν_dimethylamine"_(4_?福林代phenyl)-1 a group of butyl butanone. The composition of claim 4, wherein the initiator is 2-benzyl carbamide, phenanthroline, phenyl fluorene butanone. The composition of claim 6, wherein the solvent is an alcohol methyl ether acetate. &lt; Monoglycol or propylene A step contains a crosslinking agent. 8. The composition of claim 3, wherein the cross-linking agent comprises a composition of the total composition of the photoresist composition, wherein the cross-linking amount is from about 0.1% to about 10 Å/〇. . 10. The composition of claim 8, wherein the crosslinking agent is hexakis (methoxymethyl) melamine. π. The composition of claim 3, which further comprises a polyfunctional reactive diluent. 12. The composition of claim 11, wherein the polyfunctional reactive diluent comprises from about 0.1 to about 3 Torr/0 of the total weight of the photoresist composition. 13. The composition of claim 11, wherein the polyfunctional reactive diluent is dipentarythritol hexaacrylate. 102921-960417.doc