CN118221892A - High-heat-resistance phenolic resin with good alkali solubility and preparation method and application thereof - Google Patents
High-heat-resistance phenolic resin with good alkali solubility and preparation method and application thereof Download PDFInfo
- Publication number
- CN118221892A CN118221892A CN202211647528.9A CN202211647528A CN118221892A CN 118221892 A CN118221892 A CN 118221892A CN 202211647528 A CN202211647528 A CN 202211647528A CN 118221892 A CN118221892 A CN 118221892A
- Authority
- CN
- China
- Prior art keywords
- resin
- cresol
- solvent
- phenolic resin
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 29
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 29
- 239000003513 alkali Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 101
- 239000011347 resin Substances 0.000 claims abstract description 101
- 239000002904 solvent Substances 0.000 claims abstract description 66
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 59
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000004090 dissolution Methods 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 238000011282 treatment Methods 0.000 claims abstract description 6
- 239000003377 acid catalyst Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 31
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 5
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000000052 comparative effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229930003836 cresol Natural products 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- 239000000057 synthetic resin Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 150000007514 bases Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- -1 25xy Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- YLSVTHSRAUMJIG-UHFFFAOYSA-N 6-diazo-5,8-dioxonaphthalene-1-sulfonic acid Chemical compound O=C1C(=[N+]=[N-])CC(=O)C2=C1C=CC=C2S(=O)(=O)O YLSVTHSRAUMJIG-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a preparation method and application of high heat-resistant phenolic resin with good alkali solubility. The preparation method comprises the steps of carrying out addition condensation reaction on a reaction substrate which is high-purity m-cresol, high-purity p-cresol and a specific solvent with formaldehyde under the condition of an acid catalyst, continuously carrying out additional solvent treatment, carrying out further reaction, repeating the reaction for several times, obtaining a resin matrix with more polymer parts distributed, and then carrying out grading treatment by utilizing the difference of the solubility of the resin in a good solvent and a poor solvent, and removing small molecular parts to obtain the phenolic resin. The phenolic resin has good alkali dissolution property while having more content distribution of high molecular parts, can be applied to positive photoresist, such as LCD positive photoresist, and endows the photoresist with better heat resistance under good sensitivity.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to synthesis and application of high Tg phenolic resin with good alkali solubility for photoresist.
Background
The positive photoresist composition is composed of a novolac resin, a Diazonaphthoquinone (DNQ) type sensitizer compound and a solvent. The anti-corrosion material has the advantages of high contrast, non-organic solvent development, no swelling in the development process, strong plasma etching resistance and the like, and is widely applied to the fields of IC, LSI, liquid Crystal Display (LCD), printed circuit board manufacture and the like. In recent years, high integration of semiconductors and finer patterns have been achieved, and various heat treatments have been performed in the manufacturing process of semiconductors and the like, and there has been a demand for higher sensitivity and heat resistance of photoresists.
The simplest method of increasing the sensitivity of a photoresist is to reduce the molecular weight of the novolak resin used in the photoresist, which accelerates the solubility of the photoresist in an alkaline developer, thereby significantly increasing the sensitivity of the photoresist. However, this method causes a very serious disadvantage in that the heat resistance of the photoresist is lowered, and when the resist pattern is easily softened and flows or the shape is changed under high temperature conditions, an error occurs in the size of the etched substrate after etching or the size fluctuates, thereby affecting the resolution of the photoresist.
In order for the photoresist to have high heat resistance and good sensitivity, the development from the resin end requires that the resin have high Tg and good alkali dissolution properties. The current method for improving the heat resistance of the phenolic resin for the photoresist mainly comprises the steps of increasing the O-O structure in the phenolic resin for the photoresist, improving the regularity of a molecular chain, and under the action of a hydrogen bond, the resin has higher Tg. Xylenols such as 25xy, 35xy, etc., are introduced, and although there is some improvement in heat resistance and resolution, it is still difficult to satisfy the current requirements in the market.
In recent years, there have been proposed various patents in which a monomer combining rigidity and flexibility is introduced while improving heat resistance and alkali dissolution properties of the resin, for example, patent document CN113004478a proposes that a phenolic compound is reacted with a compound containing a benzene ring, a biphenyl ring or a condensed ring structure and an aliphatic aldehyde compound or paraformaldehyde to give a phenolic resin for resists with high Tg, wherein a polycyclic phenol structure provides heat resistance and an aliphatic aldehyde provides flexibility. Patent document CN113461884a proposes to improve the heat resistance of a resin by using 4,4' -dihydroxydiphenyl ether, 2-hydroxy 1-hydroxynaphthalene and a small amount of a phenolic polyol. The two methods have a common disadvantage in that although the flexible structure is introduced under the condition of the rigid structure to improve the alkali dissolution property, the improvement effect is small, and it is difficult to balance the introduced amounts of the two functional structures to some extent.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a high-purity phenolic resin without introducing a third monomer modification, which has higher high molecular weight distribution and high Tg and provides good heat resistance for photoresist used in the subsequent application; in addition, the resin also has higher branching degree (wherein the branching degree is characterized by bare carbon of an aromatic ring in the resin, the lower the bare carbon content is, the higher the branching degree is, the ratio of the 2, 4 and 6 bare carbon is 5-30%, and the resin has higher branching degree), so that the resin is endowed with good alkali dissolution performance, and good resolution is provided for photoresist applied subsequently.
The invention provides a high heat-resistant phenolic resin with good alkali solubility, which has high molecular weight of 4w-7w and good alkali dissolution rateThe Tg of the resin is 140-170 ℃.
The phenolic resin is high heat-resistant phenolic resin with good alkali solubility.
Wherein, the branching degree of the resin needs to be controlled in the synthetic process of the phenolic resin, thereby endowing the resin with good alkali dissolution rate; wherein, the method for controlling the branching degree needs 13 C to be characterized according to the 2-position, 4-position and 6-position bare carbon on the aromatic ring of the synthetic resin.
Wherein, the ratio of 2, 4 and 6 bare carbon is 5-30 percent; preferably 10% -20%, wherein the ratio of 2, 4, 6 bare carbon is 10% -20% and the optimum control degree of branching is provided.
The invention also provides a synthetic method of the phenolic resin, which comprises the following steps:
(1) Adding m-cresol and p-cresol into a solvent, carrying out addition polycondensation with formaldehyde in the presence of an acid catalyst, supplementing the solvent in the reaction process to regulate and control the molecular weight distribution, controlling the branching degree of the resin after the reaction, and neutralizing with an alkaline compound after the reaction is finished to obtain the resin matrix.
(2) And (3) continuously adding the solvent in the step (1) into the resin matrix, dropwise adding a poor solvent for grading treatment after the solvent is completely dissolved, and removing the poor solvent to obtain the phenolic resin.
In the step (1) of the invention, the m-cresol and the p-cresol are high-purity m-cresol and p-cresol, and the content of each of the m-cresol and the p-cresol is more than 99 percent.
In the step (1) of the invention, the feeding weight ratio of the m-cresol to the p-cresol is 6/4-8/2.
In the step (1), the concentration of formaldehyde is 35% -50%, and the dosage is 40% -60% of the total weight of m-cresol and p-cresol.
In the step (1) of the invention, the solvent supplementing method is a branching degree control method, which can regulate and control molecular weight and branching degree.
In the step (1), the solvent is a good solvent of cresol resin, including but not limited to at least one of propylene glycol monomethyl ether, ethylene glycol butyl ether, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethylene glycol diethyl ether and the like; preferably propylene glycol monomethyl ether acetate.
In the step (1), the solvent dosage is 10-30% of the total weight of the m-cresol and the p-cresol, and the subsequent adding amount is 10-30% of the total weight of the m-cresol and the p-cresol.
In the step (1), the adding times are 1-2 times; preferably 1 time.
In the step (1), the reaction temperature of each additional stage is 90-100 ℃ and the reaction time is 1-4h; preferably, the reaction temperature is 100℃and the reaction time is 2 hours.
In addition, in order to confirm that the branching degree of the obtained resin meets the requirements of the invention, the invention also provides a branching degree characterization method, the branching degree is utilized to adjust the alkali dissolution rate of the resin, the synthetic resin is characterized by NMR 13 C, the solvent is DMSO, and the characterization is carried out according to the ratio content of bare carbon at the 2 position, the 4 position and the 6 position on the aromatic ring of the synthetic resin. Wherein, the ratio of 2, 4 and 6 bare carbon is 5-30 percent; preferably 10% -20%.
The molecular weight control and the branching degree control are simultaneously carried out, and the stretching and curling degree of the resin in the solvent is utilized to expose the active site and control the bonding of the active site. The curling degree of the resin is larger under the concentrated solution of the solvent, the bonding rate among active sites is increased although the active sites are fewer, and microgel or gel can appear on the resin, so that insoluble particles can appear in the photoresist in the subsequent configuration; the resin has an increased exposure rate of the active sites of the resin under a dilute solution of the solvent, but has a decreased bonding rate of the active sites, which limits the increase in molecular weight of the resin.
In the step (1), the acid catalyst is at least one of oxalic acid, lewis acid, hydrochloric acid, sulfuric acid and the like; preferably oxalic acid.
In the step (1) of the invention, the alkaline compound is at least one of ammonium hydroxide, tetramethylammonium hydroxide, 2-amino-2-methyl-1-propanol and the like; preferably tetramethylammonium hydroxide.
In the step (2), the classification treatment is to fully dissolve the resin in a good solvent, and then dropwise add a poor solvent into a good solvent solution of the resin for classification treatment, wherein the addition proportion of the good solvent is 3 times of the total weight of m-cresol and p-cresol; the good solvent is one or more of propylene glycol monomethyl ether, ethylene glycol butyl ether, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethylene glycol diethyl ether and the like;
The poor solvent is at least one of n-hexane, n-heptane, toluene and the like; preferably n-heptane;
the amount of the poor solvent used is 2 times the total weight of m-cresol and p-cresol.
In the step (2), the condition for removing the poor solvent is 40-80 ℃, the vacuum degree is-99 kpa-90 kpa, and the time is 3-6h; preferably, the conditions for removing the poor solvent are 50 ℃, the vacuum degree is-80 kpa, and the time is 3 hours.
The resin has good alkali dissolution performance under high molecular weight, and the main reason is that the resin has more proper branching degree. The method for controlling the branching degree in the invention relates to the following two aspects;
On the one hand, the resin contains higher m-cresol content, namely has higher m-contrast, and m-cresol has 3 active sites, so that the possibility that the branching degree of the resin is increased by introducing more m-cresol. In addition, the invention also provides the dosage of formaldehyde which is the high molecular weight resin.
Another aspect is that the resin is performed in a solvent system during the synthesis process, utilizing the extent of stretching and curling of the resin in the solvent to expose the active sites and control bonding of the active sites. The curling degree of the resin is larger under the concentrated solution of the solvent, the bonding rate among active sites is increased although the active sites are fewer, and microgel or gel can appear on the resin, so that insoluble particles can appear in the photoresist in the subsequent configuration; the resin has the advantages that under the condition of a dilute solution of a solvent, the exposure rate of active sites of the resin is increased, but the bonding rate of the active sites is reduced, the increase of the molecular weight of the resin is limited, and the requirement of the invention is not met. The present invention therefore provides a method for controlling the degree of branching and the regulation of molecular weight.
The invention also provides the phenolic resin solution containing the good solvent, which is obtained by the method, and the solid content of the phenolic resin solution is 20-50%.
The invention also provides the phenolic resin obtained by the method.
The invention also provides application of the phenolic resin in positive photoresist such as LCD and the like.
The invention has the beneficial effects that the resin with high molecular weight distribution has high Tg and provides good heat resistance for photoresist applied in downstream; the higher branching degree of the resin ensures that the resin has good alkali dissolution performance, and still has certain advantage of alkali dissolution performance under the condition of high molecular weight distribution, thereby providing good resolution for photoresist applied in downstream. In addition, the resin is high-purity phenolic resin, no third monomer is introduced, and the resin has strong application stability in the subsequent photoresist formulation and strong production line adaptability.
Drawings
FIG. 1 resin NMR- 13 C.
Figure 2 photoresist thermal test.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common knowledge and common knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
Comparative example 1
The following examples are conventional cresol formaldehyde resin synthesis methods for current panels.
162 Parts by weight of m-cresol and 162 parts by weight of p-cresol are added into a four-necked flask, heated and stirred to 90 ℃, 3.24 parts by weight of oxalic acid is added, then 150 parts by weight of 37% aqueous formaldehyde solution is added dropwise, and after the dropwise addition is completed, the reaction is carried out for 4 hours at 90-100 ℃, and the resin MW=15000.
Comparative example 2
194.4 Parts by weight of m-cresol and 129.6 parts by weight of p-cresol are added into a four-necked flask, heated and stirred to 90 ℃, 3.24 parts by weight of oxalic acid is added, 194.6 parts by weight of 37% aqueous formaldehyde solution is then added dropwise, and after the dropwise addition is completed, the reaction is carried out for 4 hours at 90-100 ℃, and resin gel is obtained.
Example 1
1) 194.4 Parts by weight of m-cresol, 129.6 parts by weight of p-cresol and 64.8 parts by weight of propylene glycol monomethyl ether acetate are added into a four-necked flask, heated and stirred to 90 ℃, 3.24 parts by weight of oxalic acid is added, then 194.6 parts by weight of 37% formaldehyde aqueous solution is dropwise added, after the dropwise addition is completed, the reaction is carried out for 2 hours at 90-100 ℃, then 64.8 parts by weight of propylene glycol monomethyl ether acetate is added, the reaction is continued for 2 hours, and after the completion, 3 parts by weight of 2-amino-2 methyl-1-propanol is added, and the high-component resin matrix is obtained. And nuclear magnetic test is carried out on the bare carbon of the aromatic ring of the resin.
2) Adding 927 parts by weight of propylene glycol monomethyl ether acetate into the obtained resin, heating to 50 ℃, slowly dropwise adding 648 parts by weight of n-heptane within 2 hours, standing for layering after the dropwise adding is completed, taking the lower layer solution, and removing the poor solvent at the temperature of 60-80 ℃ under the vacuum degree of-90 kap for 1 hour to obtain the propylene glycol monomethyl ether acetate resin solution. The resin GPC test mw=46000.
Example 2
1) 226.8 Parts by weight of m-cresol, 97.2 parts by weight of p-cresol and 64.8 parts by weight of propylene glycol monomethyl ether are added into a four-necked flask, heated and stirred to 90 ℃, 3.24 parts by weight of oxalic acid is added, then 194.6 parts by weight of 37% aqueous formaldehyde solution is dropwise added, after the dropwise addition is completed, the reaction is carried out for 2 hours at 90-100 ℃, then 64.8 parts by weight of propylene glycol monomethyl ether is added, then the reaction is continued for 2 hours, and after the completion, 3 parts by weight of 2-amino-2 methyl-1-propanol is added, thus obtaining the high-component resin matrix. And nuclear magnetic test is carried out on the bare carbon of the aromatic ring of the resin.
2) Adding 927 parts by weight of propylene glycol monomethyl ether into the obtained resin, heating to 50 ℃, slowly dropwise adding 648 parts by weight of n-heptane within 2 hours, standing for layering after the dropwise adding is completed, taking out a lower layer solution, and removing a poor solvent at the temperature of 60-80 ℃ for 1 hour under the vacuum degree of-90 kap to obtain the propylene glycol monomethyl ether acetate resin solution with the solid content of 32%. The resin GPC test mw=45000.
Example 3
1) Adding 259.2 parts by weight of m-cresol, 64.8 parts by weight of p-cresol and 64.8 parts by weight of propylene glycol monomethyl ether acetate into a four-necked flask, heating and stirring to 90 ℃, adding 3.24 parts by weight of oxalic acid, then dropwise adding 194.6 parts by weight of 37% aqueous formaldehyde solution, reacting for 2 hours at 90-100 ℃ after the dropwise adding is completed, then adding 64.8 parts by weight of propylene glycol monomethyl ether acetate, continuing to react for 2 hours, and adding 3 parts by weight of 2-amino-2 methyl-1-propanol after the completion of the reaction, thus obtaining the high-component resin matrix. And nuclear magnetic test is carried out on the bare carbon of the aromatic ring of the resin.
2) Adding 927 parts by weight of propylene glycol monomethyl ether acetate into the obtained resin, heating to 50 ℃, slowly dropwise adding 648 parts by weight of n-heptane within 2 hours, standing for layering after the dropwise adding is completed, taking out a lower layer solution, and removing a poor solvent at the temperature of 60-80 ℃ for 1 hour under the vacuum degree of-90 kap to obtain the propylene glycol monomethyl ether acetate resin solution with the solid content of 32%. The resin GPC test mw=43000.
Example 4
According to the method of the embodiment 2 of the invention, the difference is that the primary additional solvent is removed, and the reaction time is prolonged to 4 hours, so as to obtain the propylene glycol monomethyl ether acetate resin solution. The resin GPC test mw=75000.
Example 5
The method of example 2 according to the present invention was different in that the formaldehyde addition amount was increased to 210 parts by weight to obtain propylene glycol monomethyl ether acetate resin solution. The resin GPC test mw=56000.
Example 6
According to the method of example 3 of the present invention, the difference is that the number of times of adding the solvent is adjusted to 2 times, 64.8 parts by weight of the solvent is added each time, and the reaction time is prolonged to 3 hours, thereby obtaining propylene glycol monomethyl ether acetate resin solution. The resin GPC test mw=51000.
Example 7
The procedure of example 2 was followed except that the amount of the primary additional solvent was changed to 32.4 parts by weight, and the resin GPC test MW was 66000.
Example 8
The procedure of example 2 was followed except that the amount of 2 additional solvents was changed to 162 parts by weight of solvent and the resin GPC test MW was 23000.
Phenolic resin index test
(1) Weight average molecular weight M w weight average molecular weight M w was obtained by GPC testing.
(2) Resin branching degree test method, characterized by NMR 13 C, was used to determine solvent DMSO, as determined by the integration method shown in fig. 1.
(3) Resin ADR test method: the resins obtained in examples 1 to 8 of the present invention were prepared into 25% propylene glycol monomethyl ether acetate solution, which was spread on a silicon wafer having a diameter of 5 inches, and then dried at 110℃for 60 seconds to obtain a film having a thickness of 1. Mu.m. The solution was immersed in an alkali solution (2.38 mass% aqueous tetramethylammonium hydroxide solution) for 60 seconds, the film thickness after immersion was measured by a film thickness meter, and the Alkali Dissolution Rate (ADR) was measured, and the alkali solution resistance was evaluated based on the obtained values as described below.
(4) Resin Tg test: the resulting resin solvent was oven dried to remove the solvent and then tested by DSC to give the resin Tg.
Example 9
Preparation of positive photoresist composition
Using the resins obtained in examples 1 to 8 of the present invention described above, positive photoresist compositions were prepared as follows.
The resin obtained in comparative examples 1 and 2 and examples 1 to 8 of the present invention was added in an amount of 25 parts by mass to 70 parts by mass of propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), mixed and dissolved to obtain a solution, and then 5 parts by mass of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate sensitizer was added thereto, mixed and dissolved to obtain a positive photoresist composition.
Performance test of positive photoresist composition
(1) The photoresist was filtered to remove impurities using a 0.2 μm membrane filter, and then spin-coated on a silicon crystal substrate having a diameter of 5 inches to form a2 μm wet film, and uniformity of coating was observed. And the particle size analysis was performed under yellow light with a 50-fold optical magnifier, and the analytical evaluation criteria were as follows:
Preferably: particles less than 5 are good: particle 5-50 difference: particles greater than 50
(2) Drying with 100deg.C electric plate for 2min to volatilize solvent, and solidifying to obtain film.
(3) And exposing the surface of the substrate by using an exposure machine, and developing by using 2.38wt% of tetramethylammonium hydroxide according to the change of exposure energy, thereby obtaining photosensitive data.
(4) The substrate after development of the positive photoresist composition was dried with an electric hot plate at 105 c for 2 minutes under the above-mentioned proper exposure energy, and the obtained samples were subjected to a heat resistance test, and were baked at 140 c, respectively, and heat resistance was determined according to the collapse degree of the photoresist pattern.
TABLE-1 resin test data and photoresist test data
As can be obtained by comparing the invention example 1 with the comparative example 2, under the condition that the ratio of m-cresol to p-cresol is 6/4, and under the condition that the same formaldehyde addition amount is adopted, the resin gel is not added with solvent, which indicates that the solvent is added in the synthesis process to facilitate the stretching of the molecular chain of the resin, the bonding rate of an active site is reduced, and thus the risk of the resin gel is reduced; as can be seen from comparison of examples 1-3 of the present invention, at the same formaldehyde and solvent addition amounts, the resin intermediate cresol and paracresol ratios are changed from 6/4, 7/3 and 8/2, the MW and Tg of the resin tend to be reduced, but the degree of influence is not obvious due to the larger MW per se, and as the meta-cresol and paracresol ratio is increased, microgels appear in the resin, which can cause the occurrence of particulate matters which cannot be filtered in the photoresist product; meanwhile, as the ratio of m-cresol to p-cresol is increased, the proportion of bare carbon is increased, the branching degree is increased, the alkali dissolution performance of ADR is also increased, the sensitivity is improved, and the high ratio of m-cresol to p-cresol can provide high branching degree, and the high branching degree is favorable for the increase of the alkali dissolution performance of resin. Therefore, in order to achieve the combination of MW, insolubles and sensitivity of the resin, the resin of the present invention is most suitably used in the synthesis of the resin having a ratio of 7/3 between the feeds thereof to cresol. Comparing the invention of the embodiment 2,4 and 6, it can be seen that the MW can be increased and the heat resistance is excellent, but the sensitivity of ADR and photoresist of the microgel resin is seriously slower; while both the addition of 1 and the addition of 2 times can give consideration to the above properties, the addition of two times of solvents requires a longer reaction time, and thus the addition of one time of solvents is a suitable scheme in view of process simplification. Example 7 of the present invention illustrates that each addition of less solvent increases the risk of gelation, and the resin has poor alkali dissolution properties (ADR) and exhibits particulate anomalies and slow sensitivity when applied to photoresists. In the embodiment 8 of the invention, too much solvent is added each time, so that the bonding capability of active sites in a reaction system is reduced, the resin has no high molecular weight distribution, the branching degree of the resin is reduced, and the sensitivity of the resin is slow.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that would occur to one skilled in the art are included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims.
Claims (10)
1. A phenolic resin is characterized in that the molecular weight of the resin is 4w-7w, and the alkali dissolution rate isThe Tg of the resin is 140-170 ℃.
2. The phenolic resin of claim 1, wherein the resin is required to have a controlled degree of branching during the synthesis process to impart good alkali dissolution rate to the resin; and/or, the method for controlling the branching degree needs 13 C to be characterized according to bare carbons at positions 2, 4 and 6 on the aromatic ring of the synthetic resin.
3. The phenolic resin of claim 2, wherein the ratio of 2,4,6 bare carbons is 5% to 30%.
4. A method for preparing phenolic resin, which is characterized by comprising the following steps:
(1) Adding m-cresol and p-cresol into a solvent, carrying out addition polycondensation with formaldehyde in the presence of an acid catalyst, supplementing the solvent in the reaction process to regulate and control molecular weight distribution, controlling the branching degree of the resin after the reaction, and neutralizing with an alkaline compound after the reaction is finished to obtain a resin matrix;
(2) And adding a good solvent into the resin matrix, dripping the poor solvent for grading treatment after the good solvent is completely dissolved, and removing the poor solvent to obtain the phenolic resin.
5. The method according to claim 4, wherein the solvent comprises at least one of propylene glycol monomethyl ether, ethylene glycol butyl ether, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethylene glycol diethyl ether in step (1); and/or the solvent dosage is 10% -30% of the total weight of m-cresol and p-cresol, and the subsequent adding amount is 10% -30% of the phenolic compound each time; and/or the number of the supplementing times is 1-2 times; and/or the reaction temperature of each stage is 90-100 ℃; and/or the reaction time is 1-4h.
6. The process of claim 4, wherein in step (1), the m-cresol and the comparative cresol are high purity m-p-cresol with a content of >99%; and/or the feeding weight ratio of the m-cresol to the p-cresol is 6/4-8/2; and/or, the formaldehyde feeding amount is 40% -60% of the total weight of the m-cresol and the p-cresol.
7. The method of claim 4, wherein in step (1), the acidic catalyst is at least one of oxalic acid, lewis acid, hydrochloric acid, sulfuric acid; and/or the basic compound is at least one of ammonium hydroxide, tetramethylammonium hydroxide and 2-amino-2-methyl-1-propanol.
8. The method according to claim 4, wherein the good solvent in the step (2) is propylene glycol monomethyl ether, ethylene glycol butyl ether, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethylene glycol diethyl ether; and/or, the good solvent is added in a proportion of 3 times of the total weight of the m-cresol and the p-cresol; and/or the poor solvent is at least one of n-hexane, n-heptane and toluene; and/or the amount of the poor solvent used is 2 times the total weight of m-cresol and p-cresol; and/or the condition for removing the poor solvent is 40-80 ℃, the vacuum degree is-99 kpa-90 kpa, and the time is 3-6h.
9. A phenolic resin prepared by the method of any one of claims 4-8.
10. Use of the phenolic resin of claim 1 or 9 in positive photoresist.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211647528.9A CN118221892A (en) | 2022-12-21 | 2022-12-21 | High-heat-resistance phenolic resin with good alkali solubility and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211647528.9A CN118221892A (en) | 2022-12-21 | 2022-12-21 | High-heat-resistance phenolic resin with good alkali solubility and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118221892A true CN118221892A (en) | 2024-06-21 |
Family
ID=91510748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211647528.9A Pending CN118221892A (en) | 2022-12-21 | 2022-12-21 | High-heat-resistance phenolic resin with good alkali solubility and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118221892A (en) |
-
2022
- 2022-12-21 CN CN202211647528.9A patent/CN118221892A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112684661B (en) | Photoresist composition and preparation method thereof | |
| CN112094392A (en) | Phenolic resin and preparation method and application thereof | |
| US4971887A (en) | Positive-working photosensitive mixture and recording material of high thermal stability with phenolic novolak of m-cresol and 2,3,6-trialkylphenol | |
| WO1999017166A1 (en) | Fractionated novolak resin copolymer and photoresist composition therefrom | |
| CN113773460B (en) | Phenolic resin for photoresist and preparation method thereof | |
| EP0677068B1 (en) | Using a lewis base to control molecular weight of novolak resins | |
| WO2012115029A1 (en) | Photoresist resin composition | |
| IE904551A1 (en) | Method of preparing high glass transition temperature¹novolak resins useful in high resolution photoresist¹compositions | |
| CN113461884B (en) | Modified phenolic resin for photoresist and preparation method thereof | |
| EP1042381B1 (en) | Fractionated novolak resin and photoresist composition therefrom | |
| CN118221892A (en) | High-heat-resistance phenolic resin with good alkali solubility and preparation method and application thereof | |
| WO1998027129A1 (en) | Fractionated novolak resin from cresol-formaldehyde reaction mixture and photoresist composition therefrom | |
| US5977288A (en) | Fractionated novolak resin and photoresist composition therefrom | |
| US5665517A (en) | Acidic ion exchange resin as a catalyst to synthesize a novolak resin and photoresist composition therefrom | |
| CN115304727A (en) | High-heat-resistance phenolic resin, synthesis method thereof, positive type I-line photoresist composition prepared from resin and application of positive type I-line photoresist composition | |
| CN113801279B (en) | Phenolic resin and preparation method and application thereof | |
| CN111458978B (en) | Photoresist composition | |
| EP0865455B1 (en) | Isolation of novolak resin without high temperature distillation and photoresist composition therefrom | |
| CN115819695B (en) | Modified phenolic resin for photoresist and preparation method and application thereof | |
| CN116203798B (en) | I-line photoresist and its preparation method and application | |
| CN116203797B (en) | I-line photoresist and its preparation method and application | |
| KR20130105473A (en) | Photoresist resin composition | |
| EP0948552B1 (en) | Method for producing a water insoluble, aqueous alkali soluble novolak resin | |
| JPH02300752A (en) | Positive photoresist composition | |
| CN118672058A (en) | Photosensitive resin composition, resist film, resist underlayer film and resist permanent film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |