CN112094392A - Phenolic resin and preparation method and application thereof - Google Patents
Phenolic resin and preparation method and application thereof Download PDFInfo
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- CN112094392A CN112094392A CN202010555776.5A CN202010555776A CN112094392A CN 112094392 A CN112094392 A CN 112094392A CN 202010555776 A CN202010555776 A CN 202010555776A CN 112094392 A CN112094392 A CN 112094392A
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- 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
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- 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
Abstract
The phenolic resin provided by the invention has structural units of polyhydroxy and multiple benzene rings, so that the phenolic resin is endowed with high glass transition temperature, and the hydroxyl in the structure is not shielded by a large steric hindrance group; the preparation process of the phenolic resin comprises a chromatographic column separation step, so that the product has high glass transition temperature and narrow molecular weight distribution, and a large amount of chemical waste liquid is not generated in the preparation process, so that the preparation process is an environment-friendly preparation process. The phenolic resin provided by the invention is suitable for preparing positive photoresist, and the photoresist based on the phenolic resin has excellent resolution, heat resistance and substrate adhesion.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to phenolic resin and a preparation method and application thereof.
Background
Rapid development of microelectronics has benefited from the continuous improvement of semiconductor and integration technologies, and photolithography and photoresist are core technologies and key materials in microelectronics. In recent years, the innovation and improvement of microelectronic processing technology has driven the application depth of photoresist in the industry, and in the semiconductor chip processing process and the liquid crystal display FPD manufacturing process, the photoresist is used to generate fine circuit patterns, and fine circuits are formed on a substrate by etching; most of the positive photoresists used in TFT-LCD, TN/STN and LED production are mainly photoresists of phenolic resin systems.
The phenolic resin-diazonaphthoquinone positive photoresist consists of linear phenolic resin, diazonaphthoquinone sensitizer, additive and solvent, and during exposure, the diazonaphthoquinone group is converted into ketene, which is contacted with water to further generate indene carboxylic acid, so that the exposed area is washed away during alkali water development, and an etched image consistent with the pattern on the mask is obtained after development. Based on the influence of the photoresist on the performance requirement and the chemical structure of the linear phenolic resin, the photoresist of the type can generate the condition of softening and deformation when being baked at high temperature, so that the resolution ratio is deteriorated, the performance of the photoresist is deteriorated, and the high-precision microelectronic processing cannot be realized. Currently, with the development of the refinement of circuit patterns, further improvement in the sensitivity and resolution of a photoresist is required, and a phenolic resin as a film-forming resin is required to have better high-temperature resistance and alkali-soluble processability.
CN105555820A discloses a modified hydroxynaphthalene novolak resin, a method for producing the modified hydroxynaphthalene novolak resin, a photosensitive composition, a resist material and a coating film. The adhesion force of the coating film of the modified phenolic resin and a base material has a problem, the coating film is subjected to a repeated washing process of a chemical reagent and deionized water at a high frequency during high-efficiency photoetching processing, and under the pressure washing of a solution of an automatic developing and cleaning process, the phenomenon that the resin coating film falls off easily during the washing process due to insufficient adhesion force of the coating film and the base material is caused, so that the yield is greatly reduced.
CN1053616 discloses a method for preparing a high glass transition temperature novolac resin for a high resolution photoresist composition. Based on the influence of the photoresist on the performance requirement and the chemical structure of the linear phenolic resin, the content of the low-molecular-weight resin contained in the phenolic resin is higher, and is more than 7%, the low-molecular-weight resin volatilizes under the high-temperature condition when the resin is baked at high temperature, and the pattern can be softened and deformed, so that the resolution ratio is poor, the performance of the photoresist is deteriorated, and the high-precision microelectronic processing cannot be realized.
In view of the above, it is important to develop a phenolic resin with high Tg, high adhesion and narrow molecular weight distribution and an environmentally friendly and efficient method for preparing the phenolic resin in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a phenolic resin, a preparation method and application thereof, wherein the structural unit of the phenolic resin contains a plurality of hydroxyl groups and aryl groups, and the phenolic resin is endowed with the characteristics of high Tg and high adhesion.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a phenolic resin having a structure represented by formula I:
R01、R02、R03selected from substituted or unsubstituted monohydroxyphenol, polyhydroxyphenol or naphthol groups; the substitution comprises single substitution or multiple substitution, and the number of the multiple substitution is 2-3; n is an integer of 0 to 350 (a positive integer of 0, 1, 2,3 … … 350, or the like);
the substituted substituent group comprises halogen and C1～C30Straight or branched alkyl, C1～C30Straight-chain or branched alkenyl, C1～C30Straight-chain or branched alkynyl, C1～C30Alkoxy or C6～C30An aromatic hydrocarbon group; preferably halogen, C1～C10Straight or branched alkyl, C1～C10Straight-chain or branched alkenyl, C1～C10Straight-chain or branched alkynyl, C1～C10Alkoxy or C6～C10An aromatic hydrocarbon group; more preferably halogen or C1～C6Straight or branched alkyl, C1～C6Straight-chain or branched alkenyl, C1～C6Straight-chain or branched alkynyl, C1～C6Alkoxy or C6～C10An aromatic hydrocarbon group;
R01、R02、R03the phenolic resin structures are the same or different, and the phenolic resin structures simultaneously comprise substituted or unsubstituted polyhydric phenol groups or naphthol groups; optionally, the compound also comprises a substituted or unsubstituted monohydroxyphenol group.
Further, the naphthol may be a monohydroxynaphthol or a polyhydroxynaphthol. The polyhydroxy group optionally means 2 to 3 hydroxyl groups on the phenol ring.
Further, the phenolic resin structure has a hydroxyl/aromatic ring ratio greater than 1, optionally less than 1.15. The aromatic ring refers to a cyclic compound with a planar or near-planar structure and composed of a plurality of carbon atoms, for example, the number of aromatic rings of a single benzene ring is 1, the number of aromatic rings contained in bisphenol A is 2, and the number of aromatic rings of one naphthalene ring is 2.
Further, the phenol resin has a ratio of n-1 component (dimer) occupying 0 to 5% (peak area of n-1 component in a spectrum measured by gel permeation chromatography as a percentage of the total peak area, and so on).
Furthermore, the sum of the proportion of n which is 2,3, 4, 5 and 6 is 10-35 percent, and the proportion of the component with n which is more than or equal to 7 is 60-90 percent.
Furthermore, in the phenolic resin, the proportion of the n-1 component is 0-5%, the sum of the proportions of n-2, 3, 4, 5 and 6 is 10-20%, and the proportion of the component with n being more than or equal to 7 is 70-90%.
Further, the phenolic resin structure has a hydroxyl/aromatic ring ratio greater than 1, optionally less than 1.15.
Further, the phenolic resin has a structure shown in formula II:
wherein R is1、R3、R4、R5、R6、R8Each independently selected from hydroxyl, halogen, C1-C30 straight chain or branched chain alkyl, C1～C30Straight-chain or branched alkenyl, C1～C30Straight-chain or branched alkynyl, C1～C30Alkoxy or C6～C30One of aromatic hydrocarbon groups; preferably hydroxy, halogen, C1～C10Straight or branched alkyl, C1～C10Straight-chain or branched alkenyl, C1～C10Straight-chain or branched alkynyl, C1～C10Alkoxy or C6～C10One of aromatic hydrocarbon groups; more preferably hydroxyl, halogen, C1～C6Straight or branched alkyl, C1～C6Straight-chain or branched alkenyl, C1～C6Straight-chain or branched alkynyl, C1～C6Alkoxy or C6～C10One kind of aromatic hydrocarbon group.
R2、R7Each independently is one of hydrogen, halogen, C1-C30 straight chain or branched chain alkyl, C1-C30 alkoxy or C6-C30 aromatic hydrocarbon; preferably hydrogen, halogen, C1～C10Straight or branched alkyl, C1～C10Straight-chain or branched alkenyl, C1～C10Straight-chain or branched alkynyl, C1～C10Alkoxy or C6～C10One of aromatic hydrocarbon groups; more preferably hydrogen, halogen, C1～C6Straight or branched alkyl, C1～C6Straight-chain or branched alkenyl, C1～C6Straight-chain or branched alkynyl, C1～C6Alkoxy or C6～C10One kind of aromatic hydrocarbon group.
h. q, i, j are each independently selected from an integer of 0 to 4 (e.g., 0, 1, 2,3 or 4), k, l, m are each independently selected from an integer of 0 to 3 (e.g., 0, 1, 2 or 3), p is an integer of 0 to 2 (e.g., 0, 1 or 2), and n is an integer of 0 to 350 (e.g., 0, 2,4, 5, 7, 10, 15, 20, 40, 60, 80, 100, 120, 150, 180, 200, 230, 250, 280, 300 or 330, etc.).
The C1-C30 include C2, C4, C6, C8, C10, C13, C15, C17, C20, C22, C25, C28, C29 and the like.
The C6-C30 include C7, C9, C11, C13, C15, C17, C20, C22, C25, C28 or C29.
The structural unit of the phenolic resin contains benzene ring and naphthalene ring, so that the density of the large steric hindrance group in the molecular structure is high, and the glass transition temperature T of the phenolic resin can be improvedg(ii) a Meanwhile, the structural unit of the phenolic resin also contains a proper amount of hydroxyl, so that the shielding effect of a benzene ring with large steric hindrance on the hydroxyl is effectively avoided, and the phenolic resin is ensured to have good adhesive force and toughness when being applied to photoresist at a later stage. Therefore, the phenolic resin realizes high T of the phenolic resin through the special design of the structuregAnd a balance of high adhesion.
Preferably, the weight average molecular weight of the phenol resin is 2000 to 40000, for example 2500, 3000, 4000, 5000, 7000, 9000, 11000, 13000, 15000, 17000, 20000, 25000, 28000, 30000, 35000, 37000, or 39000, and more preferably 2000 to 30000.
Preferably, the mass percent content of the dimer component in the phenolic resin is less than 5%, such as 4.9%, 4.7%, 4.5%, 4.3%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, or 1%, etc.
Further, the phenolic resin Tg is >100 ℃, preferably >110 ℃.
Further, the phenolic resin has a softening point temperature of >140 ℃, preferably >145 ℃.
Optionally, the phenolic resin has a structure as shown in formula:
wherein n is an integer of 0 to 300, such as 0, 2,4, 5, 7, 10, 15, 20, 40, 60, 80, 100, 120, 150, 180, 200, 230, 250, 270, 290, etc.
In another aspect, the present invention provides a method for preparing the phenolic resin as described above, comprising the steps of:
(1) adding a phenolic compound, an aldehyde compound and a catalyst into a reaction device for condensation reaction to obtain a crude product;
(2) and (2) purifying the crude product obtained in the step (1) by a chromatographic column separation method to obtain the phenolic resin.
The phenolic resin provided by the invention is added with a purification process of chromatographic column separation in the preparation process, so that products with low polymerization degree, such as dimer components and the like in a crude product are effectively separated, the phenolic resin with narrow molecular weight distribution is obtained, and the pattern resolution of the phenolic resin applied to photoresist at the later stage is improved. In addition, compared with the methods such as water washing extraction and the like in the prior art, the chromatographic column separation method does not generate a large amount of chemical waste liquid, reduces the burden of waste liquid treatment, and is an environment-friendly preparation process.
Further, the phenolic compounds in the step (1) comprise substituted or unsubstituted monohydroxyphenol, polyhydroxy phenol and naphthol compounds; wherein the content of the first and second substances,
the substitution comprises single substitution or multiple substitution, and the number of the multiple substitution is 2-3;
the substituted substituent group comprises halogen and C1～C30Straight or branched alkyl, C1～C30Alkoxy or C6～C30An aromatic hydrocarbon group; preferably halogen, C1～C10Straight or branched alkyl, C1～C10Straight-chain or branched alkenyl, C1～C10Straight-chain or branched alkynyl, C1～C10Alkoxy or C6～C10An aromatic hydrocarbon group; more preferably halogen or C1～C6Straight or branched alkyl, C1～C6Straight-chain or branched alkenyl, C1～C6Straight-chain or branched alkynyl, C1～C6Alkoxy or C6～C10An aromatic hydrocarbon group. The naphthol group may be a monohydroxynaphthol or a polyhydroxynaphthol. The polyhydroxy group means a phenolic hydroxyl group having 2 to 3 on the phenolic ring.
Preferably, the molar ratio of the phenolic compound to the aldehyde compound in the step (1) is 1: 0.2 to 1.0, for example, 1: 0: 3, 1: 0: 4, 1: 0: 5, 1: 0: 6, 1: 0: 7, 1: 0: 8 or 1: 0: 9, more preferably 1: 0.4 to 1.0, and still more preferably 1: 0.5 to 0.9.
Preferably, the phenolic compounds of step (1) include monohydroxyphenol, polyhydric phenol and naphthol compounds.
Preferably, the monohydric phenol is selected from any one of phenol, m-cresol, p-cresol, 2, 4-xylenol, 2, 5-xylenol, 3, 5-xylenol, 2,3, 5-trimethylphenol, ethylphenol, propylphenol, nonylphenol or phenylphenol or a combination of at least two thereof.
Preferably, the polyhydric phenol is selected from any one or a combination of at least two of bisphenol a, bisphenol F, resorcinol or phloroglucinol.
Preferably, the molar ratio of the polyhydric phenol to the monohydric phenol is (0.3-0.6) to 1, such as 0.35: 1, 0.4: 1, 0.45: 1, 0.5: 1, 0.55: 1, or 0.6: 1.
Preferably, the naphthol compound is selected from any one of 1-naphthol, 2-naphthol, dihydroxynaphthalene, trihydroxynaphthol or tetrahydroxynaphthol or a combination of at least two of them.
Preferably, the molar ratio of the naphthol compound to the monohydric phenol is (0.1-0.4) to 1, for example 0.15: 1, 0.2: 1, 0.25: 1, 0.28: 1, 0.3: 1, 0.35: 1 or 0.38: 1.
Preferably, the aldehyde compound in step (1) is selected from any one of formaldehyde, acetaldehyde, butyraldehyde, furfural, valeraldehyde, trioxymethylene, tetraformaldehyde, paraformaldehyde, acrolein, salicylaldehyde, benzaldehyde, o-methylbenzaldehyde, p-methylbenzaldehyde, or p-hydroxybenzaldehyde, or a combination of at least two thereof.
Preferably, the catalyst of step (1) is an acid catalyst.
Preferably, the acid catalyst is selected from one of hydrochloric acid, oxalic acid, acetic acid, benzenesulfonic acid, phosphoric acid, nitric acid or sulfuric acid.
Preferably, the amount of the acid catalyst added is 0.5 to 5% by mass of the phenolic compound, such as 0.7%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.
Preferably, the condensation reaction in step (1) is carried out at a temperature of 90 to 130 ℃, for example, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 103 ℃, 105 ℃, 108 ℃, 110 ℃, 113 ℃, 115 ℃, 118 ℃, 120 ℃, 125 ℃ or 129 ℃.
Preferably, the condensation reaction time in step (1) is 2-6 h, such as 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5 h.
Preferably, the condensation reaction of step (1) is carried out under stirring reflux conditions.
Preferably, the chromatographic column separation method comprises the following steps: dissolving the crude product in an organic solvent to obtain a solution, and passing the solution through a silica gel chromatographic column to remove low polymerization degree units with the molecular weight below 300 in the crude product.
Preferably, the organic solvent is acetonitrile.
Preferably, the stationary phase of the silica gel chromatographic column is C8 or C18 silica gel particles.
Preferably, the mobile phase of the silica gel chromatographic column is selected from any one of acetonitrile, methanol, tetrahydrofuran or water or a combination of at least two of the above.
Preferably, the preparation method specifically comprises the following steps:
(1) adding a phenolic compound, an aldehyde compound and an acid catalyst into a reaction device, and carrying out condensation reaction for 2-6 h under the condition of stirring and refluxing at 90-130 ℃ to obtain a crude product; the molar ratio of the phenolic compound to the aldehyde compound is 1 to (0.2-1.0), and the addition amount of the acid catalyst is 0.5-5% of the mass of the phenolic compound;
(2) dissolving the crude product obtained in the step (1) in an organic solvent to obtain a solution, passing the solution through a C8 or C18 silica gel chromatographic column, removing low-polymerization-degree units with the molecular weight of less than 300 in the crude product, and distilling to obtain the phenolic resin.
On the other hand, the invention also provides the phenolic resin prepared by the preparation method.
The weight average molecular weight of the phenolic resin is 2000-40000, preferably 2000-30000, and more preferably 8000-16000.
Further, the mass percentage content of the n-1 component in the phenolic resin is less than 5%.
Further, the phenolic resin as described in any of the preceding has a Tg >100 ℃, preferably >110 ℃.
Further, the phenolic resin has a softening point temperature of >140 ℃, preferably >145 ℃ as described in any of the preceding.
In another aspect, the present invention provides an application of the above phenolic resin in the fields of photoresist preparation, semiconductor chip processing and liquid crystal panel processing.
In another aspect, the present invention provides a photoresist composition comprising the phenolic resin as described in any of the preceding,
furthermore, the photoresist composition also comprises a diazonaphthoquinone photosensitizer and the phenolic resin.
Specifically, the photoresist composition also comprises 2-40% by mass of diazonaphthoquinone photosensitizer, 0-2% by mass of surfactant and 40-90% by mass of solvent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the phenolic resin provided by the invention has structural units of polyhydroxy and benzene rings, the structure endows the phenolic resin with high glass transition temperature, and the hydroxyl in the structure is not shielded by a large steric hindrance group, so that the heat resistance and the adhesive force of the phenolic resin in application are effectively improved.
(2) The phenolic resin provided by the invention is prepared by condensing a mixed phenol monomer of monohydroxyphenol, polyhydroxy phenol and naphthol and an aldehyde monomer under the action of an acid catalyst to obtain a crude product, and then treating the crude product by a chromatographic column separation fractionation method to obtain a product with high Tg and narrow molecular weight distribution; the phenolic resin does not generate a large amount of chemical waste liquid in the preparation process, and is an environment-friendly preparation process.
(3) The photoresist based on the phenolic resin has excellent developability, heat resistance and substrate adhesion, and is suitable for etching preparation of high-resolution fine circuit structures.
Drawings
FIG. 1 is a graph of the results of GPC testing in example 1;
FIG. 2 is a graph of the results of GPC testing in example 2;
FIG. 3 is a graph of the results of GPC testing in example 3;
FIG. 4 is a graph of the results of GPC testing of example 4;
FIG. 5 is a GPC measurement result chart of comparative example 1;
FIG. 6 is a GPC measurement result chart of comparative example 2;
FIG. 7 is a GPC measurement result chart of comparative example 3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The present invention is specifically described by examples and comparative examples, and Gel Permeation Chromatography (GPC) is measured under the following conditions:
measurement conditions for Gel Permeation Chromatography (GPC):
a measuring device: "HLC-8320 GPC" manufactured by TOSOH CORPORATION "
A chromatographic column: "PLGel 5um MIXED-C300 X7.5mm" manufactured by American Agilent (Varian), "PLGel 5um MIXED-D300X 7.5 mm" manufactured by Varian + "PLGel 5um MIXED-E300X 7.5 mm" manufactured by American Agilent (Varian).
A detector: RI (differential refraction detector)
Data processing: "GPC-8320 model II data analysis System V2.01" manufactured by TOSOH CORPORATION "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran (THF) as developing solvent
Flow rate 1.0 ml/min
Sample preparation: the resulting tetrahydrofuran solution (1.0 mass% in terms of resin solid content) was filtered through a microfilter to obtain a filtrate (5. mu.l).
Standard sample: the following monodisperse polystyrene having a known molecular weight was used according to the manual of "GPC-8320 model II data analysis System V2.01" described above.
"S-0.5" manufactured by Showa Denko K.K.) "
"S-0.9" manufactured by Showa Denko K.K.) "
"S-1.3" manufactured by Showa Denko K.K.) "
"S-1.9" manufactured by Showa Denko K.K.) "
"S-3.0" manufactured by Showa Denko K.K.) "
"S-3.8" manufactured by Showa Denko K.K.) "
"S-4.9" manufactured by Showa Denko K.K.) "
"S-7.2" manufactured by Showa Denko K.K.) "
S-10 manufactured by Showa Denko K.K.) "
S-20 manufactured by Showa Denko K.K.) "
Example 1
This example provides a phenolic resin, which contains the following components by nuclear magnetic detection:
wherein n is an integer of 0 to 300.
The preparation method comprises the following steps:
(1) adding 0.4mol of p-cresol, 0.2mol of m-cresol, 0.3mol of resorcinol and 0.15mol of 2-naphthol into a reaction kettle, stirring and heating to 90 ℃; then adding 2.2g of oxalic acid and 0.9mol of formaldehyde (the raw material is a 37% formaldehyde aqueous solution, and the content of the formaldehyde is 0.9mol), stirring and heating to reflux; carrying out condensation reaction for 4 hours under the condition of stirring reflux, and carrying out reduced pressure dehydration to obtain a crude product;
(2) dissolving the crude product obtained in the step (1) in acetonitrile to obtain a solution, separating and purifying the solution by using a C18 silica gel chromatographic column (acetonitrile is used as a mobile phase for elution), removing low-polymerization-degree units with the molecular weight of below 300 in the crude product, and distilling to remove the solvent to obtain the phenolic resin, wherein the weight average molecular weight Mw of the phenolic resin is 8475.
The phenol resin product obtained by the above production method contained a polymer in which the proportion of the n-0 component (low-polymerization-degree unit, which represents a 2-mer in this example, the same applies hereinafter) occupied in the total polymer was 3.3%, the sum of the proportions of n-1, 2,3, 4, and 5 was 17.03%, and the proportion of the component having n.gtoreq.6 was 78.07%; the ratio of benzene ring to hydroxyl group was calculated from hydrogen nuclear magnetic resonance spectroscopy, and the ratio of hydroxyl group/aromatic ring was 1.10. The GPC measurement results are shown in FIG. 1.
Example 2
This example provides a phenolic resin, which was tested to contain the following components:
wherein n is 0 to 300.
The preparation method comprises the following steps:
(1) adding 0.6mol of m-cresol, 0.2mol of resorcinol and 0.2mol of 2-naphthol into a reaction kettle, stirring and heating to 95 ℃; then adding 2.1g of oxalic acid, 0.7mol of formaldehyde (the raw material is a 37% formaldehyde aqueous solution, the content of the formaldehyde is 0.7mol) and 0.2mol of salicylaldehyde, stirring and heating to reflux; carrying out condensation reaction for 3.5h under the condition of stirring reflux, and carrying out reduced pressure dehydration to obtain a crude product;
(2) dissolving the crude product obtained in the step (1) in acetonitrile to obtain a solution, separating and purifying the solution by using a C18 silica gel chromatographic column (acetonitrile is used as a mobile phase for elution), removing low-polymerization-degree units with the molecular weight of below 300 in the crude product, and distilling off the solvent to obtain the phenolic resin with the weight-average molecular weight Mw of 15120.
In the polymer included in the phenol resin product obtained by the above production method, the proportion of the component (low polymerization degree unit) having n ═ 0 was 3.7%, the sum of the proportions of the components having n ═ 1, 2,3, 4 and 5 was 13.56%, and the proportion of the component having n ≥ 6 was 84.06%; the ratio of benzene ring to hydroxyl group was calculated from hydrogen nuclear magnetic resonance spectroscopy, and the ratio of hydroxyl group/aromatic ring was 1.09. The GPC measurement results are shown in FIG. 2.
Example 3
This example provides a phenolic resin, which was tested to contain the following components:
wherein n is 0 to 300.
The preparation method comprises the following steps:
(1) adding 0.6mol of p-cresol, 0.25mol of resorcinol and 0.23mol of 1-naphthol into a reaction kettle, stirring and heating to 95 ℃; then adding 0.95mol of formaldehyde (the raw material is a 37% formaldehyde aqueous solution, the content of the formaldehyde is 0.95mol) and 1.7g of hydrochloric acid (the raw material is a 30% hydrochloric acid solution, and the mass is calculated by an effective component HCl), and heating to reflux; carrying out condensation reaction for 2.5h under the condition of stirring reflux, and carrying out reduced pressure dehydration to obtain a crude product;
(2) dissolving the crude product obtained in the step (1) in acetonitrile to obtain a solution, separating and purifying the solution by using a C18 silica gel chromatographic column (acetonitrile is used as a mobile phase for elution), removing low-polymerization-degree units with the molecular weight of below 300 in the crude product, and distilling off the solvent to obtain the phenolic resin with the weight-average molecular weight Mw of 10803.
In the polymer included in the phenol resin product obtained by the above production method, the proportion of the n-0 component (low-polymerization-degree unit) is 3.10%, the sum of the proportions of n-1, 2,3, 4 and 5 is 16.54%, and the proportion of the component with n being equal to or greater than 6 is 80.36%; the ratio of benzene ring to hydroxyl group was calculated from hydrogen nuclear magnetic resonance spectroscopy, and the ratio of hydroxyl group/aromatic ring was 1.02. The GPC measurement results are shown in FIG. 3.
Example 4
This example provides a phenolic resin, which was tested to contain the following components:
wherein n is 0 to 300.
The preparation method comprises the following steps:
(1) adding 0.4mol of p-cresol, 0.2mol of m-cresol, 0.3mol of resorcinol and 0.2mol of 1.5-dihydroxynaphthalene into a reaction kettle, and stirring and heating to 95 ℃; then adding 2.3g of oxalic acid and 0.9mol of formaldehyde (the raw material is a 37% formaldehyde aqueous solution, and the content of the formaldehyde is 0.9mol), stirring and heating to reflux; carrying out condensation reaction for 3.5h under the condition of stirring reflux, and carrying out reduced pressure dehydration to obtain a crude product;
(2) dissolving the crude product obtained in the step (1) in acetonitrile to obtain a solution, separating and purifying the solution by using a C18 silica gel chromatographic column (acetonitrile is used as a mobile phase for elution), removing low-polymerization-degree units with the molecular weight of below 300 in the crude product, and distilling off the solvent to obtain the phenolic resin with the weight-average molecular weight Mw of 9241.
In the polymer included in the phenol resin product obtained by the above production method, the proportion of the component (low polymerization degree unit) having n ═ 0 was 3.90%, the sum of the proportions of the components having n ═ 1, 2,3, 4, and 5 was 16.42%, and the proportion of the component having n ≥ 6 was 79.68%; the ratio of benzene ring to hydroxyl group was calculated from hydrogen nuclear magnetic resonance spectroscopy, and the ratio of hydroxyl group/aromatic ring was 1.10. The GPC measurement results are shown in FIG. 4.
Comparative example 1
This comparative example is different from example 1 in that the column separation and purification process in step (2) is not performed. The weight average molecular weight Mw of the obtained phenolic resin is 8121, wherein the proportion of the component with n equal to 0 is 9.6 percent, the sum of the proportions of the components with n equal to 1, 2,3, 4, 5 and 6 is 23.34 percent, and the proportion of the component with n equal to or more than 6 is 67.06 percent; the ratio of benzene ring to hydroxyl group was calculated from hydrogen nuclear magnetic resonance spectroscopy, and the ratio of hydroxyl group/aromatic ring was 1.36. The GPC measurement results are shown in FIG. 5.
Comparative example 2
This comparative example differs from example 1 in that resorcinol is replaced by an equimolar amount of m-cresol. The weight average molecular weight Mw of the resulting phenol resin was 8619, wherein the proportion of the component n ═ 0 was 3.6%, the sum of the proportions of n ═ 1, 2,3, 4, and 5 was 17.23%, and the proportion of the component n ≥ 6 was 79.08%; the ratio of benzene ring to hydroxyl group was calculated from hydrogen nuclear magnetic resonance spectroscopy, and the ratio of hydroxyl group/aromatic ring was 0.89. The GPC measurement results are shown in FIG. 6.
Comparative example 3
This comparative example differs from example 1 in that 2-naphthol is replaced by an equimolar amount of m-cresol. The weight average molecular weight Mw of the obtained phenolic resin is 8535, wherein the proportion of the component with n being 0 is 4.1 percent, the sum of the proportions of the components with n being 1, 2,3, 4 and 5 is 27.32 percent, and the proportion of the component with n being more than or equal to 6 is 68.58 percent; the ratio of benzene ring to hydroxyl group was calculated from hydrogen nuclear magnetic resonance spectroscopy, and the ratio of hydroxyl group/aromatic ring was 1.35. The GPC measurement results are shown in FIG. 7.
Testing the performance of the phenolic resin:
(1) weight average molecular weight MwPolydispersion coefficient D and dimer component content testing: the weight average molecular weight M was obtained by GPC measurementwAnd number average molecular weight MnThe polydispersity D ═ Mw/MnThe content of the n-1 component is calculated according to the peak area in a GPC spectrogram;
(2) glass transition temperature Tg: DSC measurement of its glass transition temperature TgUnder the nitrogen atmosphere, the temperature range is 0-300 ℃, and the heating rate is 10 ℃/min;
(3) softening point: the test was carried out according to the regulations of GB/T4507-.
The phenolic resins provided in examples 1 to 4 and comparative examples 1 to 3 were tested for weight average molecular weight, polydispersity, dimer component content, glass transition temperature and softening point according to the methods described above, and the test data are shown in table 1.
TABLE 1
| Mw | Polydispersity index | n is 1 content | Tg | Softening point | |
| Example 1 | 8475 | 4.2 | 3.3％ | 112℃ | 149℃ |
| Example 2 | 15120 | 4.9 | 3.7％ | 121℃ | 164℃ |
| Example 3 | 10803 | 4.6 | 3.1％ | 117℃ | 161℃ |
| Example 4 | 9241 | 4.4 | 3.9％ | 114℃ | 154℃ |
| Comparative example 1 | 8121 | 8.9 | 9.6％ | 92℃ | 131℃ |
| Comparative example 2 | 8619 | 4.9 | 3.6％ | 83℃ | 118℃ |
| Comparative example 3 | 8535 | 4.5 | 4.1％ | 79℃ | 109℃ |
As is clear from the data in Table 1, the phenolic resins obtained by the raw materials and the preparation method of the present invention have a small polydispersity D, a narrow molecular weight distribution, a small molecular component content of 5% or less, and a high glass transition temperature and a high softening point at the same Mw. When the preparation process of the phenolic resin does not comprise the step of separating and purifying the chromatographic column (comparative example 1) disclosed by the invention, the molecular weight distribution of the obtained phenolic resin is wide, the content of small molecular components reaches up to 9%, and the glass transition temperature and the softening point are reduced; when the density of benzene rings in the molecular structure of the phenol resin was decreased (comparative example 2 and comparative example 3), the glass transition temperature and softening point of the phenol resin were significantly decreased.
Application example
A photoresist composition is prepared from the following raw materials:
the phenolic resins are respectively provided in examples 1-4 and comparative examples 1-3, the diazonaphthoquinone photosensitizer is electronic-grade 215 diazonaphthoquinone sulfonyl chloride, the organic solvent is propylene glycol monomethyl ether acetate, and the surfactant is dimethyl silicone oil.
The preparation method comprises the following steps:
mixing phenolic resin, diazonaphthoquinone photosensitizer, organic solvent and surfactant to obtain the photoresist composition.
Testing the performance of the photoresist:
(1) filtering the photoresist by using a 0.2-micron membrane filter to remove impurities, spin-coating the photoresist on a silicon wafer substrate with a polished single surface to form a 15-micron wet membrane, and observing the uniformity of coating;
(2) drying with 100 deg.C electric heating plate for 2min to volatilize solvent, and curing to form film;
(3) exposing the surface of the substrate by using a stepping exposure machine, wherein the total irradiation energy is 250-350 mJ/cm2Within the range; after exposure, developing with 2.38 wt% tetramethylammonium hydroxide for 20 s;
(4) and drying the developed substrate for 2min by using an electric hot plate at 105 ℃ to obtain a test sample.
And (3) testing the resolution ratio: testing a sample to be tested by using a laser microscope, confirming the resolution of the pattern, and evaluating that the sample can be clearly distinguished when the line width of L/S (1/1) is 5 mu m as A and that the sample cannot be clearly distinguished when the line width of L/S (1/1) is 5 mu m as B;
and (3) testing heat resistance: heating a test sample for 5min, and testing the resolution according to the method, wherein when the temperature for evaluating the resolution to be changed from A to B is the heat resistance temperature, the higher the temperature is, the better the heat resistance of the photoresist is proved;
and (3) testing the adhesive force: the coating film obtained in step (2) was peeled off after rinsing with water for 4min, and the case of no peeling was evaluated as level 1, the case of a peeling degree of less than 30% of the total area of the coating film was evaluated as level 2, and the case of a peeling degree of more than 30% of the total area of the coating film was evaluated as level 3.
The photoresist resolution, heat resistance and adhesion were tested according to the above methods, and the specific test results are shown in table 2:
TABLE 2
| Phenolic resin | Resolution ratio | Heat resistance/. degree.C | Adhesion force | |
| Photoresist 1 | Example 1 | A | 155 | Level 1 |
| Photoresist 2 | Example 2 | A | 160 | Level 1 |
| Photoresist 3 | Example 3 | A | 155 | Level 1 |
| Photoresist 4 | Example 4 | A | 155 | Level 1 |
| Photoresist 5 | Comparative example 1 | B | 110 | Stage 2 |
| Photoresist 6 | Comparative example 2 | B | 105 | Grade 3 |
| Photoresist 7 | Comparative example 3 | B | 100 | Level 1 |
From the test results in table 2, it can be seen that the photoresists prepared from the phenolic resins provided in embodiments 1 to 4 of the present invention have high resolution, high heat resistance, and strong adhesion. When the preparation process of the phenolic resin does not comprise the step of separating and purifying the chromatographic column (comparative example 1), the molecular weight distribution of the obtained phenolic resin is wide, and the proportion of molecules with low polymer degree is large, so that the resolution, heat resistance and adhesive force of the photoresist are influenced; when the raw materials for preparing the phenolic resin do not contain the polyhydric phenol (comparative example 2), the adhesive force between the photoresist and the substrate is poor, and the photoresist is easy to strip and fall off after being washed by water; when the phenolic resin does not contain naphthalene rings (comparative example 3), the phenolic resin has a low glass transition temperature and poor resolution and heat resistance.
The applicant states that the present invention is illustrated by the above examples of the phenolic resin of the present invention and the preparation method and application thereof, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A phenolic resin, wherein the phenolic resin has a structure according to formula I:
R01、R03selected from substituted or unsubstituted monohydroxyphenol, polyhydroxyphenol or naphthol groups, R02Selected from H, substituted or unsubstituted monohydroxyphenol, polyhydroxyphenol or naphthol; the substitution comprises single substitution or multiple substitution, and the number of the multiple substitution is 2-3; n is an integer of 0 to 350;
the substituted substituent group comprises halogen and C1～C30Straight or branched alkyl, C1～C30Straight-chain or branched alkenyl, C1～C30Straight-chain or branched alkynyl, C1～C30Alkoxy or C6～C30An aromatic hydrocarbon group; preferably halogen, C1～C10Straight or branched alkyl, C1～C10Straight-chain or branched alkenyl, C1～C10Straight-chain or branched alkynyl, C1～C10Alkoxy or C6～C10An aromatic hydrocarbon group; more preferably halogen or C1～C6Straight or branched alkyl, C1～C6Straight-chain or branched alkenyl, C1～C6Straight-chain or branched alkynyl, C1～C6Alkoxy or C6～C10An aromatic hydrocarbon group;
R01、R02、R03the same or different, and the phenolic resin structure comprises a substituted or unsubstituted polyhydric phenol group and a naphthol group.
2. The phenolic resin according to claim 1, wherein,
the ratio of hydroxyl group/aromatic ring in the structure of the phenolic resin is more than 1.
3. The phenolic resin of claim 1, wherein the proportion of the component n-1 is 0-5%.
4. The phenolic resin as claimed in claim 3, wherein the sum of the proportion of n-2, 3, 4, 5 and 6 is 10-35%, and the proportion of the component with n being more than or equal to 7 is 60-90%; preferably, the sum of the proportion of n-2, 3, 4, 5 and 6 is 10-20%, and the proportion of the component with n being more than or equal to 7 is 70-90%.
5. A phenolic resin, wherein the phenolic resin has a structure as shown in formula II:
wherein R is1、R3、R4、R5、R6、R8Each independently selected from hydroxy, halogen, C1～C30Straight or branched alkyl, C1～C30Straight-chain or branched alkenyl, C1～C30Straight-chain or branched alkynyl, C1～C30Alkoxy or C6～C30One of aromatic hydrocarbon groups; preferably hydroxy, halogen, C1～C10Straight or branched alkyl, C1～C10Straight-chain or branched alkenyl, C1～C10Straight-chain or branched alkynyl, C1～C10Alkoxy or C6～C10One of aromatic hydrocarbon groups; more preferably hydroxyl, halogen, C1～C6Straight or branched alkyl, C1～C6Straight-chain or branched alkenyl, C1～C6Straight-chain or branched alkynyl, C1～C6Alkoxy or C6～C10One of aromatic hydrocarbon groups;
R2、R7each independently selected from hydrogen, halogen, C1～C30Straight or branched alkyl, C1～C30Straight-chain or branched alkenyl, C1～C30Straight-chain or branched alkynyl, C1～C30Alkoxy or C6～C30One of aromatic hydrocarbon groups; preferably hydrogen, halogen, C1～C10Straight or branched alkyl, C1～C10Straight-chain or branched alkenyl, C1～C10Straight-chain or branched alkynyl, C1～C10Alkoxy or C6～C10One of aromatic hydrocarbon groups; more preferably hydrogen, halogen, C1～C6Straight or branched alkyl, C1～C6Straight-chain or branched alkenyl, C1～C6Straight-chain or branched alkynyl, C1～C6Alkoxy or C6～C10One of aromatic hydrocarbon groups;
h. q, i and j are independently selected from integers of 0-4, k, l and m are independently selected from integers of 0-3, and p is an integer of 0-2.
6. The phenolic resin according to any one of claims 1 to 5, wherein the phenolic resin has a weight average molecular weight of 2000 to 40000, preferably 2000 to 30000.
7. The phenolic resin according to any one of claims 1 to 5, wherein the content of the n-0 component in the phenolic resin is less than 5% by mass.
8. The phenolic resin of claim 5, wherein the structure of formula II comprises:
wherein n is an integer of 0 to 350, and n is preferably an integer of 0 to 150.
9. The preparation method of the phenolic resin is characterized by comprising the following steps:
(1) adding a phenolic compound, an aldehyde compound and a catalyst into a reaction device for condensation reaction to obtain a crude product;
(2) and (2) purifying the crude product obtained in the step (1) by a chromatographic column separation method to obtain the phenolic resin.
10. A photoresist composition comprising the phenolic resin of any one of claims 1 to 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461884A (en) * | 2021-08-04 | 2021-10-01 | 浙江自立高分子化工材料有限公司 | Modified phenolic resin for photoresist and preparation method thereof |
| CN114031736A (en) * | 2021-12-17 | 2022-02-11 | 广东粤港澳大湾区黄埔材料研究院 | Modified phenolic resin for photoresist, preparation method thereof and photoresist composition |
| CN115304727A (en) * | 2022-08-24 | 2022-11-08 | 瑞红(苏州)电子化学品股份有限公司 | 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053616A (en) * | 1989-12-18 | 1991-08-07 | 罗姆和哈斯公司 | Preparation is used for the method for the high glass transition temperature lacquer resins of high resolution lithography glue composition |
| EP2072547A1 (en) * | 2007-12-20 | 2009-06-24 | Nanoresins AG | Modified phenolic resin |
| US20130171569A1 (en) * | 2012-01-04 | 2013-07-04 | Shin-Etsu Chemical Co., Ltd. | Resist underlayer film composition, method for producing polymer for resist underlayer film, and patterning process using the resist underlayer film composition |
| CN105190439A (en) * | 2013-03-14 | 2015-12-23 | Dic株式会社 | Modified phenolic novolac resin, resist material, coating film, and permanent resist film |
| CN105555820A (en) * | 2013-09-18 | 2016-05-04 | Dic株式会社 | Modified hydroxy naphthalene novolak resin, production method for modified hydroxy naphthalene novolak resin, photosensitive composition, resist material and coating |
| CN106699518A (en) * | 2016-10-31 | 2017-05-24 | 中国药科大学 | Method for simultaneously preparing 14C-marked bisphenol-F isomers |
-
2020
- 2020-06-17 CN CN202010555776.5A patent/CN112094392A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053616A (en) * | 1989-12-18 | 1991-08-07 | 罗姆和哈斯公司 | Preparation is used for the method for the high glass transition temperature lacquer resins of high resolution lithography glue composition |
| EP2072547A1 (en) * | 2007-12-20 | 2009-06-24 | Nanoresins AG | Modified phenolic resin |
| US20130171569A1 (en) * | 2012-01-04 | 2013-07-04 | Shin-Etsu Chemical Co., Ltd. | Resist underlayer film composition, method for producing polymer for resist underlayer film, and patterning process using the resist underlayer film composition |
| CN105190439A (en) * | 2013-03-14 | 2015-12-23 | Dic株式会社 | Modified phenolic novolac resin, resist material, coating film, and permanent resist film |
| US20160017083A1 (en) * | 2013-03-14 | 2016-01-21 | Dic Corporation | Modified novolac phenol resin, resist material, coating film, and resist permanent film |
| CN105555820A (en) * | 2013-09-18 | 2016-05-04 | Dic株式会社 | Modified hydroxy naphthalene novolak resin, production method for modified hydroxy naphthalene novolak resin, photosensitive composition, resist material and coating |
| CN106699518A (en) * | 2016-10-31 | 2017-05-24 | 中国药科大学 | Method for simultaneously preparing 14C-marked bisphenol-F isomers |
Non-Patent Citations (2)
| Title |
|---|
| KUNDU, SK，等: "A triazine-based porous organic polymer: a novel heterogeneous basic organocatalyst for facile one-pot synthesis of 2-amino-4H-chromenes", 《RSC ADVANCES》 * |
| 刘拥君: "高性能覆铜板用溴化环氧树脂的合成研究", 《上海化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461884A (en) * | 2021-08-04 | 2021-10-01 | 浙江自立高分子化工材料有限公司 | Modified phenolic resin for photoresist and preparation method thereof |
| CN114031736A (en) * | 2021-12-17 | 2022-02-11 | 广东粤港澳大湾区黄埔材料研究院 | Modified phenolic resin for photoresist, preparation method thereof and photoresist composition |
| CN114031736B (en) * | 2021-12-17 | 2023-10-10 | 广东粤港澳大湾区黄埔材料研究院 | Modified phenolic resin for photoresist, preparation method thereof and photoresist composition |
| CN115304727A (en) * | 2022-08-24 | 2022-11-08 | 瑞红(苏州)电子化学品股份有限公司 | 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 |
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