WO2022210381A1 - Sucre soluble dans l'eau, composition photosensible, et procédé de production de sucre soluble dans l'eau - Google Patents

Sucre soluble dans l'eau, composition photosensible, et procédé de production de sucre soluble dans l'eau Download PDF

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WO2022210381A1
WO2022210381A1 PCT/JP2022/014506 JP2022014506W WO2022210381A1 WO 2022210381 A1 WO2022210381 A1 WO 2022210381A1 JP 2022014506 W JP2022014506 W JP 2022014506W WO 2022210381 A1 WO2022210381 A1 WO 2022210381A1
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water
saccharide
soluble
photosensitive composition
group
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PCT/JP2022/014506
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English (en)
Japanese (ja)
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敏 竹井
達 天野
誠 小林
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群栄化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C08B30/18—Dextrin, e.g. yellow canari, white dextrin, amylodextrin or maltodextrin; Methods of depolymerisation, e.g. by irradiation or mechanically
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/10—Polymers provided for in subclass C08B
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to water-soluble saccharides, photosensitive compositions, and methods for producing water-soluble saccharides.
  • Patent Document 1 discloses unsaturated group-containing polyimides, unsaturated group-containing polyimide precursors, carboxylic acid-modified unsaturated group-containing polysiloxanes, unsaturated group-containing polybenzoxazoles, unsaturated group-containing polybenzoxazole precursors, An unsaturated group-containing resin selected from unsaturated group-containing polysiloxanes, polycyclic side chain-containing aromatic resins, acrylic resins and carboxylic acid-modified epoxy resins, and a composition comprising the unsaturated group-containing resin are described. .
  • Patent Document 2 discloses cationically polymerizable compounds such as cyclic ethers (epoxides and oxetanes, etc.), ethylenically unsaturated compounds (vinyl ethers, styrene, etc.), bicycloorthoesters, spiroorthocarbonates and spiroorthoesters, and Alkali-soluble resins having phenolic hydroxyl groups and compositions containing these cationically polymerizable compounds and alkali-soluble resins are described.
  • Patent Documents 1 and 2 do not disclose any material having a polymerizable group that is produced from saccharides as the main material.
  • the present inventors have found that by modifying a saccharide with a polymerizable group, a novel water-soluble saccharide having both polymerizability and water solubility can be obtained, and that the water-soluble saccharide is extremely useful as a novel material. Found it. Furthermore, the present inventors have conducted repeated studies and found that the water-soluble saccharide has a specific bond in the sugar chain, thereby further improving the performance, and completed the present invention.
  • an object of one aspect of the present invention is to provide a novel water-soluble saccharide having a polymerizable group and related technology.
  • a water-soluble saccharide according to one aspect of the present invention has a 1,3-bond in at least part of a sugar chain of the saccharide, and at least part of the hydroxyl groups of the sugar chain. is modified with a polymerizable group.
  • FIG. 2 is a diagram showing gel permeation chromatography (GPC) spectra of raw sugars used in Examples and Comparative Examples of the present invention.
  • FIG. 2 shows 13 C-NMR spectra of raw sugars used in Examples and Comparative Examples of the present invention.
  • 4 is a graph showing the relationship between the residual film ratio of a photosensitive composition and the exposure dose in Examples and Comparative Examples of the present invention.
  • ⁇ Term> As used herein, a numerical range indicated using “to” indicates a range including the numerical values before and after “to” as the minimum and maximum values, respectively.
  • sucrose simply means “sugars” that are raw materials for the “water-soluble sugars” according to one aspect of the present invention, unless otherwise specified.
  • sacgars includes carbohydrates as a concept in the field of food science.
  • water-soluble saccharide is a “saccharide” in which at least part of the hydroxyl groups of the saccharide are modified into polymerizable groups, and a “saccharide” having water solubility.
  • water-soluble saccharide is described as an abbreviation of “water-soluble saccharide in which at least part of the hydroxyl groups are modified with polymerizable groups”.
  • saccharide modified with “water-soluble” refer to specific examples of water-soluble sugars according to one aspect of the present invention, unless otherwise specified.
  • the term “(meth)acrylic” means one or both of acrylic and methacrylic.
  • the term “(meth)acrylic acid” means one or both of acrylic acid and methacrylic acid
  • the term “(meth)acrylate” means one or both of "acrylate” and “methacrylate”.
  • the term “(meth)acryloyl group” means one or both of “acryloyl group” and “methacryloyl group”.
  • the term "photosensitivity" means that when the composition is irradiated with actinic rays selected from the group consisting of visible light, infrared rays, ultraviolet rays, and electron beams, the Compounds contained in the composition generate radicals or protons (H + ) by absorbing actinic radiation, and compounds contained in the composition due to these radicals or protons (H + ) undergo polymerization or It means the property of exhibiting a chemical reaction such as discoloration.
  • the present inventors have found that by modifying the hydroxyl groups of saccharides with polymerizable groups, novel water-soluble saccharides having polymerizability and water solubility can be obtained, and the water-soluble saccharides are extremely useful as novel materials having photosensitivity. I found that Furthermore, the present inventors have conducted extensive research and found that (1) increasing the molecular weight of the water-soluble saccharide in order to increase the photosensitivity of the water-soluble saccharide increases the viscosity of the photosensitive composition containing the water-soluble saccharide.
  • the water-soluble saccharide according to one aspect of the present invention has a 1,3-bond in at least part of the sugar chain of the saccharide, and at least part of the hydroxyl groups of the sugar chain are modified with polymerizable groups. .
  • the water-soluble saccharide according to one aspect of the present invention realizes a novel water-soluble saccharide having both water solubility derived from the hydroxyl group of the saccharide and polymerizability derived from the polymerizable group. can be done.
  • an aqueous composition containing the water-soluble saccharide can be prepared using water instead of an organic solvent as a diluent solvent. Further, the water-soluble saccharide can be polymerized by the polymerizability of the water-soluble saccharide after the aqueous composition is applied to the object to be coated to form a coating film.
  • the water-soluble saccharide according to one aspect of the present invention can use water as a diluent solvent, and thus can be suitably used as a substitute for the polymerizable composition.
  • the solubility in water at 20° C. of the water-soluble saccharide according to one aspect of the present invention is not limited, but from the viewpoint of facilitating dilution in water, it is 50 g/L or more, preferably 200 g/L. L or more.
  • an aqueous composition containing the water-soluble saccharide can be suitably prepared.
  • a saccharide having a hydroxyl group modified to a polymerizable group and having a solubility in water at 20° C. of less than 50 g/L is herein described as a “sparingly water-soluble saccharide” and is used in the present invention. is distinguished from the "water-soluble saccharide" according to one aspect of
  • the weight average molecular weight (Mw) of the water-soluble saccharide is not limited, it is preferably 150 or more, more preferably 1000 or more. Thereby, the photosensitivity of the photosensitive composition containing the water-soluble saccharide can be enhanced, and the content of the water-soluble saccharide in the photosensitive composition can be increased. Also, the weight average molecular weight of the water-soluble saccharide is preferably 50,000 or less, more preferably 10,000 or less. Thereby, the coatability of the photosensitive composition containing the water-soluble saccharide can be improved.
  • the weight-average molecular weight of the water-soluble saccharide is 10,000 or less, it is possible to achieve a water-soluble saccharide with a high flattening ratio and filling properties.
  • the weight average molecular weight (Mw) of a water-soluble saccharide means a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.
  • the water-soluble saccharide according to one aspect of the present invention is obtained by modifying at least part of the hydroxyl groups of the sugar chain into polymerizable groups.
  • polymerizable groups include radically polymerizable groups and cationic polymerizable groups.
  • radically polymerizable groups include functional groups having unsaturated double bonds such as vinyl ester groups and (meth)acryloyl groups.
  • cationic polymerizable groups include epoxy groups and oxetane groups.
  • the polymerizable group may have, as an example, the structure shown in formula (1) below.
  • R 1 is hydrogen or a methyl group. That is, the polymerizable group represented by formula (1) is a (meth)acryloyl group.
  • the (meth)acryloyl group is covalently bonded to the saccharide via an oxygen atom.
  • the polymerizable group may have, for example, the structure of the following formula (2) or formula (3).
  • R a has the structure shown in formula (1)
  • R 2 has the structure shown in formula (4) below.
  • each R 3 is independently hydrogen or an alkyl group having 1 to 10 carbon atoms
  • each R 3a is independently an alkylene group having 1 to 10 carbon atoms
  • m is an integer from 0 to 2; Both of the polymerizable groups represented by the formulas (2) and (3) are covalently bonded to the saccharide through an oxygen atom, like the polymerizable group represented by the formula (1).
  • n is an integer of 2-10, preferably 2 or 3.
  • p is an integer of 1 to 6, preferably 1 or 2; That is, R 2 can be an oxyalkylene group or a polyoxyalkylene group.
  • the alkylene chain in the oxyalkylene group may be linear or branched.
  • polymerizable groups represented by formulas (1) to (3) above may be covalently bonded to saccharides via R 2 having the structure represented by formula (4) above.
  • R 3a —O— and R a may be covalently bonded via R 2 having the structure represented by formula (4) above.
  • the water-soluble saccharide according to one aspect of the present invention preferably contains one or more selected from the group consisting of polymerizable groups having structures represented by formulas (1) to (3) in its molecule.
  • the polymerizable group possessed by the water-soluble saccharide preferably has a (meth)acryloyl group having a structure represented by formula (1).
  • the ratio of the hydroxyl groups modified with polymerizable groups is preferably 10 mol% or more, with the total amount of hydroxyl groups provided in the raw material saccharide being 100 mol%. and more preferably 20 mol % or more.
  • the modification rate is preferably 60 mol % or less, more preferably 50 mol % or less.
  • the ratio of the hydroxyl groups modified with polymerizable groups is determined by 13 C-NMR (nuclear magnetic resonance spectroscopy), assuming that the total amount of hydroxyl groups provided in the raw material saccharides is 100 mol%. ).
  • the water-soluble saccharide according to one aspect of the present invention has 1,3-bonds in at least part of the sugar chain.
  • 1,3-bond refers to a hydroxyl group bonded to the carbon atom at position 1 of a saccharide and a carbon atom at position 3 of a saccharide, which is a molecule separate from the saccharide. It means at least one of an ⁇ -glycosidic bond and a ⁇ -glycosidic bond formed by a bonding hydroxyl group.
  • the present inventors have found that the water-soluble saccharide has a 1,3-bond in the sugar chain, so that the water-soluble saccharide has good photosensitivity without increasing the molecular weight of the water-soluble saccharide and increasing the amount of the photosensitizer added.
  • water-soluble saccharides can be realized. The inventors believe that this is due to the following factors. Sugars with 1,3-bonds in the sugar chain tend to have a bent structure rather than a straight sugar chain compared to sugars without 1,3-bonds in the sugar chain, and when polymerized, the structure is straight. It tends to have a branched structure rather than a chain structure.
  • saccharides having 1,3-bonds in the sugar chain have polymerizable groups within and between molecules even before polymerization, compared to saccharides without 1,3-bonds in the sugar chain. It is considered that the contact portion between the two groups tends to be large, and therefore the polymerization proceeds rapidly under conditions where the polymerizable groups can be polymerized.
  • the amount of 1,3-bonds is preferably 5 mol% or more, more preferably 15 mol% or more, based on 100 mol% of the total amount of glycosidic bonds in the sugar chain. .
  • the amount of 1,3-bonds is preferably 70 mol% or less, more preferably 50 mol% or less, based on the total amount of glycosidic bonds in the sugar chain being 100 mol%. Thereby, water solubility can be maintained.
  • the amount of 1,3-bonds can be determined by 13 C-NMR (nuclear magnetic resonance spectroscopy), assuming that the total amount of glycosidic bonds in the sugar chain is 100 mol %.
  • the water-soluble saccharide according to one aspect of the present invention may have one or both of 1,4-linkage and 1,6-linkage in at least part of the sugar chain.
  • the branched structure of the water-soluble saccharide can be increased, so that the polymerizability of the water-soluble saccharide can be further enhanced.
  • the total amount of 1,4-bonds and 1,6-bonds is preferably 30 mol% or more, more preferably 50 mol% or more, based on the total amount of glycosidic bonds in the sugar chain being 100 mol%. . Thereby, the polymerizability of the water-soluble saccharide can be further enhanced.
  • the total amount of 1,4-linkages and 1,6-linkages is preferably 90 mol% or less, more preferably 80 mol% or less, based on 100 mol% of the total amount of glycosidic bonds in the sugar chain. Thereby, water solubility can be maintained.
  • the 1,4-linkage and 1,6-linkage are the main bonds in the sugar chain.
  • a chain structure may be formed and the 1,3-linkage may form a side chain structure in the sugar chain.
  • the sugar chain binding mode is typically the same as that of the water-soluble saccharide, which is the raw material of the water-soluble saccharide described below, and which constitutes the skeleton of the water-soluble saccharide. That is, in water-soluble saccharides, sugar chain binding modes such as 1,3-bonds are typically derived from saccharides that are raw materials of water-soluble saccharides. However, the water-soluble saccharide may have a sugar chain binding mode different from that of the raw material of the water-soluble saccharide, depending on the steps such as hydrolysis and dehydration condensation that may be included in the production method.
  • saccharides that are raw materials for water-soluble saccharides and form the skeleton of the water-soluble saccharides are typically disaccharides, trisaccharides, tetrasaccharides, oligosaccharides, polysaccharides, carbohydrates, and One or more selected from the group consisting of dietary fiber.
  • the saccharides that are raw materials for the water-soluble saccharides may be of one type or a combination of two or more types.
  • the raw material saccharides may be artificially synthesized saccharides or natural saccharides.
  • a saccharide obtained by hydrolyzing the saccharide may be used as the raw material.
  • a saccharide having improved water solubility by introducing a hydrophilic group such as a hydroxyalkylene group into the saccharide may be used as the raw material.
  • the raw material saccharides are not limited, but may be saccharides having a solubility in water of 50 g/L or more at 20°C.
  • Sugars that are raw materials, more specifically disaccharides include sucrose, lactose, maltose, trehalose, turanose, and cellobiose.
  • trisaccharides include raffinose, melezitose, maltotriose, and the like.
  • Tetrasaccharides include, for example, acarbose and stachyose.
  • oligosaccharides include fructo-oligosaccharides, galacto-oligosaccharides, mannan-oligosaccharides, and lactose-fructose oligosaccharides.
  • polysaccharides include: polysaccharides such as glycogen, starch, pullulan, dextrin, cyclodextrin, dextrose, cellulose, glucan, fructan, and chitin; polysaccharides modified by groups; and the like, and if these saccharides have 1,3-bonds between saccharides introduced into the sugar chain by acid treatment and sintering treatment, enzyme treatment, fermentation treatment, etc. Just do it.
  • a saccharide that is a raw material for a water-soluble saccharide and that forms the skeleton of the water-soluble saccharide may have a crosslinked structure derived from a polyhydric alcohol or a polyhydric carboxylic acid in the sugar chain.
  • Polyhydric alcohols include, for example: sugar alcohols such as sorbitol, mannitol, xylitol, maltitol, and erythritol; glycerin; Examples of polyvalent carboxylic acids include citric acid and the like.
  • the sugar that is the raw material for the water-soluble sugar and that forms the skeleton of the water-soluble sugar is preferably water-soluble dietary fiber.
  • water-soluble dietary fiber has a plurality of hydroxyl groups in its molecule, it has high water solubility and can be modified into polymerizable groups.
  • water-soluble dietary fiber has many branched structures, it is suitable as a raw material for highly polymerizable water-soluble saccharides.
  • the saccharides that are the raw materials of the water-soluble saccharides are preferably water-soluble dietary fibers that form a low-viscosity aqueous solution.
  • Water-soluble dietary fibers that form low-viscosity aqueous solutions include, for example, indigestible dextrin, isomaltodextrin, dextrose, and polydextrose.
  • the saccharide that is the raw material for the water-soluble saccharide is preferably indigestible dextrin or dextrose.
  • a method for producing a water-soluble saccharide according to one aspect of the present invention includes reacting a saccharide with a compound having a polymerizable group in the presence of an organic solvent to modify at least part of the hydroxyl groups of the saccharide into polymerizable groups.
  • the organic solvent is N-methylpyrrolidone
  • the sugar has a 1,3-bond in at least part of the sugar chain
  • the compound has a (meth)acryloyl group and a halogen group .
  • the water-soluble saccharide according to one aspect of the present invention can be produced by modifying the hydroxyl group of the saccharide into a polymerizable group using the above-described compound having a polymerizable group and an electrophilic functional group.
  • a compound having a polymerizable group and an electrophilic group is referred to as a "modifier”.
  • a method for producing a water-soluble saccharide according to one aspect of the present invention includes reacting a saccharide with a compound having a polymerizable group in the presence of an organic solvent to modify at least part of the hydroxyl groups of the saccharide into polymerizable groups.
  • the step of reacting a saccharide with a compound having a polymerizable group to modify at least part of the hydroxyl groups of the saccharide to a polymerizable group is referred to as a "modification reaction step”.
  • the organic solvent used as the reaction solvent may be appropriately selected from organic solvents capable of dissolving the sugars and the modifier and not reacting with the sugars and the modifier.
  • the organic solvent is preferably an aprotic polar solvent.
  • Aprotic polar solvents such as: N-methylpyrrolidone (NMP); N,N-dimethylformamide (DMF); dimethylsulfoxide (DMSO); dimethylacetamide (DMAc); ketones such as acetone and methyl ethyl ketone; and ethers such as tetrahydrofuran;
  • the organic solvent used as the reaction solvent is preferably NMP.
  • NMP the hydrochloric acid generated as a by-product by the reaction between the halogen group of the modifier and the hydroxyl group of the saccharide
  • the hydrochloric acid gives to the saccharide. impact can be reduced. Therefore, by using NMP as the reaction solvent, the denaturant can more efficiently denature the saccharides.
  • saccharides as raw materials can be used by appropriately selecting saccharides having 1,3-bonds in at least part of the sugar chain.
  • Specific examples of such sugars include, but are not limited to, the sugars described above.
  • the raw material saccharides may be saccharides that have been modified in advance by operations such as enzymatic decomposition and acid treatment.
  • the saccharide as a raw material may be a saccharide that has been purified and fractionated in advance by an operation such as reprecipitation.
  • the modifier which is the supply source of the polymerizable group, is a compound having a polymerizable group and an electrophilic group.
  • the polymerizable group possessed by the modifier the polymerizable group described above can be suitably used.
  • the polymerizable group possessed by the modifier is preferably a (meth)acryloyl group.
  • the electrophilic group possessed by the modifier can be an electrophilic group generally used in the reaction mechanism in which the modification reaction proceeds.
  • Electrophilic groups possessed by modifiers include, for example: halogen groups such as chlorine, bromine and iodine; isocyanate groups; acid anhydride groups; Among them, the electrophilic group possessed by the modifier is preferably a halogen group.
  • modifiers used in the modification reaction step include (meth)acrylic acid chloride, (meth)acrylic anhydride, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, and 2-isocyanatoethyl (meth)acrylate.
  • the modifier is preferably (meth)acrylic acid chloride or (meth)acrylic anhydride. This allows the modification reaction to proceed more efficiently.
  • the temperature in the system is preferably ⁇ 10° C. or higher, more preferably 0° C. or higher. This makes it possible to easily control the temperature in the modification reaction. Further, in the modification reaction step, the temperature in the system is preferably 100°C or lower, more preferably 60°C or lower. Thereby, in the modification reaction step, it is possible to reduce the polymerization reaction of the modifier and the polymerizable groups of the water-soluble saccharides produced by modifying the saccharides.
  • the modification reaction may be performed under an air atmosphere or an inert gas atmosphere.
  • the modification reaction is not limited, it is preferably carried out in an inert gas atmosphere.
  • inert gas include nitrogen gas and argon gas.
  • the mixing weight ratio of the water-soluble saccharide and the denaturant in the system may be appropriately selected according to the amount of hydroxyl groups possessed by the saccharide and the desired modification rate.
  • an amine may be added to the system to neutralize the acid produced as a by-product of the modification reaction.
  • amines include tertiary amines such as triethylamine.
  • a photosensitive composition according to one aspect of the present invention contains the water-soluble saccharide according to one aspect of the present invention, water, and a photoreaction initiator.
  • the photosensitive composition according to one aspect of the present invention is capable of forming an aqueous composition due to the hydroxyl groups possessed by the water-soluble saccharides, and is polymerizable due to the polymerizable groups possessed by the water-soluble saccharides. . Therefore, the photosensitive composition can form a cured product through a polymerization reaction, and can be developed by washing with an aqueous solvent.
  • the photosensitive composition according to one aspect of the present invention contains water as a dilution solvent.
  • the content of water in the photosensitive composition is appropriately selected according to the desired viscosity of the photosensitive composition, the film thickness of the cured product, etc., so that the concentration of the water-soluble saccharides is a predetermined concentration. can be done.
  • the concentration of the water-soluble saccharide is preferably 5% by mass or more, more preferably 20% by mass or more, relative to the total amount of the photosensitive composition, but is not limited thereto. When the concentration of the water-soluble saccharide is 5% by mass or more, particularly 20% by mass or more, relative to the total amount of the photosensitive composition, the film thickness of the photosensitive composition can be easily increased.
  • the concentration of the water-soluble saccharide is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of the photosensitive composition, but is not limited thereto.
  • the concentration of water-soluble saccharides is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of the photosensitive composition.
  • the concentration of the water-soluble saccharide is 50% by mass or less, particularly 40% by mass or less, relative to the total amount of the photosensitive composition, so that the photosensitive composition can be coated in a wide range of film thickness. be able to.
  • a photosensitive composition according to one aspect of the present invention contains a photoreaction initiator.
  • the photoreaction initiator may be selected from photoradical polymerization initiators and photocationic polymerization initiators according to the type of polymerizable group.
  • the photoreaction initiator contained in the photosensitive composition may be of one type or a combination of two or more types.
  • the content of the photoreaction initiator is preferably 0.01 parts by weight or more, more preferably 0.10 parts by weight, with respect to 100 parts by weight of the water-soluble saccharide. Part by weight or more. Thereby, the photosensitivity of the photosensitive composition can be enhanced.
  • the content of the photoreaction initiator is preferably 5.00 parts by weight or less, more preferably 3 parts by weight, with respect to 100 parts by weight of the water-soluble saccharide. 00 parts by weight or less. This can reduce the manufacturing cost of the photosensitive composition.
  • the photoradical polymerization initiator contained in the photosensitive composition may be appropriately selected according to, for example, the application and functions required of the photosensitive composition.
  • photoradical polymerization initiators include ⁇ -hydroxyketone-based photopolymerization initiators, ⁇ -aminoketone-based photopolymerization initiators, benzyl ketal-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and acridine-based photopolymerization initiators.
  • benzophenone-based photopolymerization initiators acetophenone-based photopolymerization initiators, aromatic ketoester-based photopolymerization initiators, benzoic acid ester-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and titanocene-based photopolymerization initiators, etc. are mentioned.
  • the radical photopolymerization initiator may be emulsified or solubilized in an aqueous system by, for example, a surfactant and/or a polymerizable monomer. Examples of commercially available radical photopolymerization initiators include FAI-101L (manufactured by Fujifilm Corporation).
  • Examples of ⁇ -hydroxyketone-based photopolymerization initiators include 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1- one, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-1-[4-[4- (2-Hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one and the like.
  • Examples of commercially available ⁇ -hydroxyketone-based photopolymerization initiators include Omnirad 2959 (manufactured by IGM Resins B.V.).
  • ⁇ -aminoketone-based photopolymerization initiators examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, and 3,6-bis(2-methyl- 2-morpholinopropionyl)-9-octyl-9H-carbazole and the like.
  • Benzyl ketal-based photopolymerization initiators include, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one.
  • oxime ester photopolymerization initiators include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl ) oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O -benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,
  • acridine-based photopolymerization initiators examples include 1,7-bis(acridin-9-yl)-n-heptane.
  • benzophenone-based photopolymerization initiators include benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, and 4-hydroxybenzophenone. , alkylated benzophenone, 3,3′,4,4′-tetrakis(t-butylperoxycarbonyl)benzophenone, 4-methylbenzophenone, dibenzyl ketone, and fluorenone.
  • acetophenone-based photopolymerization initiators examples include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone.
  • aromatic ketoester-based photopolymerization initiators examples include methyl 2-phenyl-2-oxyacetate.
  • benzoic acid ester-based photopolymerization initiators include ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate. be done.
  • acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl). )-(2,4,4-trimethylpentyl)phosphine oxide and the like.
  • titanocene-based photopolymerization initiators include bis( ⁇ 5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (IV ), and bis( ⁇ 5-3-methyl-2,4-cyclopentadien-1-yl)-bis(2,6-difluorophenyl)titanium (IV).
  • the photosensitive composition according to one aspect of the present invention may contain a cross-linking agent.
  • the photosensitive composition contains a cross-linking agent
  • the polymerizable groups possessed by the water-soluble saccharide contained in the photosensitive composition can be cross-linked via the cross-linking agent.
  • the cross-linking agent has two or more polymerizable groups.
  • the cross-linking agent may be selected from radically polymerizable cross-linking agents and cationic polymerizable cross-linking agents according to the type of polymerizable group.
  • the cross-linking agent contained in the photosensitive composition may be of one type or a combination of two or more types.
  • the content of the cross-linking agent is preferably 0.01 parts by weight or more, more preferably 0.10 parts by weight, with respect to 100 parts by weight of the water-soluble saccharide. That's it.
  • the content of the cross-linking agent is preferably 5.00 parts by weight or less, more preferably 3.00 parts by weight, with respect to 100 parts by weight of the water-soluble saccharide. Part by weight or less.
  • radically polymerizable cross-linking agents include: cross-linking agents having a vinyl group such as 1,3-bis(vinylsulfonyl)-2-propanol; and cross-linking agents having a (meth)acryloyl group.
  • cross-linking agent having a (meth)acryloyl group include (meth)acrylic acid esters having a polyoxyalkylene group and (meth)acrylic acid esters formed from polyhydric alcohols.
  • Examples of (meth)acrylic acid esters having a polyoxyalkylene group include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.
  • (Meth)acrylic acid esters formed from polyhydric alcohols include, for example, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane ( meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di( meth)acrylates, 1,4-butanediol di(meth)acrylates, 1,6-hexanediol di(meth)acrylates, and 1,9-nonanediol di(meth)acrylates, and the like, but are not limited thereto. .
  • a polymerizable group such as an epoxy group or an oxetane group may contain a cross-linking agent having
  • the photosensitive composition according to one aspect of the present invention may contain a surfactant.
  • a surfactant By containing an appropriate amount of surfactant in the photosensitive composition, the surface tension of the photosensitive composition can be arbitrarily adjusted, the leveling property during coating is improved, and the film thickness uniformity of the coating film is improved. can be improved.
  • the surfactant contained in the photosensitive composition may be one type or a combination of two or more types.
  • the content of the surfactant is preferably 0.01 parts by weight or more, more preferably 0.30 parts by weight, relative to 100 parts by weight of the water-soluble saccharide. Department or above.
  • the content of the surfactant is preferably 10.00 parts by weight or less, more preferably 5.00 parts by weight, based on 100 parts by weight of the water-soluble saccharide. 00 parts by weight or less.
  • surfactants contained in the photosensitive composition include fluororesin-based surfactants, silicone-based surfactants, polyoxyalkylene ether-based surfactants, and acrylic resin-based surfactants. .
  • fluororesin-based surfactants include Megafac (registered trademark), and its product numbers include F-142D, F-172, F-173, F-183, F-430, F-444, F-445, F-470, F-475, F-477, F-555, F-558, and F-559 (all manufactured by DIC Corporation).
  • fluororesin-based surfactants include F-top (registered trademark), and product numbers thereof include EF301, 303, and 352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.).
  • fluororesin-based surfactants examples include: Florard (registered trademark) FC-430 and FC-431 (both of which are manufactured by Sumitomo 3M Limited); Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.). Surflon (registered trademark) S-382, SC-101, SC-102, SC-103, SC-104, SC-105, and SC-106 (all manufactured by AGC Seimi Chemical Co., Ltd.); BM-1000 , and BM-1100 (both of which are manufactured by Yusho Co., Ltd.);
  • silicone surfactants examples include SH28PA, SH7PA, SH21PA, SH30PA, and ST94PA (all manufactured by Dow Corning Toray Co., Ltd.); and 345 (both of which are manufactured by BYK-Chemie Japan Co., Ltd.); and the like.
  • polyoxyalkylene ether-based surfactants examples include Futergent (registered trademark) 212M, 209F, 208G, 240G, 212P, 220P, 228P, NBX-15, FTX-218, and DFX-218 (all of which are stock manufactured by the company Neos).
  • acrylic resin-based surfactants examples include BYK (registered trademark)-350, 352, 354, 355, 356, 358N, 361N, 392, 394, and 399 (all manufactured by BYK-Chemie Japan Co., Ltd.). mentioned.
  • the photosensitive composition according to one aspect of the present invention may contain a reaction terminator.
  • a reaction terminator By containing the reaction terminator in the photosensitive composition, it is possible to suppress overpolymerization when the photosensitive composition is photopolymerized.
  • the reaction terminator contained in the photosensitive composition may be one type or a combination of two or more types.
  • the content of the reaction terminator is preferably 0.01 parts by weight or more, more preferably 0.10 parts by weight, relative to 100 parts by weight of the water-soluble saccharide. Department or above.
  • the content of the reaction terminator is preferably 5.00 parts by weight or less, more preferably 1.00 parts by weight, per 100 parts by weight of the water-soluble saccharide. 00 parts by weight or less.
  • Examples of the reaction terminator contained in the photosensitive composition include radical polymerization terminator and the like.
  • Examples of radical polymerization terminator include 4-t-butylphenol, 4-methoxyphenol, 1,4-hydroquinone, 1,4-benzoquinone, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4- Methoxyphenol, 4-t-butylcatechol, 2-t-butyl-1,4-hydroquinone, 2,6-di-t-butylphenol, 2,4,6-tri-t-butylphenol, 2,6-di- t-butyl-4-methylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butyl-1,4-hydroquinone, 2,5-di-t-amyl- 1,4-hydroquinone, 2-nitroso-1-naphthol, N-phenyldiethanolamine and the like.
  • radical polymerization terminator examples include IRGANOX (registered trademark) series, which have product numbers 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, and 295 (all manufactured by BASF).
  • the photosensitive composition according to one aspect of the present invention may contain other additives as long as they do not impair the properties of the water-soluble saccharide according to one aspect of the present invention.
  • Other additives include adhesion aids, fillers, water-soluble resins, and the like.
  • Other additives contained in the photosensitive composition may be of one type or a combination of two or more types.
  • the photosensitive composition according to one aspect of the present invention is an aqueous composition, it can be used, for example, as a photosensitive material for a photoresist for microfabrication of semiconductors and the like.
  • the polymerizable group possessed by the water-soluble saccharide is a functional group having an unsaturated double bond such as a (meth)acryloyl group.
  • substrates to be coated with the photosensitive composition according to one aspect of the present invention include substrates such as semiconductor wafer substrates and glass substrates.
  • layers such as an insulating layer and a conductive layer may be formed in advance on the surface of the substrate.
  • the substrate may be formed with an underlying layer such as poly(2-hydroxyethyl)acrylate. Since the photosensitive composition according to one aspect of the present invention is a water-based composition, it is less likely to corrode a base such as poly(2-hydroxyethyl) acrylate as compared with a resist material containing a large amount of an organic solvent. is also one of the advantages.
  • the method of applying the photosensitive composition according to one aspect of the present invention to the substrate may be a conventionally known method.
  • Examples of the method of applying the photosensitive composition to the substrate include, but are not limited to, spin coating using a spinner.
  • baking heat drying
  • the firing temperature is preferably 50°C or higher and 300°C or lower.
  • the formation of a cured coating film by exposing the substrate on which the coating film is formed is performed by a conventionally known exposure method in the art. It can be carried out.
  • Actinic rays with which the coating film is irradiated include, for example, ultraviolet rays, visible light, and electron beams. Ultraviolet curing is superior in productivity and equipment cost is low compared to electron beam curing, so the active actinic radiation is preferably ultraviolet rays.
  • the amount of exposure can be appropriately selected according to the content of the photoreaction initiator in the photosensitive composition.
  • the exposure amount can be, for example, about 600 mJ/cm 2 and the exposure time can be, for example, about 60 seconds, but is not limited to this.
  • the wavelength of ultraviolet rays to be irradiated may be selected according to the type of photopolymerization initiator contained in the photosensitive composition.
  • the developer for the coating film is an aqueous solvent, preferably water. That is, one of the advantages of the present invention is that development can be carried out using methods known in the art, except that the developing solution is water.
  • the coating film can be etched by a method conventionally known in the art.
  • the water-soluble saccharide according to one aspect of the present invention has a 1,3-bond in at least part of the sugar chain of the saccharide, and at least part of the hydroxyl groups of the sugar chain are modified with polymerizable groups. .
  • a novel water-soluble saccharide having a polymerizable group can be provided.
  • the water-soluble saccharide it is preferable that 10 mol% or more and 60 mol% or less of the hydroxyl groups are modified with polymerizable groups, with the total amount of hydroxyl groups included in the saccharide being 100 mol%. This makes it possible to provide water-soluble saccharides having both good polymerizability and water solubility.
  • the saccharide is preferably indigestible dextrin or dextrose. This makes it possible to provide a water-soluble saccharide that allows easy preparation of a low-viscosity aqueous composition.
  • the polymerizable group preferably has a (meth)acryloyl group. This makes it possible to provide water-soluble saccharides with good polymerizability.
  • the water-soluble saccharide according to one aspect of the present invention preferably has a weight average molecular weight of 150 or more and 50,000 or less.
  • the photosensitive composition according to one aspect of the present invention contains the water-soluble saccharide according to one aspect of the present invention, water, and a photoreaction initiator. This makes it possible to provide a photosensitive composition that can form a cured product through a polymerization reaction and that can be developed by washing with an aqueous solvent.
  • the photosensitive composition according to one aspect of the present invention preferably contains a cross-linking agent.
  • a cross-linking agent preferably contains a cross-linking agent.
  • the photosensitive composition according to one aspect of the present invention preferably contains a surfactant. This makes it possible to arbitrarily adjust the surface tension of the photosensitive composition, improve the leveling property during coating, and improve the film thickness uniformity of the coating film.
  • the photosensitive composition according to one aspect of the present invention preferably contains a reaction terminator. Thereby, overpolymerization can be suppressed.
  • the saccharide and a compound having a polymerizable group are reacted in the presence of an organic solvent, and at least part of the hydroxyl groups of the saccharide are polymerized.
  • the organic solvent is N-methylpyrrolidone
  • the sugar has a 1,3-bond in at least part of the sugar chain
  • the compound is (meth)acryloyl and a halogen group.
  • Raw material saccharide 1 Indigestible dextrin (manufactured by Matsutani Chemical Industry Co., Ltd., trade name “Fibersol 2”)
  • Raw material saccharide 2 Indigestible dextrin (manufactured by ROQUETTE, trade name "NUTRIOSE", "NUTRIOSE” is a registered trademark of the company)
  • Raw material saccharide 3 Polydextrose (manufactured by Danisco Japan Co., Ltd., trade name “Lytes HF”)
  • Raw material saccharide 4 Dextrin (manufactured by Sanei Sugar Chemical Co., Ltd., trade name “NSD500”)
  • Raw material saccharide 5 High molecular weight dextrin (Manufacturing method: Add 750 g of ion-exchanged water and 750 g of saccharide 4 to a reaction vessel with an internal capacity of 3 L equipped with
  • Raw material saccharide 6 Pullulan (manufactured by Hayashibara Co., Ltd., trade name “Pullulan”)
  • GPC measurement device manufactured by Tosoh Corporation, trade name “HLC-8120GPC”("HLC” is a registered trademark of the company)
  • Column A column in which three columns are connected (respectively manufactured by Tosoh Corporation, trade name “TSKgel G3000HHR”, trade name “TSKgel G2000HHR”, trade name “TSKgel G2000HHR”, “TSKgel” are registered trademarks of the company)
  • the molecular weight distribution of raw sugars 2 to 6 was analyzed in the same manner as raw sugars 1.
  • the GPC spectra of raw sugars 1 to 6 are shown in FIG. Table 1 shows the analysis results of the molecular weight distribution of raw sugars 1 to 6.
  • Raw material saccharides 2 to 4 and 6 were also analyzed for sugar chain binding mode distribution in the same manner as raw material saccharide 1. 13 C-NMR spectra of raw sugars 2 to 4 and 6 are shown in FIG. Table 1 shows the analysis results of sugar chain binding mode distribution of raw sugars 2 to 4 and 6. Since the raw sugar 5 is a high-molecular-weight portion of the raw sugar 4, it can be considered to have the same sugar chain binding mode distribution as the raw sugar 4.
  • Example 1 100.0 g of raw sugar 1 and 185.7 g of N-methylpyrrolidone were added to a 1 L reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, and the system temperature was raised to 40° C. under a vacuum of 10 mmHg. to remove water remaining in the system. Subsequently, after cooling the system temperature to 15°C, 33.5 g (0.37 mol) of acrylic acid chloride was added dropwise over 2 hours while cooling the system temperature so as not to exceed 15°C. After dropping, the reaction was continued for 2 hours at a system temperature of 15°C.
  • Example 2 50.4 g (0.56 mol) of acrylic acid chloride was used instead of 33.5 g (0.37 mol) of acrylic acid chloride, 56.2 g (0.37 mol) of triethylamine was used instead of 37.4 g (0.37 mol) of triethylamine ( A water varnish of water-soluble saccharide 2 having a modification rate to acrylic groups of 30% (theoretical value) was obtained in the same manner as in Example 1, except that 0.56 mol) was used.
  • Example 3 Water-soluble saccharide 3 having a modification rate to acrylic groups of 30% (theoretical value) was prepared in the same manner as in Example 2, except that 100.0 g of saccharide 2 was used instead of 100.0 g of raw saccharide 1. Got a water varnish.
  • Example 4 Water-soluble saccharide 4 having a modification rate to acrylic groups of 30% (theoretical value) was prepared in the same manner as in Example 2, except that 100.0 g of saccharide 3 was used instead of 100.0 g of raw saccharide 1. Got a water varnish.
  • Water-soluble saccharides 2 to 4 and C1 to C3 water varnishes were also analyzed for viscosity in the same manner as water-soluble saccharide 1.
  • Table 2 shows the viscosity analysis results of the water varnishes of water-soluble sugars 1-4 and C1-C3.
  • Photoinitiator 1 manufactured by IGM Resins B.V., trade name "Omnirad 2959" was added to the water varnish of water-soluble saccharide 1 so as to have a concentration of 1, 2, or 3% by mass, respectively.
  • photosensitive compositions 1-3 were obtained.
  • Photoinitiator 1 was added to the aqueous varnish of water-soluble saccharide 2 so as to have a concentration of 1, 2, or 3% by mass, respectively, to obtain photosensitive compositions 4-6.
  • Photoinitiator 1 was added to the aqueous varnish of water-soluble saccharide 3 so as to have a concentration of 1, 2, or 3% by mass, respectively, to obtain photosensitive compositions 7-9.
  • Photoinitiator 1 was added to the aqueous varnish of water-soluble saccharide 4 so as to have a concentration of 1, 2, or 3% by mass, respectively, to obtain photosensitive compositions 10-12.
  • Photoreaction initiator 1 was added to the aqueous varnish of water-soluble saccharide C1 so as to have a concentration of 1, 2, or 3% by mass, respectively, to obtain photosensitive compositions C1 to C3.
  • Photoinitiator 1 was added to the aqueous varnish of water-soluble saccharide C2 at a concentration of 1, 2, or 3% by mass, respectively, to obtain photosensitive compositions C4 to C6.
  • Photoinitiator 1 was added to the aqueous varnish of water-soluble saccharide C3 so as to have a concentration of 1, 2, or 3% by mass, respectively, to obtain photosensitive compositions C7 to C9.
  • the cured film was immersed in pure water, which is a developer, for 90 seconds to remove uncured portions of the cured film, that is, develop the film.
  • the film thickness of the cured film was measured before and after development, and the residual film ratio was calculated based on the following formula (5). It can be considered that the higher the residual film ratio, the easier the photosensitive composition is cured and the higher the photosensitivity.
  • Remaining film ratio (%) film thickness of cured film after development/film thickness of cured film before development x 100 Formula (5)
  • Photosensitive compositions 5 to 12 and C1 to C9 were also analyzed for residual film rate in the same manner as for photosensitive composition 4.
  • FIG. 3 shows the analysis results of the residual film ratios of the photosensitive compositions 4 to 12 and C1 to C9.
  • Table 3 shows the exposure dose for achieving a residual film rate of 90% for the photosensitive compositions 4 to 12 and C1 to C9.
  • the photosensitive composition C3 produced by adding the photoreaction initiator 1 to the water-soluble saccharide C1 requires an exposure amount of about 1020 mJ/cm 2 in order to achieve a residual film rate of 90% or more, and the photosensitivity was of low quality.
  • the water-soluble saccharide C2 produced using the raw material saccharide 5 as a raw material has a low viscosity, it is easy to increase the solid content of the water varnish.
  • the photosensitive composition C6, which was produced by adding the photoinitiator 1 to the water-soluble saccharide C2 required an exposure amount of about 660 mJ/cm 2 in order to achieve a residual film rate of 90% or more. better than composition C5, but less photosensitivity.
  • the production process of water-soluble saccharide C2 includes a step of removing the low molecular weight portion of raw saccharide 4 in order to produce raw saccharide 5, a large amount of waste liquid was generated and the yield was low.
  • the photosensitive composition C9 produced using the raw material saccharide 6 as a raw material had good photosensitivity, but the water-soluble saccharide C3 produced in the production process had a high viscosity, and the solid content of the water varnish was reduced. It is considered difficult to adjust the film thickness because the thickness cannot be increased.
  • the water-soluble saccharides according to the present invention can be used as photosensitive materials such as photoresist materials and photocurable inks.

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Abstract

L'invention concerne un nouveau sucre soluble dans l'eau doté d'un groupe polymérisable, et une technologie associée au sucre soluble dans l'eau. Le sucre soluble dans l'eau selon un aspect de la présente invention comporte des liaisons 1,3 dans au moins certaines chaînes de sucre fournies au sucre, et au moins certains groupes hydroxyle fournis aux chaînes de sucre sont modifiés par des groupes polymérisables.
PCT/JP2022/014506 2021-03-30 2022-03-25 Sucre soluble dans l'eau, composition photosensible, et procédé de production de sucre soluble dans l'eau WO2022210381A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228640A (ja) * 1998-02-13 1999-08-24 Goo Chem Ind Co Ltd セルロース誘導体系化合物及び感光性組成物並びにフォトレジストインク
JP2001337458A (ja) * 2000-05-26 2001-12-07 Japan Science & Technology Corp フォトレジスト材料
WO2020000788A1 (fr) * 2018-06-26 2020-01-02 爱美中科硒科技（天津）有限公司 Polysaccharide sélénié estérifié et procédé de préparation et utilisation s'y rapportant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228640A (ja) * 1998-02-13 1999-08-24 Goo Chem Ind Co Ltd セルロース誘導体系化合物及び感光性組成物並びにフォトレジストインク
JP2001337458A (ja) * 2000-05-26 2001-12-07 Japan Science & Technology Corp フォトレジスト材料
WO2020000788A1 (fr) * 2018-06-26 2020-01-02 爱美中科硒科技（天津）有限公司 Polysaccharide sélénié estérifié et procédé de préparation et utilisation s'y rapportant

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