WO2022210381A1 - Water-soluble sugar, photosensitive composition, and method for producing water-soluble sugar - Google Patents
Water-soluble sugar, photosensitive composition, and method for producing water-soluble sugar Download PDFInfo
- Publication number
- 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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- WO
- WIPO (PCT)
- Prior art keywords
- water
- saccharide
- soluble
- photosensitive composition
- group
- Prior art date
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- 235000000346 sugar Nutrition 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims description 125
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Classifications
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-
- 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
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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
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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
- 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
Provided are a novel water-soluble sugar provided with a polymerizable group, and technology related to the water-soluble sugar. The water-soluble sugar according to one aspect of the present invention has 1,3- bonds in at least some sugar chains provided to the sugar, and at least some hydroxyl groups provided to the sugar chains are modified by polymerizable groups.
Description
本発明は、水溶性糖類、感光性組成物、及び水溶性糖類の製造方法に関する。
The present invention relates to water-soluble saccharides, photosensitive compositions, and methods for producing water-soluble saccharides.
例えば、特許文献１には、不飽和基含有ポリイミド、不飽和基含有ポリイミド前駆体、カルボン酸変性不飽和基含有ポリシロキサン、不飽和基含有ポリベンゾオキサゾール、不飽和基含有ポリベンゾオキサゾール前駆体、不飽和基含有ポリシロキサン、多環側鎖含有芳香族樹脂、アクリル樹脂及びカルボン酸変性エポキシ樹脂から選ばれる不飽和基含有樹脂、及び当該不飽和基含有樹脂を含む、組成物が記載されている。
For example, 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. .
また、例えば、特許文献２には、環状エーテル（エポキシド及びオキセタン等）、エチレン性不飽和化合物（ビニルエーテル及びスチレン等）、ビシクロオルトエステル、スピロオルトカーボネート及びスピロオルトエステル等のカチオン重合性化合物、及びフェノール性水酸基を有するアルカリ可溶性樹脂、並びに、これらのカチオン重合性化合物と、アルカリ可溶性樹脂とを含む、組成物が記載されている。
Further, for example, 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.
特許文献１及び２には、糖類を主たる材料として生成される重合性基を有する材料について何ら開示されていない。
Patent Documents 1 and 2 do not disclose any material having a polymerizable group that is produced from saccharides as the main material.
本発明者らは、糖類を重合性基で変性させることで、重合性と水溶性との両方を備える新規な水溶性糖類が得られ、当該水溶性糖類が新規材料として極めて有用であることを見出した。さらに、本発明者らは、研究を重ね、当該水溶性糖類が糖鎖中に特定の結合を有することにより、性能がより向上することを見出し、本発明を完成させた。
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.
すなわち、本発明の一態様は、重合性基を備える新規な水溶性糖類、及びその関連技術を提供することを目的とする。
That is, an object of one aspect of the present invention is to provide a novel water-soluble saccharide having a polymerizable group and related technology.
上記の課題を解決するために、本発明の一態様に係る水溶性糖類は、糖類が備える糖鎖の少なくとも一部に１，３－結合を有し、前記糖鎖が備える水酸基の少なくとも一部が重合性基に変性されてなる。
In order to solve the above problems, 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.
本発明の一態様によれば、重合性基を備える新規な水溶性糖類、及びその関連技術を提供することができる。
According to one aspect of the present invention, it is possible to provide a novel water-soluble saccharide having a polymerizable group and related technology.
以下に、本発明をより詳細に説明する。
The present invention will be described in more detail below.
＜用語＞
本明細書中で使用される場合、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。 <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.
本明細書中で使用される場合、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。 <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.
本明細書中で使用される場合、単に「糖類」と記載する場合、特に説明がない限り、本発明の一態様に係る「水溶性糖類」の原料である「糖類」のことを意味する。当該「糖類」は、食品科学分野における炭水化物を概念として包含する。
As used in this specification, the term "sugars" simply means "sugars" that are raw materials for the "water-soluble sugars" according to one aspect of the present invention, unless otherwise specified. The term "sugars" includes carbohydrates as a concept in the field of food science.
また、本明細書中で使用される場合、用語「水溶性糖類」は、糖類が備える水酸基の少なくとも一部が重合性基に変性された「糖類」であり、且つ水溶性を有する「糖類」を意味する。すなわち、本明細書中で使用される場合、用語「水溶性糖類」は、「水酸基の少なくとも一部が重合性基に変性されてなる水溶性の糖類」の略称として記載される。同様に「水溶性」にて修飾された「糖」の記載は、特に説明がない限り、本発明の一態様に係る水溶性糖類の具体例を意味する。
In addition, as used herein, the term "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. means That is, as used herein, the term "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". Similarly, descriptions of "sugars" modified with "water-soluble" refer to specific examples of water-soluble sugars according to one aspect of the present invention, unless otherwise specified.
また、本明細書中で使用される場合、用語「（メタ）アクリル」とは、アクリル及びメタクリルの一方又は両方を意味する。具体的には、用語「（メタ）アクリル酸」は、アクリル酸、及びメタクリル酸の一方又は両方を意味し、用語「（メタ）アクリレート」は、「アクリレート」及び「メタクリレート」の一方又は両方を意味する。また、本明細書中で使用される場合、用語「（メタ）アクリロイル基」とは、「アクリロイル基」及び「メタクリロイル基」の一方又は両方を意味する。
Also, as used herein, the term "(meth)acrylic" means one or both of acrylic and methacrylic. Specifically, the term "(meth)acrylic acid" means one or both of acrylic acid and methacrylic acid, and the term "(meth)acrylate" means one or both of "acrylate" and "methacrylate". means. Also, as used herein, the term "(meth)acryloyl group" means one or both of "acryloyl group" and "methacryloyl group".
また、本明細書中で使用される場合、用語「感光性」は、可視光、赤外線、紫外線、及び電子線からなる群から選択される活性化学線が組成物に照射されたときに、当該活性化学線を吸収することで当該組成物に含まれる化合物がラジカル又はプロトン（Ｈ＋）を発生し、これらラジカル又はプロトン（Ｈ＋）に起因して当該組成物に含まれる化合物が、重合又は変色等の化学反応を示す性質を意味する。
Also, as used herein, 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.
本発明者らは、糖類が備える水酸基を重合性基で変性させることで、重合性及び水溶性を備える新規な水溶性糖類が得られ、当該水溶性糖類が感光性を有する新規材料として極めて有用であることを見出した。さらに、本発明者らは、研究を重ね、（１）水溶性糖類の感光性を高めるために当該水溶性糖類の分子量を上げると、水溶性糖類を含有する感光性組成物の粘度が高くなるため、当該感光性組成物を塗工すること及び微細加工することが困難になること、（２）感光性組成物の粘度を小さくするために、感光性組成物の固形分を下げると、塗工した際に厚膜化が困難になること、を見出した。また、一般に、感光性組成物の感光性を高めるために、感光剤の添加量を増やすと、製造コストの増加につながる。そして、本発明者らは、さらに研究を重ね、水溶性糖類が糖鎖中に１，３－結合を有することで、水溶性糖類の分子量増加、及び感光剤の添加量の増加を伴わなくとも、良好な感光性を有する水溶性糖類を実現できることを見出した。
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. Therefore, it becomes difficult to apply and finely process the photosensitive composition, and (2) if the solid content of the photosensitive composition is lowered in order to reduce the viscosity of the photosensitive composition, It was found that it becomes difficult to thicken the film when it is processed. Moreover, generally, increasing the amount of the photosensitizer added in order to increase the photosensitivity of the photosensitive composition leads to an increase in production costs. Further, the present inventors conducted further research and found that water-soluble saccharides having 1,3-bonds in their sugar chains can be used without increasing the molecular weight of the water-soluble saccharides and increasing the amount of the photosensitizer added. found that water-soluble saccharides with good photosensitivity can be realized.
＜水溶性糖類＞
本発明の一態様に係る水溶性糖類は、糖類が備える糖鎖の少なくとも一部に１，３－結合を有し、当該糖鎖が備える水酸基の少なくとも一部が重合性基に変性されてなる。この構成によれば、本発明の一態様に係る水溶性糖類は、糖類の水酸基に由来する水溶性と、重合性基に由来する重合性との両方を兼ね備える新規な水溶性糖類を実現することができる。 <Water-soluble saccharides>
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. . According to this configuration, 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.
本発明の一態様に係る水溶性糖類は、糖類が備える糖鎖の少なくとも一部に１，３－結合を有し、当該糖鎖が備える水酸基の少なくとも一部が重合性基に変性されてなる。この構成によれば、本発明の一態様に係る水溶性糖類は、糖類の水酸基に由来する水溶性と、重合性基に由来する重合性との両方を兼ね備える新規な水溶性糖類を実現することができる。 <Water-soluble saccharides>
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. . According to this configuration, 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.
本発明の一態様に係る水溶性糖類は、その水溶性により、有機溶媒でなく水を希釈溶媒として、当該水溶性糖類を含有する水系組成物を調製できる。また、水溶性糖類は、その水系組成物を被塗工物に塗工し、塗工膜を形成させた後、当該水溶性糖類が有する重合性により重合させることができる。一般に、組成物の塗工においては、塗工作業環境における安全性を向上させる、及び溶媒排出後の環境負荷を低減する等の観点から、アルカリ等の劇毒物、及び有機溶媒等の危険物の使用を回避することが求められる。これらの観点から、本発明の一態様に係る水溶性糖類は、希釈溶媒として水を用いることができるため、重合性組成物の代替として好適に用いることができる。
Due to the water solubility of the water-soluble saccharide according to one aspect of the present invention, 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. In general, in the coating of the composition, from the viewpoint of improving the safety in the coating work environment and reducing the environmental load after the solvent is discharged, poisonous substances such as alkalis and dangerous substances such as organic solvents Avoid using it. From these points of view, 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.
本発明の一態様に係る水溶性糖類の、２０℃における水に対する溶解度は、限定されるものではないが、水への希釈を容易に行う観点から、５０ｇ／Ｌ以上であり、好ましくは２００ｇ／Ｌ以上である。特に、水溶性糖類の、２０℃における水に対する溶解度が、２００ｇ／Ｌ以上であれば、当該水溶性糖類を含有する水系組成物を好適に調製することができる。なお、糖類が備える水酸基が重合性基に変性されてなり、かつ２０℃における水に対する溶解度が５０ｇ／Ｌ未満である糖類は、本明細書中において「難水溶性糖類」として記載され、本発明の一態様に係る「水溶性糖類」とは区別される。
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. In particular, if the solubility of the water-soluble saccharide in water at 20° C. is 200 g/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
本発明の一態様に係る水溶性糖類の重量平均分子量（Ｍｗ）は、限定されるものではないが、好ましくは１５０以上であり、より好ましくは１０００以上である。これにより、水溶性糖類を含有する感光性組成物の感光性を高め、感光性組成物中の水溶性糖類の含有率を高めることができる。また、水溶性糖類の重量平均分子量は、好ましくは５０，０００以下であり、より好ましくは１０，０００以下である。これにより、水溶性糖類を含有する感光性組成物の塗工性を高めることができる。特に、水溶性糖類の重量平均分子量が１０，０００以下であることにより、高い平坦化率、及び充填性を備える水溶性糖類を実現することができる。なお、本明細書中で使用される場合、水溶性糖類の重量平均分子量（Ｍｗ）とは、ゲル浸透クロマトグラフィ（ＧＰＣ）により測定される、標準ポリスチレン換算の値を意味する。
Although the weight average molecular weight (Mw) of the water-soluble saccharide according to one aspect of the present invention 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. In particular, when 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. As used herein, 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.
〔重合性基〕
本発明の一態様に係る水溶性糖類は、糖鎖が備える水酸基の少なくとも一部が重合性基に変性されてなる。重合性基としては例えば、ラジカル重合性基及びカチオン重合性基等が挙げられる。ラジカル重合性基としては例えば、ビニルエステル基、及び（メタ）クリロイル基等の不飽和二重結合を有する官能基が挙げられる。カチオン重合性基としては例えば、エポキシ基、及びオキセタン基等が挙げられる。 [Polymerizable group]
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. Examples of polymerizable groups include radically polymerizable groups and cationic polymerizable groups. Examples of radically polymerizable groups include functional groups having unsaturated double bonds such as vinyl ester groups and (meth)acryloyl groups. Examples of cationic polymerizable groups include epoxy groups and oxetane groups.
本発明の一態様に係る水溶性糖類は、糖鎖が備える水酸基の少なくとも一部が重合性基に変性されてなる。重合性基としては例えば、ラジカル重合性基及びカチオン重合性基等が挙げられる。ラジカル重合性基としては例えば、ビニルエステル基、及び（メタ）クリロイル基等の不飽和二重結合を有する官能基が挙げられる。カチオン重合性基としては例えば、エポキシ基、及びオキセタン基等が挙げられる。 [Polymerizable group]
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. Examples of polymerizable groups include radically polymerizable groups and cationic polymerizable groups. Examples of radically polymerizable groups include functional groups having unsaturated double bonds such as vinyl ester groups and (meth)acryloyl groups. Examples of cationic polymerizable groups include epoxy groups and oxetane groups.
本発明の一態様において、重合性基は、一例として、以下の式（１）に示す構造を有し得る。
In one aspect of the present invention, the polymerizable group may have, as an example, the structure shown in formula (1) below.
式（１）中、Ｒ１は、水素又はメチル基である。すなわち、式（１）に示される重合性基は、（メタ）アクリロイル基である。本発明の一態様に係る水溶性糖類において、当該（メタ）アクリロイル基は、酸素原子を介して糖類に共有結合している。
In formula (1), R 1 is hydrogen or a methyl group. That is, the polymerizable group represented by formula (1) is a (meth)acryloyl group. In the water-soluble saccharide according to one aspect of the present invention, the (meth)acryloyl group is covalently bonded to the saccharide via an oxygen atom.
また、本発明の一態様において、重合性基は、一例として、以下の式（２）又は式（３）の構造を有し得る。
In addition, in one aspect of the present invention, the polymerizable group may have, for example, the structure of the following formula (2) or formula (3).
式（２）及び式（３）中、Ｒａは、式（１）に示す構造を有し、Ｒ２は、以下の式（４）に示す構造を有している。また、式（３）中、Ｒ３は、それぞれ独立して、水素又は炭素数１～１０のアルキル基であり、Ｒ３ａは、それぞれ独立して、炭素数１～１０のアルキレン基であり、ｍは、０～２の整数である。なお、式（２）及び式（３）に示す重合性基は、いずれも式（１）に示す重合性基と同じく、酸素原子を介して糖類に共有結合している。
In formulas (2) and (3), R a has the structure shown in formula (1), and R 2 has the structure shown in formula (4) below. Further, in formula (3), 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).
式（４）中、ｎは、２～１０の整数であり、好ましくは２又は３である。ｐは、１～６の整数であり、好ましくは１又は２である。すなわち、Ｒ２は、オキシアルキレン基、又はポリオキシアルキレン基であり得る。当該オキシアルキレン基におけるアルキレン鎖は、直鎖状であってもよく、分岐状であってもよい。
In formula (4), 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.
また、上記式（１）～（３）に示す重合性基は、上記式（４）に示す構造を有するＲ２を介して糖類に共有結合していてもよい。また、上記式（３）に示す重合性基において、Ｒ３ａ－Ｏ－とＲａとは、上記式（４）に示す構造を有するＲ２を介して共有結合していてもよい。
In addition, the 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. In the polymerizable group represented by formula (3) above, R 3a —O— and R a may be covalently bonded via R 2 having the structure represented by formula (4) above.
本発明の一態様に係る水溶性糖類は、式（１）～（３）に示す構造を有する重合性基からなる群から選択される１つ以上を、その分子内に含んでいるとよい。特に、本発明の一態様において、水溶性糖類が備える重合性基は、好ましくは、式（１）に示す構造を有する（メタ）アクリロイル基を有する。これにより、良好な重合性を有する水溶性糖類を実現することができる。
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. In particular, in one aspect of the present invention, the polymerizable group possessed by the water-soluble saccharide preferably has a (meth)acryloyl group having a structure represented by formula (1). Thereby, a water-soluble saccharide having good polymerizability can be realized.
本発明の一態様に係る水溶性糖類において、原料である糖類が備える水酸基の全量を１００ｍｏｌ％として、当該水酸基のうち重合性基に変性されている割合、すなわち変性率は、好ましくは１０ｍｏｌ％以上であり、より好ましくは２０ｍｏｌ％以上である。これにより、当該重合性基を介して水溶性糖類の分子同士が好適に重合できるので、良好な重合性を有する水溶性糖類を実現することができる。また、水溶性糖類において、変性率は、好ましくは６０ｍｏｌ％以下であり、より好ましくは５０ｍｏｌ％以下である。これにより、変性していない水酸基が好適な割合で水溶性糖類中に存在するため、良好な水溶性を有する水溶性糖類を実現することができる。なお、水溶性糖類において、原料である糖類が備える水酸基の全量を１００ｍｏｌ％として、当該水酸基のうち重合性基に変性されている割合、すなわち変性率は、１３Ｃ－ＮＭＲ（核磁気共鳴分光法）によって求めることができる。
In the water-soluble saccharide according to one aspect of the present invention, the ratio of the hydroxyl groups modified with polymerizable groups, that is, the modification rate, 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. As a result, molecules of the water-soluble saccharide can be suitably polymerized with each other through the polymerizable groups, so that a water-soluble saccharide having good polymerizability can be realized. Moreover, in water-soluble saccharides, the modification rate is preferably 60 mol % or less, more preferably 50 mol % or less. As a result, undenatured hydroxyl groups are present in the water-soluble saccharide at a suitable ratio, so that a water-soluble saccharide having good water solubility can be realized. In the water-soluble saccharides, the ratio of the hydroxyl groups modified with polymerizable groups, that is, the modification rate, 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%. ).
〔糖鎖結合様式〕
本発明の一態様に係る水溶性糖類は、糖鎖の少なくとも一部に１，３－結合を有する。本明細書中で使用される場合、用語「１，３－結合」は、糖類の１位の炭素原子に結合する水酸基と、当該糖類とは別の分子である糖類の３位の炭素原子に結合する水酸基と、によって形成されるα－グリコシド結合、及びβ－グリコシド結合のうち少なくとも１つを意味する。 [Sugar chain binding mode]
The water-soluble saccharide according to one aspect of the present invention has 1,3-bonds in at least part of the sugar chain. As used herein, the term “1,3-bond” refers to a hydroxyl group bonded to the carbon atom atposition 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 α-glycosidic bond and a β-glycosidic bond formed by a bonding hydroxyl group.
本発明の一態様に係る水溶性糖類は、糖鎖の少なくとも一部に１，３－結合を有する。本明細書中で使用される場合、用語「１，３－結合」は、糖類の１位の炭素原子に結合する水酸基と、当該糖類とは別の分子である糖類の３位の炭素原子に結合する水酸基と、によって形成されるα－グリコシド結合、及びβ－グリコシド結合のうち少なくとも１つを意味する。 [Sugar chain binding mode]
The water-soluble saccharide according to one aspect of the present invention has 1,3-bonds in at least part of the sugar chain. As used herein, the term “1,3-bond” refers to a hydroxyl group bonded to the carbon atom at
本発明者らは、水溶性糖類が糖鎖中に１，３－結合を有することで、水溶性糖類の分子量増加、及び感光剤の添加量の増加を伴わなくとも、良好な感光性を有する水溶性糖類を実現できることを見出した。これは、以下のような要因によるものであると本発明者らは考える。糖鎖中に１，３－結合を有する糖類は、糖鎖中に１，３－結合を有しない糖類と比較して、糖鎖が、直線ではなく屈曲した構造となりやすく、高分子化すると直鎖状ではなく分岐状の構造となりやすい。そのため、糖鎖中に１，３－結合を有する糖類は、糖鎖中に１，３－結合を有しない糖類と比較して、重合前であっても分子内、及び分子間で重合性基同士の接触部分が大きくなりやすいため、重合性基が重合可能な条件においては、急速に重合が進行するものと考えられる。
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. We have found that 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. Therefore, 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.
本発明の一態様に係る水溶性糖類において、糖鎖が備えるグリコシド結合の全量を１００ｍｏｌ％として、１，３－結合の量は、好ましくは５ｍｏｌ％以上であり、より好ましくは１５ｍｏｌ％以上である。これにより、水溶性糖類の重合性を高めることができる。また、糖鎖が備えるグリコシド結合の全量を１００ｍｏｌ％として、１，３－結合の量は、好ましくは７０ｍｏｌ％以下であり、より好ましくは５０ｍｏｌ％以下である。これにより、水溶性を維持することができる。なお、水溶性糖類において、糖鎖が備えるグリコシド結合の全量を１００ｍｏｌ％として、１，３－結合の量は、１３Ｃ－ＮＭＲ（核磁気共鳴分光法）によって求めることができる。
In the water-soluble saccharide according to one aspect of the present invention, 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. . Thereby, the polymerizability of water-soluble saccharides can be improved. 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. In water-soluble saccharides, 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 %.
また、本発明の一態様に係る水溶性糖類は、糖鎖の少なくとも一部に１，４－結合及び１，６－結合のうち一方又は両方を有してもよい。これにより、水溶性糖類の分岐構造を増やすことができるので、水溶性糖類の重合性をより高めることができる。水溶性糖類において、糖鎖が備えるグリコシド結合の全量を１００ｍｏｌ％として、１，４－結合及び１，６－結合の合計量は、好ましくは３０ｍｏｌ％以上であり、より好ましくは５０ｍｏｌ％以上である。これにより、水溶性糖類の重合性をより高めることができる。また、糖鎖が備えるグリコシド結合の全量を１００ｍｏｌ％として、１，４－結合及び１，６－結合の合計量は、好ましくは９０ｍｏｌ％以下であり、より好ましくは８０ｍｏｌ％以下である。これにより、水溶性を維持することができる。
In addition, 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. As a result, the branched structure of the water-soluble saccharide can be increased, so that the polymerizability of the water-soluble saccharide can be further enhanced. In water-soluble saccharides, 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.
なお、水溶性糖類が糖鎖の少なくとも一部に１，４－結合及び１，６－結合のうち一方又は両方を有する場合、当該１，４－結合及び１，６－結合が糖鎖における主鎖構造を形成し、１，３－結合が糖鎖における側鎖構造を形成していてもよい。
When the water-soluble saccharide has one or both of 1,4-linkage and 1,6-linkage in at least part of the sugar chain, 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.
なお、本発明の一態様に係る水溶性糖類において、糖鎖結合様式は、典型的には、後述する水溶性糖類の原料であり、当該水溶性糖類の骨格をなす糖類と同一である。すなわち、水溶性糖類において、１，３－結合などの糖鎖結合様式は、典型的には、水溶性糖類の原料である糖類に由来する。しかしながら、水溶性糖類は、製造方法が含み得る加水分解及び脱水縮合等の工程に応じて、水溶性糖類の原料である糖類とは異なる糖鎖結合様式を有し得る。
In addition, in the water-soluble saccharide according to one aspect of the present invention, 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.
〔糖類〕
本発明の一態様において、水溶性糖類の原料であり、当該水溶性糖類の骨格をなす糖類は、典型的には、二糖類、三糖類、四糖類、オリゴ糖類、多糖類、糖質、及び食物繊維からなる群から選択される１つ以上である。水溶性糖類の原料である糖類は、１種であってもよく、２種以上の組み合わせであってもよい。原料である糖類は、人工的に合成された糖類であってもよいし、天然の糖類であってもよい。また、原料である糖類が難水溶性である場合、当該糖類を加水分解して得た糖類を原料として用いてもよい。また、原料である糖類が難水溶性である場合、当該糖類にヒドロキシアルキレン基等の親水性基を導入し、水溶性を高めた糖類を原料として用いてもよい。 [Sugars]
In one aspect of the present invention, 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. Moreover, when the raw material saccharide is poorly water-soluble, a saccharide obtained by hydrolyzing the saccharide may be used as the raw material. In addition, when the raw material saccharide is poorly water-soluble, 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.
本発明の一態様において、水溶性糖類の原料であり、当該水溶性糖類の骨格をなす糖類は、典型的には、二糖類、三糖類、四糖類、オリゴ糖類、多糖類、糖質、及び食物繊維からなる群から選択される１つ以上である。水溶性糖類の原料である糖類は、１種であってもよく、２種以上の組み合わせであってもよい。原料である糖類は、人工的に合成された糖類であってもよいし、天然の糖類であってもよい。また、原料である糖類が難水溶性である場合、当該糖類を加水分解して得た糖類を原料として用いてもよい。また、原料である糖類が難水溶性である場合、当該糖類にヒドロキシアルキレン基等の親水性基を導入し、水溶性を高めた糖類を原料として用いてもよい。 [Sugars]
In one aspect of the present invention, 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. Moreover, when the raw material saccharide is poorly water-soluble, a saccharide obtained by hydrolyzing the saccharide may be used as the raw material. In addition, when the raw material saccharide is poorly water-soluble, 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.
原料である糖類は、限定されるものではないが、２０℃における水に対する溶解度が５０ｇ／Ｌ以上である糖類であり得る。
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.
原料である糖類は、より具体的には、二糖類としては例えば、スクロース、ラクトース、マルトース、トレハロース、ツラノース、及びセロビオース等が挙げられる。三糖類としては例えば、ラフィノース、メレジトース、及びマルトトリオース等が挙げられる。四糖類としては例えば、アカルボース、及びスタキオース等が挙げられる。オリゴ糖類としては例えば、フラクトオリゴ糖、ガラクトオリゴ糖、マンナンオリゴ糖、及び乳糖果糖オリゴ糖等が挙げられる。多糖類としては例えば：グリコーゲン、デンプン、プルラン、デキストリン、シクロデキストリン、デキストロース、セルロース、グルカン、フルクタン、及びキチン等の多糖類；これらの多糖類が備える水酸基の一部がヒドロキシアルキレン基等の親水性基によって変性された多糖類；等が挙げられ、これら糖類が、酸処理及び焼結処理、若しくは、酵素処理、又は発酵処理等により糖類同士の１，３－結合が糖鎖に導入されていればよい。
Sugars that are raw materials, more specifically disaccharides, include sucrose, lactose, maltose, trehalose, turanose, and cellobiose. Examples of trisaccharides include raffinose, melezitose, maltotriose, and the like. Tetrasaccharides include, for example, acarbose and stachyose. Examples of oligosaccharides include fructo-oligosaccharides, galacto-oligosaccharides, mannan-oligosaccharides, and lactose-fructose oligosaccharides. Examples of 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.
本発明の一態様において、水溶性糖類の原料であり、当該水溶性糖類の骨格をなす糖類は、糖鎖中に多価アルコール又は多価カルボン酸に由来する架橋構造を有してもよい。多価アルコールとしては例えば：ソルビトール、マンニトール、キシリトール、マルチトール、及びエリスリトール等の糖アルコール；グリセリン；等が挙げられる。多価カルボン酸としては例えば、クエン酸等が挙げられる。
In one aspect of the present invention, 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.
本発明の一態様において、水溶性糖類の原料であり、当該水溶性糖類の骨格をなす糖類は、好ましくは水溶性食物繊維である。水溶性食物繊維は、分子内に水酸基を複数有しているため、水溶性が高いと共に、重合性基へと変性させることができる。また、水溶性食物繊維は、分岐構造を多く有するため、重合性が高い水溶性糖類の原料として、好適である。水溶性糖類の原料である糖類は、低粘度の水系組成物を容易に調製する観点から、水溶性食物繊維の中でも、低粘度の水溶液を形成する水溶性食物繊維であることが好ましい。低粘度の水溶液を形成する水溶性食物繊維としては例えば、難消化性デキストリン、イソマルトデキストリン、デキストロース、及びポリデキストロースが挙げられる。本発明の一態様において、水溶性糖類の原料である糖類は、好ましくは難消化性デキストリン、又はデキストロースである。
In one aspect of the present invention, 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. Since 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. In addition, since water-soluble dietary fiber has many branched structures, it is suitable as a raw material for highly polymerizable water-soluble saccharides. From the viewpoint of easily preparing a low-viscosity aqueous composition, 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. In one aspect of the present invention, the saccharide that is the raw material for the water-soluble saccharide is preferably indigestible dextrin or dextrose.
＜水溶性糖類の製造方法＞
本発明の一態様は、水溶性糖類の製造方法に関する。本発明の一態様に係る水溶性糖類の製造方法は、有機溶媒の存在下で、糖類と重合性基を有する化合物とを反応させて、糖類が備える水酸基の少なくとも一部を重合性基に変性させる工程を包含し、有機溶媒は、Ｎ－メチルピロリドンであり、糖類は、糖鎖の少なくとも一部に１，３－結合を有し、化合物は、（メタ）アクリロイル基とハロゲン基とを有する。本発明の一態様に係る水溶性糖類は、上述した重合性基と求電子性官能基とを有する化合物によって、糖類が備える水酸基を重合性基へと変性させることで製造することができる。以下では、便宜上、「重合性基と求電子性基とを有する化合物」のことを「変性剤」と記載する。 <Method for producing water-soluble saccharide>
One aspect of the present invention relates to a method for producing water-soluble saccharides. 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, and 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. Hereinafter, for the sake of convenience, "a compound having a polymerizable group and an electrophilic group" is referred to as a "modifier".
本発明の一態様は、水溶性糖類の製造方法に関する。本発明の一態様に係る水溶性糖類の製造方法は、有機溶媒の存在下で、糖類と重合性基を有する化合物とを反応させて、糖類が備える水酸基の少なくとも一部を重合性基に変性させる工程を包含し、有機溶媒は、Ｎ－メチルピロリドンであり、糖類は、糖鎖の少なくとも一部に１，３－結合を有し、化合物は、（メタ）アクリロイル基とハロゲン基とを有する。本発明の一態様に係る水溶性糖類は、上述した重合性基と求電子性官能基とを有する化合物によって、糖類が備える水酸基を重合性基へと変性させることで製造することができる。以下では、便宜上、「重合性基と求電子性基とを有する化合物」のことを「変性剤」と記載する。 <Method for producing water-soluble saccharide>
One aspect of the present invention relates to a method for producing water-soluble saccharides. 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, and 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. Hereinafter, for the sake of convenience, "a compound having a polymerizable group and an electrophilic group" is referred to as a "modifier".
本発明の一態様に係る水溶性糖類の製造方法は、有機溶媒の存在下で、糖類と重合性基を有する化合物とを反応させて、糖類が備える水酸基の少なくとも一部を重合性基に変性させる工程を包含する。以下では、便宜上、「糖類と重合性基を有する化合物とを反応させて、糖類が備える水酸基の少なくとも一部を重合性基に変性させる工程」のことを「変性反応工程」と記載する。
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 allowing Hereinafter, for the sake of convenience, "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".
〔反応溶媒〕
変性反応工程において、反応溶媒として用いられる有機溶媒は、糖類及び変性剤を溶解でき、糖類及び変性剤と反応しない有機溶媒を適宜に選択すればよい。有機溶媒は、好ましくは非プロトン性極性溶媒である。非プロトン性極性溶媒としては例えば：Ｎ－メチルピロリドン（ＮＭＰ）；Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）；ジメチルスルホキシド（ＤＭＳＯ）；ジメチルアセトアミド（ＤＭＡｃ）；アセトン及びメチルエチルケトン等のケトン類；並びに、ジオキサン及びテトラヒドロフラン等のエーテル類；等が挙げられる。 [Reaction solvent]
In the 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;
変性反応工程において、反応溶媒として用いられる有機溶媒は、糖類及び変性剤を溶解でき、糖類及び変性剤と反応しない有機溶媒を適宜に選択すればよい。有機溶媒は、好ましくは非プロトン性極性溶媒である。非プロトン性極性溶媒としては例えば：Ｎ－メチルピロリドン（ＮＭＰ）；Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）；ジメチルスルホキシド（ＤＭＳＯ）；ジメチルアセトアミド（ＤＭＡｃ）；アセトン及びメチルエチルケトン等のケトン類；並びに、ジオキサン及びテトラヒドロフラン等のエーテル類；等が挙げられる。 [Reaction solvent]
In the 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;
変性反応工程において、変性剤が有する求電子性基がハロゲン基である場合、反応溶媒として用いられる有機溶媒は、好ましくはＮＭＰである。これにより、変性剤が有するハロゲン基と、糖類が有する水酸基との反応により副生成物として生成する塩酸が、ＮＭＰが有する窒素原子の孤立電子対と親和することができ、当該塩酸が糖類に与える影響を減じることができる。したがって、反応溶媒がＮＭＰであることにより、変性剤がより効率的に糖類を変性させることができる。
In the modification reaction step, when the electrophilic group possessed by the modifier is a halogen group, the organic solvent used as the reaction solvent is preferably NMP. As a result, 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 can have an affinity with the lone electron pair of the nitrogen atom of NMP, and 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.
〔糖類〕
変性反応工程において、原料である糖類は、糖鎖の少なくとも一部に１，３－結合を有する糖類を適宜に選択して用いることができる。このような糖類としては具体的には、上述した糖類を挙げられるが、これらに限定されない。 [Sugars]
In the denaturation reaction step, 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.
変性反応工程において、原料である糖類は、糖鎖の少なくとも一部に１，３－結合を有する糖類を適宜に選択して用いることができる。このような糖類としては具体的には、上述した糖類を挙げられるが、これらに限定されない。 [Sugars]
In the denaturation reaction step, 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.
変性反応工程において、原料である糖類は、予め酵素分解、及び酸処理等の操作により修飾された糖類であってもよい。また、原料である糖類は、予め再沈殿等の操作により、精製及び分画された糖類であってもよい。
In the denaturation reaction step, the raw material saccharides may be saccharides that have been modified in advance by operations such as enzymatic decomposition and acid treatment. In addition, the saccharide as a raw material may be a saccharide that has been purified and fractionated in advance by an operation such as reprecipitation.
〔変性剤〕
変性反応工程において、重合性基の供給源である変性剤は、重合性基と求電子性基とを有する化合物である。 [Modifying agent]
In the modification reaction step, the modifier, which is the supply source of the polymerizable group, is a compound having a polymerizable group and an electrophilic group.
変性反応工程において、重合性基の供給源である変性剤は、重合性基と求電子性基とを有する化合物である。 [Modifying agent]
In the modification reaction step, the modifier, which is the supply source of the polymerizable group, is a compound having a polymerizable group and an electrophilic group.
変性剤が有する重合性基は、上述した重合性基を好適に用いることができる。中でも、変性剤が有する重合性基は、好ましくは（メタ）アクリロイル基である。
As the polymerizable group possessed by the modifier, the polymerizable group described above can be suitably used. Among them, the polymerizable group possessed by the modifier is preferably a (meth)acryloyl group.
変性剤が有する求電子性基は、変性反応が進行する反応機構において一般的に用いられる求電子性基を用いることができる。変性剤が有する求電子性基としては例えば：塩素、臭素、及びヨウ素等のハロゲン基；イソシアネート基；酸無水物基；等が挙げられる。中でも、変性剤が有する求電子性基は、好ましくはハロゲン基である。
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.
より具体的には、変性反応工程において用いられる変性剤としては例えば、（メタ）アクリル酸クロリド、（メタ）アクリル酸無水物、２－（２－（メタ）アクリロイルオキシエチルオキシ）エチルイソシアナート、及び２－イソシアナトエチル（メタ）アクリレート等が挙げられる。中でも、変性剤は、好ましくは（メタ）アクリル酸クロリド、又は（メタ）アクリル酸無水物である。これにより、より効率的に変性反応を進行させることができる。
More specifically, examples of 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. Among them, the modifier is preferably (meth)acrylic acid chloride or (meth)acrylic anhydride. This allows the modification reaction to proceed more efficiently.
〔反応条件〕
変性反応工程において、系内温度は、好ましくは－１０℃以上であり、より好ましくは０℃以上である。これにより、変性反応における温度制御を容易に行うことできる。また、変性反応工程において、系内温度は、好ましくは１００℃以下であり、より好ましくは６０℃以下である。これにより、変性反応工程において、変性剤、及び糖類が変性して生じた水溶性糖類が有する重合性基が重合反応することを減じることができる。 [Reaction conditions]
In the modification reaction step, 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.
変性反応工程において、系内温度は、好ましくは－１０℃以上であり、より好ましくは０℃以上である。これにより、変性反応における温度制御を容易に行うことできる。また、変性反応工程において、系内温度は、好ましくは１００℃以下であり、より好ましくは６０℃以下である。これにより、変性反応工程において、変性剤、及び糖類が変性して生じた水溶性糖類が有する重合性基が重合反応することを減じることができる。 [Reaction conditions]
In the modification reaction step, 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.
変性反応工程において、変性反応は、大気雰囲気下、又は不活性ガス雰囲気下で行ってもよい。変性反応は、限定されるものではないが、不活性ガス雰囲気下で行うことが好ましい。不活性ガスとしては例えば、窒素ガス、アルゴンガス等が挙げられる。
In the modification reaction step, the modification reaction may be performed under an air atmosphere or an inert gas atmosphere. Although the modification reaction is not limited, it is preferably carried out in an inert gas atmosphere. Examples of inert gas include nitrogen gas and argon gas.
変性反応工程において、系内の水溶性糖類と変性剤との混合重量比は、糖類が有している水酸基の量、及び所望の変性率に応じて、適宜に選択すればよい。
In the modification reaction step, 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.
変性反応工程において、反応終了後、系にアミンを加えることにより、変性反応の副生成物として生成する酸を中和してもよい。アミンとしては例えば、トリエチルアミン等の三級アミン等が挙げられる。
In the modification reaction step, after the reaction is completed, an amine may be added to the system to neutralize the acid produced as a by-product of the modification reaction. Examples of amines include tertiary amines such as triethylamine.
＜感光性組成物＞
本発明の一態様は、感光性組成物に関する。本発明の一態様に係る感光性組成物は、本発明の一態様に係る水溶性糖類と水と光反応開始剤とを含有してなる。本発明の一態様に係る感光性組成物は、水溶性糖類が有する水酸基に由来して水系組成物を形成できると共に、水溶性糖類が有する重合性基に由来して重合性を有している。そのため、感光性組成物は、重合反応により硬化物を形成できると共に、水系溶媒を用いた洗浄により現像することができる。 <Photosensitive composition>
One aspect of the present invention relates to photosensitive compositions. 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.
本発明の一態様は、感光性組成物に関する。本発明の一態様に係る感光性組成物は、本発明の一態様に係る水溶性糖類と水と光反応開始剤とを含有してなる。本発明の一態様に係る感光性組成物は、水溶性糖類が有する水酸基に由来して水系組成物を形成できると共に、水溶性糖類が有する重合性基に由来して重合性を有している。そのため、感光性組成物は、重合反応により硬化物を形成できると共に、水系溶媒を用いた洗浄により現像することができる。 <Photosensitive composition>
One aspect of the present invention relates to photosensitive compositions. 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.
〔希釈溶媒〕
本発明の一態様に係る感光性組成物は、希釈溶媒として水を含有する。感光性組成物における水の含有量は、感光性組成物の所望の粘度、及び硬化物の膜厚等に応じて、水溶性糖類の濃度が所定の濃度となるように、適宜に選択することができる。水溶性糖類の濃度は、感光性組成物の全量に対して、好ましくは５質量％以上であり、より好ましくは２０質量％以上であるが、これに限定されない。水溶性糖類の濃度が、感光性組成物の全量に対して、５質量％以上であること、特に２０質量％以上であることにより、感光性組成物を容易に厚膜化することができる。また、水溶性糖類の濃度は、感光性組成物の全量に対して、好ましくは５０質量％以下であり、より好ましくは４０質量％以下であるが、これに限定されない。水溶性糖類の濃度は、感光性組成物の全量に対して、好ましくは５０質量％以下、より好ましくは４０質量％以下である。水溶性糖類の濃度が、感光性組成物の全量に対して、５０質量％以下であること、特に４０質量％以下であることにより、感光性組成物を広い範囲の膜厚にて塗工することができる。 [Dilution 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. Moreover, 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.
本発明の一態様に係る感光性組成物は、希釈溶媒として水を含有する。感光性組成物における水の含有量は、感光性組成物の所望の粘度、及び硬化物の膜厚等に応じて、水溶性糖類の濃度が所定の濃度となるように、適宜に選択することができる。水溶性糖類の濃度は、感光性組成物の全量に対して、好ましくは５質量％以上であり、より好ましくは２０質量％以上であるが、これに限定されない。水溶性糖類の濃度が、感光性組成物の全量に対して、５質量％以上であること、特に２０質量％以上であることにより、感光性組成物を容易に厚膜化することができる。また、水溶性糖類の濃度は、感光性組成物の全量に対して、好ましくは５０質量％以下であり、より好ましくは４０質量％以下であるが、これに限定されない。水溶性糖類の濃度は、感光性組成物の全量に対して、好ましくは５０質量％以下、より好ましくは４０質量％以下である。水溶性糖類の濃度が、感光性組成物の全量に対して、５０質量％以下であること、特に４０質量％以下であることにより、感光性組成物を広い範囲の膜厚にて塗工することができる。 [Dilution 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. Moreover, 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.
〔光反応開始剤〕
本発明の一態様に係る感光性組成物は、光反応開始剤を含有する。光反応開始剤は、重合性基の種類に応じて、光ラジカル重合開始剤、及び光カチオン重合開始剤から選択すればよい。感光性組成物が含有する光反応開始剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Photoinitiator]
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.
本発明の一態様に係る感光性組成物は、光反応開始剤を含有する。光反応開始剤は、重合性基の種類に応じて、光ラジカル重合開始剤、及び光カチオン重合開始剤から選択すればよい。感光性組成物が含有する光反応開始剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Photoinitiator]
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.
本発明の一態様に係る感光性組成物において、光反応開始剤の含有量は、１００重量部の水溶性糖類に対して、好ましくは０．０１重量部以上であり、より好ましくは０．１０重量部以上である。これにより、感光性組成物の感光性を高めることができる。また、本発明の一態様に係る感光性組成物において、光反応開始剤の含有量は、１００重量部の水溶性糖類に対して、好ましくは５．００重量部以下であり、より好ましくは３．００重量部以下である。これにより、感光性組成物の製造コストを減じることができる。
In the photosensitive composition according to one aspect of the present invention, 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. In the photosensitive composition according to one aspect of the present invention, 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.
感光性組成物が含有する光ラジカル重合開始剤は、例えば、感光性組成物に求められる用途、及び機能に応じて適宜に選択すればよい。光ラジカル重合開始剤としては例えば、α－ヒドロキシケトン系光重合開始剤、α－アミノケトン系光重合開始剤、ベンジルケタール系光重合開始剤、オキシムエステル系光重合開始剤、アクリジン系光重合開始剤、ベンゾフェノン系光重合開始剤、アセトフェノン系光重合開始剤、芳香族ケトエステル系光重合開始剤、安息香酸エステル系光重合開始剤、アシルホスフィンオキシド系光重合開始剤、及びチタノセン系光重合開始剤等が挙げられる。光ラジカル重合開始剤は例えば、界面活性剤及び／又は重合性モノマー等によって、水系に乳化又は可溶化されていてもよい。商業的に入手可能な光ラジカル重合開始剤としては例えば、ＦＡＩ－１０１Ｌ（富士フイルム株式会社製）が挙げられる。
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. Examples of photoradical polymerization initiators include α-hydroxyketone-based photopolymerization initiators, α-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).
α－ヒドロキシケトン系光重合開始剤としては例えば、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチルプロパン－１－オン、及び２－ヒドロキシ－１－［４－［４－（２－ヒドロキシ－２－メチルプロピオニル）ベンジル］フェニル］－２－メチルプロパン－１－オン等が挙げられる。
Examples of α-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.
商業的に入手可能なα－ヒドロキシケトン系光重合開始剤としては例えば、Ｏｍｎｉｒａｄ ２９５９（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）等が挙げられる。
Examples of commercially available α-hydroxyketone-based photopolymerization initiators include Omnirad 2959 (manufactured by IGM Resins B.V.).
α－アミノケトン系光重合開始剤としては例えば、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、２－ジメチルアミノ－２－（４－メチルベンジル）－１－（４－モルホリノフェニル）－ブタン－１－オン、及び３，６－ビス（２－メチル－２－モルホリノプロピオニル）－９－オクチル－９Ｈ－カルバゾール等が挙げられる。
Examples of α-aminoketone-based photopolymerization initiators 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.
ベンジルケタール系光重合開始剤としては例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等が挙げられる。
Benzyl ketal-based photopolymerization initiators include, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one.
オキシムエステル系光重合開始剤としては例えば、１－フェニルプロパン－１，２－ジオン－２－（Ｏ－エトキシカルボニル）オキシム、１－フェニルブタン－１，２－ジオン－２－（Ｏ－メトキシカルボニル）オキシム、１，３－ジフェニルプロパン－１，２，３－トリオン－２－（Ｏ－エトキシカルボニル）オキシム、１－［４－（フェニルチオ）フェニル］オクタン－１，２－ジオン－２－（Ｏ－ベンゾイル）オキシム、１－［４－［４－（カルボキシフェニル）チオ］フェニル］プロパン－１，２－ジオン－２－（Ｏ－アセチル）オキシム、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン－１－（Ｏ－アセチル）オキシム、１－［９－エチル－６－［２－メチル－４－［１－（２，２－ジメチル－１，３－ジオキソラン－４－イル）メチルオキシ］ベンゾイル］－９Ｈ－カルバゾール－３－イル］エタノン－１－（Ｏ－アセチル）オキシム、及び１－（９－エチル－６－ニトロ－９Ｈ－カルバゾール－３－イル）－１－［２－メチル－４－（１－メトキシプロパン－２－イルオキシ）フェニル］メタノン－１－（Ｏ－アセチル）オキシム等が挙げられる。
Examples of 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-(2,2-dimethyl-1 ,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime and 1-(9-ethyl-6-nitro-9H-carbazole- 3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime and the like.
アクリジン系光重合開始剤としては例えば、１，７－ビス（アクリジン－９－イル）－ｎ－ヘプタン等が挙げられる。
Examples of acridine-based photopolymerization initiators include 1,7-bis(acridin-9-yl)-n-heptane.
ベンゾフェノン系光重合開始剤として例えば、ベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４－フェニルベンゾフェノン、４，４－ジクロロベンゾフェノン、４－ヒドロキシベンゾフェノン、アルキル化ベンゾフェノン、３，３’，４，４’－テトラキス（ｔ－ブチルパーオキシカルボニル）ベンゾフェノン、４－メチルベンゾフェノン、ジベンジルケトン、及びフルオレノン等が挙げられる。
Examples of 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.
アセトフェノン系光重合開始剤としては例えば、２，２－ジエトキシアセトフェノン、２，３－ジエトキシアセトフェノン、４－ｔ－ブチルジクロロアセトフェノン、ベンザルアセトフェノン、及び４－アジドベンザルアセトフェノン等が挙げられる。
Examples of acetophenone-based photopolymerization initiators include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone.
芳香族ケトエステル系光重合開始剤としては例えば、２－フェニル－２－オキシ酢酸メチル等が挙げられる。
Examples of aromatic ketoester-based photopolymerization initiators include methyl 2-phenyl-2-oxyacetate.
安息香酸エステル系光重合開始剤としては例えば、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸（２－エチル）ヘキシル、４－ジエチルアミノ安息香酸エチル、及び２－ベンゾイル安息香酸メチル等が挙げられる。
Examples of benzoic acid ester-based photopolymerization initiators include ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate. be done.
アシルホスフィンオキシド系光重合開始剤としては例えば、２，４，６－トリメチルベンゾイル－ジフェニルホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキシド、及びビス（２，６－ジメトキシベンゾイル）－（２，４，４－トリメチルペンチル）ホスフィンオキシド等が挙げられる。
Examples of 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.
チタノセン系光重合開始剤としては例えば、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス［２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル］チタン（ＩＶ）、及びビス（η５－３－メチル－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロフェニル）チタン（ＩＶ）等が挙げられる。
Examples of titanocene-based photopolymerization initiators include bis(η5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (IV ), and bis(η5-3-methyl-2,4-cyclopentadien-1-yl)-bis(2,6-difluorophenyl)titanium (IV).
〔架橋剤〕
本発明の一態様に係る感光性組成物は、架橋剤を含有してもよい。感光性組成物が架橋剤を含むことによって、当該架橋剤を介して感光性組成物に含まれる水溶性糖類が有する重合性基同士を架橋できる。架橋剤は、２つ以上の重合性基を有していることがより好ましい。架橋剤は、重合性基の種類に応じて、ラジカル重合性架橋剤、及びカチオン重合性架橋剤から選択すればよい。感光性組成物が含有する架橋剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Crosslinking agent]
The photosensitive composition according to one aspect of the present invention may contain a cross-linking agent. When 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. More preferably, 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.
本発明の一態様に係る感光性組成物は、架橋剤を含有してもよい。感光性組成物が架橋剤を含むことによって、当該架橋剤を介して感光性組成物に含まれる水溶性糖類が有する重合性基同士を架橋できる。架橋剤は、２つ以上の重合性基を有していることがより好ましい。架橋剤は、重合性基の種類に応じて、ラジカル重合性架橋剤、及びカチオン重合性架橋剤から選択すればよい。感光性組成物が含有する架橋剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Crosslinking agent]
The photosensitive composition according to one aspect of the present invention may contain a cross-linking agent. When 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. More preferably, 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.
本発明の一態様に係る感光性組成物において、架橋剤の含有量は、１００重量部の水溶性糖類に対して、好ましくは０．０１重量部以上であり、より好ましくは０．１０重量部以上である。また、本発明の一態様に係る感光性組成物において、架橋剤の含有量は、１００重量部の水溶性糖類に対して、好ましくは５．００重量部以下であり、より好ましくは３．００重量部以下である。
In the photosensitive composition according to one aspect of the present invention, 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. In the photosensitive composition according to one aspect of the present invention, 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.
ラジカル重合性架橋剤としては例えば：１，３－ビス（ビニルスルホニル）－２－プロパノール等のビニル基を有する架橋剤；及び（メタ）クリロイル基を有する架橋剤；等が挙げられる。（メタ）クリロイル基を有する架橋剤としては例えば、ポリオキシアルキレン基を有する（メタ）アクリル酸エステル、多価アルコールから形成される（メタ）アクリル酸エステル等が挙げられる。
Examples of 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. Examples of the 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.
ポリオキシアルキレン基を有する（メタ）アクリル酸エステルとしては例えば、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、及びテトラエチレングリコールジ（メタ）アクリレート等が挙げられる。
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.
多価アルコールから形成される（メタ）アクリル酸エステルとしては例えば、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパンジ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、及び１，９－ノナンジオールジ（メタ）アクリレート等が挙げられるが、これらに限定されない。
(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. .
本発明の一態様に係る感光性組成物は、上述した架橋剤に加えて、又は代替して、水溶性糖類が有する重合性基の種類に応じて、エポキシ基又はオキセタン基等の重合性基を有する架橋剤を含有してもよい。
In the photosensitive composition according to one aspect of the present invention, in addition to or instead of the above-described crosslinking agent, depending on the type of polymerizable group possessed by the water-soluble saccharide, a polymerizable group such as an epoxy group or an oxetane group may contain a cross-linking agent having
〔界面活性剤〕
本発明の一態様に係る感光性組成物は、界面活性剤を含有してもよい。感光性組成物が界面活性剤を適量含有することにより、当該感光性組成物の表面張力を任意に調整することができ、塗工時のレベリング性が向上し、塗工膜の膜厚均一性を向上させることができる。感光性組成物が含有する界面活性剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Surfactant]
The photosensitive composition according to one aspect of the present invention may contain 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.
本発明の一態様に係る感光性組成物は、界面活性剤を含有してもよい。感光性組成物が界面活性剤を適量含有することにより、当該感光性組成物の表面張力を任意に調整することができ、塗工時のレベリング性が向上し、塗工膜の膜厚均一性を向上させることができる。感光性組成物が含有する界面活性剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Surfactant]
The photosensitive composition according to one aspect of the present invention may contain 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.
本発明の一態様に係る感光性組成物において、界面活性剤の含有量は、１００重量部の水溶性糖類に対して、好ましくは０．０１重量部以上であり、より好ましくは０．３０重量部以上である。また、本発明の一態様に係る感光性組成物において、界面活性剤の含有量は、１００重量部の水溶性糖類に対して、好ましくは１０．００重量部以下であり、より好ましくは５．００重量部以下である。
In the photosensitive composition according to one aspect of the present invention, 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. In the photosensitive composition according to one aspect of the present invention, 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.
感光性組成物が含有する界面活性剤としては例えば、フッ素樹脂系界面活性剤、シリコーン系界面活性剤、ポリオキシアルキレンエーテル系界面活性剤、及びアクリル樹脂系界面活性剤の界面活性剤が挙げられる。
Examples of surfactants contained in the photosensitive composition include fluororesin-based surfactants, silicone-based surfactants, polyoxyalkylene ether-based surfactants, and acrylic resin-based surfactants. .
フッ素樹脂系界面活性剤としては例えば、メガファック（登録商標）が挙げられ、その品番としては例えば、Ｆ－１４２Ｄ、Ｆ－１７２、Ｆ－１７３、Ｆ－１８３、Ｆ－４３０、Ｆ－４４４、Ｆ－４４５、Ｆ－４７０、Ｆ－４７５、Ｆ－４７７、Ｆ－５５５、Ｆ－５５８、及びＦ－５５９（以上、いずれもＤＩＣ株式会社製）が挙げられる。また、フッ素樹脂系界面活性剤としては例えば、エフトップ（登録商標）が挙げられ、その品番としては、ＥＦ３０１、３０３、及び３５２（以上、いずれも三菱マテリアル電子化成株式会社製）が挙げられる。また、フッ素樹脂系界面活性剤としては例えば：フロラード（登録商標）ＦＣ－４３０、及びＦＣ－４３１（以上、いずれも住友スリーエム株式会社製）；アサヒガード（登録商標）ＡＧ７１０（旭硝子株式会社製）；サーフロン（登録商標）Ｓ－３８２、ＳＣ－１０１、ＳＣ－１０２、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、及びＳＣ－１０６（以上、いずれもＡＧＣセイミケミカル株式会社製）；ＢＭ－１０００、及びＢＭ－１１００（以上、いずれも裕商株式会社製）；並びに、フタージェント（登録商標）７１０ＦＭ、７３０ＬＭ（以上、いずれも株式会社ネオス製）；等が挙げられる。
Examples of 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). Examples of 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.). Examples of fluororesin-based surfactants 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.);
シリコーン系界面活性剤としては例えば、ＳＨ２８ＰＡ、ＳＨ７ＰＡ、ＳＨ２１ＰＡ、ＳＨ３０ＰＡ、及びＳＴ９４ＰＡ（以上、いずれも東レ・ダウコーニング株式会社製）；ＢＹＫ（登録商標）３０１、３０６、３０７、３３１、３３３、３３７、及び３４５（以上、いずれもビックケミー・ジャパン株式会社製）；等が挙げられる。
Examples of silicone surfactants 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.
ポリオキシアルキレンエーテル系界面活性剤としては例えば、フタージェント（登録商標）２１２Ｍ、２０９Ｆ、２０８Ｇ、２４０Ｇ、２１２Ｐ、２２０Ｐ、２２８Ｐ、ＮＢＸ－１５、ＦＴＸ－２１８、及びＤＦＸ－２１８（以上、いずれも株式会社ネオス製）等が挙げられる。
Examples of polyoxyalkylene ether-based surfactants 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).
アクリル樹脂系界面活性剤としては例えば、ＢＹＫ（登録商標）－３５０、３５２、３５４、３５５、３５６、３５８Ｎ、３６１Ｎ、３９２、３９４、及び３９９（以上、いずれもビックケミー・ジャパン株式会社製）等が挙げられる。
Examples of acrylic resin-based surfactants include BYK (registered trademark)-350, 352, 354, 355, 356, 358N, 361N, 392, 394, and 399 (all manufactured by BYK-Chemie Japan Co., Ltd.). mentioned.
〔反応停止剤〕
本発明の一態様に係る感光性組成物は、反応停止剤を含有してもよい。感光性組成物が反応停止剤を含有することで、当該感光性組成物が光重合する際に、過重合することを抑制することができる。感光性組成物が含有する反応停止剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Reaction terminator]
The photosensitive composition according to one aspect of the present invention may contain 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.
本発明の一態様に係る感光性組成物は、反応停止剤を含有してもよい。感光性組成物が反応停止剤を含有することで、当該感光性組成物が光重合する際に、過重合することを抑制することができる。感光性組成物が含有する反応停止剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Reaction terminator]
The photosensitive composition according to one aspect of the present invention may contain 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.
本発明の一態様に係る感光性組成物において、反応停止剤の含有量は、１００重量部の水溶性糖類に対して、好ましくは０．０１重量部以上であり、より好ましくは０．１０重量部以上である。また、本発明の一態様に係る感光性組成物において、反応停止剤の含有量は、１００重量部の水溶性糖類に対して、好ましくは５．００重量部以下であり、より好ましくは１．００重量部以下である。
In the photosensitive composition according to one aspect of the present invention, 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. In the photosensitive composition according to one aspect of the present invention, 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.
感光性組成物が含有する反応停止剤としては例えば、ラジカル重合停止剤等が挙げられる。ラジカル重合停止剤としては例えば、４－ｔ－ブチルフェノール、４－メトキシフェノール、１，４－ヒドロキノン、１，４－ベンゾキノン、２－ｔ－ブチル－４－メトキシフェノール、３－ｔ－ブチル－４－メトキシフェノール、４－ｔ－ブチルカテコール、２－ｔ－ブチル－１，４－ヒドロキノン、２，６－ジ－ｔ－ブチルフェノール、２，４，６－トリ－ｔ－ブチルフェノール、２，６－ジ－ｔ－ブチル－４－メチルフェノール、２，６－ジ－ｔ－ブチル－４－メトキシフェノール、２，５－ジ－ｔ－ブチル－１，４－ヒドロキノン、２，５－ジ－ｔ－アミル－１，４－ヒドロキノン、２－ニトロソ－１－ナフトール、及びＮ－フェニルジエタノールアミン等が挙げられる。また、商業的に入手可能なラジカル重合停止剤としては例えば、ＩＲＧＡＮＯＸ（登録商標）シリーズが挙げられ、その品番としては１０１０、１０３５、１０７６、１０９８、１１３５、１３３０、１７２６、１４２５、１５２０、２４５、２５９、３１１４、５６５、及び２９５（以上、いずれもＢＡＳＦ社製）が挙げられる。
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. Examples of commercially available radical polymerization terminator 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).
〔その他の添加剤〕
本発明の一態様に係る感光性組成物は、本発明の一態様に係る水溶性糖類の性質を損なわない限りで、その他の添加剤を含有してもよい。その他の添加剤としては例えば、密着助剤、充填剤、及び水溶性樹脂等が挙げられる。感光性組成物が含有するその他の添加剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Other additives]
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.
本発明の一態様に係る感光性組成物は、本発明の一態様に係る水溶性糖類の性質を損なわない限りで、その他の添加剤を含有してもよい。その他の添加剤としては例えば、密着助剤、充填剤、及び水溶性樹脂等が挙げられる。感光性組成物が含有するその他の添加剤は、１種類であってもよいし、２種類以上の組み合わせであってもよい。 [Other additives]
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.
＜感光性組成物の用途＞
本発明の一態様に係る感光性組成物は、水系組成物でありながら、例えば半導体等の微細加工用フォトレジスト用感光性材料に利用することができる。 <Application of photosensitive composition>
Although 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.
本発明の一態様に係る感光性組成物は、水系組成物でありながら、例えば半導体等の微細加工用フォトレジスト用感光性材料に利用することができる。 <Application of photosensitive composition>
Although 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.
以下に、本発明の一態様に係る感光性組成物を半導体の微細加工におけるネガ型フォトレジストとして利用するための実施形態を、例示のために述べる。しかしながら、本発明の一態様に係る感光性組成物の用途は、本実施形態に限定されないことに留意されたい。
An embodiment for using the photosensitive composition according to one aspect of the present invention as a negative photoresist in semiconductor microfabrication will be described below for illustration. However, it should be noted that the application of the photosensitive composition according to one aspect of the present invention is not limited to this embodiment.
〔重合性基の選択〕
本発明の一態様に係る感光性組成物をネガ型フォトレジストとして用いる場合、水溶性糖類が有する重合性基は、（メタ）アクリロイル基等の不飽和二重結合を有する官能基である。 [Selection of polymerizable group]
When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, the polymerizable group possessed by the water-soluble saccharide is a functional group having an unsaturated double bond such as a (meth)acryloyl group.
本発明の一態様に係る感光性組成物をネガ型フォトレジストとして用いる場合、水溶性糖類が有する重合性基は、（メタ）アクリロイル基等の不飽和二重結合を有する官能基である。 [Selection of polymerizable group]
When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, the polymerizable group possessed by the water-soluble saccharide is a functional group having an unsaturated double bond such as a (meth)acryloyl group.
〔基板の選択〕
本発明の一態様に係る感光性組成物の塗工対象となる基板としては例えば、半導体ウェハー基板、及びガラス基板等の基板が挙げられる。また、基板の表面には、例えば絶縁層及び導電層等の層が予め形成されていてもよい。また、基板には、例えばポリ（２－ヒドロキシエチル）アクリレート等の下地となる層が形成されていてもよい。本発明の一態様に係る感光性組成物は、水系組成物であるため、有機溶媒を多量に含有するレジスト材料と比較して、ポリ（２－ヒドロキシエチル）アクリレート等の下地を腐食し難いことも利点の１つである。 [Substrate selection]
Examples of 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. In addition, layers such as an insulating layer and a conductive layer may be formed in advance on the surface of the substrate. Further, 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.
本発明の一態様に係る感光性組成物の塗工対象となる基板としては例えば、半導体ウェハー基板、及びガラス基板等の基板が挙げられる。また、基板の表面には、例えば絶縁層及び導電層等の層が予め形成されていてもよい。また、基板には、例えばポリ（２－ヒドロキシエチル）アクリレート等の下地となる層が形成されていてもよい。本発明の一態様に係る感光性組成物は、水系組成物であるため、有機溶媒を多量に含有するレジスト材料と比較して、ポリ（２－ヒドロキシエチル）アクリレート等の下地を腐食し難いことも利点の１つである。 [Substrate selection]
Examples of 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. In addition, layers such as an insulating layer and a conductive layer may be formed in advance on the surface of the substrate. Further, 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.
〔塗工膜の形成〕
本発明の一態様に係る感光性組成物を基板に塗工する方法は、従来公知の方法であってよい。感光性組成物を基板に塗工する方法としては例えば、スピナーを用いたスピンコーティング等が挙げられるが、これに限定されない。 [Formation of coating film]
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.
本発明の一態様に係る感光性組成物を基板に塗工する方法は、従来公知の方法であってよい。感光性組成物を基板に塗工する方法としては例えば、スピナーを用いたスピンコーティング等が挙げられるが、これに限定されない。 [Formation of coating film]
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.
感光性組成物を基板に塗工した後、典型的には、感光性組成物が形成する塗工膜中の水を除去するために、焼成（加熱乾燥）が行われる。焼成温度は、好ましくは５０℃以上、３００℃以下である。
After the photosensitive composition is applied to the substrate, baking (heat drying) is typically performed to remove water in the coating film formed by the photosensitive composition. The firing temperature is preferably 50°C or higher and 300°C or lower.
〔露光による硬化塗工膜の形成〕
本発明の一態様に係る感光性組成物をネガ型フォトレジストとして用いる場合、塗工膜を形成した基板を露光することによる硬化塗工膜の形成は、当技術分野で従来公知の露光方法で行うことができる。塗工膜に照射する活性化学線としては例えば、紫外線、可視光、及び電子線等が挙げられる。紫外線硬化は、電子線硬化に比べ、生産性に優れ、装置コストが安価であるため、活性化学線は、好ましくは紫外線である。露光量は、感光性組成物における光反応開始剤の含有量等に応じて、適宜に選択することができる。露光量としては例えば６００ｍＪ／ｃｍ２程度、露光時間としては例えば６０秒間程度とすることができるが、これに限定されない。なお、照射すべき紫外線の波長は、感光性組成物に含まれる光重合開始剤の種類に応じて選択すればよい。 [Formation of cured coating film by exposure]
When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, 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.
本発明の一態様に係る感光性組成物をネガ型フォトレジストとして用いる場合、塗工膜を形成した基板を露光することによる硬化塗工膜の形成は、当技術分野で従来公知の露光方法で行うことができる。塗工膜に照射する活性化学線としては例えば、紫外線、可視光、及び電子線等が挙げられる。紫外線硬化は、電子線硬化に比べ、生産性に優れ、装置コストが安価であるため、活性化学線は、好ましくは紫外線である。露光量は、感光性組成物における光反応開始剤の含有量等に応じて、適宜に選択することができる。露光量としては例えば６００ｍＪ／ｃｍ２程度、露光時間としては例えば６０秒間程度とすることができるが、これに限定されない。なお、照射すべき紫外線の波長は、感光性組成物に含まれる光重合開始剤の種類に応じて選択すればよい。 [Formation of cured coating film by exposure]
When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, 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.
〔現像〕
本発明の一態様に係る感光性組成物をネガ型フォトレジストとして用いる場合、塗工膜の現像液は、水系溶媒であり、好ましくは水である。すなわち、現象液が水であることを除いて、当技術分野で従来公知の方法を用いて、現像を行うことができることが本発明の利点の１つである。 〔developing〕
When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, 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.
本発明の一態様に係る感光性組成物をネガ型フォトレジストとして用いる場合、塗工膜の現像液は、水系溶媒であり、好ましくは水である。すなわち、現象液が水であることを除いて、当技術分野で従来公知の方法を用いて、現像を行うことができることが本発明の利点の１つである。 〔developing〕
When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, 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.
〔エッチング〕
本発明の一態様に係る感光性組成物をネガ型フォトレジストとして用いる場合、塗工膜のエッチングは、当技術分野で従来公知の方法で行うことができる。 〔etching〕
When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, the coating film can be etched by a method conventionally known in the art.
本発明の一態様に係る感光性組成物をネガ型フォトレジストとして用いる場合、塗工膜のエッチングは、当技術分野で従来公知の方法で行うことができる。 〔etching〕
When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, the coating film can be etched by a method conventionally known in the art.
＜まとめ＞
本発明の一態様に係る水溶性糖類は、糖類が備える糖鎖の少なくとも一部に１，３－結合を有し、当該糖鎖が備える水酸基の少なくとも一部が重合性基に変性されてなる。これにより、重合性基を備える新規な水溶性糖類を提供することができる。 <Summary>
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. . Thereby, a novel water-soluble saccharide having a polymerizable group can be provided.
本発明の一態様に係る水溶性糖類は、糖類が備える糖鎖の少なくとも一部に１，３－結合を有し、当該糖鎖が備える水酸基の少なくとも一部が重合性基に変性されてなる。これにより、重合性基を備える新規な水溶性糖類を提供することができる。 <Summary>
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. . Thereby, a novel water-soluble saccharide having a polymerizable group can be provided.
本発明の一態様に係る水溶性糖類は、前記糖類が備える水酸基の全量を１００ｍｏｌ％として、当該水酸基のうちの１０ｍｏｌ％以上、６０ｍｏｌ％以下が重合性基に変性されてなることが好ましい。これにより、良好な重合性と水溶性とを兼ね備える水溶性糖類を提供することができる。
In the water-soluble saccharide according to one aspect of the present invention, 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.
本発明の一態様に係る水溶性糖類において、前記糖類は、難消化性デキストリン、又はデキストロースであることが好ましい。これにより、低粘度の水系組成物を容易に調製することができる水溶性糖類を提供することができる。
In the water-soluble saccharide according to one aspect of the present invention, 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.
本発明の一態様に係る水溶性糖類において、前記重合性基は、（メタ）アクリロイル基を有することが好ましい。これにより、良好な重合性を有する水溶性糖類を提供することができる。
In the water-soluble saccharide according to one aspect of the present invention, the polymerizable group preferably has a (meth)acryloyl group. This makes it possible to provide water-soluble saccharides with good polymerizability.
本発明の一態様に係る水溶性糖類において、重量平均分子量は、１５０以上、５０，０００以下であることが好ましい。これにより、水溶性糖類を含有する感光性組成物の感光性を高めることができると共に、水溶性糖類を含有する感光性組成物の塗工性を高めることができる。
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. As a result, the photosensitivity of the photosensitive composition containing the water-soluble saccharide can be enhanced, and the coatability of the photosensitive composition containing the water-soluble saccharide can be enhanced.
また、本発明の一態様に係る感光性組成物は、本発明の一態様に係る水溶性糖類と水と光反応開始剤とを含有してなる。これにより、重合反応により硬化物を形成できると共に、水系溶媒を用いた洗浄により現像することができる感光性組成物を提供することができる。
In addition, 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.
本発明の一態様に係る感光性組成物は、架橋剤を含有してなることが好ましい。これにより、架橋剤を介して感光性組成物に含まれる水溶性糖類が有する重合性基同士を架橋できる。
The photosensitive composition according to one aspect of the present invention preferably contains a cross-linking agent. Thereby, the polymerizable groups possessed by the water-soluble saccharides contained in the photosensitive composition can be cross-linked via the cross-linking agent.
本発明の一態様に係る感光性組成物は、界面活性剤を含有してなることが好ましい。これにより、感光性組成物の表面張力を任意に調整することができ、塗工時のレベリング性が向上し、塗工膜の膜厚均一性を向上させることができる。
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.
本発明の一態様に係る感光性組成物は、反応停止剤を含有してなることが好ましい。これにより、過重合を抑制することができる。
The photosensitive composition according to one aspect of the present invention preferably contains a reaction terminator. Thereby, overpolymerization can be suppressed.
また、本発明の一態様に係る水溶性糖類の製造方法は、有機溶媒の存在下で、糖類と重合性基を有する化合物とを反応させて、前記糖類が備える水酸基の少なくとも一部を前記重合性基に変性させる工程を包含し、前記有機溶媒は、Ｎ－メチルピロリドンであり、前記糖類は、糖鎖の少なくとも一部に１，３－結合を有し、前記化合物は、（メタ）アクリロイル基とハロゲン基とを有する。これにより、重合性基を備える新規な水溶性糖類を製造することができる。
Further, in the method for producing a water-soluble saccharide according to one aspect of the present invention, 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, and the compound is (meth)acryloyl and a halogen group. Thereby, a novel water-soluble saccharide having a polymerizable group can be produced.
本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。
The present invention is not limited to the above-described embodiments, but can be modified in various ways within the scope of the claims, and can be obtained by appropriately combining technical means disclosed in different embodiments. is also included in the technical scope of the present invention.
本発明の一実施例について以下に説明する。本実施例において、種類が異なる糖類を用い、（メタ）アクリル変性された水溶性糖類を製造した。次いで、水溶性糖類を含有する感光性組成物を製造し、当該感光性組成物の感光性を評価した。
An embodiment of the present invention will be described below. In this example, different types of saccharides were used to produce (meth)acrylic-modified water-soluble saccharides. Next, a photosensitive composition containing a water-soluble saccharide was produced, and the photosensitivity of the photosensitive composition was evaluated.
＜主な原料＞
本実施例において、水溶性糖類を製造するための原料として、以下の糖類を用いた。
原料糖類１：難消化性デキストリン（松谷化学工業株式会社製、商品名「ファイバーソル２」）
原料糖類２：難消化性デキストリン（ＲＯＱＵＥＴＴＥ社製、商品名「ＮＵＴＲＩＯＳＥ」、「ＮＵＴＲＩＯＳＥ」は同社の登録商標）
原料糖類３：ポリデキストロース（ダニスコジャパン株式会社製、商品名「ライテスＨＦ」）
原料糖類４：デキストリン（サンエイ糖化株式会社製、商品名「ＮＳＤ５００」）
原料糖類５：高分子量デキストリン（製造方法：温度計、撹拌機、及び冷却管を備えた内容量３Ｌの反応容器にイオン交換水を７５０ｇ、糖類４を７５０ｇ加え、糖類４をイオン交換水に完全に溶解させた。次いで、メタノール１５００ｇをゆっくり加え、溶解させた糖類４の高分子量部分のみを沈殿させる操作を２回行った。次いで、Ｎ－メチルピロリドンを１０００ｇ加え、１０ｍｍＨｇの真空下で４０℃まで昇温させ、系内に残留するメタノールと水を除去し、糖類５を得た。）
原料糖類６：プルラン（株式会社林原製、商品名「プルラン」） <Main raw materials>
In this example, the following saccharides were used as raw materials for producing water-soluble saccharides.
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 a thermometer, a stirrer, and a cooling tube, and completely add saccharide 4 to the ion-exchanged water. Next, 1500 g of methanol was slowly added to precipitate only the high molecular weight portion of the dissolved saccharide 4. Next, 1000 g of N-methylpyrrolidone was added, and the mixture was heated to 40° C. under a vacuum of 10 mmHg. and the residual methanol and water in the system were removed to obtain saccharide 5.)
Raw material saccharide 6: Pullulan (manufactured by Hayashibara Co., Ltd., trade name “Pullulan”)
本実施例において、水溶性糖類を製造するための原料として、以下の糖類を用いた。
原料糖類１：難消化性デキストリン（松谷化学工業株式会社製、商品名「ファイバーソル２」）
原料糖類２：難消化性デキストリン（ＲＯＱＵＥＴＴＥ社製、商品名「ＮＵＴＲＩＯＳＥ」、「ＮＵＴＲＩＯＳＥ」は同社の登録商標）
原料糖類３：ポリデキストロース（ダニスコジャパン株式会社製、商品名「ライテスＨＦ」）
原料糖類４：デキストリン（サンエイ糖化株式会社製、商品名「ＮＳＤ５００」）
原料糖類５：高分子量デキストリン（製造方法：温度計、撹拌機、及び冷却管を備えた内容量３Ｌの反応容器にイオン交換水を７５０ｇ、糖類４を７５０ｇ加え、糖類４をイオン交換水に完全に溶解させた。次いで、メタノール１５００ｇをゆっくり加え、溶解させた糖類４の高分子量部分のみを沈殿させる操作を２回行った。次いで、Ｎ－メチルピロリドンを１０００ｇ加え、１０ｍｍＨｇの真空下で４０℃まで昇温させ、系内に残留するメタノールと水を除去し、糖類５を得た。）
原料糖類６：プルラン（株式会社林原製、商品名「プルラン」） <Main raw materials>
In this example, the following saccharides were used as raw materials for producing water-soluble saccharides.
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 a thermometer, a stirrer, and a cooling tube, and completely add saccharide 4 to the ion-exchanged water. Next, 1500 g of methanol was slowly added to precipitate only the high molecular weight portion of the dissolved saccharide 4. Next, 1000 g of N-methylpyrrolidone was added, and the mixture was heated to 40° C. under a vacuum of 10 mmHg. and the residual methanol and water in the system were removed to obtain saccharide 5.)
Raw material saccharide 6: Pullulan (manufactured by Hayashibara Co., Ltd., trade name “Pullulan”)
＜原料糖類の分析＞
水溶性糖類の原料である原料糖類１～６の分子量分布、及び糖鎖結合様式を分析した。 <Analysis of Raw Sugars>
The molecular weight distribution and sugar chain binding mode ofraw sugars 1 to 6, which are raw materials for water-soluble sugars, were analyzed.
水溶性糖類の原料である原料糖類１～６の分子量分布、及び糖鎖結合様式を分析した。 <Analysis of Raw Sugars>
The molecular weight distribution and sugar chain binding mode of
〔分子量分布分析〕
原料糖類１を無水酢酸で処理し、原料糖類１が備える水酸基をアセチル化した後、ゲル浸透クロマトグラフィ（ＧＰＣ）を用いることにより、原料糖類１の分子量分布を分析し、数平均分子量Ｍｎ、及び重量平均分子量Ｍｗを算出した。ＧＰＣの条件は、以下の通りであった。
ＧＰＣ測定装置：東ソー株式会社製、商品名「ＨＬＣ－８１２０ＧＰＣ」（「ＨＬＣ」は同社の登録商標）
カラム：３つのカラムを連結したカラム（それぞれ東ソー株式会社製、商品名「ＴＳＫｇｅｌ Ｇ３０００ＨＨＲ」、商品名「ＴＳＫｇｅｌ Ｇ２０００ＨＨＲ」、商品名「ＴＳＫｇｅｌ Ｇ２０００ＨＨＲ」、「ＴＳＫｇｅｌ」は同社の登録商標） [Molecular weight distribution analysis]
After treating theraw sugar 1 with acetic anhydride to acetylate the hydroxyl groups of the raw sugar 1, the molecular weight distribution of the raw sugar 1 was analyzed by gel permeation chromatography (GPC), and the number average molecular weight Mn and the weight The average molecular weight Mw was calculated. The conditions of GPC were as follows.
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)
原料糖類１を無水酢酸で処理し、原料糖類１が備える水酸基をアセチル化した後、ゲル浸透クロマトグラフィ（ＧＰＣ）を用いることにより、原料糖類１の分子量分布を分析し、数平均分子量Ｍｎ、及び重量平均分子量Ｍｗを算出した。ＧＰＣの条件は、以下の通りであった。
ＧＰＣ測定装置：東ソー株式会社製、商品名「ＨＬＣ－８１２０ＧＰＣ」（「ＨＬＣ」は同社の登録商標）
カラム：３つのカラムを連結したカラム（それぞれ東ソー株式会社製、商品名「ＴＳＫｇｅｌ Ｇ３０００ＨＨＲ」、商品名「ＴＳＫｇｅｌ Ｇ２０００ＨＨＲ」、商品名「ＴＳＫｇｅｌ Ｇ２０００ＨＨＲ」、「ＴＳＫｇｅｌ」は同社の登録商標） [Molecular weight distribution analysis]
After treating the
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)
原料糖類２～６についても、原料糖類１と同様に分子量分布を分析した。原料糖類１～６のＧＰＣスペクトルを図１に示す。また、原料糖類１～６の分子量分布の分析結果を表１に示す。
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.
〔糖鎖結合様式分布分析〕
１３Ｃ－ＮＭＲを用いることにより、原料糖類１の糖鎖結合様式分布を分析した。１３Ｃ－ＮＭＲの条件は、以下の通りであった。
ＮＭＲ測定装置：日本電子株式会社製、商品名「ＥＣＺ－５００Ｒ／Ｓ１」
溶媒：重水（Ｄ２Ｏ） [Glycan binding mode distribution analysis]
By using 13 C-NMR, the sugar chain binding mode distribution ofraw sugar 1 was analyzed. The conditions for 13 C-NMR were as follows.
NMR measuring device: manufactured by JEOL Ltd., trade name “ECZ-500R/S1”
Solvent: heavy water ( D2O)
１３Ｃ－ＮＭＲを用いることにより、原料糖類１の糖鎖結合様式分布を分析した。１３Ｃ－ＮＭＲの条件は、以下の通りであった。
ＮＭＲ測定装置：日本電子株式会社製、商品名「ＥＣＺ－５００Ｒ／Ｓ１」
溶媒：重水（Ｄ２Ｏ） [Glycan binding mode distribution analysis]
By using 13 C-NMR, the sugar chain binding mode distribution of
NMR measuring device: manufactured by JEOL Ltd., trade name “ECZ-500R/S1”
Solvent: heavy water ( D2O)
原料糖類２～４、及び６についても、原料糖類１と同様に糖鎖結合様式分布を分析した。原料糖類２～４、及び６の１３Ｃ－ＮＭＲスペクトルを図２に示す。また、原料糖類２～４、及び６の糖鎖結合様式分布の分析結果を表１に示す。なお、原料糖類５は、原料糖類４の高分子量部分であるため、原料糖類４と同一の糖鎖結合様式分布を有すると考えることができる。
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.
＜水溶性糖類の製造＞
〔実施例１〕
温度計、撹拌機、冷却管を備えた内容量１Ｌの反応容器に原料糖類１を１００．０ｇ、Ｎ－メチルピロリドンを１８５．７ｇ加え、１０ｍｍＨｇの真空下で系内温度を４０℃まで昇温させ、系内に残留する水を除去した。次いで、系内温度を１５℃まで冷却した後、系内温度が１５℃を超えないように冷却しながら、アクリル酸クロリドを３３．５ｇ（０．３７ｍｏｌ）、２時間かけて滴下した。滴下後、系内温度１５℃にて、２時間反応を継続させた。 <Production of water-soluble saccharides>
[Example 1]
100.0 g ofraw 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.
〔実施例１〕
温度計、撹拌機、冷却管を備えた内容量１Ｌの反応容器に原料糖類１を１００．０ｇ、Ｎ－メチルピロリドンを１８５．７ｇ加え、１０ｍｍＨｇの真空下で系内温度を４０℃まで昇温させ、系内に残留する水を除去した。次いで、系内温度を１５℃まで冷却した後、系内温度が１５℃を超えないように冷却しながら、アクリル酸クロリドを３３．５ｇ（０．３７ｍｏｌ）、２時間かけて滴下した。滴下後、系内温度１５℃にて、２時間反応を継続させた。 <Production of water-soluble saccharides>
[Example 1]
100.0 g of
次いで、トリエチルアミンを３７．４ｇ（０．３７ｍｏｌ）加えて中和し、中和塩及びＮ－メチルピロリドンを精製除去した。次いで、原料糖類１のアクリル酸変性物の系内含有量が２５質量％になるようにイオン交換水を加え、アクリル基への変性率２０％（理論値）を有する水溶性糖類１の水ワニスを得た。
Then, 37.4 g (0.37 mol) of triethylamine was added for neutralization, and the neutralized salt and N-methylpyrrolidone were purified and removed. Next, ion-exchanged water is added so that the content of the acrylic acid-modified raw material saccharide 1 in the system is 25% by mass, and a water varnish of water-soluble saccharide 1 having a modification rate to acrylic groups of 20% (theoretical value) is obtained. got
〔実施例２〕
アクリル酸クロリドを３３．５ｇ（０．３７ｍｏｌ）の代わりにアクリル酸クロリドを５０．４ｇ（０．５６ｍｏｌ）用いたこと、トリエチルアミンを３７．４ｇ（０．３７ｍｏｌ）の代わりにトリエチルアミンを５６．２ｇ（０．５６ｍｏｌ）用いたことを除いて、実施例１と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類２の水ワニスを得た。 [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.
アクリル酸クロリドを３３．５ｇ（０．３７ｍｏｌ）の代わりにアクリル酸クロリドを５０．４ｇ（０．５６ｍｏｌ）用いたこと、トリエチルアミンを３７．４ｇ（０．３７ｍｏｌ）の代わりにトリエチルアミンを５６．２ｇ（０．５６ｍｏｌ）用いたことを除いて、実施例１と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類２の水ワニスを得た。 [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.
〔実施例３〕
原料糖類１を１００．０ｇの代わりに糖類２を１００．０ｇ用いたことを除いて、実施例２と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類３の水ワニスを得た。 [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.
原料糖類１を１００．０ｇの代わりに糖類２を１００．０ｇ用いたことを除いて、実施例２と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類３の水ワニスを得た。 [Example 3]
Water-
〔実施例４〕
原料糖類１を１００．０ｇの代わりに糖類３を１００．０ｇ用いたことを除いて、実施例２と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類４の水ワニスを得た。 [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 ofsaccharide 3 was used instead of 100.0 g of raw saccharide 1. Got a water varnish.
原料糖類１を１００．０ｇの代わりに糖類３を１００．０ｇ用いたことを除いて、実施例２と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類４の水ワニスを得た。 [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
〔比較例１〕
原料糖類１を１００．０ｇの代わりに糖類４を１００．０ｇ用いたことを除いて、実施例２と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類Ｃ１の水ワニスを得た。 [Comparative Example 1]
Water-soluble saccharide C1 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 ofraw saccharide 1 was replaced with 100.0 g of saccharide 4. Got a water varnish.
原料糖類１を１００．０ｇの代わりに糖類４を１００．０ｇ用いたことを除いて、実施例２と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類Ｃ１の水ワニスを得た。 [Comparative Example 1]
Water-soluble saccharide C1 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
〔比較例２〕
原料糖類１を１００．０ｇの代わりに糖類５を１００．０ｇ用いたことを除いて、実施例２と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類Ｃ２の水ワニスを得た。 [Comparative Example 2]
Water-soluble saccharide C2 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 ofraw saccharide 1 was replaced with 100.0 g of saccharide 5. Got a water varnish.
原料糖類１を１００．０ｇの代わりに糖類５を１００．０ｇ用いたことを除いて、実施例２と同様にして、アクリル基への変性率３０％（理論値）を有する水溶性糖類Ｃ２の水ワニスを得た。 [Comparative Example 2]
Water-soluble saccharide C2 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
〔比較例３〕
温度計、撹拌機、冷却管を備えた内容量２Ｌの反応容器に原料糖類６を１００．０ｇ、Ｎ－メチルピロリドンを９００．０ｇ加え、１０ｍｍＨｇの真空下で系内温度を４０℃まで昇温させ、系内に残留する水を除去した。次いで、系内温度を１５℃まで冷却した後、系内温度が１５℃を超えないように冷却しながら、アクリル酸クロリドを５０．４ｇ（０．５６ｍｏｌ）、２時間かけて滴下した。滴下後、系内温度１５℃にて、２時間反応を継続させた。 [Comparative Example 3]
100.0 g of raw sugar 6 and 900.0 g of N-methylpyrrolidone are added to a 2 L reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, and the temperature inside the system is raised to 40° C. under a vacuum of 10 mmHg. to remove water remaining in the system. Then, after cooling the system temperature to 15°C, 50.4 g (0.56 mol) of acrylic acid chloride was added dropwise over 2 hours while cooling the system temperature so that the system temperature did not exceed 15°C. After dropping, the reaction was continued for 2 hours at a system temperature of 15°C.
温度計、撹拌機、冷却管を備えた内容量２Ｌの反応容器に原料糖類６を１００．０ｇ、Ｎ－メチルピロリドンを９００．０ｇ加え、１０ｍｍＨｇの真空下で系内温度を４０℃まで昇温させ、系内に残留する水を除去した。次いで、系内温度を１５℃まで冷却した後、系内温度が１５℃を超えないように冷却しながら、アクリル酸クロリドを５０．４ｇ（０．５６ｍｏｌ）、２時間かけて滴下した。滴下後、系内温度１５℃にて、２時間反応を継続させた。 [Comparative Example 3]
100.0 g of raw sugar 6 and 900.0 g of N-methylpyrrolidone are added to a 2 L reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, and the temperature inside the system is raised to 40° C. under a vacuum of 10 mmHg. to remove water remaining in the system. Then, after cooling the system temperature to 15°C, 50.4 g (0.56 mol) of acrylic acid chloride was added dropwise over 2 hours while cooling the system temperature so that the system temperature did not exceed 15°C. After dropping, the reaction was continued for 2 hours at a system temperature of 15°C.
次いで、トリエチルアミンを５６．２ｇ（０．５６ｍｏｌ）加えて中和し、中和塩及びＮ－メチルピロリドンを精製除去した。次いで、原料糖類６のアクリル酸変性物の系内含有量が１０質量％になるようにイオン交換水を加え、アクリル基への変性率３０％（理論値）を有する水溶性糖類Ｃ３の水ワニスを得た。なお、水溶性糖類Ｃ３は、粘度が高すぎたため、水溶性糖類１～４、及びＣ１～Ｃ２と同様にアクリル酸変性物の系内含有量が２５質量％になるように製造することができなかった。
Then, 56.2 g (0.56 mol) of triethylamine was added for neutralization, and the neutralized salt and N-methylpyrrolidone were purified and removed. Next, ion-exchanged water is added so that the content of the acrylic acid-modified raw material saccharide 6 in the system is 10% by mass, and a water varnish of water-soluble saccharide C3 having a modification rate to acrylic groups of 30% (theoretical value). got Since the water-soluble saccharide C3 has too high viscosity, it can be produced so that the content of the acrylic acid-modified product in the system is 25% by mass, as with the water-soluble saccharides 1 to 4 and C1 to C2. I didn't.
＜水溶性糖類の分析＞
水溶性糖類１～４、及びＣ１～Ｃ３のアクリル基への変性率、及びその水ワニスの粘度を分析した。 <Analysis of water-soluble saccharides>
The water-soluble saccharides 1-4 and C1-C3 were analyzed for the modification rate to acrylic groups and the viscosity of the water varnish.
水溶性糖類１～４、及びＣ１～Ｃ３のアクリル基への変性率、及びその水ワニスの粘度を分析した。 <Analysis of water-soluble saccharides>
The water-soluble saccharides 1-4 and C1-C3 were analyzed for the modification rate to acrylic groups and the viscosity of the water varnish.
〔アクリル基への変性率分析〕
１３Ｃ－ＮＭＲを用いることにより、水溶性糖類１の原料である糖類１が備える水酸基がアクリル基へと変性した割合、すなわちアクリル基への変性率を分析した。１３Ｃ－ＮＭＲの条件は、〔糖鎖結合様式分布分析〕の項目と同様であった。 [Modification rate analysis to acrylic group]
By using 13 C-NMR, the rate at which the hydroxyl groups of the raw material of the water-soluble saccharide 1 were modified into acrylic groups, that is, the rate of modification into acrylic groups was analyzed. The conditions for 13 C-NMR were the same as in [Analysis of glycan binding mode distribution].
１３Ｃ－ＮＭＲを用いることにより、水溶性糖類１の原料である糖類１が備える水酸基がアクリル基へと変性した割合、すなわちアクリル基への変性率を分析した。１３Ｃ－ＮＭＲの条件は、〔糖鎖結合様式分布分析〕の項目と同様であった。 [Modification rate analysis to acrylic group]
By using 13 C-NMR, the rate at which the hydroxyl groups of the raw material of the water-
水溶性糖類２～４、及びＣ１～Ｃ３についても、水溶性糖類１と同様に、アクリル基への変性率を分析した。水溶性糖類１～４、及びＣ１～Ｃ３のアクリル基への変性率の分析結果を表２に示す。
For water-soluble saccharides 2 to 4 and C1 to C3, the rate of modification to acrylic groups was analyzed in the same manner as water-soluble saccharide 1. Table 2 shows the analysis results of the rate of modification of water-soluble saccharides 1 to 4 and C1 to C3 to acryl groups.
〔粘度分析〕
Ｅ型粘度計を用いることにより、水溶性糖類１の水ワニスの粘度を測定した。測定条件は、以下の通りであった。
測定温度：２５℃ [Viscosity analysis]
The viscosity of the water varnish of water-soluble sugar 1 was measured by using an E-type viscometer. The measurement conditions were as follows.
Measurement temperature: 25°C
Ｅ型粘度計を用いることにより、水溶性糖類１の水ワニスの粘度を測定した。測定条件は、以下の通りであった。
測定温度：２５℃ [Viscosity analysis]
The viscosity of the water varnish of water-
Measurement temperature: 25°C
水溶性糖類２～４、及びＣ１～Ｃ３の水ワニスについても、水溶性糖類１と同様に、粘度を分析した。水溶性糖類１～４、及びＣ１～Ｃ３の水ワニスの粘度の分析結果を表２に示す。
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.
＜感光性組成物の製造＞
〔製造例１～３〕
水溶性糖類１の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製、商品名「Ｏｍｎｉｒａｄ ２９５９」）を加え、感光性組成物１～３を得た。 <Production of photosensitive composition>
[Production Examples 1 to 3]
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. In addition, photosensitive compositions 1-3 were obtained.
〔製造例１～３〕
水溶性糖類１の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製、商品名「Ｏｍｎｉｒａｄ ２９５９」）を加え、感光性組成物１～３を得た。 <Production of photosensitive composition>
[Production Examples 1 to 3]
Photoinitiator 1 (manufactured by IGM Resins B.V., trade name "Omnirad 2959") was added to the water varnish of water-
〔製造例４～６〕
水溶性糖類２の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物４～６を得た。 [Production Examples 4 to 6]
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.
水溶性糖類２の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物４～６を得た。 [Production Examples 4 to 6]
〔製造例７～９〕
水溶性糖類３の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物７～９を得た。 [Production Examples 7 to 9]
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.
水溶性糖類３の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物７～９を得た。 [Production Examples 7 to 9]
〔製造例１０～１２〕
水溶性糖類４の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物１０～１２を得た。 [Production Examples 10 to 12]
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.
水溶性糖類４の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物１０～１２を得た。 [Production Examples 10 to 12]
〔比較製造例１～３〕
水溶性糖類Ｃ１の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物Ｃ１～Ｃ３を得た。 [Comparative Production Examples 1 to 3]
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.
水溶性糖類Ｃ１の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物Ｃ１～Ｃ３を得た。 [Comparative Production Examples 1 to 3]
〔比較製造例４～６〕
水溶性糖類Ｃ２の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物Ｃ４～Ｃ６を得た。 [Comparative Production Examples 4 to 6]
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.
水溶性糖類Ｃ２の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物Ｃ４～Ｃ６を得た。 [Comparative Production Examples 4 to 6]
〔比較製造例７～９〕
水溶性糖類Ｃ３の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物Ｃ７～Ｃ９を得た。 [Comparative Production Examples 7 to 9]
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.
水溶性糖類Ｃ３の水ワニスに対して、それぞれ１、２、又は３質量％の濃度になるように、光反応開始剤１を加え、感光性組成物Ｃ７～Ｃ９を得た。 [Comparative Production Examples 7 to 9]
＜感光性組成物の感光性分析＞
シリコンウェハー上に感光性組成物４を３ｍＬ滴下し、スピナー（東京エレクトロン株式会社製、商品名「ＣＬＥＡＮ ＴＲＡＣＫ ＡＣＴ８」）を用いて、３０００ｒｐｍで３０秒間スピンコートした。次いで、８０℃にて６０秒間焼成することにより、水を揮発除去した。次いで、マスク密着露光装置（リソテックジャパン株式会社製、商品名「ＬＴＣＥＴ－５００」）と感度確認用マスク（Ｔａｉｙｏ－ｉｎｋ Ｃｏｒｐｏｒａｔｉｏｎ：５ｉｎｃｈ Ｍｕｌｔｉ－Ｔｒａｎｓｍｉｓｓｉｏｎ Ｍａｓｋ）とを用いて、露光量を調整しながら紫外線を照射し、感光性組成物１を硬化させた。次いで、硬化膜を現像液である純水に９０秒間浸漬し、硬化膜における未硬化部分を除去、すなわち現像を行った。現像前後における硬化膜の膜厚を測定し、下記式（５）に基づいて、残膜率を算出した。残膜率が高いほど、感光性組成物が硬化しやすく、感光性が高いと考えることができる。
残膜率（％）＝現像後の硬化膜の膜厚／現像前の硬化膜の膜厚×１００ 式（５） <Photosensitivity analysis of photosensitive composition>
3 mL of the photosensitive composition 4 was dropped onto a silicon wafer, and spin-coated at 3000 rpm for 30 seconds using a spinner (manufactured by Tokyo Electron Ltd., trade name "CLEAN TRACK ACT8"). Then, water was volatilized and removed by baking at 80° C. for 60 seconds. Next, using a mask contact exposure apparatus (manufactured by Litho Tech Japan, trade name “LTCET-500”) and a sensitivity confirmation mask (Taiyo-ink Corporation: 5 inch Multi-Transmission Mask), while adjusting the exposure amount Thephotosensitive composition 1 was cured by irradiation with ultraviolet rays. Next, 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)
シリコンウェハー上に感光性組成物４を３ｍＬ滴下し、スピナー（東京エレクトロン株式会社製、商品名「ＣＬＥＡＮ ＴＲＡＣＫ ＡＣＴ８」）を用いて、３０００ｒｐｍで３０秒間スピンコートした。次いで、８０℃にて６０秒間焼成することにより、水を揮発除去した。次いで、マスク密着露光装置（リソテックジャパン株式会社製、商品名「ＬＴＣＥＴ－５００」）と感度確認用マスク（Ｔａｉｙｏ－ｉｎｋ Ｃｏｒｐｏｒａｔｉｏｎ：５ｉｎｃｈ Ｍｕｌｔｉ－Ｔｒａｎｓｍｉｓｓｉｏｎ Ｍａｓｋ）とを用いて、露光量を調整しながら紫外線を照射し、感光性組成物１を硬化させた。次いで、硬化膜を現像液である純水に９０秒間浸漬し、硬化膜における未硬化部分を除去、すなわち現像を行った。現像前後における硬化膜の膜厚を測定し、下記式（５）に基づいて、残膜率を算出した。残膜率が高いほど、感光性組成物が硬化しやすく、感光性が高いと考えることができる。
残膜率（％）＝現像後の硬化膜の膜厚／現像前の硬化膜の膜厚×１００ 式（５） <Photosensitivity analysis of photosensitive composition>
3 mL of the photosensitive composition 4 was dropped onto a silicon wafer, and spin-coated at 3000 rpm for 30 seconds using a spinner (manufactured by Tokyo Electron Ltd., trade name "CLEAN TRACK ACT8"). Then, water was volatilized and removed by baking at 80° C. for 60 seconds. Next, using a mask contact exposure apparatus (manufactured by Litho Tech Japan, trade name “LTCET-500”) and a sensitivity confirmation mask (Taiyo-ink Corporation: 5 inch Multi-Transmission Mask), while adjusting the exposure amount The
Remaining film ratio (%) = film thickness of cured film after development/film thickness of cured film before development x 100 Formula (5)
感光性組成物５～１２、及びＣ１～Ｃ９についても、感光性組成物４と同様に、残膜率を分析した。感光性組成物４～１２、及びＣ１～Ｃ９の残膜率の分析結果を図３に示す。また、感光性組成物４～１２、及びＣ１～Ｃ９について、残膜率９０％を達成するための露光量を表３に示す。
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.
＜議論＞
表１及び２に示すように、糖鎖に１，３－結合を有する原料糖類１～３を原料として用いて製造された水溶性糖類１～４は、粘度が低いため、水ワニスの固形分を上げることが容易である。また、水溶性糖類２～４それぞれに対して、３質量％の濃度になるように光反応開始剤１を加えて製造した感光性組成物６、９及び１２は、３００ｍＪ／ｃｍ２～４００ｍＪ／ｃｍ２の露光量で残膜率９０％以上を示し、良好な感光性を有していた。 <Discussion>
As shown in Tables 1 and 2, the water-soluble saccharides 1 to 4 produced using the raw material saccharides 1 to 3 having 1,3-bonds in the sugar chain as raw materials have low viscosity, so the solid content of the water varnish is easy to raise. Photosensitive compositions 6, 9 and 12, which were produced by adding photoreaction initiator 1 to a concentration of 3% by mass with respect to each of water-soluble saccharides 2 to 4, were 300 mJ/cm 2 to 400 mJ/cm 2 . It showed a residual film rate of 90% or more at an exposure amount of cm 2 and had good photosensitivity.
表１及び２に示すように、糖鎖に１，３－結合を有する原料糖類１～３を原料として用いて製造された水溶性糖類１～４は、粘度が低いため、水ワニスの固形分を上げることが容易である。また、水溶性糖類２～４それぞれに対して、３質量％の濃度になるように光反応開始剤１を加えて製造した感光性組成物６、９及び１２は、３００ｍＪ／ｃｍ２～４００ｍＪ／ｃｍ２の露光量で残膜率９０％以上を示し、良好な感光性を有していた。 <Discussion>
As shown in Tables 1 and 2, the water-
原料糖類４を原料として用いて製造された水溶性糖類Ｃ１は、粘度が低いため、水ワニスの固形分を上げることが容易である。しかし、水溶性糖類Ｃ１に光反応開始剤１を加えて製造した感光性組成物Ｃ３は、残膜率９０％以上を達成するためには約１０２０ｍＪ／ｃｍ２の露光量が必要であり、感光性が低かった。
Since the water-soluble saccharide C1 produced using the raw material saccharide 4 as a raw material has a low viscosity, it is easy to increase the solid content of the water varnish. However, 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.
原料糖類５を原料として用いて製造された水溶性糖類Ｃ２は、粘度が低いため、水ワニスの固形分を上げることが容易である。しかし、水溶性糖類Ｃ２に光反応開始剤１を加えて製造した感光性組成物Ｃ６は、残膜率９０％以上を達成するためには約６６０ｍＪ／ｃｍ２の露光量が必要であり、感光性組成物Ｃ５よりは良好であるが、感光性が低かった。また、水溶性糖類Ｃ２の製造工程は、原料糖類５を製造するために原料糖類４の低分子量部分を除去する工程を含むため、多くの廃液を発生させ、歩留まりも低かった。
Since 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. However, 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. In addition, since 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.
原料糖類６を原料として用いて製造された感光性組成物Ｃ９は、良好な感光性を有していたが、製造過程で生じた水溶性糖類Ｃ３は、粘度が高く、水ワニスの固形分を上げることができないため、膜厚調整が困難であると考えられる。
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.
本発明に係る水溶性糖類は、例えば、フォトレジスト材料、及び光硬化型インキ等といった感光性材料として利用することができる。
The water-soluble saccharides according to the present invention can be used as photosensitive materials such as photoresist materials and photocurable inks.
Claims (10)
- 糖類が備える糖鎖の少なくとも一部に１，３－結合を有し、当該糖鎖が備える水酸基の少なくとも一部が重合性基に変性されてなる、水溶性糖類。 A water-soluble saccharide that has a 1,3-bond in at least part of the sugar chain of the saccharide and at least part of the hydroxyl group of the sugar chain is modified with a polymerizable group.
- 前記糖類が備える水酸基の全量を１００ｍｏｌ％として、当該水酸基のうちの１０ｍｏｌ％以上、６０ｍｏｌ％以下が重合性基に変性されてなる、請求項１に記載の水溶性糖類。 The water-soluble saccharide according to claim 1, wherein 10 mol% or more and 60 mol% or less of the hydroxyl groups are modified with polymerizable groups, assuming that the total amount of hydroxyl groups provided in the saccharide is 100 mol%.
- 前記糖類は、難消化性デキストリン、又はデキストロースである、請求項１又は２に記載の水溶性糖類。 The water-soluble saccharide according to claim 1 or 2, wherein the saccharide is indigestible dextrin or dextrose.
- 前記重合性基は、（メタ）アクリロイル基を有する、請求項１～３の何れか一項に記載の水溶性糖類。 The water-soluble saccharide according to any one of claims 1 to 3, wherein the polymerizable group has a (meth)acryloyl group.
- 重量平均分子量は、１５０以上、５０，０００以下である、請求項１～４の何れか一項に記載の水溶性糖類。 The water-soluble saccharide according to any one of claims 1 to 4, which has a weight average molecular weight of 150 or more and 50,000 or less.
- 請求項１～５の何れか一項に記載の水溶性糖類と水と光反応開始剤とを含有してなる、感光性組成物。 A photosensitive composition comprising the water-soluble saccharide according to any one of claims 1 to 5, water, and a photoreaction initiator.
- 架橋剤を含有してなる、請求項６に記載の感光性組成物。 The photosensitive composition according to claim 6, comprising a cross-linking agent.
- 界面活性剤を含有してなる、請求項６又は７に記載の感光性組成物。 The photosensitive composition according to claim 6 or 7, comprising a surfactant.
- 反応停止剤を含有してなる、請求項６～８の何れか一項に記載の感光性組成物。 The photosensitive composition according to any one of claims 6 to 8, comprising a reaction terminator.
- 有機溶媒の存在下で、糖類と重合性基を有する化合物とを反応させて、前記糖類が備える水酸基の少なくとも一部を前記重合性基に変性させる工程を包含し、
前記有機溶媒は、Ｎ－メチルピロリドンであり、
前記糖類は、糖鎖の少なくとも一部に１，３－結合を有し、
前記化合物は、（メタ）アクリロイル基とハロゲン基とを有する、
水溶性糖類の製造方法。 A step of 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 to the polymerizable group;
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,
A method for producing a water-soluble saccharide.
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| JP2021058755A JP2022155318A (en) | 2021-03-30 | 2021-03-30 | Water-soluble sugar, photosensitive composition, and method for producing water-soluble sugar |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228640A (en) * | 1998-02-13 | 1999-08-24 | Goo Chem Ind Co Ltd | Cellulose derivative compound and photosensitive composition and photoresist ink |
| JP2001337458A (en) * | 2000-05-26 | 2001-12-07 | Japan Science & Technology Corp | Photoresist material |
| WO2020000788A1 (en) * | 2018-06-26 | 2020-01-02 | 爱美中科硒科技（天津）有限公司 | Esterified selenium polysaccharide and preparation method and use therefor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228640A (en) * | 1998-02-13 | 1999-08-24 | Goo Chem Ind Co Ltd | Cellulose derivative compound and photosensitive composition and photoresist ink |
| JP2001337458A (en) * | 2000-05-26 | 2001-12-07 | Japan Science & Technology Corp | Photoresist material |
| WO2020000788A1 (en) * | 2018-06-26 | 2020-01-02 | 爱美中科硒科技（天津）有限公司 | Esterified selenium polysaccharide and preparation method and use therefor |
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