Water-soluble saccharides, photosensitive compositions, and methods for producing water-soluble saccharides

Abstract

To provide a novel water-soluble sugar having a polymerizable group and related techniques.SOLUTION: A water-soluble sugar according to one aspect of the present invention has 1,3-bonds in at least some sugar chains included in the sugar, and at least some hydroxyl groups included in the sugar chains are modified by polymerizable groups.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to water-soluble saccharides, a photosensitive composition, and a method for producing water-soluble saccharides.

Background Art

[0002] For example, Patent Document 1 describes an unsaturated group-containing resin selected from an unsaturated group-containing polyimide, an unsaturated group-containing polyimide precursor, a carboxylic acid-modified unsaturated group-containing polysiloxane, an unsaturated group-containing polybenzoxazole, an unsaturated group-containing polybenzoxazole precursor, an unsaturated group-containing polysiloxane, a polycyclic side chain-containing aromatic resin, an acrylic resin, and a carboxylic acid-modified epoxy resin, and a composition containing the unsaturated group-containing resin.

[0003] Further, for example, Patent Document 2 describes a cationically polymerizable compound such as a cyclic ether (epoxide, oxetane, etc.), an ethylenically unsaturated compound (vinyl ether, styrene, etc.), a bicyclic orthoester, a spiro orthocarbonate, and a spiro orthoester, an alkali-soluble resin having a phenolic hydroxyl group, and a composition containing these cationically polymerizable compounds and the alkali-soluble resin.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Patent Documents 1 and 2 disclose nothing about a material having a polymerizable group produced using saccharides as a main material.

[0006] The inventors have found that by modifying saccharides with polymerizable groups, novel water-soluble saccharides having both polymerizability and water solubility can be obtained, and that such water-soluble saccharides are extremely useful as novel materials. Furthermore, through extensive research, the inventors have found that the performance of such water-soluble saccharides is further improved by having specific bonds in the sugar chain, and have thus completed the present invention.

[0007] That is, one aspect of the present invention aims to provide novel water-soluble saccharides having polymerizable groups and related technologies.

Means for Solving the Problems

[0008] In order to solve the above problems, the water-soluble saccharide according to one aspect of the present invention has a 1,3-bond in at least a part of the sugar chain included in the saccharide, and at least a part of the hydroxyl groups included in the sugar chain is modified with a polymerizable group.

Effects of the Invention

[0009] According to one aspect of the present invention, it is possible to provide novel water-soluble saccharides having polymerizable groups and related technologies.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0011] The present invention will be described in more detail below.

[0012] <Terms> As used herein, a numerical range indicated using "~" indicates a range that includes the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

[0013] As used herein, when simply described as "saccharides", unless otherwise specified, it means "saccharides" which are raw materials of "water-soluble saccharides" according to one aspect of the present invention. The "saccharides" conceptually includes carbohydrates in the field of food science.

[0014] Also, as used herein, the term "water-soluble saccharide" means a "saccharide" in which at least a part of the hydroxyl groups of the saccharide is modified to a polymerizable group and which has water solubility. That is, as used herein, the term "water-soluble saccharide" is described as an abbreviation for "water-soluble saccharide in which at least a part of the hydroxyl groups is modified to a polymerizable group". Similarly, the description of "sugar" modified with "water-soluble" means a specific example of water-soluble saccharide according to one aspect of the present invention unless otherwise specified.

[0015] Also, as used herein, the term "(meth)acryl" 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". Also, as used herein, the term "(meth)acryloyl group" means one or both of "acryloyl group" and "methacryloyl group".

[0016] 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 compound contained in the composition generates radicals or protons (H + ) by absorbing the actinic rays, and due to these radicals or protons (H + ), the compound contained in the composition exhibits chemical reactions such as polymerization or discoloration.

[0017] The inventors of the present invention 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 that these water-soluble saccharides are extremely useful as novel photosensitive materials. Furthermore, the inventors of the present invention have conducted extensive research and found that: (1) when the molecular weight of a water-soluble saccharide is increased to enhance its photosensitivity, the viscosity of the photosensitive composition containing the water-soluble saccharide increases, making it difficult to coat and microfabricate the photosensitive composition; (2) when the solid content of the photosensitive composition is decreased to reduce its viscosity, it becomes difficult to form a thick film when coating. In general, increasing the amount of photosensitizer added to enhance the photosensitivity of a photosensitive composition leads to an increase in manufacturing costs. The inventors of the present invention have further conducted research and found that by having a 1,3-bond in the sugar chain of a water-soluble saccharide, a water-soluble saccharide having good photosensitivity can be realized without increasing the molecular weight of the water-soluble saccharide and without increasing the amount of photosensitizer added.

[0018] <Water-soluble saccharide> The water-soluble saccharide according to one aspect of the present invention has a 1,3-bond in at least a part of the sugar chain of the saccharide, and at least a part of the hydroxyl groups of the sugar chain is modified with a polymerizable group. According to this configuration, the water-soluble saccharide according to one aspect of the present invention can realize a novel water-soluble saccharide that combines both water solubility derived from the hydroxyl groups of the saccharide and polymerizability derived from the polymerizable group.

[0019] Due to its water solubility, the water-soluble saccharide according to one aspect of the present invention can be used to prepare an aqueous composition containing the water-soluble saccharide using water as a diluent solvent instead of an organic solvent. In addition, after coating the aqueous composition containing the water-soluble saccharide on an object to be coated to form a coating film, the water-soluble saccharide can be polymerized by its polymerizability. Generally, in the coating of a composition, from the viewpoints of improving safety in the coating work environment and reducing the environmental load after solvent discharge, it is required to avoid the use of highly toxic substances such as alkalis and dangerous substances such as organic solvents. From these viewpoints, since the water-soluble saccharide according to one aspect of the present invention can use water as a diluent solvent, it can be suitably used as an alternative to a polymerizable composition.

[0020] The solubility of the water-soluble saccharide according to one embodiment of the present invention in water at 20 °C is, although not limited, 50 g / L or more, preferably 200 g / L or more, from the viewpoint of facilitating dilution with water. 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 preferably prepared. Note that a saccharide in which a hydroxyl group included in the saccharide is modified into a polymerizable group and has a solubility in water at 20 °C of less than 50 g / L is described as a "poorly water-soluble saccharide" in the present specification and is distinguished from the "water-soluble saccharide" according to one embodiment of the present invention.

[0021] The weight average molecular weight (Mw) of the water-soluble saccharide according to one embodiment of the present invention is, although not limited, 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 rate of the water-soluble saccharide in the photosensitive composition can be increased. Further, 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 enhanced. In particular, when the weight average molecular weight of the water-soluble saccharide is 10,000 or less, a water-soluble saccharide having a high planarization rate and filling property can be realized. Note that, as used in the present specification, the weight average molecular weight (Mw) of the water-soluble saccharide means a value in terms of standard polystyrene measured by gel permeation chromatography (GPC).

[0022] 〔Polymerizable Group〕 In the water-soluble saccharide according to one embodiment of the present invention, at least a part of the hydroxyl groups included in the sugar chain is modified into a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. Examples of the radical polymerizable group include functional groups having an unsaturated double bond such as a vinyl ester group and a (meth)acryloyl group. Examples of the cationic polymerizable group include an epoxy group and an oxetane group.

[0023] In one aspect of the present invention, the polymerizable group may, for example, have a structure represented by the following formula (1).

[0024]

Chemical formula

[0025] In formula (1), R 1 is a hydrogen or 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.

[0026] Further, in one aspect of the present invention, the polymerizable group may, for example, have a structure of the following formula (2) or formula (3).

[0027]

Chemical formula

[0028] In formulas (2) and (3), R a has the structure shown in formula (1), R 2 has a structure represented by the following formula (4). Further, in formula (3), R 3 are each independently a hydrogen or an alkyl group having 1 to 10 carbon atoms, and R 3a are each independently an alkylene group having 1 to 10 carbon atoms, and m is an integer of 0 to 2. It should be noted that the polymerizable groups represented by formulas (2) and (3) are both covalently bonded to the saccharide via an oxygen atom, just like the polymerizable group represented by formula (1).

[0029]

Chemical formula

[0030] In formula (4), n is an integer of 2 to 10, preferably 2 or 3. p is an integer of 1 to 6, preferably 1 or 2. That is, R 2It may be an oxyalkylene group or a polyoxyalkylene group. The alkylene chain in the oxyalkylene group may be linear or branched.

[0031] In addition, the polymerizable groups represented by the above formulas (1) to (3) may be covalently bonded to the saccharide via R having the structure represented by the above formula (4). 2 In the polymerizable group represented by the above formula (3), R 3a -O- and R a may be covalently bonded via R having the structure represented by the above formula (4). 2

[0032] The water-soluble saccharide according to one aspect of the present invention may contain one or more selected from the group consisting of polymerizable groups having the structures represented by formulas (1) to (3) in its molecule. In particular, in one aspect of the present invention, the polymerizable group included in the water-soluble saccharide preferably has a (meth)acryloyl group having the structure represented by formula (1). Thereby, a water-soluble saccharide having good polymerizability can be realized.

[0033] In the water-soluble saccharide according to one aspect of the present invention, assuming that the total amount of the hydroxyl groups included in the saccharide as the raw material is 100 mol%, the ratio of the hydroxyl groups that have been modified into polymerizable groups, that is, the modification rate, is preferably 10 mol% or more, more preferably 20 mol% or more. Thereby, since the molecules of the water-soluble saccharide can be preferably polymerized via the polymerizable group, a water-soluble saccharide having good polymerizability can be realized. Further, in the water-soluble saccharide, the modification rate is preferably 60 mol% or less, more preferably 50 mol% or less. Thereby, since the unmodified hydroxyl groups are present in the water-soluble saccharide in a suitable proportion, a water-soluble saccharide having good water solubility can be realized. In the water-soluble saccharide, assuming that the total amount of the hydroxyl groups included in the saccharide as the raw material is 100 mol%, the ratio of the hydroxyl groups that have been modified into polymerizable groups, that is, the modification rate, 13 can be determined by 13C-NMR (nuclear magnetic resonance spectroscopy).

[0034] 〔Sugar chain binding mode〕 The water-soluble saccharide according to one aspect of the present invention has a 1,3-bond in at least a part of the sugar chain. As used herein, the term "1,3-bond" means at least one of an α-glycoside bond and a β-glycoside bond formed by a hydroxyl group bonded to the carbon atom at the 1-position of a saccharide and a hydroxyl group bonded to the carbon atom at the 3-position of a saccharide which is a molecule different from the saccharide.

[0035] The inventors have found that by having a 1,3-bond in the sugar chain, it is possible to realize a water-soluble saccharide having good photosensitivity without increasing the molecular weight of the water-soluble saccharide and without increasing the addition amount of the photosensitizer. The inventors consider that this is due to the following factors. A saccharide having a 1,3-bond in the sugar chain is more likely to have a bent structure rather than a straight structure in the sugar chain, and is more likely to have a branched structure rather than a linear structure when polymerized, compared to a saccharide having no 1,3-bond in the sugar chain. Therefore, a saccharide having a 1,3-bond in the sugar chain is more likely to have a larger contact portion between polymerizable groups within and between molecules even before polymerization, compared to a saccharide having no 1,3-bond in the sugar chain. Thus, it is considered that polymerization proceeds rapidly under conditions where the polymerizable groups can be polymerized.

[0036] In the water-soluble saccharide according to one aspect of the present invention, assuming that the total amount of glycoside bonds in the sugar chain is 100 mol%, the amount of 1,3-bonds is preferably 5 mol% or more, more preferably 15 mol% or more. Thereby, the polymerizability of the water-soluble saccharide can be enhanced. Further, assuming that the total amount of glycoside bonds in the sugar chain is 100 mol%, the amount of 1,3-bonds is preferably 70 mol% or less, more preferably 50 mol% or less. Thereby, water solubility can be maintained. In the water-soluble saccharide, assuming that the total amount of glycoside bonds in the sugar chain is 100 mol%, the amount of 1,3-bonds is 13 It can be determined by C-NMR (carbon nuclear magnetic resonance spectroscopy).

[0037] 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 a part of the sugar chain. Thereby, since the branched structure of the water-soluble saccharide can be increased, the polymerizability of the water-soluble saccharide can be further enhanced. In the water-soluble saccharide, assuming that the total amount of glycosidic linkages in the sugar chain is 100 mol%, the total amount of 1,4-linkage and 1,6-linkage is preferably 30 mol% or more, more preferably 50 mol% or more. Thereby, the polymerizability of the water-soluble saccharide can be further enhanced. Also, assuming that the total amount of glycosidic linkages in the sugar chain is 100 mol%, the total amount of 1,4-linkage and 1,6-linkage is preferably 90 mol% or less, more preferably 80 mol% or less. Thereby, water solubility can be maintained.

[0038] In addition, when the water-soluble saccharide has one or both of 1,4-linkage and 1,6-linkage in at least a part of the sugar chain, the 1,4-linkage and 1,6-linkage may form the main chain structure in the sugar chain, and the 1,3-linkage may form the side chain structure in the sugar chain.

[0039] In addition, in the water-soluble saccharide according to one aspect of the present invention, the sugar chain linkage pattern is typically the raw material of the water-soluble saccharide described later and is the same as the saccharide forming the backbone of the water-soluble saccharide. That is, in the water-soluble saccharide, the sugar chain linkage pattern such as 1,3-linkage typically originates from the saccharide that is the raw material of the water-soluble saccharide. However, depending on the processes such as hydrolysis and dehydration condensation that the manufacturing method may include, the water-soluble saccharide may have a sugar chain linkage pattern different from that of the saccharide that is the raw material of the water-soluble saccharide.

[0040] 〔Saccharides〕 In one aspect of the present invention, as a raw material of water-soluble saccharides, the saccharides forming the backbone of the water-soluble saccharides are typically one or more selected from the group consisting of disaccharides, trisaccharides, tetrasaccharides, oligosaccharides, polysaccharides, carbohydrates, and dietary fibers. The saccharides as the raw material of water-soluble saccharides may be one kind or a combination of two or more kinds. The saccharides as the raw material may be artificially synthesized saccharides or natural saccharides. Further, when the saccharides as the raw material are poorly water-soluble, the saccharides obtained by hydrolyzing the saccharides may be used as the raw material. Further, when the saccharides as the raw material are poorly water-soluble, a hydrophilic group such as a hydroxyalkylene group may be introduced into the saccharides, and the saccharides with enhanced water solubility may be used as the raw material.

[0041] The saccharides as the raw material are not limited, but may be saccharides having a solubility in water at 20 °C of 50 g / L or more.

[0042] More specifically, examples of disaccharides include sucrose, lactose, maltose, trehalose, turanose, and cellobiose. Examples of trisaccharides include raffinose, melezitose, and maltotriose. Examples of tetrasaccharides include acarbose and stachyose. Examples of oligosaccharides include fructooligosaccharide, galactooligosaccharide, mannan oligosaccharide, and lactosucrose oligosaccharide. Examples of polysaccharides include polysaccharides such as glycogen, starch, pullulan, dextrin, cyclodextrin, dextrose, cellulose, glucan, fructan, and chitin; polysaccharides in which a part of the hydroxyl groups included in these polysaccharides are modified by a hydrophilic group such as a hydroxyalkylene group; etc. These saccharides only need to have a 1,3-bond introduced into the sugar chain between the saccharides by acid treatment and sintering treatment, or enzyme treatment, or fermentation treatment, etc.

[0043] In one aspect of the present invention, as a raw material of a water-soluble saccharide, the saccharide forming the skeleton of the water-soluble saccharide may have a crosslinked structure derived from a polyhydric alcohol or a polycarboxylic acid in the sugar chain. Examples of the polyhydric alcohol include sugar alcohols such as sorbitol, mannitol, xylitol, maltitol, and erythritol; glycerin; and the like. Examples of the polycarboxylic acid include citric acid and the like.

[0044] In one aspect of the present invention, as a raw material of a water-soluble saccharide, the saccharide forming the skeleton of the water-soluble saccharide is preferably a water-soluble dietary fiber. Since the water-soluble dietary fiber has a plurality of hydroxyl groups in the molecule, it has high water solubility and can be modified into a polymerizable group. In addition, since the water-soluble dietary fiber has many branched structures, it is suitable as a raw material of a water-soluble saccharide having high polymerizability. From the viewpoint of easily preparing an aqueous composition having a low viscosity, the saccharide as a raw material of the water-soluble saccharide is preferably a water-soluble dietary fiber that forms an aqueous solution having a low viscosity among water-soluble dietary fibers. Examples of the water-soluble dietary fiber that forms an aqueous solution having a low viscosity include resistant dextrin, isomalto-dextrin, dextrose, and polydextrose. In one aspect of the present invention, the saccharide as a raw material of the water-soluble saccharide is preferably resistant dextrin or dextrose.

[0045] <Method for producing water-soluble saccharide> One aspect of the present invention relates to a method for producing a water-soluble saccharide. The method for producing a water-soluble saccharide according to one aspect of the present invention includes a step of reacting a saccharide with a compound having a polymerizable group in the presence of an organic solvent to modify at least a part of the hydroxyl groups of the saccharide into polymerizable groups. The organic solvent is N-methylpyrrolidone, the saccharide has a 1,3-bond in at least a 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 groups of the saccharide into polymerizable groups with a compound having the above-described polymerizable group and an electrophilic functional group. Hereinafter, for convenience, the "compound having a polymerizable group and an electrophilic group" will be referred to as a "modifying agent".

[0046] The method for producing a water-soluble saccharide according to one aspect of the present invention includes a step of reacting a saccharide with a compound having a polymerizable group in the presence of an organic solvent to modify at least a part of the hydroxyl groups of the saccharide into polymerizable groups. Hereinafter, for convenience, the step of "reacting a saccharide with a compound having a polymerizable group to modify at least a part of the hydroxyl groups of the saccharide into polymerizable groups" will be referred to as the "modification reaction step".

[0047] 〔Reaction solvent〕 In the modification reaction step, as the organic solvent used as the reaction solvent, an organic solvent that can dissolve the saccharide and the modifier and does not react with the saccharide and the modifier may be appropriately selected. The organic solvent is preferably an aprotic polar solvent. Examples of the aprotic polar solvent include N-methylpyrrolidone (NMP); N,N-dimethylformamide (DMF); dimethyl sulfoxide (DMSO); dimethylacetamide (DMAc); ketones such as acetone and methyl ethyl ketone; and ethers such as dioxane and tetrahydrofuran; and the like.

[0048] In the modification reaction step, when the electrophilic group of the modifier is a halogen group, the organic solvent used as the reaction solvent is preferably NMP. Thereby, 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 affinity with the lone pair of electrons of the nitrogen atom of NMP, and the influence of the hydrochloric acid on the saccharide can be reduced. Therefore, when the reaction solvent is NMP, the modifier can modify the saccharide more efficiently.

[0049] 〔Saccharides〕 In the modification reaction step, as the saccharide as the raw material, a saccharide having a 1,3-bond in at least a part of the sugar chain can be appropriately selected and used. Specific examples of such saccharides include, but are not limited to, the saccharides described above.

[0050] In the modification reaction step, the saccharide as the raw material may be a saccharide that has been previously modified by operations such as enzymatic decomposition and acid treatment. Further, the saccharide as the raw material may be a saccharide that has been purified and fractionated by operations such as reprecipitation in advance.

[0051] 〔Denaturing agent〕 In the modification reaction step, the denaturing agent that is the source of the polymerizable group is a compound having a polymerizable group and an electrophilic group.

[0052] As the polymerizable group of the denaturing agent, the above-described polymerizable groups can be preferably used. Among them, the polymerizable group of the denaturing agent is preferably a (meth)acryloyl group.

[0053] As the electrophilic group of the denaturing agent, an electrophilic group generally used in the reaction mechanism in which the modification reaction proceeds can be used. Examples of the electrophilic group of the denaturing agent include: halogen groups such as chlorine, bromine, and iodine; isocyanate groups; acid anhydride groups; and the like. Among them, the electrophilic group of the denaturing agent is preferably a halogen group.

[0054] More specifically, examples of the denaturing agent used in the modification reaction step include (meth)acryloyl chloride, (meth)acrylic anhydride, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, and 2-isocyanatoethyl (meth)acrylate. Among them, the denaturing agent is preferably (meth)acryloyl chloride or (meth)acrylic anhydride. Thereby, the modification reaction can proceed more efficiently.

[0055] 〔Reaction conditions〕 In the modification reaction step, the temperature inside the system is preferably -10°C or higher, more preferably 0°C or higher. Thereby, temperature control in the modification reaction can be easily performed. Further, in the modification reaction step, the temperature inside 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 polymerizable group of the denaturing agent and the water-soluble saccharide generated by the modification of the saccharide.

[0056] In the modification reaction step, the modification reaction may be carried out in an air atmosphere or an inert gas atmosphere. The modification reaction is preferably carried out in an inert gas atmosphere, although it is not limited thereto. Examples of the inert gas include nitrogen gas, argon gas, and the like.

[0057] In the modification reaction step, the mixing weight ratio of the water-soluble saccharide and the modifier in the system may be appropriately selected according to the amount of hydroxyl groups possessed by the saccharide and the desired modification rate.

[0058] In the modification reaction step, after the reaction is completed, an amine may be added to the system to neutralize the acid generated as a by-product of the modification reaction. Examples of the amine include tertiary amines such as triethylamine.

[0059] <Photosensitive composition> One aspect of the present invention relates to a photosensitive composition. The photosensitive composition according to one aspect of the present invention comprises a water-soluble saccharide, water, and a photoinitiator according to one aspect of the present invention. The photosensitive composition according to one aspect of the present invention can form an aqueous composition derived from the hydroxyl groups possessed by the water-soluble saccharide and has polymerizability derived from the polymerizable groups possessed by the water-soluble saccharide. Therefore, the photosensitive composition can form a cured product by a polymerization reaction and can be developed by washing with an aqueous solvent.

[0060] 〔Dilution solvent〕 The photosensitive composition according to one aspect of the present invention contains water as a diluting solvent. The water content in the photosensitive composition can be 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 saccharide becomes a predetermined concentration. The concentration of the water-soluble saccharide is preferably 5% by mass or more, more preferably 20% by mass or more, but not limited thereto, based on the total amount of the photosensitive composition. When the concentration of the water-soluble saccharide is 5% by mass or more, particularly 20% by mass or more, based on the total amount of the photosensitive composition, the photosensitive composition can be easily made into a thick film. Also, the concentration of the water-soluble saccharide is preferably 50% by mass or less, more preferably 40% by mass or less, but not limited thereto, based on the total amount of the photosensitive composition. The concentration of the water-soluble saccharide is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total amount of the photosensitive composition. When the concentration of the water-soluble saccharide is 50% by mass or less, particularly 40% by mass or less, based on the total amount of the photosensitive composition, the photosensitive composition can be applied with a wide range of film thicknesses.

[0061] 〔Photoinitiator〕 The photosensitive composition according to one aspect of the present invention contains a photoinitiator. The photoinitiator may be selected from a photo radical polymerization initiator and a photo cationic polymerization initiator according to the type of the polymerizable group. The photoinitiator contained in the photosensitive composition may be one type or a combination of two or more types.

[0062] In the photosensitive composition according to one aspect of the present invention, the content of the photoinitiator is preferably 0.01 part by weight or more, more preferably 0.10 part by weight or more, based on 100 parts by weight of the water-soluble saccharide. Thereby, the photosensitivity of the photosensitive composition can be enhanced. Also, in the photosensitive composition according to one aspect of the present invention, the content of the photoinitiator is preferably 5.00 parts by weight or less, more preferably 3.00 parts by weight or less, based on 100 parts by weight of the water-soluble saccharide. Thereby, the production cost of the photosensitive composition can be reduced.

[0063] The photoinitiator contained in the photosensitive composition may be appropriately selected according to, for example, the intended use and function required for the photosensitive composition. Examples of the photoinitiator include α-hydroxyketone-based photoinitiators, α-aminoketone-based photoinitiators, benzyl ketal-based photoinitiators, oxime ester-based photoinitiators, acridine-based photoinitiators, benzophenone-based photoinitiators, acetophenone-based photoinitiators, aromatic ketoester-based photoinitiators, benzoic acid ester-based photoinitiators, acylphosphine oxide-based photoinitiators, and titanocene-based photoinitiators. The photoinitiator may be emulsified or solubilized in an aqueous system by, for example, a surfactant and / or a polymerizable monomer. Examples of commercially available photoinitiators include FAI-101L (manufactured by Fujifilm Corporation).

[0064] Examples of the α-hydroxyketone-based photoinitiator include 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl 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.

[0065] Examples of commercially available α-hydroxyketone-based photoinitiators include Omnirad 2959 (manufactured by IGM Resins B.V.).

[0066] Examples of α-amino ketone-based photoinitiators include, for example, 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, etc.

[0067] Examples of benzyl ketal-based photoinitiators include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.

[0068] Examples of oxime ester-based photoinitiators include, for example, 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-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime, etc.

[0069] Examples of acridine-based photoinitiators include, for example, 1,7-bis(acridin-9-yl)-n-heptane, etc.

[0070] Examples of benzophenone-based photoinitiators include benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone, alkylated benzophenone, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 4-methylbenzophenone, dibenzyl ketone, and fluorenone, etc.

[0071] Examples of acetophenone-based photoinitiators include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone, etc.

[0072] Examples of aromatic ketoester-based photoinitiators include methyl 2-phenyl-2-oxyacetate, etc.

[0073] Examples of benzoate-based photoinitiators include ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate, etc.

[0074] Examples of acylphosphine oxide-based photoinitiators 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, etc.

[0075] Examples of titanocene-based photoinitiators 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), etc.

[0076] [Crosslinking agent] The photosensitive composition according to one embodiment of the present invention may contain a crosslinking agent. By including a crosslinking agent in the photosensitive composition, the polymerizable groups of the water-soluble saccharides contained in the photosensitive composition can be crosslinked via the crosslinking agent. It is more preferable that the crosslinking agent has two or more polymerizable groups. The crosslinking agent may be selected from a radical polymerizable crosslinking agent and a cationic polymerizable crosslinking agent according to the type of the polymerizable group. The crosslinking agent contained in the photosensitive composition may be one type or a combination of two or more types.

[0077] In the photosensitive composition according to one embodiment of the present invention, the content of the crosslinking agent is preferably 0.01 parts by weight or more, more preferably 0.10 parts by weight or more, based on 100 parts by weight of the water-soluble saccharide. Further, in the photosensitive composition according to one embodiment of the present invention, the content of the crosslinking agent is preferably 5.00 parts by weight or less, more preferably 3.00 parts by weight or less, based on 100 parts by weight of the water-soluble saccharide.

[0078] Examples of the radical polymerizable crosslinking agent include crosslinking agents having a vinyl group such as 1,3-bis(vinylsulfonyl)-2-propanol; and crosslinking agents having a (meth)acryloyl group; and the like. Examples of the crosslinking agent having a (meth)acryloyl group include (meth)acrylic acid esters having a polyoxyalkylene group, (meth)acrylic acid esters formed from polyhydric alcohols, and the like.

[0079] Examples of the (meth)acrylic acid ester having a polyoxyalkylene group include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.

[0080] Examples of the (meth)acrylate ester formed from a polyhydric alcohol include, but are not limited to, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(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)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate.

[0081] In addition to or instead of the above-described crosslinking agent, the photosensitive composition according to one embodiment of the present invention may contain a crosslinking agent having a polymerizable group such as an epoxy group or an oxetane group, depending on the type of the polymerizable group of the water-soluble saccharide.

[0082] 〔Surfactant〕 The photosensitive composition according to one embodiment of the present invention may contain a surfactant. By containing an appropriate amount of the surfactant in the photosensitive composition, the surface tension of the photosensitive composition can be arbitrarily adjusted, the leveling property during coating can be improved, and the film thickness uniformity of the coating film can be improved. The surfactant contained in the photosensitive composition may be of one type or a combination of two or more types.

[0083] In the photosensitive composition according to one embodiment of the present invention, the content of the surfactant is preferably 0.01 part by weight or more, more preferably 0.30 part by weight or more, based on 100 parts by weight of the water-soluble saccharide. Further, in the photosensitive composition according to one embodiment 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 or less, based on 100 parts by weight of the water-soluble saccharide.

[0084] Examples of the surfactant contained in the photosensitive composition include surfactants such as fluororesin-based surfactants, silicone-based surfactants, polyoxyalkylene ether-based surfactants, and acrylic resin-based surfactants.

[0085] Examples of the fluororesin-based surfactant include, for example, Megafac (registered trademark), and its product numbers include, for example, 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 of the above are manufactured by DIC Corporation). Further, examples of the fluororesin-based surfactant include, for example, F-Top (registered trademark), and its product numbers include EF301, 303, and 352 (all of the above are manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.). Also, examples of the fluororesin-based surfactant include, for example: Fluorad (registered trademark) FC-430 and FC-431 (both 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 of the above are manufactured by AGC Seimi Chemical Co., Ltd.); BM-1000 and BM-1100 (both are manufactured by Yusho Co., Ltd.); and, Fujent (registered trademark) 710FM, 730LM (both are manufactured by Neos Co., Ltd.); etc.

[0086] Examples of the silicone-based surfactant include, for example, SH28PA, SH7PA, SH21PA, SH30PA, and ST94PA (all of the above are manufactured by Toray Dow Corning Co., Ltd.); BYK (registered trademark) 301, 306, 307, 331, 333, 337, and 345 (all of the above are manufactured by BYK-Chemie Japan Co., Ltd.); etc.

[0087] Examples of the polyoxyalkylene ether surfactant include, for example, Ftergent (registered trademark) 212M, 209F, 208G, 240G, 212P, 220P, 228P, NBX-15, FTX-218, and DFX-218 (all of the above are manufactured by Neos Co., Ltd.).

[0088] Examples of the acrylic resin surfactant include, for example, BYK (registered trademark)-350, 352, 354, 355, 356, 358N, 361N, 392, 394, and 399 (all of the above are manufactured by BYK-Chemie Japan Co., Ltd.).

[0089] 〔Reaction terminator〕 The photosensitive composition according to one embodiment of the present invention may contain a reaction terminator. By containing a reaction terminator in the photosensitive composition, it is possible to suppress over-polymerization when the photosensitive composition undergoes photopolymerization. The reaction terminator contained in the photosensitive composition may be of one type or a combination of two or more types.

[0090] In the photosensitive composition according to one embodiment of the present invention, the content of the reaction terminator is preferably 0.01 part by weight or more, more preferably 0.10 part by weight or more, based on 100 parts by weight of the water-soluble saccharide. Also, in the photosensitive composition according to one embodiment of the present invention, the content of the reaction terminator is preferably 5.00 parts by weight or less, more preferably 1.00 part by weight or less, based on 100 parts by weight of the water-soluble saccharide.

[0091] Examples of the reaction terminator contained in the photosensitive composition include radical polymerization terminators. Examples of the 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, and N-phenyldiethanolamine. Examples of commercially available radical polymerization terminators include the IRGANOX (registered trademark) series, and their product numbers include 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, and 295 (all of the above are manufactured by BASF).

[0092] 〔Other Additives〕 The photosensitive composition according to one aspect of the present invention may contain other additives as long as the properties of the water-soluble saccharides according to one aspect of the present invention are not impaired. Examples of other additives include adhesion aids, fillers, and water-soluble resins. The other additives contained in the photosensitive composition may be of one type or a combination of two or more types.

[0093] <Use of the Photosensitive Composition> The photosensitive composition according to one aspect of the present invention, although being an aqueous composition, can be used, for example, as a photosensitive material for a photoresist for microfabrication such as semiconductors.

[0094] Hereinafter, embodiments for using the photosensitive composition according to one aspect of the present invention as a negative photoresist in semiconductor microfabrication will be described for illustrative purposes. However, it should be noted that the use of the photosensitive composition according to one aspect of the present invention is not limited to this embodiment.

[0095] 〔Selection of polymerizable group〕 When the photosensitive composition according to one embodiment of the present invention is used as a negative photoresist, the polymerizable group of the water-soluble saccharide is a functional group having an unsaturated double bond such as a (meth)acryloyl group.

[0096] 〔Selection of substrate〕 Examples of the substrate to be coated with the photosensitive composition according to one embodiment of the present invention include substrates such as semiconductor wafer substrates and glass substrates. Further, layers such as an insulating layer and a conductive layer may be formed in advance on the surface of the substrate. Further, a base layer such as poly(2-hydroxyethyl) acrylate may be formed on the substrate. Since the photosensitive composition according to one embodiment of the present invention is an aqueous composition, it is also one of the advantages that it is difficult to corrode a base layer such as poly(2-hydroxyethyl) acrylate as compared with a resist material containing a large amount of organic solvent.

[0097] 〔Formation of coating film〕 The method of coating the substrate with the photosensitive composition according to one embodiment of the present invention may be a conventionally known method. Examples of the method of coating the substrate with the photosensitive composition include, but are not limited to, spin coating using a spinner.

[0098] After coating the substrate with the photosensitive composition, typically, baking (heating and drying) is performed to remove water in the coating film formed by the photosensitive composition. The baking temperature is preferably 50°C or higher and 300°C or lower.

[0099] 〔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 a substrate on which a coating film has been formed can be performed by an exposure method conventionally known in the art. Examples of the actinic radiation irradiated on the coating film include ultraviolet rays, visible light, and electron beams. Since ultraviolet curing is superior in productivity and has a lower equipment cost compared to electron beam curing, the actinic radiation is preferably ultraviolet rays. The exposure amount can be appropriately selected according to the content of the photoinitiator in the photosensitive composition. For example, the exposure amount can be about 600 mJ / cm 2 or so, and the exposure time can be about 60 seconds, for example, but is not limited thereto. The wavelength of the ultraviolet rays to be irradiated may be selected according to the type of the photopolymerization initiator contained in the photosensitive composition.

[0100] 〔Development〕 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 performed using a method conventionally known in the art except that the developing solution is water.

[0101] 〔Etching〕 When the photosensitive composition according to one aspect of the present invention is used as a negative photoresist, the etching of the coating film can be performed by a method conventionally known in the art.

[0102] <Summary> The water-soluble saccharide according to one aspect of the present invention has a 1,3-bond in at least a part of the sugar chain included in the saccharide, and at least a part of the hydroxyl groups included in the sugar chain is modified into a polymerizable group. Thereby, a novel water-soluble saccharide having a polymerizable group can be provided.

[0103] In one aspect of the present invention, the water-soluble saccharide preferably has 10 mol% or more and 60 mol% or less of the total amount of hydroxyl groups in the saccharide modified into polymerizable groups, with the total amount of hydroxyl groups in the saccharide being 100 mol%. Thereby, it is possible to provide a water-soluble saccharide having both good polymerizability and water solubility.

[0104] In the water-soluble saccharide according to one aspect of the present invention, the saccharide is preferably resistant dextrin or dextrose. Thereby, it is possible to provide a water-soluble saccharide capable of easily preparing an aqueous composition with a low viscosity.

[0105] In the water-soluble saccharide according to one aspect of the present invention, the polymerizable group preferably has a (meth)acryloyl group. Thereby, it is possible to provide a water-soluble saccharide having good polymerizability.

[0106] In the water-soluble saccharide according to one aspect of the present invention, the weight average molecular weight is preferably 150 or more and 50,000 or less. Thereby, it is possible to enhance the photosensitivity of the photosensitive composition containing the water-soluble saccharide and to enhance the coatability of the photosensitive composition containing the water-soluble saccharide.

[0107] Further, 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 photoinitiator. Thereby, it is possible to provide a photosensitive composition capable of forming a cured product by a polymerization reaction and capable of being developed by washing with an aqueous solvent.

[0108] The photosensitive composition according to one aspect of the present invention preferably contains a crosslinking agent. Thereby, it is possible to crosslink the polymerizable groups of the water-soluble saccharide contained in the photosensitive composition via the crosslinking agent.

[0109] The photosensitive composition according to one aspect of the present invention preferably contains a surfactant. Thereby, 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 can be improved.

[0110] The photosensitive composition according to one embodiment of the present invention preferably contains a reaction terminator. Thereby, over-polymerization can be suppressed.

[0111] In addition, a method for producing a water-soluble saccharide according to one embodiment of the present invention includes a step of reacting a saccharide with a compound having a polymerizable group in the presence of an organic solvent to modify at least a part of the hydroxyl groups included in the saccharide with the polymerizable group. The organic solvent is N-methylpyrrolidone, the saccharide has a 1,3-bond in at least a part of the sugar chain, and the compound has a (meth)acryloyl group and a halogen group. Thereby, a novel water-soluble saccharide having a polymerizable group can be produced.

[0112] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

Examples

[0113] One example of the present invention will be described below. In this example, saccharides of different types were used to produce (meth)acryl-modified water-soluble saccharides. Next, a photosensitive composition containing the water-soluble saccharide was produced, and the photosensitivity of the photosensitive composition was evaluated.

[0114] <Main raw materials> In this example, the following saccharides were used as raw materials for producing the water-soluble saccharide. Raw material saccharide 1: Resistant dextrin (manufactured by Matsutani Chemical Industry Co., Ltd., trade name "Fibersol 2") Raw material saccharide 2: Resistant 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 "Litesse HF") Raw material saccharide 4: Dextrin (manufactured by San-Ei Sugar Co., Ltd., trade name "NSD500") Starting saccharides 5: High molecular weight dextrin (Production method: 750 g of ion-exchanged water and 750 g of saccharides 4 were added to a 3 L reaction vessel equipped with a thermometer, a stirrer, and a cooling pipe, and saccharides 4 were completely dissolved in the ion-exchanged water. Next, 1500 g of methanol was slowly added, and the operation of precipitating only the high molecular weight portion of the dissolved saccharides 4 was performed twice. Next, 1000 g of N-methylpyrrolidone was added, the temperature was raised to 40 °C under a vacuum of 10 mmHg, and the methanol and water remaining in the system were removed to obtain saccharides 5.) Starting saccharides 6: Pullulan (manufactured by Hayashibara Co., Ltd., trade name "Pullulan")

[0115] <Analysis of starting saccharides> The molecular weight distribution and sugar chain binding mode of starting saccharides 1 to 6, which are raw materials for water-soluble saccharides, were analyzed.

[0116] 〔Molecular weight distribution analysis〕 Starting saccharides 1 were treated with acetic anhydride to acetylate the hydroxyl groups contained in starting saccharides 1, and then the molecular weight distribution of starting saccharides 1 was analyzed by using gel permeation chromatography (GPC), and the number average molecular weight Mn and the weight average molecular weight Mw were calculated. The conditions of GPC were as follows. GPC measuring device: manufactured by Tosoh Corporation, trade name "HLC-8120GPC" ("HLC" is a registered trademark of the company) Column: A column connecting three columns (each manufactured by Tosoh Corporation, trade name "TSKgel G3000HHR", trade name "TSKgel G2000HHR", trade name "TSKgel G2000HHR", "TSKgel" is a registered trademark of the company)

[0117] For starting saccharides 2 to 6 as well, the molecular weight distribution was analyzed in the same manner as starting saccharides 1. The GPC spectra of starting saccharides 1 to 6 are shown in Fig. 1. Also, the analysis results of the molecular weight distribution of starting saccharides 1 to 6 are shown in Table 1.

[0118] 〔Analysis of sugar chain binding mode distribution〕 13 The sugar chain binding mode distribution of starting saccharides 1 was analyzed by using C-NMR. 13 The conditions of C-NMR were as follows. NMR measuring device: manufactured by JEOL Ltd., trade name "ECZ-500R / S1" Solvent: heavy water (D 2 O)

[0119] For raw material saccharides 2 to 4 and 6 as well, the sugar chain binding mode distribution was analyzed in the same manner as for raw material saccharide 1. The 13 13C-NMR spectra of raw material saccharides 2 to 4 and 6 are shown in Fig. 2. Also, the analysis results of the sugar chain binding mode distribution of raw material saccharides 2 to 4 and 6 are shown in Table 1. Note that since raw material saccharide 5 is the high molecular weight part of raw material saccharide 4, it can be considered to have the same sugar chain binding mode distribution as raw material saccharide 4.

[0120]

Table 1

[0121] <Production of water-soluble saccharides> 〔Example 1〕 100.0 g of raw material saccharide 1 and 185.7 g of N-methylpyrrolidone were added to a 1 L reaction vessel equipped with a thermometer, a stirrer, and a condenser tube. The temperature inside the system was raised to 40 °C under a vacuum of 10 mmHg to remove the water remaining inside the system. Next, after cooling the temperature inside the system to 15 °C, while cooling so that the temperature inside the system did not exceed 15 °C, 33.5 g (0.37 mol) of acryloyl chloride was added dropwise over 2 hours. After the dropwise addition, the reaction was continued at 15 °C for 2 hours.

[0122] Next, 37.4 g (0.37 mol) of triethylamine was added for neutralization, and the neutralization salt and N-methylpyrrolidone were removed by purification. Next, ion-exchanged water was added so that the content of the acrylate-modified product of raw material saccharide 1 in the system became 25% by mass, and an aqueous varnish of water-soluble saccharide 1 having a modification rate of 20% (theoretical value) to the acryloyl group was obtained.

[0123] 〔Example 2〕 A water varnish of water-soluble saccharide 2 having a modification rate of 30% (theoretical value) to an acrylic group was obtained in the same manner as in Example 1, except that 50.4 g (0.56 mol) of acryloyl chloride was used instead of 33.5 g (0.37 mol) of acryloyl chloride, and 56.2 g (0.56 mol) of triethylamine was used instead of 37.4 g (0.37 mol) of triethylamine.

[0124] [Example 3] A water varnish of water-soluble saccharide 3 having a modification rate of 30% (theoretical value) to an acrylic group was obtained 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 material saccharide 1.

[0125] [Example 4] A water varnish of water-soluble saccharide 4 having a modification rate of 30% (theoretical value) to an acrylic group was obtained 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 material saccharide 1.

[0126] [Comparative Example 1] A water varnish of water-soluble saccharide C1 having a modification rate of 30% (theoretical value) to an acrylic group was obtained in the same manner as in Example 2, except that 100.0 g of saccharide 4 was used instead of 100.0 g of raw material saccharide 1.

[0127] [Comparative Example 2] A water varnish of water-soluble saccharide C2 having a modification rate of 30% (theoretical value) to an acrylic group was obtained in the same manner as in Example 2, except that 100.0 g of saccharide 5 was used instead of 100.0 g of raw material saccharide 1.

[0128] [Comparative Example 3] Into a reaction vessel with an internal volume of 2 L equipped with a thermometer, a stirrer, and a cooling pipe, 100.0 g of raw material saccharide 6 and 900.0 g of N-methylpyrrolidone were added. The temperature inside the system was raised to 40 °C under a vacuum of 10 mmHg to remove the water remaining in the system. Next, after cooling the temperature inside the system to 15 °C, while cooling so that the temperature inside the system did not exceed 15 °C, 50.4 g (0.56 mol) of acryloyl chloride was added dropwise over 2 hours. After the dropwise addition, the reaction was continued for 2 hours at a temperature of 15 °C inside the system.

[0129] Next, 56.2 g (0.56 mol) of triethylamine was added for neutralization, and the neutralization salt and N-methylpyrrolidone were purified and removed. Next, ion-exchanged water was added so that the content of the acrylate-modified product of raw material saccharide 6 in the system became 10% by mass, and an aqueous varnish of water-soluble saccharide C3 having a modification rate of 30% (theoretical value) to the acrylic group was obtained. Note that since the viscosity of water-soluble saccharide C3 was too high, it could not be produced so that the content of the acrylate-modified product in the system became 25% by mass as in the case of water-soluble saccharides 1 to 4 and C1 to C2.

[0130] <Analysis of water-soluble saccharides> The modification rates of water-soluble saccharides 1 to 4 and C1 to C3 to the acrylic group and the viscosities of their aqueous varnishes were analyzed.

[0131] 〔Analysis of modification rate to acrylic group〕 13 By using C-NMR, the ratio of the hydroxyl groups of saccharide 1, which is the raw material of water-soluble saccharide 1, that were modified to acrylic groups, that is, the modification rate to the acrylic group, was analyzed. 13 The conditions of C-NMR were the same as those in the item of 〔Analysis of sugar chain linkage mode distribution〕.

[0132] For water-soluble saccharides 2 to 4 and C1 to C3 as well, the modification rate to the acrylic group was analyzed in the same manner as for water-soluble saccharide 1. The analysis results of the modification rates of water-soluble saccharides 1 to 4 and C1 to C3 to the acrylic group are shown in Table 2.

[0133] 〔Viscosity analysis〕 The viscosity of the aqueous varnish of water-soluble saccharide 1 was measured by using an E-type viscometer. The measurement conditions were as follows. Measurement temperature: 25 °C

[0134] The viscosities of water-soluble saccharides 2 to 4 and the aqueous varnishes of C1 to C3 were also analyzed in the same manner as water-soluble saccharide 1. Table 2 shows the analysis results of the viscosities of water-soluble saccharides 1 to 4 and the aqueous varnishes of C1 to C3.

[0135]

Table 2

[0136] <Production of photosensitive composition> 〔Production Examples 1 to 3〕 To the aqueous varnish of water-soluble saccharide 1, photoinitiator 1 (manufactured by IGM Resins B.V., trade name "Omnirad 2959") was added so as to have a concentration of 1, 2, or 3 mass%, respectively, to obtain photosensitive compositions 1 to 3.

[0137] 〔Production Examples 4 to 6〕 To the aqueous varnish of water-soluble saccharide 2, photoinitiator 1 was added so as to have a concentration of 1, 2, or 3 mass%, respectively, to obtain photosensitive compositions 4 to 6.

[0138] 〔Production Examples 7 to 9〕 To the aqueous varnish of water-soluble saccharide 3, photoinitiator 1 was added so as to have a concentration of 1, 2, or 3 mass%, respectively, to obtain photosensitive compositions 7 to 9.

[0139] 〔Production Examples 10 to 12〕 To the aqueous varnish of water-soluble saccharide 4, photoinitiator 1 was added so as to have a concentration of 1, 2, or 3 mass%, respectively, to obtain photosensitive compositions 10 to 12.

[0140] 〔Comparative Production Examples 1 to 3〕 To the aqueous varnish of water-soluble saccharide C1, photoinitiator 1 was added so as to have a concentration of 1, 2, or 3 mass%, respectively, to obtain photosensitive compositions C1 to C3.

[0141] 〔Comparative Production Examples 4 to 6〕 To the aqueous varnish of water-soluble saccharide C2, Photoinitiator 1 was added so as to have a concentration of 1, 2, or 3% by mass, respectively, to obtain photosensitive compositions C4 to C6.

[0142] 〔Comparative Production Examples 7 to 9〕 To the aqueous varnish of water-soluble saccharide C3, Photoinitiator 1 was added so as to have a concentration of 1, 2, or 3% by mass, respectively, to obtain photosensitive compositions C7 to C9.

[0143] <Photosensitivity Analysis of Photosensitive Composition> 3 mL of 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 Limited, trade name "CLEAN TRACK ACT8"). Then, by baking at 80°C for 60 seconds, water was volatilized and removed. Next, using a mask contact exposure apparatus (manufactured by Resotec Japan Co., Ltd., trade name "LTCET-500") and a sensitivity confirmation mask (Taiyo-ink Corporation: 5-inch Multi-Transmission Mask), ultraviolet rays were irradiated while adjusting the exposure amount to cure Photosensitive Composition 1. Then, the cured film was immersed in pure water as a developing solution for 90 seconds to remove the uncured portion in the cured film, that is, development was performed. The film thickness of the cured film before and after development was measured, and the remaining film ratio was calculated based on the following formula (5). The higher the remaining film ratio, the easier it is for the photosensitive composition to cure, and it can be considered that the photosensitivity is high. Remaining film ratio (%) = Film thickness of cured film after development / Film thickness of cured film before development × 100 Formula (5)

[0144] For Photosensitive Compositions 5 to 12 and C1 to C9 as well, the remaining film ratio was analyzed in the same manner as for Photosensitive Composition 4. The analysis results of the remaining film ratios of Photosensitive Compositions 4 to 12 and C1 to C9 are shown in Figure 3. Also, for Photosensitive Compositions 4 to 12 and C1 to C9, the exposure amount for achieving a remaining film ratio of 90% is shown in Table 3.

[0145]

Table 3

[0146] <Discussion> As shown in Tables 1 and 2, water-soluble saccharides 1 to 4 produced using raw material saccharides 1 to 3 having a 1,3-bond in the sugar chain as raw materials are easy to increase the solid content of the aqueous varnish because of their low viscosity. Further, for each of water-soluble saccharides 2 to 4, photosensitive compositions 6, 9, and 12 produced by adding a photoinitiator 1 so as to have a concentration of 3% by mass showed a residual film ratio of 90% or more at an exposure amount of 300 mJ / cm 2 ~400 mJ / cm 2 and had good photosensitivity.

[0147] Water-soluble saccharide C1 produced using raw material saccharide 4 as a raw material is easy to increase the solid content of the aqueous varnish because of its low viscosity. However, photosensitive composition C3 produced by adding photoinitiator 1 to water-soluble saccharide C1 required an exposure amount of about 1020 mJ / cm 2 to achieve a residual film ratio of 90% or more, and had low photosensitivity.

[0148] Water-soluble saccharide C2 produced using raw material saccharide 5 as a raw material is easy to increase the solid content of the aqueous varnish because of its low viscosity. However, photosensitive composition C6 produced by adding photoinitiator 1 to water-soluble saccharide C2 required an exposure amount of about 660 mJ / cm 2 to achieve a residual film ratio of 90% or more, was better than photosensitive composition C5, but had low photosensitivity. Further, the production process of water-soluble saccharide C2 included a step of removing the low molecular weight portion of raw material saccharide 4 to produce raw material saccharide 5, thus generating a large amount of waste liquid and having a low yield.

[0149] Photosensitive composition C9 produced using raw material saccharide 6 as a raw material had good photosensitivity, but water-soluble saccharide C3 generated during the production process had a high viscosity and it was considered difficult to adjust the film thickness because the solid content of the aqueous varnish could not be increased.

Industrial Applicability

[0150] The water-soluble saccharides according to the present invention can be used as photosensitive materials such as, for example, photoresist materials and photocurable inks.

Claims

1. At least a part of the sugar chain of the resistant dextrin has a 1,3-bond. Taking the total amount of hydroxyl groups in the sugar chain as 100 mol%, 10 mol% or more and 60 mol% or less of the hydroxyl groups are modified into polymerizable groups having (meth)acryloyl groups, The water-soluble saccharide has a weight average molecular weight of 150 or more and 50,000 or less.

2. A water-soluble saccharide in which at least a part of the sugar chain of the saccharide has a 1,3-bond and at least a part of the hydroxyl groups in the sugar chain are modified into polymerizable groups, A photosensitive composition containing water and a photoinitiator, wherein the saccharide is resistant dextrin or polydextrose.

3. The photosensitive composition according to claim 2, which contains a crosslinking agent.

4. The photosensitive composition according to claim 2 or 3, which contains a surfactant.

5. The photosensitive composition according to any one of claims 2 to 4, which contains a reaction terminator.

6. The photosensitive composition according to any one of claims 2 to 5, wherein, taking the total amount of hydroxyl groups in the saccharide as 100 mol%, 10 mol% or more and 60 mol% or less of the hydroxyl groups are modified into polymerizable groups.

7. The photosensitive composition according to any one of claims 2 to 6, wherein the polymerizable group has a (meth)acryloyl group.

8. The photosensitive composition according to any one of claims 2 to 7, wherein the weight average molecular weight of the water-soluble saccharide is 150 or more and 50,000 or less.

9. The polymerizable group has a (meth)acryloyl group, wherein, taking the total amount of hydroxyl groups in the saccharide as 100 mol%, 10 mol% or more and 60 mol% or less of the hydroxyl groups are modified into polymerizable groups, The photosensitive composition according to any one of claims 2 to 5, wherein the weight average molecular weight of the water-soluble saccharide is 150 or more and 50,000 or less.

10. A method for producing a water-soluble saccharide, which includes a step of reacting a saccharide with a compound having a polymerizable group in the presence of an organic solvent to modify at least a part of the hydroxyl groups in the saccharide into the polymerizable groups, wherein the organic solvent is N-methylpyrrolidone, the saccharide is resistant dextrin or polydextrose having a 1,3-bond in at least a part of the sugar chain, the compound has a (meth)acryloyl group and a halogen group, A method for producing a water-soluble saccharide. **Claim 11**: In the step of modification, with the total amount of hydroxyl groups included in the saccharide being 100 mol%, 10 mol% or more and 60 mol% or less of the hydroxyl groups are modified into the polymerizable groups. The weight average molecular weight of the water-soluble saccharide is 150 or more and 50,000 or less. The method for producing a water-soluble saccharide according to claim 10.

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