JP5236195B2 - Monomer solution composition - Google Patents

Description

  The present invention relates to a monomer solution composition, and more particularly to a monomer solution composition obtained by dissolving hydroxyalkylchitosan in a vinyl monomer.

  Chitosan, which is conventionally known as a natural polysaccharide, is industrially produced by deacetylating chitin separated from crustaceans such as shrimps and crabs, and produces 2-amino-2-deoxy-D-glucose. It is a basic polysaccharide as one constituent unit. Chitosan has unique properties such as film-forming properties, antibacterial properties, water retention and aggregating ability, and is used in various fields as a functional polymer.

  In recent years, various researches on chitin and chitosan have been conducted, and chitosan has a reactive amino group, and various functions are provided by using the amino group to form various derivatives, and new application development is progressing. . For example, chitosan is used as a coating material for imparting antibacterial properties to various films, nonwoven fabrics, and textile products in the material field, as a wound dressing agent in the medical field, as a powder property improving agent in the cosmetic field, As a thickener, a dispersant, or a film-forming agent, in the design field, attempts have been made to use it as a coloring agent for seeds with antibacterial properties and pigmentation.

  Further, hydroxyalkyl chitosan, which is a kind of chitosan derivative, is described in, for example, Patent Document 1 and discloses the usefulness as a semipermeable membrane-like material composed of a crosslinked polymer of the hydroxyalkyl chitosan. Patent Document 2 discloses a technique for producing water-soluble hydroxyalkyl chitosan having a high degree of substitution and a film-forming agent as an application thereof. Patent Document 3 describes a production method and hydroxyalkyl chitosan as a film. It is described that it is useful for various uses centering on a forming agent. Furthermore, Patent Document 4 discloses a dispersion solution of chitin or chitosan and a vinyl monomer and a method for using the same, and Patent Document 5 discloses a photosensitive resin composition containing a salt of chitosan acid. Yes.

JP 51-006879 A JP-A-57-180602 Japanese Patent Publication No. 64-005601 JP-A-6-263919 Japanese Patent Laid-Open No. 10-101721

  Patent Documents 1, 2, and 3 describe examples in which a crosslinking agent is used during film formation as a method for obtaining a stable strength of the film. However, these methods still have problems in terms of environmental limitations and processes, such as requiring a subsequent crosslinking process by heating in addition to the solvent removal process during film formation. Furthermore, Patent Document 4 discloses a chitosan dispersion, but this dispersion has a problem in applications where uniformity is required for the film, and is limited in use. Patent Document 5 discloses a chitosan salt. Since this chitosan salt is a salt, it has strong hydrophilicity, and a hydrophilic monomer must be used as a monomer. There is a limit.

  Chitosan itself does not dissolve in water or an organic solvent, and chitosan dissolves in a dilute acid aqueous solution of an organic acid such as acetic acid and lactic acid including citric acid by forming a salt with the acid. By coating this article with a dilute acid aqueous solution of chitosan and evaporating the water, it becomes a strong film in the dry state, and the function of chitosan can be easily imparted to various articles. However, since the organic acid remains in the dry film obtained from the chitosan aqueous solution, when the dry film comes into contact with water, it is dissolved again, and there is a problem that a film having water resistance cannot be obtained. .

  Furthermore, when a chitosan aqueous solution is applied to the substrate surface, if the substrate surface is particularly hydrophobic or oleophilic, repelling occurs in the hydrophilic chitosan aqueous solution, and a uniform coating film cannot be obtained. Accordingly, an object of the present invention is to provide a monomer solution of a chitosan derivative containing a chitosan derivative, which can be applied to the surface of a hydrophobic substrate and can form a smooth and stable coating film.

The above object is achieved by the present invention described below. That is, the present invention provides a monomer solution composition comprising hydroxyalkyl chitosan dissolved in a vinyl monomer (except for those containing an organic acid or a derivative thereof) . Examples of the vinyl monomer include N-vinylformamide, N-vinyl-2-pyrrolidone, acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethyl. It is preferably at least one selected from aminopropyl (meth) acrylamide and glycerin mono (meth) acrylate.

  The hydroxyalkyl chitosan is at least one selected from hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan and hydroxypropyl hydroxybutyl chitosan; hydroxyalkyl chitosan (A) and vinyl monomer (B) The mass ratio is A: B = 1: 99 to 80:20; hydroxyalkyl chitosan is a reaction product of chitosan and alkylene oxide, and the degree of substitution of alkylene oxide with chitosan constitutes chitosan It is preferably at least 0.5 mole per mole of pyranose ring.

  The present invention further includes a photopolymerization initiator and / or a photopolymerization accelerator, and the above-mentioned monomer solution composition that is photosensitive; an article having a cured layer made of the monomer solution composition. provide. The surface of the article can be printed by an ink jet recording method.

  ADVANTAGE OF THE INVENTION According to this invention, the monomer solution composition which can form easily the coating film which has the smooth and excellent strength which consists of a vinyl polymer containing hydroxyalkyl chitosan on the surface of articles | goods, and also has hydrophilicity is provided.

  Next, the present invention will be described more specifically with reference to preferred embodiments. Chitosan, which is a raw material for the hydroxyalkyl chitosan used in the present invention, has already been industrially produced and is available in various grades, and there is no particular limitation on the origin and production method of chitosan used in the present invention. Any chitosan that has been industrially produced in the past can be used. As the chitosan, it is preferable to use a chitosan having a deacetylation degree of 30% or more, a chitosan 1 mass%, and an acetic acid 1 mass% having a viscosity of 1 mPa · s to 10000 mPa · s.

  Hydroxyalkyl chitosan used in the present invention can be obtained by addition reaction of alkylene oxide with the amino group and / or hydroxyl group of the chitosan. Alternatively, chitin as a starting material, which may be hydroxyalkylated and then deacetylated. Preferred examples of the hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and a hydroxypropylhydroxybutyl group.

  As described above, when the hydroxyalkylated chitosan used in the present invention is produced by reacting chitosan with alkylene oxide, for example, chitosan is stirred and dispersed in a hydroalcoholic medium such as hydrous isopropyl alcohol or in water. Hydroxyalkylchitosan can be obtained by adjusting the mixture to alkali with sodium hydroxide and the like, adding alkylene oxide, and stirring with heating at normal pressure or under pressure. In addition, the manufacturing method of hydroxyalkyl chitosan is not limited to the said method.

  In the hydroxyalkyl chitosan used in the present invention, the degree of substitution of alkylene oxide with chitosan is at least 0.5 mol, preferably 1 to 3 mol, per mol of pyranose ring constituting chitosan. If the degree of substitution is less than 0.5, the solubility of the hydroxyalkyl chitosan in the vinyl monomer is insufficient, and such a monomer solution does not form a uniform coating film. On the other hand, even when the degree of substitution exceeds 3 mol, there is no particular improvement in the solubility in vinyl monomers and the physical properties of the resulting coating film, which is uneconomical due to an increase in cost for increasing the degree of substitution. .

  Examples of vinyl monomers that dissolve hydroxyalkylchitosan include N-vinylformamide, N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, and N, N-dimethylaminoethyl. (Meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, and glycerin mono (meth) acrylate are preferred, and other (meth) acrylic acid methyl, ethyl, propyl, isopropyl, cyclohexyl, 2-ethylhexyl, 2-hydroxy Ethyl ester; vinyl acetate, vinyl propionate, vinyl butyrate; styrene, chloroprene; (meth) acrylonitrile; (meth) acrylamide, allyl alcohol, vinyl pyridine and the like.

The monomer solution composition of the present invention is obtained by dissolving the hydroxyalkyl chitosan in the monomer. As a manufacturing method (dissolution method) of the monomer solution composition, either a hydroxyalkyl chitosan may be added to the monomer or a monomer may be added to the hydroxyalkyl chitosan, and stirring at room temperature is sufficient for dissolution. You may heat as needed. Also, but it may also be dissolving the hydroxyalkyl chitosan and / or the monomer mixture of a plurality. However, those containing organic acids or their derivatives are excluded.

  The mass ratio of the hydroxyalkyl chitosan (A) and the vinyl monomer (B) in the production of the monomer solution composition is A: B = 1: 99 to 80:20 when the total of both is 100 mass%. is there. If the amount of hydroxyalkyl chitosan used is less than 1% by mass, the characteristics of hydroxyalkyl chitosan will not be exhibited. On the other hand, if the amount of hydroxyalkyl chitosan exceeds 80% by mass, problems such as cracking and peeling may occur during coating film formation. There is. Furthermore, A: B = 1: 99 to 60:40 is preferable from the viewpoint that the hydroxyalkylchitosan is easily dissolved and a smoother and more uniform coating film is efficiently formed.

  The monomer solution composition of the present invention is used in the same manner as the monomer used in the composition, for example, various coating agents, UV curable inks, wood paints, fiber modifiers, adhesives, cosmetics / pharmaceuticals / medicals. Useful for applications such as materials. A particularly preferred use is as a photosensitive resin paint (coating agent). When used in the application, the monomer solution composition of the present invention further contains a photopolymerization initiator and / or a photopolymerization accelerator. The photosensitive resin paint may also contain a reactive diluent or a reactive oligomer for the purpose of preparing various physical properties. The photosensitive resin paint can be applied to a base material and then cured by irradiation with active energy rays such as ultraviolet rays or electron beam irradiation to form a uniform, smooth and stable coating film on the surface of the base material.

  Examples of the photopolymerization initiator include acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone; benzophenones such as benzophenone and p-phenylbenzophenone; benzoin Benzoins such as benzoin methyl ether and benzoin ethyl ether; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; thioxanthones such as 2,4-diethylthioxanthone and 2-isopropylthioxanthone; 2-ethylanthraquinone, 2- Anthraquinones such as chloroanthraquinone and 2-tertiarybutylanthraquinone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,4 - trimethyl benzoyl) - phosphine oxides such as triphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, etc. can be used, it can also be used in mixing of two or more kinds in combination. The usage-amount of the said photoinitiator is the same as that of a prior art, for example, is about 0.1-10 mass parts per 100 mass parts of said monomer solution compositions of this invention.

  The photopolymerization accelerator is one that reduces the influence of oxygen during curing of the photosensitive composition and increases the curing speed. For example, isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, Ethyl p-diethylaminobenzoate can be used, and these can be used alone or in a mixture of two or more. The usage-amount of the said photoinitiator is the same as that of a prior art, for example, it is about 0.1-10 mass parts per 100 mass parts of said monomer solution compositions of this invention.

  The reactive diluent, reactive oligomer, and the like are appropriately selected according to the type of coating substrate and each application, and are preferably acrylic prepolymers having two or more acryloyl groups in one molecule. For example, polyester acrylate, urethane acrylate, epoxy acrylate, polyfluoroalkyl acrylate, silicone acrylate, melamine acrylate and the like can be used, and these can be used alone or in combination of two or more. The amount of the reactive diluent or reactive oligomer used is the same as in the prior art, and is, for example, about 0 to 50 parts by mass per 100 parts by mass of the monomer solution composition of the present invention.

  The monomer solution composition of the present invention can further contain an organic solvent depending on the purpose of the base material, film thickness, coating film forming method and the like in the coating film formation. The organic solvent is not particularly limited as long as it is an organic solvent that does not adversely affect the monomer solution composition of the present invention. For example, alcohols such as methanol, ethanol, isopropanol, isobutanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, and ethyl lactate can be used. More preferably, methanol A low boiling point organic solvent such as acetone, methyl ethyl ketone, dichloromethane, or tetrahydrofuran is preferable because it is easy to remove the solvent when forming the coating film and is efficient. The usage-amount of an organic solvent is 0-500 mass parts per 100 mass parts of monomer solution compositions, More preferably, it is 0-100 mass parts.

  In addition to the above components, the monomer solution composition includes, for example, an antiblocking agent, an organic resin, a curing agent resin, a slip agent, an extender pigment, an antistatic agent, an antisettling agent, a leveling agent, an antifoaming agent, and a surface active agent. Additives, preservatives, antifungal agents, algaeproofing agents, coloring agents, ultraviolet absorbers, antioxidants, plasticizers, thickeners, adhesives, inorganic fillers, and the like are added, and there is no particular limitation.

  Examples of the anti-blocking agent include fatty acid amides such as oleic acid amide, erucic acid amide, stearic acid amide, and palmitic acid amide, silicones such as epoxy-modified silicone, amino-modified silicone, and polyester-modified silicone, and silicon dioxide pigments. . The organic resin is preferably an aqueous resin, an emulsion resin, and the like, and examples thereof include an aqueous resin such as polyvinyl alcohol, acrylic resin, vinyl acetate, urethane, starch, and cellulose, and an emulsion resin.

  As a hardening | curing agent resin, a phenol resin, an amino resin, etc. are mentioned from the reason for improving the sclerosis | hardenability of a monomer solution composition, for example. Examples of the slip agent include low molecular weight polyethylene wax, low molecular weight fluorinated polyethylene wax, crystal wax, and carnauba wax.

  As extender pigments, it is also preferable to use heavy calcium carbonate obtained by grinding calcium carbonate or natural limestone, and also slaked lime that performs the same function, such as improving film formability during coating film formation and preventing cracks, etc. Is added as necessary. Examples of the colorant include organic pigments, inorganic pigments, and the like that are commonly used for paints, printing, and plastics.

  Antistatic agent, anti-settling agent, leveling agent, antifoaming agent, surfactant, antiseptic agent, antifungal agent, antialgae agent, ultraviolet absorber, antioxidant, plasticizer, thickener, adhesive, inorganic As the filler and the like, those generally used as various inks and paint compositions are added as necessary. These additives are preferably added in an amount of 2% by mass or less in the monomer solution composition of the present invention.

  Examples of the base material to which the monomer solution composition of the present invention is applied include paper, resin molded body, metal, glass plate, wood and the like. Examples of the application method include a bar coater, a gravure coater, Conventionally known methods such as a roll coater, a blade coater, a spin coater, a flow coater, a dip coater, and a spray can be used.

  The above solution is dried as necessary after coating, and the coating film is cured. Examples of the drying method include a method in which a heat source is brought into contact with the coated substrate itself, a method in which heating is performed without contacting the coated substrate by hot air blowing, and irradiation drying using infrared rays or microwaves. The coating film is cured by using ultraviolet irradiation or electron beam irradiation which is usually used for a photocurable coating. The light source for ultraviolet irradiation is not particularly limited, and mercury lamps, metal halide lamps, xenon lamps, incandescent lamps, lasers, and the like are used. High pressure mercury lamps and metal halide lamps are preferable. In the case of electron beam irradiation, it is generally preferable to use a low energy electron beam accelerator having a voltage of 300 keV or less.

  Although the film thickness of the coating film formed with the monomer solution composition of this invention is not specifically limited, It is 0.1-100 micrometers, Preferably it is 1-50 micrometers. In addition, when the coating thickness is less than 0.1 μm, the coating film is weak in bending and scratching. On the other hand, when it exceeds 50 μm, particularly more than 100 μm, the curing rate of the coating film decreases, the components in the coating film are uncured, and the drying is poor. It is not preferable because it tends to cause blocking and the like, and also leads to a decrease in coating strength.

  In addition, the deacetylation degree of chitosan in this invention is computed from the titer measured by colloid titration. Specifically, a toluidine blue solution is used as an indicator and colloidal titration with an aqueous polyvinyl potassium sulfate solution to quantify the free amino groups in the chitosan molecule and determine the degree of deacetylation of chitosan. Hereinafter, sample preparation and titration tests were performed at room temperature of about 20 ° C.

Sample preparation and titration test A predetermined amount of chitosan is added to a 0.5% by mass acetic acid aqueous solution, and the prepared solution with a pure chitosan concentration of 0.5% by mass is made exactly 100 g and dissolved with stirring. Next, 10 g of this prepared solution and 90 g of ion-exchanged water are accurately collected, and a 0.05 mass% chitosan solution is prepared by stirring and mixing. Further, 10 g is accurately weighed from this 0.05 mass% chitosan solution, and 50 ml of ion exchange water and about 0.2 ml of toluidine blue solution are added thereto, and titrated with a polyvinyl potassium sulfate solution (N / 400 PVSK). The titration rate is set to 2 ml / min to 5 ml / min, and the point at which the measurement solution is maintained in color for 30 seconds or more after the color changes from blue to magenta is defined as the end point titration.

-Blank test The same titration test is performed using ion-exchanged water instead of the preparation solution used in the above titration test.
Calculation method X = 1/400 × 161 × f × (V−B) /1000=0.4025×f× (V−B) / 1000
Y = 0.5 / 100-X

X: free amino group mass in chitosan (equivalent to glucosamine residue mass)
Y: Mass of bound amino group in chitosan (N-acetylglucosamine residue)
Equivalent to mass)
f: titer of N / 400 PVSK V: titration of sample (ml)
B: Blank test titration (ml)
Deacetylation degree (%) = (free amino group) / {(free amino group) + (bound amino group)} × 100 = (X / 161) / (X / 161 + Y / 203) × 100
161 is the equivalent molecular weight of the glucosamine residue, and 203 is the equivalent molecular weight of the N-acetylglucosamine residue.

  Moreover, the viscosity measurement of the chitosan solution in this invention was performed with the following method. A predetermined amount of chitosan is added to a 1% by mass acetic acid aqueous solution to prepare a chitosan pure concentration of 1% by mass. After this prepared solution was dissolved by stirring, the viscosity was measured using a B-type rotational viscometer while maintaining the temperature at 20 ° C. in a thermostatic bath. In addition, chitosan pure content means solid content conversion in a chitosan sample, and is specifically solid content mass calculated | required by drying a chitosan sample at 105 degreeC for 2 hours.

Next, the present invention will be described more specifically with reference to examples and comparative examples. “Part” or “%” in the text is based on mass unless otherwise specified.
Table 1 shows the compositions of the monomer solution compositions used as examples and comparative examples.

<Example 1>
In 90 g of N-vinylformamide (Aldrich reagent), 10 g of hydroxybutyl chitosan (raw material chitosan: 1% acetic acid aqueous solution viscosity 6 mPa · s, deacetylation degree 83% / hydroxybutylation degree 1.1) is dispersed, and at room temperature for 4 hours. After stirring and dissolving, the mixture was allowed to stand overnight, and again stirred and dissolved at room temperature for 1 hour to prepare 100 g of the monomer solution composition of the present invention.

<Examples 2 to 16>
As shown in Table 1, the monomer solution composition of the present invention in which the kind of hydroxyalkyl chitosan, the degree of hydroxyalkylation (substitution degree), the blending ratio of hydroxyalkyl chitosan and various vinyl monomers, and the kind of vinyl monomers were changed Was prepared in the same manner as in Example 1.

<Comparative Example 1>
In Comparative Example 1, chitosan not subjected to hydroxyalkylation reaction (hydroxyalkylation degree = 0, 1 mass% acetic acid aqueous solution viscosity 6 mPa · s, deacetylation degree 85%, hereinafter simply referred to as “chitosan”) was used. Is. After 10 g of chitosan was dispersed in 90 g of N-vinylformamide (Aldrich reagent), the mixture was stirred at room temperature for 4 hours, but did not dissolve. Therefore, although the mixture was further stirred at room temperature for 72 hours, it was not dissolved at all, and an N-vinylformamide solution of chitosan could not be obtained.

<Comparative example 2>
In Comparative Example 2, 10 g of chitosan was dispersed in 90 g of N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd .: trade name DMAA) and then stirred at room temperature for 4 hours, but did not dissolve. Therefore, although the mixture was further stirred at room temperature for 72 hours, it was not dissolved at all, and an N, N-dimethylacrylamide solution of chitosan could not be obtained.

Evaluation of hydroxyalkyl chitosan or chitosan solubility for the vinyl monomers of Examples 1 to 16 and Comparative Examples 1 and 2 was performed according to the following criteria, and the results are shown in Table 1.
<Solubility evaluation criteria>
○: All can be dissolved to obtain a uniform solution.
Δ: Partially dissolved, but a uniform solution cannot be obtained.
X: Not dissolved at all.

<Example 17>
The following components were mixed to prepare a photosensitive resin composition.
-Monomer solution composition of Example 1 70 parts-Trimethylolpropane triacrylate 30 parts-Polyester acrylate 20 parts (Aronix M-8030, manufactured by Toagosei Co., Ltd.)
-Photopolymerization initiator 5 parts (1-hydroxycyclohexyl phenyl ketone)
・ Photopolymerization accelerator (ethyl p-diethylaminobenzoate) 3 parts

<Example 18>
-Monomer solution composition of Example 3 55 parts-Tripropylene glycol diacrylate 25 parts-2-Hydroxyethyl acrylate 20 parts-Polyester acrylate 30 parts (Aronix M-8030, manufactured by Toagosei Co., Ltd.)
-Photopolymerization initiator 5 parts (1-hydroxycyclohexyl phenyl ketone)
・ Photopolymerization accelerator (ethyl diethylaminobenzoate) 3 parts

<Example 19>
-60 parts of the monomer solution composition of Example 4-40 parts of pentaerythritol triacrylate-6 parts of polyester acrylate (Aronix M-7100 manufactured by Toagosei Co., Ltd.)
-Photopolymerization initiator 5 parts (1-hydroxycyclohexyl phenyl ketone)
・ Photopolymerization accelerator (ethyl diethylaminobenzoate) 3 parts

<Comparative Example 3>
-50 parts of acryloylmorpholine-25 parts of trimethylolpropane triacrylate-20 parts of 2-hydroxyethyl acrylate-30 parts of polyester acrylate (Aronix M-8030, manufactured by Toagosei Co., Ltd.)
-Photopolymerization initiator 5 parts (1-hydroxycyclohexyl phenyl ketone)
・ Photopolymerization accelerator (ethyl diethylaminobenzoate) 3 parts

The photosensitive resin compositions prepared in Examples 17 to 19 and Comparative Example 3 were applied to one side of a 100 μm thick biaxially stretched polyethylene terephthalate film with a bar coater so that the film thickness was about 10 μm. Then, the cured coating film was produced by irradiating the ultraviolet-ray of the integrated irradiation light quantity of 900 mJ / cm < ² > with the ultraviolet irradiation device carrying a high pressure mercury lamp. All of the obtained coating films had no cracks and had a smooth, homogeneous and stable coating film.

  Next, when the coating film obtained in Example 18 and Comparative Example 3 was printed with an ink jet printer using aqueous ink, the printed material of the coating film obtained in Example 18 was clear, whereas the Comparative Example The printed matter of the coating film obtained in 3 was unclear.

  According to the present invention as described above, there is provided a monomer solution composition capable of easily forming a smooth, excellent and hydrophilic coating film made of a vinyl polymer containing hydroxyalkyl chitosan on the surface of an article. Is done. The coating film can be printed by an ink jet method using water-based ink.

Claims (8)

A monomer solution composition comprising hydroxyalkyl chitosan dissolved in a vinyl monomer (excluding those containing an organic acid or a derivative thereof) . The vinyl monomer is N-vinylformamide, N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N The monomer solution composition according to claim 1, which is at least one selected from dimethylaminopropyl (meth) acrylamide and glycerin mono (meth) acrylate. The monomer solution composition according to claim 1 or 2 , wherein the hydroxyalkyl chitosan is at least one selected from hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan, and hydroxypropyl hydroxybutyl chitosan. Said hydroxyalkyl chitosan (A), the mass ratio of the vinyl monomer (B), A: B = 1: 99~80: monomer solution according to any one of claims 1 to 3 is 20 Composition. Said hydroxyalkyl chitosan is a reaction product of chitosan and an alkylene oxide, the degree of substitution of the alkylene oxide to the chitosan, the chitosan is at least 0.5 mol per pyranose ring 1 mol of constituting claim 1 The monomer solution composition as described in any one of -4 . The monomer solution composition according to any one of claims 1 to 5, which further contains a photopolymerization initiator and / or a photopolymerization accelerator and is photosensitive.   An article having a cured layer comprising the monomer solution composition according to claim 6.   The article according to claim 7, which is an article printed by an ink jet recording method.