Composition

Abstract

Disclosed is a composition comprising: a product of crosslinking of a hydrophilic polymer having a crosslinkable functional group; and a photo-radical generator. The product of crosslinking is a hydrophilic polymer having been crosslinked through a disulfide bond.

Description

[Technical Field]

[0001] The present disclosure relates to compositions. [Background technology]

[0002] Hydrophilic polymers such as carboxymethyl cellulose and crosslinked polymers thereof are being investigated for use in various applications such as scaffolding materials for cell culture (for example, Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] International Journal of Biological Macromolecules 134 (2019) 413-421 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of one aspect of the present invention is to provide a composition that contains a crosslinked hydrophilic polymer and exhibits photomeltability. [Means for solving the problem]

[0005] One aspect of the present invention relates to a composition comprising a crosslinked product of a hydrophilic polymer having a crosslinkable functional group and a photoradical generator, wherein the crosslinked product is a hydrophilic polymer crosslinked via a disulfide bond.

[0006] The composition contains a crosslinked product of a hydrophilic polymer having a crosslinkable functional group and a photoradical generator, and since the crosslinked product is a hydrophilic polymer crosslinked via a disulfide bond, it exhibits photomeltability.

[0007] The mechanism by which such an effect is obtained is presumed to be, for example, as follows, but is not limited to this. When the composition is irradiated with light, the disulfide bond reacts with the photoradical generator, causing the disulfide bond to decompose (cleave). It is presumed that the cleavage of the disulfide bond also decomposes the crosslinked structure of the crosslinked hydrophilic polymer, resulting in a lower molecular weight and melting of the composition. This reaction can be said to be an irreversible reaction.

[0008] The crosslinkable functional group may include at least one group selected from the group consisting of a carboxy group and an amino group. The hydrophilic polymer may be carboxymethyl cellulose.

[0009] The crosslinked material may be a condensation reaction product of the hydrophilic polymer and a reactive compound having a disulfide bond and a reactive group capable of reacting with the crosslinkable functional group to form a bond.

[0010] The crosslinked product may be a condensation reaction product between a hydrophilic polymer having a carboxy group and a reactive compound having a disulfide bond and an amino group, or a condensation reaction product between a hydrophilic polymer having an amino group and a reactive compound having a disulfide bond and a carboxy group. [Effects of the Invention]

[0011] According to one aspect of the present invention, it is possible to provide a composition that contains a crosslinked hydrophilic polymer and exhibits photomeltability. [Brief explanation of the drawings]

[0012] [Figure 1] 3 is a photograph showing the evaluation results of the photomeltability of the compositions of Examples 1 to 3. [Figure 2] 1 is a photograph showing the evaluation results of the photomeltability of the composition of Example 4. [Figure 3] 1 is a photograph showing the evaluation results of the photomeltability of the compositions of Examples 5 to 7. [Figure 4] 1 is a photograph showing the evaluation results of the photomeltability of the composition of Example 8. [Figure 5] 1 is a photograph showing the evaluation results of the photomeltability of the compositions of Examples 9 to 11. [Figure 6] 1 is a photograph showing the evaluation results of the photomeltability of the composition of Example 12. [Figure 7] 1 is a photograph showing the evaluation results of the photomeltability of the composition of Example 12 after immersion in water. [Figure 8] 1 is a photograph showing the results of evaluating the photo-melting properties of water-swollen products of the compositions of Examples 13 to 15. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0014] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. Furthermore, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively.

[0015] In this specification, the content of each component in a composition means the total amount of the components in the composition when the composition contains multiple substances corresponding to the component, unless otherwise specified. Furthermore, unless otherwise specified, the exemplified materials may be used alone or in combination of two or more.

[0016] Furthermore, in the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both.

[0017] The composition of one embodiment contains a crosslinked hydrophilic polymer having a crosslinkable functional group (hereinafter, sometimes referred to as "component (A)") and a photoradical generator (hereinafter, sometimes referred to as "component (B)"). The crosslinked hydrophilic polymer is crosslinked via a disulfide bond.

[0018] Component (A): Crosslinked hydrophilic polymer having crosslinkable functional groups Component (A) is a component formed by crosslinking a hydrophilic polymer having a crosslinkable functional group. The crosslinkable functional group is a group capable of forming a new bond by reaction. The crosslinkable reactive group may be, for example, a carboxy group (-COOH) or an amino group (-NH2). The hydrophilic polymer may have one or more types of crosslinkable functional groups. The hydrophilic polymer may have at least one group selected from the group consisting of a carboxy group and an amino group.

[0019] Examples of hydrophilic polymers having crosslinkable functional groups include hydrophilic polymers having carboxy groups but no amino groups, hydrophilic polymers having amino groups but no carboxy groups, and hydrophilic polymers having carboxy groups and amino groups.

[0020] Examples of hydrophilic polymers having at least a carboxy group include carboxymethyl cellulose, carboxymethyl chitosan, carboxymethyl dextran, N,N-dicarboxymethyl chitosan, carboxymethylhexanoyl chitosan, polylactic acid, alginic acid, gellan gum, hyaluronic acid, xanthan gum, pectin, pectinic acid, polygalacturonic acid, chondroitin 4-sulfate, chondroitin 6-sulfate, dermatan sulfate, succinoglycan, Agrobacterium succinoglycan, gum arabic, tragacanth gum, agar, carrageenan, polylactic acid, polyglutamic acid, polyaspartic acid, polymethacrylic acid, polyacrylic acid, acrylic acid / maleic acid copolymer, or salts thereof.

[0021] Examples of hydrophilic polymers having at least an amino group include chitosan, carboxymethylchitosan, N,N-dicarboxymethylchitosan, carboxymethylhexanoylchitosan, polyethyleneimine, polylysine, polyarginine, polyornithine, aminoethylated acrylic polymers, and salts thereof.

[0022] The weight-average molecular weight of the hydrophilic polymer having a crosslinkable functional group may be 10,000 to 10,000,000, 100,000 to 2,000,000, or 250,000 to 820,000. The weight-average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0023] The hydrophilic polymer may be a polysaccharide having a degree of etherification (DS) of 0.6 to 1.5. The degree of etherification of the hydrophilic polymer may be, for example, 0.6 to 0.8, or 1.0 to 1.5. The degree of etherification is the number of functional groups per monosaccharide constituting the sugar chain.

[0024] The hydrophilic polymer may be, for example, carboxymethyl cellulose, which tends to provide a composition with better photo-melting properties.

[0025] Component (A) may be crosslinked by a reactive compound having a disulfide bond and a reactive group capable of forming a bond with the crosslinkable functional group. The reactive group in the reactive compound may be a group capable of forming an amide bond (—C(═O)—NH—) with the crosslinkable functional group.

[0026] Examples of reactive groups capable of reacting with crosslinkable functional groups to form bonds include reactive groups capable of reacting with carboxy groups to form bonds and reactive groups capable of reacting with amino groups to form bonds. Examples of reactive groups capable of reacting with carboxy groups to form bonds include amino groups. Examples of reactive groups capable of reacting with amino groups to form bonds include carboxy groups, ester groups, etc.

[0027] Examples of reactive compounds that have a disulfide bond and a reactive group that can react with a carboxy group to form a bond include cystamine, cystine (L(-)-cystine, etc.), and salts thereof.

[0028] Examples of reactive compounds that have a disulfide bond and a reactive group that can react with an amino group to form a bond include dithiodipropionic acid, dithiodiglycolic acid, glutathione (oxidized), dithiodibutyric acid, and di(N-succinimidyl) 3,3'-dithiodipropionate.

[0029] The reactive compound having a disulfide bond and a reactive group capable of reacting with a crosslinkable functional group to form a bond may be a compound having a thiol group (—SH) and formed by an oxidation reaction of the thiol group in a compound having a reactive group.

[0030] Examples of reactive compounds that have a thiol group and a reactive group that can react with a carboxy group to form a bond include cysteine, 2-aminoethanethiol, 2,5-diamino-1,4-benzenedithiol, and salts thereof.

[0031] Examples of reactive compounds that have a thiol group and a reactive group that can react with an amino group to form a bond include cysteine, thioglycolic acid, 11-mercaptoundecanoic acid, glutathione (reduced), 4-mercaptobenzoic acid, 2-mercaptonicotinic acid, and 3-mercaptonicotinic acid.

[0032] The content of the reactive compound may be 10 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the hydrophilic polymer.

[0033] Component (A) can be formed by a condensation reaction between a hydrophilic polymer and a component having a disulfide bond. Component (A) may be, for example, a condensation reaction product between a hydrophilic polymer having a crosslinkable functional group and a reactive compound having a disulfide bond and a reactive group capable of reacting with the crosslinkable functional group to form a bond, a condensation reaction product between a hydrophilic polymer having a carboxy group and a reactive compound having a disulfide bond and an amino group, or a condensation reaction product between a hydrophilic polymer having an amino group and a reactive compound having a disulfide bond and a carboxy group.

[0034] A suitable combination of a hydrophilic polymer and a reactive compound may be a combination of carboxymethyl cellulose and cystamine, which is likely to provide a composition with superior photo-melting properties.

[0035] A condensing agent may be used for the condensation reaction, such as a conventional condensing agent capable of forming a peptide bond (—C(═O)—NH—) by reaction between a carboxy group and an amino group.

[0036] Examples of condensing agents include N,N'-diisopropylcarbodiimide (DIC), N,N'-di-(tert-butyl)carbodiimide, N,N'-dicyclohexylcarbodiimide (DCC), N-(tert-butyl)-N'-ethylcarbodiimide (BEC), N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide (CMC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC.HCl). Carbodiimides such as 1,1'-carbonyldiimidazole (CDI), 1,1'-carbonyldi(1,2,4-triazole) (CDT) Imidazolium compounds such as phosphoniums such as 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP), 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate (PyBOP), (7-azabenzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate (PyAOP), chlorotripyrrolidinophosphonium hexafluorophosphate (PyCloP), bromotris(dimethylamino)phosphonium hexafluorophosphate (Brop), 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazin-4(3H)-one (DEPBT), and (ethylcyano(hydroxyimino)acetato-O2)-tri-(1-pyrrolidinyl)phosphonium hexafluorophosphate (PyOxim); O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU), O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU), O-(benzotriazol-1-yl)-N,N,N',N'-bis(tetramethylene)uronium hexafluorophosphate (HBPyU), O-(benzotriazol-1-yl)-N,N,N',N'-bis( pentamethylene)uronium hexafluorophosphate (HBPipU), O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HCTU), O-(3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HDBTU), O-(2-oxo-1(2H)pyridyl)-N,N,N',N'-tetramethyluronium O-((ethoxycarbonyl)cyanomethyleneamino)-N,N,N',N'-tetramethyluronium hexafluorophosphate (TPTU), O-((ethoxycarbonyl)cyanomethyleneamino)-N,N,N',N'-tetramethyluronium tetrafluoroborate (TOTU), N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium hexafluorophosphate (HSTU), N,N,N',N'-tetramethyl -O-(N-succinimidyl)uronium tetrafluoroborate (TSTU), dipyrrolidino(N-succinimidyloxy)carbenium hexafluorophosphate (HSPyU), S-(1-oxido-2-pyridyl)-N,N,N',N'-tetramethylthiouronium tetrafluoroborate (TOTT), ((((1-cyano-2-ethoxy-2-oxoethylidene)amino)oxy)-4-morpholinomethylene)dimethylammonium hexafluorophosphate (COMU) Uronium compounds such as 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholium chloride n-hydrate (DMT-MM) triazine-based condensing agents such as Diphenylphosphoryl azide (DPPA) 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ), Di-tert-butyl dicarbonate (BocO) Examples include:

[0037] The content of the condensing agent may be 80 parts by mass or more and 180 parts by mass or less based on 100 parts by mass of the hydrophilic polymer.

[0038] In the condensation reaction, a reaction aid may be used, such as 4-dimethylaminopyridine (DMAP), 1-hydroxybenzotriazole (HOBt), or N-hydroxysuccinimide (HOSu).

[0039] The content of the reaction aid may be 15 parts by mass or more and 60 parts by mass or less based on 100 parts by mass of the condensing agent.

[0040] The temperature of the condensation reaction may be, for example, 0 to 50° C. The time of the condensation reaction may be, for example, 0.5 to 24 hours.

[0041] Component (B): Photoradical generator Component (B) may be a component that reacts with the thiyl radical generated when the composition is irradiated with light, or a component that generates a photoinduced radical. A photoradical polymerization initiator or the like can be used as the photoradical generator. Component (B) may be used alone or in combination of two or more.

[0042] Examples of component (B) include intramolecular cleavage-type photoradical polymerization initiators and hydrogen abstraction-type photoradical polymerization initiators. Examples of intramolecular cleavage-type photoradical polymerization initiators include benzyl ketal-based photoradical polymerization initiators; α-hydroxyacetophenone-based photoradical polymerization initiators; benzoin-based photoradical polymerization initiators; aminoacetophenone-based photoradical polymerization initiators; oxime ketone-based photoradical polymerization initiators; acylphosphine oxide-based photoradical polymerization initiators; titanocene-based photoradical polymerization initiators; S-phenyl thiobenzoate polymerization initiators; and high molecular weight derivatives thereof. Examples of hydrogen abstraction-type photoradical polymerization initiators include benzophenone-based photoradical polymerization initiators, thioxanthone-based photoradical polymerization initiators, and anthraquinone-based photoradical polymerization initiators.

[0043] Component (B) may be a water-soluble photoradical generator. In this case, the photomeltability of the composition becomes even more pronounced. A "water-soluble photoradical generator" is a photoradical generator that is soluble in water at a concentration of 0.2 mass % or more (0.2 g or more soluble in 100 g of water). Water solubility can be determined by visual inspection.

[0044] Specific examples of water-soluble photoradical generators include 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (for example, trade name H1361 (manufactured by Tokyo Chemical Industry Co., Ltd.)) and lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate (trade name L0290 (manufactured by Tokyo Chemical Industry Co., Ltd.)).

[0045] The amount of the component (B) may be 40 parts by mass or more, or 200 parts by mass or more, per 100 parts by mass of the component (A).

[0046] The content of component (B) may be, for example, greater than 0 mass % and not greater than 0.6 mass %, or greater than 0 mass % and not greater than 3 mass %, based on the total mass of the composition.

[0047] The composition may further contain water, or may not contain water. When the composition contains water, it can form a gel-like composition (hydrogel) because it contains a crosslinked hydrophilic polymer. When the composition does not contain water, it can be used as a powdery composition. The water content in the composition may be, for example, 90% by mass or more, or 95% by mass or more, or 99% by mass or less, based on the total mass of the composition.

[0048] The composition may contain, for example, sodium hydroxide in combination with water, which allows for even more efficient photofusion.

[0049] The composition may further contain other components in addition to the above-mentioned components. These components may be appropriately selected from known components. The total content of the other components may be 0 to 95% by mass, 0.01 to 50% by mass, or 0.1 to 10% by mass, based on the total amount of the composition.

[0050] The composition can be prepared, for example, by a method comprising a step of mixing or kneading components (A) and (B), water, and optional components. Mixing and kneading can be carried out using an appropriate combination of dispersing machines such as a conventional mixer, a mortar and pestle mixer, a triple-roll mill, a ball mill, or a bead mill.

[0051] The composition may be in the form of, for example, a powder, a gel, a film, etc. The composition according to this embodiment contains a crosslinked hydrophilic polymer, and therefore can form a hydrogel containing water therein.

[0052] The composition has the property that, upon light irradiation, the disulfide bonds in component (A) are cleaved, the compound having the disulfide bond is reduced in molecular weight, and thereby the composition melts. By utilizing this property, the composition according to the present embodiment can be used as a scaffold for cell culture because it has the property of melting upon light irradiation.

[0053] A melt of the composition according to one embodiment can be produced by a method comprising irradiating the composition described above with light to melt at least a portion of the composition to form a melt of the composition.

[0054] The light for the light irradiation is not particularly limited, and may be, for example, ultraviolet light or visible light. The wavelength of the light for the light irradiation may be 150 to 830 nm. The light irradiation may be carried out, for example, using a light irradiation device at an irradiation dose of 100 mJ / cm. 2 The irradiation can be carried out under the above conditions. The irradiation amount means the product of illuminance and irradiation time (seconds). Examples of light sources for irradiating ultraviolet light or visible light include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LED lamps. The light irradiation may be carried out directly on the composition or through glass or the like.

[0055] The composition may be irradiated with light while being heated, for example, at a temperature of 40 to 200°C.

[0056] A kit according to one embodiment includes a crosslinked product of a hydrophilic polymer having a crosslinkable functional group and a photoradical generator, the crosslinked product being a hydrophilic polymer crosslinked via a disulfide bond. The kit may be, for example, a kit for producing a scaffold for cell culture.

[0057] A kit according to another embodiment includes a hydrophilic polymer having a crosslinkable functional group, a reactive compound having a disulfide bond and a reactive group capable of forming a bond with the crosslinkable functional group, a photoradical generator, and a condensing agent. The kit may further include a reaction auxiliary. The kit may be a kit for producing a scaffold for cell culture. [Example]

[0058] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0059] As carboxymethyl cellulose (CMC), two types, A and B shown below, were prepared. Carboxymethyl cellulose A: manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 350,000 or less, n=1050 Carboxymethyl cellulose B: manufactured by Daicel Corporation, molecular weight: 250,000, degree of etherification (DS) = 0.6 to 0.8

[0060] 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) N-hydroxysuccinimide (NHS) Cystamine dihydrochloride

[0061] The following photoradical generators were prepared. 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name Omnirad TPO H) 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (trade name Omnirad127): manufactured by IGM Resins BV 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone (trade name Omnirad2959): manufactured by IGM Resins BV 2-Hydroxy-2-methyl-1-phenylpropanone (trade name Omnirad 1173): manufactured by IGM Resins BV 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (H1361): Tokyo Chemical Industry Co., Ltd. Lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate (L0290): manufactured by Tokyo Chemical Industry Co., Ltd.

[0062] Compositions of Examples 1 to 15 containing a crosslinked hydrophilic polymer, a photoradical generator, and water were prepared according to the formulations shown in the table below. The specific preparation methods are as follows. To an aqueous solution prepared by dissolving a hydrophilic polymer in water with stirring, a condensing agent and a reaction promoter were added in the amounts shown in the table below, and the solution was stirred for a certain period of time to dissolve. At the same time, an aqueous solution was prepared by dissolving a photoradical generator and a reactive compound in water with stirring. The two resulting aqueous solutions were then mixed.

[0063] In Examples 14 and 15, the solution containing the photoradical generator, cystamine, and sodium hydroxide was heated during addition in order to mix the photoradical generator as uniformly as possible.

[0064] The prepared composition was gelled. Gelling was confirmed by touching and visually confirming that the solution had solidified into a jelly-like substance.

[0065] <Evaluation of photodegradability> The compositions prepared by the above method were irradiated with light having a wavelength of 365 nm using a mercury lamp. For the compositions of Examples 1 to 7, the cumulative light dose was 4200 mJ / cm. 2 and cumulative light intensity of 8400mJ / cm 2 The photomeltability of the compositions was evaluated based on the results of light irradiation under the conditions. In the evaluation of the photomeltability of the compositions of Examples 1 to 7, "A" in the table indicates that deformation believed to be due to photomelt was confirmed, and "B" indicates that slight photomelt was confirmed. When photomelt was not confirmed, the composition was evaluated as "C." Figure 1 is a photograph showing the evaluation results of the photomeltability of the compositions of Examples 1 to 3. Figure 2 is a photograph showing the evaluation results of the photomeltability of the composition of Example 4. Figure 3 is a photograph showing the evaluation results of the photomeltability of the compositions of Examples 5 to 7.

[0066] [Table 1]

[0067] [Table 2]

[0068] For the compositions of Examples 8 to 12, the cumulative light dose was 2000 mJ / cm2 , cumulative light intensity 6000mJ / cm 2 , and 12000 mJ / cm 2 The photomeltability of the compositions was evaluated based on the results of light irradiation under the conditions shown in Figure 4. Figure 4 is a photograph showing the evaluation results of the photomeltability of the composition of Example 8. Figure 5 is a photograph showing the evaluation results of the photomeltability of the compositions of Examples 9 to 11. Figure 6 is a photograph showing the evaluation results of the photomeltability of the composition of Example 12. It was shown that when sodium hydroxide (NaOH) was contained, more significant photomeltability was exhibited (Comparison of Example 12 with Examples 11 and 12).

[0069] After the composition of Example 12 was immersed in water for a predetermined period of time, the obtained sample was irradiated with light having a wavelength of 365 nm using a mercury lamp. 2 , 400mJ / cm 2 and 800 mJ / cm 2 The results of irradiating a sample with light under the conditions shown in Figure 7 are shown. As shown in Figure 7, it was confirmed that the composition of Example 12 exhibited photomeltability even after immersion in water for 34 days. The results in Figure 7 confirm that the photoradical generator was not eluted and the photomeltability was not lost even when the composition was immersed in water for a long period of time. By immersing the composition in water, the amount of light required to melt it into a liquid state was significantly reduced.

[0070] [Table 3]

[0071] For the compositions of Examples 13 to 15, the cumulative light dose was 800 mJ / cm 2 The photomeltability of the compositions was evaluated based on the results of light irradiation under the conditions of Fig. 8. Fig. 8 is a photograph showing the evaluation results of the photomeltability when the water-swollen products obtained by immersing the compositions of Examples 13 to 15 in water were irradiated with light. For the compositions of Examples 13 to 15, the cumulative light dose was 800 mJ / cm2. 2 It was photo-melted into a liquid under the conditions.

[0072] [Table 4]

[0073] The composition of Example 16 was prepared in the same manner as in Example 13, except that the amount of CMC was changed to 0.60 g. It was confirmed that the composition gelled. Compared to the composition of Example 16, the composition of Example 13 had greater gel elasticity.

[0074] A composition of Example 16 was prepared having the formulation shown in Table 5. The specific preparation method was the same as in Examples 1 to 15. The composition of Example 16 prepared was gelled.

[0075] [Table 5]

[0076] The photomeltability of the composition of Example 16 was evaluated in the same manner as for the compositions of Examples 8-12.

[0077] The composition of Example 16, which contained an increased amount of cystamine, was also shown to have photo-melting properties.

Claims

1. a crosslinked hydrophilic polymer having a crosslinkable functional group; and a photoradical generator, the crosslinked material is a hydrophilic polymer crosslinked via a disulfide bond, The composition, wherein the hydrophilic polymer is carboxymethyl cellulose.

2. 2. The composition according to claim 1, wherein the crosslinked product is a condensation reaction product of the hydrophilic polymer and a reactive compound having a disulfide bond and a reactive group capable of reacting with the crosslinkable functional group to form a bond.

3. 3. The composition according to claim 1, wherein the crosslinked product is a condensation reaction product of the hydrophilic polymer and a reactive compound having a disulfide bond and an amino group.

Images