JP4978949B2 - Photosensitive resin, photosensitive composition and photocrosslinked product - Google Patents

Description

  The present invention relates to a photosensitive resin, a photosensitive composition, and a photocrosslinked body thereof, and in particular, photocrosslinking that can modify an arbitrary location on a substrate surface to a surface that is hydrophilic and suppresses nonspecific adsorption of a physiologically active substance. The present invention relates to a body and a pattern cell culture substrate using the same.

  Conventionally, various photosensitive resins and photosensitive compositions having a hydrophilic polymer in the main chain have been proposed. For example, photosensitive resins having a saponified polyvinyl acetate in the main chain have been developed (see Patent Document 1). ). This polyvinyl saponified product is water-soluble and can be applied in the form of a water-based solution, but the photocrosslinked product is water-resistant enough to be developed with water. However, the surface of the photocrosslinked body prepared using this photosensitive resin has a high static contact angle with respect to water, which is a hydrophilic index, of about 50 °, and the surface of the substrate is modified to be hydrophilic. From a viewpoint, it was not always sufficient.

The present inventors apply a polyethylene glycol-based photosensitive resin to the surface of a structure such as a medical device to modify the surface to control adsorption of physiologically active substances or cells to the structure interface. Have been invented and a patent application has been filed recently (Japanese Patent Application No. 2005-104768). The photosensitive resin introduced with a photosensitive group having an azide group at both ends or one end of the polyethylene glycol described in this application specification becomes a photosensitive composition when dissolved in a solvent, and is irradiated with light such as UV. It becomes a photocrosslinked substance insoluble in water. However, this photosensitive composition has a relatively low sensitivity, and the exposure amount for producing a water-insoluble photocrosslinked product is about 500 to 1000 mJ / cm ^2. If it had to be done, further sensitivity enhancement was required.

JP 2003-292477 A (paragraph numbers [0013], [0046], etc.)

  In view of such circumstances, the present invention can easily construct a hydrophilic and highly biocompatible surface coating by photocrosslinking, and a highly sensitive photosensitive resin and photosensitive composition, and a photocrosslinked product thereof. It is an issue to provide.

A first aspect of the present invention for solving the above-described problems resides in a photosensitive resin having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

(R ₁ and R ₂ are each independently an alkylene group having 2 to 5 carbon atoms, and R ₃ is a photosensitive group represented by the following formula (3) .)

(R ₄ is a group selected from the following formula (4), R ₅ is a group selected from the following formula (5), and at least one of R ₄ and R ₅ has at least one azide group.)

A second aspect of the present invention resides in the photosensitive resin according to the first aspect, wherein R ₄ is represented by the following formula (6) and R ₅ is represented by the following formula (7).

In the third aspect of the present invention, the number m of repeating units of the formula (1) and the number of repeating units n of the formula (2) are n + m = 40 to 400 and m / (m + n) = 0.001 to 0. .3 at the same time, the photosensitive resin according to the first or second aspect.

In a fourth aspect of the present invention, the terminal groups of the main chain are —R ₆ and —OR ₇ , wherein R ₆ and R ₇ are each independently a hydrogen atom or a methyl group. 3. The photosensitive resin according to any one of aspects 3 .

According to a fifth aspect of the present invention, there is provided a photosensitive composition characterized by being a solution in which the photosensitive resin according to any one of the first to fourth aspects is dissolved in a solvent.

According to a sixth aspect of the present invention, there is provided a photocrosslinked product obtained by applying the photosensitive composition according to the fifth aspect on a base material and then exposing the same to the base material, and being fixed on the base material. It is in the photocrosslinking body characterized by these.

According to a seventh aspect of the present invention, there is provided a pattern-constructed photocrosslinked product obtained by applying the photosensitive composition according to the fifth aspect on a base material, followed by pattern exposure and development. It is in the photocrosslinking body characterized by being fixed to.

An eighth aspect of the present invention is the photocrosslinked body according to the seventh aspect, which is a cell culture substrate.

  The photosensitive resin of the present invention can be dissolved in a solvent to form a photosensitive composition. When this photosensitive composition is irradiated with light such as UV, the surface becomes a hydrophilic photocrosslinked substance, and a gelling material, There exists an effect that it can be used suitably as a surface modifier, for example, the material which provides biocompatibility to the surface of a medical device.

  The photosensitive resin of the present invention is a compound having a repeating unit represented by the above general formula (1) and a repeating unit represented by the above formula (2), and is attached to the side chain of the main chain consisting of repeating units of oxyethylene. This is a structure in which a photosensitive group having an azide group is bonded via a spacer. Assuming that the number of repeating units represented by formula (1) is m and the number of repeating units represented by formula (2) is n, the average value of the degree of polymerization represented by m + n is as long as polymerization is possible. Although there is no restriction | limiting in particular, Preferably it is 40-400, Especially preferably, it is 60-310. When m + n = 40 to 400, the solubility of the obtained photosensitive resin in water can be sufficiently maintained even if the introduction rate of the photocrosslinking group is arbitrarily changed, and the photocrosslinked body can be formed using the photosensitive resin. When formed, the solubility of the photocrosslinked body in water becomes remarkable, so the contrast between the exposed area and the unexposed area increases. In addition, the surface is sufficient to maintain hydrophilicity even after photocrosslinking, and has sufficient molecular chain flexibility and excluded volume to exhibit biocompatibility. Moreover, it is preferable that it is m / (m + n) = 0.001-0.3, More preferably, m / (m + n) = 0.01-0.1, More preferably, m / (m + n) = 0.03 ~ 0.07. When m / (m + n) is within this range, the hydrophilicity of the surface of the photocrosslinked body and the decrease in solubility in water can more effectively exhibit the physical properties required particularly when applied to medical devices. It is.

R ₁ and R _{2 in} the general formula (1) are each independently an alkylene group having 2 to 5 carbon atoms and both are hydrophobic groups. R ₃ is a photosensitive group having an azide group, and is particularly preferably a photosensitive group represented by the above formula (3). This is because when R ₃ is a photosensitive group of the above formula (3), the photosensitive resin of the present invention has water solubility and can maintain the hydrophilicity of the surface even after photocrosslinking. In the above formula (3), R ₄ is a group selected from the above formula (4), R ₅ is a group selected from the above formula (5), and at least one of R ₄ and R ₅ is at least one. Having an azido group of The above formula (3) can have the same structure as a monovalent group in which Y—N—Z is eliminated from the photosensitive group unit represented by the general formula (1) in Patent Document 1. Specific examples of the formula (3) include structures (3) -1 to (3) -13 shown in Table 1 below. These structures have the substituents shown in Table 1 in the substituents R ₄ and R ₅ in the above formula (3). For example, structures (3) -1 to (3) -4 have an azide group as R ₅ , and (3) -5 has an azide group in both R ₄ and R ₅ . In particular, it is preferable that R ₄ is the above formula (6) and R ₅ is the above formula (7).

In the photosensitive resin of the present invention, the terminal group of the main chain is preferably —R ₆ and —OR ₇ (R ₆ and R ₇ are each independently a hydrogen atom or a methyl group). It becomes the photosensitive resin represented by 8). R ₆ and R ₇ can be arbitrarily determined depending on the polymerization initiator and the stopping reagent when the base polymer is synthesized.

(R _{1 to} R ₃ are the same as those in the above formula (1), and R ₆ and R ₇ are each independently a hydrogen atom or a methyl group. The bond form of each repeating unit is random, block, (Alternatively, any may be used. M + n = 40 to 400.)

  In addition, the photosensitive resin of the present invention has other structures in addition to the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) as long as the effects of the present invention are not impaired. For example, you may have the structure of following formula (9) and Formula (10) further. For example, when having the structure of the following formula (9), the repeating number p of the repeating unit represented by the formula (9) is p / (m + n) ≦ 0.01, preferably p / (m + n) ≦ 0.006. What should be done.

(R ₁ and R ₂ are the same as those in the above formula (1), and R ₈ represents an alkenyl group having 2 to 5 carbon atoms.)

The manufacturing method of the photosensitive resin of this invention which has a repeating unit represented by Formula (1) and a repeating unit represented by Formula (2) is not specifically limited. For example, polyethylene glycol having an amino group in the side chain, specifically, polyethylene glycol having —CH ₂ —O—R ₁ —S—R ₂ —NH ₂ and the amino group of this compound are combined with the above formula. What is necessary is just to make it react with the compound which forms the structure of (3).

  As polyethylene glycol having an amino group in the side chain, for example, alkenyl glycidyl ether such as allyl glycidyl ether and ethylene oxide are copolymerized at an arbitrary ratio, and then the side chain vinyl group and aminoalkylthiol of this compound are combined. The polymer obtained by making it react can be mentioned.

  Examples of the compound that combines with the amino group of polyethylene glycol having an amino group in the side chain to form the structure of the above formula (3) include 4-((4-azidophenyl) methylene) -2-phenyl-1, 3-Oxazolin-5-one (photofunctional compound 1), 4-((4-azidophenyl) methylene-2- (3-pyridyl) -1,3-oxazolin-5-one) (photofunctional compound 2) ), 2- (4-azidophenyl) -4- (3-pyridylmethylene) -1,3-oxazolin-5-one (photofunctional compound 3), 2- (2- (4-azidophenyl) vinyl) -4- (3-pyridylmethylene) -1,3-oxazolin-5-one (photofunctional compound 4), 4- (4-azido-β-methyl-cinnamylidene) -2-phenyl-2-oxazoline-5 -ON (photo sensory Compound 5), 4- (4-azido-β-methyl-cinnamylidene) -2- (3-pyridyl) -2-oxazolin-5-one (photofunctional compound 6), etc. A base unit is mentioned. In addition, this photofunctional compound can be manufactured by the method described in Patent Document 1.

  When the structure of the above formula (3) is introduced into polyethylene glycol having an amino group in the side chain, for example, a compound that combines with the amino group to form the structure of the above formula (3) is converted to an amino group present in the side chain. What is necessary is just to make it react with the quantity used as 1.2 times or more of molar equivalents. When the amount of the photosensitive group introduced into the side chain is arbitrarily adjusted, the amount of the alkenyl glycidyl ether is adjusted to a desired ratio when the base polymer is synthesized, or the above formula ( What is necessary is just to make it react by the molar equivalent corresponding to the ratio which requires the compound which forms the structure of 3).

  The photosensitive composition of the present invention is obtained by dissolving a photosensitive resin having a repeating unit represented by the above formula (1) and a repeating unit represented by the formula (2) in a solvent. The solvent of the photosensitive composition is not particularly limited as long as the photosensitive resin can be dissolved, but water, an organic solvent compatible with water, or a mixture thereof is preferable. Examples of the organic solvent compatible with water include ketones such as acetone, alcohols such as ethanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide.

  Although the ratio of the photosensitive resin contained in the photosensitive composition of the present invention is not particularly limited as long as the photosensitive resin can be dissolved, it is preferably 0.1 to 30% by weight. Note that one type or a plurality of types of photosensitive resins may be used, and the introduction rate of the photosensitive group may be constant or not constant.

  Here, when a photosensitive composition is formed using a photosensitive resin having a relatively large molecular weight, for example, a molecular weight of 3000 or more, an association or the like may be formed by interaction between photosensitive groups in the photosensitive composition. . In addition, fine particles existing in the atmosphere may be mixed during the preparation of the photosensitive composition. A photocrosslinked product obtained by irradiating a photosensitive composition containing such an aggregate or fine particles with light such as UV sometimes forms a phase separation structure or defect of a size of several tens of μm. . The phase separation structure is a structure in which photosensitive groups that are hydrophobic groups are aggregated by hydrophobic interaction and separated from the polymer main chain phase. Although it is possible to use a photocrosslinked body as it is, it is desirable that the formation of such a large phase separation structure and defects are removed depending on the application. For example, when a portion having a size larger than the wavelength of light and having a different refractive index of light is present in the photocrosslinked body, the transparency may be remarkably lowered due to light scattering and turbidity. Therefore, it is possible to remove the fine particles from the photosensitive composition so that the photosensitive composition does not contain, for example, particles having an average particle diameter of 100 nm or more. Filtration is suitable as a method for removing fine particles from the photosensitive composition, and examples of the filtration method include known pressure filtration and vacuum filtration. The filtration membrane is not particularly limited as long as it can destroy or filter aggregates and fine particles, but a cellulose acetate filtration membrane is preferable.

  Moreover, the photosensitive group of the photosensitive resin contained in the photosensitive composition may have an ionic dissociation group such as a pyridyl group or a pyranidyl group. In an aqueous photosensitive composition containing such a photosensitive resin, the pH of the solution is particularly important. This is because the photosensitive group can take two states of dissociation and non-dissociation of the ionic group depending on the surrounding pH environment, so that the water solubility locally (around the photosensitive group) changes greatly. That is, the pH greatly affects the wettability of the photosensitive composition to the substrate, the sensitivity when irradiated with light, and the mechanical strength of the formed photocrosslinked body. The pH of the photosensitive composition of the present invention is preferably 0 to 10, more preferably 1 to 7.

  The photosensitive composition of this invention may contain the additive in the range which does not inhibit formation of a photocrosslinked body. Examples of the additive include mineral acids, organic acids and the like as acids for adjusting the pH of the photosensitive composition, and sodium hydroxide, potassium hydroxide and aqueous ammonia as bases. Further, a salt such as sodium chloride for adjusting the salt strength, a buffer solution such as a phosphate buffer for stabilizing the pH, an antifoaming agent, and the like can also be added.

  When the photosensitive composition is heated to a temperature higher than the temperature at which the azide group decomposes, or is irradiated with light such as UV, a crosslinked product is obtained. As one form of the photocrosslinked body of the present invention, a photosensitive composition is applied onto a substrate to form a coating film, and the coating film is irradiated with light to form a photocrosslinked body (resin film) on the surface of the substrate. Can be mentioned in a fixed state.

  The surface of such a photocrosslinked product of the present invention is very hydrophilic. This is because the cross-linked structure produced by photoreaction of a hydrophobic photosensitive group is relatively hydrophobic, and contact with water at the interface is disadvantageous in terms of free energy. This is presumed to be because the structure portion made of is in contact with water on the surface. Therefore, since the hydrophobic part is not substantially exposed on the surface, the photocrosslinked product of the present invention can be used, for example, for a purpose of hydrophilizing the substrate.

  An example of a method for measuring a static contact angle serving as an index of hydrophilicity is as follows. Using a measuring device “FTÅ125” manufactured by First Ten Angstroms, the temperature is 25 ° C. and the humidity is 50%. There can be mentioned a method in which about 2 μl of water droplets are dropped on the surface of the photocrosslinked body under the conditions and the static contact angle after 8 seconds is read. The static contact angle of the surface of the photocrosslinked body with respect to water is preferably 35 ° or less, more preferably 25 ° or less.

  The material and shape of the substrate are not particularly limited. Examples of the material of the base material include glass, thermoplastic resin, thermosetting resin, silicon, diamond, metal, and ceramic, and glass and thermoplastic resin are particularly preferable. On the glass, the photo-crosslinked product and the substrate can be firmly bonded by, for example, complexing the polyethylene glycol chain as the main chain with an alkali metal or the like present on the glass surface. On the thermoplastic resin, a radical formed by photoirradiation of a photosensitive functional group of the photosensitive resin forms a covalent bond by drawing out hydrogen or the like in the base resin, thereby forming a photocrosslinked product. Can be firmly bonded to the substrate. Examples of the shape of the substrate include a plate shape, a plate shape having a curved surface, a fiber shape, a substrate having a microporous surface structure, a capillary shape, and a tubular shape, and a plate shape is particularly preferable. This is because it can be suitably used when a patterned photocrosslinked body is formed on a substrate through a mask. Further, a substrate whose surface is modified, for example, a glass in which an alkyl group or an amino group is introduced with a silane coupling agent or the like may be used. This is because the azide group, which is a photosensitive group of the photosensitive resin, becomes a nitrene group upon irradiation with light and reacts radically, so that the photocrosslinked body and the substrate are more firmly bonded. Furthermore, you may use what coat | covered the surface with physiologically active substances like collagen. In this case as well, the photocured film and the coated physiologically active substance can be firmly bonded by forming a covalent bond by light irradiation, and if exposed through a mask, the photosensitive resin is removed from the unexposed area. After that, there is an advantage that the physiologically active substance is exposed and its function can be utilized.

  When the surface of the substrate is contaminated, phase separation in the film is likely to occur after application of the photosensitive composition and before light irradiation, or defects may be generated. In order to prevent such unintended deterioration of the shape, the substrate surface may be washed. The glass substrate is cleaned by a known method, for example, a wet cleaning method such as organic solvent cleaning, alkaline aqueous solution cleaning or hydrofluoric acid aqueous solution cleaning, or a dry cleaning method such as compressed air cleaning, ozone cleaning or plasma treatment cleaning. be able to.

  The photocrosslinked product of the present invention comprises a step of applying a photosensitive composition on a substrate to form a photosensitive composition coating film, and exposing the photosensitive composition coating film to form a photocrosslinked product. It can fix to a base material by the process and the process of developing with water or an aqueous | water-based developing solution as needed, and forming a pattern-form photocrosslinked body.

  Although the thickness of the photosensitive composition apply | coated on the base material is not specifically limited as long as application | coating is possible, A suitable film thickness is 5 nm-10 micrometers. If the film thickness is less than 5 nm, it is not easy to form a film uniformly. Further, when a film having a film thickness exceeding 10 μm is prepared, it is necessary to increase the viscosity of the solution of the photosensitive composition, and problems in the coating process are likely to occur. Of course, it is possible to set the film thickness outside the above range in consideration of this problem.

  You may heat-process as needed after apply | coating the photosensitive composition on a base material. There are no particular limitations on the heat treatment conditions, but usually it is 30 to 150 ° C. for 1 minute to 10 hours, preferably 35 ° C. to 120 ° C. for 3 minutes to 1 hour.

  Moreover, even if the whole surface of the photosensitive composition apply | coated on the base material is exposed, a desired pattern area may be exposed. In the case of pattern exposure, a photocrosslinked product having a pattern shape can be obtained by developing after exposure and removing the unexposed portion. When exposing a desired pattern area, a mask having a structure in which a pattern corresponding region transmits light and other areas do not transmit light may be used for exposure through the mask.

The light source for exposure is not particularly limited as long as it is a light source capable of exposing the photosensitive resin of the present invention. Examples of the light source include an X-ray, an electron beam, an excimer laser (F ₂ , ArF, KrF laser, etc.), a xenon lamp, a metal halide lamp, and a high-pressure mercury lamp. Structure of exposure energy photosensitive functional group, used may be appropriately set according to the energy of the light source is usually ^{0.1mJ / cm 2 ~1000mJ / cm 2} , particularly 1mJ / cm ² ~200mJ / cm ² of about Is preferred. Moreover, when exposing, you may give heat in the range which does not impair the effect by this invention as needed.

In the case of a photosensitive composition using a photosensitive resin having a photosensitive group introduced at both ends or one end of polyethylene glycol described in Japanese Patent Application No. 2005-104768, when forming a patterned photocrosslinked body Although exposure amount was about 500~1000mJ / cm ² required, when the photosensitive composition using a photosensitive resin of the present invention having a photosensitive group in the side chain, the optimal exposure amount 1 to 200 mJ / It becomes cm ^2, and its sensitivity is about 1000 times 2 times.

  When the entire surface is exposed, washing with water may be performed after heating as necessary. The conditions for the heat treatment are usually 30 to 150 ° C. for about 1 minute to 10 hours, preferably 35 to 120 ° C. for about 3 minutes to 1 hour. Further, after pattern exposure, if necessary, development can be performed after heating. The conditions for this heat treatment are the same as when the entire surface is exposed.

  The developing solution for development is not particularly limited as long as it has a sufficient difference in solubility between the unexposed area and the exposed area. As a solvent that can dissolve the unexposed region of the coating film of the photosensitive composition, water, an organic solvent compatible with water, a mixed solution thereof, or the like can be used. Non-limiting examples of organic solvents that are compatible with water include ketones such as acetone, alcohols such as ethanol, acetonitrile, tetrahydrofuran, and the like. When these solvents are used, a good pattern having no development residue can be suitably produced. Further, the developer may be a mixed solution as described above, and the concentration thereof is not particularly limited as long as it dissolves the unexposed area. For example, if the developer is a mixed solution of water and methanol, The density can be any value greater than 0 and less than 100%. The development can be performed by a method of immersing the object to be processed after exposure in a developer, a method of applying and spraying the developer to the object to be processed, or the like. After pattern formation by development, rinsing and drying may be performed as necessary.

  What fixed the photocrosslinked body of this invention on the base material can be used suitably also in any environment in a dry state, a humidified state, and a solution. Not only can the structure be sufficiently maintained in a dry state or a humidified state, but also stably in an organic solvent, water or an aqueous solvent for a long period of time, for example, 1 day or more, and further 10 days or more. Maintain its structure. Since it can exist stably in a solution, particularly in water or an aqueous solvent, it can be used as a medical device. This is because when used for a medical device or the like, the surface of the device is often exposed to a dry state, an aqueous solution, or an organic solvent solution, and it is required to have resistance to any of them. The photocrosslinked product of the present invention is suitable as a medical device because it is stable even in water at about 37 ° C. or in an aqueous solvent.

  Here, the aqueous solvent is not particularly limited as long as it is a solution containing water. Examples of the aqueous solvent include ketones such as acetone, alcohols such as ethanol, a mixture of water and an organic solvent compatible with water such as acetonitrile and tetrahydrofuran, potassium dihydrogen phosphate / disodium hydrogen phosphate aqueous solution, carbonic acid Buffers such as sodium hydrogen carbonate and sodium carbonate solutions, inorganic and organic salt solutions such as sodium chloride, potassium chloride, and ammonium chloride, and saccharide solutions containing monosaccharides and polysaccharides such as glucose, galactose, glucose, starch, heparin, heparan sulfate, etc. , Protein aqueous solutions, DNA, RNA aqueous solutions, liquid media, and mixtures thereof. Further, it may include those that do not dissolve in water or an aqueous solvent, for example, minerals such as clay, metal fine particles such as gold nanoparticles, polymer fine particles such as polystyrene beads and latex particles, animal cells, There may be mentioned plant cells, microorganisms, viruses and the like, and mixtures thereof.

  In addition, the photocrosslinked body according to the present invention is preferably used under a temperature condition in which the photocrosslinked body itself or the composite composed of the photocrosslinked body and the substrate does not become unstable, and a particularly preferable temperature is 10 ° C to 60 ° C. is there.

  Furthermore, by using a culture substrate or collagen-coated substrate as a substrate, creating a photocrosslinked body on the surface, the surface of the substrate can be modified to be hydrophilic, or a hydrophilic surface and a hydrophobic surface. Can be constructed and can be easily used in new culture systems such as pattern culture. The cell culture substrate has a desired shape such as holes or stripes after coating with collagen or the like, if necessary, using glass or hydrophilized polystyrene as the substrate, for example. Thus, a photocrosslinked product having a pattern formed thereon. This realizes a cell culture substrate in which cells do not adhere to the part where the photosensitive resin is photocured, and cells adhere only to the part where the substrate is exposed, resulting in cells being arranged in a pattern. it can.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples at all.

(Example 1) Synthesis of photosensitive resin A Amino group-introduced polyethylene glycol having a repeating unit of the following formula (a) and having both ends of the main chain being hydroxyl groups (manufactured by NOF Corporation, molecular weight 3200, Average repeating unit number x = 3.1, y = 60.0) 0.5 g, 0.2 g of the above-mentioned photofunctional compound 4 (1.5 times molar equivalent to the amino group of the polyethylene glycol derivative), Tetrahydrofuran (THF) 7 g was mixed and reacted at 25 ° C. for 19 hours. After completion of the reaction, THF was removed under reduced pressure, and then 7 g of water and 7 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 7 g of ethyl acetate was newly added, and liquid separation extraction was performed again. After standing, the aqueous phase was separated. This aqueous phase is freeze-dried to have each repeating unit of the following formula (b), both ends of the main chain are hydroxyl groups, and the average number of repeating units is m = 3.0 and n = 60. 0.6 g of photosensitive resin A with 0 and p = 0.1 was obtained. When the obtained photosensitive resin A was measured by ¹ H-NMR, it was derived from the proton peak of the methylene chain of polyethylene oxide found at 3.5 ppm and the photofunctional compound 4 found from 6.8 ppm to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. Moreover, m / (m + n) was 0.048 from the integration ratio of these peaks.

(Example 2) Synthesis of photosensitive resin B Amino group-introduced polyethylene glycol having each repeating unit of the above formula (a) and having both ends of the main chain being hydroxyl groups (manufactured by NOF Corporation, molecular weight 5400, Average repeating unit number x = 5.3, y = 100.0) 0.5 g, 0.2 g of the above-mentioned photofunctional compound 4 (1.5 times molar equivalent to the amino group of the polyethylene glycol derivative), Tetrahydrofuran (THF) 7 g was mixed and reacted at 25 ° C. for 19 hours. After completion of the reaction, THF was removed under reduced pressure, and then 7 g of water and 7 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 7 g of ethyl acetate was newly added, and liquid separation extraction was performed again. After standing, the aqueous phase was separated. This aqueous phase is freeze-dried to have each repeating unit of the above formula (b), both ends of the main chain are hydroxyl groups, and the average number of repeating units is m = 5.0, n = 100. 0.6 g of photosensitive resin B with 0 and p = 0.3 was obtained. When the obtained photosensitive resin B was measured by ¹ H-NMR, it was derived from the proton peak of the methylene chain of polyethylene oxide found at 3.5 ppm and the photofunctional compound 4 found from 6.8 ppm to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. Moreover, m / (m + n) was 0.047 from the integration ratio of these peaks.

(Example 3) Synthesis of photosensitive resin C Amino group-introduced polyethylene glycol having a repeating unit of the above formula (a) and having both ends of the main chain being hydroxyl groups (manufactured by NOF Corporation, molecular weight 10800, 0.5 g of the average number of repeating units x = 10.5, y = 200.0), 0.2 g of the above-mentioned photofunctional compound 4 (1.5 molar equivalent to the amino group of the polyethylene glycol derivative), Tetrahydrofuran (THF) 7 g was mixed and reacted at 25 ° C. for 19 hours. After completion of the reaction, THF was removed under reduced pressure, and then 7 g of water and 7 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 7 g of ethyl acetate was newly added, and liquid separation extraction was performed again. After standing, the aqueous phase was separated. This aqueous phase is freeze-dried to have each repeating unit of the above formula (b), both ends of the main chain are hydroxyl groups, and the average number of repeating units is m = 10.0, n = 200. 0.5 g of photosensitive resin C with 0 and p = 0.5 was obtained. When the obtained photosensitive resin C was measured by ¹ H-NMR, it was derived from the proton peak of the polyethylene oxide methylene chain found at 3.5 ppm and the photofunctional compound 4 found from 6.8 ppm to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. Moreover, m / (m + n) was 0.048 from the integration ratio of these peaks.

(Example 4) Synthesis of photosensitive resin D An amino group-introduced polyethylene glycol having each repeating unit of the above formula (a) and having both ends of the main chain being hydroxyl groups (manufactured by NOF Corporation, molecular weight 15400, Average repeating unit number x = 15.0, y = 286.0) 0.5 g, 0.2 g of the above-mentioned photofunctional compound 4 (1.5 molar equivalents with respect to the amino group of the polyethylene glycol derivative), Tetrahydrofuran (THF) 7 g was mixed and reacted at 25 ° C. for 19 hours. After completion of the reaction, THF was removed under reduced pressure, and then 7 g of water and 7 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 7 g of ethyl acetate was newly added, and liquid separation extraction was performed again. After standing, the aqueous phase was separated. This aqueous phase is freeze-dried to have each repeating unit of the above formula (b), both ends of the main chain are hydroxyl groups, and the average number of repeating units is m = 13.5, n = 286. 0.6 g of photosensitive resin D with 0 and p = 1.5 was obtained. When the obtained photosensitive resin D was measured by ¹ H-NMR, it was derived from the proton peak of the methylene chain of polyethylene oxide found at 3.5 ppm and the photofunctional compound 4 found from 6.8 ppm to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. Moreover, m / (m + n) was 0.045 from the integration ratio of these peaks.

(Example 5) Synthesis of photosensitive resin E Amino group-introduced polyethylene glycol having each repeating unit of the above formula (a) and having both ends of the main chain being hydroxyl groups (manufactured by NOF Corporation, molecular weight 3200, Average repeating unit number x = 3.1, y = 60.0) 0.5 g, 0.2 g of the above-mentioned photofunctional compound 3 (1.5 times molar equivalent to the amino group of the polyethylene glycol derivative), Tetrahydrofuran (THF) 7 g was mixed and reacted at 25 ° C. for 19 hours. After completion of the reaction, THF was removed under reduced pressure, and then 7 g of water and 7 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 7 g of ethyl acetate was newly added, and liquid separation extraction was performed again. After standing, the aqueous phase was separated. This aqueous phase is freeze-dried to have each repeating unit of the following formula (c), both ends of the main chain are hydroxyl groups, and the average number of repeating units is m = 2.9 and n = 60. 0.6 g of photosensitive resin E with 0 and p = 0.2 was obtained. When the obtained photosensitive resin E was measured by ¹ H-NMR, it was derived from the proton peak of the polyethylene oxide methylene chain found at 3.5 ppm and the photofunctional compound 3 found from 6.8 ppm to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. Moreover, m / (m + n) was 0.046 from the integration ratio of these peaks.

(Example 6) Synthesis of photosensitive resin F Amino group-introduced polyethylene glycol having each repeating unit of the above formula (a) and having both ends of the main chain being hydroxyl groups (manufactured by NOF Corporation, molecular weight 3200, Average repeating unit number x = 3.1, y = 60.0) 0.5 g, 0.2 g of the above-mentioned photofunctional compound 6 (1.5 times molar equivalent to the amino group of the polyethylene glycol derivative), Tetrahydrofuran (THF) 7 g was mixed and reacted at 25 ° C. for 19 hours. After completion of the reaction, THF was removed under reduced pressure, and then 7 g of water and 7 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 7 g of ethyl acetate was newly added, and liquid separation extraction was performed again. After standing, the aqueous phase was separated. This aqueous phase is freeze-dried to have each repeating unit of the following formula (d), both ends of the main chain are hydroxyl groups, and the average number of repeating units is m = 2.95 and n = 60. 0.6 g of photosensitive resin F with 0 and p = 0.15 was obtained. When the obtained photosensitive resin F was measured by ¹ H-NMR, it was derived from the proton peak of the polyethylene oxide methylene chain found at 3.5 ppm and the photofunctional compound 6 found from 6.8 ppm to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. Moreover, m / (m + n) was 0.047 from the integration ratio of these peaks.

(Example 7) Synthesis of photosensitive resin G Amino group-introduced polyethylene glycol having each repeating unit of the above formula (a) and having both ends of the main chain being hydroxyl groups (manufactured by NOF Corporation, molecular weight 3200, Average repeating unit number x = 3.1, y = 60.0) 0.5 g, 0.2 g of the above-mentioned photofunctional compound 5 (1.5 times molar equivalent to the amino group of the polyethylene glycol derivative), Tetrahydrofuran (THF) 7 g was mixed and reacted at 25 ° C. for 19 hours. After completion of the reaction, THF was removed under reduced pressure, and then 7 g of water and 7 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 7 g of ethyl acetate was newly added, and liquid separation extraction was performed again. After standing, the aqueous phase was separated. This aqueous phase is freeze-dried to have each repeating unit of the following formula (e), both ends of the main chain are composed of hydroxyl groups, and the average number of repeating units is m = 2.95 and n = 60, respectively. 0.5 g of photosensitive resin G with 0.0 and p = 0.15 was obtained. When the obtained photosensitive resin G was measured by ¹ H-NMR, it was derived from the proton peak of the methylene chain of polyethylene oxide found at 3.5 ppm and the photofunctional compound 5 found from 6.8 ppm to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. Moreover, m / (m + n) was 0.047 from the integration ratio of these peaks.

(Example 8) Synthesis of photosensitive resin H An amino group-introduced polyethylene glycol having each repeating unit of the above formula (a) and having both ends of the main chain being hydroxyl groups (manufactured by NOF Corporation, molecular weight 3200, Average repeating unit number x = 3.1, y = 60.0) 0.5 g, 0.2 g of the above-mentioned photofunctional compound 1 (1.5 times molar equivalent to the amino group of the polyethylene glycol derivative), Tetrahydrofuran (THF) 7 g was mixed and reacted at 25 ° C. for 19 hours. After completion of the reaction, THF was removed under reduced pressure, and then 7 g of water and 7 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 7 g of ethyl acetate was newly added, and liquid separation extraction was performed again. After standing, the aqueous phase was separated. This aqueous phase is freeze-dried to have each repeating unit of the following formula (f), both ends of the main chain are hydroxyl groups, and the average number of repeating units is m = 2.8 and n = 60. 0.6 g of photosensitive resin H with 0 and p = 0.3 was obtained. When the obtained photosensitive resin H was measured by ¹ H-NMR, it was derived from the proton peak of the methylene chain of polyethylene oxide found at 3.5 ppm and the photofunctional compound 1 found from 6.8 ppm to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. Moreover, m / (m + n) was 0.045 from the integration ratio of these peaks.

(Example 9) Preparation of photosensitive composition I The photosensitive resin A obtained in Example 1 was dissolved in water adjusted to the pH shown in Table 2 with hydrochloric acid or sodium hydroxide, and shown in Table 2. Each concentration solution was adjusted. Each obtained aqueous solution was filtered with a 0.2 μm cellulose acetate membrane filter (hereinafter referred to as “filter”) to obtain photosensitive compositions I-1 to I-7.

(Example 10) Preparation of photosensitive composition II The same procedure as in Example 9 was carried out except that the photosensitive resin B obtained in Example 2 was used instead of the photosensitive resin A, and the concentrations shown in Table 2 were obtained. Solution was obtained. Photosensitive compositions II-1 to II-7 were obtained by filtering each aqueous solution obtained with a 0.2 μm filter.

(Example 11) Preparation of photosensitive composition III The same operations as in Example 9 were performed except that the photosensitive resin C obtained in Example 3 was used instead of the photosensitive resin A, and the concentrations shown in Table 2 were obtained. Solution was obtained. Each aqueous solution obtained was filtered through a 0.2 μm filter to obtain photosensitive compositions III-1 to III-7.

(Example 12) Preparation of photosensitive composition IV Except that photosensitive resin D obtained in Example 4 was used instead of photosensitive resin A, the same operations as in Example 9 were performed, and the concentrations shown in Table 2 were obtained. Solution was obtained. The obtained aqueous solutions were filtered with a 0.2 μm filter to obtain photosensitive compositions IV-1 to IV-7.

(Example 13) Preparation of photosensitive compositions V to VII The photosensitive resin A obtained in Example 1 was mixed with water: methanol = 80: 20 (for preparing photosensitive composition V), 50:50 (photosensitive). Dissolved in a mixed solution of composition VI for preparation) or 20:80 (for preparation of photosensitive composition VII) (each in a weight ratio) to obtain a 5% by weight solution. Photosensitive compositions V to VII were obtained by filtering each obtained solution with a 0.2 μm filter.

(Example 14) Preparation of photosensitive compositions VIII to XI The photosensitive resins E to H obtained in Examples 5 to 8 were dissolved in pure water so as to be 5% by weight, respectively. XI was obtained (photosensitive resin E aqueous solution = photosensitive composition VIII, photosensitive resin F aqueous solution = photosensitive composition IX, photosensitive resin G aqueous solution = photosensitive composition X, photosensitive resin H aqueous solution = photosensitive composition. Thing XI). Photosensitive compositions VIII to XI were obtained by filtering each obtained solution through a 0.2 μm filter.

Example 15 Photocrosslinked Body Using Photosensitive Composition I A soda lime slide glass (manufactured by Matsunami Glass Industry Co., Ltd., hereinafter abbreviated as “non-coated glass”) was used as a substrate. The photosensitive composition I-4 was dropped on a non-coated glass, formed into a film by a spin coating method (1000 rpm × 30 seconds), dried at 60 ° C. for 10 minutes, and then cooled to room temperature. Thereafter, whole surface exposure (exposure amount: 200 mJ / cm ² ) was performed with a high-pressure mercury lamp. After washing in water at 25 ° C. for 1 minute, drying was performed at 60 ° C. for 10 minutes to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 16)
Except having used photosensitive composition I-2 instead of photosensitive composition I-4, operation similar to Example 15 was performed and the photocrosslinked body fixed on the base material by photocrosslinking was obtained.

(Example 17)
In the same manner as in Example 15 except that exposure is performed through a mask so as to obtain a pattern in which a large number of holes having a diameter of 100 μm are provided at the time of exposure, the hole pattern is fixed on the substrate by photocrosslinking and the surface has a hole pattern. A formed photocrosslinked product was obtained.

(Example 18)
In the same manner as in Example 16 except that exposure is performed through a mask so as to obtain a pattern in which a large number of holes having a diameter of 100 μm are provided at the time of exposure, the hole pattern is fixed on the substrate by photocrosslinking and is formed on the surface. A formed photocrosslinked product was obtained.

(Example 19)
In the same manner as in Example 15 except that exposure is performed through a mask so that a line / space pattern of 100 μm / 200 μm is obtained during exposure, the film is fixed on the substrate by photocrosslinking and has a line of 100 μm / 200 μm / A photocrosslinked product in which a space pattern was formed was obtained.

(Example 20)
The same operation as in Example 15 except that the soda lime glass used was immersed in a 5% by weight hydrofluoric acid aqueous solution for 1 minute, washed, rinsed with pure water and then dried with nitrogen gas as the base material. Then, a photocrosslinked body fixed on the substrate by photocrosslinking was obtained.

(Example 21)
In the same manner as in Example 20, except that the exposure is performed through a mask so that a pattern in which a large number of holes having a diameter of 100 μm are provided is obtained, the hole pattern is fixed on the substrate by photocrosslinking and the surface has a hole pattern. A formed photocrosslinked product was obtained.

(Example 22)
The soda lime glass was immersed in an alkaline aqueous solution (pure water: isopropyl alcohol: sodium hydroxide weight ratio = 93: 5: 2 (weight ratio)) for 2 minutes for cleaning, rinsed with pure water, and then dried with nitrogen gas. The same operation as in Example 17 was performed except that the product was used as a base material to obtain a photocrosslinked body fixed on the base material by photocrosslinking and having a hole pattern formed on the surface.

(Example 23)
In the same manner as in Example 22 except that exposure is performed through a mask so as to obtain a pattern in which a large number of holes having a diameter of 100 μm are provided at the time of exposure, the hole pattern is fixed on the substrate by photocrosslinking and is formed on the surface. A formed photocrosslinked product was obtained.

(Example 24)
An aminosilane-coated cover glass (21 mm in diameter, manufactured by Matsunami Glass Industry Co., Ltd.), which is a glass substrate that is surface-modified with an amino group, was used as the substrate. This aminosilane-coated cover glass was immersed in a pig skin-derived collagen type I aqueous solution (0.02% by weight) overnight, washed and dried with pure water for a predetermined time, and a collagen-coated glass was produced. Photosensitive composition I-4 was dropped onto this collagen-coated glass, a film was formed by spin coating (1000 rpm × 30 seconds), dried at 60 ° C. for 10 minutes, and then cooled to room temperature. Thereafter, whole surface exposure (exposure amount: 200 mJ / cm ² ) was performed with a high-pressure mercury lamp. After washing in water at 25 ° C. for 1 minute, drying was performed at 60 ° C. for 10 minutes to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 25)
In the same manner as in Example 24 except that the exposure is performed through a mask so that a pattern in which a large number of holes having a diameter of 100 μm are arranged is obtained, the hole pattern is fixed on the substrate by photocrosslinking and the surface has a hole pattern. A formed photocrosslinked product was obtained.

(Example 26)
A substrate made of Permanox Plastic (manufactured by Nunk, Cell Culture Slide 160005, hereinafter abbreviated as “Permanox Slide”) was used as the substrate. The photosensitive composition I-4 was dropped on a Permanox slide, formed into a film by a spin coating method (1000 rpm × 30 seconds), dried at 60 ° C. for 10 minutes, and then cooled to room temperature. Thereafter, whole surface exposure (exposure amount: 200 mJ / cm ² ) was performed with a high-pressure mercury lamp. After washing in water at 25 ° C. for 1 minute, drying was performed at 60 ° C. for 10 minutes to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 27)
Plastics with amino group surface modified on the base material (Nunk, Microarray Slide, Black, Aminosilane Coated Polymer Slide for Microarray, hereinafter abbreviated as “Amination Slide”) It was used. The photosensitive composition I-4 was dropped on an aminated slide, formed into a film by a spin coating method (1000 rpm × 30 seconds), dried at 60 ° C. for 10 minutes, and then cooled to room temperature. Thereafter, whole surface exposure (exposure amount: 200 mJ / cm ² ) was performed with a high-pressure mercury lamp. After washing in water at 25 ° C. for 1 minute, drying was performed at 60 ° C. for 10 minutes to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 28) Photocrosslinked product using photosensitive composition II Example except that photosensitive composition II-4 was used instead of photosensitive composition I-4, and the exposure amount was 100 mJ / cm ^2. The same operation as in No. 15 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 29)
Except that photosensitive composition II-2 was used instead of photosensitive composition II-4, the same operation as in Example 28 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 30)
In the same manner as in Example 28 except that exposure is performed through a mask so as to obtain a pattern in which a large number of holes having a diameter of 100 μm are provided at the time of exposure, the hole pattern is fixed on the substrate by photocrosslinking and is formed on the surface. A formed photocrosslinked product was obtained.

(Example 31)
In the same manner as in Example 28 except that exposure is performed through a mask so that a line / space pattern of 100 μm / 200 μm can be obtained at the time of exposure, it is fixed on the substrate by photocrosslinking and has a line / 100 μm / 200 μm on the surface. A photocrosslinked product in which a space pattern was formed was obtained.

(Example 32) Photocrosslinked product using photosensitive composition III Example except that photosensitive composition III-4 was used instead of photosensitive composition I-4, and the exposure amount was 10 mJ / cm ^2. The same operation as in No. 15 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 33)
Except for using the photosensitive composition III-2 instead of the photosensitive composition III-4, the same operation as in Example 32 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 34)
In the same manner as in Example 32 except that exposure is performed through a mask so as to obtain a pattern in which a large number of holes having a diameter of 100 μm are provided at the time of exposure, the hole pattern is fixed on the substrate by photocrosslinking and the surface has a hole pattern. A formed photocrosslinked product was obtained.

(Example 35)
In the same manner as in Example 32 except that exposure is performed through a mask so that a line / space pattern of 100 μm / 200 μm can be obtained at the time of exposure, it is fixed on the substrate by photocrosslinking and has a line / 100 μm / 200 μm on the surface. A photocrosslinked product in which a space pattern was formed was obtained.

(Example 36) Photocrosslinked product using photosensitive composition IV Example except that photosensitive composition IV-4 was used instead of photosensitive composition I-4, and the exposure amount was 1 mJ / cm ^2. The same operation as in No. 15 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 37)
Except that photosensitive composition IV-2 was used in place of photosensitive composition IV-4, the same operation as in Example 36 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 38)
In the same manner as in Example 36 except that exposure is performed through a mask so as to obtain a pattern in which a large number of holes having a diameter of 100 μm are provided at the time of exposure, the hole pattern is fixed on the substrate by photocrosslinking and the surface has a hole pattern. A formed photocrosslinked product was obtained.

(Example 39)
In the same manner as in Example 36 except that exposure is performed through a mask so that a line / space pattern of 100 μm / 200 μm can be obtained at the time of exposure, it is fixed on the substrate by photocrosslinking and has a line / 100 μm / 200 μm on the surface. A photocrosslinked product in which a space pattern was formed was obtained.

(Example 40) Photocrosslinked product using photosensitive compositions V to VII The same operations as in Example 15 were carried out except that photosensitive compositions V to VII were used instead of photosensitive composition I-4, respectively. And a photocrosslinked product fixed on the substrate by photocrosslinking was obtained.

(Comparative Example 1) Photosensitive composition containing sensitized polyethylene glycol at both ends as a main component Both ends sensitized polyethylene glycol (molecular weight 2600) synthesized according to Example 3 of Japanese Patent Application No. 2005-104768 was dissolved in pure water. A 5 wt% solution was obtained. Each obtained solution was filtered with a 0.2 μm filter to obtain a photosensitive composition. The obtained photosensitive composition was dropped on a non-coated glass, formed into a film by a spin coating method (1000 rpm × 30 seconds), dried at 60 ° C. for 10 minutes, and then cooled to room temperature. Thereafter, the entire surface exposure was performed with a high-pressure mercury lamp (exposure amounts: 1, 10, 100, and ²⁰⁰ mJ / cm ^2, respectively). When it was washed in water at 25 ° C. for 1 minute, it completely dissolved due to insufficient curing, and no photocrosslinked product was obtained.

(Test Example 1) Static contact angle measurement with respect to water on the surface of the photocrosslinked body The static contact angle measurement with respect to the water on the surface of the obtained photocrosslinked body was carried out for those subjected to the entire surface exposure in Examples 15-40. . The apparatus used is a static contact angle meter “FTÅ125” manufactured by First Ten Angstroms, and the measurement environment is 25 ° C. and 50% relative humidity in the atmosphere. The measurement was performed by dropping about 2 μl of water droplets onto the surface of the photocrosslinked body fixed on the substrate and reading the contact angle after 8 seconds. The results are shown in Tables 2 and 3. The surface of the photocrosslinked body prepared using the photosensitive composition I has a contact angle of about 25 ° to 30 °. In the photosensitive compositions evaluated in other examples, the contact is about 5 ° to 20 °. Showed corners, both showing very hydrophilic surfaces.

(Test Example 2) Solvent exposure test of photocrosslinked bodies The photocrosslinked bodies obtained in Examples 15 to 40 were immersed in water or various aqueous solvents at 25 ° C or 37 ° C, and light after 3 days and 10 days. The shape of the crosslinked body and the peeling stability from the substrate were evaluated. The solvent used was pure water, potassium dihydrogen phosphate / disodium hydrogen phosphate aqueous solution (phosphate buffer, pH 7.4), 10% acetone aqueous solution, 5% sodium dodecyl sulfate aqueous solution, 10% fetal bovine serum. Containing Dulbecco's modified Eagle medium (manufactured by Nissui Pharmaceutical Co., Ltd .: Dolbecco's Modified Eagle's Medium). Moreover, about the water and phosphate buffer solution, the immersion test at 60 degreeC was also performed, and the structure which consists of a photocrosslinked body and a base material after 3 days and 10 days was observed. As an example, FIG. 1 shows the state of the photocrosslinked body before and after immersion in the photocrosslinked body of Example 17 immersed in a phosphate buffer at 37 ° C.

  In the tests immersed in various solvents in all of Examples 15 to 40, the surface shape of the photocrosslinked body was unchanged before and after the immersion, and the photocrosslinked body was not peeled off from the substrate due to swelling or stable. It was in a state. When using a photocrosslinked product fixed to a substrate in a state exposed to a solvent, it has sufficient stability in water, a mixed solvent of polar solvent and water, or a solution in which an additive is mixed in water. Confirmed that.

(Test Example 3) Patterned cell culture evaluation Patterned cell culture was performed using the substrate prepared in Example 25. After sterilizing the substrate, vascular endothelial cells were seeded on the substrate and cultured for 24 hours. After confirming pattern formation, hepatocytes were collected from 5-week-old Wistar rats and cultured for 2 weeks. In the meantime, follow-up was performed with a microscope as appropriate. 2 and 3 show micrographs in a state of being cultured in a pattern after 2 weeks. The cells did not adhere at all to the site where the photocrosslinked body was cured, but adhered only to the hole where the substrate was exposed. From this, it was confirmed that the photocured product can suppress nonspecific adhesion of cells.

It is a figure which shows an example of the state of the photocrosslinked body of this invention before and behind a solvent exposure test. It is a figure which shows the result of pattern cell culture evaluation. It is a figure which shows the result of pattern cell culture evaluation.

Claims (8)

A photosensitive resin having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

(R ₁ and R ₂ are each independently an alkylene group having 2 to 5 carbon atoms, and R ₃ is a photosensitive group represented by the following formula (3) .)

(R ₄ is a group selected from the following formula (4), R ₅ is a group selected from the following formula (5), and at least one of R ₄ and R ₅ has at least one azide group.)

The photosensitive resin according to claim 1 , wherein R ₄ is represented by the following formula (6), and R ₅ is represented by the following formula (7).

The number m of repeating units of the formula (1) and the number of repeating units n of the formula (2) satisfy n + m = 40 to 400 and m / (m + n) = 0.001 to 0.3 at the same time. The photosensitive resin according to claim 1 or 2 . End groups of the main chain is a -R ₆ and -OR _7, photosensitive according to any one of claims 1 to 3, characterized in that R ₆ and R ₇ are each independently a hydrogen atom or a methyl group Resin. The photosensitive composition, characterized in that the photosensitive resin according to any one of claims 1-4 which is a solution dissolved in a solvent. A photocrosslinked body obtained by applying the photosensitive composition according to claim 5 on a base material and then exposing to light, and being fixed on the base material. A pattern-constructed photocrosslinked product obtained by pattern exposure and development after applying the photosensitive composition according to claim 5 onto a substrate, wherein the photopolymerizable composition is fixed on the substrate. Photocrosslinked product. The photocrosslinked product according to claim 7 , which is a cell culture substrate.

Images