JP4248000B2 - 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 more particularly, to a photocrosslinked body having a higher order structure that can modify any portion of a substrate surface to be hydrophilic.

  Conventionally, photosensitive resins and photosensitive compositions having various hydrophilic polymers in the main chain have been proposed. For example, photosensitive resins having a polyvinyl saponification product in the main chain have been developed (Patent Document 1). reference). 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.

  In addition, this Patent Document 1 discloses that both ends of a polyoxypropylene and polyoxyethylene copolymer are aminated, and polyoxyethyleneamine (trade name: Jeffamine (manufactured by Huntsman Corporation)). Photosensitive compounds into which are introduced are also described. However, the photosensitive compound using both the terminal amination product (Jephamine ED-600) and polyoxyethylene amine (Jephamine EDR-148) of the copolymer of polyoxypropyleneamine and polyoxyethylene is based on water. Solubility is extremely low. Furthermore, the photocrosslinked product could not maintain sufficient film strength and surface hydrophilicity.

  On the other hand, for the purpose of controlling the adsorption of physiologically active substances to the structure interface of medical devices and the like, a hydrophilic surface is formed using a photocrosslinked product of a photosensitive composition having a hydrophilic polymer having an azide group. It has been proposed to form a surface excellent in biocompatibility (see Patent Document 2). However, the photosensitive composition using an acrylamide derivative or the like described as a hydrophilic polymer having an azide group in Patent Document 2 has insufficient characteristics such as film strength and surface hydrophilicity maintenance. .

JP 2003-292477 A (paragraph numbers [0013], [0046], etc.) JP-A-9-103481 (paragraph number [0044] etc.)

  In view of such circumstances, the present invention provides a photosensitive resin and a photosensitive composition capable of easily constructing a hydrophilic and highly biocompatible surface coating by photocrosslinking, and a photocrosslinked product thereof. Let it be an issue.

  The 1st aspect of this invention which solves the said subject exists in the photosensitive resin represented by following formula (1).

(In formula (1), the average value n of the degree of polymerization is 5 or more. R ₁ and R ₂ are an alkylene group, an arylene group, an oxyalkylene group or a single bond, and R ₁ and R ₂ are the same, respectively. X and Y are each independently a photosensitive group unit represented by the following formula (2), or one of them is a photosensitive group unit represented by the formula (2) and the other is an amino group. R ₃ is a group selected from the following formula (3), R ₄ is a group selected from the following formula (4), and has at least one azide group in at least one of R ₃ and R ₄ R ₅ represents a hydrogen atom, an alkyl group, an alkyl group having an acetal group, an aryl group, an aralkyl group, or a substituent containing basic nitrogen.)

In a second aspect of the present invention, R ₁ and R ₂ are each independently a methylene group or a single bond, X and Y are the same photosensitive group unit represented by the formula (2), and R ₃ is equation (5), R ₄ is in the photosensitive resin according to the first aspect, which is a group represented by the following formula (6).

  A third aspect of the present invention resides in the photosensitive resin according to the first or second aspect, wherein the average value n of the degree of polymerization is 20 to 230.

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

  According to a fifth aspect of the present invention, there is provided the photosensitive composition according to the fourth aspect, wherein the photosensitive composition contains an aggregate having a particle diameter of 2 nm to 5 μm formed from the photosensitive resin.

  A sixth aspect of the present invention is the photosensitive composition according to the fourth or fifth aspect, wherein the concentration of the photosensitive resin is 0.1 to 30% by weight.

  According to a seventh aspect of the present invention, in the photosensitive composition according to any one of the fourth to sixth aspects, the solvent is water, an organic solvent compatible with water, or a mixture thereof. is there.

  An eighth aspect of the present invention resides in the photosensitive composition according to any one of the fourth to seventh aspects, wherein the pH is 0 to 10.

  A ninth aspect of the present invention is a photocrosslinked product obtained by light irradiation after applying the photosensitive composition of any one of the fourth to eighth aspects onto a base material, and is fixed on the base material. It is in the photocrosslinking body characterized by being made.

  A tenth aspect of the present invention is the photocrosslinked body according to the ninth aspect, wherein a static contact angle with respect to water on the surface of the photocrosslinked body is 35 ° or less.

  The novel photosensitive resin of the present invention can be dissolved in a solvent to form a photosensitive composition, and when this photosensitive composition is irradiated with light, the surface always becomes a hydrophilic photocrosslinked product, It can be suitably used as a surface modifier, for example, a material that imparts biocompatibility to the surface of a medical device, and has the effect of contributing to the construction of a medical device.

  The photosensitive resin of the present invention is a compound represented by the above general formula (1), and has a structure in which a photosensitive group is bonded to the end of the main chain composed of an oxyalkylene group. In formula (1), the average value n of the degree of polymerization is 5 or more, preferably 20 to 230. When the average degree of polymerization n is less than 5, water solubility is low, and when a photocrosslinked structure (hereinafter referred to as “photocrosslinked body”) obtained by irradiating the photosensitive resin with light is formed, it is hydrophilic. This is because it becomes difficult to maintain the sex. In particular, when n is 20 to 230, the surface of the photocrosslinker is sufficiently hydrophilic to maintain the hydrophilicity when it is formed, and the molecular chain is suitable for exhibiting biocompatibility. And have an excluded volume. When n is larger than 230, the molar concentration of one molecule of the photosensitive group is lowered, so that the photocrosslinking efficiency is lowered and the mechanical strength of the photocrosslinked body tends to be weakened.

R ₁ and R ₂ are each independently an alkylene group, an arylene group, an oxyalkylene group or a single bond, and preferably an alkylene group having 1 to 20 carbon atoms, an arylene group, an oxyalkylene group or a single bond. More preferably, it is a 1-6 alkylene group, an arylene group, an oxyalkylene group or a single bond, most preferably a single bond or a methylene group.

X and Y may be at least one photosensitive group unit represented by the above formula (2), and only one of X and Y is a photosensitive group unit independently represented by the above formula (2). May be a photosensitive group unit represented by the formula (2). In particular, it is preferable that X and Y have the same structure represented by the formula (2). In the case where only one of X and Y is a photosensitive group unit represented by the formula (2), the other is an amino group. In the formula (2), R ₃ is a group selected from the above formula (3), R ₄ is a group selected from the above formula (4), and at least one of at least one of R ₃ and R ₄ Has an azide group. R ₅ is a hydrogen atom, an alkyl group, an alkyl group having an acetal group, an aryl group, an aralkyl group, or a substituent containing basic nitrogen, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, An alkyl group having an acetal group, an aryl group, an aralkyl group, or a substituent containing basic nitrogen. In addition, Formula (2) can take the same structure as the monovalent group which the substituent Z remove | eliminated from the photosensitive group unit represented by General formula (1) of patent document 1. FIG. Specific examples of formula (2) include structures (2) -1 to (2) -15 shown in Table 1 below. These structures have the substituents shown in Table 1 in the substituents R _{3 to} R ₅ in the above formula (2). For example, the structure (2) -1 (2) -4 having a azide group as _{R 4,} (2) -5 have _{R 3} and _{R 4} together azido group. In particular, it is preferable that R ₃ is the above formula (5) and R ₄ is the formula (6).

  Although the manufacturing method of the photosensitive resin of this invention represented by the said Formula (1) is not specifically limited, For example, it couple | bonds with this amino group and the said formula ( What is necessary is just to make it react with the compound which forms the structure of 2).

When producing the photosensitive resin of the formula (1) in which R ₁ and R ₂ are single bonds, polyethylene glycol diamine or the like can be used as polyethylene glycol having an amino group at the terminal. Moreover, when producing the photosensitive resin of the formula (1) in which R ₁ or R ₂ is present, the amino group has an amino group at the end of the polyethylene glycol via R ₁ or R ₂ as the polyethylene glycol having an amino group at the end. A bonded compound such as polyethylene glycol dipropylamine can be used.

  Examples of the compound that combines with the amino group of polyethylene glycol having an amino group at its end to form the structure of the above formula (2) together with the amino group 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) (photofunctionality) 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 Patents such as 5-one (photofunctional compound 5), 4- (4-azido-β-methyl-cinnamylidene) -2- (3-pyridyl) -2-oxazolin-5-one (photofunctional compound 6), etc. The photosensitive group unit described in the literature 1 is mentioned. In addition, this photofunctional compound can be manufactured by the method described in Patent Document 1.

  When the same structure of the above formula (2) is introduced at both ends, that is, to obtain a photosensitive resin of the formula (1) in which X and Y are the same structure of the formula (2), it is bonded to an amino group. The compound that forms the structure of the above formula (2) together with the amino group may be reacted in an amount that is twice or more the molar equivalent of polyethylene glycol having an amino group at the terminal. Further, by using polyethylene glycol having a hydroxyl group or a methoxy group at one end and an amino group at the other end, a photosensitive resin of formula (1) having a structure of formula (2) only at one end is obtained. be able to. In addition, when it is desired to obtain both the photosensitive resin having the structure of the formula (2) at both ends and the photosensitive resin having the structure of the formula (2) at one end at an arbitrary ratio, the required ratio A corresponding molar equivalent may be reacted.

  The photosensitive composition of the present invention is a solution obtained by dissolving the photosensitive resin represented by the above formula (1) 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 methanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and the like.

  The concentration of the photosensitive resin to be contained in the photosensitive composition of the present invention is not particularly limited, but the formation of aggregates to be described later depends on the concentration of each component in the photosensitive composition. In order to obtain an adhesive composition, 0.1 to 30% by weight is preferable. The photosensitive resin may be used alone or in a plurality of types.

  Since the photosensitive resin contained in the photosensitive composition of the present invention has a hydrophobic photosensitive group unit represented by the formula (2) introduced at both ends or one end of a hydrophilic polyethylene glycol chain, Aggregates such as micelles can be formed. In the photosensitive resin, the formation of aggregates is particularly remarkable in water. Therefore, the photosensitive group unit, which is a hydrophobic and terminal unit having an amide site, has a core with a hydrophobic interaction or hydrogen bond as a driving force. It is presumed that it takes a polymer micelle structure that forms a shell that is formed and covered with a more hydrophilic polyethylene glycol unit. Therefore, it is preferable to use water, an organic solvent compatible with water, or a mixture thereof as the solvent of the photosensitive composition of the present invention because the driving force due to the above interaction can contribute to the formation of aggregates. .

  In such a photosensitive composition, it is presumed that the photosensitive resin forming the aggregate and the free photosensitive resin not formed are in an equilibrium state. The bias in equilibrium depends on the hydrophobic strength of the hydrophobic group represented by the formula (2) introduced at the end of the photosensitive resin. Therefore, all the photosensitive resins present in the solution may form an aggregate, or only a part may form an aggregate and the rest may exist in a free state. In any case, in the photosensitive composition of the present invention, it is preferable that at least a part of the photosensitive resin contained in the photosensitive composition forms an aggregate.

  When the aggregate is formed in the photosensitive composition, this aggregate can be detected by using, for example, a dynamic light scattering measurement device, a particle size distribution meter, or the like. For example, by performing a dynamic light scattering measurement, it is possible to detect an aggregate having a diameter of about 1 nm to about 5 μm and to measure its abundance ratio. As an example of the method for measuring the particle size of the aggregate, a measurement cell made of polymethylmethacrylate is used at 25 ° C. when the solvent is water at 25 ° C. using “HPPS Zeta Sizer Nano” as a dynamic light scattering measurement device. In the case where the solvent is an organic solvent, a method can be used in which measurement is performed for 90 seconds using a quartz cell and the average is obtained.

  Here, the photosensitive composition of this invention in case the photosensitive resin density | concentration shall be about 0.1 to 30 weight% is explained in full detail. At this concentration, an aggregate having a diameter of 2 nm to 5 μm is formed by the photosensitive resin, and at least one peak of the aggregate diameter, and in many cases, a peak of three aggregate diameters is detected. The first peak has a diameter of about 2 to 50 nm and is presumed to have a micelle structure. The second peak has a diameter of about 50 nm to 1 μm, and is presumed to be a structure in which the photosensitive group units at both ends of some photosensitive resins are bridged between the cores of micelles to increase the size. . Furthermore, the third peak has a diameter of 1 μm or more, and is presumed to be a structure in which hydrophobic cores are aggregated to further increase in size. The photosensitive composition of the present invention preferably contains at least an aggregate having an average particle diameter of 2 to 50 nm. In the case of a photosensitive composition in which only one peak is detected by dynamic light scattering measurement, the average particle size is about 2 to 50 nm.

  When a photosensitive resin having a hydrophobic photosensitive group unit introduced at both ends is present in the composition, the first peak is gathered at the core by hydrophobic interaction or hydrogen bonding at both ends. It is speculated that the hydrophilic polyethylene glycol chain connecting both assembled ends has a flower micelle structure (primary structure) that is solvated through a loop. The second peak has a structure (secondary structure) in which the two micelles having different hydrophobic ends of one polyethylene glycol chain are bridged between the flower micelle structures of the first peak. Guessed. The third peak is presumed to have an aggregate structure (tertiary structure) in which hydrophobic interactions are aggregated to cause macro phase separation. When the photosensitive composition is a dilute solution, the proportion of primary structure is large, and it is presumed that the proportion of secondary and tertiary structures increases as the concentration increases.

  When a large aggregate having an average particle diameter of 1 μm or more, which is presumed to have a tertiary structure, is present in the solution, the photocrosslinked product obtained by irradiating this with light sometimes has several tens of μm. A phase-separated structure having a size may be formed. Although it is possible to use the photocrosslinked product as it is, it may be desirable to remove the formation of a large phase separation structure 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, it causes light scattering and turbidity, and the transparency is significantly reduced. Therefore, in order to remove large aggregates such as tertiary structures from the photosensitive composition, the photosensitive composition may be filtered. Although the filtration method can be performed by a publicly known method, pressure filtration, vacuum filtration and the like can be mentioned as filtration methods. The filtration membrane is not particularly limited as long as the tertiary structure can be separated by filtration, and examples thereof include a cellulose acetate membrane filtration membrane.

  The photosensitive group unit of the photosensitive resin contained in the photosensitive composition may have an ionic dissociation 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 unit can take two states of dissociation and non-dissociation depending on the surrounding pH environment, so that the local water solubility changes greatly. In other words, when the photosensitive group unit is in the dissociated state, the ability to form aggregates due to hydrophobic interaction is reduced. Conversely, when the photosensitive group unit is in a non-dissociated state, aggregates are formed due to hydrophobic interaction. The ability is expected to be enhanced. As a result, pH greatly affects the diameter of the aggregate, the wettability of the photosensitive composition with respect to the substrate, the sensitivity when irradiated with light, and the mechanical strength of the photocrosslinked body to be formed. The photosensitive composition of this invention can be used suitably by pH 0-10, Most preferably, it is pH 1-7.

  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. Since the core part of the formed aggregate may be formed by a hydrophobic interaction, a hydrophobic substance may be added. For example, hydrophobic drugs, physiologically active substances, dyes, pigments and the like can be mentioned without limitation.

  When the photosensitive composition is irradiated with light, the photocrosslinked product of the present invention is obtained. When the photosensitive composition is irradiated with light in the form of a solution, a photocrosslinked product having a particle size of 2 nm to 5 μm (measured by dynamic light scattering) is obtained. Such a photocrosslinked body reflects the size of the aggregate before light irradiation, and has a feature that the particle size does not change even when the external environment changes, such as by changing the concentration.

  Moreover, as another form of the photocrosslinked body of the present invention, a state where the photocrosslinked body (resin film) is fixed on the surface of the substrate by applying the photosensitive composition onto the substrate and then irradiating with light. Can be mentioned. In that case, it is estimated that the photocrosslinked body of this invention is bridge | crosslinked, maintaining the structural state in the used photosensitive composition. Such a photocrosslinked body is presumed to have a higher-order structure having an aggregate as a cross-linking point, unlike a substantially uniform network structure of curing and gelation by a normal photoreaction.

  The surface of such a photocrosslinked product of the present invention is very hydrophilic. This is presumed to be because there is a structure in which a hydrophobic polyethylene group is always present in the core where the hydrophobic photosensitive unit is always associated, and a hydrophilic polyethylene glycol chain is surrounded around it, and the hydrophobic part is not exposed to the surface. The Therefore, the photocrosslinked product of the present invention can be used, for example, for a purpose of hydrophilizing the substrate.

  As an example of a method for measuring a static contact angle serving as a hydrophilic index, a measurement apparatus “FTÅ125” manufactured by First Ten Angstroms Co., Ltd. is used, and the temperature is 25 ° C. and the humidity is 50%. There may be mentioned a method of dropping about 2 μl of water droplets on the surface of the photocrosslinked body under the conditions and reading the contact angle after 8 seconds. The contact angle of water on the surface of the photocrosslinked body is preferably 35 ° or less, and more preferably 20 ° or less.

  The shape and material of the substrate are not particularly limited. Examples of the material for the substrate 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. A plate shape is particularly preferable. It is because it can be used suitably when creating a pattern structure through a mask. Further, a substrate whose surface is modified can be used as a substrate. For example, a base material in which an alkyl group or an amino group is introduced onto glass with a silane coupling agent or the like can be used. This is because, when the photosensitive group of the photosensitive resin is an azide group, the nitrene group by light irradiation reacts radically, so that the photocrosslinked body and the substrate are more firmly bonded.

  In addition, when the surface of the substrate is contaminated, higher-order aggregate aggregation may easily occur. In order to prevent aggregate aggregation, the substrate surface can be optionally washed. The glass substrate cleaning method may be a known method. For example, wet cleaning methods such as organic solvent cleaning, alkaline aqueous solution cleaning, and hydrofluoric acid aqueous solution cleaning, dry cleaning such as compressed air cleaning, ozone cleaning, and plasma treatment cleaning. A method is mentioned.

  In addition, the photosensitive composition of this invention can also form a crosslinked body not only by light but by heating. However, in order to form a crosslinked body by heat, heating at 100 ° C. or higher is required. Therefore, the formation of the crosslinked body of the photosensitive composition of the present invention is preferably performed by light irradiation.

  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 developing solution as needed, and forming a 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 confirm whether the film is uniformly formed. 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 make the film thickness out of 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, you may expose to a desired pattern. In the case of pattern exposure, a photocrosslinked body having an arbitrary pattern shape can be obtained by developing after exposure and removing unexposed areas.

  When pattern exposure is performed, exposure may be performed through a mask. As a mask for forming an arbitrary pattern, a mask from which a desired pattern is cut out or a mask composed of only a desired pattern can be used.

The light source at the time of exposure is not particularly limited as long as it is a light source capable of exposing a photosensitive resin. For example, an X-ray, an electron beam, an excimer laser (F ₂ , ArF, KrF laser, etc.) and a high-pressure mercury lamp can be used as the light source. 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 ~100J / cm 2} , especially 100mJ ^/ cm ² ~10J ^/ cm 2 of about Is preferred.

  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. Moreover, after the physical property of the photosensitive composition coating film is changed by pattern exposure, the development treatment can be performed after heating as necessary. 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 capable of dissolving the unexposed region of the photosensitive composition coating film, water, a mixed solution of water and an organic solvent compatible with water, or the like can be used. Non-limiting examples of organic solvents compatible with water include ketones such as acetone, alcohols such as methanol, acetonitrile, tetrahydrofuran and the like. In the case of using these, 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%.

  Development can be performed by a method of immersing the processed object 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, a drying process, etc. can be added 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 in an organic solvent at about 37 ° C., in water or in an aqueous solvent, for a long period of time, for example, 1 day or more, and further 10 Maintain its structure stably for more than a day. It is important to be able to exist stably in a solution, particularly in water or an organic solvent compatible with water. Especially when used for medical devices, the surface of the device is in a dry state, an aqueous solution, or an organic solvent solution. This is because it is required to have resistance to any of them.

  Here, the organic solvent compatible with water is not particularly limited as long as it is a solution containing water. Examples of water-compatible organic solvents include ketones such as acetone, alcohols such as methanol, mixtures of water and organic solvents compatible with water such as acetonitrile and tetrahydrofuran, potassium dihydrogen phosphate and phosphoric acid. Buffered solutions such as disodium hydrogen solution, sodium bicarbonate / sodium carbonate solution, inorganic / organic salt solutions such as sodium chloride, potassium chloride, ammonium chloride, monosaccharides such as glucose, galactose, glucose, starch, heparin, heparan sulfate Saccharide aqueous solution containing polysaccharide, protein aqueous solution, DNA, RNA aqueous solution, liquid medium, and mixtures thereof. In addition, it may include those that do not dissolve in water or an organic solvent that is compatible with water, and non-limiting examples include minerals such as clay, metal fine particles such as gold nanoparticles, polystyrene beads, Polymer fine particles such as latex particles, animal cells, plant cells, microorganisms, viruses and the like, and mixtures thereof can be mentioned.

  The temperature at which the photocrosslinked body according to the present invention can be used is not particularly limited as long as the photocrosslinked body or the composite composed of the photocrosslinked body and the substrate does not become unstable, but it is between 4 ° C and 80 ° C. It can be used suitably, and it can use especially suitably between 10-60 degreeC. If the temperature is lower than 4 ° C, water may partially freeze to impair the stability of the photocrosslinked product or the composite. If the temperature exceeds 80 ° C, the photosensitive group of the photosensitive resin may be decomposed and the composite cannot be retained. Because there is a possibility.

  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 Polyethylene glycol diamine (manufactured by NOF Corporation, number average molecular weight 1000) 7.9 g, 10.0 g of the above-mentioned photofunctional compound 4 (on the amino group of polyethylene glycol diamine) 2.0 molar equivalents) and 70 g of tetrahydrofuran (THF) were mixed and reacted at 25 ° C. for 18 hours. After completion of the reaction, THF was removed under reduced pressure, and then 50 g of water and 50 g of ethyl acetate were added to perform a liquid separation extraction operation. The organic layer was discarded, 50 g of ethyl acetate was newly added, and the liquid separation extraction operation was performed again. After standing, an oil phase of the lowest phase separated into three phases was obtained. This oil phase was freeze-dried to obtain 7.2 g of photosensitive resin A represented by the following formula (a) and n = 23. When the obtained photosensitive resin A 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 4 was 95%.

(Example 2) Synthesis of photosensitive resin B 13.1 g of polyethylene glycol diamine (manufactured by NOF Corporation, number average molecular weight 1000), 10.0 g of the above-mentioned photofunctional compound 4 (on the amino group of polyethylene glycol diamine) Except that the molar equivalent was 1.2), 13.2 g of the photosensitive resin B represented by the above formula (a) and n = 23 was obtained. When the obtained photosensitive resin B 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 4 was 72%.

Example 3 Synthesis of Photosensitive Resin C 7.9 g of polyethylene glycol diamine (manufactured by NOF Corporation, number average molecular weight 2000), 6.0 g of the above-mentioned photofunctional compound 4 (on the amino group of polyethylene glycol diamine) Except that it was 2.4 times the molar equivalent), and the aqueous phase was washed twice with the organic phase by the liquid separation extraction operation, and then the aqueous phase was freeze-dried, 7.0 g of photosensitive resin C represented by the above formula (a) and n = 45 was obtained. When the obtained photosensitive resin C 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 4 was 96%.

(Example 4) Synthesis of photosensitive resin D 15.8 g of polyethylene glycol diamine (manufactured by Nippon Oil & Fats Co., Ltd., number average molecular weight 2000), 6.0 g of the aforementioned photofunctional compound 4 (on the amino group of polyethylene glycol diamine) The amount of the photosensitive resin D represented by the above formula (a) and n = 45 was 19.8 g except that the amount was 1.2 times the molar equivalent). When the obtained photosensitive resin D 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 4 was 83%.

(Example 5) Synthesis of photosensitive resin E 23.7 g of polyethylene glycol dipropylamine (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight 9,000 to 10,000), 4 of the above-mentioned photofunctional compound 4 0.0 g (2.4 molar equivalents relative to the amino group of polyethylene glycol dipropylamine), 65 g of tetrahydrofuran, and acetonitrile 65 were mixed, and the same operation as in Example 3 was performed. As a result, 23.2 g of n = 216 photosensitive resin E 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 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. Further, from the integration ratio of these peaks, the introduction ratio of the photofunctional compound 4 was 90%.

(Example 6) Synthesis of photosensitive resin F 23.7 g of polyethylene glycol dipropylamine (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight 9,000 to 10,000), 2 of the above-mentioned photofunctional compound 4 0.0 g (1.2 molar equivalents relative to the amino group of polyethylene glycol dipropylamine), the same operation as in Example 5 was performed, and the photosensitivity represented by the above formula (b) and n = 216 was obtained. 22.1 g of Resin F 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 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 4 was 74%.

(Example 7) Synthesis of photosensitive resin G 17.2 g of polyethylene glycol diamine (manufactured by NOF Corporation, number average molecular weight 2000), 6.0 g of the above-mentioned photofunctional compound 3 (on the amino group of polyethylene glycol diamine) 19.7 g of photosensitive resin G represented by the following formula (c) and n = 45 was obtained except that the molar equivalent was 1.2 times the molar equivalent). When the obtained photosensitive resin G 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 to 8.7 ppm. The compound was identified as the target compound by the proton peak of the aromatic ring. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 3 was 70%.

(Example 8) Synthesis of photosensitive resin H 15.1 g of polyethylene glycol diamine (manufactured by Nippon Oil & Fats Co., Ltd., number average molecular weight 2000), 6.0 g of the aforementioned photofunctional compound 6 (on the amino group of polyethylene glycol diamine) 18.4 g of photosensitive resin H represented by the following formula (d) and n = 45 was obtained except that the molar equivalent was changed to 1.2 times the molar equivalent). When the obtained photosensitive resin H 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 6 was 71%.

(Example 9) Synthesis of photosensitive resin I 15.2 g of polyethylene glycol diamine (manufactured by NOF Corporation, number average molecular weight 2000), 6.0 g of the above-mentioned photofunctional compound 5 (amino group of polyethylene glycol diamine) 18.8 g of photosensitive resin I represented by the following formula (e) and n = 45 was obtained except that the molar equivalent was 1.2 times the molar equivalent). When the obtained photosensitive resin H 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 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 5 was 78%.

(Example 10) Synthesis of photosensitive resin J 17.2 g of polyethylene glycol diamine (manufactured by Nippon Oil & Fats Co., Ltd., number average molecular weight 2000), 6.0 g of photofunctional compound 1 described above (amino group of polyethylene glycol diamine) The amount of the photosensitive resin J represented by the following formula (f) and n = 45 was 21.5 g. When the obtained photosensitive resin J 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 1 was 81%.

(Comparative Example 1) Synthesis of Photosensitive Resin K 0.19 g of Jeffermine EDR-148 (manufactured by Huntsman Corporation, number average molecular weight 148) having the structure of the following formula (7), the aforementioned photofunctional compound 4 Was mixed with 2.0 g (2.5 times molar equivalent of the amino group of Jeffamine EDR-148) and 20 g of tetrahydrofuran, and reacted at 25 ° C. for 18 hours. After completion of the reaction, THF was removed under reduced pressure, and then 20 g of water and 20 g of ethyl acetate were added to perform a liquid separation extraction operation. At that time, the precipitated solid was separated by filtration and dried at 45 ° C. under reduced pressure for 18 hours to obtain 0.81 g of photosensitive resin K represented by the following formula (g). When the obtained photosensitive resin K 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. Further, from the integration ratio of these peaks, the introduction ratio of the photofunctional compound 4 was 90%.

Comparative Example 2 Synthesis of Photosensitive Resin L Jeffamine HK-511 (manufactured by Huntsman Corporation, number average molecular weight 220) having the structure of the following formula (8) instead of Jeffamine EDR-148 The same operation as in Comparative Example 1 was performed except that 28 g was used, and 0.86 g of photosensitive resin L represented by the following formula (h) was obtained. When the obtained photosensitive resin L 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. From the integration ratio of these peaks, the introduction ratio of the photofunctional compound 4 was 92%.

(Example 11) 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, and the solutions having the concentrations shown in Table 2 were respectively prepared. It 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-6.

(Example 12) Preparation of photosensitive composition II The photosensitive resin C obtained in Example 3 was dissolved in water adjusted to the pH shown in Table 2 with hydrochloric acid or sodium hydroxide, and the concentrations shown in Table 2 were obtained. Each solution was prepared. Photosensitive compositions II-1 to II-7 were obtained by filtering each aqueous solution obtained with a 0.2 μm filter.

(Example 13) Preparation of photosensitive composition III The same procedure as in Example 12 was performed except that the photosensitive resin D obtained in Example 4 was used instead of the photosensitive resin C, 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 14) Preparation of photosensitive composition IV Except for using photosensitive resin E obtained in Example 5 instead of photosensitive resin C, the same operations as in Example 12 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 15) Preparation of photosensitive composition V The photosensitive resin G obtained in Example 7 was dissolved in pure water to prepare a 5 wt% aqueous solution. The obtained aqueous solution was filtered with a 0.2 μm filter to obtain a photosensitive composition V.

(Example 16) Preparation of photosensitive composition VI The photosensitive resin H obtained in Example 8 was dissolved in pure water to prepare a 5 wt% aqueous solution. The obtained aqueous solution was filtered with a 0.2 μm filter to obtain a photosensitive composition VI.

(Example 17) Preparation of photosensitive compositions VII to IX The photosensitive resin C obtained in Example 3 was mixed with water: methanol = 80: 20 (for preparing photosensitive composition VII), 50:50 (photosensitive). It was dissolved in a mixed solution of composition VIII for preparation) or 20:80 (for preparation of photosensitive composition IX) (each in a weight ratio) to obtain a 5% by weight solution. Photosensitive compositions VII to IX were obtained by filtering each obtained solution through a 0.2 μm filter.

(Example 18) Preparation of photosensitive compositions X to XIV For photosensitive resin C obtained in Example 3, methanol (for preparing photosensitive composition X), acetone (for preparing photosensitive composition XI), acetonitrile It was dissolved in (for preparing photosensitive composition XII), tetrahydrofuran (for preparing photosensitive composition XIII) or toluene (for preparing photosensitive composition XIV) to obtain a 5% by weight solution. Each obtained solution was filtered with a 0.2 μm filter to obtain photosensitive compositions X to XIV.

(Comparative Example 3) Preparation of Photosensitive Composition XV The photosensitive resin K obtained in Comparative Example 1 was adjusted to pH 1 with hydrochloric acid (for preparation of photosensitive composition XV-1) or (photosensitive composition XV). -2 For preparation) It was mixed with THF to prepare the concentrations shown in Table 3. The obtained THF solution was filtered through a 0.2 μm filter to obtain a photosensitive composition XV-2. Since the photosensitive resin K was insoluble in water having a pH of 1, subsequent evaluation was impossible.

(Comparative Example 4) Preparation of Photosensitive Composition XVI The photosensitive resin L obtained in Comparative Example 2 was adjusted to pH 1 with hydrochloric acid (for preparing photosensitive composition XV-1) or THF (photosensitive composition). XV-2 preparation) was dissolved to prepare the concentrations shown in Table 3. Photosensitive compositions XVI-1 and XVI-2 were obtained by filtering each obtained solution with a 0.2 μm filter.

(Test Example 1) Particle size measurement For each of the photosensitive compositions of Examples 11 to 18 and Comparative Examples 3 to 4, a dynamic light scattering measurement device (measurement device manufactured by Malvern, "HPPS Zetasizer Nano S") was used. Used to perform dynamic light scattering (DLS) measurements. The measurement was carried out by integrating for 90 seconds in an air atmosphere at 25 ° C., and the average was obtained. The obtained results are shown in Tables 2 and 3.

  As a result, the photosensitive compositions of each Example and Comparative Example formed aggregates in a wide range with a particle size of 5 nm to 2 μm or more. Most of the photosensitive compositions had small aggregates having a particle size of 5 nm to 20 nm and large aggregates having a particle size of 100 nm to 2 μm or more, and were obtained as having a very wide particle size distribution. On the other hand, photosensitive compositions II-3, II-4, III-3, III-4, etc., which use photosensitive compound C or D and have a pH of 7, 5% by weight or less, are in a very monodispersed state. Only 5 to 20 nm particle size. Therefore, the particle size and polydispersity of the aggregate are balanced by the balance of the strength of the interaction such as the hydrophobic interaction of the photosensitive group of the photosensitive resin and the stability of the solvation of the aggregate due to the length of the polyethylene glycol chain. It was found that the degree of control is possible.

(Example 19) Formation of fine gel (photocrosslinked product) by exposure of photosensitive composition I 2 ml of photosensitive composition I-6 prepared in Example 11 was dropped into a 100 ml beaker (diameter: about 54 mm), and high pressure was applied. Whole surface exposure was performed with a mercury lamp (exposure amount 100 to 750 mJ / cm ² ). The exposed solution is diluted with 10 ml of pH 3 hydrochloric acid and lyophilized, and then the pH 3 hydrochloric acid is adjusted so that the solid concentration is 0.1 wt%, 1 wt%, 10 wt% and 20 wt%. Each was diluted with water. When the DLS measurement of the obtained solution was performed, the particle size at the time of an unexposed solution (Table 2 I-6: solid content concentration 5 weight%) was maintained, and the production | generation of the microgel was confirmed.

(Example 20) Formation of fine gel (photocrosslinked product) by exposure of photosensitive composition II 2 ml of photosensitive composition II-4 prepared in Example 12 was dropped into a 100 ml beaker (diameter of about 54 mm), and high pressure was applied. Whole surface exposure was performed with a mercury lamp (exposure amount 100 to 750 mJ / cm ² ). The solution after exposure is diluted with 10 ml of pure water and then lyophilized. Thereafter, each solution is diluted with pure water so that the solid concentration is 0.1 wt%, 1 wt%, 10 wt% and 20 wt%. Diluted. When the DLS measurement of the obtained solution was performed, the particle size at the time of an unexposed solution (Table 2 II-4: solid content concentration 5 weight%) was maintained, and the production | generation of the microgel was confirmed.

Example 21 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. Photosensitive composition I-2 was dropped on non-coated glass, formed into a film 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: 1000 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 22)
Except having used photosensitive composition I-6 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinking body fixed by photocrosslinking on the base material was obtained.

(Example 23)
In the same manner as in Example 21 except that 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 24)
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 25)
In the same manner as in Example 22 except that exposure is performed through a mask so that a line / space pattern of 100 μm / 200 μm is obtained upon 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 26)
The same operation as in Example 22 except that the soda lime glass used was immersed in a 5 wt% 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 27)
In the same manner as in Example 26 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 28)
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 22 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 29)
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 30)
An aminosilane-coated slide glass (manufactured by Matsunami Glass Industry Co., Ltd., hereinafter abbreviated as “APS-coated glass”), which is a glass substrate that is surface-modified with an amino group, was used as the substrate. The photosensitive composition I-7 was dropped on the APS-coated glass, then 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: 1000 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 31)
In the same manner as in Example 30 except that 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 32)
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-7 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: 1000 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 33)
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-7 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: 1000 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 34) Photocrosslinked product using photosensitive composition II The same procedure as in Example 21 was performed, except that photosensitive composition II-1 was used instead of photosensitive composition I-2. A photocrosslinked product fixed on the material by photocrosslinking was obtained.

(Example 35)
Except having used photosensitive composition II-2 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 36)
Except having used photosensitive composition II-3 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 37)
Except for using the photosensitive composition II-4 instead of the photosensitive composition I-2, the same operation as in Example 21 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 38)
Except having used photosensitive composition II-5 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 39)
Except having used photosensitive composition II-7 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 40)
In the same manner as in Example 37 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 41)
In the same manner as in Example 37 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, the film 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 42)
The soda lime glass was immersed in a 5 wt% hydrofluoric acid aqueous solution for 1 minute, washed, rinsed with pure water and then dried with nitrogen gas, and the same operation as in Example 37 was performed. A photocrosslinked product fixed on the substrate by photocrosslinking was obtained.

(Example 43)
In the same manner as in Example 42 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 44)
Except having used photosensitive composition II-4 instead of photosensitive composition I-7, operation similar to Example 30 was performed and the photocrosslinking body fixed by photocrosslinking on the base material was obtained.

(Example 45)
Except having used photosensitive composition II-4 instead of photosensitive composition I-7, operation similar to Example 32 was performed and the photocrosslinked body fixed on the base material by photocrosslinking was obtained.

(Example 46) Photocrosslinked product using photosensitive composition III The same procedure as in Example 21 was performed, except that photosensitive composition III-1 was used instead of photosensitive composition I-2. A photocrosslinked product fixed on the material by photocrosslinking was obtained.

(Example 47)
Except having used photosensitive composition III-2 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinking body fixed by photocrosslinking on the base material was obtained.

(Example 48)
Except having used photosensitive composition III-3 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 49)
Except having used photosensitive composition III-4 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 50)
Except having used photosensitive composition III-5 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 51)
Except having used photosensitive composition III-7 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 52)
In the same manner as in Example 49 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 53)
In the same manner as in Example 49 except that exposure is performed through a mask so that a line / space pattern of 100 μm / 200 μm can be obtained during exposure, the film 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 54)
A soda lime glass was immersed in a 5 wt% hydrofluoric acid aqueous solution for 1 minute, washed, rinsed with pure water and then dried with nitrogen gas, and the same operation as in Example 49 was performed. A photocrosslinked product fixed on the substrate by photocrosslinking was obtained.

(Example 55)
In the same manner as in Example 54 except that exposure is performed through a mask so that a pattern having a large number of holes having a diameter of 100 μm is obtained 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 56)
Except having used photosensitive composition III-4 instead of photosensitive composition I-7, operation similar to Example 30 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 57)
Except having used photosensitive composition III-4 instead of photosensitive composition I-7, operation similar to Example 32 was performed and the photocrosslinking body fixed by photocrosslinking on the base material was obtained.

(Example 58) Photocrosslinked product using photosensitive composition IV Except for using photosensitive composition IV-1 in place of photosensitive composition I-2, the same procedure as in Example 21 was performed, A photocrosslinked product fixed on the material by photocrosslinking was obtained.

(Example 59)
Except that photosensitive composition IV-2 was used instead of photosensitive composition I-2, the same operation as in Example 21 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 60)
Except having used photosensitive composition IV-3 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinking body fixed by photocrosslinking on the base material was obtained.

(Example 61)
Except for using photosensitive composition IV-4 instead of photosensitive composition I-2, the same operation as in Example 21 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking.

(Example 62)
Except having used photosensitive composition IV-5 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 63)
Except having used photosensitive composition IV-7 instead of photosensitive composition I-2, operation similar to Example 21 was performed and the photocrosslinked body fixed by photocrosslinking on the base material was obtained.

(Example 64)
In the same manner as in Example 61 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 65)
In the same manner as in Example 61 except that the 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, the film 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 66
A soda lime glass was immersed in a 5 wt% hydrofluoric acid aqueous solution for 1 minute, washed, rinsed with pure water, and then dried with nitrogen gas. A photocrosslinked product fixed on the substrate by photocrosslinking was obtained.

(Example 67)
In the same manner as in Example 66 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, a hole pattern is fixed on the substrate by photocrosslinking and on the surface. A formed photocrosslinked product was obtained.

(Example 68) Photocrosslinked product using photosensitive compositions V to XIV The same operation as in Example 21 was carried out except that photosensitive compositions V to XIV were used instead of photosensitive composition I-2, respectively. And a photocrosslinked product fixed on the substrate by photocrosslinking was obtained.

(Comparative Example 5) Photocrosslinked product using photosensitive compositions XV and XVI The same operation as in Example 21 was conducted except that photosensitive composition XV or XVI was used instead of photosensitive composition I-2. And a photocrosslinked product fixed on the substrate by photocrosslinking was obtained.

(Test Example 2) Static Contact Angle Measurement for Water on Photocrosslinked Body Surface In Examples 21 to 68 and Comparative Example 5 where the entire surface was exposed, the static contact angle for water on the obtained photocrosslinked body surface Measurements were made. 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.

  On the other hand, among the photocrosslinked bodies prepared from Comparative Example 5, those prepared from the tetrahydrofuran solution showed a contact angle of about 90 °, and it was confirmed that the surface was very hydrophobic. In addition, even those prepared from an aqueous solution of pH 1 did not reach a sufficient hydrophilicity with a contact angle of about 50 °.

(Test Example 3) Solvent exposure test of photocrosslinked product The photocrosslinked product obtained in Examples 21 to 68 was added at 25 ° C or 37 ° C in water, in an organic solvent compatible with various waters, or in an organic solvent. It was immersed, and the shape of each photocrosslinked body after 3 days and 10 days 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 .: Doulbecco's Modified Eagle's Medium), acetone. 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. In addition, as an example, about the photocrosslinked body of Example 26 and Example 43 immersed in the phosphate buffer at 37 degreeC and acetone at 25 degreeC, the state of the photocrosslinked body before and behind immersion is shown in FIG.

  Of Examples 21 to 68, except for the one using photosensitive composition XIV, in the test immersed in various solvents, the surface shape of the photocrosslinked body did not change before and after the immersion, and the substrate of the photocrosslinked body by swelling It was in a stable state in which no peeling or collapse was observed.

  On the other hand, the photocrosslinked product prepared using the photosensitive composition XIV was in a stable state in which peeling or collapse of the photocrosslinked product from the substrate due to swelling was not observed after 3 days, but after 10 days, Although the shape of the film was maintained, the adhesion with the base material was slightly weak, and part of the film was lifted from the base material. Although the photosensitive composition XIV uses a nonpolar solvent (toluene) as a solvent, it forms a large aggregate in the solution, but the aggregate formed in water, a polar solvent, or a mixture thereof In contrast, it is assumed that the adhesion to the substrate is weak. Therefore, when using a photocrosslinked body fixed to a substrate in a state exposed to a solvent, a photocrosslinked body using a photosensitive composition prepared with water, a polar solvent, or a mixed solution thereof is more preferable. Confirmed that it can be used.

  Moreover, the surface of the photocrosslinking film has sites with different color tones, and higher-order aggregation or phase separation in the resin film affects the macro form of the resin film, forming a uniform network. Unlike the photocrosslinked film, it was confirmed that the photocrosslinked product of the present invention had a structure in which the aggregate was crosslinked.

(Example 69) Synthesis of photosensitive resin M Example 3 was used except that 15.8 g of a polymer represented by the following formula (9) (n = 45, number average molecular weight 2000) was used instead of polyethylene glycol diamine. The same operation was performed to obtain 19.2 g of photosensitive resin M represented by the following formula (i) and n = 45. When the obtained photosensitive resin M 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. From the integration ratio of these peaks, the introduction ratio of photofunctional compound 4 was 80%.

(Example 70) Preparation of photosensitive composition XVII The photosensitive resin M obtained in Example 69 was dissolved in water adjusted to the pH shown in Table 6 with hydrochloric acid or sodium hydroxide, and the concentrations shown in Table 4 were obtained. Each solution was prepared. The obtained aqueous solutions were filtered through a 0.2 μm filter to obtain photosensitive compositions XVII-1 to XVII-7.

(Example 71)
Except for using photosensitive composition XVII-5 in place of photosensitive composition I-2, the same operation as in Example 21 was performed to obtain a photocrosslinked product fixed on the substrate by photocrosslinking. When this photocrosslinked product was subjected to a solvent exposure test in the same manner as in Test Example 3, the photocrosslinked product had no change in surface shape before and after immersion, and the photocrosslinked product was peeled off or collapsed from the substrate due to swelling. It was a stable condition that I could not see.

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.

Claims (10)

The photosensitive resin represented by following formula (1).

(In formula (1), the average value n of the degree of polymerization is 5 or more. R ₁ and R ₂ are an alkylene group, an arylene group, an oxyalkylene group or a single bond, and R ₁ and R ₂ are the same, respectively. X and Y are each independently a photosensitive group unit represented by the following formula (2), or one of them is a photosensitive group unit represented by the formula (2) and the other is an amino group. R ₃ is a group selected from the following formula (3), R ₄ is a group selected from the following formula (4), and has at least one azide group in at least one of R ₃ and R ₄ R ₅ represents a hydrogen atom, an alkyl group, an alkyl group having an acetal group, an aryl group, an aralkyl group, or a substituent containing basic nitrogen.)

R ₁ and R ₂ are each independently a methylene group or a single bond, X and Y are the same photosensitive group unit represented by the formula (2), R ₃ is the following formula (5), and R ₄ is the following It is group represented by Formula (6), The photosensitive resin of Claim 1 characterized by the above-mentioned.

The photosensitive resin according to claim 1 or 2, wherein an average value n of the degree of polymerization is 20 to 230. A photosensitive composition comprising a solution obtained by dissolving the photosensitive resin according to claim 1 in a solvent. 5. The photosensitive composition according to claim 4, comprising an aggregate having a particle diameter of 2 nm to 5 μm formed of the photosensitive resin. 6. The photosensitive composition according to claim 4, wherein the concentration of the photosensitive resin is 0.1 to 30% by weight. The photosensitive composition according to claim 4, wherein the solvent is water, an organic solvent compatible with water, or a mixture thereof. pH is 0-10, The photosensitive composition in any one of Claims 4-7 characterized by the above-mentioned. A photocrosslinked product obtained by irradiating light after applying the photosensitive composition according to any one of claims 4 to 8 onto the substrate, and being fixed on the substrate. Photocrosslinked product. The photocrosslinked body according to claim 9, wherein a static contact angle with water on the surface of the photocrosslinked body is 35 ° or less.

Images