JP4768569B2 - Photosensitive composition and polymer composite - Google Patents

Description

  The present invention relates to a photosensitive composition and a polymer composite formed using the same, and more particularly to a polymer composite having a hydrophilic surface and excellent mechanical strength.

  A polymer complex in which a polymer film is provided on a substrate is used as a biochemical / medical device such as a biosensor or a cell culture substrate (see Patent Document 1). This polymer composite is required to have a hydrophilic surface, that is, a polymer film provided on a substrate is hydrophilic. As a photosensitive composition capable of forming a polymer film of such a polymer composite, the present inventors have proposed a photosensitive composition having a photosensitive resin having a photosensitive group added to polyethylene glycol and an aqueous solvent. Filed earlier. The polymer film obtained by irradiating and curing the photosensitive composition described in this document has a hydrophilic surface and is also biocompatible. The polymer composite formed by using is suitable for use in biochemical / medical devices.

  However, the above photosensitive composition can obtain a hydrophilic surface by using a water-soluble polymer called polyethylene glycol, but the photo-cured polymer composite is greatly swelled in water. Therefore, there are problems that the resolution is low and that the photocured polymer film has a relatively weak mechanical strength in water and can be broken by a small load.

JP 2005-280076 A

  In view of such circumstances, the present invention has a photosensitive resin composition capable of forming a polymer composite having good resolution, a hydrophilic surface, and high mechanical strength in water, and the same. It is an object of the present invention to provide a formed polymer composite.

  A first aspect of the present invention that solves the above problems comprises a photosensitive composition comprising nanoparticles having an average particle size of 150 nm or less, a solvent, and a photosensitive resin represented by the following formula (1). It is in.

(In formula (1), the average value n of the degree of polymerization is 5 or more. R ₁ and R ₂ are each independently an alkylene group, an arylene group, an oxyalkylene group or a single bond. 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 following formula (2) and the other is an amino group.

(In formula (2), R ₃ is a group selected from the following formula (3), R ₄ is a group selected from the following formula (4), and an azide group is present in at least one of R ₃ and R _4. Have)

  A second aspect of the present invention resides in the photosensitive composition according to the first aspect, which has a nonionic surfactant.

  According to a third aspect of the present invention, there is provided the photosensitive composition according to the first or second aspect, wherein the nano fine particles are a metal, a ceramic, or a polymer.

  According to a fourth aspect of the present invention, there is provided the photosensitive composition according to the third aspect, wherein the nano fine particles are colloidal silica or silsesquioxane.

  According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the mass ratio of the photosensitive resin to the nanoparticle is 1: 2 to 2: 1. In the composition.

  A sixth aspect of the present invention resides in the photosensitive composition according to any one of the first to fifth aspects, wherein the solvent is water or an aqueous solvent.

  A seventh aspect of the present invention includes a base material and a polymer film provided on the base material, and the polymer film is any one of the first to sixth aspects applied on the base material. It is obtained by irradiating the photosensitive composition as described in 1 above and curing it.

  According to an eighth aspect of the present invention, the polymer film is obtained by developing after light irradiation through a mask having a desired pattern during the light irradiation. The polymer composite according to the seventh aspect.

  A ninth aspect of the present invention is characterized in that a static contact angle with respect to water on the surface of the polymer film is 45 ° or less, and a storage elastic modulus (G ′) of the polymer film is 15 Pa · s or more. In the polymer composite according to the seventh or eighth aspect.

  The photosensitive composition of the present invention having a photosensitive resin in which a predetermined photosensitive group is imparted to polyethylene glycol, nanoparticles having an average particle size of 150 nm or less, and a solvent has high resolution and high hydrophilicity on the substrate. A polymer complex that can form a molecular film and is composed of the polymer film and a substrate has an effect of high mechanical strength in water. Since this polymer composite has the characteristics of having a hydrophilic surface and high mechanical strength in water, it can contribute to the construction of biochemical and medical devices.

  The photosensitive composition of this invention has the photosensitive resin represented by the said Formula (1), the nanoparticle with an average particle diameter of 150 nm or less, and a solvent.

  The average value n of the polymerization degree of the polyethylene glycol main chain of the photosensitive resin represented by the above formula (1) is 5 or more, preferably 20 to 230. If the average degree of polymerization is less than 5, the water solubility is low, and it becomes difficult to maintain the hydrophilicity of the polymer film obtained by curing the photosensitive resin by light irradiation. . In particular, when the degree of polymerization is 20 to 230, the polymer film obtained by curing by light irradiation becomes hydrophilic enough to maintain hydrophilicity, and is suitable for exhibiting biocompatibility. Has molecular chain flexibility and excluded volume. If the degree of polymerization is larger than 230, the molar concentration of one molecule of the photosensitive group is decreased, so that the photocrosslinking rate is decreased and the strength of the polymer film obtained by curing by light irradiation becomes weak. The mechanical strength of the polymer composite composed of the material and the polymer film is weakened.

R ₁ and R ₂ are each independently an alkylene group, an arylene group, an oxyalkylene group or a single bond, preferably an alkylene group having 1 to 20 carbon atoms, an arylene group, an oxyalkylene group or a single bond. And more preferably an alkylene group having 1 to 6 carbon atoms, 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. 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 and R ₄ in the above formula (2). For example, structures (2) -1 to (2) -4 have an azide group as R ₄ , and (2) -5 has an azide group in both R ₃ and R ₄ .

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

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 manufacturing the photosensitive resin of Formula (1) in which R ₁ or R ₂ is present, the amino group has an amino group at the terminal of polyethylene glycol via R ₁ or R ₂ as the polyethylene glycol having an amino group at the terminal. 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 the end thereof to form the structure of the above formula (2) together with the amino group include 3- (4-azidophenyl) -N- (4,4 '-Dimethoxybutyl) -2-phenylcarbonylamino-prop-2-enamide, 2- (3- (4-azidophenyl) prop-2-enoylamino) -N- (4,4-dimethoxybutyl) -3- ( 3-pyridyl) prop-2-enamide, 3- (4-azidophenyl) -N- (4,4′-dimethoxybutyl) -2-[(3-pyridyl) carbonylamino] -prop-2-enamide, 4-((4-azidophenyl) methylene) -2-phenyl-1,3-oxazolin-5-one, 4-((4-azidophenyl) methylene-2- (3-pyridyl) 1,3-oxazolin-5-one, 2- (4-azidophenyl) -4- (3-pyridylmethylene) -1,3-oxazolin-5-one, 2- (2- (4-azidophenyl) vinyl ) -4- (3-pyridylmethylene) -1,3-oxazolin-5-one, 4- (4-azido-β-methyl-cinnamylidene) -2-phenyl-2-oxazolin-5-one, 4- ( Examples include 4-azido-β-methyl-cinnamylidene) -2- (3-pyridyl) -2-oxazolin-5-one, and the compounds described in JP-A No. 2003-292477. It can be produced by the method described in JP-A No. 2003-292477.

  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.

  Nanoparticles contained in the photosensitive composition of the present invention may have an average particle size of 150 nm or less, but an average particle size of 5 to 150 nm is particularly preferable. If the average particle size is larger than 150 nm, the coating film becomes non-uniform when the coating film of the photosensitive composition is formed on the substrate, and it is obtained by irradiating the coating film with light and curing. This is because the nano-particles are exposed from the polymer film and affect the surface physical properties of the polymer composite, which causes problems such as difficulty in building a hydrophilic surface. Further, the polydispersity of the particle size of the nanoparticles is not particularly limited, but a monodispersed one is more preferable. The average particle size and polydispersity can be detected by using, for example, a dynamic light scattering measurement device, a particle size distribution meter, or the like. As an example of the measurement method of the average particle size of the nano-particles, “HPPS Zeta Sizer Nano” manufactured by Malvern Co., Ltd. is used as a dynamic light scattering measurement device. When the solvent is water at 25 ° C., it is made of polymethyl methacrylate. If the solvent is an organic solvent, the measurement cell can be measured for 90 seconds using a quartz cell, and the average can be obtained.

  The material of the nanoparticle is not particularly limited as long as it is a publicly known nanoparticle, but for example, simple metals such as gold, silver, copper, platinum, and aluminum, ceramics, inorganic oxides, inorganic carbonates, Examples thereof include inorganic sulfates and phosphates. Examples of inorganic oxides include colloidal silica, aerosil, silica glass, alumina, titania, zirconia, zinc oxide, copper oxide, lead oxide, yttrium oxide, tin oxide, indium oxide, and magnesium oxide. , Calcium carbonate, magnesium carbonate and the like. Examples of the phosphate include calcium phosphate and magnesium phosphate. The ceramic fine particles include sols and gels prepared by a sol-gel method or the like. Moreover, organic fine particles such as polymers may be used as the nano fine particles. Examples of the organic fine particles include (meth) acrylic resins such as polymethyl methacrylate, styrene resins, polyester resins, polyamide resins, and polycarbonate resins. And particles made of thermoplastic resins such as particles, particles made of crosslinked or cured resins such as crosslinked (meth) acrylic resins and crosslinked styrene resins, and organic pigments. Of these, colloidal silica and silsesquioxane are preferred.

  The shape of the nanoparticles is not particularly limited, and examples thereof include spherical, elliptical, flat, rod-like, or fiber-like nanoparticles. Of these, spherical ones are preferred.

  The photosensitive composition of the present invention is a mixture of the photosensitive resin represented by the above formula (1) and nanoparticles in a solvent. Note that one type or a plurality of types of photosensitive resins and nanoparticles may be used. The solvent is not particularly limited as long as it can dissolve the components contained in the photosensitive composition, but water or a mixed solution of water and an organic solvent compatible with water can be used. Non-limiting examples of organic solvents that are compatible with water include ketones such as acetone, lower alcohols such as methanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and the like.

  The concentration of the photosensitive resin represented by the above formula (1) to be contained in the photosensitive composition of the present invention is not particularly limited as long as there is compatibility between the photosensitive resin and the solvent. More preferably, it is 0.5-10 mass% with respect to the capacity. It is because the viscosity of a photosensitive composition will become high and uniform application | coating becomes difficult as it is 10 mass% or more.

  Further, the concentration of the nano fine particles contained in the photosensitive composition is not limited as long as the nano fine particles and the photosensitive resin are compatible, but the mass ratio of the photosensitive resin to the nano fine particles is 1: 2 to 2: 1. Is preferred.

  In addition, when using the photosensitive resin represented by the said Formula (1) in which a photosensitive group unit has an ionic dissociation group, pH of a photosensitive composition becomes especially 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 greatly changes. As a result, the pH of the photosensitive composition greatly affects the wettability of the photosensitive composition to the substrate, the sensitivity when irradiated with light, and the mechanical strength of the photocured polymer film to be formed. The photosensitive composition of this invention can be used suitably by pH 0-10, Most preferably, it is pH 1-7.

  Here, the form of the photosensitive resin and nanoparticle represented by the said Formula (1) in the photosensitive composition of this invention is demonstrated. First, in the photosensitive resin represented by the above formula (1), a hydrophobic photosensitive group unit represented by the above formula (2) is introduced at both ends or one end of a hydrophilic polyethylene glycol chain. Therefore, aggregates such as micelles can be formed in the photosensitive composition. 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 to have a polymer micelle structure that forms a shell that is formed and covered with a more hydrophilic polyethylene glycol unit. 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.

  Nanoparticles, such as the above-mentioned aggregates of polymer micelles, are not in the form of an equilibrium state in which there are ones in the form of single particles and those in the form of single particles, It is dispersed without dissolving in the solvent, that is, the nanoparticles are stably present in a particle state without forming an aggregate.

  A part of the photosensitive resin and nanoparticles forms an aggregated structure in which aggregates and nanoparticles formed of the photosensitive resin are used as cores, and the free photosensitive resin bridges the cores. I guess that. This aggregated structure has a particle size of 1 μm or more.

  In addition, when this aggregated structure and impurities in the air are present in the photosensitive composition, the polymer film obtained by applying the photosensitive composition to the substrate and irradiating with light is sometimes several tens of μm. A phase-separated structure having a size may be formed. Although it can be used as it is as a polymer composite, it may be desirable to remove the formation of a large phase separation structure depending on the application. For example, if a part having a size larger than the wavelength of light and having a different refractive index of light is present in the photocured polymer film, the transparency is significantly reduced due to light scattering and turbidity. It is. Therefore, in order to remove large particles such as an aggregate structure 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, for example, a filter having a size of 1 μm or more can be filtered, and examples thereof include a membrane filtration membrane made of cellulose acetate.

  In addition, the photosensitive composition of this invention may contain surfactant. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a polymer micelle material made of a block copolymer having a hydrophilic-hydrophobic unit, and the like. Among these, nonionic surfactants are preferable, and nonionic surfactants having a repeating unit composed of oxyethylene without a photocrosslinkable photosensitive group are particularly preferable. Non-limiting examples of nonionic surfactants having a repeating unit composed of oxyethylene without having a photocrosslinkable photosensitive group include linear alkyl groups such as 2-ethyl-hexyl, lauryl, and stearyl. Are polyethylene glycol (oligomer and polymer) having one or both ends.

  Such a photosensitive composition of the present invention is applied onto a substrate to form a coating film, and the coating film is irradiated with light and cured to form a polymer film. A polymer composite composed of the polymer film provided thereon is formed.

  The polymer film obtained by photocuring the photosensitive composition of the present invention is rich in hydrophilicity. This is because, in polyethylene glycol, photosensitive groups are introduced at both ends of the photosensitive resin, and in the form of hydrophobic-hydrophilic-hydrophobic, the core portion where hydrophobic photosensitive group units are always associated. This is presumed to be due to the structure in which hydrophilic polyethylene glycol chains are surrounded around the periphery and there is no exposure of the hydrophobic portion to the surface. In addition, since the size of the nanoparticle, which is estimated to affect the hydrophilic surface, is an average particle size of 150 nm or less, the nanoparticle exists inside the polymer film and serves as a cross-linking point between the coating film and the photocured polymer film. Since it contributes, it is estimated that it is not exposed to the polymer film surface. Therefore, the polymer film obtained by photocuring the photosensitive composition of the present invention can be used, for example, for the purpose of hydrophilizing the substrate.

  The contact angle of the polymer film photocured with the photosensitive composition of the present invention, that is, the polymer composite surface, with respect to water is preferably 70 ° or less, more preferably 45 ° or less. As an example of a method for measuring the static contact angle, which is an index of hydrophilicity, a measurement apparatus “FTÅ125” manufactured by First Ten Angstroms Co., Ltd. is used, and a temperature of 25 ° C. and a humidity of 50 are used. An example is a method in which about 2 μl of water droplets are dropped on the surface of the polymer film of the polymer composite photocured under the condition of%, and the contact angle after 8 seconds is read.

  In addition, the shape and material of the base material to which the photosensitive composition is applied are not particularly limited. Examples of the material for the base material include glass, thermoplastic resin, thermosetting resin, silicon, diamond, metal, and ceramics. 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. Of these, glass and thermoplastic resin can be preferably used as the material, and a plate can be used as the shape. This is because it can be suitably used to create a pattern structure through a mask.

  Application | coating operation on the base material of the photosensitive composition of this invention may be a generally known method. Examples of coating methods include spin coating, dipping, and casting. Particularly preferred is a spin coating method.

  In addition, when the surface of the base material is contaminated, high-order aggregation of the photosensitive resin or nano-particles may easily occur. In order to prevent agglomeration, the substrate surface can be optionally washed. The 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, and dry cleaning methods such as compressed air cleaning, ozone cleaning, and plasma treatment cleaning. Is mentioned.

  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, you may expose the whole surface of the photosensitive composition apply | coated on the base material to a desired pattern, even if it exposes (light irradiation). In the case of pattern exposure, a polymer composite having a polymer film having an arbitrary pattern shape on a substrate can be obtained by developing after exposure and removing an unexposed region.

  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. In addition, although the photosensitive composition of this invention has the said predetermined photosensitive resin, since it has a nanoparticle with an average particle diameter of 150 nm or less, the resolution is favorable.

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. In addition, after the physical properties of the polymer composite photocured by pattern exposure change, development processing 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 that can dissolve the unexposed region of the coating film of the photosensitive composition, 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.

  The polymer composite having the above-described polymer film obtained by photocuring the photosensitive composition of the present invention on a substrate is preferably used in any of a dry state, a humidified state, and a solution. Can do. 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 aqueous solvent, and the surface of the device is often exposed to a dry state, an aqueous solution, or an organic solvent solution, particularly when used for medical devices. This is because it is required to have resistance to any of them.

  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 methanol, 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. In addition, it may include those that do not dissolve in water or aqueous solvents, and non-limiting examples include minerals such as clay, metal nanoparticles such as gold nanoparticles, polystyrene beads, latex particles, and the like. Examples thereof include molecular nanoparticles, animal cells, plant cells, microorganisms, viruses and the like, and mixtures thereof.

  The temperature at which the polymer composite of the present invention can be used is not particularly limited as long as the polymer film or the polymer composite comprising the polymer film and the substrate does not become unstable. It can be used suitably, and it can use especially suitably between 10-60 degreeC. If the temperature is lower than 4 ° C, the water may partially freeze and the stability of the polymer film or polymer composite may be impaired. If the temperature exceeds 80 ° C, the photosensitive group of the photosensitive resin is decomposed and the polymer is decomposed. This is because the composite may not be retained.

  Since the storage elastic modulus G ′ of the polymer film of the polymer composite of the present invention is 15 Pa · s or more, the mechanical strength in water is high. The storage elastic modulus G ′ is a parameter representing the characteristics of a rubber-like elastic body, and the higher the value, the harder it is meant that the mechanical strength is excellent. The storage elastic modulus G ′ value indicates the density of cross-linking points in the solution. In the system of the photosensitive composition of the present invention, the crosslinking point density in the solution is the number of crosslinking points of the structure (secondary structure) that is crosslinked (crosslinked) formed by the hydrophobic interaction between the aggregates and the aggregates. It is thought that it shows. That is, it is suggested that a polymer film having a higher storage elastic modulus G ′ value has a network structure due to more crosslinking points in the solution, and the hydrophobic concentration increases in the process of forming the coating film. It is expected that the acting aggregates aggregate to form a denser structure. Therefore, the polymer composite having a polymer film having a higher storage elastic modulus G ′ value has higher mechanical strength in water. In particular, the storage elastic modulus G ′ is preferably 25 Pa · s or more.

  As an example of a method for measuring the storage elastic modulus G ′, the storage elastic modulus G ′ is measured using a measuring device “VAR-50 / 100 Viscoanalyzer” manufactured by REOLOGICA. This device is a device capable of performing dynamic viscoelasticity measurement while irradiating light. In addition, a photocured material can be obtained by using a spot light source that uses a high-pressure mercury lamp as a light source as an exposure apparatus to irradiate, and irradiating light onto the sample placed on the quartz glass from below. On quartz glass, the sample is sandwiched between the plate and the quartz glass in the order of sample-measurement plate. Storage elasticity after irradiation (after photocuring) from when light is not irradiated (uncured) to during irradiation (photocuring) It is possible to measure the rate G ′. Details of the measurement conditions of the storage modulus G ′ are described in Test Example 3.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples at all.
Example 1 Preparation of Photosensitive Compositions I and II Photosensitive Resin A represented by the following formula, which is a polyethylene glycol having a phenyl azide group and a photosensitive group having a cinnamoyl structure at both ends. An aqueous solution having an average molecular weight of 2000 (n = 45)) or photosensitive resin B (polyethylene glycol main chain having an average molecular weight of 10000 (n = 225)) (both manufactured by Toyo Gosei Co., Ltd.) and each nanoparticle shown in Table 2 An aqueous dispersion having an average particle size of 150 nm or less and water were mixed, and solutions were prepared so that the concentrations of the photosensitive resin and nanoparticles were as shown in Table 3. By filtering each obtained solution with a 0.45 μm filter, photosensitive compositions I-1 to I-8 and II-1 to II-8 were obtained.

(Comparative Example 1) Preparation of Photosensitive Composition III Solutions having the concentrations shown in Table 3 were prepared in the same manner as in Example 1 except that each nanoparticle was not added. Each obtained solution was filtered with a 0.45 μm filter to obtain photosensitive compositions III-1 to III-2.

(Example 2) Preparation of photosensitive composition IV A solution having the concentration shown in Table 3 was prepared in the same manner as in Example 1 except that photosensitive resin C represented by the following formula was used instead of photosensitive resin A. Was prepared. Each obtained solution was filtered with a 0.45 μm filter to obtain photosensitive compositions IV-1 to IV-8.

(Example 3) Preparation of photosensitive composition V An aqueous solution of photosensitive resin A, colloidal silica (manufactured by DuPont: LUDOX) in Table 2 and water were mixed, and the concentrations of the photosensitive resin and nanoparticles were expressed. Solutions were prepared so that the concentrations shown in 4 were obtained. The obtained aqueous solution was filtered with a 0.45 μm filter to obtain photosensitive compositions V-1 to V-6.

(Example 4) Preparation of photosensitive composition VI Single-terminal laurylated polyethylene glycol (nonionic surfactant, number of oxyethylene units = 20, trade name: Peganol L-20S: manufactured by Toho Chemical Industry Co., Ltd.) And photosensitive resin A, colloidal silica (DuPont: LUDOX) in Table 2 and water are mixed, and the concentrations of the nonionic surfactant, the photosensitive resin, and the nanoparticles are the concentrations shown in Table 5. Each solution was prepared as follows. The obtained aqueous solution was filtered with a 0.45 μm filter to obtain photosensitive compositions VI-1 and VI-2.

(Comparative Example 2) Preparation of Photosensitive Composition VII A solution having a concentration shown in Table 3 was prepared in the same manner as in Example 1 except that an aluminum oxide dispersion (manufactured by Aldrich) having an average particle diameter of 185 nm was used as the nanoparticle. Prepared. Since the obtained aqueous solution was not able to be filtered with a 0.45 micrometer filter, it was set as the photosensitive composition VII in the unfiltered state.

(Example 5) Preparation of photosensitive composition VIII-1 An aqueous solution of photosensitive resin A, colloidal silica shown in Table 2 (manufactured by DuPont: LUDOX), and water were mixed, and the concentration of the photosensitive resin and nanoparticles was mixed. Was prepared so that the concentration becomes as shown in Table 6. The obtained aqueous solution was filtered with a 0.45 μm filter to obtain a photosensitive composition VIII-1.

(Comparative Example 3) Preparation of Photosensitive Composition VIII-2 Solutions having the concentrations shown in Table 6 were prepared in the same manner as in Example 5 except that the nanoparticles were not added. Each obtained solution was filtered with a 0.45 μm filter to obtain a photosensitive composition VIII-2.

(Test example 1) Average particle diameter measurement About each photosensitive composition of Examples 1-4 and Comparative Examples 1-2, a dynamic light-scattering measuring apparatus (The measuring apparatus by Malvern, "HPPS zeta sizer nano S") Was used for dynamic light scattering (DLS) measurement. The measurement was carried out by integrating for 90 seconds in an air atmosphere at 25 ° C., and the average was obtained. In addition, each nanoparticle dispersion shown in Table 2 was measured in the same manner to obtain an average particle size. The obtained results are shown in Tables 2 to 5.

  As a result, it was found that the photosensitive composition of each example formed an aggregate in a wide range having a particle diameter of 5 nm to 2 μm or more. In addition, the particle size distribution of the obtained photosensitive composition had a large particle size distribution indicating monodispersion, and the average particle size of nanoparticles shown in Table 2 and the results of dynamic light scattering measurement of the photosensitive composition However, since the average particle size does not apply to the average particle size obtained by simply combining the size of the nanoparticle alone and the size of the photosensitive resin alone, the nanoparticle and the photosensitive resin are each in the solvent alone. Polyethylene glycol (photosensitive resin) with functional groups capable of photocrosslinking at both ends is bridged between the cores, with aggregates and nanoparticles formed from photosensitive resin as the core. It is presumed that an aggregate with an increased size is formed. In the photosensitive compositions V-1 to V-6 in which the photosensitive resin concentration is fixed to 5 wt% and the added nanoparticle concentration is 0.5 to 10 wt%, the particle size distribution is monodisperse, It was found that the average particle size in the dynamic light scattering measurement result of the photosensitive composition also increased and decreased by increasing and decreasing the concentration of the nano-particles to be added. Therefore, it was found that the particle size of the aggregate can be controlled by changing the concentration of the added nanoparticle.

(Example 6) Polymer composite using photosensitive composition I The photosensitive composition I-1 was dropped onto a soda lime slide glass (manufactured by Matsunami Glass Industry Co., Ltd.), and then a spin coating method (1000 rpm x 30). Second), a coating film was prepared, 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 polymer composite having a polymer film photocured on the substrate.

(Example 7)
In the same manner as in Example 6 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, a polymer film having holes is formed on the substrate surface. A molecular complex was obtained.

(Example 8)
A polymer film on which a 100 μm / 200 μm line / space pattern was formed was used in the same manner as in Example 6 except that the exposure was performed through a mask so that a 100 μm / 200 μm line / space pattern was obtained. A polymer composite on the material surface was obtained.

Example 9
The photosensitive composition I-1 was dropped on a soda lime 22 mmφ cover glass (manufactured by Matsunami Glass Industry Co., Ltd.), a coating film was prepared by spin coating (2500 rpm × 30 seconds), and dried at 60 ° C. for 10 minutes. And 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 polymer composite having a polymer film photocured on the substrate.

(Example 10)
When exposing, a polymer film having holes formed thereon is provided on the substrate surface in the same manner as in Example 9 except that exposure is performed through a mask so as to obtain a pattern in which many holes having a diameter of 100 μm are provided. A polymer composite was obtained.

(Example 11)
A polymer composite having a photocured polymer film on a substrate was obtained in the same manner as in Example 9 except that the photosensitive composition I-5 was used instead of the photosensitive composition I-1. .

(Example 12)
Except for using photosensitive composition I-5 instead of photosensitive composition I-1, a polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10. Obtained.

(Example 13)
A polymer composite having a photocured polymer film on a substrate was obtained in the same manner as in Example 9 except that the photosensitive composition I-7 was used instead of the photosensitive composition I-1. .

(Example 14) Polymer composite using photosensitive composition II In the same manner as in example 8, except that photosensitive composition II-1 was used instead of photosensitive composition I-1, 100 µm / A polymer composite having a polymer film with a 200 μm line / space pattern formed on the substrate surface was obtained.

(Example 15)
A polymer composite having a photocured polymer film on a substrate was obtained in the same manner as in Example 9 except that the photosensitive composition II-4 was used instead of the photosensitive composition I-1.

(Example 16)
A polymer composite having a polymer film with holes formed on the substrate surface is obtained in the same manner as in Example 10 except that the photosensitive composition II-7 is used instead of the photosensitive composition I-1. Obtained.

(Example 17) Polymer composite using photosensitive composition IV On the substrate in the same manner as in Example 9, except that photosensitive composition IV-5 was used instead of photosensitive composition I-1. A polymer composite having a photocured polymer film was obtained.

(Example 18)
A polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10 except that the photosensitive composition IV-8 was used instead of the photosensitive composition I-1. Obtained.

(Example 19) Polymer composite using photosensitive composition V-1 Except that photosensitive composition V-1 was used instead of photosensitive composition I-1, the same procedure was followed as in Example 9. A polymer composite having a polymer film photocured on the material was obtained.

(Example 20)
A polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10 except that the photosensitive composition V-1 was used instead of the photosensitive composition I-1. Obtained.

(Example 21) Polymer composite using photosensitive composition V-2 Except for using photosensitive composition V-2 instead of photosensitive composition I-1, the same as in Example 8, A polymer composite having a polymer film with a 100 μm / 200 μm line / space pattern formed on the substrate surface was obtained.

(Example 22)
A polymer composite having a polymer film photocured on a substrate was obtained in the same manner as in Example 9 except that the photosensitive composition V-2 was used instead of the photosensitive composition I-1.

(Example 23)
Except for using photosensitive composition V-2 instead of photosensitive composition I-1, a polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10. Obtained.

(Example 24) Polymer composite using photosensitive composition V-3 Except that photosensitive composition V-3 was used instead of photosensitive composition I-1, the same procedure was followed as in Example 9. A polymer composite having a polymer film photocured on the material was obtained.

(Example 25)
Except for using photosensitive composition V-3 instead of photosensitive composition I-1, a polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10. Obtained.

(Example 26) Polymer composite using photosensitive composition V-4 Except for using photosensitive composition V-4 instead of photosensitive composition I-1, the same as in Example 8, A polymer composite having a polymer film with a 100 μm / 200 μm line / space pattern formed on the substrate surface was obtained.

(Example 27)
A polymer composite having a polymer film photocured on a substrate was obtained in the same manner as in Example 9 except that the photosensitive composition V-4 was used instead of the photosensitive composition I-1.

(Example 28)
Except for using photosensitive composition V-4 instead of photosensitive composition I-1, a polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10. Obtained.

(Example 29) Polymer composite using photosensitive composition V-5 In the same manner as in Example 9, except that photosensitive composition V-5 was used instead of photosensitive composition I-1. A polymer composite having a polymer film photocured on the material was obtained.

(Example 30)
Except for using photosensitive composition V-5 instead of photosensitive composition I-1, a polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10. Obtained.

(Example 31) Polymer composite using photosensitive composition V-6 Except for using photosensitive composition V-6 instead of photosensitive composition I-1, the same as in Example 8, A polymer composite having a polymer film with a 100 μm / 200 μm line / space pattern formed on the substrate surface was obtained.

(Example 32)
A polymer composite having a photocured polymer film on a substrate was obtained in the same manner as in Example 9 except that the photosensitive composition V-6 was used instead of the photosensitive composition I-1.

(Example 33)
Except for using photosensitive composition V-6 instead of photosensitive composition I-1, a polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10. Obtained.

(Example 34) Polymer composite using photosensitive composition VI-1 Except for using photosensitive composition VI-1 instead of photosensitive composition I-1, the same as in Example 8, A polymer composite having a polymer film with a 100 μm / 200 μm line / space pattern formed on the substrate surface was obtained.

(Example 35)
A polymer composite having a polymer film photocured on a substrate was obtained in the same manner as in Example 9 except that the photosensitive composition VI-1 was used instead of the photosensitive composition I-1.

(Example 36)
Except for using photosensitive composition VI-1 instead of photosensitive composition I-1, a polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10. Obtained.

(Example 37) Polymer composite using photosensitive composition VI-2 In the same manner as in Example 9, except that photosensitive composition VI-2 was used instead of photosensitive composition I-1. A polymer composite having a polymer film photocured on the material was obtained.

(Example 38)
A polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10 except that the photosensitive composition VI-2 was used instead of the photosensitive composition I-1. Obtained.

(Comparative Example 4)
A polymer composite having a polymer film on the substrate surface was obtained in the same manner as in Example 9, except that the photosensitive composition VII was used instead of the photosensitive composition I-1. However, a uniform surface such as the photosensitive compositions I-1 to I-8 was not obtained, and a nonuniform and phase-separated surface was obtained. This is because the addition of nanoparticles having an average particle size of greater than 150 nm resulted in dense aggregates between the aggregates after forming the aggregates with the nanoparticles as the core, and formed larger particles. It is presumed that aggregates were exposed on the surface and phase separation occurred.

(Comparative Example 5)
A polymer composite having a polymer film with holes formed on the substrate surface was obtained in the same manner as in Example 10 except that the photosensitive composition III-2 was used instead of the photosensitive composition I-1. Obtained.

  When comparing the uniformity of the coating film of photosensitive composition III-2 (Comparative Example 5) and photosensitive compositions I-1 to I-8, compared to photosensitive composition III-2 without the addition of nanoparticles, A more uniform film was obtained with photosensitive compositions I-1 to I-8 to which nanoparticles were added. Based on this result, it was confirmed that the coating film preparation process was improved by adding nano fine particles.

(Test Example 2) Measurement of static contact angle with respect to water of photocured polymer composite Static contact angle measurement with respect to water on the surface of the polymer film was performed for Examples 9 to 38 on which the entire surface was exposed. . 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 polymer film provided on the substrate and reading the contact angle after 8 seconds. The results are shown in Table 2 and Table 3. The polymer film surface of the polymer composite prepared using the photosensitive compositions I, II, IV and V has a contact angle in the range of 17 ° to 66 °, and most of the surface is 17 ° to 45 °. Shown surface.

(Test Example 3) Measurement of Storage Elastic Modulus G ′ of Polymer Film A polymer film formed using the photosensitive composition VIII-1 of Example 5 and the photosensitive composition VIII-2 of Comparative Example 3 The storage elastic modulus G ′ was measured during irradiation or after light irradiation of 5000 mJ / cm ² . Specifically, the measurement was performed using a UV curing measuring cell of a measuring device “VAR-50 / 100 Visco Analyzer” manufactured by REOLOGICA. In addition, as a common measurement condition, a parallel plate (20 mmφ) was used as a measuring instrument, and the frequency was 1 Hz and the stress was 1 Pa. The measurement environment was measured under conditions of 25 ° C. and 50% relative humidity in the atmosphere. The conditions for irradiating the photosensitive composition with light were as follows: illuminance of light irradiation (UV 365 nm illuminometer) 5 mW, irradiation time 1000 sec. Was set. Table 6 shows the measurement results.

From the result of the storage elastic modulus G ′ value after irradiation with light of 5000 mJ / cm ² at a solid content concentration of 20 wt%, the photosensitive compositions VIII-1 and VIII-2 were compared. Was about 5 times higher and showed G ′ = 28.1 Pa · s. Therefore, the polymer film after photocuring a photosensitive composition in which a photosensitive resin and nanoparticles are mixed has higher film strength than the polymer film of the photosensitive composition to which no nanoparticles are added. It was confirmed that a film with improved physical performance can be obtained.

(Test Example 4) Solvent exposure test of polymer composite The polymer composite obtained in Examples 6 to 38 was immersed in water, various aqueous solvents, or an organic solvent at 25 ° C or 37 ° C. The polymer composites after 3 days and 10 days were observed to evaluate the shape of the polymer film in water, various aqueous solvents, or organic solvents, and the peeling stability from the substrate. 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. As an example, FIG. 1 shows the state of the polymer film before and after immersion for the polymer film of Example 8 immersed in a phosphate buffer at 37 ° C.

  In Examples 6 to 38, all the polymer films were not immersed in various solvents and the surface shape did not change before and after the immersion, and the polymer film was peeled off or collapsed due to swelling. It was in a stable state.

It is a figure which shows an example of the state of the polymer film before and behind a solvent exposure test.

Claims (9)

A photosensitive composition comprising nanoparticles having an average particle size of 150 nm or less, a solvent, and a photosensitive resin represented by the 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 each independently an alkylene group, an arylene group, an oxyalkylene group or a single bond. 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 following formula (2) and the other is an amino group.

(In formula (2), R ₃ is a group selected from the following formula (3), R ₄ is a group selected from the following formula (4), and an azide group is present in at least one of R ₃ and R _4. Have)

  The photosensitive composition according to claim 1, further comprising a nonionic surfactant.   The photosensitive composition according to claim 1, wherein the nano fine particles are a metal, a ceramic, or a polymer.   The photosensitive composition according to claim 3, wherein the nanoparticle is colloidal silica or silsesquioxane.   The photosensitive composition according to claim 1, wherein a mass ratio of the photosensitive resin to the nano fine particles is 1: 2 to 2: 1.   The photosensitive composition according to claim 1, wherein the solvent is water or an aqueous solvent.   It has a base material and the polymer film provided on this base material, The said polymer film light-irradiates the photosensitive composition in any one of Claims 1-6 apply | coated on the said base material. And a polymer composite obtained by curing.   The polymer composite according to claim 7, wherein the polymer film is obtained by developing after light irradiation through a mask having a desired pattern during the light irradiation. body.   The static contact angle with respect to water of the polymer film surface is 45 ° or less, and the storage elastic modulus (G ′) of the polymer film is 15 Pa · s or more. Polymer composite.

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