WO2015198779A1

WO2015198779A1 - Novel polymer and use thereof

Info

Publication number: WO2015198779A1
Application number: PCT/JP2015/065118
Authority: WO
Inventors: 優木村; 寛仁窪; 武士徳永; 西村　功
Original assignee: Jsr株式会社
Priority date: 2014-06-24
Filing date: 2015-05-26
Publication date: 2015-12-30
Also published as: JP6217857B2; JPWO2015198779A1

Abstract

[Problem] To provide a polymer which makes it possible to form a resinous film that contains a water-soluble resin and is thick and a photosensitive resin composition containing the polymer. [Solution] A polymer (A) having a structural unit represented by formula (1a). [In formula (1a), the R¹ moieties are each independently a hydrogen atom or a C_1-20 alkyl group; R² is a C_1-20 alkanediyl group or a C_6-20 arylene group; R³ is a group having a hydroxy group; and R⁴ is a hydrogen atom or a C_1-20 alkyl group.]

Description

Novel polymers and their uses

The present invention relates to a novel polymer and photosensitive resin composition suitably used for forming a resin film containing a water-soluble resin and having a large film thickness, as well as a resin film, a patterned resin film and a method for producing the same, and The present invention relates to a cell culture apparatus.

In the cell culture technology, the culture of a tissue (spheroid) having a function equivalent to that in a living body has attracted attention. A spheroid is a three-dimensional cellular tissue formed by aggregation of many cells. Spheroid culture is a culture method that can maintain the function of cells for a long period of time compared to conventional monolayer culture, and is closer to a living body. It is known that the survival state can be maintained over a long period of time by culturing cells in three dimensions as compared to culturing cells in two dimensions (Patent Document 1).

However, in 3D culture, a cell culture substrate having a surface to which cells adhere relatively weakly compared to 2D culture is used, so that the problem that the formed spheroids are released into the culture solution is known. (Patent Document 1).

In order to solve this problem, a method of culturing cells in a cell holding cavity for holding cells has been disclosed (Patent Document 1). As the partition wall forming the cavity, a photosensitive resin composition containing a water-soluble resin, which is a partition wall having a weak adhesive force with the cell tissue body in consideration of the ease of taking out the cultured cell tissue body In some cases, a partition wall formed from (Patent Documents 2 to 3) is used.

JP 2006-121991 A Japanese Patent Laid-Open No. 03-007576 JP 2014-023508 A

When cell culture is performed in three dimensions, the deeper the holes for holding cells such as cell holding cavities, the better the cultured cells can be held. For this reason, it is desired that a resin film having a large film thickness can be formed in the photosensitive resin composition.

In order to form a resin film having a large film thickness using a photosensitive resin composition containing a resin and a solvent, for example, it is conceivable to increase the resin content. However, increasing the resin content in the composition increases the viscosity of the composition and makes it difficult to apply. In particular, when a water-soluble resin is used, the viscosity of the composition tends to increase because the water-soluble resin has a large interaction between the resins. For this reason, it becomes difficult to form a resin film containing a water-soluble resin and having a large film thickness.

An object of the present invention is to provide a polymer, a photosensitive resin composition containing the polymer, and a resin film and a patterned resin, which can form a resin film containing a water-soluble resin and having a large film thickness. An object of the present invention is to provide a membrane, a manufacturing method thereof, and a cell culture apparatus.

The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by using a polymer and a photosensitive resin composition having the following configurations, and have completed the present invention.

The present invention includes, for example, the following [1] to [13].
[1] A polymer (A) having a structural unit represented by the formula (1a).

[In the formula (1a), each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ² is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms. R ³ is a group having a hydroxyl group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
[2] The polymer (A) according to [1], wherein R ³ is a monovalent group represented by the formula (g1).

[In the formula (g1), a is an integer of 0 to 4. ]
[3] A polymer (A ′) having a structural unit represented by the formula (1b).

[In the formula (1b), each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ² is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms. R ³ is a group having a hydroxyl group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
[4] The polymer (A ′) according to [3], wherein R ³ is a monovalent group represented by the formula (g1).

[In the formula (g1), a is an integer of 0 to 4. ]
[5] A photosensitive resin composition containing the polymer (A) according to [1] or [2], a photoresponsive compound (B), and a crosslinking agent (C).

[6] The photosensitive resin composition according to [5], wherein the photoresponsive compound (B) is a photoacid generator, and the crosslinking agent (C) is a compound that undergoes a crosslinking reaction by the action of an acid. .
[7] The above [5], wherein the crosslinking agent (C) is a compound having at least two groups represented by —CH ₂ OR (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acetyl group). Or the photosensitive resin composition as described in [6].

[8] A resin film containing the polymer (A) according to [1] or [2].
[9] Step 1 of forming a resin film of the photosensitive resin composition according to any one of [5] to [7] on a substrate; Step 2 of selectively exposing the film; And a step 3 of developing the exposed film with an aqueous developer.

[10] The method for producing a patterned resin film according to [9], wherein the substrate is a cell culture substrate.
[11] A patterned resin film obtained by the production method according to [9] or [10].

[12] A patterned resin film containing the polymer (A) according to [1] or [2].
[13] A cell culture device having the patterned resin film according to [11] or [12].

ADVANTAGE OF THE INVENTION According to this invention, the polymer which can form the resin film containing a water-soluble resin and a large film thickness, the photosensitive resin composition containing this polymer, and a resin film and patterned resin A membrane, a production method thereof, and a cell culture device can be provided.

FIG. 1 is a ¹ H NMR spectrum of the polymer obtained in Synthesis Example A1. FIG. 2 is a ¹ H NMR spectrum of the polymer obtained in Example A1. FIG. 3 is a ¹ H NMR spectrum of the polymer obtained in Example A2.

Hereinafter, modes for carrying out the present invention will be described including preferred embodiments. In the present specification, the structural unit represented by the formula (n) is also simply referred to as “structural unit (n)”. n is a formula number.

(Polymer)
The polymer of the present invention has a structural unit represented by the formula (1ab).

In the formula (1ab), X is —S— or —S (═O) —, R ¹ is each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom, ² is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, preferably an alkanediyl group having 1 to 20 carbon atoms, R ³ is a group having a hydroxyl group, R ⁴ is A hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom.

In the following description, for convenience, a polymer having the above structural unit in which X is —S (═O) — is also referred to as “polymer (A)”, and a polymer having the above structural unit in which X is —S—. The polymer is also referred to as “polymer (A) precursor” or “polymer (A ′)”. However, the polymer having both the structural unit in which X is —S (═O) — and the structural unit in which X is —S— corresponds to the polymer (A). The polymer (A) is obtained by oxidizing the precursor as described later. Hereinafter, the term “polymer of the present invention” is used to collectively refer to the polymers (A) and (A ′).

Although the reason is not clear, when the polymer (A) of the present invention is used, a composition having a low viscosity can be obtained as compared with the case where a conventional water-soluble resin is used. For this reason, even if there is much content of a polymer (A), the composition which has the viscosity which can be apply | coated can be prepared. Therefore, a resin film having a large film thickness can be formed by a single coating.

In addition, since the polymer (A) is a water-soluble resin, it is possible to form a resin film having a cell non-adhesive property with weak adhesion to a cell tissue. The “water-soluble resin” in the present invention refers to a resin having a solubility in 100 g of water at 25 ° C. and 1 bar of 0.1 g or more.

Examples of the alkyl group having 1 to 20 carbon atoms in R ¹ and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, a decyl group, etc. are mentioned. The number of carbon atoms of the alkyl group is preferably 1-15, more preferably 1-10.

Examples of the alkanediyl group having 1 to 20 carbon atoms in R ² include a methylene group, a 1,2-ethanediyl group, an n-propylene group, an isopropylene group, and an isobutylene group. The carbon number of the alkanediyl group is preferably 1-15, more preferably 1-10.

Examples of the arylene group having 6 to 20 carbon atoms in R ² include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, , 8-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group and the like. The arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 15 carbon atoms.

The group having a hydroxyl group in R ³ is, for example, formed by substituting at least one hydrogen atom contained in an alkyl group having usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10 carbon atoms with a hydroxyl group. Examples include OH-containing groups and OH / ether-containing groups in which a part of —CH ₂ — contained in the OH-containing group is replaced with an oxygen atom. The number of hydroxyl groups is usually 1 or more, preferably 1 to 5, more preferably 1 to 2. In particular, R ³ is preferably a monovalent group represented by the formula (g1).

In the formula (g1), a is an integer of 0 to 4, preferably an integer of 0 to 1.
The structural unit (1ab) is preferably a part of the structural unit represented by the formula (1).

In the formula (1), X and R ¹ to R ⁴ have the same meanings as the same symbols in the formula (1ab). Incidentally, it is preferable that two R ¹ attached to the carbon atom C ₁ is a hydrogen atom, it is more preferred that all of R ¹ is a hydrogen atom.

The content of the structural unit (1) in which X is —S (═O) — is usually 20 mol% or more, preferably 20 to 20 mol per 100 mol% of all the structural units constituting the polymer (A) of the present invention. 90 mol%, more preferably 30 to 80 mol%. The content of the structural unit (1) in which X is —S— is usually 20 mol% or more, preferably 20 to 90 mol% in 100 mol% of all the structural units constituting the polymer (A ′) of the present invention. More preferably, it is 30 to 80 mol%. When the content of the structural unit (1) is in the above range, a resin excellent in balance between water solubility and viscosity when contained in the composition tends to be obtained.
The structural unit indicates a structure derived from a monomer (for example, a conjugated diene compound). The content of each structural unit can be measured by NMR analysis.

The polymer of the present invention may further have a structural unit represented by the formula (2), and from the structural unit represented by the formula (3) and the structural unit represented by the formula (4). You may have further at least 1 sort chosen.

In the formulas (2) to (4), X and R ¹ to R ⁴ have the same meanings as the same symbols in the formula (1ab). In the formula (2), the cis-trans isomer of the double bond is not particularly limited. Incidentally, it is preferable that two R ¹ attached to the carbon atom C ₁ is a hydrogen atom, it is more preferred that all of R ¹ is a hydrogen atom.

The total content of the structural unit (1) and the structural unit (2) in which X is —S (═O) — is usually 20 mol in 100 mol% of all structural units constituting the polymer (A) of the present invention. % Or more, preferably 20 to 95 mol%, more preferably 30 to 90 mol%. The content of the structural unit (1) and the structural unit (2) in which X is —S— is usually 20 mol% or more, preferably 100 mol% or more in all the structural units constituting the polymer (A ′) of the present invention. Is 20 to 95 mol%, more preferably 30 to 90 mol%.

The content of the structural unit (3) is usually 80 mol% or less, preferably 5 to 80 mol%, more preferably 100 mol% of all the structural units constituting the polymer (A) or (A ′) of the present invention. Is from 10 to 70 mol%. The content of the structural unit (4) in which X is —S (═O) — is usually 10 mol% or less in 100 mol% of all the structural units constituting the polymer (A) of the present invention. The content of the structural unit (4) in which X is —S— is usually 10 mol% or less in 100 mol% of all the structural units constituting the polymer (A ′) of the present invention.

The weight average molecular weight (Mw) measured by the gel permeation chromatography method of the polymer of the present invention is usually 1,000 to 100,000, preferably 2,000 to 50,000, more preferably in terms of polystyrene. 3,000 to 30,000. Further, the molecular weight distribution of the polymer of the present invention represented by weight average molecular weight (Mw) / number average molecular weight (Mn) is usually 1 to 5, preferably 1.1 to 3, more preferably 1.2 to 2. It is.

When Mw is in the above range, a resin film having a higher resolution and a larger film thickness can be formed. It is preferable in terms of resolution that Mw / Mn is in the above range. The details of the measuring method of Mw and Mn are as described in the examples.

[Production method of polymer]
The polymer (A) of the present invention includes, for example, a step A1 of obtaining an epoxidized polymer by epoxidizing a carbon-carbon double bond contained in a conjugated diene polymer, and an epoxy ring contained in the epoxidized polymer. On the other hand, ring-opening addition of a compound represented by R ³ —R ² —SH (R ² and R ³ have the same meanings as R ² and R ³ in the formula (1ab), respectively) It can be synthesized by a production method having Step A2 for obtaining a containing polymer and Step A3 for converting a sulfide group contained in the sulfide group-containing polymer into a sulfinyl group using an oxidizing agent.

<Step A1: Epoxidation>
Step A1 is a step of obtaining an epoxidized polymer by epoxidizing the carbon-carbon double bond contained in the conjugated diene polymer. In this step, the carbon-carbon double bond contained in the conjugated diene polymer having the structural unit represented by the formula (a1) is epoxidized, and the epoxidized polymer having the structural unit represented by the formula (a2) Is obtained.

In the above reaction formula, R ¹ has the same meaning as the same symbol in formula (1ab). In the formula (a1), the cis-trans isomer of the double bond is not particularly limited.

Examples of the conjugated diene compound constituting the conjugated diene polymer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, and 1,3- Examples include pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, and 4,5-diethyl-1,3-octadiene. Of these, 1,3-butadiene and isoprene are preferred. A conjugated diene compound may be used individually by 1 type, and may use 2 or more types together. As the conjugated diene polymer, polybutadiene and polyisoprene are preferable.

The vinyl bond content in the conjugated diene polymer is usually 80 mol% or less, preferably 5 to 80 mol%, more preferably 10 to 70 mol%. In the present specification, the vinyl bond content is a conjugated diene compound that is incorporated in a conjugated diene polymer in a 1,2-bond, 3,4-bond, or 1,4-bond bond mode. This is the total ratio (based on mol%) of compounds incorporated by 1,2-bonds and 3,4-bonds. The vinyl bond content can be measured by the Hampton method by infrared spectroscopic analysis.

Step A1 can be performed, for example, by epoxidizing the carbon-carbon double bond derived from the conjugated diene compound contained in the conjugated diene polymer with an epoxidizing agent in an organic solvent. In this epoxidation, an epoxidation catalyst can also be used.

Examples of the epoxidizing agent include hydrogen peroxide; organic peracids such as peracetic acid, perbenzoic acid, performic acid, and trifluoroperacetic acid. Among these, hydrogen peroxide is preferable. Examples of the epoxidation catalyst include formic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristylic acid, palmitic acid, palmitoyl acid, margaric acid, stearic acid, oleic acid Vaccenoic acid, linoleic acid, (9,12,15) -linolenic acid, (6,9,12) -linolenic acid, eleostearic acid, tuberculostearic acid, arachidic acid, 8,11-icosadienoic acid, 5 , 8,11-icosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, serotic acid, montanic acid, melicic acid and other carboxylic acids, and acid anhydrides thereof.

Examples of organic solvents that can be used for epoxidation include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cycloheptane, benzene, naphthalene, toluene, and xylene. Aromatic hydrocarbons, aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, and propyl acetate, and halogenated hydrocarbons such as chloroform. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

The reaction temperature in step A1 may be appropriately selected below the boiling point of the solvent, but is usually 0 to 200 ° C., preferably 40 to 150 ° C. The reaction time in step A1 is usually 0.5 to 30 hours, preferably 1 to 10 hours.

The amount of epoxidizing agent and epoxidation catalyst used is not particularly limited. An appropriate amount can be used depending on conditions such as the reactivity of the epoxidizing agent, the performance of the epoxidation catalyst, the desired epoxidation rate, the number of carbon-carbon double bonds contained in the conjugated diene polymer.

The epoxidation rate of the epoxidized polymer is usually 10 to 100%, preferably 30 to 90%, more preferably 40 to 80%. Epoxidation rate is [number of double bonds epoxidized among all carbon-carbon double bonds contained in conjugated diene polymer / number of all carbon-carbon double bonds contained in conjugated diene polymer before epoxidation] × 100 (%). The epoxidation rate can be calculated by ¹ H NMR.

<Step A2: Sulfidation>
Step A2 is a step of obtaining a sulfide group-containing polymer by ring-opening addition of a compound (sulfiding agent) represented by R ³ —R ² —SH to the epoxy ring contained in the epoxidized polymer. . If necessary, the hydroxyl group after the epoxy ring is opened is alkoxylated. In this step, the structural unit represented by the formula (a2) is converted into the structural unit represented by the formula (a3) to obtain the precursor of the polymer (A) of the present invention.

In the above reaction formula, R ¹ to R ⁴ are respectively synonymous with the same symbols in formula (1ab).

In sulfidizing agent, R ² and R ³ are as defined the same symbols in each formula (1ab). Specific examples include thioglycerol and mercaptoethanol. The sulfiding agent may be used alone or in combination of two or more. The amount of the sulfidizing agent to be used is generally 0.5 to 20 mol, preferably 1 to 10 mol, per 1 mol of structural unit (a2).

Step A2 is preferably performed in the presence of a catalyst. Examples of the catalyst include basic catalysts such as lithium hydroxide, triethylamine and N, N-dimethyl-4-aminopyridine. A catalyst may be used individually by 1 type and may use 2 or more types together. The amount of the catalyst to be used is generally 0.01-30 mol, preferably 0.1-10 mol, per 1 mol of structural unit (a2).

Step A2 is preferably performed in the presence of an organic solvent. Examples of the organic solvent include alcohol solvents such as methanol and ethanol, amide solvents such as dimethylformamide and dimethylacetamide, sulfoxide solvents such as dimethyl sulfoxide, ester solvents such as ethyl acetate, butyl acetate and γ-butyrolactone, toluene, benzene and the like. And an aromatic solvent such as tetrahydrofuran, dioxane, diethyl ether and the like. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

The reaction temperature in step A2 may be appropriately selected below the boiling point of the solvent, but is usually 30 to 150 ° C., preferably 40 to 100 ° C. The reaction time in step A2 is usually 1 to 20 hours, preferably 2 to 10 hours.

The alkoxylation of the hydroxyl group formed by opening the epoxy ring can be performed by a known method. For example, it can be carried out according to the method described in JP-A-56-104831 or JP-A-2005-305280. The alkoxylation of the hydroxyl group may be performed after sulfinylation.

<Step A3: Sulfinylation>
Step A3 is a step of converting a sulfide group contained in the sulfide group-containing polymer into a sulfinyl group using an oxidizing agent. In this step, the structural unit represented by the formula (a3) is converted into the structural unit represented by the formula (a4), and the polymer (A) of the present invention is obtained.

Examples of the oxidizing agent include organic oxidizing agents such as peracetic acid, perbenzoic acid, and metachloroperbenzoic acid, and inorganic oxidizing agents such as hydrogen peroxide, chromic acid, and permanganate. An oxidizing agent may be used individually by 1 type, and may use 2 or more types together. The amount of the oxidizing agent to be used is generally 1 to 10 mol, preferably 2 to 5 mol, per 1 mol of structural unit (a3). An oxidizing agent may be used individually by 1 type, and may use 2 or more types together.

Process A3 is preferably performed in the presence of a solvent. Examples of the solvent include water; alcohol solvents such as methanol and ethanol; amide solvents such as dimethylformamide and dimethylacetamide. Among these, water and alcohol solvents are preferable. A solvent may be used individually by 1 type and may use 2 or more types together.

The reaction temperature in step A3 may be appropriately selected below the boiling point of the solvent, but is usually 23 to 100 ° C., preferably 30 to 70 ° C. The reaction time in step A3 is usually 0.5 to 30 hours, preferably 1 to 10 hours.

In each of the above steps, isolation of each reaction product is carried out as usual by filtration, washing, drying, recrystallization, reprecipitation, dialysis, centrifugation, extraction with various solvents, neutralization, chromatography, etc. The means may be combined appropriately.

[Photosensitive resin composition]
The photosensitive resin composition of this invention contains the polymer (A) mentioned above, a photoresponsive compound (B), and a crosslinking agent (C). The photosensitive resin composition of the present invention is also referred to as “the composition of the present invention”. Since the composition of this invention contains a polymer (A), it can form the resin film which has a large film thickness and hydrophilic property.

The viscosity of the composition of the present invention is usually 0.1 to 100 cP, preferably 0.5 to 50 cP, more preferably 1 to 10 cP. The viscosity is a value measured by a method based on JIS Z8803.

<Polymer (A)>
The content of the polymer (A) is usually 10 to 60% by mass, preferably 15 to 55% by mass, and more preferably 20 to 50% by mass in 100% by mass of the composition of the present invention. When the content of the polymer (A) is within the above range, a composition capable of forming a resin film having a large film thickness and high resolution can be obtained. Moreover, even if content of a polymer (A) exists in the said range, the composition which has the viscosity which can be apply | coated can be obtained.

<Photoresponsive compound (B)>
The photosensitive resin composition of the present invention contains a photoresponsive compound (B). Examples of the photoresponsive compound (B) include a photoacid generator and a photoradical polymerization initiator.

As the photoresponsive compound (B), a photoacid generator is preferable. The photoacid generator is a compound that generates an acid by a treatment including light irradiation. By the process including the exposure process for the resin film formed from the composition of the present invention, an acid is generated in the exposed part based on the acid generator, and the solubility of the exposed part in the aqueous developer is changed based on the action of this acid. To do.

The composition of the present invention may be either a negative type or a positive type. The kind of photoresponsive compound (B) can be suitably selected according to a negative composition or a positive composition. Among these, from the viewpoint of the mechanical strength of the resin film, a negative composition is preferable.

Examples of the photoacid generator include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and compounds having a quinonediazide group. Hereinafter, the compound having a quinonediazide group is also referred to as “quinonediazide compound (B2)”, and the other exemplified photoacid generators are also referred to as “acid generator (B1)”.

The acid generator (B1) is a compound that generates an acid when irradiated with light. By irradiating the resin film obtained from the composition containing the acid generator (B1) with light, the generated acid acts on the crosslinking agent (C) and the like to form a crosslinked structure. On the other hand, it becomes a hardly soluble film. A negative pattern is formed by utilizing the fact that the film changes from an easily soluble state to an insoluble state in an aqueous developer by light irradiation.

The quinonediazide compound (B2) is a compound in which a quinonediazide group is decomposed to generate a carboxyl group by light irradiation and contact treatment with water. The resin film obtained from the composition containing the quinonediazide compound (B2) is a film that is hardly soluble in an aqueous developer. A positive pattern is formed by utilizing the fact that the film changes from a hardly soluble state to an easily soluble state in an aqueous developer by light irradiation.

<< Acid generator (B1) >>
The acid generator (B1) is at least one selected from, for example, an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound.

Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Specific examples of preferred onium salts include iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate; L-methanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7- Di-n-butoxynaphthyltetrahydrothiofe Um trifluoromethanesulfonate, 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, etc. A sulfonium salt is mentioned.

Examples of the halogen-containing compound include a haloalkyl group-containing heterocyclic compound and a haloalkyl group-containing hydrocarbon compound. Specific examples of preferred halogen-containing compounds include phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl S-triazine derivatives such as bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine; 1 , 10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.

Examples of sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.

Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy). ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide.

Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

The acid generator (B1) may be used alone or in combination of two or more.
In the composition of the present invention, when the acid generator (B1) is used as the photoresponsive compound (B), the content of the acid generator (B1) is preferably 100 parts by mass of the polymer (A). The amount is 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 5 parts by mass.

When the content of the acid generator (B1) is equal to or higher than the lower limit, the exposed area is sufficiently cured and the heat resistance is easily improved. When the content of the acid generator (B1) is not more than the above upper limit value, a patterned resin film having a high resolution is easily obtained without lowering the transparency to exposure light.

<< Quinonediazide compound (B2) >>
Examples of the quinonediazide compound (B2) include a naphthoquinonediazide compound, specifically, a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphtho Examples include ester compounds with quinonediazide-5-sulfonic acid.

Examples of the quinonediazide compound (B2) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2 , 3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [ 1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and 1,1 A compound selected from bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-4-sulfonic acid or 1 , 2-naphthoquinonediazide-5-sulfonic acid ester compounds.

A quinonediazide compound (B2) may be used by 1 type, and may use 2 or more types together.
In the composition of the present invention, when the quinonediazide compound (B2) is used as the photoresponsive compound (B), the content of the quinonediazide compound (B2) is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the polymer (A). 50 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 15 to 30 parts by mass.

When the content of the quinonediazide compound (B2) is equal to or higher than the lower limit, the remaining film ratio in the unexposed area is improved and an image faithful to the mask pattern is easily obtained. When the content of the quinonediazide compound (B2) is less than or equal to the above upper limit value, a resin film excellent in pattern shape is easily obtained and foaming during film formation tends to be prevented.

<Crosslinking agent (C)>
The composition of the present invention contains a crosslinking agent (C). The crosslinking agent (C) is, for example, a compound that undergoes a crosslinking reaction by the action of an acid; a compound that is polymerized by heat or radical, such as a (meth) acrylate compound. As the crosslinking agent (C), a compound that proceeds with a crosslinking reaction by the action of an acid is preferable. By using the crosslinking agent (C), the mechanical strength, heat resistance, and chemical resistance of the patterned resin film can be improved.

Examples of the crosslinking agent (C) include a crosslinking agent (C1) having at least two groups represented by —CH ₂ OR and other crosslinking agents (C2). In the above formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group. The (C1) is also referred to as “active methylene group-containing crosslinking agent (C1)”. Among these, a crosslinking agent (C1) is preferable from the viewpoint that a high-thickness resin film can be formed.

In the composition of the present invention, the content of the crosslinking agent (C) is usually 1 to 50 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 20 parts per 100 parts by weight of the polymer (A). Part by mass. When the content of the crosslinking agent (C) is in the above range, a composition excellent in sensitivity and resolution tends to be obtained.

<< Active methylene group-containing crosslinking agent (C1) >>
The active methylene group-containing crosslinking agent (C1) is a crosslinking agent having at least two groups represented by —CH ₂ OR. In the formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acetyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the crosslinking agent (C1) include a compound having two or more groups represented by the formula (C1-1) and a compound having two or more groups represented by the formula (C1-2).

In the formulas (C1-1) and (C1-2), m is 1 or 2, n is 0 or 1, m + n is 2, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or An acetyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * is a bond.

Examples of the crosslinking agent (C1) include nitrogen compounds such as polymethylolated melamine, polymethylolated glycoluril, polymethylolated guanamine, and polymethylolated urea; active methylol groups in the nitrogen compounds (CH bonded to N atom) ₂ OH group) or all of a part thereof are alkyl etherified or acetoxylated. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be the same as or different from each other. Moreover, the active methylol group which is not alkyletherified or acetoxylated may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.

Examples of the crosslinking agent (C1) include crosslinking agents described in JP-A-6-180501, JP-A-2006-178059, and JP-A-2012-226297. Specifically, melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, tetrabutoxy Glycoluril-based crosslinking agents such as methylglycoluril; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5.5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetraoxospiro [5.5] undecane A compound obtained by methylolating guanamine, etc., and all of the active methylol groups in the compound Or guanamine-based crosslinking agent such as an alkyl etherified or acetoxylation the compounds of the part. Among these, a melamine type crosslinking agent and a guanamine type crosslinking agent are preferable.

Other examples of the crosslinking agent (C1) include a methylol group-containing phenol compound, an alkylmethylol group-containing phenol compound, and an acetoxymethyl group-containing phenol compound. Specific examples include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and compounds represented by the following formulae. It is done.

A crosslinking agent (C1) may be used by 1 type, and may use 2 or more types together.

<< Other cross-linking agent (C2) >>
Examples of the other crosslinking agent (C2) include an oxirane ring-containing compound, an oxetane ring-containing compound, an isocyanate group-containing compound (including a blocked one), an oxazoline ring-containing compound, and an aldehyde group-containing phenol compound. . The other crosslinking agent (C2) may be used alone or in combination of two or more.

<Solvent (D)>
The composition of the present invention preferably contains a solvent (D). By using the solvent (D), the handleability of the composition can be improved, and the viscosity and storage stability can be adjusted.

As the solvent (D), for example, water or a mixed solvent containing water is preferable. Examples of the solvent other than water constituting the mixed solvent include organic solvents that can be uniformly mixed with water, for example, alcohols such as methanol, ethanol, n-butanol, and ethyl lactate, and alkylene glycols such as propylene glycol monomethyl ether. . In the mixed solvent, usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more is water.

A solvent (D) may be used individually by 1 type, and may use 2 or more types together.
In the composition of the present invention, when the solvent (D) is used, the content of the solvent (D) is such that the solid content concentration in the composition usually exceeds 10% by mass and is 70% by mass or less, preferably 15% by mass. Is more than 60% by mass, more preferably more than 20% by mass and 55% by mass or less. The solid content usually means all components other than the solvent (D) contained in the composition.

<Other additives>
In the composition of the present invention, other additives such as adhesion assistant, acid diffusion controller, crosslinked fine particles, leveling agent, surfactant, sensitizer, inorganic filler, quencher, etc. It can be contained as long as the characteristics are not impaired.

<Method for preparing photosensitive resin composition>
The composition of this invention can be prepared by mixing each component uniformly. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.

[Resin film and manufacturing method thereof]
The resin film of the present invention contains the polymer (A) described above. The resin film containing the polymer (A) can be formed, for example, according to Step 1 described below, using the above-described photosensitive resin composition of the present invention. The thickness of the resin film is usually 1 to 200 μm, preferably 3 to 100 μm, more preferably 5 to 50 μm.

[Patterned resin film and manufacturing method thereof]
The patterned resin film of the present invention contains the polymer (A) described above, and is formed, for example, from the photosensitive resin composition of the present invention. By using the composition, a hydrophilic resin film having a large film thickness can be formed. In addition, a patterned resin film with high resolution can be formed.

An example of production of the patterned resin film of the present invention is shown below. In this production example, Step 1 for forming a resin film of the photosensitive resin composition of the present invention on a substrate, Step 2 for selectively exposing the film, and development of the exposed film with an aqueous developer. And a step 3 of forming a patterned resin film. This manufacturing example may further include a step 4 of heat-treating the patterned resin film.

[Step 1]
In step 1, for example, the photosensitive resin composition of the present invention is applied onto a substrate and dried to form a resin film. As drying conditions, for example, heating is performed at 50 to 90 ° C. for 1 to 30 minutes using an oven or a hot plate. The thickness of the resin film is usually 1 to 200 μm, preferably 3 to 100 μm, more preferably 5 to 50 μm. If the film thickness is insufficient, the resin film may be formed by coating twice.

As the substrate, for example, polystyrene, polycarbonate, polyacetal, triacetyl cellulose, polyamide, polyimide, polyethylene, polypropylene, vinyl chloride, vinylidene chloride, polyphenylene sulfide, polyethersulfone, polyurethane, polyethylene terephthalate, polyethylene naphthalate, polyacrylate, Examples include a resin substrate made of at least one resin selected from polymethacrylate and cellulose; a substrate made of a material such as glass, ceramic, and stainless steel. It may be a resin substrate made of a biodegradable polymer such as polylactic acid, polyglycolic acid, and polycaprolactan. As the substrate, a known cell culture substrate described in JP-A-2002-335949 can also be used.

Examples of the coating method of the composition include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method.

[Step 2]
In step 2, the film is exposed through a desired mask pattern using, for example, a contact aligner, a stepper, or a scanner. Examples of exposure light include ultraviolet light and visible light, and light with a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is usually used. The exposure dose of exposure light varies depending on the type and content of each component in the photosensitive resin composition, the thickness of the resin film, and the like. 000 mJ / cm ² .

In the case of using a negative photosensitive resin composition, it is preferable to perform a heat treatment after exposure in order to further promote the crosslinking reaction. Hereinafter, this processing is also referred to as “PEB processing”. The PEB condition varies depending on the type and content of each component in the photosensitive resin composition and the thickness of the resin film, but is usually 50 to 90 ° C. and about 1 to 60 minutes.

[Step 3]
In step 3, the exposed film is developed with an aqueous developer, and a non-exposed portion is removed in the case of a negative type, and an exposed portion is removed in the case of a positive type, thereby forming a desired pattern on the substrate. A resin film is formed.

As the aqueous developer, for example, water or a mixed solvent containing water is preferable. As a mixed solvent, the mixed solvent described in the column of the solvent (D) is mentioned. Examples of the development method include a shower development method, a spray development method, an immersion development method, and a paddle development method. The development conditions are usually about 20 to 40 ° C. for about 1 to 10 minutes.

[Step 4]
If necessary, the patterned resin film is further cured by heating. The heating conditions are not particularly limited, but for example, the heating is performed at a temperature of 100 to 300 ° C. for about 30 minutes to 10 hours depending on the use of the patterned resin film. In order to sufficiently advance the curing or to prevent the deformation of the pattern shape, heating can be performed in multiple stages.

[Cell culture equipment]
The cell culture device of the present invention has the patterned resin film described above. The apparatus preferably includes a cell culture substrate and the patterned resin film described above formed on the substrate.

Hereinafter, an aspect of the cell culture apparatus will be described.
The patterned resin film possessed by the cell culture device of the present invention is a resin film formed from the photosensitive resin composition of the present invention for retaining cells and cell tissues formed from these cells, particularly spheroids. It has a structure in which one or a plurality of holes are formed. The patterned resin film is a partition wall that forms a hole.

The hole is formed through the resin film. The bottom surface of the hole is constituted by the surface of the cell culture substrate, and the side surface of the hole is constituted by a resin film. The surface of the cell culture substrate preferably has cell adhesion from the viewpoint of cell retention.

The patterned resin film preferably has cell non-adhesiveness in consideration of the ease of removing the cell tissue from the pores after culturing. Since the photosensitive resin composition of the present invention contains the polymer (A) which is a water-soluble resin, a patterned resin film having the above properties can be formed.

The shape of the bottom surface of the hole is not particularly limited, and examples thereof include a circular shape, an elliptical shape, and a polygonal shape. The area of the bottom of the pore is appropriately determined depending on the size and type of cells, but is usually 1,000 to 40,000 μm ² , preferably 5,000 to 20,000 μm ² .

The patterned resin film in which holes are formed in the resin film can be formed, for example, according to the above-described method for producing a patterned resin film. At that time, a cell culture substrate is used as the substrate to which the photosensitive resin composition is applied.

The bottom surface of the hole is preferably a surface having cell adhesiveness from the viewpoint of holding cells and forming a cell tissue body. Cell adhesive surfaces include, for example, surfaces into which charged functional groups such as carboxyl groups and amino groups have been introduced, surfaces into which cell adhesive peptides such as arginine, glycine, and aspartic acid sequences have been introduced. It is the surface where the polymer which it has was fixed.

The functional group having an electric charge can be introduced by treating the substrate surface with radiation such as plasma. Examples of the polymer having cell adhesion include, for example, synthetic polymers having a charge such as polyacrylic acid, polyvinyl sulfate, polystyrene sulfonic acid, polyallylamine, chondroitin sulfate, dermatan sulfate, dextran sulfate, keratan sulfate, heparan sulfate, Examples thereof include polysaccharides having a charge such as hyaluronic acid and chitin, cell adhesive proteins such as collagen, gelatin, fibronectin, hydronectin and laminin, and synthetic polymers on which cell adhesive proteins and cell adhesive peptides are immobilized.

For example, a cell culture substrate having a cell adhesive surface can be used. Further, after the patterned resin film is formed on the cell culture substrate, the exposed surface of the substrate (bottom surface of the hole) may be subjected to radiation treatment or a cell-adhesive polymer may be immobilized.

The substrate surface that is the bottom surface of the hole may have an uneven structure. By providing such a concavo-convex structure, the adhesion of the cell tissue body to the bottom surface can be improved. Examples of the shape in the planar direction of the convex portion or concave portion in the concavo-convex structure include a circular shape, an elliptical shape, and a polygonal shape.

The depth of the hole is determined by the thickness of the patterned resin film, and is usually 1 to 200 μm, preferably 3 to 100 μm, and more preferably 5 to 50 μm. If it is this range, a cell and a cell tissue body can be favorably hold | maintained in a hole.

When culturing cells using the cell culture apparatus of the present invention, the cells are cultured in the pores of the patterned resin film to form cell tissues, particularly spheroids. For example, a culture solution containing cells is put into the hole, and cells seeded on the bottom surface of the hole form a cell tissue body that is three-dimensionally bonded on the surface of the cell culture substrate that is the bottom surface. The cell tissue is cultured for a long period of time while being stably held in the hole formed by the partition wall while adhering to the bottom surface of the hole without floating in the culture solution.

The type of animal species and organs / tissues is not particularly limited as long as the cells form a bond between cells. For example, primary cells collected from livers, pancreas, kidneys, nerves, skin, ES cells (Embryonic Stem cell), established cell lines, or these derived from animals such as humans, pigs, dogs, rats, mice, etc. And cells subjected to genetic manipulation. A cell may be used individually by 1 type and may use 2 or more types together. As the culture solution, an aqueous solution containing necessary salts and / or nutrient components at an appropriate concentration can be used so that the survival state and function of the cells can be maintained.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.

[1] Method for measuring physical properties [1-1] Method for measuring Mw, Mn and Mw / Mn of polymer The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer are: The measurement was performed by gel permeation chromatography under the following conditions.
Column: Tosoh column “TSKgel αM” and “TSKgel α2500” connected in series. Solvent: N-methyl-2-pyrrolidone with lithium bromide and phosphoric acid added. Temperature: 40 ° C.
・ Detection method: Refractive index method ・ Standard material: Polystyrene ・ GPC apparatus: manufactured by Tosoh Corporation, apparatus name “HLC-8020-GPC”

[1-2] Method for measuring content of structural unit contained in polymer The content of the structural unit contained in the polymer was measured by ¹ H-NMR and ¹³ C-NMR analysis. Using a device name “ECP-400P” (manufactured by JEOL), a heavy solvent having the highest solubility of the polymer was selected from deuterated chloroform, deuterated methanol and deuterated water.

[2] Synthesis of polymer (A) Polymer (A) was synthesized based on the following scheme.

[Synthesis Example A1] Synthesis of Polymer (A1) In a 500 ml flask equipped with a stirrer, polybutadiene (Cis-1,4 bond content = 20 mol%, Trans-1,4 bond content = 55 mol%, 1,2 bond content). = 25 mol%) 23.6 g, formic acid 5.9 g and toluene 240 ml were added. The mixture was heated to 60 ° C., and 55.9 g of 31 mass% hydrogen peroxide was added over 15 minutes while stirring. The reaction was allowed to proceed for 150 minutes, followed by cooling to 23 ° C. This reaction solution was washed with an aqueous sodium hydrogen carbonate solution and water, and the solvent was distilled off to obtain a polymer (A1). ^{From 1} H NMR, the polymer (A1) is a polymer in which a part of unsaturated groups of polybutadiene is epoxidized, and the epoxidation rate [(number of epoxidized unsaturated groups / polybutadiene before epoxidation is included) Number of unsaturated groups) × 100 (%)] was 60%. The ¹ H NMR spectrum of the polymer (A1) is shown in FIG. Moreover, Mn was 5400, Mw was 9500, and Mw / Mn was 1.76.

[Example A1] Synthesis of polymer (A2) In a 100 ml flask, 5.2 g of the above polymer (A1), 4.4 g of α-thioglycerol, 0.85 g of lithium hydroxide monohydrate, methanol (MeOH). 6.6 ml and tetrahydrofuran (THF) 5.8 ml were added and heated and stirred at 60 ° C. for 2 hours. Then, it cooled to 23 degreeC and reprecipitated with water. The precipitate was vacuum dried at 60 ° C. to obtain a polymer (A2). ^{From 1} H NMR, it was found that the polymer (A2) had a thioether structure. The ¹ H NMR spectrum of the polymer (A2) is shown in FIG.

[Example A2] Synthesis of polymer (A3) To a 100 ml flask, 5.0 g of the above polymer (A2), 4.6 g of 31% by mass hydrogen peroxide, and 25.3 ml of methanol (MeOH) were added. The mixture was stirred with heating at ° C for 2 hours. Then, it cooled to 23 degreeC and reprecipitated with isopropanol. The precipitate was vacuum dried at 60 ° C. to obtain a white solid polymer (A3). ^{From 1} H NMR, it was found that the polymer (A3) had a sulfinyl group. The ¹ H NMR spectrum of the polymer (A3) is shown in FIG.

[3] Formation of photosensitive resin composition and patterned resin film [Example 1B]
Polymer (A3) 100 parts, 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate 3 parts, methylated melamine resin (trade name “Nicalac MW-30HM”, manufactured by Sanwa Chemical Co., Ltd.) 10 parts were uniformly dissolved in a mixed solvent composed of 120 parts of water and 20 parts of methanol so that the solid content concentration was 5 to 50% by mass to obtain a photosensitive resin composition.

[Example 1C]
On the glass substrate, the photosensitive resin composition prepared in Example 1B was applied by spin coating, heated at 70 ° C. for 20 minutes using a hot plate, and the film thickness was 1 μm, 2 μm, 5 μm, 10 μm, and 20 μm. A resin film was formed. Next, using an aligner (manufactured by Suss Microtec, device name “MA-100”), UV light from a high-pressure mercury lamp is passed through a pattern mask so that the exposure amount at a wavelength of 365 nm is 1,000 mJ / cm ^2. The film was irradiated. The exposed resin film was heated at 70 ° C. for 730 seconds using a hot plate, immersed and developed (23 ° C., 1 minute) using water, and the diameter was 400 μm and the height was 1 μm, 2 μm, 5 μm, 10 μm, and 20 μm, respectively. A patterned resin film having a hole pattern with a rectangular cross section was formed. It was revealed that the photosensitive resin composition prepared in Example 1B can form a good patterned resin film up to a thickness of 20 μm.

[Comparative Example 1C]
Comparative Example 1C was performed in the same manner as Example 1C, except that a commercially available photosensitive resin composition (trade name “Biosurfine-AWP”, manufactured by Toyo Gosei Co., Ltd.) was used as the photosensitive resin composition. In Comparative Example 1C, a patterned resin film having a diameter of 400 μm, a height of 1 μm, and 2 μm and a hole pattern having a rectangular cross section could be formed, but a patterned resin film having a thickness of 5 μm or more could not be formed. . It was revealed that a commercially available photosensitive resin composition can form a good patterned resin film only up to a thickness of 2 μm.

Claims

The polymer (A) which has a structural unit represented by Formula (1a).

[In the formula (1a), each R 1 is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 2 is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms. R 3 is a group having a hydroxyl group, and R 4 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
The polymer (A) according to claim 1, wherein R 3 is a monovalent group represented by the formula (g1).

[In the formula (g1), a is an integer of 0 to 4. ]
The polymer (A ') which has a structural unit represented by Formula (1b).

[In the formula (1b), each R 1 is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 2 is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms. , R 3 is a group having a hydroxyl group, R 4 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ]
The polymer (A ') according to claim 3, wherein R 3 is a monovalent group represented by the formula (g1).

[In the formula (g1), a is an integer of 0 to 4. ]
The polymer (A) according to claim 1 or 2,
A photoresponsive compound (B);
A photosensitive resin composition containing a crosslinking agent (C).
The photoresponsive compound (B) is a photoacid generator,
The photosensitive resin composition according to claim 5, wherein the crosslinking agent (C) is a compound that undergoes a crosslinking reaction by the action of an acid.
7. The crosslinking agent (C) is a compound having at least two groups represented by —CH 2 OR (R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acetyl group). Photosensitive resin composition.
A resin film containing the polymer (A) according to claim 1 or 2.
A process 1 for forming a resin film of the photosensitive resin composition according to any one of claims 5 to 7, a process 2 for selectively exposing the film, and a film after the exposure. A method for producing a patterned resin film, comprising: a step 3 of developing with an aqueous developer.
The method for producing a patterned resin film according to claim 9, wherein the substrate is a substrate for cell culture.
A patterned resin film obtained by the production method according to claim 9 or 10.
A patterned resin film containing the polymer (A) according to claim 1 or 2.
A cell culture device having the patterned resin film according to claim 11 or 12.