JP6544035B2 - PHOTOSENSITIVE RESIN COMPOSITION AND USE THEREOF - Google Patents

Description

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

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

  However, since a cell culture substrate having a surface to which cells adhere relatively weakly is used in three-dimensional culture compared to two-dimensional culture, there is known a problem that the formed spheroid is released in the culture solution. (Patent Document 1).

  In order to solve this problem, a method of culturing cells in a cell holding cavity for holding cells is disclosed (Patent Document 1). The partition wall forming the cavity is formed of a photosensitive resin composition containing a water-soluble resin, which has a weak adhesive force with the cell tissue in consideration of the ease when taking out the cell tissue after culture. Bulkheads may be used (patent documents 2 and 3).

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

  When the cell culture is performed in three dimensions, the cell holding cavity such as the cell holding cavity can hold the cultured cell better as it is deeper. For this reason, it is desired that the photosensitive resin composition can form a resin film having a large film thickness. In addition, since the culture solution contains water, it is also desired that the photosensitive resin composition can form a resin film having excellent water resistance.

  The object of the present invention is to provide a photosensitive resin composition capable of forming a resin film having a large film thickness and excellent water resistance, a patterned resin film and a method for producing the same, a cell culture apparatus, and a novel polymer. It is to provide.

  The present inventors diligently studied to solve the above problems. As a result, by using the photosensitive resin composition which has the following structure, it discovers that the said subject is solvable and came to complete this invention.

The present invention is, for example, the following [1] to [8].
[1] A polymer having an ethylenic unsaturated double bond, which has a structural unit (A1) represented by the formula (A1) and a structural unit (A2) represented by the formula (A2), The photosensitive resin composition containing the compound (B) which has 2 or more of mercapto groups, and a radical photopolymerization initiator (C).

［式（Ａ１）中、Ｒ¹はそれぞれ独立に−Ｓ−または−Ｓ（＝Ｏ）−である。式（Ａ２）中、Ｒ²はそれぞれ独立に直接結合、炭素数１〜１０のアルカンジイル基または炭素数６〜２０のアリーレン基であり、Ｒ³は炭素数１〜１０のアルカンジイル基または炭素数６〜２０のアリーレン基であり、Ｒ³が複数ある場合はそれぞれ同一でも異なってもよく、ｎは１以上の整数である。］
［２］重合体（Ａ）が、さらに、式（Ａ３）に示す構造単位（Ａ３）を有する前記［１］に記載の感光性樹脂組成物。

[In formula (A1), R ¹ is each independently —S— or —S (= O) —. In formula (A2), R ² is each independently a direct bond, an alkanediyl group having 1 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ³ is an alkanediyl group having 1 to 10 carbon atoms or carbon It is an arylene group of the formulas 6 to 20, and when there are a plurality of R ^{3 's} , they may be the same or different, and n is an integer of 1 or more. ]
[2] The photosensitive resin composition according to [1], wherein the polymer (A) further has a structural unit (A3) represented by the formula (A3).

［式（Ａ３）中、Ｒ⁴はそれぞれ独立に直接結合または２価の有機基であり、Ｒ⁵は３価の有機基であり、Ｒ⁶はエチレン性不飽和二重結合を有する１価の基である。］
［３］構造単位（Ａ３）が、式（Ａ３１）に示す構造単位（Ａ３１）および式（Ａ３２）に示す構造単位（Ａ３２）から選ばれる少なくとも１種である前記［２］に記載の感光性樹脂組成物。

[In Formula (A3), R ⁴ is each independently a direct bond or a divalent organic group, R ⁵ is a trivalent organic group, and R ⁶ is a monovalent having an ethylenically unsaturated double bond] It is a group. ]
[3] The photosensitivity described in the above [2], wherein the structural unit (A3) is at least one selected from the structural unit (A31) shown in the formula (A31) and the structural unit (A32) shown in the formula (A32) Resin composition.

［式（Ａ３１）および（Ａ３２）中、Ｒ⁴およびＲ⁶は、それぞれ前記式（Ａ３）中の同一記号と同義である。］

[In Formula (A31) and (A32), R ⁴ and R ⁶ each have the same meaning as the same symbol in Formula (A3). ]

[4] A step 1 of forming a resin film of the photosensitive resin composition according to any one of the above [1] to [3] on a substrate, a step of selectively exposing at least a part of the resin film 2 and a process for producing a patterned resin film, which has a step 3 of developing the resin film after exposure with a developer.
[5] The method for producing a patterned resin film according to [4], wherein the substrate is a cell culture substrate.
[6] A patterned resin film obtained by the method according to [4] or [5].
[7] A cell culture apparatus having the patterned resin film according to the above [6].
[8] A polymer having an ethylenically unsaturated double bond, which has a structural unit (A1) represented by the formula (A1) and a structural unit (A2) represented by the formula (A2).

［式（Ａ１）中、Ｒ¹はそれぞれ独立に−Ｓ−または−Ｓ（＝Ｏ）−である。式（Ａ２）中、Ｒ²はそれぞれ独立に直接結合、炭素数１〜１０のアルカンジイル基または炭素数６〜２０のアリーレン基であり、Ｒ³は炭素数１〜１０のアルカンジイル基または炭素数６〜２０のアリーレン基であり、Ｒ³が複数ある場合はそれぞれ同一でも異なってもよく、ｎは１以上の整数である。］

[In formula (A1), R ¹ is each independently —S— or —S (= O) —. In formula (A2), R ² is each independently a direct bond, an alkanediyl group having 1 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ³ is an alkanediyl group having 1 to 10 carbon atoms or carbon It is an arylene group of the formulas 6 to 20, and when there are a plurality of R ^{3 's} , they may be the same or different, and n is an integer of 1 or more. ]

  According to the present invention, a photosensitive resin composition capable of forming a resin film having a large film thickness and excellent water resistance, a patterned resin film and a method for producing the same, a cell culture apparatus, and a novel polymer are disclosed. Can be provided.

Hereinafter, modes for carrying out the present invention will be described including preferred modes.
[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains a polymer (A) described below, a compound (B) having two or more mercapto groups, and a radical photopolymerization initiator (C). Hereinafter, the composition is simply referred to as "the composition of the present invention".

Since the composition of the present invention contains the polymer (A), the compound (B) and the initiator (C), it can form a patterned resin film having a large film thickness and excellent water resistance.
The viscosity at 23 ° C of the composition of the present invention is usually 0.1 to 10,000 cP, preferably 100 to 5,000 cP, more preferably 500 to 3,000 cP. The viscosity is a value measured by a method in accordance with JIS Z8803.

<Polymer (A)>
A polymer (A) is a polymer which has an ethylenically unsaturated double bond, Comprising: It has a structural unit (A1) shown to a formula (A1), and a structural unit (A2) shown to a formula (A2).

式（Ａ１）中、Ｒ¹はそれぞれ独立に−Ｓ−または−Ｓ（＝Ｏ）−である。
式（Ａ２）中、Ｒ²はそれぞれ独立に直接結合、炭素数１〜１０のアルカンジイル基または炭素数６〜２０のアリーレン基であり、Ｒ³は炭素数１〜１０のアルカンジイル基または炭素数６〜２０のアリーレン基であり、Ｒ³が複数ある場合はそれぞれ同一でも異なってもよく、ｎは１以上の整数である。

In formula (A1), each R ¹ is independently -S- or -S (= O)-.
In formula (A2), R ² is each independently a direct bond, an alkanediyl group having 1 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ³ is an alkanediyl group having 1 to 10 carbon atoms or carbon It is an arylene group of the formulas 6 to 20, and when there are a plurality of R ^{3 's} , they may be the same or different, and n is an integer of 1 or more.

In R ² and R ³ , the alkanediyl group having 1 to 10 carbon atoms is, for example, methylene, 1,2-ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,4 -A butane diyl group, a 2, 2- dimethyl 1, 2- ethane diyl group, 1, 6- hexane diyl group is mentioned. The carbon number of the alkanediyl group is preferably 1 to 5, and more preferably 1 to 3.

In R ² and R ³ , the arylene group having 6 to 20 carbon atoms is, for example, a group represented by phenylene group, toluylene group, xylylene group, naphthylene group, anthracenylene group, phenanthrylene group, -Ph-R-Ph- (Wherein, Ph is a phenylene group which may have a substituent such as an alkyl group, and R is a direct bond, or a divalent group such as an alkylene group having 1 to 8 carbon atoms). The carbon number of the arylene group is preferably 6 to 10.

R ² is preferably an alkanediyl group having 1 to 10 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms. R ³ is preferably an alkanediyl group having 1 to 10 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms.

n is preferably an integer of 1 to 40, more preferably 3 to 30.
Since the polymer (A) has the structural unit (A1), a resin film having excellent adhesion to the substrate and excellent water resistance can be obtained by using the composition of the present invention containing the polymer (A). It can be formed. In addition, since the polymer (A) has the structural unit (A2), a resin film having a weak adhesion to the cell body is formed by using the composition of the present invention containing the polymer (A). Can.

Since the polymer (A) has an ethylenically unsaturated double bond, a resin film having a crosslinked structure and excellent in water resistance is formed by using the composition of the present invention containing the polymer (A). be able to. Therefore, in the development step using a developing solution containing water, a sufficient residual film thickness at the exposed portion can be maintained, and a patterned resin film having a large film thickness can be formed.
It is more preferable that a polymer (A) has a structural unit (A3) shown to a formula (A3).

式（Ａ３）中、Ｒ⁴はそれぞれ独立に直接結合または２価の有機基であり、Ｒ⁵は３価の有機基であり、Ｒ⁶はエチレン性不飽和二重結合を有する１価の基である。

In formula (A3), R ⁴ is each independently a direct bond or a divalent organic group, R ⁵ is a trivalent organic group, and R ⁶ is a monovalent group having an ethylenically unsaturated double bond. It is.

In R ^4, examples of the divalent organic group, for example, an alkanediyl group having 1 to 10 carbon atoms, -R ⁴¹ -O-R ⁴² - include divalent groups represented by. R ⁴¹ and R ⁴² are each independently an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkanediyl group having 1 to 10 carbon atoms include methylene, 1,2-ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,4-butanediyl, and the like. -Dimethyl-1, 2-ethanediyl group, 1, 6- hexanediyl group is mentioned. The carbon number of the alkanediyl group is preferably 1 to 5, and more preferably 1 to 3. Examples of the divalent group represented by, for _{example, -CH 2 -O-CH 2 CH} 2 - - -R 41 -O-R 42 can be mentioned.

In R ⁵ , examples of the trivalent organic group include a trivalent group obtained by removing 3 hydrogen atoms from an alkane having 1 to 20 carbon atoms, a trivalent group having an aromatic ring, and a trivalent alicyclic group. And a trivalent group having an isocyanurate ring, and a trivalent group having a triazine ring. When R ⁵ is a trivalent group having an aromatic ring, a trivalent group having an alicyclic ring, a trivalent group having an isocyanurate ring, or a trivalent group having a triazine ring, R ⁴ and R ⁶ are It is preferably bonded to an aromatic ring, an alicyclic ring, an isocyanurate ring or a triazine ring.

  Examples of alkanes leading to trivalent groups include linear alkanes such as methane, ethane, n-propane, n-butane, n-pentane, n-hexane, n-heptane, etc .; 2-methylpropane, 2-methylbutane And branched alkanes such as 2,2-dimethylpropane, 2,2-diethylpropane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane and 2,4-dimethylpentane Can be mentioned. The carbon number of alkane is preferably 2 to 10.

  Examples of the trivalent group having an aromatic ring include arenetriyl groups such as the groups shown in the following 1 to 2, and examples of the trivalent group having an alicyclic ring include the groups shown in the following 3 And the like. Examples of the trivalent group having an isocyanurate ring include the groups shown in the following 4, and examples of the trivalent group having a triazine ring include the following: Groups shown in 5 can be mentioned.

上記式１〜５中、＊は結合手を示し；Ｒは、アルキル基、アリール基、水酸基、アルコキシ基、ハロゲン原子等の置換基であり；ａは０〜３の整数であり、ｂは０〜５の整数である。

In the above formulas 1 to 5, * represents a bond; R is a substituent such as an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or a halogen atom; a is an integer of 0 to 3, b is 0 It is an integer of ~ 5.

R ⁵ is preferably a trivalent group having an isocyanurate ring and a trivalent group having a triazine ring, since a resin film having excellent water resistance can be formed, and a trivalent group having an isocyanurate ring is more preferable.

In R ⁶ , the monovalent group having an ethylenically unsaturated double bond includes, for example, an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and 2 to 20 carbon atoms, preferably 2 to 20 carbon atoms An oxy group, an alkenyloxyalkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acryloyloxyalkyl group (the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 10). Specific examples thereof include _{^{-R 62 -CR 61 = CH 2,}} -R 62 -O-CR 61 = CH 2, -CO-CR 61 = CH 2, -R 62 -OCO-CR 61 = CH 2 . R ⁶¹ is a hydrogen atom or a methyl group, and R ⁶² is a direct bond or an alkanediyl group having 1 to 10 carbon atoms.

R ⁶ is preferably the above alkenyl group.
The structural unit (A3) is preferably at least one selected from the structural unit (A31) represented by the formula (A31) and the structural unit (A32) represented by the formula (A32).

式（Ａ３１）および（Ａ３２）中、Ｒ⁴およびＲ⁶は、それぞれ前記式（Ａ３）中の同一記号と同義である。

In formulas (A31) and (A32), R ⁴ and R ⁶ each have the same meaning as the same symbol in formula (A3).

When a polymer (A) further has a structural unit (A3), the resin film which is excellent in water resistance can be formed by using the composition of this invention containing a polymer (A).
The content of each structural unit in the polymer (A) is preferably in the following range.

  The content of the structural unit (A1) is usually 10 to 70 mol%, preferably 20 to 60 mol%, more preferably 25% of the total 100 mol% of the structural units (A1), (A2) and (A3). 60 mol%. When the content of the structural unit (A1) is in the above range, a resin film having excellent adhesion to the substrate and excellent water resistance tends to be obtained.

  The content of the structural unit (A2) is usually 10 to 70 mol%, preferably 20 to 60 mol%, more preferably 20% of the total 100 mol% of the structural units (A1), (A2) and (A3). It is -45 mol%. When the content of the structural unit (A2) is in the above range, a resin film having a weak adhesion to the cell assembly tends to be obtained.

  The content of the structural unit (A3) is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, still more preferably 10 to 100 mol%, based on the total 100 mol% of the structural units (A1), (A2) and (A3). It is 20-45 mol%. When the content of the structural unit (A3) is in the above range, a resin film having excellent water resistance tends to be obtained.

The structure and content of structural units of the polymer can be determined by ¹ H-NMR and ¹³ C-NMR analysis. For example, using the apparatus name "ECP-400P" (manufactured by JEOL), the heavy solvent having the highest solubility of the polymer is selected from heavy chloroform, heavy methanol and heavy water.

  The weight average molecular weight (Mw) of the polymer (A) is usually 1,000 to 100,000, preferably 2,000 to 50,000, and more preferably 3,000 to 30,000. Further, the molecular weight distribution represented by weight average molecular weight (Mw) / number average molecular weight (Mn) of the polymer (A) is usually 1.0 to 5.0, preferably 1.0 to 3.0. . These Mw and Mn can be measured by gel permeation chromatography (in terms of polystyrene).

  When Mw is in the above range, a resin film having a high resolution and a large film thickness can be formed. It is preferable in the point of resolution that Mw / Mn is in the said range. The details of the measurement methods of Mw and Mn are as described in the examples.

  Since the polymer (A) is a water-soluble resin, it is possible to form a resin film having non-adhesiveness to cells, which has weak adhesion to the cell assembly. The "water-soluble resin" in the present invention refers to a resin having a solubility of 0.1 g or more in 100 g of water at 25 ° C. and 1 bar.

  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 in the above range, a composition capable of forming a resin film having a large film thickness, high adhesion to a substrate, 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.

<< Synthesis of Polymer (A) >>
The polymer (A) can be synthesized by a polyaddition reaction of 2,5-dimercapto-1,3,4-thiadiazole and an epoxy compound having at least two glycidyl groups. As the epoxy compound, at least an epoxy compound having an ethylenically unsaturated double bond may be used, and if necessary, an epoxy compound having no ethylenically unsaturated double bond may be further used.

  In one embodiment, the polymer (A) is a polyaddition of a compound (a1) represented by the formula (a1), a compound (a2) represented by the formula (a2), and a compound (a3) represented by the formula (a3) It can be synthesized by reaction.

式（ａ２）〜（ａ３）中、Ｒ²〜Ｒ⁶およびｎは、それぞれ式（Ａ２）〜（Ａ３）中の同一記号と同義である。

In formulas (a2) to (a3), R ^{2 to} R ⁶ and n each have the same meaning as the same symbol in formulas (A2) to (A3).

  As the compound (a2), for example, alkylene glycol diglycidyl ethers such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether; polyethylene glycol Polyalkylene glycol diglycidyl ethers such as diglycidyl ether, polypropylene glycol diglycidyl ether; 1,2-bis (2,3-epoxypropoxy) benzene, 1,3-bis (2,3-epoxypropoxy) benzene, 1, Benzenediol diglycidyl ethers such as 4-bis (2,3-epoxypropoxy) benzene; diglycidyl ethers of bisphenols such as bisphenol A diglycidyl ether It is.

  As the compound (a3), for example, isocyanurate ring-containing compounds such as monoallyl diglycidyl isocyanuric acid; 2-allyl-1,3,5-triazine-4,6-diglycidyl ether, 2-vinyl-1,3 5-triazine-4,6-diglycidyl ether, 2-acryloyl-1,3,5-triazine-4,6-diglycidyl ether, 2-methacryloyl-1,3,5-triazine-4,6-di And triazine ring-containing compounds such as glycidyl ether.

  The polyaddition reaction can be carried out in a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone and cyclopentanone; ester solvents such as ethyl lactate and butyl lactate; and glycol ether solvents such as propylene glycol monomethyl ether Glycol ester solvents such as propylene glycol monomethyl ether acetate; nitrogen-containing solvents such as N-methyl pyrrolidone.

  The polyaddition reaction can be carried out by appropriately selecting the reaction temperature from 30 to 100 ° C. under the reaction time of 0.5 to 6 hours, preferably 2 to 4 hours of reaction time, 40 to 80 ° C. Conditions can be selected appropriately from the range.

  A catalyst can be used in the polyaddition reaction. As the catalyst, for example, alcohols such as methanol and ethanol; phenolic hydroxyl group-containing compounds such as phenol; tertiary amines such as triethylamine, tributylamine and benzyldimethylamine; fourth ones such as triethylbenzyl ammonium chloride and tetramethyl ammonium chloride Examples of the ammonium salt include imidazoles such as 2-methylimidazole and 2-methyl-4-ethylimidazole.

  When a catalyst is used, the amount of the catalyst is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.2 parts by mass with respect to 100 parts by mass of all the monomers used in the polyaddition reaction. 1 to 3 parts by mass.

In the polyaddition reaction, as the compounds (a2) to (a3), only one type of compound can be used, or two or more types of compounds can be used in combination.
The ratio of 2,5-dimercapto-1,3,4-thiadiazole used in the polyaddition reaction to the epoxy compound having at least two glycidyl groups is preferably a molar ratio (the epoxy compound / the thiadiazole). Is 0.5 to 2, more preferably 1 to 1.5.

The compound in which R ¹ is —S (= O) — is converted to a sulfinyl group by converting a sulfide group corresponding to R ¹ contained in the polymer obtained by the above polyaddition reaction using an oxidizing agent, You can get it.

  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. The oxidizing agent may be used alone or in combination of two or more.

  In the above production method, isolation of the polymer (A) can be carried out, as required, by filtration, washing, drying, recrystallization, reprecipitation, dialysis, centrifugation, extraction with various solvents, neutralization, chromatography, etc. The following means may be combined as appropriate.

Compound (B)
The compound (B) is a compound other than the polymer (A) which has two or more mercapto groups (-SH groups). The number of mercapto groups in the compound (B) is preferably 2 or more, more preferably 3 to 10.

  The composition of the present invention contains a polymer (A) having an ethylenically unsaturated double bond, and a compound (B) having two or more mercapto groups. The mercapto group and the double bond can be reacted without oxygen damage. In the present invention, a resin film having a large film thickness, in which peeling of the resin film is prevented when the substrate excellent in water resistance, specifically, the substrate on which the resin film is formed is immersed by the reaction of these components. Can be formed.

As the compound (B), for example,
Mercaptocarboxylic acid ester of polyhydric alcohol (B1),
Alkanedithiol (B2),
Aromatic ring-containing dithiol (B3),
Isocyanurate ring-containing trithiol (B4), and mercaptoether (B5)
Can be mentioned.

  In the above ester (B1), examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, and diethylene glycol, particularly a dihydric alcohol having 2 to 20 carbon atoms; trimethylol Examples thereof include tri- to hexahydric alcohols such as propane, pentaerythritol and dipentaerythritol, and in particular, tri- to hexahydric alcohols having 2 to 20 carbon atoms.

  In the ester (B1), as the mercaptocarboxylic acid, for example, mercaptocarboxylic acid having 2 to 20 carbon atoms can be mentioned, and specifically, mercaptoacetic acid, mercaptopropionic acid and mercaptobutanoic acid can be mentioned.

As the compound (B1), for example,
Mercapto carboxylic acid esters of dihydric alcohols, specifically ethylene glycol bis (2-mercapto propionate), 1,2-propylene glycol bis (2- mercapto propionate), diethylene glycol bis (2-mercapto propio) ), Bis-mercaptopropionates such as 1,4-butanediol bis (2-mercaptopropionate) and 1,8-octanediol bis (2-mercaptopropionate), and 1,4-butanediol Bis mercapto acetate, and bis mercapto acetate such as ethylene glycol bis mercapto acetate;
Mercapto carboxylic acid esters of trihydric to hexahydric alcohols, specifically, tris, tetrakis or hexa, such as trimethylolpropane trismercaptopropionate, pentaerythritol tetrakis mercaptopropionate, and dipentaerythritol hexakis mercaptopropionate Tris, tetrakis or hexakis mercapto butyrates such as kiss mercapto propionate, pentaerythritol tetrakis mercapto butyrate, and tris, tetrakis or hexakis mercapto acetates such as trimethylolpropane tris mercaptoacetate, pentaerythritol tetrakis mercaptoacetate;
Can be mentioned.

  Examples of the alkanedithiol (B2) include alkanedithiol having 2 to 20 carbon atoms. Specifically, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,2 6-hexamethylenedithiol and 1,10-decanedithiol can be mentioned.

  Examples of the aromatic ring-containing dithiol (B3) include benzene dithiol which may have an alkyl group, and specifically, 1,2-benzene dithiol, 1,3-benzene dithiol, p-xylene dithiol, And m-xylenedithiol.

As the isocyanurate ring-containing trithiol (B4), for example, 1,3,5-tris (2-mercaptoethyl) isocyanurate, 1,3,5-tris (3-mercaptopropyl) isocyanurate, 1,3,5 -Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.
Examples of the ether (B5) include di (mercaptoethyl) ether.

Among these, from the viewpoint of the reaction rate, mercaptocarboxylic acid esters (B1) of polyhydric alcohols are preferable, and mercaptocarboxylic acid esters of tri- to hexahydric alcohols are more preferable. In addition, an isocyanurate ring-containing trithiol (B4) is also preferable because a resin film having a large film thickness and excellent water resistance can be obtained.
The molecular weight of the compound (B) is generally 50 to 10,000, preferably 75 to 3,000, and particularly preferably 100 to 1,000, from the viewpoint of developability as a photosensitive resin composition.

  The content of the compound (B) in the composition of the present invention is usually 1 to 100 parts by mass, preferably 2 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the polymer (A) It is a department. If the content of the compound (B) is not less than the lower limit, the curing speed of the composition of the present invention, the hardness and the water resistance of the patterned resin film are exhibited better, and if it is not more than the upper limit, The developability of the photosensitive resin composition of the present invention is exhibited more favorably.

<Photo radical polymerization initiator (C)>
The photosensitive resin composition of the present invention contains a photo radical polymerization initiator (C).
A radical photopolymerization initiator (C) is a compound which generates a radical by light irradiation. By irradiating the resin film obtained from the composition containing the initiator (C), a radical is generated based on the initiator (C), and the radical acts on the mercapto group contained in the compound (B) As a result, a thiyl radical is generated, and this thiyl radical is added to the ethylenically unsaturated double bond contained in the polymer (A) to form a crosslinked structure, which is presumed to be a film hardly soluble in the developer. A negative pattern can be formed by utilizing the fact that the film changes from a soluble state to a poorly soluble state in the developing solution by light irradiation.

  As the initiator (C), for example, JP-A 2008-276194, JP-A 2003-241372, JP-A 2009-519991, JP-A 2009-531730, WO 2010/001691, And the photoinitiator as described in Unexamined-Japanese-Patent No. 2011-132215 etc. is mentioned.

  As an initiator (C), an alkyl phenone compound, an acyl phosphine oxide compound, a biimidazole compound, a triazine compound, an oxime ester compound, a benzoin compound, and a benzophenone compound are mentioned, for example.

  As the alkyl phenone compound, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl- Α-hydroxyalkylphenones such as propan-1-one; 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) buta 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, and 2 Α-aminoalkylphenones such as-(2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone; 2,2-dimethoxy-1,2-diphenylethan-1-one, and 2, 2, And dialkoxyacetophenones such as 2-diethoxyacetophenone.

  Examples of the acyl phosphine oxide compound include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide and bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide.

  As a biimidazole compound, for example, 2,2′-bis (2,4-dichlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4', 5'- Tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2 '-Bis (2-methylphenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole, and 2,2'-diphenyl-4,5,4 ', 5'-tetra And phenyl-1,2'-biimidazole.

  As a triazine compound, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-) Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2 -Methylphenyl) Thenyl] -1,3,5-triazine, and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  As an oxime ester compound, for example, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropan-1-one-2-imine N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] ethane-1-imine and N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl] } -9H-carbazol-3-yl] ethane-1-imine.

  The benzoin compounds include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-bis (diethylamino) benzophenone, 4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethyl benzophenone are included.

A radical photopolymerization initiator (C) may be used individually by 1 type, and may use 2 or more types together.
In the photosensitive resin composition of the present invention, the content of the initiator (C) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts with respect to 100 parts by mass of the polymer (A). It is a mass part, more preferably 0.5 to 5 mass parts. When the content of the initiator (C) is equal to or more than the above lower limit, curing of the exposed portion becomes sufficient, and the heat resistance tends to be improved. When the content of the initiator (C) is less than or equal to the above upper limit value, a patterned resin film having a high resolution can be easily obtained without decreasing the transparency to exposure light.

<Silane coupling agent having a mercapto group (D)>
By using a silane coupling agent (D) having a mercapto group as a component of the composition of the present invention, a patterned resin film is formed which has more excellent adhesion to a substrate and is more excellent in water resistance. be able to. The silane coupling agent (D) is also considered to be added to the ethylenically unsaturated double bond contained in the polymer (A) at the time of exposure.

The silane coupling agent (D) is an organosilicon compound having one mercapto group, and examples thereof include a compound represented by the formula (D1), and a compound represented by the formula (D2) is preferable.
Si (R ¹ ) (R ² ) _3-n (OR ³ ) _n (D1)
In formula (D1), R ¹ is a monovalent organic group having one mercapto group, and R ² and R ³ may be the same or different, provided that they have no mercapto group, and R ² Is a monovalent organic group different from R ¹ , such as an alkyl group or an aromatic group, R ³ is a monovalent organic group such as an alkyl group, an alkoxyalkyl group or an acetyl group, and n is It is an integer of 1 to 3.

式（Ｄ２）中、Ｒ²は炭素数１〜２０のアルキル基または炭素数６〜２０の芳香族基であり、Ｒ³は炭素数１〜２０のアルキル基、炭素数２〜２０のアルコキシアルキル基、またはアセチル基であり、Ｒは炭素数１〜２０のアルカンジイル基であり、ｎは１〜３の整数である。

In formula (D2), R ² is an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms, R ³ is an alkyl group having 1 to 20 carbon atoms, and an alkoxyalkyl having 2 to 20 carbon atoms R is an alkanediyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 3.

  Examples of the silane coupling agent (D) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane.

A silane coupling agent (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 silane coupling agent (D) is used, the content of the (D) is preferably 0.001 to 10 parts by mass, more preferably 100 parts by mass of the polymer (A). Preferably it is 0.01-5 mass parts, More preferably, it is 0.05-1 mass part.

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

  As the solvent (E), for example, water or a mixed solvent containing water is preferable. Examples of solvents other than water constituting the mixed solvent include organic solvents which can be uniformly mixed with water, such as alcohols such as methanol, ethanol, n-butanol, propylene glycol monomethyl ether and ethyl lactate, and ketones such as cyclopentanone And the like. In the mixed solvent, usually 20% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more is water.

A solvent (E) 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 (E) is used, the content of the solvent (E) is usually 10 to 70% by mass, preferably 15 to 60% by mass, of the solid content concentration in the composition Preferably, it is in the range of 20 to 55% by mass. The solid content generally refers to all components other than the solvent (E) contained in the composition.

<Other additives>
The composition of the present invention further includes various additives such as adhesion assistants, acid diffusion control agents, crosslinked fine particles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers, etc. It can be contained in the range which does not impair a characteristic.

<Method of preparing composition>
The composition of the present invention can be prepared by uniformly mixing the components. Also, in order to remove dust, the components obtained may be uniformly mixed, and then the resulting mixture may be filtered with a filter or the like.

[Patterned resin film and manufacturing method thereof]
The patterned resin film is formed from the photosensitive resin composition of the present invention. By using the composition, a resin film having a large film thickness and water resistance can be formed. In addition, a patterned resin film with high resolution can be formed.

  The production example of the patterned resin film of the present invention is shown below. In this production example, a step 1 of forming a resin film of the photosensitive resin composition of the present invention on a substrate, a step 2 of selectively exposing at least a portion of the resin film, and the resin film after exposure And 3) developing with a developer. This production example may further include the step 4 of heat-treating the patterned resin film.

[Step 1]
In step 1, the photosensitive resin composition of the present invention is applied onto a substrate and dried to form a resin film. The drying conditions are, for example, heating at 50 to 120 ° 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, and more preferably 5 to 50 μm. If the film thickness is insufficient, the resin film may be formed by double coating.

  As the substrate, for example, polystyrene, polycarbonate, polyacetal, triacetylcellulose, polyamide, polyimide, polyethylene, polypropylene, vinyl chloride, vinylidene chloride, polyphenylene sulfide, polyether sulfone, polyurethane, polyethylene terephthalate, polyethylene naphthalate, polyacrylate, Resin substrates comprising at least one resin selected from polymethacrylate and cellulose; substrates comprising materials such as glass, ceramic, stainless steel, etc .; silicon wafer substrates. It may be a resin substrate made of biodegradable polymers such as polylactic acid, polyglycolic acid and polycaprolactone. As a board | substrate, the well-known substrate for cell cultures of Unexamined-Japanese-Patent No. 2002-335949 grade | etc., Can also be used.

  Examples of the method of applying the composition include dipping, spraying, bar coating, roll coating, spin coating, curtain coating, gravure printing, silk screening, and inkjet printing.

[Step 2]
In step 2, the resin film is exposed through a desired mask pattern, for example, using a contact aligner, a stepper or a scanner. The exposure light may, for example, be ultraviolet light or visible light. Usually, light having a wavelength of 200 to 500 nm (e.g., i-line (365 nm)) is used. The amount of exposure varies depending on the type and content of each component in the photosensitive resin composition, the thickness of the resin film, etc. When i-line is used for exposure light, the amount of exposure is usually 100 to 10,000 mJ / cm. ²

  In order to further accelerate the crosslinking reaction, it is preferable to carry out heat treatment after exposure. Hereinafter, this process is also referred to as "PEB process". The PEB conditions vary depending on the type and content of each component in the photosensitive resin composition, the thickness of the resin film, and the like, but are usually 50 to 120 ° C. and about 1 to 60 minutes.

[Step 3]
In step 3, the resin film after the exposure is developed with a developer to dissolve and remove the non-exposed area, thereby forming a desired patterned resin film on the substrate.

  As a developing solution, water or a mixed solvent containing water is preferable, for example. As a mixed solvent, the mixed solvent described in the column of solvent (E) is mentioned. Examples of the developing method include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. For example, as the development conditions in the immersion development method, conditions in which the substrate on which the resin film is formed are immersed in a developer at 20 to 40 ° C. for about 1 to 10 minutes may be mentioned.

[Step 4]
If necessary, the patterned resin film is further cured by heating. Although the heating conditions are not particularly limited, the heating is performed, for example, 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 allow the curing to proceed sufficiently or to prevent the deformation of the pattern shape, heating can be performed in multiple steps.

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

Hereinafter, one aspect of the cell culture apparatus will be described.
The patterned resin film possessed by the cell culture apparatus of the present invention is for holding cells and a cell assembly formed from the cells, particularly spheroids, on the resin film formed from the photosensitive resin composition of the present invention. The structure has one or more holes formed therein. The patterned resin film is a partition which forms a hole.

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

  The patterned resin film is preferably noncell-adherent in consideration of the ease of taking out the cell assembly from the pores after culture. 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-mentioned properties can be formed.

The shape of the bottom 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 surface of the hole is appropriately determined by the cell size and type, etc., usually 1,000～40,000Myuemu ^2, preferably 5,000~20,000μm ^2.

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

  The bottom of the pore is preferably a surface having cell adhesion, in terms of retaining cells and forming a cell assembly. For example, a surface to which a cell adhesive surface is introduced is a surface to which a functional group having a charge such as a carboxyl group or an amino group has been introduced, a surface to which a cell adhesion peptide such as an arginine / glycine / aspartic acid sequence is introduced, or a cell adhesion. It is the surface where the macromolecule which it has is fixed.

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

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

  The substrate surface which is the bottom of the hole may have an uneven structure. By providing such a concavo-convex structure, the adhesion of the cell assembly to the bottom surface can be improved. The shape in the plane direction of the convex portion or the concave portion in the concavo-convex structure includes, for example, a circular shape, an elliptical shape, and a polygonal shape.

  The depth of the holes is determined by the film thickness of the patterned resin film, and is usually 1 to 200 μm, preferably 3 to 100 μm, more preferably 5 to 50 μm. Within this range, cells and cell bodies can be well retained in the pores.

  When culturing cells using the cell culture apparatus of the present invention, cells are cultured in the pores of the patterned resin film to form a cell assembly, in particular, a spheroid. For example, a culture solution containing cells is placed in a pore, and cells seeded on the bottom of the pore form a three-dimensionally bound cell assembly on the surface of the cell culture substrate which is the bottom. The cell assembly is cultured for a long time while being stably retained in the pore formed by the partition, in a state of being attached to the bottom of the pore without being suspended in the culture solution.

  There are no particular limitations on the species of animal or the type of organ or tissue, as long as the cells form a bond between the cells. For example, primary cells, ES cells (Embryonic Stem cells), established cell lines, or cells collected from livers such as humans, pigs, dogs, rats, mice and the like, pancreas, kidney, nerve, skin etc. These include cells subjected to genetic manipulation and the like. The cells may be used alone or in combination of two or more. As a culture solution, an aqueous solution containing necessary salts and / or nutrient components at an appropriate concentration can be used so as to maintain cell survival state and function.

  Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In the description of the following examples and the like, "part" is used in the meaning of "part by mass" unless otherwise stated.

[1] Measuring method of physical properties
[1-1] Measurement Method of 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 gels under the following conditions. It measured by the permeation chromatography method.
・ Column: "TSKgel αM" of Tosoh columns and
Connecting "TSKgel α2500" in series · Solvent: N-methyl-2-pyrrolidone with added lithium bromide and phosphoric acid · Temperature: 40 ° C
Detection method: refractive index method Standard substance: polystyrene GPC apparatus: Tosoh Corporation, apparatus name "HLC-8020-GPC"

[1-2] NMR Analysis of Polymer The chemical shift of the polymer (A) was measured by nuclear magnetic resonance (NMR) under the following conditions.
-Device: manufactured by JEOL, trade name: ECP-400P
Solvent: CDCl ₃

[2] Synthesis of polymer (A)
Example A1 Synthesis of Polymer (A1) In a flask under a nitrogen atmosphere, 2 g of 2,5-dimercapto-1,3,4-thiadiazole, 6 g of polyethylene glycol diglycidyl ether (number of oxyethylene units: about) 15) A solution of 2 g of monoallyl diglycidyl isocyanuric acid and 19 g of cyclopentanone was prepared. After 0.05 g of triethylamine as a catalyst was added to the solution and stirred, the solution was allowed to react at 60 ° C. for 4 hours and then cooled to 23 ° C. The reaction solution was purified by reprecipitation to obtain a polymer (A1). Mn of the polymer (A1) was 6,000, Mw was 9,600, and Mw / Mn was 1.6. As a result of NMR measurement, a peak derived from a hydrogen atom bonded to carbon (α-carbon) to which a hydroxyl group formed by ring opening of glycidyl ether is bonded is in the vicinity of 4.0 to 4.5 ppm an ethylene glycol unit The peak derived from appears in 3.4-3.7 ppm vicinity, and it became clear that a polymer (A1) has following structural unit (1)-(3). The solubility in 100 g of water at 25 ° C. and 1 bar of the polymer (A1) was at least 20 g.

式（２）中のｎは約１５である。

N in Formula (2) is about 15.

[3] Formation of photosensitive resin composition and patterned resin film
[Examples B1 and B2 and Comparative Example B1]
By mixing the components shown in Table 1, photosensitive resin compositions of Examples B1 and B2 and Comparative Example B1 were produced. The solvent was used in such an amount that the viscosity (in accordance with JIS Z8803) of the photosensitive resin composition at 23 ° C. was in the range of 500 to 2000 cP.
The details of the various components shown in Table 1 are as follows.
A1: Polymer (A1) produced in Example A1
A2: Polyethylene glycol (trade name "Polyethylene Glycol 4000", manufactured by Wako Pure Chemical Industries, Ltd.)
B1: A mixture containing pentaerythritol tetrakis (3-mercaptobutyrate) as a main component (trade name "Kalens MT PE1", manufactured by Showa Denko KK)
B2: 1,3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione-based mixture (trade name) "Karens MT NR1" (manufactured by Showa Denko KK)
C1: Diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide (trade name "LUCIRIN TPO", manufactured by BASF Corporation)
E1: Water E2: Ethyl lactate

Comparative Example B2
In Comparative Example B2, a commercially available photosensitive resin composition (trade name "Biosurfine-AWP", manufactured by Toyo Gosei Co., Ltd.) was used as the photosensitive resin composition.

[4] Evaluation
[4-1] Production of Patterned Resin Film A photosensitive resin composition is applied by spin coating on a silicon wafer as a substrate, heated at 70 ° C. for 10 minutes using a hot plate, and the film thickness is 2 μm, 3 μm The resin films of 5 μm, 10 μm, 15 μm and 20 μm were formed. Next, using aligner (Suss Microtec, device name “MA-100”), UV light from a high pressure mercury lamp is made to be 1,000 mJ / cm ² with a wavelength of 365 nm through a pattern mask. The film was irradiated. The exposed resin film is heated at 70 ° C. for 600 seconds using a hot plate, immersed in water (23 ° C., 3 minutes), and developed with a diameter of 100 μm and a height of 2 μm, 3 μm, 5 μm, 10 μm, respectively. A patterned resin film having a hole pattern of 15 μm and 20 μm and having a rectangular cross section was formed. The film thickness was measured by a stylus film thickness meter. The maximum height at which a good patterned resin film can be formed is shown in Table 1.
In Example B2, a glass substrate was used as the substrate.

[4-2] Water Resistance of Patterned Resin Film A substrate having a patterned resin having the maximum height obtained in the above-mentioned [Production of [4-1] Patterned Resin Film] is brought into pure water at 23 ° C. Soaked for 1 week. Water resistance was evaluated by the presence or absence of peeling of the patterning resin film after immersion.

Claims (7)

A polymer having an ethylenically unsaturated double bond, wherein the polymer (A) has a structural unit (A1) represented by the formula (A1) and a structural unit (A2) represented by the formula (A2);
A compound (B) having two or more mercapto groups,
Photosensitive resin composition containing a radical photopolymerization initiator (C).

[In formula (A1), R ¹ is each independently —S— or —S (= O) —.
In formula (A2), R ² is each independently a direct bond, an alkanediyl group having 1 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ³ is an alkanediyl group having 1 to 10 carbon atoms or carbon It is an arylene group of the formulas 6 to 20, and when there are a plurality of R ^{3 's} , they may be the same or different, and n is an integer of 1 or more. ] The photosensitive resin composition according to claim 1, wherein the polymer (A) further has a structural unit (A3) represented by the formula (A3).

[In Formula (A3), R ⁴ is each independently a direct bond or a divalent organic group, R ⁵ is a trivalent organic group, and R ⁶ is a monovalent having an ethylenically unsaturated double bond] It is a group. ] The photosensitive resin composition according to claim 2, wherein the structural unit (A3) is at least one selected from the structural unit (A31) represented by the formula (A31) and the structural unit (A32) represented by the formula (A32).

[In Formula (A31) and (A32), R ⁴ and R ⁶ each have the same meaning as the same symbol in Formula (A3). ]   A step 1 of forming a resin film of the photosensitive resin composition according to any one of claims 1 to 3 on a substrate, a step 2 of selectively exposing at least a part of the resin film, and a step after exposure A method for producing a patterned resin film, comprising the step 3 of developing the resin film with a developer.   The method for producing a patterned resin film according to claim 4, wherein the substrate is a cell culture substrate.   The patterned resin film obtained by the manufacturing method of Claim 4 or 5.   A cell culture apparatus comprising the patterned resin film according to claim 6.