KR20190028646A - Photosensitive composition, method for producing polymer, method for producing photosensitive composition, method for producing laminate - Google Patents

Abstract

A method of producing the same, a method of producing the same, a method of producing the same, a method of producing the same, a method of producing the same, and a method of producing the same. Provided is a method for producing a laminate.
At least one of the following resins P1 and P2, and a photoinitiator. Resin P1: A resin comprising a polymer A having a unit u1 having an organic group having at least one fluorine atom and at least one unit u2 having a crosslinking group, and having a terminal group represented by any one of the following formulas 1, 2 and 3: Resin P2: a polymer B other than the polymer A having the unit u1, and a polymer C other than the polymer A having the unit u2, wherein at least one of the polymer B and the polymer C has a terminal group / RTI >
-X ¹ -C (R ¹ ) (R ² ) (R ³ )
-X ² -R ⁴ ... 2,
^{-X 3 -N (R 5) (} R 6) ··· 3

Description

Photosensitive composition, method for producing polymer, method for producing photosensitive composition, method for producing laminate

The present invention relates to a photosensitive composition, a method for producing a polymer, a method for producing a photosensitive composition, and a method for producing a laminate.

Conventionally, as a method of manufacturing a device such as a biochip, a method of using a photosensitive composition capable of forming a lyophobic film of a predetermined pattern by photolithography has been proposed (for example, Patent Document 1). By using such a photosensitive composition, a water repellent film is formed on a hydrophilic substrate, exposed in a predetermined pattern, developed, and a part of the hydrophilic substrate is exposed, whereby the hydrophilic portion and the water repellent portion can be separately produced.

As the photosensitive composition as described above, a fluorine-containing polymer having a specific fluorine concentration and a mass obtained by polymerizing a monomer containing an? -Position substituted acrylate having a fluoroalkyl group having 4 to 8 carbon atoms, an unsaturated organic acid, an epoxy group-containing monomer and an alkyleneoxy group at a predetermined ratio A positive type liquid-repellency resist composition comprising a fluorine-based polymer having an average molecular weight has been proposed (Patent Document 1).

As a method for adjusting the molecular weight, a method of using a chain transfer agent is generally known. In the example of Patent Document 1, polymerization is carried out using lauryl mercaptan as a chain transfer agent, and a fluorine-based polymer having a mass average molecular weight of 4600 to 6800 is synthesized.

Japanese Patent No. 5516484

According to the investigations of the present inventors, there is a problem that unevenness (uneven coating) is locally observed in the coating film when the positive type liquid-repellent resist composition described in Patent Document 1 is applied on a substrate to form a coating film. The problem of uneven application is remarkable when the mass average molecular weight of the fluorine-based polymer is about 6,000 to 20,000.

An object of the present invention is to provide a photosensitive composition capable of forming a lyophobic coating film free from coating irregularities and a process for producing the same, a process for producing a polymer capable of forming a lyophobic coating film having no coating unevenness when used in a photosensitive composition, And a method for producing a laminate using the photosensitive composition.

The present invention provides a photosensitive composition, a method for producing a polymer, a method for producing a photosensitive composition, and a method for producing a laminate, which have the following structures [1] to [14].

[1] A photosensitive composition comprising at least one of the following resins P1 and P2 and a photoinitiator.

Resin P1: a polymer having a terminal group u1 which is a unit having an organic group having at least one fluorine atom, a unit u2 which is a unit having a crosslinking group, and a terminal group represented by any one of the following formulas 1, 2 and 3: A resin.

Resin P2: a polymer B which has the unit u1 and does not have the unit u2, and a polymer C which has the unit u2 and does not have the unit u1, and at least the polymer B and the polymer C Is a polymer having a terminal group represented by any one of the formulas (1), (2) and (3).

-X ¹ -C (R ¹ ) (R ² ) (R ³ )

-X ² -R ⁴ ... 2

^{-X 3 -N (R 5) (} R 6) ··· 3

R ¹ to R ³ each independently represents a chain hydrocarbon group having 40 or less carbon atoms, a cyclic group having 40 or less carbon atoms, a hydroxyl group, a halogen atom, an amino group, or a hydrogen atom, which may have an ether group, Atoms, at least two of R ¹ to R ³ are atoms or groups other than hydrogen atoms,

R ⁴ represents a cyclic group having 40 or less carbon atoms,

R ⁵ and R ⁶ each independently represent a chain hydrocarbon group having 40 or less carbon atoms, or a cyclic group having 40 or less carbon atoms, which may have a hydroxyl group, an oxo group or an etheric oxygen atom,

X ¹ to X ³ each independently represents a single bond, -S-, -SR ⁷ -, -R ⁸ -, -OR ⁹ - or -O-, R ⁷ , R ⁸ and R ⁹ each independently represent a carbon number Represents a linear alkylene group of 1 to 40 carbon atoms.

[2] The photosensitive composition according to [1], wherein the polymer A, the polymer B, and the polymer C each have a mass average molecular weight of 6,000 to 20,000.

[3] The photosensitive composition according to [1] or [2], wherein the photoinitiator is a photoacid generator, and the polymer A further has a unit u3 which is a unit having an alkali-soluble group protected with an acid-dissociable group.

[4] The photosensitive resin composition according to [1] or [2], wherein the photoinitiator is a photoacid generator and at least one of the polymer B and the polymer C further has a unit u3 which is a unit having an alkali-soluble group protected with an acid- Sensitive composition.

[5] The polymer composition according to any one of [1] to [5], wherein at least one of the polymer A, the polymer B and the polymer C further comprises a unit u4 which is a unit other than the unit u3 which is a unit having the unit u1, the unit u2 and the alkali- The photosensitive composition according to any one of [1] to [4].

[6] The photosensitive composition according to any one of [1] to [5], wherein the total content of the resin P1 and the resin P2 is 10 to 70% by mass with respect to the total mass of the photosensitive composition.

[7] A monomer component comprising a monomer a1 as a monomer having an organic group having at least one fluorine atom and a monomer a2 as a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) 11, the following formula 12, and the following formula 13 to obtain a polymer.

Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )

Z ² -X ² -R ⁴ ... 12

^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13

R ¹ to R ³ each independently may have a hydroxyl group or an oxo group, a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, a cyclic group having 40 or less carbon atoms, a hydroxyl group, a halogen atom , An amino group or a hydrogen atom, at least two of R ¹ to R ³ are atoms or groups other than hydrogen atoms,

R ⁴ represents a cyclic group having 40 or less carbon atoms,

R ⁵ and R ⁶ each independently represent a chain hydrocarbon group having 40 or less carbon atoms or a cyclic group having 40 or less carbon atoms which may have a hydroxyl group or an oxo group and may have an etheric oxygen atom,

X ¹ to X ³ each independently represents a single bond, -S-, -SR ⁷ -, -R ⁸ -, -OR ⁹ - or -O-, R ⁷ , R ⁸ and R ⁹ each independently represent a carbon number A straight chain alkylene group having 1 to 40 carbon atoms,

Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom.

[8] A monomer component comprising a monomer a1 which is a monomer having an organic group having at least one fluorine atom and a monomer a2 'which is a monomer having a reaction site is represented by any one of the following formulas 11, 12 and 13 Wherein the polymer is obtained by polymerizing in the presence of a chain transfer agent and then reacting the polymer with a compound having a reactive functional group capable of binding with the reaction site and a crosslinking group to obtain a polymer having a unit u2 which is a unit having a crosslinking group Gt;

Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )

Z ² -X ² -R ⁴ ... 12

^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13

R ¹ to R ³ each independently may have a hydroxyl group or an oxo group, a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, a cyclic group having 40 or less carbon atoms, a hydroxyl group, a halogen atom , An amino group or a hydrogen atom, at least two of R ¹ to R ³ are atoms or groups other than hydrogen atoms,

R ⁴ represents a cyclic group having 40 or less carbon atoms,

R ⁵ and R ⁶ each independently represent a chain hydrocarbon group having 40 or less carbon atoms or a cyclic group having 40 or less carbon atoms which may have a hydroxyl group or an oxo group and may have an etheric oxygen atom,

X ¹ to X ³ each independently represents a single bond, -S-, -SR ⁷ -, -R ⁸ -, -OR ⁹ - or -O-, R ⁷ , R ⁸ and R ⁹ each independently represent a carbon number A straight chain alkylene group having 1 to 40 carbon atoms,

Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom.

[9] A process for producing a photosensitive composition as described in any one of [1] to [6]

A monomer component comprising a monomer a1 as a monomer having an organic group having at least one fluorine atom and a monomer a2 as a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) Polymer A is prepared by polymerization in the presence of a chain transfer agent represented by any one of formulas 12 and 13,

Wherein at least the polymer A and the photoinitiator are mixed to obtain a photosensitive composition.

Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )

Z ² -X ² -R ⁴ ... 12

^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13

Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,

Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom.

[10] A method for producing a photosensitive composition according to any one of [1] to [6]

A monomer component comprising a monomer a1 which is a monomer having an organic group having at least one fluorine atom is polymerized in the presence of a chain transfer agent represented by any one of the following formulas 11, 12 and 13 to obtain a polymer B,

A monomer component comprising a monomer a2 which is a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) is polymerized in the presence of the chain transfer agent to obtain a polymer C,

Wherein at least the polymer B, the polymer C and the photoinitiator are mixed to obtain a photosensitive composition.

Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )

Z ² -X ² -R ⁴ ... 12

^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13

Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,

Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom.

[11] A method for producing a photosensitive composition according to any one of [1] to [6]

A monomer component comprising a monomer a1 which is a monomer having an organic group having at least one fluorine atom is polymerized in the presence of a chain transfer agent represented by any one of the following formulas 11, 12 and 13 to obtain a polymer B,

Wherein at least the polymer B, the polymer C and the photoinitiator are mixed to obtain a photosensitive composition.

Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )

Z ² -X ² -R ⁴ ... 12

^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13

Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,

Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom.

[12] A method for producing a photosensitive composition according to any one of [1] to [6]

A monomer component containing a monomer a2 which is a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) is polymerized in the presence of a chain transfer agent represented by any one of the following formulas 11, 12 and 13: To obtain a polymer C,

And at least the polymer C, the polymer B and the photoinitiator are mixed to obtain a photosensitive composition.

Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )

Z ² -X ² -R ⁴ ... 12

^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13

Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,

Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom.

[13] A method for producing a laminate having a substrate and a coated film laminated on the substrate,

A photosensitive composition according to any one of [1] to [6] is applied on a substrate to form a photosensitive film, and the photosensitive film is exposed to form a coated film.

[14] The coating film according to any one of [

Wherein the photosensitive film is exposed in a pattern corresponding to the hole or groove and the photosensitive film is developed after exposure.

According to the photosensitive composition of the present invention, a lyophobic coating film free from coating unevenness can be formed.

According to the method for producing a polymer of the present invention, a polymer capable of forming a liquid-repellent coating film having no coating unevenness when used in a photosensitive composition is obtained.

According to the method for producing a photosensitive composition of the present invention, a photosensitive composition capable of forming a liquid-repellent coating film free from uneven coating can be obtained.

According to the method for producing a laminate of the present invention, a laminate having a lyophobic coating film free from uneven coating can be obtained.

An object of the present invention is to provide a photosensitive composition capable of forming a lyophobic coating film free from coating irregularities and a process for producing the same, a process for producing a polymer capable of forming a lyophobic coating film having no coating unevenness when used in a photosensitive composition, And a method for producing a laminate using the photosensitive composition.

The meanings of the following terms in this specification are as follows.

The "photoinitiator" means a compound which generates at least one of a radical and an acid by irradiation of light.

The term " photo-radical generator " means a compound that generates radicals upon irradiation with light.

The "photoacid generator" means a compound which generates an acid upon irradiation of light.

The term " liquid-repellent film " means a film that exhibits lyophobicity over portions other than the film, specifically, a film having a contact angle of a predetermined liquid larger than that of the film.

The "lyophilic substrate" refers to a substrate exhibiting lyophilicity compared to the liquid-repellent film, specifically, a substrate having a contact angle of a predetermined liquid smaller than that of the liquid-repellent film.

The "(meth) acryloyloxy group" is a generic term for an acryloyloxy group and a methacryloyloxy group.

The term "(meth) acrylate" is a collective term for acrylate and methacrylate.

The term "(meth) acrylic acid" is a generic term for acrylic acid and methacrylic acid.

[Photosensitive composition]

The photosensitive composition of the present invention (hereinafter also referred to as " the present composition ") includes at least one of resin P1 and resin P2 and a photoinitiator.

The composition may further comprise a solvent.

The present composition may further contain components other than polymer A, polymer B, polymer C, photoinitiator and solvent.

(Terminal group)

The polymer A constituting the resin P1 and the polymer constituting the resin P2 (at least one of the polymer B and the polymer C) have the following specific terminal group (hereinafter also referred to as "terminal group J").

The terminal group J is a terminal group represented by any one of the following formulas (1), (2) and (3). When the polymer has the terminal group J, it is possible to suppress occurrence of uneven application in forming a coating film with the present composition.

-X ¹ -C (R ¹ ) (R ² ) (R ³ )

-X ² -R ⁴ ... 2

^{-X 3 -N (R 5) (} R 6) ··· 3

R ¹ to R ³ each independently represents a chain hydrocarbon group having 40 or less carbon atoms, a cyclic group having 40 or less carbon atoms, a hydroxyl group, a halogen atom, an amino group, or a hydrogen atom, which may have an ether group, Atoms, at least two of R ¹ to R ³ are atoms or groups other than hydrogen atoms,

R ⁴ represents a cyclic group having 40 or less carbon atoms,

R ⁵ and R ⁶ each independently represent a hydroxyl group, an oxo group or a chain-like hydrocarbon group having 40 or less carbon atoms, which may have an etheric oxygen atom between carbon atoms, or a cyclic group having 40 or less carbon atoms,

X ¹ to X ³ each independently represents a single bond, -S-, -SR ⁷ -, -R ⁸ -, -OR ⁹ - or -O-, R ⁷ , R ⁸ and R ⁹ each independently represent a carbon number Represents a linear alkylene group of 1 to 40 carbon atoms.

In R ¹ to R ³ , the chain hydrocarbon group having 40 or less carbon atoms may be linear or branched. They may also be saturated hydrocarbons or unsaturated hydrocarbons. The number of unsaturated bonds (double bonds, triple bonds, etc.) of the unsaturated hydrocarbon group may be, for example, 1 to 20.

The chain hydrocarbon group may have a hydroxyl group, an oxo group (= O), or an ether oxygen atom (-O-). That is, at least one of the hydrogen atoms of the chain hydrocarbon group may be substituted with a hydroxyl group, at least one of the methylene groups of the chain hydrocarbon group may be substituted with> C = O, the terminal of the chain hydrocarbon group and / A group having an etheric oxygen atom between carbon atoms, or a combination of two or more of these groups.

When the chain hydrocarbon group has a hydroxyl group, the bonding position of the hydroxyl group in the chain hydrocarbon group is not particularly limited. The number of hydroxyl groups contained in the chain hydrocarbon group may be, for example, 1 to 4.

When the chain hydrocarbon group has an oxo group, the bonding position of the oxo group in the chain hydrocarbon group is not particularly limited. The number of oxo groups contained in the chain hydrocarbon group may be, for example, 1 to 10.

When the chain hydrocarbon group has an etheric oxygen atom, the position of the etheric oxygen atom in the chain hydrocarbon group is not particularly limited. For example, the terminal of the chain hydrocarbon group (the end on the side bonded to C in the formula 1), the carbon atom of the chain hydrocarbon group, or both of them. The number of etheric oxygen atoms of the chain hydrocarbon group may be, for example, 1 to 10.

The number of carbon atoms of the chain-like hydrocarbon group is preferably 1 to 40, more preferably 1 to 20, in the case of not having an etheric oxygen atom between carbon atoms. In the case of having an etheric oxygen atom between carbon atoms, it is 2 to 40, preferably 2 to 20.

Specific examples of the chain hydrocarbon group in R ¹ to R ³ include alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group and 2-ethylhexyl group, Group, an alkenyl group such as -C ₃ H ₆ CH═CH ₂ , an acyl group such as -C (═O) CH ₂ CH ₃ , and an acetyl group.

In R ¹ to R ³ , the cyclic group having 40 or less carbon atoms may be monocyclic or polycyclic. It may also be an alicyclic or aromatic group. In addition, a heterocyclic group having a hydrocarbon ring-like structure and containing an atom (hetero atom) other than a carbon atom in the ring skeleton may be used. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.

The number of carbon atoms of the cyclic group is preferably from 3 to 40, more preferably from 5 to 20, in the case of a hydrocarbon cyclic group. In the case of a heterocyclic group, it is 2 to 40, preferably 2 to 20.

A substituent may be bonded to the ring skeleton of the cyclic group. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group, and the like.

Specific examples of the hydrocarbon ring group in the cyclic group in R ¹ to R ³ include alicyclic hydrocarbon groups such as cyclohexyl group, adamantyl group and norbornyl group, aromatic hydrocarbon groups such as phenyl group and naphthyl group and the like . Specific examples of the heterocyclic group include a furyl group, a thiophenyl group, and a pyridinyl group.

Examples of the halogen atom in R ¹ to R ³ include a chlorine atom, an iodine atom and a bromine atom.

R ¹ to R ³ may be the same or different. Provided that at least two of R ¹ to R ³ are atoms or groups other than hydrogen atoms, that is, the above-mentioned chain-like hydrocarbon group, cyclic group, hydroxyl group, halogen atom or amino group. (1) has a bulky structure because at least two atoms or groups having a larger size than the hydrogen atom are bonded to C (R ¹ to R ³ -bonded carbon atoms) in the formula (1) .

R ⁴ is the same as the cyclic group having 40 or less carbon atoms in R ¹ to R ³ , and preferred embodiments are also the same.

The chain hydrocarbons having 40 or less carbon atoms in R ⁵ and R ⁶ include the same cyclic groups having 40 or less carbon atoms in R ¹ to R ³ , and preferred embodiments are also the same. However, when the chain hydrocarbon group in R ⁵ and R ⁶ has an etheric oxygen atom, the position of the etheric oxygen atom is between the carbon atoms of the chain hydrocarbon group.

The cyclic group having 40 or less carbon atoms in R ⁵ and R ⁶ includes the same cyclic group having 40 or less carbon atoms in R ¹ to R ³ , and preferred embodiments are also the same.

The linear alkylene group of R ⁷ and R ⁸ may be represented by - (CH ₂ ) _n -. The carbon number of the straight chain alkylene group (the value of n of - (CH ₂ ) _n -) is 1 to 40, preferably 1 to 20.

As X ¹ to X ³ , -SR ⁷ - and -O- are preferable in terms of easiness of chain transfer when a polymer is produced by using a corresponding chain transfer agent.

Specific examples of the terminal group J include -S-CH ₂ -CH (OH) -CH ₂ OH, -S-CH ₂ -CH (CH ₂ CH ₃ ) -CH ₂ CH ₂ CH ₂ CH ₃ , -SR ¹⁰ (R ¹⁰ is a cyclohexyl ^{_{group), -S-CH 2 -R 11}} (R 11 is a furyl group or a phenyl _{group), -CCl 3, -O-CH} 2 CH (CH 3) 2, -CH (CH 3) - _{C (= O) CH 2 CH} 3, -O-CH 2 CH 2 R 10, -O-CH 2 CH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) CH 2 CH 2 CH 2 CH 2 CH 2 CH ₂ CH ₂ CH ₃ , and the like. In the low odor point castle, a _{-S-CH 2 -CH (OH)} -CH 2 OH being preferred.

The terminal group J is a group derived from a chain transfer agent typically represented by the following formula 11, the following formula 12 and the following formula 13 (hereinafter also referred to as " chain transfer agent j ").

Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )

Z ² -X ² -R ⁴ ... 12

^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13

Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,

Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom.

Examples of the halogen atom in Z ¹ to Z ³ include a chlorine atom, an iodine atom and a bromine atom.

Specific examples of the chain transfer agent j include thioglycerol, 2-ethylhexanethiol, cyclohexanethiol, furfurylmercaptan, benzylthiol, carbon tetrachloride, isobutyl alcohol, 3-pentanone, cyclohexylethanol, 2- - decanol, and the like.

As the chain transfer agent j, it is preferable that X ¹ in the formula 11 is -SR ⁷ - because the molecular weight can be easily controlled and easily handled because of its high boiling point. In view of low odor, thioglycerol is preferred.

The unit u1 is a unit having an organic group having at least one fluorine atom (hereinafter also referred to as " fluorinated organic group "). By having the polymer A and the polymer B having the unit u1, the coating film formed from this composition can exhibit lyophobicity.

Examples of the fluorinated organic group include a fluoroalkyl group which may have an etheric oxygen atom between carbon atoms, and an alicyclic group having at least one fluorine atom, and an etheric oxygen atom between carbon atoms A fluoroalkyl group which may be present is preferred.

The fluoroalkyl group may be either linear or branched. The number of fluorine atoms relative to the total number of hydrogen atoms and fluorine atoms in the fluoroalkyl group is preferably at least 50%.

As the fluoroalkyl group, a fluoroalkyl group having a perfluoroalkyl moiety which may have an etheric oxygen atom between carbon atoms is preferable.

Examples of the fluoroalkyl group having a perfluoroalkyl moiety include a fluoroalkyl group represented by -R ¹³ -R ^f . Provided that R ^f represents a perfluoroalkyl moiety which may have an etheric oxygen atom between carbon atoms and R ¹³ represents an alkylene moiety having no fluorine atom.

When R ^f is a perfluoroalkyl moiety having no etheric oxygen atom, the number of carbon atoms thereof is preferably 4, 5 or 6, and particularly preferably 6. R ^f may be a linear chain or a branched chain, but a linear chain is preferred.

When R ^f is a perfluoroalkyl moiety having an etheric oxygen atom, the number of etheric oxygen atoms is preferably 1 to 3. The number of carbon atoms of the perfluoroalkyl moiety at the terminal side (the side opposite to the R ¹³ side) is preferably 1 to 6 than the etheric oxygen atom. The number of carbon atoms of the perfluoroalkylene moiety between the etheric oxygen atoms and between the etheric oxygen atom and R < ¹³ > is preferably 1 to 4. The perfluoroalkyl moiety having an etheric oxygen atom may be an entire linear chain or a branched chain, and the total number of carbon atoms thereof is preferably from 3 to 12, more preferably from 4 to 8.

Roneun R ^f, specifically, _{- (CF 2) 3 CF 3} , - (CF 2) 4 CF 3, - (CF 2) 5 CF 3, -CF (CF 3) OCF 2 CF 2 CF 3, -CF 2 OCF ₂ CF ₂ OCF ₃ , -CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , -CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₃ , and the like.

R < ¹³ > may be a linear or branched type, but is preferably a linear type. The carbon number of R ¹³ is preferably from 1 to 6, more preferably from 2 to 4. As R ¹³ , -CH ₂ CH ₂ - is particularly preferable.

The unit u1 is preferably a unit based on the monomer a1 which is a monomer having a fluorinated organic group. Monomer a1 is typically a compound having a fluorinated organic group and an ethylenic double bond.

As the monomer a1, a monomer comprising an ester of a monool represented by HO-R ¹³ -R ^f and an unsaturated monocarboxylic acid is preferable. The unsaturated monocarboxylic acid includes, for example, methacrylic acid, acrylic acid, and? -Haloacrylic acid.

As the monomer a1, (meth) acrylate and? -Haloacrylate having a fluoroalkyl group represented by -R ¹³ -R ^f are particularly preferable. Examples of such monomers include monomers represented by CH ₂ ═C (R ¹² ) COO-R ¹³ -R ^f . Provided that R ¹² represents a hydrogen atom, a methyl group or a halogen atom. Examples of the halogen atom of R ¹² include a fluorine atom and a chlorine atom.

Roneun specific monomers _{a1, CH 2 = C (CH} 3) COO-C 2 H 4 - (CF 2) 3 CF 3, CH 2 = CHCOO-C 2 H 4 - (CF 2) 3 CF 3, CH 2 = C _{(CH 3) COO-C 2} H 4 - (CF 2) 4 CF 3, CH 2 = CHCOO-C 2 H 4 - (CF 2) 4 CF 3, CH 2 = C (CH 3) COO-C 2 H _{4 - (CF 2) 5 CF} 3, CH 2 = CHCOO-C 2 H 4 - (CF 2) 5 CF 3, CH 2 = C (CH 3) COO-CH 2 CF (CF 3) OCF 2 CF 2 CF ₃ , CH ₂ ═CHCOO-CH ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ , CH ₂ ═C (CH ₃ ) COO-CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₃ , CH ₂ ═CHCOO-CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₃ , CH ₂ = C (CH ₃ ) COO-CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , CH ₂ = CHCOO-CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , CH ₂ = C (CH ₃ ) COO-CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₃ , CH ₂ = CHCOO-CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₃ . At this point of the preferred liquid-repellency can be _{obtained, CH 2 = C (CH 3} ) COO-C 2 H 4 - (CF 2) 5 CF 3, and _{CH 2 = C (CH 3)} COO-CH 2 CF 2 OCF 2 CF ₂ OCF ₃ is preferred.

The monomers a1 may be used singly or two or more of them may be used in combination.

The unit u2 is a unit having a crosslinking group (except unit u1). The crosslinking group is a group which can be crosslinked by a radical or an acid. When the composition or the photosensitive film formed from the composition is exposed, radicals or acids are generated from the photoinitiator in the exposed portion, and the crosslinking group is crosslinked (cured) by the action.

Examples of the group capable of crosslinking by a radical include a group containing an ethylenic double bond. Examples of the group containing an ethylenic double bond include a (meth) acryloyl group, an allyl group, and a vinyl group.

Examples of the group capable of being crosslinked by an acid include a group containing a 3-membered cyclic ether structure, a group containing a 4-membered cyclic ether structure, and a vinyloxy group. Examples of the group containing a 3-membered cyclic ether structure include an epoxy group and 3,4-epoxycyclohexyl group. Examples of the group containing a quaternary cyclic ether structure include an oxetane group and the like.

The group containing a 3-membered cyclic ether structure or the group containing a 4-membered cyclic ether structure may be substituted with an alkyl group as long as it does not impair the reactivity. The alkyl group preferably has 1 to 6 carbon atoms.

The epoxy group and 3,4-epoxycyclohexyl group are preferably amorphous. The oxetane group may be unsubstituted or substituted with an alkyl group, and is preferably a (3-alkyloxetan-3-yl) group.

As the crosslinking group, a group containing an ethylenic double bond, a group containing a tricyclic ether structure, or a group containing a quaternary cyclic ether structure is preferable, and a (meth) acryloyl group, a vinyloxy group, an epoxy group , Oxetanyl group and (3-alkyloxetan-3-yl) group are more preferable because of high crosslinking reactivity.

As a method for obtaining a polymer having a unit u2, there are (1) a method of copolymerizing a monomer a2, which is a monomer having a crosslinking group (except for the group containing an ethylenic double bond), and another monomer, (2) (Hereinafter also referred to as " compound b ") is reacted with a polymer having a reactive functional group capable of bonding with the above-mentioned reactive site and a crosslinking group .

The unit u2 of the polymer obtained by the above method (1) is a unit based on the monomer a2. The unit u2 of the polymer obtained by the method of (2) is a unit formed by introducing a crosslinking group into the reactive site of the unit based on the monomer a2 '. The unit u2 of the polymer A and the polymer C may be any.

When the crosslinking group is a group containing an ethylenic double bond, the monomer having the crosslinking group in the polymerization reaction during the production of the polymer also reacts. Therefore, when the crosslinking group is a group containing an ethylenic double bond, the unit u2 is preferably a unit formed by introducing a crosslinking group into the above-mentioned reactive site of the unit based on the monomer a2 '.

When the crosslinking group is a group containing a 3-membered or 4-membered cyclic ether structure, the monomer having the crosslinking group in the polymerization reaction is usually not reacted. Therefore, when the crosslinking group is a group containing a 3-membered or 4-membered cyclic ether structure, the unit u2 may be a unit based on the monomer a2 having a crosslinking group or may be a unit based on the monomer a2 ' Or a unit formed by introducing a group. In view of ease of production, it is preferable that the unit is based on the monomer a2 having a crosslinking group.

Monomer a2 is typically a compound having the crosslinking group and an ethylenic double bond.

As the monomer a2, (meth) acrylate having a crosslinking group is preferable.

As the crosslinking group in the monomer a2, a group containing a cyclic ether structure of a 3-membered or 4-membered ring is preferable, and an epoxy group, oxetane group or (3-alkyloxetan-3-yl) group is particularly preferable.

Examples of the (meth) acrylate having a group containing a cyclic ether structure of a 3-membered or 4-membered ring as a crosslinking group include monomers represented by CH ₂ ═C (R ²¹ ) COO-R ²² -R ²³ have. Provided that R ²¹ represents a hydrogen atom or a methyl group, R ²² represents an alkylene group, and R ²³ represents a group containing a cyclic ether structure of a 3-membered or 4-membered ring. The carbon number of R ²² is preferably 1 to 20.

Specific examples of the monomer a2 include glycidyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, (3-ethyloxetan- Cyclohexylmethyl (meth) acrylate, and the like. As the monomer a2, one type may be used alone, or two or more types may be used in combination.

Examples of the reaction site in the monomer a2 'include a hydroxyl group, a carboxyl group, an isocyanate group, an epoxy group and an amino group.

As the monomer a2 ', a monomer having an ethylenic double bond and a reaction site thereof is preferable. Examples of such a monomer include (meth) acrylate having a hydroxyl group or a carboxyl group.

Specific examples of the monomer having a hydroxyl group as a reactive site in the monomer a2 'include 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and 4-hydroxycyclohexyl (meth) acrylate.

Specific examples of the monomer having a carboxyl group as a reactive site in the monomer a2 'include acrylic acid, methacrylic acid, and vinyl acetic acid.

The monomers a2 'may be used singly or in combination of two or more kinds.

Examples of the reactive functional group of the compound b include an isocyanate group, a carboxyl group, a haloacyl group (such as an acyl chloride group), and an epoxy group when the reactive site is a hydroxyl group. When the reaction site is a carboxyl group, a hydroxyl group, an isocyanate group, an epoxy group and the like can be mentioned.

Examples of the compound having an isocyanate group and a crosslinking group include 2- (meth) acryloyloxyethyl isocyanate and the like. Examples of the compound having a chlorinated acyl group and a crosslinking group include (meth) acryloyl chloride and the like. Examples of the compound having an epoxy group and a crosslinking group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and 3,4-epoxycyclohexylmethyl (meth) have.

The unit u3 is a unit having an alkali-soluble group protected with an acid-dissociable group. In this case, the photoinitiator preferably includes a photoacid generator. The polymer constituting the resin P1 or the resin P2 has the unit u3 and the photoinitiator contains the photoacid generator so that the photosensitive film can be developed with an alkaline developer.

The alkali-soluble group protected by the acid-cleavable group is, for example, ^{-C (O) OC (R 31} ) (R 32) group represented by ^{OR 33, -C (O) OC} (R 34) (R 35) (R 36 ), And the like. However, R ³¹ is an alkyl group or a cycloalkyl group, R ³² is a hydrogen atom, an alkyl group or a cycloalkyl group, R ³³ is, even if a part of alkyl groups, hydrogen atoms, which may be part of the hydrogen atoms is substituted with optionally substituted Or an aralkyl group in which a part of hydrogen atoms may be substituted, and R ³¹ and R ³³ may be connected to form a cyclic ether. Each of R ³⁴ to R ³⁶ independently represents an alkyl group having 1 to 40 carbon atoms.

As R ³¹ , a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a methyl group is particularly preferable in view of availability of raw monomers.

As R ³² , a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms are preferable, and a hydrogen atom is particularly preferable in view of availability of raw material monomers.

As R ³³ , a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms are preferable.

When R ³¹ and R ³³ are connected to form a cyclic ether, it is preferable that R ³¹ and R ³³ are connected to form an alkylene group having 2 to 5 carbon atoms.

When a part of the hydrogen atoms in the alkyl group, cycloalkyl group or aralkyl group of R ³³ is substituted, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom and the like have.

Examples of the group represented by -C (O) OC (R ³¹ ) (R ³² ) OR ³³ include 1-ethoxyethyl group, 1-methoxyethyl group, 1-n-butoxyethyl group, Ethylhexyloxyethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1- 1-benzyloxyethyl group and the like.

A group represented by ^{-C (O) OC (R 34} ) (R 35) (R 36) is, for example, there may be mentioned a tert- butoxycarbonyl group (-C (O) OC (CH 3) 3).

The unit u3 may be used singly or two or more of them may be used in combination.

In unit u3 is, a unit having a group represented by ^{-C (O) OC (R 31} ) (R 32) OR 33 are preferred. The group represented by -C (O) OC (R ³¹ ) (R ³² ) OR ³³ has lower activation energy of acid decomposition than the group represented by -C (O) OC (R ³⁴ ) (R ³⁵ ) (R ³⁶ ) It is easily hydrolyzed by the acid from the photoacid generator. Therefore, a phenomenon can be achieved without performing post-exposure bake (PEB) after exposure.

The preferred unit is typically a unit based on a monomer represented by CH ₂ ═CH (R ³⁰ ) C (O) OC (R ³¹ ) (R ³² ) OR ³³ . Provided that R ³⁰ is a hydrogen atom or a methyl group, and R ³¹ to R ³³ are as defined above.

Specific examples of the monomer include 1-ethoxyethyl (meth) acrylate, 1-methoxyethyl (meth) acrylate, 1-n-butoxyethyl (meth) acrylate, 1-isobutoxyethyl (Meth) acrylate, 1-n-propoxyethyl (meth) acrylate, 1-cyclohexyl (Meth) acrylate, 1- (2-cyclohexylethoxy) ethyl (meth) acrylate and 1-benzyloxyethyl (meth) acrylate.

The unit u4 is a unit other than the unit u1, the unit u2, and the unit u3.

Examples of the unit u4 include a unit based on the fluorine-containing organic group, the crosslinking group, and the monomer a4 which is a unit having no alkali-soluble group protected with the acid-dissociable group.

The monomer a4 is typically a compound having an ethylenic double bond, which has no fluorine-containing organic group, the crosslinking group and an alkali-soluble group protected with the acid-dissociable group.

Specific examples of the monomer a4 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, decyl (meth) acrylate, isooctyl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, ethoxypolyethylene glycol (Meth) acrylate, propoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate (the number of oxyethylene groups in the polyethylene glycol chain ranges from 2 to 300), 2- (Meth) acryloyloxy} ethyl-2 '- (trimethylammonio) ethylphosphate, 3 - {(meth) acryloyloxy} (Meth) acryloyloxy} butyl-2 '- (trimethylammonio) ethylphosphate, 5 - {(meth) acryloyloxy} pentyl- Acryloyloxy} hexyl-2 '- (trimethylammonio) ethylphosphate, 2 - {(meth) acryloyloxy} ethyl- 2 '- (tributylammonio) ethylphosphate, 2 - {(meth) acryloyloxy} ethyl- 2 - {(meth) acryloyloxy} ethyl-2 '- (tricyclohexylammonio) ethylphosphate, 2 - { Ethyl 2 - {(meth) acryloyloxy} ethyl-2 '- (trimethanolammonio) ethylphosphate, 2 - {(meth) acryloyloxy} (Trimethylammonio) ethylphosphate, 2 - {(meth) acryloyloxy} pentyl-2 '- (trimethylammonio) ethylphosphate, 2- (Meth) acryloyloxy} hexyl-2 '- (trimethylammonio) ethylphosphate, 2- (vinyloxy) ethyl-2'- (trimethylammonio) ethylphosphate, 2- (Trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyloxy) ethyl-2 '- (trimethylammonio) ethylphosphate, 2- Ammonio) ethyl phosphate, 2- (styryl 2 '- (trimethylammonio) ethylphosphate, 2- (p-vinylbenzyl) ethyl-2'- (trimethylammonio) ethylphosphate, 2- (vinyloxycarbonyl) (Trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl-2 '- (trimethylammonio) ethylphosphate, 2- - (vinylcarbonylamino) ethyl-2 '- (trimethylammonio) ethylphosphate, ethyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, butyl- (2'-trimethylammonioethylphosphorylethyl) ) Fumarate, hydroxy- (2'-trimethylammonioethylphosphorylethyl) fumarate, ethyl- (2'-trimethylammonioethylphosphorylethyl) malate, butyl- (2'-trimethylammonioethyl Phosphoylethyl) malate, or hydroxyethyl- (2'-trimethylammonioethylphosphorylethyl) malate, and the like. .

The monomers a4 may be used singly or in combination of two or more.

Polymer A has units u1 and u2. Polymer A may further have unit u3. Polymer A may further have unit u4.

In the polymer A, the ratio of the unit u1 to the total of all the units is preferably from 10 to 90 mol%, and more preferably from 20 to 90 mol%.

The ratio of the unit u2 to the total of all the units is preferably from 10 to 90 mol%, and more preferably from 10 to 80 mol%.

The ratio of the unit u3 to the total of all the units is preferably 0 to 80 mol%, more preferably 0 to 70 mol%.

The ratio of the unit u4 to the total of all the units is preferably 0 to 80 mol%, more preferably 0 to 60 mol%.

The ratio of each constitutional unit in the polymer can be obtained from, for example, the integral ratio of peaks unique to each unit in ¹ H-NMR (nuclear magnetic resonance analysis).

As preferred embodiments of the polymer A, the following Polymers A1 and A2 can be mentioned.

Polymer A1: A polymer having unit u1 and unit u2, not having unit u3, and end group J.

Polymer A2: a polymer having a unit u1, a unit u2 and a unit u3, a crosslinking group of the unit u2 being capable of crosslinking by an acid, and a terminal group J;

Polymers A1 and A2 may further have unit u4.

The polymer A1 preferably has a unit u1 of 10 to 29 mol% and a unit u2 of 10 to 90 mol% based on the total of all the units. The ratio of the sum of the units u1 and u2 to the total of the total units is preferably 30 mol% or more, and may be 100 mol%.

The polymer A2 preferably has 10 to 29 mol% of unit u1, 10 to 60 mol% of unit u2, and 20 to 80 mol% of unit u3 with respect to the total of all the units. The ratio of the total of the units u1 to u2 to the total of the units u3 and u3 is preferably 40 mol% or more, and may be 100 mol%.

The mass average molecular weight (Mw) of the polymer A is not particularly limited, but is preferably 4,000 to 500,000, more preferably 5,000 to 200,000, still more preferably 6,000 to 20,000, and particularly preferably 6,000 to 19,000. When the mass average molecular weight is within this range, the lithographic processing can be stably performed. Particularly, when the mass average molecular weight is 6,000 to 20,000, uneven application of the coating film when the terminal group J is not present is remarkable, and the usefulness of the present invention is high.

The mass average molecular weight of the polymer A is a value in terms of standard polymethyl methacrylate measured from gel permeation chromatography (GPC). The mass average molecular weights of Polymers B and C are also the same.

As the production method of the polymer A, for example, the following two production methods can be mentioned. By carrying out the polymerization in the presence of the chain transfer agent j, a polymer having an end group J at the main chain end is obtained.

A method for polymerizing a monomer component comprising the monomer a1 and the monomer a2 in the presence of the chain transfer agent j.

A method of polymerizing a monomer component containing the monomer a1 and the monomer a2 'in the presence of the chain transfer agent j to obtain a polymer, and reacting the polymer b with the polymer.

In each of the above two production methods, the monomer component may further include at least one member selected from the group consisting of monomer a3 and monomer a4.

The polymerization of the monomer component can be carried out by a known polymerization method such as a solution polymerization method, a bulk polymerization method and an emulsion polymerization method. Of these, the solution polymerization method is preferable. A polymerization initiator may be used in the polymerization.

In the solution polymerization, the ratio of the total amount of the monomers to the polymerization solvent is preferably from 5 to 70 mass%, more preferably from 10 to 40 mass%. The higher the ratio, the better the production efficiency of the present composition. When the photosensitive composition contains a solvent, the polymerization solvent is preferably the same as the solvent of the photosensitive composition.

The amount of the chain transfer agent j to be used can be appropriately selected according to the molecular weight of the polymer to be produced and varies depending on the amount of the polymerization initiator used and the monomer concentration but is typically from 0.1 to 20 mol% To 10 mol% is preferable. Further, when the amount of the polymerization initiator used is increased, the amount of the chain transfer agent necessary for achieving the desired molecular weight tends to be reduced. In addition, when the monomer concentration is low, the amount of the chain transfer agent required to obtain the desired molecular weight tends to be small.

Polymerization conditions include, for example, conditions at 40 to 60 DEG C for 5 to 30 hours.

In the second production method, the amount of the compound b to be used is preferably 10 to 100 mol%, more preferably 80 to 100 mol% based on 100 mol% of the total number of reaction sites of the unit based on the monomer a2 ' % Is more preferable. The total number of reactive sites in the unit based on the monomer a2 'is the total number of moles of the units based on the monomer a2' when the unit based on the monomer a2 'is one kind of units (reaction of units based on the monomer a2' Number of sites). When the number of units based on the monomer a2 'is plural, the value of the unit (the total number of moles of the unit based on the monomer a2') x (the number of reaction sites of the unit based on the monomer a2 ') And the total of them is defined as the total number of reaction sites of the unit based on the monomer a2 '.

The reaction conditions for the reaction of compound (b) include, for example, conditions of 0 to 60 ° C and 5 to 48 hours.

After the polymerization, or after the compound b is reacted, purification treatment such as filtration and reprecipitation, solvent distillation removal, solvent substitution and the like may be carried out if necessary.

Polymer B is a polymer having unit u1 and no unit u2. Polymer B may further have unit u3. Polymer B may further have unit u4.

In the polymer B, the ratio of the unit u1 to the total of all the units is preferably 10 to 100 mol%, more preferably 10 to 29 mol%.

The ratio of the unit u3 to the total of all the units is preferably 0 to 80 mol%, more preferably 0 to 70 mol%.

The ratio of the unit u4 to the total of all the units is preferably 0 to 80 mol%, more preferably 0 to 70 mol%.

As preferred embodiments of the polymer B, the following polymer B1 or polymer B2 can be mentioned.

Polymer B1: Polymer having unit u1, unit u2 and unit u3, and terminal group J.

Polymer B2: A polymer having unit u1 and unit u3, not having unit u2, and end group J.

Polymers B1 and B2 may further have unit u4.

The polymer B1 preferably has a unit u1 of 10 to 100 mol% relative to the total of all the units.

The polymer B2 preferably has a unit u1 of 10 to 90 mol% and a unit u3 of 20 to 80 mol% based on the total of all the units. The ratio of the sum of the units u1 and u3 to the total of the total units is preferably 30 mol% or more, and may be 100 mol%.

The preferable range of the mass average molecular weight (Mw) of the polymer B is the same as that of the polymer A.

As the method for producing the polymer B in the case where the polymer B has the terminal group J, for example, the following production methods can be mentioned.

A method for polymerizing a monomer component comprising the monomer a1 in the presence of the chain transfer agent j.

In the above production method, the monomer component does not usually contain the monomer a2. The monomer component may further include at least one member selected from the group consisting of monomer a3 and monomer a4.

The polymerization of the monomer component can be carried out in the same manner as in the above-mentioned production method of the polymer A.

As the method for producing the polymer B in the case where the polymer B does not have the terminal group J, for example, the following production methods can be mentioned.

A method of polymerizing a monomer component comprising the monomer a1 in the absence of the chain transfer agent j.

The monomer component is the same as the above-mentioned production method.

Polymerization of the monomer component can be carried out in the same manner as in the above-mentioned production method of the polymer A, except that the chain transfer agent j is not used. In the polymerization, a chain transfer agent other than the chain transfer agent j may be used.

Polymer C is a polymer having unit u2 and no unit u1. Polymer C may further have unit u3. Polymer C may further have unit u4.

In the polymer C, the ratio of the unit u2 to the total of all the units is preferably 10 to 100 mol%, and more preferably 10 to 90 mol%.

The ratio of the unit u3 to the total of all the units is preferably 0 to 90 mol%, more preferably 0 to 70 mol%.

The ratio of the unit u4 to the total of all the units is preferably 0 to 90 mol%, more preferably 0 to 80 mol%.

As a preferred embodiment of the polymer C, the following polymer C1 or polymer C2 can be mentioned.

Polymer C1: A polymer having the unit u2, the unit u1 and the unit u3, and the terminal group J.

Polymer C2: A polymer having unit u2 and unit u3, no unit u1, and terminal group J.

Each of the polymers C1 and C2 may further have a unit u4.

The polymer C1 preferably has a unit u2 of 10 to 100 mol% relative to the total of all the units.

The polymer C2 preferably has a unit u2 of 10 to 80 mol% and a unit u3 of 20 to 90 mol% based on the total of all the units. The total ratio of the units u2 and u3 to the total of all the units is preferably 30 mol% or more, and may be 100 mol%.

The preferable range of the mass average molecular weight (Mw) of the polymer C is the same as that of the polymer A.

As a production method of the polymer C in the case where the polymer C has the terminal group J, for example, the following two production methods can be mentioned.

A method for polymerizing a monomer component comprising the monomer a2 in the presence of the chain transfer agent j.

A method of polymerizing a monomer component containing the monomer a2 'in the presence of the chain transfer agent j to obtain a polymer, and reacting the polymer b with the polymer.

In each of the above two production methods, the monomer component does not usually contain the monomer a1. The monomer component may further include at least one member selected from the group consisting of monomer a3 and monomer a4.

The polymerization of the monomer components and the reaction with the compound b in the above two production methods can be carried out in the same manner as the two production methods in the above-mentioned production method of the polymer A.

As a production method of the polymer C in the case where the polymer C does not have the terminal group J, for example, the following two production methods can be mentioned.

A method for polymerizing a monomer component comprising the monomer a2 in the absence of the chain transfer agent j.

A method of polymerizing a monomer component containing the monomer a2 'in the absence of the chain transfer agent j to obtain a polymer, and reacting the polymer b with the polymer.

In each of the above two production methods, the monomer component does not usually contain the monomer a1. The monomer component may further include at least one member selected from the group consisting of monomer a3 and monomer a4.

Polymerization of the monomer component can be carried out in the same manner as in the above-mentioned production method of the polymer A, except that the chain transfer agent j is not used. In the polymerization, a chain transfer agent other than the chain transfer agent j may be used.

The reaction with the compound b can be carried out in the same manner as the reaction with the compound b in the above-mentioned production method of the polymer A.

One kind of the polymer A constituting the resin P1 may be used, or two or more kinds may be used.

The polymer B and the polymer C constituting the resin P2 may be used individually or in a mixture of two or more.

In the resin P2, the ratio of the polymer B to the total amount of the polymer B and the polymer C is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, , And particularly preferably 20% by mass or more. It is preferably 90 mass% or less, more preferably 80 mass% or less, and particularly preferably 70 mass% or less, from the viewpoint of curability and patternability.

Therefore, the ratio of the polymer B to the total amount of the polymer B and the polymer C is preferably 1 to 90% by mass. When the polymer B does not have the unit 3, it is more preferably 1 to 50% by mass, and further preferably 1 to 40% by mass. When the polymer B has the unit 3, it is more preferably 1 to 90 mass%, more preferably 1 to 80 mass%, and particularly preferably 5 to 70 mass%.

Either one of the resin P1 and the resin P2 may be used, or both resins P1 and P2 may be used in combination.

Examples of the photoinitiator include a photo-radical generator and a photo-acid generator. These can be appropriately selected from known photo-radical generating agents and photoacid generators, respectively.

When the crosslinking group in polymer A and polymer C is a group capable of crosslinking by radicals, when a photo-radical generator is used as the photoinitiator and the crosslinking group is a group capable of crosslinking by an acid, the photoacid generator Is used.

The photoinitiator preferably has an extinction coefficient at a wavelength of 365 nm of 400 [mL · g ^-1 · cm ^-1 ] or less. When the extinction coefficient is 400 [mL · g ^-1 · cm ^-1 ] or less, processing by lithography is possible. In addition, as a fluorescence analysis biochip formed on a substrate, a laminate on which a coating film formed of the present composition is formed on a substrate is used to suppress the light that becomes noises when performing fluorescence analysis. Specifically, light that becomes noise is light observed as fluorescence when measured by a laser light excitation fluorescence analyzer. The cause of such light generation is not clear, but stray light due to autofluorescence or scattering is conceivable.

The extinction coefficient of the photoinitiator at a wavelength of 365 nm is more preferably 200 [mL · g ^-1 · cm ^-1 ] or less. The extinction coefficient is preferably 1 [mL · g ^-1 · cm ^-1 ] or higher, more preferably 10 [mL · g ^-1 · cm ^-1 ] or higher.

Specific examples of the photoradical generator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1-phenylacetophenone, methylphenyl ketone, dibenzoyl, benzophenone, benzo Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-1- {4- [4- (2- Methyl-propan-1-one, and the like. 2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexyl-phenyl- Ketone and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) Is preferable because it is small and excellent in photo-curing performance. These photo-radical generators may be used alone or in combination of two or more.

IRGACURE (registered trademark) 651 (manufactured by BASF), IRGACURE 184 (manufactured by BASF), IRGACURE 127 (manufactured by BASF), IRGACURE 500 (manufactured by BASF), IRGACURE 2959 ), 1173 (manufactured by BASF), and the like.

Examples of the photoacid generator include triarylsulfonium salts, diaryliodonium salts, and sulfonyldiazomethane.

Specific examples of the cationic moiety of the triarylsulfonium salt and the diaryliodonium salt include triphenylsulfonium, diphenyl-4-methylphenylsulfonium, tris (4-methylphenyl) sulfonium, diphenyl-2,4,6 -Methyldiphenyliodonium, 4-methyl-4'-methylpropyldiphenyliodonium, 4-methylphenyldiphenylsulfonium, 4- , Bis (4-tert-butylphenyl) iodonium, and 4-methoxyphenylphenyliodonium. Examples of the anion moiety include trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluorophosphate, tetrafluoroborate, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) tri Tris (nonafluoroisobutyl) trifluorophosphate, bis (nonafluoroisobutyl) tetrafluorophosphate, and the like can be given.

Specific examples of sulfonyldiazomethane include bis (phenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis Sulfonyldiazomethane, and the like.

Of these, preferred are tetrafluoroboric acid salts such as 4- (phenylthio) phenyldiphenylsulfoniumtris (heptafluoropropyl) trifluorophosphate, 4- (phenylthio) phenyldiphenylsulfoniumtris (nonafluoroisobutyl) Tetrafluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium bis (nonafluoroisobutyl) tetrafluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium (pentafluoroethyl) trifluorophosphate, diphenyl- , 4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium nonafluorobutanesulfonate, bis (phenylsulfonyl) diazomethane, bis (p- Toluenesulfonyl) diazomethane is preferable because the fluorescence of the obtained coating film is small and the photocuring performance is excellent. These photoacid generators may be used alone or in combination of two or more.

Specific product names of the photoacid generators include IRGACURE 250 (manufactured by BASF), CPI (registered trademark) -100P (manufactured by SANA PRO), CPI-210S (manufactured by SANA PRO), WPAG199 (manufactured by Wako Pure Chemical Industries, .

As preferable combinations of the resin P1 and the photoinitiator in the present composition, the following combinations (1) to (3) can be given. Among them, the combination (1) or (2) is preferable, and the combination (2) is particularly preferable.

Combination (1): Combination wherein the resin P1 is polymer A1, the crosslinking group of unit u2 of polymer A1 is a group capable of crosslinking by an acid, and the photoinitiator is a photo acid generator.

Combination (2): A combination in which the resin P1 is polymer A2 and the photoinitiator is a photoacid generator.

Combination (3): Combination wherein the resin P1 is polymer A1, the crosslinking group of unit u2 of polymer A1 is a group capable of crosslinking by radicals, and the photoinitiator is a photo-radical generator.

A preferable combination of the resin P2 and the photoinitiator in the present composition is a combination in which the polymer A1 is changed to the following resin P21 in the above combination (1) or (3) A2 is changed to the following resin P22, P23 or P24. Of these, the resin P21 or P24 is preferable from the viewpoint of easy patterning of the photosensitive film. The preferable ratio of the polymers B1 and B2 to the total amount of the polymers of the respective resins is the same as the preferable ratio of the polymer B to the total amount of the polymers of the above-mentioned resin P2.

Resin P21: Resin having polymer B1 and polymer C1 and at least one of them having terminal group J.

Resin P22: Resin comprising polymer B1 and polymer C2, at least one of which has terminal group J.

Resin P23: Resin comprising polymer B2 and polymer C1, at least one of which has terminal group J.

Resin P24: a resin comprising a polymer B2 and a polymer C2, wherein at least one of them has an end group J;

The solvent should be one which dissolves or disperses the resins P1 and P2 and the photoinitiator, and more preferably dissolves the resin. Volatile components such as a solvent are removed before forming the coating film before exposure.

Examples of the solvent include a fluorine-based solvent and a non-fluorine-based solvent.

Specific examples of the fluorine-based solvent include Asahi Clean (trademark) manufactured by Asahi Glass Industries Co., Ltd., 1H-tridecafluorohexane (AC2000), 1,1,1,2,2,3,3,4,4,5,5 , 6,6-tridecafluorooctane (AC6000), 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (AE3000), dichloropentafluoro Propane (AK-225), and the like. In addition, as other examples, there may be mentioned Cytop CT-solv100E (manufactured by Asahi Glass Co., Ltd.), 1-methoxynonafluorobutane (Novec (registered trademark) 7100, (Novec (trademark) 7200, manufactured by SUREM Japan), 1,1,1,2,3,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy ) Novec (trademark) 7600), 2H, 3H-perfluoropentane (Vertrel XF manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), 3,3,4,4,5 , 5,6,6,7,7,8,8,8-tridecafluoro-1-octanol, 4,4,5,5,6,6,7,7,8,8,9,9 , 9-tridecafluoro-1-nonanol, hexafluorobenzene, hexafluoro-2-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol , 1H, 1H, 7H-dodecafluoro-1-heptanol and the like.

Specific examples of the non-fluorine-containing solvent include ketones such as cyclopentanone, cyclohexanone, methyl amyl ketone and 2-butanone, ethyl lactate, methyl benzoate, ethyl benzoate, benzyl benzoate, methyl cellosolve acetate, , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene carbonate; ethers such as tetrahydrofuran, dioxane, dimethoxyethane, diethoxyethane, anisole, diglyme and triglyme And the like.

These solvents may be used alone or in combination of two or more.

Of these solvents, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, hexafluoro-2-propanol, 2,2,3,3,4,4,4-hexanediol, and the like are preferable because of their high solubility and high boiling point, , 5,5-octafluoro-1-pentanol, 1H, 1H, 7H-dodecafluoro-1-heptanol are preferable.

Other components include, for example, radical crosslinking agents, acid crosslinking agents, adhesion promoters, and other additives.

As the radical crosslinking agent, there can be mentioned a compound having two or more ethylenic double bonds. Particularly, a compound having 2 to 6 acryloyloxy groups is preferable.

Specific examples of the radical crosslinking agent include diethyleneglycol di (meth) acrylate, tetraethyleneglycol di (meth) acrylate, tripropyleneglycol di (meth) acrylate, neopentylglycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7 , 7,8,8,9,9-hexadecafluoro-1,10-decanediol di (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7 , 7-dodecafluoro-1,8-octanediol di (meth) acrylate, 2,2,3,3,4,4,5,5-decafluoro-1,6-hexanediol di ) _{acrylate, (CH 2 = CHCOO-CH} 2) 2 C (CH 3) NHCOO-CH 2 - (CF 2) 4 -CH 2 -OCONHC (CH 3) (CH 2 OCOCH = CH 2) 2, (CH _{2 = CHCOO-CH 2) 2} C (CH 3) NHCOO-CH 2 - (CF 2) 6 -CH 2 -OCONHC (CH 3) (CH 2 OCOCH = CH 2) 2, (CH 2 = CHCOO-CH 2 and the _{(CF 2) 8 -CH 2 -OCONHC} (CH 3) (CH 2 OCOCH = CH 2) 2 , etc. _{-) 2 C (CH 3)} NHCOO-CH 2 There.

Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) _{acrylate, (CH 2 = CHCOO-CH} 2) 2 C (CH 3) NHCOO-CH 2 - (CF 2) 4 -CH _{2 -OCONHC (CH 3) (CH} 2 OCOCH = CH 2) 2, (CH 2 = CHCOO-CH 2) 2 C (CH 3) NHCOO-CH 2 - (CF 2) 6 -CH 2 -OCONHC (CH 3 _{) (CH 2 OCOCH = CH 2} ) 2, (CH 2 = CHCOO-CH 2) 2 C (CH 3) NHCOO-CH 2 - (CF 2) 8 -CH 2 -OCONHC (CH 3) (CH 2 OCOCH = CH ₂ ) ₂ is highly compatible with the resin and has high curability.

Examples of the acid crosslinking agent include compounds having a group capable of crosslinking by the action of an acid. Specific examples of the acid crosslinking agent include hexamethylolmethoxymethylmelamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 4,5-dimethoxy-1,3-bis (methoxymethyl) imide (Methoxymethyl) urea, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether , Ethyleneglycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl [(3-ethyloxetan- Methyl oxetane, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, cyclohexyldivinyl ether, 3- (3,3,4,4,5,5,6,6,7,7,8,8 , 8-tridecafluorooctyloxy) -1,2-epoxypropane, and 2,2,3,3,4,4,5,5,5-nonafluoropentyloxirane.

As the adhesion imparting agent, a coupling agent such as a silane coupling agent can be used. Examples of the silane coupling agent include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacroyloxypropyltrimethoxysilane, heptadecafluorooctyltrimethoxysilane, 3-chloro- Propyl trimethoxysilane, vinyl trichlorosilane, vinyl trimethoxysilane, and the like.

The total content of the resin P1 and the resin P2 in the composition is preferably 10 to 70 mass%, more preferably 10 to 60 mass%, still more preferably 10 to 50 mass%, and even more preferably 10 To 40 mass% is particularly preferable. When the total content of the resin P1 and the resin P2 in the composition is not less than the lower limit value of the above range, the film thickness control becomes easy, and when it is not more than the upper limit value,

The content of the photoinitiator in the composition is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and particularly preferably 0.5 to 10 mass%, based on the total mass of the composition.

The content of the other components in the composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass with respect to the total mass of the composition.

The content of the solvent in the composition is the balance of the present composition excluding the resin P1, the resin P2, the photoinitiator and other components.

The present composition preferably contains at least one of resin P1 and resin P2 in an amount of 10 to 70 mass%, a photoinitiator in an amount of 1 to 10 mass%, a solvent in an amount of 20 to 89 mass%, and other components in an amount of 0 to 59 % By mass of at least one of resin P1 and resin P2, from 1 to 4% by mass of a photoinitiator, from 46 to 89% by mass of a solvent, and from 0 to 10% by mass of other components % Of the composition.

The present composition can be produced by mixing at least one of resin P1 and resin P2 with a photoinitiator. At this time, a solvent or other components may be mixed as necessary.

The mixing order of the respective components is not particularly limited.

When the composition contains the resin P2, the polymer B and the polymer C may be mixed beforehand with the photoinitiator or the like, or may be mixed when mixing the photoinitiator and the like.

A process for producing Polymer A, Polymer B or Polymer C may be performed before mixing the respective components. The preparation of each polymer can be carried out in the above order.

Therefore, the production method of the present composition may be any one of the following production methods 1 to 4.

Production method 1: A monomer component comprising monomer a1 and monomer a2 is polymerized in the presence of chain transfer agent j to prepare polymer A,

Wherein at least the polymer A and the photoinitiator are mixed to obtain a photosensitive composition.

Production Method 2: A monomer component comprising monomer a1 is polymerized in the presence of chain transfer agent j to obtain polymer B,

A monomer component comprising monomer a2 is polymerized in the presence of chain transfer agent j to obtain polymer C,

Wherein at least the polymer B, the polymer C and the photoinitiator are mixed to obtain a photosensitive composition.

Production method 3: A monomer component comprising monomer a1 is polymerized in the presence of chain transfer agent j to obtain polymer B,

Wherein at least the polymer B, the polymer C and the photoinitiator are mixed to obtain a photosensitive composition.

Production method 4: A monomer component comprising monomer a2 is polymerized in the presence of chain transfer agent j to obtain polymer C,

Wherein at least the polymer C, the polymer B and the photoinitiator are mixed to obtain a photosensitive composition.

Polymer C in Production Method 3 and Polymer B in Production Method 4 do not usually have terminal group J, but they may be present. As these polymers, commercially available polymers may be used.

As one embodiment of the production method 1, the polymerization is carried out by a solution polymerization method in the production of the polymer A to obtain a polymer solution containing the polymer A and a solvent, and a photoinitiator or the like is added to the polymer solution to obtain the composition Method.

In the present composition, a liquid repellent coating film having no coating irregularity can be formed because it contains at least one of resin P1 and resin P2 and a photoinitiator.

Since the composition has photosensitivity, the coating film formed from the composition of the present invention may have holes or grooves penetrating in the thickness direction by photolithography as described below.

The composition is coated on a substrate and dried as required, whereby a photosensitive film containing at least one of the resin P1 and the resin P2 and a photoinitiator is formed. When this photosensitive film is selectively exposed to a pattern corresponding to a hole or groove to be formed, a radical or an acid is generated from the photo initiator in the exposed portion of the photosensitive film, and the crosslinking group is crosslinked (cured) by the action.

When the polymer constituting the resin P1 and the resin P2 does not have the unit u3, or when the photoinitiator is not the photoacid generator even with the unit u3, the solubility of the exposed portion in the developer is lowered by crosslinking of the crosslinking agent. On the other hand, in the unexposed portion, the solubility in the developer does not substantially change. Therefore, when the exposed photosensitive film is developed with a developing solution, the unexposed portion is dissolved and removed in the developing solution, and the exposed portion remains without being removed. As a result, a laminate having a base film and a coating film formed on the surface of the base film is obtained, in which a coating film (cured film) having holes or grooves penetrating in the thickness direction is formed at the position of the unexposed portion.

When at least one of the polymers constituting the resin P1 and the resin P2 has the unit u3 and the photoinitiator is a photoacid generator, the acid dissociable group is dissociated by the action of an acid generated from the photoacid generator in the exposure unit upon exposure, An alkali-soluble group such as a carboxyl group is produced. As a result, the solubility of the exposed portion in the alkali developing solution is enhanced. On the other hand, in the unexposed portion, the solubility in an alkali developing solution does not substantially change. Therefore, when the exposed photosensitive film is developed with an alkali developing solution, the exposed portion is dissolved and removed in the alkaline developer, and the unexposed portion remains without being removed. Thus, a laminate having a base film and a coating film formed on the surface of the base film is obtained, in which a coating film (cured film) having holes or grooves penetrating in the thickness direction is formed at the position of the exposure section.

In the method for producing a laminate of the present invention, the composition is applied onto a substrate to form a photosensitive film, and the photosensitive film is exposed to form a coated film. Thereby, a laminate having a base material and a coating film laminated on the base material is obtained.

The material of the substrate is not particularly limited, and examples thereof include various glass plates, thermoplastic plastic sheets such as polypropylene, polyethylene, polycarbonate, polymethyl methacrylate, and polystyrene. In view of heat resistance, a glass plate, particularly a quartz glass plate, is preferable.

The application method of the composition is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coat method, and a bar coating method.

When the composition contains a solvent, the wet coating film obtained by applying the composition is preferably baked (hereinafter, also referred to as prebake). By pre-baking, the solvent volatilizes quickly and a dry film (photosensitive film) having no fluidity is obtained.

The prebake condition varies depending on the kind of each component, blending ratio, and the like, but is preferably about 50 to 120 DEG C for about 10 to 2000 seconds.

The thickness of the dry coating film is not particularly limited, but is preferably 0.1 to 20 占 퐉, more preferably 0.5 to 10.0 占 퐉.

The exposure may be an entire surface exposure for exposing the entire surface of the dried coating film or a selective exposure for selectively exposing a part of the dried coating film. In the case of forming a coating film in which holes or grooves penetrating in the thickness direction are formed, selective exposure is performed in a pattern corresponding to a hole or groove to be formed. For example, the dry film may be exposed through a mask of a predetermined pattern.

When the polymer constituting the resin P1 and the resin P2 does not have the unit u3 or when the photoinitiator is the photoacid generator even when the polymer has the unit u3, the hole or the groove forming part is not exposed and the other part Exposure. When at least one of the polymers constituting the resin P1 and the resin P2 has the unit u3 and the photoinitiator is a photoacid generator, the hole or groove forming portion is exposed, and the other portions are not exposed.

The light used for exposure is a light beam having a wavelength of 100 to 500 nm, preferably a light ray of 200 to 450 nm, and particularly preferably an i-ray (365 nm). As the irradiation device, it is preferable to use a high-pressure mercury lamp, an (ultraviolet) LED, a laser or the like as a light source. The exposure dose is preferably in the range of 5 to 2000 mJ / cm < 2 >.

After the exposure, a post-exposure baking (PEB) treatment may be carried out to accelerate the crosslinking reaction on the coated film after exposure, if necessary. The PEB treatment conditions are preferably in the range of 50 to 150 DEG C for 10 to 2000 seconds.

After the exposure or after the PEB treatment, the exposed dried coating film is developed as necessary. The development can be carried out using a developer.

When the developer is a solvent-based developer containing a solvent, the unexposed portion is dissolved and removed by development.

When at least one of the polymers constituting the resin P1 and the resin P2 has the unit u3 and the photo initiator is a photoacid generator, the exposed portion is dissolved and removed by development.

The solvent used in the solvent-based developer may be any solvent capable of selectively dissolving the unexposed portion. For example, the solvent exemplified above may be used.

Examples of the alkali of the alkali developing solution (alkali aqueous solution) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as methyl ammonium hydroxide, tetraethyl ammonium hydroxide and choline hydroxide, sodium silicate, sodium metasilicate and the like. The pH of the aqueous alkali solution is preferably 10 to 14. The alkaline aqueous solution may contain a water-soluble organic solvent (methanol, ethanol, etc.), a surfactant, and the like. Examples of the surfactant include nonionic surfactants.

Examples of the developing method include a puddle method, a dipping method, and a shower method. The developing time is preferably 5 to 180 seconds.

After development, the coating film on the substrate may be rinsed (rinsed) using a solvent, water or the like which does not dissolve the coating film.

After the development or after the rinsing, it is preferable to dry the coating film.

Thereafter, the coating film may be subjected to exposure (post exposure) and heat treatment (cure) in order to promote crosslinking. The exposure can be carried out in the same manner as described above. The heat treatment can be carried out using a heating apparatus such as a hot plate or an oven. The heat treatment is preferably carried out at 120 to 250 ° C for 5 to 90 minutes.

The coating film (cured film) obtained as described above contains a fluorinated organic group and can thus function as a liquid-repelling film. Further, the coating film is suppressed from uneven application.

As an index of coating unevenness, a touch-sensitive step system for measuring thin films can be used. According to the present invention, it is possible to obtain a flat coating film having no step on the film surface of the portion other than the hole or groove.

The fluorine content (fluorine atom content in the film) of the coating film is preferably from 15 to 75% by mass, and more preferably from 15 to 60% by mass. If the fluorine content is at least the lower limit of the above range, the liquid repellency is more excellent. When the content of fluorine is not more than the upper limit of the above range, the solubility of the portion to be dissolved and removed by the developing solution in the developing solution at the time of forming the coating film is good.

The fluorine content of the coating film can be adjusted by the fluorine content of the polymers A and B, the ratio of the polymers A and B in the photosensitive composition, and the like.

The fluorine content of the coating film is calculated from the fluorine content of the polymers A and B, the ratio of the polymers A and B in the coating film, and the like. The fluorine content of the polymers A and B can be adjusted by the content ratio of the unit u1 and the like.

The fluorine content of each of the polymers A and B is the proportion (% by mass) of fluorine atoms in the polymer, and is obtained by the following formula.

Q _F = [19 x N _F / M _A ] x 100

However, Q _F is a fluorine content, N _F is, for each type of the units constituting the polymer, the number of fluorine atoms of the units and, the sum of the product of the molar ratio of such units for the entire unit, M _A is, The sum of the atomic weights of all the atoms constituting the unit and the molar ratio of the unit to the whole unit multiplied by the total of the units constituting the polymer.

The finally obtained coating film preferably has a contact angle of water of 90 degrees or more, and particularly preferably a contact angle of water of 95 degrees or more. If the contact angle of water is not less than the above lower limit value, the liquid repellency is sufficiently excellent. The contact angle was measured by the method described in the following example. The contact angle can be adjusted by the fluorine content of the coating film.

In the case where the coating film has holes or grooves penetrating in the thickness direction, the obtained laminate can be used, for example, as a biochip. In this case, as the substrate, a lyophilic substrate is preferable. Examples of the lyophilic substrate include the above-mentioned various glass plates, thermoplastic plastic sheets and the like. As the lyophilic substrate, it is preferable that the contact angle of water is less than 50 degrees.

The holes or grooves of the coating film are typically plural.

When the biochip is a fluorescence analysis biochip, the coating film preferably has a fluorescence intensity of 15,000 or less, more preferably 10,000 or less, more preferably 5,000 or less, and a fluorescence intensity of 4,000 or less, as measured by the measuring method described in Examples described later Is particularly preferable. When the fluorescence intensity is not more than the upper limit value, it is useful for fluorescence analysis.

The fluorescence intensity can be adjusted by the type and content of the photoinitiator.

Fluorescence analysis In fluorescence analysis using a biochip, a fluorescence analysis biochip is irradiated with a light beam and the emitted fluorescence is measured. The fluorescence analysis is preferably carried out using a fluorescence microscope and a microarray scanner. It is preferable to use laser light as the excitation light source. The excitation wavelength is preferably between 450 nm and 800 nm, and preferably at 488 nm, 532 nm, 594 nm, 635 nm and 650 nm in order to excite fluorescent dyes generally used. In particular, a wavelength of 532 nm and 635 nm is preferable. For the measurement of emitted fluorescence, it is preferable to use an optical double tube.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. "%" Represents "% by mass" unless otherwise specified.

Examples 1, 8 to 16, 19, 21, and 23 to 25 are examples, and the other examples are comparative examples.

[Raw materials, etc.]

The following compounds were used as raw materials and the like.

(Monomer a1)

C6FMA: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate. C6FMA was obtained by the method described in Example 1 of Japanese Laid-Open Patent Publication No. 2004-359616.

(Monomer a2)

GMA: glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).

(Monomer a3)

EEMA: 1-ethoxyethyl methacrylate.

EEMA was synthesized in the following sequence.

55.8 g of ethyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.5 g of pyridinium p-toluenesulfonate (manufactured by ACROS Co., Ltd.) were mixed and purged with nitrogen in an ice bath for 30 minutes with stirring. 50.1 g of methacrylic acid (manufactured by Junsei Chemical Co., Ltd.) was added dropwise to the mixture, and the mixture was stirred overnight at room temperature. 0.8 g of sodium hydrogencarbonate (manufactured by Kanto Chemical Co.) and 1.4 g of sodium sulfate (manufactured by Kanto Chemical Co., Ltd.) were added to the reaction solution, and the solid content was filtered with polytetrafluoroethylene (hereinafter also referred to as PTFE) filter having a diameter of 3 탆 Filtered, and the filtrate was distilled off under reduced pressure. The remaining liquid was distilled under reduced pressure to 10 mmHg, and the liquid obtained at 40 占 폚 was collected to obtain 1-ethoxyethyl methacrylate (EEMA).

Of ^{EEMA 1 H-NMR (300.4 MHz} , solvent: d- acetone, standard: tetramethylsilane (TMS)) δ (ppm) : 1.1 (t, 3H), 1.4 (d, 3H), 1.9 (s, 3H) , 3.5-3.7 (m, 2H), 5.6 (s, IH), 5.9 (q, IH), 6.1 (s, IH).

(Solvent, polymerization solvent)

PGMEA: Propylene glycol monomethyl ether acetate.

(Polymerization initiator)

V65: 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.).

(Chain transfer agent)

j-1: thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.).

j-2: Dodecanethiol (manufactured by Kanto Chemical).

j-3: Octadecanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.).

j-4: Mercaptoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.).

j-5: 2-ethylhexanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.).

j-6: Cyclohexanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.).

j-7: Furfuryl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.).

j-8: Benzylthiol (manufactured by Tokyo Chemical Industry Co., Ltd.).

(Photoacid generator (hereinafter also referred to as " PAG "))

CPI210S: CPI (trade name) -210S, manufactured by SANA PRO, wavelength: 365 nm, absorption: 98 mL · g ^-1 · cm ^-1 ).

(IRGAGURE (trade name) PAG103, manufactured by BASF) at a wavelength of 365 nm, and the mixture was stirred at room temperature for 3 hours. IRPAG103: 2- [2- (propylsulfonyloxyimino) thiophene- Lt; ^-1 > cm < ^-1 > cm ^-1 ).

[Property and evaluation]

( ¹ H-NMR)

The ¹ H-NMR spectrum of the compound was measured using an FT-NMR apparatus (JNM-AL300, manufactured by Nippon Electronics Co., Ltd.).

(Mass average molecular weight: Mw)

The mass average molecular weight of the polymer was determined from a chromatogram obtained by a high-speed gel permeation chromatography (GPC) apparatus (Hosokawa, HLC-8220) using a calibration curve prepared using a standard polymethylmethacrylate sample whose molecular weight was already known Respectively.

(Coating property)

The photosensitive composition was spin-coated on the surface of a 6-inch silicon wafer (manufactured by Mitsubishi Matrix Trading Co., Ltd.) at 1,000 revolutions / minute for 30 seconds to form a photosensitive film in a wet state. Immediately after spin-coating, the formed photosensitive film was visually inspected for coating irregularity by cratering. (Good), and those having at least one coating unevenness were rated as poor (poor).

Separately, 200 μL of the photosensitive composition was bar-coated on the surface of a 6-inch silicon wafer using a bar No. 1 to form a photosensitive film in a wet state. Immediately after the bar coating, the formed photosensitive film was visually inspected for coating irregularity by cratering. Similarly to the above, those having no coating unevenness were evaluated as? (Good), and those having at least one coating unevenness were evaluated as? (Poor).

(resolution)

A photosensitive composition was spin-coated on the surface of a silicon substrate (30 mm square) on which an SiO ₂ film was formed for 30 seconds under the following conditions and heated at 100 ° C for 300 seconds using a hot plate to form a photosensitive film having a dry thickness of 3 μm .

Spin coat conditions: 1,000 revolutions / minute when the solution concentration of the polymer PGMEA solution used in the photosensitive composition is 30%, 2,000 revolutions / minute when the solution concentration is 40%.

Next, a high-pressure mercury lamp is used as a light source, and an i-line is irradiated through a photomask (a mask capable of forming a circular hole pattern whose diameter is changed from 2 mu m to 10 mu m by 1 mu m) (Exposed) to the photosensitive film.

Exposure dose: 300 mJ / cm 2 when PAG is CPI 210S and 100 mJ / cm 2 when PAG is IRPAG 103.

The exposed photosensitive film was subjected to development for 5 to 60 seconds using the following developer, or for 40 seconds using the following developer, and then rinsed with pure water for 30 seconds. In order to remove the developing solution and the rinsing liquid, spin-drying was carried out at 2,000 rpm for 30 seconds. Thereafter, in order to promote curing, the i-line was irradiated (post exposure) so that the exposure amount was 100 mJ / cm 2 and heat treatment (curing) was performed at 150 캜 for 30 minutes using a hot plate. Thus, a liquid-repellent film having a hole pattern was obtained.

In the case of using Polymers A-1, 30, and 31, heat treatment (Post Exposure Bake) was performed at 120 占 폚 for 120 seconds before development.

Developer: When the polymer has an EEMA unit (unit u3), use is made of NMD-W (aqueous solution of tetramethylammonium hydroxide, 2.38 mass%, manufactured by Tokyo Ohka Kogyo Co., Ltd., containing surfactant) PGMEA was used.

The obtained liquid-repellent film was observed with a microscope (VHX DIGITAL MICROSCOPE, manufactured by KEYENCE), and the minimum hole pattern diameter (μm) in which the holes were opened was measured.

(Water contact angle)

The photosensitive composition was spin-coated on the surface of a quartz glass substrate (25 mm x 50 mm) at 1,000 revolutions / minute for 30 seconds, heated at 100 占 폚 for 120 seconds using a hot plate, and then heated at 150 占 폚 for 30 minutes, Thereby forming a photosensitive film having a dry state of 3 占 퐉. The contact angle of about 2 μL of distilled water placed on the surface of the photosensitive film was measured using a contact angle measuring apparatus (DM-701, manufactured by Kyowa Interface Science Co., Ltd.).

(Fluorescence intensity)

The photosensitive composition was spin-coated on the surface of a quartz glass substrate (25 mm x 50 mm) at 1,000 revolutions / minute for 30 seconds and heated at 100 占 폚 for 120 seconds using a hot plate to form a photosensitive film having a dry thickness of 2 占 퐉 Respectively. A high-pressure mercury lamp was used as a light source, and a photosensitive film was exposed so that the exposure amount was 500 mJ / cm 2. Subsequently, post-baking was performed at 150 캜 for 30 minutes using a hot plate.

The fluorescence intensity of the photosensitive film after post-baking was measured with a microarray scanner (GenePix4000B, manufactured by Molecular Devices) (excitation wavelength: 532 nm, resolution: 5 μm, laser output: 100%, voltage of the photomultiplier: 1,000 V).

[Production Example A-7]

4.00 g of C6FMA, 1.97 g of GMA, 3.66 g of EEMA, 0.10 g of a chain transfer agent j-1 (thioglycerol) and 0.40 g of V65 were dissolved in 22.4 g of PGMEA, For 24 hours. Thereafter, the temperature was raised to 70 캜 and shook for 2 hours. The obtained reaction solution was filtered with a nylon filter having a pore diameter of 0.45 mu m to obtain a PGMEA solution of the polymer (A-7).

Table 1 shows the molar ratio (copolymerization ratio) of each unit in the polymer (A-7), the kind and amount of the chain transfer agent used in the polymerization, the mass average molecular weight (Mw) and the solution concentration. The copolymerization ratios were obtained from the integrating ratios of 2.5 ppm, 3.2 ppm, 4.3 ppm, and 5.7 ppm. The sample for NMR measurement was added to hexane of 20 times the amount of the PGMEA solution of the polymer, and the precipitated solid was filtered with a PTFE filter having a pore diameter of 3 占 퐉 and dried under reduced pressure. The amount of the chain transfer agent used was expressed as a ratio (mol%) to the total number of moles of the monomers used in the polymerization. The solution concentration is the concentration of the polymer (% by mass) in the PGMEA solution.

Polymer ^{(A-7) 1 H-} NMR of (300.4 MHz, solvent: acetone d-, standard: TMS) δ (ppm): 1.4 ~ 1.9 (m, 14H), 2.5 (br, 0.02H), 2.7 (br , 1.8 (br, 1H), 2.8 ppm (br, 1.9H), 3.2 (br, 0.5H) 1H).

2.5 (br, 0.02H) corresponds to the peak of the terminal group derived from thioglycerol. From the measurement results, it was confirmed that the polymer had the terminal group J.

[Production Examples A-1 to A-6, A-8 to A-32]

(A-1) to (A-6) and (A-6) were obtained in the same manner as in Production Example A-7, except that the types and amounts of the chain transfer agent, the kind of copolymerizable monomer and the copolymerization ratio were changed as shown in Table 1. [ -8) to (A-32).

[Example 1]

3.0 g of the PGMEA solution of the polymer (A-1) was filtered with a PTFE filter having a pore size of 0.50 占 퐉 and then poured into a glass vial (20 ml) together with 0.3 g of CPI210S and sufficiently stirred to obtain a photosensitive composition Was prepared.

The resulting photosensitive composition was evaluated for coatability, resolution, water contact angle and fluorescence intensity. The results are shown in Table 2.

[Examples 2 to 29, 31, 32]

Photosensitive compositions of Examples 2 to 29, 31, and 32 were prepared in the same manner as in Example 1 except that the kind of polymer or the kind of PAG was changed as shown in Table 2.

[Example 30]

A photosensitive composition was prepared in the same manner as in Example 1 except that 3.0 g and 7.0 g of the reaction liquid of the polymer (A-28) and the reaction liquid of the polymer (A-29) were mixed, respectively.

[Example 33]

A photosensitive composition was prepared in the same manner as in Example 1 except that 1.0 g and 9.0 g of the reaction liquid of the polymer (A-30) and the reaction liquid of the polymer (A-32) were mixed, respectively.

The resulting photosensitive composition was evaluated for coatability, resolution, water contact angle and fluorescence intensity. The results are shown in Table 2.

In Examples 1, 8 to 16, 19, 21, 23 to 31, and 33 including the polymer obtained by using the chain transfer agent (j-1, j-5 to j-8) corresponding to the chain transfer agent j, A coating film excellent in lyophobic property could be formed. In addition, patterning by photolithography was also possible. Further, it was confirmed that the fluorescence intensity was sufficiently low and could be used for fluorescence analysis.

In Examples 2 to 7, 17, 18, 20, 22, and 32, in which the polymer obtained by using the chain transfer agent (j-2 to j-4) other than the chain transfer agent j and having a mass average molecular weight of 6,000 to 20,000, There was uneven application.

In Examples 24 to 27 in which the polymer does not have a unit u1, there was no coating unevenness, but the liquid repellency of the coating film was inferior.

Industrial availability

The photosensitive composition of the present invention can be applied to a member or apparatus having a patterned liquid repellent film, for example, a biochip having a patterned liquid repellent film, a substrate for forming a pixel having a patterned liquid repellent bank material, Wetting apparatuses and the like.

In addition, Japanese Patent Application No. 2016-136414 filed on Jul. 08, 2016, Japanese Patent Application No. 2016-136415 filed on Jul. 08, 2016, and Japanese Patent Application No. 2017- The entire contents of the specification of 090779, the claims and the abstract are hereby incorporated herein by reference as the disclosure of the specification.

Claims (14)

And at least one of the following resins P1 and P2 and a photoinitiator.
Resin P1: a polymer having a terminal group u1 which is a unit having an organic group having at least one fluorine atom, a unit u2 which is a unit having a crosslinking group, and a terminal group represented by any one of the following formulas 1, 2 and 3: A resin.
Resin P2: a polymer B which has the unit u1 and does not have the unit u2, and a polymer C which has the unit u2 and does not have the unit u1, and at least the polymer B and the polymer C Is a polymer having a terminal group represented by any one of the formulas (1), (2) and (3).
-X ¹ -C (R ¹ ) (R ² ) (R ³ )
-X ² -R ⁴ ... 2
^{-X 3 -N (R 5) (} R 6) ··· 3
R ¹ to R ³ each independently represents a chain hydrocarbon group having 40 or less carbon atoms, a cyclic group having 40 or less carbon atoms, a hydroxyl group, a halogen atom, an amino group, or a hydrogen atom, which may have an ether group, Atoms, at least two of R ¹ to R ³ are atoms or groups other than hydrogen atoms,
R ⁴ represents a cyclic group having 40 or less carbon atoms,
R ⁵ and R ⁶ each independently represent a chain hydrocarbon group having 40 or less carbon atoms, or a cyclic group having 40 or less carbon atoms, which may have a hydroxyl group, an oxo group or an etheric oxygen atom,
X ¹ to X ³ each independently represents a single bond, -S-, -SR ⁷ -, -R ⁸ -, -OR ⁹ - or -O-, R ⁷ , R ⁸ and R ⁹ each independently represent a carbon number Represents a linear alkylene group of 1 to 40 carbon atoms. The method according to claim 1,
Wherein the polymer A, the polymer B and the polymer C each have a mass average molecular weight of 6,000 to 20,000. 3. The method according to claim 1 or 2,
Wherein the photoinitiator is a photoacid generator,
Wherein the polymer A further has a unit u3 which is a unit having an alkali-soluble group protected with an acid-dissociable group. 3. The method according to claim 1 or 2,
Wherein the photoinitiator is a photoacid generator,
Wherein at least one of the polymer B and the polymer C further has a unit u3 which is a unit having an alkali-soluble group protected with an acid-dissociable group. 5. The method according to any one of claims 1 to 4,
Wherein at least one of the polymer A, the polymer B and the polymer C further has a unit u4 which is a unit other than the unit u3 in which the unit u1, the unit u2 and the alkali-soluble group protected with an acid-dissociable group are protected, Composition. 6. The method according to any one of claims 1 to 5,
Wherein the total content of the resin P1 and the resin P2 is 10 to 70 mass% with respect to the total mass of the photosensitive composition. A monomer component comprising a monomer a1 as a monomer having an organic group having at least one fluorine atom and a monomer a2 as a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) In the presence of a chain transfer agent represented by any one of formulas (12) and (13) to obtain a polymer.
Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )
Z ² -X ² -R ⁴ ... 12
^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13
R ¹ to R ³ each independently may have a hydroxyl group or an oxo group, a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, a cyclic group having 40 or less carbon atoms, a hydroxyl group, a halogen atom , An amino group or a hydrogen atom, at least two of R ¹ to R ³ are atoms or groups other than hydrogen atoms,
R ⁴ represents a cyclic group having 40 or less carbon atoms,
R ⁵ and R ⁶ each independently represent a chain hydrocarbon group having 40 or less carbon atoms or a cyclic group having 40 or less carbon atoms which may have a hydroxyl group or an oxo group and may have an etheric oxygen atom,
X ¹ to X ³ each independently represents a single bond, -S-, -SR ⁷ -, -R ⁸ -, -OR ⁹ - or -O-, R ⁷ , R ⁸ and R ⁹ each independently represent a carbon number A straight chain alkylene group having 1 to 40 carbon atoms,
Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom. A monomer component containing a monomer a1 which is a monomer having an organic group having at least one fluorine atom and a monomer a2 'which is a monomer having a reaction site is reacted with a chain transfer agent represented by any one of the following formulas 11, 12 and 13 To obtain a polymer and then reacting the polymer with a compound having a reactive functional group capable of binding with the reaction site and a crosslinking group to obtain a polymer having a unit u2 which is a unit having a crosslinking group.
Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )
Z ² -X ² -R ⁴ ... 12
^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13
R ¹ to R ³ each independently may have a hydroxyl group or an oxo group, a chain hydrocarbon group having 40 or less carbon atoms which may have an etheric oxygen atom, a cyclic group having 40 or less carbon atoms, a hydroxyl group, a halogen atom , An amino group or a hydrogen atom, at least two of R ¹ to R ³ are atoms or groups other than hydrogen atoms,
R ⁴ represents a cyclic group having 40 or less carbon atoms,
R ⁵ and R ⁶ each independently represent a chain hydrocarbon group having 40 or less carbon atoms or a cyclic group having 40 or less carbon atoms which may have a hydroxyl group or an oxo group and may have an etheric oxygen atom,
X ¹ to X ³ each independently represents a single bond, -S-, -SR ⁷ -, -R ⁸ -, -OR ⁹ - or -O-, R ⁷ , R ⁸ and R ⁹ each independently represent a carbon number A straight chain alkylene group having 1 to 40 carbon atoms,
Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom. A process for producing a photosensitive composition according to any one of claims 1 to 6,
A monomer component comprising a monomer a1 as a monomer having an organic group having at least one fluorine atom and a monomer a2 as a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) Polymer A is prepared by polymerization in the presence of a chain transfer agent represented by any one of formulas 12 and 13,
Wherein at least the polymer A and the photoinitiator are mixed to obtain a photosensitive composition.
Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )
Z ² -X ² -R ⁴ ... 12
^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13
Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,
Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom. A process for producing a photosensitive composition according to any one of claims 1 to 6,
A monomer component comprising a monomer a1 which is a monomer having an organic group having at least one fluorine atom is polymerized in the presence of a chain transfer agent represented by any one of the following formulas 11, 12 and 13 to obtain a polymer B,
A monomer component comprising a monomer a2 which is a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) is polymerized in the presence of the chain transfer agent to obtain a polymer C,
Wherein at least the polymer B, the polymer C and the photoinitiator are mixed to obtain a photosensitive composition.
Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )
Z ² -X ² -R ⁴ ... 12
^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13
Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,
Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom. A process for producing a photosensitive composition according to any one of claims 1 to 6,
A monomer component comprising a monomer a1 which is a monomer having an organic group having at least one fluorine atom is polymerized in the presence of a chain transfer agent represented by any one of the following formulas 11, 12 and 13 to obtain a polymer B,
Wherein at least the polymer B, the polymer C and the photoinitiator are mixed to obtain a photosensitive composition.
Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )
Z ² -X ² -R ⁴ ... 12
^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13
Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,
Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom. A process for producing a photosensitive composition according to any one of claims 1 to 6,
A monomer component containing a monomer a2 which is a monomer having a crosslinking group (excluding a group containing an ethylenic double bond) is polymerized in the presence of a chain transfer agent represented by any one of the following formulas 11, 12 and 13: To obtain a polymer C,
And at least the polymer C, the polymer B and the photoinitiator are mixed to obtain a photosensitive composition.
Z ¹ -X ¹ -C (R ¹ ) (R ² ) (R ³ )
Z ² -X ² -R ⁴ ... 12
^{Z 3 -X 3 -N (R 5} ) (R 6) ··· 13
Provided that R ¹ to R ⁶ and X ¹ to X ³ are each as defined above,
Z ¹ to Z ³ each independently represent a hydrogen atom or a halogen atom. A method for producing a laminate having a base material and a coating film laminated on the base material,
A photosensitive composition according to any one of claims 1 to 6, which is applied on a substrate to form a photosensitive film, and the photosensitive film is exposed to form a coated film. 14. The method of claim 13,
Wherein the coating film has a hole or groove penetrating in the thickness direction,
Wherein the exposure of the photosensitive film is performed in a pattern corresponding to the hole or groove and the photosensitive film is developed after exposure.