TW201807150A - Surface treatment method and surface treatment liquid - Google Patents

Abstract

To provide: a surface treatment method which is able to achieve good hydrophilization or hydrophobization of the surface of an object to be processed, and which is capable of forming a region that has a high surface treatment effect and a region that has a low surface treatment effect on the object to be processed; and a surface treatment liquid which is suitably used in this surface treatment method. A surface treatment method wherein a thin film that has a surface modification function, while having a film thickness of 10 nm or less is formed by rinsing a coating film which is formed from a photosensitive surface treatment liquid and has been exposed to light and then baked. In this surface treatment method, the photosensitive surface treatment liquid is configured to contain (A) a resin, (B) a photoacid generator and (C) a solvent; a resin having a functional group I that is composed of one or more groups selected from the group consisting of a hydroxyl group, a cyano group and a carboxy group and a functional group II that is a hydrophilic group or a hydrophobic group other than the functional group I is used as the resin (A); and a compound that generates a strong acid having a pKa of 1 or less by the action of light is used as the photoacid generator (B).

Description

Surface treatment method and surface treatment liquid

The present invention relates to a surface treatment method and a surface treatment liquid which is preferably used in the surface treatment method.

In the past, various surface treatment liquids have been used to modify the surface properties of various articles. In the surface modification, the requirements for the hydrophilization or hydrophobization of the surface of the article are increased, and most of the surface treatment methods for hydrophilization or hydrophobization are proposed, and the surface treatment liquid used in the method.

Regarding this surface treatment method, it has been proposed to use a copolymer containing at least 1,500 to 50,000 of a weight average molecular weight obtained by copolymerizing at least an acrylamide monomer and a silicon-containing mono (meth) acrylate monomer having a specific skeleton. A method for imparting hydrophilicity and antifouling properties to the surface of a film by using a surface conditioner (Patent Document 1).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5435223

However, when the surface conditioner described in Patent Document 1 is used for the hydrophilization treatment, even if the surface of the object to be treated is treated with a solution containing only the surface conditioner, the surface conditioner does not easily adhere to the surface of the object to be treated, and it is difficult to obtain expectations. Hydrophilizing effect.

Therefore, the method described in Patent Document 1 uses a resin such as an acrylic resin, a polyester resin, a urethane resin, an alkyd resin, an epoxy resin, or a polyamine resin as a coating film to be used in a solution of a surface conditioner. The component-forming liquid is used as a surface treatment liquid.

Therefore, when a surface treatment liquid containing a surface conditioner and a film-forming component described in Patent Document 1 is used, the surface of the object to be treated is covered with a resin-containing film, so even if it is well hydrophilized, it will damage the treated object. Useful surface properties of the body.

In addition, depending on the use of the surface-treated material, it may be necessary to make a difference in the surface treatment effect between the part where the surface treatment should be performed and the part where the surface treatment should not be performed. Ideally, the surface-treated part and the non-surface-treated part are better patterned.

However, the method of using the surface conditioner used in the method described in Patent Document 1 makes it difficult to make a difference in the surface treatment effect for each part, and it is also difficult to apply the surface treatment agent finely and precisely to provide a surface-treated part and an untreated part. Surface treated area. As a result, with the method described in Patent Document 1, it is difficult to make the surface treatment effect different between the part where surface treatment should be performed and the part where surface treatment should not be performed.

The present invention is made in view of the above-mentioned problems, and an object thereof is to provide a good affinity for the surface of an object to be treated even without a film-forming resin. A surface treatment method that hydrates or hydrophobs and can form a region with a high surface treatment effect and a region with a low surface treatment effect on the object to be treated, and a surface treatment liquid that is preferably used in the surface treatment method.

The present inventors have discovered that by cleaning a coating film made of a photosensitive surface treatment liquid subjected to exposure and baking, a surface treatment method for forming a thin film having a surface modification function with a film thickness of 10 nm or less, The photosensitive surface treatment liquid contains (A) a resin, (B) a photoacid generator, and (C) a solvent, and as the (A) resin, one or more members selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group are used. Functional group I of functional groups and functional groups II of hydrophilic groups or hydrophobic groups other than functional groups I, and (B) a photoacid generator that uses a light to generate a strong acid with a pKa of 1 or less The compound can solve the above-mentioned problems, and thus completed the present invention. Specifically, the present invention provides the following.

The first aspect of the present invention is a surface treatment method, which is a surface treatment method using a photosensitive surface treatment liquid, and includes the following steps: applying a photosensitive surface treatment liquid on a surface of a subject to form a coating film, Exposing at least a part of the coating film, baking the exposed coating film, and cleaning the baked coating film, and forming a thin film with a thickness of 10 nm or less on the exposed portion of the surface of the object to be treated, The photosensitive surface treatment liquid contains (A) a resin, (B) a photoacid generator, and (C) a solvent. The (A) resin has a functional group of one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. A functional group II of a hydrophilic group or a hydrophobic group other than I and the functional group I, (B) the photoacid generator generates a strong acid having a pKa of 1 or less.

A second aspect of the present invention is a photosensitive surface treatment liquid, which is the photosensitive surface treatment liquid used in the surface treatment method in the first aspect, and contains (A) a resin, (B) a photoacid generator, and (C) a solvent, (A) a resin having a functional group I of one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II of a hydrophilic group or a hydrophobic group other than the functional group I (B) The photoacid generator generates a strong acid with a pKa of 1 or less.

A third aspect of the present invention is a photosensitive surface treatment liquid containing (A) a resin, (B) a photoacid generator, and (C) a solvent. (A) the resin has a member selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. The functional group I of one or more groups of the group and the functional group II of a hydrophilic group or a hydrophobic group other than the functional group I, (B) the photoacid generator generates a strong acid having a pKa of 1 or less.

According to the present invention, even if the film-forming resin is not contained, the surface of the object to be treated can be hydrophilized or hydrophobized well. A region having a high surface treatment effect and a region having a low surface treatment effect are formed on the processing body.

《Surface treatment method》

Hereinafter, a surface treatment method using a photosensitive surface treatment liquid will be described.

The surface treatment method includes a method of applying a photosensitive surface treatment liquid on the surface of a treatment object to form a coating film, exposing at least a part of the coating film, and baking the exposed coating film. And the baked coating film is cleaned, and a thin film with a thickness of 10 nm or less is formed on the surface of the object to be treated through the exposed portion.

As the photosensitive surface treatment liquid (hereinafter also referred to as "treatment liquid"), a treatment liquid containing (A) a resin, (B) a photoacid generator, and (C) a solvent is used, and (A) the resin has a material selected from Functional group I of one or more groups consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II of a hydrophilic group or a hydrophobic group other than the aforementioned functional group I, (B) The photoacid generator generates pKa Strong acid below 1.

Hereinafter, each step included in the photosensitive surface treatment liquid and the surface treatment method will be described.

<Photosensitive surface treatment liquid>

The necessary or optional components contained in the photosensitive surface treatment liquid are described below.

[(A) Resin]

(A) The resin has a functional group I of one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. The strong acid having a pKa of 1 or less generated by the (B) photoacid generator described later increases the reactivity or interaction between the functional group I and the surface of the non-treated body, thereby binding (A) the resin or attaching it to the substrate. Treat the body surface.

(A) The resin has a functional group II of a hydrophilic group or a hydrophobic group other than the functional group I. If a treatment liquid containing a resin having a hydrophilic group (A) is used, the hydrophilization treatment can be performed, and if a treatment liquid containing a resin having a hydrophobic group (A) is used, the hydrophobization treatment can be performed.

The hydrophilic group or the hydrophobic group is not particularly limited as long as it is a functional group which has been recognized as a hydrophilic group or a hydrophobic group by those skilled in the art, and may be appropriately selected among them.

The type of (A) resin is not particularly limited as long as it has a specific functional group and is soluble in the (C) solvent. Examples of the (A) resin include a (meth) acrylic resin, a novolac resin, a polyester resin, a polyamide resin, a polyimide resin, a polyimide resin, and a silicone resin. Among these resins, a (meth) acrylic resin is preferred from the viewpoint of introduction of a functional group and the ease of adjusting the content ratio of a unit having a functional group.

As specific examples of the hydrophilic group, polyoxyalkylene (e.g., polyoxyethylene, polyoxypropyl, oxyethyl and oxypropyl through a block or random bonding of polyoxyethylene) Alkyl groups, etc.), amine groups, carboxyl groups, hydroxyl groups, sulfonic groups, and the like. Moreover, an organic group containing these groups is also preferable as a hydrophilic group.

When the hydrophilic group is an acidic group, the acidic group may form a salt. The cation constituting the salt is not particularly limited, and may be a metal ion or an organic cation. The cation is preferably a metal ion, more preferably an alkali metal ion, and particularly preferably a sodium ion or a potassium ion.

(A) When the resin has a hydrophilic group or a hydrophobic group containing a hydroxyl group, a cyano group, and a carboxyl group as the functional group II, a hydroxyl group, a cyano group, or a carboxyl group contained in the hydrophilic group or the hydrophobic group may also function as a functional group. The role of I.

Therefore, when the (A) resin has a hydrophilic group or a hydrophobic group containing a hydroxyl group, a cyano group, and a carboxyl group as the functional group II, the (A) resin may not have the functional group I.

The hydrophilic group containing a hydroxyl group and a carboxyl group includes the hydroxyl group itself and the carboxyl group itself.

From the viewpoint of improving the hydrophilizing effect of the treatment liquid, as the hydrophilic group, a group represented by the following formula (A1) is preferred: -NH-R ¹ ‧‧‧ (A1)

(In the formula (A1), R ¹ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amine group, a sulfonic acid group, and a hydroxyl group).

Specific examples of R ¹ in the hydrophilic group represented by the formula (A1) include an amine group and a group represented by the following formula.

Among specific examples of R ¹ in the hydrophilic group represented by the above formula (A1), the more preferable examples are the following groups.

Among the specific examples of R ¹ in the hydrophilic group represented by the above formula (A1), examples of particularly preferred examples include the following examples.

Specific examples of the hydrophobic group include a fluorinated hydrocarbon group, a silyl group, a siloxyalkyl group, an alkyl group having 6 to 20 carbon atoms, and an aromatic hydrocarbon group having 10 to 20 carbon atoms.

The fluorinated hydrocarbon group is preferably a group described later in the formula (A3).

A preferable example of the silane group is a group in which n represented by the formula (A4) described later is 0. Specific examples of the silyl group include, for example, trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, third butyldimethylsilyl, and triphenylsilyl. .

The silyloxy group may be linear or branched. The silyloxy group may be a monovalent group or a polyvalent group having a divalent or higher valence. Therefore, the so-called organosiloxane compound corresponds to a compound having a siloxane group as a hydrophobic group. A preferable example of the siloxane group is a group in which n represented by the formula (A4) described below is 1 or more.

The resin (A) is preferably a polymer of an unsaturated bond-containing monomer, from the viewpoints that various functional groups can be easily introduced and the amount of functional groups can be easily adjusted. The polymer may be a homopolymer or a copolymer.

In this case, it is preferable that the functional group I possessed by the (A) resin is derived from a monomer represented by the following formula (A2) or the following formula (A2-1): CH ₂ = CR ^2- (R ³ ) _a- CO-R ⁴ ‧‧‧ (A2)

(In the formula (A2), R ² is a hydrogen atom or a methyl group, R ³ is a divalent hydrocarbon group, a is 0 or 1, R ⁴ is -OH, -OR ⁵ , or -NH-R ⁵ , and R ⁵ is A hydrocarbon group substituted with one or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group), CH ₂ = CR ^2- (R ³ ) _a -SO ₃ X‧‧‧ (A2-1)

(In the formula (A2-1), R ² , R ^3, and a are the same as those in the formula (A2), and X is a hydrogen atom or an alkali metal).

In the formula (A2), R ³ is a divalent hydrocarbon group. The number of carbon atoms of the divalent hydrocarbon group is not particularly limited as long as it does not hinder the object of the present invention. From the viewpoint of easily obtaining or preparing the (A) resin, the carbon number of the divalent hydrocarbon group as R ³ is preferably 1 to 20, more preferably 1 to 12, particularly preferably 1 to 10, and most preferably 1 to 6. .

The divalent hydrocarbon group as R ³ may be an aliphatic group, an aromatic group, or a hydrocarbon group containing an aliphatic portion and an aromatic portion. When the divalent hydrocarbon group is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. In addition, the structure of the aliphatic group may be linear, branched, or cyclic, or a combination of these structures.

As specific examples of R ³ , methylene, ethane-1,2-diyl, ethane-1,1-diyl, propane-1,3-diyl, propane-1,1-di Base, propane-2,2-diyl, n-butane-1,4-diyl, n-pentane-1,5-diyl, n-hexane-1,6-diyl, n-heptane-1,7 -Diyl, n-octane-1,8-diyl, n-nonane-1,9-diyl, n-decane-1,10-diyl, o-phenylene, m-phenylene, p-phenylene -Phenylene, naphthalene-2,6-diyl, naphthalene-2,7-diyl, naphthalene-1,4-diyl, biphenyl-4,4'-diyl, etc.

R ⁴ is -OH, -OR ⁵ , or -NH-R ⁵ , and R ⁵ is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group.

The hydrocarbon group constituting the main skeleton of the R ⁵ group may be a linear, branched, or cyclic aliphatic group, or an aromatic hydrocarbon group.

The number of carbon atoms of the linear, branched, or cyclic aliphatic group is preferably from 1 to 20, more preferably from 1 to 12.

Specific examples of the linear or branched aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third butyl. , N-pentyl, isopentyl, neopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like.

Examples of preferred examples of the cyclic aliphatic group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; Boronane, tricyclodecane, and tetracyclodecane polycyclic alkanes remove one hydrogen atom, or these polycycloalkane C ₁ -C ₄ alkyl substituents remove one hydrogen atom. .

As specific examples of the aromatic hydrocarbon group, phenyl, naphthyl, Anthracenyl, phenanthryl and biphenyl. The aromatic hydrocarbon group may be substituted with a C1-C4 alkyl group such as a methyl group or an ethyl group.

Particularly preferred specific examples of the unit derived from the monomer represented by the formula (A2) are the units of a2-1 to a2-9 below. Among the following units a2-1 to a2-9, the units a2-1 to a2-4 are more preferable.

Preferred examples of the monomer represented by the formula (A2-1) include p-vinylbenzenesulfonic acid, sodium p-vinylbenzenesulfonate, potassium p-vinylbenzenesulfonate, and m-vinylbenzenesulfonate. Acid, sodium m-vinylbenzenesulfonate, potassium m-vinylbenzenesulfonate, vinylsulfonic acid, sodium vinylsulfonate and potassium vinylsulfonate.

(A) When the resin has a hydrophobic group as the functional group II, the functional group II is preferably derived from a monomer represented by the following formula (A3): CH ₂ = CR ^2- (CO-O) _b -R ⁶ ‧‧ ‧ (A3)

(In the formula (A3), R ² is a hydrogen atom or a methyl group, b is 0 or 1, R ⁶ is a fluorinated hydrocarbon group or a group represented by the following formula (A4): -SiR ⁷ R ⁸ -(-O-SiR ⁷ R ^8- ) _n -R ⁹ ‧‧‧ (A4)

R ⁷ , R ⁸ and R ⁹ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 or more).

In formula (A3), when R ⁶ is a fluorinated hydrocarbon group, the hydrocarbon group constituting the main skeleton of the fluorinated hydrocarbon group is the same as the hydrocarbon group constituting the main skeleton of the aforementioned R ⁵ group. The fluorinated hydrocarbon group may be a group in which all hydrogen atoms in the hydrocarbon group are substituted with fluorine atoms.

Specific examples of the fluorinated hydrocarbon group of R ⁶ include -CF ₃ , -CF ₂ CF ₃ ,-(CF ₂ ) ₂ CF ₃ ,-(CF ₂ ) ₃ CF ₃ ,-(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-(CF ₂ ) ₉ CF ₃ , -CH ₂ CF ₃ , -CH ₂ CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₂ CF ₃ , -CH ₂ (CF ₂ ) ₃ CF ₃ , -CH ₂ (CF ₂ ) ₄ CF ₃ , -CH ₂ (CF ₂ ) ₅ CF ₃ , -CH ₂ (CF ₂ ) ₆ CF ₃ , -CH ₂ (CF ₂ ) ₇ CF ₃ , -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₂ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₃ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₆ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ , -CH ₂ CF ₂ H, -CH ₂ CF ₂ CF ₂ H, -CH ₂ (CF ₂ ) ₂ CF ₂ H, -CH ₂ (CF ₂ ) ₃ CF ₂ H, -CH ₂ (CF ₂ ) ₄ CF ₂ H, -CH ₂ (CF ₂ ) ₅ CF ₂ H, -CH ₂ ( CF ₂ ) ₆ CF ₂ H, -CH ₂ (CF ₂ ) ₇ CF ₂ H, -CH ₂ (CF ₂ ) ₈ CF ₂ H, -CH ₂ CH ₂ CF ₂ H, -CH ₂ CH ₂ CF ₂ CF ₂ H, -CH ₂ CH ₂ (CF ₂ ) ₂ CF ₂ H, -CH ₂ CH ₂ (CF ₂ ) ₃ CF ₂ H, -CH ₂ CH ₂ (CF ₂ ) ₄ CF ₂ H, -CH ₂ CH ₂ ( CF ₂ ) ₅ CF ₂ H, -CH ₂ CH ₂ (CF ₂ ) ₆ CF ₂ H, -CH ₂ CH ₂ (CF ₂ ) ₇ CF ₂ H, and -CH (CF ₃ ) ₂ Groups; fluorinated aromatic hydrocarbon groups such as pentafluorophenyl, o-trifluoromethylphenyl, m-trifluoromethylphenyl, and p-trifluoromethylphenyl; fluorination of octafluoroadamantyl Alicyclic base.

In formula (A3), when R ⁶ is a group represented by formula (A4), R ⁷ , R ⁸ and R ^{9 are} preferably independently methyl, ethyl or phenyl, more preferably R ⁷ , R ⁸ and R ⁹ Both are methyl.

In the formula (A4), the upper limit of n is not particularly limited as long as the object of the present invention is not impaired. n is preferably an integer of 0 to 35, more preferably an integer of 0 to 10.

Hydrophobic group as a monomer derived from the formula (A3) Specific examples of the unit are particularly preferable as the units of a3-1 to a3-24 below. Among the following units, the units a3-8, a3-12, a3-18, a3-19, and a3-22 are more preferable.

When the (A) resin has a hydrophilic group as the functional group II, the functional group II is preferably derived from a monomer represented by the following formula (A5): CH ₂ = CR ² -CO-NH-R ¹ ‧‧‧ ( A5)

(In formula (A5), R ¹ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amine group, a sulfonic acid group, and a hydroxyl group, and R ² is Hydrogen atom or methyl).

In formula (A5), R ¹ is as described above.

A particularly preferable specific example of the unit having a hydrophilic group derived from the monomer represented by the formula (A5) is a unit of the following a5-1 to a5-5. Among the following units, the units of a5-1 to a5-4 are more preferable.

(A) When the resin is a polymer of a monomer having an unsaturated bond, the polymer may contain a unit derived from the monomer represented by the formula (A2) and a source as long as the polymer does not hinder the object of the present invention. The unit of the monomer represented by the formula (A3) and constituent units other than the unit derived from the monomer represented by the formula (A5).

Examples of other constituent units are derived from, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, or n- (meth) acrylate Butyl ester, isobutyl (meth) acrylate, third butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, phenyl (meth) acrylate, N- Methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- N-butyl (meth) acrylic acid Amine, N-n-pentyl (meth) acrylamide, N-isoamyl (meth) acrylamide, N-phenyl (meth) acrylamide, N, N-dimethyl (methyl) Acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamine Amine, N, N-di-n-pentyl (meth) acrylamide, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene -A constituent unit of monomers such as methylstyrene and chlorostyrene.

(A) When the resin is a polymer of a monomer having an unsaturated bond, the molar ratio of the constituent units derived from the monomer represented by the formula (A2) in all the constituent units contained in the polymer is preferably 0.1 to 50 mol%, more preferably 1-20 mol%, particularly preferred is 1-15 mol%.

(A) When the resin is a polymer of a monomer having an unsaturated bond, the molar ratio of the constituent units derived from the monomer represented by formula (A3) or (A5) in all constituent units contained in the polymer is smaller than It is preferably 50 to 99.9 mole%, more preferably 60 to 99 mole%, and particularly preferably 70 to 99 mole%.

However, when the constituent unit derived from the monomer represented by the formula (A5) contains any one of a hydroxyl group, a cyano group, and a carboxyl group, the constituent derived from the monomer represented by the formula (A5) among all the constituent units contained in the polymer The ratio of units can be 100%.

In addition, a siloxane compound represented by the following formula (A6) is also preferable as the (A) resin: A ¹ -SiR ¹⁰ R ¹¹ -O-(-SiR ¹⁰ A ² -O-) _p -SiR ¹⁰ R ¹¹ A ³ ‧‧‧ (A6)

(In the formula (A6), R ¹⁰ and R ¹¹ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and A ¹ , A ² and A ³ are each independently a hydroxyl group, a cyano group, a carboxyl group, or a hydrocarbon group having 1 to 6 carbon atoms. , At least one of A ¹ , A ² and A ³ is a hydroxyl group, a cyano group or a carboxyl group, and p is an integer of 0 or more). The siloxane compound represented by the formula (A6) is quite a (A) resin having a silaneoxy group as a hydrophobic group.

In formula (A6), each of R ^{10 in} plural may be the same or different. Moreover, in formula (A6), R ¹¹ existing ^plurally may be the same or different.

Preferably, R ¹⁰ and R ¹¹ are independently methyl, ethyl or phenyl, and more preferably R ¹⁰ and R ¹¹ are both methyl.

When A ¹ , A ² and A ³ are hydrocarbon groups having 1 to 6 carbon atoms, it is preferred that A ¹ , A ² and A ³ are each independently methyl, ethyl or phenyl, and more preferably methyl.

The amount of the (A) resin contained in the treatment liquid is not particularly limited as long as it does not hinder the object of the present invention, and can be appropriately determined in consideration of the applicability of the treatment liquid and the like. Typically, the amount of the (A) resin in the treatment liquid is preferably an amount having the following relationship between the amount of the (A) resin in the treatment liquid and the amount of the (C) solvent described later.

When the mass of the resin in the treatment liquid is 100 parts by mass, the amount of the solvent (C) described later is preferably 100 to 100,000 parts by mass, more preferably 500 to 80,000 parts by mass, and particularly preferably 1,000 to 60,000 parts by mass.

[(B) Photoacid generator]

The treatment liquid contains (B) a photoacid generator. (B) The photoacid generator generates a strong acid with a pKa of 1 or less by the action of light. In addition, pKa is a value in water.

The strong acid produced by the (B) photoacid generator acts on the functional group I of the (A) resin to promote the adhesion or bonding of the (A) resin to the surface of the object to be treated.

(B) The type of the photoacid generator is not particularly limited as long as it is a compound that generates a strong acid with a pKa of 1 or less by the action of light. (B) A photoacid generator can be used in combination of 2 or more type.

Preferred examples of the strong acid generated by the (B) photoacid generator include fluorinated aliphatic carboxylic acids (e.g., trifluoroacetic acid, etc.), fluorosulfonic acids, and alkanesulfonic acids having 1 to 30 carbon atoms (e.g., methanesulfonic acid). Acid, dodecanesulfonic acid, etc.), arylsulfonic acids (e.g., benzenesulfonic acid, p-toluenesulfonic acid, etc.), fluoroalkanesulfonic acids having 1 to 30 carbon atoms (e.g., trifluoromethanesulfonic acid, pentafluoroethyl) Sulfonic acid, heptafluoropropane sulfonic acid, nonafluorobutane sulfonic acid, undecyl pentane sulfonic acid, and tridecafluorohexane sulfonic acid), bissulfinoimide compounds, and two sulfofluorenyl groups connected by fluoroalkylene Cyclic sulfonimide compounds and N-fluorenyl fluoransulfonium sulfonamide.

When the strong acids contain a fluoroalkyl group or a fluoroalkylene group, the groups may be a partially fluorinated fluoroalkyl group or a fluoroalkylene group, or a fully fluorinated perfluoroalkyl group or a perfluoroalkylene group.

Among these strong acids, fluorosulfonic acid, alkanesulfonic acid having 1 to 30 carbon atoms, fluoroalkanesulfonic acid having 1 to 30 carbon atoms, bis (fluoroalkylsulfonyl) fluorenimine, and 2 Cyclic sulfoimino acids and N-fluorenylfluoroalkanesulfonamides whose sulfofluorenyl groups are connected by a fluoroalkylene group, preferably fluoroalkanesulfonic acids and bissulfimidines having 1 to 30 carbon atoms Compound, cyclic sulfoimine compound in which two sulfofluorenyl groups are connected by a fluoroalkylene group, and fluorenamine N-fluorenylfluoroalkanesulfonate.

The fluoroalkanesulfonic acid having 1 to 30 carbon atoms is preferably trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorononanesulfonic acid, and the like.

The bissulfinoimide compound is preferably represented by the following formula (B1) Shown compounds.

In the formula (B1), X ¹ and X ² each independently represent a hydrocarbon group substituted with at least one electron-withdrawing group. The hydrocarbon group may be substituted with various groups other than the electron-withdrawing group within a range that does not impair the strong acidity of the compound represented by (B1). The carbon number of X ¹ and X ² is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 7.

The hydrocarbon group substituted with an electron-withdrawing group is preferably a fluorinated alkyl group or an aryl group having a nitro group. The fluorinated alkyl group may be linear, branched, or cyclic. The fluorinated alkyl group is preferably a fully fluorinated perfluoroalkyl group. As the aryl group having a nitro group, preferred are o-nitrophenyl, m-nitrophenyl and p-nitrophenyl, and more preferred is p-nitrophenyl.

Preferred specific examples of the compound represented by the formula (B1) include compounds of the following formula.

The cyclic sulfoimide compound in which the two sulfofluorenyl groups are connected by a fluoroalkylene group is preferably a compound represented by the following formula (B2).

In the formula (B2), X ³ represents a linear or branched alkylene group having at least one hydrogen atom substituted with a fluorine atom. The carbon number of X ³ is preferably 2 to 6, more preferably 3 to 5, and particularly preferably 3.

Preferred specific examples of the compound represented by the formula (B2) include compounds of the following formula.

As the N-fluorenylfluoroalkanesulfonamide, a compound represented by the following formula (B3) is preferred.

In the formula (B3), X ⁴ represents a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom. The carbon number of X ⁴ is preferably from 1 to 10, more preferably from 1 to 7, and particularly preferably from 1 to 3.

X ⁵ is a hydrocarbon group. The hydrocarbon group is the same as the hydrocarbon group constituting the main skeleton of the aforementioned R ⁵ group.

Preferred specific examples of the compound represented by the formula (B3) include compounds of the following formula.

The (B) photoacid generator is preferably a compound capable of generating the above-mentioned preferred strong acid.

The compound is preferably an onium salt compound composed of an anion derived from the strong acid and an onium ion. As an onium ion, a sulfonium ion and a sulfonium ion are more preferable, and a sulfonium ion is more preferable.

Preferred examples of onium ions are triphenylphosphonium, tri-p-tolylfluorene, 4- (phenylthio) phenyldiphenylphosphonium, and bis [4- (diphenylphosphonium) phenyl] sulfur. Ether, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] 鋶} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) 鋶] phenyl} sulfide 4-, 4- (4-benzylidene-2-chlorophenylthio) phenylbis (4-fluorophenyl) fluorene, 7-isopropyl-9-oxo-10-thia-9, 10- Dihydroanthracene-2-yldi-p-toluenehydrazone, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylphosphonium, 2-[(di Phenyl) fluorene] thioxanthone, 4- [4- (4-Third-butylbenzylidene) phenylthio] phenyldi-p-tolylfluorene, 4- (4-benzylidenebenzene) Thio) fluorene diphenylfluorene, diphenylbenzylmethylfluorene, 4-hydroxyphenylmethylbenzylfluorene, 2-naphthylmethyl (1-ethoxycarbonyl) ethylfluorene, 4-hydroxy Phenylmethyl benzamidinemethylfluorene, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylfluorene, phenyl [4- (4-biphenylthio) benzene Group] 3-biphenylfluorene, [4- (4-ethylfluorenylphenylthio) phenyl] diphenylfluorene, octadecylmethylbenzylmethylfluorene, diphenylfluorene, di- P-Tolylfluorene, bis (4-dodecylphenyl) fluorene, bis (4-methoxyphenyl) fluorene, (4-octyloxyphenyl) phenyl Fluorene, bis (4-decoxy) phenylfluorene, 4- (2-hydroxytetradecanyloxy) phenylphenylfluorene, 4-isopropylphenyl (p-tolyl) fluorene, or 4-iso Butylphenyl (p-tolyl) fluorene and the like.

Moreover, a sulfonium ion represented by the following formula (B4) is also preferable as the onium ion constituting the onium salt.

In the formula (B4), R ^b1 each independently represents a member selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an aryl group which may have a substituent, The group formed by a carbonyl group. X ^{6 has a} structure represented by the following formula (B5).

In the formula (B5), X ⁷ represents an alkylene group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms, and X ⁷ It can also be formed from alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, aryl groups having 6 to 10 carbon atoms, hydroxyl, cyano, nitro groups and halogen Group selected at least one substitution. X ⁸ represents -O-, -S-, -SO-, -SO _2- , -NH-, -NR ^b2- , -CO-, -COO-, -CONH-, butane with 1 to 3 carbon atoms Or phenylene. h represents the number of repeating units constructed in parentheses. The h + 1 X ⁶ and h X ⁷ may be the same or different. R ^b2 is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Specific examples of the phosphonium ion represented by the above formula (B4) are 4- (phenylthio) phenyldiphenylphosphonium, 4- (4-benzylmethyl-2-chlorophenylthio) phenylbis (4 -Fluorophenyl) fluorene, 4- (4-benzylidenephenylthio) phenyldiphenylfluorene, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylfluorene, Phenyl [4- (4-biphenylthio) phenyl] 3-biphenylphosphonium, [4- (4-Ethylphenylthio) phenyl] diphenylphosphonium, diphenyl [4- (P-bitriphenylthio) phenyl] diphenylphosphonium.

In addition, an onium salt formed from a cationic moiety having a naphthalene ring and an anion moiety derived from the strong acid is also preferably used as the (B) photoacid generator. The "having a naphthalene ring" means having a structure derived from naphthalene, and means maintaining a structure of at least two rings and an aromatic nature thereof. The naphthalene ring may have substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (one free atomic valence), or may be a divalent group or more (free atomic valence is two), but it is desired to be a monovalent group (but in this case, the substitution with the above) Except for the base bond, the free atomic valence is counted). The number of naphthalene rings is preferably 1 to 3.

The onium ion having a naphthalene ring is preferably an onium ion represented by the following formula (B6).

In the above formula (B6), at least one of R ^b3 , R ^b4 , and R ^b5 represents a group represented by the following formula (B7), and the rest are linear or branched alkyl groups having 1 to 6 carbon atoms. A phenyl group having a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, at least one of R ^b3 , R ^b4 , and R ^b5 may be a group represented by the following formula (B7), and the remaining two are each a linear or branched linear alkylene group having 1 to 6 carbon atoms. And the ends of these are bonded to form a ring.

In the above formula (B7), R ^b6 and R ^b7 each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms. Alkyl group, R ^b8 represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer from 0 to 2, and l + m is 3 or less. However, when R ^b6 is plural, these may be the same as or different from each other. When there is a plural number of R ^b7 , these may be the same as or different from each other.

The number of the bases represented by the above formula (B7) in the above R ^b3 , R ^b4 , and R ^b5 is preferably one from the viewpoint of the stability of the compound, and the rest are linear or 1 to 6 carbon atoms. The branched alkylene group may be bonded to form a ring. In this case, the above-mentioned two alkylene groups constitute a 3 to 9-membered ring containing a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 to 6.

In addition, examples of the substituent which the above-mentioned alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.

Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

Preferred examples of the cationic moiety include those represented by the following formula (B8) and (B9), and particularly preferred is a structure represented by the following formula (B9).

The content of the (B) photoacid generator in the processing liquid is not particularly limited as long as the surface treatment with the processing liquid can be performed satisfactorily. The content of the (B) photoacid generator in the treatment liquid is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin (A).

[(C) Solvent]

The solvent (C) is not particularly limited as long as it is a solvent capable of dissolving (A) the resin and (B) the photoacid generator. If the (A) resin and (B) photoacid generator are dissolved in the treatment solution in a specific amount, the treatment liquid may also contain (A) resin and (B) photoacid generator in an undissolved state. (A) The resin and (B) the photoacid generator are preferably completely dissolved in the treatment liquid.

When the treatment liquid contains insoluble matter, insoluble matter may be adhered to the surface of the object during surface treatment. In this case, the surface of the object to be treated may be cleaned by a method described later to remove insoluble matter adhering to the surface of the object to be treated.

(C) The solvent may be water, an organic solvent, or an aqueous solution of an organic solvent.

Specific examples of the organic solvent used as the (C) solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, isobutanol, third butanol, n-pentanol, and second C1-C5 alcohols such as pentanol, isoamyl alcohol, tertiary pentanol, etc .; fluorenes such as dimethyl fluorene, dimethyl fluorene, diethyl fluorene, bis (2-hydroxyethyl) fluorene , Tetramethylene hydrazone, etc .; N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N , N-diethylacetamide and other amines; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N- Limonamines such as hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, etc .; 1,3-dimethyl-2-imidazolidone, 1,3-diethyl- 2-imidazolidone, 1,3-diisopropyl-2-imidazolidone and other imidazolidinones; dimethyl glycol, dimethyl diethylene glycol, dimethyl triethylene glycol; methyl ethyl diethylene glycol, di Dioxane glycol ethers such as ethyl diethylene glycol, triethylene glycol butyl methyl ether; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether (Poly) alkanediol monoalkanes such as tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethyl ether (Poly) alkanediol monoalkyl ether acetates such as glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; dimethyl ether, diethyl ether, and methyl ethyl ether ,two Ethers, diisopropyl ether, dibutyl ether, diisopentyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl Ketones such as ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2- Ethyl methyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxy Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate Acetic acid Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, Isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, ethyl 2-oxobutanoate, etc. Other esters; β-butyrolactone, γ-butyrolactone, δ-valerolactone and other lactones; n-hexane, n-heptane, n-octane, n-nonane, methyloctane, n-decane , N-undecane, n-dodecane, 2,2,4,6,6-pentamethylheptane, 2,2,4,4,6,8,8-heptamethylnonane, cyclohexane Linear, branched chain or cyclic aliphatic hydrocarbons such as methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, and naphthalene; Terpenoids such as p-menthane, diphenylmenthane, limonene, terpinene, norbornane, norbornane, pinane, etc .; etc.

When (C) the solvent is a mixed solvent of water and an organic solvent, the content of the organic solvent in the (C) solvent is preferably 10% by mass or more, more preferably 20% by mass or more.

<Other ingredients>

The treatment liquid may contain various components other than (A) a resin, (B) a photoacid generator, and (C) a solvent within the scope of the present invention. Examples of the other components include a coloring agent, a surfactant, a defoaming agent, and a viscosity adjusting agent.

<Method for preparing treatment liquid>

The method for preparing the treatment liquid is not particularly limited. The treatment liquid is typically prepared by uniformly mixing individual specific amounts of (A) resin, (B) photoacid generator and (C) solvent, and other components as necessary.

<Coated film formation step>

The surface treatment liquid described above is applied to the surface of the object to be treated to form a coating film.

The method for applying the surface treatment liquid is not particularly limited. Specific examples of the coating method include a spin coating method, a spray method, a roll coating method, and a dipping method. When the object to be processed is a substrate, the surface of the substrate can be uniformly hydrophilicized or hydrophobized based on the uniform application of the surface treatment liquid, and a spin coating method is preferred as the coating method.

The material of the surface of the object to be coated with the surface treatment liquid is not particularly limited, and may be an organic material or an inorganic material.

Examples of organic materials include polyester resins such as PET resins and PBT resins, various nylons, polyimide resins, polyimide resins, polyolefins such as polyethylene and polypropylene, polystyrene, (methyl ) Various resin materials such as acrylic resin.

In addition, photosensitive resin components and alkali-soluble resin components contained in various resist materials are also preferable as organic materials.

Examples of the inorganic material include various metals such as glass, silicon, ketone, aluminum, iron, and tungsten. The metal may also be an alloy.

Material of the surface to be surface-treated with the aforementioned surface treatment liquid The quality of the surface treatment liquid is not particularly limited. When the material of the surface to which the surface treatment liquid is applied is an organic material, a surface treatment liquid containing a (A) resin having a hydroxyl group and / or a carboxyl group as the functional group I is preferably used.

When the material of the surface to which the surface treatment liquid is applied is an inorganic material, the functional group I included in the (A) resin is preferably any of a hydroxyl group, a carboxyl group, and a cyano group.

The shape of the object to be processed is not particularly limited. The object to be processed may be a flat substrate such as a spherical shape, and may be a three-dimensional shape such as a columnar shape. In addition, the surface of the object to be treated may be smooth or may have irregularities or irregularities.

After the surface treatment liquid is applied on the surface of the object to be treated, the coating film may be heated to remove at least a part of the solvent (C) as necessary.

<Exposure Step>

The coating film formed as described above is irradiated with ultraviolet rays or visible rays having a wavelength of 300 to 500 nm, for example. The exposure is performed on a site to be hydrophilized or hydrophobized.

When it is desired to highly hydrophilize or hydrophobize the entire portion where the coating film is formed, the entire coating film is exposed. When it is desired to make a part of the coating film forming part highly hydrophilized or hydrophobized, and the degree of hydrophilization or hydrophobization of the other parts is reduced, only the positions to be highly hydrophilized or hydrophobized are selectively exposed.

The method for positionally selective exposure is not particularly limited, but is usually performed through a photomask.

As the radiation source, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, and the like can be used. The radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, gamma rays, electron beams, positron beams, neutron beams, ion beams, and the like. The radiation exposure amount (exposure amount) is typically 100 to 10,000 mJ / cm ² when an ultrahigh-pressure mercury lamp is used, for example.

<Baking step>

Second, the exposed coated film is baked. The baking temperature is typically preferably 40 to 200 ° C, more preferably 60 to 150 ° C. The baking time is preferably 10 to 6000 seconds, and more preferably 10 to 300 seconds.

<Washing steps>

The baked coating film is cleaned.

As described above, when a surface treatment liquid containing (A) a resin having a specific functional group and (B) a photoacid generator is applied on the surface of the object to be treated and exposed, a strong acid generated from the (B) photoacid generator is used. This action allows the (A) resin to adhere or bond well to the surface of the object to be treated.

However, the surface of the object to be treated, especially the unexposed portion, also contains (A) resin which is not adhered or bonded to the surface in a certain amount.

Therefore, the (A) resin or the like that is not adhered or bonded to the surface is washed away by cleaning the coating film.

As a result, a thin film having a thickness of 10 nm or less is formed on the exposed portion of the surface of the object by cleaning.

The film thickness can be measured using a spectroscopic ellipsometry.

When the surface treatment liquid containing the (A) resin having a hydrophilic group as the functional group II is used, washing with water is preferred. When a surface treatment liquid containing a (A) resin having a hydrophobic group as the functional group II is used, it is preferred that the surface treatment liquid be washed with an organic solvent. The organic solvent is preferably an organic solvent contained as the (C) solvent in the surface treatment liquid.

After cleaning, the surface of the object to be treated is dried to obtain a good hydrophilized or hydrophobized article.

Various articles surface-treated by the method described above can be highly hydrophilized or hydrophobized only in necessary parts, and on the other hand, the degree of hydrophilization or hydrophobization in other parts can be reduced. As the article to be subjected to the surface treatment, for example, a cell culture device, a micro-flow path device for circulating a liquid including a biological sample including cells, and the like are preferable. Through surface treatment, various articles are provided with antifouling properties and antifogging properties.

[Example]

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited by these examples.

[Examples 1 to 10 and Comparative Examples 1 to 4]

In each of Examples and Comparative Examples, the resin described in Table 1 was used as the (A) resin.

The constituent units A-1a to A-6a described in Table 1 are constituent units that impart a hydrophilic group or a hydrophobic group to the (A) resin. In the formula of A-6a, n is the unit repeat number in parentheses.

The constituent units A-1b to A-3b described in Table 1 are constituent units that impart a hydroxyl group, a cyano group, or a carboxyl group to the (A) resin.

The constituent units A-1c to A-2c described in Table 1 are constituent units that do not have any of a hydrophilic group, a hydrophobic group, a hydroxyl group, a cyano group, and a carboxyl group.

Compounds 1 to 4 described in Table 1 are organosiloxane compounds having the following structures, respectively. In the formulas for compounds 1 to 4, n, n1, and n2 are unit repeat numbers in parentheses, respectively.

Among the following siloxane compounds, the hydroxyl amount of Compound 1 is 58 mgKOH / mol, the carboxyl amount of Compound 3 is 4000 g / mol, and the hydrogen atom amount of Compound 4 directly bonded to the silicon atom is 60 g / mol.

In Examples and Comparative Examples, the following photoacid generators B1 to B3 were used. B1 and B2 are photoacid generators that generate strong acids with a pKa of 1 or less, and B3 are photoacid generators that generate acids with a pKa of more than 1.

10 parts by mass of (A) resin of the kind described in Table 1 and (B) photoacid generator of the kind and amount described in Table 2 were uniformly mixed in the (C) solvent of the kind and amount described in Table 2 to obtain each implementation. Examples and Comparative Examples.

In Table 2, PGME is propylene glycol monomethyl ether, and PGMEA is propylene glycol monomethyl ether acetate.

The obtained surface treatment liquid was spin-coated on a glass substrate at 1000 rpm for 30 seconds, and then dried at 100 ° C for 60 seconds to obtain a coating film.

The obtained coating film was exposed through a mask using HMW-532D (manufactured by ORC) at an exposure amount of 1000 mJ / cm ² .

After the exposed coating film was baked at 100 ° C. for 60 seconds, it was washed to obtain a surface-treated glass substrate.

Examples 1 to 3, Example 7, Comparative Examples 1 and 4 using hydrophilic resins were washed with water. Other examples and comparative examples were cleaned with PGMEA.

After the cleaned glass substrate is dried, the water contact angle of the glass substrate is measured for the exposed portion and the unexposed portion, respectively. The measurement of the water contact angle was performed using Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) by dropping pure water droplets (2.0 μL) on the surface of the surface-treated substrate, and measuring the contact angle after dropping for 10 seconds. The measurement results of the water contact angle are shown in Table 2.

In addition, with respect to the dried substrate, the exposed portion was confirmed with a spectroscopic ellipsometer, and the presence of a thin film with a thickness of 10 nm or less was observed in the examples, and the thin film was not observed in the comparative examples.

According to the examples, it can be seen that a functional group II (A having a functional group I having one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group and a hydrophilic group or a hydrophobic group other than the functional group I is used. ) For resins and surface treatment liquids that generate (B) photoacid generators with a strong acid with a pKa of 1 or less, the coating film formed from the surface treatment liquid is exposed, followed by baking and Cleaning can make only the exposed part of the substrate well hydrophilic or hydrophobic.

According to Comparative Examples 1 to 3, when (A) the resin does not contain any of hydroxyl, cyano, and carboxyl groups, even if the surface treatment liquid contains (B) a photoacid generator that generates a strong acid with a pKa of 1 or less, The exposed part is well hydrophilized or hydrophobized.

From Comparative Example 4, it can be seen that even if (A) the resin has a functional group I of a carboxyl group and a functional group II of a hydrophilic group, when the (B) photoacid generator which generates an acid having a pKa of more than 1, the exposed portion cannot be made good. It is hydrophilized or hydrophobized.

[Examples 11 to 15]

In Example 11, a surface treatment liquid obtained by uniformly mixing 10 parts by mass of (A) resin with 0.1 parts by mass of (B) photoacid generator and 1,000 parts by mass of PGMEA was used.

The resin contained in the surface treatment liquid of Example 11 is a resin containing the above-mentioned A-4a unit and A-2b unit at a molar ratio of 95: 5 (A-4a: A-2b).

The (B) photoacid generator contained in the surface treatment liquid of Example 11 is the aforementioned B2 compound.

The contact angle of water after the surface treatment was measured in the same manner as in Example 1, except that the surface treatment liquids of the types described in Table 3 were used, and the substrate type was changed to the type described in Table 3, and the coating film was fully exposed. . The measurement results are shown in Table 1. In addition, the water contact angle of the PET film and silicon wafer in the unprocessed state is about 70 ° for the PET film and about 10 ° for the silicon wafer.

According to Example 11, it can be seen that when the resin (A) contained in the surface treatment liquid has a cyano group as the functional group I, the surface of the substrate made of an inorganic material (silicon) is well hydrophobicized.

According to Examples 12 to 15, when the resin (A) contained in the surface treatment liquid has a hydroxyl group or a carboxyl group as the functional group I, the substrate surface made of an inorganic material (silicon) and the organic material (PET) The substrate surface is well hydrophobicized.

Claims (11)

A surface treatment method is a surface treatment method using a photosensitive surface treatment liquid, and includes the steps of applying the photosensitive surface treatment liquid on a surface of a treatment object to form a coating film, and at least the coating film is Partial exposure, baking the exposed coating film, and cleaning the baked coating film, and forming a thin film with a film thickness of 10 nm or less on the exposed portion of the surface of the object to be processed. The surface treatment liquid contains (A) a resin, (B) a photoacid generator, and (C) a solvent. The (A) resin has a functional group I of one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. And a functional group II of a hydrophilic group or a hydrophobic group other than the functional group I, the (B) photoacid generator generates a strong acid with a pKa of 1 or less. The surface treatment method according to claim 1, wherein the exposure of the aforementioned coating film is selectively performed through the position of the photomask. The surface treatment method of claim 1 or 2, wherein the aforementioned hydrophilic group of the aforementioned functional group II is a group represented by the following formula (A1): -NH-R ¹ ‧‧‧ (A1) (in the formula (A1), R ¹ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amine group, a sulfonic acid group, and a hydroxyl group; The surface treatment method according to claim 1 or 2, wherein the aforementioned functional group I is derived from a monomer represented by the following formula (A2) or the following formula (A2-1): CH ₂ = CR ^2- (R ³ ) _a -CO-R ⁴ ‧‧‧ (A2) (In the formula (A2), R ² is a hydrogen atom or a methyl group, R ³ is a divalent hydrocarbon group, a is 0 or 1, and R ⁴ is -OH, -OR ⁵ Or -NH-R ⁵ , R ⁵ is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of hydroxyl, cyano, and carboxyl groups), CH ₂ = CR ^2- (R ³ ) _a -SO ₃ X‧‧‧ (A2-1) (In the formula (A2-1), R ² , R ³ and a are the same as the formula (A2), and X is a hydrogen atom or an alkali metal). The surface treatment method according to claim 1 or 2, wherein the hydrophobic group of the functional group II is one or more groups selected from the group consisting of a fluorinated hydrocarbon group, a silane group, and a siloxane group. The surface treatment method according to claim 1 or 2, wherein the aforementioned functional group II is a hydrophobic group and is derived from a monomer represented by the following formula (A3): CH ₂ = CR ^2- (CO-O) _b -R ⁶ ‧ ‧ (A3) (In the formula (A3), R ² is a hydrogen atom or a methyl group, b is 0 or 1, R ⁶ is a fluorinated hydrocarbon group or a group represented by the following formula (A4): -SiR ⁷ R ^8- ( -O-SiR ⁷ R ^8- ) _n -R ⁹ ‧‧‧ (A4) R ⁷ , R ⁸ and R ⁹ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 or more). The surface treatment method of claim 1 or 2, wherein the aforementioned functional group II is a hydrophilic group and is derived from a monomer represented by the following formula (A5): CH ₂ = CR ² -CO-NH-R ¹ ‧‧‧ ( A5) (In the formula (A5), R ¹ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amine group, a sulfonic acid group, and a hydroxyl group; R ² is a hydrogen atom or a methyl group). The surface treatment method according to claim 5, wherein the hydrophobic group is the aforementioned siloxane group, and the aforementioned (A) resin is a siloxane compound represented by the following formula (A6): A ¹ -SiR ¹⁰ R ¹¹ -O -(-SiR ¹⁰ A ² -O-) _p -SiR ¹⁰ R ¹¹ A ³ ‧‧‧ (A6) (in formula (A6), R ¹⁰ and R ¹¹ are each independently a hydrocarbon group having 1 to 6 carbon atoms, A ¹ , A ² and A ³ are each independently a hydroxyl group, a cyano group, a carboxyl group or a hydrocarbon group having 1 to 6 carbon atoms; at least one of A ¹ , A ² and A ³ is a hydroxyl group, a cyano group or a carboxyl group; Integer). The surface treatment method according to claim 1 or 2, wherein a material of the surface on which the surface treatment liquid is applied is an organic material, and the resin (A) has a hydroxyl group and / or a carboxyl group as the functional group I. A photosensitive surface treatment liquid, such as the surface of claim 1 or 2 The photosensitive surface treatment liquid used in the treatment method contains (A) a resin, (B) a photoacid generator, and (C) a solvent. The (A) resin has a group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. The functional group I of one or more groups, and the functional group II of a hydrophilic group or a hydrophobic group other than the functional group I, the (B) photoacid generator generates a strong acid with a pKa of 1 or less. A photosensitive surface treatment liquid comprising (A) a resin, (B) a photoacid generator, and (C) a solvent, wherein the (A) resin has at least one selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group; The functional group I of the group I, and the functional group II of a hydrophilic group or a hydrophobic group other than the functional group I, the (B) photoacid generator generates a strong acid having a pKa of 1 or less.