KR20180129803A - A surface treatment method, and a surface treatment liquid - Google Patents

Abstract

A surface treatment method capable of forming a region having a high surface treatment effect on the object to be treated and a region having a low surface treatment effect can be performed with good hydrophilization or hydrophobicity of the surface of the object to be treated, To provide a surface treatment solution to be used.
A surface treatment method for forming a thin film having a surface modifying function with a film thickness of 10 nm or less by rinsing a coating film comprising a photosensitive surface treatment liquid subjected to exposure and baking, (A) a resin, (B) a photoacid generator, and (C) a solvent, wherein the resin (A) comprises at least one functional group I selected from the group consisting of hydroxyl group, cyano group and carboxyl group, A compound having a functional group II which is a hydrophilic group or a hydrophobic group is used and (B) a photoacid generator is used which generates a strong acid having a pKa of 1 or less by the action of light.

Description

A surface treatment method, and a surface treatment liquid

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

BACKGROUND ART Conventionally, various surface treatment liquids have been used to modify the properties of various articles. Among the surface modification, there are many proposals for a surface treatment method in which the hydrophilization or hydrophobicity of the surface of the article is large, hydrophilization or hydrophobization, or a surface treatment solution used in the method.

With respect to such a surface treatment method, for example, by using a surface conditioner containing a copolymer of at least an acrylamide monomer and a siloxy group-containing mono (meth) acrylate monomer having a specific skeleton and having a weight average molecular weight of 1,500 to 50,000 , And a method of imparting hydrophilicity and antifouling property to the surface of the film has been proposed (Patent Document 1).

Japanese Patent No. 5437523

However, when the hydrophilic treatment is carried out using the surface conditioner described in Patent Document 1, even if the surface of the subject is treated with a solution containing only the surface conditioner, the surface conditioner hardly adheres to the surface of the subject, It is difficult to obtain a hydrophilic effect.

Therefore, in the method described in Patent Document 1, a solution prepared by blending 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 film forming component into a solution of a surface- Solution.

In the case of using the surface conditioner described in Patent Document 1 and a surface treatment liquid containing a film forming component, since the surface of the object to be treated is covered with a film containing resin, even if good hydrophilization is possible, The useful surface properties possessed by the Lychee are impaired.

Depending on the application of the surface-treated material, it may be necessary to make a difference in the effect of the surface treatment at the point where the surface treatment is to be performed and at the point where the surface treatment is not performed. Ideally, the surface-treated point and the non-surface-treated point are preferably finely patterned.

However, in the method of using the surface modifier used in the method described in Patent Document 1, the difference in the effect of the surface treatment for each site is not particularly limited as long as the surface treatment agent is finely and precisely separated and applied to the surface treated surface It is also difficult to form a point. As a result, in the method described in Patent Document 1, it is difficult to make a difference in the effect of the surface treatment at the point where the surface treatment should be performed and at the point where the surface treatment should not be performed.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide an image forming apparatus capable of satisfactorily hydrophilizing or hydrophobizing the surface of an object to be processed, , A surface treatment method capable of forming a region having a low surface treatment effect, and a surface treatment liquid suitably used in the surface treatment method.

The present inventors have found that in a surface treatment method for forming a thin film having a surface modifying function with a film thickness of 10 nm or less by rinsing a coating film comprising a photosensitive surface treatment liquid subjected to exposure and baking, (A) a resin, (B) a photoacid generator, and (C) a solvent, wherein the resin (A) contains at least one functional group I and at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, , A resin having a functional group II which is a hydrophilic group other than the functional group I or a hydrophobic group, and (B) a compound which generates a strong acid having a pKa of 1 or less by the action of light as the photoacid generator (B) The present invention has been accomplished on the basis of these findings. Specifically, the present invention provides the following.

A first aspect of the present invention is a surface treatment method using a photosensitive surface treatment liquid,

Applying a photosensitive surface treatment liquid to the surface of the object to be processed to form a coating film,

Exposing at least a part of the coating film,

Baking the exposed coating film,

Rinsing the baked coating film to form a thin film having a film thickness of 10 nm or less at the exposed spot on the surface of the object to be processed,

Wherein the photosensitive surface treatment liquid comprises (A) a resin, (B) a photoacid generator, and (C) a solvent,

Wherein the resin (A) has at least one functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,

(B) a photoacid generator generates a strong acid having a pKa of 1 or less.

A second aspect of the present invention is the photosensitive surface treatment liquid used in the surface treatment method according to the first aspect,

(A) a resin, (B) a photoacid generator, and (C) a solvent,

Wherein the resin (A) has at least one functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,

(B) a photoacid generator, which generates a strong acid having a pKa of 1 or less.

A third aspect of the present invention is a process for producing a photoresist composition comprising (A) a resin, (B) a photoacid generator, and (C)

Wherein the resin (A) has at least one functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,

(B) a photoacid generator, which generates a strong acid having a pKa of 1 or less.

According to the present invention, even when a film-forming resin is not contained, good hydrophilization or hydrophobicity of the surface of the object can be performed, and a region having a high surface treatment effect and a region having a low surface treatment effect .

«Surface treatment method»

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

In the surface treatment method,

Applying a photosensitive surface treatment liquid to the surface of the object to be processed to form a coating film,

Exposing at least a part of the coating film,

Baking the exposed coating film,

And rinsing the baked coating film to form a thin film having a film thickness of 10 nm or less at the exposed spot on the surface of the object to be processed.

The photosensitive surface treatment liquid (hereinafter also referred to as "treatment liquid") includes a resin (A), a photo acid generator (B), and a solvent (C)

Wherein the resin (A) has at least one functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,

(B) a photoacid generator generates a strong acid having a pKa of 1 or less.

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

≪ Photosensitive surface treatment liquid >

Hereinafter, essential or optional components included in the photosensitive surface treatment liquid will be described.

[(A) Resin]

The resin (A) has a functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. (A) the resin is bonded or adhered to the surface of the object to be treated, because the reactivity or interaction between the functional group I and the surface of the non-treating agent is increased by a strong acid of pKa 1 or less generated by the photoacid generator (B)

The resin (A) has a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I. The hydrophilic treatment can be carried out using a treatment liquid containing a resin (A) having a hydrophilic group, and a hydrophobic treatment can be performed using a treatment liquid containing a resin (A) having a hydrophobic group.

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

The type of the resin (A) is not particularly limited as long as the resin (A) has a predetermined functional group and is soluble in the solvent (C). Examples of the resin (A) include (meth) acrylic resin, novolac resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin and silicone resin. Among these resins, a (meth) acrylic resin is preferable because it is easy to introduce a functional group and adjust the content ratio of a unit having a functional group.

Specific examples of the hydrophilic group include a polyoxyalkylene group (e.g., a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are blocked or randomly bonded), an amino group, a carboxyl group, a hydroxyl group, And the like. Also, these groups are preferable as the organic group-containing 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. As the cation, a metal ion is preferable, an alkali metal ion is more preferable, and a sodium ion or a potassium ion is particularly preferable.

When the resin (A) 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 hydroxyl group, cyano group or carboxyl group contained in the hydrophilic group or the hydrophobic group also serves as the functional group I.

Therefore, when the resin (A) 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 resin (A) may not have the functional group I.

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

From the viewpoint of excellent hydrophilization effect of the treatment liquid, the hydrophilic group is preferably a hydrophilic 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 at least one group selected from the group consisting of an amino group, a sulfonic acid group and a hydroxyl group.)

Is preferable.

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

[Chemical Formula 1]

(2)

(3)

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

[Chemical Formula 4]

Of the specific examples of R ^{1 in} the hydrophilic group represented by the formula (A1), particularly preferred groups include the following groups.

[Chemical Formula 5]

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

As the fluorinated hydrocarbon group, a group described later with respect to the formula (A3) is preferable.

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

The siloxane group may be linear or branched. The siloxane group may have a monovalent group or a multivalent group with a valence of 2 or more. For this reason, 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 represented by the formula (A4) described later and n is 1 or more.

The resin (A) is preferably a polymer of a monomer having an unsaturated bond, since it is easy to introduce various functional groups and the amount of functional groups can be easily adjusted. Such a polymer may be a homopolymer or a copolymer.

In this case, the functional group (I) of the resin (A)

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 at least one functional group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group.

Or the following formula (A2-1):

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 in the formula (A2), and X is a hydrogen atom or an alkali metal.)

Is a group derived from a monomer represented by the formula

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 within the range not hindering the object of the present invention. The number of carbon atoms of the divalent hydrocarbon group as R ³ is preferably from 1 to 20, more preferably from 1 to 12, particularly preferably from 1 to 10, from the standpoint that the resin (A) 1 to 6 is most preferable.

The divalent hydrocarbon group as R ^{3 may be} an aliphatic group, an aromatic group, or a hydrocarbon group including 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. The structure of the aliphatic group may be a linear chain, branched chain, cyclic, or a combination of these structures.

Specific preferred examples of R ³ include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, N-butane-1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n- n-nonane-1,9-diyl group, n-decane-1,10-diyl group, o-phenylene group, m-phenylene group, p-phenylene group, naphthalene Diyl group, a naphthalene-2,7-diyl group, a naphthalene-1,4-diyl group, and a biphenyl-4,4'-diyl group.

R ⁴ is -OH, -OR ⁵ , or -NH-R ⁵ , and R ⁵ is a hydrocarbon group substituted with at least one functional group 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 group of R < ⁵ > 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.

Preferred examples of the linear or branched aliphatic group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like can be given .

Preferable examples of the cyclic aliphatic group include a cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, a cycloalkyl group such as adamantane, norbornane, isobor A group in which one hydrogen atom has been removed from a polycycloalkane such as tricyclodecane and tetracyclododecane, or a group in which one hydrogen atom has been removed from a C1-C4 alkyl substituent of the polycycloalkane.

Preferable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a biphenyl group. 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 units derived from the monomer represented by the formula (A2) include the following units a2-1 to a2-9. Among the units of the following a2-1 to a2-9, units of a2-1 to a2-4 are more preferable.

[Chemical Formula 6]

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

When the resin (A) has a hydrophobic group as the functional group II, the functional group II is represented by the following formula (A3):

CH ₂ = CR ² - (CO-O) _b -R ⁶ (A 3)

(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,

-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 of 1 to 6 carbon atoms, and n is an integer of 0 or more.

Is preferably derived from a monomer represented by the following general formula (1).

In the 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 R ⁵ group described above. The fluorinated hydrocarbon group may be a group in which all the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms.

Concrete examples of the fluorinated hydrocarbon group as R ⁶ _{is, -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 ; A fluorinated aromatic hydrocarbon group such as a pentafluorophenyl group, an o-trifluoromethylphenyl group, an m-trifluoromethylphenyl group and a p-trifluoromethylphenyl group; And a fluorinated alicyclic group such as octafluoroadamantyl group.

When R ⁶ is a group represented by the formula (A4), R ⁷ , R ⁸ , and R ⁹ are each independently preferably a methyl group, an ethyl group, or a phenyl group, and R ⁷ , R ⁸ , And R < ⁹ > are all methyl groups.

In the formula (A4), the upper limit of n is not particularly limited within the range not hindering the object of the present invention. n is preferably an integer of 0 or more and 35 or less, and more preferably an integer of 0 or more and 10 or less.

Particularly preferred specific examples of the unit having a hydrophobic group derived from the monomer represented by the formula (A3) include units represented by the following a3-1 to a3-24. Among the following units, units of a3-8, a3-12, a3-18, a3-19, and a3-22 are more preferable.

(7)

When the resin (A) has a hydrophilic group as the functional group II, the functional group II is 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 at least one group selected from the group consisting of an amino group, a sulfonic acid group and a hydroxyl group, and R ² is a hydrogen atom or a methyl group to be.)

Is preferably derived from a monomer represented by the following general formula (1).

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

Particularly preferred specific examples of the unit having a hydrophilic group derived from the monomer represented by the formula (A5) include units represented by the following a5-1 to a5-5. Among the units shown below, units represented by a5-1 to a5-4 are more preferable.

[Chemical Formula 8]

When the resin (A) is a polymer of a monomer having an unsaturated bond, such a polymer may contain a unit derived from the monomer represented by the above-mentioned formula (A2) and a monomer derived from the monomer represented by the formula (A3) within the range not hindering the object of the present invention A monomer-derived unit, and other structural units other than the monomer-derived units represented by formula (A5).

Examples of other structural units include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (Meth) acrylate, isobutyl, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl Amide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nn- (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di (Meth) acrylamide, styrene,? -Methylstyrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, p- Methyl styrene, There may be mentioned a structural unit derived from a styrene monomer such as chlorobenzene.

When the (A) resin is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural unit derived from the monomer represented by the formula (A2) in the total structural units contained in such a polymer is preferably from 0.1 to 50 mol% More preferably 1 to 20 mol%, and particularly preferably 1 to 15 mol%.

When the (A) resin is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural unit derived from the monomer represented by the formula (A3) or (A5) in the total structural units contained in such a polymer is preferably 50 to 99.9 mol% , More preferably 60 to 99 mol%, and particularly preferably 70 to 99 mol%.

When the constitutional 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 unit derived from the monomer represented by the formula (A5) May be 100%.

In 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 the formula (A6), R ¹⁰ and R ¹¹ are each independently a hydrocarbon group of 1 to 6 carbon atoms, and A ¹ , A ² and A ³ are each independently a hydroxyl group, a cyano group, 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.

Is also preferable as the resin (A). The siloxane compound represented by the formula (A6) corresponds to the resin (A) having a siloxane group as a hydrophobic group.

In the formula (A6), a plurality of R < ¹⁰ > each present may be the same or different. In the formula (A6), plural R < ¹¹ > s present may be the same or different.

It is preferable that R ¹⁰ and R ¹¹ are each independently a methyl group, an ethyl group, or a phenyl group, and it is more preferable that R ¹⁰ and R ¹¹ are all methyl groups.

When A ¹ , A ² , and A ³ are hydrocarbon groups having 1 to 6 carbon atoms, A ¹ , A ² , and A ³ are each preferably independently a methyl group, an ethyl group, or a phenyl group, Is more preferable.

The amount of the resin (A) contained in the treatment liquid is not particularly limited within a range that does not impair the object of the present invention, and is appropriately determined in consideration of the coating property of the treatment liquid and the like. Typically, the amount of the resin (A) in the treatment liquid is preferably such that the relationship between the amount of the resin (A) in the treatment liquid and the amount of the solvent (C) described below is as follows.

When the mass of the resin in the treatment liquid is 100 parts by mass, the amount of the solvent (C) to be described later is preferably 100 to 100000 parts by mass, more preferably 500 to 80000 parts by mass, particularly preferably 1000 to 60000 parts by mass Do.

[(B) Photo acid generator]

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

The strong acid generated by the photoacid generator (B) acts on the functional group (I) of the resin (A), thereby accelerating the attachment or binding of the resin (A) to the surface of the object.

The type of the photoacid generator (B) is not particularly limited as long as it is a compound which generates a strong acid having a pKa of 1 or less by the action of light. The photoacid generator (B) may be used in combination of two or more.

(For example, trifluoroacetic acid), fluorosulfonic acid, an alkanesulfonic acid having 1 to 30 carbon atoms (e.g., methanesulfonic acid, methanesulfonic acid, methanesulfonic acid, etc.) (E.g., benzenesulfonic acid, p-toluenesulfonic acid, etc.), fluoroalkanesulfonic acid having 1 to 30 carbon atoms (e.g., trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptadecanesulfonic acid, Nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, and tridecafluorohexanesulfonic acid), bissulfonylimide compounds, cyclic sulfonylimides in which two sulfonyl groups are linked by a fluoroalkylene group Compounds, and N-acylfluoroalkanesulfonic acid amide.

When these strong acids include a fluoroalkyl group or a fluoroalkylene group, they may be a partially fluorinated fluoroalkyl group, or a perfluoroalkyl group which may be fluoroalkylene-substituted, a fully fluorinated perfluoroalkyl group, or a perfluoroalkyl It also contributes to Len.

Among these strong acids, fluorosulfonic acid, an alkanesulfonic acid having 1 to 30 carbon atoms, a fluoroalkanesulfonic acid having 1 to 30 carbon atoms, bis (fluoroalkylsulfonyl) imidic acid, and two sulfonyl groups are fluoroalkyl Cyclic sulfone imidic acid and N-acylfluoroalkanesulfonic acid amide linked with each other are preferable, and fluoroalkanesulfonic acid having 1 to 30 carbon atoms, bissulfonylimide compound, two sulfonyl groups, fluoroalkyl Cyclic sulfonylimide compounds linked by a linker, and N-acylfluoroalkanesulfonic acid amide are preferable.

As the fluoroalkanesulfonic acid having 1 to 30 carbon atoms, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid and the like are preferable.

As the bis-sulfonylimide compound, a compound represented by the following formula (B1) is preferable.

[Chemical Formula 9]

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 the range in which the strong acidity of the compound represented by the formula (B1) is not inhibited. The number of carbon atoms of X ¹ and X ² is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 7.

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

Specific preferred examples of the compound represented by the formula (B1) include the following compounds.

[Chemical formula 10]

The cyclic sulfonylimide compound in which two sulfonyl groups are linked by a fluoroalkylene group is preferably a compound represented by the following formula (B2).

(11)

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

Specific preferred examples of the compound represented by the formula (B2) include the following compounds.

[Chemical Formula 12]

As the N-acylfluoroalkanesulfonic acid amide, a compound represented by the following formula (B3) is preferable.

[Chemical Formula 13]

In the formula (B3), X ⁴ represents a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The number of carbon atoms in 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. Is the same as the hydrocarbon group constituting the main skeleton of the aforementioned R ⁵ group with respect to the hydrocarbon group.

Specific preferred examples of the compound represented by the formula (B3) include the following compounds.

[Chemical Formula 14]

As the (B) photoacid generator, a compound capable of generating the above-described preferable strong acid is preferable.

As such a compound, an anion derived from the strong acid and an onium salt compound comprising an onium ion are preferable. As the onium ion, an iodonium ion and a sulfonium ion are preferable, and a sulfonium ion is more preferable.

Preferable examples of the onium ion include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) (4-fluorophenyl) sulfonium] phenyl} sulfide, 4- (4-hydroxyphenyl) (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene- 2-yldiphenylsulfonium, 2 - [(diphenyl) sulfonio] thioxanthone, 4- [ 4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4- benzoylphenylthio) phenyldiphenylsulfonium, diphenylphenazylsulfonium, 4- Sulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenazylsulfonium, phenyl [4- (4-acetophenylthio) phenyl] diphenylsulfonium, octadecylsulfonium, phenyl [4- (4-ethylphenylthio) phenyl] (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, iodonium iodonium, Phenyl iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, or 4-isobutylphenyl p-tolyl) iodonium, and the like.

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

[Chemical Formula 15]

In the formula (B4), each R ^b1 is independently a hydrogen atom, an alkyl, a hydroxy, an alkoxy, an alkylcarbonyl, an alkylcarbonyloxy, an alkyloxycarbonyl, a halogen atom, an aryl which may have a substituent, ≪ / RTI > X ⁶ is a structure represented by the following formula (B5).

[Chemical Formula 16]

In the formula (B5), X ⁷ represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms, and X ⁷ is At least one member selected from the group consisting of alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms, aryl of 6 to 10 carbon atoms, each group of hydroxy, cyano and nitro, Or may be substituted. X ⁸ represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^b2- , -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms , Or a phenylene group. h represents the number of repeating units in the structure in parentheses. h + 1 X ⁶ and h X ⁷ may be the same or different. R ^b2 is an alkyl group of 1 to 5 carbon atoms or an aryl group of 6 to 10 carbon atoms.

Specific examples of the sulfonium ion represented by the formula (B4) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) Phenyl [4- (4-biphenylythio) phenyl] phenylsulfonium, phenyl [4- ] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium, diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium.

It is also preferable as the onium salt (B) photoacid generator comprising a cation unit having a naphthalene ring and an anion derived from the strong acid. The term "having a naphthalene ring" means having a structure derived from naphthalene and means that the structure of at least two rings and the aromaticity thereof are maintained. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be monovalent (having one free valence) or two valences (having two free valences), but preferably has a valence of 1, provided that the moiety bonded to the substituent is excluded And the valence of the free valences 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).

[Chemical Formula 17]

At least one of R ^b3 , R ^b4 and R ^b5 in the formula (B6) represents a group represented by the following formula (B7), and the remainder is 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. Or one of R ^b3 , R ^b4 and R ^b5 is a group represented by the following formula (B7), and the remaining two are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, And the ends may be bonded to form a ring.

[Chemical Formula 18]

In the 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 And R ^b8 represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent. l and m each independently represent an integer of 0 to 2, and 1 + m is 3 or less. However, when a plurality of R ^b6 exist, they may be the same or different. When a plurality of R ^b7 exist, they may be the same or different.

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

Examples of the substituent which the alkylene group may have include an oxygen atom (in this case, forms a carbonyl group together with a carbon atom constituting the alkylene group), and a hydroxyl group.

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, and a linear or branched alkyl group having 1 to 6 carbon atoms .

Preferable examples of the cation portion include those represented by the following formulas (B8) and (B9), and in particular, a structure represented by the following formula (B9) is preferable.

[Chemical Formula 19]

The content of the photoacid generator (B) in the treatment liquid is not particularly limited as long as it can satisfactorily perform the surface treatment with the treatment liquid. The content of the photoacid generator (B) 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, relative 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 in which the resin (A) and the photoacid generator (B) are soluble. When the resin (A) and the photoacid generator (B) are dissolved in a predetermined amount in the treatment liquid, the treatment liquid may contain the resin (A) in an undissolved state and the photoacid generator (B) . The resin (A) and the photoacid generator (B) are preferably completely dissolved in the treatment liquid.

When the treatment liquid contains an insoluble matter, insoluble matter may adhere to the surface of the subject in the surface treatment. In this case, the surface of the subject to be surface-treated can be rinsed by a method as described later to remove the insoluble matter adhering to the surface of the subject.

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

Specific examples of the organic solvent used as the solvent (C)

Examples of C1 include C1 to C20 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentyl alcohol, sec-pentyl alcohol, -C5 alkanol;

Sulfoxides such as dimethyl sulfoxide;

Sulfone such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, tetramethylene sulfone and the like;

Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide and N, N-diethylacetamide;

Pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxy-ethyl-2- Lactams such as pyrrolidone;

Imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone and 1,3-diisopropyl-2-imidazolidinone;

Dialkyl glycol ethers such as dimethyl glycol, dimethyl diglycol, dimethyltriglycol, methylethyl diglycol, diethyl glycol and 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- -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- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

(Poly) alkylene ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Glycol monoalkyl ether acetates;

Examples of the solvent include dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetra Other ethers such as hydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethoxyacetonate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, Propyl acetate, n-propyl butyrate, n-butyl butyrate, n-butyl , Other esters such as methyl pyruvate, ethyl pyruvate, pyruvic acid-n-propyl, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

lactones such as? -propiolactone,? -butyrolactone and? -pentyrolactone;

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-heptamethyl nonane, cyclohexane, methylcyclohexane and the like; aliphatic hydrocarbons such as cyclohexane, cyclohexane and cyclohexane;

Aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene and naphthalene;

terpenes such as p-menthane, diphenylmethane, limonene, terpinene, borane, norbornane, and pinane; And the like.

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

<Other ingredients>

The treatment liquid may contain various components other than the resin (A), the photoacid generator (B), and the solvent (C) within the range not hindering the object of the present invention. Examples of other components include a colorant, a surfactant, a defoaming agent, and a viscosity adjusting agent.

&Lt; Process for Preparing Treatment Liquid &gt;

The method of preparing the treatment liquid is not particularly limited. The treatment liquid is typically prepared by uniformly mixing a predetermined amount of the resin (A), the photoacid generator (B), the solvent (C), and other components as required.

&Lt; Coating film forming step &

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

The method of applying the surface treatment liquid is not particularly limited. Specific examples of the application method include a spin coat method, a spray method, a roller coat method and a dipping method. In the case where the object to be treated is a substrate, the spin coat method is preferable as the application method in that the surface of the substrate can be uniformly hydrophilized or hydrophobized by uniformly applying the surface treatment liquid.

The material of the surface to which the surface treatment liquid of the object to be treated is applied is not particularly limited and may be an organic material or an inorganic material.

Examples of the organic material include various resin materials such as polyester resins such as PET resins and PBT resins, various nylons, polyimide resins, polyamideimide resins, polyolefins such as polyethylene and polypropylene, polystyrene, and (meth) .

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

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

The material of the surface treated with the above-mentioned 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, the resin (A) having a hydroxyl group and / or a carboxyl group as the functional group I It is preferable to use a surface treatment liquid containing a surfactant.

When the material of the surface to which the surface treatment liquid is applied is an inorganic material, both the hydroxyl group, the carboxyl group and the cyano group are preferable as the functional group (I) of the resin (A).

The shape of the object to be processed is not particularly limited. The object to be processed may be a flat substrate, for example, a three-dimensional shape such as a spherical shape or a columnar shape. The surface of the object to be treated may be smooth or may have irregular irregularities regularly or irregularly.

After the surface treatment liquid is applied to the surface of the object to be treated, (C) at least part of the solvent may be removed by heating the coating film as necessary.

<Exposure Step>

The coating film thus formed is irradiated with ultraviolet rays or visible rays having a wavelength of 300 to 500 nm, for example, and exposure is performed. The exposure is carried out at a point where hydrophilization or hydrophobization is desired.

When it is desired to highly hydrophilize or hydrophobicize the entire spot where the coating film is formed, the whole surface of the coating film is exposed. When a part of the spot where the coating film is formed is highly hydrophilized or hydrophobized and the degree of hydrophilization or hydrophobization at other points is desired to be lowered, the positional selective exposure is performed only at a place where high hydrophilization or hydrophobicity is desired.

A method of performing position selective exposure is not particularly limited, but is usually carried out through a photomask.

As a source of radiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. The radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X rays,? Rays, electron rays, proton rays, neutron rays, and ion rays. The irradiation dose (exposure dose) is typically 100 to 10000 mJ / cm &lt; 2 &gt; in the case of using, for example, an ultra-high pressure mercury lamp.

<Bake process>

Then, the exposed coating film is baked. The baking temperature is preferably 40 to 200 DEG C, more preferably 60 to 150 DEG C. The baking time is preferably 10 to 6000 seconds, more preferably 10 to 300 seconds.

<Rinse process>

The baked coating film is rinsed.

As described above, when the surface treatment liquid containing the resin (A) having a predetermined functional group and the photoacid generator (B) is applied to the surface of the object to be exposed, exposure is carried out, and (B) By the action of the strong acid, the resin (A) adheres or bonds well to the surface of the object to be treated.

Incidentally, on the surface of the object to be treated, in particular, the unexposed portion, some amount of the resin (A) which is not adhered or bonded to the surface exists.

However, by rinsing the coating film, the resin (A) not attached to the surface of the object to be treated is washed away.

As a result, a thin film having a film thickness of 10 nm or less is formed at the exposed position of the surface of the object to be processed by rinsing.

The film thickness of the thin film can be measured using spectroscopic ellipsometry.

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

After rinsing, the surface of the object to be treated is dried to obtain an article that is preferably hydrophilized or hydrophobized.

Various articles surface-treated by the method described above can be highly hydrophilized or hydrophobized only at necessary points, while the degree of hydrophilization or hydrophobization at other points can be reduced. As the article subjected to such surface treatment, for example, a cell culture apparatus or a micro flow device for circulating a liquid containing a biological sample such as a cell is preferable. Antifouling and anti-fogging properties are imparted to various articles by surface treatment.

Example

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

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

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

The structural units A-1a to A-6a shown in Table 1 are structural units which impart a hydrophilic group or a hydrophobic group to the resin (A). In the equation representing A-6a, n is a repetition number of units in parentheses.

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

The constituent units A-1c and A-2c shown in Table 1 are constitutional units having neither a hydrophilic group, a hydrophobic group, a hydroxyl group, a cyano group or a carboxyl group.

Compounds 1 to 4 described in Table 1 are each an organosiloxane compound having the following structure. In the formulas representing compounds 1 to 4, n, n1 and n2 are the number of repeating units in each parenthesis.

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

The amount of the hydroxyl group of compound 1 is 58 mgKOH / mol, the content of carboxyl group of compound 3 is 4000 g / mol, and the amount of hydrogen atom directly bonding to the silicon atom of compound 4 is 60 g / mol, with respect to the following siloxane compounds.

(23)

In Examples and Comparative Examples, the following photo acid generators B1 to B3 were used. B1 and B2 are photoacid generators generating a strong acid with a pKa of 1 or less and B3 are photoacid generators generating an acid with a pKa of more than 1.

&Lt; EMI ID =

10 parts by mass of the resin (A) of the kind shown in Table 1 and the type and amount of the photoacid generator (B) shown in Table 2 were uniformly mixed with the solvent of the kind and amount described in Table 2, To obtain surface treating solutions of Examples and Comparative Examples.

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

The obtained surface treatment solution was spin-coated on a glass substrate at 1000 rpm for 30 seconds and then dried at 100 캜 for 60 seconds to obtain a coated film.

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

The exposed coated film was baked at 100 캜 for 60 seconds and then rinsed to obtain a surface-treated glass substrate.

In Examples 1 to 3, Example 7, Comparative Example 1, Comparative Example 2 and Comparative Example 4 using a resin having a hydrophilic group, rinsing with water was performed. In other Examples and Comparative Examples, rinsing with PGMEA was performed.

After the rinsed glass substrate was dried, the contact angle of water on the glass substrate was measured for each of the exposed portion and the unexposed portion. The contact angle of water was measured as a contact angle after dropping pure liquid (2.0 L) onto the surface of the surface-treated substrate using Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) and dropping 10 seconds thereafter. The measurement results of the contact angle of water are shown in Table 2.

Further, the exposed substrate was confirmed by spectroscopic ellipsometry with respect to the substrate after drying, but in the examples, the presence of a thin film having a film thickness of 10 nm or less was observed, and in the comparative example, the presence of the thin film was not observed.

According to the embodiment, a resin (A) having a functional group I of at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group and a functional group II being a hydrophilic group or a hydrophobic group other than the functional group I and a strong acid having a pKa of 1 or less In the case of using the surface treatment liquid containing the photoacid generator (B) to be used, the coating film composed of the surface treatment liquid is exposed, and then baking and rinsing are carried out so that only the exposed points on the substrate can be satisfactorily hydrophilized or hydrophobic .

According to Comparative Examples 1 to 3, when the resin (A) has neither a hydroxyl group, a cyano group nor a carboxyl group, the surface treatment liquid contains (B) a photoacid generator that generates a strong acid with a pKa of 1 or less , It can be understood that the exposed portion can not be satisfactorily hydrophilized or hydrophobized.

According to Comparative Example 4, in the case where the resin (A) contains a functional group (I) which is a carboxyl group and a functional group (II) which is a hydrophilic group, and the surface treatment liquid contains a (B) photoacid generator that generates an acid having a pKa of more than 1 , It can be understood that the exposed portion can not be satisfactorily hydrophilized or hydrophobized.

[Examples 11 to 15]

In Example 11, a surface treatment solution obtained by uniformly mixing 10 parts by mass of the resin (A), 0.1 part by mass of the photoacid generator (B), and 1000 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 in 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 above-mentioned B2 compound.

The same procedures as in Example 1 were carried out except that the surface treatment liquids of the types shown in Table 3 were used, the kinds of the substrates were changed to the types described in Table 3, and the exposure was performed on the entire surface of the coating film , And the contact angle of water after the surface treatment was measured. The measurement results are shown in Table 1. In the PET film and the silicon wafer, the contact angle of water in the untreated state is about 70 deg. For the PET film and about 10 deg. For the silicon wafer.

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

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 surface of the substrate made of the inorganic material (silicon) The surface is also preferably hydrophobized.

Claims (11)

A surface treatment method using a photosensitive surface treatment liquid,
Applying the photosensitive surface treatment liquid to the surface of the object to be processed to form a coating film,
Exposing at least a part of the coating film,
Baking the exposed coating film,
Rinsing the baked coating film to form a thin film having a film thickness of 10 nm or less at the exposed position of the surface of the object to be processed,
Wherein the photosensitive surface treatment liquid comprises (A) a resin, (B) a photoacid generator, and (C) a solvent,
Wherein the resin (A) has a functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,
Wherein the photoacid generator (B) generates a strong acid having a pKa of 1 or less. The method according to claim 1,
Wherein the exposure of the coating film is performed in a position-selective manner through a photomask. 3. The method according to claim 1 or 2,
Wherein the hydrophilic group of the functional group II is represented by the following formula (A1):
-NH-R &lt; ¹ &gt; (A1)
(In the formula (A1), R ¹ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with at least one group selected from the group consisting of an amino group, a sulfonic acid group and a hydroxyl group.)
And the surface treatment method. 4. The method according to any one of claims 1 to 3,
Wherein the functional group I is represented by the following formula (A2):
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 at least one functional group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group.
Alternatively, the following formula (A2-1):
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 in the formula (A2), and X is a hydrogen atom or an alkali metal.)
&Lt; / RTI &gt; 5. The method according to any one of claims 1 to 4,
Wherein the hydrophobic group of the functional group II is at least one group selected from the group consisting of a fluorinated hydrocarbon group, a silyl group, and a siloxane group. The method according to any one of claims 1, 2, 4, and 5,
Wherein the functional group II is a hydrophobic group, and the following formula (A3):
CH ₂ = CR ² - (CO-O) _b -R ⁶ (A 3)
(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,
-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.
Of the total amount of the monomers. 5. The method according to any one of claims 1 to 4,
Wherein the functional group II is a hydrophilic group, and 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 at least one group selected from the group consisting of an amino group, a sulfonic acid group and a hydroxyl group, and R ² is a hydrogen atom or a methyl group to be.)
&Lt; / RTI &gt; 6. The method of claim 5,
Wherein the hydrophobic group is the siloxane group,
Wherein the resin (A) is 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 the formula (A6), R ¹⁰ and R ¹¹ are each independently a hydrocarbon group of 1 to 6 carbon atoms, and A ¹ , A ² and A ³ are each independently a hydroxyl group, a cyano group, 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.
Is a siloxane compound represented by the following general formula (1). 9. The method according to any one of claims 1 to 8,
Wherein the surface of the surface to 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 for use in the surface treatment method according to any one of claims 1 to 8,
(A) a resin, (B) a photoacid generator, and (C) a solvent,
Wherein the resin (A) has a functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,
Wherein the photoacid generator (B) generates a strong acid having a pKa of 1 or less. (A) a resin, (B) a photoacid generator, and (C) a solvent,
Wherein the resin (A) has a functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,
Wherein the photoacid generator (B) generates a strong acid having a pKa of 1 or less.