JP2017061682A - Surface treatment liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment liquid capable of adequately hydrophilizing or hydrophobing the surface of a treated body even without containing a coating film forming resin, and to provide a surface treatment method using the surface treatment liquid.SOLUTION: A surface treatment liquid contains (A) a resin and (C) a solvent, where (A) the resin is used as the resin which has a functional group I that is 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 that is a hydrophilic group or a hydrophobic group other than the functional group I, and (B) a strong acid having a pKa of 1 or less is added to the surface treatment liquid.SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment liquid and a surface treatment method using the surface treatment liquid.

  Conventionally, various surface treatment liquids have been used to modify the surface properties of various articles. Among surface modification, there is a great demand for hydrophilization or hydrophobization of the surface of articles, and many proposals have been made on drugs for hydrophilization or hydrophobization and surface treatment liquids.

  With regard to such a surface treatment agent, for example, at least an acrylamide monomer and a siloxy group-containing mono (meth) acrylate monomer having a specific skeleton are copolymerized as a surface conditioner capable of imparting hydrophilicity and antifouling properties to the coating surface. A copolymer having a weight average molecular weight of 1500 to 50,000 has been proposed (Patent Document 1).

Japanese Patent No. 5437523

However, when the hydrophilic treatment is performed using the surface conditioning agent described in Patent Document 1, even if the surface of the object to be treated is treated with a solution containing only the surface conditioning agent, the surface conditioning agent is not treated. It is difficult to adhere to the surface, and it is difficult to obtain a desired hydrophilic effect.
For this reason, in patent document 1, the liquid which mix | blended resin, such as an acrylic resin, a polyester resin, a urethane resin, an alkyd resin, an epoxy resin, a polyamine resin, as a film formation component is used as a surface treatment liquid. ing.

  And when using the surface treatment liquid containing the surface conditioning agent of patent document 1, and a film formation component, since the surface of a to-be-processed body will be coat | covered with the film containing resin, favorable hydrophilization can be performed. However, even useful surface properties of the object to be processed are impaired.

  The present invention has been made in view of the above-described problems, and can provide a surface treatment liquid that can satisfactorily hydrophilize or hydrophobize the surface of an object to be treated without containing a film-forming resin. And a surface treatment method using the surface treatment liquid.

  In the surface treatment liquid containing (A) resin and (C) solvent, the present inventors have (A) resin as one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. By using a resin having a certain functional group I and a functional group II that is a hydrophilic group or a hydrophobic group other than the functional group I, and adding (B) a strong acid of pKa1 or less to the surface treatment liquid, The present inventors have found that the above problems can be solved and have completed the present invention.

The first aspect of the present invention includes (A) a resin, (B) a strong acid, and (C) a solvent,
(A) The resin is a functional group I that is 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 that is a hydrophilic group or a hydrophobic group other than the functional group I. And
However, when the functional group II includes one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the (A) resin may not have the functional group I;
(B) A surface treatment solution having a pKa of a strong acid of 1 or less.

  The second aspect of the present invention is a surface treatment method including application of the surface treatment liquid according to the first aspect to the surface of an object to be treated.

  ADVANTAGE OF THE INVENTION According to this invention, even if it does not contain film forming resin, the surface treatment liquid which can perform favorable hydrophilicity or hydrophobicity of the surface of a to-be-processed object, and surface treatment using the said surface treatment liquid A method can be provided.

≪Surface treatment liquid≫
The surface treatment liquid (hereinafter also simply referred to as a treatment liquid) contains (A) a resin, (B) a strong acid, and (C) a solvent.
(A) The resin includes a functional group I that is 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 that is a hydrophilic group or a hydrophobic group other than the functional group I. Have In addition, when the functional group II includes one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the (A) resin may not have the functional group I.
(B) The pKa of the strong acid is 1 or less.

  When the treatment liquid contains the (A) resin having the functional group I and the (B) strong acid having a pKa of 1 or less, the (A) resin binds or adheres well to the surface of the object to be treated during the surface treatment. . For this reason, the hydrophilic or hydrophobic functional group II of the (A) resin is introduced into the surface of the object to be processed with high efficiency. As a result, when surface treatment is performed using a treatment liquid containing (A) resin and (B) strong acid, the surface of the object to be treated is highly hydrophilized or hydrophobized.

  Hereinafter, essential or optional components contained in the treatment liquid will be described.

<(A) Resin>
(A) The resin has a functional group I that is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. (B) The strong acid enhances the reaction or interaction between the functional group I and the surface of the non-treated body, whereby (A) the resin binds or adheres to the substrate surface.

(A) The resin has a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I. Hydrophilic treatment can be performed using a treatment liquid containing a hydrophilic group-containing (A) resin, and hydrophobic treatment can be performed using a treatment liquid containing a hydrophobic group-containing (A) resin.
The hydrophilic group or the hydrophobic group is not particularly limited as long as it is a functional group conventionally recognized as a hydrophilic group or a hydrophobic group by those skilled in the art, and can be appropriately selected from the functional groups.

  The type of (A) resin is not particularly limited as long as (A) the resin has a predetermined functional group and is soluble in (C) the solvent. Examples of (A) resin 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 units having a functional group.

  Specific examples of the hydrophilic group include a polyoxyalkylene group (for example, 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, and the like. Group, hydroxyl group, sulfonic acid group and the like. Moreover, the organic group containing these groups is also preferable as a hydrophilic group.

(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, the hydroxyl group, cyano group, or carboxyl contained in the hydrophilic group or hydrophobic group The group also serves as the functional group 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 does not have the functional group I. Also good.
The hydrophilic group containing a hydroxyl group and a carboxyl group includes the hydroxyl group itself and the carboxyl group itself.

As the hydrophilic group, the following formula (A1):
-NH-R ¹ (A1)
(In Formula (A1), R ¹ is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom. .)
The group represented by these is preferable.

Specific examples of the hydrophilic group represented by the formula (A1) include an amino group and a group represented by the following formula.

Among the specific examples of the hydrophilic group represented by the above formula (A1), more preferred groups include the following groups.

Among the specific examples of the hydrophilic group represented by the above formula (A1), particularly preferable groups include the following groups.

Specific examples of the hydrophobic group include 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 for the formula (A3) is preferable.
Preferable examples of the silyl group include a group represented by the formula (A4) described later and n is 0. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group.
Preferable examples of the siloxane group include a group represented by the formula (A4) described later and n is 1 or more.

  The resin (A) is preferably a monomer polymer having an unsaturated bond because various functional groups can be easily introduced and the amount of the functional groups can be easily adjusted. Such polymers may be homopolymers or copolymers.

In this case, the functional group I of the resin (A) has the following formula (A2):
^{_{CH 2 = CR 2 - (R}} 3) a -CO-R 4 ··· (A2)
(In 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, —O—R ^5. Or —NH—R ⁵ , where 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.
It is preferably a group derived from a monomer represented by

In the above 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 the object of the present invention is not impaired. (A) The number of carbon atoms of the divalent hydrocarbon group as R ³ is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 10 because it is easy to obtain and prepare the resin. 1 to 6 are 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 linear, branched, cyclic, or a combination of these structures.

Preferable specific examples of R ³ include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,1-diyl group, propane -2,2-diyl group, n-butane-1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl Group, n-octane-1,8-diyl group, n-nonane-1,9-diyl group, n-decane-1,10-diyl group, o-phenylene group, m-phenylene group, p-phenylene group, Naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, biphenyl-4,4′-diyl group and the like can be mentioned.

R ⁴ is —OH, —O—R ⁵ , or —NH—R ⁵ , and R ⁵ is substituted with one or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. It is a hydrocarbon 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.
1-20 are preferable and, as for carbon number of a linear, branched, or cyclic aliphatic group, 1-12 are more preferable.
Preferred examples of the linear or branched aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. N-pentyl group, isopentyl group, neopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Suitable examples of the cyclic aliphatic group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, adamantane, norbornane, isobornane, tricyclodecane, And a group obtained by removing one hydrogen atom from a polycycloalkane such as tetracyclododecane, and a group obtained by removing one hydrogen atom from a C1-C4 alkyl substituent of these polycycloalkanes.
Preferable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a biphenylyl group. The aromatic hydrocarbon group may be substituted with a C1-C4 alkyl group such as a methyl group or an ethyl group.

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

(A) When the resin 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 ··· (A3)
(In 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 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. )
It is preferably derived from a monomer represented by

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 hydrocarbon group constituting the main skeleton of the group of R ⁵ described above. It is the same. The fluorinated hydrocarbon group may be a group in which all hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms.
Specific examples of the fluorinated hydrocarbon group as 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 , and chain-like fluorinated alkyl groups such as —CH (CF ₃ ) ₂ ; pentafluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl Groups, fluorinated aromatic hydrocarbon groups such as p-trifluoromethylphenyl group; and fluorinated alicyclic groups such as octafluoroadamantyl group.

In the formula (A3), when R ⁶ is a group represented by the formula (A4), R ⁷ , R ⁸ , and R ⁹ are each independently a methyl group, an ethyl group, or a phenyl group. Preferably, R ⁷ , R ⁸ and R ⁹ are all methyl groups.
In 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 or more and 35 or less, and more preferably an integer of 0 or more and 10 or less.

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

When (A) the resin 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 Formula (A5), R ¹ is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom. R ² is a hydrogen atom or a methyl group.)
It is preferably derived from a monomer represented by

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

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

  (A) When the resin is a polymer of a monomer having an unsaturated bond, the polymer is derived from the monomer represented by the formula (A2) as long as the object of the present invention is not impaired. Other structural units other than the unit derived from the monomer represented by Formula (A3) and the unit derived from the monomer represented by Formula (A5) may be included.

  Other structural units include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate-n-propyl, (meth) acrylate-n-butyl, (Meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid isopentyl, (meth) acrylic acid phenyl, N-methyl (meth) acrylamide, N -Ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nn-pentyl (meth) acrylamide, N-isopentyl (meta ) Acrylamide, N-phenyl (meth) acrylamide, N, N-dimethyl ( T) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-di-n- Examples include structural units derived from monomers such as pentyl (meth) acrylamide, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and chlorostyrene.

  (A) When the 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 all the structural units contained in the polymer Is preferably 0.1 to 50 mol%, more preferably 1 to 20 mol%, and particularly preferably 1 to 15 mol%.

(A) When resin is a polymer of the monomer which has an unsaturated bond, the structure derived from the monomer represented by Formula (A3) or (A5) in all the structural units contained in this polymer The molar ratio of the units is preferably 50 to 99.9 mol%, more preferably 60 to 99 mol%, and particularly preferably 70 to 99 mol%.
However, when the structural unit derived from the monomer represented by the formula (A5) contains any one group of a hydroxyl group, a cyano group, and a carboxyl group, the formula (A5) in all the structural units contained in the polymer The ratio of the structural unit derived from the monomer represented by may be 100%.

The amount of the resin (A) contained in the treatment liquid is not particularly limited as long as the object of the present invention is not impaired, and is appropriately determined in consideration of the application property of the treatment liquid. Typically, the amount of the (A) resin in the treatment liquid is preferably 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 10000 parts by mass, more preferably 500 to 8000 parts by mass, and 1000 to 1000 parts by mass. The amount is particularly preferably 6000 parts by mass.

<(B) Strong acid>
The treatment liquid contains (B) a strong acid. (B) The pKa of the strong acid is 1 or less. Note that pKa is a value in water.
(B) The strong acid acts on the functional group I of the (A) resin to promote (A) adhesion or bonding of the resin to the surface of the object to be treated.
(B) The type of strong acid is not particularly limited as long as pKa is 1 or less. (B) As the strong acid, two or more acids having a pKa of 1 or less can be used in combination.

  (B) Suitable examples of strong acids include fluorinated aliphatic carboxylic acids (such as trifluoroacetic acid), fluorosulfonic acids, and alkanesulfonic acids having 1 to 30 carbon atoms (such as methanesulfonic acid and dodecanesulfonic acid). Arylsulfonic acid (for example, benzenesulfonic acid, p-toluenesulfonic acid, etc.), fluoroalkanesulfonic acid having 1 to 30 carbon atoms (for example, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluoro) Butanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), bissulfonylimide compound, cyclic sulfonylimide compound in which two sulfonyl groups are linked by a fluoroalkylene group, and N-acylfluoroalkanesulfone Acid amide.

  When these (B) strong acids contain a fluoroalkyl group or a fluoroalkylene group, these groups may be partially fluorinated fluoroalkyl groups or fluoroalkylene groups and are fully fluorinated. It may be a perfluoroalkyl group or a perfluoroalkylene group.

  Among these (B) strong acids, fluorosulfonic acid, alkanesulfonic acid having 1 to 30 carbon atoms, fluoroalkanesulfonic acid having 1 to 30 carbon atoms, bis (fluoroalkylsulfonyl) imidic acid, two sulfonyl groups Are preferably cyclic sulfonimidic acid linked with a fluoroalkylene group and N-acylfluoroalkanesulfonic acid amide, fluoroalkanesulfonic acid having 1 to 30 carbon atoms, bissulfonylimide compound, and two sulfonyl groups are fluoroalkylene groups A cyclic sulfonylimide compound linked with a N-acylfluoroalkanesulfonic acid amide is preferable.

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

式（Ｂ１）中、Ｘ^１及びＸ^２は、それぞれ独立に、少なくとも１つの電子吸引性基で置換された炭化水素基を表す。炭化水素基は、式（Ｂ１）で表される化合物の強酸性が損なわれない範囲で、電子吸引性基以外の種々の基で置換されていてもよい。Ｘ^１及びＸ^２の炭素原子数は、１〜２０が好ましく、１〜１０がより好ましく、１〜７が特に好ましい。
電子吸引性基で置換された炭化水素基としては、フッ素化アルキル基、ニトロ基を有するアリール基が好ましい。フッ素化アルキル基は、直鎖状でも、分岐鎖状でも、環状でもよい。フッ素化アルキル基は、完全にフッ素化されたパーフルオロアルキル基であるのが好ましい。ニトロ基を有するアリール基としては、ｏ−ニトロフェニル基、ｍ−ニトロフェニル基、及びｐ−ニトロフェニル基が好ましく、ｐ−ニトロフェニル基がより好ましい。 As the bissulfonylimide compound, a compound represented by the following formula (B1) is preferable.

In 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 as long as the strong acidity of the compound represented by the formula (B1) is not impaired. X ¹ and the carbon atoms of ^{X 2} is preferably 1 to 20, more preferably 1 to 10, 1 to 7 is particularly preferable.
The hydrocarbon group substituted with an 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 fully fluorinated perfluoroalkyl group. As an 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.

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

式（Ｂ２）中、Ｘ^３は、少なくとも１つの水素原子がフッ素原子で置換された直鎖状又は分岐状のアルキレン基を表す。Ｘ^３の炭素原子数は、２〜６が好ましく、３〜５がより好ましく、３が特に好ましい。 As the cyclic sulfonylimide compound in which two sulfonyl groups are linked by a fluoroalkylene group, a compound represented by the following formula (B2) is preferable.

In 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 2-6, more preferably 3-5, most preferably 3.

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

式（Ｂ３）中、Ｘ^４は、少なくとも１つの水素原子がフッ素原子で置換された直鎖状又は分岐状のアルキル基を表す。Ｘ^４の炭素原子数は、１〜１０が好ましく、１〜７がより好ましく、１〜３が特に好ましい。
Ｘ^５は、炭化水素基である。炭化水素基について、前述のＲ^５の基の主骨格を構成する炭化水素基と同様である As the N-acylfluoroalkanesulfonic acid amide, a compound represented by the following formula (B3) is preferable.

In 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 are 1-10, more preferably 1-7, 1-3 are particularly preferred.
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.

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

  The content of (B) strong acid in the treatment liquid is not particularly limited as long as the surface treatment with the treatment liquid can be satisfactorily performed. 0.1-20 mass parts is preferable with respect to 100 mass of (A) resin, 0.1-10 mass parts is more preferable, and content of (B) strong acid in a process liquid is 0.1-5 mass Part is particularly preferred.

<(C) Solvent>
(C) A solvent will not be specifically limited if (A) resin and (B) strong acid are soluble solvents. If (A) resin and (B) strong acid are dissolved in a predetermined amount in the treatment liquid, the treatment liquid contains (A) resin in an undissolved state and (B) strong acid. May be. The (A) resin and (B) strong acid are preferably completely dissolved in the treatment liquid.
When the treatment liquid contains insoluble matter, the insoluble matter may adhere to the surface of the object to be treated during the surface treatment. In this case, the insoluble matter adhering to the surface of the object to be processed can be removed by rinsing the surface of the object to be processed by a method described later.

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

(C) As a specific example of the organic solvent used as a solvent,
Sulfoxides such as dimethyl sulfoxide;
Sulfones such as dimethylsulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone, tetramethylenesulfone;
Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide;
Lactams such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone;
Imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone;
Dialkyl glycol ethers such as dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, diethyl 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, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;
(Poly) alkylene glycol monoalkyl ether acetates 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, propylene glycol monoethyl ether acetate;
Other ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, acetic acid Ethyl, acetic acid-n-propyl, acetic acid-i-propyl, acetic acid-n-butyl, acetic acid-i-butyl, formic acid-n-pentyl, acetic acid-i-pentyl, propionic acid-n-butyl, ethyl butyrate, butyric acid -N-propyl, i-propyl butyrate, n-butyl butyrate, Methyl bottles, ethyl pyruvate, pyruvate -n- propyl, methyl acetoacetate, ethyl acetoacetate, other esters such as ethyl 2-oxobutanoate;
Lactones such as β-propyrolactone, γ-butyrolactone, δ-pentyrolactone;
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, methylcyclohexane and the like linear, branched or cyclic aliphatic hydrocarbons;
Aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, naphthalene;
and terpenes such as p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and pinane;

  When the (C) 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, and more preferably 20% by mass or more.

<Other ingredients>
The treatment liquid may contain various components other than (A) a resin, (B) a strong acid, and (C) a solvent as long as the object of the present invention is not impaired. Examples of other components include a colorant, a surfactant, an antifoaming agent, a viscosity modifier, and a surfactant.

<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 a predetermined amount of (A) resin, (B) strong acid, (C) solvent, and other components as necessary.

  The treatment liquid described above is, for example, a surface treatment for preventing cell adhesion, such as a cell culture instrument or a micro-channel device for circulating a liquid containing a biological sample such as a cell, antifouling property or prevention of various articles. It is suitably used for surface treatment for the purpose of imparting haze.

≪Surface treatment method≫
The surface treatment method using the surface treatment liquid described above usually includes applying the surface treatment liquid to the surface of the object to be treated. The method for applying the surface treatment liquid is not particularly limited. Specific examples of the coating method include spin coating, spraying, roller coating, and dipping. When the object to be processed is a substrate, the surface of the substrate can be uniformly hydrophilized or hydrophobized by uniformly applying the surface treatment liquid. Therefore, the spin coating method is preferable as the coating method.

The material of the surface to which the surface treatment liquid 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 resin and PBT resin, various nylons, polyimide resins, polyamideimide resins, polyolefins such as polyethylene and polypropylene, polystyrene, and (meth) acrylic resins.
Photosensitive resin components and alkali-soluble resin components contained in various resist materials are also preferable as the organic material.
Examples of the inorganic material include various metals such as glass, silicon, copper, aluminum, iron, and tungsten. The metal may be an alloy.

The material of the surface to be surface-treated with the surface treatment liquid is not particularly limited. However, when the material of the surface to which the surface treatment liquid is applied is an organic material, the functional group I has a hydroxyl group and / or a carboxyl group ( A) It is preferable to use a surface treatment liquid containing a resin.
When the material of the surface to which the surface treatment liquid is applied is an inorganic material, it is preferable to use a surface treatment liquid containing (A) a resin having a hydroxyl group and / or a cyano group as the functional group I.

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

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

  It is preferable that the part on which the surface treatment liquid is applied is rinsed. As described above, when a surface treatment liquid containing (A) resin having a predetermined functional group and (B) strong acid is applied to the surface of the object to be treated, (A) resin adheres well to the surface of the object to be treated. Or join. However, a certain amount of (A) resin not attached or bonded to the surface is also present on the surface of the object to be processed. Therefore, in order to reduce the influence of (A) resin on the surface characteristics of the object to be processed as much as possible, it is preferable to wash away (A) resin that is not attached or bonded to the surface of the object to be processed by rinsing.

  When the surface treatment liquid contains water as the solvent (C), it is preferable to perform rinsing with water. Moreover, when the surface treatment liquid contains an organic solvent as the solvent (C), it is also preferable to perform rinsing with an organic solvent. When rinsing with an organic solvent, it is preferable to use the same organic solvent as the organic solvent contained in the surface treatment liquid.

  After the surface treatment liquid is applied or rinsed, the surface of the object to be treated is dried to obtain an article that is well hydrophilized or hydrophobized.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Examples 1 to 16 and Comparative Examples 1 to 6]
In each Example and Comparative Example, a resin containing structural units described below at the ratio shown in Table 1 was used as the resin (A).
Units A-1 to A-7 are structural units that introduce a functional group II, which is a hydrophilic group or a hydrophobic group, into the resin (A).
Units B-1 to B-4 are structural units for introducing the functional group I into the resin (A).
Units C-1 to C-3 are structural units having neither functional group I nor functional group II.

About the Example and the comparative example, the following Ac1-Ac4 was used as an acid component. Ac1 (trifluoromethanesulfonic acid) and Ac2 which is a compound of the following formula are strong acids of pKa1 or less. Ac3 (phosphoric acid) and Ac4 (acetic acid) are acids exceeding pKa1.

  In Examples and Comparative Examples, (C) S1: pure water, S2: propylene glycol monomethyl ether, and S3: propylene glycol monomethyl ether acetate were used as the solvent.

(Preparation of surface treatment solution)
(A) Resin 100 mass part which consists of a structural unit of the kind and molar ratio which are described in Tables 1-3, the acid component of the mass part described in Tables 1-3, and the mass described in Tables 1-3 Part of the solvent was uniformly mixed to obtain surface treatment liquids of Examples and Comparative Examples.
In Comparative Example 1, no acid component was used.

  In Example 8, a resin consisting only of the unit A-4 was used, and in Example 15, a resin consisting only of the unit A-1 and the unit A-4 was used. The 2-hydroxyethylamino group contained in the unit A-4 is a hydrophilic group and a hydroxyl group-containing group. For this reason, the hydroxyl group contained in the unit A-4 also serves as the functional group I.

(Evaluation of surface treatment effect)
Using the surface treatment liquids of Examples 1 to 15 and Comparative Examples 1 to 5 obtained by the above method, the surface treatment of the PET film was performed according to the following method.
First, a surface treatment liquid was applied onto a PET film by a spin coating method to form a coating film having a thickness of 500 nm.
The formed coating film was heated at 40 ° C. for 60 seconds, and then the surface of the PET film was rinsed. About Examples 1-4, Examples 8-13, Example 15, and Comparative Examples 1-4, it rinsed with the pure water. For Examples 5 to 7, Example 14, and Comparative Example 5, rinsing with propylene glycol monomethyl ether was performed.
After the rinsed PET film was dried, the contact angle of water on the surface of the PET film was measured. The contact angle of water is measured by dropping a pure water droplet (2.0 μL) on the surface of the surface-treated substrate using Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) and measuring the contact angle 10 seconds after the dropping. did. The measurement results of the water contact angle are shown in Tables 1-3.
The water contact angle of the untreated PET film is 70.6 °.

  According to Examples 1-16, the surface of a PET film is used by using the surface treatment liquid containing (A) resin which has a predetermined functional group, (B) strong acid below pKa1, and (C) solvent. It can be seen that it is well hydrophilized or hydrophobized.

According to Comparative Example 1, when a surface treatment liquid containing (A) resin having a predetermined functional group and (C) solvent but not containing an acid component is used, a good surface treatment effect cannot be obtained. I understand.
According to Comparative Examples 2 and 3, a surface treatment liquid containing (A) a resin having no hydrophilic group or hydrophobic group as the functional group II, (B) a strong acid of pKa1 or less, and (C) a solvent. It can be seen that even when the surface treatment of the PET film is performed, the water contact angle of the PET film does not change significantly from the untreated state.
According to Comparative Examples 4 and 5, a surface treatment solution containing (A) a resin having a predetermined functional group, an acid component, and (C) a solvent but not containing pBal or less (B) a strong acid, It can be seen that even when the surface treatment of the film is performed, the water contact angle of the PET film does not change significantly from the untreated state.
According to Comparative Example 6, even if the surface treatment of the PET film is performed with a surface treatment liquid containing (A) a resin having no functional group I, (B) a strong acid having a pKa1 or less, and (C) a solvent, It can be seen that the water contact angle of the PET film does not change significantly from the untreated state.

[Example 17, Example 18, and Comparative Example 7]
100 parts by mass of (A) resin composed of structural units of the types and molar ratios described in Table 4, the acid component of parts by mass described in Table 4, and the solvent of parts by mass described in Table 4 are uniform. The surface treatment liquids of Example 17, Example 18, and Comparative Example 7 were obtained.
The surface treatment of the glass substrate is carried out in the same manner as in Example 1 except that the PET film is changed to a glass substrate using the obtained surface treatment liquid, and the water contact angle of the glass substrate after the surface treatment is determined. It was measured. Table 4 shows the measurement results of the water contact angle of the glass substrate.
The water contact angle of the untreated glass substrate is 41.9 °.

According to Examples 17 and 18, (A) resin consisting of unit B-4 containing cyano group as functional group I and hydrophilic unit A-1, (B) strong acid of pKa1 or less, (C) When using the surface treatment liquid containing a solvent, it turns out that the surface of the board | substrate which consists of glass which is an inorganic material can be made hydrophilic favorably.
On the other hand, from Comparative Example 7, the glass substrate was subjected to surface treatment using a surface treatment liquid containing (A) a resin not containing the functional group I, (B) a strong acid having a pKa1 or less, and (C) a solvent. It can also be seen that the water contact angle of the glass substrate does not change significantly from the untreated state.

Example 19
Using the surface treatment liquid of Example 1, the surface of the glass substrate was treated in the same manner as in Example 1 except that the PET film was changed to a glass substrate to obtain six surface-treated glass substrates. It was.
The obtained surface-treated glass substrate was immersed in pure water, ethanol, propylene glycol monomethyl ether acetate (PGMEA), physiological saline, and 1N NaOH aqueous solution for 6 months at room temperature, and then contact angles were measured. .
Moreover, after the surface-treated glass substrate was immersed in a 0.1 M H ₂ SO ₄ aqueous solution at 100 ° C. for 100 hours, the contact angle was measured.
Under any condition, the contact angle did not change before and after the immersion, and it was confirmed that the chemical solution resistance was excellent.

Claims (11)

(A) a resin, (B) a strong acid, and (C) a solvent,
The (A) resin is a functional group I that is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group that is a hydrophilic group or a hydrophobic group other than the functional group I. II,
However, when the functional group II includes one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the (A) resin may not have the functional group I;
(B) The surface treatment liquid in which the pKa of the strong acid is 1 or less. The hydrophilic group of the functional group II is represented by the following formula (A1):
-NH-R ¹ (A1)
(In Formula (A1), R ¹ is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom. .)
The surface treatment liquid according to claim 1, which is a group represented by: The functional group I is represented by the following formula (A2):
_{^{CH 2 = CR 2 - (R}} 3) a -CO-R 4 ··· (A2)
(In 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, —O—R ^5. Or —NH—R ⁵ , where 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 surface treatment liquid according to claim 1, which is derived from a monomer represented by:   The surface treatment liquid according to claim 1 or 3, wherein the hydrophobic group is one or more groups selected from the group consisting of a fluorinated hydrocarbon group, a silyl group, and a siloxane group. The functional group II is a hydrophobic group, and the following formula (A3):
_{^{CH 2 = CR 2 - (CO}} -O) b -R 6 ··· (A3)
(In 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 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 liquid according to claim 1, which is derived from a monomer represented by: The functional group II is a hydrophilic group, and 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 substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom. R ² is a hydrogen atom or a methyl group.)
The surface treatment liquid according to any one of claims 1 to 3, derived from a monomer represented by:   The surface treatment method including the application | coating to the surface of a to-be-processed object of the surface treatment liquid of any one of Claims 1-6.   The surface treatment method of Claim 7 including the rinse of the location where the said surface treatment liquid on the to-be-processed object was apply | coated.   The surface treatment method according to claim 7 or 8, wherein the object to be treated is a substrate, and the surface treatment liquid is applied by spin coating.   The 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. The surface treatment method as described.   The material of the surface on which the surface treatment liquid is applied is an inorganic material, and the resin (A) has a hydroxyl group and / or a cyano group as the functional group I. The surface treatment method as described.