JP7079643B2 - Two-component surface treatment liquid, surface treatment method, and liquid composition - Google Patents

Description

The present invention relates to a two-component surface treatment liquid, a surface treatment method, and a liquid composition.

Conventionally, various surface treatment liquids have been used to modify the surface properties of various articles. Among the surface modifications, there is a great demand for hydrophilization or hydrophobization of the surface of the article, and a large number of agents and surface treatment liquids for hydrophilization or hydrophobization have been proposed.

Regarding such a chemical for surface treatment, 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 property to the film surface. A surface conditioner containing a copolymer having a weight average molecular weight of 1500 to 50,000 has been proposed (Patent Document 1).

Japanese Patent No. 5347523

By the way, in many cases, the object of surface treatment is an article having irregularities having a size of several nm to several tens of μm on its surface, such as a microchannel device. However, when such an article is surface-treated with the surface conditioner described in Patent Document 1, the fine recesses may be filled with the copolymer or the dimensions of the fine recesses may be significantly narrowed. There's a problem.

For example, by rinsing the treated surface with an organic solvent after the surface treatment, the film made of the copolymer can be made extremely thin. However, in this case, since the ultrathin film made of the copolymer is easily peeled off, there is a problem that the effect of the surface treatment is easily impaired.

The present invention has been made in view of the above problems, and is a two-component type capable of firmly bonding the film to the surface of the object to be treated while covering the surface of the object to be treated with an ultrathin film. It is an object of the present invention to provide a surface treatment liquid, a surface treatment method using the surface treatment liquid, and a liquid composition preferably used for forming an underlayer film in the surface treatment method.

The present inventors have a structural unit (a1) having an epoxy group and / or an oxetanyl group, a structural unit (a2) having a silyl group containing a silanol group or a group that produces a silanol group by hydrolysis, and an acid-degradable property. One or more selected from a first liquid containing a resin (A) containing a structural unit (a3) having a group, a primary amino group, a secondary amino group, a carboxy group, and a phenolic hydroxyl group. We have found that the above problems can be solved by using a two-component surface treatment solution composed of a second solution containing a resin (B) containing a structural unit (b1) having a group, and complete the present invention. It came to. More specifically, the present invention provides the following:

The first aspect of the present invention comprises a structural unit (a1) having an epoxy group and / or an oxetanyl group, and a structural unit (a2) having a silyl group containing a silanol group or a group that produces a silanol group by hydrolysis. A first liquid containing a resin (A) containing a structural unit (a3) having an acid-degradable group,
It comprises a second liquid containing a resin (B) containing a structural unit (b1) having one or more groups selected from a primary amino group, a secondary amino group, a carboxy group, and a phenolic hydroxyl group. It is a two-component surface treatment liquid.

A second aspect of the present invention is a surface treatment method using a two-component surface treatment liquid according to the first aspect.
By applying the first liquid to the surface of the object to be treated to form the first layer,
Including applying a second liquid on the first layer to form a second layer.
When the second liquid contains an acid generator, it is a surface treatment method further comprising generating a strong acid from the acid generator after the application of the second liquid.

A third aspect of the present invention is a liquid composition used for forming an underlayer film on the surface of an object to be treated.
A structural unit (a1) having an epoxy group and / or an oxetanyl group, a structural unit (a2) having a silyl group containing a silanol group or a group that produces a silanol group by hydrolysis, and a structural unit having an acid-degradable group (a2). It is a liquid composition containing a resin (A) containing a3).

The present invention has been made in view of the above problems, and is a two-component type capable of firmly bonding the film to the surface of the object to be treated while covering the surface of the object to be treated with an ultrathin film. It is possible to provide a surface treatment liquid, a surface treatment method using the surface treatment liquid, and a liquid composition preferably used for forming an underlayer film in the surface treatment method.

≪Two-component surface treatment liquid≫
The two-component surface treatment liquid contains a structural unit (a1) having an epoxy group and / or an oxetanyl group, and a structural unit (a2) having a silyl group containing a silanol group or a group that produces a silanol group by hydrolysis. A first liquid containing a resin (A) containing a structural unit (a3) having an acid-degradable group,
It comprises a second liquid containing a resin (B) containing a structural unit (b1) having one or more groups selected from a primary amino group, a secondary amino group, a carboxy group, and a phenolic hydroxyl group. ..
Hereinafter, the first liquid and the second liquid will be described.

<Liquid 1>
As described above, the first liquid contains a structural unit (a1) having an epoxy group and / or an oxetanyl group, and a structural unit (a2) having a silyl group containing a silanol group or a group that produces a silanol group by hydrolysis. It contains a resin (A) containing a structural unit (a3) having an acid-degradable group.
Hereinafter, the resin (A) and other components will be described with respect to the components that can be contained in the first liquid.

[Resin (A)]
The type of the resin (A) is not particularly limited as long as it includes a structural unit that satisfies the above-mentioned predetermined requirements. The resin (A) may be, for example, a condensation type resin such as a polyester resin or a polycarbonate resin, or an addition polymerization type resin such as a (meth) acrylic resin or a styrene resin.
The resin (A) may be a random copolymer or a block copolymer. The resin (A) is preferably a random copolymer because an intramolecular reaction between the epoxy group and / or the oxetanyl group is unlikely to occur in the resin (A).
The resin (A) is preferably an addition polymerization type resin because it is easy to synthesize or obtain a resin containing a predetermined constituent unit and it is easy to adjust the type and ratio of the constituent units. A (meth) acrylic resin obtained by copolymerizing a monomer having an unsaturated double bond containing a (meth) acrylic acid derivative is more preferable.
Hereinafter, when the resin (A) is a (meth) acrylic resin, the constituent unit (a1), the constituent unit (a2), the constituent unit (a3), and other constituent units will be described.

(Constituent unit (a1))
The resin (A) contains a structural unit (a1) having an epoxy group and / or an oxetanyl group. Therefore, by forming the second layer on the first layer formed by using the first liquid containing the resin (A) using the second liquid containing the resin (B) described later, the first layer is formed. The epoxy group and / or the oxetanyl group of the second layer reacts with the functional group of the second layer, so that the first layer and the second layer are chemically bonded. As a result, a robust film is formed on the surface of the object to be treated.

The structural unit (a1) is not particularly limited as long as it is a structural unit derived from a monomer having an epoxy group and / or an oxetanyl group.
Further, the structural unit (a1) is not limited to the structural unit derived from the (meth) acrylic acid derivative having an epoxy group and / or an oxetanyl group.
When the resin (A) contains a structural unit derived from a (meth) acrylic acid derivative as a structural unit other than the structural unit (a1), the structural unit (a1) is an unsaturated double bond such as, for example, an allylglycidyl ether. It may be a structural unit derived from a monomer having a double bond and an epoxy group and / or an oxetanyl group.

As the monomer giving the structural unit (a1), (meth) acrylic acid having an epoxy group and / or an oxetanyl group because it is easy to obtain and prepare and it does not easily impair the storage stability of the first liquid. Esters are preferred.

The (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group, which will be described later, even if it is a (meth) acrylic acid ester having a chain aliphatic epoxy group. There may be. Further, the (meth) acrylic acid ester having an epoxy group may contain an aromatic group.

Examples of (meth) acrylic acid esters having an aromatic group and an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, 2-glycidyloxyphenyl (meth) acrylate, and the like. Examples thereof include 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, and 2-glycidyloxyphenylmethyl (meth) acrylate.

Examples of aliphatic (meth) acrylic acid esters having a chain aliphatic epoxy group include ester groups (-O-CO-) such as epoxyalkyl (meth) acrylates and epoxyalkyloxyalkyl (meth) acrylates. ), A (meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to an oxy group (—O—) can be mentioned. The chain aliphatic epoxy group contained in such a (meth) acrylic acid ester may contain one or more oxy groups (—O—) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and particularly preferably 3 or more and 10 or less.

Specific examples of the aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylates; 2-glycidyloxyethyl (meth) acrylates, 3-glycidyloxy-n-propyl (meth) acrylates, 4-glycidyloxy-n-butyl (meth). ) Epoxyalkyloxyalkyl (meth) acrylates such as acrylates, 5-glycidyloxy-n-hexyl (meth) acrylates and 6-glycidyloxy-n-hexyl (meth) acrylates.

Specific examples of the aliphatic (meth) acrylic acid ester having an alicyclic epoxy group include compounds represented by the following formulas (a1-1) to (a1-15). Among these, the compounds represented by the following formulas (a1-1) to (a1-5) are preferable, and the compounds represented by the following formulas (a1-1) to (a1-3) are more preferable. Further, with respect to each of these compounds, the binding site of the oxygen atom of the ester group to the alicyclic is not limited to that shown here, and may contain a partial positional isomer.

In the above formula, R ^a01 represents a hydrogen atom or a methyl group, and R ^a02 represents a divalent aliphatic saturated hydrocarbon group having 1 or more and 6 or less carbon atoms. R ^{a03 represents} a divalent hydrocarbon group having 1 or more and 10 or less carbon atoms, and t ⁰ represents an integer of 0 or more and 10 or less. As ^Ra02 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a03 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group and a cyclohexylene group are preferable.

Examples of the (meth) acrylic acid ester having an oxetanyl group include (3-ethyloxetane-3-yl) methyl acrylate (OXE-10 (manufactured by Osaka Organic Chemical Industry Co., Ltd.)) and (3-ethyloxetane-3-yl). ) Methyl methacrylate (OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.)) and the like.

The ratio of the mass of the structural unit (a1) to the mass of the resin (A) is not particularly limited as long as the desired surface treatment effect can be obtained. The ratio of the structural unit (a1) to all the structural units constituting the resin (A) is, for example, because the surface treatment effect is good and the film is easily formed from the surface of the object to be treated. 20 mol% or more and 80 mol% or less are preferable, 25 mol% or more and 80 mol% or less are more preferable, and 30 mol% or more and 75 mol% or less are particularly preferable.
The preferable ratio of the structural unit (a1) is the same even when the resin (A) is a resin other than the (meth) acrylic resin.

(Constituent unit (a2))
The structural unit (a2) has a structural unit (a2) having a silanol group or a silyl group containing a group that produces a silanol group by hydrolysis. By having such a structural unit (a2), the resin (A) can be bonded to a public response group having an active hydrogen group such as a hydroxyl group or an amino group on the surface of the object to be treated.
Therefore, by applying the first liquid to the surface of the other surface to be treated, the first layer firmly bonded to the surface of the object to be treated can be formed.
Depending on the material of the object to be treated, the amount of functional groups that can cause the above-mentioned reaction with the silyl group may be small. In this case, a hydroxyl group can be introduced into the surface of the object to be treated by plasma treatment with oxygen plasma, steam plasma, or the like.

The structural unit (a2) is not particularly limited as long as it is a structural unit derived from the above-mentioned monomer having a silyl group.
Further, the structural unit (a2) is not limited to the structural unit derived from the (meth) acrylic acid derivative having the above-mentioned silyl group.
When the resin (A) contains a structural unit derived from a (meth) acrylic acid derivative as a structural unit other than the structural unit (a2), the structural unit (a2) is unsaturated, for example, allyltrimethoxysilane. It may be a structural unit derived from a monomer having a double bond and the above-mentioned silyl group.

As the monomer giving the structural unit (a2), the above-mentioned (meth) acrylic acid ester having a silyl group is preferable because it is easily available and prepared.

As the silyl group, the following formula (a2-1):
-SiR ⁰¹ _x R ⁰² _(3-x) ... (a2-1)
(In the formula (a2-1), R ⁰¹ is an organic group, R ⁰² is a hydroxyl group or a group that produces a silanol group by hydrolysis, and x is 0, 1, or 2.)
It is preferably a group represented by.

The organic group as R ⁰¹ is not particularly limited as long as it does not impair the object of the present invention. The organic group may be a hydrocarbon group or a group having one or more heteroatoms. Examples of the heteroatom that the organic group may have include N, O, S, P, B, Si, and halogen atoms.
Since it is easy to obtain and prepare the monomer giving the structural unit (a2), the organic group as R ⁰¹ is preferably a hydrocarbon group.

As the hydrocarbon group as R ⁰¹ , an alkyl group, an aralkyl group, or an aryl group is preferable. When R ⁰¹ is an alkyl group, the number of carbon atoms thereof is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and preferably 1 or 2.
Preferable examples of the case where R ⁰¹ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group, and a methyl group and an ethyl group are more preferable.
As the aralkyl group, a benzyl group and a phenethyl group are preferable.
As the aryl group, a phenyl group, a naphthalene-1-yl group, and a naphthalene-2-yl group are preferable, and a phenyl group is more preferable.

^R02 is a hydroxyl group or a group that produces a silanol group by hydrolysis. Among these groups, a group that produces a silanol group by hydrolysis is preferable from the viewpoint of storage stability of the first liquid. Examples of the group that produces a silanol group by hydrolysis include an alkoxy group, an aryloxy group, a halogen atom, and an isocyanate group.
Among these groups, the monomer giving the structural unit (a2) is easily available, the storage stability of the first liquid is not excessively impaired, and the reaction with the surface of the object to be treated is not performed. An alkoxy group is preferable because it is easy to obtain a first liquid having good properties.
The number of carbon atoms of the alkoxy group is not particularly limited. The number of carbon atoms of the alkoxy group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and particularly preferably 1 or 2.
Preferable examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, and an n-butyloxy group, and a methoxy group and an ethoxy group are more preferable.

Preferred specific examples of the monomer giving the structural unit (a2) are vinyltrimethoxylan, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1-hexenyltrimethoxysilane, and 1-hexenyltriethoxy. Silane, 1-octenyltrimethoxysilane, 1-octenyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloylpropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropyl Triethoxysilane can be mentioned.

The ratio of the mass of the structural unit (a2) to the mass of the resin (A) is not particularly limited as long as the desired surface treatment effect can be obtained. The ratio of the structural unit (a2) to all the structural units constituting the resin (A) is, for example, 0.5 mol% or more and 20 mol% or less because it is difficult to peel off from the surface of the object to be treated and it is easy to form a film. Preferably, it is more preferably 0.7 mol% or more and 15 mol% or less, and particularly preferably 1 mol% or more and 10 mol% or more.
The preferable ratio of the structural unit (a1) is the same even when the resin (A) is a resin other than the (meth) acrylic resin.

(Constituent unit (a3))
The resin (A) contains a structural unit (a3) having an acid-degradable group. The acid-degradable group is a group in which a functional group such as a hydroxyl group or a carboxy group is protected by an acid-dissociating protecting group.
Regarding the second liquid, when the resin (B) has a group showing strong acidity such as a sulfonic acid group, or when the second liquid contains a strong acid or an acid generator capable of generating a strong acid, the first liquid is used. When the second liquid is applied onto the first layer formed therein, the acid-degradable groups in the first layer are decomposed.
When the acid-degradable group in the resin (A) is decomposed in the first layer, the steric hindrance around the epoxy group and / or the oxetanyl group contained in the resin (A) is alleviated. As a result, the reaction between the epoxy group and / or the oxetanyl group in the first layer and the functional group such as the amino group or the phenolic hydroxyl group of the structural unit (b1) in the second layer is likely to occur.
Further, when the acid-decomposable group in the resin (A) is decomposed in the first layer, in addition to the tightness of the first layer by alleviating the steric hindrance, a hydrogen bond is formed between the first layer and the second layer. Is easy to form, so that a robust film composed of a first layer and a second layer is formed.

Further, the structural unit (a3) having an acid-degradable group suppresses the reaction between the epoxy group and / or the oxetanyl group in the structural unit (a1) in the resin (A) due to the steric hindrance of the acid-degradable group. .. Therefore, when the first layer is formed on the surface of the object to be treated by using the first liquid containing the resin (A), the amino acid contained in the structural unit (b1) in the second layer is formed on the surface of the first layer. There are abundant epoxy groups and / or oxetanyl groups that can react with functional groups such as groups and phenolic hydroxyl groups. Therefore, on the first layer formed by using the first liquid containing the resin (A),
The resin (B) contained in the second liquid is likely to be uniformly bonded.
For this reason, when surface treatment is performed using the first liquid having a predetermined composition and the second liquid described later, it is easy to uniformly treat the surface of the object to be treated.

The acid-degradable group of the structural unit (a3) is not particularly limited as long as it is a group protected by an acid-dissociative protecting group. As the acid-degradable group, a carboxy group protected by an acid-dissociable protecting group or a phenolic hydroxyl group protected by an acid-dissociable protecting group is preferable.
Examples of the acid-degradable group include a group represented by the following formula (a-I) or the following formula (a-II), and a linear, branched, or cyclic alkyl having 1 or more and 6 or less carbon atoms. Examples include a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the above formulas (a-I) and (a-II), ^Ra1 and ^Ra2 each independently have a hydrogen atom or a linear or branched alkyl group having 1 or more and 6 or less carbon atoms. show. R ^a3 represents a linear, branched, or cyclic alkyl group having 1 or more and 10 or less carbon atoms. R ^a4 represents a linear, branched, or cyclic alkyl group having 1 or more and 6 or less carbon atoms. o represents 0 or 1.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Be done. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

Here, as the acid dissociative dissolution inhibitory group represented by the above formula (a-I), specifically, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-iso Propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy- Examples thereof include 1-methyl-ethyl group and 1-ethoxy-1-methylethyl group.
Specific examples of the acid dissociative dissolution inhibitory group represented by the above formula (a-II) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group.
Examples of the trialkylsilyl group include groups having 1 or more and 6 or less carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

As the structural unit (a3), structural units represented by the following formulas (a-III) to (aV) derived from a (meth) acrylic acid ester having an acid-degradable group are preferable.

In the above formulas (a-III) to (a-V), ^{Ra5, Ra9, and Ra12 each independently} represent a hydrogen atom or a methyl group. R ^a10 , R ^a11 , R ^a13 , and R ^a14 independently have a hydrogen atom, a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, a fluorine atom, or 1 or more and 6 or less carbon atoms. Represents a linear or branched fluorinated alkyl group. R ^a6 to R ^a8 are independently linear or branched alkyl groups having 1 to 6 carbon atoms, linear or branched fluorinated alkyl groups having 1 to 6 carbon atoms, or carbon. Represents an aliphatic cyclic group having 5 or more and 20 or less atoms. R ^a7 and R ^a8 may be bonded to each other to form a hydrocarbon ring having 5 or more and 20 or less carbon atoms together with the carbon atom to which both are bonded. Ya represents an aliphatic cyclic group or an alkyl group which may have ^a substituent. p represents an integer of 0 or more and 4 or less. q represents 0 or 1.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Can be mentioned. Further, the fluorinated alkyl group is one in which a part or all of the hydrogen atom of the above alkyl group is substituted with a fluorine atom.
Specific examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, a group obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Can be mentioned. In particular, a group obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have a substituent) is preferable.

When the R ^a7 and R ^a8 do not bond with each other to form a hydrocarbon ring, the R ^a6 , R ^a7 , and R ^a8 include linear or branched alkyl groups having 2 or more and 4 or less carbon atoms. preferable. The R ^a10 , R ^a11 , R ^a13 , and R ^a14 are preferably hydrogen atoms or methyl groups.

The above ^Ra 7 and Ra ⁸ may form an aliphatic cyclic group having 5 or more and 20 or less carbon atoms together with the carbon atom to which both are bonded. Specific examples of such an aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group is mentioned. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Further, when the aliphatic cyclic group formed by ^Ra 7 and Ra ⁸ has a substituent on its ring skeleton, examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (= O). ) And the like, and linear or branched alkyl groups having 1 or more and 4 or less carbon atoms can be mentioned. As the polar group, an oxygen atom (= O) is particularly preferable.

The above ^Ya is an aliphatic cyclic group or an alkyl group, and examples thereof include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. .. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The basis etc. can be mentioned. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferable.

Further, when the aliphatic cyclic group of Ya has ^a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxy group, a cyano group and an oxygen atom (= O). Examples thereof include a linear or branched alkyl group having 1 or more and 4 or less carbon atoms. As the polar group, an oxygen atom (= O) is particularly preferable.

When Ya is an alkyl group, it is preferably ^a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, preferably 6 or more and 15 or less. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, and 1-isopropoxy. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -Ethyl-1-methylethyl group and the like can be mentioned.

As a preferable specific example of the structural unit represented by the above formula (a-III), the structural units represented by the following formulas (a-III-1) to (a-III-33) can be mentioned.

In the above formulas (a-III-1) to (a-III-33), ^Ra15 represents a hydrogen atom or a methyl group.

As a preferable specific example of the structural unit represented by the above formula (a-IV), the structural units represented by the following formulas (a-IV-1) to (a-IV-26) can be mentioned.

In the above formulas (a-IV-1) to (a-IV-26), ^Ra15 represents a hydrogen atom or a methyl group.

Among the structural units described above, the above-mentioned equations (a-III-1), equations (a-III-2), equations (a-III-4), equations (a-III-5), and equations (a) -III-26) or the structural unit represented by the formula (a-III-27) is preferable as the structural unit (a3).

The ratio of the structural unit (a3) to all the structural units constituting the resin (A) is not particularly limited as long as the desired surface treatment effect can be obtained. The ratio of the constituent unit (a3) to all the constituent units constituting the resin (A) is, for example, preferably 5 mol% or more and 80 mol% or less, more preferably 7 mol% or more and 70 mol% or less, and 10 mol% or more and 60. More than mol% is particularly preferable.
The preferable ratio of the structural unit (a3) is the same even when the resin (A) is a resin other than the (meth) acrylic resin.

(Other building blocks)
The polymer (A) may contain a structural unit (a1), a structural unit (a2), and other structural units other than the structural unit (a3) as long as the object of the present invention is not impaired.

Other building blocks include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, -n-propyl (meth) acrylate, -n-butyl (meth) acrylate, and the like. Isobutyl (meth) acrylate, -n-pentyl (meth) acrylate, isopentyl (meth) acrylate, phenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide , N, N-di-n-propyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-di-n-pentyl (meth) acrylamide, styrene, α-methylstyrene, Examples thereof include structural units derived from monomers such as β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and chlorstyrene.

The concentration of the resin (A) in the first liquid is not particularly limited as long as the first layer having a desired film thickness can be formed by using the first liquid. Since it is easy to form the first layer having a desired thickness, the concentration of the resin (A) in the first liquid is preferably 0.1% by mass or more and 20% by mass or less, and 0.2% by mass or more and 10% by mass. % Or less is more preferable, and 0.5% by mass or more and 5% by mass or less is particularly preferable.

[Other ingredients]
The first liquid usually contains a solvent in addition to the resin (A). The solvent contained in the first liquid is not particularly limited as long as it does not have reactivity with the resin (A) and dissolves the resin (A) satisfactorily. As the solvent, a solvent containing an organic solvent is usually used. The solvent may be an organic solvent or an aqueous solution of an organic solvent.

Preferable examples of organic solvents include alcohol. Examples of the alcohol include aliphatic alcohols, and alcohols having 1 or more and 3 or less carbon atoms are preferable. Specific examples thereof include methanol, ethanol, n-propyl alcohol, and isopropyl alcohol (IPA), with methanol, ethanol, and isopropyl alcohol being preferred. The alcohol may be used alone or in combination of two or more. As the solvent contained in the first liquid, specifically, it is preferable to use a mixed solvent with at least one alcohol selected from the group consisting of methanol, ethanol and isopropyl alcohol.

Other preferred embodiments of the organic solvent include
Sulfoxides such as dimethyl sulfoxide;
Sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, tetramethylene sulfone;
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;
Iimidazolidinones 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 (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl 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 (PGMEA), propylene glycol monoethyl ether acetate, etc. Kind;
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-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, acetic acid Ethyl, acetic acid-n-propyl, acetate-i-propyl, acetate-n-butyl, acetate-i-butyl, formic acid-n-pentyl, acetate-i-pentyl, propionic acid-n-butyl, ethyl butyrate, buty acid Other esters such as -n-propyl, -i-propyl butyic acid, -n-butyl butyrate, methyl pyruvate, ethyl pyruvate, -n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc. Kind;
Lactones such as β-propyrolactone, γ-butyrolactone, δ-pentilolactone;
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-Heptane methylnonane, cyclohexane, methylcyclohexane and other linear, branched or cyclic aliphatic hydrocarbons;
Aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, naphthalene;
Examples thereof include p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, terpenes such as pinan; and the like.

Further, the first liquid may contain various additives as long as it does not hinder the good formation of the first layer. Examples of such additives include thermal polymerization inhibitors, photopolymerization inhibitors, antioxidants, UV absorbers, colorants, defoamers, viscosity modifiers and the like.

The first liquid is obtained by uniformly mixing and dissolving the desired amounts of the above-described components.

<Liquid 2>
As described above, the second liquid is a resin (B) containing a structural unit (b1) having one or more groups selected from a primary amino group, a secondary amino group, a carboxy group, and a phenolic hydroxyl group. Contains. The above-mentioned functional group of the resin (B) reacts with the epoxy group and / or the oxetanyl group of the first layer containing the resin (A) formed by using the above-mentioned first liquid. By such a reaction, the first layer formed by using the first liquid and the second layer formed by using the second liquid are chemically bonded at the interface between the two.

Further, the above-mentioned functional group included in the structural unit (b1) is generally hydrophilic. Therefore, by forming the first layer on the surface of the object to be treated using the first liquid and then forming the second layer on the first layer using the second liquid, the surface of the object to be treated becomes hydrophilic. Be made.
Hereinafter, the resin (B) and other components will be described with respect to the components that can be contained in the second liquid.

[Resin (B)]
As with the resin (A), the type of the resin (B) is not particularly limited as long as it includes a structural unit that satisfies the above-mentioned predetermined requirements. The resin (B) may be, for example, a condensation type resin such as a polyester resin or a polycarbonate resin, or an addition polymerization type resin such as a (meth) acrylic resin or a styrene resin.
The resin (B) may be a random copolymer or a block copolymer. The resin (B) is a random copolymer because it is easy to increase the probability that the above-mentioned predetermined functional group of the resin (B) reacts with the epoxy group and / or the oxetanyl group of the resin (A). Is preferable.
The resin (B) is preferably an addition polymerization type resin because it is easy to synthesize or obtain a resin containing a predetermined constituent unit and it is easy to adjust the type and ratio of the constituent units. A (meth) acrylic resin obtained by copolymerizing a monomer containing a (meth) acrylic acid derivative is more preferable.
Hereinafter, when the resin (B) is a (meth) acrylic resin, the constituent unit (b1) and other constituent units will be described.

[Constituent unit (b1)]
The structural unit (b1) is a structural unit having one or more groups selected from a primary amino group, a secondary amino group, a carboxy group, and a phenolic hydroxyl group.
The monomer giving the structural unit (b1) is not particularly limited as long as it is a monomer having an unsaturated double bond and the above-mentioned predetermined functional group.
The resin (B1) may be a homopolymer composed of only one type of structural unit (b1), or may be a copolymer composed of two or more types of structural units (b1), or may be a copolymer composed of two or more types of structural units (b1). It may be a copolymer composed of b1) and other structural units other than the structural unit (b1).

Examples of the monomer giving the structural unit (b1) having a primary amino group include (meth) acrylamide and the following formula (BI):
CH ₂ = CR ^b02 -CO-X ^b -R ^b01 ... (BI)
(In the formula (BI), R ^b01 is an alkyl group having 1 or more and 4 or less carbon atoms substituted with a primary amino group, R ^b02 is a hydrogen atom or a methyl group, and X ^b is. -O- or -NH-)
Examples include the compound represented by.

Preferable specific examples of R ^b01 include the following groups.

When the structural unit (b1) has a secondary amino group, the monomer giving the structural unit (b1) is particularly limited as long as it is a monomer having an unsaturated double bond and a secondary amino group. Not done.
When the structural unit (b1) has a secondary amino group, a preferred example of the monomer giving the structural unit (b1) is the above-mentioned suitable structural unit (b1) having a primary amino group. Examples of the compound include N-monoalkyl substituents, N-monoaryl substituents, and N-monoaralkyl substituents.
Regarding the N-monoalkyl substituent, the alkyl group constituting the secondary amino group is preferably an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms. Specific examples of the alkyl group having 1 or more and 4 or less carbon atoms 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. Be done.
Regarding the N-monoaryl substituent, the aryl group constituting the secondary amino group is preferably an aryl group having 6 or more carbon atoms and 10 or less carbon atoms. Specific examples of the aryl group having 6 or more and 10 or less carbon atoms include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a naphthalene-1-yl group, and a naphthalene2-yl group. Can be mentioned.
Regarding the N-monoaralkyl substituent, the aralkyl group constituting the secondary amino group is preferably an aralkyl group having 7 or more and 10 or less carbon atoms. Specific examples of the aralkyl group having 7 or more and 10 or less carbon atoms include a benzyl group and a phenethyl group.

When the structural unit (b1) has a carboxy group, specific examples of the single amount giving the structural unit (b1) are unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; maleic acid, fumaric acid and itacon. Unsaturated dicarboxylic acids such as acids; 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexa. Examples thereof include carboxy groups such as hydrophthalic acid and methacrylic acid derivatives having an ester bond.

When the structural unit (b1) has a phenolic hydroxyl group, specific examples of the monomer giving the structural unit (b1) include 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, and 2-hydroxy-α-. Methyl styrene, 3-hydroxy-α-methyl styrene, 4-hydroxy-α-methyl styrene, 2-hydroxy-α-ethyl styrene, 3-hydroxy-α-ethyl styrene, 4-hydroxy-α-ethyl styrene, 2- Hydroxyphenyl (meth) acrylate, 3-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate and the like can be mentioned.

Among the monomers giving the structural unit (b1) described above, it is easy to obtain, has good reactivity with an epoxy group and / or an oxetanyl group, and has a good effect of hydrophilization. Therefore, (meth) acrylamide is preferable.

The ratio of the constituent unit (b1) to all the constituent units constituting the resin (B) is not particularly limited as long as the desired surface treatment effect can be obtained. The ratio of the constituent unit (b1) to all the constituent units constituting the resin (B) is, for example, preferably 1 mol% or more and 100 mol% or less, more preferably 2 mol% or more and 90 mol% or less, and 3 mol% or more and 70. More preferably, it is mol% or less, and particularly preferably 5 mol% or more and 50 mol% or less.
When the resin (B) contains the structural unit (b1) at a ratio within such a range, the second layer formed by using the second liquid can be satisfactorily bonded to the first layer, and The surface of the object to be treated can be satisfactorily hydrophilized.
The preferable ratio of the above-mentioned structural unit (b1) is the same even when the resin (B) is a resin other than the (meth) acrylic resin.

(Constituent unit (b2))
The second liquid is the following (i) and (ii):
(I) The resin (B) contains a structural unit (b2) having a sulfonic acid group.
(Ii) Contains a strong acid having a pKa of 2 or less and / or an acid generator capable of generating a strong acid having a pKa of 2 or less.
It is preferable to satisfy at least one of the conditions of.
Hereinafter, the structural unit (b2), which is a preferable structural unit that the resin (B) can contain, will be described. Strong acids and acid generators will be described later.

The sulfonic acid group contained in the structural unit (b2) is contained in the epoxy group and / or the oxetanyl group of the first layer made of the resin (A), which is formed by using the first liquid, and the resin (B). It promotes the reaction with the functional group of the structural unit (b1).
Further, the sulfonic acid group contained in the structural unit (b2) decomposes the acid-degradable group contained in the structural unit (a3) in the resin (A).
When the acid-degradable group in the resin (A) is decomposed in the first layer, the steric hindrance around the epoxy group and / or the oxetanyl group contained in the resin (A) is alleviated. As a result, the reaction between the epoxy group and / or the oxetanyl group in the first layer and the functional group of the structural unit (b1) in the second layer is likely to occur.
Further, when the acid-decomposable group in the resin (A) is decomposed in the first layer, in addition to the tightness of the first layer by alleviating the steric hindrance, a hydrogen bond is formed between the first layer and the second layer. Is easily formed, and a robust film composed of a first layer and a second layer is formed.

The monomer giving the structural unit (b2) having a sulfonic acid group is not particularly limited as long as it is a compound having an unsaturated double bond and a sulfonic acid group.
Examples of the monomer giving the structural unit (b2) having a sulfonic acid group include vinylbenzene sulfonic acids such as 2-vinylbenzenesulfonic acid, 4-vinylbenzenesulfonic acid, and 3-vinylbenzenesulfonic acid, and the following formula ( B-II):
CH ₂ = CR ^b02 -CO-X ^b -R ^b03 ... (B-II)
(In the formula (B-II), R ^b02 and X ^b are the same as those in the formula (BI). R ^b03 is an alkyl group having 1 or more and 4 or less carbon atoms substituted with a sulfonic acid group. Is.)
Examples include the compound represented by.

Preferable specific examples of R ^b03 include the following groups.

The ratio of the constituent unit (b2) to all the constituent units constituting the resin (B) is not particularly limited as long as the desired surface treatment effect can be obtained. The ratio of the constituent unit (b2) to all the constituent units constituting the resin (B) is, for example, preferably 5 mol% or more and 99 mol% or less, more preferably 20 mol% or more and 95 mol% or less, and 50 mol% or more and 90. More preferably, it is mol% or less.
When the resin (B) contains the structural unit (b2) at a ratio within such a range, the second layer formed by using the second liquid can be satisfactorily bonded to the first layer, and The surface of the object to be treated can be satisfactorily hydrophilized.
The preferable ratio of the above-mentioned structural unit (b2) is the same even when the resin (B) is a resin other than the (meth) acrylic resin.

(Constituent unit (b3))
The resin (B) is a structural unit having a hydrophilic group other than a primary amino group, a secondary amino group, a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group for the purpose of further enhancing the hydrophilic effect by surface treatment. (B3) may be included.
Such a hydrophilic group is a group generally recognized by those skilled in the art as a hydrophilic group, and is a primary amino group, a secondary amino group, a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group. Other than that, it is not particularly limited.

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), and an alcoholic hydroxyl group. Is preferable.

Further, a cationic group composed of an anion portion and a cation portion bonded to the resin (B) is also preferable as the hydrophilic group. Examples of the cation portion constituting the cationic group include a nitrogen-containing cation portion, a sulfur-containing cation portion, an iodine-containing cation portion, and a phosphorus-containing cation portion.

The anion constituting the anion portion is not particularly limited. The valence of the anion is not particularly limited, and a monovalent anion or a divalent anion is preferable, and a monovalent anion is more preferable.
Preferable examples of the monovalent anion as the anion moiety include halide ions, hydroxide ions, nitrate ions, organic acid ions derived from various organic carboxylic acids or organic sulfonic acids, and the like. Among these, halide ions are preferable, chloride ions, bromide ions, iodide ions and fluoride ions are more preferable, chloride ions and bromide ions are even more preferable, and chloride ions are particularly preferable.

Preferred examples of the cationic group include a group containing a quaternary ammonium base, a group containing a salt of a nitrogen-containing aromatic heterocyclic group, a group containing a sulfonium base, a group containing an iodonium base, a group containing a phosphonium base and the like. Be done.
Among these cationic groups, a group containing a quaternary ammonium base is preferable because it can be easily introduced into the resin (B) and has a high effect of hydrophilization.

As the quaternary ammonium base as a cationic group, the following formula (B-IV):
-R ^b08 -N ⁺ R ^b05 R ^b06 R ^b07・ X -... (B ^- IV)
(In the formula (B-IV), R ^b05 , R ^b06 , and R ^b07 are alkyl groups having 1 or more and 4 or less carbon atoms independently bonded to N ⁺ , respectively, and R ^b05 , R ^b06 , and R ^b07. Two of them may be bonded to each other to form a ring, R ^b08 is an alkylene group having 1 or more carbon atoms and 4 or less carbon atoms, and X ⁻ is a monovalent anion.)
The group represented by is preferable.

The alkyl groups having 1 or more and 4 or less carbon atoms as R ^b05 , R ^b06 , and R ^b07 may be linear or branched, and are preferably linear. Suitable specific examples of R ^b05 , R ^b06 , and R ^b07 include methyl group, ethyl group, n-propyl group, and n-butyl group.

The alkylene group having 1 or more and 4 or less carbon atoms as R ^b08 may be linear or branched, and is preferably linear. Preferable specific examples of R ^b08 include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group.

Preferable examples of X ⁻ are the same as the preferred examples of the anions constituting the anion portion described above.

As the monomer giving the structural unit (b3), an unsaturated double bond and a hydrophilic group other than a primary amino group, a secondary amino group, a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group are used. The compound is not particularly limited as long as it has.
As the monomer giving the structural unit (b3), the following formula (B-III):
CH ₂ = CR ^b02 -CO-X ^b -R ^b04 ... (B-III)
(In the formula (B-III), R ^b02 and X ^b are the same as those in the formula (BI). R ^b04 is a hydroxyl group or a group represented by the above-mentioned formula (B-IV). be.)
Examples include the compound represented by.

Preferable specific examples of R ^b04 include the following groups.

The ratio of the constituent unit (b3) to all the constituent units constituting the resin (B) is not particularly limited as long as the desired surface treatment effect can be obtained. The ratio of the constituent unit (b3) to all the constituent units constituting the resin (B) is, for example, preferably 0.1 mol% or more and 99 mol% or less, more preferably 1 mol% or more and 50 mol% or less, and 2 mol%. More preferably, it is 30 mol% or less.
When the resin (B) contains the structural unit (b3) at a ratio within such a range, the surface of the object to be treated can be satisfactorily hydrophilized.
The preferable ratio of the above-mentioned structural unit (b3) is the same even when the resin (B) is a resin other than the (meth) acrylic resin.

(Other building blocks)
The polymer (B) may contain a structural unit (b1), a structural unit (b2), and other structural units other than the structural unit (b3) as long as the object of the present invention is not impaired.

Other building blocks include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, -n-propyl (meth) acrylate, -n-butyl (meth) acrylate, and the like. Isobutyl (meth) acrylate, -n-pentyl (meth) acrylate, isopentyl (meth) acrylate, phenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide , N, N-di-n-propyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-di-n-pentyl (meth) acrylamide, styrene, α-methylstyrene, Examples thereof include structural units derived from monomers such as β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and chlorstyrene.

The concentration of the resin (B) in the second liquid is not particularly limited as long as the second layer having a desired film thickness can be formed by using the second liquid. Since it is easy to form a second layer having a desired thickness, the concentration of the resin (B) in the second liquid is preferably 0.1% by mass or more and 20% by mass or less, and 0.2% by mass or more and 10% by mass. % Or less is more preferable, and 0.5% by mass or more and 5% by mass or less is particularly preferable.

[Strong acid or acid generator]
As described above, the second liquid contains a strong acid having a pKa of 2 or less and / or an acid generator capable of generating a strong acid having a pKa of 2 or less. In addition, pKa is a value in water.
The strong acid, or the strong acid generated by the acid generator, has the same effect as the sulfonic acid groups in the building block (b2).

(Strong acid)
The strong acid is not particularly limited as long as it is an acid showing pKa. The strong acid may be an organic acid or an inorganic acid.
Suitable examples of strong acids include sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, dichloroacetic acid, trichloroacetic acid, fluorinated aliphatic carboxylic acids (eg trifluoroacetic acid, etc.), fluorosulfonic acid, carbon atoms of 1 to 30. Alcan sulfonic acid (for example, methane sulfonic acid, dodecane sulfonic acid, etc.), aryl sulfonic acid (for example, benzene sulfonic acid, p-toluene sulfonic acid, etc.), fluoroalkane sulfonic acid having 1 to 30 carbon atoms (for example, trifluoromethane sulfonic acid). Acid, pentafluoroethane sulfonic acid, heptafluoropropane sulfonic acid, nonafluorobutane sulfonic acid, undecafluoropentane sulfonic acid and tridecafluorohexane sulfonic acid), bissulfonylimide compound, two sulfonyl groups linked by fluoroalkylene group Examples thereof include the cyclic sulfonylimide compound and N-acylfluoroalkanesulfonic acid amide.

If these strong acids contain a fluoroalkyl group or a fluoroalkylene group, these groups may be a partially fluorinated fluoroalkyl group or a fluoroalkylene group and may be a fully fluorinated per. It may be a fluoroalkyl group or a perfluoroalkylene group.

Among these strong acids, fluorosulfonic acid, alkanesulfonic acid having 1 to 30 carbon atoms, fluoroalcansulfonic acid having 1 to 30 carbon atoms, bis (fluoroalkylsulfonyl) imide acid, and two sulfonyl groups are included. Cyclic sulfonylimide acid linked with a fluoroalkylene group and N-acylfluoroalkanesulfonic acid amide are preferable, and fluoroalcansulfonic acid having 1 or more and 30 or less carbon atoms, a bissulfonylimide compound, and two sulfonyl groups are fluoroalkylene groups. Cyclic sulfonylimide compounds linked with N-acylfluoroalkanesulfonic acid amide are preferred.

As the fluoroalcan sulfonic acid having 1 or more and 30 or less 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以上２０以下が好ましく、１以上１０以下がより好ましく、１以上７以下が特に好ましい。
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, the 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. The number of carbon atoms of X ¹ and X ² is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 7 or less.
As the hydrocarbon group substituted with the electron-withdrawing group, a fluorinated alkyl group and an aryl group having a nitro group are preferable. The fluorinated alkyl group may be linear, branched or cyclic. The fluorinated alkyl group is preferably a fully fluorinated perfluoroalkyl group. As the aryl group having a nitro group, 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 the compound of 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以上６以下が好ましく、３以上５以下がより好ましく、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), X3 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 X3 is preferably 2 or more and 6 or less, more preferably ³ or more and 5 or less, and particularly preferably 3.

Preferable specific examples of the compound represented by the formula (B2) include the compound of 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以上１０以下が好ましく、１以上７以下がより好ましく、１以上３以下が特に好ましい。
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), X4 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 of X4 is preferably ¹ or more and 10 or less, more preferably 1 or more and 7 or less, and particularly preferably 1 or more and 3 or less.
^X5 is a hydrocarbon group. The hydrocarbon group is the same as the hydrocarbon group constituting the main skeleton of the above ^- mentioned R5 group.

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

The content of the strong acid in the second liquid is not particularly limited as long as the surface treatment can be performed well. The content of the strong acid in the second liquid is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 0.1 part by mass or more and 10 parts by mass or less, and 0 by mass with respect to 100 parts by mass of the resin (B). .1 part by mass or more and 5 parts by mass or less is particularly preferable.

(Acid generator)
The acid generator is not particularly limited as long as it is an acid generator that generates an acid by energy such as heat or light. A photoacid generator is preferable as the acid generator from the viewpoint of stability in the second liquid and the like.
As the photoacid generator, a compound capable of generating the above-mentioned preferable strong acid is preferable.
As such a compound, an onium salt compound composed of an anion derived from the above-mentioned strong acid and an onium ion is preferable. As the onium ion, iodonium ion and sulfonium ion are preferable, and sulfonium ion is more preferable.

The content of the acid generator in the second liquid is not particularly limited as long as the surface treatment can be performed well. The content of the strong acid in the second liquid is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 0.1 part by mass or more and 10 parts by mass or less, and 0 by mass with respect to 100 parts by mass of the resin (B). .1 part by mass or more and 5 parts by mass or less is particularly preferable.

[Other ingredients]
The second liquid usually contains a solvent in addition to the resin (B). The solvent contained in the second liquid is not particularly limited as long as it does not have reactivity with the resin (B) and dissolves the resin (B) satisfactorily. As the solvent, a solvent containing an organic solvent is usually used. The solvent may be an organic solvent or an aqueous solution of an organic solvent, and an aqueous solution of an organic solvent is preferable.
When an aqueous solution of an organic solvent is used, the content of water in the aqueous solution of the organic solvent is preferably 1% by mass or more and 90% by mass or less, preferably 5% by mass or more and 50% by mass or less, based on the mass of the aqueous solution of the organic solvent. Is preferable.

Preferable examples of organic solvents include alcohol. Examples of the alcohol include aliphatic alcohols, and alcohols having 1 or more and 3 or less carbon atoms are preferable. Specific examples thereof include methanol, ethanol, n-propyl alcohol, and isopropyl alcohol (IPA), with methanol, ethanol, and isopropyl alcohol being preferred. The alcohol may be used alone or in combination of two or more. As the solvent contained in the second liquid, specifically, it is preferable to use a mixed solvent of water and at least one alcohol selected from the group consisting of methanol, ethanol and isopropyl alcohol, and it is preferable to use a mixed solvent of water and methanol. It is more preferable to use a mixed solvent, a mixed solvent of water and ethanol, and a mixed solvent of water and isopropyl alcohol, and a mixed solvent containing water and two or more kinds of alcohols may be used.
The other preferable examples of the organic solvent described above are the same as the preferred examples of the organic solvent which may be contained in the first liquid.

In addition, the second liquid may contain various additives as long as it does not hinder the good formation of the second layer. Examples of such additives include thermal polymerization inhibitors, photopolymerization inhibitors, antioxidants, UV absorbers, colorants, defoamers, viscosity modifiers and the like.

The second liquid is obtained by uniformly mixing and dissolving the desired amounts of the above-described components.

≪Surface treatment method≫
The surface treatment method is performed using the above-mentioned two-component surface treatment liquid.
The surface treatment method is
By applying the above-mentioned first liquid to the surface of the object to be treated to form the first layer,
By applying the above-mentioned second liquid on the first layer to form the second layer,
including.
The surface treatment method further comprises generating a strong acid from the acid generator after the application of the second liquid when the second liquid contains an acid generator.

According to such a surface treatment method, the first layer is well bonded to the surface of the object to be treated, and the first layer and the second layer are well bonded. Therefore, while the surface of the object to be treated is covered with an ultra-thin film, the film formed by using the surface treatment liquid can be firmly bonded to the surface of the object to be treated. As a result, even if friction or the like is applied to the surface-treated object, the film does not easily peel off and the surface treatment effect is unlikely to deteriorate.

<Formation of the first layer>
The method of applying the first liquid is not particularly limited. Specific examples of the coating method include a spin coating method, a spray method, a roller coating method, a dipping method and the like. When the object to be treated is a substrate, the spin coating method is preferable as the coating method because it is easy to evenly form the first layer having a uniform film thickness on the surface of the substrate.

The material of the surface to which the first of the object to be coated is applied is not particularly limited, and may be an organic material or an inorganic material.
Examples of the organic material include polyester resins such as PET resin and PBT resin, various nylons, polyimide resins, polyamide-imide resins, polyolefins such as polyethylene and polypropylene, polystyrenes, and (meth) acrylic resins.
Further, a photosensitive resin component contained in various resist materials and an alkali-soluble resin component are also preferable as the 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 resin (A) contained in the first liquid typically often binds to a hydroxyl group on the surface of the object to be treated.
Therefore, before forming the first layer, a treatment for introducing a hydroxyl group to the surface of the object to be treated may be performed for the purpose of satisfactorily forming the first layer. Preferable examples of such treatment include plasma treatment using oxygen plasma, steam plasma, or the like.

The shape of the object to be processed is not particularly limited. The object to be processed may be a flat substrate, and may have a three-dimensional shape such as a spherical shape or a columnar shape. Further, the surface of the object to be treated may be smooth or may have regular or irregular irregularities. Examples of the object to be processed having regular or irregular unevenness include a microchannel device and the like.

After the first liquid is applied to the surface of the object to be treated, at least a part of the solvent may be removed from the coating film made of the first liquid, if necessary, by a well-known drying method.

The film thickness of the first layer is not particularly limited as long as the desired surface treatment effect can be obtained. The total of the film thickness of the first layer and the film thickness of the second layer is preferably, for example, 10 nm or less, and more preferably 0.1 nm or more and 10 nm or less. The film thickness of the first layer is preferably 0.1 nm or more and 5 nm or less, and more preferably 0.1 nm or more and 5 nm.
When the film thickness of the first layer is within the above range, it is easy to evenly cover the surface of the object to be treated by the first layer, and the surface of the object to be treated is firmly bonded to the second layer via the first layer. Easy to hold.

In order to provide the first layer having such a film thickness, it is preferable to apply the first liquid to the surface of the object to be treated and then rinse with an organic solvent or water. By rinsing, the resin (A) in a free state is washed away from the surface of the object to be treated and the coating film made of the first liquid, for example, a thin first film having a film thickness of 0.1 nm or more and 5 nm or less. Easy to form layers.

After forming the first layer as described above, the second layer is provided on the first layer by using the above-mentioned second liquid.

<Formation of the second layer>
The formation of the second layer is carried out in the same manner as the formation of the first layer except that the above-mentioned second liquid is used. Further, the film thickness of the second layer is preferably the same as that of the first layer.

When the second liquid contains an acid generator, it is preferable to expose or heat the second layer depending on the type of the acid generator. The exposure conditions and the heating conditions are not particularly limited, and preferable conditions for generating an acid from the acid generator are selected.

It is preferable to heat the first layer and the second layer after forming the first layer and the second layer according to the above method. By doing so, the epoxy group and / or the oxetanyl group in the structural unit (a1) of the resin (A) in the first layer and the functional group in the structural unit (b1) of the resin (B) in the second layer. Can promote the reaction with.
Therefore, by heating the first layer and the second layer after forming the first layer and the second layer, it is possible to suppress the peeling from the first layer due to the friction of the second layer. As a result, a robust film is formed on the surface of the object to be treated so that the surface treatment effect is not easily reduced by friction.

The conditions for heating the first layer and the second layer are not particularly limited as long as they do not impair the object of the present invention. As conditions for heating the first layer and the second layer, for example, 60 ° C. or higher and 250 ° C. or lower are preferable, and 100 ° C. or higher and 200 ° C. or lower are more preferable. The heating time is preferably 1 minute or more and 60 minutes or less, and more preferably 5 minutes or more and 30 minutes or less.

By the above method, the surface of the object to be treated can be uniformly and satisfactorily hydrolyzed by performing the surface treatment of the object to be treated using the above-mentioned two-component surface treatment solution.
The standard deviation obtained from the measurement results of three or more points of the contact angle of water on the surface of the surface-treated object is preferably 1 or less.
Further, since the film formed by using the above-mentioned two-component surface treatment liquid is robust, even if the surface of the surface-treated object is rubbed with a sponge, steel wool, or the like, the surface treatment effect is impaired. It is hard to get rid of.

≪Liquid composition≫
The liquid composition is a liquid composition used for performing a surface treatment for forming an underlayer film on the surface of an object to be treated. The composition of such a liquid composition is the same as that of the first liquid described above.
That is, the liquid composition has a structural unit (a1) having an epoxy group and / or an oxetanyl group, a structural unit (a2) having a silanol group containing a silanol group or a group that produces a silanol group by hydrolysis, and an acid decomposition. It contains a resin (A) containing a structural unit (a3) having a functional group.
The components other than the obtained resin (A) contained in the liquid composition are the same as those of the first liquid. Further, the preferable ratio of each component contained in the liquid composition is the same as that of the first liquid.

By subjecting the surface of the object to be treated to a surface treatment using such a liquid composition, an underlayer film made of the above-mentioned resin (A) is formed on the surface of the object to be treated. Since the resin (A) has the above-mentioned structural unit (a2), it adheres well to the surface of the object to be treated, and since it has the above-mentioned structural unit (a1), further surface treatment is applied to the underlayer film. In addition, it easily binds well to the surface treatment agent that comes into contact with the underlayer film.

That is, in the surface treatment using the above liquid composition, by forming the underlayer film (underlayer), the adhesion to the surface treatment agent further applied to the surface of the underlayer film is enhanced and the surface treatment effect is improved. It can be said that this is a surface treatment to be performed.
Further, since the liquid composition contains the resin (A), the storage stability of the liquid composition is good.

A non-film-forming surface treatment agent may be further bonded to the lower layer film formed by using the above liquid composition, or one or more upper layer films may be provided. Preferably, a liquid surface treatment agent is applied onto the lower layer film formed by using the liquid composition to form one or more upper layer films.
The type of the surface treatment agent is not particularly limited, but typically, a surface treatment agent containing a substance having reactivity with an epoxy group and / or an oxetanyl group is preferable.

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

[Examples 1 to 10 and Comparative Example 5]
A silicon wafer was used as the object to be processed. A first liquid containing the resin (A) at a concentration of 1% by mass is applied to a silicon wafer in a mixed solvent consisting of PGMEA / IPA (1/1: mass ratio) by a spin coating method, and then rinsed with acetone. , A primer layer having a film thickness of 1 nm was formed.
As the resin (A), a (meth) acrylic resin containing the structural units of the types shown in Tables 1 and 2 at the ratios shown in Tables 1 and 2 was used.
In Comparative Example 1, 3-methacryloxypropyltrimethoxysilane was used in the form of a monomer instead of the resin (A). In Table 2, for the convenience of Comparative Example 1, it is described in the composition column of the resin (A) that the ratio of the following structural unit A1-1 is 100 mol%.
The structural units shown in Tables 1 and 2 are as follows.

A second liquid containing the resin (B) at a concentration of 1% by mass is applied onto the first layer in a mixed solvent consisting of water / IPA (1/9: mass ratio) by a spin coating method, and the temperature is 150 ° C. for 5 minutes. After heating with a hot plate, rinsing with water was performed to form a second layer having a thickness of 2 nm.
As the resin (B), a (meth) acrylic resin composed of the following structural units was used. In the following formula, the number in the lower right of the parentheses represents the ratio (mol%) of each constituent unit to all the constituent units in the resin.

Using the silicon wafers immediately after surface treatment obtained in Examples 1 to 10 and Comparative Examples 1 to 5 and 2 cm square Scotch-Brite antibacterial urethane (manufactured by 3M) after surface treatment, the resistance to 10 round trips under a load of 2 kg. The contact angle of the silicon wafer after the scratch test was evaluated according to the following method. The results of these evaluations are shown in Tables 1 and 2.

<Contact angle evaluation>
Pure water droplets (2.0 μL) were dropped on the surface-treated surface of a silicon wafer using Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle of water was measured as the contact angle 10 seconds after the drop. .. The average values of the contact angles of water at three points on the silicon wafer are shown in Tables 1 and 2.
In addition, the standard deviation was obtained from the measured values of the contact angles of water at three points on the silicon wafer immediately after the surface treatment. The standard deviation values are shown in Tables 1 and 2.

According to Table 1, the first layer is formed by using the first liquid containing the structural unit (a1), the structural unit (a2), and the resin (A) containing the structural unit (a3), respectively, which satisfy predetermined requirements. Then, when the second layer is formed on the first layer by using the second liquid containing the resin (B) containing the structural unit (b1) satisfying a predetermined requirement, the surface of the silicon wafer is uniform and good. It can be seen that it is hydrophilized. Further, from the comparison between the initial water contact angle and the water contact angle after friction, the film formed by using the above first liquid and the second liquid is a robust film that is hard to be peeled off by friction. You can see that.

Claims (10)

A structural unit (a1) having an epoxy group and / or an oxetanyl group, a structural unit (a2) having a silyl group containing a silanol group or a group that produces a silanol group by hydrolysis, and a structural unit having an acid-degradable group (a2). The first liquid containing the resin (A) containing a3) and
It comprises a second liquid containing a resin (B) containing a structural unit (b1) having one or more groups selected from a primary amino group, a secondary amino group, a carboxy group, and a phenolic hydroxyl group. A two-component surface treatment liquid ,
The acid-degradable group has the following formula (a-I) or the following formula (a-II):

(In the formulas (a-I) and (a-II), ^Ra1 and ^Ra2 each independently have a hydrogen atom or a linear or branched alkyl group having 1 or more and 6 or less carbon atoms. R ^a3 represents a linear, branched or cyclic alkyl group having 1 or more and 10 or less carbon atoms. R ^a4 represents a linear, branched or cyclic group having 1 or more and 6 or less carbon atoms. Represents an alkyl group of. O represents a group represented by 0 or 1), a linear, branched or cyclic alkyl group having 1 or more and 6 or less carbon atoms, a vinyloxyethyl group, and a tetrahydropyranyl. A two-component surface treatment solution having a group, a tetrahydrofuranyl group, or a trimethylsilyl group . The silyl group has the following formula (a2-1):
-SiR ⁰¹ _x R ⁰² _(3-x) ... (a2-1)
(In the formula (a2-1), R ⁰¹ is an organic group, R ⁰² is a hydroxyl group or a group that produces a silanol group by hydrolysis, and x is 0, 1, or 2.)
The two-component surface treatment liquid according to claim 1, which is a group represented by. The second liquid is the following (i) and (ii):
(I) The resin (B) contains a structural unit (b2) having a sulfonic acid group.
(Ii) Contains a strong acid having a pKa of 2 or less and / or an acid generator capable of generating a strong acid having a pKa of 2 or less.
The two-component surface treatment liquid according to claim 1 or 2 , which satisfies at least one of the conditions of. The two-component type according to any one of claims 1 to 3 , wherein the ratio of the structural unit (a1) to all the structural units constituting the resin (A) is 20 mol% or more and 80 mol% or less. Surface treatment liquid. The two liquids according to any one of claims 1 to 4 , wherein the ratio of the structural unit (a2) to all the structural units constituting the resin (A) is 0.5 mol% or more and 20 mol% or less. Mold surface treatment liquid. A surface treatment method using the two-component surface treatment liquid according to any one of claims 1 to 5 .
By applying the first liquid to the surface of the object to be treated to form the first layer,
The present invention comprises applying the second liquid onto the first layer to form the second layer.
A surface treatment method further comprising generating the strong acid from the acid generator after the application of the second liquid when the second liquid contains the acid generator. The surface treatment method according to claim 6 , wherein the total of the thickness of the first layer and the thickness of the second layer is 10 nm or less. The surface treatment method according to claim 6 or 7 , which comprises heating the first layer and the second layer after forming the first layer and the second layer. A liquid composition used to form an underlayer film on the surface of an object to be treated.
A structural unit (a1) having an epoxy group and / or an oxetanyl group, a structural unit (a2) having a silyl group containing a silanol group or a group that produces a silanol group by hydrolysis, and a structural unit having an acid-degradable group (a2). A liquid composition containing the resin (A) containing a3).
The acid-degradable group has the following formula (a-I) or the following formula (a-II):

(In the formulas (a-I) and (a-II), ^Ra1 and ^Ra2 each independently have a hydrogen atom or a linear or branched alkyl group having 1 or more and 6 or less carbon atoms. R ^a3 represents a linear, branched or cyclic alkyl group having 1 or more and 10 or less carbon atoms. R ^a4 represents a linear, branched or cyclic group having 1 or more and 6 or less carbon atoms. Represents an alkyl group of. O represents a group represented by 0 or 1), a linear, branched or cyclic alkyl group having 1 or more and 6 or less carbon atoms, a vinyloxyethyl group, and a tetrahydropyranyl. A liquid composition which is a group, a tetrahydrofuranyl group, or a trimethylsilyl group . The silyl group has the following formula (a2-1):
-SiR ⁰¹ _x R ⁰² _(3-x) ... (a2-1)
(In the formula (a2-1), R ⁰¹ is an organic group, R ⁰² is a hydroxyl group or a group that produces a silanol group by hydrolysis, and x is 0, 1, or 2.)
The liquid composition according to claim 9 , which is a group represented by.