JP2001187764A - Surface active compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surface active compound having a surface activating ability and a polymerization-initiating ability. SOLUTION: This surface active compound is represented by the formula: [R1a-(B1)r-(X1-B2)t]p-(S)k-[(B3-X2)u-(B4)s-R2a]q (R1a is a unit having a hydrophobic group; R2a is a unit having a hydrophilic group; B1 and B4 are each a unit for binding R1 or R2 with active groups X1 or X2, B2 and B3 are each a unit for binding a spacer to X; (k), (r), (s), (t) and (u) are each 0 or 1; with the proviso that both of (t) and (u) are not simultaneously 0; and (p) and (q) are each an integer of 1-3). The active group is ordinarily the group generating a radical by heat or light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a compound having a polymerization initiating group and having a surface activity and a use of the compound (namely, a substrate on which the compound is adsorbed, and a surface-active compound adsorbed on the substrate. And a method for producing the same), and an intermediate for obtaining the compound.

[0002]

2. Description of the Related Art Conventionally, the dispersibility of a base material in a medium or a matrix has been improved by modifying the surface of the base material such as fillers, pigments, and inorganic fine particles. In general, a method of coating the surface of a substrate with an organic substance has been used to modify the surface of the substrate.

Conventional surface modification methods include, for example,
(1) a method of adsorbing a polymer on the surface of a substrate, (2) a method of adsorbing a surface active compound on the surface of a substrate, and (3) introducing a radical initiating group such as an azo group or a peroxide group to the surface of the substrate. And then polymerizing the monomer to graft the polymer compound onto the surface of the substrate. (4) introducing a compound having an unsaturated double bond onto the surface of the substrate, and then polymerizing the monomer to bring the polymer compound onto the surface. A method of grafting, (5) a method of adsorbing a surface active compound having an unsaturated double bond on the surface of a substrate, and then polymerizing a monomer to graft a polymer compound to the surface of the substrate are performed.

However, in the method (1), it is difficult to efficiently adsorb a polymer on the surface of a substrate, and a large number of polymers are required for surface modification. Further, not only is the type of polymer specified, but it is not easy to find such a specific polymer. Further, in the method (2), not only is the use restricted due to the hydrophilicity, but also the surface cannot be sufficiently modified.

In the method (3), in the case of a substrate having a highly reactive group on the surface, such as carbon black, a polymer compound starting from an azo group or a peroxide group bonded to the substrate surface is used as a starting point. Grows, so that the surface modification effect and the grafting efficiency are high. However, when the surface is an inert or low-reactive substrate, such as a general organic or inorganic pigment, it is usually difficult to chemically bond an azo group, a peroxide group, etc. to the substrate surface. And the surface cannot be efficiently modified.

In the above method (4), the grafting of the polymer compound onto the substrate surface occurs only when the unsaturated double bond bonded to the surface reacts with the radical species generated by the polymerization reaction. The probability of grafting is low, and many free polymer compounds that do not graft are generated. Generally, it is difficult to chemically bond an unsaturated double bond to the surface. Therefore, the method (4) is also effective for a substrate having a highly reactive group on the surface, but a sufficient effect is obtained for a substrate having no highly reactive group. Absent.

In the above method (5), more unsaturated double bonds can be easily introduced into the surface of the substrate than in the method (4), but the probability of grafting is low as in the method (4). Many non-grafted free polymer compounds are produced. In addition, steric hindrance is generally increased due to adsorption of a surfactant compound, and the reactivity of the double bond is reduced. Therefore, it is difficult to form a sufficient polymer compound layer on the substrate surface.

As described above, in the conventional method, since the effect of modifying the surface of the substrate is still insufficient and the graft ratio of the organic substance to the substrate is low, it is difficult to improve the dispersibility of the substrate in the matrix. Have difficulty.

Japanese Unexamined Patent Publication No. 11-194471 discloses that a highly reactive group (hydroxyl group) on the surface of silica fine particles has three
-Describes that a photosensitive group can be introduced by bonding methacryloxypropyltrimethoxysilane. Also in this method, it is necessary to have a highly reactive group on the particle surface, and the usable base material is limited.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a surface-active compound which has a surface-active ability and also functions as a polymerization initiator, and a micelle formed with this surface-active compound. is there.

Another object of the present invention is to provide a surface active compound which can control the surface state of a substrate to be hydrophobic or hydrophilic and can be dispersed in a desired medium, and a substrate to which the surface active compound is adsorbed. It is in.

Still another object of the present invention is to increase the bonding ratio of a polymer to the surface of a substrate, effectively modify the surface of the substrate, and greatly improve the dispersibility of the substrate in a predetermined matrix. An object of the present invention is to provide a substrate and a method for producing the same.

Another object of the present invention is to provide a composite substrate capable of effectively covering the entire surface of the substrate with a polymer and controlling the degree of coating, and a method for producing the composite substrate.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the use of a surface active compound having a surface active ability and a polymerization initiating ability makes it possible to effectively use the surface of a substrate. Thus, the present invention was completed.

That is, the surfactant compound of the present invention is represented by the following formula (1).

(R ¹ ) _m -Z- (R ² ) _n (1) (wherein, R ¹ is a unit having at least a hydrophobic group,
R ² represents a unit having at least a hydrophilic group;
Represents a unit having at least one active group, and m
And n represent an integer of 1 to 3. The type of R ¹ and R ² is m
Or may differ depending on the value of n) The compound represented by the formula (1) may be a compound represented by the following formula (2).

[R^1a− (B¹)_r− (X¹−B^Two)_t]_p− (S)_k− [(B^Three−X^Two)_u− (B^Four)_s−R^2a]_q (2) (where R^1aIs a unit having at least a hydrophobic group,
R^2aRepresents a unit having at least a hydrophilic group, and X
¹And X^TwoRepresents the same or different and represents an active group. B¹Passing
And B^FourIs R¹Or R^TwoAnd the active group X¹Or X^TwoJoin with
Unit, B ^TwoAnd B^ThreeIs the spacer S and the active group
X¹Or X^TwoAnd a unit that combines k, r, s,
t and u represent 0 or 1. Where t and u are simultaneously
Not zero. p and q each represent an integer of 1 to 3)
The group is an aliphatic hydrocarbon group having 5 to 60 carbon atoms,
60 aromatic hydrocarbon groups, heterocyclic groups, polysiloxane residues
And the hydrophilic group may be a polysaccharide group or a polyether group.
Group, hydroxyl group, carboxyl group, sulfate group, sulfo group
Phonic acid group, phosphate group, phosphonium base, heterocyclic group,
Mino groups, their salts, their esters, etc.
Good. In particular, the hydrophobic group is C_8-22Long chain aliphatic hydrocarbon group or
Is C_1-20Alkyl-C_6-12May be an aryl group,
Hydrophilic group, carboxyl group, sulfate group, sulfonic acid group,
These salts and polyoxyethylene groups may be used.
No. Active group X¹And X^TwoIs a radical by heat or light,
Groups that generate cations or anions (especially azo groups,
Oxidized groups, keto groups capable of generating radicals, etc.)
No. Coupling unit B¹, B^Two, B^ThreeAnd B^FourIs an ester bond
Amide bond, urea bond, urethane bond, ether
Bond, thioether bond, imino bond, etc.
You may have. The spacer S is an alkylene group,
Even if it is composed of polyvalent groups such as a arylene group and a heterocyclic group
Often, these groups may have various substituents.
In equation (2), (i) k = 0, p = 1 and q = 1,
Or (ii) k = 1, p = 1 or 2 and q = 1 or 2
You may.

The compound for obtaining the surface active compound represented by the above formula (1) is represented by the following formula (3).

(E ¹ ) _m -Z- (E ² ) _n (3) (wherein E ¹ is a hydrophobic group corresponding to R ¹ in the formula (1) or a reaction for forming a hydrophobic group by a reaction) A functional group, E ²
Represents a hydrophilic group corresponding to R ² in the formula (1) or a reactive group that forms a hydrophilic group by a reaction. Provided that at least one of E ¹ and E ² is a reactive group;
And n is the same as in claim 1) The reactive group may be an activated carboxyl group.

The present invention also includes a method for producing the surfactant compound of the above formula (1). Further, in the present invention, a micelle formed of the surfactant compound, a substrate to be treated (for example, particles such as a pigment), and the surfactant compound adsorbed on the surface of the substrate to be treated are constituted. A base material, a composite base material in which a polymer of a polymerizable monomer is bonded to the base material using a surfactant compound adsorbed on the base material surface as an initiator,
A method for producing a composite substrate in which a surface active compound is adsorbed on the surface of the substrate to be treated to polymerize the polymerizable monomer is also included.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the surface active compound of the present invention, examples of the hydrophobic group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, and a polysiloxane residue. These hydrophobic groups may be used alone or in combination of two or more.

Examples of the aliphatic hydrocarbon group include saturated or unsaturated linear or branched aliphatic hydrocarbon groups [for example, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (lauryl) ), Tridecyl, tetradecyl, pentadecyl, hexadecyl (cetyl), heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, hexacosyl (seryl), triacontyl, hentriacontyl (merisyl), α-olefin polymers, etc. Preferably 6-30, more preferably 8-25, especially 8
~ 20) alkyl group, hexenyl, tridecenyl, octadecadienyl, octadecenyl, nonadecenyl, docosenyl, hexacosenyl, α-olefin polymer (olefin oligomer having unsaturated double bond)
An alkenyl group having about 5 to 60 (preferably 6 to 30, more preferably 8 to 20) carbon atoms, such as hexynyl,
C5 to C60 (preferably 6 to 3) such as nonadecinyl
0, more preferably about 8 to 20) alkynyl group or the like], a saturated or unsaturated cyclic aliphatic hydrocarbon group [for example,
C5 to C60 (preferably 6 to 2) such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, cyclopentadecyl, etc.
0) cycloalkyl group having about 6 to 60 (preferably 6 to 20) carbon atoms such as cycloalkyl group, cyclohexenyl, cyclohexadienyl, cyclooctenyl, cyclodecenyl, etc.], saturated or unsaturated polycyclic hydrocarbon group [For example, a group corresponding to a bicyclic hydrocarbon such as carane, pinane, bornane, norpinane, norbornane (a bridged monocyclic saturated or unsaturated hydrocarbon group), a group corresponding to a tricyclic hydrocarbon such as adamantane ( Cross-linked polycyclic saturated or unsaturated hydrocarbons), groups corresponding to polycyclic hydrocarbons such as cholester-5-ene, etc.].

Examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, fluorenyl, anthracenyl,
Phenanthrenyl, benzanthrenyl, pyrenyl,
Aryl groups such as triphenylel and perylenyl, isopropylphenyl, butylphenyl, amylphenyl, hexylphenyl, octylphenyl, nonylphenyl,
Alkyl-aryl groups such as decylphenyl, dodecylphenyl and tetradecylphenyl (preferably C _1-20 alkyl-C _6-18 aryl groups, more preferably C _6-18 alkyl-C _6-12 aryl groups, especially C _{6 -16} alkyl-phenyls) and the like.

As the heterocyclic group, 12-crown-4,
15-crown-5, 18-crown-6, dicyclohexano-24-crown-8, dibenzo-18-crown-6, cyclen, hexacyclene, 1-aza-12-
Crown or ether such as crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6; oxygen as a hetero atom such as tetraoxadiazacyclooctadecane and pentaoxadiazabicyclotricosan; Heterocyclic compounds having a nitrogen atom, ethioporphyrin, octaethylporphyrin, protoporphyrin,
Examples include porphyrins such as hematoporphyrin, coproporphyrin, mesoporphyrin, tetraphenylporphyrin, phthalocyanine, naphthalocyanine and the like. The heterocyclic group may hold a metal in the skeleton. Examples of the metal include an alkali metal such as lithium, sodium and potassium, an alkaline earth metal such as magnesium, and a periodic table 3B such as aluminum and gallium.
Group 4B metals of the periodic table such as metal, silicon, tin, and lead, and transition metals such as vanadium, manganese, iron, cobalt, nickel, ruthenium, copper, and zinc. Also,
Anions for these metals may coexist, and examples of the anion include a halogen ion, an organic acid ion (such as an acetate ion), an inorganic acid ion (such as a sulfate ion), a tetrafluoroboron ion, and a hexafluorophosphate ion.

The polysiloxane residue includes, for example, a group represented by the following formula.

CH _3- (Si (CH ₃ ) ₂ O) _h- (where h is an integer of 5 to 30, preferably 10 to 20) The hydrophobic group is a different type of hydrophobic group. Also include complex hydrophobic groups bonded to each other.

These hydrophobic groups may have various substituents. Examples of the substituent include a carbonyl group, a thiocarbonyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, a mercapto group, an oxime group, an imino group, an isocyanato group (isocyanate group), and a thioisocyanato group ( Thioisocyanate group), cyano group, tertiary amino group, nitro group, carboxyl group, chain hydrocarbon group (C _1-12 alkyl group), monocyclic aliphatic hydrocarbon group (C _3-15 Cycloalkyl group). For example, perfluorophenyl, perfluoropentyl, perfluorododecyl and the like may be used.

Preferred hydrophobic groups include groups which sufficiently exhibit a hydrophobic function as a surfactant, for example, nonyl,
C _8-22 long chain aliphatic hydrocarbon groups such as dodecyl (lauryl), tetradecyl, hexadecyl (cetyl) and octadecyl (preferably C _10-18 long chain aliphatic hydrocarbon groups, more preferably C _12-16 long chain aliphatic hydrocarbon group), octylphenyl, nonylphenyl, decylphenyl, C _1-20 alkyl -C _6-12 aryl (preferably C _6-20 alkyl -C _6-12 aryl, such as dodecylphenyl, more preferably C _8-16 alkyl-C _6-12 aryl (e.g.,
_C8-16 alkyl-phenyl)) and the like.

Examples of the hydrophilic group include a nonionic group (eg, an ether group, a hydroxyl group, etc.), an anionic group (eg, a carboxyl group, a sulfonic group, a sulfate group, a phosphate group, a phosphonium group, a salt thereof, Esters), a cationic group (eg, a heterocyclic group, an amino group, or a salt thereof). These hydrophilic groups may be used alone or in combination of two or more.
The unit R ² may be composed of the hydrophilic group, or may be composed of a group derived from the compound having the hydrophilic group. A C _2-4 alkylene oxide may be added to the hydrophilic group.

Examples of the ether group include a polyoxy C _2-4 alkylene group such as a polyoxyethylene group and a polyoxypropylene group (particularly, a polyoxyethylene group). The compound having a hydroxyl group may be a monohydric alcohol, but is usually a polyhydric alcohol. Examples of the polyhydric alcohol include polysaccharides (such as sucrose, sorbitol (sorbitol), and sorbitan (eg, 1,5-sorbitan, 3,6-sorbitan, etc.).
Molecular dehydrates, bimolecular dehydrates such as sorbide), esters thereof, etc.), trihydric alcohols such as glycerin,
And dihydric alcohols such as N, N-dihydroxy C _1-4 alkylamide. In addition, the compound having a hydroxyl group may have C _2-4 alkylene oxide (particularly, ethylene oxide) added thereto.

Among the anionic groups, examples of the compound having a carboxyl group include C _1-6 aliphatic carboxylic acids and amino acids having about 1 to 6 carbon atoms (eg, N-acyl amino acids). Examples of the compound having a sulfonic acid group include C _6-12 arylsulfonic acids such as benzenesulfonic acid group, C _2-6 aliphatic carboxylic acids having a sulfonic acid group such as sulfoacetic acid and sulfosuccinic acid, and N—C _1-4 Amino C _1-6 alkanesulfonic acids such as acylmethyltaurine and the like are also included. Further, the compound having a sulfate group also includes esters of sulfuric acid such as glycerin monosulfate and alcohols. The compound having a phosphate group includes a phosphate ester and the like. The anionic group and the compound having an anionic group include C _2-4
Alkylene oxide (especially ethylene oxide) may be added. Such compounds include, for example, polyoxyalkylene ether carboxylic acid, polyoxyethylene ether sulfuric acid, polyoxyethylene ether phosphoric acid, and the like.

When the hydrophilic group is an anionic group (such as carboxylic acid and sulfonic acid), it may form a salt with various bases. As the base, an inorganic base (for example, lithium,
Examples thereof include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium, ammonia and the like, and organic bases (eg, amines).

Among the cationic groups, the heterocyclic group includes a group corresponding to a 5- to 8-membered heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom as a hetero atom. It is. In particular, a quaternary ammonium salt of a heterocyclic group having a nitrogen atom as a hetero atom, for example,
Heterocyclic groups such as pyridinium salts and imidazolinium salts represented by the following formulas are exemplified.

[0034]

Embedded image

[0035] (wherein, R ⁵ represents an alkyl group) as the alkyl group represented by R ⁵ include methyl, ethyl,
And C _1-6 lower alkyl groups such as propyl and hexyl.

In the heterocyclic group, the bond may be possessed by a hetero atom, or may be possessed by a ring-constituting carbon atom other than the hetero atom.

Examples of the amino group include primary, secondary, tertiary and quaternary amino groups. In the case of primary to tertiary amino groups,
A salt or amide with an inorganic acid (eg, hydrochloric acid) or an organic acid (eg, acetic acid) may be formed. Class 2 ~
Examples of the quaternary amino group include mono to tetra C _1-30 such as methylamino, dimethylamino, diethylamino, trimethylamino, tetramethylamino, and trimethyllauryl.
Alkylamino group (mono, di, tri or tetra C _1-10 alkylamino group (preferably C _1-6 alkylamino group,
More preferably, a C _1-4 alkylamino group)), mono-tetra C _6-12 such as phenylamino and diphenylamino
Mono, such as an arylamino group and a benzalkonium base,
It may be a di or tri C _1-4 alkyl C _7-20 aralkyl group.

In addition, cationic groups (particularly, amino groups)
May form an amphoteric group together with an anionic group (particularly, a carboxyl group or a sulfate group). Examples of the group forming such a zwitterion include an aminocarboxylic acid residue such as a carboxyethylamino group (—NHCH ₂ CH ₂ COOH) and a dihydroxymethylamino group (—N (CH ₂ CH ₂ O
H) ₂ ), a dicarboxymethylamino group (—N (CH ₂ COO
H) ₂ ), dicarboxyethylamino group (-N (CH ₂ CH ₂ COO
H) ₂ ), a group having a carboxyl group and / or a hydroxyl group and an amino group such as an aminosulfate group (—NHOSO ₃ H) and a carboxyethylcarbonylamino group (—NHCOCH ₂ CH ₂ COOH). Examples of the compound having a carboxyl group and an amino group include carboxybetaine (an N-triC _1-4 alkyl-substituted amino acid), sulfobetaine, and an alkyl group having a carboxyl group or a hydroxyl group at a hetero atom of a heterocyclic ring. A heterocyclic compound (for example, a compound in which a carboxyl C _1-4 alkyl group and a hydroxy C _1-4 alkyl group are substituted on the nitrogen atom of imidazoline), a phosphate group such as an amine oxide group and a phosphatidylcholine group, and an amino group. And the like.

The hydrophilic group may be substituted with various substituents. Examples of the substituent include the substituents exemplified in the section of the hydrophobic group. The hydrophilic group also includes a composite hydrophilic group in which different types of hydrophilic groups are bonded to each other.

Preferred hydrophilic groups include hydrophilic groups that sufficiently fulfill the role of a hydrophilic group as a surfactant, such as a carboxyl group, a sulfate group, a sulfonic group, a salt thereof, and a polyether group. No.

The unit R¹And R^1aIs at least
May also have a hydrophobic group, and the hydrophilic group exemplified above is
You may have it in a unit. Also, the unit R^TwoPassing
And R^{Two a}Also has at least a hydrophilic group
And may further have the above-mentioned hydrophobic group.
For example, the hydrophilic group (for example, a heterocyclic group, an N-substituted
Mino group), the hydrophobic group (C_8-22Long chain aliphatic hydrocarbon
And the like). like this
The group is a heteroatom of a heterocyclic group as a hydrophilic group
A group substituted by a long-chain aliphatic hydrocarbon group (the heterocyclic group
In the formula, R ^FiveIs C_8-16Such as an alkyl group)
And the like.

The units R ¹ and R ² are connected via a unit Z. As the active group (active groups X ¹ and X ² described below) contained in the unit Z, a group that functions as a polymerization initiator, for example, a group that generates a radical, a cation, an anion, or the like by heat or light (for example, an azo group) And a group having a peroxide group (peroxy group), a keto group or a polymerization initiator group such as a carbonyl group (a keto group capable of generating a radical) or a persulfate group. The active group is usually a radical generating group.

The active group having an azo group is represented by the following formula:
The group represented by (i) can be exemplified.

[0044]

Embedded image

(R ^a , R ^b , R ^c and R ^d are the same or different and each represent a hydrogen atom, an oxygen atom, an alkyl group or an electron-withdrawing group) Examples of the alkyl group include methyl, ethyl, propyl and the like. C _1-4 alkyl group (preferably C _1-2 alkyl group, particularly methyl group).

Examples of the electron-withdrawing group include a cyano group, an acyl group (C _1-4 acyl group such as acetyl group) and an alkoxycarbonyl group (C _1-4 alkoxycarbonyl group such as methoxycarbonyl and ethoxycarbonyl group). No. At least one of R ^a and R ^b may be an electron withdrawing group, and at least one of R ^c and R ^d may be an electron withdrawing group. Note that ^Ra and ^Rb ( ^Rc
And R ^d ) is an oxygen atom, the other is a bond of a double bond between an adjacent carbon atom and the oxygen atom, and R ^a and R ^b (R ^c and R ^d ) are adjacent A carbonyl group (-C (= O)-) can be formed together with a carbon atom.

The active groups may be asymmetric,
It preferably has a structure symmetrical about the active group.

Examples of the active group having a peroxy group include groups represented by the following formula (ii) or (iii).

[0049]

Embedded image

Where R^e, R^f, R^gAnd R^hAre the same or
Are different from hydrogen, halogen, alkyl,
Chloroalkyl group, aryl group, hydroxyl group, acyl
Group or an alkoxycarbonyl group. R^eAnd R^gIs
They may combine with each other to form a ring. a is 0 or 1
Show. M represents an alkali metal) As the alkyl group, C_1-20Alkyl groups (especially methyl
C, such as a group or an ethyl group _1-4Alkyl group, etc.)
And the cycloalkyl group includes C_3-8Cycloalkyl
Groups (especially cyclohexyl groups) and the like. Also,
Examples of the aryl group include a phenyl group and the like._6-12Aryl
And the like. As the halogen atom, fluorine,
Chlorine atom and the like. As the acyl group, acetyl
C such as _1-4Acyl group, alkoxycarbonyl group and
As a result, C_{1 -Four}Alkoxyka
And a rubonyl group. In particular, S in which a is 1
In the case of a tell-type peroxide group, R^e, R^f, R^gOr R
^hIs C_1-20Alkyl group (long chain C_{6- 18}Alkyl group
) And an aryl group such as a phenyl group in many cases.

Examples of the alkali metal represented by Y include sodium and potassium. The formula (ii)
Since the active group represented by i) also functions as a hydrophilic group, it may constitute the unit -ZR ² of the formula (1).

The active group having a keto group is represented by the following formula (iv).

[0053]

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[0054] (In the formula, A represents a carbon atom or a phosphorus atom, y is .R ^k or R ^m represents 0 or 1, represents an alkylene group, a cycloalkylene group or an arylene group, R ⁿ
Represents an alkyl group. R ⁿ may be a bond of a double bond formed by an adjacent oxygen atom.) Examples of the alkylene group include a C _1-4 alkylene group such as methylene and an ethylene group, particularly a methylene group. Examples of the cycloalkylene group include a C _3-8 cycloalkylene group such as a cyclohexylene group.
Examples of the arylene group include a C _6-12 arylene group such as a phenylene group, particularly a phenylene group. Examples of the alkyl group represented by R ⁿ include the aforementioned C _1-6 alkyl group (particularly, a C _1-4 alkyl group). In particular, the site adjacent to the keto group is often a bulky group having steric hindrance.

The alkylene group, cycloalkylene group and arylene group may have various substituents (for example, a substituent (C _1-4 alkyl group (especially methyl group, ethyl group),
_7-20 aralkyl group, hydroxyl group, alkoxy group (C _1-4 alkoxy group such as methoxy or ethoxy group), carboxyl group, C _1-4 alkoxycarbonyl group, halogen atom (chlorine atom, etc.), amino group, N- Substituted amino groups (such as mono- or di-C _1-4 alkyl-substituted amino groups such as dimethylamino), heterocyclic groups (such as morpholino groups)
May be substituted.

The keto group capable of generating a radical may form a hydrocarbon ring or a hetero ring having a hetero atom such as a sulfur atom. Further, the hydrocarbon ring and the hetero ring are not limited to a single ring, and a hydrocarbon ring (a non-aromatic hydrocarbon ring or an aromatic hydrocarbon ring) or a hetero ring is condensed (ortho-condensation, ortho-and-peri condensation, etc.). May be a fused heterocyclic ring. Note that a bond may be possessed by any ring, and in the case of a heterocyclic ring, a hetero atom may be possessed, or a carbon atom constituting the heterocycle may be possessed.

The compound represented by the formula (1) may be a compound represented by the following formula (2).

[R^1a− (B¹)_r− (X¹−B^Two)_t]_p− (S)_k− [(B^Three−X^Two)_u− (B^Four)_s−R^2a]_q (2) (where R^1aIs a unit having at least a hydrophobic group,
R^2aRepresents a unit having at least a hydrophilic group, and X
¹And X^TwoRepresents the same or different and represents an active group. B¹Passing
And B^FourIs R¹Or R^TwoAnd the active group X¹Or X^TwoJoin with
Unit, B ^TwoAnd B^ThreeIs the spacer S and the active group
X¹Or X^TwoAnd a unit that combines k, r, s,
t and u represent 0 or 1. Where t and u are simultaneously
Not zero. p and q each represent an integer of 1 to 3) R^1aAnd R^2aAs the R¹And R^TwoUnits similar to
R¹And R^TwoThe units exemplified in the section
I can do it.

The coupling units B ¹ , B ² , B ³ and B ^4
It can be appropriately selected according to the kind of ¹ , R ² , X, S and the like, and is usually a polyvalent group. Such a binding unit is, for example, an alkylene group (methylene, ethylene, propylene,
A C _1-10 alkylene group such as a butylene, pentylene or hexylene group, preferably a C _2-6 alkylene group; a cycloalkylene group (a C _4-12 cycloalkylene group such as a cyclohexylene group, preferably a C _4-8 cycloalkylene) Group);
Arylene group (C _6-18 such as phenylene and naphthalene group
An arylene group, preferably a C _6-12 arylene group);
Heterocyclic group [a divalent heterocyclic group containing at least one hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (having a nitrogen atom as a hetero atom such as pyrrolidinediyl, piperidinediyl, pyridinediyl, pyrazinediyl, etc.) A 5- or 6-membered heterocyclic group, a 5- or 6-membered condensed heterocyclic group having a nitrogen atom as a hetero atom such as quinolinediyl), etc.]. The heterocyclic group may be non-aromatic or aromatic. Further, in the condensed heterocyclic group in which the heterocyclic ring and the hydrocarbon ring are condensed, either the heterocyclic ring or the hydrocarbon ring may have a bond. Also,
The molecular chain may be composed of the polyvalent group alone, or a molecular chain composed of a plurality of polyvalent groups (for example, -R-Ar-
(R represents the alkylene group and Ar represents the arylene group).

Such bonding units B ¹ , B ² , B ³ and B ⁴ often have various bonds (for example, bonds such as ester bonds and amide bonds) in the molecular chain. . Examples of the type of the bond include an ester bond, an amide bond, a urea bond, a urethane bond, an ether bond, a thioether bond (sulfide bond), and an imino bond. Such a bond is composed of units R ¹ , R ² , S, X
(X ¹ and X ² may be collectively referred to as X), etc.
Since the compound is introduced using a compound having a reactive group (for example, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a thiol group, a carboxyl group, an isocyanate group, or a halogen atom) described below, the reaction of these reactive groups is performed. Generated by

The bonding mode produced by the reaction of the reactive group is, for example, a method in which an alkoxy group is bonded to a group reactive with the alkoxy group (for example, a hydroxyl group, a mercapto group, a carboxyl group, an isocyanate group, etc.). A bond formed by the reaction (eg, an ether bond, a thioether bond, an ester bond, a urethane bond, etc.);
A bond (eg, a thioether bond, an ester bond, a urethane bond, etc.) formed by a reaction between a hydroxyl group and a group reactive with the hydroxyl group (eg, a mercapto group, a carboxyl group, an isocyanate group, etc.); a halogen atom (E.g., an ether bond) formed by the reaction of a compound with a group having reactivity with a halogen atom (such as a hydroxyl group or an alkoxy group); and an amino group and a group having reactivity with the amino group ( For example, a bond (for example, an amide bond, an imino bond, a urea bond, or the like) formed by a reaction with a carboxyl group, an epoxy group, an isocyanate group, or the like; an epoxy group and a group having reactivity with the epoxy group (for example, Bond formed by reaction with amino group, carboxyl group, etc. A mercapto group and a group reactive with the mercapto group (eg, an alkoxy group); a carboxyl group and a group reactive with the carboxyl group (eg, a hydroxyl group, A bond (ester bond, amide bond, ester bond, etc.) formed by a reaction with an amino group, an epoxy group, or the like; an isocyanate group, and a group reactive with the isocyanate group (for example, a hydroxyl group,
And a bond (eg, a urethane bond, a urea bond, an ester bond, and the like) generated by a reaction with an amino group, a carboxyl group, and the like.

As the active groups X ¹ and X ² , the active groups exemplified above can be mentioned.

The spacer S is selected according to the values of p and q, and is usually a polyvalent group (2-6 hexavalent group, especially 2-4 tetravalent group).
It is. The polyvalent group is, for example, a compound whose molecular chain is a polyvalent C _1-10 alkane (preferably C _1-6 alkane) group, a C _3-20 cycloalkane (preferably C _3-10 cycloalkane) group,
_{A 6-20} aryl (preferably C _6-12 aryl) group or a heterocyclic group (a divalent heterocyclic group containing at least one hetero atom selected from the nitrogen, oxygen and sulfur atoms described above); It is configured. The molecular chain may be composed of the polyvalent group alone, or a molecular chain composed of a plurality of polyvalent groups (for example, -R-Ar- (R represents an alkylene group, Ar represents an arylene group), and the like. ).

[0064] Incidentally, the spacer S is a variety of substituents in the molecular chain (C _1-4 alkyl groups, C _1-4 alkoxy group, a cyano group, an amino group, N- substituted amino group (N-C _1-4 Alkyl-substituted amino group) and halogen atom).

In the compounds of the formulas (1) and (2), a preferable combination of groups is, for example, a case where the hydrophobic group is a C _8-22 long-chain aliphatic hydrocarbon group (particularly, a C _10-18 long-chain aliphatic group). A hydrocarbon group) or a C _6-20 alkyl-C _6-12 aryl group (particularly,
C _6-18 alkyl-phenyl group), and the hydrophilic group is a polyether group (particularly a polyoxyethylene group), a carboxyl group, a sulfate group, a sulfonic acid group or a salt thereof.
In the compound of the formula (2), the bonding units B ¹ to
It is preferred that at least one of B ⁴ has an ester bond or amide bond mode. Preferred combinations of coefficients are (i) k = 0, p = 1 and q = 1 (in particular, k =
0, p = 1, q = 1, r = 1, s = 0, t = 1 and u =
0) or (ii) k = 1, p = 1 or 2 and q = 1 or 2 (especially k = 0, p = 2, q = 1, r = 1, s =
1, t = 1 or 0 and u = 0 or 1).

[Production method] Production method of surfactant compound
Is not particularly limited, and the R¹, R^TwoFor Z and Z
Compound (or group R¹, R^Two, B¹~ B^Four, X¹, X^TwoAnd S
May be sequentially reacted,
R¹, R^TwoAnd Z groups (or groups R¹, R^Two, B ¹~ B^Four, X
¹, X^TwoAnd a single compound corresponding to a plurality of groups in S)
And one or more compounds corresponding to the residual groups
You may let it. For example, by the following method,
May be prepared.

A compound represented by the following formula (4): R ¹ -F ¹ (4) (wherein F ¹ represents a reactive group; R ¹ is the same as described above). And a method of reacting the compound with the compound.

(F ² ) _m -Z- (R ² ) _n (5) (wherein F ² represents a reactive group corresponding to the reactive group F ^1. Z, R ² , m and n represent more specifically identical) to the compound corresponding to group -R ¹ (e.g., such as alkyl phenols having a reactive group), group -Z- (R ²⁾ compounds corresponding to _n (e.g., an azo group Having a reactive group corresponding to the reactive group at the terminal).

Particularly, in the case of the surfactant compound represented by the formula (2), when (i) k is 0, the compound represented by the following formula (6) and the compound represented by the following formula (7) a method of reacting a ^{compound; R 1a - (B 1)} r - (X 1 -B 2) t -F 3 (6) (F 4) p - [(B 3 -X 2) u - (B 4) _{^{s -R 2a] q (7)}} ( wherein, F ³ represents a reactive group .F ⁴ is the reactive group F ³
Represents a reactive group corresponding to R ^1a , R ^2a , B ¹ , B ² , B
³ , B ⁴ , X ¹ , X ² , p, q, r, s, t and u are the same as described above.) (Ii) When k is 1, a compound represented by the following formula (8): A compound represented by the formula (9):
And the like.

(F^Five)_p-S- (F⁶)_q (8) R^1a− (B¹)_r− (X¹-B^Two)_t-F⁷ (9) F⁸− (B^Three-X^Two)_u− (B^Four)_s-R^2a (10) (where F^FiveAnd F⁶Represents a reactive group. F⁷And F⁸Is
The same or different, the reactive group F^FiveOr F⁶Corresponding to
Shows a reactive group. S, R^1a, R^2a, B¹, B^Two, B ^Three,
B^Four, X¹, X^Two, P, q, r, s, t and u are as defined above.
More specifically, for example, when (i) k is 0, the reaction
Functional group and at least unit R^1aCompounds having (e.g.,
For example, long-chain fats with hydroxyl or carboxyl groups
Aliphatic hydrocarbons) and the reactivity corresponding to the reactive group
Group and at least unit X¹And / or X^TwoAnd R^2aWith
[For example, (B¹)_r− (X¹-B^Two)_t-(B^Three
-X^Two)_u-(B_Four)_s-R^TwoCompounds corresponding to
It has a sil group or an amino group, and has an active group such as an azo group.
(Esterification or amide)
) May be prepared.

(Ii) when k is 1, a compound having a plurality of reactive groups and at least a spacer S (for example, an aliphatic hydrocarbon having a hydroxyl group and an amino group, etc.) and a compound corresponding to the reactive group Having at least a unit R ^1a and a reactive group [eg, R ^1a- (B ¹ ) _r
-(X ¹ -B ² ) Compound corresponding to _t (acid halide having a long-chain alkyl group or the like)] and a compound having a reactive group corresponding to the reactive group and at least units R ² and X ² [for example, , A compound corresponding to R ^2a- (B ⁴ ) _r- (X ² -B ³ ) _t (eg, a compound having a carboxyl group and having an active group such as an azo group)]. Is also good.

The active group X may be introduced by using a compound having the active group X (compound having at least the group X and R ¹ or R ² ) in advance. After the introduction of R ¹ and / or R ² into the group, it may be introduced. For example, when the active group is a peroxide group, the peroxide group may be introduced by reacting a compound having ^a precursor unit Xa of the active group with a peroxide.

The combination of the corresponding reactive groups (F ¹ and F ² , F ³ and F ⁴ , and F ⁵ and F ⁶ and F ⁷ and F ⁸ ) depends on the type of the reactive group. Can be selected, for example,
When one reactive group is a carboxyl group, the other reactive group may be a hydroxyl group, an amino group, an epoxy group, or the like, and when one is a hydroxyl group,
The other may be a carboxyl group, an isocyanate group, an epoxy group, or the like. Further, when one is an amino group, the other may be a carboxyl group, an isocyanate group or an epoxy group.

The compounds (4) to (10) include the reactive groups [groups corresponding to the bonds exemplified in the section of the bonding units B ^{1 to} B ⁴ (carboxyl group, hydroxyl group, amino group, isocyanate group, A reactive group such as an epoxy group)] at the terminal. As the compound (8), for example, polyhydric alcohols, polycarboxylic acids, hydroxycarboxylic acids, polyamines, polyisocyanates and the like can be used.

The unit R ¹ (and R ^1a ) having a hydrophobic group may be introduced or formed by, for example, a Friedel-Crafts reaction or a substitution reaction. For example, a compound having at least a group X and R ¹ (for example, a C _8-22 fatty acid halide such as lauroyl chloride) and a compound having at least a group -Z (for example, having a benzene ring and having at least groups Z and R ²⁾ R ¹ may be introduced by a Friedel-Crafts acylation reaction with a compound having the formula Further, a compound corresponding to the group R ¹ (for example,
C _8-22 alkoxide such as lauroyl alkoxide) and a compound having at least a group -Z (for example, a compound having a halogen atom and corresponding to the group -ZR ² ) are subjected to a substitution reaction. A hydrophobic group R ¹ may be introduced.

The amount of the compounds (4) to (10) used is appropriately selected according to the reactive group, and the reaction conditions (temperature, time, solvent, etc.) can be appropriately selected from the reaction conditions described later.

The unit R ² (and R ^2a ) having a hydrophilic group may be introduced or formed by, for example, Grignard reaction, hydrolysis, addition of ethylene oxide, or the like. For example, compounds having at least group -Z (e.g., a halogen atom, the corresponding compounds based on Z-R ¹⁾ subjected to the Grignard reaction, may be introduced carboxyl group. Further, a compound having at least group -Z by the (e.g., having an ester group, the compound corresponding to group Z-R ¹⁾ hydrolyzing, may be introduced carboxyl group is a hydrophilic group R ² The said at least group-
Ethylene oxide may be added to the compound having Z. The order of introducing the hydrophobic group R ¹ or the hydrophilic group R ² is as follows.
There is no particular limitation.

In the method of introducing each unit (for example, R ¹ , R ^2, etc.) using the above reactive group, (I) the reactive group may be protected, and (II) the reactive group may be activated. Or (III) a coupling reagent may be used.

In the method (I), as the protecting group, a conventional protecting group, a sterically hinderable removable group such as a benzyl group or a tertiary butyl group can be used. In particular, an amino protecting group ( Benzyloxycarbonyl group which may have a substituent such as benzyloxycarbonyl group, p-nitrobenzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group; tertiary butyloxycarbonyl group; acyl group such as phthaloyl group , An aralkyl group such as triphenylmethyl group), a carboxyl protecting group (benzyl ester group; tertiary butyl ester group, C _1-2 alkyl ester group, etc.), a hydroxyl protecting group (benzyl group, dimethylcarbamoylbenzyl group, etc.) A benzyl group which may have a substituent; a tertiary butyl group; a tetrahydropyranyl group; And the like. By protecting the terminal of the reactive group with a protecting group, a hydrophobic group, a hydrophilic group and / or an active group can be bound to a predetermined site. The protecting group can be easily eliminated by a conventional elimination means, for example, a catalytic reduction method, an acid treatment, or an alkali treatment.

In the method (II), the formation of by-products and the like can be suppressed, and a surface-active compound can be obtained at a high yield. For example, after using a compound having a reactive group (such as a carboxyl group) and activating the reactive group, a hydrophobic group,
When a compound having a hydrophilic group and / or an active group and a group capable of reacting with the reactive group (such as an amino group) is reacted,
Surfactant compounds can be prepared efficiently. The activation of the reactive group usually advantageously activates the carboxyl group. A conventional method can be used for activating the reactive group, for example, a method for activating a carboxyl group (an active esterification method, a mixed acid anhydride method, a C-terminal activation method such as an azide method) or the like. be able to.

For example, (i) In the active esterification method,
Examples of the compound that activates a carboxyl group include a compound having an electron-withdrawing group. Examples of the electron-withdrawing group include a cyano group, a nitro group, and an acyl group (especially C
_1-4 acyl group), carboxyl group, alkoxycarbonyl group (especially C _1-4 alkoxycarbonyl group), sulfonic acid group, mercapto group, halogen atom (fluorine, chlorine, bromine atom, etc.). Examples of the compound having an electron-withdrawing group include p-nitrophenol,
Nitrophenols such as dinitrophenol; thiophenol; nitrothiophenol; halogen-substituted phenols such as trichlorophenol, tetrachlorophenol, trifluorophenol, tetrafluorophenol, etc.], hydroxyamines [N-hydroxyphthalimide, N-hydroxy N-hydroxy C _4-20 dicarboxylic imides such as succinimide, N-hydroxy-5-norbornene-2,3-dicarboxylic imide;
1-hydroxybenzotriazole, 2-hydroxyimino-2-cyanoacetic acid ethyl ester or amide thereof], a heterocyclic compound having a hydroxyl group and having a nitrogen atom as a hetero atom [quinolines such as hydroxyquinoline, hydroxypyridine and the like] Pyridines and the like]; aromatic compounds having a hydroxyl group [catechols having an adjacent hydroxyl group such as catechol and phenacyl catechol and the like] and the like can be used. These compounds can be used alone or in combination of two or more.

(Ii) In the mixed acid anhydride method, a compound having a carboxyl group and an acid (for example, monoalkyl carbonate (eg, isobutyl chloroformate)), valeric acid, isovaleric acid, phosphoric acid (tripropyltrimethalin Acid, etc.)
Activation is carried out by using a combination of these methods. (iii)
In the azide method, for example, a compound having a carboxyl group is reacted with hydrazine to produce hydrazide,
It is then converted to azide with nitrous acid. A compound in which a carboxyl group is converted into an azide and activated reacts efficiently with a compound having an amino group.

In the method (III), the coupling reagent may be a conventional coupling reagent such as N, N'-dicyclohexylcarbodiimide (DCC), carbonyldiimidazole, N-ethyl-5-phenylisoxazolium -3'-sulfonic acid salt and the like can be used. Further, a coupling reagent is obtained by combining DCC with a compound having an electron-withdrawing group exemplified in the section of the active esterification method (for example, hydroxyamines such as N-hydroxysuccinimide and 1-hydroxybenzotriazole). (DCC-additive
Law).

When a surface active compound is prepared by the above methods (I) to (II), a compound represented by the following formula (3) is obtained as an intermediate. The compound of the formula (3) is particularly useful for producing the surfactant compound of the present invention.

(E ¹ ) _m -Z- (E ² ) _n (3) (wherein E ¹ is a hydrophobic group corresponding to R ¹ in the formula (1) or a reaction for forming a hydrophobic group by a reaction) A functional group, E ²
Represents a hydrophilic group corresponding to R ² in the formula (1) or a reactive group that forms a hydrophilic group by a reaction. Provided that at least one of E ¹ and E ² is a reactive group;
And n are the same as in claim 1) Examples of the reactive group represented by E ¹ and E ² include an activated reactive group (for example,
Reactive groups protected by the protecting groups exemplified above, p-nitrophenyloxycarbonyl groups, thiophenyloxycarbonyl groups, and reactive groups activated by electron-withdrawing compounds such as N-hydroxyphthalimide ester groups (particularly active groups) Carboxyl group)) and the like.

Among the compounds of the formula (3), a particularly preferred compound is a compound corresponding to the compound of the above formula (2), such as a compound represented by the following formula (11).

[E ^1a − (B ¹ ) _r − (X ¹ −B ² ) _t ] _p − (S) _k − [(B ³ −X ² ) _u − (B ⁴ ) _s −E ^2a ] _q ( 11) (wherein, E ^1a and E ^{2a each} represent an active group; B ¹ , B ² ,
B ³ , B ⁴ , S, k, p, q, r, s, t and u are the same as described above.) The compound represented by the formula (3) is, for example, one or more reactive groups (carboxyl group). A compound having at least a unit Z (or a unit having at least X in the formula (11)), a compound corresponding to the protective group and / or a compound activating the reactive group. Can be prepared by reacting For example, corresponding to the unit Z-R ¹ or unit Z-R ^2, and a compound having one carboxyl group, be reacted with a compound that activates a compound or said reactive group corresponding to the protective group A compound corresponding to the unit Z and having two carboxyl groups may be reacted with a compound corresponding to the protective group or a compound activating the reactive group. The amount of the compound corresponding to the protective group or the compound that activates the reactive group is about 1 to 3 equivalents, preferably about 1.5 to 2 equivalents, per equivalent of the reactive group.

Reactive groups (carboxyl groups, etc.) are activated
The compound of the above formula (3) ¹Or R^TwoAnd the reaction
Reaction with a compound having a reactive group and a reactive group.
By this, the surfactant compound (1) of the present invention can be obtained.
it can. Of a compound having a group capable of reacting with the reactive group
The amount used is per equivalent of the reactive group of the compound of the formula (3),
It is about 1 to 3 equivalents, preferably about 1.5 to 2 equivalents.

The above reaction may be performed in the presence of a solvent. Examples of the solvent include common solvents (for example, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene,
Halogenated hydrocarbons such as methylene chloride and ethylene chloride, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, amides such as dimethylformamide, alcohols such as methanol, ethanol, isopropyl alcohol, and butanol)
Can be used. When the acid anhydride method is used among the activation methods, the solvent is preferably an anhydride.

The reaction temperature can be selected from the range of 0 to 150 ° C., for example, 10 to 120 ° C., preferably 20 to 10 ° C.
It is about 0 ° C. The reaction can be carried out under normal pressure, reduced pressure or increased pressure. The reaction may be performed under an atmosphere of an inert gas (eg, nitrogen, argon, helium, etc.).

After completion of the reaction, the compound (1) and the compound (3) formed by the above reaction are separated by a conventional method, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, and column chromatography. Alternatively, separation and purification can be easily performed by separation means combining these.

The surfactant compound of the present invention can be dissolved or dispersed in various media, and can form normal-phase or reverse-phase micelles depending on the type of the medium. As a medium,
There is no particular limitation, for example, water, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride. Alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. And ketones.

The surfactant compound of the present invention has a surfactant activity and also functions as a polymerizable initiator. Therefore, when the substrate to be treated is treated with the surface active compound of the present invention, the surface of the substrate to be treated can be effectively modified, and by cleaving the active group, the state of the surface can be controlled to be hydrophobic or hydrophilic. . Therefore, depending on the application, the treated substrate
It can be dispersed in a desired medium.

The substrate to be treated is not particularly limited, and can be selected from a wide range of inorganic or organic substrates according to the application. Also, the shape of the substrate to be treated is not particularly limited,
For example, spherical, elliptical, flat, rod, fibrous,
It may be a flat plate or the like. In addition, as a substrate to be treated,
Plastic films and molded plastics may be used. As the substrate to be treated, particles (particularly, functional particles) are usually used.

The particles include an insulator, a low dielectric, a colorant, a conductor, a dielectric, a magnetic substance, and the like. These particles can be composed of organic or inorganic particles.

As the insulator or the low dielectric substance, an organic polymer, for example, a fluororesin (eg, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTF), polyvinylidene fluoride (PVD)
F), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (P
FEP), tetrafluoroethylene-ethylene copolymer (PETFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), etc.),
Polymethyl methacrylate resin, melamine resin, cross-linked styrene resin, silicone resin; inorganic insulator materials such as silica (SiO ₂ ) and alumina (Al ₂ O ₃ );

Examples of the coloring agent include organic pigments such as red pigments (eg, toluidine red, permanent red, brilliant fast scarlet, balkan fast red, pyrazolone red, lithol red, lake red, brilliant carmine, lake bordeaux and the like). Pigments, lake pigments such as rhodamine lake), orange pigments (e.g., pyrazolone orange, vulcan orange, permanent orange, etc.), yellow pigments (e.g., Hansa yellow, benzidine yellow, vulcan fast yellow, permanent yellow, etc.),
Green pigments (for example, phthalocyanine pigments such as phthalocyanine green, lake pigments such as Final Yellow Green, etc.), blue pigments (for example, phthalocyanine pigments such as phthalocyanine blue and fast sky blue, lake pigments such as methyl violet lake and Victoria Pure Blue lake) Inorganic pigments such as white pigments (eg, zinc oxide, lithopone, titanium oxide (such as rutile type)), red pigments (eg, iron oxide red, red lead oxide, molybdenum red, etc.), and orange pigments (eg, , Molybdate orange, etc.), yellow pigments (eg, iron oxide yellow, yellow lead oxide, chrome yellow, nickel titanium yellow, etc.), green pigments (eg, chrome green, chromium oxide, etc.), blue pigments (eg, navy blue, ultramarine, Cobalt blue), purple Pigments (e.g., such as manganese violet), black pigment (e.g., channel black, carbon black such as furnace black, iron oxide black, etc.) and the like.

Further, organic pigments such as quinacridone-based, perylene-based, isoindolinone-based, dioxazine-based, and sulene-based pigments may be used. An extender pigment (for example, calcium carbonate, barium sulfate, aluminum hydroxide, etc.) may be used.

As the magnetic material, for example, iron, nickel,
Magnetic materials including metals such as cobalt and aluminum or alloys thereof, such as ferrite, ultrafine ferrite, permalloy, supermalloy, permender, and the like;
Examples of the ferroelectric include barium titanate and lithium niobate; and examples of the conductor include gold, silver,
A simple metal such as copper, platinum, and aluminum or an alloy thereof, a transparent conductive material (for example, tin oxide, indium oxide, I
_{TO, SnO 2 -Sb, SnO 2} -F, ZnO-Al, Z
nO-F, such as Cd ₂ SnO _4), and the like; as the photosensitive agent,
For example, zinc oxide, titanium oxide (photooxidation catalyst such as anatase type), the above-mentioned organic pigments and the like can be mentioned. Further, functional particles such as a piezoelectric material, a fluorescent material, a superconductor, and a sensor material may be used.

The average particle size of the functional dispersion particles is, for example,
It can be selected from the range of about 1 nm to 1 μm, preferably about 5 nm to 0.5 μm, and more preferably about 10 nm to 0.3 μm.

When the functional particles are used, they may be used in the form of a sol.

Examples of the plastic film or molded product include polyolefins such as polyethylene and polypropylene, polyvinyl acetate, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, poly (meth) acrylate, polystyrene, and polyester (polyethylene terephthalate, polybutylene). Polyalkylene terephthalate such as terephthalate, etc.), polyamide (polyamide 6, polyamide 66, polyamide 610, etc.),
Examples include polycarbonate, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, and cellulose derivatives such as cellulose acetate.

These substrates to be treated can be used alone or in combination of two or more, depending on the desired function.

The amount of the surface active compound to be used with respect to the substrate to be treated is not particularly limited, and is 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, per 100 parts by weight of the substrate to be treated.
Parts by weight, more preferably about 0.05 to 5 parts by weight.

When a particulate substrate is used as the substrate to be treated, the average particle size of the substrate to which the surface active compound is adsorbed varies depending on the average particle size of the substrate particles.
μm, preferably 5 nm to 1 μm, more preferably 1 μm
It is about 0 nm to 0.5 μm.

The treatment of the substrate to be treated with the surfactant compound may be directly applied by spraying, dipping, impregnating the surfactant compound, or by spraying the compound and the medium containing the compound.
It can be carried out by immersion, impregnation, adsorption or adhesion treatment. [Composite Substrate] The substrate on which the surface active compound is adsorbed can polymerize the polymerizable monomer using the surface active compound as an initiator to obtain a composite substrate in which the polymer is efficiently bonded to the surface of the substrate. it can. Therefore, the obtained composite base material can provide a new function and further greatly improve the dispersibility in the polymer matrix. In addition, by selecting the type of polymer to be bonded to the substrate, the surface of the composite substrate can be controlled to be hydrophilic or hydrophobic, so that the dispersibility of the composite substrate in various media can also be controlled. Furthermore, since the composite substrate of the present invention polymerizes a polymerizable monomer starting from an active group (for example, an azo group) that is more easily cleaved than an unsaturated bond such as a vinyl group,
The bonding ratio (graft ratio) between the substrate and the polymerizable monomer can be greatly improved, and the entire surface of the substrate can be effectively coated with the polymer.

Examples of the polymerizable monomer include a monomer capable of initiating polymerization by cleavage of the active group (polymerization initiating group), for example, a vinyl monomer. Examples of the vinyl monomer include aromatic vinyl compounds [eg, styrene, alkyl styrene (eg, vinyl toluene), α-alkyl styrene (eg, α-methyl styrene, etc.); α, β-unsaturated carboxylic acids [E.g., monocarboxylic acids such as (meth) acrylic acid, polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and their acid anhydrides (e.g., maleic anhydride)]; (meth)
Esters of acrylic acid [for example, (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate C
_1-14 alkyl ester, hydroxyalkyl (meth) acrylate (hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, etc.), glycidyl (meth) acrylate]; (meth) acrylamide or a derivative thereof (eg, N-methylol (meth) acrylamide, etc.); maleimide or a derivative thereof (eg, N-methylmaleimide, N- (Meth) acrylonitrile; vinyl carboxylate [eg, vinyl acetate]; conjugated diene monomer [eg, butadiene, isoprene, etc.]; olefin monomer [eg, ethylene, propylene] Vinyl halide [eg, vinyl chloride, etc.];
Vinylidene halide [for example, vinylidene chloride]
And the like.

Further, as the crosslinkable monomer, for example, a polyfunctional polymerizable monomer [ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropanetri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, methylenebisacrylamide, etc.] may be used.

As the crosslinkable monomer, for example, a monomer having a crosslinkable functional group [epoxy group-containing monomer [glycidyl (meth) acrylate, (meth) allyl glycidyl ether, 1-allyloxy-3, 4-epoxybutane, 1- (3-butenyloxy) -2,3-epoxypropane, 4-vinyl-1-cyclohexene-1,2-epoxide, etc.), a methylol group-containing monomer or a derivative thereof [N-methylol ( (Meth) acrylamide, N-methoxymethyl (meth) acrylamide, etc., and NC _1-4 alkoxymethyl (meth) acrylamide, N-butyrol (meth) acrylamide, etc.] may be used.

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

When these crosslinkable monomers are used,
A tough film can be formed on the surface of the substrate and encapsulated.
Further, by adjusting the amount of the polymerizable monomer used, the thickness of the polymer covering the substrate surface can be adjusted.

The amount of the polymerizable monomer used is 0.1 to 10000 parts by weight, preferably 0.5 to 1000 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the base material.
It is about parts by weight.

When granular functional particles are used as the substrate, the average particle size of the obtained composite substrate (composite particles) varies depending on the average particle size of the substrate particles.
It can be selected from the range of about nm to 50 μm, preferably about 50 nm to 10 μm, and more preferably about 100 nm to 5 μm. [Method for Producing Composite Substrate] The composite substrate can be produced by treating the substrate to be treated with the surfactant compound of the present invention and polymerizing the polymerizable monomer. In particular, it can be produced by polymerizing a polymerizable monomer by heat or light irradiation (for example, ultraviolet irradiation) in the presence of a surface-active compound adsorbed on the substrate surface. The active group (polymerization initiating group) of the surface active compound is cleaved by heat or light irradiation, and the polymerizable monomer is polymerized starting from the group (particularly a radical) generated by the cleaving, and the weight of the polymerized substrate surface is reduced. The coalescence is combined (especially grafted).

The polymerization can be carried out in the presence or absence of a solvent, in particular in the medium mentioned above.

As the heating temperature, for example, 50 to 120
° C, preferably in the range of about 60 to 100 ° C.

In the polymerization, a photopolymerization accelerator (for example, a tertiary aliphatic amine, a tertiary aromatic amine, a phosphine-based polymerization accelerator), a thermal polymerization accelerator, or the like may be used, if necessary. Is also good.

As the surface active compound and the substrate, a substrate obtained by treating a substrate to be treated with a surface active compound may be used. In an aqueous medium, a substrate obtained by treating a substrate to be treated with a surface active compound may be used. You may.

When the active group of the surface active compound is cleaved, either the hydrophilic group or the hydrophobic group is released into the medium. Then, as the polymerization on the surface of the substrate to be treated and the polymerization starting from the released group progress, the hydrophilicity or hydrophobicity of both components advances depending on the type of the monomer, and the components are aggregated or aggregated with each other. It seems.

The composite substrate of the present invention has good dispersibility in a matrix and a medium and can adjust the degree of coating on the surface of the substrate, so that it can be used for various uses. For example, even when a pigment or the like is added to a plastic product having transparency, the composite base material of the present invention has high dispersibility in a polymer matrix, so that while maintaining transparency,
Since a pigment can be added, it is useful as a printing ink, an ink material, or an ink jet ink. Also,
If organic or inorganic particles such as drugs are used as the base material,
Capsulation is possible, and controlled release of the drug is possible. Further, it is also useful as a cold insulator and a heat storage material. As the matrix, a polymer of the above-mentioned polymerizable monomer can be used.

[0120]

According to the present invention, since a surface active compound having a surface active ability and a polymerization initiating ability is used, the polymer can be effectively bonded to the surface of the base material and can be dispersed in a polymer matrix or a medium. Performance can be greatly improved. Furthermore, the base material surface can be efficiently coated with the polymer, and the coating amount on the base material surface can be controlled.

[0121]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Production of surfactant compound]

[0123]

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The 4,4'-azobis (4
-Cyanopentanoic acid) (2.8 g, manufactured by Wako Pure Chemical Industries, Ltd.)
(0.01 mol) was dissolved in 200 mL of acetone, and p
2.6 g (0.01 mol) of dodecylphenol and N,
2.1 g of N'-dicyclohexylcarbodiimide (0.
01 mol) and stirred at 5 ° C. for 24 hours. Thereafter, the precipitated dicyclohexylurea was removed, 200 mL of distilled water was added to the acetone solution, and a 10% by weight aqueous sodium hydroxide solution was added to adjust the pH to 10. After removing the separated oil layer, a few drops of concentrated hydrochloric acid were added to adjust the pH of the solution.
Was adjusted to 3. The separated oil layer is separated into diethyl ether 1
Extracted with 00 mL and washed several times with distilled water. After drying the ether layer with anhydrous magnesium sulfate, ether was distilled off at 5 ° C. under vacuum. The crude product was purified by silica gel column chromatography to obtain a compound 1 represented by the following formula.
2 g were obtained.

[0125]

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This compound was dissolved in 20 mL of methanol, a 1 mol / L (1N) aqueous sodium hydroxide solution was added, and the mixture was stirred overnight to obtain Compound 1 represented by the following formula. This compound 1 is represented by the formula (2), wherein k = 0, p = 1,
This corresponds to a compound in which q = 1, r = 1, s = 0, t = 1, and u = 0.

[0127]

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In the same manner as above, except that 2.0 g of dodecyl alcohol was used instead of p-dodecylphenol,
Compound 2 represented by the following formula was obtained. This compound 2 is represented by the formula (2) where k = 0, p = 1, q = 1, and r =
1, corresponding to compounds where s = 0, t = 1 and u = 0.

[0129]

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Example 2 [Production of adsorbed particles] 100 mL of a 5% by weight aqueous solution of titanium chloride (TiCl)
Then, about 12 mL of a 10% by weight aqueous solution of sodium carbonate (Na ₂ CO ₃ ) was added thereto, and the pH of the solution was controlled to prepare a titanium oxide hydrosol. To this hydrosol was added 10 mL of a 10% by weight aqueous solution of the above compound 1, and then 2
Wt% sodium dodecylbenzenesulfonate (SD
S) About 15 mL of an aqueous solution was added to obtain titanium oxide particles having Compound 1 adsorbed thereon. The particles separated from the aqueous phase were collected and dried at 20 ° C. in a vacuum drier to obtain particles having a surface active compound adsorbed thereon.

The obtained particles were powders easily dispersed in toluene and chloroform, and had an average particle diameter of 1.7 nm.

Example 3 [Adsorbed Particles] Adsorbed particles were obtained in the same manner as in Example 2 except that Compound 2 was used instead of Compound 1. The resulting particles are toluene,
The powder was easily dispersed in chloroform and had an average particle size of 1.7 nm.

Example 4 [Production of Particles Obtained by Cleaving Active Groups of Adsorbed Particles] 1 g of the titanium oxide particles having the compound 1 adsorbed thereon were heated at 70 ° C. for 10 minutes. After heating, the particles were dispersed in ethanol. The particles that did not disperse before heating were uniformly dispersed after heating. That is, it was recognized that the surface of the particles changed from hydrophobic to hydrophilic due to the decomposition of the active group (decomposable functional group) of the surface active compound.

Example 5 [Composite Particle] 1 g of the titanium oxide particle having the compound 1 adsorbed thereon was 30 mL.
Was dispersed in toluene, and 0.5 g of a styrene monomer was added, followed by stirring at 70 ° C. for 24 hours under a nitrogen stream. Thereafter, the above solution was added to 200 mL of methanol, and the polymer was recovered by reprecipitation. The recovered polymer is dried under vacuum at 60 ° C. for 2 hours.
After drying for 4 hours, composite particles were obtained.

The composite particles had titanium oxide particles held at the center of the skeleton thereof by observation with a transmission electron microscope. When the composite particles were mixed with a styrene polymer, a titanium oxide-styrene composite maintaining transparency was obtained.

Similarly, 1 g of the titanium oxide particles having the compound 1 adsorbed thereon was dispersed in 30 mL of toluene.
0.5 g of N′-dimethylacrylamide was added, and the mixture was stirred at 70 ° C. for 24 hours under a nitrogen stream. Then, the above solution was
The polymer was recovered by reprecipitation in addition to 00 mL of normal hexane. The recovered polymer was dried at 60 ° C. for 24 hours under vacuum to obtain composite particles.

The composite particles had titanium oxide particles held at the center of the skeleton by observation with a transmission electron microscope. When the composite particles were mixed with an acrylic resin, a composite of titanium oxide and an acrylic resin having maintained transparency was obtained. Further, it was confirmed that the composite particles were uniformly dispersed in methanol.

Example 6 [Composite particles] 2 mL of a 10% by weight aqueous solution of the compound 2 and 0.02 g of sodium dodecylbenzenesulfonate were added to ion-exchanged water 1
The resultant was dissolved in 00 mL, and 2 mL of a 5% by weight copper phthalocyanine pigment acetone dispersion was dispersed with an ultrasonic homogenizer. The aqueous dispersion was a blue translucent liquid, and the volume average particle diameter of the pigment particles in the liquid was 170 nm. Next, 7 mL of styrene was added to the aqueous dispersion, and polymerization was performed at 70 ° C. for 17 hours under a nitrogen stream. The liquid became a blue translucent water emulsion. The volume average particle diameter of the pigment particles in the liquid is 110 nm.
Met. When this emulsion was acidified, a blue precipitate was obtained. Observation of this precipitate with a scanning electron microscope (SEM) revealed that it was spherical fine particles, and almost all the pigment particles were covered with polystyrene.

Example 7 2 mL of a 2% by weight aqueous solution of the compound 2 and 0.09 g of sodium dodecylbenzenesulfonate were added to ion-exchanged water 10
The solution was dissolved in 0 mL, and 20 mL of a 5% by weight copper phthalocyanine pigment acetone dispersion was dispersed with an ultrasonic homogenizer. The dispersion was a blue translucent liquid, and the volume average particle diameter of the pigment particles in the liquid was 210 nm. Next, 1 mL of styrene was added to the dispersion, and polymerization was performed at 80 ° C. for 2 hours under a nitrogen stream. Next, nitrogen-substituted acrylamide (0.2 g) / methylenebisacrylamide (0.5 g)
g) An aqueous solution was added, and polymerization was further performed. After the polymerization, a blue translucent liquid was obtained. The volume average particle diameter of the pigment particles in the liquid was 100 nm. This dispersion was stable without aggregation under both strong alkalinity and strong acidity. When the particles in the liquid were dried and observed by SEM, the particles were spherical fine particles, and almost all the pigment particles were covered with the polymer. The dried particles were redispersible in water and became a blue translucent liquid.

Example 8 5.6 g of 4,4'-azobis (4-cyanopentanoic acid) (manufactured by Wako Pure Chemical Industries, Ltd.) used in Example 1 was dissolved in 50 ml of tetrahydrofuran (THF), and N- 4.6 g of hydroxysuccinimide and 8.24 g of N, N'-dicyclohexylcarbodiimide (DCC) were added, and the mixture was stirred at room temperature for 24 hours. After distilling off THF from the reaction mixture, the reaction mixture was dispersed in 500 ml of acetone, and the generated precipitate was removed. Then, acetone was distilled off from the reaction mixture to obtain a crystal of a compound in which a carboxyl group represented by the following formula was esterified.

[0141]

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1.76 g of the above crystals were dissolved in 35 ml of dimethylformamide (DMF), and 0.77 g of dodecylamine was dissolved.
4 g was added and stirred overnight. 300 ml of water in the reaction mixture
, And the precipitated precipitate is filtered and washed with water, redissolved in dimethoxyethane, dried over magnesium sulfate, the solvent (dimethoxyethane) is distilled off, and further washed and dried with ethyl acetate to obtain the diester. In which one of the ester groups was replaced by dodecylamine. This product is represented by the following formula.

[0143]

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Subsequently, 1.7 g of the above product was dispersed in 20 ml of methanol, 1.6 ml of an aqueous sodium hydroxide solution (2 mol / L = 2N) was added, and the mixture was stirred at room temperature to hydrolyze the other ester. As a result, the following target compound was obtained. This compound is represented by the formula (2) wherein k =
0, p = 1, q = 1, r = 1, s = 0, t = 1 and u =
0 corresponds to the compound.

[0145]

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Example 9 2.72 g of a product obtained by substituting one of the above diesters with dodecylamine was dispersed in 40 ml of methanol, 0.87 g of sulfanilic acid was added, and the mixture was stirred overnight.
Next, an aqueous sodium hydroxide solution (2 mol / L = 2N) 2
The compound represented by the following formula was obtained by adding ml. This compound is represented by the formula (2), wherein k = 0, p = 1, q =
1, r = 1, s = 0, t = 1 and u = 0.

[0147]

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Example 10 21.2 g (0.1 mol) of benzoin was dissolved in 300 mL of methanol, and 7.9 g of acetyl chloride was further dissolved.
(0.1 mol) and 15 g (0.15 mol) of triethylamine were added, and the mixture was heated under reflux for 8 hours. Then, 500 mL of 1% by weight hydrochloric acid was added to the reaction mixture, and 500 mL of the product was added.
After extraction with diethyl ether, the ether solution was dried over anhydrous magnesium sulfate, and the ether was distilled off under vacuum.
The crude product was purified by silica gel column chromatography to obtain a benzoin ester compound 1 represented by the following formula.
Oa (22.9 g) was obtained.

[0149]

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Compound 10a (22.9 g) was added to 300
It was dissolved in mL of tetrahydrofuran (THF), and 16.5 g (0.075) of lauroyl chloride and 10.0 g (0.075 mol) of aluminum chloride (III) were added.
Heated to reflux for an hour. After slowly adding 100 mL of distilled water to the reaction mixture, the solid content was filtered off, and the reaction solution was 500 mL.
Extracted with diethyl ether. After drying the ether solution with anhydrous magnesium sulfate, the ether was distilled off under vacuum. The crude product was purified by silica gel column chromatography, and the compound 10b (14.
1 g).

[0151]

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The compound 10b (14.1 g) was dissolved in a 5% by weight potassium hydroxide solution in ethanol (EtOH) 200
Then, the mixture was heated and stirred at 80 ° C. for 1 hour. Then 1
The pH of the reaction mixture was adjusted to 7 with wt% hydrochloric acid, the product was extracted with 500 mL of diethyl ether, and the ether layer was washed with 500 mL of a 10 wt% sodium hydrogencarbonate solution. After drying the ether solution over anhydrous magnesium sulfate, the ether was distilled off under vacuum to obtain a compound 10 represented by the following formula.
c (12.1 g) was obtained.

[0153]

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Compound 10c (12.1 g) was added to 300
dissolved in THF, and 6.6 g (0.03 mol) of 4-chlorosulfonylbenzoic acid and triethylamine 1
0 g (0.1 mol) was added, and the mixture was heated under reflux for 8 hours. After adding 5% by weight hydrochloric acid to the reaction mixture and adjusting the pH to 3,
The product was extracted with 500 mL of diethyl ether. After drying the ether solution with anhydrous magnesium sulfate, the ether was distilled off under vacuum. The crude product was purified by silica gel column chromatography, and then, as in Example 1, an aqueous sodium hydroxide solution (0.5 mol / L = 0.
5N) and the compound 10d (1
2.6 g) were obtained. This compound 10d is represented by the formula (2)
Where k = 0, p = 1, q = 1, r = 1, s = 0,
It corresponds to the compound where t = 1 and u = 0.

[0155]

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Example 11 21.4 g of 4,4'-dihydroxybenzophenone (0.
1 mol) was dissolved in 500 mL of THF, and 20.0 g (0.1 mol) of lauric acid and 20.6 g of DCC were further dissolved.
(0.1 mol) and stirred at room temperature for 24 hours. Thereafter, the precipitated dicyclohexylurea (DCU) was removed, and the crude product was purified by silica gel column chromatography. Then, in the same manner as in Example 1, compound 11a (24.8 g) represented by the following formula was obtained. .

[0157]

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The compound 11a (24.8 g (0.06 g)
mol)) was dissolved in 300 mL of DMF, and 6.0 g (0.06 mol) of succinic anhydride, 10 g (0.1 mol) of triethylamine, and 1.2 g (0.4 g) of 4,4-dimethylaminopyridine (DAP) were further dissolved. 01 mol) and 100
The mixture was heated and stirred at 8 ° C for 8 hours. Thereafter, 300 mL of distilled water was added to the reaction mixture, the pH was adjusted to 3 with 10% by weight hydrochloric acid, and the product was extracted with 500 mL of diethyl ether. After drying the ether solution with anhydrous magnesium sulfate, the ether was distilled off under vacuum. The crude product was purified by silica gel column chromatography, and an aqueous sodium hydroxide solution (0.5 mol / L = 0.5N) was added to obtain a compound 11b (21.9 g) represented by the following formula. This compound 11b is represented by the formula (2) where k = 0 and p =
1, q = 1, r = 1, s = 0, t = 1 and u = 0.

[0159]

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Example 12 28.0 g (0.1 mol) of 4,4'-azobis (4-cyanopentanoic acid) (manufactured by Wako Pure Chemical Industries, Ltd.) used in Example 1 was dissolved in 500 mL of DMF. , And 18.6 g (0.1 mol) of lauryl alcohol and 20.6 g of DCC
(0.1 mol) and stirred at 5 ° C. for 24 hours. Thereafter, the precipitated DCU was removed, 300 mL of distilled water was added, and the pH was adjusted to 10 by adding a 10% by weight aqueous solution of sodium hydroxide. After removing the separated oil layer,
The pH of the solution was adjusted to 3 by adding 5% by weight hydrochloric acid. The separated oil layer was extracted with diethyl ether (500 mL), the ether solution was dried over anhydrous magnesium sulfate, and ether was distilled off under vacuum. The crude product was purified by silica gel column chromatography, and then in the same manner as in Example 1, an aqueous sodium hydroxide solution (0.5 mol / L = 0.5
N) to give compound 12a (24.
2 g) were obtained.

[0161]

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Compound 12a (24.2 g) was added to 300
Dissolved in 9.0 mL of DMF and 9.0 g of sulfanilic acid (0.
052 mol), 10.7 g (0.052 mol) of DCC and 10.0 g (0.1 mol) of triethylamine were added, and the mixture was stirred at room temperature for 24 hours. Thereafter, the precipitated DCU was removed, 300 mL of distilled water was added, and then 5 wt% hydrochloric acid was added to adjust the pH of the solution to 3. The separated oil layer was extracted with diethyl ether (500 mL), the ether solution was dried over anhydrous magnesium sulfate, and ether was distilled off under vacuum. The crude product was purified by silica gel column chromatography, and then an aqueous sodium hydroxide solution (0.5 mol / L = 0.5N) was added as in Example 1.
Compound 12b (26.7 g) represented by the following formula was obtained.
This compound 12b is represented by the formula (2), wherein k = 0,
This corresponds to a compound in which p = 1, q = 1, r = 1, s = 0, t = 1, and u = 0.

[0163]

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Example 13 2,6.6 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] (manufactured by Wako Pure Chemical Industries, Ltd.)
(1 mol) was dissolved in 300 mL of methanol, and 49.8 g (0.2 mol) of lauryl bromide and 20 g (0.2 mol) of triethylamine were added, and the mixture was reacted at 50 ° C. for 8 hours. Thereafter, 200 mL of distilled water was added, a 10% by weight aqueous sodium hydroxide solution was added, and the pH of the solution was adjusted to 10%.
Was adjusted. The separated oil layer is separated into diethyl ether 500
After extraction with mL, the ether solution was dried over anhydrous magnesium sulfate, and the ether was distilled off under vacuum. The crude product was purified by silica gel column chromatography to obtain a compound 13a (52.4 g) represented by the following formula.

[0165]

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The compound 13a (52.4 g (0.08
7 mol) was dissolved in 300 mL of dichloromethane, and 50 mL (0.35 mol) of methyl iodide was added thereto.
Stirred at 50 ° C. for hours. Thereafter, the solvent was distilled off, and the resulting solid was washed with 200 mL of dichloromethane to obtain a compound 13b (38.4 g) represented by the following formula. This compound 13b is represented by the formula (2), wherein k = 0, p = 1,
This corresponds to a compound in which q = 1, r = 0, s = 0, t = 0, and u = 0.

[0167]

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Example 14 2,2'-Azobis [2-methyl-N- (2-hydroxyethyl) propioamide] (manufactured by Wako Pure Chemical Industries, Ltd.) 2
8.8 g (0.1 mol) dissolved in 500 mL DMF,
Further, 20.0 g (0.1 mol) of lauric acid and DCC2
0.6 g (0.1 mol) was added, and the mixture was stirred at 5 ° C. for 24 hours. Thereafter, the precipitated DCU was removed, 300 mL of distilled water was added, and a 10% by weight aqueous solution of sodium hydroxide was added to adjust the pH to 10. Then, the reaction product was extracted with diethyl ether (500 mL), and anhydrous magnesium sulfate was added. After drying the ether solution with, ether was distilled off under vacuum.
The crude product was purified by silica gel column chromatography, and compound 14a (31.6 g) represented by the following formula was obtained.
I got

[0169]

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The compound 14a (31.6 g (0.06
Was dissolved in 300 mL of DMF, and 6.7 g (0.067 mol) of succinic anhydride, 10 g (0.1 mol) of triethylamine and 1.2 g of 4,4-dimethylaminopyridine (DAP) were added. 0.01 mol), and the mixture was heated and stirred at room temperature for 8 hours. Thereafter, 300 mL of distilled water was added to the reaction mixture, the pH was adjusted to 3 with 10% by weight hydrochloric acid, and the reaction product was extracted with 500 mL of diethyl ether. After drying the ether solution with anhydrous magnesium sulfate,
The ether was distilled off under vacuum. The crude product was purified by silica gel column chromatography and
In the same manner as described above, an aqueous sodium hydroxide solution (0.5 mol /
L = 0.5N) to give a compound 14 represented by the following formula:
b (34 g) was obtained. This compound 14b is represented by the formula (2), wherein k = 0, p = 1, q = 1, r = 1, s
= 0, t = 1 and u = 0.

[0171]

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Example 15 15.0 g (0.1 mol) of ethyl benzoate in 300 mL
Was dissolved in tetrahydrofuran (THF), 22.0 g (0.1 mol) of lauroyl chloride and 13.3 g (0.1 mol) of aluminum chloride (III) were added, and the mixture was heated under reflux for 8 hours. After gradually adding 100 mL of distilled water to the reaction mixture, the solid content was filtered off, and the reaction mixture was added to 500 mL of the reaction mixture.
Extracted with mL of diethyl ether. After drying the ether solution with anhydrous magnesium sulfate, the ether was distilled off under vacuum. The crude product was purified by silica gel column chromatography, and ethyl p-lauroylbenzoate 24.6 was obtained.
g was obtained.

The above ethyl p-lauroylbenzoate (2
4.6 g) was added to 200 mL of an ethanol solution containing 5% by weight of potassium hydroxide (KOH), and the mixture was heated and stirred at 80 ° C. for 1 hour. Then, the pH of the reaction mixture is adjusted with 1% by weight hydrochloric acid.
Was adjusted to 7, the reaction mixture was extracted with 500 mL of diethyl ether, and the ether layer was washed with 500 mL of a 10% by weight sodium bicarbonate solution. After drying the ether solution with anhydrous magnesium sulfate, ether was distilled off under vacuum,
-21.4 g of lauroyl benzoic acid were obtained.

The above-mentioned p-lauroylbenzoic acid (3.0 g)
(0.01 mol)) in 200 mL of methanol, and dibenzoyl peroxide (BPO) 4.8 under ice cooling.
g (0.02 mol) and sodium methoxide 1.1 g
(0.02 mol) was added, and the reaction mixture was heated to 15 ° C. and stirred for 24 hours. Thereafter, 200 mL of distilled water was slowly added to the reaction mixture, and the pH of the solution was adjusted to 3 with 1% by weight hydrochloric acid. The separated oil layer was collected, 300 mL of distilled water was added to the oil layer, and the pH of the solution was adjusted to 7 with a 1% by weight aqueous sodium hydroxide solution. Further, the remaining oil layer was removed to obtain an aqueous solution (about 1% by weight) of a sodium salt of the compound 15 represented by the following formula. This compound 15 is represented by the formula (2), wherein k = 0, p = 1, q =
1, corresponding to compounds where r = 0, s = 0, t = 0 and u = 1.

[0175]

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Example 16 5.6 g of 4,4′-azobis (4-cyanopentanoic acid) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to tetrahydrofuran (THF).
3. Dissolve in 50 mL and add N-hydroxysuccinimide
6 g and N, N-dicyclohexylcarbodiimide 8.2
4 g was added, and the mixture was stirred at room temperature for 24 hours. Then, THF
Was distilled off, the remaining solid was dispersed in 500 mL of acetone, and the resulting precipitate was filtered. Acetone was distilled off from the filtrate to obtain 4,4′-azobis (4-cyanopentanoic acid) diester.

1.81 g of the obtained diester was dispersed in 20 mL of methanol, 2 mL of a 2N (2 mol / L) aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 5 hours. After neutralization with, the solvent was distilled off. The residue was dissolved in THF, then 0.65 g of benzyl bromide was added, and the mixture was stirred for 3 hours.

Next, 2- (2-aminoethylamino) ethanol (manufactured by Aldrich) 0.2 was added to the obtained solution.
g was added and stirred at room temperature for 24 hours.

To the reaction mixture was added 0.56 g of sulfoacetic acid and 0.82 g of dicyclohexylcarbodiimide, and the mixture was stirred at room temperature for 24 hours. Then, a 2N (2 mol / L) aqueous sodium hydroxide solution was added in an amount of 1 mL per 10 mL of methanol.
And stirred at room temperature for 5 hours. Next, the solvent was distilled off, and the remaining oil was gently dissolved in water, and unnecessary substances were filtered to obtain a compound 16 represented by the following formula. This compound 16 is represented by the formula (2), wherein k = 1, p = 2, q
= 1, r = 1, s = 1, t = 1 and u = 0.

[0180]

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Example 17 4.5 g of 1,3-diamino-2-hydroxypropane was dissolved in dioxane / water (60 mL / 20 mL).
15.1 g of triethylamine was added, and 2-t-butoxycarbonyloxyimino-2 was further added as an amino-protecting group.
-Phenylacetonitrile (27.1 g) was added at room temperature for 3 hours.
Stirred for hours. After 3 hours, 200 mL of water was added to the reaction solution, and the precipitated product was recovered and dried under reduced pressure.

7.26 g of the obtained product and 2.53 g of triethylamine were dissolved in 30 mL of THF, 5.5 g of lauroyl chloride was added, the mixture was stirred at room temperature for 3 hours, 5 mL of methanol was added, and the mixture was allowed to stand for 30 minutes.

After evaporating the solvent from the reaction solution, ether was added to the residue to collect impurities. Then, trifluoroacetic acid was added until the insolubles were dissolved, and the mixture was stirred at room temperature for 1 hour for elimination of the protecting group. One hour later, the trifluoroacetic acid was distilled off and dried under reduced pressure.

Then, 9.4 g of a diester of 4,4′-azobis (4-cyanopentanoic acid) synthesized in the same manner as in Example 16 was added to 60 m of dimethylformamide (DMF).
L, and 1.7 g of the above product was added.
Stir for 8 hours.

The reaction solution was mixed with 500 mL of water, and the precipitated solid was recovered. Next, the obtained solid was dispersed in 60 mL of dimethoxyethane, and insolubles were separated by filtration.
(1 mol / L) sodium hydroxide aqueous solution
10 mL was added to 0 mL, and the mixture was stirred at room temperature for 5 hours, and the solvent was distilled off to obtain Compound 17 represented by the following formula. This compound 17 is represented by the formula (2) where k = 1 and p =
1, q = 2, r = 1, s = 1, t = 0 and u = 1.

[0186]

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──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C07C 309/51 C07C 309/51 309/77 309/77 409/24 409/24 C07D 233/24 C07D 233 / 24 C08F 2/00 C08F 2/00 C 4/00 4/00 C08J 7/16 CER C08J 7/16 CER CEZ CEZ // C08L 101: 00 C08L 101: 00

Claims (21)

[Claims] 1. A surfactant compound represented by the following formula (1). (R ¹ ) _m -Z- (R ² ) _n (1) (wherein, R ¹ is a unit having at least a hydrophobic group,
R ² represents a unit having at least a hydrophilic group;
Represents a unit having at least one active group, and m
And n represent an integer of 1 to 3. The type of R ¹ and R ² is m
Or may vary depending on the value of n) 2. A compound represented by the formula (1):
(2) [R^1a− (B¹)_r− (X¹−B^Two)_t]_p− (S)_k− [(B^Three−X^Two)_u− (B^Four)_s−R^2a]_q (2) (where R^1aIs a unit having at least a hydrophobic group,
R^2aRepresents a unit having at least a hydrophilic group, and X
¹And X^TwoRepresents the same or different and represents an active group. B¹Passing
And B^FourIs R¹Or R^TwoAnd the active group X¹Or X^TwoJoin with
Unit, B ^TwoAnd B^ThreeIs the spacer S and the active group
X¹Or X^TwoAnd a unit that combines k, r, s,
t and u represent 0 or 1. Where t and u are simultaneously
Not zero. p and q represent an integer of 1 to 3)
The surfactant compound according to claim 1. 3. The hydrophobic group is at least one group selected from an aliphatic hydrocarbon group having 5 to 60 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, a heterocyclic group and a polysiloxane residue. Is a polysaccharide group, a polyether group, a hydroxyl group, a carboxyl group, a sulfate group, a sulfonic acid group,
3. The surface-active compound according to claim 1, which is at least one selected from a phosphate group, a phosphonium base, a heterocyclic group, an amino group, a salt thereof, and an ester thereof. 4. The hydrophobic group is a C _8-22 long-chain aliphatic hydrocarbon group or a C _6-20 alkyl-C _6-12 aryl group, and the hydrophilic group is a polyether group, a carboxyl group, or a sulfuric acid. The surface active compound according to claim 1 or 2, which is a sulfonic acid group or a salt thereof. 5. The method according to claim 1, wherein the active group is a radical by heat or light.
3. The surfactant compound according to claim 1, which generates a cation or an anion. 6. The surface active compound according to claim 1, wherein the active group is at least one selected from an azo group, a peroxide group, and a keto group capable of generating a radical. 7. At least one of the bonding units B ¹ , B ² , B ³ and B ⁴ is an ester bond,
3. The surfactant compound according to claim 2, which has a bonding mode selected from an amide bond, a urea bond, a urethane bond, an ether bond, a thioether bond, and an imino bond. 8. The surfactant compound according to claim 2, wherein the spacer S comprises at least one polyvalent group selected from an alkylene group, an arylene group and a heterocyclic group. 9. The compound of formula (2) wherein (i) k =
The surfactant compound according to claim 2, wherein 0, p = 1 and q = 1, or (ii) k = 1, p = 1 or 2 and q = 1 or 2. 10. A compound for obtaining the surfactant compound represented by the formula (1) according to claim 1, wherein the compound for obtaining the surfactant compound is represented by the following formula (3). Compound. (E ¹ ) _m -Z- (E ² ) _n (3) (wherein E ¹ represents a hydrophobic group corresponding to R ¹ in the formula (1) or a reactive group that forms a hydrophobic group by a reaction. Shows, E ²
Represents a hydrophilic group corresponding to R ² in the formula (1) or a reactive group that forms a hydrophilic group by a reaction. Provided that at least one of E ¹ and E ² is a reactive group;
And n are the same as in claim 1) 11. The compound according to claim 10, wherein the reactive group is an activated carboxyl group. 12. A method of making a surfactant compound of claim 1, wherein the following formula ^{(4) R 1 -F 1 (} 4) ( wherein, .R ¹ F ¹ is showing a reactive group (Same as claim 1)
And a compound represented by the following formula (5) (F ² ) _m -Z- (R ² ) _n (5) (wherein F ² represents a reactive group corresponding to the reactive group F ¹ ). Wherein Z, R ² , m and n are the same as defined in claim 1). 13. The method according to claim 12, wherein the compound represented by the formula (3) is a compound represented by the formula (3). 14. The following formula (2)^1a− (B¹)_r− (X¹−B^Two)_t]_p− (S)_k− [(B^Three−X^Two)_u− (B^Four)_s−R^2a]_q (2) (where R^1aIs a unit having at least a hydrophobic group,
R^2aRepresents a unit having at least a hydrophilic group, and X
¹And X^TwoRepresents the same or different and represents an active group. B¹Passing
And B^FourIs R¹Or R^TwoAnd the active group X¹Or X^TwoJoin with
Unit, B ^TwoAnd B^ThreeIs the spacer S and the active group
X¹Or X^TwoAnd a unit that combines k, r, s,
t and u represent 0 or 1. Where t and u are simultaneously
Not zero. p and q represent an integer of 1 to 3)
A method for producing a compound, wherein (i) when k is 0,
In the case, the following formula (6) R^1a− (B¹)_r− (X¹-B^Two)_t-F^Three (6) (where F^ThreeRepresents a reactive group. R^1a, B¹, B^Two, X¹,
r and t are the same as defined above) and the following formula:
(7) (F^Four)_p− [(B^Three-X^Two)_u− (B^Four)_s-R^2a]_q (7) (where F^FourIs the reactive group F^ThreeIndicates a reactive group corresponding to
You. R^2a, B^Three, B^Four, X ^Two, P, q, s and u are as described above.
The same as above); (ii) when k is 1
In some cases, the following equation (8) (F^Five)_p-S- (F⁶)_q (8) (where F^FiveAnd F⁶Represents a reactive group. S, p and q are
A compound represented by the same formula) as defined above,^1a− (B¹)_r− (X¹-B^Two)_t-F⁷ (9) (where F⁷Is the reactive group F^FiveOr F⁶Reaction corresponding to
Represents a functional group. R^1a, B¹, B^Two, X¹, R and t are as described above.
The compound represented by the following formula (10)⁸− (B^Three-X^Two)_u− (B^Four)_s-R^2a (10) (where F⁸Is the reactive group F^FiveOr F⁶Reaction corresponding to
Represents a functional group. R^2a, B^Three, B^Four, X^Two, U and s are the same as above.
13. The compound according to claim 12, which is reacted with a compound represented by the formula
Production method. 15. A normal-phase or reverse-phase micelle formed by the surfactant compound according to claim 1. 16. A substrate comprising a substrate to be treated and the surface-active compound according to claim 1 adsorbed on the surface of the substrate to be treated. 17. The substrate according to claim 16, wherein the substrate to be treated is a particle. 18. The ratio between the substrate to be treated and the surface active compound is 0.001 to 1 with respect to 100 parts by weight of the substrate to be treated.
The base material according to claim 16, which is 0 parts by weight. 19. A composite substrate comprising a polymer of a polymerizable monomer bonded to the substrate using the surfactant compound according to claim 1 adsorbed on the substrate surface as an initiator. 20. A method for producing a composite substrate, wherein the surface active compound according to claim 1 is adsorbed on the surface of the substrate to be treated, and the polymerizable monomer is polymerized. 21. A substrate 100 on which a surface active compound is adsorbed.
The method for producing a composite substrate according to claim 20, wherein 0.1 to 10,000 parts by weight of the polymerizable monomer is polymerized with respect to parts by weight.