JP5506299B2 - Star polymer - Google Patents

Description

  The present invention relates to star polymers.

A stimulus-responsive polymer is a substance that responds sensitively to external changes (external stimuli) such as light irradiation, electric field application, temperature change, pH change, and addition of chemical substances, and its physical properties change significantly. is there. Stimulus responsive polymers are attracting attention as highly functional materials and are expected to be applied in various fields. For example, stimuli-responsive polymers that cause changes in bioactive molecule (drug molecule) release and the like due to external stimuli (for example, changes in pH and temperature) are expected to be applied in the field of drug delivery systems.
Although polymers that exhibit stimulus responsiveness are rare, linear polymers that are block polymers that change from amphiphilic to lyophobic or from lyophobic to amphiphilic in response to a stimulus have been known. (See Patent Document 1).
Furthermore, a star polymer having excellent stimulus responsiveness has also been reported (see Patent Document 2).
However, there is still a need to develop a variety of star polymers.
On the other hand, as a star polymer having a fluorine atom, for example, Patent Document 3 discloses a star block polymer obtained by a reaction between a perfluoro capping agent and a star polymer core. Patent Document 4 discloses a star polymer in which a branch having a specific structure branches from a central core.

By the way, generally, as a technique for imparting stain resistance to a coating film, a technique for making the coating film water-repellent and a technique for making it hydrophilic are known. Any method can be selected according to the type and nature of the possible stain component.
A fluororesin is known as a resin that makes the coating film water-repellent. For example, Patent Document 5 discloses a fluorine-containing acrylic polymer aqueous emulsion. In addition, for example, Patent Document 6 discloses an aqueous coating composition comprising a fluororesin emulsion made of a fluoroolefin copolymer.
On the other hand, as a method for making the coating film surface hydrophilic, a method in which a modified condensate of organosilicate is blended in a paint is known (see Patent Document 7). The modified organosilicate is considered to be hydrolyzed by moisture such as rain water in the coating film to form a silanol group and to make the coating surface layer hydrophilic.
Further, Patent Document 8 is obtained by polymerizing a fluorinated olefin polymer, a fluorinated (meth) acrylate, a hydrophilic structural unit-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers. A coating composition comprising a copolymer, a compound having a hydrolyzable silyl group as an essential component, and further comprising a polymer of a monomer containing a (meth) acryloyl group is disclosed. According to the composition described in the document, a copolymer obtained by polymerizing a fluorinated (meth) acrylate, a hydrophilic structural unit-containing ethylenically unsaturated monomer and other ethylenically unsaturated monomers However, the action of the perfluoroalkyl group and the hydrophilic structure can modify the membrane surface to be hydrophilic together with the compound having a hydrolyzable silyl group.

JP 2003-119342 A JP 2005-154497 A JP-A-8-208780 JP 2006-45550 A JP-A-5-17538 JP 2005-248157 A WO99 / 05228 JP 10-36754 A

In the above situation, the present inventors have come to consider that a star polymer having a unique property derived from a fluorine atom can be obtained by introducing a fluorine atom into a specific portion of the star polymer.
However, even if it is a star polymer having a fluorine atom, the star polymer described in Patent Document 3 is synthesized by an anionic polymerization method. It is thought that it is not suitable as. Moreover, it has not been shown to have stimulus responsiveness.
In addition, since the number of branches (arms) of the star polymer described in Patent Document 4 is limited by the core to be used, it is difficult to obtain various star polymers, and the star shape has a large number of branches. Is difficult to get. Moreover, it has not been shown to have stimulus responsiveness.
That is, an object of the present invention is to provide a novel star polymer having stimulus responsiveness, particularly a star polymer having a fluorine atom at the end of a branch.

On the other hand, regarding the prevention of contamination for water-based paints, the fluororesin emulsions described in Patent Document 5 and Patent Document 6 can be stably produced even in the presence of water, and the composition containing the emulsion is a film having water repellency. However, since it is a water-repellent film, hydrophobic dirt tends to adhere to the film surface.
In addition, the method described in Patent Document 7 has an advantage of being able to exert a self-cleaning action of washing away dirt components adhering to rainwater or the like, but it takes time to make the coating surface hydrophilic, It has the problem that dirt adheres before the onset. In addition, the compatibility with the fluorine-based paint is essentially not good.
Moreover, although the coating composition described in Patent Document 8 can form a coating film excellent in raindrop stain resistance, the copolymer is hardly compatible with water and the resin in the water-based paint. Has a problem.

The present invention provides a star polymer described in the following [1] to [9], a production method thereof, a coating composition using the same, and the like.
[1]
A star-shaped polymer having a core and three or more branches connected to the core,
The core is composed of a crosslinked polymer of a dialkenyl compound,
A part or all of the branch part has the formula (I _f )
-(CH (-X-R < ¹ >)-CH (-R < ² >)) p- ^Rf ( _If )
[Where:
R ¹ is an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group; or , A cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group; Having a monovalent organic group,
R ² represents a hydrogen atom or an alkyl group,
R ^f is a group in which a monovalent organic group represented by R ¹ is fluorinated, or a group represented by the formula (I _{rf ′} )
—CHR ^a —X ¹ — ( YX ² ) _m — (CH ₂ ) _n —R ^{f ′} (I _{rf ′} )
[Where:
R ^a represents an alkyl group,
X ¹ and X ² each independently represents a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —,
Y represents an alkylene chain having 1 to 3 carbon atoms,
R ^{f ′} is (a) a C 1-12 perfluoroalkyl group, or (b) one selected from —C ₃ F ₆ O—, —C ₂ F ₄ O— and —CF ₂ O—. Represents a perfluoroether group having 2 to 50 carbon atoms and having the above repeating units;
m represents an integer of 0 to 10,
n represents an integer of 1 to 18,
Other symbols are as defined above. ]
Represents a group represented by
X represents a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —,
p represents an integer of 1 or more. ]
And a monovalent organic group having a number average molecular weight of 1,000 to 1,000,000,
The remainder of the branch is the formula (I _o ):
— (CH (—X—R ¹ ) —CH (—R ² )) p—R ^o (I _o )
[Where:
R ^o is an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group; carbon A cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group; or carbon of the alkyl group -Represents a C1-C12 alkyl group in which one or more selected from amide, imide, urethane and urea bond may be inserted into the carbon bond ,
Other symbols are as defined above. ]
And a monovalent organic group having a number average molecular weight of 1,000 to 1,000,000.
[2]
The dialkenyl compound has the formula (II)
^{CHR 3 = CH-X c1 -R} 4 -X c2 -CH = CHR 5 (II)
[Where:
R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group,
R ⁴ is an alkylene chain having 1 or more carbon atoms, or
^{_{- (CH 2) p1 -R 4}} '- (CH 2) p2 -
(Where
p1 and p2 each independently represent an integer of 1 or more,
R ^{4 ′} represents —O—, —O-phenylene-O—, —O-phenylene-C (CH ₃ ) ₂ -phenylene-O—, or cycloalkylene having 3 or more carbon atoms. )
Represents a group represented by
X ^c1 and X ^c2 each independently represent a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —. ]
The star polymer as described in [1 ] above, which is a compound represented by the formula:
[3]
The formula (I _f ) is represented by the formula (I _{f ′} ):
^{- (CH (-X-R 1} ) -CH (-R 2)) p-CHR a -X 1 - (Y-X 2) m - (CH 2) n -R f '(I f')
[Where:
R ¹ is an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group, or Represents a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group ;
R ^a represents an alkyl group,
X ¹ and X ² each independently represents a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —,
Y represents an alkylene chain having 1 to 3 carbon atoms,
R ^{f ′} is (a) a C 1-12 perfluoroalkyl group, or (b) one selected from —C ₃ F ₆ O—, —C ₂ F ₄ O— and —CF ₂ O—. Represents a perfluoroether group having 2 to 50 carbon atoms and having the above repeating units;
m represents an integer of 0 to 10,
n represents an integer of 1 to 18,
Other symbols are as defined above. ]
The star polymer according to [1] above, wherein
[4]
All the branches are monovalent organic groups represented by the formula (I _f ) and having a number average molecular weight of 1,000 to 1,000,000. The star polymer according to any one of [3].
[5]
A part of the branch part is a monovalent organic group represented by the formula (I _o ) and having a number average molecular weight of 1,000 to 1,000,000. The star polymer according to any one of the above [3].
[6]
The ratio of the branch part which is a monovalent organic group represented by the formula (I _o ) and having a number average molecular weight of 1,000 to 1,000,000 is 50 mol% or less based on the total branch part. The star polymer according to [5] above, wherein
[7]
The star polymer according to any one of [1] to [6] above, which has a weight average molecular weight of 10,000 to 5,000,000 and a molecular weight distribution of 1 to 2.
[8]
The method for producing a star polymer according to the above [1], comprising the following step 1, step 2 and step 3, or including step 1, step 1 ′, step 2 and step 3.
Step 1: Formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[Wherein each symbol has the same meaning as described in [1] above. ]
A vinyl compound represented by formula (IVf):
R ^b —CO—O—R ^f (IV _f )
[Wherein, R ^b represents an aliphatic hydrocarbon group, phenyl, a perfluoroalkyl group, or a perfluoroether group, and other symbols have the same meanings as described in the above [1]. ]
In about Engineering to living cationic polymerization presence of a compound represented by in
Engineering as 1 ': the formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[Wherein each symbol has the same meaning as described in [1] above. ]
A vinyl compound represented by formula (IV ₀ )
R ^b —CO—O—R ^o (IV ₀ )
[Wherein, R ^b is as defined above, and R ^o is as defined above in [1]. ]
Living cationic polymerization is to factory as <br/> Step 2 in the presence of a compound represented by in: from step 1 and optionally the reaction mixture obtained in step 1 ', the addition of dialkenyl compound as engineering to further living cationic polymerization <br/> step 3: to the reaction mixture obtained in step 2, a polymerization inhibitor is added, as engineering stopping the living cationic polymerization [9]
Step 1: Formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[The symbols in the formula are as defined in the above [1]. ]
A vinyl compound represented by formula (IV ₀ )
R ^b —CO—O—R ^o (IV ₀ )
[Wherein R ^o represents the same meaning as described in the above [1], and R ^b represents an aliphatic hydrocarbon group, a phenyl, a perfluoroalkyl group, or a perfluoroether group . ]
A step of living cationic polymerization in the presence of a compound represented by the following: and step 2: a step of adding a dialkenyl compound to the reaction mixture obtained in step 1 and further conducting a living cationic polymerization.
Step 3: To the reaction mixture obtained in Step 2,
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[The symbols in the formula are as defined in the above [1]. ]
A step of adding a vinyl compound represented by
Step 4: The reaction mixture obtained in Step 3 is added to the formula (a) R ^f —OH
[ Wherein , R ^f represents the same meaning as described in the above [1] . ]
Or a compound represented by (b) R ^f —OH
[ Wherein , R ^f represents the same meaning as described in the above [1] . ]
And a compound represented by R ^o —OH
[The symbols in the formula are as defined in the above [1]. ]
The method for producing a star polymer according to the above [ 1 ], which comprises a step of adding a combination of compounds represented by the formula and terminating the living cationic polymerization.
[10]
The antifouling agent comprising the star polymer according to any one of [1] to [7].
[11]
(A) A coating composition containing the antifouling agent according to [10] and (B) a coating resin .
[12]
The coating resin is at least one resin selected from a functional group-containing fluororesin, a functional group-free fluororesin, a non-fluoroacrylic resin, a polyester resin, a urethane resin, an epoxy resin, an amino resin, and an inorganic material. The coating composition according to [11].
[13]
The composition for paint according to [11] or [12] above, which is prepared as an organic solvent-type paint containing an organic solvent.
[14]
The coating composition according to any one of [11] to [13], which is prepared as an aqueous dispersion type coating material dispersed in an aqueous medium.

The star polymers of the present invention have a characteristic stimulus response.
Further, the star polymer of the present invention is useful as an antifouling agent for paints, and the paint composition containing it is excellent in antifouling properties.

1 is an NMR chart of a star polymer of one embodiment of the present invention and its starting species. It is a GPC chart of the star-shaped polymer of 1 aspect of this invention, and its branch polymer. It is a graph which shows the temperature response measurement of the star-shaped polymer of 1 aspect of this invention. It is a photograph at the time of contact angle measurement. (Example 10) It is a photograph at the time of contact angle measurement. (Comparative Example 1)

  The present invention is described in detail below.

<Star polymer>
The star polymer of the present invention has a core (central core) and three or more branches connected to the core.

なども挙げられる。 1. Core part The said core part consists of a crosslinked polymer of a dialkenyl compound. The “crosslinked polymer of dialkenyl compound” means a crosslinked polymer formed from a dialkenyl compound.
Examples of the dialkenyl compound include formula (II)
^{CHR 3 = CH-X c1 -R} 4 -X c2 -CH = CHR 5 (II)
[Where:
R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group,
R ⁴ represents a divalent organic group, and X ^c1 and X ^c2 each independently represent a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —. . ]
Is preferred.
As the “divalent organic group” represented by R ⁴ ,
Carbon number 1 or more (preferably, 4-8) alkylene chain and the ^{_{- (CH 2) p1 -R 4}} '- (CH 2) p2 -
(Where
p1 and p2 each independently represent an integer of 1 or more (preferably 1 to 10),
R ^{4 ′} represents —O—, —O-phenylene-O—, —O-phenylene-C (CH ₃ ) ₂ -phenylene-O—, or a cycloalkylene having 3 or more carbon atoms (preferably cyclohexylene (eg, 1,4-cyclohexylene)). )
Is mentioned. It is preferable that p1 and p2 are the same.
X ^c1 and X ^c2 are each independently preferably a single bond or —O—. Among them, more preferred is a single bond or —O—, and particularly preferred is —O—. X ^c1 and X ^c2 may be the same or different, but are preferably the same.
The dialkenyl compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, bisphenol A bis (vinyloxyethylene) ether, bis (vinyloxyethylene) ether, hydroquinone bis (vinyloxyethylene) ether, 1,4-cyclohexanedimethanol divinyl ether,

And so on.

2. Branches The number of the branch parts is 3 or more, preferably 10 or more, more preferably 20 or more. This number can be appropriately selected depending on the properties desired for the star polymer of the present invention, but the upper limit is usually about 1,000.
When the number of branches is reduced, the characteristics as a star polymer are reduced, but there is a tendency to be advantageous in the synthesis process, and when the number of branches is increased, the characteristics as a star polymer is improved. It tends to be difficult.

A part or all of the branch part has the formula (I _f )
-(CH (-X-R < ¹ >)-CH (-R < ² >)) p- ^Rf ( _If )
[Where:
R ¹ has a monovalent organic group that is not fluorinated,
R ² represents a hydrogen atom or an alkyl group,
R ^f represents a monovalent organic group that is fluorinated,
X represents a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —,
p represents an integer of 1 or more. ]
And a monovalent organic group having a number average molecular weight of 1,000 to 1,000,000.
In the present specification, “fluorinated” means that part or all of the hydrogen atoms of the compound or a part thereof are substituted with fluorine atoms.
The remainder of the branch is of the formula (I _o )
— (CH (—X—R ¹ ) —CH (—R ² )) _p —R ^o (I _o )
[Where:
R ^o represents a monovalent organic group that has not been fluorinated, and other symbols are as defined above. ]
And a monovalent organic group having a number average molecular weight of 1,000 to 1,000,000.
R ¹ , R ² , and X in the formula (I _f ) and the formula (I _o ) may be the same or different from each other. Moreover, p in the formula (I _f ) and the formula (I _o ) may be the same or different from each other, but is preferably a close number.
R ¹ , R ² , R ^f , R ^o and X in each branch may be the same or different from each other, but are preferably the same. Moreover, p in each branch part may be the same or different, but is preferably a close number.
Further, R ¹ , R ² and X in the repetition of p may be the same or different from each other, but are preferably the same.

  X is preferably -O-.

The “unfluorinated monovalent organic group ” represented by R ¹ is an optionally substituted alkoxyalkyl group having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms) and a substituted one. It is a good cycloalkyl group having 3 to 10 carbon atoms.
Substituents of these optionally substituted groups is a cycloalkyl group, hydroxy group, an amino group, a substituent selected from carboxy groups and phosphoric acid groups of carbon number 3-10.

As the alkyl group represented by R ² , an alkyl group having 1 to 18 carbon atoms is preferable.
Particularly preferred examples of R ² include a hydrogen atom and a methyl group.

The “monovalent organic group that is fluorinated” represented by R ^f is a group represented by the formula (I _{rf) wherein the} “monovalent organic group that is not fluorinated” represented by R ¹ is fluorinated. _' )
—CHR ^a —X ¹ — (YX ² ) _m — (CH ₂ ) _n —R ^{f ′} (I _{rf ′} )
[Where:
R ^a represents an alkyl group,
X ¹ and X ² are each independently a single bond, —O—, —S—, —NH—, or —N
(—CH ₃ ) —
Y represents an alkylene chain having 1 to 3 carbon atoms,
R ^{f ′} represents (a) a C 1-12 perfluoroalkyl group, or (b) —C ₃ F ₆ O.
-, - C ₂ F ₄ O- and having at least one repeating unit selected from -CF ₂ O-, represents a perfluoroalkyl ether group having 2 to 50 carbon atoms,
m represents an integer of 0 to 10,
n represents an integer of 1 to 18,
Other symbols are as defined above. ]
In Ru groups der represented.

Among these, a preferable example of R ^f includes a group represented by the formula (I _{rf ′} ).
In the formula (I _{rf ′} ), examples of the alkyl group represented by ^Ra include an alkyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms). Among them, for example, a methyl group Is preferred.
As the X ^1, for example, -O- is preferable.
As the X ^2, for example, -O- is preferable.
Moreover, m is preferably an integer of 0 to 6, for example.
Moreover, n is preferably an integer of 1 to 6, for example.

Examples of the “non-fluorinated monovalent organic group” represented by R ^o are the same as those exemplified for the “non-fluorinated monovalent organic group” represented by R ^1. Can be mentioned.
Is a R ^o,
An alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms) (the carbon-carbon bond of the alkyl group includes one or more selected from amide, imide, urethane, and urea bond (preferably 1 to 3) which may be inserted) and carbon which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group 2-20 (preferably having 2 to 10 carbon atoms) Ru alkoxyalkyl groups der of.

As will be apparent to those skilled in the art, the upper limit of p is determined according to the weight average molecular weight of the branch.

  The number average molecular weight of the branch is preferably 1,000 to 1,000,000, more preferably 2000 to 500,000).

From the viewpoint of the excellent stimulus responsiveness of the star polymer, preferably, all of the branches are represented by the formula (I _f ), and are 1,000 to 1,000,000 (preferably 2000 to 500,000). Is a monovalent organic group having a number average molecular weight.

From the viewpoint of compatibility with other materials, preferably, a part of the branch portion is represented by the formula (I _o ), and is 1,000 to 1,000,000 (preferably 2000 to 500,000). It is a monovalent organic group having a number average molecular weight.

From the viewpoint of ease of synthesis and production, a monovalent monomer having a number average molecular weight of 1,000 to 1,000,000 (preferably 2000 to 500,000), preferably represented by the above formula (I _o ). The ratio of the branch part which is an organic group is 50 mol% or less with respect to all the branch parts.

The star polymer of the present invention has a weight average molecular weight of preferably 10,000 to 10,000,000. Thereby, the effect that the shape as a star polymer is maintained is acquired.
The star polymer of the present invention has a molecular weight distribution of preferably 1 to 2, more preferably 1 to 1.5, still more preferably 1 to 1.3, and particularly preferably 1 to 1.2. Thereby, the effect that the stimulus responsiveness is remarkably exhibited is obtained.
In the present specification, the molecular weight distribution means a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), Mw / Mn. The average molecular weight and molecular weight distribution are determined based on the following GPC (gel filtration chromatography) measurement.
(GPC measurement)
Measurement is performed using the following columns connected in series in order.
TOSOH TSK guard column HXL-L (6.0 mm ID × 4 cm)
TOSOH TSKgel G4000HXL (7.8 mm ID x 30 cm)
TOSOH TSKgel G3000HXL (7.8 mm ID x 30 cm)
TOSOH TSKgel G2000HXL (7.8 mm ID x 30 cm)
Eluent: The molecular weight is calibrated with chloroform standard polystyrene.

The particle size of the star polymer of the present invention is preferably 5 to 500 nm, more preferably 10 to 200 nm, and still more preferably 10 to 50 nm. Thereby, the effect that it becomes transparent without scattering visible light is acquired.
In the present specification, the particle size means a numerical value analyzed by dynamic light scattering (DLS). DLS can be measured by an apparatus available from, for example, Otsuka Electronics Co., Ltd.

<Manufacturing method>
Below, the manufacturing method of the star-shaped polymer of this invention is demonstrated.
The raw material compounds in the following production methods can be obtained as commercial products or synthesized according to known methods.
The star polymer of the present invention can be produced by a production method described below and a method analogous thereto.
The star polymer of the present invention is produced by living cationic polymerization.
In living cationic polymerization, the following Lewis acid and initiating species function as a polymerization initiator.

(1) Manufacturing method 1
The method 1 for producing a star polymer of the present invention has the following step 1, step 1 ′, step 2 and step 3 as desired.
Optional step 1 ′ is performed when producing a star polymer in which part of the branch is not fluorinated, and is performed when producing a star polymer in which all of the branch is fluorinated. Not.

In step 1, formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[Wherein each symbol is as defined above. ]
A vinyl compound represented by
Lewis acid and formula (IV _f )
R ^b —CO—O—R ^f (IV _f )
[Wherein, R ^b represents an aliphatic hydrocarbon group, phenyl, perfluoroalkyl group, or perfluoroether group, and other symbols are as defined above. ]
Living cationic polymerization in the presence of a compound represented by

  The vinyl compound may be protected with a conventional protecting group. For example, when the vinyl compound has a hydroxyl group, the hydroxyl group may be protected with a protecting group such as a tert-butyldimethylsilyl group. Such protecting groups can be removed from the resulting star polymer by conventional methods.

  Examples of the Lewis acid include a compound represented by the following formula (VI) and a compound represented by the following formula (VII).

AlX ^a X ^b X ^c (VI)
(Wherein, X ^a , X ^b and X ^c each independently represent a halogen atom, an alkyl group, an aryl group, an alkoxy group or an allyloxy group.)
An aluminum compound represented by
Examples of the “halogen atom” represented by X ^a , X ^b and X ^c include chlorine, bromine and iodine.
Examples of the “alkyl group” represented by X ^a , X ^b and X ^c include an alkyl group having 1 to 10 carbon atoms.
Examples of the “aryl group” represented by X ^a , X ^b and X ^c include aryl groups having 6 to 10 carbon atoms.
Examples of the “alkoxy group” represented by X ^a , X ^b and X ^c include an alkoxy group having 1 to 10 carbon atoms.
Examples of the “aryl group” represented by X ^a , X ^b and X ^c include aryl groups having 6 to 10 carbon atoms.
Specifically as an aluminum compound represented by Formula (VI), for example,
Diethylaluminum chloride, diethylaluminum bromide, diethylaluminum fluoride, diethylaluminum iodide, diisopropylaluminum chloride, diisopropylaluminum bromide, diisopropylaluminum fluoride, diisopropylaluminum iodide, dimethylaluminum sesquichloride, methylaluminum chloride, ethylaluminum dichloride, ethyl Aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum diiodide, isobutyl aluminum dichloride, octyl aluminum dichloride, ethoxy aluminum dichloride, vinyl aluminum dichloride, phenyl aluminum dichloride, ethyl acetate Organic aluminum halide compounds such as minium sesquichloride, ethylaluminum sesquibromide, aluminum trichloride, aluminum tribromide, ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide and dialkoxyalkylaluminums such as diethoxyethylaluminum, Examples thereof include bis (2,6-di-t-butylphenoxy) methylaluminum and bis (alkyl-substituted allyloxy) alkylaluminum such as bis (2,4,6-tri-t-butylphenoxy) methylaluminum. These aluminum compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

MYaY ^b YcY ^d (VII)
(In the formula, M represents tetravalent Ti or Sn, and Y ^a , Y ^b , Y ^c and Y ^d each represent a halogen atom, an alkyl group, an aryl group, an alkoxy group or an allyloxy group.)
Respectively. Tetravalent titanium or tetravalent tin compounds.
“Halogen atom”, “alkyl group”, “aryl group” and “alkoxy group” represented by Y ^a , Y ^b , Y ^c and Y ^d , respectively, are exemplified for X ^a , X ^b and X ^c , respectively. The same thing as what was done is mentioned.
Specific examples of the tetravalent titanium compound represented by the formula (VII) include titanium halides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, titanium triethoxy chloride, titanium tri-n-butoxide chloride, and the like. And titanium alkoxides such as titanium tetraalkoxide, titanium tetraethoxide, and titanium n-butoxide.
Specific examples of the tetravalent tin compound represented by the formula (VII) include tin halides such as tin tetrachloride, tin tetrabromide and tin tetraiodide.
These tetravalent titanium compounds and tetravalent tin compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The compound represented by the formula (IV _f ) is preferably
R ^b —CO—O—CHR ^a —X ¹ — (Y—X ² ) _m — (CH ₂ ) _n —R ^{f ′} (IV _{f ′} )
[The symbols in the formula are as defined above. ]
It is a compound represented by these.

Hereinafter, symbols in the formula (IV _{f ′} ) will be described.
Examples of the “aliphatic hydrocarbon group” represented by R ^b include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms.
Examples of the “perfluoroalkyl group” represented by R ^b include a C 1-12 perfluoroalkyl group.
Examples of the “perfluoroether group” represented by R ^b include one or more repeating units selected from —C ₃ F ₆ O—, —C ₂ F ₄ O—, and —CF ₂ O—. And a perfluoroether group having 2 to 50 carbon atoms.

In the living cationic polymerization, an oxygen-containing or nitrogen-containing compound is preferably used for the purpose of stabilizing the growing species. Here, the growing species means the active species (ie, cation) present at the terminal of the living polymer that is a polymer having the active species (cation).
Examples of the oxygen-containing or nitrogen-containing compound include esters, ethers, acid anhydrides, ketones, imides, phosphoric acid compounds, pyridine derivatives, and amines. Specifically, the ester includes ethyl acetate, butyl acetate, phenyl acetate, methyl chloroacetate, methyl dichloroacetate, ethyl butyrate, ethyl stearate, ethyl benzoate, phenyl benzoate, diethyl phthalate, diethyl isophthalate, etc. Can be mentioned.
Examples of the ether include chain ethers such as diethyl ether and ethylene glycol, and cyclic ethers such as dioxane and tetrahydrofuran.
Examples of the acid anhydride include acetic anhydride.
Examples of the ketone include acetone and methyl ethyl ketone.
Examples of the imide include ethyl phthalimide.
Examples of the phosphoric acid compound include triethyl phosphate.
Examples of the pyridine derivative include 2,6-dimethylpyridine.
Examples of the amine include tributylamine.
These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The amount of the Lewis acid used is preferably a vinyl compound represented by the formula (III) / Lewis acid (molar ratio) = 2 to 1000, and more preferably 10 to 1000.
The amount of the oxygen-containing or nitrogen-containing compound used is preferably oxygen-containing or nitrogen-containing compound / Lewis acid (molar ratio) = 0.1 to 2000, more preferably 1 to 2000.
The concentration of the compound (starting species) represented by the formula (IV _f ) is preferably 0.1 to 1000 mM, and more preferably 1 to 100 mM.

The reaction may be performed in bulk, but preferably a solvent is used.
Examples of the solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and dichloroethane, and dimethyl ether. Examples include ether. A nonpolar solvent is particularly preferable. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the solvent used is usually solvent: vinyl compound (volume ratio) = 1: 1 to 100: 1, preferably 5: 1 to 30: 1.
The reaction temperature is usually −80 ° C. to 150 ° C., preferably −78 to 80 ° C.
The reaction time is usually 1 minute to 1 month, preferably 1 minute to 100 hours.

In optional step 1 ′, the formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[Where:
Each symbol represents the same meaning as described above. ]
A vinyl compound represented by
Lewis acid and formula (IV ₀ )
R ^b —CO—O—R ^o (IV ₀ )
[The symbols in the formula are as defined above. ]
Living cationic polymerization in the presence of a compound represented by
Step 1 ′ may be carried out in the same manner as in Step 1 except that the compound represented by the formula (IV ₀ ) is used instead of the compound represented by the formula (IV _f ).

  In step 1 and optional step 1 ′, each of the produced living polymers preferably has a weight average molecular weight in the range of 500 to 1,000,000, more preferably 1,000 to 500,000. Within range. The molecular weight distribution is preferably 1 to 2, more preferably 1 to 1.5, and still more preferably 1 to 1.2.

  Next, step 2 is performed without stopping the living polymerization reaction.

Step 2 is a step in which a dialkenyl compound is added to the reaction mixture obtained in Step 1 and optional Step 1 ′, and then living cationic polymerization is performed.
When Step 1 ′ is performed, the dialkenyl compound is added to the mixture of the reaction mixture obtained in Step 1 and the reaction mixture obtained in Step 1 ′.
By adjusting the molar ratio between the living polymer obtained in Step 1 and the living polymer obtained in Step 1 ′, the molar ratio of the non-fluorinated branches to all branches can be arbitrarily adjusted. .
Examples of the dialkenyl compound include those exemplified above.

The dialkenyl compound is preferably added in an amount of 1 to 100 equivalents, more preferably 3 to 20 equivalents, per 1 equivalent of the growing species of the living polymer. The dialkenyl compound is preferably added when the degree of polymerization of the alkenyl ether polymer is 10 to 10,000.
The reaction temperature is usually −80 ° C. to 150 ° C., preferably −78 to 80 ° C.
The reaction time is usually 1 minute to 1 month, preferably 1 minute to 100 hours.
When a dialkenyl compound is added to the living polymer, first, a polymer having an alkenyl group in the side chain is obtained, and subsequently, these intermolecular crosslinking reactions occur to produce a high molecular weight star polymer. This can be observed by measurement of GPC-MALLS.

In step 3, a polymerization terminator is added to the reaction mixture obtained in step 2, the active species are lost, and living cationic polymerization is stopped.
As the polymerization terminator, for example, alcohol or carboxylic acid can be used, but alcohol is preferably used.
As the alcohol, the formula: R ^s -OH
[Wherein R ^s represents an alkyl group having 1 to 12 carbon atoms. ]
The compound represented by these is mentioned.
As the carboxylic acid, the formula: R ^s -COOH
[Wherein R ^s represents an alkyl group having 1 to 12 carbon atoms. ]
The compound represented by these is mentioned.
The amount of the polymerization terminator used is usually an excess amount (2 equivalents or more), preferably 10 equivalents or more.

The yield of the star polymer by the production method (conversion rate of the chain polymer to the star polymer) is usually 90 to 100%.
According to the production method, a star polymer having a weight average molecular weight of preferably 10,000 to 5,000,000 is obtained.
According to the production method, a star polymer having a molecular weight distribution of preferably 1 to 2, more preferably 1 to 1.5, still more preferably 1 to 1.3, and particularly preferably 1 to 1.2. can get.

(2) Manufacturing method 2
The production method 2 of the star polymer of the present invention includes the following steps 1 to 4.

In step 1, formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[The symbols in the formula are as defined above. ]
A vinyl compound represented by formula (IV ₀ )
R ^b —CO—O—R ^o (IV ₀ )
[Wherein R ^o and R ^b represent the same meaning as described above. ]
Living cationic polymerization in the presence of a compound represented by
The said process 1 should just be implemented by the method similar to process 1 'of the said manufacturing method 1. FIG.

In step 2, a dialkenyl compound is added to the reaction mixture obtained in step 1 and further living cationic polymerization is performed.
The said process 2 should just be implemented by the method similar to the process 2 of the said manufacturing method 1. FIG.

In step 3, the reaction mixture obtained in step 2 is added to the reaction mixture.
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[The symbols in the formula are as defined above. ]
A vinyl compound represented by the following formula is added, and further living cationic polymerization is performed.
The vinyl compound represented by the formula (III) may be the same as or different from the vinyl compound represented by the formula (III) in Step 1.
The reaction temperature is usually −80 ° C. to 150 ° C., preferably −78 to 80 ° C.
The reaction time is usually 1 minute to 1 month, preferably 1 minute to 100 hours.

In step 4, the reaction mixture obtained in step 3 is added to the reaction mixture.
(A) R ^sf -OH
[Wherein R ^sf represents a monovalent organic group that is fluorinated. ]
Or a compound represented by (b) R ^sf —OH
[Wherein R ^sf represents a monovalent organic group that is fluorinated. ]
And a compound represented by R ^o —OH
[The symbols in the formula are as defined above. ]
The combination of the compounds represented by is added to stop the living cationic polymerization.
The said process 4 should just be implemented by the method similar to the process 3 of the said manufacturing method 1. FIG.
Here, by ^adjusting the molar ratio of R ^sf —OH and R ^o —OH in (b), the molar ratio of the non-fluorinated branches to the total branches of the obtained star polymer can be arbitrarily set. Can be adjusted to.
However, the molar ratio in the star polymer obtained by the production method 2 is 50% at the maximum.

The yield of the star polymer by the production method (conversion rate of the chain polymer to the star polymer) is usually 90 to 100%.
According to the production method, a star polymer having a weight average molecular weight of preferably 10,000 to 5,000,000 is obtained.
According to the production method, a star polymer having a molecular weight distribution of preferably 1 to 2, more preferably 1 to 1.5, still more preferably 1 to 1.3, and particularly preferably 1 to 1.2. can get.

  The star polymer thus obtained can be purified using a conventional method such as distillation under reduced pressure, if necessary.

<Mode of use>
The star polymer of the present invention responds sensitively to a minute change (external stimulus) in the external environment such as a temperature change, and has a stimulus responsiveness in which physical properties and the like change remarkably. In particular, the star polymer of the present invention has the characteristics that the transition temperature is shifted as compared with the conventionally known star polymer and the hysteresis is exhibited with respect to the temperature sensitive property. Therefore, the star polymer of the present invention can be used as a new high-performance material.
As a specific application, for example, the star polymer of the present invention is used as a dispersion aid for coatings, a rheology control agent, a fixing agent (which improves adhesion to a substrate), or an anti-staining agent (details of the application). Can be used as follows. Here, the star polymer of the present invention may have appropriate dispersibility in a solvent, appropriate paint viscosity, appropriate adhesion to a substrate, etc., depending on the fluorine content at the branch end. it can.
Further, the star polymer of the present invention can be used as a highly functional surface treatment agent (eg, water / oil repellent for textiles, carpet repellent, paper repellent and release agent). Here, the star polymer of the present invention effectively has water repellency, oil repellency, or antifouling property by orienting efficiently on the surface of the coating due to the effect of fluorine introduced at the branch ends. It can be expressed. Therefore, the star polymer of the present invention can be used as an excellent water and oil repellent having environmental responsiveness.
In addition, the star polymer of the present invention is a resin additive (eg, compatibilizer, internally added repellent, internally added antifouling agent, release agent, flame retardant, anti-drip agent, impact resistance improver). , Rigidity improver and reinforcing agent, etc. Here, the star polymer of the present invention controls the compatibility with the resin based on the hydrophobic action of the fluorine at the branch end and the hydrophilic action of the branch, for example, by adjusting the fluorine content at the branch end. In addition, it can have appropriate compatibility with the resin to be added. The star polymer of the present invention can have a particle size equal to or lower than the wavelength level, and such a star polymer is particularly suitable as an additive for a transparent resin.
Further, as described above, the star polymer of the present invention exhibits excellent temperature-sensitive characteristics, and by controlling the temperature, it is possible to control the release of the drug, so that the DDS (drug delivery system) It can be used as a carrier or the like.
In addition, the star polymer of the present invention forms a large aggregate (higher order structure) by the self-organization of fluorine introduced at the branch ends between molecules and within molecules by hydrophobic interaction. The aggregate field obtained by this self-assembly can be used for various purposes (eg, a solidified carrier for a catalyst such as an enzyme).
In particular, when the particle size of the star polymer of the present invention is about several tens of nanometers, it is very excellent in transparency, so various optical member materials or additives (eg, refractive index adjusting agent, antifouling agent, It can be used as a light emitting element material, a lens material, an optical device material, a display material, an optical recording material, an optical signal transmission material (optical transmission medium), and a sealing member material.
In addition, the star polymer of the present invention can exhibit slipperiness, water repellency, antifouling properties derived from fluorine due to excellent molecular orientation due to the presence of fluorine at the branch ends, Cosmetics (face wash, lotion, milky lotion, cream, gel, skin care product, foundation, lipstick, point makeup product, body shampoo, liquid soap, sunscreen cosmetics and other sun care products, hand care products, deodorant cosmetics, bath salts, etc. It can be used as a property modifier for cosmetics; hair cosmetics such as shampoos, rinses, conditioners, treatments, hair liquids, hair sprays, hair nail polishes, set foams and hair gels.
In addition, the star polymer of the present invention includes a gelling agent that utilizes the hydrophobic interaction of fluorine at the end of the branch, a sensor (eg, temperature sensor, humidity sensor) that utilizes excellent temperature sensitive characteristics, a mechanochemical material, and It can be used in adhesives and the like.

Hereinafter, the case where the star polymer of the present invention is added to a coating composition as a contamination inhibitor and used will be described in detail.
In particular, when used as an antifouling agent for water-based paints, among the star polymers of the present invention, R ¹ in the formula (I _f ) corresponding to the branch portion of the star polymer has 1 to 1 carbon atoms. A group having 4 to 50 carbon atoms in which 2 to 30 alkyl groups having 12 (preferably 1 to 6 carbon atoms) are linked via —O— (eg, —C ₃ H ₆ O—, —C ₂ H ₄ A polymer that is one or more repeating units selected from O— and —CH ₂ O— (preferably a polyether group having _{4 to} 50 carbon atoms and having —C ₂ H ₄ O—) is preferred. Such a star-shaped polymer having a hydrophilic group is very stably dispersed in water, and is extremely effective as a hydrophilic contamination adhesion preventing agent.
Here, as the water-based paint, a fluororesin emulsion-based water-based paint is particularly preferable.
Hereinafter, the mechanism assumed by the present inventors will be described, but this does not limit the present invention.
The antifouling action seems to be derived from the very characteristic structure of the star polymer of the present invention having fluorine at the branch end.
That is, the fluorine at the branch end is compatible with the fluororesin-based paint composed of the fluororesin emulsion and contributes to the orientation of the star polymer with hydrophilic branches on the coating surface. Seems to have given. It is considered that due to the effect of the fluorine at the branch end, the star-shaped polymer oriented on the surface hydrophilizes the surface of the coating film by the hydrophilic action of the branch portion, and functions to prevent the coating film from being contaminated.
Here, as the fluororesin emulsion, a fluoropolymer obtained by polymerizing fluoroolefin, or a fluoropolymer obtained by copolymerizing a monomer capable of copolymerization with fluoroolefin and fluoroolefin Or an emulsion of a fluorine-containing seed polymer obtained by seed polymerization of a monomer having a reactive α, β-unsaturated group in the presence of particles of the fluorine-containing polymer.
Examples of the fluoroolefin include carbon such as vinyl fluoride, vinylidene fluoride (VdF), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene, and pentafluoropropylene. A fluoroolefin having a number of about 2 to 4 is preferably employed, but VdF, TFE, CTFE, and HFP are preferred from the viewpoint of polymerizability.
Examples of the monomer that can be copolymerized with the fluoroolefin include, for example, cyclohexyl vinyl ether (CHVE), ethyl vinyl ether (EVE), butter vinyl ether, alkyl vinyl ethers such as methyl vinyl ether, polyoxyethylene allyl ether (POEAE), ethyl, and the like. Alkenyl vinyl ethers such as allyl ether, organosilicon compounds having reactive α, β-unsaturated groups such as vinyltrimethoxysilane (VSi), vinyltriethoxysilane, vinyltris (methoxyethoxy) silane, methyl acrylate, ethyl acrylate Such as acrylic esters such as methyl methacrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, vinyl benzoate, and “Beoba” (a vinyl ester manufactured by Shell). Nyl ester, etc. are mentioned, but from the viewpoints of copolymerizability, film formability, weather resistance and the like, alkyl vinyl ether, allyl vinyl ether, vinyl ester, and an organosilicon compound having a reactive α, β-unsaturated group are preferred. CHVE, EVE More preferred are vinyl benzoate, vinyl crotonate, POEAE, and VSi.
The fluorine-containing seed polymer is obtained by polymerizing a monomer having a reactive α, β-unsaturated group in the presence of particles of the fluorine-containing polymer.
Examples of the monomer having a reactive α, β-unsaturated group include acrylic acid esters such as methyl acrylate, butyl acrylate (BA), ethyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate (MMA). , Methacrylates such as butyl methacrylate and polyoxyethylene methacrylate (POEMA), and reactive α, β-unsaturations such as γ-methacryloyloxypropyl-trimethoxysilane (SiMA) and γ-methacryloyloxypropyltriethoxysilane Examples thereof include organosilicon compounds having a group, vinyl acetate, vinyl benzoate, vinyl esters such as “Beoba” (vinyl ester manufactured by Shell), and aromatic vinyl compounds such as styrene and P-tert-butyl-styrene. In terms of film formation and weather resistance. Esters, methacrylic acid esters, organic silicon compounds having a reactive alpha, beta-unsaturated groups, vinyl esters are preferred, BA, MMA, POEMA, SiMA is more preferable.
Even when an excessive amount of an organosilicon compound having a reactive α, β-unsaturated group is used during the polymerization or copolymerization, the same effect as that obtained by blending the organosilicon compound after the polymerization or copolymerization can be obtained. It is done.

<Resin composition for paint>
The coating resin composition of the present invention is
(A) The star polymer of the present invention and (B) a resin for paints are contained.

  The concentration of the “star polymer” in the coating resin composition of the present invention is usually 0.01 to 50% (% by weight, the same applies hereinafter), preferably 0, based on the weight of the entire solid component. .1-20%. If the concentration is less than 0.01%, the anti-contamination effect tends to be insufficient, and if it exceeds 50%, the weather resistance tends to deteriorate and the film-forming property tends to deteriorate.

The “paint resin” used in the paint resin composition of the present invention is not particularly limited. For example, a functional group-containing fluororesin, a functional group-free fluororesin, a non-fluorine acrylic resin, a polyester resin, a urethane resin, Examples thereof include epoxy resins, amino resins, and inorganic materials. The said resin for coating materials may be used individually by 1 type, and may be used in combination of 2 or more type.
The functional group-containing fluororesin includes the following forms.
(I) a copolymer of a fluoroolefin and a functional group-containing non-fluorinated monomer (hereinafter sometimes referred to as copolymer (I)),
(II) a copolymer of a functional group-containing fluoroolefin and a non-functional group-containing fluoroolefin (that is, a fluoroolefin) (hereinafter sometimes referred to as copolymer (II));
(III) Functional group-containing fluororesin blend prepared by blending two or more kinds of resins (hereinafter sometimes referred to as blend (II)),
(IV) A composite resin (seed polymer) obtained by seed-polymerizing a fluorine-containing resin particle with a functional group-containing non-fluorine monomer (hereinafter sometimes referred to as composite resin (seed polymer) (IV)). .

  In this specification, examples of the fluoroolefin include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), perfluoro (alkyl vinyl ether), trifluoroethylene, and vinylidene fluoride (VdF). ) And vinyl fluoride. Moreover, as a functional group containing fluoroolefin, the following can be illustrated, for example.

(I) CF ₂ = CF (CF ₂ ) _a Z
(Z is SO ₃ M or COOM (M is H, NH ₄ or alkali metal); a is an integer of 1 to 10)
As a specific example,
CF ₂ = CFCF ₂ -COOH
Etc.

_{(Ii) CF 2 = CF (} CF 2 CF (CF 3)) b -Z
(Z is SO ₃ M or COOM (M is H, NH ₄ or alkali metal); b is an integer of 1 to 5)
As a specific example,
_{CF 2 = CFCF 2 CF (CF} 3) -COOH,
_{CF 2 = CF (CF 2 CF} (CF 3)) 2 -COONH 4
Etc.

_{(Iii) CF 2 = CF-} O- (CFR f3) c -Z
(R ^f3 is F or CF ₃ ; Z is SO ₃ M or COOM (M is H, NH ₄ or alkali metal); c is an integer of 1 to 10)
As a specific example,
_{CF 2 = CF-O-CF} 2 CF 2 CF 2 COOH
Etc.

_{(Iv) CF 2 = CF-} O- (CF 2 CFR f3 O) d -Z
(R ^f3 is F or CF ₃ ; Z is SO ₃ M or COOM (M is H, NH ₄ or alkali metal); d is an integer of 1 to 10)
As a specific example,
_{CF 2 = CF-OCF 2 CF} (CF 3) OCF 2 CF 2 COOH,
_{CF 2 = CF-OCF 2 CF} (CF 3) OCF 2 CF 2 SO 3 H
Etc.

などが挙げられる。 _{(V) CH 2 = CFCF 2} -O- (CF (CF 3) CF 2 O) e -CF (CF 3) -Z
(Z is SO ₃ M or COOM (M is H, NH ₄ or alkali metal); e is 0 or an integer of 1 to 10)
As a specific example,

Etc.

_{(Vi) CF 2 = CFCF 2} -O- (CF (CF 3) CF 2 O) f -CF (CF 3) -Z
(Z is SO ₃ M or COOM (M is H, NH ₄ or alkali metal); f is an integer of 1 to 10)
As a specific example,
CF ₂ = CFCF ₂ O—CF (CF ₃ ) CF ₂ O—CF (CF ₃ ) COOH,
_{CF 2 = CFCF 2 O-CF} (CF 3) CF 2 O-CF (CF 3) SO 3 H
Etc.

Although it does not specifically limit as a functional group in the said functional group containing non-fluorine-type monomer, For example, a hydroxyl group, a hydrolysable alkyl silicate residue, and a carboxyl group are mentioned.
Among the functional group-containing non-fluorinated monomers, the hydroxyl group-containing non-fluorinated monomers may be represented by the formula: CH ₂ = CHR ^b1 (wherein R ^b1 is —OR ^b2 or —CH ₂ OR ^b2 (where R ^b2 Is a hydroxyalkyl vinyl ether or hydroxyallyl ether represented by the following formula: R ^b2 is, for example, a group in which 1 to 3, preferably 1 hydroxyl group is bonded to a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of these include, for example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether. , 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, and the like. Other examples include allyl alcohol.

  Examples of non-fluorinated monomers containing hydrolyzable alkyl silicate residues include vinyl alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, and trimethoxysilylethyl. Examples include vinyl ether, triethoxysilylethyl vinyl ether, triethoxysilylpropyl vinyl ether, triisopropenyloxysilylethyl vinyl ether, and γ- (meth) acryloyloxypropyltrimethoxysilane.

  Examples of the carboxyl group-containing non-fluorinated monomer include unsaturated group-containing organic acids represented by the formula (5) or (6) described later (for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3 -Allyloxypropionic acid, itaconic acid, itaconic acid monoester, itaconic anhydride, succinic anhydride, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, pyro And carboxyl group-containing monomers such as vinyl melitrate and 3-allyloxypropionic acid).

  Other functional group-containing non-fluorine monomers include epoxy group-containing monomers such as glycidyl (meth) acrylate, epoxy vinyl, and epoxy vinyl ether; diacetone acrylamide, (meth) acrylamide, N-methylol (meth) Examples include amino group-containing monomers such as acrylamide; nitrile group-containing monomers such as (meth) acrylonitrile; and carbonyl group-containing monomers such as acrolein, vinyl ethyl ketone, and diacetone acrylamide. It is not a thing.

  Moreover, you may use the monomer which does not have a functional group as a comonomer. Examples of such monomers include, but are not limited to, α-olefins such as ethylene, propylene, and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, poly vinyl Vinyl ethers such as oxyethylene vinyl ether; alkenyls such as polyoxyethylene allyl ether, ethyl allyl ether, allyl ether; vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, Veova 9 and Veova 10 (all Vinyl esters such as saturated carboxylic acid (made by Shell Chemical Co., Ltd.); Unsaturated carboxylic acid diesters such as dimethyl maleate; (Metals such as methyl methacrylate and butyl acrylate) Acrylate; styrene, and vinyl aromatic compounds such as vinyl toluene can be used.

  Among the copolymers (I), the hydroxyl group-containing copolymer is a copolymer of the fluoroolefin and the functional group-containing monomer, and if necessary, a monomer copolymerizable with these monomers. A polymer is mentioned. A typical example of the hydroxyl group-containing monomer is hydroxybutyl vinyl ether, and a typical example of the carboxyl group-containing monomer is maleic acid. Examples of other comonomers include alkyl vinyl esters, alkyl vinyl ethers, olefins such as ethylene, propylene, and isobutene, (meth) acrylates, and styrene.

  Specifically, for example, as described in JP-B-60-21686, JP-A-3-121107, JP-A-4-279612, JP-A-4-28707, JP-A-2-232221, and the like. The thing is mentioned. The number average molecular weight (by GPC) of the copolymer is 1,000 to 100,000, preferably 1,500 to 30,000. If the molecular weight is less than 1,000, curability and weather resistance tend to be insufficient, and if it exceeds 100,000, workability and paintability tend to be problematic.

  More specifically, TFE / alkyl vinyl ether / HBVE copolymer, CTFE / alkyl vinyl ether / HBVE copolymer, TFE / alkyl vinyl ether / maleic acid copolymer, CTFE / alkyl vinyl ether / maleic acid copolymer Copolymers such as coalescence can be mentioned, but the invention is not limited to these.

  As a hydroxyl value of the said copolymer, it is 0-200 (mgKOH / g), and it is preferable that it is 0-150 (mgKOH / g). When the hydroxyl group is decreased, the curing tends to be poor, and when it exceeds 200 (mgKOH / g), the flexibility of the coating film tends to be problematic.

  The acid value of the copolymer is 0 to 200 (mgKOH / g), and more preferably 0 to 100 (mgKOH / g). When the acid value decreases, the curing tends to be poor, and when it exceeds 200 (mg KOH / g), the flexibility of the coating film tends to be problematic.

  Examples of commercial products of the copolymer include ZEFFLE manufactured by Daikin Industries, Ltd., Lumiflon manufactured by Asahi Glass Co., Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., Fluonate manufactured by Dainippon Ink & Chemicals, Inc., Toa Gosei Co., Ltd. Examples include ZAFLON made.

  Among the functional group-containing fluorine-containing copolymer (I), examples of the fluoroolefin resin having a hydrolyzable alkyl silicate residue as a functional group include those described in JP-A-4-4246. Can be mentioned. The number average molecular weight (by GPC) of the copolymer is 1,000 to 100,000, preferably 1,500 to 30,000. If the molecular weight is less than 1000, curability and weather resistance tend to be insufficient, and if it exceeds 100,000, workability and paintability tend to be problematic.

  Specifically, a copolymer such as a copolymer containing TFE / vinylmethoxysilane and a copolymer containing TFE / trimethoxysilylethyl vinyl ether can be given.

  The content of the hydrolyzable alkyl silicate residue of the copolymer is 1 to 50 mol%, preferably 5 to 40 mol%. When the hydrolyzable alkyl silicate residue is reduced, the curing tends to be poor, and when it is too much, the flexibility of the coating film tends to be problematic.

  Other examples of the copolymer (I) include CTFE / ethyl vinyl ether / 2-hydroxybutyl vinyl ether copolymer, TFE / cyclohexyl vinyl ether / veova 10 / crotonic acid copolymer, and the like.

  Examples of the copolymer (II) include, for example, TFE / HFP / functional group-containing fluorine-containing monomer-based copolymers represented by the above formulas (i) to (vi).

  The blend (III) includes a blend of the copolymers (I) and (II), a blend of the copolymer (I) and / or (II) and a functional group-containing non-fluorinated resin, Examples thereof include a blend of the combination (I) and / or (II) with a functional group-free non-fluorine resin, a blend of a functional group-containing non-fluorine resin and a functional group-free fluorine resin, and the like.

  Examples of the functional group-containing non-fluorinated resin include (co) polymers of the above functional group-containing monomers, and specific examples include acrylic polyols and urethane polyols. Examples of the functional group-free non-fluorinated resin include acrylic resin and polyester. Examples of the functional group-free fluororesin include, for example, VdF homopolymer, VdF / TFE copolymer, VdF / HFP copolymer, VdF / CTFE copolymer, VdF / TFE / CTFE copolymer. VdF polymers such as polymers, VdF / TFE / HFP copolymers; TFE / HFP copolymers; fluoroolefins and non-fluorinated monomers having no functional group (for example, vinyl ethers and vinyl esters, α -Copolymers with olefins and vinyl aromatic compounds).

  The blend ratio may be appropriately selected depending on the functional group content, fluorine content, and the like. Usually, the functional group is an amount capable of sufficiently reacting with the antifouling component (B) and further the curing agent (C). Such blending is desirable from the viewpoint of excellent antifouling effect.

  The composite resin (seed polymer) (IV) was produced by seed polymerization of a functional group-containing non-fluorinated monomer in an aqueous dispersion of the functional group-containing or non-containing fluororesin particles. A thing can be illustrated preferably. Specifically, a composite resin obtained by seed polymerization of acrylic acid, methacrylic acid, (meth) acrylic acid ester, a functional group-containing vinyl compound or the like in an aqueous dispersion of VdF copolymer particles is preferable.

  The functional group-containing fluororesin can be used in the form of an organic solvent-type paint or an aqueous dispersion-type paint, but the composite resin is particularly useful in the form of an aqueous-dispersion-type paint.

When used as an aqueous dispersion type paint, the solid content concentration is about 20 to 70% by weight, preferably about 30 to 60% by weight, from the viewpoint of excellent stability when formed into a paint. The average particle size is about 50 to 300 nm, preferably about 100 to 250 nm, from the viewpoint of excellent stability of the aqueous dispersion. It is preferable that the pH is usually in the range of 5 to 10.
Examples of the functional group-free fluororesin include a vinylidene fluoride homopolymer or copolymer. Examples of the homopolymer or copolymer of vinylidene fluoride include those described in JP-B 43-10363, JP-A-3-28206, JP-A-4-189879, and the like. Is mentioned.
In the case where only a resin having no functional group is used as the coating resin in the coating composition of the present invention, it is not necessary to use a curing agent or a curing catalyst in the coating composition of the present invention. .

  As the non-fluorine acrylic resin, the following acrylic polyol resin or acrylic silicon resin is preferable.

  Examples of the acrylic polyol resin include polymers having the following hydroxyl group-containing polymerizable unsaturated monomer (a) and, if necessary, other polymerizable unsaturated monomer (b) as monomer components. Good.

  Examples of the monomer (a) include compounds represented by the following formulas (1) to (4).

［式中、Ｒ^a1は水素原子またはヒドロキシアルキル基を示す。］

[Wherein R ^a1 represents a hydrogen atom or a hydroxyalkyl group. ]

［式中、Ｒ^a1は前記に同じ。］

[Wherein R ^a1 is the same as defined above. ]

［式中、Ｚは水素原子またはメチル基を示し、ｒ１は２〜８の整数、ｒ２は２〜１８の整数、ｒ３は０〜７の整数を示す。］

[In the formula, Z represents a hydrogen atom or a methyl group, r1 represents an integer of 2 to 8, r2 represents an integer of 2 to 18, and r3 represents an integer of 0 to 7. ]

［式中、Ｚは前記に同じであり、Ｔ₁およびＴ₂は、同一もしくは異なって、炭素数１〜２０の２価の炭化水素基を示す。ｒ４およびｒ５はそれぞれ０〜１０の整数を示す。ただし、ｒ４とｒ５の和は、１〜１０である。］

[Wherein, Z is the same as defined above, and T ₁ and T ₂ are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms. r4 and r5 each represents an integer of 0 to 10. However, the sum of r4 and r5 is 1-10. ]

In formulas (1) and (2), the hydroxyalkyl group is a hydroxyalkyl group having 1 to 6 carbon atoms in the alkyl moiety. _{Specifically, -C 2 H 4 OH, -C} 3 H 6 OH, and the like -C ₄ H ₈ OH.

  Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in the formula (11) include:

などを挙げることができる。

And so on.

As the monomer component of the formula (1), for example, CH ₂ ═CHOH,
CH ₂ = CHO (CH ₂ ) ₄ OH
And so on.

  Examples of the monomer component of the formula (2) include

などを挙げることができる。

And so on.

  As a monomer component of Formula (3), for example,

などを挙げることができる。

And so on.

  As a monomer component of Formula (4), for example,

などを挙げることができる。

And so on.

  In addition to the above, adducts of hydroxyl group-containing unsaturated monomers represented by the above formulas (1) to (4) with lactones such as ε-caprolactone and γ-valerolactone can be used.

  Examples of the other polymerizable unsaturated monomer (b) include the following (b-1) to (b-9).

  (B-1) Olefin compounds: For example, ethylene, propylene, butylene, isoprene, chloroprene and the like.

  (B-2) Vinyl ether and allyl ether: for example, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1-pentyl vinyl ether, etc. Chain alkyl vinyl ethers, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, o-, m-, and p-trivinyl ethers, aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether, etc. .

  (B-3) Vinyl esters and propenyl esters; for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate, vinyl caprate and isopropenyl acetate, Propenyl esters such as isopropenyl propionate.

  (B-4): An ester of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate Acrylic acid such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc., or alkyl ester having 1 to 18 carbon atoms of methacrylic acid; methoxybutyl acrylate, C2-C1 of acrylic acid or methacrylic acid such as methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate Such as alkoxyalkyl esters.

  (B-5) Vinyl aromatic compound: For example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene and the like.

  (B-6) Others: Acrylonitrile, methacrylonitrile and the like.

  (B-7) Carboxyl group-containing monomer: Formula (5):

（式中、Ｒ^a2、Ｒ^a3およびＲ^a4は同じかまたは異なり、いずれも水素原子、アルキル基、フェニル基、カルボキシル基またはエステル基であり、ｒ６は０または１である）
または式（１３）：

(In the formula, R ^a2 , R ^a3 and R ^a4 are the same or different, and all are hydrogen atom, alkyl group, phenyl group, carboxyl group or ester group, and r6 is 0 or 1)
Or formula (13):

（式中、Ｒ^a5およびＲ^a6は同じかまたは異なり、いずれも飽和または不飽和の直鎖または環状アルキル基であり、ｒ７は０または１であり、ｒ８は０または１である）
で表されるカルボキシル基含有ビニル単量体が挙げられる。具体例としては、例えばアクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、桂皮酸、３−アリルオキシプロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸無水物、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニルなどが挙げられる。

(Wherein R ^a5 and R ^a6 are the same or different and both are saturated or unsaturated linear or cyclic alkyl groups, r7 is 0 or 1, and r8 is 0 or 1)
The carboxyl group-containing vinyl monomer represented by these is mentioned. Specific examples include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid. Examples thereof include acid, fumaric acid monoester, vinyl phthalate, and vinyl pyromellitic acid.

  (B-8) Epoxy group-containing monomer:

  (B-9) Amino-containing monomer:

  The acrylic polyol resin may have a hydroxyl group, a carboxyl group, an epoxy group, or an amino group, but a hydroxyl group is particularly preferable.

  The hydroxyl value of the acrylic polyol resin is 0 to 200 (mgKOH / g), and preferably 0 to 100 (mgKOH / g). When the hydroxyl value decreases, the curing tends to be poor, and when it exceeds 200 (mgKOH / g), the flexibility of the coating film tends to be problematic.

  Examples of the acrylic polyol resin include Dainal manufactured by Mitsubishi Rayon Co., Ltd., Acridic manufactured by Dainippon Ink & Chemicals, Hitaroid manufactured by Hitachi Chemical Co., Ltd., Olester manufactured by Mitsui Toatsu Chemical Co., Ltd., Japan Commercially available products such as Acryset manufactured by Catalyst Co., Ltd., Polysol manufactured by Showa Polymer Co., Ltd., and Movinyl manufactured by Clariant Polymer Co., Ltd. can be used.

  Examples of the acrylic silicon resin include those obtained by polymerizing the following acrylic silicon monomers together with the compounds of the formulas (1) to (4) and / or other polymerizable unsaturated monomers (b).

  The acrylic silicon monomer is a compound having at least one silane group and a radically polymerizable unsaturated group in one molecule. Examples of the radical polymerizable unsaturated group include:

ＣＨ₂＝Ｃ（−Ｒ^a9）−、
ＣＨ₂＝ＣＨ−Ｏ−、
ＣＨ₂＝ＣＨＣＨ₂−Ｏ―
［式中、Ｒ^a9は水素原子またはメチル基である］
などを挙げることができる。 CH ₂ ═C (—R ^a9 ) —CO—O—,

CH ₂ = C (-R ^a9 )-,
CH ₂ = CH-O-,
CH ₂ = CHCH ₂ -O-
[Wherein R ^a9 is a hydrogen atom or a methyl group]
And so on.

  Radically polymerizable unsaturated groups

のシラン基含有重合性不飽和単量体としては、例えば下記式（７）で表わされる化合物を
挙げることができる：

Examples of the silane group-containing polymerizable unsaturated monomer include compounds represented by the following formula (7):

［式中、Ｒ^a9は前記と同意義であり、Ｒ^a10は炭素数１〜２０の２価の炭化水素基を示し、Ｗは各出現において同一または異なって、水素原子、水酸基、加水分解性基、炭素数１〜８のアルキル基、アリール基またはアラルキル基を示す。ただし、Ｗの少なくとも１個は加水分解性基である］。

[Wherein, R ^a9 is as defined above, R ^a10 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and W is the same or different at each occurrence, and represents a hydrogen atom, a hydroxyl group, a hydrolyzable group. Group, a C1-C8 alkyl group, an aryl group, or an aralkyl group. However, at least one of W is a hydrolyzable group].

  Specific examples of the compound represented by the formula (7) include, for example, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxy. Silane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxy Silane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyldipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxy Silane, γ- (meth) ac Roxypropylphenylmethylmethoxysilane, γ- (meth) acryloxypropylphenylmethylethoxysilane, γ- (meth) acryloxypropyltrisilanol, γ- (meth) acryloxypropylmethyldihydroxysilane, γ- (meth) acryloxy Examples thereof include butylphenyl dihydroxysilane, γ- (meth) acryloxypropyldimethylhydroxysilane, γ- (meth) acryloxypropylphenylmethylhydroxysilane, and the like.

  The acrylic silicone resin may further have a hydroxyl group or an epoxy group.

  Commercially available products such as Kaneka Chemical Co., Ltd. Zemlac, Sanyo Kasei Co., Ltd. clearer, Clariant Polymer Co., Ltd., can be used as the acrylic silicone resin.

  Examples of the polyester resin include alkyd resins, commercially available products such as ESPEC manufactured by Hitachi Chemical Co., Ltd., desmophene manufactured by Sumitomo Bayer Urethane Co., Ltd., and beccosol manufactured by Dainippon Ink Manufacturing Co., Ltd.

  Examples of the urethane resin include commercially available products such as Bibond manufactured by Sumitomo Bayer Urethane Co., Ltd., Suncure manufactured by BF Goodrich, Neorec manufactured by Avisia, and Daotan manufactured by Clariant Polymer.

Examples of the epoxy resin include commercially available products such as Epicoat and Epiletz manufactured by Japan Epoxy Resin Co., Ltd.
Examples of the amino resin include melamine resin.

Examples of the method for introducing a functional group (carboxyl group, epoxy group, amino group, carbonyl group, nitrile group) other than a hydroxyl group and a hydrolyzable alkylsilicate residue into the coating resin in the coating composition of the present invention include, for example, What is necessary is just to copolymerize the monomer containing these functional groups as a comonomer. Examples of functional group-containing monomers include (meth) acrylic acid, maleic acid, and succinic anhydride for introducing a carboxyl group; glycidyl (meth) acrylate for introducing an epoxy group; diacetone acrylamide for introducing an amino group; Acrylamide and the like; (meth) acrylonitrile and the like for introducing a nitrile group; and acrolein and vinyl ethyl ketone and the like for introducing a carbonyl group.
Examples of the inorganic material include fluorine-free non-hydrolyzable group-containing metal (Si, Ti, Al, etc.) alkoxide, fluorine-free non-hydrolyzable group-containing organopolysiloxane, fluorine-free metal (Si, Ti, Al, etc.) alkoxide and the like. Examples of such inorganic materials include Gunze Sangyo Co., Ltd. Ecoleton, Nippon Synthetic Rubber Co., Ltd. Glasca, Toupe Co., Ltd. Porcelain, Nippon Oil & Fats Co., Ltd. Bell Clean, Bell Hard, Toray Dow Corning・ SH, SR and DC series manufactured by Silicone Co., Ltd., KR series manufactured by Shin-Etsu Chemical Co., Ltd., Prenact manufactured by Ajinomoto Co., Inc., Organic titanate manufactured by Nippon Soda Co., Ltd., Aluminum alcoholate manufactured by Kawaken Fine Chemical Co., Ltd. and Commercial products such as an aluminum chelate compound, zirconium alkoxide manufactured by Hokuko Chemical Co., Ltd., composite modified silicone oil manufactured by Nippon Unicar Co., Ltd., and MMCA can be used.
Examples of the inorganic material include a fluorine silicone resin. Examples of the fluorosilicone resin include those described in JP-A-4-279612.

  Among these, as the coating resin used in the present invention, a functional group-containing fluoroolefin resin is preferable from the viewpoint of excellent weather resistance.

  The coating composition of the present invention essentially comprises the coating resin (B) (hereinafter sometimes referred to simply as “resin (B)”) and the star polymer (A) of the present invention. Depending on the functional group of the resin for resin (B), a curing agent (C) may be further contained.

  Specifically, for example, when the resin (B) has a functional group selected from a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and a hydrolyzable alkyl silicate residue, the coating composition of the present invention is cured. It is preferable to contain an agent (C).

  A preferable curing agent (C) may be an appropriate curing agent depending on the functional group.

Specific examples include amino compounds, epoxy compounds, organic acids, hydrazide compounds, aziridine compounds, carbodiimide compounds and / or Si (OR ^c1 ) ₄ (R ^c1 is a non-fluorinated alkyl group having 1 to 10 carbon atoms), R ^c2 At least selected from the group consisting of Si (OR ^c3 ) ₃ (R ^c2 and R ^c3 are the same or different and a non-fluorinated alkyl group having 1 to 10 carbon atoms), a single condensed oligomer thereof, and a co-condensed co-oligomer thereof One type is mentioned.

  The blending amount of the curing agent (C) may be appropriately selected depending on the type of the curing agent, but is usually 0 to 200 parts by weight with respect to 100 parts by weight in total of the resin (B) and the star polymer (A). . A preferable upper limit is 100 parts by weight, further 80 parts by weight, and a preferable lower limit is 5 parts by weight, and further 10 parts by weight.

  Hereinafter, although the example with the hardening | curing agent (C) suitable for the functional group of resin (B) is given, this invention is not limited to these examples.

(1) When the functional group of the resin (B) is a hydroxyl group:
As the curing agent (C), an isocyanate compound is preferable.

  The isocyanate compound also includes a blocked isocyanate compound. Specific examples include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, Trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts and burettes thereof, polymers having two or more isocyanate groups, and further blocking However, it is not limited to these.

  In addition, an isocyanate compound having a hydrolyzable alkyl silicate residue can also be preferably used.

  Preferred examples of the hydrolyzable alkyl silicate residue include those described for the resin (B).

Specific examples of the isocyanate compound having a hydrolyzable alkyl silicate residue include, for example, OCNC ₃ H ₆ Si (OCH ₃ ) ₃ , OCNC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ , OCNC ₃ H ₆ Si (OCOCH ₃ ) ₃ , OCNC ₃ H ₆ Si (CH ₃ ) (OCH ₃ ) _{3 and the} like.

  The mixing ratio of the isocyanate compound and the resin (B) is preferably NCO / OH (molar ratio) of 0.5 to 5.0, more preferably 0.8 to 1.5. Moreover, 1.1-1.5 are preferable when isocyanate is a moisture hardening type.

As the curing agent (C), instead of or in addition to the isocyanate compound, Si (OR ^c1 ) ₄ (R ^c1 is a non-fluorine alkyl group having 1 to 10 carbon atoms), R ^c2 Si (OR ^c3 ) ₃ (R ^c2 and R ^c3 may be the same or different and may be at least one selected from the group consisting of a non-fluorinated alkyl group having 1 to 10 carbon atoms), a single condensed oligomer thereof, and a co-condensed co-oligomer thereof. .

  As these tetrafunctional or trifunctional non-fluorinated alkyl silicates, for example, those described in US Pat. No. 5,635,572 and the like can be used.

  Specific examples include tetraalkoxysilane or its condensate, alkyltrialkoxysilane or its condensate, polysilsesquioxane, colloidal silica, and the like.

  Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, or a condensate thereof, and commercially available products such as MS51, MS56, and MS57 manufactured by Mitsubishi Chemical Corporation, manufactured by Colcoat. Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48, etc. can be used.

  Examples of the polysilsesquioxane include polyphenylsilsesquioxane, polymethylsilsesquioxane, polyhydrogensilsesquioxane, and the like.

  As colloidal silica, for example, Snowtex manufactured by Nissan Chemical Co., Ltd. can be used.

  Of these, a tetraalkoxysilane condensate is preferred because it has a high crosslinking density and can form a strong film.

  The blending amount of the silicate curing agent may be appropriately selected depending on the kind of the curing agent, but is usually 0 to 100 parts by weight with respect to 100 parts by weight of the total of the resin (B) and the star polymer (A). . A preferred upper limit is 50 parts by weight, and a preferred lower limit is 10 parts by weight.

(2) When the functional group of the resin (B) is a carboxyl group:
The curing agent (C) is preferably an amino compound, an epoxy compound, an aziridine compound or a carbodiimide compound.

  Examples of the amino compound-based curing agent include melamine resin, urea resin, guanamine resin, amine adduct, and polyamide.

  Commercially available products include Cymel manufactured by Mitsui Cytec Co., Ltd., Ancamine manufactured by Air Products, Epilink, Versamine manufactured by Henkel, Versamide, Tomide manufactured by Fuji Kasei Kogyo Co., Ltd., Fuji Cure, Daiichi General Co., Ltd. Examples include Versamide manufactured by Japan, Epoxy Cure manufactured by Japan Epoxy Resin Co., Ltd., Sanmide manufactured by Sanwa Chemical Co., Ltd., and Epomet manufactured by Ajinomoto Co., Inc.

  Examples of the epoxy compound-based curing agent include an epoxy resin, an epoxy-modified silane coupling agent, and the like, and commercially available products include Epicoat, Epirec, Cardlight manufactured by Cardlight, Nippon Unicar ( Coat Jill 1770, A-187, etc.

  Examples of the aziridine compound-based curing agent include XAMA2 and XAMA7 manufactured by BF-Goodrich.

  Examples of the carbodiimide compound-based curing agent include Nisshinbo Carbodilite, Union Carbide UCARLNK Crosslinker XL-29SE, and the like.

(3) When the functional group of the resin (B) is an amino group:
The curing agent (C) is preferably an epoxy compound or an organic acid.

  As the epoxy compound-based curing agent, those exemplified in (2) can be used.

  Examples of the organic acid curing agent include polyvalent carboxylic acids such as phthalic anhydride, adipic acid, and succinic acid, and polyacrylic acid.

(4) When the functional group of the resin (B) is an epoxy group:
The curing agent (C) is preferably an organic acid or an amino compound.

  As the organic acid curing agent, those exemplified in (3) can be used.

  As the amino compound-based curing agent, those exemplified in (2) can be used.

  Among these, a particularly preferred combination is advantageous in that the functional group of the resin (B) is a hydroxyl group and the curing agent (C) is an isocyanate compound in consideration of reactivity and ease of synthesis.

  In the present invention, a curing catalyst (D) may be used instead of or in addition to the curing agent (C).

  Examples of the curing catalyst (D) include an organic tin compound, an organic acidic phosphate ester, an organic titanate compound, a reaction product of an acidic phosphate ester and an amine, a saturated or unsaturated polyvalent carboxylic acid or an acid anhydride thereof, and an organic compound. Examples include sulfonic acid, amine compounds, aluminum chelate compounds, titanium chelate compounds, zirconium chelate compounds and the like.

  Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin diacetate and the like.

  As a specific example of the organic acid phosphate ester,

などが挙げられる。

Etc.

  Examples of the organic titanate compound include titanate esters such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate.

  Specific examples of the amine compound include, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine. Amine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), etc. Of low molecular weight polyamide resins obtained from salts of carboxylic acids, excess polyamines and polybasic acids, excess polyamines and epoxy compounds. Such as response products, and the like.

  Specific examples of the chelate compound include aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), zirconium tetrakis (acetylacetonate), diisopropoxy bis (ethylacetoacetate) titanate and the like.

  1 type may be used for a curing catalyst (D) and it may use 2 or more types together. Preferable curing catalysts include organotin compounds and aluminum chelate compounds. The compounding amount of the curing catalyst is 0 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the resin (B), the star polymer (A), and the curing agent (C).

  In the present invention, an organic solvent can be blended in the coating composition to prepare an organic solvent-type coating.

Examples of the organic solvent include hydrocarbon solvents such as xylene, toluene, Solvesso 100, Solvesso 150, hexane, methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoacetate. Ester solvents such as butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol monobutyl ether, acetic acid ethylene glycol, acetic acid diethylene glycol, dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, ethylene glycol dimethyl Ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetrahydrofuran and other ether solvents, methyl ethyl ketone, methyl isobutyl ketone, acetone Ketone solvents such as N, N-dimethylacetamide, N-methylacetamide, acetamide, N, N-dimethylformamide, N, N-diethylformamide, amide solvents such as N-methylformamide, and sulfonic acids such as dimethylsulfoxide Ester solvent, methanol, ethanol Nord, isopropanol, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (polymerization degree of _{3~100), CF 3 CH 2 OH} , F (CF 2) 2 CH 2 OH, (CF 3) 2 CHOH, F (CF 2) 3 Alcohol solvents such as CH ₂ OH, F (CF ₂ ) ₄ C ₂ H ₅ OH, H (CF ₂ ) ₂ CH ₂ OH, H (CF ₂ ) ₃ CH ₂ OH, H (CF ₂ ) ₄ CH ₂ OH However, alcohol solvents such as lower alcohols and lower fluorine alcohols are preferred from the viewpoints of compatibility, coating film appearance, and storage stability.

  About the compounding ratio of the said resin (B) and alcohol solvent, alcohol is 1-50 weight part with respect to 100 weight part of resin (B), 1-25 weight part from the point of sclerosis | hardenability and a coating-film external appearance. More preferably.

  In addition, when the curing agent is highly reactive with an alcohol such as a room-temperature curable isocyanate, the alcohol is preferably 1 to 15 parts by weight, and the type of alcohol is preferably a secondary or tertiary alcohol. .

  The solvent-based paint composition of the present invention has excellent solvent solubility, and the formed coating film has a high degree of weather resistance. It has excellent properties, optical properties, mechanical properties, adhesion to a substrate, heat-resistant yellowing and the like. In addition, the composition can be used directly on metal, concrete, plastic, etc. as a paint for indoor use such as building materials and interior materials, or outdoor materials such as automobiles, aircraft, ships, and trains, as in the case of ordinary curing compositions. It can be applied over an undercoat such as a wash primer, rust preventive paint, epoxy resin, acrylic resin paint, polyester resin paint or urethane paint. Furthermore, it can be used as a sealing agent or a film forming agent.

  Various forms such as clear, solid, and filler (filler) blending can be adopted as the coating composition.

  Various methods such as spray, brush, roller, curtain flow, roll, dip and the like are used as the coating method.

  Examples of the coating composition of the present invention include pigments, pigment dispersants, thickeners, leveling agents, antifoaming agents, film-forming aids, UV absorbers, HALS, matting agents, fillers, colloidal silica, and antifungal agents. Agent, silane coupling agent, anti-skinning agent, antioxidant, flame retardant, anti-sagging agent, antistatic agent, rust inhibitor, water-soluble resin (polyvinyl alcohol, polyethylene oxide, etc.), antiseptic, antifreeze agent, etc. It is also possible to add a coating additive.

  Examples of the pigment include titanium oxide, iron oxide, aluminum metallic pigment, carbon black, calcined pigment, phthalocyanine pigment, organic pigment, extender pigment and the like.

  As the ultraviolet absorber, for example, benzophenone-based and benzotriazole-based ones are suitable, and among these, benzophenone-based ones are 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy. -4-methoxybenzophenone and 2,2 ′, 4,4′-tetrahydroxybenzophenone are 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-) in the benzotriazole series. 5'-methylphenyl) -5,6-dichlorobenzotriazole), 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- Di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2′-hydroxy-5′-phenyl) Nylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tertbutylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditertbutylphenyl) Benzotriazole and 2- (2′-hydroxy-5′-tert octylphenyl) benzotriazole are effective.

  A particularly suitable UV absorber is of the formula:

（式中、Ｒ^a9およびＲ^a10は同じかまたは異なり、いずれも水素原子、低級アルキル基、なかでも分岐鎖状の低級アルキル基、またはアリール基、とくにフェニル基を表し、Ｘ^a1は水素原子またはハロゲン原子、とくに塩素原子である）
で示されるものである。

(Wherein R ^a9 and R ^a10 are the same or different and each represents a hydrogen atom, a lower alkyl group, especially a branched lower alkyl group, or an aryl group, particularly a phenyl group, and X ^a1 represents a hydrogen atom or Halogen atoms, especially chlorine atoms)
It is shown by.

  Examples of the HALS include Tinuvin-770, 292, 622123, and 440 manufactured by Ciba Geigy Co., Ltd.

  Examples of the matting agent include Hoechst wax PE520, white carbon, and the like, such as Celidust # 3620, # 9615A, # 9612A, # 3715, and # 3910 manufactured by Hoechst Industry Co., Ltd.

  Examples of the silane coupling agent include methyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, vinyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, and N- (2-aminoethyl). ) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropyl isocyanate, 3-triethoxysilylpropyl isocyanate, Examples include methyltris (ethylmethylketoxime) silane, and those containing an alkylketoxime group or an isocyanate group are preferred.

  As described in the explanation of the functional group-containing fluororesin, the coating composition of the present invention can be prepared not only in an organic solvent type coating but also in an aqueous dispersion type by dispersing in an aqueous medium.

  When used as an aqueous dispersion-type paint, as described above, the solid content concentration is about 20 to 70% by weight, preferably about 30 to 60% by weight, from the viewpoint of excellent stability when formed into a paint. The average particle size is about 50 to 300 nm, preferably about 100 to 250 nm, from the viewpoint of excellent stability of the aqueous dispersion. It is preferable that the pH is usually in the range of 5 to 10.

  When preparing an aqueous dispersion-type paint, it is preferable to use a water-soluble or water-dispersible curing agent (C) and curing catalyst (D), but are not limited thereto.

  In the water-dispersed paint, the various additives described above can be blended. Furthermore, it is preferable to add a film-forming aid in order to improve the film-forming property. Examples of film-forming aids include diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethyl adipate, and dibutyl adipate, as well as CS-12 manufactured by Chisso Corporation, DBE manufactured by DuPont, and DBE-IB. Goods can be used.

Further, in order to provide dispersion stability of the aqueous dispersion, it is preferable that a surfactant is present. Examples of the surfactant include fluorine-based surfactants such as ammonium perfluorooctanoate and ammonium perfluorononanoate; nonionic non-fluorine-based surfactants such as polyoxyethylene alkyl ether and sorbitan alkyl ester; alkylsulfonic acid Anionic non-fluorine surfactants such as sodium and sodium dialkyl ester sulfonates; amphoteric surfactants such as lauryl betaine and sodium polyoxyethylene nonyl ether sulfate can be exemplified, but are not limited thereto. .
The concentration of the coating resin in the coating resin composition of the present invention is usually from 30 to 60% (% by weight, the same applies hereinafter), preferably from 35 to 55%, based on the entire coating composition. If the concentration is less than 30%, it tends to be difficult to adjust the viscosity during coating, and if it exceeds 60%, the storage stability of the dispersion tends to decrease.
The coating resin composition using the antifouling agent comprising the star polymer of the present invention may contain additives known in the field of coatings as necessary. Examples of such additives include pigments, plasticizers, solvents, dispersants, thickeners, antifoaming agents, antiseptics, antifungal agents, antisettling agents, leveling agents, and ultraviolet absorbers. Examples of the pigment include, but are not limited to, white pigments such as titanium dioxide, calcium carbonate, barium carbonate, and kaolin; colored pigments such as carbon black, petal, and cyanine blue.
The coating composition of the present invention may be used in a conventional manner in the same manner as a normal coating, depending on the form of an organic solvent-type coating, an aqueous dispersion-type coating, and the like.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 (star polymer having fluorine at all branch ends)
All the glass instruments used for polymerization were dried for 3 hours in a blown low-temperature dryer (130 ° C.). A glass reaction vessel fitted with a three-way stopcock was heated under a nitrogen gas stream, allowed to cool to room temperature under nitrogen pressure, and returned to normal pressure with dry nitrogen, to sufficiently dry the inside of the vessel. Under a nitrogen atmosphere, in a container, 2.6 ml of toluene, 0.5 ml of 1,4-dioxane, 1.2 ml of 2-methoxyethyl vinyl ether (MOVE) as a monomer (vinyl compound), and a starting species to a concentration of 200 mM in hexane 0.25 ml of diluted perfluorohexyl propoxyethyl acetate (monomer: starting species = approximately 200: 1 mol) was added under dry nitrogen and the whole was cooled to 0 ° C. to 4.5 ml Then, it put on the ice bath under nitrogen pressurization, stirred using the magnetic stirrer, and made it thermostat at 0 degreeC. To this, 0.5 ml of 1 mM ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) previously diluted with toluene as a polymerization solvent and kept at 0 ° C. was quickly added under dry nitrogen to initiate polymerization. After 33 minutes, about 0.05 mL was sampled for molecular weight measurement, 1% ammonia in methanol was added to stop the reaction, and GPC measurement was performed. The results will be described later. This process forms a polymer corresponding to the branch. This polymer is hereinafter referred to as a branch polymer. The sampled polymer also corresponds to the branch polymer.
To the remaining reaction solution, 0.5 ml of 1,4-cyclohexanedimethanol divinyl ether solution diluted with toluene and kept at 0 ° C. was added to the reaction system, and the reaction was continued for 15.5 hours to obtain a star polymer. .
The resulting star polymer was purified by adding a methanol solution of 1% ammonia as a polymerization terminator, diluting the reaction solution after termination of polymerization with dichloromethane, and then removing the catalyst residue three times with 0.6N HCl aqueous solution. After washing once with ion-exchanged water and once with a 0.6N NaOH aqueous solution, the solution was washed with ion-exchanged water until neutral. This solution was transferred to an eggplant-shaped flask, and the solvent, unreacted monomer and added base were distilled off under reduced pressure using a rotary evaporator, and then dried under reduced pressure for 8 hours or more in a desiccator containing silica gel (room temperature, 0.1 mmHg). , 100% of the star polymer having fluorine at the branch ends was obtained.
The resulting branched polymer (sampled) and star polymer were calculated by calculating the monomer conversion (polymerization rate, conversion) by a gravimetric method, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer by GPC measurement. ) Was calculated. Further, the remaining of the starting species was confirmed by NMR measurement. The GPC measurement and NMR measurement were performed under the following conditions. In the following examples, each operation basically followed the above method unless otherwise specified. In addition, since the obtained polymer is a star-shaped polymer, (1) Since the weight average molecular weight by normal GPC is small compared with the weight average molecular weight by GPC (GPC-MALLS) with a multi-angle light scattering photometer, it is branched. It was judged from the fact that it has a compact structure with a large amount of (2), and (2) it is clear from the analysis of the particle size that the molecules exist without being associated with each other. The same applies to the following embodiments.

<GPC measurement>
In the GPC measurement, the following columns were sequentially connected in series.
TOSOH TSK guard column HXL-L (6.0 mm ID × 4 cm)
TOSOH TSKgel G4000HXL (7.8 mm ID x 30 cm)
TOSOH TSKgel G3000HXL (7.8 mm ID x 30 cm)
TOSOH TSKgel G2000HXL (7.8 mm ID x 30 cm)
Moreover, chloroform (Nacalai Tesque special grade) was used as an eluent, and the molecular weight was calibrated with standard polystyrene.

<NMR measurement conditions>
JEOL JNM-EX 270 Spectrometer (FT NMR SYSTEM) resonance frequency: 270 MHz as an NMR measuring apparatus, or JEOL JNM-EX 500 Spectrometer (FT NMR SYSTEM) resonance frequency: 500 MHz
Was used.
Solvent: d-chloroform [CDCl ₃ ] (Setty Company Limited)
Reference material for d-chloroform: tetramethylsilane [Chloroform D + 1% TMS, CDCl ₃ + Si (CH ₃ ) ₄ ] (Setty Company Limited)
Measurement temperature: 30 ° C

The molecular weight and molecular weight distribution of the branched polymer were measured by gel filtration chromatography (GPC) according to the above method, and the molecular weight was calibrated with a polystyrene standard sample.
The weight average molecular weight of the branched polymer is 2.66 × 10 ⁴ , the number average molecular weight is 2.40 × 10 ⁴ , and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 1.11. It was. The average degree of polymerization calculated from the number average molecular weight was about 200 (hereinafter referred to as a 200-mer branched polymer), which coincided with the ratio of monomer to starting species.
Further, from the NMR measurement results of the star polymer and the starting species, it was confirmed that the starting species did not remain. An NMR chart is shown in FIG. 1 (upper line: starting species, lower line: star polymer).
A GPC chart of the branch polymer and the star polymer is shown in FIG. 2 (upper line: branch polymer, lower line: star polymer).
Thereby, it can be seen that the peak of the branched polymer (200-mer in length) disappeared completely.
Moreover, when the weight average molecular weight of the obtained star-shaped polymer was measured by GPC-MALLS (manufactured by Wyatt Technology) which is GPC connected with a light scattering detector, it was 3.27 × 10 ⁶ , which was obtained based on this The number of branches was 147 and the particle size was 37 nm.
The measurement conditions for GPC-MALLS are shown below.
GPC: Agilent Technology 1200series
Column: Shodex GPC K803, K804, K805
MALLS: DAWN HELEOS (Wyatt Technology) Ga-As laser λ = 690 nm
Eluent: Chloroform (Nacalai Tesque, special grade)
The number of branches f was determined according to the following equation.
f (number of branches) = (weight fraction of vinyl compound) × [weight average molecular weight of star polymer] / [number average molecular weight of branch polymer]
Furthermore, the weight average molecular weight by normal GPC is 2.0 × 10 ^5, which is smaller than the weight average molecular weight by GPC-MALLS. From this it is clear that the resulting star polymer has a compact structure with many branches. Furthermore, from the analysis of the particle size, it is clear that the molecules exist without being associated with each other. Thus, the resulting polymer is a star polymer. The conversion rate was about 99%.

(Influence of degree of polymerization of branch polymer)
In the same manner as described above except that 2-methoxyethyl vinyl ether was used as the monomer, the degree of polymerization was set to 50 and 100 (the molar ratio of the monomer to the starting species was 50: 1 and 100: 1, respectively), and the branched polymer (Poly (2-Methoxyethyl vinyl ether (MOVE)) was polymerized, and 1,4-cyclohexanedimethanol divinyl ether was further added, followed by reaction for 12 hours to obtain a star polymer.
The molecular weight of a star polymer composed of a branch polymer with a polymerization degree of 50 is Mn = 9.8 × 10 ⁴ , and the molecular weight of a star polymer composed of a branch polymer with a polymerization degree of 100 is Mn = 19.69 × 10 ⁴ , The molecular weight of the star polymer increased with the degree of polymerization.
The weight average molecular weight determined by GPC-MALLS of the obtained star polymer is larger than the weight average molecular weight measured by ordinary GPC. From this, it is clear that the star polymer of the present invention has many branches and is compact and has a fluorine structure at the terminal.

Example 2 (star polymer having fluorine at all branch ends)
All the glass instruments used for polymerization were dried for 3 hours in a blown low-temperature dryer (130 ° C.). A glass reaction vessel fitted with a three-way stopcock was heated under a nitrogen gas stream, allowed to cool to room temperature under nitrogen pressure, and returned to normal pressure with dry nitrogen, to sufficiently dry the inside of the vessel. Under a nitrogen atmosphere, 2.6 ml of toluene, 0.5 ml of 1,4-dioxane, 0.4 ml of 20 mM 2,6-di-tert-butylpyridine diluted with toluene, 0.28 ml of cyclohexyl vinyl ether (CHVE) as a monomer As a starting species, 0.4 mL of 50 mM perfluorohexylpropoxyethyl acetate diluted in hexane was added under dry nitrogen to make a total of 1.6 ml, cooled to 0 ° C., then placed in an ice bath under nitrogen pressure and magnetic. The mixture was stirred using a stirrer and kept at 0 ° C. To this, 0.4 ml of 100 mM ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) previously diluted with toluene as a polymerization solvent and kept at a constant temperature of 0 ° C. was quickly added under dry nitrogen to initiate polymerization. After 5 minutes, 0.2 ml of toluene-diluted 1,4-cyclohexanedimethanol divinyl ether solution that had been kept at 0 ° C. was added to the reaction system, and the reaction was continued for 3 hours.
Purification was performed in the same manner as in Example 1 to obtain a star polymer having fluorine at 100% branch ends. As a polymerization terminator, a 1% ammonia methanol solution was used as in Example 1.
The number average molecular weight of the branched polymer is 1.28 × 10 ⁴ , the weight average molecular weight is 1.48 × 10 ⁴ , and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 1.15. It was. On the other hand, the number average molecular weight of the star polymer was 1.11 × 10 ⁵ , the weight average molecular weight was 2.03 × 10 ⁵ , and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) was 1.83.

Example 3 (Star polymer with fluorine at all branch ends)
(1) The glassware used for polymerization was all dried for 3 hours with a blowing low-temperature dryer (130 ° C.). A glass reaction vessel fitted with a three-way stopcock was heated under a nitrogen gas stream, allowed to cool to room temperature under nitrogen pressure, and returned to normal pressure with dry nitrogen, to sufficiently dry the inside of the vessel. In a nitrogen atmosphere, in a container, 2.96 ml of toluene, 0.5 ml of 1,4-dioxane, 0.287 ml of 2-tert-butyldimethylsilyloxyethoxyethyl vinyl ether (Si-HOEOVE) as a monomer, and hexane as a starting species 0.25 mL of diluted 200 mM perfluorohexyl propoxyethyl acetate was added under dry nitrogen to make a total of 4.5 ml, cooled to 0 ° C., then placed in an ice bath under nitrogen pressure, stirred with a magnetic stirrer, 0 ° C. To constant temperature. To this, 0.4 ml of 200 mM ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) previously diluted in toluene as a polymerization solvent and kept at 0 ° C. was quickly added under dry nitrogen to initiate polymerization. After 2.5 hours, toluene-diluted 1,4-cyclohexanedimethanol divinyl ether solution that had been kept at 0 ° C. was added to the 0.5 ml reaction system, and the reaction was continued for 12 hours. Purification was performed in the same manner as in Example 1 to obtain a star polymer having fluorine at 100% branch ends. As a polymerization terminator, a 1% ammonia methanol solution was used as in Example 1.

(2) Deprotection The purified polymer (1 g) was dissolved in THF (45 mL), and 3.0N hydrochloric acid ethanol (5 mL) was added dropwise at 0 ° C. The mixture was stirred at 0 ° C. for 3 hours, ethanol (20 mL) was added, and the mixture was further stirred for 3 hours. After neutralizing this with sodium bicarbonate, insolubles were removed using a glass filter (P160) and filter paper, and this solution was transferred to an eggplant-shaped flask and concentrated using a rotary evaporator. The ethanol solution of the obtained product was added to a large excess of hexane for reprecipitation, decanted, and then dried under reduced pressure in a desiccator containing silica gel (room temperature, 0.1 mmHg). This product was dissolved in water and dialyzed against Mili-Q water using a cellulose tube (Viskase Sales; pore size 30/32, molecular weight cut off: 12,000-14,000) for 3 days. The aqueous solution after dialysis was evaporated under reduced pressure, and further dried under reduced pressure overnight in a desiccator containing silica gel (room temperature, 0.1 mmHg) to obtain a star polymer having 100% of fluorine at the branch ends.
In the same manner as in Example 1, the produced polymer was calculated for monomer conversion (polymerization rate, conversion), polymer number average molecular weight (Mn), and molecular weight distribution (Mw / Mn). The results are summarized in Table 1.

Example 4 (Star polymer having fluorine at some branch ends)
All the glass instruments used for polymerization were dried for 3 hours in a blown low-temperature dryer (130 ° C.). A glass reaction vessel fitted with a three-way stopcock was heated under a nitrogen gas stream, allowed to cool to room temperature under nitrogen pressure, and returned to normal pressure with dry nitrogen, to sufficiently dry the inside of the vessel. In a nitrogen atmosphere, 0.32 ml of toluene, 0.2 ml of 1,4-dioxane, 0.4 ml of 20 mM 2,6-di-tert-butylpyridine (DTBP) diluted with toluene, and cyclohexyl vinyl ether ( CHVE) 0.28 mL, 50 mM cyclohexylethyl acetate (CHEA) diluted in hexane as the starting species was added under dry nitrogen to a total volume of 1.6 ml, cooled to 0 ° C., and then placed in an ice bath under nitrogen pressure. The mixture was stirred using a magnetic stirrer and kept at 0 ° C. To this, 0.4 mL of 100 mM ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) previously diluted in toluene as a polymerization solvent and kept at 0 ° C. was quickly added under dry nitrogen to start polymerization. After 1 minute, 0.2 ml of toluene-diluted 1M 1,4-cyclohexanedimethanol divinyl ether solution that had been kept at 0 ° C. was added to the reaction system, the reaction was continued for 3 hours, and then the toluene 1 cooled to 0 ° C. .54 mL and 0.46 mL of 2-methoxyethyl vinyl ether (MOVE) diluted with 2-fold toluene were added, reacted for 40 minutes, and fluorine alcohol (C ₂ F ₅ CH ₂ CH ₂ OH) diluted with tetrahydrofuran (THF) was added. The reaction was stopped by adding.
For purification of the produced polymer, first the reaction solution after termination of polymerization was diluted with dichloromethane, and then the catalyst residue was removed three times with 0.6N HCl aqueous solution, once with ion-exchanged water, and 1 with 0.6N NaOH aqueous solution. After washing twice, it was washed with ion exchange water until neutral. This solution was transferred to an eggplant-shaped flask, and the solvent, unreacted monomer and added base were distilled off under reduced pressure using a rotary evaporator, and then dried under reduced pressure in a desiccator containing silica gel (room temperature, 0.1 mmHg) for 8 hours or more. A star polymer having 50% branch ends with fluorine was obtained.
Purification was carried out in the same manner as in Example 1 to obtain a star polymer having fluorine at 50% of branch ends.
In the same manner as in Example 1, the produced polymer was calculated for monomer conversion (polymerization rate, conversion), polymer number average molecular weight (Mn), and molecular weight distribution (Mw / Mn). The results are summarized in Table 1.

Example 5 (Star polymer having fluorine at some branch ends)
A star polymer having 50% of fluorine at the branch ends was obtained in the same manner as in Example 4 except that C ₄ F ₉ CH ₂ CH ₂ OH was used as the fluoroalcohol. Table 1 summarizes the measurement results of monomer conversion (polymerization rate, conversion), polymer number average molecular weight (Mn), weight average molecular weight (Mn), and molecular weight distribution (Mw / Mn).

Example 6 (star polymer having fluorine at some branch ends)
A star polymer having 50% of fluorine at the branch ends was obtained in the same manner as in Example 4 except that C ₆ F ₁₃ CH ₂ CH ₂ OH was used as the fluoroalcohol. Table 1 summarizes the measurement results of monomer conversion (polymerization rate, conversion), polymer number average molecular weight (Mn), weight average molecular weight (Mn), and molecular weight distribution (Mw / Mn).

Example 7 (Star polymer having fluorine at some branch ends)
A star polymer having 50% fluorine at a branch end was obtained in the same manner as in Example 4 except that C ₈ F ₁₇ CH ₂ CH ₂ OH was used as the fluoroalcohol. Table 1 summarizes the measurement results of monomer conversion (polymerization rate, conversion), polymer number average molecular weight (Mn), weight average molecular weight (Mn), and molecular weight distribution (Mw / Mn).
[Table 1]

Example 8 (star polymer having fluorine at some branch ends)
(1) A glass reaction vessel equipped with a three-way cock was heated under a nitrogen gas stream, allowed to cool to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and the interior of the vessel was sufficiently dried. Under a nitrogen atmosphere, 2.6 ml of toluene, 0.5 ml of 1,4-dioxane, 0.4 ml of 20 mM 2,6-di-tert-butylpyridine diluted with toluene, 0.28 ml of cyclohexyl vinyl ether (CHVE) as a monomer As a starting species, 0.4 mL of 50 mM perfluorohexylpropoxyethyl acetate diluted in hexane was added under dry nitrogen to make a total of 1.6 ml, cooled to 0 ° C., then placed in an ice bath under nitrogen pressure and magnetic. The mixture was stirred using a stirrer and kept at 0 ° C. To this, 0.4 ml of 100 mM ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) previously diluted with toluene as a polymerization solvent and kept at a constant temperature of 0 ° C. was quickly added under dry nitrogen to start polymerization for 4 minutes. .

(2) A glass reaction vessel equipped with another three-way stopcock was heated under a nitrogen gas stream to sufficiently dry the inside of the vessel. In a nitrogen atmosphere, put 2- (2-ethoxy) ethoxyethyl vinyl ether (1.0 M), 1,4-dioxane (1.0 M), 1-isobutoxyethyl acetate (10 mM) and toluene as starting species. The whole was brought to 4.5 mL, and after cooling to 0 ° C., 0.50 mL (20 mM) of a 200 mM toluene solution of (CH ₃ CH ₂ ) _1.5 AlCl _1.5 was added to initiate polymerization. After 30 minutes, the reaction solution was added to the reaction system of (1) above, and further reacted for 2 minutes. 10 equivalents (r = 10) of 1,4-bis (vinyloxymethyl) cyclohexane relative to equivalents were added and the reaction continued for 8 hours.
Purification was carried out in the same manner as in Example 1 to obtain a star polymer having fluorine at some (50%) branch ends. Table 2 summarizes the measurement results of monomer conversion (polymerization rate, conversion), polymer number average molecular weight (Mn), weight average molecular weight (Mn), and molecular weight distribution (Mw / Mn).

[Table 2]

Example 9 (temperature response measurement)
A 1% by weight aqueous solution of a star-shaped polymer having 100% branch ends and fluorine produced according to the method of Example 1 was prepared, and the light transmittance at 500 nm for this solution was measured using a UV spectrophotometer with a temperature control function (Japan). (Spectros Co., Ltd.). When the temperature was raised from 20 to 50 ° C. at a rate of temperature rise / fall of 1 ° C./min, the polymer aqueous solution changed from a transparent state to a cloudy state with high sensitivity at 48 ° C. when the temperature was raised from 20 ° C. FIG. 3 shows a graph of changes in light transmittance. This change is reversible, but when the temperature was returned from the high temperature to the low temperature, it returned to the transparent state with high sensitivity at a temperature (about 32 ° C.) different from the temperature rising process.
UV detector: JASCO V-550 UV-VIS Spectrophotometer (JASCO)
Variable temperature controller: JASCO ETC-505T Peltier Type Thermostatic cell holder (JASCO)
Measurement conditions: 1 wt% aqueous solution, heating rate 1 ° C / min

Example 10 (water wettability test)
A star having 15 parts of diethyl adipate as a film-forming aid and 100 parts of fluorine synthesized at Example 1 for 100 parts of a hydroxyl group-containing fluororesin emulsion SE-30 (solid content of about 50%) manufactured by Daikin Industries, Ltd. 100 parts of a 10% by weight isopropyl alcohol solution of the shaped polymer was added and applied to a glass plate using a 3 mil applicator. The film was dried at room temperature for 7 days to obtain a uniform coating film. Then, after being immersed in ion-exchange water overnight, the static contact angle with respect to water was measured by the θ / 2 method. The contact angle was 10 °. A photograph at the time of measurement is shown in FIG.

Comparative Example 1
For comparison, were formed in the same manner as in Example 10 without adding only star polymer, the contact angle was measured for dip coating film of ion-exchanged water. The contact angle was 83 °.
A photograph at the time of measurement is shown in FIG.

The star polymer of the present invention has a characteristic stimulus responsiveness and can be used as a highly functional material in the pharmaceutical field.
Further, the star polymer of the present invention is useful as an antifouling agent for paints and can be used in the paint field.

Claims (14)

A star-shaped polymer having a core and three or more branches connected to the core,
The core is composed of a crosslinked polymer of a dialkenyl compound,
A part or all of the branch part has the formula (I _f )
-(CH (-X-R < ¹ >)-CH (-R < ² >)) p- ^Rf ( _If )
[Where:
R ¹ is an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group; or , A cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group; Having a monovalent organic group,
R ² represents a hydrogen atom or an alkyl group,
R ^f is a group in which a monovalent organic group represented by R ¹ is fluorinated, or a group represented by the formula (I _{rf ′} )
—CHR ^a —X ¹ — ( YX ² ) _m — (CH ₂ ) _n —R ^{f ′} (I _{rf ′} )
[Where:
R ^a represents an alkyl group,
X ¹ and X ² each independently represents a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —,
Y represents an alkylene chain having 1 to 3 carbon atoms,
R ^{f ′} is (a) a C 1-12 perfluoroalkyl group, or (b) one selected from —C ₃ F ₆ O—, —C ₂ F ₄ O— and —CF ₂ O—. Represents a perfluoroether group having 2 to 50 carbon atoms and having the above repeating units;
m represents an integer of 0 to 10,
n represents an integer of 1 to 18,
Other symbols are as defined above. ]
Represents a group represented by
X represents a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —,
p represents an integer of 1 or more. ]
And a monovalent organic group having a number average molecular weight of 1,000 to 1,000,000,
The remainder of the branch is the formula (I _o ):
— (CH (—X—R ¹ ) —CH (—R ² )) p—R ^o (I _o )
[Where:
R ^o is an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group; carbon A cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group; or carbon of the alkyl group -Represents a C1-C12 alkyl group in which one or more selected from amide, imide, urethane and urea bond may be inserted into the carbon bond ,
Other symbols are as defined above. ]
And a monovalent organic group having a number average molecular weight of 1,000 to 1,000,000. The dialkenyl compound has the formula (II)
^{CHR 3 = CH-X c1 -R} 4 -X c2 -CH = CHR 5 (II)
[Where:
R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group,
R ⁴ is an alkylene chain having 1 or more carbon atoms, or
^{_{- (CH 2) p1 -R 4}} '- (CH 2) p2 -
(Where
p1 and p2 each independently represent an integer of 1 or more,
R ^{4 ′} represents —O—, —O-phenylene-O—, —O-phenylene-C (CH ₃ ) ₂ -phenylene-O—, or cycloalkylene having 3 or more carbon atoms. )
Represents a group represented by
X ^c1 and X ^c2 each independently represent a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —. ]
The star polymer according to claim 1 , which is a compound represented by the formula: The formula (I _f ) is represented by the formula (I _{f ′} ):
^{- (CH (-X-R 1} ) -CH (-R 2)) p-CHR a -X 1 - (Y-X 2) m - (CH 2) n -R f '(I f')
[Where:
R ¹ is an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group, or Represents a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a substituent selected from a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an amino group, a carboxy group and a phosphate group ;
R ^a represents an alkyl group,
X ¹ and X ² each independently represents a single bond, —O—, —S—, —NH—, or —N (—CH ₃ ) —,
Y represents an alkylene chain having 1 to 3 carbon atoms,
R ^{f ′} is (a) a C 1-12 perfluoroalkyl group, or (b) one selected from —C ₃ F ₆ O—, —C ₂ F ₄ O— and —CF ₂ O—. Represents a perfluoroether group having 2 to 50 carbon atoms and having the above repeating units;
m represents an integer of 0 to 10,
n represents an integer of 1 to 18,
Other symbols are as defined above. ]
The star polymer according to claim 1, wherein All of the said branch part is a monovalent organic group which is represented by the said formula ( _If ), and has a number average molecular weight of 1,000-1,000,000, It is characterized by the above-mentioned. The star polymer according to any one of the above items. A part of the branch part is a monovalent organic group represented by the formula (I _o ) and having a number average molecular weight of 1,000 to 1,000,000. The star polymer of any one of these. The ratio of the branch part which is a monovalent organic group represented by the formula (I _o ) and having a number average molecular weight of 1,000 to 1,000,000 is 50 mol% or less based on the total branch part. The star polymer according to claim 5. The star polymer according to any one of claims 1 to 6, having a weight average molecular weight of 10,000 to 5,000,000 and a molecular weight distribution of 1 to 2. The method for producing a star polymer according to claim 1, comprising the following step 1, step 2 and step 3, or comprising step 1, step 1 ′, step 2 and step 3.
Step 1:
Formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[Wherein each symbol has the same meaning as described in claim 1. ]
A vinyl compound represented by formula (IVf):
R ^b —CO—O—R ^f (IV _f )
[Wherein, R ^b represents an aliphatic hydrocarbon group, phenyl, perfluoroalkyl group, or perfluoroether group, and other symbols have the same meaning as described in claim 1. ]
In about Engineering to living cationic polymerization presence of a compound represented by in
Engineering as 1 ':
Formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[Wherein each symbol has the same meaning as described in claim 1. ]
A vinyl compound represented by
Lewis acid and formula (IV ₀ )
R ^b —CO—O—R ^o (IV ₀ )
[Wherein, R ^b represents the same meaning as described above, and R ^o represents the same meaning as described in claim 1. ]
As Engineering to living cationic polymerization in the presence of a compound represented by in <br/> Step 2:
Step reaction mixture obtained in 1 and Engineering about 1 ', the addition of dialkenyl compound, further living cationic polymerization is to factory as <br/> Step 3:
To the reaction mixture obtained in step 2, a polymerization inhibitor is added, as engineering stopping the living cationic polymerization Step 1: Formula (III)
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[The symbols in the formula are as defined in claim 1. ]
A vinyl compound represented by formula (IV ₀ )
R ^b —CO—O—R ^o (IV ₀ )
[Wherein R ^o represents the same meaning as described in claim 1, and R ^b represents an aliphatic hydrocarbon group, a phenyl, a perfluoroalkyl group, or a perfluoroether group . ]
A step of living cationic polymerization in the presence of a compound represented by the following: and step 2: a step of adding a dialkenyl compound to the reaction mixture obtained in step 1 and further conducting a living cationic polymerization.
Step 3: To the reaction mixture obtained in Step 2,
CH (—X—R ¹ ) ═CH (—R ² ) (III)
[The symbols in the formula are as defined in claim 1. ]
A step of adding a vinyl compound represented by
Step 4: Add the reaction mixture obtained in Step 3 to the formula (a) R ^f —OH
[Wherein, R ^f represents the same meaning as described in claim 1 . ]
Or (b) R ^f —OH
[Wherein, R ^f represents the same meaning as described in claim 1 . ]
And a compound represented by R ^o —OH
[The symbols in the formula are as defined in claim 1. ]
The method for producing a star polymer according to claim 1 , further comprising a step of adding a combination of compounds represented by the formula and terminating the living cationic polymerization. The contamination adhesion preventing agent which consists of a star-shaped polymer of any one of Claims 1-7. (A) A coating composition containing the antifouling agent according to claim 10 and (B) a coating resin.   The coating resin is at least one resin selected from a functional group-containing fluororesin, a functional group-free fluororesin, a non-fluorine acrylic resin, a polyester resin, a urethane resin, an epoxy resin, an amino resin, and an inorganic material. The coating composition according to claim 11. The coating composition according to claim 11 or 12 , which is prepared as an organic solvent-type coating material containing an organic solvent. The composition for coating materials according to any one of claims 11 to 13, which is prepared as an aqueous dispersion type coating material dispersed in an aqueous medium.

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