JP7193751B2 - Sealant composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sealant composition containing a fluorine-containing copolymer containing a fluorine-containing monomer having a specific fluoroalkyl group and a sealant, and having excellent antifouling properties and water and oil repellency. The sealant composition can be used as a sealant for civil engineering, construction (for example, kitchens and washrooms, particularly sinks and bathrooms), and interior or exterior materials for automobiles and the like.

For the purpose of preventing water, dust, etc. from entering through gaps between exterior and interior members of buildings such as concrete, wood, siding boards, aluminum sashes, etc., and improving airtightness. Sealing materials are generally used. There are various types of sealing materials, such as silicone, urethane, and acrylic, and they are used according to their respective uses. These sealants contain various additives from the standpoint of workability and surface protection. There is a problem that dirt easily adheres.

Various techniques have been conventionally proposed to solve this problem.
For example, Japanese Unexamined Patent Application Publication No. 2010-275481 proposes a technique of imparting antifouling properties by applying a coating composition containing a fluorine-based surfactant containing a perfluoroalkyl group to the surface of a sealant. there is However, this method has a work-related problem that it takes time and labor to additionally coat the surface of the sealing material. In addition, the sealant may contain additives such as antibacterial agents and antifungal agents for the purpose of protecting the surface, but there is a problem that the effect cannot be exhibited if the coating is applied on the surface of the sealant. .

Further, Japanese Patent Laid-Open No. 2008-291159 proposes a technique of adding a perfluoroalkyl group-containing surfactant that imparts hydrophilicity to a sealant composition to impart antifouling properties. Although this method can provide antifouling properties against soot and soil, since the sealant is hydrophilic, mold and microorganisms tend to adhere to the surface, resulting in the problem that the surface of the sealant becomes dirty. be.

In JP-A-2001-234157 and JP-A-2001-81330, a copolymer containing a monomer containing a perfluoroalkyl group having an average carbon number of 9 and a photocurable monomer and sealing A technique for a curable composition having excellent antifouling properties has been proposed. Although this technique also improves the antifouling property, it is necessary to take measures to suppress the progress of photocuring during the storage period before application.

JP 2010-275481 A JP 2008-291159 A Japanese Patent Application Laid-Open No. 2001-234157 Japanese Unexamined Patent Application Publication No. 2001-81330

An object of the present invention is to express water and oil repellency as well as antifouling properties by mixing a specific fluoropolymer with a sealing material used for interior or exterior materials for civil engineering, construction, automobiles, etc. The object of the present invention is to provide a composition comprising a sealant and a fluoropolymer.

The present invention
(1) a sealing material;
(2) A sealant composition containing a structural unit derived from a fluorine-containing monomer (a) and a fluorine-containing polymer containing a structural unit derived from a non-fluorine-containing monomer (b).
More specifically, the present invention provides a sealing material,
Fluorine-containing monomer (a): a fluorine-containing monomer having a fluoroalkyl group having 4 to 6 carbon atoms, and a non-fluorine-containing monomer (b): a non-fluorine having an acyclic hydrocarbon group or a cyclic hydrocarbon group A sealant composition containing a fluorine-containing copolymer containing a monomer as a structural unit.
In addition to the monomers (a) and (b), the fluorine-containing copolymer of the present invention may optionally contain a monomer (c) other than the monomers (a) and (b). It may be contained as a structural unit.

Preferred aspects of the present invention are as follows.
Aspect 1:
A sealant composition containing (1) a sealant and (2) a fluorine-containing copolymer,
The fluorine-containing copolymer (2) is
(a) Formula:
_CH2 =C(-X)-C(=O)-YZ-Rf
[Wherein, X is a hydrogen atom, a methyl group or a halogen atom,
Y is -O-
Z is a direct bond or a linear or branched alkylene group having 1 to 20 carbon atoms,
Rf is a perfluoroalkyl group having 4 to 6 carbon atoms. ]
A structural unit derived from a fluorine-containing monomer having a fluoroalkyl group having 4 to 6 carbon atoms, and (b) formula:
_CH2 =CA21-C ⁽ =O) ^-OA22
[In the formula, A ²¹ is a hydrogen atom or a methyl group,
A ²² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. ]
Including a structural unit derived from a non-fluorine monomer represented by
A sealant composition in which the fluorine-containing copolymer (2) does not have a polyoxyalkylene group.
Aspect 2:
The sealant composition according to aspect 1, wherein in the fluorine-containing monomer (a), X is a methyl group.
Aspect 3:
Non-fluorine monomer (b) is cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate and 2-ethyl-2-adamantyl ( The sealant composition according to aspect 1 or 2, which is at least one selected from the group consisting of meth)acrylates.
Aspect 4:
The fluorine-containing copolymer further contains a non-fluorine crosslinkable monomer (c) as a structural unit, and the amount of the monomer (c) is the total of the monomer (a) and the monomer (b) The sealant composition according to any one of aspects 1 to 3, which is 1 to 30 parts by weight per 100 parts by weight.
Aspect 5:
The sealant composition according to aspect 4, wherein the non-fluorine crosslinkable monomer (c) is a vinyl monomer having a hydroxyl group.
Aspect 6:
The sealant composition according to any one of aspects 1 to 5, wherein the fluorine-containing copolymer (2) is produced by solution polymerization.
Aspect 7:
The sealant composition according to any one of aspects 1 to 6, wherein the sealant is at least one sealant selected from silicone sealants, urethane sealants and acrylic sealants.
Aspect 8:
The sealant composition according to any one of aspects 1 to 7, which is a one-component form comprising a mixture of a sealant and a fluoropolymer.
Aspect 9:
The sealant according to any one of aspects 1 to 8, wherein the sealant composition is a two-component type containing a main agent and a curing agent, the main agent containing the sealing material, and the curing agent containing the fluorine-containing copolymer. Composition.
Aspect 10:
The sealant composition according to any one of Embodiments 1 to 9, wherein the weight ratio of the sealant to the fluorine-containing copolymer is 99.9:0.1 to 85:15.
Aspect 11:
11. The sealant composition according to any one of aspects 1 to 10, wherein the weight ratio of monomer (a) to monomer (b) is 20:80 to 80:20.
Aspect 12:
A method for producing a sealant composition according to any one of aspects 1 to 11,
A production method comprising polymerizing the monomer (a) and the monomer (b) to obtain a fluorine-containing copolymer (2), and then mixing the polymer with a sealant.
Aspect 13:
The sealant composition according to any one of aspects 1 to 11 is filled in the border of interior or exterior materials for civil engineering, construction, or automobiles, and then the sealant composition is cured to form a sealant. A method of sealing a perimeter comprising:

ADVANTAGE OF THE INVENTION According to this invention, the sealant composition excellent in antifouling property can be obtained, without reducing the water repellency of a sealant. The sealant composition has excellent anti-adhesion and releasability (washability) against dirt such as carbon (soot), sand and ocher. Furthermore, oil repellency can be imparted to the sealing material. Furthermore, the sealant composition also provides stain resistance and water and oil repellency durability, as well as antibacterial and antifungal properties.
The sealant composition is useful as a sealant used for interior or exterior materials for civil engineering, construction, automobiles, and the like.

More specifically, since the sealant and the fluorine-containing polymer exhibiting antifouling properties are applied as a mixture, the problem that the effect of the sealant is not exhibited due to the surface coating does not occur. Moreover, the work of applying the fluoropolymer to the surface of the sealing material is not required. In addition, since the sealing material used in the present invention is hydrophobic, it exhibits antifouling properties against various stains, and the water and oil repellency of the fluorine-containing polymer prevents mold and microorganisms from adhering to the surface of the sealing material. become difficult.

(1) Sealing material Sealing material is used to prevent outside air and water from entering from the boundaries when combining materials such as concrete, siding boards, and tiles in building exterior and interior materials. For the purpose of protecting the It is also used for the same purpose not only in buildings, but also in automotive interior materials, aluminum sashes, and the like.

Examples of sealing materials include silicone-based, polysulfide-based, polyurethane-based, acrylic-based, SBR-based, butyl rubber-based, oil-based caulk-based, acrylic urethane-based sealing materials, and the like. Among silicone-based and polysulfide-based sealants, there are modified silicone-based and modified polysulfide-based sealants for further improving protection.

In the present invention, silicone, modified silicone, urethane and acrylic sealants are preferred. Silicone-based sealants and modified silicone-based sealants are more preferred. The sealing material may contain an organic solvent, but preferably does not contain an organic solvent. Sealants generally do not contain water. The sealant cures, for example, with moisture in the air after application.

A silicone-based or modified silicone-based sealant contains a polymer having a siloxy group (generally, a siloxane group) (a siloxy group-containing polymer). A siloxy group-containing polymer is generally A _m SiO _(4-m)/2 [wherein A is a hydrogen atom, a halogen atom or a monovalent organic group, and m is 0-3. ] has the indicated structural unit. Siloxy group-containing polymers have monofunctional siloxy groups (A ₃ SiO _0.5 ) and difunctional siloxy units (A ₂ SiO), and optionally trifunctional siloxy units (ASiO _1.5 ) (and optionally tetrafunctional siloxy units (SiO ₂ )). The A group may be a hydrocarbon group having 1 to 20 carbon atoms, such as an alkyl group. Alternatively, the A group may be a reactive group or a group having a reactive group. Examples of reactive groups are halogen atoms (e.g. chlorine atoms, bromine atoms, iodine atoms), amino groups, epoxy groups, carboxyl groups, carbinol groups, mercapto groups, aminooxy groups, hydroxyl groups, alkoxy groups and oxime groups. is. Preferably, the reactive groups are hydroxyl groups (OH groups), alkoxy groups (eg methoxy groups) and oxime groups (eg ketoxime groups such as methylethylketoxime groups).

In the modified silicone sealant, the siloxy group-containing polymer is a polymer having structural units other than siloxy groups, such as (poly)oxyalkylene groups, amide groups, imide groups, or alkylene groups, in addition to siloxy groups. (the number of carbon atoms in alkylene is, for example, 1 to 5, especially 2 or 3). Modified silicone-based sealants may, for example, have (poly)organosiloxane groups (eg, monofunctional siloxy groups (A ₃ SiO _0.5 )) at the ends of organic polymers (eg, polyethers). .

The silicone-based sealant may contain a silane compound. Silane compounds generally have hydrolyzable groups. Specific examples of hydrolysable groups are oxime groups, alkoxy groups, alkoxy-substituted alkoxy groups, acyloxy groups, alkenoxy groups, ketoxime groups, aminoxy groups and amido groups. Representative examples of silane compounds are oxime-type or de-oxime-type silane compounds (oxime-type or de-oxime-type silicones). Oxime-type or de-oxime-type silicones are cured by elimination of oxime (eg, methyl ethyl ketoxime) during curing after application. Oxime-type silicones contain a silane compound having an oxime group. Examples of silane compounds with oxime groups are methyltri(methylethylketoxime)silane and vinyltri(methylethylketoxime)silane.
Other curing systems include alcohol-type or dealcoholized-type silicones, and acetone-type, acetic acid-type, and aminoxy-type sealants. Like the oxime type, these are sealants that harden by desorption of alcohol, acetone, acetic acid, etc. when effective after application.
Silicone-based sealants may contain fumed silica powder, such as dimethyldichlorosilane-treated silica powder, in addition to the silane compound.

Examples of urethane-based sealants include reaction-curing urethane that cures when a polyol compound (urethane prepolymer) reacts with isocyanate (especially polyisocyanate), which is the main component of the curing agent, and urethane that cures with moisture in the air. Moisture-curing urethane that reacts with isocyanate (especially polyisocyanate) and cures from the surface. The polyol compound has two or more hydroxy groups. Examples of polyol compounds are, for example, polyether polyols (polyoxyalkylene polyols), polyester polyols, mixed polyols thereof, and the like. A polyisocyanate compound has two or more isocyanate groups in the molecule. Examples of polyisocyanate compounds include aromatic polyisocyanates in which the isocyanate groups are bonded to aromatic hydrocarbons, aliphatic polyisocyanates in which the isocyanate groups are bonded to aliphatic hydrocarbons, and isocyanate groups to alicyclic hydrocarbons. It is a bound alicyclic polyisocyanate.

An acrylic sealant is generally based on an acrylic polymer, and is a sealant that dries and hardens as the contained solvent evaporates after application.
The acrylic sealant contains an acrylic polymer. The acrylic polymer is a polymer having repeating units of acrylate monomers. Acrylate monomers include (meth)acrylic acid esters, for example, (meth)acrylic acid alkyl esters (alkyl group having 1 to 30 carbon atoms), oxyalkylene groups (the number of oxyalkylene groups is 1 to 30, for example, 1 to 25), and the like. Specific examples of acrylic polymers include acrylic acid alkyl ester copolymers, acrylonitrile-acrylic acid alkyl ester copolymers, acrylic acid-methacrylic acid-acrylic acid alkyl ester copolymers, acrylonitrile-acrylic acid-acrylic acid alkyl ester copolymers. Polymers, styrene-acrylic acid alkyl ester copolymers, styrene-methacrylic acid alkyl ester-acrylic acid alkyl ester copolymers, styrene-acrylonitrile-acrylic acid alkyl ester copolymers, and styrene-acrylonitrile-methacrylic acid alkyl ester-acryl It is an acid alkyl ester copolymer.

In the present invention, a commercially available sealant can be used. For example, in the case of silicone, Dow Corning Toray SE5007, SH780, SH5010, SE960, SE990F, SE930, SE931, SE936, SE797, etc., Shin-Etsu Silicone Co., Ltd. Sealant 45, Sealant 4588, Sealant 4515, Sealant 70, Sealant 701 SR Seal S70, SR Seal NB50, Bond Silicon Coke, Bond MS Seal, Bond MS Seal NB, Bond Hind Seal, etc. manufactured by Konishi Co., Ltd. Sharpy Silicone S, Hensei Silicone M, etc. manufactured by Sharp Chemical Industry Co., Ltd., Cemedine Co., Ltd. 8000, 8060, 8070, 8051N, POS seal, POS seal type II, S750NB, etc. In the case of acrylic, sharpie paint acrylic manufactured by Sharp Chemical Industry Co., Ltd., and acrylic caulk manufactured by Konishi Co., Ltd. are available.
Sealing materials are not limited to these uses, and commercially available products other than those described above are also useful.

Fillers, antibacterial agents, antifungal agents, colorants, pigments, preservatives, plasticizers, weather resistance improvers, anti-aging agents (ultraviolet absorbers and heat stabilizers, etc.), curing catalysts, anti-tack agents, solvents and the like.

Curing catalysts (curing agents) include, for example, tin octoate, dibutyltin dilaurate, dibutyltin octoate, dibutyltin oxide, dioctyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin bisacetylacetonate, dibutyltin bis-2-ethylhexanoate, Examples include tin-based catalysts exemplified by organic tin compounds such as dibutyltin diacetyl, and amine-based catalysts exemplified by organic amine compounds such as laurylamine. These can be used individually by 1 type or in combination of 2 or more types as appropriate.
The curing catalyst may be a mixture of a tin-based catalyst and an amine-based catalyst (generally in a weight ratio of 10:90 to 90:10). This mixture has a high curing acceleration effect.

The sealant composition of the present invention may be one-component (one-component) or two-component (two-component). In the case of the one-component type, the sealant and the fluorine-containing copolymer may be mixed in advance, and in the case of the two-component type, the curing agent and the fluorine-containing copolymer may be mixed.

A one-component sealant composition comprises a mixture of a sealant and a fluoropolymer. A one-component sealant composition cures by itself after being applied, so it has the advantage of being easy to work with.
On the other hand, a two-component sealant composition contains a main agent containing a sealant and a curing agent containing a fluoropolymer. A two-component sealant composition does not cure as a sealant alone, but cures when mixed with a curing agent as a second component and then applied. A two-component sealant composition requires more work for mixing the two components, but has the advantage of being superior to a one-component sealant composition in protecting properties after application.

In the case of a two-component type, the curing agent generally contains a component capable of curing the sealant (a component capable of curing together with the sealant and/or a curing catalyst that accelerates the curing of the sealant). The curing agent may contain an organic solvent.
In a sealant composition, particularly a one-component sealant composition, the fluorine-containing polymer is preferably produced by solution polymerization.
The sealing material may be used alone or in combination of two or more.

(2) Fluoropolymer The fluoropolymer is a copolymer containing a fluoromonomer (a) and a non-fluoromonomer (b) as structural units. The fluorine-containing monomer (a) is a monomer having a fluoroalkyl group having 4 to 6 carbon atoms, and the non-fluorine monomer (b) is an acyclic hydrocarbon group and/or nitrogen, oxygen, Alternatively, it is a monomer having a cyclic hydrocarbon group which may contain a sulfur atom. The non-fluorine monomer (b) is preferably a non-fluorine non-crosslinkable monomer having a non-cyclic hydrocarbon group having 14 or more carbon atoms and/or a cyclic hydrocarbon group. Moreover, it is good also as a copolymer containing another monomer (c) as a structural unit as needed.

The fluorine-containing monomer (a) has the formula:
_CH2 =C(-X)-C(=O)-YZ-Rf
[Wherein, X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
Rf is a perfluoroalkyl group having 4 to 6 carbon atoms. ]
is a compound represented by

X is, for example, a hydrogen atom, a methyl group, a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX ¹ X ² group (provided that X ¹ and X ² are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. be.
In the fluorine-containing copolymer of the present invention, X is preferably a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom. More preferably, X is a hydrogen atom or a methyl group, particularly a methyl group.

Y is preferably -O-.

Z is, for example, a direct bond, a straight-chain alkylene group having 1 to 20 carbon atoms or a branched alkylene group [for example, the formula -(CH ₂ ) _x - (wherein x is 1 to 10.) A group represented by the formula], or a group represented by the formula —SO ₂ N(R ¹ )R ² — or —CON(R ¹ )R ² — (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms and R ² is a straight or branched alkylene group having 1 to 10 carbon atoms.) or the formula —CH ₂ CH(OR ³ )CH ₂ — (wherein R ³ is , a hydrogen atom, or an acyl group having 1 to 10 carbon atoms (e.g., formyl or acetyl)), or a group represented by the formula —Ar—(CH ₂ ) _r — (wherein Ar is a substituted an arylene group optionally having a group, and r is 0 to 10.), or -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n - group or -(CH ₂ ) _m - S—(CH ₂ ) _n — group (where m is 1-10 and n is 0-10).
In the fluorine-containing copolymer of the present invention, Z is preferably a direct bond, an alkylene group having 1 to 20 carbon atoms, or -SO ₂ N(R ¹ )R ² -.

Rf is preferably a perfluoroalkyl group, but may be a fluoroalkyl group having a hydrogen atom. Rf has 4 to 6 carbon atoms, such as 4 or 6 carbon atoms. It is particularly preferred that Rf has 6 carbon atoms. Examples of Rf are _{-CF2CF2CF2CF3 , -CF2CF ( CF3} ) _{2 ,} -C _{( CF3} ) _{3 ,} -(CF2) _5CF3 , -( _CF2 ) _3CF ( CF ₃ ) ₂ and so on.

Specific examples of the fluorine-containing monomer (a) include, but are not limited to, the following.
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₂ -Rf
_CH2 =C(-H)-C(=O)-O- _{C6H4 -} Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 )2N _{( -CH3} )SO2 _- Rf
_CH2 =C(-H)-C ₍ =O)-O-( _CH2 )2N _{( -C2H5} )SO2 _- Rf
_CH2 =C(-H)-C(=O)-O-CH2CH(-OH) _{CH2 -} Rf
_CH2 =C(-H)-C(=O)-O-CH2CH( _-OCOCH3 ) _{CH2 -} Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-H)-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -Rf
_CH2 =C( _-CH3 )-C(=O)-O- _{C6H4 -} Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 )2N _{( -CH3} )SO2 _- Rf
_CH2 =C( _-CH3 )-C ₍ =O)-O-( _CH2 )2N _{( -C2H5} )SO2 _- Rf
_CH2 =C( _-CH3 )-C(=O)-O-CH2CH(-OH) _{CH2 -} Rf
_CH2 =C( _-CH3 )-C(=O)-O-CH2CH( _-OCOCH3 ) _{CH2 -} Rf

_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CH3 )-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-F)-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-Cl)-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CF3 )-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-CF2H)-C(=O)-NH-( _CH2 ) _{2 -} Rf

_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-CN)-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 = _{C ( -CF2CF3} )-C(=O)-O-( _CH2 ) ₂ -SO2-Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-O-( _CH2 ) _{2 -} SO2-( _CH2 ) ₂ -Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-F)-C(=O)-NH-( _CH2 ) ₃ -Rf

_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CF2CF3 )-C(=O)-O-( _CH2 ) _{3 -} S-Rf
_CH2 =C( _-CF2CF3 )-C(=O)-O-( _CH2 ) _{3 -} S-( _CH2 ) ₂ -Rf
_CH2 = _{C (-CF2CF3)-C(=O)-O-(CH2)3 - SO2 -} Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-O-( _CH2 ) _{2 -} SO2-( _CH2 ) ₂ -Rf
Of these, _CH2 =CH-C(=O)-O-( _CH2 ) ₂ -Rf, _CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -Rf is preferred.

The non-fluorine monomer (b) may be a non-fluorine non-crosslinkable monomer (b1).
A specific example of the non-fluorine non-crosslinkable monomer (b1) is represented by the formula:
_CH2 =CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom),
T is a hydrogen atom, a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom), an acyclic or cyclic hydrocarbon group having 1 to 30 carbon atoms, preferably 14 to 30 carbon atoms, or an ester bond. is an acyclic or cyclic hydrocarbon group having 1 to 30, preferably 14 to 30 carbon atoms. ]
It may be a compound represented by

Examples of acyclic or cyclic hydrocarbon groups having 1 to 30 carbon atoms are linear or branched saturated or unsaturated (eg, ethylenically unsaturated) hydrocarbon groups having 1 to 30 carbon atoms, preferably 14 to 30 carbon atoms. Aliphatic hydrocarbon group, saturated or unsaturated (eg, ethylenically unsaturated) cycloaliphatic group having 4 to 30 carbon atoms, preferably 6 to 30 carbon atoms, such as 14 to 30 carbon atoms, preferably 14 carbon atoms It is an aromatic hydrocarbon group of ∼30 and an araliphatic hydrocarbon group of 7 to 30 carbon atoms, preferably 14 to 30 carbon atoms.

Examples of acyclic or cyclic C1-C30 organic groups having an ester bond are -C(=O)-OQ and -OC(=O)-Q, where Q is C1-C30 , preferably 14-30 linear or branched saturated or unsaturated (e.g., ethylenically unsaturated) aliphatic hydrocarbon groups, C 4-30, preferably 14-30 saturated or unsaturated ( (e.g., ethylenically unsaturated) cycloaliphatic group, aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 14 to 30 carbon atoms, araliphatic hydrocarbon group having 7 to 30 carbon atoms, preferably 14 to 30 carbon atoms) is.
In addition, non-fluorine non-crosslinkable monomers may be (meth)acrylate ester monomers (b1-1) and halogenated olefin monomers (b1-2).

Specific examples of the (meth)acrylate ester monomer (b1-1) are
_CH2 =CA21-C ⁽ =O) ^-OA22
[In the formula, A ²¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 14 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl or a monovalent organic group that is a halogen atom other than a fluorine atom,
A ²² is a hydrocarbon group having 1-30 carbon atoms, preferably 14-30 carbon atoms. ]
It may be a compound represented by
A ²¹ is a hydrogen atom, a methyl group, a linear or branched alkyl group having 2 to 30 carbon atoms, preferably 14 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group , or a chlorine group.
A ²² is a hydrocarbon group having 1 to 30 carbon atoms, preferably 4 to 30 carbon atoms, more preferably 6 to 30 carbon atoms, especially 14 to 30 carbon atoms. A ²² (hydrocarbon group) includes non-cyclic hydrocarbon groups having 14 to 30 carbon atoms (linear or branched hydrocarbon groups such as alkyl groups) and cyclic hydrocarbon-containing groups having 4 to 30 carbon atoms. (eg, saturated or unsaturated monocyclic group, polycyclic group, bridged ring group).

Specific examples of (meth)acrylate ester monomers having an acyclic hydrocarbon group include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth) Acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate and the like. Among (meth)acrylate ester monomers having an acyclic hydrocarbon group, stearyl (meth)acrylate and behenyl (meth)acrylate are preferred.

Specific examples of (meth)acrylate ester monomers having a cyclic hydrocarbon-containing group include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopenta Nil (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylates, 2-ethyl-2-adamantyl (meth)acrylate and the like.

Halogenated olefin monomer (b1-2) does not have a fluorine atom.
Halogenated olefin monomers may be C2-20 olefins substituted with 1-10 chlorine, bromine or iodine atoms. The halogenated olefin monomer is preferably an olefin having 2 to 5 carbon atoms and having 2 to 20 carbon atoms, particularly 1 to 5 chlorine atoms. Preferred examples of halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred because they increase the water and oil repellency (especially the durability of the water and oil repellency).

Since the fluorine-containing copolymer preferably does not have a polyoxyalkylene group, the non-fluorine monomer (b) preferably does not have a polyoxyalkylene group. Thereby, the fluoropolymer can impart good antifouling properties and water and oil repellency.

In addition, the fluorine-containing copolymer of the present invention can be a copolymer containing another monomer (c) as a structural unit, if necessary, and the other monomer (c) is preferably It is a non-fluorine crosslinkable monomer and a monomer containing no fluorine atom. Non-fluorine crosslinkable monomers may be fluorine-free compounds having at least one reactive group and/or an olefinic carbon-carbon double bond (preferably a (meth)acrylate group). The non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably (meth)acrylate groups), or at least one olefinic carbon-carbon double bond and at least one It may be a compound having a reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, glycidyl groups, and the like.
By having a reactive group such as a hydroxyl group, it is possible to impart durability to antifouling properties and water and oil repellency.

Non-fluorine crosslinkable monomers may be mono(meth)acrylates, di(meth)acrylates or mono(meth)acrylamides with reactive groups. Alternatively, the non-fluorine crosslinkable monomer may be a di(meth)acrylate.

One example of a non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group (particularly a (meth)acrylate monomer).
Non-fluorine crosslinkable monomers include, for example, diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth) ) acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. are exemplified, but are not limited to these.

Other non-fluorine crosslinkable monomers may be isocyanatoacrylate monomers and the like.
Specific examples of isocyanatoacrylate monomers are 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate. 2-butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate pyrazole adduct, 2-isocyanatoethyl (meth)acrylate 3,5-dimethylpyrazole adduct, 2-isocyanatoethyl (meth)acrylate 3-methylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate ε-caprolactam adduct, 3-isocyanatopropyl (meth)acrylate 2-butanone oxime adduct, 3-isocyanatopropyl (meth)acrylate pyrazole adduct, 3-isocyanatopropyl (meth)acrylate 3,5-dimethylpyrazole adduct, 3-isocyanatopropyl (meth)acrylate 3-methylpyrazole adduct, 3-isocyanatopropyl (meth)acrylate ε-caprolactam adduct of 4-isocyanatobutyl (meth)acrylate 2-butanone oxime adduct, 4-isocyanatobutyl (meth)acrylate pyrazole adduct, 4-isocyanatobutyl (meth)acrylate 3, 5-dimethylpyrazole adduct, 4-isocyanatobutyl (meth)acrylate-3-methylpyrazole adduct, 4-isocyanatobutyl (meth)acrylate-ε-caprolactam adduct, and the like.

As used herein, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

Each of the monomers (a) to (c) may be used alone or in combination of two or more.
The fluorine-containing polymer may be used alone or in combination of two or more.

In the fluorine-containing copolymer, the weight ratio of monomer (a) to monomer (b) is 20:80 to 80:20, 30:70 to 70:30, for example 35:60 to 65:35. It's okay.

In the fluorine-containing copolymer containing the monomer (c), the weight ratio of the monomer (a) to the monomer (b) to the monomer (c) is 20:75:5 to 80:5: 15, preferably 30:65:5 to 70:15:15, such as 40:53:7 to 65:25:10. Alternatively, the amount of the monomer (c) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 100 parts by weight in total of the monomers (a) and (b). may be from 5 to 15, such as from 7 to 12 parts by weight.

The fluorine-containing copolymer can be polymerized by a known method using a polymerization initiator, a solvent and, if necessary, a chain transfer agent. The fluorine-containing copolymer can be produced by solution polymerization in an organic solvent, emulsion polymerization in water, or the like. A fluorine-containing copolymer can be obtained by removing (by distillation or the like) a liquid medium from a polymerization mixture containing a liquid medium (organic solvent or water) obtained by polymerization. The fluorine-containing copolymer preferably does not contain water.

The molecular weight of the fluorine-containing copolymer may be, for example, generally 1,000 to 1,000,000, particularly 2,000 to 50,000, when converted to polystyrene by GPC (gel permeation chromatography) measurement.

The mixing ratio of the sealant and the fluorine-containing copolymer in the composition is 99.9:0.1 to 85:15, for example, 99.5:0.5 to 90:10, further 99:1 by weight. ~95:5. This weight ratio allows the fluorocopolymer and the sealant to exhibit the properties (particularly, antifouling properties and water and oil repellency) required.

In the present invention, the method of mixing the sealant and the fluorocopolymer may be a one-component method in which a mixture obtained by mixing the sealant and the fluorocopolymer in advance is applied, or a substrate based on the sealant. It may be any two-component type that has a material and a curing agent containing a fluorine-containing copolymer and is mixed immediately before use. When the curing agent contains a fluorine-containing copolymer, organic solvents such as ethyl acetate, butyl acetate, toluene and xylene may be used as the solvent.

A one-component sealant can be produced by mixing a sealant and a fluorocopolymer.

The present invention also provides a method for sealing gaps, which comprises filling gaps in interior or exterior materials for civil engineering, construction, or automobiles with the composition described above, and then curing the composition to form a sealant. We also provide a method.

Although details will be described below with reference to examples, the present invention is not limited only to these examples.
Physical properties were measured as follows.

Water and Oil Repellency Contact angle measurements (at room temperature (25° C.) and 2 μl drops) were carried out with water and n-hexadecane (HD).

Antifouling property Prepare the following antifouling test solution, put 20 ml of the antifouling test solution on the coating film formed on the plate from the sealant and the fluorine-containing copolymer, and dry in an oven at 60°C for 1 hour. After the water was sufficiently dried with a plate, the plate was tilted 90 degrees and the dried antifouling test liquid was wiped off with a cloth, and the degree of stain remaining was visually evaluated.
Kanto loam: JIS Z8901 test powder Type 8 (Kanto loam layer) A liquid obtained by mixing a particle size of 8 µm and water at a weight ratio of 1:2.
Yellow ocher: A liquid obtained by mixing JSTM (Construction Materials Testing Center Standard) synthetic ocher for pigments (SiO ₂ 54%) and water at a weight ratio of 1:2.
Carbon black: A liquid obtained by mixing 12 types of JIS Z9801 test powder (carbon black, particle size 0.03 to 0.2 μm) and water at a weight ratio of 1:3.
Evaluation criteria
◯: Dirt is wiped off cleanly.
Δ: Stain remains to some extent, but can be wiped off relatively cleanly.
x: Dirt cannot be wiped off at all.

A coating film formed on a plate from a washable sealant and a fluorine-containing copolymer was attached to the wall of a drain outlet for domestic wastewater, and an exposure test was conducted for one month. After testing, the plates were removed and washed using a commercial household detergent and sponge. Before and after washing, the color difference (ΔE ^* ) before and after the test was calculated by measuring the L ^* value, a ^* value, and b ^* value with a D65 light source using a color difference meter.

Polymer Examples 1-9 and Comparative Polymer Examples 1-3
A solution of a fluorine-containing copolymer was produced by mixing the monomers (fluorine-containing monomers and non-fluorine-containing monomers) shown in Table 1 with 100 parts by weight of isopropyl alcohol (IPA) and polymerizing the mixture. Then, the organic solvent (IPA) was removed by distillation to obtain a bulk fluorine-containing copolymer. The monomer composition in the fluorine-containing copolymer was almost the same as the composition of the charged monomers.

Examples 1-15 and Comparative Examples 1-7
As shown in Table 2, the fluorine-containing copolymers obtained in Polymer Examples 1 to 9 and Comparative Polymer Examples 1 to 3 were mixed with a silicone sealant. At that time, polymer examples 1 to 9 and comparative polymer examples 1 to 3 were obtained by adding 10 parts by weight of ethyl acetate to the parts by weight shown in Table 2 and mixing them with the sealant. A fluorine sealant composition was obtained.
This composition was applied onto a glass plate using an applicator, dried at room temperature for 24 hours, and then evaluated for contact angle and antifouling properties. Table 3 shows the results.
In addition, Examples 1 to 10, Example 14 and Example 15 are reference examples not included in the present invention (that is, "Examples 1 to 10 (reference)", "Example 14 (reference)" and "Example 15 (Reference)”).

C6SFA: _CH2 =C ₍ -H)-C(=O)-O-( _CH2 ) _{2 -} C6F13
C6SFMA: _CH2 =C _{( -CH3} )-C(=O)-O-( _CH2 ) _{2 -} C6F13
LA: Lauryl acrylate StA: Stearyl acrylate VA: Behenyl acrylate CHMA: Cyclohexyl acrylate EOA-1: CH ₂ =C(-H)-C(=O)-O-(CH ₂ CH ₂ O) _n - Hn=2
EOA- ₂ : _CH2 =C(-H)-C(=O)-O-( _CH2CH2O ) _n -Hn=10
2-HEA: 2-hydroxyethyl acrylic acid silicone system (45): oxime silicone (sealant 45 manufactured by Shin-Etsu Silicone Co., Ltd.)
Silicone-based (SE): containing dimethyldichlorosilane-treated silica, methyltri(methylethylketoxime)silane and vinyltri(methylethylketoxime)silane as main components (SE-5010 manufactured by Dow Corning Toray Co., Ltd.)
Silicone-based (C): oxime-based silicone (8000 manufactured by Cemedine)
Silicone-based (S): modified silicone-based sealant (MSC1-22 manufactured by Sharp Corporation)
Silicone type (70): Two-component aminoxy-type silicone sealant (Sealant 70 manufactured by Shin-Etsu Silicone Co., Ltd.) main agent, curing agent Silicone type (SEII): Two-component alcohol-type silicone sealant (SE990F, Toray Dow Co., Ltd.) main agent, curing agent silicone System (P): Two-component modified silicone sealant (Cemedine POS seal type II) main agent, curing agent Acrylic system: water-based acrylic sealant

Examples 16-19 (reference) and Comparative Examples 8-10
As shown in Table 2, the fluorine-containing copolymers obtained in Polymer Examples 2 and 3 and Comparative Polymer Examples 1 and 2 were mixed with an acrylic sealant. At that time, polymer examples 2 and 3 and comparative polymer examples 1 and 2 were obtained by adding 10 parts by weight of ethyl acetate to the parts by weight shown in Table 4 and mixing them with the sealant. A fluorine sealant composition was obtained.
This composition was applied onto a glass plate using an applicator, dried at room temperature for 24 hours, and then evaluated for contact angle and antifouling properties. Table 5 shows the results.

Examples 20-23 (reference) and Comparative Example 11
As shown in Table 6, the fluorine-containing copolymers obtained in Polymer Examples 2 and 3 were mixed with a silicone sealant. At that time, polymer examples 2 and 3 were obtained by adding 10 parts by weight of ethyl acetate to the parts by weight shown in Table 6 and mixing them with the sealant to obtain a fluorine-containing sealant composition. rice field.
This composition was applied onto a PET film using an applicator, dried at room temperature for 24 hours, and then evaluated for washability. Table 7 shows the results.

Examples 24-27 (reference) and Comparative Examples 12-15
As shown in Table 8, the fluorine-containing copolymers obtained in Polymer Examples 2 and 3 and Comparative Polymer Examples 1 and 2 were mixed with a silicone sealant to obtain a fluorine-containing sealant composition.
This composition was applied onto a glass plate using an applicator, dried at room temperature for 24 hours, and then evaluated for contact angle and antifouling properties. Table 9 shows the results.

Examples 28-31 (reference) and Comparative Examples 16-19
The fluorine-containing copolymers obtained in Polymer Examples 2 and 3 and Comparative Polymer Examples 1 and 2 were mixed with sealant curing agents as shown in Table 10 to obtain fluorine-containing polymer-containing curing agents. By mixing 4 parts by weight of this curing agent with 100 parts by weight of the main agent of the sealing material shown in Table 10, a fluorine-containing sealing material composition was obtained.
This composition was applied onto a glass plate using an applicator, dried at room temperature for 24 hours, and then evaluated for antifouling properties. The results are shown in Table 11.

The sealant composition of the present invention is excellent in antifouling properties without lowering the water repellency of the sealant. Moreover, oil repellency can be imparted to the sealing material. The sealant composition of the present invention is useful as a sealant for civil engineering, construction (for example, kitchens and washrooms, particularly sinks and bathrooms), and interior or exterior materials for automobiles.

Another aspect of the present invention is as follows.
Aspect 1:
A sealant composition containing (1) a sealant and (2) a fluorine-containing copolymer,
The fluorine-containing copolymer (2) is
(a) Formula:
_CH2 =C(-X)-C(=O)-YZ-Rf
[Wherein, X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
Rf is a perfluoroalkyl group having 4 to 6 carbon atoms. ]
and (b) a structural unit derived from a non-fluorinated monomer having a hydrocarbon group, represented by wood composition.
Aspect 2:
In the fluorine-containing monomer (a),
X is a hydrogen atom, a methyl group, a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom, a chlorine atom , a bromine atom, or an iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group,
Z is a direct bond, a straight-chain alkylene group having 1 to 20 carbon atoms or a branched alkylene group, or formula -SO ₂ N(R ¹ )R ² - or formula -CON(R ¹ )R ² - (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms and R ² is a linear or branched alkylene group having 1 to 10 carbon atoms), or A group represented by the formula —CH ₂ CH(OR ³ )CH ₂ — (wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms), or a group of the formula —Ar—(CH ₂ ) _r — (wherein Ar is an arylene group optionally having a substituent, and r is 0 to 10), or —(CH ₂ ) _m —SO ₂ —(CH ₂ ) The sealant composition according to aspect 1, which is an _n - group or -(CH ₂ ) _m -S-(CH ₂ ) _n - group (where m is 1 to 10 and n is 0 to 10). .
Aspect 3:
The sealant composition according to aspect 1, wherein in the fluorine-containing monomer (a), X is a methyl group.
Aspect 4:
Aspect 1, wherein the non-fluorine monomer (b) is a non-fluorine non-crosslinkable monomer having a non-cyclic hydrocarbon group having 14 to 30 carbon atoms or a cyclic hydrocarbon group having 4 to 30 carbon atoms. sealant composition.
Aspect 5:
The fluorine-containing copolymer further contains a non-fluorine crosslinkable monomer (c) as a structural unit, and the amount of the monomer (c) is the total of the monomer (a) and the monomer (b) The sealant composition according to aspect 1, which is 1 to 30 parts by weight per 100 parts by weight.
Aspect 6:
The sealant composition according to aspect 5, wherein the non-fluorine crosslinkable monomer (c) is a vinyl monomer having a hydroxyl group.
Aspect 7:
The sealant composition according to aspect 1, wherein the fluorine-containing copolymer (2) does not have a polyoxyalkylene group.
Aspect 8:
The sealant composition according to aspect 1, wherein the fluorine-containing copolymer (2) is produced by solution polymerization.
Aspect 9:
The sealant composition according to aspect 1, wherein the sealant is at least one sealant selected from silicone sealants, urethane sealants and acrylic sealants.
Aspect 10:
A sealant composition according to aspect 1, which is a one-component form comprising a mixture of a sealant and a fluoropolymer.
Aspect 11:
The sealant composition according to aspect 1, wherein the sealant composition is a two-component type containing a base material and a curing agent, the base material containing the sealant, and the curing agent containing the fluorine-containing copolymer.
Aspect 12:
The sealant composition according to aspect 1, wherein the weight ratio of the sealant to the fluorine-containing copolymer is 99.9:0.1 to 85:15.
Aspect 13:
The sealant composition according to aspect 1, wherein the weight ratio of monomer (a) to monomer (b) is 20:80 to 80:20.
Aspect 14:
A method for producing a sealant composition according to any one of aspects 1 to 13,
A production method comprising polymerizing the monomer (a) and the monomer (b) to obtain a fluorine-containing copolymer (2), and then mixing the polymer with a sealant.
Aspect 15:
The sealant composition according to any one of aspects 1 to 13 is filled in the boundary of interior or exterior materials for civil engineering, construction, or automobiles, and then the sealant composition is cured to form a sealant. A method of sealing a perimeter comprising:

Claims (13)

A sealant composition containing (1) a sealant and (2) a fluorine-containing copolymer,
The fluorine-containing copolymer (2) is
(a) Formula:
_CH2 =C(-X)-C(=O)-YZ-Rf
[Wherein, X is a hydrogen atom, a methyl group or a halogen atom,
Y is -O-
Z is a direct bond or a linear or branched alkylene group having 1 to 20 carbon atoms,
Rf is a perfluoroalkyl group having 4 to 6 carbon atoms. ]
A structural unit derived from a fluorine-containing monomer having a fluoroalkyl group having 4 to 6 carbon atoms represented by
(b) Formula:
_CH2 =CA21-C ⁽ =O) ^-OA22
[In the formula, A ²¹ is a hydrogen atom or a methyl group,
A ²² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. ]
A structural unit derived from a non-fluorine monomer represented by, and
(c) structural units derived from non-fluorine crosslinkable monomers;
including
The fluorine-containing copolymer (2) does not have a polyoxyalkylene group,
A sealant composition in which the amount of monomer (c) is 1 to 30 parts by weight with respect to a total of 100 parts by weight of monomers (a) and (b) . 2. The sealant composition according to claim 1, wherein in the fluorine-containing monomer (a), X is a methyl group. Non-fluorine monomer (b) is cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate and 2-ethyl-2-adamantyl ( The sealant composition according to claim 1 or 2, which is at least one selected from the group consisting of meth)acrylates. Non-fluorine crosslinkable monomer (c) is diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) ) acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylates, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate , and
2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate, 2-isocyanate Natoethyl (meth)acrylate pyrazole adduct, 2-isocyanatoethyl (meth)acrylate 3,5-dimethylpyrazole adduct, 2-isocyanatoethyl (meth)acrylate 3-methylpyrazole adduct, 2-isocyanate ε-caprolactam adduct of natoethyl (meth)acrylate, 2-butanone oxime adduct of 3-isocyanatopropyl (meth)acrylate, pyrazole adduct of 3-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl ( 3,5-dimethylpyrazole adduct of meth)acrylate, 3-methylpyrazole adduct of 3-isocyanatopropyl (meth)acrylate, ε-caprolactam adduct of 3-isocyanatopropyl (meth)acrylate, 4-isocyanato Butyl (meth)acrylate 2-butanone oxime adduct, 4-isocyanatobutyl (meth)acrylate pyrazole adduct, 4-isocyanatobutyl (meth)acrylate 3,5-dimethylpyrazole adduct, 4-isocyanato 3-methylpyrazole adduct of butyl (meth)acrylate and ε-caprolactam adduct of 4-isocyanatobutyl (meth)acrylate,
The sealant composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of: The sealant composition according to any one of claims 1 to 4, wherein the non-fluorine crosslinkable monomer (c) is a vinyl monomer having a hydroxyl group. The sealant composition according to any one of claims 1 to 5, wherein the fluorine-containing copolymer (2) is produced by solution polymerization. The sealant composition according to any one of claims 1 to 6, wherein the sealant (1) is at least one sealant selected from silicone sealants, urethane sealants and acrylic sealants. thing. The sealant composition according to any one of claims 1 to 7, which is a one-component type comprising a mixture of the sealant (1) and the fluorine-containing copolymer (2) . 9. Any one of claims 1 to 8, wherein the sealant composition is a two-component type containing a main agent and a curing agent, the main agent comprising the sealing agent (1) and the curing agent comprising the fluorine-containing copolymer (2) . 2. The sealant composition according to item 1. The sealant composition according to any one of claims 1 to 9, wherein the weight ratio of the sealant (1) to the fluorine-containing copolymer (2) is 99.9:0.1 to 85:15. The sealant composition according to any one of claims 1 to 10, wherein the weight ratio of monomer (a) to monomer (b) is 20:80 to 80:20. A method for producing the sealant composition according to any one of claims 1 to 11,
A production method comprising polymerizing a monomer (a) and a monomer (b) to obtain a fluorine-containing copolymer (2), and then mixing the polymer with a sealant (1) . The sealant composition according to any one of claims 1 to 11 is filled in the boundary part of interior or exterior materials for civil engineering, construction, or automobiles, and then the sealant composition is cured to form a sealant. A method of sealing a perimeter comprising forming.