JP6953722B2 - Sealant composition - Google Patents

Description

The present invention relates to a sealing material composition containing a fluorine-containing copolymer containing a fluorine-containing monomer having a specific fluoroalkyl group and a sealing material, and having excellent antifouling property and water- and oil-repellent properties. The sealant composition can be used for sealant applications used in civil engineering, construction (eg, kitchens and washrooms, especially sinks, and bathrooms), interior and exterior materials such as automobiles.

It is applied to the boundary between exterior and interior members of buildings, such as concrete, wood, siding boards, and aluminum sashes, for the purpose of preventing water and dust from entering through the gaps and improving airtightness. Generally, a sealing material is used. There are various types of sealing materials such as silicone type, urethane type, and acrylic type, and they are used according to each application. These sealants contain various additives from the viewpoint of work and surface protection, and they bleed over a long period of time, causing stains and the nature of the base resin. There is a problem that dirt easily adheres.

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

Further, Japanese Patent Application Laid-Open No. 2008-291159 proposes a technique for imparting antifouling property by adding a perfluoroalkyl group-containing surfactant that imparts hydrophilicity to a sealing material composition. Although this method can impart antifouling properties to soot and soil, the hydrophilic nature of the sealant makes it easier for mold and microorganisms 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 perfluoroalkyl group having an average carbon number of 9 and a photocurable monomer is sealed. A technique for a curable composition having excellent antifouling properties, including a material, has been proposed. Although the antifouling property is improved by this technique as well, it is necessary to take measures to suppress the progress of photocuring during the storage period until application.

Japanese Unexamined Patent Publication No. 2010-275481 Japanese Unexamined Patent Publication No. 2008-291159 Japanese Unexamined Patent Publication No. 2001-234157 Japanese Unexamined Patent Publication No. 2001-81330

An object of the present invention is to express antifouling property while exhibiting water and oil repellency by mixing a specific fluorine-containing polymer with a sealing material used for interior materials or exterior materials of civil engineering, construction, automobiles and the like. It is an object of the present invention to provide a composition comprising a sealing material and a fluorine-containing polymer.

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

According to the present invention, it is possible to obtain a sealing material composition having excellent antifouling properties without lowering the water repellency of the sealing material. The sealant composition has excellent adhesion prevention property and release property (cleaning property) against stains such as carbon (soot), sand and loess. Further, oil repellency can be imparted to the sealing material. In addition, the sealant composition also provides antifouling and water and oil repellent durability, as well as antibacterial and antifungal properties.
The sealing material composition is useful as a sealing material used for interior materials or exterior materials of civil engineering, construction, automobiles and the like.

More specifically, since the sealant and the fluorine-containing polymer exhibiting antifouling property are applied as a mixture, there is no problem that the effect of the sealant is not exhibited by the surface coating. Further, it is not necessary to apply the fluorine-containing polymer to the surface of the sealing material. Further, since the sealing material used in the present invention is hydrophobic, it exhibits antifouling property against various stains, and mold and microorganisms adhere to the surface of the sealing material due to the water and oil repellency of the fluorine-containing polymer. It becomes difficult.

(1) Sealing material Sealing material is a structure that prevents outside air and water from entering from the boundary when materials such as concrete, siding board, and tile are combined in the exterior and interior materials of a building. It is painted on the boundary part made of a combination of exterior materials and interior materials for the purpose of protecting. It is also used for the same purpose not only in buildings but also in automobile interior materials and aluminum sashes.

Examples of the sealing material include silicone-based, polysulfide-based, polyurethane-based, acrylic-based, SBR-based, butyl rubber-based, oil-based caulking material-based, and acrylic urethane-based sealing materials. Among the silicone-based and polysulfide-based sealing materials, there are modified silicone-based and modified polysulfide-based sealing materials in order to further improve the protection property.

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

The silicone-based or modified silicone-based sealing material contains a polymer (syroxy group-containing polymer) having a siloxy group (generally, a siloxane group). Siloxy group-containing polymer is generally, A _m SiO in _{(4-m) / 2} [wherein, A is a hydrogen atom, a halogen atom or a monovalent organic group, m is 0-3. ] Has the indicated structural unit. The siloxy group-containing polymer has a monofunctional siloxy group (A ₃ SiO _0.5 ) and a bifunctional siloxy unit (A ₂ SiO), and if necessary, a trifunctional siloxy unit (ASiO _1.5). ) (In some cases, it may have a _{tetrafunctional siloxy unit (SiO 2)).} The A group may be a hydrocarbon group having 1 to 20 carbon atoms, for example, 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 (eg chlorine atom, bromine atom, iodine atom), amino group, epoxy group, carboxyl group, carbinol group, mercapto group, aminooxy group, hydroxyl group, alkoxy group and oxime group. Is. The reactive group is preferably a hydroxyl group (OH group), an alkoxy group (for example, a methoxy group) and an oxime group (for example, a ketooxime group such as a methylethylketooxime group).

In the modified silicone-based sealing material, the syroxy group-containing polymer is a polymer having a structural unit other than the syroxy group, for example, a (poly) oxyalkylene group, an amide group, an imide group, or an alkylene group in addition to the syroxy group. (The number of carbon atoms in the alkylene is, for example, 1 to 5, especially 2 or 3). Modified silicone sealant, for example, an organic polymer (e.g., polyether) to the end of the (poly) organosiloxane groups (e.g., monofunctional siloxy group (A 3 _{SiO 0.5))} may have a ..

The silicone-based sealant may contain a silane compound. Silane compounds generally have a hydrolyzable group. Specific examples of the hydrolyzable group are an oxime group, an alkoxy group, an alkoxy-substituted alkoxy group, an asyloxy group, an alkenoxy group, a ketooxime group, an aminoxy group and an amide group. A typical example of a silane compound is an oxime-type or de-oxime-type silane compound (oxime-type or de-oxime-type silicone). Oxime-type or de-oxime-type silicones are cured by desorbing oxime (for example, methylethylketooxime) when they are cured after application. The oxime-type silicone contains a silane compound having an oxime group. Examples of silane compounds having an oxime group are methyltri (methylethylketooxime) silanes and vinyltri (methylethylketooxime) silanes.
Other curing systems include alcohol-type or de-alcohol-type silicones, and acetone-type, acetic acid-type, and aminoxy-type sealants. Similar to the oxime type, these are sealing materials that are cured by desorption of alcohol, acetone, acetic acid, etc. when they are effective after application.
The silicone-based sealant may contain fumed silica powder, for example, dimethyldichlorosilane-treated silica powder, in addition to the silane compound.

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

The acrylic sealant is generally based on an acrylic polymer, and is a sealant that dries and cures when the solvent contained in the material evaporates after application.
The acrylic sealant contains an acrylic polymer. The acrylic heavy body is a polymer having an acrylate monomer as a repeating unit. The acrylate monomer is a (meth) acrylic acid ester, for example, a (meth) acrylic acid alkyl ester (alkyl group having 1 to 30 carbon atoms), an oxyalkylene group (having an oxyalkylene group number of 1 to 30, for example, 1). It may be a (meth) acrylic acid ester having ~ 25). Specific examples of the acrylic polymer include an acrylic acid alkyl ester copolymer, an acrylonitrile-acrylic acid alkyl ester copolymer, an acrylic acid-methacrylic acid-acrylic acid alkyl ester copolymer, and an acrylic acid-acrylic acid-acrylic acid alkyl ester. 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-acrylic acid alkyl ester-acrylic It is an acid alkyl ester copolymer.

In the present invention, a commercially available product can be used as the sealing material. For example, in the case of silicone type, SE5007, SH780, SH5010, SE960, SE990F, SE930, SE931, SE936, SE797, etc. manufactured by Toray Dow Corning, etc., Sealant 45, Sealant 4588, Sealant 4515, Sealant 70, Sealant 701 manufactured by Shinetsu Silicone Co., Ltd. SR Seal S70, SR Seal NB50, Bond Silicon Cork, Bond MS Seal, Bond MS Seal NB, Bond Hind Seal, etc., Sharpy Silicone S, Hensei Silicone M, etc., manufactured by Konishi Co., Ltd. 8000, 8060, 8070, 8051N, POS seal, POS seal type II, S750NB, etc. In the case of acrylics, there are Sharpy Paint Acrylic made by Sharp Chemical Industry Co., Ltd. and Acrylic Cork made by Konishi Co., Ltd.
The sealing material is not limited to these uses, and commercially available products other than the above are also useful.

Sealants are fillers, antibacterial agents, antifungal agents, colorants, pigments, preservatives, plasticizers, weather resistance improvers, anti-aging agents (ultraviolet absorbers and anti-aging agents) according to the effect required for the place where they are used. It may contain a heat stabilizer, etc.), a curing catalyst, an anti-tack agent, a solvent, and the like.

Examples of the curing catalyst (curing agent) include tin octylate, dibutyltin dilaurate, dibutyltin octate, dibutyltin oxide, dioctyltinoxide, dibutyltin bistriethoxysilicate, dibutyltin bisacetylacetonate, and dibutyltin bis-2-ethylhexanoate. Examples thereof include tin-based catalysts such as dibutyltin diacetyl and other organic tin compounds, and amine-based catalysts such as laurylamine and other organic amine compounds. These can be used alone or in combination of two or more.
The curing catalyst may be a mixture of a tin-based catalyst and an amine-based catalyst (weight ratio is generally 10:90 to 90:10). This mixture has a high curing promoting effect.

The sealant composition of the present invention may be a one-component type (one-component type) or a two-component type (two-component type). 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.

The one-component sealant composition comprises a mixture of the sealant and the fluorinated polymer. The one-component sealant composition itself has the advantage of being easy to work with because it cures after application.
On the other hand, the two-component sealant composition contains a main agent containing a sealant and a curing agent containing a fluorine-containing polymer. The two-component sealant composition is not cured by the sealant alone, but is cured by being mixed with a curing agent as the second component and then applied. The two-component sealant composition has the advantage that the protection after application is superior to that of the one-component type, although it takes time and effort to mix the two components.

In the case of the two-component type, in the curing agent, a component capable of curing the sealing material (a component that can be cured together with the sealing material and / or a curing catalyst that accelerates the curing of the sealing material) is generally mixed. The curing agent may contain an organic solvent.
In the sealing material composition, particularly in the one-component type sealing material 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) Fluorine-containing polymer The fluorine-containing polymer is a copolymer containing a fluorine-containing monomer (a) and a non-fluorine monomer (b) as constituent 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, 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 a cyclic hydrocarbon group. Further, if necessary, it may be a copolymer containing another monomer (c) as a constituent unit.

The fluorine-containing monomer (a) has the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[In the formula, X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or divalent organic group,
Rf is a perfluoroalkyl group having 4 to 6 carbon atoms. ]
It is a compound indicated 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, and a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom and a fluorine atom. It is 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. It is more preferable that 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 linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group [for example, the formula − (CH ₂ ) _x − (where x is 1 to 10 in the formula). Group represented by], or a group represented by the formula −SO ₂ N (R ¹ ) R ² − or the formula −CON (R ¹ ) R ² − (in the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms. R ² is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group), or the formula −CH ₂ CH (OR ³ ) CH ₂ − (in the formula, R ³ is , A hydrogen atom, or a group represented by an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl), or the formula −Ar − (CH ₂ ) _r − (in the equation, Ar is substituted. It is an arylene group having a group as required, 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 to 10 and n is 0 to 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, and −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, for example 4 or 6. It is particularly preferable that Rf has 6 carbon atoms. Examples of Rf are −CF ₂ CF ₂ CF ₂ CF ₃ , −CF ₂ CF (CF ₃ ) ₂ , −C (CF ₃ ) ₃ , − (CF ₂ ) ₅ CF ₃ , − (CF ₂ ) ₃ CF ( CF ₃ ) ₂ and so on.

Specific examples of the fluorine-containing monomer (a) include, but are not limited to, the following.
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O−C ₆ H ₄ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ N (−CH ₃ ) SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ N (−C ₂ H ₅ ) SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O−CH ₂ CH (−OH) CH ₂ −Rf
CH ₂ = C (−H) −C (= O) −O−CH ₂ CH (−OCOCH ₃ ) CH _{2 −Rf}
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −NH− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O−C ₆ H ₄ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ N (−CH ₃ ) SO ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ N (−C ₂ H ₅ ) SO ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O−CH ₂ CH (−OH) CH ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O−CH ₂ CH (−OCOCH ₃ ) CH _{2 −Rf}

CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −NH− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −NH− (CH ₂ ) ₂ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−Cl) −C (= O) −NH− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −NH− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −NH− (CH ₂ ) ₂ −Rf

CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −NH− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −NH− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −NH− (CH ₂ ) ₃ −Rf

CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
Of these, CH ₂ = CH−C (= O) −O− (CH ₂ ) ₂ −Rf, CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −Rf Is preferable.

The non-fluorine monomer (b) may be a non-fluorine non-crosslinkable monomer (b1).
Specific examples of the non-fluorine non-crosslinkable monomer (b1) include the formula:
CH ₂ = CA-T
[In the formula, A is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom).
T has a hydrogen atom, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom), an acyclic or cyclic hydrocarbon group having 1 to 30, preferably 14 to 30, or an ester bond. It 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 with 1-30 carbon atoms are linear or branched saturated or unsaturated (eg, ethylenically unsaturated) with 1-30 carbon atoms, preferably 14-30 carbon atoms. Aliphatic hydrocarbon groups, 4-30 carbon atoms, preferably 6-30, eg 14-30 saturated or unsaturated (eg ethylenically unsaturated) cyclic aliphatic groups, 6-30 carbon atoms, preferably 14 It is an aromatic hydrocarbon group of ~ 30 and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms, preferably 14 to 30 carbon atoms.

Examples of acyclic or cyclic organic groups with 1 to 30 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1 to 30 carbon atoms. , Preferably 14-30 linear or branched saturated or unsaturated (eg, ethylenically unsaturated) aliphatic hydrocarbon groups, 4-30 carbon atoms, preferably 14-30 saturated or unsaturated (eg, ethylenically unsaturated) For example, an ethylenically unsaturated) cyclic aliphatic group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 14 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms, preferably 14 to 30 carbon atoms). Is.
In addition, the non-fluorine non-crosslinkable monomer may be a (meth) acrylate ester monomer (b1-1), a halogenated olefin monomer (b1-2), or the like.

Specific examples of the (meth) acrylate ester monomer (b1-1) include
CH ₂ = CA ²¹ -C (= O) -OA ²²
[In the formula, A ²¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 30, preferably 14 to 30, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl. A monovalent organic group that is a group or a halogen atom other than a fluorine atom,
A ²² is a hydrocarbon group having 1 to 30, preferably 14 to 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, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group. , Or a chlorine group is preferable.
A ²² is a hydrocarbon group having 1 to 30, preferably 4 to 30, more preferably 6 to 30, especially 14 to 30 carbon atoms. A ²² (hydrocarbon group) is a non-cyclic hydrocarbon group having 14 to 30 carbon atoms (linear or branched hydrocarbon group, for example, an alkyl group) and a cyclic hydrocarbon group having 4 to 30 carbon atoms. (For example, a saturated or unsaturated monocyclic group, polycyclic group, bridging ring group) is preferable.

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

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

The halogenated olefin monomer (b1-2) does not have a fluorine atom.
The halogenated olefin monomer may be an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms, particularly 2 to 5 carbon atoms having a chlorine atom of 1 to 5 carbon atoms. Preferred specific examples of the halogenated olefin monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide and vinylidene halides such as vinylidene chloride, vinylidene bromide and vinylidene iodide. Vinyl chloride and vinylidene chloride are preferable because they have high water and oil repellency (particularly, durability of 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 fluorine-containing polymer can impart good antifouling property and water-repellent and oil-repellent property.

Further, the fluorine-containing copolymer of the present invention can be a copolymer containing another monomer (c) as a constituent unit, if necessary, and the other monomer (c) is preferable. It is a non-fluorocrosslinkable monomer and is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer may be a fluorine-free compound having at least one reactive group and / or an olefinic carbon-carbon double bond (preferably a (meth) acrylate group). The non-fluorinated 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, for example, a hydroxyl group, durability of antifouling property and water-repellent oil-repellent property can be imparted.

The non-fluorine crosslinkable monomer may be a mono (meth) acrylate, a di (meth) acrylate or a mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer may be a di (meth) acrylate.

One example of a non-fluorinated crosslinkable monomer is a vinyl monomer having a hydroxyl group (particularly, a (meth) acrylate monomer).
Examples of the non-fluorinated crosslinkable monomer include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2,3-dihydroxypropyl (meth) acrylate. ) Acrylate, 4-Hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, monochloroacetate, vinyl methacrylate, glycidyl (Meta) 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. Is exemplified, but the present invention is not limited to these.

In addition, the non-fluorine crosslinkable monomer may be an isocyanato acrylate monomer or the like.
Specific examples of the isocyanatoacrylate monomer are 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, and 2-isocyanatoethyl (meth) acrylate. 2-Butanone oxime adduct, 2-Isocyanatoethyl (meth) acrylate pyrazole adduct, 2-Isocyanatoethyl (meth) acrylate 3,5-dimethylpyrazole adduct, 2-Isocyanatoethyl (meth) acrylate 3-Methylpyrazole adduct, 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, 2-butanone oxime adduct of 4-isocyanatobutyl (meth) acrylate, pyrazole adduct of 4-isocyanatobutyl (meth) acrylate, 3, of 4-isocyanatobutyl (meth) acrylate These include 5-dimethylpyrazole adduct, 3-methylpyrazole adduct of 4-isocyanatobutyl (meth) acrylate, and ε-caprolactam adduct of 4-isocyanatobutyl (meth) acrylate.

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 the monomer (a) to the monomer (b) is 20:80 to 80:20, 30:70 to 70:30, for example, 35:60 to 65:35. It may be there.

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: It may be 15, preferably 30:65: 5 to 70:15:15, for example 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 with respect to 100 parts by weight of the total of the monomer (a) and the monomer (b). May be 5 to 15, for example 7 to 12 parts by weight.

As the fluorine-containing copolymer, one polymerized by a known method using a polymerization initiator, a solvent, and if necessary, a chain transfer agent can be used. The fluorine-containing copolymer can be produced by solution polymerization in an organic solvent, emulsion polymerization in water, or the like. The fluorine-containing copolymer can be obtained by removing the liquid medium (by distillation or the like) from the polymerization mixture containing the liquid medium (organic solvent or water) obtained by the 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 by weight, for example, 99.5: 0.5 to 90:10, and further 99: 1. It may be ~ 95: 5. With this weight ratio, the performance required for the fluorine-containing copolymer and the sealing material (particularly, antifouling property and water-repellent and oil-repellent property) can be exhibited.

In the present invention, the method for mixing the sealing material and the fluorine-containing copolymer may be a one-component type in which a mixture obtained by previously mixing the sealing material and the fluorine-containing copolymer is applied, or a group based on the sealing material. It may be any of the two-component forms having the material and the curing agent containing a fluorine-containing copolymer and mixing immediately before use. When the curing agent contains a fluorine-containing copolymer, an organic solvent such as ethyl acetate, butyl acetate, toluene, or xylene may be used as the solvent.

The one-component type sealing material can be produced by mixing the sealing material and the fluorine-containing copolymer.

The present invention also comprises filling the gaps in the interior or exterior materials of civil engineering, construction, or automobiles with the above composition, and then curing the composition to form a sealant. It also provides a method.

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

Contact angle measurements (room temperature (25 ° C.) and droplets 2 μl) were performed with water- and oil-repellent water and n-hexadecane (HD).

Antifouling property The following antifouling test solution is prepared, 20 ml of the antifouling test solution is placed on a coating film formed on a plate from a sealant and a fluorine-containing copolymer, and dried in an oven at 60 ° C. for 1 hour. After the water was sufficiently dried, the degree of residual stain when the plate was tilted 90 degrees and the dried antifouling test solution was wiped off with a cloth was visually evaluated.
Kanto Loam: A liquid obtained by mixing 8 types of JIS Z8901 test powder (Kanto Loam layer) with a particle size of 8 μm and water at a weight ratio of 1: 2.
Yellow Ocher: JSTM 1 with (Construction Materials Testing Center Standard) pigments for synthesis ocher _(SiO 2 54%) and water weight ratio: mixed liquid at 2.
Carbon black: A liquid obtained by mixing 12 kinds of JIS Z9801 test powders (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: Some dirt remains, but it is wiped off relatively cleanly.
X: Dirt cannot be wiped off at all.

A coating film formed on the plate from the detergency sealant and the fluorine-containing copolymer was attached to the wall surface of the drainage port where domestic wastewater is discharged, and an exposure test was conducted for one month. After the test, the plate was removed and washed with a commercially available household cleaner and sponge. ^{The L *} value, a ^* value, and b ^* value were measured with a D65 light source using a color difference meter before and after cleaning, and the color difference (ΔE ^* ) before and after the test was calculated.

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 monomer and non-fluorine-containing monomer) shown in Table 1 with 100 parts by weight of isopropyl alcohol (IPA) and polymerizing them. Then, the organic solvent (IPA) was removed by distillation to obtain a massive fluorine-containing copolymer. The monomer composition of the fluorine-containing copolymer was almost the same as the composition of the charged monomer.

Examples 1 to 15 and Comparative Examples 1 to 7
The fluorine-containing copolymers obtained in Polymer Examples 1 to 9 and Comparative Polymer Examples 1 to 3 were mixed with a silicone-based sealing material as shown in Table 2. At that time, Polymer Examples 1 to 9 and Comparative Polymer Examples 1 to 3 contained 10 parts by weight of ethyl acetate added to the parts by weight shown in Table 2 and mixed with the sealing material. A fluorine sealant composition was obtained.
This composition was applied onto a glass plate with an applicator, dried at room temperature for 24 hours, and then evaluated for contact angle and antifouling property. The results are shown in Table 3.
In addition, Examples 11 to 13 and Example 15 are reference examples (that is, "Examples 11 to 13 (reference)" and "Example 15 (reference)") that are not included in the present invention.

C6SFA: CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) _2- C ₆ F ₁₃
C6SFMA: CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) _2- C ₆ F ₁₃
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- H n = 2
EOA-2: CH ₂ = C (-H) -C (= O) -O- (CH ₂ CH ₂ O) _n- H n = 10
2-HEA: 2-Hydroxyethyl acrylate Silicone-based (45): Oxime-based silicone (Sealant 45 manufactured by Shin-Etsu Silicone Co., Ltd.)
Silicone-based (SE): Contains dimethyldichlorosilane-treated silica, methyltri (methylethylketooxime) silane and vinyltri (methylethylketooxime) silane as main components (SE-5010 manufactured by Toray Dow Corning).
Silicone-based (C): Oxime-based silicone (8000 manufactured by Cemedine Co., Ltd.)
Silicone-based (S): Modified silicone-based sealant (MSC1-22 manufactured by Sharp Industries, Ltd.)
Silicone type (70): Two-component aminoxy type silicone sealant (Shinetsu Silicone Co., Ltd. sealant 70) Main agent, hardener Silicone type (SEII): Two-component alcohol type silicone sealant (Toredau Co., Ltd. SE990F) Main agent, hardener Silicone System (P): Two-component modified silicone sealant (POS seal type II manufactured by Cemedyne) Main agent, curing agent Acrylic system: Aqueous acrylic sealant

Examples 16-19 and Comparative Examples 8-10
The fluorine-containing copolymers obtained in Polymer Examples 2 and 3 and Comparative Polymer Examples 1 and 2 were mixed with an acrylic sealant as shown in Table 2. At that time, Polymer Examples 2 to 3 and Comparative Polymer Examples 1 to 2 were mixed by adding 10 parts by weight of ethyl acetate to the parts by weight shown in Table 4, and mixed with a sealing material to contain the mixture. A fluorine sealant composition was obtained.
This composition was applied onto a glass plate with an applicator, dried at room temperature for 24 hours, and then evaluated for contact angle and antifouling property. The results are shown in Table 5.

Examples 20-23 and Comparative Example 11
The fluorine-containing copolymers obtained in Polymer Examples 2 and 3 were mixed with a silicone-based sealant as shown in Table 6. At that time, in Examples 2 to 3 of the polymer, 10 parts by weight of ethyl acetate was added to the parts by weight shown in Table 6 and mixed, and the mixture was mixed with the sealing material to obtain a fluorine-containing sealing material composition. rice field.
This composition was applied onto a PET film with an applicator, dried at room temperature for 24 hours, and then the detergency was evaluated. The results are shown in Table 7.

Examples 24-27 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-based sealing material to obtain a fluorine-containing sealing material composition.
This composition was applied onto a glass plate with an applicator, dried at room temperature for 24 hours, and then evaluated for contact angle and antifouling property. The results are shown in Table 9.

Examples 28-31 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 a sealant curing agent as shown in Table 10 to obtain a fluorine-containing polymer-containing curing agent. A fluorine-containing sealing material composition was obtained by mixing 4 parts by weight of the curing agent and 100 parts by weight of the sealing material main agent as shown in Table 10.
This composition was applied onto a glass plate with an applicator, dried at room temperature for 24 hours, and then evaluated for antifouling property. The results are shown in Table 11.

The sealing material composition of the present invention is excellent in antifouling property without lowering the water repellency of the sealing material. It is also possible to impart oil repellency to the sealing material. The sealing material composition of the present invention is useful as a sealing material used for interior materials or exterior materials of civil engineering, construction (for example, kitchens and washrooms, particularly sinks, and bathrooms), automobiles, and the like.

Claims (13)

A sealing material composition containing (1) a sealing material and (2) a fluorine-containing copolymer.
The fluorine-containing copolymer (2)
Equation (a):
CH ₂ = C (-X) -C (= O) -YZ-Rf
[In the formula, X is a hydrogen atom, a methyl group or a halogen atom,
Y is -O-
Z is a direct bond or a linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group .
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 the formula (b):
CH ₂ = CA ²¹ -C (= O) -OA ²²
[In the formula, A ²¹ is a hydrogen atom or a methyl group,
A ²² is an acyclic hydrocarbon group having 14 to 30 carbon atoms . ]
In comprising a structural unit derived from non-fluorinated monomers represented,
A sealant composition in which the fluorine-containing copolymer (2) does not have a polyoxyalkylene group. The sealant composition according to claim 1, wherein X is a methyl group in the fluorine-containing monomer (a). The sealant composition according to claim 1 or 2, wherein the non-fluorine monomer (b) is stearyl (meth) acrylate or behenyl (meth) acrylate. The fluorine-containing copolymer further contains a non-fluorinated crosslinkable monomer (c) as a constituent 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 claims 1 to 3, which is 1 to 30 parts by weight with respect to 100 parts by weight. The sealant composition according to claim 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 is at least one sealant selected from a silicone-based sealant, a urethane-based sealant, and an acrylic-based sealant. The sealing material composition according to any one of claims 1 to 7, which is a one-component form containing a mixture of a sealing material and a fluorine-containing polymer. The sealing according to any one of claims 1 to 8, wherein the sealing material composition is a two-component form containing a main agent and a curing agent, the main agent contains a sealing material, and the curing agent contains a fluorine-containing copolymer. Material composition. The sealing material composition according to any one of claims 1 to 9, wherein the weight ratio of the sealing material to the fluorine-containing copolymer 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 the monomer (a) to the monomer (b) is 20:80 to 80:20. The method for producing a sealing material 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 with a sealing material. The sealant composition according to any one of claims 1 to 11 is filled in the boundary portion of the interior material or exterior material of civil engineering, construction, or automobile, and then the sealant composition is cured to obtain a sealant. Boundary sealing methods, including forming.