CN107099151A - Encapulant composition - Google Patents
Encapulant composition Download PDFInfo
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- CN107099151A CN107099151A CN201710035741.7A CN201710035741A CN107099151A CN 107099151 A CN107099151 A CN 107099151A CN 201710035741 A CN201710035741 A CN 201710035741A CN 107099151 A CN107099151 A CN 107099151A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Sealing Material Composition (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The problem of the present invention is：There is provided and show water-repellent oil-repellent and also performance soil resistance, the Encapulant composition containing encapsulant and fluorinated copolymer by mixing specific fluorinated copolymer in the encapsulant for the interior material of building, building, automobile etc. or outer exterior material.The method for solving problem is：The Encapulant composition contains (1) encapsulant and (2) fluorinated copolymer, construction unit that fluorinated copolymer (2) contains the fluorochemical monomer for being derived from fluoroalkyl that (a) has carbon number 4~6 and have from (b) alkyl non-fluorine monomer construction unit.
Description
Technical field
The present invention relates to a kind of Encapulant composition, the Encapulant composition contains：Containing with specific fluothane
The fluorinated copolymer of the fluorochemical monomer of base；And encapsulant, its soil resistance and water-repellent oil-repellent are excellent.Encapulant composition energy
Enough interior materials for building, building (for example, kitchen and washroom, particularly lavatory basin and bathroom), automobile etc. or
Used in the encapsulant purposes of outer exterior material.
Background technology
For being coated on the exterior part and inner-decoration component of building etc., such as concrete, timber, wallboard, aluminium alloy system
The boundary portion of frame etc., is prevented from its gap encroached water and dust etc., and improves the purpose of air-tightness, usually using sealing material
Material.Encapsulant has the various species such as silicon-type, polyurethane series, acrylic acid series, can be made according to respective purposes
With.Operationally with surface protection from the viewpoint of, various additives are added in these encapsulants, by compared with
After long-time, these additives will ooze out, thus exist attachment spot or from the resin as substrate in nature from the point of view of hold
The problem of easily attachment spot is such.
In order to solve the problem, various technologies are had been presented at present.
For example, in Japanese Unexamined Patent Publication 2010-275481 publications, it is proposed that by the way that the fluorine comprising perfluoroalkyl will be contained
It is that the coating composition of surfactant is coated on the surface of encapsulant and assigns the technology of soil resistance.But, in this method
In, there is operational problem as the time and time on the surface for needing further to be coated on encapsulant.In addition, sometimes
For the purpose on protection surface, containing additive as antiseptic and antimycotic agent in encapsulant, but in encapsulant
When implementing coating on surface, the problem of its effect is such can not be played by existing.
In addition, in Japanese Unexamined Patent Publication 2008-291159 publications, it is proposed that add and assign in Encapulant composition
The hydrophilic technology that soil resistance is assigned containing the surfactant of perfluoroalkyl.In the method, although pin can be assigned
To the soil resistance of coal dust and soil, but it is due to that encapsulant is hydrophilic, therefore material as mould and microorganism is easy
Surface is attached to, the problem of as a result there is pollution sealant surface.
In Japanese Unexamined Patent Publication 2001-234157 publications and Japanese Unexamined Patent Publication 2001-81330 publications, it is proposed that contain
The technology of following copolymer and encapsulant and the excellent solidification compound of soil resistance, the copolymer contains comprising average carbon
Atomicity is the monomer and photo-curable monomer of 9 perfluoroalkyl.In the art, soil resistance is also improved, but until applying
The measure of the progress of suppression photocuring in advance is needed during the keeping of cloth.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-275481 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-291159 publications
Patent document 3：Japanese Unexamined Patent Publication 2001-234157 publications
Patent document 4：Japanese Unexamined Patent Publication 2001-81330 publications
The content of the invention
Invent problem to be solved
It is an object of the invention to：There is provided by the interior material for building, building, automobile etc. or outer exterior material
Specific fluoropolymer is mixed in encapsulant and show water-repellent oil-repellent and also performance soil resistance, contain encapsulant
With the composition of fluoropolymer.
Method for solving problem
The Encapulant composition of the present invention contains：
(1) encapsulant；With
(2) fluoropolymer of the construction unit from fluorochemical monomer (a) and the construction unit from non-fluorine monomer (b) is contained
Thing.
More specifically, Encapulant composition of the invention contains：
Encapsulant；With
Containing fluorochemical monomer (a) and fluorinated copolymer of the non-fluorine monomer (b) as construction unit,
Fluorochemical monomer (a)：The fluorochemical monomer of fluoroalkyl with carbon number 4~6；With
Non-fluorine monomer (b)：Non-fluorine monomer with non-annularity alkyl or cyclic hydrocarbon group.
The fluorinated copolymer of the present invention is in addition to monomer (a) and (b), as needed, can also containing monomer (a) and
(b) other monomers (c) beyond are used as construction unit.
The effect of invention
Using the present invention, the water-repellancy for not reducing encapsulant is resulted in and the excellent encapsulant combination of soil resistance
Thing.Encapulant composition has excellent anti-attachment and detachment (cleaning for the spot such as carbon (coal dust), sand and loess
Property).Oiliness is dialled in addition, can also be assigned to encapsulant.Furthermore, Encapulant composition also assigns soil resistance and dialled
The durability and antibiotic property of water-repellent oil and mould proof property.
Encapulant composition is in the encapsulant for the interior material of building, building, automobile etc. or outer exterior material
It is useful.
More specifically, because the fluoropolymer of encapsulant and performance soil resistance is applicable as mixture, therefore not
Can occur because surface apply and do not play encapsulant effect it is such the problem of.In addition, it is not necessary that fluoropolymer is fitted
Operation for the surface of encapsulant.In addition, encapsulant used in the present invention is hydrophobic, therefore for a variety of dirts
Stain plays soil resistance, and additionally by the water-repellent oil-repellent using fluoropolymer, mould and microorganism are difficult to be attached to sealing material
The surface of material.
Embodiment
(1) encapsulant
So-called encapsulant refers to, in the outer exterior material and interior material of building, by concrete and wallboard, ceramic tile
During such combination of materials, for preventing from being mixed into the purpose of extraneous gas and water and protection structure thing from its boundary portion, it is coated on
The material of the boundary portion of the outer exterior material of combination and interior material.In addition, however it is not limited to building, can also be for same
Purpose is used in the interior material of automobile and aluminium alloy frame etc..
As the example of encapsulant, there are silicon-type, polysulfide, polyurethane series, acrylic acid series, SBR systems, butyl
Rubber series, oiliness pointing system, encapsulant of acroleic acid polyurethane system etc..In the sealing of silicon-type and polysulfide
In material, in order to further improve protectiveness, also as the encapsulant of modified organic silicon system and modified polysulfide compound system
Material.
In the present invention, it is preferred to silicon-type, modified organic silicon system, the encapsulant of polyurethane series and acrylic acid series.Enter
The encapsulant of the preferred silicon-type of one step and the encapsulant of modified organic silicon system.Encapsulant can contain organic solvent,
But it is preferred that without organic solvent.Encapsulant is typically free of water.Encapsulant is for example consolidated using the moisture in air after coating
Change.
Silicon-type or the encapsulant of modified organic silicon system contain the polymerization with siloxy (being usually siloxy group)
Thing (polymer containing siloxy).Polymer containing siloxy generally has AmSiO(4-m)/2[in formula, A is hydrogen atom, halogen
The organic group of atom or monovalence, m is 0~3.] shown in construction unit.Polymer containing siloxy has a functionality silicon
Epoxide (A3SiO0.5) and two functionality siloxy units (A2SiO), there can be trifunctional's siloxy units as needed
(ASiO1.5) (there can also be tetrafunctional siloxy units (SiO as needed2)).A bases can be carbon number 1~20
Alkyl, for example, alkyl.Or, A bases are reactive group, or can be the group with reactive group.Reactive base
The example of group is halogen atom (for example, chlorine atom, bromine atoms, iodine atom), amino, epoxy radicals, carboxyl, methanol-based, sulfydryl, ammonia oxygen
Base, hydroxyl, alkoxy and oximido.Reactive group is preferably hydroxyl (OH yls), alkoxy (for example, methoxyl group) and oximido (example
Such as, the ketoxime base of methyl ethyl ketone oximido etc.).
In the encapsulant of modified organic silicon system, the polymer containing siloxy is that in addition to siloxy, also have
Construction unit, the polymer (alkylidene of such as (poly-) oxyalkylene group, amide groups, imide or alkylidene beyond siloxy
Carbon number be, for example, 1~5, specifically for 2 or 3.).The encapsulant of modified organic silicon system for example can be in organic polymer
The end of (for example, polyethers) has (poly-) organosiloxane base (for example, a functionality siloxy (A3SiO0.5))。
The encapsulant of silicon-type contains silane compound.Silane compound generally has hydrolization group.It is water-disintegrable
The concrete example of group is oximido, alkoxy, alkoxy substituted alkoxy, acyloxy, alkenyloxy group, ketoxime base, aminooxy group and acid amides
Base.The typical example of silane compound is the silane compound (organosilicon of oxime type or de-oxime type) of oxime type or de-oxime type.Oxime type or
Oxime (for example, methyl ethyl ketone oxime) is removed when the organosilicon of de-oxime type solidifies after coating and is solidified.The organosilicon of oxime type contains
Silane compound with oximido.The example of silane compound with oximido is (methyl ethyl ketone oxime) silane of methyl three and second
Alkenyl three (methyl ethyl ketone oxime) silane.
In addition, as other solidification systems, there is organosilicon, acetone type, acetic acid type, the aminooxy group of ethanol-type or de- ethanol-type
The encapsulant of type.These are solidified when being the effect of performance after coating same with oxime type by removing ethanol, acetone, acetic acid etc.
Encapsulant.
The encapsulant of silicon-type can also contain fumed silica powder, example in addition to silane compound
As dimethyldichlorosilane handles SiO 2 powder.
The example of polyurethane series encapsulant is polyol compound (polyurethane prepolymer) with being used as the main of curing agent
Isocyanates (particularly polyisocyanates) reaction of composition and moisture in the reaction-curable polyurethane and air that solidify with
Isocyanates (particularly polyisocyanates) reaction and from the moisture-curable polyurethane of surface cure.Polyol compound has
The hydroxyl of more than 2.The example of polyol compound is, for example, PPG (polyoxyalkylene polylol), polyester polyols
Alcohol, their polyols blend etc..Polyisocyanate compound has the NCO of more than 2 in intramolecular.Many isocyanides
The example of ester compound is aromatic polyisocyanate, NCO and the fat that NCO is combined with aromatic hydrocarbon
The alicyclic polyisocyanates that aliphatic polyisocyante, the NCO of race's hydrocarbon combination are combined with ester ring type hydrocarbon.
The encapsulant of acrylic acid series is typically that, using acrylate copolymer as substrate, what is contained after coating by evaporating is molten
Agent and the encapsulant of dry solidification.
The encapsulant of acrylic acid series contains acrylate copolymer.Acrylate copolymer is using acrylate monomer as repetition
The polymer of unit.Acrylate monomer can be (methyl) acrylate, such as (methyl) alkyl acrylate (carbon of alkyl
Atomicity be 1~30)；With oxyalkylene group, (number of oxyalkylene group is 1~30, for example, 1~(methyl) acrylate 25)
Deng.The concrete example of acrylate copolymer is alkyl acrylate copolymer, acrylonitrile-acrylic acid alkyl ester copolymer, propylene
Acid-methacrylic acid-acrylic acid alkyl ester copolymer, acrylonitrile-acrylic acid-alkyl acrylate copolymer, benzene second
Alkene-alkyl acrylate copolymer, styrene-t Arrcostab-alkyl acrylate copolymer, styrene-
Acrylonitrile-acrylic acid alkyl ester copolymer and styrene-acrylonitrile-alkyl methacrylate-alkyl acrylate are common
Polymers.
In the present invention, encapsulant can use commercially available product.For example, the situation of silicon-type has Toray Dow
SE5007, SH780, SH5010, SE960, SE990F, SE930, SE931, SE936, SE797 of Corning company systems etc.；Letter
The more Sealant 45 of organosilicon company system, Sealant 4588, Sealant 4515, Sealant 70, Sealant 701
Deng；The SR Seal S70 of Konishi company systems, SR Seal NB50, Bond Silicon Caulk, Bond MS Seal,
Bond MS Seal NB, Bond Hind Seal etc.；The Sharpie Silicone S of chemical industrial company of Sharp,
Modified Silicone M etc.；Cemedine company systems 8000,8060,8070,8051N, POS Seal, POS Seal
Type II, S750NB etc..In addition, the situation of acrylic acid series has the Sharpie Paintable of chemical industrial company of Sharp
Acrylic Caulk of Acrylic, Konishi company system etc..
On encapsulant, these utilization is not limited to, is also useful for commercially available product other than the above.
On encapsulant, coordinate with the effect required by the position that uses, filler, antiseptic, anti-mildew can be included
Microbial inoculum, colouring agent, pigment, preservative agent, plasticizer, weatherability modifying agent, age resister (ultra-violet absorber and heat stabilizer
Deng), curing catalysts, antitack agent, solvent etc..
As curing catalysts (curing agent), for example, it can enumerate tin octoate, dibutyl tin laurate, sad dibutyl
Tin, Dibutyltin oxide, dioctyl tin oxide, double triethoxy silicic acid dibutyl tins, bis-acetylacetonate dibutyl tin, it is double-
Tin series catalysts illustrated in the organo-tin compound of 2 ethyl hexanoic acid dibutyl tin, diacetyl dibutyl tin etc.；Dodecyl amine
Deng organic amine compound illustrated in amine system catalyst.These compounds be can be used alone, or two or more is fitted
When being applied in combination.
Curing catalysts can (weight be than the usually ﹕ of 10 ﹕ 90~90 for the mixture of tin series catalysts and amine system catalyst
10).The solidification facilitation effect of the mixture is high.
The Encapulant composition of the present invention can be one pack system (a liquid type) or bi-component (two-liquid type).In one pack system
In the case of, encapsulant and fluorinated copolymer can be mixed in advance, can be by curing agent and fluorine-containing in addition, in bi-component
Copolymer is mixed.
Mixture of the Encapulant composition of one pack system comprising encapsulant and fluoropolymer.On the close of one pack system
Closure material composition, itself individually solidifies after coating, therefore there is maneuverable advantage.
On the other hand, the Encapulant composition of bi-component contains the host comprising encapsulant and comprising fluoropolymer
Curing agent.On the Encapulant composition of bi-component, do not solidify when encapsulant is independent, by with being used as second composition
It is coated and solidifies after curing agent mixing.The Encapulant composition of bi-component needs the operational of two kinds of compositions of mixing
Time, but with the such advantage more excellent than one pack system of the protectiveness after coating.
In the case of bi-component, in curing agent, the composition that encapsulant can be solidified by being generally mixed with (can be with
Composition, and/or the curing catalysts of promotion encapsulant solidification that encapsulant solidifies together).Curing agent can contain organic
Solvent.
In Encapulant composition, the particularly Encapulant composition of one pack system, fluoropolymer is preferably by molten
Liquid polymerize and manufactured.
Encapsulant can be single, or can also be combination of more than two kinds.
(2) fluoropolymer
Fluoropolymer is containing fluorochemical monomer (a) and copolymer of the non-fluorine monomer (b) as construction unit.Fluorochemical monomer
(a) it is the monomer of the fluoroalkyl with carbon number 4~6, non-fluorine monomer (b) is the alkyl with non-annularity, and/or can contain
There is the monomer of the alkyl of the ring-type of nitrogen, oxygen or sulphur atom.Non-fluorine monomer (b) is preferably the non-annularity with carbon number more than 14
The non-crosslinked property monomer of non-fluorine of alkyl, and/or cyclic hydrocarbon group.In addition, as needed, or contain other monomers (c)
It is used as the copolymer of construction unit.
Fluorochemical monomer (a) is formula：CH2Compound shown in=C (- X)-C (=O)-Y-Z-Rf.
[in formula, X be hydrogen atom, the organic group or halogen atom of monovalence,
Y is-O- or-NH-,
Z is the organic group of Direct Bonding or divalence,
Rf is the perfluoroalkyl of carbon number 4~6.]
X is, for example, alkyl, the CFX of hydrogen atom, methyl, halogen, the straight-chain of carbon number 2~21 or branched1X2Base
(wherein, X1And X2For hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom.), cyano group, the straight-chain of carbon number 1~21
Or fluoroalkyl, substituted or non-substituted benzyl, the substituted or non-substituted phenyl of branched.
In the fluorinated copolymer of the present invention, X is preferably hydrogen atom, methyl, fluorine atom or chlorine atom.X is further preferred
For hydrogen atom or methyl, specifically for methyl.
Y is preferably-O-.
Z is, for example, Direct Bonding；The alkylidene of the straight-chain of carbon number 1~20 or the alkylidene of branched [for example,
Formula-(CH2)x- (in formula, x is 1~10.) shown in group]；Or formula-SO2N(R1)R2- or formula-CON (R1)R2- institute
Show group (in formula, R1For the alkyl of carbon number 1~10, R2For the alkylidene or side chain of the straight-chain of carbon number 1~10
The alkylidene of shape.)；Or formula-CH2CH(OR3)CH2- (in formula, R3Represent the acyl group of hydrogen atom or carbon number 1~10
(for example, formoxyl or acetyl group etc.).) shown in group；Or formula-Ar- (CH2)r- (in formula, Ar is to be had according to needs
The arlydene of substituent, r is 0~10.) shown in group；Or-(CH2)m- SO2- (CH2)n- base or-(CH2)m-
S- (CH2)n(wherein, m is that 1~10, n is 0~10 to-base.).
In the fluorinated copolymer of the present invention, Z is preferably Direct Bonding, the alkylidene of carbon number 1~20 ,-SO2N
(R1)R2-.
Rf is preferably perfluoroalkyl, but it is also possible to be the fluoroalkyl with hydrogen atom.Rf carbon number is 4~6, for example
For 4 or 6.Rf carbon number is particularly preferably 6.Rf example is-CF2CF2CF2CF3,-CF2CF(CF3)2,-C
(CF3)3,-(CF2)5CF3,-(CF2)3CF(CF3)2Deng.
As the concrete example of fluorochemical monomer (a), for example, following compound can be illustrated, but be not limited to these chemical combination
Thing.
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
In these compounds, preferably CH2=CH-C (=O)-O- (CH2)2- Rf, CH2=C (- CH3)-C (=O)-
O- (CH2)2- Rf.
Non-fluorine monomer (b) can be the non-crosslinked property monomer (b1) of non-fluorine.
The concrete example of the non-crosslinked property monomer (b1) of non-fluorine can be formula：CH2Compound shown in=CA-T.
[in formula, A is the halogen atom (for example, chlorine atom, bromine atoms and iodine atom) beyond hydrogen atom, methyl or fluorine atom,
T is hydrogen atom；Halogen atom (for example, chlorine atom, bromine atoms and iodine atom) beyond fluorine atom；Non-annularity or ring-type
Carbon number 1~30, preferably 14~30 alkyl；Or non-annularity or the carbon number 1~30 of ring-type with ester bond, preferably
14~30 alkyl.]
The example of the alkyl of non-annularity or the carbon number of ring-type 1~30 be carbon number 1~30, preferably 14~30 it is straight
The aliphatic alkyl of the saturation or unsaturation (for example, ethene is unsaturated) of chain or branched；Carbon number 4~30, preferably 6
~30, the cyclic aliphatic group of such as 14~30 saturation or unsaturation (for example, ethene is unsaturated)；Carbon number 6~
30th, preferably 14~30 aromatic hydrocarbon group；Carbon number 7~30, preferably 14~30 aromatic-aliphatic hydrocarbyl group.
The example of the organic group of the carbon number 1~30 of non-annularity or ring-type with ester bond is-C (=O)-O-Q
(wherein, Q is carbon number 1~30, the saturation of preferably 14~30 straight-chain or branched or insatiable hunger with-O-C (=O)-Q
The aliphatic alkyl of (for example, ethene is unsaturated)；Carbon number 4~30, preferably 14~30 saturation or unsaturation (example
Such as, ethene is unsaturated) cyclic aliphatic group；Carbon number 6~30, preferably 14~30 aromatic hydrocarbon group；Carbon is former
Subnumber 7~30, preferably 14~30 aromatic-aliphatic hydrocarbyl group).
The non-crosslinked property monomer of other non-fluorine can also be (methyl) acrylate monomer (b1-1) and alkenyl halide monomer
(b1-2) etc..
The concrete example of (methyl) acrylate monomer (b1-1) can be CH2=CA21- C (=O)-O-A22Shown
Compound.
[in formula, A21For the alkyl of hydrogen atom, carbon number 1~30, preferably 14~30 straight-chain or branched, cyano group,
The organic group of the monovalence of halogen atom beyond substituted or non-substituted benzyl, substituted or non-substituted phenyl or fluorine atom,
A22For carbon number 1~30, preferably 14~30 alkyl.]
A21Preferably alkyl, the cyanogen of hydrogen atom, methyl, carbon number 2~30, preferably 14~30 straight-chain or branched
Base, substituted or non-substituted benzyl, substituted or non-substituted phenyl or chloro.
A22For carbon number 1~30, preferably 4~30, more preferably 6~30, particularly preferred 14~30 alkyl.A22(hydrocarbon
Base) be preferably carbon number 14~30 non-annularity alkyl (alkyl of straight-chain or branched, such as alkyl) and carbon number 4
~30 (for example, saturation or undersaturated monocyclic groups, polycyclic moiety, bridging cyclic group) containing cyclic hydrocarbon group.
The concrete example of (methyl) acrylate monomer with non-annularity alkyl is (methyl) ethyl acrylate, (methyl) third
Olefin(e) acid butyl ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) lauryl ester, (methyl) acrylic acid hexadecane ester,
(methyl) octadecyl ester, (methyl) behenyl ester etc..In (methyl) acrylic acid with non-annularity alkyl
In ester monomer, preferably (methyl) octadecyl ester, (methyl) behenyl ester.
Concrete example with (methyl) acrylate monomer containing cyclic hydrocarbon group is (methyl) cyclohexyl acrylate, (first
Base) t-butylcyclohexyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, the ring of (methyl) acrylic acid two
Pentyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid bicyclopentyl epoxide ethyl ester, the ring penta of (methyl) acrylic acid three
Ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid -2- methyl -2- Buddha's warrior attendants alkyl ester, (methyl) acrylic acid -2-
Ethyl -2- Buddha's warrior attendant alkyl esters etc..
Alkenyl halide monomer (b1-2) does not have fluorine atom.
Alkenyl halide monomer can be the carbon number 2~20 replaced by the chlorine atom of 1~10, bromine atoms or iodine atom
Alkene.Alkenyl halide monomer is preferably carbon number 2~20, specifically for the carbon number 2~5 with 1~5 chlorine atom
Alkene.The preferred concrete example of alkenyl halide monomer is vinyl halides, such as vinyl chloride, bromine ethene, iodoethylene；Vinylidene halide,
Such as vinylidene chloride, inclined dibromoethylene, inclined acetylene diiodide.Because water-repellent oil-repellent (the particularly durability of water-repellent oil-repellent)
Improve, preferably vinyl chloride and vinylidene chloride.
Fluorinated copolymer does not preferably have polyoxyalkylenes, therefore non-fluorine monomer (b) does not preferably have polyoxyalkylenes.By
This, soil resistance and water-repellent oil-repellent that can be good to fluoropolymer imparting.
In addition, as needed, fluorinated copolymer of the invention can be to be used as construction unit containing other monomers (c)
Copolymer, other monomers (c) are preferably non-fluorine cross-linkable monomer, for the monomer without fluorine atom.Non-fluorine cross-linkable monomer can
Think with least one reactive group and/or alkene carbon-to-carbon double bond (preferably (methyl) is acrylate-based) and not fluorine-containing
Compound.Non-fluorine cross-linkable monomer can be with least two alkene carbon-to-carbon double bond (preferred (methyl) acrylate
Base) compound, or the compound with least one alkene carbon-to-carbon double bond and at least one reactive group.Reactivity
The example of group is hydroxyl, epoxy radicals, chloromethyl, blocked isocyanate base, amino, carboxyl, glycidyl etc..
By the way that with reactive group, such as hydroxyl, soil resistance and the durability of water-repellent oil-repellent can be assigned.
Non-fluorine cross-linkable monomer can be list (methyl) acrylate with reactive group, two (methyl) acrylate
Or single (methyl) acrylamide.Or, non-fluorine cross-linkable monomer can be two (methyl) acrylate.
1 example of non-fluorine cross-linkable monomer is the vinyl monomer with hydroxyl (specifically for (methyl) acrylate list
Body).
As non-fluorine cross-linkable monomer, for example, it can illustrate two acetone (methyl) acrylamide, N- methylols (methyl) third
Acrylamide, (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2,3- dihydroxy third
Ester, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 3- chlorine-2-hydroxyls propyl ester, (methyl) acrylic acid 2- acetyl
Acetoxyethyl, butadiene, isoprene, chlorobutadiene, monochloro acetic acid vinyl acetate, vinyl methacrylate, (methyl)
Glycidyl acrylate, two (methyl) acrylic acid 1,4- butanediol esters, two (methyl) acrylic acid 1,6-HD esters, two
(methyl) acrylic acid 1,9- nonanediols ester, two (methyl) acrylic acid DOPCPs etc., but it is not limited to these compounds.
Other non-fluorine cross-linkable monomers can be isocyanato acrylates monomer etc..
The concrete example of isocyanato acrylates monomer is 2- isocyanato-s (methyl) ethyl acrylate, 3- isocyanides
Acid group closes (methyl) propyl acrylate, 4- isocyanato-s (methyl) butyl acrylate, 2- isocyanato-s (methyl) propylene
2- diacetylmonoxime additions body, the pyrazoles addition body, the 2- isocyanos of 2- isocyanato-s (methyl) ethyl acrylate of acetoacetic ester
Close the 3,5- dimethyl pyrazole additions body, the 3- of 2- isocyanato-s (methyl) ethyl acrylate of (methyl) ethyl acrylate
Epsilon-caprolactams addition body, the 3- isocyanato-s of methylpyrazole addition body, 2- isocyanato-s (methyl) ethyl acrylate
The 2- diacetylmonoxime additions body of (methyl) propyl acrylate, the pyrazoles addition body of 3- isocyanato-s (methyl) propyl acrylate,
3,5- dimethyl pyrazole additions body, 3- isocyanato-s (methyl) propylene of 3- isocyanato-s (methyl) propyl acrylate
The 3- methylpyrazole additions body of propyl propionate, the epsilon-caprolactams addition body of 3- isocyanato-s (methyl) propyl acrylate,
2- diacetylmonoxime additions body, 4- isocyanato-s (methyl) butyl acrylate of 4- isocyanato-s (methyl) butyl acrylate
Pyrazoles addition body, the 3,5- dimethyl pyrazole additions body, 4- isocyanos of 4- isocyanato-s (methyl) butyl acrylate
Close the 3- methylpyrazole additions body of (methyl) butyl acrylate, 4- isocyanato-s (methyl) butyl acrylate ε-oneself in
Acid amides addition body etc..
In this manual, so-called " (methyl) acrylate ", refers to acrylate or methacrylate, so-called " (first
Base) acrylamide ", refer to acrylamide or Methacrylamide.
Monomer (a)~(c) can be each single, or can also be combination of more than two kinds.
Fluoropolymer can be single, or can also be combination of more than two kinds.
In fluorinated copolymer, the weight ratio of monomer (a) and monomer (b) can be the ﹕ 20 of 20 ﹕ 80~80, the ﹕ of 30 ﹕ 70~70
30, for example, 35 ﹕ 60~65 ﹕ 35.
In the fluorinated copolymer containing monomer (c), the weight ratio of monomer (a), monomer (b) and monomer (c) can be 20 ﹕
5~70 ﹕ of 75 ﹕, 5~80 ﹕ 5 ﹕ 15,65 ﹕ of preferably 30 ﹕ 15 ﹕ 15, the ﹕ 10 of 53 ﹕ of for example, 40 ﹕, 7~65 ﹕ 25.Or, monomer (c)
Total 100 parts by weight measured relative to monomer (a) and monomer (b) can be 1~30 parts by weight, preferably 3~20 parts by weight, more
Preferably 5~15, for example, 7~12 parts by weight.
Fluorinated copolymer can be used utilizes known side using polymerization initiator, solvent, chain-transferring agent as needed
The material that method is polymerized.Fluorinated copolymer can be made by the polymerisation in solution in organic solvent or emulsion polymerization in water etc.
Make.Fluorinated copolymer can be by from the polyblend containing liquid medium (organic solvent or water) obtained using polymerization
Remove liquid medium (by distillation etc.) and obtain.Fluorinated copolymer is not preferably aqueous.
On the molecular weight of fluorinated copolymer, for example, being converted being determined using GPC (gel permeation chromatography) with polystyrene
When, typically 1,000~1,000,000, specifically for 2,000~50,000.
The mixed proportion of encapsulant and fluorinated copolymer in composition can be for the ﹕ of 99.9 ﹕ 0.1~85 with weight ratio meter
15, for example, 99.5 ﹕ 0.5~90 ﹕ 10, are further the ﹕ 5 of 99 ﹕ 1~95.Using the weight ratio can play fluorinated copolymer and
Performance (particularly soil resistance and water-repellent oil-repellent) required by encapsulant.
In the present invention, the mixed method on encapsulant and fluorinated copolymer, can be that will be pre-mixed sealing material
Material and the one pack system that is coated of mixture obtained from fluorinated copolymer or with the base material using encapsulant as substrate and
Any of curing agent containing fluorinated copolymer, the bi-component mixed before it will use.For containing fluorine-containing
In the case of the curing agent of copolymer, the organic solvents such as ethyl acetate, butyl acetate, toluene, dimethylbenzene can be used as molten
Agent.
The encapsulant of one pack system can be manufactured by the way that encapsulant and fluorinated copolymer are mixed.
In addition, the present invention also provides the interior material for including that combinations of the above thing is filled in building, building or automobile etc.
Or the gap of outer exterior material, then make the encapsulating method in the gap for the step of said composition is solidified to form fluid sealant.
Embodiment
Hereinafter, embodiment is enumerated to illustrate details, but the present invention is not limited to these embodiments.
Physical property is measured as follows.
Water-repellancy and group oiliness
Contact angle determination (room temperature (25 DEG C) and μ l of drop 2) is carried out using water and hexadecane (HD).
Soil resistance
Following antifouling test liquid are made, are put on the film onboard formed by encapsulant and fluorinated copolymer anti-
Dirty experimental liquid 20ml, is dried 1 hour using baking box at 60 DEG C, after moisture is fully dried, and plate is tilted into 90 degree, cloth is utilized
Dried antifouling test liquid is wiped, visually the residual degree to spot now is evaluated.
Northeast loam：JIS Z8901 experiments is more mixed than 1 ﹕ 2 with weight with water with 8 kinds of 8 μm of (Northeast loam layer) particle diameters of powder
Liquid after conjunction.
Loess：By JSTM (building materials testing central standard) pigment synthesis loess (SiO254%) with water with weight than 1 ﹕ 2
Mixed liquid.
Carbon black：JIS Z9801 experiments is more mixed than 1 ﹕ 3 with weight with 12 kinds of powder (0.03~0.2 μm of carbon black, particle diameter) and water
Liquid after conjunction.
Metewand
○：Spot can be with wiped clean.
△：Spot is remained a little, but can be wiped and must be compared clean.
×：Spot is not wiped completely.
Cleaning
The film onboard formed by encapsulant and fluorinated copolymer is pasted onto to the discharge outlet of discharge household drain
On wall, implement the exposure test of 1 month.Plate is removed after experiment, is cleaned using commercially available home-use detergent and sponge.
D65 light sources are utilized to L using colour difference meter afterwards before cleaning*Value, a*Value, b*Value is measured, and calculates the aberration (Δ before and after experiment
E*)。
Polymer example 1~9 and comparative polymers example 1~3
Monomer (fluorochemical monomer and non-fluorine monomer) shown in table 1 is mixed with the parts by weight of isopropanol (IPA) 100, gathered
Close, thus manufacture the solution of fluorinated copolymer.Then, organic solvent (IPA) is removed by distillation, the fluorine-containing copolymerization of bulk is obtained
Thing.The composition of monomer of the monomer composition with loading in fluorinated copolymer is roughly the same.
Embodiment 1~15 and comparative example 1~7
According to shown in table 2, by the fluorinated copolymer obtained in polymer example 1~9 and comparative polymers example 1~3 with it is organic
Silicon systems encapsulant is mixed.Now, polymer example 1~9 and comparative polymers example 1~3 are using relative to the parts by weight shown in table 2
The mixture that the parts by weight of ethyl acetate 10 are obtained by mixing is added, by being mixed with encapsulant, fluorine-containing sealing material is obtained
Feed composition.
Said composition is coated with a glass using coating machine, is dried at room temperature for after 24 hours, to contact angle, antifouling
Property is evaluated.It the results are shown in table 3.
[table 1]
C6SFA：CH2=C (- H)-C (=O)-O- (CH2)2- C6F13
C6SFMA：CH2=C (- CH3)-C (=O)-O- (CH2)2- C6F13
LA：Lauryl ester
StA：Octadecyl ester
VA：Behenyl ester
CHMA：Cyclohexyl acrylate
EOA-1：CH2=C (- H)-C (=O)-O- (CH2CH2O)n- H, n=2
EOA-2：CH2=C (- H)-C (=O)-O- (CH2CH2O)n- H, n=10
2-HEA：Acrylic acid 2- hydroxy methacrylates
Silicon-type (45)：Oxime system organosilicon (SHIN-ETSU HANTOTAI organosilicon company system Sealant 45)
Silicon-type (SE)：Contain dimethyldichlorosilane processing silica, methyl three (methyl ethyl ketone oxime) silane
Main component (Toray Dow Corning company system SE-5010) is used as with (methyl ethyl ketone oxime) silane of vinyl three
Silicon-type (C)：Oxime system organosilicon (Cemedine company systems 8000)
Silicon-type (S)：Modified organic silicon system fluid sealant (Sharp industrial group MSC1-22)
Silicon-type (70)：Bi-component aminooxy group type organosilicon sealant (SHIN-ETSU HANTOTAI organosilicon company system Sealant 70) is main
Agent, curing agent
Silicon-type (SEII)：It is bi-component ethanol-type organosilicon sealant (Toray Dow company system SE990F) host, solid
Agent
Silicon-type (P)：Bi-component modified organic silicon fluid sealant (Cemedine company system POS Seal Type II) is main
Agent, curing agent
Acrylic acid series：Water soluble acrylic acid fluid sealant
[table 2]
[table 3]
Embodiment 16~19 and comparative example 8~10
According to shown in table 2, the fluorinated copolymer and propylene that will be obtained in polymer example 2~3 and comparative polymers example 1~2
The encapsulant mixing of acid system.Now, polymer example 2~3 and comparative polymers example 1~2 are using relative to the parts by weight shown in table 4
The mixture that the parts by weight of ethyl acetate 10 are obtained by mixing is added, by being mixed with encapsulant, fluorine-containing sealing material is obtained
Feed composition.
Said composition is coated with a glass using coating machine, is dried at room temperature for after 24 hours, to contact angle, antifouling
Property is evaluated.It the results are shown in table 5.
[table 4]
[table 5]
Embodiment 20~23 and comparative example 11
According to shown in table 6, the fluorinated copolymer obtained in polymer example 2~3 is mixed with silicon-type encapsulant.This
When, polymer example 2~3 adds what the parts by weight of ethyl acetate 10 were obtained by mixing using relative to the parts by weight shown in table 6
Mixture, by being mixed with encapsulant, obtains fluorine-containing Encapulant composition.
Said composition is coated in PET films using coating machine, is dried at room temperature for after 24 hours, cleaning is carried out
Evaluate.It the results are shown in table 7.
[table 6]
[table 7]
Embodiment 24~27 and comparative example 12~15
According to shown in table 8, by the fluorinated copolymer obtained in polymer example 2~3 and comparative polymers example 1~2 with it is organic
Silicon systems encapsulant is mixed, and thus obtains fluorine-containing Encapulant composition.
Said composition is coated with a glass using coating machine, is dried at room temperature for after 24 hours, to contact angle, antifouling
Property is evaluated.It the results are shown in table 9.
[table 8]
[table 9]
Embodiment 28~31 and comparative example 16~19
According to shown in table 10, by the fluorinated copolymer obtained in polymer example 2~3 and comparative polymers example 1~2 and sealing
Materials curing agent is mixed, and thus obtains the curing agent containing fluoropolymer.Will be close shown in the parts by weight of curing agent 4 and table 10
The parts by weight of closure material host 100 are mixed, and thus obtain fluorine-containing Encapulant composition.
Said composition is coated with a glass using coating machine, is dried at room temperature for after 24 hours, soil resistance is carried out
Evaluate.It the results are shown in table 11.
[table 10]
[table 11]
Industrial applicability
The Encapulant composition of the present invention does not reduce the water-repellancy of encapsulant and soil resistance is excellent.In addition, also can
Encapsulant is assigned and dials oiliness.The present invention Encapulant composition as building, build (for example, kitchen and washing
Room, particularly lavatory basin and bathroom), the encapsulant of the interior material of automobile etc. or outer exterior material be useful.
Claims (15)
1. a kind of Encapulant composition, it contains (1) encapsulant and (2) fluorinated copolymer, the Encapulant composition
It is characterised by：
Fluorinated copolymer (2) contains (a) formula of being derived from：CH2There is carbon number shown in=C (- X)-C (=O)-Y-Z-Rf
The construction unit of the fluorochemical monomer of 4~6 fluoroalkyl and from (b) have alkyl non-fluorine monomer construction unit,
In formula, X be hydrogen atom, the organic group or halogen atom of monovalence,
Y is-O- or-NH-,
Z is the organic group of Direct Bonding or divalence,
Rf is the perfluoroalkyl of carbon number 4~6.
2. Encapulant composition as claimed in claim 1, it is characterised in that：
In fluorochemical monomer (a),
X is alkyl, the CFX of hydrogen atom, methyl, halogen, the straight-chain of carbon number 2~21 or branched1X2Base, cyano group, carbon are former
The straight-chain of subnumber 1~21 or the fluoroalkyl of branched, substituted or non-substituted benzyl, substituted or non-substituted phenyl, wherein,
X1And X2For hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom,
Z is：
Direct Bonding；
The alkylidene of the straight-chain of carbon number 1~20 or the alkylidene of branched；Or
Formula-SO2N(R1)R2- or formula-CON (R1)R2In-shown group, formula, R1For the alkyl of carbon number 1~10, R2
The alkylidene of alkylidene or branched for the straight-chain of carbon number 1~10；Or
Formula-CH2CH(OR3)CH2In-shown group, formula, R3Represent the acyl group of hydrogen atom or carbon number 1~10；Or
Formula-Ar- (CH2)rIn-shown group, formula, Ar is that according to needing the arlydene with substituent, r is 0~10；Or
Person
- (CH2)m- SO2- (CH2)n- base or-(CH2)m- S- (CH2)n- base, wherein, m is that 1~10, n is 0~10.
3. Encapulant composition as claimed in claim 1, it is characterised in that：
In fluorochemical monomer (a), X is methyl.
4. Encapulant composition as claimed in claim 1, it is characterised in that：
Non-fluorine monomer (b) for carbon number 14~30 non-annularity alkyl or carbon number 4~30 cyclic hydrocarbon group it is non-
The non-crosslinked property monomer of fluorine.
5. Encapulant composition as claimed in claim 1, it is characterised in that：
Fluorinated copolymer also containing non-fluorine cross-linkable monomer (c) as construction unit, the amount of monomer (c) relative to monomer (a) and
Total 100 parts by weight of monomer (b) are 1~30 parts by weight.
6. Encapulant composition as claimed in claim 5, it is characterised in that：
Non-fluorine cross-linkable monomer (c) is the vinyl monomer with hydroxyl.
7. Encapulant composition as claimed in claim 1, it is characterised in that：
Fluorinated copolymer (2) does not have polyoxyalkylenes.
8. Encapulant composition as claimed in claim 1, it is characterised in that：
Fluorinated copolymer (2) is manufactured by polymerisation in solution.
9. Encapulant composition as claimed in claim 1, it is characterised in that：
Encapsulant be in silicon-type encapsulant, polyurethane series encapsulant and acrylic acid series encapsulant at least
1 kind of encapsulant.
10. Encapulant composition as claimed in claim 1, it is characterised in that：
It is the one pack system of the mixture containing encapsulant and fluoropolymer.
11. Encapulant composition as claimed in claim 1, it is characterised in that：
Encapulant composition is the bi-component containing host and curing agent,
Host contains encapsulant, and curing agent contains fluorinated copolymer.
12. Encapulant composition as claimed in claim 1, it is characterised in that：
The weight ratio of encapsulant and fluorinated copolymer is the ﹕ 15 of 99.9 ﹕ 0.1~85.
13. Encapulant composition as claimed in claim 1, it is characterised in that：
The weight ratio of monomer (a) and monomer (b) is the ﹕ 20 of 20 ﹕ 80~80.
14. a kind of manufacture method of Encapulant composition, for the sealing material any one of manufacturing claims 1~13
Feed composition, the manufacture method is characterised by：
Including：After monomer (a) and monomer (b) polymerization are obtained into fluorinated copolymer (2), the step of being mixed with encapsulant.
15. a kind of encapsulating method of boundary portion, it is characterised in that：
Including：Encapulant composition any one of claim 1~13 is filled in building, building or automobile
The boundary portion of exterior material or outer exterior material, then solidifies the Encapulant composition, the step of forming fluid sealant.
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| JP7040726B2 (en) * | 2018-06-26 | 2022-03-23 | 株式会社竹中工務店 | Water-repellent composition and method for producing water-repellent composition |
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Also Published As
| Publication number | Publication date |
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| JP7193751B2 (en) | 2022-12-21 |
| JP2017128725A (en) | 2017-07-27 |
| JP6953722B2 (en) | 2021-10-27 |
| JP2021102780A (en) | 2021-07-15 |
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