CN106833372B - Coating composition, application member, the manufacturing method of application member and washing machine - Google Patents
Coating composition, application member, the manufacturing method of application member and washing machine Download PDFInfo
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- CN106833372B CN106833372B CN201611105108.2A CN201611105108A CN106833372B CN 106833372 B CN106833372 B CN 106833372B CN 201611105108 A CN201611105108 A CN 201611105108A CN 106833372 B CN106833372 B CN 106833372B
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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
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
-
- 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
-
- 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
- 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
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00
- D06F39/08—Liquid supply or discharge arrangements
- D06F39/083—Liquid discharge or recirculation arrangements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Main Body Construction Of Washing Machines And Laundry Dryers (AREA)
Abstract
Project of the invention, which provides, has antibacterial effect than the application member of previous excellent film.Application member (20) of the invention is characterized in that, repellency film (11) (the first film (11a) for having substrate (10) and being formed on above-mentioned substrate (10), second film (11b)), above-mentioned repellency film (11) includes to contain amino silicones, compared with the inside of above-mentioned repellency film (11), above-mentioned the amino (- NHR containing amino silicones1: where R1For hydrogen atom or monovalent hydrocarbon) more it is present in the surface of repellency film (11).
Description
Technical field
The present invention relates to coating composition, application member, the manufacturing method of application member and washing machines.
Background technique
In general, in the part of the contact washing water such as sink, drainpipe of washing machine, it is easy to attach de- from washings
From the organic matters such as sebum, the food stains of people.Therefore, in the part of contact washing water, it is easy bacterial growth, mould.
In the past, for degerming, it is known that have the washing machine of hypochlorous acid generation device (for example, referring to patent document 1).So
And the hypochlorous acid generation device of the washing machine not only additionally needs the electrolysis mechanism of the regulating mechanism of salt water, the salt water, it is also necessary to
Regular replenishment salt.Therefore for the washing machine, not only just period cost increases, and operating cost also increases.
Accordingly it is contemplated that forming the painting of antibiotic property coating (for example, referring to patent document 2) on the component of contact washing water
Film.According to such antibiotic property coating, the structure without substantially changing washing machine also can be to washing machine endowing antibacterial energy.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-90813 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2003-277686 bulletin
Summary of the invention
Problems to be solved by the invention
However, the film of previous antibiotic property coating is in host agent due to being dispersed with antimicrobial component, exist even if existing
It is easy in the components such as bacterial growth, mould washing machine using the project that also cannot get sufficient antibacterial effect.
Therefore, problem of the present invention is that, provide can be formed antibacterial effect than previous excellent film coating composition,
The manufacturing method of the application member, the application member that are formed using the coating composition and washing for the application member is used
Clothing machine.
The method used for solving the problem
The coating composition of the invention for solving the above subject is characterized in that, comprising containing aminoalkoxysilane and containing
Alkyl monocarboxylic acid or salt containing hydrocarbyl sulfonic and the high-molecular compound for making above-mentioned salt dispersion.
In addition, the application member of the invention for solving the above subject is characterized in that, has substrate and be formed in above-mentioned
Repellency film on substrate, above-mentioned repellency film include to contain amino silicones, the inside phase with above-mentioned repellency film
Than the above-mentioned amino containing amino silicones is more present in the surface of above-mentioned repellency film.
In addition, the manufacturing method for solving the application member of the invention of the above subject is characterized in that, comprising: will be above-mentioned
Coating composition is coated on substrate and forms the process of the first film, is coated on above-mentioned first film and contains carbon atom number 3
The coating of the dialkoxy silicane of the alkoxy silane or alkyl with carbon atom number 1~5 of~18 fluorine-containing organic group and
The process for forming the process of the second film and cleaning the second film coated surface with alkaline solution.
In addition, the washing machine of the invention for solving the above subject is characterized in that having above-mentioned application member.
Invention effect
In accordance with the invention it is possible to provide to be formed antibacterial effect than the coating composition of previous excellent film, using the painting
Feed composition and the manufacturing method of application member, the application member formed and the washing machine for having used the application member.
Detailed description of the invention
Fig. 1 is the composition explanatory diagram of the washing machine of embodiments of the present invention.
Fig. 2 is the sectional view of application member used in the washing machine of Fig. 1.
Fig. 3 is the manufacturing procedure picture of the application member of Fig. 2.
Fig. 4 is the sectional view of the application member of other embodiments of the invention.
Symbol description
1: casing, 2: outer groove, 3: inside groove, 4: inner cover, 5: outer cover, 6: agitating paddle, 7: motor, 8: water supply mechanism, 9: draining
Pipe, 10: substrate, 11: repellency film, the 11a: the first film, the 11b: the second film, 20: application member, 20a: application member,
L: washing machine
Specific embodiment
Next, for embodiments of the present invention, it is described in detail on one side be suitable for referring to attached drawing while.
Application member of the invention is characterized mainly in that, with the film (aftermentioned repellency film) being formed on substrate
Inside compare, there are more amino for playing antibacterial effects on the surface of film.In other words, on substrate, amino is in film
Being locally present of surface.
Hereinafter, being illustrated by taking application member used in washing machine as an example, then, for being used in the application member
Coating composition and used the manufacturing method of the application member of the coating composition to be illustrated.
< washing machine >
Fig. 1 is the composition explanatory diagram of the washing machine of embodiments of the present invention.
As shown in Figure 1, the washing machine L of present embodiment has the outer groove 2 and inside groove as sink in the inside of casing 1
3, inner cover 4 is equipped on the top of sink.In addition, being equipped with outer cover 5 in the top of inner cover 4 in casing 1.
Bottom in inside groove 3, equipped with the agitating paddle 6 for stirring clothing together with washing water.
Agitating paddle 6 is driven in rotation by motor 7.
It is carried out to the supply of the water of inside groove 3 using water supply mechanism 8.The draining when draining and dehydration of the washing water after washing
Collector nozzle (not shown) is directed to from outer groove 2 via drainpipe 9.
In such washing machine L, residual washing water is easy in the inside of outer groove 2, the outside of inside groove 3.In addition, in drainpipe
9 inner face is also easy residual washing water.Also, sebum, food in washing water as described above containing the people being detached from from washings
The organic matters such as spot.Therefore, on the surface of the component of these contact washing waters, it is however generally that be easy bacterial growth, mould (fungi
Class).
In the washing machine L of present embodiment, at the position of such easy bacterial growth, mould (Mycophyta), configured with
The application member of lower explanation.
< application member >
Fig. 2 is the sectional view for schematically showing application member 20 used in the washing machine L of Fig. 1.
As shown in Fig. 2, the repellency that the application member 20 of present embodiment has substrate 10 and is formed on substrate 10 applies
Film 11.
As for example above-mentioned outer groove of component, the inside groove, row for being easy bacterial growth etc. in substrate 10, with previous washing machine
Water pipe etc. is corresponding.The application member 20 of present embodiment is constituted and forming repellency film 11 on these parts.
Therefore, the material and shape of the substrate 10 in present embodiment and outer groove, inside groove, draining in previous washing machine
Pipe etc. is corresponding.
Repellency film 11 has the first film 11a being formed on substrate 10 and is formed on first film 11a
Second film 11b.
First film 11a is coated with aftermentioned first coating on substrate 10 as being hereinafter described in detail and is formed.
It is explained, which is equivalent to coating composition of the invention.
In addition, the second film 11b is coated on the first film 11a the second coating and shape as being hereinafter described in detail
At.
In the first film 11a in present embodiment, comprising containing amino silicones and making to disperse containing amino silicones
High-molecular compound in the first film 11a.
Polysiloxane structure containing amino silicones passes through the alcoxyl that will form salt contained in aftermentioned first coating
Base silane polycondensation and formed.
In addition, the amino containing amino silicones is being cleaned to form the with alkaline solution as being hereinafter described in detail
It is generated after salt contained in the first coating of one film 11a.
The amino be show antibiotic property functional group, as previously mentioned, with compared with the inside of repellency film 11 more
Mode of the segregation in the surface of repellency film 11 generates.Though that is, containing amino silicones be the first film 11a composition at
Point, but its amino part the aftermentioned second film 11b being formed on the first film 11a being locally present of surface and formed.
In addition, for compared with the inside of repellency film 11 amino be more formed in the inventive principle on surface, with painting
The manufacturing method for covering component is described in detail below together.
The thickness of such first film 11a is preferably 10~100nm.
The second film 11b in present embodiment includes repellency compound and constitutes.The repellency compound pass through by
Alkoxy silane contained in aftermentioned second coating carries out polycondensation and is formed.As the repellency compound, can enumerate for example
The poly-diakyl silicon of the polysiloxanes of fluorine-containing organic group with carbon atom number 3~18, alkyl with carbon atom number 1~5
Oxygen alkane, but not limited to this.
In addition, the second film 11b in present embodiment although it is assumed that carry out polycondensation comprising above-mentioned alkoxy silane and
At the repellency compound such as polysiloxanes (include polysiloxane) layer, but as the second film 11b in the present invention,
Alkoxy silane contained in second coating and the high-molecular compound for constituting the first film 11a carry out chemical bonded refractory and are formed
The monomolecular film of siloxanes is also allowed.That is, as the second film 11b in the present invention, as long as can be with the first film 11a
High-molecular compound chemical bonded refractory and import aftermentioned repellency functional group and be just not particularly limited.
The thickness of the second film 11b in the present invention is preferably 1~10nm.
< coating composition >
As described above, the first film 11a is to be coated with following first coating (coating composition of the invention) on substrate 10
And formed, the second film 11b is to be coated with following second coating on the first film 11a and formed.
" the first coating "
First coating includes containing aminoalkoxysilane and monocarboxylic acid containing alkyl or the salt containing hydrocarbyl sulfonic and to make above-mentioned salt
The high-molecular compound of dispersion.
(salt)
Contain aminoalkoxysilane as the above-mentioned salt of composition, for example, can enumerate shown in following formula (1) and following formula (2)
Substance etc..
(R3O)2SiR2-X-NHR1Formula (1)
(wherein, in above-mentioned formula (1), R1For hydrogen atom or monovalent hydrocarbon, R2For alkyl, R3It may be the same or different each other
Alkyl, X are bivalent hydrocarbon radical)
(R3O)3Si-X-NHR1Formula (2)
(wherein, in above-mentioned formula (2), R1、R3And the R of X and above-mentioned formula (1)1、R3And X is synonymous)
R as above-mentioned formula (1) and above-mentioned formula (2)1Shown in monovalent hydrocarbon, for example, can enumerate straight-chain, branched or
Cricoid alkyl, alkynyl, aryl, aralkyl etc..
As R1Shown in alkyl, for example, can enumerate methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
Amyl, hexyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, decyl etc..In addition it is also possible to be carbon-to-carbon
Between the group with oxygen atom, such as methoxy, ethoxyl methyl, propoxy methyl, butoxymethyl, propoxyl group second
Base, propoxypropyl etc..
As R1Shown in alkynyl, for example, acetenyl, 2-propynyl, butynyl, hexin base, heptynyl, octyne can be enumerated
Base, decynyl, hendecyne base, dodecyne base, 13 carbyne bases, 14 carbyne bases, pentadecane alkynyl, hexadecine base,
17 carbyne bases, octadecyne base etc..
As R1Shown in aryl, for example, phenyl, tolyl, xylyl, naphthalene, azulenyl, xenyl etc. can be enumerated.
As R1Shown in aralkyl, for example, benzyl, 1- phenethyl, 2- phenethyl, 1- phenyl propyl, 2- benzene can be enumerated
Base propyl, 3- phenyl propyl, diphenyl methyl, adjacent methylbenzyl, methylbenzyl, to methylbenzyl, adjacent Ethylbenzyl, second
Base benzyl, to Ethylbenzyl, o-isopropyl benzyl, isopropyl benzyl, p-isopropyl benzyl, neighbour (tert-butyl) benzyl, (uncle
Butyl) benzyl, to (tert-butyl) benzyl, 2,3- dimethyl benzyl, 2,4- dimethyl benzyl, 2,5- dimethyl benzyl, 2,6- bis-
Methylbenzyl, 3,4- dimethyl benzyl, 3,5- dimethyl benzyl, 2,3,4- trimethyl benzyl, 2,3,4- trimethyl benzyl, 3,4,
5- trimethyl benzyl, 2,4,6- trimethyl benzyl, 5- isopropyl -2- methylbenzyl, 2- isopropyl -5- methylbenzyl, 2- methyl -
5- (tert-butyl) benzyl, 2,4- diisopropyl benzyl, 2,5- diisopropyl benzyl, 3,5- diisopropyl benzyl, (the tertiary fourth of 3,5- bis-
Base) benzyl, 1- (2- aminomethyl phenyl) ethyl, 1- (3- isopropyl phenyl) ethyl, 1- (4- isopropyl phenyl) ethyl, 1- (2- (uncle
Butyl) benzyl ethyl, 1- (4- (tert-butyl) benzyl ethyl, 1- (2- isopropyl-4-methyl phenyl) ethyl, 1- (4- isopropyl-
2- aminomethyl phenyl) ethyl, 1- (2,4- 3,5-dimethylphenyl) ethyl, 1- (2,5- 3,5-dimethylphenyl) ethyl, 3,5- 3,5-dimethylphenyl
Ethyl, 1- (3,5- bis--(tert-butyl) phenyl) ethyl etc..
R as above-mentioned formula (1)2, above-mentioned formula (1) and above-mentioned formula (2) R3Shown in alkyl, for example, can enumerate methyl,
Ethyl, propyl etc..
As bivalent hydrocarbon radical shown in the X of above-mentioned formula (1) and above-mentioned formula (2), for example, methylene, ethylidene, three can be enumerated
Methylene, isopropylidene, pentamethylene, hexa-methylene, heptamethylene etc..In addition it is also possible to be that there is between carbon-to-carbon oxygen atom
Group, for example, methylene oxygroup methylene, ethyleneoxy group methylene, propylidene oxygroup methylene, butylene oxide methylene,
Propylidene oxygroup ethylidene, propylenoxypropylene etc..
As the monocarboxylic acid containing alkyl for constituting salt or containing the alkyl in hydrocarbyl sulfonic, preferably the one of carbon atom number 1~12
Valency alkyl, more preferably straight-chain, branched or cyclic alkyl.
As the alkyl of such carbon atom number 1~12, for example, methyl, ethyl, n-propyl, isopropyl, positive fourth can be enumerated
It is base, isobutyl group, tert-butyl, n-pentyl, isopentyl, neopentyl, 2- amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, different pungent
Base, 2- ethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl,
Suberyl, cyclooctyl, cyclononyl, cyclodecyl, ring undecyl, cyclo-dodecyl etc..
Salt in present embodiment can be by every 1 stoichiometric monocarboxylic acid containing alkyl or containing being added in hydrocarbyl sulfonic
0.9~1.1 it is stoichiometric containing aminoalkoxysilane and obtain.
Then, such that there are following formula (3) containing aminoalkoxysilane and monocarboxylic acid containing alkyl or the salt containing hydrocarbyl sulfonic
Or the functional group containing ionic bond shown in following formula (4).
-R1NH+-COO-R4Formula (3)
(wherein, in formula (3), R1With the R of above-mentioned formula (1) and (2)1It is synonymous, R4For above-mentioned monocarboxylic acid containing alkyl or above-mentioned contain
Alkyl in hydrocarbyl sulfonic)
-R1NH+-SO3 -R4Formula (4)
(wherein, in formula (4), R1And R4With the R of above-mentioned formula (3)1And R4It is synonymous)
(high-molecular compound)
High-molecular compound contained in first coating disperses above-mentioned salt in the first coating, and on substrate 10
In first film 11a, keep containing aminoalkoxysilane.
As the high-molecular compound in present embodiment, for example, polyalkoxysilane can be enumerated, side chain has ester bond
Hydrocarbon resin, main chain resin, main chain with urethane bond have resin of ehter bond etc..These high-molecular compounds can also incite somebody to action
One or more are combined and are used.
As polyalkoxysilane, can enumerate makes the alcoxyls such as tetraalkoxysilane, trialkoxy silane, dialkoxy silicane
Silica solution made of base silane polycondensation.
As side chain have ester bond hydrocarbon resin, for example, can by make containing alkyl, hydroxyl, glycidyl, carboxyl,
Amide groups,The acrylate or methacrylate of oxazoline base etc., butadiene, vinyl acetate, vinyl chloride, propylene, second
The polymerization such as alkene, vinylidene chloride, methacrylonitrile, acrylonitrile or copolymerization obtain.
As main chain have urethane bond resin, can by make polyalcohol with polyisocyanate polyisocyanate polyaddition and obtain.
As polyalcohol, for example, can enumerate polyester polyol, polyether polyol, acrylic polyol, low molecular weight it is more
First alcohol.
As polyester polyol, for example, polyethylene adipate diol, polybutene adipate diol, poly- second can be enumerated
Alkene butylene adipate esterdiol, polyhexamethylene isophthalic acid ester adipate diol, polyethylene succinate esters glycol, poly- fourth
Alkene succinate glycol, polyethylene sebacate glycol, polybutene sebacate glycol, poly- 6-caprolactone glycol, poly- (3- first
Base -1,5- amylene adipate ester) glycol, 1,6-HD and the condensation polymer of dimeric dibasic acid etc..
As polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and epoxy third can be enumerated
Alkane, the random copolymer of ethylene oxide and epoxy butane, block copolymer etc..Further, it is possible to use there is ehter bond and ester bond
Polyether polyester polyalcohol etc..
As low molecular weight polyols, for example, ethylene glycol, 1,4-butanediol, 1,5-PD, 3- methyl-1 can be enumerated,
5- pentanediol, 1,6-HD, 1,9- nonanediol, 2- methyl-1,8- ethohexadiol, 1,4 cyclohexane dimethanol, 1,3- hexamethylene
Dimethanol, 1,4- cyclohexanediol etc..Further, it is possible to use the low molecular weights such as trimethylolpropane, pentaerythrite, D-sorbite
Polyalcohol.
As polyisocyanate, for example, 2,4- toluene di-isocyanate(TDI), 2 can be enumerated, 6 toluene di-isocyanate(TDI)s, diformazan
Benzene -1,4- diisocyanate, dimethylbenzene -1,3- diisocyanate, 4,4 '-methyl diphenylene diisocyanates, 2,4 '-diphenyl
Methane diisocyanate, 4,4 '-phenyl ether diisocyanate, 2- diphenyl -4,4 '-diisocyanate, 2,2 '-diphenylprops
Alkane -4,4 '-diisocyanate, 3,3 '--4,4 '-diisocyanate of Dimethyl diphenylmethane, 4,4 '-diphenyl propane, two isocyanide
Acid esters, metaphenylene diisocyanate, to phenylene vulcabond, naphthalene-1,4-disocyanate, naphthalene -1,5- diisocyanate
Ester, 3,3 '-dimethoxydiphenyl -4, the aromatic diisocyanates such as 4 '-diisocyanate, polyphenylene polymethylene gathers different
The aromatic poly-isocyanates such as cyanate, crude toluene diisocynate, tetramethylene diisocyanate, hexa-methylene diisocyanate
The aliphatic diisocyanates such as ester, decamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate,
Hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenyl methane diisocyanate, tetramethyl xylene
The alicyclic diisocyanates such as diisocyanate, biuret modified object, urea diketone modifier, the carbon two of organic polyisocyanates are sub-
Amine modifier, isocyanurate-modified object, uretonimine-modified object, their mixed and modified object etc..
There is the resin of ehter bond as main chain, for example, can enumerate is made using curing agent containing alkyl, hydroxyl, carboxyl, amide
Base,Substance made of the polymerization of epoxy resins such as oxazoline base.
It may include solvent in first coating.First coating can be coated on substrate 10 and dried as described later by solvent
When, consider drying temperature, drying time, chemical affect of substrate 10 etc. is selected.
As solvent, can be used alone a kind of organic solvent or mixes two or more organic solvents and is used.Wherein, excellent
It is selected as alcohol.
As alcohol, for example, methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl-1-the third can be enumerated
Alcohol, 1- amylalcohol, 3- methyl-1-butanol, 2- methyl -2- butanol etc..
In addition, the substance for dissolving the resin on a small quantity can also be made an addition to solvent in the case where substrate 10 is formed by resin.
By using such solvent, additionally it is possible to make the roughing in surface of substrate 10 and improve the adaptation of the first film Yu substrate 10.
In addition, the condensation catalyst of above-mentioned alkoxy silane can also optionally be added in the first coating.
The mixing ratio of salt and high-molecular compound in above such first coating is preferably set to by quality ratio
High-molecular compound is more than the use level of salt.Specifically, by quality ratio, salt/(salt+high-molecular compound) ratio is excellent
Choosing is set with 0.1~0.3 range.
In addition, the mixing ratio of solvent can be suitable for setting according to the coating method of the first coating to substrate 10, but the
Solvent in one coating is preferably 90 mass % or more.
" the second coating "
The second coating in present embodiment includes the polysiloxanes formed in the second film 11b as repellency compound
Alkoxy silane, i.e., the above-mentioned alkoxy silane with repellency functional group.
As the alkoxy silane, the alkoxyl silicone of such as fluorine-containing organic group with carbon atom number 3~18 can be enumerated
Alkane, dialkoxy silicane of alkyl with carbon atom number 1~5 etc., but not limited to this.
As the fluorine-containing organic group of carbon atom number 3~18, can enumerate such as perfluoroalkyl, holo-fluorine polyester, but not
It is limited to this.
In addition, as the second coating of the invention, as long as having the high-molecular compound with the first film 11a of composition
It learns the reactive functional groups of bond and assigns the substance of the repellency functional group of repellency to the second film 11b, be then not limited to
Above-mentioned alkoxy silane, dialkoxy silicane etc. also allow comprising other silane compounds.
In addition, may include solvent in the second coating.First coating can be coated on substrate 10 by solvent as described later
And when drying, considers drying temperature, drying time, chemical affect of substrate 10 etc. is selected.
As solvent, can be used alone a kind of organic solvent or mixes two or more organic solvents and is used.Wherein, excellent
It is selected as alcohol.
As alcohol, for example, methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl-1-the third can be enumerated
Alcohol, 1- amylalcohol, 3- methyl-1-butanol, 2- methyl -2- butanol etc..
In addition, the condensation catalyst of above-mentioned alkoxy silane can also optionally be added in the second coating.
Alkoxy silane in second coating is preferably 0.01~1.0 mass %.
In addition, the solvent in the second coating is preferably 99 mass % or more.
The manufacturing method > of < application member
The manufacturing method of the application member 20 (referring to Fig. 2) of present embodiment is included the first coating (coating composition)
It is coated on substrate 10 (referring to Fig. 2) and forms the process of the first film 11a (referring to Fig. 2), is coated on the first film 11a the
Two coating and form the process of the second film 11b (referring to Fig. 2) and clean on the surface of the second film 11b with alkaline solution
Process.
As the method for being coated with the first coating on substrate 10, for example, the side for carrying out wet coating in an atmosphere can be enumerated
Method.Specifically, the first coating can be coated on substrate 10 for example, by dip-coating, spraying, spin coating etc., but coating method is unlimited
In this.Coating method can be suitable for selection according to shape, the material of substrate 10.
In addition, can implement to be surface-treated to substrate 10 when the first coating is coated on substrate 10.As surface treatment, example
Such as, oxygen plasma irradiation, blasting treatment, prime treatment etc. can be enumerated.It is surface-treated and by being suitable for that selection is such to base
Material 10 is implemented, and the flatness of the first film 11a etc. in the adaptation of the first film 11a and substrate 10, substrate 10 improves.
Then, make to constitute the alkoxy silane polycondensation for being coated on salt contained in the first coating of substrate 10 and generate poly- silicon
Oxygen alkane, and solvent is evaporated, to form the first film 11a on substrate 10.
When forming the first film 11a on substrate 10, the polycondensation of alkoxy silane is carried out even if room temperature, but if examining
The evaporation time for considering solvent, then heat the first film 11a preferably on substrate 10.It, can basis as the heating temperature
Used solvent may be set to 60~80 DEG C of degree being suitable for setting, such as in the case that solvent is ethyl alcohol.
In addition, about such first film 11a, in the high-molecular compound of the constituent as the first coating,
Maintain carboxylate or sulfonate containing amino silicones.
It then, include the functional group of ionic bond on the surface of the first film 11a shown in above-mentioned formula (3) or above-mentioned formula (4)
Being locally present.For the being locally present principle, it is described in detail below.
As the method for being coated with the second coating on the first film 11a, it can be used and be coated with the first coating on substrate 10
The same coating method of method.
Then, make alkoxy silane polycondensation contained in the second coating being coated on the first film 11a and generate poly- silicon
Oxygen alkane, and solvent is evaporated, to form the second film 11b on the first film 11a.
In addition, when forming the second film 11b on the first film 11a, the polycondensation of alkoxy silane even if room temperature into
Row then preferably heats the second coating on the first film 11a but if considering the evaporation time of solvent.As this plus
In the case that hot temperature can be suitable for setting according to used solvent, such as solvent is ethyl alcohol, it may be set to 60~80 DEG C of journeys
Degree.
In addition, on the surface of such second film 11b, comprising ionic bond shown in above-mentioned formula (3) or above-mentioned formula (4)
Being locally present of functional group of first film 11a.For the being locally present principle, it is described in detail below.
Then, the surface of the second film 11b is cleaned with alkaline solution.
As alkaline solution, can enumerate such as sodium hydrate aqueous solution, potassium hydroxide aqueous solution.The pH of alkaline solution is excellent
It is selected as 9~12.
Fig. 3 is that the cleaning process of the second film 11b of alkaline solution is utilized in the manufacturing procedure picture of the application member 20 of Fig. 2
Figure.
Here, in case where including the polysiloxanes with functional group shown in above-mentioned formula (3) in the first film 11a
The cleaning process of second film 11b is illustrated.
The surface of repellency film 11 (the second film 11b) before the cleaning indicated on the left of the paper of Fig. 3, the first film
The functional group (- R of polysiloxanes contained in 11a1NH+-COO-R4) being locally present.Wherein, R1For hydrogen atom or monovalent hydrocarbon
Base, R4For monovalent hydrocarbon.
If cleaning the surface of second film 11b with alkaline solution, as shown in the paper right side of Fig. 3, functional group (-
R1NH+-COO-R4) chemical change at play antibiotic property amino (- NHR1).Later, clean the second film 11b's using pure water
Surface and drying, to complete the application member of present embodiment.
< being locally present principle >
Next, for amino (- NHR1) repellency film 11 (the second film 11b) being locally present of surface original
Reason is illustrated.
As described above, being coated with the first coating on substrate 10 in the manufacturing process of application member 20.At this point, the first coating
Contained in disperse together containing aminoalkoxysilane and monocarboxylic acid containing alkyl or the salt containing hydrocarbyl sulfonic and high-molecular compound
In in the first coating.Also, when polysiloxanes made of alkoxy silane polycondensation is kept by high-molecular compound, the carboxylic of list containing alkyl
Sour or alkyl containing hydrocarbyl sulfonic shows repellency, therefore includes the function of ionic bond shown in above-mentioned formula (3) or above-mentioned formula (4)
Surface be locally present of the group in the first film 11a.
Then, if being coated with the second coating on first film 11a, on the surface of the first film 11a, formation includes
Second film 11b of polysiloxanes made of alkoxy silane polycondensation contained in the second coating.
In addition, when being coated with the second coating on the first film 11a, the above-mentioned functional group comprising ionic bond each other it
Between, the above-mentioned high-molecular compound and alkoxy silane contained in the second coating of the constituent as the first film 11a are anti-
It answers.Specifically, in the case that high-molecular compound is polyalkoxysilane (silica solution), remaining alkane in polyalkoxysilane
With the alkoxy of alkoxy silane contained in the second coating polycondensation can occur for oxygroup, silanol group.In addition, such as producing high-molecular
Closing object is that hydrocarbon resin, main chain of the side chain with ester bond resin, main chain with urethane bond have ehter bond (epoxy group etc.)
Resin in the case where, remaining hydroxyl can contract with the alkoxy of alkoxy silane contained in the second coating in them
It is poly-.
As a result, on the surface for the second film 11b being formed on the first film 11a, by the above-mentioned packet of the first film 11a
Functional group containing ionic bond almost remaining state as former state, assigns reprimand by surface of the second film 11b to repellency film 11
It is aqueous.
Also, as described above, by using alkaline solution cleaning repellency film 11 (the second film 11b) surface, from
And amino (- NHR1) in being locally present of surface of repellency film 11 (the second film 11b).Such repellency film 11 has
There are the first film 11a and the second film 11b, the second film 11b is in the function on the surface for being formed in first film 11a
Group-X-NHR1(wherein, X, R1With X, R of above-mentioned formula (1) and above-mentioned formula (2)1It is synonymous) between, at least make-NHR1Part is hydrophobic
Property film 11 surface expose mode be formed on the first film 11a.
According to above such application member 20, the amino (- NHR of antibiotic property is played1) in repellency film 11, (second is applied
Film 11b) being locally present of surface, therefore it is different from the application member for being dispersed with antimicrobial component in film, can play excellent
Antibacterial, anti-mold effect.
In addition, the second film 11b includes repellency compound, therefore application member 20 is difficult to adhesive water, the moisture institute
The organic matter contained.Therefore, bacterium, mould breeding are able to suppress.That is, application member 20 according to the present embodiment, passes through part
It is present in the amino (- NHR on the surface of repellency film 111) and the second film 11b contained in repellency compound one act as
With can synergistically and more reliably inhibit bacterium, mould breeding.
More than, embodiments of the present invention are illustrated, but the present invention is not limited by above embodiment, energy
Enough implemented in the form of various.
In above embodiment, as shown in Fig. 2, there is the first film 11a and the second film 11b on substrate 10, but
It can be set as being equipped with the composition of other layers on substrate 10.
Fig. 4 is the sectional view of the application member 20a of other embodiments of the invention.
As shown in figure 4, application member 20a has between substrate 10 and the first film 11a of composition repellency film 11
Third layer.As the third layer, can enumerate the adhesive layers such as prime coat, repellency film 11 is supplied other antimicrobial components containing anti-
Microbial inoculum layer etc..
In addition, amino (- NHR1) R1In the case where for the alkyl with repellency, the second film 11b can also be omitted.
Amino contained in repellency film 11 preferably in being locally present of surface of repellency film 11, but as long as be with
Compare the composition for being more present in the surface of repellency film 11 in the inside of repellency film 11.Therefore, it can also be set as
Amino is in repellency film 11 in a manner of the gradually decreasing inwardly there are ratio from the surface of repellency film 11 of amino
Application member 20, the 20a of distribution.
In addition, application member 20,20a are not limited to the component of washing machine L, can be applied to such as air-conditioning, humidifier, refrigerator
Other all devices, the device of moisture participation.In addition, application member 20,20a not only can be a component of unit,
It can also be used independently with piping etc..
Embodiment
It has more next, Duiing the present invention while showing the Examples and Comparative Examples for demonstrating function and effect of the invention
Body it is illustrated.
(embodiment 1)
In the present embodiment, production is assumed to the test piece of application member used in washing machine.The test piece is as substrate
Quartz glass plate (40mm × 40mm × 1mm) surface be coated with following first coating and after forming the first film, this first
The surface of film is coated with following second coating and forms the test piece of the second film.
The modulation > of the first coating of <
Firstly, being added in solution made of dissolution 70 mass parts of tetraethoxysilane in 980 mass parts of ethyl alcohol micro
As the nitric acid of acid catalyst, heated 1 hour at 50 DEG C.Thus to obtain 1 mass % of silicon concentration, 2 mass % of silica concentration
1000 mass parts of silica sol liquid.
Then, make as 2 mass parts of cyclohexane-carboxylic acid of monocarboxylic acid and as the 3- aminopropan containing aminoalkoxysilane
2 mass parts of base trimethoxy silane are dissolved in 196 mass parts of ethyl alcohol, obtain the carboxylate ethanol solution containing aminoalkoxysilane
200 mass parts.
Then, resulting 5 mass parts of silica sol liquid and 1 mass parts of carboxylate ethanol solution are mixed, to obtain first
Coating.
The modulation > of the second coating of <
Make the alkoxy silane (OPTOOL [registered trademark] of Daikin Ind Ltd with modified holo-fluorine polyester
DSX) 1 mass parts are dissolved in 1000 mass parts of ethyl alcohol, obtain the second coating.
The production > of < test piece
The first coating is coated with using dip coating (pull rate 1.3mm/s) on substrate.The base of the first coating will be coated with
Material is heated 30 minutes using heating furnace at 60 DEG C, to form the first film on substrate.After the substrate is cooled to room temperature, survey
The surface of fixed first film and the contact angle of water.Contact angle is 19 degree.
Then, the second coating is coated with using dip coating (pull rate 1.3mm/s) on the first film of substrate.It will be
The substrate that the second coating is coated on one film is heated 30 minutes using heating furnace at 60 DEG C, thus on the first film of substrate
Form the second film.
After the above-mentioned substrate for foring the second film is cooled to room temperature, the surface of the second film is used as alkaline solution
Sodium hydrate aqueous solution (0.001mol/L) cleaning.Then, it after the surface of the second film being cleaned with pure water, is dried,
To make the test piece in the present embodiment.
Measure the surface of test piece and the contact angle of water.Contact angle is 115 degree.The surface of test piece has repellency.
The verifying > of being locally present of amine of < strip
Using XPS analysis find out the film coated surface of test piece as the ratio of the nitrogen-atoms of the constitution element of amine.Nitrogen-atoms
Ratio be 2.4%.In addition, the ratio of nitrogen-atoms when distance with a thickness of the surface of the film of 50nm is 10nm depth is
0.8%.That is, the nitrogen-atoms ratio of the strip in the present embodiment is 3 times of the nitrogen-atoms ratio inside film.Thus it verifies
Being locally present of strip of amine in the present embodiment.
(embodiment 2)
Use aluminium sheet (20mm × 30mm × 0.2mm) as substrate, in addition to this, operate similarly with example 1, makes
Test piece.In addition, in the present embodiment, as control test piece, make in not formed first film in the surface of above-mentioned aluminium sheet and only shape
At the test piece of the second film.
In the present embodiment, the test piece and control test piece are anchored on the interior of the outer groove (symbol 2 referring to Fig.1) of washing machine
Face carries out washing operating using the washing machine with the water of the maximum amount of stockpiling of sink.After the washing operating, it will do washing
Machine be maintained in constant-humidity constant-temperature slot 30 DEG C, 90%RH and place 1 week.
Detect by an unaided eye the inner face of outer groove, as a result confirms the inner face in outer groove, other than the test piece part installed,
Substantially entire surface (including control test piece part) generates black mould.Thereby confirm that the anti-mold effect of the test piece in the present embodiment.
(embodiment 3)
In the present embodiment, the first coating is coated in a part of the drainpipe (symbol 9 referring to Fig.1) of washing machine and shape
After the first film, following second coating are coated on the surface of first film and form the second film.
The a part for foring the drainpipe of the first film and the second film is with attached with outer groove (symbol 2 referring to Fig.1)
Cylindrical member (the internal diameter 45mm, length for the resin system (polypropylene) that the corresponding mode of close drain parts separately makes
100mm)。
In addition, the first coating and the second coating use coating similarly to Example 1.The shape of first film and the second film
At using dip coating (pull rate 1.3mm/s), using the heating of heating furnace, cooling, the second film using alkaline solution
Cleaning and washing carry out under the condition that is similarly to Example 1 respectively.Hereinafter, a part of the drainpipe is known as experimental
Water pipe.
In addition, as control drainpipe, separately making not formed first film in the present embodiment and only forming the second film
Drainpipe a part.
In the present embodiment, test drainpipe is installed on washing machine and is carried out a succession of until the draining of washing water
Washing operating.In addition, concurrently carrying out being mounted with to compare drainpipe with the washing operating for the washing machine for being mounted with test drainpipe
Washing machine washing operating.Then, after washing operating, each washing machine is maintained in constant-humidity constant-temperature slot 30 DEG C,
90%RH and place 1 week.
The test drainpipe that is removed with endoscopic observation from each washing machine and the inside for compareing drainpipe, as a result confirm pair
The inside whole face of phototypesetting water pipe is mouldy, but the inside for testing drainpipe does not generate black mould.Thereby confirm that the examination in the present embodiment
Test the anti-mold effect of drainpipe.
(comparative example)
In above-described embodiment 1, when modulating the first coating, it is mixed with 1 matter of 5 mass parts of silica sol liquid and carboxylate ethanol solution
Part is measured, and in the comparative example, 1 mass of carboxylate ethanol solution is replaced using the ethanol solution below containing aminoalkoxysilane
Part.
Ethanol solution containing aminoalkoxysilane is by being dissolved in second for 2 mass parts of 3- TSL 8330
98 mass parts of alcohol and obtain.Hereinafter, the ethanol solution containing aminoalkoxysilane is known as third coating.
In comparative example, the surface coating third for being produced on the quartz glass plate (40mm × 40mm × 1mm) as substrate is applied
Expect after forming third film, is coated with the second coating (referring to embodiment 1) on the surface of the third film and forms the second painting
The comparison test piece of film (referring to embodiment 1).
< compares the production > of test piece
Third coating is coated with using dip coating (pull rate 1.3mm/s) on substrate.The base of third coating will be coated with
Material is heated 30 minutes using heating furnace at 60 DEG C, to form third film on substrate.After the substrate is cooled to room temperature, survey
Determine the surface of third film and the contact angle of water.Contact angle is 17 degree.
Then, the second coating is coated with (referring to real using dip coating (pull rate 1.3mm/s) on the third film of substrate
Apply example 1).The substrate that the second coating is coated on third film is heated 30 minutes using heating furnace at 60 DEG C, thus in base
The second film similarly to Example 1 is formed on the third film of material.
After the above-mentioned substrate for foring the second film is cooled to room temperature, the surface of the second film is used as alkaline solution
Sodium hydrate aqueous solution (0.001mol/L) cleaning.Then, it after the surface of the second film being cleaned with pure water, is dried,
To comparison test piece.
The surface of test piece and the contact angle of water are compared in measurement.Contact angle is 115 degree.The surface of test piece has repellency.
In addition, found out using XPS analysis the film coated surface for comparing test piece as the ratio of the nitrogen-atoms of the constitution element of amine
Rate.The ratio of nitrogen-atoms is 2.4%.In addition, nitrogen-atoms when distance with a thickness of the surface of the film of 50nm is 10nm depth
Ratio is 2.1%.That is, the nitrogen-atoms ratio for comparing strip is 1.1 times of the nitrogen-atoms ratio inside film.It thereby confirms that
To amine not in being locally present of surface of relatively test piece, but substantially uniformly it is distributed in film.
Claims (9)
1. a kind of coating composition is, characterized by comprising: salt containing aminoalkoxysilane and cyclohexane-carboxylic acid and make institute
State the silica solution of salt dispersion.
2. coating composition according to claim 1, which is characterized in that the aminoalkoxysilane that contains is by following formula
(1) it indicates,
(R3O)2SiR2-X-NHR1Formula (1)
Wherein, in the formula (1), R1For hydrogen atom or monovalent hydrocarbon, R2For alkyl, R3For the alkyl that may be the same or different each other,
X is bivalent hydrocarbon radical.
3. coating composition according to claim 1, which is characterized in that the aminoalkoxysilane that contains is by following formula
(2) it indicates,
(R3O)3Si-X-NHR1Formula (2)
Wherein, in the formula (2), R1For hydrogen atom or monovalent hydrocarbon, R3For the alkyl that may be the same or different each other, X is divalent hydrocarbon
Base.
4. a kind of application member, which is characterized in that the repellency film for having substrate and being formed on the substrate,
The repellency film contains coating composition according to any one of claims 1 to 3,
The repellency film includes to contain amino silicones,
Compared with the inside of the repellency film, the amino containing amino silicones is more present in the repellency
The surface of film.
5. application member according to claim 4, which is characterized in that the repellency film, which has, is formed in the substrate
On the first film and the second film for being formed on first film,
First film includes to keep the high-molecular compound containing amino silicones,
Second film includes repellency compound.
6. application member according to claim 5, which is characterized in that the repellency compound is with carbon atom number 3
The polysiloxanes of~18 fluorine-containing organic group.
7. application member according to claim 5, which is characterized in that the repellency compound is with carbon atom number 1
The polydialkysiloxane of~5 alkyl.
8. a kind of manufacturing method of application member comprising:
Coating composition according to any one of claims 1 to 3 is coated on substrate and formed the first film process,
Coating is comprising having the alkoxy silane of the fluorine-containing organic group of carbon atom number 3~18 or having on first film
The coating of the dialkoxy silicane of the alkyl of carbon atom number 1~5 and formed the second film process and
The process for cleaning the second film coated surface with alkaline solution.
9. a kind of washing machine, which is characterized in that have application member described in any one of claim 4~7.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015237582A JP6483595B2 (en) | 2015-12-04 | 2015-12-04 | Coating composition and method for producing painted parts |
| JP2015-237582 | 2015-12-04 |
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| CN106833372A CN106833372A (en) | 2017-06-13 |
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| CN111748972B (en) * | 2019-03-27 | 2022-05-03 | 无锡小天鹅电器有限公司 | Bucket subassembly and washing machine |
| DE202020104665U1 (en) * | 2020-08-11 | 2020-11-04 | MAXI-PRESS Elastomertechnik GmbH | Membrane for a dewatering press |
| KR20240026349A (en) * | 2022-08-18 | 2024-02-28 | 삼성전자주식회사 | Textured urethane powder coating exterior material for home appliances and washing machine comprising the same |
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| CN104105766A (en) * | 2011-12-20 | 2014-10-15 | 株式会社钟化 | Waterproof coating material and building roof having coating film formed therefrom |
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| JPH07126417A (en) * | 1993-10-13 | 1995-05-16 | Toyoda Gosei Co Ltd | Surface treating method for rubber article and rubber article treated with the same method |
| JPH09255910A (en) * | 1996-03-25 | 1997-09-30 | Teijin Ltd | Coating composition |
| ATE556122T1 (en) * | 2004-10-22 | 2012-05-15 | Essilor Int | SUBSTRATE WITH DIRT-REPELLENT COATING |
| JP2009256564A (en) * | 2007-09-26 | 2009-11-05 | Fujifilm Corp | Composition for formation of hydrophilic film, and hydrophilic member |
| TWI500814B (en) * | 2009-09-24 | 2015-09-21 | Kansai Paint Co Ltd | Composition for metal surface treatment, metal surface treatment method and coating method of metal material |
| CN104114598B (en) * | 2011-12-15 | 2017-03-01 | 莫门蒂夫性能材料股份有限公司 | The organopolysiloxane composition of moisturecuring |
| SG10201707760QA (en) * | 2012-11-13 | 2017-11-29 | Chugoku Marine Paints | Curable organopolysiloxane antifouling composite coating film, and antifouling substrate coated with the same |
| KR20140069801A (en) * | 2012-11-30 | 2014-06-10 | 삼성전자주식회사 | Mutifunctional coating structure and forming method for the same |
| DE102013218981A1 (en) * | 2013-09-20 | 2015-03-26 | Evonik Industries Ag | Room temperature curing silicone-polyester binder |
| JP2016222787A (en) * | 2015-05-29 | 2016-12-28 | 株式会社日立製作所 | Coating, coated film formed by the same, and washing machine, refrigerator and air conditioner using the same |
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| JP6483595B2 (en) | 2019-03-13 |
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