CN106029799A - Aqueous resin composition for forming thick film, manufacturing method therefor, surface treatment method, and concrete structure - Google Patents
Aqueous resin composition for forming thick film, manufacturing method therefor, surface treatment method, and concrete structure Download PDFInfo
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- CN106029799A CN106029799A CN201580008809.1A CN201580008809A CN106029799A CN 106029799 A CN106029799 A CN 106029799A CN 201580008809 A CN201580008809 A CN 201580008809A CN 106029799 A CN106029799 A CN 106029799A
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- thick film
- construction water
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- overlay film
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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
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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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
- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
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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
- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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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
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
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- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The present invention is an aqueous resin composition for forming thick films, the composition comprising an aqueous synthetic resin emulsion (A) and a filler (B) and the non-volatile components being 65-80 mass%. The aqueous resin composition for forming thick films is characterized in that the percentage of the observed specific gravity with respect to the theoretical specific gravity is 97% or more. Using said aqueous resin composition for forming thick films: drying within twelve hours after thick film formation and coating is possible; odors are not generated during work; and it is possible to form a coating with excellent water resistance, acid resistance and alkali resistance. In particular, it is possible to form a coating that conforms to the quality standards of standard types C and D provided in the Sewer Concrete Structure Corrosion-Limiting Technology and Corrosion-Proofing Technology Manual (April 2012).
Description
Technical field
The present invention relates to a kind of thick film construction water resin combination and preparation method thereof, surface treatment method and
Concrete structure.Specifically, the present invention relates to a kind of for carrying out the coagulation used in building and/or building field
Thick film construction water resin combination that the surface of soil structure thing processes and preparation method thereof, surface treatment method and mixed
Xtah Crude Clay structure thing.
Background technology
In concrete structure, owing to the deterioration under various environmental conditions forms a difficult problem, to improve concrete structure
Durability for the purpose of, the surface carrying out employing various resin material processes.
On the other hand, due to trend and the raising rapidly of environmental protection consciousness of society of VOC regulation strengthening, though with
In the resin material that surface processes, from the conversion of organic solvent resinous materials hydrotropism's resin material also development.Special
It not in the surface process of concrete structure in building and/or building field, from environmental problem angularly, foul smell
And the regulation etc. of the regulation of volatile ingredient and use raw material becomes strict, the eager exploitation expecting water-base resin material.
But, use in the case of water-base resin material in the surface of concrete structure processes, due to needs long time
The film of chien shih water-base resin material is to being completely dried, it is impossible to obtain sufficient treatment effeciency.Additionally, from overlay film resistance to formed
For a long time from the point of view of property one side, owing to employing the organic molten of vinylester resin, polyester resin, epoxy resin, polyureas, polyurethane resin etc.
Agent resinous materials can form the overlay film that resistance to water, acid resistance and alkali resistance are excellent, and therefore present situation is organic for generally using
Solvent resin material.Therefore, water-base resin material is headed by application property, due to can not be as organic solvent resinous materials
There is multiple crosslinking points and cause obtaining sufficient overlay film intensity, be therefore not particularly suited for the surface of concrete structure
Reason.
In this type of situation, it is proposed that a kind of containing macromolecule Emulsion, acrylic emulsion or synthetic rubber Emulsion, Pulvis Talci
Concrete structure water borne base regulation material (referenced patent document 1).But, this bottom regulation material is constructed
The restriction of method, and acid resistance, the sufficient overlay film of alkali resistance cannot be obtained in thick film is constructed.
Further it is proposed that one is added with glass fibre, cement, sand etc. in vinylacetate-ethylenic copolymer Emulsion
Strengthening mortar with compositions (referenced patent document 2).But, due to the non-volatile component mistake of this strengthening mortar compositions
Many, cause viscosity extremely to rise, operability has problems.
On the other hand, as the aqueous resin composition that with the addition of organic filler in synthetic resin Emulsion, it is proposed that
A kind of styrene butadiene copolymers resinoid latex and at least one in neoprene latex of such as containing, and acrylic acid
The adhesion agent composition (referenced patent document 3) of resinoid powder (organic filler).But, this adhesion agent composition is to make
For the purpose of using for sticker, process by the surface of concrete structure not such, formed for the purpose of thick film.
Furthermore disclosed a kind of damping and amortization compositions, it is characterised in that employing the substrate Emulsion of Core-shell Emulsion
(Base emulsion) forms (referenced patent document 4) containing organic filler, but deposits when forming thick film according to drying condition
In the probability cracked.
Here, the present inventor etc. are in order to solve foregoing problems, it is proposed that one is containing aqueous synthetic-resin Emulsion and has
Machine implant or glass-filled thing, non-volatile component be the thick film construction water resin combination (ginseng of 65～80 mass %
Examine patent documentation 5 and 6).This thick film construction water resin combination can be carried out to processed surface such as concrete structures
Thick film is constructed, and can be dried within 12 hours after coating, and the overlay film of formation has durability, such as, has resistance to water, resistance to
Acidity and alkali resistance.
Prior art literature
Patent documentation
Patent documentation 1: JP 2009-149767 publication
Patent documentation 2: JP 2002-179450 publication
Patent documentation 3: JP 2009-102606 publication
Patent documentation 4: JP 2005-126645 publication
Patent documentation 5: JP 2011-256289 publication
Patent documentation 6: JP 2011-57802 publication
Summary of the invention
The technical problem to be solved in the present invention
Nowadays the surface of concrete structure processes needs to adapt to stricter construction environment.Such as, sewer facility
In widely used concrete structure due to the development of the coveringization of facility, cause the corruption of concrete structure because generating sulphuric acid
Lose the most serious.In this context, the surface process requirement of concrete structure meets general juridical person's sewer thing
The anticorrosion technique of the sewer concrete structure of industry support center distribution and anticorrosion technique guide (in April, 2012) institute
Specification C of regulation and the quality specification of D kind.
But, the present inventor etc. is found that while that the thick film construction water resin combination that patent documentation 5 and 6 proposes can
The overlay film excellent to form resistance to water, acid resistance and alkali resistance, but the most not up to have and meet above-mentioned specification C and D kind
The characteristic of quality specification.
The present invention is to solve that above-mentioned such problem forms, its object is to provide a kind of thick film construction water resin
Compositions and preparation method thereof, surface treatment method and concrete structure thereof, described thick film construction water resin combination
Can be formed and can not produce foul smell, resistance to water, acid resistance when thick film construction and being dried within being coated with latter 12 hours, operation
And the overlay film that alkali resistance is excellent, it is particularly possible to form anticorrosion technique and the anticorrosion meeting sewer concrete structure
Specification C of technical manual (in April, 2012) defined and the overlay film of the quality specification of D kind.
Solve the technological means of technical problem
The present inventor etc. have been carried out conscientiously studying to solve problem above, it was found that by closing containing aqueous
Resin Emulsion and implant, non-volatile component be that the thick film construction water resin combination of 65～80 mass % is carried out
Vacuum defoamation processes, and relative to the ratio of Theoretical specific gravity, actual specific gravity is adjusted to more than 97%, can be formed and meet above-mentioned rule
The overlay film of the quality specification of lattice C and D kind, thus complete the present invention.
That is, the present invention is following (1)～the content of (8).
(1) a kind of thick film construction water resin combination, it is characterised in that it is containing aqueous synthetic-resin Emulsion
And thick film construction water resin combination that implant (B), non-volatile component are 65～80 mass %, its actual ratio (A)
Heavy phase for the ratio of Theoretical specific gravity more than 97%.
(2) according to the thick film construction water resin combination described in (1st) item, it is characterised in that carried out vacuum and taken off
Bubble processes.
(3) according to the thick film construction water resin combination described in (1st) or (2) item, it is characterised in that described aqueous
Synthetic resin Emulsion (A) is styrene-acrylic resin Emulsion.
(4) according to the thick film construction water resin combination described in any one in (1st)～(3), it is characterised in that
Described implant (B) is be made up of polystyrene, polyethylene, polypropylene, glass dust, glass flake, Pulvis Talci and clay
At least one selected in group.
(5) preparation method of a kind of thick film construction water resin combination, it is a kind of containing aqueous synthetic-resin breast
Agent (A) and implant (B), non-volatile component are that 65～80 mass %, actual specific gravity exist relative to the ratio of Theoretical specific gravity
The preparation method of the thick film construction water resin combination of more than 97%, it is characterised in that mix described aqueous synthetic-resin
After Emulsion (A) and described implant (B), carry out vacuum defoamation process.
(6) a kind of surface treatment method, it is characterised in that by will be according to the thickness described in any one in (1st)～(4)
Film construction water resin combination is coated on the surface of treated object and makes it be dried formation overlay film.
(7) according to the surface treatment method described in (6th) item, it is characterised in that described treated object is xoncrete structure
Thing.
(8) a kind of concrete structure, it is the concrete structure on surface with protection overlay film, it is characterised in that
Described protection overlay film will be for by being coated with according to the thick film construction water resin combination described in any one in (1st)～(4)
Cloth makes it be dried the overlay film formed on the surface of treated object.
Invention effect
The present invention provide a kind of thick film construction water resin combination and preparation method thereof, surface treatment method and
Concrete structure, described thick film construction water resin combination can form that make can be 12 little after thick film construction and coating
Be dried time within, operation time do not produce foul smell, resistance to water, overlay film that acid resistance and alkali resistance are excellent, it is particularly possible to form symbol
Close the anticorrosion technique of sewer concrete structure and specification C of anticorrosion technique guide (in April, 2012) defined and D
The overlay film of the quality specification of kind.
Detailed description of the invention
The present invention is described in detail below.
The thick film construction water resin combination of the present invention contains aqueous synthetic-resin Emulsion (A) and implant (B).
Aqueous synthetic-resin Emulsion (A) is can to make containing olefinic not by using water soluble polymer or surfactant etc.
The compositions etc. of saturated monomer carries out emulsion polymers or the emulsion polymer that radical polymerization obtains.
As emulsion polymers, styrene-acrylic resin Emulsion, acrylic resin emulsion, ethylene-vinegar can be enumerated
Vinyl acetate class Emulsion, vinyl acetate esters Emulsion, urethane esters Emulsion, urethane-acrylic class Emulsion,
Polyesters Emulsion, polyester-acrylics Emulsion etc..Additionally, as emulsion polymer, styrene-butadiene resinoid can be enumerated
Latex, acrylonitrile-butadiene resinoid latex, chloro-butyric resin emulsion etc..Can be used alone or be used in combination of two or more
These materials.In addition it is also possible to use organic resin emulsifying with emulsion polymers or emulsion polymer, be dispersed in water simultaneously
Suspension.
Additionally, in above-mentioned various compositions, with the tune of the character of the non-volatile component etc. of aqueous synthetic-resin Emulsion (A)
From the perspective of whole, the planning of resin Tg, miscibility are with transitivity, optimization styrene-acrylic resin emulsion, acrylic compounds
Resin emulsion, with from the point of view of the point that acid resistance, alkali resistance are excellent, particularly preferred styrene-acrylic resin Emulsion.
Styrene-acrylic resin Emulsion can be by making containing olefinic in the presence of water solublity or water dispersible polyethylene
The compositionss of unsaturated monomer etc. carry out radical polymerization and obtain.
In the resinous principle of styrene-acrylic resin Emulsion, the composition from styrene monomer is preferably 10～80
Quality %, more preferably 40～60 mass %.If the composition from styrene monomer is less than 10 mass %, then under the toughness of overlay film
Fall.On the other hand, if the composition from styrene monomer is more than 80 mass %, then film property declines, and the physical property of overlay film declines.This
Outward, in order to improve film property then need increase coalescents amount.
It is not particularly limited as implant (B), it is possible to use organic filler, inorganic filler or their mixture.
It is not particularly limited as organic filler, is preferably insoluble in the organic polymer powder of water.Here, be insoluble in water
Refer to 23 DEG C, under 1atm relative to the dissolubility of 100g water at below 0.1g.
Be not particularly limited as organic filler, it is possible to use for prevent unsaturated polyester resin molding crackle or
Thermoplastic resin powder's (shrinking agent) etc. of warpage.As the example of organic filler, polyethylene, polypropylene can be enumerated, gather
Styrene, polymethyl methacrylate and copolymer thereof, vinylacetate and copolymer thereof, unsaturated polyester (UP) (aliphatic ester, virtue
Fragrant race ester), acetylbutyrylcellulose, 6-caprolactone polymer, polybutadiene, polrvinyl chloride etc..Additionally, be used as such as benzene
The polymer of elastomer class of ethylene-butadiene-styrene (SBS) block polymer, starch powder, cellulose powder.Permissible
It is used alone or is used in combination of two or more these materials.Additionally, in these compositions, from miscibility and the angle of durability
From the point of view of, preferably polystyrene, polyethylene, polypropylene, particularly preferred polystyrene.
Be not particularly limited as inorganic filler, can enumerate such as glass dust, glass flake, glass microballoon, glass fibre,
Silica sand, Pulvis Talci, Muscovitum, Kaolin clay or burn till the clays such as clay, aluminium hydroxide, zinc oxide, titanium oxide, silicic acid, silicic acid
Salt, magnesium oxide, silicon dioxide etc..Can be used alone or be applied in combination these materials two or more.Additionally, at these compositions
In, from the perspective of miscibility and durability, particularly preferred glass dust, glass flake, Pulvis Talci, clay.
The content of implant (B) is not particularly limited, relative to the non-volatile component of thick film construction water resin combination,
It is preferably more than 15 mass %, more than more preferably 20 mass %, more preferably more than 25 mass %, most preferably 30 matter
Amount more than %.Relative to thick film construction water resin combination non-volatile component implant (B) if content less than 15 matter
, there is thick film drying property and sealing, acid resistance, the tendency of alkali resistance reduction in amount %.The upper content limit of implant (B) is without spy
Do not limit, be preferably below 85 mass % relative to the non-volatile component of thick film construction water resin combination, more preferably
Below 80 mass %, more preferably below 75 mass %, below most preferably 70 mass %.
The mean diameter of implant (B) is not particularly limited, and from the perspective of dispersibility, is 1 μm～150 μm, and preferably 1
μm～100 μm, more preferably 1 μm～50 μm.Here, in this specification " mean diameter " refer to according to laser diffraction and scattering method or
The mean diameter that coulter counter method (Coulter counter method) etc. is measured, preferably according to laser diffraction and scattering method
The mean diameter measured.Refer to according to this according to the mean diameter that laser diffraction and scattering method or coulter counter method etc. are measured
The particle diameter of aggregate-value 50% in particle size distribution obtained by a little methods.Implant (B) if mean diameter less than 1 μm, then fill
Thing (B) easily coagulation, it is impossible to obtain desired dispersibility.On the other hand, implant (B) if mean diameter more than 150 μm,
Then it is difficult to be evenly dispersed in thick film construction water resin combination, is difficult to form uniform overlay film, the thing of overlay film simultaneously
Property (intensity, durability) also can reduce.
In the thick film construction water resin combination of the present invention, the solid constituent of aqueous synthetic-resin Emulsion (A) is (no
Volatile ingredient) it is not particularly limited with the ratio (mass ratio) of the solid constituent of implant (B), preferably 8/2～2/8, more preferably
7/3～3/7, most preferably 6/4～4/6.Here, in this manual, aqueous synthetic-resin Emulsion (A) and implant (B)
Solid constituent refer to be formed non-volatile during overlay film and the nonvolatile component that remains in overlay film.Aqueous synthetic-resin Emulsion (A)
Solid constituent and implant (B) solid constituent ratio (hereinafter referred to as " solid constituent than ".) in the case of more than 8/2,
In the case of i.e. the solid constituent of aqueous synthetic-resin Emulsion (A) is too much, it is impossible to obtain desired drying property, overlay film can be reduced
Physical property (intensity, durability etc.).On the other hand, solid constituent ratio is in the case of less than 2/8, i.e. the solid of implant (B) becomes
In the case of dividing too much, while can not obtaining the stability of thick film construction water resin combination fully, due to difficulty
To form uniform overlay film, the durability (resistance to water, acid resistance, alkali resistance) of overlay film can be reduced.
Under the scope not hindering effect of the present invention, the thick film construction water resin combination of the present invention can be according to making
Known plasticizer, tackifying resin, viscosifier, firming agent, defoamer, preservative etc. are added aptly by purpose.
By carrying out vacuum defoamation process after mixing mentioned component, the thick film construction water resin of the present invention can be prepared
Compositions.Here, " vacuum defoamation process " refers to use vacuum pump etc. to use mixing dress while reducing pressure in this specification
Put and carry out mixed processing.It is not particularly limited as mixing arrangement, it is possible to use disperser, Banbury (trade mark) blender, planet
Blender, pellet blender, mixing roller, vacuum kneader etc..
The thick film construction water resin combination actual specific gravity of the present invention relative to the ratio of Theoretical specific gravity be 97% with
On.Here, the Theoretical specific gravity proportion that refers to be calculated by the proportion of ingredient in thick film construction water resin combination
Theoretical value, actual specific gravity refers to the measured value of the proportion of the thick film construction water resin combination of actual preparation.The survey of proportion
Surely gravimetric method can be used to be measured.
As by actual specific gravity relative to the ratio of Theoretical specific gravity adjust to more than 97% method be not particularly limited, permissible
Adjust by carrying out above-mentioned vacuum defoamation process.By by actual specific gravity relative to the ratio of Theoretical specific gravity adjust to 97% with
On, the acid resistance of the overlay film of formation can be significantly improved, make formation meet the anticorrosion technique of sewer concrete structure with
And the overlay film of the quality specification of specification C of anticorrosion technique guide (in April, 2012) defined and D kind is possibly realized.Additionally,
Generally, in order to actual specific gravity be adjusted to more than 97% relative to the ratio of Theoretical specific gravity, need interpolation (the most usual
More than 10 times of addition) defoamer, be not required to increase the amount of defoamer by using vacuum defoamation to process.
The minimum film formation temperature of the thick film construction water resin combination of the present invention is not particularly limited, preferably 0～5
DEG C, more preferably 0 DEG C.If minimum film formation temperature is higher than 5 DEG C, then easily affected by baking temperature condition, reduced film property, no
The overlay film with desired durability can be obtained.Additionally, the minimum film formation temperature of thick film construction water resin combination
Method of adjustment is not particularly limited, can be by adding coalescents or by aqueous synthetic-resin Emulsion low for minimum film formation temperature
(A) it is added in the aqueous synthetic-resin Emulsion (A) that minimum film formation temperature is high and carries out.
About the thick film construction water resin combination of the present invention, non-volatile component is 65～80 mass %, is preferably
65～75 mass %.By being adjusted by non-volatile component to above-mentioned scope, the drying property of excellence can be showed.If non-volatile component
Less than 65 mass %, then drying property is insufficient, needs a large amount of additives in order to ensure operability.On the other hand, non-volatile component
If more than 80 mass %, then the stability of thick film construction water resin combination reduces, and extremely rising due to viscosity can be behaviour
Come into question in the property made.Additionally, non-volatile component is not particularly limited, can survey according to method known in this technical field
Fixed, the value preferably measured according to method described in embodiment.
The viscosity of the thick film construction water resin combination of the present invention is not particularly limited, preferably 8,000mPa s～
80,000mPa s, more preferably 9,000mPa s～60,000mPa s, most preferably 10,000mPa s～50,
000mPa·s.By viscosity being adjusted to above-mentioned scope, the thick film of more than the 1mm that can construct.If viscosity is less than 8,000mPa
S, can produce sagging after coating, and also the defect of crackle etc. when can produce dry.On the other hand, if viscosity is more than 80,
000mPa s, owing to application property reduces, majority can not be practically applicable in this purposes.Additionally, viscosity is not particularly limited, Ke Yiyi
It is measured according to method known in this technical field, the value preferably measured according to method described in embodiment.
About the thick film construction water resin combination of the present invention, coated and dried on treated object surface after cover
The thickness of film is preferably 0.1mm～2mm, more preferably 0.5mm～2mm.Here, as the assay method of thickness of overlay film without spy
Do not limit, it is possible to use commercially available film thickness gauge is measured.If the thickness of overlay film is less than 0.1mm, though depending on treated object table
Surface state, but the seriality that can not obtain overlay film fully can be caused because of the generation of pin hole etc..On the other hand, the thickness of overlay film
If more than 2mm, the main cause postponing to be dried can be become, can cause playing sufficient performance.
The thick film construction water resin combination of the present invention is not owing to containing organic solvent etc. or comprising only a small amount of having
Machine solvent etc., do not produce foul smell during operation, gentle to environment, and drying property is the best.Additionally, due to by the thick film of the present invention
Construction water resin combination is coated on the surface of the treated objects such as concrete structure, by making it naturally dry with room temperature
Dry, the overlay film that resistance to water, acid resistance and alkali resistance are excellent can be formed, it is believed that this overlay film is as protection overlay film, with quilt
The raising of the durability on processed material surface is relevant.Here, concrete structure refers to by common concrete, mortar etc.
The concept of the works constituted.
Coating process as the thick film construction water resin combination of the present invention is not particularly limited, and can enumerate and such as spray
Painting, roller coat, blade coating etc..Coating weight (solid constituent) suitably can determine according to application target, preferably 0.1kg/m2~
3.0kg/m2, more preferably 0.5kg/m2～2.5kg/m2.If coating weight is less than 0.1kg/m2, then overlay film can not be obtained fully
Seriality, pin hole etc. can be produced.On the other hand, if coating weight is more than 3.0kg/m2, the main cause postponing to be dried can be become,
Can cause playing sufficient performance.
Thick film construction water resin combination by the present invention is coated on the surface of the treated objects such as concrete structure
Time upper, it is possible to use subbing.As subbing, such as acrylic emulsion class subbing (priming paint, closing can be enumerated
Paint), epoxies subbing, urethane esters subbing etc..
Embodiment
Below according to embodiment and comparative example, the present invention is described in detail, and the present invention is not limited by these examples
Fixed.Additionally, about the aqueous synthetic-resin Emulsion used in embodiment and comparative example, the thick film construction water tree of preparation
The various characteristics of oil/fat composition make to be evaluated using the following method.
(non-volatile component)
In the aluminum ware of diameter 5cm, weigh the aqueous synthetic-resin Emulsion of about 1g, with 105 DEG C carry out 1 hour be dried,
Calculate by weighing residual fraction.
(viscosity)
Use Brooker Fil moral (Brookfield) rotating cylinder viscometer with temperature of liquid 23 DEG C, rotation number 10rpm, use
No. 5 rotors are determined.
(pH)
Hydrogen ion determination apparatus is used to determine the pH of thick film construction water resin combination.
(minimum film formation temperature (MFT))
The MFT of thick film construction water resin combination is determined on the basis of JIS K 6828.
(drying property)
Make housing on a glass, to make the dried thickness mode as 2mm, inject thick film construction water wherein
Property resin combination, under 20 DEG C × 50%RH environment, measure dry tack free until the state that leaves no trace when touching with hands
Time.
(crackle)
In the evaluation of above-mentioned drying property, whether crack after drying with visual valuation.
Zero: do not crack
△: overlay film surface produces fold etc. (by drying process it is observed that cosmetic variation)
×: crack
(actual specific gravity is relative to the ratio of Theoretical specific gravity)
Actual specific gravity calculates according to actual specific gravity/Theoretical specific gravity × 100 relative to the ratio of Theoretical specific gravity.
The actual specific gravity of thick film construction water resin combination is constructed by adding thick film in the container of a constant volume
With aqueous resin composition, gravimetric method is used to be measured and obtain.
The Theoretical specific gravity of thick film construction water resin combination based on following composition proportion at 23 DEG C, by
The addition of each composition obtains the volume of each composition, uses below equation (1) to calculate.
(copolymer in cinnamic acrylic ester, from styrene in non-volatile component 50 mass %, resinous principle for Emulsion
Composition 50 mass %, composition 50 mass % from acrylate, viscosity 4500mPa s, minimum film formation temperature 0 DEG C):
1.06mg/mL
Polystyrene type powdex (SGP-70C): 1.05mg/mL
Glass-filled thing (CF0007-05B): 2.6mg/mL
Pulvis Talci (PKP-80): 2.8mg/mL
Defoamer (Nopco 8034L): 0.92mg/mL
The cumulative volume (mL) (1) of gross weight (the mg)/constituent of Theoretical specific gravity (mg/mL)=constituent
(embodiment 1)
Emulsion (copolymer in cinnamic acrylic ester, non-volatile component 50 is employed as aqueous synthetic-resin Emulsion (A)
From cinnamic composition 50 mass %, composition 50 mass % from acrylate, viscosity in quality %, resinous principle
4500mPa s, minimum film formation temperature 0 DEG C), as implant (B) employ polystyrene type powdex (SGP-70C, combine
Grind KCC's system, mean diameter 19 μm).
Relative to the Emulsion of 100 mass parts, add the polystyrene type powdex of 50 mass parts, add 0.05 further
After the defoamer (Nopco 8034L: Co., Ltd.'s SAN NOPCO system) of mass parts, use planetary mixer (PRIMIX strain formula meeting
Society's T.K.HIVIS DISPER MIX3D-5 type), make planetary mixer carry out rotating mix and blend 5 minutes with 45rpm.It
After, use oil rotary vacuum pump carry out decompression make gauge pressure to-0.09MPaG, by 10 minutes continuously mix and blend obtain
Thick film construction water resin combination.Use 80 mesh filter-cloth filtering gained thick film construction water resin combinations, its result,
Confirm not produce coarse grain, agglutinator.
(embodiment 2)
Emulsion is same as in Example 1, except employing glass-filled thing (CF0007-05B, Japan's FRIT strain as implant
Formula commercial firm system, mean diameter: 15 μm) outside, obtain thick film construction water resin combination in the same manner as example 1
Thing.Use 80 mesh filter-cloth filtering gained thick film construction water resin combinations, its result, confirm not produce coarse grain, coagulation
Thing.
(embodiment 3)
Aqueous synthetic-resin Emulsion (A) is same as in Example 1, except employing polystyrene type powder as implant (B)
End resin (SGP-70C, Soken Chemical & Engineering Co., Ltd.'s system, mean diameter 19 μm) and glass-filled thing (CF0007-05B, Japan
FRIT Co., Ltd. system, mean diameter: 15 μm) outside, obtain thick film construction water tree in the same manner as example 1
Oil/fat composition.Here, relative to the Emulsion of 100 mass parts, polystyrene type powdex and the addition of glass-filled thing
It is respectively 25 mass parts.Use 80 mesh filter-cloth filtering gained thick film construction water resin combinations, its result, confirm not produce
Raw coarse grain, agglutinator.
(embodiment 4)
Aqueous synthetic-resin Emulsion (A) is same as in Example 1, except employing polystyrene type powder as implant (B)
End resin (SGP-70C, Soken Chemical & Engineering Co., Ltd.'s system, mean diameter 19 μm) and Pulvis Talci (PKP-80, Fuji's Pulvis Talci work
Industry Co., Ltd. system, mean diameter: 13 μm) outside, obtain thick film construction water resin in the same manner as example 1
Compositions.Here, relative to the Emulsion of 100 mass parts, the addition of polystyrene type powdex and PKP-80 is respectively
25 mass parts.Use 80 mesh filter-cloth filtering gained thick film construction water resin combinations, its result, confirm not produce slightly
Grain, agglutinator.
(comparative example 1)
Employ material same as in Example 1.
Relative to the aqueous synthetic-resin Emulsion (A) of 100 mass parts, add the polystyrene type powder tree of 50 mass parts
Fat, after adding the defoamer (Nopco 8034L: Co., Ltd.'s SAN NOPCO system) of 0.05 mass parts further, divides by using
Dissipate the mix and blend that machine is carried out with 3000rpm 10 minutes, obtain thick film construction water resin combination.Use 80 mesh filter cloth mistakes
Filter gained thick film construction water resin combination, its result, confirm not produce coarse grain, agglutinator.
(comparative example 2)
Except employing glass-filled thing (CF0007-05B, FRIT Co., Ltd. of Japan system, average particle as implant (B)
Footpath: 15 μm) outside, in the way of identical with comparative example 1, obtained thick film construction water resin combination.Use 80 mesh filter clothes
Filter gained thick film construction water resin combination, its result, confirm not produce coarse grain, agglutinator.
(comparative example 3)
(SGP-70C, Soken Chemical & Engineering Co., Ltd.'s system, flat except employing polystyrene type powdex as implant (B)
All particle diameter 19 μm) and glass-filled thing (CF0007-05B, FRIT Co., Ltd. of Japan system, mean diameter: 15 μm) outside, with
The mode identical with comparative example 1 has obtained thick film construction water resin combination.Here, relative to the aqueous of 100 mass parts
Synthetic resin Emulsion (A), the addition of polystyrene type powdex and glass-filled thing is respectively 25 mass parts.Use 80
Mesh filter-cloth filtering gained thick film construction water resin combination, its result, confirm not produce coarse grain, agglutinator.
(comparative example 4)
In addition to the addition of defoamer is changed to 0.25 mass parts, in the way of identical with comparative example 3, obtain thickness
Film construction water resin combination.Use 80 mesh filter-cloth filtering gained thick film construction water resin combinations, its result, really
Recognize and do not produce coarse grain, agglutinator.
(comparative example 5)
In addition to the addition of defoamer is changed to 0.50 mass parts, in the way of identical with comparative example 3, obtain thickness
Film construction water resin combination.Use 80 mesh filter-cloth filtering gained thick film construction water resin combinations, its result, really
Recognize and do not produce coarse grain, agglutinator.
Composition according to the thick film construction water resin combination prepared by above-described embodiment and comparative example and each
Plant characteristic to be summarized in table 1.
[table 1]
As shown in Table 1, the thick film construction water resin combination of embodiment 1～4 and the thick film of comparative example 1～5
Construction water resin combination is identical, and drying property is good, does not also crack as thick film.
Pasting on the glass plate forming housing while mould release membrance, with thickness 2mm (coating weight (solid constituent):
2.5kg/m2) mode inject according to the thick film construction water resin combination prepared by above-described embodiment and comparative example.
Afterwards, carrying out 4 days dried at normal temperatures, peeled off for the time being by overlay film from glass plate, surface and the inner face of upset overlay film exist
Carry out 3 days inner face under room temperature being dried, make overlay film.
Following evaluation has been carried out for gained overlay film.
(overlay film swelling ratio)
Prepared overlay film is cut into 40 × 40mm, and measures its quality, obtain impregnating the quality of front overlay film.Afterwards, will
This overlay film is immersed in after impregnating 7 days at 40 DEG C in 10% aqueous sulfuric acid, takes out overlay film and is impregnated by measuring its quality
The quality of rear overlay film.These quality are used to calculate overlay film swelling ratio by below equation.Additionally, as overlay film swelling ratio from acidproof
The angle of property is preferably less than 10%.
Quality × 100 of overlay film before overlay film swelling ratio=(quality of overlay film before the quality-dipping of overlay film after dipping)/dipping
(overlay film dissolution rate)
Prepared overlay film is cut into 40 × 40mm, and measures its quality, obtain impregnating the quality of front overlay film.Afterwards, will
After this overlay film impregnates 7 days in 10% aqueous sulfuric acid at 40 DEG C, take out the overlay film use water after dipping and clean, then enter at 50 DEG C
Row 24 hours measures its quality after drying and obtains the quality of overlay film after impregnation drying.These quality are used to be calculated by below equation
Overlay film dissolution rate.It is preferably less than 5% from acid proof angle as overlay film dissolution rate.
The quality of overlay film before overlay film dissolution rate=(quality of overlay film after the quality-impregnation drying of overlay film before dipping)/dipping
×100
(overlay film strength retention and overlay film stretching strength retentivity)
Prepared overlay film (25 × 100mm) is cut into the shape of dumbbell 2, with temperature 23 DEG C, draw speed 200mm/
Point carry out tension test, be stretched as basis with maximum intensity and graticule 20mm, cover before determining dipping film strength and
Hot strength.Afterwards, after the overlay film (25 × 100mm) additionally made is impregnated 7 days in 10% aqueous sulfuric acid at 40 DEG C,
Carrying out 12 hours being dried at 40 DEG C, the overlay film after fall impregnation drying cuts into the shape of dumbbell 2, with side similar to the above
Method determines intensity and hot strength.Overlay film strength retention and overlay film stretching strength retentivity are calculated according to below equation
Go out.Additionally, as overlay film strength retention and overlay film stretching strength retentivity from acid proof angle be preferably 80%～
120%.
Film strength × 100 are covered before covering film strength/dipping after overlay film strength retention=impregnation drying
The hot strength of overlay film before the hot strength/dipping of overlay film after overlay film stretching strength retentivity=impregnation drying ×
100
Above-mentioned each evaluation result is as shown in table 2.
[table 2]
As shown in table 2, by carrying out vacuum defoamation method process, by actual specific gravity relative to the ratio of Theoretical specific gravity adjust to
More than 97%, the overlay film that formed by the thick film construction water resin combination of embodiment 1～4, and by comparative example 1～5
The overlay film that formed of thick film construction water resin combination same have good overlay film swelling ratio, overlay film dissolution rate,
Overlay film strength retention and the result of overlay film stretching strength retentivity.
(anticorrosion technique of sewer concrete structure and anticorrosion technique guide (in April, 2012) defined
The quality specification test of specification C and D kind)
(1) outward appearance
Test body is prepared, by its outward appearance of visual valuation on the basis of JIS K5600-1-1:1999 (4.4).Test body
By flexible board (200mm × 150mm × 6mm) the upper coating thick film construction water resin at JIS A5430:2004 defined
Compositions, carries out indoor ripening in 24 hours and prepares in indoor.Additionally, specification C kind design thickness is set as 0.6mm, will
Specification D kind design thickness is set as 0.8mm (setting design thickness in following test similarly).
During this evaluates, by corrugationless on overlay film, inequality, peel off, rupture be expressed as zero, by have on overlay film fold, inequality,
Peel off, rupture be expressed as ×.
(2) cementability and between concrete
Standard state and the cementability of water suction state is have rated on the basis of JIS A6909:2003 (7.9.2 item).
Use on the reinforced cement-mortar board (70 × 70 × 20mm) of preparation on the basis of JIS R5201:1997 (10.4)
Coating thick film construction water resin combination the cementability carrying out standard state in the indoor ripening test body of 24 hours are commented
Valency.
The reinforced cement-mortar board (70 × 70 × 20mm) of preparation on the basis of JIS R5201:1997 (10.4) is immersed in
In the clear water of 23.2 DEG C after 24 hours, use the cloth wiping surface of cleaning, above coating thick film construction water resin group
Compound, indoor ripening 24 hours, uses this test body to carry out the cementability evaluation of water suction state.
In evaluating at this, it is desirable to specification C and D kind under standard state are 1.5N/mm2Above, under water suction state
Specification C and D kind be 1.2N/mm2Above.
(3) acid resistance
Acid resistance is have rated on the basis of JIS K5600-6-1:1999 (7).
About the acid resistance of specification C kind, will be at the cement bonded sand of preparation on the basis of JISR 5201:1997 (10.4)
Pulpboard (150 × 70 × 20mm) upper coating thick film construction water resin combination, and at the indoor ripening test body of 7 days dipping
Enter 10% aqueous sulfuric acid of 20 DEG C after 45 days, by visual valuation on the overlay film of test body whether without expanding, rupturing, soft
Change, dissolution.
About the acid resistance of specification D kind, will be at the cement bonded sand of preparation on the basis of JIS R5201:1997 (10.4)
Pulpboard (150 × 70 × 20mm) upper coating thick film construction water resin combination, and at the indoor ripening test body of 7 days dipping
Enter 10% aqueous sulfuric acid of 20 DEG C after 60 days, by visual valuation on the overlay film of test body whether without expanding, rupturing, soft
Change, dissolution.
In evaluating at this, by overlay film without expanding, rupture, soften, dissolution be expressed as zero, will have expansion on overlay film, break
Split, soften, being expressed as of dissolution ×.
(4) sulfur depth of invasion
Will be in the upper painting of the reinforced cement-mortar board (150 × 70 × 20mm) of preparation on the basis of JIS R5201:1997 (10.4)
Cloth thick film construction water resin combination, and 10% aqueous sulfuric acid of 20 DEG C it is impregnated in the indoor ripening test body of 7 days
After 120 days, take out test body, use mortar cutting machine with the sample starting to be cut out thickness as 1cm from test body middle body
Product.Afterwards, using electronic analysis grinder its section to be ground until being mirrored, implementing metal evaporation also above
Make it for analyzing.Analyzing and use electron probe (EPMA), making analytical element is sulfur, determines in mapping graph picture from the beginning of surface
Sulfur depth of invasion.Relative to background, after invading with the part that x-ray count is more than 15 countings of sulfur for sulfur, sulfur is evaluated in field
Depth of invasion.Additionally, the condition determination of EPMA is as shown below.
Accelerating potential: 15kV
Irradiation electric current: 100 10nA
Electron beam diameter: 2 μm
Sampling time: 50ms
Data point: X-direction 512 × Y-direction 512
In evaluating at this, specification C kind apoplexy due to endogenous wind, it is desirable to the sulfur depth of invasion started from surface is 10% relative to design thickness
Hereinafter, and it is below 200 μm, specification D kind apoplexy due to endogenous wind, it is desirable to the sulfur depth of invasion started from surface is 5% relative to design thickness
Hereinafter, and be below 100 μm.
(5) alkali resistance
Alkali resistance is have rated on the basis of JIS K5600-6-1:1999 (7).
About the alkali resistance of specification C kind, will be at the cement bonded sand of preparation on the basis of JIS R5201:1997 (10.4)
Pulpboard (150 × 70 × 20mm) upper coating thick film construction water resin combination, and at the indoor ripening test body of 7 days dipping
Enter the calcium hydroxide saturated solution of 20 DEG C after 45 days, by visual valuation on the overlay film of test body whether without expanding, rupturing, soft
Change, dissolution.
About the alkali resistance of specification D kind, will be at the cement bonded sand of preparation on the basis of JIS R5201:1997 (10.4)
Pulpboard (150 × 70 × 20mm) upper coating thick film construction water resin combination, and at the indoor ripening test body of 7 days dipping
Enter the calcium hydroxide saturated solution of 20 DEG C after 60 days, by visual valuation on the overlay film of test body whether without expanding, rupturing, soft
Change, dissolution.
In evaluating at this, by overlay film without expanding, rupture, soften, dissolution be expressed as zero, will have expansion on overlay film, break
Split, soften, being expressed as of dissolution ×.
(6) water penetration
Water penetration is have rated on the basis of JIS A1404:1999 (11.5).
By being coated with thick film construction water resin combination on the flexible board of JIS A5430:2004 defined, and
3kgf/cm is applied in the test body that indoor carry out ripening in 24 hours and prepare2Hydraulic pressure after, determine permeable amount.
In evaluating at this, it is desirable to the permeable amount of specification C kind is below 0.20g, and the permeable amount of specification D kind is 0.15g
Below.
Above-mentioned each evaluation result is as shown in table 3 and table 4.Table 3 is the evaluation result of specification C kind, and table 4 is specification D kind
The evaluation result of class.Additionally, only carried out the evaluation of specification D kind for comparative example.
[table 3]
[table 4]
Understand as shown in table 3 and table 4, by carrying out vacuum defoamation method process by actual specific gravity relative to Theoretical specific gravity
The overlay film that thick film construction water resin combination that ratio adjusts to more than 97%, by embodiment 1～4 is formed, meets
The anticorrosion technique of sewer concrete structure and specification C of anticorrosion technique guide (in April, 2012) defined and D kind
The quality specification of class.In contrast, understand the film that formed by the thick film construction water resin combination of comparative example 1～5
The result insufficient of sulfur depth of invasion test, the quality specification of the D kind that at least falls short of specifications.Although especially by improving
The amount of defoamer can improve the actual specific gravity ratio (comparative example 4 and 5) relative to Theoretical specific gravity, but sulfur depth of invasion is tried
The result tested is the most insufficient.
Knowable to result above, can be within thick film construction and being coated with latter 12 hours according to the present invention it is possible to formed
Foul smell is not produced, the overlay film that resistance to water, acid resistance and alkali resistance are excellent, it is particularly possible to provide the one can during that be dried, operation
The anticorrosion technique of sewer concrete structure and anticorrosion technique guide (in April, 2012) defined is met to be formed
Thick film construction water resin combination of the overlay film of the quality specification of specification C and D kind and preparation method thereof, surface process
Method and concrete structure.
Additionally, this international application is based on Japanese patent application filed in 18 days February in 2014 the 2014-028218th
CLAIM OF PRIORITY, is referenced to the full content of these Japanese patent applications in this international application.
Claims (8)
1. a thick film construction water resin combination, its be containing aqueous synthetic-resin Emulsion (A) and implant (B),
Non-volatile component is the thick film construction water resin combination of 65～80 mass %, it is characterised in that its actual specific gravity is relative
In the ratio of Theoretical specific gravity more than 97%.
Thick film construction water resin combination the most according to claim 1, it is characterised in that it has carried out vacuum defoamation
Process.
Thick film construction water resin combination the most according to claim 1 and 2, it is characterised in that described aqueous synthesizes
Resin emulsion (A) is styrene-acrylic resin Emulsion.
4. according to the thick film construction water resin combination described in any one in claims 1 to 3, it is characterised in that institute
Stating implant (B) is the group being made up of polystyrene, polyethylene, polypropylene, glass dust, glass flake, Pulvis Talci and clay
Selected at least one.
5. a preparation method for thick film construction water resin combination, its be containing aqueous synthetic-resin Emulsion (A) and
Implant (B), non-volatile component are that 65～80 mass %, actual specific gravity are relative to thickness more than 97% of the ratio of Theoretical specific gravity
The preparation method of film construction water resin combination, this preparation method is characterised by, mixes described aqueous synthetic-resin breast
Vacuum defoamation process is carried out after agent (A) and described implant (B).
6. a surface treatment method, it is characterised in that by by according to the thick film described in any one in Claims 1 to 4
Construction water resin combination is coated on the surface of treated object and makes it be dried formation overlay film.
Surface treatment method the most according to claim 6, it is characterised in that described treated object is concrete structure.
8. a concrete structure, it is the concrete structure on surface with protection overlay film, it is characterised in that described guarantor
Protecting overlay film is by being coated on according to the thick film construction water resin combination described in any one in Claims 1 to 4
It is made to be dried the overlay film formed on the surface of treated object.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-028218 | 2014-02-18 | ||
| JP2014028218 | 2014-02-18 | ||
| PCT/JP2015/053117 WO2015125605A1 (en) | 2014-02-18 | 2015-02-04 | Aqueous resin composition for forming thick film, manufacturing method therefor, surface treatment method, and concrete structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106029799A true CN106029799A (en) | 2016-10-12 |
Family
ID=53878116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580008809.1A Pending CN106029799A (en) | 2014-02-18 | 2015-02-04 | Aqueous resin composition for forming thick film, manufacturing method therefor, surface treatment method, and concrete structure |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPWO2015125605A1 (en) |
| CN (1) | CN106029799A (en) |
| AU (1) | AU2015220158B2 (en) |
| MY (1) | MY177821A (en) |
| PH (1) | PH12016501626A1 (en) |
| SG (1) | SG11201605931XA (en) |
| WO (1) | WO2015125605A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI749787B (en) * | 2020-09-25 | 2021-12-11 | 譚詠雪 | Paint layer and manufacturing method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017141320A (en) * | 2016-02-08 | 2017-08-17 | 旭化成アドバンス株式会社 | Aqueous lining material for water supply facilities |
| CN114181556B (en) * | 2021-11-23 | 2022-05-27 | 苏州大乘环保新材有限公司 | Water-based EAU high-barrier thick film anticorrosive paint |
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| JPH07157709A (en) * | 1993-12-10 | 1995-06-20 | Toyo Ink Mfg Co Ltd | Aqueous coating composition |
| JP2002309181A (en) * | 2001-04-13 | 2002-10-23 | Mitsubishi Heavy Ind Ltd | Coating material and coating method |
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| JPS551633A (en) * | 1978-06-20 | 1980-01-08 | Hitachi Maxell Ltd | Production of magnetic recording medium |
| JPS551632A (en) * | 1978-06-20 | 1980-01-08 | Hitachi Maxell Ltd | Production of magnetic recording medium |
| JPH10330958A (en) * | 1997-05-28 | 1998-12-15 | Laser Noshuku Gijutsu Kenkyu Kumiai | Coating material and coating method |
| JP2000044843A (en) * | 1998-08-04 | 2000-02-15 | Mitsubishi Heavy Ind Ltd | Coating material and its production |
| JP2007039573A (en) * | 2005-08-04 | 2007-02-15 | Kinki Kankyo Service Kk | Uncured resin-impregnated sheet for protection of structure |
| JP4796469B2 (en) * | 2005-09-30 | 2011-10-19 | ニッタ株式会社 | Sheet body, antenna device, and electronic information transmission device |
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2015
- 2015-02-04 AU AU2015220158A patent/AU2015220158B2/en not_active Ceased
- 2015-02-04 JP JP2016504022A patent/JPWO2015125605A1/en active Pending
- 2015-02-04 SG SG11201605931XA patent/SG11201605931XA/en unknown
- 2015-02-04 WO PCT/JP2015/053117 patent/WO2015125605A1/en active Application Filing
- 2015-02-04 CN CN201580008809.1A patent/CN106029799A/en active Pending
- 2015-02-04 MY MYPI2016702956A patent/MY177821A/en unknown
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2016
- 2016-08-15 PH PH12016501626A patent/PH12016501626A1/en unknown
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| JPH07157709A (en) * | 1993-12-10 | 1995-06-20 | Toyo Ink Mfg Co Ltd | Aqueous coating composition |
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| TWI749787B (en) * | 2020-09-25 | 2021-12-11 | 譚詠雪 | Paint layer and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015125605A1 (en) | 2015-08-27 |
| PH12016501626A1 (en) | 2017-02-06 |
| AU2015220158A1 (en) | 2016-09-01 |
| MY177821A (en) | 2020-09-23 |
| SG11201605931XA (en) | 2016-09-29 |
| JPWO2015125605A1 (en) | 2017-03-30 |
| AU2015220158B2 (en) | 2016-12-01 |
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