CN103857755B - Electrodeposition coating composition - Google Patents
Electrodeposition coating composition Download PDFInfo
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- CN103857755B CN103857755B CN201280047541.9A CN201280047541A CN103857755B CN 103857755 B CN103857755 B CN 103857755B CN 201280047541 A CN201280047541 A CN 201280047541A CN 103857755 B CN103857755 B CN 103857755B
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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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Wood Science & Technology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides heating loss electrodeposition coating composition less than in the past.The electrodeposition coating composition of the present invention is to be substantially free of cross-linking agent, make to carry out electrodeposition coating and after the electrodeposition coating that formed is dried 3 hours at 105 DEG C, the electrodeposition coating composition below 10 mass % of the heating loss after 200 DEG C of heating 25 minutes.The electrodeposition coating composition of the present invention preferably comprises amine-modified epoxy resin (A) obtained by the epoxy resin amines modification that will have bisphenol backbone and the plasticizer (B) as aromatic alcohols compound.
Description
Technical field
The present invention relates to the electrodeposition coating composition that heating loss is few.
Background technology
Currently for metal material, implement electrodeposition coating to give high corrosion protection.Electro-deposition
Application is possible not only to be coated with the thin portion of the coated article being filled to have complicated shape, and can automatically and continuously
Application, is therefore widely used as the primary coat application of the coated article of requirement height corrosion protection.
Electrodeposition coating generally includes electro-deposition operation and curing process.In electro-deposition operation, will be coated with
Thing impregnated in electrodeposition coating composition, in this condition to coated article and electrodeposition coating composition
Between apply voltage.Thus, paint ingredient separates out the surface in coated article, thus forms electro-deposition and be coated with
Film.In curing process, the electrodeposition coating on the surface that will be formed in coated article enters at 120 DEG C～260 DEG C
Row sinters and makes it solidify.
Electrodeposition coating composition is scattered in aqueous medium by binding agent and the pigment etc. making ionizing
The emulsion obtained is constituted.As binding agent, generally use compositions of thermosetting resin.Such as, amine change
Property epoxy resin and the corrosion protection, closely sealed of curing system that formed of the combination of blocked isocyanate solidfied material
Property and all plating property etc. good, be widely used as the binding agent of cation electrodeposition coating.
It addition, in above-mentioned curing system, the end-capping reagent of blocked isocyanate departs from because of heating, from
And carry out curing reaction.Therefore, at painting site, the end-capping reagent of disengaging forms elaioleucite and is attached to do
Dry stove etc., and can be vaporized to air, cause atmospheric pollution.Additionally, be difficult to make end-blocking during solidification
Agent all departs from, and the film after solidification also occurs the volatilization of end-capping reagent, with the film forming remaining in film
Auxiliary agents etc. are released in air together as VOC.From environmental problem and unpleasant odour, sick room (sick
House) from the viewpoint of syndrome and chemical substance anaphylaxis etc. are on the impact of human body, it is desirable to as far as possible
Reduce the VOC (VOC) discharged from dried film.It is therefore desirable to reduce solidification
Time and solidification after heating loss, such as propose have by so that lower temperature makes curing reaction carry out
The electrodeposition coating composition (with reference to patent documentation 1) of heating loss when decreasing solidification.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2002-275413 publication
The summary of invention
Invent technical problem to be solved
But, even if using the electrodeposition coating composition of patent documentation 1, dried electro-deposition is coated with
Film 200 DEG C heating 25 minutes after heating loss also above 10 mass %, it is desirable to reduce heating further
Decrement.
The present invention is the invention completed in view of the foregoing, its object is to provide heating loss than ever
Less electrodeposition coating composition.
Solve the technical scheme that technical problem is used
To achieve these goals, the present invention provides the electrodeposition coating composition that heating loss is few, its
In, it is substantially free of cross-linking agent, makes to carry out electrodeposition coating and the electrodeposition coating that formed is done at 105 DEG C
After dry 3 hours, the heating loss after heating 25 minutes at 200 DEG C is below 10 mass %.
Above-mentioned electrodeposition coating composition preferably comprises will have the epoxy resin amination of bisphenol backbone
Amine-modified epoxy resin obtained by polymer modified (A) and include the plasticising formed by aromatic alcohols compound
The plasticizer (B) of agent (B-1).
Above-mentioned plasticizer (B-1) preferably has the structure represented with following formula (1), and relative to upper
State when amine-modified epoxy resin (A) mixes 10 times amount by quality ratio and dissolve above-mentioned amine-modified epoxy resin
(A)。
[changing 1]
Formula (1)
In formula (1), R is CpH2p(p is the integer of 1～3, lower with), O (CmH2mO)p(m be 2～5 whole
Number, lower same) or CH2O-(CmH2mO)n(n is 1 or 2), X is H or OCH3。
Above-mentioned plasticizer (B) preferably also includes the plasticizer (B-2) in addition to above-mentioned plasticizer (B-1),
Plasticizer (B-2) is in water-insoluble, and viscosity is at below 1000mPa s, and relative to above-mentioned amine modification ring
Above-mentioned amine-modified epoxy resin (A) is dissolved during epoxy resins (A) mixed in equal amounts by quality ratio.
The content summation of above-mentioned plasticizer (B-1) and above-mentioned plasticizer (B-2) is preferably relative to above-mentioned amine
Modified epoxy (A) is more than 39 mass %.
The molecular weight of the above-mentioned epoxy resin with bisphenol backbone is preferably more than 2000.
Additionally, the present invention provides through carry out above-mentioned electrodeposition coating composition electrodeposition coating in base material
Form the electrodeposition coating forming method of electrodeposition coating.
The effect of invention
If the employing present invention, then in the case of without cross-linking agent, constitute electrodeposition coating composition,
Therefore, it is possible to after the electrodeposition coating making to carry out electrodeposition coating and being formed is dried 3 hours at 105 DEG C,
200 DEG C heating 25 minutes after heating loss below 10 mass %, it is possible to provide heating loss is the most more
Few electrodeposition coating composition.Electrodeposition coating based on the present invention has above-mentioned feature, thus
Dried chemical substance can be reduced from film being vaporized in air, such as, can make will heat 40 at 200 DEG C
Electrodeposition coating after minute 240 DEG C heating 25 minutes after high-temperature heating decrement below 2%.
The mode carried out an invention
<electrodeposition coating composition>
The electrodeposition coating composition of present embodiment is the electro-deposition making to carry out electrodeposition coating and being formed
Film is dried after 3 hours at 105 DEG C, the heating loss after 200 DEG C of heating 25 minutes 10 mass % with
Under, and it is substantially free of the electrodeposition coating composition of cross-linking agent.That is, current electrocoating paint group
In compound, above-mentioned heating loss is more than 10 mass %, and the electrodeposition coating composition of present embodiment
In, above-mentioned heating loss is below 10 mass %, and heating loss is less than in the past.Preferably above-mentioned heating
Decrement is below 5 mass %
Here, " heating loss " refers to specifically carry out the operation of following (a)～(g), by following
The value that formula (1) calculates.But, it is impossible to obtain good film property and electrodeposition coating cannot be formed
In the case of, it is impossible to calculate heating loss, therefore not included in present embodiment " heating loss exists
Below 10 mass % " in the range of.Here, film property has the temperature (bath of electrodeposition coating composition
Temperature) the highest the highest characteristic in common scope, it is generally acknowledged preferred bath temperature 10 DEG C～40 DEG C
In the range of can ensure that film property, if heating loss is below 10 mass %, be then included in this enforcement
In the range of mode.
(a) first, accurate weighing bread board, try to achieve bread board weight A before electrodeposition coating.
B () makes bread board impregnated in electrodeposition coating composition, reach 20 μm with dried thickness
Condition implements electrodeposition coating.
C bread board after electrodeposition coating is washed by () after, make to be formed at the moistening of bread board surface
Film is dried 3 hours at 105 DEG C.
D () is dried, bread board is cooled in exsiccator accurate weighing after room temperature, obtains dried
Bread board weight B.
E (), for dried bread board, implements the sintering of 25 minutes at 200 DEG C.
After (f) sintering, bread board is cooled in exsiccator accurate weighing after room temperature, after obtaining sintering
Bread board weight C.
G () is by bread board weight A before the electrodeposition coating that will try to achieve as mentioned above, dried examination
Test bread board weight C after plate weight B and sintering and substitute into following formula (1), calculate heating loss D.
[several 1]
D (%)=[1-(C-A)/(B-A)] × 100 formulas (1)
Additionally, " high-temperature heating decrement " refers in the operation of above-mentioned (a)～(g), implement 40 at 200 DEG C
Minute (c) drying condition and 240 DEG C implement 25 minutes (e) drying condition in the case of
Heating loss.High-temperature heating decrement can be passed through, to the film after chemical substance self-desiccation in air
It is vaporized and is evaluated.
Additionally, " being substantially free of cross-linking agent " refers to without being solidified with electrodeposition coating meaningful
The cross-linking agent of amount of contribution.That is, the electrodeposition coating composition of present embodiment is to be not based on crosslinking
React but by making solvent volatilization obtain volatilization (Lacquer) the type electricity of the film with corrosion protection
Electrodeposition coating compositions.The content of cross-linking agent is preferably in 10 mass relative to electrodeposition coating composition
Below %, more preferably below 5 mass %, the most more preferably below 1 mass %.
The electrodeposition coating composition of present embodiment preferably comprises will have the asphalt mixtures modified by epoxy resin of bisphenol backbone
Amine-modified epoxy resin (A) obtained by fat amines modification and including by aromatic alcohols compound shape
The cation electric deposition paint composition of the plasticizer (B) of the plasticizer (B-1) become.
Amine-modified epoxy resin (A) is modified by the epoxy resin amines that will have bisphenol backbone
And obtain.The outspoken nature of the epoxy resin with bisphenol backbone is high, and resin itself possesses good corrosion protection.
The representational epoxy resin with bisphenol backbone has bisphenol-A and bisphenol-A as shown in following formula (2)
Diglycidyl ether condensation obtained by structure.N in following formula (2) represents integer.
[changing 2]
... formula (2)
Having in the epoxy resin of bisphenol backbone, the ratio shared by bisphenol backbone is preferably in 90 mass %
Above.Use the epoxy that the ratio shared by bisphenol backbone is high, outspoken nature is high in epoxy resin like this
Resin, can obtain good corrosion protection.Here, " bisphenol backbone " refers to represent with above-mentioned formula (2)
Skeleton.
The molecular weight of the epoxy resin with bisphenol backbone is preferably more than 2000.More preferably 2000～
9000, the most more preferably 3000～8000.As having the epoxy resin of bisphenol backbone, by making
With the resin of such high molecular, good film can be formed, it is thus achieved that good corrosion protection, also may be used
Obtain good resistance to water.Here, " molecular weight " refers to have the structure as shown in above-mentioned formula (2)
In the case of the value that calculates with epoxide equivalent × 2.
Epoxide equivalent in the present invention can pass through method based on JIS K7236, but uses methyl ethyl ketone
(MEK) replace determining as the chloroform of the solvent of dissolving resin.
As having the epoxy resin of bisphenol backbone, commercially available product be can be used directly, it be also possible to use and make bisphenol-A
The resin being condensed with the diglycidyl ether of bisphenol-A and synthesize.As synthetic method, can use arbitrarily
Proper method.Such as, following method can be enumerated: by mixing bisphenol-A relative to bisphenol-A excess
Diglycidyl ether, makees organic bases such as dimethyl benzylamines in the organic solvents such as methyl iso-butyl ketone (MIBK)
Carry out heating synthesizing for catalyst.Carry out reaction tracking preferably by measuring epoxide equivalent, reaching
Reaction is made to terminate to during as the epoxide equivalent of target.If it is considered that use the modification of amines to exist
The organic solvents such as methyl iso-butyl ketone (MIBK) are carried out, make solid epoxy be dissolved in organic solvent need flower
Time etc., then preferably use the resin being synthesized into.The electrodeposition coating composition of present embodiment
The organic solvent used when can comprise the synthesis of amine-modified epoxy resin (A), but preferably enter in post synthesis
Row solvent is replaced so that it is the organic solvent used when being substantially free of synthesis.
The amine of the epoxy resin with bisphenol backbone is modified typically by the amination with active hydrogen
Compound makes the epoxy ring-opening addition of the epoxy resin as raw material carry out.The degree of modification of epoxy radicals is relatively
It is more than 90% well, the most substantially makes whole epoxy-modified.Here, " epoxy radicals
Degree of modification " refer to the amino of the amines of institute's addition total mole number relative to having bisphenol backbone
The ratio of the total mole number of epoxy radicals that had of epoxy resin.
The modified amount of amine-modified epoxy resin (A) is preferably below 10 mass %.By making modified amount exist
Below 10 mass %, good corrosion protection can be obtained.Additionally, the lower limit of modified amount is not particularly limited,
As long as the amount that amine-modified epoxy resin (A) is dispersed among in water.This is because as described later, amine
Whether modified epoxy (A) is dispersed in water and is determined by various factors.Here, " modified amount " refers to
Quality relative to epoxy resin and the epoxy radicals to epoxy resin carry out open loop addition compound (with
Quality %=of the open loop additive compound of the total amount of quality the most also referred to as " open loop additive compound ") is opened
The quality of cycloaddition compound/(quality of the quality of epoxy resin+open loop additive compound) × 100.Open
In the case of cycloaddition compound uses diketimine compound, the quality of open loop additive compound refers to
The amount of the amines generated in resin after hydrolysis.
As the epoxy radicals of epoxy resin being carried out the compound of open loop addition, can enumerate butylamine, octylame,
Diethylamine, dibutyl amine, methyl butyl amine, monoethanolamine, diethanolamine, N-methylethanolamine, ammonia
Base ehtylethanolamine, the ketimide compound of these amine and diethylenetriamines and diethylenetriamines
The amines such as diketimine compound, single phenols such as phenol, cresol, nonyl phenol, nitrophenol,
The unary alcohols such as hexanol, 2-Ethylhexyl Alcohol, stearyl alcohol, ethylene glycol, monohexyl ether, stearic acid, octanoic acid
Deng aliphatic monocarboxylic acid class, glycolic, dihydromethyl propionic acid, hydroxyl trimethylace tonitric, lactic acid, lemon
The aliphatic hydroxyl carboxylic acids such as lemon acid, the sulfydryl alkanol etc. such as mercaptoethanol.These open loop additive compounds can
It is used alone, it is possible to two or more is applied in combination.Wherein, it is preferred to use diketimine compound.By making
Using diketimine compound, during neutralization described later, can generate primary amino radical, the Physical properties of coating film such as adaptation improves.
It is taken as modification (open loop addition) method of amines, arbitrary proper method can be used.
Such as, following method can be enumerated: make to be dissolved in as the epoxy resin with bisphenol backbone of raw material
In machine solvent, the approximately equal amounts of amines adding the epoxy radicals that epoxy resin is had mixes
After, heat as required.
Amine-modified epoxy resin (A) is preferably its amino and is neutralized by acid compound.Thus, amine can be made
Modified epoxy (A) is uniformly dispersed in water.The neutralization ratio of amine-modified epoxy resin (A), i.e. acid
The ratio of the equivalent of the amino that the equivalent of compound is had relative to amine-modified epoxy resin (A) is preferable
It is 10%～100%.
As acid compound, the mineral acids such as such as hydrochloric acid, nitric acid, phosphoric acid and sulfamic acid can be enumerated,
The organic acid of carboxylic acid compound such as including formic acid, acetic acid, propanoic acid and lactic acid.These acid compounds can be single
Solely use, it is possible to two or more is applied in combination.Wherein, organic acid is preferably used, particularly preferably uses carboxylic
Acid compound.By amine-modified epoxy resin (A) being neutralized with these acid compounds, can obtain preferably
Corrosion protection.In carboxylic acid compound, from the viewpoint of volatility, acetic acid is preferably used.Such as, use
The diethylenetriamines modified epoxy (A) that acetic acid has neutralized represents with following formula (3).Following logical
N in formula (3) represents integer.
[changing 3]
... formula (3)
Amine-modified epoxy resin (A) whether be dispersed in water the molecular weight by amine-modified epoxy resin (A) and
The equivalent of amino, the kind of amines for modified, the kind of acid compound and incorporation (neutralize
Rate) etc. determine.Therefore, can carry out lo-tionized by adjusting these parameters.
Plasticizer (B) includes the plasticizer (B-1) formed by aromatic alcohols compound.By comprising so
Plasticizer (B-1), it can be ensured that film property during electro-deposition, it is thus achieved that possess based on epoxy resin upright and outspoken
The electrodeposition coating of the high corrosion protection of property.
Plasticizer (B-1) is to have the structure represented with following formula (1), and relative to amine modified epoxy
Resin (A) dissolves the plasticizer of amine-modified epoxy resin (A) when mixing 10 times amount by quality ratio.Here,
" dissolve " when referring to mix amine-modified epoxy resin (A) and plasticizer (B-1) with the mass ratio of 1:10,
Without muddy, uniformly mix, it is thus achieved that transparent solution.
[changing 4]
Formula (1)
In formula (1), R is CpH2p(p is the integer of 1～3, lower with), O (CmH2mO)p(m be 2～5 whole
Number, lower same) or CH2O-(CmH2mO)n(n is 1 or 2), X is H or OCH3。
As the object lesson of plasticizer (B-1), benzylalcohol (BzOH), 2-phenylethanol can be enumerated
(2-pH-EtOH), 3-phenyl-1-propanol (3-pH-1-PrOH), 4-methoxyl group benzylalcohol (4-MeO-BzOH),
Ethyleneglycol monophenylether (PhG), ethylene glycol monobenzyl ether (BzG) etc..Wherein, it is preferred to use lower boiling benzyl
Alcohol.
Plasticizer (B) may also include the plasticizer (B-2) in addition to above-mentioned plasticizer (B-1).Plasticizer
(B-2) in aqueous under room temperature (25 DEG C), its viscosity is at below 1000mPa s, preferably at 500mPa
Below s.Additionally, plasticizer (B-2) is in water-insoluble.Here, " water-insoluble " refer to cannot be with
The state that water freely mixes, is the most substantially not dissolved in the state of water.Specifically, plasticizer (B-2)
Water solubility under room temperature (25 DEG C) preferably relative to 100 mass parts water below 10 mass parts.Logical
Cross interpolation plasticizer (B-2), the raising effect of outward appearance based on plasticizer (B-1) can be improved.Plasticizer
(B-2) viscosity refers to use E type viscometer (such as Toki Sangyo Co., Ltd. (society) system)
20 DEG C of values measured.
Additionally, plasticizer (B-2) is relative to amine-modified epoxy resin (A) mixed in equal amounts by quality ratio
Time dissolve amine-modified epoxy resin (A) plasticizer.But, plasticizer (B-2) is with plasticizer (B-1) no
With, amine modification ring cannot be dissolved when mixing 10 times amount by quality ratio relative to amine-modified epoxy resin (A)
Epoxy resins (A) and occur be separated.Here, " dissolving " refers to amine-modified epoxy resin (A) and increases
When moulding agent (B-2) mixed in equal amounts, without muddy, uniformly mix, it is thus achieved that transparent solution.
As the object lesson of plasticizer (B-2), can enumerate dibutyl ethylene glycol ether (diethylene glycol dibutyl ether,
DBDG), dipropylene glycol monopropyl ether (dipropyl glycol list propyl ether, PFDG), propylene glycol monobutyl ether (PnB),
Dipropylene glycol mono-n-butyl Ether (DPnB), dipropyl ethylene glycol monobutyl ether (BFDG), Tri(propylene glycol)butyl ether,mixture of isomers (TPnB)
With the glycol ethers compounds such as polypropylene glycol #1000, phthalic acid dibutyl ester (DBP), phthalic acid two
-2-ethyl hexyl ester (DOP), phthalic acid dinonyl (DINP), phthalic acid two isodecyl ester
(DIDP), phthalic acid two heptyl ester (DHP), phthalic acid di-n-octyl (N-DOP), phthalic acid fourth
Benzyl ester (BBP), phthalic acid monoethylene glycol ester, adipic acid two-2-ethyl hexyl ester (DOA) and adipic acid
The carboxylic acid ester compounds such as double butoxyethyls (BXA), methyl iso-butyl ketone (MIBK) (MIBK), methyl ethyl ketone
(MEK), methyl amyl ketone (MAK) etc..Additionally, as the commercially available product of plasticizer (B-2), can enumerate
Solvesso200 (exxon chemical company (エ Network ソ Application KCC) system).These plasticizers
(B-2) can be used alone, it is possible to two or more is applied in combination.Wherein, come from the viewpoint of long-time stability
See, the compound without ester bond is preferably used in molecule.Additionally, from the viewpoint of foul smell, excellent
Choosing uses glycol ethers compound.
The content summation of plasticizer (B-1) and plasticizer (B-2) is preferably relative to amine-modified epoxy resin
(A) quality is more than 39 mass %.Thus, can further improve film property during electro-deposition, it is possible to
Obtain the electrodeposition coating of the high corrosion protection possessing outspoken nature based on epoxy resin more reliably.More preferably
Be the content of plasticizer (B-1) more than 26 mass %, and the containing of plasticizer (B-1) and plasticizer (B-2)
Amount summation is more than 49 mass %.
The electrodeposition coating composition of present embodiment can comprise water as main component, comprises plasticizer
(B) organic solvent beyond.As organic solvent, the organic solvent being dissolved in water can be comprised.As having
The object lesson of machine solvent, can enumerate methanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
The alcohols such as methoxypropanol, the ether such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether
Class, the ketone such as acetylacetone,2,4-pentanedione, the esters such as ethylene glycol monoethylether acetate, hexane etc..These are organic molten
Agent can only use one, it is possible to multiple is used in mixed way.But, from the viewpoint of VOC emission limits,
The amount of organic solvent is the fewest more good.
It is 5 that the electrodeposition coating composition of present embodiment is preferably the content of amine-modified epoxy resin (A)
Quality %～30 mass %.Thus, good electrodeposition coating can be obtained, and the stability of coating obtains
To guaranteeing.
The electrodeposition coating composition of present embodiment can comprise pigment.As the object lesson of pigment,
The colouring materials such as titanium white, white carbon black and iron oxide red, Kaolin, Talcum, aluminium silicate, carbonic acid can be enumerated
The filler pigments such as calcium, Muscovitum, clay and silicon dioxide, iron phosphate, aluminum phosphate, calcium phosphate, trimerization
The rust resisting pigments etc. such as aluminum phosphate, molybdic acid aluminum, calcium molybdate and phosphomolybdic acid aluminum.These pigment by advance with
High concentration is scattered in aqueous medium formation thickener shape and adds it to electrodeposition coating composition
Mix.Additionally, in the case of incorporation pigment, the pigment concentration in electrodeposition coating composition is preferably
Relative to all solids composition of electrodeposition coating composition more than the amount of 50 mass %.Thus, can obtain
Obtain electrodeposition coating well, and the stability of coating is guaranteed.
The electrodeposition coating composition of present embodiment can comprise additive.Concrete example as additive
Son, can enumerate dispersant, viscosity adjusting agent, surface conditioner, defoamer, coalescents, ultraviolet
Light absorbers, antioxidant etc..
The electrodeposition coating composition of present embodiment manufactures as follows: by amine-modified epoxy resin (A), increase
Mould agent (B), acid compound and other composition (pigment, additive etc.) respectively reasonable time with regulation
Amount is added to aqueous medium, makes amine-modified epoxy resin (A) be scattered in aqueous medium.Concrete system
Under making such as.
First, after synthesizing amine-modified epoxy resin (A) in suitable plasticizer (B) or organic solvent,
In this solution, add plasticizer (B), then add acid compound and prepare mixture.Then, by gained
Mixture drops to make it disperse in aqueous medium, or adds aqueous medium in the mixture of gained
Make it disperse.Then, as desired by evaporating organic solvent to carry out solvent displacement.Finally, logical
Cross and add plasticizer (B) and the water used as required and acetic acid, formic acid and nitric acid etc. with ormal weight
Acid, thus obtain electrodeposition coating composition.It addition, pigment thickener can be added as needed on.
Manufacturing as described above shown in example, plasticizer (B) makes an addition to the breast of amine-modified epoxy resin (A) after passing through
Outside liquid mixes in electrodeposition coating composition, also by as by amine-modified epoxy resin (A)
Synthetic time lo-tionized makes for mixing in electrodeposition coating composition.By like this by plasticising
Agent (B) is used as synthetic, can reduce the usage amount of organic solvent beyond plasticizer (B).
<electrodeposition coating forming method>
The electrodeposition coating forming method of present embodiment is by the electro-deposition of above-mentioned embodiment being coated with
The method that feed composition electrodeposition coating forms electrodeposition coating in the base material as coated article.As
Method for electrocoating, is not particularly limited, and can use currently known cationic electrodeposition coating method.
Specifically, the electrodeposition coating forming method of present embodiment includes: be impregnated in by coated article above-mentioned
Operation in the electrodeposition coating composition of embodiment；Using coated article as negative electrode to its with anode it
Between apply voltage so that electrodeposition coating separates out the operation on the surface in coated article；The most right
After the electrodeposition coating separated out is washed, make the operation of dried coating film at set point of temperature sintering.
As long as the base material as coated article has electric conductivity, it is not particularly limited.Such as, can use
Metal (ferrum, steel, copper, aluminum, magnesium, stannum, zinc etc. and the alloy etc. containing these metals), iron plate, steel
Plate, aluminium sheet and to they implement surfaces process (such as phosphoric acid class, chromic acid class or the chemical treatment of zirconium class)
Obtained by base material and their molding etc..
The bath temperature of electrodeposition coating composition is preferably 10 DEG C～40 DEG C, more preferably 10 DEG C～30 DEG C.Execute
Making alive is preferably 50V～450V, more preferably 100V～400V.It is preferably conduction time 1 second～300 seconds,
More preferably 30 seconds～180 seconds.Sintering temperature is preferably below 260 DEG C, more preferably 60 DEG C～220 DEG C.
The dry film thickness of electrodeposition coating is preferably 5 μm～25 μm.By meeting these conditions, can be more reliable
Ground obtains good electrodeposition coating.
For electrodeposition coating formed as discussed above, implement the most currently known topcoating application, can
Base material obtains multilayer coating film.
The present invention is not limited to above-mentioned embodiment, can realize the change in the range of the purpose of the present invention
Shape, improvement etc. are included in the present invention.
Embodiment
Below, based on embodiment, the present invention will be described in more detail, but the present invention is not limited in
These embodiments.Unless otherwise specified, part and all quality criterias of %.
<embodiment 1>
The diglycidyl ether of 1939 parts of bisphenol-As and 1061 parts of bisphenol-As are dissolved in 1000 parts of methyl different
Butyl ketone (hereinafter referred to as " MIBK ").Being added to 4 parts of dimethyl benzylamines, sustained response is to epoxy
Equivalent is 3000 and molecular weight is 6000.Thus, it is thus achieved that as the epoxy with bisphenol backbone of raw material
Resin.
For the epoxy resin with bisphenol backbone obtained in above-mentioned, add 324 parts of diethylenetriamines
MIBK diketimine compound (hereinafter referred to as " DETA diketimine "), 120 DEG C react 1 hour.
Thus, it is thus achieved that the amine-modified epoxy resin (A) of modified amount 3%.
For the amine-modified epoxy resin (A) obtained in above-mentioned, add 1059 parts of (phases as synthetic
When in being 34 mass % relative to amine-modified epoxy resin (A)) be equivalent to plasticizer (B-1) benzylalcohol (with
It is referred to as " BzOH " down) after, add 51 part of 90% acetic acid as acid compound and be neutralized (neutralization ratio 40
%).While being stirred in the case of being held in 90 DEG C, it is slowly added into 4724 parts of water, carries out all
Homogenize.Then, under reduced pressure evaporate the mixture of 2324 parts of MIBK and water in 50 DEG C to put to carry out solvent
Change.Finally, rear add 6824 parts of water and 800 parts (being equivalent to relative to amine-modified epoxy resin (A) is 26
Quality %) BzOH that is equivalent to plasticizer (B-1) mixes, thus obtains electrodeposition coating composition
(aqueous dispersion).
<embodiment 2～6>
Except rear interpolation 800 parts (being equivalent to relative to amine-modified epoxy resin (A) is 26 mass %) 2-benzene
Beyond the BzOH that base ethanol (hereinafter referred to as " 2-pH-EtOH ") adds after replacing in embodiment 1, carry out
Operation similarly to Example 1, using the electrodeposition coating composition that obtains as embodiment 2.Similarly,
By rear interpolation 800 parts (being equivalent to relative to amine-modified epoxy resin (A) is 26 mass %) 3-phenyl-1-
The electrodeposition coating composition of propanol (hereinafter referred to as " 3-pH-1-PrOH ") as embodiment 3, after add
Add 800 parts of (being equivalent to relative to amine-modified epoxy resin (A) is 26 mass %) 4-methoxyl group benzylalcohols (with
Electrodeposition coating composition the most referred to as " 4-MeO-BzOH "), as embodiment, adds 800 parts of (phases afterwards
When in being 26 mass % relative to amine-modified epoxy resin (A)) ethyleneglycol monophenylether (hereinafter referred to as " PhG ")
Electrodeposition coating composition as embodiment 5, rear add 800 parts and (be equivalent to relative to amine modified epoxy
Resin (A) is 26 mass %) electrodeposition coating composition of ethylene glycol monobenzyl ether (hereinafter referred to as " BzG ")
As embodiment 6.
<embodiment 7～13>
Suitable except adding 1059 parts (being equivalent to relative to amine-modified epoxy resin (A) is 34 mass %)
Dipropylene glycol mono-n-butyl Ether (hereinafter referred to as " DPnB ") in plasticizer (B-2) replaces conduct in embodiment 1
BzOH that synthetic adds and last except water and plasticizer (B-1) in addition to 32 part of 90% acetic acid of interpolation (in
With rate 65%) beyond, carry out operation similarly to Example 1, the electrodeposition coating composition that will obtain
As embodiment 7.Similarly, obtained by the operation that will carry out similarly to Example 2 in addition, electricity is heavy
Long-pending coating composition, as embodiment 8, carries out electricity obtained by operation similarly to Example 3 in addition
Electrodeposition coating compositions, as embodiment 9, is carried out obtained by operation similarly to Example 4 in addition
Electrodeposition coating composition, as embodiment 10, carries out operation similarly to Example 5 in addition and obtains
Electrodeposition coating composition as embodiment 11, carry out operation similarly to Example 6 in addition and
The electrodeposition coating composition obtained is as embodiment 12.
Additionally, except adding 1059 parts (being equivalent to relative to amine-modified epoxy resin (A) is 34 mass %)
The propylene glycol monobutyl ether (hereinafter referred to as " PnB ") being equivalent to plasticizer (B-2) replaces being equivalent to as conjunction
Become beyond the DPnB of plasticizer (B-2) of solvent, carry out operation similarly to Example 7, by obtain
Electrodeposition coating composition is as embodiment 13.
<embodiment 14～17>
(be equivalent to relative to amine except the addition of the BzOH added rear in embodiment 1 is set to 620 parts
Modified epoxy (A) is 20 mass %) beyond, carry out operation similarly to Example 1, by obtain
Electrodeposition coating composition is as embodiment 14.Similarly, the addition of the BzOH of rear interpolation is set to
The electrodeposition coating composition of 464 parts (being equivalent to relative to amine-modified epoxy resin (A) is 15 mass %)
As embodiment 15, the addition of the rear BzOH added is set to 310 parts and (is equivalent to relative to amine modification ring
Epoxy resins (A) is 10 mass %) electrodeposition coating composition as embodiment 16, the rear BzOH added
Addition be set to 155 parts (being equivalent to relative to amine-modified epoxy resin (A) they is 5 mass %) electricity sink
Long-pending coating composition is as embodiment 17.
<embodiment 18～21>
(be equivalent to relative to amine except the addition of the BzOH added rear in embodiment 7 is set to 620 parts
Modified epoxy (A) is 20 mass %) beyond, carry out operation similarly to Example 7, by obtain
Electrodeposition coating composition is as embodiment 18.Similarly, the addition of the BzOH of rear interpolation is set to
The electrodeposition coating composition of 464 parts (being equivalent to relative to amine-modified epoxy resin (A) is 15 mass %)
As embodiment 19, the addition of the rear BzOH added is set to 310 parts and (is equivalent to relative to amine modification ring
Epoxy resins (A) is 10 mass %) electrodeposition coating composition as embodiment 20, the rear BzOH added
Addition be set to 155 parts (being equivalent to relative to amine-modified epoxy resin (A) they is 5 mass %) electricity sink
Long-pending coating composition is as embodiment 21.
<embodiment 22>
Diglycidyl ether and 495 parts of bisphenol-As of 1005 parts of bisphenol-As are dissolved in 500 parts of methyl tert-butyl
Base ketone (hereinafter referred to as " MIBK ").Being added to 2 parts of dimethyl benzylamines, sustained response to epoxy is worked as
Amount is 1500 and molecular weight is 3000.Thus, it is thus achieved that as the asphalt mixtures modified by epoxy resin with bisphenol backbone of raw material
Fat.
For the epoxy resin with bisphenol backbone obtained in above-mentioned, add 123 parts of dibutyl amine, 120
DEG C reaction 1 hour.Thus, it is thus achieved that the amine-modified epoxy resin (A) of modified amount 8%.
For the amine-modified epoxy resin (A) obtained in above-mentioned, add 286 parts (quite as synthetic
In being 18 mass % relative to amine-modified epoxy resin (A)) be equivalent to the DPnB of plasticizer (B-2) after, make
Add 26 part of 90% acetic acid for acid compound and be neutralized (neutralization ratio 40%).In the feelings being held in 90 DEG C
While being stirred under condition, it is slowly added into 2300 parts of water, carries out homogenization.Then, under reduced pressure
In 50 DEG C of mixture evaporating 1000 parts of MIBK and water to carry out solvent displacement.Then, 4119 parts are added
Water and 16 part of 90% acetic acid, carry out homogenization.Finally, rear interpolation 422 parts (is equivalent to change relative to amine
Property epoxy resin (A) is 26 mass %) BzOH that is equivalent to plasticizer (B-1) mixes, thus obtains
Electrodeposition coating composition (aqueous dispersion).
<embodiment 23>
It is 4000 using 4000 parts of epoxide equivalents being used as the epoxy resin with bisphenol backbone as raw material
Epoxy resin (epoxy resin Co., Ltd. of Japan (ジ ャ パ Application エ Port キ シ レ ジ Application society) system, 1010
Level) add in 1167 parts of MIBK, while heating, add 100 parts of diethanolamine, react 1 at 120 DEG C
Hour.Thus, it is thus achieved that the amine-modified epoxy resin (A) of modified amount 3%.
For the amine-modified epoxy resin (A) obtained in above-mentioned, add 1543 parts of (phases as synthetic
When in being 38 mass % relative to amine-modified epoxy resin (A)) be equivalent to the 3 the third two of plasticizer (B-2)
After alcohol monobutyl ether (hereinafter referred to as " TPnB "), in carrying out as acid compound 41 part of 90% acetic acid of interpolation
(neutralization ratio 65%).While being stirred in the case of being held in 90 DEG C, it is slowly added into 5426
Part water, carries out homogenization.Then, under reduced pressure 2333 parts of MIBK and the mixture of water are evaporated in 50 DEG C
Carry out solvent displacement.Finally, rear add 9326 parts of water and 1066 parts (be equivalent to relative to amine modification ring
Epoxy resins (A) is 26 mass %) BzOH that is equivalent to plasticizer (B-1) mixes, thus it is heavy to obtain electricity
Long-pending coating composition (aqueous dispersion).
<embodiment 24>
Except changing, as the epoxy resin with bisphenol backbone of raw material, the epoxy that epoxide equivalent is 925 into
Beyond resin (epoxy resin Co., Ltd. of Japan system, 1004 grades), grasp similarly to Example 22
Make, it is thus achieved that electrodeposition coating composition (aqueous dispersion).
<embodiment 25>
Except rear interpolation 800 parts (being equivalent to relative to amine-modified epoxy resin (A) is 26 mass %) is suitable
Beyond the BzOH added after the MIBK of plasticizer (B-2) replaces in embodiment 1, carry out same with embodiment 1
The operation of sample, using the electrodeposition coating composition that obtains as embodiment 25.
<embodiment 26>
The diglycidyl ether of 1627 parts of bisphenol-As, 873 parts of bisphenol-As and 22 parts of octanoic acids are dissolved in 834
Part MIBK.Being added to 4 parts of dimethyl benzylamines, sustained response to epoxide equivalent is 2500 and molecule
Amount is 5000.Thus, it is thus achieved that as the epoxy resin with bisphenol backbone of raw material.This is had
The epoxy resin of bisphenol backbone, adds 288 parts of DETA diketimine, reacts 1 hour at 120 DEG C.Thus,
Obtain amine (and octanoic acid) modified epoxy (A) of modification amount 4%.
For the amine-modified epoxy resin (A) obtained in above-mentioned, add 666 parts (quite as synthetic
In being 26 mass % relative to amine-modified epoxy resin (A)) be equivalent to the BzOH of plasticizer (B-1) after, make
Add 43 part of 90% acetic acid for acid compound and be neutralized (neutralization ratio 40%).In the feelings being held in 90 DEG C
While being stirred under condition, it is slowly added into 4183 parts of water, carries out homogenization.Then, under reduced pressure
In 50 DEG C of mixture evaporating 2082 parts of MIBK and water to carry out solvent displacement.Then, 5459 parts are added
Water and 21 part of 90% acetic acid, carry out homogenization.Finally, rear interpolation 875 parts (is equivalent to change relative to amine
Property epoxy resin (A) is 34 mass %) DPnB that is equivalent to plasticizer (B-2) mixes, thus obtains
Electrodeposition coating composition (aqueous dispersion).
<comparative example 1～4>
Be equivalent to except adding 800 parts (being equivalent to relative to amine-modified epoxy resin (A) is 26 mass %)
Beyond the BzOH that the DPnB of plasticizer (B-2) adds after replacing in embodiment 7, carry out similarly to Example 7
Operation, using the electrodeposition coating composition that obtains as comparative example 1.Similarly, by 800 parts of (phases of interpolation
When in being 26 mass % relative to amine-modified epoxy resin (A)) be equivalent to add after the MIBK of plasticizer replaces
The electrodeposition coating composition of the BzOH added, as comparative example 2, adds 800 parts and (is equivalent to change relative to amine
Property epoxy resin (A) is 26 mass %) do not correspond to the first of any one in plasticizer (B-1) and (B-2)
The electrocoating paint combination of the BzOH that epoxide propanol (hereinafter referred to as " MP ", water solublity) adds after replacing
Thing, as comparative example 3, adds 800 parts (being equivalent to relative to amine-modified epoxy resin (A) is 26 mass %)
Do not correspond to the butyl cellosolve of any one in plasticizer (B-1) and (B-2) (hereinafter referred to as " fourth is fine ",
Water solublity) replace after the electrodeposition coating composition of BzOH that adds as comparative example 4.
<comparative example 5>
In addition to not carrying out being equivalent to the rear interpolation of the DPnB of plasticizer (B-2), carry out and comparative example 1
Same operation, using the electrodeposition coating composition that obtains as comparative example 5.
<comparative example 6>
In addition to not carrying out the rear interpolation of plasticizer, carry out operation similarly to Example 1, will obtain
Electrodeposition coating composition as comparative example 6.
<comparative example 7>
Add 800 parts (being equivalent to relative to amine-modified epoxy resin (A) is 26 mass %) not correspond to increase
The electricity moulding the MIBK added after the fourth fibre of any one in agent (B-1) and (B-2) replaces in embodiment 26 sinks
Long-pending coating composition is as comparative example 7.
<comparative example 8>
[synthesis of amine-modified epoxy resin (B)]
By 950 in the reaction vessel possessing agitating device, nitrogen ingress pipe, condensing tube and thermometer
Part epoxide equivalent is bisphenol A type epoxy resin (Toto Kasei KK's (being all melted into society) system of 950
EPOTOHTO YD-014) it is heated up to 100 DEG C together with 237.5 parts of methyl iso-butyl ketone (MIBK)s and makes it be completely dissolved.
Then, 60 parts of positive methylethanolamines, the methyl-isobutyl diketimine of 73 parts of diethylenetriamines are added
73% methyl iso-butyl ketone (MIBK), obtains amine-modified epoxy resin by this mixture 120 DEG C of insulations 1 hour
(B)。
[synthesis of blocked isocyanate curing agent (1)]
222 are added in the reaction vessel possessing agitating device, thermometer, condensing tube and nitrogen ingress pipe
Part isophorone diisocyanate, with 56 parts of methyl iso-butyl ketone (MIBK)s dilutions.After being warming up to 50 DEG C,
174 parts of methyl ethyl ketone oxime are added under conditions of temperature is less than 70 DEG C.1 hour is kept directly at 70 DEG C
Substantially disappearing to the absorption of NCO of infrared absorption spectroscopy, then with 43 parts of n-butyl alcohol
Dilute and obtain blocked isocyanate curing agent (1).
[synthesis of blocked isocyanate curing agent (2)]
By 1250 parts of 4,4 '-methyl diphenylene diisocyanates and 685 parts of methyl iso-butyl ketone (MIBK)s, 6.25 parts
Tri-n-butylamine adds in reaction vessel, is heated to 60 DEG C.By with 3 hours wherein constant speed drip 120 parts
Methanol and 173 parts of ethanol make it react.Then, add 112.5 parts of trimethylolpropanes, 237.5 parts
Methyl iso-butyl ketone (MIBK) after being warming up to 110 DEG C, reacts about 2 hours, confirms the different of infrared absorption spectrum
Stopped reaction after the absorption disappearance of cyanic acid ester group, it is thus achieved that as the blocked isocyanate curing agent of object
(2)。
[preparation of cation electric deposition paint composition]
By 210 parts of amine-modified epoxy resins (B), 57 parts of blocked isocyanate curing agent (1), 35 parts of end-blockings
Isocyanate curing agent (2) uniformly mixes.Used in 5 parts of acetic acid and 1 part of zinc acetate and after, add 100
Part deionized water is diluted, it is thus achieved that main emulsion (solid constituent 36.0%).To 278 parts of (solid constituents
100 parts) this main emulsion mixes 332 parts of deionized waters, by the cation electric deposition paint composition of gained
(blocked isocyanate curing type) is as comparative example 8.
For the plasticizer (B-2) used in embodiment and comparative example, at 20 DEG C with E type viscometer
The viscosity that (RE-215 type viscometer, Toki Sangyo Co., Ltd.'s system) measures is as shown in table 1.
[table 1]
| Plasticizer (B-2) | Viscosity (mPa s) |
| DPnB | 5 |
| PnB | 3 |
| TPnB | 10 |
| MIBK | 1 |
<evaluation>
For the electrodeposition coating composition obtained in each embodiment and comparative example, implement heating loss,
The evaluation of film property, corrosion protection and stability.Each evaluation methodology is as follows.Evaluation result is shown in table 1.
[heating loss]
For the electrodeposition coating composition obtained in each embodiment and comparative example, carry out following (a)～
G the operation of (), calculates heating loss by following formula (1).But, do not obtain good film property
And the compositions that cannot be carried out heating loss evaluation is denoted as "-", it is shown in table 2.
(a) first, accurate weighing bread board (zinc phosphate process plate), try to achieve the test before electrodeposition coating
Plate weight A.
B () makes bread board impregnated in electrodeposition coating composition, reach 20 μm with dried thickness
Condition implements cationic electrodeposition coating.Electrodeposition coating divides under conditions of bath temperature is 30 DEG C and 40 DEG C
Do not implement.
C bread board after electrodeposition coating is washed by () after, make to be formed at the moistening of bread board surface
Film is dried 3 hours at 105 DEG C.
D () is dried, bread board is cooled in exsiccator accurate weighing after room temperature, obtains dried
Bread board weight B.
E (), for dried bread board, implements the sintering of 25 minutes at 200 DEG C.
After (f) sintering, bread board is cooled in exsiccator accurate weighing after room temperature, after obtaining sintering
Bread board weight C.
G () is by bread board weight A before the electrodeposition coating that will try to achieve as mentioned above, dried examination
Test bread board weight C after plate weight B and sintering and substitute into following formula (1), calculate heating loss D.
[several 2]
D (%)=[1-(C-A)/(B-A)] × 100 formulas (1)
[high-temperature heating decrement]
" heating loss " is evaluated in the operation of above-mentioned (a)～(g) that mention, implements 40 minutes at 200 DEG C
The drying condition of (c) and implement the drying condition of (e) of 25 minutes at 240 DEG C, calculate high-temperature heating and subtract
Amount.
[film property]
For the electrodeposition coating composition obtained in each embodiment and comparative example, to as mentioned above in bath
Film property when temperature implements electrodeposition coating under conditions of being 30 DEG C and 40 DEG C respectively is evaluated.Comment
Valency observes by the naked eye and carries out, and is formed at the group that the electrodeposition coating on bread board surface is glossy and still
Compound is denoted as "○", matt and have the compositions of bubble to be denoted as "×".Additionally, electrocoating paint
There is thickening or precipitation etc. and cannot be carried out the compositions of film property evaluation and be denoted as "-" in compositions.
[corrosion protection]
For the electrodeposition coating composition obtained in each embodiment and comparative example, for above-mentioned heating
(b) of the evaluation of decrement implements electrodeposition coating obtained by the sintering of 100 DEG C × 20 minutes afterwards and implements 500
Hour salt spraytest (SST), corrosion protection is evaluated.In evaluation, the rust of cut portion
Unilateral Breadth Maximum be denoted as "○" in the compositions of below 3mm, the compositions more than 3mm is denoted as "×".
Do not obtain good film property and cannot be carried out the compositions of corrosion protection evaluation and be denoted as "-".At all groups
In compound, all do not find that corrosion protection there are differences because of the difference of bath temperature.Additionally, for only bath temperature be
The compositions of good film property is obtained, only to real under conditions of being 40 DEG C in bath temperature in the case of 40 DEG C
The corrosion protection executing electrodeposition coating obtained by electrodeposition coating implements evaluation.
[stability]
When preparing electrodeposition coating composition, by being denoted as "○" without the compositions of thickening or precipitation, have
The compositions of thickening or precipitation is denoted as "×".
[table 2]
As shown in table 2, in the comparative example 1～7 without cross-linking agent, all do not obtain good film property and nothing
Method forms electrodeposition coating.That is, confirm these comparative examples 1～7 not included in the present invention " heating subtracts
Amount is below 10 mass % " in the range of.Additionally, be equivalent to comprising of the embodiment 1 of patent documentation 1
In the comparative example 8 of cross-linking agent, the heating loss of 30 DEG C of films of bath temperature and 40 DEG C of films is all more than 10 mass
%, confirms not included in the scope of the present invention.In contrast, the embodiment 1～26 without cross-linking agent
In, all obtain good film property during bath temperature 40 DEG C, and heating loss is less than 5 mass %, confirms to include
In the range of " heating loss is below 10 mass % " of the present invention.Additionally, further acknowledge that by tool
Having above-mentioned feature, high-temperature heating decrement is below 2 mass %.
Additionally, from the result of embodiment 1～26, without in the electrodeposition coating composition of cross-linking agent,
Either as interpolation or the rear interpolation of synthetic, comprise the plasticizers such as BzOH (B-1) and plasticizer
(B-1) and the summation of content of plasticizer (B-2) relative to amine-modified epoxy resin (A) in 39 mass %
In the case of above, it is thus achieved that good film property, heating loss is below 10 mass %.Additionally, also
Understanding in the case of being somebody's turn to do, high-temperature heating decrement is below 2 mass %.
Additionally, by the results verification of embodiment 24, the molecular weight of the epoxy resin with bisphenol backbone exists
In the case of more than 2000, good corrosion protection can be obtained.
Industrial utilizability
The electrodeposition coating composition of the present invention is the electrocoating paint combination that heating loss reduces than ever
Thing, therefore as the electricity of the environment care type using environment with respect to the goods with electrodeposition coating
Electrodeposition coating compositions, preferably uses.
Claims (5)
1. an electrodeposition coating composition, it is the electrodeposition coating composition that heating loss is few, its
It is characterised by,
It is substantially free of cross-linking agent, makes to carry out electrodeposition coating and the electrodeposition coating that formed is done at 105 DEG C
After dry 3 hours, 200 DEG C heating 25 minutes after heating loss below 10 mass %,
Comprise and will there is amine modified epoxy tree obtained by the epoxy resin amines modification of bisphenol backbone
Fat A and include the plasticizer B-1 formed by aromatic alcohols compound and in addition to described plasticizer B-1
The plasticizer B of plasticizer B-2,
Relative to described amine-modified epoxy resin A, the content of described plasticizer B-1 more than 26 mass %,
And the content summation of described plasticizer B-1 and described plasticizer B-2 is more than 49 mass %.
2. electrodeposition coating composition as claimed in claim 1, it is characterised in that described plasticizer
B-1 has the structure represented with following formula 1, and relative to described amine-modified epoxy resin A with mass ratio
Described amine-modified epoxy resin A is dissolved during meter mixing 10 times amount；
In formula 1, R is CpH2p、O(CmH2mO)pOr CH2O-(CmH2mO)n, X is H or OCH3, wherein, p
It is the integer of 1～3, lower same；M is the integer of 2～5, lower same；N is 1 or 2.
3. electrodeposition coating composition as claimed in claim 1 or 2, it is characterised in that described increasing
It is water-insoluble for moulding agent B-2, and viscosity is at below 1000mPa s, and relative to described amine modified epoxy tree
Described amine-modified epoxy resin A is dissolved during fat A mixed in equal amounts by quality ratio.
4. electrodeposition coating composition as claimed in claim 1, it is characterised in that described in have double
The molecular weight of the epoxy resin of phenol skeleton is more than 2000.
5. electrodeposition coating forming method, it is characterised in that arbitrary by by Claims 1 to 4
Electrodeposition coating composition electrodeposition coating described in Xiang forms electrodeposition coating in base material.
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| JP2011216555A JP5846828B2 (en) | 2011-09-30 | 2011-09-30 | Electrodeposition coating composition |
| JP2011-216555 | 2011-09-30 | ||
| PCT/JP2012/074058 WO2013047319A1 (en) | 2011-09-30 | 2012-09-20 | Electrodeposition coating composition |
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| CN103857755B true CN103857755B (en) | 2016-09-21 |
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| DE102012223387A1 (en) | 2012-12-17 | 2014-06-18 | Evonik Industries Ag | Use of substituted benzyl alcohols in reactive epoxy systems |
| JP6398025B1 (en) * | 2018-02-06 | 2018-09-26 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Electrodeposition coating composition and electrodeposition coating method |
| CN111393683B (en) * | 2020-04-20 | 2023-05-23 | 广东科德环保科技股份有限公司 | Modified cationic microgel and preparation method and application thereof |
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| US5034109A (en) * | 1989-04-20 | 1991-07-23 | Kansai Paint Company, Limited | Resin coating compositions and electrophoretic coating method using same |
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|---|---|
| JP2013075982A (en) | 2013-04-25 |
| WO2013047319A1 (en) | 2013-04-04 |
| CN103857755A (en) | 2014-06-11 |
| JP5846828B2 (en) | 2016-01-20 |
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