CN1908082B

CN1908082B - Cationic electrodeposition coating composition and coated article therewith

Info

Publication number: CN1908082B
Application number: CN2006101285600A
Authority: CN
Inventors: 坂本聪明; 坂本胜; 平原芳宪; 重永勉
Original assignee: Mazda Motor Corp; Nippon Paint Co Ltd
Current assignee: Mazda Motor Corp; Nippon Paint Automotive Coatings Co Ltd; Nippon Paint Holdings Co Ltd
Priority date: 2005-08-05
Filing date: 2006-08-04
Publication date: 2011-07-13
Anticipated expiration: 2026-08-04
Also published as: JP2007039617A; DE102006036557A1; CN1908082A

Abstract

The present invention relates to a cationic electrodeposition coating composition comprising silica particles having pore volume of 0.44 to 1.8 ml/g and average particle size of no more than 10 mum, the composition showing square root of diffusion coefficient square root of no less than 2.5 upon diffusing a solution onto a coating film therewith; a cationic electrodeposition coating composition comprising silica particles having pore volume of 0.44 to 1.8 ml/g and average particle size of no more than 10 mum, wherein the composition shows minimum deposition pH of 11.90 to 12.00 during electrodeposition coating, and film resistance of 1,000 to 1,500 kOmega.cm<2> at film thickness of 15 mum and applied voltage of 240 V; and an article coated with such cationic electrodeposition coating composition. Therefore, the present invention can also provide a coating film formed with the cationic electrodeposition coating composition which can ensure higher corrosion resistance and higher throwing power in addition to other excellent coating properties, even if the resulting coating has extremely thin film thickness (e.g., about 7 mum).

Description

Cation electric deposition paint composition and with the goods of its coating

Technical field

The present invention relates to a kind of cation electric deposition paint composition, also have filming of higher erosion resistance even said composition especially provides under the very thin situation of the coating that forms, and the goods that apply with said composition.

Background technology

Galvanic deposit applies as a kind of primary coat coating method and is widely used in having big and profile complexity, and the goods that need the tool high corrosion resistance to film, as car body, because even goods have complicated profile, galvanic deposit applies also can form coating in thin portion, and can be automatically and coating is provided continuously.Galvanic deposit applies also usually as industrial coating method because when the applied coatings composition with other coating method relatively, galvanic deposit apply be economy and have high efficient.By goods to be coated are immersed cation electric deposition paint composition as negative electrode, and apply voltage and carry out cationic electrodeposition and apply.

As mentioned above,, recently relatively require higher effect, even in the field of electroprecipitation coating based on resource-effective notion and ordinary method though apply and be economical substantially and have higher efficient applying galvanic deposit aspect the coating composition.For example, the thickness that the routine that the cationic electrodeposition coating method forms is filmed is approximately 20 μ m, yet expectation recently is that the thickness of the surface coatings on the panel is approximately 15 μ m outside.

Because thin film allows to use the coating composition of less amount, resources conservation just can have been set up theoretically.Conventionally, by in the galvanic deposit coating procedure, shortening the electric weight that time that galvanic deposit applies and/or minimizing apply, just can be easy to obtain the film that approaches.Yet, be difficult to guarantee the erosion resistance of filming, the especially back side of goods panel that form.Because it is under the condition of surface film thickness that goods are carried out the outside that galvanic deposit apply to require obtains to be no more than 15 μ m, the promptly inner thickness of filming in the back side that forms on goods also can reduce.From this aspect, can see that following technology is necessary: can offer the gordian technique of thin external surface coating of thin portion and enough coated inside, these coatings all are to be formed by the same composition with the throwing power (throwing power) that has improved; And be used for the technology of raising in the erosion resistance of lining, internal coat zone (or coating region), wherein the thickness of interior coated film is not more than 10 μ m, particularly is no more than 7 μ m.

JP-A-2003-268315 discloses a kind of unleaded cation electric deposition paint composition, and said composition comprises silica (silica) particle that has 0.44～1.8ml/g pore volume and be not more than 10 μ m mean particle sizes.This cation electric deposition paint composition is characterised in that formed filming has ganoid effect.Yet, do not mention in JP-A-2003-268315 that coating has high corrosion resistance and composition has high throwing power, the very thin thickness of its floating coat for example is no more than 10 μ m, especially is approximately 7 μ m.

JP-A-2004-269627 discloses a kind of unleaded cation electric deposition paint composition, said composition comprises water medium, binder resin, neutralizing acid, organic solvent, pigment and metal catalyst, they are dispersed or dissolved in the water medium, the sheet resistance that it is characterized in that the electrodeposition coating of thickness 20 μ m on the goods is 1,000～2,500k Ω cm ², the specific conductivity of this coating composition be 1,500～2,000 μ S/cm and in galvanic deposit applies minimal deposition pH be 11.90～12.00.In addition, JP-A-2004-269627 disclose solution diffusion to make with it film on the time spread coefficient that obtains square root be 2.5～3.2 (see claim 3).Yet, in JP-A-2004-269627, do not relate to very thin the filming (for example thickness is about 7 μ m) that forms by cation electric deposition paint composition.

Summary of the invention

The invention provides a kind of cation electric deposition paint composition, even the coating that forms has film thickness (for example about 7 μ m) as thin as a wafer, the coating that said composition also can guarantee to form also has higher erosion resistance and throwing power except that other good coating properties.

Therefore, in order to solve the above problems, the invention provides a kind of cation electric deposition paint composition that has 0.44～1.8ml/g pore volume and be not more than the silica particle of 10 μ m mean particle sizes that comprises, with solution diffusion to the filming of its formation the time, the square root that said composition demonstrates spread coefficient (promptly

Figure S061C8560020060908D00002124950QIETU

) be not less than 2.5; And a kind of cation electric deposition paint composition that has 0.44～1.8ml/g pore volume and be not more than the silica particle of 10 μ m mean particle sizes that comprises, wherein said composition demonstrates that minimal deposition pH is 11.90～12.00 in galvanic deposit applies, and at the film thickness of 15 μ m with apply under the 240V voltage, membrane resistance is 1,000～1,500k Ω cm ²

According to the preferred embodiment of the invention, this cation electric deposition paint composition also comprises amine-modified epoxy resin (A) and blocked isocyanate solidifying agent (B), wherein the part by weight of amine-modified epoxy resin (A) and blocked isocyanate solidifying agent (B) is 50/50～90/10 (A/B), and blocked isocyanate solidifying agent (B) comprises end-blocking aliphatic polyisocyanate and end-blocking aromatic polyisocyanate, and wherein the part by weight of end-blocking aliphatic polyisocyanate and end-blocking aromatic polyisocyanate is 3/1～1/3 (end-blocking aliphatic polyisocyanate/end-blocking aromatic polyisocyanate).

In a more preferred embodiment, with respect to the gross weight of pigment, the content of silica particle is 1～30% by weight in the composition.

In addition, the invention provides the goods that apply with described cation electric deposition paint composition.

Description of drawings

Fig. 1 is a schematic cross-section, is used for illustrating determining to film the embodiment of measuring system of spread coefficient, and it comprises

The sheet (100) that applies,

Film (101),

Silicon rubber gasket (packing) (102) and (102 '),

Platinum loop electrode (103),

Ring (104),

Goods to be coated (105),

Electrometer (106) and register (107).

Fig. 2 describes the graphic representation that applies voltage and the dependency between conducting period (conducting period), is used for determining minimal deposition pH.

Fig. 3 is the synoptic diagram that is used for describing the instrument of measuring throwing power, and it comprises

Electrocoating paint container (201),

Pipe (202),

Test specimen plate (203),

Interface (204),

Agitator (205),

Power supply (206) and electrodeposition coating composition (207).

Embodiment

The present invention will describe in detail below.

Usually, cation electric deposition paint composition consists essentially of cation epoxy resin (particularly amine-modified epoxy resin) and is used for the solidifying agent (particularly blocked isocyanate solidifying agent) of resin, and they are scattered in the water medium.In addition, pigment and/or other additives also can be included in the cation electric deposition paint composition of dispersion state.

Silica particle

As mentioned above, cation electric deposition paint composition of the present invention is characterised in that said composition comprises specific silica particle.This silica particle is a porous, and has the pore volume of 0.44～1.8ml/g, preferred 0.8～1.6ml/g.When the pore volume of silica particle during less than 0.44ml/g, it provides the insufficient effect of filming (as bad erosion resistance).When pore volume further less than this value, this trend can be more obvious.When the pore volume of silica particle during greater than 1.6ml/g, their dispersion stabilization is insufficient.When pore volume further greater than this value, their dispersion stabilization is very insufficient.Here, " pore volume " is meant that the volume at porous silica particle mesopore is a porosity.Pore volume can be measured with mercury penetration method.Mercury penetration method comprises infiltrates through in the hole in the material (powdered form) mercury, measures the pressure of infiltration and the amount of infiltration mercury then and determines specific surface and pore distribution.The mercury injection apparatus that is used for the pore distribution measurement can be used to measure specific surface and pore distribution.

Silica particle has the mean particle size that is no more than 10 μ m, preferred 5～0.1 μ m.When mean particle size during less than 0.1 μ m, it provides insufficient dispersion stabilization.When mean particle size during greater than 10 μ m, it provides bad erosion resistance.Here, " mean particle size " generally is used for representing particulate particle size (or the expression size of particles is big or little).For example, use is corresponding to median size, arithmetical mean size, surface-area mean sizes, the volume-area mean sizes of 50 weight %.Here, " mean particle size " determined by laser method and represented.Laser method is included in dispersed particle in the solvent, determines mean particle size, size-grade distribution etc. at scattered light that disperses illuminating laser beam on the thing, measurement to form and calculating.

Though silica generally is meant the solid matter that mainly contains silicon-dioxide, the silica particle that uses among the present invention is a porous, as mentioned above, and should have the pore volume of 0.44～1.8ml/g and be no more than the mean particle size of 10 μ m.Silica particle with these performances is special preparation, so it is different from the silica particle or the clay (for example filler pigment such as kaolin) of the silica gel of called optical imaging, natural generation.The silica particle that the present invention uses is mixed and made into just so-called wet method with water glass and acid.Employed concrete silica particle comprises SYLYSIA among the present invention, and it can be bought from FUJI SILYSIA CHEMICAL LTD. and obtain.

Usually, to require the pH around it be that alkalescence is so that corrosion in the corrosion of negative electrode.Yet, think that the existence of silica particle provides the shock absorption of pH to stop alkalization in said composition, this makes filming of forming have higher erosion resistance.

Think that employed silica particle is solid-state and can is the part of following described pigment among the present invention.In this case, think that also the also available silica particle of the present invention of a part of pigment substitutes.Therefore, with respect to the gross weight of pigment, the content of preferred silica particle is 1～30% by weight, more preferably is 10～25% by weight.Interpolation is more than 30% silica particle, and the slickness of filming of formation is bad.On the contrary, interpolation is less than 1% silica particle by weight, their effect inadequate (as bad erosion resistance).

The cation electric deposition paint composition that the present invention is unleaded except that comprising above-mentioned specific silica particle, also comprises cation epoxy resin and solidifying agent, can also randomly comprise pigment and/or other additives.Hereinafter, each component will be described respectively.

Amine-modified epoxy resin

The amine-modified epoxy resin that uses among the present invention comprises those Resins, epoxy with the amine modification.These amine-modified epoxy resins are known resin, and they are open in JP-B-54-4978, JP-B-56-34186 etc.

Amine-modified epoxy resin usually is by making with introducing epoxy group(ing) all in the bisphenol-type epoxy resin of cation group active dydrogen compounds modification; Perhaps, make with introducing remaining epoxy group(ing) of active dydrogen compounds modification of cation group by active dydrogen compounds modification part epoxy group(ing) with other.

The exemplary of bisphenol-type epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin.The product that the former can buy comprises Epikote828 (Yuka-Shell Epoxy Co, Ltd. manufacturing, epoxy equivalent (weight): 180～190), Epikote1001 is (the same, epoxy equivalent (weight): 450～500), Epikote1010 (the same, epoxy equivalent (weight): 3000～4000) etc.The product that the latter can buy comprise Epikote807 (the same, 170) or the like epoxy equivalent (weight):.

The Resins, epoxy of Han oxazolidine ketone groups, the structure that it has is open in JP-A-5-306327 (seeing [0004] section), this Resins, epoxy can be used as amine-modified epoxy resin and use, because by its film good thermotolerance and erosion resistance that forms.

, for example exist to heat under the basic catalyst condition and use lower alcohol such as the end capped blocked polyisocyanates of methyl alcohol and polyepoxide, and lower alcohol is distilled out from system as byproduct Ba the method for oxazolidone group introducing Resins, epoxy as a kind of with insulation.

The Resins, epoxy of particularly preferred Resins, epoxy Wei Han oxazolidone group.This is because can obtain to have filming of good thermotolerance, erosion resistance and shock resistance.

As everyone knows, react the Resins, epoxy that obtains to contain the oxazolidine ketone groups by dual functional Resins, epoxy with the end capped vulcabond of monohydroxy-alcohol (i.e. two urethane).For example contain in the open No128959/2000 of Japanese Patent 0012～0047 section of the object lesson of Resins, epoxy of oxazolidine ketone group and preparation method open.

Can these Resins, epoxy of modification with appropriate resin (as polyester polyol, polyether polyol, carboxylic acid and xylene resin) or sulfhydryl compound.In addition, utilize the reaction of epoxy group(ing) and glycol or dicarboxylic acid, extensible its chain of Resins, epoxy.

The group of expectation in the Resins, epoxy is 0.3～4.0meq/g with the active dydrogen compounds reaction so that opening the later amine equivalent of ring, more preferably primary amine fiduciary point 5～50% wherein.

Can introduce the active dydrogen compounds of cation group, comprise acid salt, thioether and the acid mixture of primary amine, secondary amine and tertiary amine.According to the present invention, in order to prepare the Resins, epoxy that contains primary amino, secondary amino group and/or uncle's amino, with primary amine, secondary amine or/and the acid salt of tertiary amine use as the active dydrogen compounds that can introduce cation group.

Concrete example comprises: butylamine, octylame, diethylamine, dibutylamine, methyl butyl amine, monoethanolamine, diethanolamine, N-Mono Methyl Ethanol Amine, Triethylammonium chloride, N, the mixture of N-dimethylethanolamine acetate, diethyl disulfide and acetate etc., the secondary amine that also has the end-blocking primary amine is as the ketoimine of amino ethyl ethanolamine, two ketoimines of diethylenetriamine.Various kinds of amine can be used in combination.

Sulfonium-modified epoxy

Cation electric deposition paint composition of the present invention can comprise the sulfonium modified epoxy.The sulfonium modified epoxy is meant modified resin, wherein during the epoxide group on opening resin, comes modified epoxy to form the sulfonium salt part with sulfide compound and neutralizing acid.The sulfonium modified epoxy can comprise conventionally use with the known sulfonium modified epoxy of ability technician (for example JP-A-6-128351, JP-A-7-206968 etc.).The sulfonium modified epoxy is typically made by the ring of opening epoxide group in the Resins, epoxy of bis-phenol type with sulfide compound and neutralizing acid.

Comprise the sulfide compound that all energy and epoxide group react and reaction is interrupted group with the sulfide compound of Resins, epoxy reaction.Reaction between Resins, epoxy and the sulfide compound must be carried out in the presence of neutralizing acid, so that introduce the sulfonium group in Resins, epoxy.

For example, sulfide compound can comprise aliphatic thioether, contain thioether, aralkyl thioether or the cyclic thioether of aliphatic series and aromatic group.The example of the thioether that uses is diethyl thioether, propyl thioether, ethylphenyl thioether, tetramethylene thioether and pentamethylene thioether etc.

Particularly preferred sulfide compound is a kind of sulfo-glycol that following formula is represented:

HO-R-S-R′-OH

Wherein R and R ' are separately respectively the alkylidene group that contains the straight or branched of 2～8 carbon atoms.Such sulfonium modified epoxy allows to apply the foundation (about 10 seconds) of voltage instantaneous phase shift films resistance in electrodeposition process, and is provided at the binder resin that has dispersion stabilization in the water.

The example that the sulfo-glycol comprises is thiodiethanol, sulfo-two propyl alcohol, sulfo-two butanols, 1-(2-hydroxyethyl sulphur)-2-propyl alcohol, 1-(2-hydroxyethyl sulphur)-2, ammediol, 1-(2-hydroxyethyl sulphur)-2-butanols, 1-(2-hydroxyethyl sulphur)-3-butoxy-1-propyl alcohol etc.Most preferred sulfide compound is 1-(2-hydroxyethyl sulphur)-2-propyl alcohol.

The blocked polyisocyanates solidifying agent

The blocked isocyanate solidifying agent that uses among the present invention preferably includes the blocked polyisocyanates that makes by with the end-capping reagent blocked polyisocyanates, and wherein polyisocyanates is meant and has 2 or the compound of polyisocyanates group more in molecule.As polyisocyanates, any in for example aliphatic class, the alicyclic ring same clan, aromatic species, the aromatic-aliphatic class etc. all can use.

The object lesson of polyisocyanates comprises inferior cresyl vulcabond (TDI), aromatic diisocyanate such as diphenylmethanediisocyanate (MDI), to phenylene vulcabond and naphthalene diisocyanate; The vulcabond that contains the aliphatic series of 3～12 carbon atoms is as hexamethylene diisocyanate (HDI), 2,2,4-trimethyl cyclohexane vulcabond and lysinediisocyanate; The alicyclic vulcabond that contains 5～18 carbon atoms, as 1,4-cyclohexyl diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methane diisocyanate (hydrogenant MDI), methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4 '-vulcabond and 1,3-two isocyanato methylcyclohexanes (hydrogenant XDI), hydrogenant TDI, 2,5-or 2,6-two (isocyanato methyl)-two rings [2,2,1] heptane (being also referred to as norbornene alkyl diisocyanate); Aliphatic vulcabond with aromatic ring is as eylylene diisocyanate (XDI) and tetramethyl-eylylene diisocyanate (TMXDI); The modified product of these vulcabond (product of polyurethane-reinforcement, carbodiimide, urethano diketone (urethodione), urethano imines (urethonimine), biuret and/or isocyanurate-modified product) etc.These polyisocyanates can use separately or two or more is used in combination.

By polyisocyanates and polyvalent alcohol, for example ethylene glycol, propylene glycol, TriMethylolPropane(TMP) and hexanetriol, the ratio of NCO/OH be 2 or higher situation under reaction obtain adducts or prepolymer, they also can be used as the blocked isocyanate solidifying agent and use.

Polyisocyanates preferably uses with aliphatic polyisocyanate and aromatic polyisocyanate array mode, and this is because because filming of forming has good slickness and weather resisteant.The weight ratio of the polyisocyanates of aliphatic polyisocyanate and aromatics is 3/1～1/3, preferred 7/3～3/7 (aliphatic polyisocyanate/aromatic polyisocyanate (w/w)).When weight ratio greater than 3/1 the time, the slickness of filming is bad.When weight ratio less than 1/3 the time, the weather resisteant of filming is bad.

Preferred aliphatic polyisocyanate comprises as hexamethylene diisocyanate, hydrogenant TDI, hydrogenant MDI, hydrogenant XDI, IPDI, norbornene alkyl diisocyanate and its dipolymer (biuret) and trimer (isocyanuric acid ester) etc.

Preferred aromatic polyisocyanate comprises as inferior cresyl vulcabond (TDI), diphenylmethanediisocyanate (MDI), eylylene diisocyanate and its dipolymer, trimer and condensation product etc.

End-capping reagent be added to polyisocyanate-based on, it at room temperature is stable, but when being heated to dissociation temperature or higher temperature, can produce free isocyanate groups group again.

Under lesser temps (for example being lower than 160 ℃), be cured under the situation of process ideally; use lactan type end-capping reagent such as ε-Ji Neixianan, δ-Valerolactim, butyrolactam and azetidinone, and oxime type end-capping reagent such as formoxime, ethylidenehydroxylamine, acetoxime, methyl ethyl ketone oxime, diacetyl monoxime and hexanaphthene oxime.

The content that contains the binder resin of amine-modified epoxy resin and solidifying agent generally is 25～85% with respect to the total solids level of electrodeposition coating composition by weight, preferably by weight 40～70%.

Pigment

Typical electrodeposition coating composition comprises pigment as tinting material.Electrodeposition coating composition of the present invention also can comprise the pigment that conventionally uses.For example, pigment comprises: tinting pigment such as titanium white, carbon black and colcother; Filler pigment such as kaolin, talcum, pure aluminium silicate, lime carbonate, mica and clay; Anticorrosive pigment such as zinc phosphate, tertiary iron phosphate, aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminium triphosphate, zinc molybdate, molybdic acid aluminium, calcium molybdate, phospho-molybdic acid aluminium and aluminium zinc phosphomolybdate etc.

The content of pigment generally is 1～35% with respect to total solids level in the electrodeposition coating composition by weight, preferably by weight 10～30%.As mentioned above, think that the specific silica particle that uses among the present invention is a kind of solids component, and can be used as a part of pigment and use.In this case, think that also a part of pigment can substitute with silica particle.Can be used as at silica particle under the situation of additive, the content of pigment reduces to by weight 0.01～15% with respect to total solids level in the electrodeposition coating composition, and preferably by weight 0.2～2%.

Preferably cation electric deposition paint composition of the present invention is unleaded aspect environment.Therefore, composition should not comprise corrosion inhibitor such as alkaline silicate lead, alkaline lead sulfate and the red lead of lead-containing compounds, does not also comprise the anticorrosive pigment such as the lead cyanamide of lead-containing compounds.Even allocate them into, also should in the coating composition (promptly be in and got the state that can be injected in the electrocoating paint bath ready) of dilution, use the concentration of lead ion to be no more than 100ppm.Higher plumbum ion concentration pollute the environment and the slickness of filming that forms bad.

Pigment disperse sizing agent

When pigment is used as the component of electrodeposition coating composition, usually pigment and the resin that is called pigment dispersing resin are scattered in the water medium in advance with high density, form pulp-like.Because pigment is powder, it is dispersed into the even lower concentration state that is used for electrodeposition coating composition so be difficult to a step.This type of slurry is commonly referred to pigment disperse sizing agent.

Pigment disperse sizing agent is by disperseing pigment dispersing resin and pigment together to prepare in water medium.In the preferred embodiment of the invention, with pigment and the combined pigment disperse sizing agent for preparing of silica particle.As pigment dispersing resin, generally use low-molecular-weight tensio-active agent of positively charged ion or nonionic and cationic polymers as having the modified epoxy of quaternary ammonium group and/or uncle's sulfonium group.As water medium, use ion exchanged water, contain the water of a small amount of alcohol etc.The weight ratio of pigment dispersing resin and pigment is generally 1:10～1:1, with the benchmark (pigment dispersing resin: pigment (w/w)) of solids content.

Electrodeposition coating composition

Electrodeposition coating composition of the present invention is to prepare by the pigment disperse sizing agent that disperses amine-modified epoxy resin, solidifying agent and contain silica particle in water medium.Usually, water medium comprises that neutralizing agent is used for improving the dispersiveness of amine-modified epoxy resin.Neutralizing agent comprises mineral acid and organic acid, example hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid and lactic acid.The amount of the neutralizing agent that uses is the amount that is enough to reach at least 20%, preferred 30～60% neutralization ratio.

In solidification process, the amount of the solidifying agent of use should be enough to and amine-modified epoxy resin (or sulfonium modified epoxy) in primary, the second month in a season and/or uncle are amino or contain the functional group of active hydrogen such as hydroxyl reaction so that the amount of good cured coating film to be provided.The weight ratio of amine-modified epoxy resin (A) and end capped polyisocyanate curing agent (B) is 50/50～90/10, preferred 55/45～80/20 (A/B (w/w)).When the weight ratio (A/B (w/w)) of amine-modified epoxy resin (A) and end capped polyisocyanate curing agent (B) less than 50/50 the time, the slickness of filming is poor.When weight ratio greater than 90/10 the time, the erosion resistance deficiency.

Under the situation that sulfonium modified epoxy and cationic amine modified epoxy are used in combination, the mass ratio of sulfonium modified epoxy and amine-modified epoxy resin is in 10/90～50/50 scope, and is preferred 25/75～50/50, and more preferably 40/60～50/50.When mass ratio less than 10/90 the time, the anti-cratering characteristic (so-called gas-pin hole) of filming of formation is bad.When mass ratio greater than 50/50 the time, be difficult to improve the inadequate outward appearance of filming of formation.

Electrodeposition coating composition of the present invention can comprise as the organo-tin compound of catalyzer such as dibutyl tin dilaurate, dibutyl tin oxide and the conventional urethane catalyst for cracking that uses.Because these catalyzer are substantially free of lead compound, the usage quantity of catalyzer is with respect to the total amount of blocked polyisocyanates compound preferably by weight 0.1～5%.

This electrodeposition coating composition can comprise additive that routine is used for coating composition as can with organic solvent, tensio-active agent, antioxidant, uv-absorbing agent and the pigment of water compatible.

Electrodeposition coating composition of the present invention can be used for galvanic deposit and applies, and wherein according to method well known to those skilled in the art said composition is applied in to wait to be coated with to form on the goods and films.The goods that preferred pending galvanic deposit applies and will be applied by cation electric deposition paint composition are surface treated conductor in advance, flood or spraying method carries out zinc phosphate processing etc. as adopting.Selectively, the surface of goods can be through not handling.Here, conductor be meant any can be when galvanic deposit applies as the material of negative electrode and preferred but be not limited to metal base.

Such metal base can comprise steel plate such as cold rolling steel plate and zinc-nickel steel plate.This steel plate also can be the works of being convenient to use in application-specific, car body as mentioned above.Here, works is meant the top listed metal base that carries out following processing, and for example embossing forms the convexo-concave shape, is convenient to use in automobile product and other field.Consider from the erosion resistance aspect that especially the automobile product field, goods preferably to be coated with are structures of being made by the zinc-nickel steel plate.

The condition of galvanic deposit and those normal conditions of using in arbitrary galvanic deposit applies are similar.The voltage that applies can change in the scope of 1～several hectovolts significantly.Current density generally is about 10～160 amperes/m ²Current density trends towards reducing in galvanic deposit.

After galvanic deposit, the conventional process that bakes of experience at high temperature of filming of formation, this method is included in electric furnace or the baking oven or under the infrared heating lamp and bakes.Generally, baking temperature can change in about 140～about 180 ℃ scope.

In galvanic deposit applied, electrodeposition coating composition of the present invention must have 11.90～12.00 minimal deposition pH.When minimal deposition pH less than 11.90 the time, galvanic deposit applies the poor stability of the composition in bathing.When minimal deposition pH greater than 12.00 the time, the throwing power of composition is poor.Here, minimal deposition pH is meant a pH value of calculating based on the essential hydroxide ion concentration of the binder resin in the deposition cation electric deposition paint composition.

The numerical value of minimal deposition pH is by applying promptly at constant current density (mA/cm in the constant current galvanic deposit ²) under the galvanic deposit coating procedure in the galvanic deposit behavior determine.In case be contained in the surface that resin in the electrodeposition composition begins to be deposited on the goods that will apply, deposition has increased resistance, therefore require in constant current galvanic deposit coating procedure, to apply higher voltage (see figure 2).Deposit the hydroxide ion concentration (C that resin needs here, _OH-) can be to determine the dielectric time (dielectric time) from increase required conducting period until resistance according to following formula:

Wherein

F (Faraday's number) is 96486.7

D (spread coefficient of hydroxide ion [OH-]) is 5 * 10 ^-5

Can determine minimal deposition pH according to following formula:

Minimal deposition pH=14-log ₁₀(l/C _OH-)

PH is associated with minimal deposition, and Fig. 2 is the graphic representation that explanation applies voltage and the dependency between conducting period.

Electro-deposition method comprises goods to be coated is immersed in step in the cation electric deposition paint composition, and applies voltage deposit the step of filming between described goods negative electrode and anode.Here, the cycle that applies voltage is depended on electrodeposition condition, but it generally can be 2～4 minutes.Here " the filming of galvanic deposit " of Shi Yonging be meant recited above after deposition process and bake with solidification process before film, just refer to uncured the filming after galvanic deposit applies.

The thickness of electrodeposition coating is preferably 5～30 μ m, more preferably 7～25 μ m.When the thickness of electrodeposition coating during less than 5 μ m, the erosion resistance deficiency.When the thickness of electrodeposition coating during, will waste application composition greater than 30 μ m.In the present invention, be characterised in that as mentioned above, even reduce thickness (7 μ m according to appointment), compare this electrodeposition coating composition with the film thickness that the conventional electrodeposition coating composition that is used for film forms for filming of 10 μ m a kind of filming of higher corrosion resistance (being erosion resistance) that have also can be provided.

And, preferably when film thickness be 15 μ m and the voltage that applies when being 240V, the membrane resistance of electrodeposition coating is 1000～1500k Ω cm ²When the membrane resistance of electrodeposition coating less than 1000k Ω cm ²The time, mean that resistance is not enough and throwing power is poor.When membrane resistance greater than 1500k Ω cm ²The time, the outward appearance of filming is very poor.More preferably the membrane resistance of electrodeposition coating is 1100～1200k Ω cm ²

Can control the membrane resistance of electrodeposition coating by amount and its viscosity of regulating charge transfer medium in the deposited film.

After electrodeposition process, with the electrodeposition coating that so obtains directly or washing the back with water, bake 10～30 minutes to solidify under preferred 140～220 ℃ at 120～260 ℃.Here, bake with solidification process after film and be called " cured coating film ".

The square root of the spread coefficient of the cured coating film that forms with cation electric deposition paint composition of the present invention Be not less than 2.5, preferred 2.5～3.2, more preferably 2.7～3.0.Here, spread coefficient (Tc) is an expression solution infiltration and be diffused on the cured coating film/in the index of degree, it is an eigenwert that is associated with the cross-linking density of cured coating film.The cross-linking density of cured coating film is high more, and the value of spread coefficient (Tc) is high more.

Increasing of cured coating film spread coefficient (Tc) or cross-linking density reduced the ionogen such as the Na that are contained in mud or the dirt ⁺, CI ^-, SO ₄ ^2-Enter into the diffusibility of cured coating film.Therefore, suppressed the perviousness that material passes cured coating film, this material is corrosive to the goods that apply.The result is to make this cured coating film have fabulous prevention by adhering to of mud or dirt caused goods corrosive effect.

The mensuration of the spread coefficient (Tc) of cured coating film is described below.At first, coated surface and the solution with the galvanic deposit sheet contacts.Secondly, between plate and solution, apply galvanic voltage.When measuring resistance over time the time, can see that resistance reduces significantly.At this moment, solution is generated ion by electrolysis, and these ions are attached to the surface of filming, pass and film and be diffused on the goods then.Here, spread coefficient (Tc) is the cycle (min) the time point that reduces from the time point that applies voltage to resistance.

The measuring method of spread coefficient (Tc) is disclosed in " SHIKIZAI ", Hitoshi Kawai, and TakashiYamamoto and Hirosi Amago, 47 (1974), 396 pages of left hurdle the 24th row reciprocal are to the 398th page of left hurdle the 12nd row.Description in this piece document is hereby incorporated by.

In the present invention, use the zinc steel plate as the goods to be coated of measuring spread coefficient.As sample panel, by coating composition is prepared coated board with the coating thickness galvanic deposit of 7 μ m on zine plate, 150 ℃ of oven dry are 25 minutes then.As contact solution, use mixing solutions (water/methyl alcohol=1/3 (v/v)).

Fig. 1 has described a surveying instrument, this instrument comprise on film (101) that are placed on the sheet (100) that has applied platinum loop electrode (103) and

Figure S061C8560020060908D00012125326QIETU

Ring (104), and the silicon rubber gasket (102) and (102 ') that are placed on the both sides of electrode (103).This instrument is put in the air themperature constant baking box, and with temperature regulation to 28 ℃, tolerance range is at ± 0.1 ℃ then.

Between goods to be coated with (105) and platinum loop electrode (103), apply galvanic voltage.In ring (104), inject solution (water/methyl alcohol=1/3 (v/v)).In case injection solution by 610 ℃ of electrometers (106) of being made by Keithley Instruments Inc., is measured electric current and is also come record by register (107) over time.The surface temperature of coated article plate is by (PHILIPS PR6452A) measures (not showing) attached to the copper-constantan thermocouple on this plate.

Make graphic representation, wherein, the ratio resistance (Ω cm) of filming was drawn with respect to the time (min).In the drawings, Tc (min) is corresponding to the initial point that changes of slope.

According to the present invention, this cation electric deposition paint composition contains the silica particle with ad hoc structure, has controlled spread coefficient with filming of its formation, even compare with filming of routine, this is filmed and has reduced thickness (as the about 7 μ m of thickness) significantly, the film coated surface slickness that it can provide corrosion resistance (being erosion resistance) and improve.In addition, in electrodeposition process, when applying voltage is that 240V and film thickness are when being 15 μ m, control the membrane resistance of the minimal deposition pH and the control electrodeposition coating of the cation electric deposition paint composition of the present invention that contains specific silica particle, except the photocatalytic coating film slippery that corrosion resistance (being erosion resistance) is provided and improves, can also provide higher throwing power, film and reduced thickness (as the about 7 μ m of thickness) significantly even compare this with filming of routine.Cation electric deposition paint composition of the present invention can also provide fabulous erosion resistance on the zinc steel plate, this approves by humidity cabinet test and cyclic wetting and drying test.

Embodiment

Further describe the present invention according to embodiment and embodiment the mode for preparing below, but the present invention is not limited to these embodiment with illustration.In these preparation embodiment and embodiment, except as otherwise noted, " part " and " % " is according to weight basis.

Embodiment A

Preparation embodiment A 1: amine-modified epoxy resin synthetic

188), 77.0 parts of methyl alcohol, 200.3 parts of methyl iso-butyl ketone (MIBK) and 0.3 part of dibutyl tin laurate put into the flask that is equipped with agitator, cooling tube, nitrogen input tube, thermometer and dropping funnel take by weighing 752.0 parts of bisphenol A type epoxy resins (epoxy equivalent (weight):.At room temperature stir this mixture and form homogeneous solution.Dropwise add 174.2 part 2 in 50 minutes, 4-and 2, the mixture of 6-inferior cresyl vulcabond (2,4-type/2,6-type=80/20 are benchmark with the mass ratio), because liberated heat, the temperature in the system is elevated to 70 ℃.IR spectrum demonstrates corresponding to isocyanate group 2280cm ^-1The disappearance of the absorption peak at place and corresponding with carbonyl in the urethane at 1730cm ^-1The appearance of the absorption peak at place.

With 2.7 parts of N, the N-dimethyl benzyl amine joins in the reaction mixture, and the temperature with reaction system is elevated to 120 ℃ then.Reaction is proceeded to reach 463 up to epoxy equivalent (weight), removes methyl alcohol as byproduct with decanting vessel.IR spectrum demonstrates corresponding to carbonyl in the urethane 1730cm ^-1The place absorption peak disappearance He the carbonyl in the oxazolidone ring corresponding at 1750cm ^-1The appearance of the absorption peak at place.

Methyl iso-butyl ketone (MIBK) sad with 158.3 parts and 83.3 parts are added in the reaction mixture, and reaction was proceeded to reach 1146 up to epoxy equivalent (weight) under temperature remained on 125 ℃.Continue cooling and drop to 110 ℃ up to the temperature of reaction system.The ketoimine (in the methyl isobutyl ketone solution of 79 quality %) of 47.2 parts of amino ethyl ethanolamines, 42.0 parts of diethanolamine, 30.0 parts of N-Mono Methyl Ethanol Amines and 17.3 parts of methyl iso-butyl ketone (MIBK) are joined in the reaction mixture, and temperature is elevated to 120 ℃ then.Under this temperature, continue this reaction 2 hours, obtain to contain non-volatile content and be 80% the aminoepoxy resin that contains.

Preparation embodiment A 2: end-blocking aliphatic polyisocyanate solidifying agent synthetic

Taking by weighing the isocyanuric acid ester type tripolymer (NIPPONPOLYURETHANE INDUSTRY CO., the CORONATE HX that LTD. makes) of 199 parts of hexamethylene diisocyanates, 122.8 parts of methyl iso-butyl ketone (MIBK) and 0.2 part of dibutyl tin laurate puts into the flask that is equipped with agitator, cooling tube, nitrogen input tube, thermometer and dropping funnel and is heated to 50 ℃.With exterior cooling temperature is remained on 50 ℃, dropwise add 87 parts of methyl ethyl ketone oxime in 2 hours.After adding, temperature is risen to 70 ℃.Keep this temperature, reaction continues to demonstrate exhausting of isocyanate group up to the IR analysis, thereby obtains end-blocking aliphatic polyisocyanate solidifying agent.

Preparation embodiment A 3: end-blocking aromatic polyisocyanate solidifying agent synthetic

Take by weighing 723 parts of ditans-4,4 '-vulcabond, 350 parts of methyl iso-butyl ketone (MIBK) (MIBK) and 0.01 part of dibutyl tin laurate put into and prepare embodiment A 1 similar flask.The reaction mixture that forms is heated to 70 ℃ and dissolving equably.131 parts of ε-Ji Neixianan are dissolved in 546 parts of ethylene glycol butyl ethers.Dropwise add this solution in 2 hours.After adding, under temperature of reaction kept 90 ℃, reaction continued to disappear up to absorption peak corresponding with isocyanate group in the IR spectral measurement, thereby obtained end-blocking aromatic polyisocyanate solidifying agent (resin solid content: 80%).

Preparation embodiment A 4: the preparation of pigment dispersing resin

222.0 parts of isophorone diisocyanates (being abbreviated as IPDI hereinafter) are put into the reaction vessel that is equipped with agitator, cooling tube, nitrogen input tube and thermometer.Add 39.1 parts of MIBK dilutions, add 0.2 part of dibutyl tin laurate then in mixture.Subsequently, temperature is raised to 50 ℃, is doing under the nitrogen atmosphere, in 2 hours, drip 131.5 parts of 2-Ethylhexyl Alcohols while stirring.With suitable cooling temperature of reaction is remained on 50 ℃, obtain 2-Ethylhexyl Alcohol half end-blocking IPDI.

Subsequently, with 376.0 parts of Epikote828 (by Yuka-Shell Epoxy Co., Ltd. the dihydroxyphenyl propane type of epoxy resin of Zhi Zaoing, 182～194), 114.0 parts of dihydroxyphenyl propanes and 29.2 parts of sad joining in the reaction vessel that is equipped with agitator, cooling tube, nitrogen input tube and thermometer epoxy equivalent (weight):.Under nitrogen atmosphere, reaction mixture is heated to 130 ℃.0.15 part of dimethyl benzyl amine is joined in the mixture.Thermopositive reaction kept 1 hour down at 170 ℃, made bisphenol A type epoxy resin (epoxy equivalent (weight): 649).

Subsequently, reaction system is cooled to 140 ℃.The 2-Ethylhexyl Alcohol half end-blocking IPDI of 396.8 parts of above-mentioned preparations is joined in the reaction mixture.Being reflected at 140 ℃ kept 1 hour down.Then, add 323.2 parts of ethylene glycol monobutyl ether diluted mixture things.Reaction mixture is cooled to 100 ℃, adds 188.8 parts of 78.3%MIBK solution then, this MIBK solution contains the methyl-isobutyl single ketones group with imine moiety (mono-ketiminated compound) of amino ethyl ethanolamine.

Reaction mixture kept 1 hour down at 110 ℃, was cooled to 90 ℃ then, added 360.0 parts of ion exchanged waters inward.Reaction system keep was stirred 30 minutes, being corresponding primary amino ketoimine fractional conversion in the Resins, epoxy.Remove water excessive in the mixture and MIBK in a vacuum.With 588.1 parts of ethylene glycol monobutyl ether dilutions, thereby acquisition contains the pigment dispersing resin (resin solid content: 50%) of primary amino.

Preparation embodiment A 5: the preparation of pigment disperse sizing agent

Pigment dispersing resin (based on solids content), 100.0 parts of pigment and 221.7 parts of ion exchanged waters of listing in the table 1 of 60 parts of preparations in preparation embodiment A 4 are put into sand mill, purpose is the pigment that fineness of dispersion is not more than 10 μ m, thereby makes pigment disperse sizing agent (slurry AA～AF).

Table 1

Composition	No.1	No.2	No.3	No.4	No.5	No.6	No.7
								Pigment disperse sizing agent	Slurry AA	Slurry AB	Slurry AC	Slurry AD	Slurry AD	Slurry AE	Slurry AF
	Embodiment A 1	Embodiment A 2	Embodiment A 3	Comparative Example A An 1	Comparative Example A An 2	Comparative Example A An 3	Comparative Example A An 4
								Carbon black	2	2	2	2	2	2	2
Titanium	48	48	48	48	48	48	48
								Calcined kaolin	30	40	20	50	50	50	30
Silica particle A ^*1(pore volume: 0.8ml/g, mean particle size: 2.5 μ m)	20	0	30	0	0	0	0
								Silica particle B ^*2(pore volume: 1.6ml/g, mean particle size: 4.0 μ m)	0	10	0	0	0	0	20
Silica particle C ^*3(pore volume: 0.44ml/g, mean particle size: 6.5 μ m)	0	0	25	0	0	0	0
								The content of silicon dioxide compound in pigment	20	10	30	0	0	0	20
Dispersion resin	60	60	60	60	60	60	60

^{* 1}Silica particle: the SYLYSIA530 that FUJI SILYSIA CHEMICAL LTD. makes

^{* 2}Silica particle: the SYLYSIA350 that FUJI SILYSIA CHEMICAL LTD. makes

^{* 3}Silica particle: the SYLYSIA770 that FUJI SILYSIA CHEMICAL LTD makes

Embodiment A 1

Amine-modified epoxy resin that will in preparation embodiment A 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the embodiment A 2 and the polyisocyanate curing agent that in preparation embodiment A 3, obtains, preparation embodiment A 2/ prepares embodiment A 3=1/1)) and uniform mixing (based on solids content, resin: solidifying agent=6:40).Adding is with respect to the glycol monomethyl-2-ethylhexyl ether of mixture solid content 3%.In mixture, add 90% acetate, reaching 43.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1500.0 parts of main emulsions are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides with 541.7 parts of pigment disperse sizing agent AA that prepare in preparation embodiment A 5 by the pigment dispersing resin that uses preparation in preparation embodiment A 4, to obtain cation electric deposition paint composition (solids content: 20.0%).

On steel plate galvanized, the thickness of the cured coating film that make to form is 7 μ m with the cation electric deposition paint composition galvanic deposit of preparation like this.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.The results are shown in Table 2.

Embodiment A 2

Amine-modified epoxy resin that will in preparation embodiment A 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the embodiment A 2 and the polyisocyanate curing agent that in preparation embodiment A 3, obtains, preparation embodiment A 2/ prepares embodiment A 3=1/3)) and uniform mixing (based on solids content, resin: solidifying agent=80:20).Adding is with respect to the glycol monomethyl-2-ethylhexyl ether of mixture solid content 3%.In mixture, add 90% acetate, reaching 43.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1500.0 parts of main emulsions and 541.7 parts of pigment disperse sizing agent AB by pigment dispersing resin preparation in preparation embodiment A 5 of use preparation in preparation embodiment A 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides, to obtain cation electric deposition paint composition (solids content: 20,0%).

Embodiment A 3

Amine-modified epoxy resin that will in preparation embodiment A 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the embodiment A 2 and the polyisocyanate curing agent that in preparation embodiment A 3, obtains, preparation embodiment A 2/ prepares embodiment A 3=3/1)) and uniform mixing (based on solids content, resin: solidifying agent=50:50).Adding is with respect to the glycol monomethyl-2-ethylhexyl ether of mixture solid content 3%.In mixture, add 90% acetate, reaching 43.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1500.0 parts of main emulsions and 541.7 parts of pigment disperse sizing agent AC by pigment dispersing resin preparation in preparation embodiment A 5 of use preparation in preparation embodiment A 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides, with acquisition cation electric deposition paint composition (solids content: 20.0%).

Comparative Examples A 1

Amine-modified epoxy resin that will in preparation embodiment A 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent of the polyisocyanate curing agent that obtains in polyisocyanate curing agent that obtains in the preparation embodiment A 2 and the preparation embodiment A 3, preparation embodiment A 2/ prepares embodiment A 3=9/1)) and uniform mixing (based on solids content, resin: solidifying agent=80:20).Adding is with respect to the glycol monomethyl-2-ethylhexyl ether of mixture solid content 3%.In mixture, add 90% acetate, reaching 43.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1500.0 parts of main emulsions and 541.7 parts of pigment disperse sizing agent AD by pigment dispersing resin preparation in preparation embodiment A 5 of use preparation in preparation embodiment A 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides, with acquisition cation electric deposition paint composition (solids content: 20.0%).

On steel plate galvanized, the thickness of the cured coating film that make to form is 10 μ m with the cation electric deposition paint composition galvanic deposit of preparation like this.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.The results are shown in Table 2.

Comparative Examples A 2

The cation electric deposition paint composition galvanic deposit that will prepare in Comparative Examples A 1 is on steel plate galvanized, and the thickness of the feasible cured coating film that forms is 7 μ m.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.The results are shown in Table 2.

Comparative Examples A 3

Amine-modified epoxy resin that will in preparation embodiment A 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent of the polyisocyanate curing agent that obtains in polyisocyanate curing agent that obtains in the preparation embodiment A 2 and the preparation embodiment A 3, preparation embodiment A 2/ prepares embodiment A 3=1/1)) and uniform mixing (based on solids content, resin: solidifying agent=60:40).Adding is with respect to the glycol monomethyl-2-ethylhexyl ether of mixture solid content 3%.In mixture, add 90% acetate, reaching 43.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1500.0 parts of main emulsions and 541.7 parts of pigment disperse sizing agent AF by pigment dispersing resin preparation in preparation embodiment A 5 of use preparation in preparation embodiment A 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides, with acquisition cation electric deposition paint composition (solids content: 20.0%).

Comparative Examples A 4

Amine-modified epoxy resin that will in preparation embodiment A 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent of the polyisocyanate curing agent that obtains in polyisocyanate curing agent that obtains in the preparation embodiment A 2 and the preparation embodiment A 3, preparation embodiment A 2/ prepares embodiment A 3=9/1)) and uniform mixing (based on solids content, resin: solidifying agent=95:5).Adding is with respect to the glycol monomethyl-2-ethylhexyl ether of mixture solid content 3%.In mixture, add 90% acetate, reaching 43.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1500.0 parts of main emulsions and 541.7 parts of pigment disperse sizing agent AG by pigment dispersing resin preparation in preparation embodiment A 5 of use preparation in preparation embodiment A 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides, with acquisition cation electric deposition paint composition (solids content: 20.0%).

Zhi Bei cation electric deposition paint composition galvanic deposit is on steel plate galvanized like this, and the thickness of the feasible cured coating film that forms is 7 μ m.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.The results are shown in Table 2.

Estimate in the following method and be used in electrodeposition coating and the cured coating film thereof that the cation electric deposition paint composition that obtains among embodiment and the comparative example is made.

＜spread coefficient 〉

According to method recited above, the steel plate that uses zinc phosphate processing (wherein using the SURFDINE SD-2500 that defines in JIS G 3141 SPCC-SD) to cross is measured spread coefficient.Please note in the table 2 that its with the square root of spread coefficient (promptly below

) represent.

＜erosion resistance 〉

Be used among the JP-A-2001-294816 disclosed circulation pattern and estimate erosion resistance.Metewand is as follows.

◎: the foaming zone is no more than 30% after 120 circulations

Zero: the foaming zone is no more than 50% after 120 circulations

*: the foaming zone is no more than 80% after 120 circulations

* *: foaming zone after 120 circulations is no less than 80%

Table 2

Embodiment B

Preparation Embodiment B 1: amine-modified epoxy resin synthetic

188), 77.0 parts of methyl alcohol, 200.3 parts of methyl iso-butyl ketone (MIBK) and 0.3 part of dibutyl tin laurate put into the flask that is equipped with agitator, cooling tube, nitrogen input tube, thermometer and dropping funnel take by weighing 752.0 parts of bisphenol A type epoxy resins (epoxy equivalent (weight):.At room temperature stir this mixture and form homogeneous solution.Dropwise add 174.2 part 2 in 50 minutes, 4-and 2, the mixture of 6-inferior cresyl vulcabond (2,4-type/2,6-type=80/20 are benchmark with the mass ratio), the temperature in the system is elevated to 70 ℃ because of liberated heat.IR spectrum demonstrates corresponding to isocyanate group 2280cm ^-1The disappearance of the absorption peak at place and corresponding with carbonyl in the urethane at 1730cm ^-1The appearance of the absorption peak at place.

With 2.7 parts of N, N-diformazan benzylamine adds in the reaction mixture, and the temperature with reaction system is elevated to 120 ℃ then.Reaction is proceeded to reach 463 up to epoxy equivalent (weight), removes methyl alcohol as byproduct with decanting vessel.IR spectrum demonstrates corresponding to carbonyl in the urethane 1730cm ^-1The place absorption peak disappearance He the carbonyl in the oxazolidone ring corresponding at 1750cm ^-1The appearance of the absorption peak at place.

Methyl iso-butyl ketone (MIBK) sad with 158.3 parts and 83.3 parts are added in the reaction mixture, and reaction was proceeded to reach 1146 up to epoxy equivalent (weight) under temperature remained on 125 ℃.Continue cooling and drop to 110 ℃ up to the temperature of reaction system.The ketoimine (in the methyl isobutyl ketone solution of 79 quality %) of 47.2 parts of amino ethyl ethanolamines, 42.0 parts of diethanolamine, 30.0 parts of N-Mono Methyl Ethanol Amines and 17.3 parts of methyl iso-butyl ketone (MIBK) are added in the reaction mixture, temperature is elevated to 120 ℃ then.Under this temperature, continue this reaction 2 hours, obtain to contain non-volatile content and be 80% the aminoepoxy resin that contains.

Preparation Embodiment B 2: end-blocking aliphatic polyisocyanate solidifying agent synthetic

Taking by weighing the isocyanuric acid ester type tripolymer (the CORONATE HX that NIPPONPOLYURETHANE INDUSTRY CO.LTD. makes) of 199 parts of hexamethylene diisocyanates, 122.8 parts of methyl iso-butyl ketone (MIBK) and 0.2 part of dibutyl tin laurate puts into the flask that is equipped with agitator, cooling tube, nitrogen input tube, thermometer and dropping funnel and is heated to 50 ℃.With exterior cooling temperature is remained on 50 ℃, in 2 hours, dropwise add 87 parts of methyl ethyl ketone oxime.After adding, temperature is increased to 70 ℃.Keep this temperature, reaction continues to demonstrate exhausting of isocyanate group up to the IR analysis, thereby obtains end-blocking aliphatic polyisocyanate solidifying agent.

Preparation Embodiment B 3: end-blocking aromatic polyisocyanate solidifying agent synthetic

Take by weighing 723 parts of ditans-4,4 '-vulcabond, 350 parts of methyl iso-butyl ketone (MIBK) (MIBK) and 0.01 part of dibutyl tin laurate put into and prepare Embodiment B 1 similar flask.The reaction mixture that forms is heated to 70 ℃ and dissolving equably.131 parts of ε-Ji Neixianan are dissolved in 546 parts of ethylene glycol butyl ethers.In 2 hours, dropwise add solution.After adding, temperature of reaction remains on 90 ℃, and reaction continues to disappear up to absorption peak corresponding with isocyanate group in the IR spectral measurement, thereby obtains end-blocking aromatic polyisocyanate solidifying agent (resin solid content: 80%).

Preparation Embodiment B 4: the preparation of sulfonium modified epoxy

Take by weighing 87 part 2,4-and 2, (mass ratio=8:2), 85 parts of MIBK and 0.1 part of dibutyl tin laurate are put into the flask that is equipped with agitator, cooling tube, nitrogen input tube, thermometer and dropping funnel to the mixture of 6-inferior cresyl vulcabond.Stirred reaction mixture dropwise adds 32 parts of methyl alcohol.Reaction is at room temperature carried out.Because liberated heat raises the temperature to 60 ℃.Reaction mainly remains on 60～65 ℃, and absorption peak corresponding with isocyanate group up to the IR spectral measurement time disappears.

Subsequently, with 550 parts of Resins, epoxy made from dihydroxyphenyl propane and Epicholorohydrin according to known method (epoxy equivalent (weight): 188) join in the reaction mixture and with mixture heating up to 125 ℃.Then, in mixture, add 1.0 parts of benzyl dimethyl amine.Be reflected at 130 ℃ and continue down, to obtain 330 epoxy equivalent (weight).

Subsequently, it is sad to add 100 parts dihydroxyphenyl propane and 36 parts in reaction mixture.Reaction remains on 120 ℃, to obtain 1030 epoxy equivalent (weight).Then, in reaction mixture, add 107 parts of MIBK.Cool off this reaction mixture.In mixture, add the lactic acid of 52 parts of SHP-100 (Ltd. makes for 1-(2-hydroxyethyl sulphur)-2-propyl alcohol, SanyoChemical Industries), 21 parts of ion exchanged waters and 39 part 88%.Reaction remains on 80 ℃.Reaction continues up to acid number less than 5, to obtain to contain the Resins, epoxy (resin solid content: 80%) of uncle's sulfonium group.

Resin that forms and the blocked isocyanate solidifying agent that makes are mixed equably (resin/blocked isocyanate solidifying agent=60/40 (with solids content as benchmark) in preparation Embodiment B 2).Then, add ion exchanged water lentamente and dilute this mixture.Remove MIBK in a vacuum to obtain to contain the sulfonium modified epoxy resin emulsion (solids content: 36%) of blocked isocyanate.Milligramequivalent corresponding to the alkali of 100g resin solid content in this emulsion is 10.

Preparation Embodiment B 5: the preparation of pigment dispersing resin

222.0 parts of isophorone diisocyanates (being abbreviated as IPDI hereinafter) are added in the reaction vessel that is equipped with agitator, cooling tube, nitrogen input tube and thermometer.Add 39.1 parts of MIBK with dilution, add 0.2 part of dibutyl tin laurate then in mixture.Subsequently, reaction mixture is heated to 50 ℃, is doing under the nitrogen atmosphere, in 2 hours, drip 131.5 parts of 2-Ethylhexyl Alcohols while stirring.With suitable cooling temperature of reaction is remained on 50 ℃, obtain 2-Ethylhexyl Alcohol half end-blocking IPDI.

Subsequently, take by weighing 376.0 parts of Epikote828 (by the dihydroxyphenyl propane type of epoxy resin that Yuka-Shell Epoxy Co.Ltd. makes, 182～194), 114.0 parts of dihydroxyphenyl propanes and 29.2 parts of sad joining in the reaction vessel that is equipped with agitator, cooling tube, nitrogen input tube and thermometer epoxy equivalent (weight):.Under nitrogen atmosphere, reaction mixture is heated to 130 ℃.0.15 part of dimethyl benzyl amine is joined in the mixture.Thermopositive reaction kept 1 hour down at 170 ℃, made bisphenol A type epoxy resin (epoxy equivalent (weight): 649).

Subsequently, reaction system is cooled to 140 ℃.The 2-Ethylhexyl Alcohol half end-blocking IPDI of 396.8 parts of above-mentioned preparations is joined in the reaction mixture.Being reflected at 140 ℃ kept 1 hour down.Then, add 323.2 parts of ethylene glycol monobutyl ether with the diluted mixture thing.Reaction mixture is cooled to 100 ℃, adds 188.8 parts of 78.3%MIBK solution then, this MIBK solution contains the methyl-isobutyl single ketones group with imine moiety of amino ethyl ethanolamine.

Reaction mixture kept 1 hour down at 110 ℃, was cooled to 90 ℃ then, added 360.0 parts of ion exchanged waters inward.Reaction system keep was stirred 30 minutes, with the ketoimine fractional conversion in the Resins, epoxy to be corresponding primary amino group.From mixture, remove excessive water and MIBK in a vacuum.With 588.1 parts of ethylene glycol monobutyl ether dilutions, thereby acquisition contains the pigment dispersing resin (resin solid content: 50%) of primary amino.

Preparation Embodiment B 6: the preparation of pigment disperse sizing agent

Pigment dispersing resin (based on solids content), 100.0 parts of pigment and 221 of listing in the table 3 with 60 parts of preparations in preparation Embodiment B 5,7 parts of ion exchanged waters are put into sand mill, purpose is the pigment that fineness of dispersion is not more than 10 μ m, thereby makes pigment disperse sizing agent (slurry BA～BF).

Table 3

Composition	No.1	No.2	No.3	No.4	No.5	No.6	No.7
								Pigment disperse sizing agent	Slurry BA	Slurry BB	Slurry BC	Slurry BD	Slurry BE	Slurry BE	Slurry BF
	Embodiment B 1	Embodiment B 2	Embodiment B 3	Comparative Examples B 1	Comparative Examples B 2	Comparative Examples B 3	Comparative Examples B 4
								Carbon black	2	2	2	2	2	2	2
Titanium	48	48	48	48	48	48	48
								Calcined kaolin	30	40	20	20	50	50	30
Silica particle A ^*1(pore volume: 0.8ml/g, mean particle size: 2.5 μ m)	20	0	30	30	0	0	0
								Silica particle B ^*2(pore volume: 1.6ml/g, mean particle size: 4.0 μ m)	0	10	0	0	0	0	20
Silica particle C ^*3(pore volume: 0.44ml/g, mean particle size: 6.5 μ m)	0	0	25	0	0	0	0
								The content of silicon dioxide compound in pigment	20	10	30	30	0	0	20
Dispersion resin	60	60	60	60	60	60	60

^{* 1}Silica particle: the SYLYSIA530 that FUJI SILYSIA CHEMICAL LTD. makes

^{* 2}Silica particle: the SYLYSIA350 that FUJI SILYSIA CHEMICAL LTD. makes

^{* 3}Silica particle: the SYLYSIA770 that FUJI SILYSIA CHEMICALLTD. makes

Embodiment B 1

Amine-modified epoxy resin that will in preparation Embodiment B 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the Embodiment B 2 and the polyisocyanate curing agent that in preparation Embodiment B 3, obtains, preparation Embodiment B 2/ prepares Embodiment B 3=1/1)) and uniform mixing (based on solids content, resin: solidifying agent=60:40).In mixture, add 90% acetate, reaching 38.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1100.0 parts of main emulsions, 400 parts of resin emulsion and 541.7 parts of pigment disperse sizing agent BA that obtain in preparation Embodiment B 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides.Add ethylene glycol mono hexyl ether so that 1200 membrane resistance to be provided.Add acetate so that minimal deposition pH11.96 to be provided.Make the cation electric deposition paint composition of solids content 20.0%.

On steel plate galvanized, the thickness of the cured coating film that make to form is 7 μ m with the cation electric deposition paint composition galvanic deposit of preparation like this.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.And estimate pipe-throwing power (pipe-throwing power).The results are shown in Table 4.

Embodiment B 2

Amine-modified epoxy resin that will in preparation Embodiment B 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the Embodiment B 2 and the polyisocyanate curing agent that in preparation Embodiment B 3, obtains, preparation Embodiment B 2/ prepares Embodiment B 3=1/3)) and uniform mixing (based on solids content, resin: solidifying agent=80:20).In mixture, add 90% acetate, reaching 38.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1100.0 parts of main emulsions, 400 parts of resin emulsion and 541.7 parts of pigment disperse sizing agent BB that obtain in preparation Embodiment B 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides.Add ethylene glycol mono hexyl ether so that 1400 membrane resistance to be provided.Add acetate so that minimal deposition pH11.99 to be provided.Make the cation electric deposition paint composition of solids content 20.0%.

On steel plate galvanized, the thickness of the cured coating film that make to form is 7 μ m with the cation electric deposition paint composition galvanic deposit of preparation like this.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.And estimated pipe-throwing power.The results are shown in Table 4.

Embodiment B 3

Amine-modified epoxy resin that will in preparation Embodiment B 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the Embodiment B 2 and the polyisocyanate curing agent that in preparation Embodiment B 3, obtains, preparation Embodiment B 2/ preparation Embodiment B 3=3/1)) uniform mixing (resin: solidifying agent=50:50 is based on solids content).In mixture, add 90% acetate, reaching 38.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1100.0 parts of main emulsions, 400 parts of resin emulsion and 541.7 parts of pigment disperse sizing agent BC that obtain in preparation Embodiment B 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides.Add ethylene glycol mono hexyl ether so that 1400 membrane resistance to be provided.Add acetate so that minimal deposition pH11.91 to be provided.Make the cation electric deposition paint composition of solids content 20.0%.

On steel plate galvanized, the thickness of the cured coating film that make to form is 7 μ m with the cation electric deposition paint composition galvanic deposit of preparation like this.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.And evaluation pipe-throwing power.The results are shown in Table 4.

Comparative example B1

Amine-modified epoxy resin that will in preparation Embodiment B 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the Embodiment B 2 and the polyisocyanate curing agent that in preparation Embodiment B 3, obtains, preparation Embodiment B 2/ prepares Embodiment B 3=1/1)) and uniform mixing (based on solids content, resin: solidifying agent=80:20).In mixture, add 90% acetate, reaching 38.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1100.0 parts of main emulsions, 400 parts of resin emulsion and 541.7 parts of pigment disperse sizing agent BD that obtain in preparation Embodiment B 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides.Add ethylene glycol mono hexyl ether so that 900 membrane resistance to be provided.Add acetate so that minimal deposition pH11.94 to be provided.Make the cation electric deposition paint composition of solids content 20.0%.

Comparative example B2

Amine-modified epoxy resin that will in preparation Embodiment B 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the Embodiment B 2 and the polyisocyanate curing agent that in preparation Embodiment B 3, obtains, preparation Embodiment B 2/ prepares Embodiment B 3=9/1)) and uniform mixing (based on solids content, resin: solidifying agent=80:20).In mixture, add 90% acetate, reaching 38.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1100.0 parts of main emulsions, 400 parts of resin emulsion and 541.7 parts of pigment disperse sizing agent BE that obtain in preparation Embodiment B 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides.Add ethylene glycol mono hexyl ether so that 1100 membrane resistance to be provided.Add acetate so that minimal deposition pH12.05 to be provided.Make the cation electric deposition paint composition of solids content 20.0%.

Comparative example B3

Amine-modified epoxy resin that will in preparation Embodiment B 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the Embodiment B 2 and the polyisocyanate curing agent that in preparation Embodiment B 3, obtains, preparation Embodiment B 2/ prepares Embodiment B 3=1/1)) and uniform mixing (based on solids content, resin: solidifying agent=60:40).In mixture, add 90% acetate,, add ion exchanged water simultaneously and little by little dilute to reach 38.0% neutralization ratio.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).1100.0 parts of main emulsions, 400 parts of resin emulsion and 541.7 parts of pigment disperse sizing agent BE that obtain in preparation Embodiment B 4 are mixed with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides.Add ethylene glycol mono hexyl ether so that 1200 membrane resistance to be provided.Add acetate so that minimal deposition pH11.95 to be provided.Make the cation electric deposition paint composition of solids content 20.0%.

On steel plate galvanized, the thickness of the cured coating film that make to form is 7 μ m with the cation electric deposition paint composition galvanic deposit of preparation like this.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.And measured pipe-throwing power.The results are shown in Table 4.

Comparative example B4

Amine-modified epoxy resin that will in preparation Embodiment B 1, obtain and the blocked polyisocyanates solidifying agent (mixture (part by weight of solidifying agent that is preparing polyisocyanate curing agent that obtains in the Embodiment B 2 and the polyisocyanate curing agent that in preparation Embodiment B 3, obtains, preparation Embodiment B 2/ prepares Embodiment B 3=9/1)) and uniform mixing (based on solids content, resin: solidifying agent=95:5).In mixture, add 90% acetate, reaching 38.0% neutralization ratio, and add ion exchanged water and little by little dilute.Remove MIBK in a vacuum and obtain main emulsion (solids content 36.0%).Resin emulsion and 541.7 parts of pigment disperse sizing agent BF of mixing 1100.0 parts of main emulsions, 400 parts of acquisitions in preparation Embodiment B 4 mix with 1949.3 parts of ion exchanged waters and 9.0 parts of dibutyltin oxides.Add ethylene glycol mono hexyl ether so that 1200 membrane resistance to be provided.Add acetate so that minimal deposition pH11.96 to be provided.Make the cation electric deposition paint composition of solids content 20.0%.

On steel plate galvanized, the thickness of the cured coating film that the result forms is 7 μ m with the cation electric deposition paint composition galvanic deposit of preparation like this.This coated board was obtained electrodeposition coating in 30 minutes in 170 ℃ of bakings in baking box.Estimate the erosion resistance of this film.And evaluation pipe-throwing power.The results are shown in Table 4.

＜pipe-throwing power 〉

The Instrument measuring that the throwing power of each cation electric deposition paint composition for preparing in each embodiment and comparative example is described in Fig. 3.The electrodeposition coating composition (207) that 3L is prepared in advance is injected into be furnished with agitator conduction galvanic deposit coating container (201) (internal diameter: 105mm, the height: 370mm), and stir of (205).Test specimen plate (203) (size: 15mm * 400mm, the thickness: 0.7mm) of (wherein using the SURFDINE SD-2500 that defines to handle) steel plate is excessively handled in use in JIS G3141SPCC-SD with zinc phosphate.(wall thickness: pipe 1.8mm) (202) telescopically is placed on coating container (201) lining for internal diameter: 17.5mm, longitudinal length 375mm to have opening end.Test specimen plate (203) is placed in the pipe (202), each other not contact.Test specimen plate (203) and pipe (202) all are immersed in the electrodeposition coating composition together.The longitudinal length of the immersion part of test specimen plate (203) and pipe (202) is 30cm.

Galvanic deposit applies by making anodic coating container (201) and doing to apply voltage between the test specimen plate (203) of negative electrode and carry out.After applying voltage, immediately voltage is increased to 240V in 30 seconds, and in coating procedure, kept set-point 150 seconds.With the temperature regulation in the container at 28 ℃.The test specimen plate water that applies cleans, and toasts 25 minutes down at 150 ℃ then.The longitudinal length of measuring test specimen plate coating part i.e. distance from the bottom line (the immersion end of this bottom line and pipe is parallel) of test specimen plate to uncoated part.Pipe-throwing power is represented with the ratio (cm/cm) of coated length and immersion length in following table 4.

The membrane resistance of＜electrodeposition coating 〉

With steel plate (size: 70mm * 150mm, thickness: 0.7mm) be immersed in (length that immerses part is 10cm) in the cation electric deposition paint composition in the electrodeposition groove, this steel plate is to handle (wherein using the SURFDINESD-2500 that defines to handle) with zinc phosphate in JIS G 3141 SPCC-SD.Apply voltage for this steel plate, in 30 seconds, voltage is increased to 240V and this voltage and in the galvanic deposit coating procedure, kept 150 seconds.Measuring the thickness of filming of residual current and last formation after baking, is that 15 μ m calculate membrane resistance (k Ω cm based on the thickness of supposing electrodeposition coating ²) value.

＜minimal deposition pH 〉

The steel plate that to handle (wherein using the SURFDINESD-2500 that defines to handle) mistake with zinc phosphate in JIS G 3141 ' SPCC-SD covers and makes coated area be 50mm * 50mm.The steel plate that will cover is immersed in galvanic deposit and applies in a kind of cation electric deposition paint composition (4L) by previous embodiment or comparative example's preparation in the groove.Carry out constant current galvanic deposit coating with the current density of 1mA/cm2 at 28 ℃ by applying voltage.Determine minimal deposition pH according to above-mentioned method.

＜erosion resistance 〉

Estimate erosion resistance with disclosed circulation pattern among the JP-A-2000-113726.Metewand is as follows.

◎: be no more than 30% in foaming zone, 120 circulation back

Zero: be no more than 50% in foaming zone, 120 circulation back

*: be no more than 80% in foaming zone, 120 circulation back

* *: is not less than 80% in foaming zone, 120 circulation back

Table 4

Embodiment B 1

Embodiment B 2

Embodiment B 3

Comparative example B1

Comparative example B2

Comparative example B3

Comparative example B4

The silica kind that adds

A

B

C

A

B

Pore volume

0.8ml/g

1.6ml/g

0.44ml/g

0.8ml/g

1.6ml/g

Mean particle size

2.5μm

4μm

6.5μm

2.5μm

4μm

Minimal deposition pH

11.96

11.99

1191

11.94

12.05

11.95

11.96

Membrane resistance (thickness: 15 μ m voltages: 240V) (k Ω cm ²)

1200

1400

1000

900

1100

1200

Amine-modified epoxy resin (A)/solidifying agent (B)

60/40

80/20

50/50

80/20

60/40

95/5

Aliphatic series BI/ aromatics B1

1/1

1/3

3/1

1/1

9/1

1/1

9/1

The content of silicon dioxide compound

20

10

30

0

20

Pipe-throwing power

30cm/30cm

25cm/30cm

30cm30cm

30cm/30cm

Erosion resistance (thickness: 7 μ m)

◎

○

×

In describing linguistic context of the present invention (in the linguistic context of claim especially below), the use of term " a kind of " and " being somebody's turn to do " and similar denotion should be interpreted as having contained odd number and plural number, unless indicate in addition in this article or have tangible contradiction in linguistic context.Except as otherwise noted, term " comprises ", " having ", " comprising " and " containing " should be understood that open-ended term (that is, refer to including, but not limited to).Unless indicate in addition in this article, being set forth in of numerical range only is in order to refer to the short-cut method of each independent value in this scope as a seed ginseng herein, and each independent numerical value all is included in the specification sheets, just looks like that each numerical value is all enumerated equally in this article singly.All methods of Miao Shuing can be undertaken by any suitable order in this article, unless indicate in addition in this article or have tangible contradiction in linguistic context.Any or all example that is provided herein or the use of exemplary language (as " for example ") only are in order to set forth the present invention better, and are not to limit the scope of the invention, unless stated otherwise.Do not have language to be understood as that in the specification sheets key element of any failed call protection is represented to become enforcement requisite item of the present invention.

The preferred embodiment of the invention is here described, and comprises enforcement known for inventor best mode of the present invention.To those skilled in the art, by reading the description of front, the various variations of those preferred embodiments can be easy to understand.The contriver wishes that those skilled in the art adopts these to change according to circumstances, and contriver's the people that are intended that adopt the mode except that the specifically described method of this paper to implement the present invention.Therefore, present invention resides in all improvement and the equivalent of theme cited in the claim thereafter, this is that governing law is permitted.In addition, might version any combination of above-mentioned key element all comprise in the present invention, unless indicate in addition herein or have obvious contradiction hereinafter preceding.

The disclosure of Japanese patent application No.2005-228252 that comprises specification sheets and claims that submits on August 5th, 2005 and the Japanese patent application No.2005-228255 that comprises specification sheets and claims that submits on August 5th, 2005, mode integral body is by reference incorporated this paper into.

Claims

1. cation electric deposition paint composition that comprises amine-modified epoxy resin A, blocked isocyanate solidifying agent B, pigment and silica particle,

Wherein the part by weight of amine-modified epoxy resin A and blocked isocyanate solidifying agent B is 50/50～90/10, described blocked isocyanate solidifying agent B comprises end-blocking aliphatic polyisocyanate and end-blocking aromatic polyisocyanate, wherein the part by weight of end-blocking aliphatic polyisocyanate and end-blocking aromatic polyisocyanate is 3/1～1/3

The content of described pigment is 1～35% with respect to total solids level in the electrodeposition coating composition by weight,

Described silica particle has the pore volume of 0.44～1.8ml/g and is not more than the mean particle size of 10 μ m, and the content of described silica particle is 1～30wt% with respect to the gross weight of pigment,

When the mixing solutions that with volume ratio is 1/3 water and methyl alcohol is diffused into when going up with filming of forming of cation electric deposition paint composition, said composition demonstrates the square root of spread coefficient

Be not less than 2.5.

2. cation electric deposition paint composition according to claim 1, wherein said blocked isocyanate solidifying agent B is as the isocyanuric acid ester type tripolymer of the hexamethylene diisocyanate of aliphatic polyisocyanate and ditan-4 as aromatic polyisocyanate, 4 '-combination of vulcabond, the isocyanuric acid ester type tripolymer of described hexamethylene diisocyanate and ditan-4,4 '-vulcabond end-capping reagent end-blocking.

3. cation electric deposition paint composition according to claim 2, wherein the trimerical end-capping reagent of isocyanuric acid ester type of hexamethylene diisocyanate is a methyl ethyl ketone oxime.

4. cation electric deposition paint composition according to claim 2, wherein ditan-4,4 '-end-capping reagent of vulcabond is a ε-Ji Neixianan.

5. cation electric deposition paint composition according to claim 1, wherein said blocked isocyanate solidifying agent B comprise the isocyanuric acid ester type tripolymer of the end capped hexamethylene diisocyanate of methyl ethyl ketone oxime and ε-Ji Neixianan end capped ditan-4,4 '-vulcabond.

6. goods that apply with the cation electric deposition paint composition of claim 1.