CN104629605B

CN104629605B - Single-component water-based metal flashing paint and preparation method thereof

Info

Publication number: CN104629605B
Application number: CN201510053941.6A
Authority: CN
Inventors: 张育波; 阮伟明; 李柏文; 王炼石; 伍琪卓; 秦中海; 冯兆华
Original assignee: GUANGDONG YATU CHEMICAL CO Ltd
Current assignee: Yatu high tech materials Co., Ltd
Priority date: 2015-02-02
Filing date: 2015-02-02
Publication date: 2017-02-22
Anticipated expiration: 2035-02-02
Also published as: CN104629605A

Abstract

The invention discloses a single-component water-based metal flashing paint for automobiles containing a solvent-free anionic/nonionic polyurethane-acrylate graft copolymer (PUA) with interpenetrating network polymer structure (IPN) and a preparation method thereof. The water-based metal flashing paint belongs to an automobile ground color paint, and is mainly composed of a solvent-free anionic/nonionic PUV with IPN structure, an aluminum paste, an assistant, a cosolvent, deionized water and an amine neutralizer. The PUV is free of any organic solvent; PU (polyurethane) and PA (polyamide) form a crosslinked structure inside, and the two crosslinked networks are interpenetrated; and the PU and PA components are connected through a chemical bond. Therefore, the VOC (volatile organic compound) content of the water-based metal flashing paint prepared from the PUV and assistant is lower than 5%, and thus, the water-based metal flashing paint belongs to an environment-friendly product. The paint film has the advantages of excellent aluminum powder arrangement effect, excellent physical and mechanical properties, excellent water resistance, excellent chemical resistance and excellent weather resistance.

Description

A kind of automobile single-component water-based metal flash paint and preparation method thereof

Technical field

The invention belongs to high-molecular organic material preparing technical field, be related to a kind of containing have IPN structure solvent-free cloudy/ The automobile of nonionic PUA single-component water-based metal flash paint and preparation method thereof.

Background technology

Polyurethane aqueous dispersion body (PU) has excellent wearability, pliability, adhesive force and endurance, but it is from thickening property Difference, solid content are low, resistance to water and glossiness be not good.Acrylate aqueous dispersion (PA) have excellent resistance to water, weatherability and Physical and mechanical properties, but pliability, wearability, endurance are poor, such as organically combine the advantage of the two, are formed and have complementary advantages, The combination property that material can be made is significantly improved.PUA is that polyacrylate and polyurethane two are birdsed of the same feather flock together compound in microstate Under the heterozygosis aqueous dispersion for preparing, it has the advantage of PU and PA concurrently, is current to study most commonly used heterozygosis aqueous dispersion Resin.

, still based on solvent-borne type, a large amount of VOCs (VOCs) are in coating process for the car paint of China at present In serious pollution is caused to ecological environment, also human health is brought with great harm simultaneously.With people's environmental protection meaning The raising known, national governments have all put into effect the discharge capacity to limit VOCs for a large amount of related regulations.For the development in the epoch of complying with, The positive environmentally friendly direction of car paint changes, and wherein to include water paint, powdery paints, UV solid for Environmentally friendly coatings Change coating and high solid coating, and water paint is a class wherein with fastest developing speed.

Car paint is broadly divided into priming paint, middle painting, base coat and finishing varnish, and base coat can be divided into plain color paint and metal to dodge again Lac varnish, base coat is that in all coatings, VOCs discharge capacity is maximum, and its organic solvent content is up to 85%, and construction solid part only has 15% about, account for 50% about of the VOCs total release of each road coating used by Car Body Painting.Therefore, all grinding both at home and abroad Study carefully the aqueous automobile base coat of exploitation, with the quick VOCs discharge capacity reducing car paint.

The report of water-based metal metallic finishe is related at present on lot of domestic and international professional journals magazine, and as Du Pont, Ah Gram Soviet Union and PPG have corresponding product commercially to sell, but these products have its defect：(1) the resistance to water of paint film, resistance toization Property and weatherability all do not reach the level of solvent-borne type metal flash paint；(2) the physical and mechanical properties of paint film is compared with solvent-borne type flash metal luster Paint is poor；(3) solvent reaches 15%-25%, though being far below solvent-borne type metal flash paint, remains at higher level；When When acrylic emulsion is used as matrix resin, the wet paint film of the metal flash paint spraying gained of preparation can carry blue light, and is dried Blue light disappears afterwards, thus leading to the humidity difference of paint film substantially, is unfavorable for that toning personnel mix colours.

Content of the invention

It is an object of the present invention to provide a kind of there is excellent storage stability, good physical and mechanical properties, resistance to Aqueous, acid resistance, alkali resistance and weatherability, have the solvent-free the moon/non-ion aqueous polyurethane-acrylic acid of IPN structure The synthesizing formula of ester graft copolymer and its synthesis technique.

It is a further object to provide a kind of containing having the solvent-free cloudy/non-ion aqueous poly- of IPN structure The automobile of urethane-acrylate graft copolymers the preparation formula of single-component water-based metal flash paint and its preparation technology.

The technical solution adopted for the present invention to solve the technical problems is：

A kind of single-component water-based metal flash paint of automobile containing the solvent-free the moon/nonionic PUA with IPN structure Preparation method it is characterised in that comprising the following steps：

(1) prepare the solvent-free the moon/nonionic PUA with IPN structure：1. component a is added reactor, be warming up to 130-140 DEG C, then dropping component b, component c, the mixing of component d, component e and initiator and chain-transferring agent toward in reactor Thing, synthesizes PA prepolymer by bulk polymerization, is higher than 98% entrance next stage to monomer conversion；2. lower the temperature, then Component f, component g, component h, component i, component j and catalyst are mixed, adds in PA prepolymer, treat that nco value reaches pre- Next stage is entered after definite value；3. add amine neutralizer neutralization, add deionized water emulsification；

(2) prepare the single-component water-based flash metal luster of automobile containing the solvent-free the moon/nonionic PUA with IPN structure Paint：Solvent-free the moon/nonionic PUA containing IPN structure adds in auxiliary agent, cosolvent, aluminum paste, deionized water and amine And agent, stir, standing obtains water-based metal metallic finishe after filtering；Wherein,

Component a is that viscosity is low, the reactive diluent with versatic acid ester group and epoxy radicals, and its consumption is mix monomer a-j The 5%-20% of gross mass；

Component b is the acrylic ester monomer with carboxyl and big steric group, and its consumption is mix monomer a-j gross mass 5%-20%；

Component c is that its homopolymer glass transition temperature (Tg) is higher than 20 DEG C, can improve the methacrylic acid of hardness of paint film Esters monomer, its consumption is the 5%-20% of mix monomer a-j gross mass；

Component d is the acrylate monomer with nonionic hydrophilic side chain, and its consumption is mix monomer a-j gross mass 5%-20%；

Component e is the acrylate monomer at least provided with three unsaturated double-bonds, and its consumption is mix monomer a-j gross mass 0.1%-3%；

Component f is that its consumption is mixed as PU soft component, the PCDL for 1000-2000 for the number-average molecular weight Close the 0%-40% of monomer a-j gross mass；

Component g be as PU soft component, number-average molecular weight be 1000-2000, on strand with hydrophilic radical poly- oneself Lactone dihydroxylic alcohols, its consumption is the 10%-50% of mix monomer a-j gross mass；

Component h is component hard as PU, is dihydric hydrophilic monomer with nonionic water-wet side segment, main chain terminal, Its consumption is the 10%-30% of mix monomer a-j gross mass；

Component i is the cross-linking monomer with least three hydroxyls or amido, and its consumption is mix monomer a-j gross mass 0.1%-3%；

J be as in the hard component of PU, molecular structure without phenyl ring, the aliphatic monomer of good weatherability or alicyclic two different Cyanate ester monomer, its consumption is the 10%-30% of mix monomer a-j gross mass.

Preferably, described viscosity is low, carry versatic acid ester group and the reactive diluent of epoxy radicals is tertiary carbonic acid glycidyl Ester.

Preferably, the described acrylic ester monomer with carboxyl and big steric group is adjacent cyclohexane diacid -1- [1- first Base -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester.

Preferably, described methacrylate-based monomer is methyl methacrylate (MMA).

Preferably, the described acrylate monomer with nonionic hydrophilic side chain is 2- acrylic acid -2- methoxy acrylate, second Epoxide ethoxyethyl acrylate, triethylene glycol monomethyl ether acrylate, methoxy poly (ethylene glycol) 400 acrylate and methoxy The mixture of one or more of base polyethylene glycol 550 acrylate.

Preferably, the described acrylate monomer at least provided with three unsaturated double-bonds is trimethylolpropane tris acrylic acid In ester, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate and tripentaerythritol eight acrylate A kind of or wherein several mixtures.

Preferably, in described synthesis PA pre-polymer route, initiator used is azo-initiator or peroxide draws Send out agent, its consumption is the 0.1%-2% of mix monomer a-j gross mass.

Preferably, in described synthesis PA pre-polymer route, peroxide type initiators used are di t-amyl peroxide.

Preferably, in described synthesis PA pre-polymer route, chain-transferring agent used is mercaptan type chain transfer agent, and its consumption is The 0.1%-2% of mix monomer a-j gross mass.

Preferably, the hydrophilic radical that described polycaprolactone diols is carried is in carboxyl, sulphonate-base or hydrophilic ether chain A kind of.

Preferably, described is several equal molecule with nonionic water-wet side segment, main chain terminal for dihydric hydrophilic monomer Measure the dihydromethyl propionic acid poly glycol monomethyl ether ester for 1000.

Preferably, the described cross-linking monomer at least provided with three hydroxyls is trimethylolpropane.

Preferably, described aliphatic or alicyclic diisocyanate are IPDI (IPDI), two hexamethylenes One of dicyclohexylmethane diisocyanate (HMDI), cyclohexanedimethyleterephthalate diisocyanate (HXDI) or wherein several mixing Thing.

Preferably, the catalyst used by described synthesis PU prepolymer is tertiary amine catalyst, bridged piperazine derivatives catalyst, morpholine One of class catalyst, imidazole derivatives species catalyst and organo-metallic catalyst.

Preferably, the organo-metallic catalyst used by described synthesis PU prepolymer is organic bismuth catalyst.

Preferably, the amine neutralizer used in the process of described synthesis PUA is in ammoniacal liquor, triethylamine and dimethylethanolamine One kind, its consumption is the 0.1%-3% of mix monomer a-j gross mass.

Preferably, the amount ratio of PA prepolymer is carried secondary hydroxyl and the material of NCO that PU prepolymer is carried is 1.2-1.7:1, hydroxyl is excessive.

Preferably, the building-up process with the solvent-free the moon/nonionic PUA of IPN structure is：1. prepare PA pre-polymerization Thing：First component a add reactor, be warming up to 130-140 DEG C, toward reactor in drip component b, constituent part c, component d, Component e and the mixture of part initiator and chain-transferring agent, drip off in 3-4h, then add remaining component c and initiator, Drip off in 0.5h, last 150 DEG C of insulation 2h, be higher than to enter next rank after 98%, acid number is less than 7mgKOH/g after monomer conversion Section；2. it is cooled to 70 DEG C, component f, component g, component h, component i, component j and catalyst are mixed, add PA prepolymer In, 75 DEG C of insulation 1h, then 85 DEG C -90 DEG C insulation 2-3h, reach entrance next stage after predetermined value after nco value；③85℃-90 DEG C dropping amine neutralizer, neutralize 30min, be cooled to 80 DEG C add deionized waters emulsification.

Preferably, aluminum paste, cosolvent and part of auxiliary are mixed standby, in stirred tank add PUA, at the uniform velocity Add remaining auxiliary agent and portions of de-ionized water under stirring action, stir 5min, be subsequently adding aluminum paste solution, stir 10min, Then (rich Le flies viscosimeter, and 25 DEG C, No. 3 rotors, under 5 turns to 1000-2000cps to adjust viscosity with remaining deionized water Viscosity number), finally adjusting pH value with amine neutralizer is 8-9, and standing, filtering and discharging obtain final product water-based metal metallic finishe.

The present invention also provides a kind of solvent-free the moon/non-ion aqueous polyurethane-acrylate with IPN structure to connect The preparation method of graft copolymer, comprises the following steps：

1. component a is added reactor, be warming up to 130-140 DEG C, then dropping component b, component c, group toward in reactor Divide the mixture of d, component e and initiator and chain-transferring agent, PA prepolymer is synthesized by bulk polymerization, to monomer conversion Rate was higher than 98% entrance next stage；2. lower the temperature, then component f, component g, component h, component i, component j and catalyst are mixed Uniformly, add in PA prepolymer, reach entrance next stage after predetermined value after nco value；3. add amine neutralizer neutralization, addition is gone Ion water emulsification；Wherein,

Component e is the acrylate monomer at least provided with three unsaturated double-bonds, and its consumption is mix monomer a-j gross mass 0.1%-3%；Component f is as PU soft component, the PCDL for 1000-2000 for the number-average molecular weight, its consumption 0%-40% for mix monomer a-j gross mass；

The predetermined value that in the present invention, nco value reaches is 0, and the effect of big steric group in the present invention is that offer is sterically hindered, Weaken intermolecular force, thus reducing resin viscosity.

This has the preparation method of the solvent-free the moon/non-ion aqueous polyurethane-acrylate graft copolymers of IPN structure It is characterised by：1., when synthesizing PA prepolymer, replace common solvent using the diluent with reactivity, can prepare solvent-free PUA；2., when synthesizing PA prepolymer, using the monomer with big steric group and carboxyl, reactive diluent is on the one hand made to connect Enter in strand, the viscosity of the PA synthesizing on the other hand can be made to substantially reduce, be conducive to follow-up PA to graft on PU；3. closing When becoming PA and PU, introduce the cross-linking monomer with trifunctional respectively, in PA and PU structure, form partial cross-linking network, and two Individual cross-linked network interts mutually；4., when synthesizing PA prepolymer, retain the secondary hydroxyl that epoxy radicals and carboxyl reaction generate, in synthesis During polyurethane reaction, PA prepolymer is accessed polyurethane molecular chain by its hydroxyl, obtains polyurethane component and polypropylene Nonionic functional segments are all carried on the PUA by chemical bonds for the acid esters component, wherein PU and PA chain, PU chain also carries the moon Ionic hydrophilic segments.

This has an excellent storage stability, good physical and mechanical properties, resistance to water, endurance and weatherability, and has The automobile that excellent aluminium powder arranges is had to be characterised by, preparing raw material includes with the preparation method of single-component water-based metal flash paint：Tool There are solvent-free the moon/nonionic PUA, aluminum paste, auxiliary agent, cosolvent, deionized water and the amine neutralizer of IPN structure；Wherein Have IPN structure solvent-free the moon/nonionic PUA be metal flash paint provide excellent physical and mechanical properties, resistance to water, Endurance and weatherability, and aluminium orientation can be helped；Auxiliary agent can improve the storage stability of metal flash paint, helps Aluminium powder arranges, and can also improve application property of metal flash paint etc. simultaneously；Cosolvent can help aluminium powder more preferable in resin Dispersion；Deionized water can be used for adjusting the viscosity of metal flash paint；Amine neutralizer can adjust metal flash paint pH value it is ensured that its Storage stability.

The invention has the beneficial effects as follows：In technical solution of the present invention preparation containing have IPN structure solvent-free cloudy/non-from Compared with prior art, tool has the advantage that the method for the automobile water-based property metal flash paint of subtype PUA：

(1) adopt when synthesizing PA prepolymer reactive diluent as bottom solvent, can avoid in building-up process China and foreign countries Plus cosolvent, save cost, and the water-base resin without VOC can be prepared；

(2), in the monomer used by synthesis PA prepolymer, contain 4 kinds of functional monomers is simultaneously：Containing huge tertiary carbon The reactive diluent of perester radical and epoxy radicals, the acrylate monomer containing carboxyl and big steric group, contain non-ionic segments Acrylate monomer and with least three unsaturated double-bonds cross-linking monomer.Prepared PA prepolymer side chain simultaneous with Big steric group, secondary hydroxyl and nonionic functional segments, and PA prepolymer molecule is internally formed partial mesh structure.PA pre-polymerization The secondary hydroxyl that thing side chain carries can be reacted with the isocyanate groups of PU prepolymer end, connects PU prepolymer and PA pre-polymerization Thing；The nonionic functional segments that PA prepolymer side chain carries can play the synergy of non-ionic segments, provides more excellent Electrolyte-resistant, in addition the price of the acrylate monomer containing non-ionic segments used by the present invention be less than usually introduce side chain Polyether Glycols used by non-ionic segments, such as trimethylolpropane poly glycol monomethyl ether；It is big that PA prepolymer side chain carries Steric group is by tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] second Base] product of ester provides, and the presence of big steric group weakens the active force of molecule interchain, so that the viscosity of PA prepolymer is dropped Low, also simplify the operation of subsequent polyurethane synthesis, additionally, big steric group can also lift the resistance to water of paint film, resistance toization simultaneously Property and weatherability；The partial mesh structure that PA prepolymer is formed, improves the physical and mechanical properties of PUA film, resistance to water, endurance And weatherability；

(3), when synthesizing PA prepolymer, the reactive diluent containing epoxy radicals reacts generation with carboxylic acrylate monomer One secondary hydroxyl, the activity of secondary hydroxyl is far below primary hydroxyl, so the building-up process of PU prepolymer will not be subject to PA prepolymer institute The interference of the hydroxyl of band, after PU prepolymer is formed completely, the secondary hydroxyl ability that PA prepolymer is carried and the PU prepolymer end of the chain are carried Isocyano reaction, on the one hand ensure that the cross-linked network of PU and PA component can intert mutually, on the other hand also ensure that PU Chemical bond is had to be connected and PA component between, so that the final PUA obtaining can have the performance of PU and PA simultaneously.

(4), in the monomer used by synthesis PU prepolymer, comprising 4 kinds of functional monomers is：PCDL, band are hydrophilic The polycaprolactone glycol of group, the dihydroxylic alcohols with nonionic functional segments, the cross-linking monomer with trifunctional.Prepared PU master Chain carries polycarbonate chain section, polycaprolactone segment, and side chain carries anionic hydrophilic group and nonionic functional segments, and PU Prepolymer molecule is internally formed partial mesh structure.The polycarbonate structure that PU pre-polymer backbone carries improves the physics of PUA Mechanical performance, hydrolytic resistance, endurance and weatherability；The polycaprolactone structure that PU pre-polymer backbone carries improves the soft of PUA Toughness, and with the compatibility of various types of resins and auxiliary agent so that follow-up flash metal luster paint formula is designed with wider selection Property；The anionic hydrophilic group that PU prepolymer side chain carries can provide enough water solubilitys, the nonionic that side chain carries for PUA Hydrophilic segment can provide more excellent electrolyte-resistant for PUA；The partial mesh structure that PU prepolymer is formed improves PUA film Physical and mechanical properties, resistance to water, endurance and weatherability；

(5) with the water-based metal metallic finishe of the PUA preparation without cosolvent there is excellent outward appearance, excellent stable storing Property, excellent physical and mechanical properties, resistance to water, endurance and weatherability, and also the VOC content of this water-based metal metallic finishe is less than 5%, belong to environmentally friendly product.

Brief description

Fig. 1 is the schematic arrangement of PA prepolymer, wherein R₁、R₂For alkyl；

Fig. 2 is the schematic arrangement of ethoxyethoxyethyl acrylate used by the present invention；

Fig. 3 is the schematic arrangement of triethylene glycol monomethyl ether acrylate used by the present invention；

Fig. 4 is the schematic arrangement of methoxy poly (ethylene glycol) used by the present invention (400 or 550) acrylate；

Fig. 5 is adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester used by the present invention Schematic arrangement；

Fig. 6 is the schematic arrangement of ethoxylated trimethylolpropane triacrylate used by the present invention；

Fig. 7 is the schematic arrangement of pentaerythritol triacrylate used by the present invention, wherein,Or H；

Fig. 8 is the schematic arrangement of tripentaerythritol eight acrylate used by the present invention, wherein,Or H；

Fig. 9 is polycaprolactone glycol schematic arrangement used by the present invention；

Figure 10 is dihydromethyl propionic acid poly glycol monomethyl ether ester molecular structure schematic diagram used by the present invention；

Figure 11 is the water-soluble schematic diagram of the solvent-free the moon/nonionic PUA with IPN structure；

Figure 12 is the synthesis process flow diagram of the solvent-free the moon/nonionic PUA with IPN structure；

Figure 13 is the single-component water-based flash metal luster of automobile containing the solvent-free the moon/nonionic PUA with IPN structure The preparation technology flow chart of paint.

Specific embodiment

With reference to embodiments the present invention is described further, but is not limited thereto.

In certain embodiments of the present invention, the automobile containing the solvent-free the moon/nonionic PUA with IPN structure Include three steps with the preparation of water-based metal flash of light paint film：

1. there is the synthesis of the solvent-free the moon/nonionic PUA of IPN structure

There is the synthesizing formula of solvent-free the moon/nonionic PUA of IPN structure as shown in table 1, its synthesis process As follows：1., in the reactor being equipped with agitator, condenser pipe, thermometer, electric jacket and vavuum pump, it is firstly added versatic acid contracting Water glyceride, is heated to 130-140 DEG C, then adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) Epoxide] ethyl] ester, part methyl acrylate, component d, PA cross-linking monomer, part di t-amyl peroxide and lauryl mercaptan Mixture dropping enters in reactor, and 3-4h drips off, and adds remaining methacrylate and initiator, drips off in 0.5h, 150 DEG C of insulation 2h afterwards, prepared PA prepolymer；2. it is cooled to 70 DEG C, PCDL, polycaprolactone glycol, component h, group Divide i, component j and catalyst to mix, add in reactor, be warming up to 75 DEG C, be incubated 1h, then heat to 85 DEG C -90 DEG C, Insulation 2-3h；3. 85 DEG C -90 DEG C dropping amine neutralizers, neutralize 30min, are cooled to 80 DEG C and add deionized water emulsification.

Table 1 has the synthesizing formula of the solvent-free the moon/nonionic PUA of IPN structure

Wherein initiator is di t-amyl peroxide, and consumption is the 0.1-2% of monomer a-j gross mass；Chain-transferring agent is ten Two mercaptan, consumption is the 0.1-2% of monomer a-j gross mass；Catalyst is organo-bismuth, and consumption is monomer a-j gross mass 0.01%；Amine neutralizer is ammoniacal liquor/triethylamine/dimethylethanolamine, and consumption is the 0.1-3% of monomer a-j gross mass.

Wherein, component a is tertiary carbonic acid glycidyl ester, and it is with reactive functional groups, reduces PA viscosity, improves PUA The reactive diluent of resistance to water, endurance and weatherability, its consumption is the 5%-20% of mix monomer a-j gross mass.

Wherein, component b is adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester, its Be with carboxyl and big steric group, improve have IPN structure the physical and mechanical properties of solvent-free the moon/nonionic PUA, Resistance to water, endurance and weatherability, reduce the monomer of PA prepolymer viscosity, and its consumption is the 5%- of mix monomer a-j gross mass 20%.

Wherein, component c is methyl methacrylate, and it is to improve the solvent-free the moon/nonionic with IPN structure The hardness of PUA and the methacrylate-based monomer of weatherability, its consumption is the 5%-20% of mix monomer a-j gross mass.

Wherein, component d is 2- acrylic acid -2- methoxy acrylate, ethoxyethoxyethyl acrylate, triethylene glycol list One of methyl ether acetate, methoxy poly (ethylene glycol) 400 acrylate, methoxy poly (ethylene glycol) 550 acrylate or several The mixture planted, more preferably triethylene glycol monomethyl ether acrylate, its consumption is the 5%- of mix monomer a-j gross mass 20%, it can be with hydrophilic ether chain, improve and have the pliability of solvent-free the moon/nonionic PUA of IPN structure, hydrophilic The acrylic ester monomer of property.

Wherein, component e is ethoxylated trimethylolpropane triacrylate, and its consumption is mix monomer a-j gross mass 0.1%-3%, it is with multiple unsaturated double-bonds, improves the solvent-free the moon/nonionic PUA's with IPN structure Physical and mechanical properties, resistance to water, endurance, the PA cross-linking monomer of weatherability.

Wherein, have used by synthesis PA prepolymer in the solvent-free the moon/nonionic PUA building-up process of IPN structure Initiator is di t-amyl peroxide, and its consumption is the 0.1%-2% of mix monomer a-j gross mass.

Wherein, have used by synthesis PA prepolymer in the solvent-free the moon/nonionic PUA building-up process of IPN structure Chain-transferring agent is lauryl mercaptan, and its consumption is the 0.1%-2% of mix monomer a-j gross mass.

Wherein, component f is the PCDL that number-average molecular weight is 1000, and it is to improve to have the no molten of IPN structure The monomer of the physical and mechanical properties, hydrolytic resistance and weatherability of the moon of agent/nonionic PUA, its consumption is mix monomer 0%-40%.

Wherein, component g be number-average molecular weight be 2000, in strand carry carboxyl polycaprolactone glycol, its be improve There is the pliability of the solvent-free the moon/nonionic PUA of IPN structure, with other types resin, the compatibility of auxiliary agent and carry The water miscible monomer of high PUA, its consumption is the 10%-50% of mix monomer a-j gross mass.

Wherein, component h be number-average molecular weight be 1000, side chain be long ether chain dihydromethyl propionic acid poly glycol monomethyl ether Ester, it is the water miscible monomer improving the solvent-free the moon/nonionic PUA with IPN structure, and it belongs to response type emulsification Agent, its consumption is the 10%-30% of mix monomer a-j gross mass.

Wherein, component i be one of trimethylolethane (TME), trimethylolpropane (TMP), pentaerythrite or its In several mixture, more preferably trimethylolpropane, it is to improve the solvent-free the moon/nonionic with IPN structure The physical and mechanical properties of type PUA and the cross-linking monomer of lifting metal flash paint application property, its consumption is mix monomer a-j gross mass 0.1%-3%.

Wherein, component j is IPDI (IPDI), dicyclohexyl methyl hydride diisocyanate (HMDI) and ring One of hexane dimethylene diisocyanate (HXDI) or wherein several mixtures, more preferably IPDI, it is to carry Height has the molecule chain rigidity of the solvent-free the moon/nonionic PUA of IPN structure, belongs to aliphatic or alicyclic two isocyanic acids The monomer of ester, its consumption is the 10%-30% of mix monomer a-j gross mass.

Wherein, have used by synthesis PU prepolymer in the solvent-free the moon/nonionic PUA building-up process of IPN structure Catalyst is organo-metallic catalyst, more preferably organic bismuth catalyst, and its consumption is mix monomer a-j gross mass 0.01%.

Wherein, having amine neutralizer used in the solvent-free the moon/nonionic PUA building-up process of IPN structure is ammonia One of water, triethylamine and dimethylethanolamine, more preferably dimethylethanolamine, its consumption is that mix monomer a-j is total The 0.1%-3% of quality.

Wherein, the amount of PA prepolymer is carried secondary hydroxyl and the material of NCO that PU prepolymer is carried is than for 1.2- 1.7：1, more preferably 1.4-1.5：1, most preferably 1.4：1.

2. contain the automobile of the solvent-free the moon/nonionic PUA with IPN structure with single-component water-based metal flash paint Preparation

Table 2 contains the preparation of the automobile water-based property metal flash paint of solvent-free the moon/nonionic PUA with IPN structure Formula

Automobile joining with single-component water-based metal flash paint containing the solvent-free the moon/nonionic PUA with IPN structure Side is as shown in table 2.Preparation is containing the automobile water-based property metal flash paint of solvent-free the moon/nonionic PUA with IPN structure Technical process is as follows：Aluminum paste, cosolvent and wetting dispersing agent are mixed standby；In stirred tank add PUA, in low Add defoamer, substrate wetting agents, auxiliary rheological agents and portions of de-ionized water under fast stirring action, stir 5min, be subsequently adding State aluminum paste, cosolvent and wetting dispersing agent mixed solution, stir 10min, then use remaining deionized water regulation viscosity to 1500-2000cps (rich Le flies viscosimeter, 25 DEG C, No. 3 rotors, the viscosity number under 5 turns), finally adjusts pH value with amine neutralizer For 8-9, stand, filtering and discharging obtains final product water-based metal metallic finishe.3. contain the solvent-free the moon/nonionic PUA with IPN structure Automobile water-based property metal flash paint construction

It is to apply about -4 glasss of 20s (25 DEG C) that the metal flash paint preparing is adjusted working viscosity with homemade diluent, It is sprayed on the tinplate polished, after paint film dries up, spray homemade coating varnish, then toast 1h at 70 DEG C, that is, Obtain the water-based metal flash of light paint film of excellent performance.

Below by way of specific embodiment, the present invention is further described.

Embodiment 1

1. contain the synthesis of the solvent-free the moon/nonionic PUA of IPN structure

There is the synthesizing formula of solvent-free the moon/nonionic PUA of IPN structure as shown in table 3, its synthesis process As follows：1., in the reactor being equipped with agitator, condenser pipe, thermometer, electric jacket and vavuum pump, it is firstly added versatic acid contracting Water glyceride, is heated to 130-140 DEG C, then adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) Epoxide] ethyl] ester, part MMA, triethylene glycol monomethyl ether acrylate, ethoxylated trimethylolpropane triacrylate with And the mixture dropping of part di t-amyl peroxide and lauryl mercaptan enters in reactor, 3-4h drips off, and adds remaining MMA And initiator, drip off in 0.5h, last 150 DEG C of insulation 2h, prepared PA prepolymer；2. be cooled to 70 DEG C, PCDL, Polycaprolactone glycol, dihydromethyl propionic acid poly glycol monomethyl ether ester, trimethylolpropane and IPDI mix, and add reaction In kettle, it is warming up to 75 DEG C, is incubated 1h, then heats to 85 DEG C -90 DEG C, be incubated 2-3h；3. 85 DEG C -90 DEG C addition dimethyl ethanols Amine, neutralizes 30min, is cooled to 80 DEG C and adds deionized water emulsification.

Table 3 changes tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) oxygen Base] ethyl] ester consumption synthesis have IPN structure solvent-free the moon/nonionic PUA basic recipe

2. contain the preparation of the automobile water-based property metal flash paint of solvent-free the moon/nonionic PUA with IPN structure

Preparation formula containing the automobile water-based property metal flash paint of solvent-free the moon/nonionic PUA with IPN structure As shown in table 4, preparation process is as follows：Aluminum paste, cosolvent and wetting dispersing agent are mixed standby；In stirred tank Add PUA, add defoamer, substrate wetting agents, auxiliary rheological agents and portions of de-ionized water, stirring under the effect of middle stirring at low speed 5min, is subsequently adding above-mentioned aluminum paste, cosolvent and wetting dispersing agent mixed solution, stirs 10min, then with remaining go from Sub- water adjusts viscosity to 1500-2000cps (rich Le flies viscosimeter, 25 DEG C, No. 3 rotors, the viscosity number under 5 turns), finally uses amine It is 8-9 that nertralizer adjusts pH value, and standing, filtering and discharging obtain final product water-based metal metallic finishe.

Table 4 contains the preparation of the automobile water-based property metal flash paint of solvent-free the moon/nonionic PUA with IPN structure Formula

3. contain the construction of the automobile water-based property metal flash paint of solvent-free the moon/nonionic PUA with IPN structure

The spraying of the automobile water-based property metal flash paint prepared with the PUA of formula 1, formula 2, formula 3 and formula 4 preparation Construction technology is identical.

Construction technological process：It is to apply -4 glasss that the metal flash paint preparing is adjusted working viscosity with homemade diluent About 20s (25 DEG C), is sprayed on the tinplate polished, and after paint film dries up, sprays coating varnish, then dries at 70 DEG C Roasting 1h, that is, obtain the water-based metal flash of light paint film of excellent performance.

Table 5 is embodiment 1 in the case of ensureing that other monomers consumption is constant, is stepped up tertiary carbonic acid glycidyl ester Consumption is 23g, 35g, 47g and 59g, is stepped up adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) simultaneously Epoxide] ethyl] ester consumption be 27.2g, 41.4g, 55.6g and 69.8 (ensure epoxy radicals：Carboxyl=1：1) synthesize under conditions of There is the formula that feeds intake of the solvent-free the moon/nonionic PUA of IPN structure, for ensureing initiator and the chain tra nsfer of each formula Agent consumption all keeps a fixed value with the ratio of PA pre-polymerization monomer total amount, so when each formulation monomer total amount changes, phase The initiator answered and chain-transferring agent consumption all change, and following examples are such as not added with illustrating, then follow identical principle.

Table 5 tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] second Base] consumption and the water-based metal of ester glisten the relation of paint film property

Note：1. paint film pencil hardness is the hardness of monometallic flash of light enamelled coating.

Performance by formula 1, the automobile water-based property metal flash paint of formula 2, formula 3 and formula 4 preparation is as shown in table 5. As seen from table, when tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] second Base] ester consumption be respectively 23g and 27.2g when, PUA emulsification when gel；As tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- When the consumption of [1- methyl -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester is respectively 35g and 41.4g, PUA viscosity is too big Cannot emulsify；When tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] second Base] ester consumption be respectively 47g and 55.6g when, PUA be in light blue translucent shape, the no black silk of metal flash paint white appearance, aluminium Powder arrangement effect is qualified, and the hardness of paint film, adhesive force, impact strength, bending property, resistance to water, endurance and weatherability are all closed Lattice；When tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester Consumption be respectively 59g and 69.8g when, PUA be in light blue near-transparent, the no black silk of metal flash paint white appearance, aluminium powder arrange Effect is qualified, but the adhesive force of paint film, impact strength, bending property are qualified, and resistance to water, endurance and weatherability all do not conform to Lattice.This is because as tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] Ethyl] ester consumption be 23g and 27.2g when, the secondary hydroxyl quantity on PA strand is fewer than the isocyano on PU prepolymer, reaction Also remain isocyano on last PUA strand, during emulsification, isocyano and water react, and finally result in gel；When Tertiary carbonic acid glycidyl ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester consumption are During 35g and 41.4g, the mole of the isocyanate group on secondary hydroxyl and PU prepolymer on PA strand, than for 1, is prepared The molecular weight of PUA would tend to infinity, and finally resulting in the huge PUA of viscosity cannot emulsify；When tertiary carbonic acid glycidyl ester and When adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester consumption is 47g and 55.6g, PA divides For 1.4, hydroxyl is excessive for the mole of the isocyanate group on the secondary hydroxyl in subchain and PU prepolymer ratio, and the PUA at this moment preparing divides Son amount is moderate, water-soluble moderate, so preparing the metal flash paint of excellent performance；When tertiary carbonic acid glycidyl ester and adjacent hexamethylene When diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester consumption is 59g and 69.8g, on PA strand Secondary hydroxyl and PU prepolymer on isocyanate group mole ratio for 1.75, hydroxyl is excessive too many, the PUA molecule at this moment prepared Amount is less, water-soluble very good, leads to resistance to water, endurance and the weatherability of paint film all unqualified.Therefore, tertiary carbonic acid glycidyl The consumption of ester and adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxo -2- acrylic) epoxide] ethyl] ester with 47g and 55.6g is Preferably.

Embodiment 2

Table 6 is embodiment 2 in the case of ensureing that other monomers consumption is constant, uses ethoxyethoxyethyl propylene respectively Acid esters, triethylene glycol monomethyl ether acrylate, methoxy poly (ethylene glycol) 400 acrylate and methoxy poly (ethylene glycol) 550 propylene Acid esters synthesis has the formula that feeds intake of the solvent-free the moon/nonionic PUA of IPN structure, and its formula number is followed successively by 5,6,7 and 8, have 4 formulas.The synthesis process of each formula is identical.

Shown in the technical process synthesis table 6 of the solvent-free the moon/nonionic PUA that there is IPN structure as embodiment 1 synthesis Numbering is 5～8 4 kinds of PUA, prepares the formula of coating by embodiment 1 and the preparation of lacquer man's skill process contains the nothing with IPN structure The single-component water-based metal flash paint of automobile of the moon of solvent/nonionic PUA, by the construction of metal flash paint in embodiment 1 Method prepares paint film.

Performance by formula 5, the automobile water-based property metal flash paint of formula 6, formula 7 and formula 8 preparation is as shown in table 7. As seen from table, when in PUA formula using ethoxyethoxyethyl acrylate, the transparent shape of PUA outward appearance, metallic paint outward appearance Pure white no black silk, the arrangement effect of aluminium powder is qualified, and the hardness of paint film, adhesive force, impact strength and bending property are all qualified, but paint The resistance to water of film, endurance and weatherability are unqualified；When in PUA formula using triethylene glycol monomethyl ether acrylate, outside PUA See transparent shape, the no black silk of metallic paint white appearance, the arrangement effect of aluminium powder is qualified, the hardness of paint film, adhesive force, impact strength All qualified with bending property, resistance to water, endurance and weatherability；Using methoxy poly (ethylene glycol) 400 acrylic acid in PUA fills a prescription When ester or methoxy poly (ethylene glycol) 550 acrylate, PUA outward appearance is in sub-translucent blueing light shape, and metallic paint appearance surfaces black, aluminium The arrangement effect of powder is unqualified, and the adhesive force of paint film, impact strength, bending property, resistance to water, endurance and weatherability all do not conform to Lattice.This is because in the case of same amount, ethoxyethoxyethyl acrylate is than triethylene glycol monomethyl ether acrylic acid Ester provides more hydrophilic side chain so that the water solubility of PUA is very good, ultimately results in the resistance to water of paint film, endurance and resistance to Time property is unqualified；In the case of same amount, methoxy poly (ethylene glycol) 400 acrylate and methoxy poly (ethylene glycol) 550 third Olefin(e) acid ester is more less than the hydrophilic side chain that triethylene glycol monomethyl ether acrylate provides so that the water solubility of PUA is poor, leads to be obtained PUA particle diameter big, stability difference, it is impossible to coat aluminium powder well, makes aluminium powder be directly exposed in water, thus occurring oxidation to send out Black, the properties of prepared paint film are not also up to standard.Therefore, component d is to select triethylene glycol monomethyl ether acrylate to be advisable.

The type synthesis of table 6 change component d has the basic recipe of the solvent-free the moon/nonionic PUA of IPN structure

Table 7 component d type and the relation of water-based metal metallic finishe performance

Embodiment 3

The consumption that table 8 changes triethylene glycol monomethyl ether acrylate synthesizes the solvent-free the moon/nonionic with IPN structure The basic recipe of type PUA

Table 8 is embodiment 3 in the case of ensureing that other monomers consumption is constant, is stepped up triethylene glycol monomethyl ether propylene The consumption of acid esters has the solvent-free the moon/nonionic PUA's of IPN structure for synthesis under conditions of 11g, 18g, 25g and 32g Feed intake formula, and its formula number is followed successively by 9,10,11 and 12, has 4 formulas.The synthesis process of each formula is identical.

Shown in the technical process synthesis table 8 of the solvent-free the moon/nonionic PUA that there is IPN structure as embodiment 3 synthesis Numbering is 9～12 4 kinds of PUA, prepares the formula of coating and the preparation of lacquer man's skill process containing having IPN structure by embodiment 1 The single-component water-based metal flash paint of automobile of solvent-free the moon/nonionic PUA, by the applying of metal flash paint in embodiment 1 Work method prepares paint film.

Performance such as table 9 institute by formula 9, the automobile water-based property metal flash paint of formula 10, formula 11 and formula 12 preparation Show.As seen from table, when the consumption of triethylene glycol monomethyl ether acrylate in PUA formula is 11g, PUA is creamy white, by PUA The metal flash paint of preparation blacks, and aluminium powder arrangement effect is unqualified, the adhesive force of paint film, impact strength, bending property, water-fast Property, endurance and resistance to ag(e)ing are all unqualified；When the consumption of triethylene glycol monomethyl ether acrylate in PUA formula is respectively 18g When, PUA is in sub-translucent blueing light, is slightly blacked by metal flash paint prepared by PUA, and aluminium powder arrangement effect is unqualified, paint film Adhesive force, impact strength, bending property, resistance to water, endurance and resistance to ag(e)ing are all unqualified；When triethylene glycol in PUA formula When the consumption of monomethyl ether acrylate is 25g, PUA is in light blue translucent, and the metal flash paint prepared by PUA is pure white no black Silk, aluminium powder arrangement effect is qualified, the hardness of paint film, adhesive force, impact strength, bending property, resistance to water, endurance and ageing-resistant Property is all qualified；When the consumption of triethylene glycol monomethyl ether acrylate in PUA formula is 32g, PUA is in light blue near-transparent shape, The pure white no black silk of metal flash paint prepared by PUA, aluminium powder arrangement effect is qualified, and the adhesive force of paint film, bending property, impact are strong Degree is qualified, and hardness, resistance to water, endurance and resistance to ag(e)ing are unqualified.This is because triethylene glycol monomethyl ether acrylate exists Not only provide hydrophilic segment in PUA strand, and provide enhancing flexible segment, when triethylene glycol monomethyl ether third in formula When olefin(e) acid ester consumption is very few, not prepared PUA particle diameter is big for PUA water-soluble, stability difference it is impossible to coat aluminium powder well, Aluminium powder is made to be directly exposed in water, thus there is oxidizing blackening, the properties of prepared paint film are not also up to standard；Work as triethylene glycol When the consumption of monomethyl ether acrylate is excessive, the water solubility of PUA is excessively good, and pliability is excessively good, lead to the hardness of paint film, resistance to water, Endurance and weatherability are unqualified.Therefore, the consumption of triethylene glycol monomethyl ether acrylate is advisable with 25g.

The consumption of table 9 triethylene glycol monomethyl ether acrylate and the relation of water-based metal flash of light paint film property

Embodiment 4

Table 10 changes the basic recipe that the synthesis of component e type has the solvent-free the moon/nonionic PUA of IPN structure

Table 10 is embodiment 4 in the case of ensureing that other monomers consumption is constant, uses trimethylolpropane tris propylene respectively Acid esters, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate and tripentaerythritol eight acrylate Synthesis has the formula that feeds intake of the solvent-free the moon/nonionic PUA of IPN structure, and its formula number is followed successively by 13,14,15 and 16, have 4 formulas.The synthesis process of each formula is identical.

There is technical process synthesis table 10 institute of the solvent-free the moon/nonionic PUA of IPN structure by embodiment 1 synthesis Show 4 kinds of PUA that numbering is 13～16, prepare the formula of coating and the preparation of lacquer man's skill process containing having IPN structure by embodiment 1 Solvent-free the moon/nonionic PUA the single-component water-based metal flash paint of automobile, by metal flash paint in embodiment 1 Construction method prepares paint film.

Performance such as table 11 by formula 13, the automobile water-based property metal flash paint of formula 14, formula 15 and formula 16 preparation Shown.As seen from table, when in PUA formula using trimethylolpropane trimethacrylate or pentaerythritol triacrylate, PUA Outward appearance is in light blue translucent shape, the no black silk of metallic paint white appearance, and the arrangement effect of aluminium powder is qualified, the hardness of paint film, attachment Power, resistance to water, endurance and weatherability are all qualified, and impact strength and bending property are unqualified；Using ethoxy in PUA fills a prescription During base trimethylolpropane trimethacrylate, PUA outward appearance is in light blue translucent shape, the no black silk of metallic paint white appearance, aluminium The arrangement effect of powder is qualified, and the hardness of paint film, adhesive force, impact strength, bending property, resistance to water, endurance and weatherability are all Qualified；When in PUA formula using tripentaerythritol eight acrylate, PUA outward appearance is in light blue translucent shape, metallic paint outward appearance Pure white no black silk, the arrangement effect of aluminium powder is qualified, and the adhesive force of paint film, impact strength, bending property are qualified, and hardness, water-fast Property, endurance and weatherability are all unqualified.This is because in the case of same amount, trimethylolpropane trimethacrylate or Pentaerythritol triacrylate provides more crosslinked group than ethoxylated trimethylolpropane triacrylate, thus Increased the crosslink density of paint film, the hardness, resistance to water, endurance and the weatherability that ultimately result in paint film are qualified, and pliability is not Foot；In the case of same amount, tripentaerythritol eight acrylate carries than ethoxylated trimethylolpropane triacrylate For crosslinked group few, thus reducing the crosslink density of paint film, ultimately result in the hardness of paint film, resistance to water, endurance and resistance to Time property is qualified.Therefore, the acrylate monomer with crosslinked group is to select the ethoxylated trimethylolpropane triacrylate to be Preferably.

Table 11 component e and the relation of water-based metal metallic finishe performance

Embodiment 5

The consumption synthesis that table 12 changes ethoxylated trimethylolpropane triacrylate has the solvent-free of IPN structure The basic recipe of the moon/nonionic PUA

Table 12 is embodiment 5 in the case of ensureing that other monomers consumption is constant, is stepped up ethoxylation trihydroxy methyl The consumption of propane triacrylate is 0,2g, 4g and 6g (because the consumption of ethoxylated trimethylolpropane triacrylate changes Become very little, the therefore change of PA pre-polymerization monomer total amount less, so not needing to change the consumption of initiator and chain-transferring agent) condition Lower synthesis has the formula that feeds intake of the solvent-free the moon/nonionic PUA of IPN structure, and its formula number is followed successively by 17,18,19 With 20, have 4 formulas.The synthesis process of each formula is identical.

There is technical process synthesis table 12 institute of the solvent-free the moon/nonionic PUA of IPN structure by embodiment 1 synthesis Show 4 kinds of PUA that numbering is 17～20, prepare the formula of coating and the preparation of lacquer man's skill process containing having IPN structure by embodiment 1 Solvent-free the moon/nonionic PUA the single-component water-based metal flash paint of automobile, by metal flash paint in embodiment 1 Construction method prepares paint film.

Performance such as table 13 by formula 17, the automobile water-based property metal flash paint of formula 18, formula 19 and formula 20 preparation Shown.As seen from table, when no ethoxylated trimethylolpropane triacrylate in PUA formula, PUA is in light blue translucent Shape, the pure white no black silk of the metal flash paint prepared by PUA, the aluminium powder arrangement effect of paint film is qualified, and the adhesive force of paint film, impact are strong Degree, bending property are qualified, but the hardness of paint film, resistance to water, endurance and resistance to ag(e)ing are all unqualified；When ethoxy in PUA formula When the consumption of base trimethylolpropane trimethacrylate is 2g, PUA is in light blue translucent shape, is dodged by metal prepared by PUA The pure white no black silk of lac varnish, the aluminium powder arrangement effect of paint film is qualified, and the adhesive force of paint film, impact strength, bending property are qualified, but paint The hardness of film, resistance to water, endurance and resistance to ag(e)ing are all unqualified；When ethoxylated trimethylolpropane 3 third in PUA formula When the consumption of olefin(e) acid ester is 4g, PUA is in light blue translucent shape, the pure white no black silk of the metal flash paint prepared by PUA, paint film Aluminium powder arrangement effect is qualified, the hardness of paint film, adhesive force, impact strength, bending property, resistance to water, endurance and resistance to ag(e)ing All qualified；When the consumption of ethoxylated trimethylolpropane triacrylate in PUA formula is 6g, PUA is in light blue semi-transparent Bright shape, the pure white no black silk of the metal flash paint prepared by PUA, the aluminium powder arrangement effect of paint film is qualified, the hardness of paint film, water-fast Property, endurance and resistance to ag(e)ing are all qualified, but the adhesive force of paint film, impact strength, bending property are all unqualified.This is because second Epoxide trimethylolpropane trimethacrylate carries three unsaturated double-bonds, can be formed lightly crosslinked in PA component, therefore, When in PUA formula, no ethoxylated trimethylolpropane triacrylate or its consumption are inadequate, the crosslink density of PUA is little, leads Cause hardness, resistance to water, endurance and the resistance to ag(e)ing of paint film poor, and work as the use of ethoxylated trimethylolpropane triacrylate When measuring excessive, the paint film crosslink density eventually forming is too big, leads to the pliability of paint film unqualified.Therefore, ethoxylation three hydroxyl The consumption of propane tri is advisable with 4g.

The consumption of table 13 ethoxylated trimethylolpropane triacrylate and the relation of water-based metal flash of light paint film property

Embodiment 6

The consumption synthesis that table 14 changes PCDL, polycaprolactone glycol and dimethylethanolamine has IPN structure Solvent-free the moon/nonionic PUA basic recipe

Table 14 is embodiment 6 in the case of ensureing that other monomers consumption is constant, PCDL and polycaprolactone two The consumption of alcohol be respectively 0 and 182.6g, 22.8g and 137g, 45.6g and 91.3g and 68.4g and 45.6g (both provide total Hydroxyl value is constant), the consumption simultaneously changing dimethylethanolamine successively is synthesis tool under conditions of 7g, 5.25g, 3.5g and 1.75g There is the formula that feeds intake of the solvent-free the moon/nonionic PUA of IPN structure, its formula number is followed successively by 21,22,23 and 24, have 4 formulas.The synthesis process of each formula is identical.Because catalyst amount is only PU pre-polymerization monomer total amount in formula 0.01%, so when the total amount of PU pre-polymerization monomer in formula changes little, the change very little in fact of catalyst, so embodiment When middle PU pre-polymerization monomer total amount changes, the amount of catalyst keeps constant, and following examples are such as not added with illustrating, then follow identical Principle.

There is technical process synthesis table 14 institute of the solvent-free the moon/nonionic PUA of IPN structure by embodiment 1 synthesis Show 4 kinds of PUA that formula number is 21～24, prepare the formula of coating and the preparation of lacquer man's skill process containing having IPN by embodiment 1 The single-component water-based metal flash paint of automobile of the solvent-free the moon/nonionic PUA of structure, by flash metal luster in embodiment 1 The construction method of paint prepares paint film.

Performance such as table 15 by formula 21, the automobile water-based property metal flash paint of formula 22, formula 23 and formula 24 preparation Shown.As seen from table, when not having PCDL in formula, polycaprolactone glycol consumption is 182.6g, dimethylethanolamine Consumption when being 7g, the transparent shape of gained PUA, metal flash paint outward appearance prepared therefrom is good, and aluminium powder arrangement effect is qualified, institute The adhesive force of paint film of preparation, impact strength and bending property are all good, but the hardness of paint film, resistance to water, endurance and resistance to old The property changed is poor；When in formula, PCDL and polycaprolactone glycol consumption are respectively 22.8g and 137g, dimethylethanolamine Consumption when being 5.25g, PUA is in light blue near-transparent shape, and metal flash paint outward appearance prepared therefrom is good, and aluminium powder arranges effect Qualified, the prepared adhesive force of paint film, impact strength, bending property all reach the standard that uses, but the hardness of paint film, water-fast Property, endurance and weatherability are unqualified；When formula in PCDL and polycaprolactone glycol consumption be respectively 45.6g and 91.3g, when the consumption of dimethylethanolamine is 3.5g, PUA is in light blue translucent shape, metal flash paint outward appearance prepared therefrom Well, aluminium powder arrangement effect is qualified, the prepared hardness of paint film, adhesive force, bending property, impact strength, resistance to water, resistance toization Property and weatherability all reach and use standard；When the consumption of PCDL and polycaprolactone glycol in formula is respectively 68.4g During with 45.6g, when the consumption of dimethylethanolamine is 1.75g, PUA is in sub-translucent blueing light shape, flash metal luster prepared therefrom Paint outward appearance is good, and aluminium powder arrangement effect is qualified, and the prepared hardness of paint film, adhesive force, resistance to water, endurance and weatherability are all Reach the standard that uses, but the impact strength of paint film, bending property are all unqualified.This is because it is poly- in PCDL structure Structural carbonate is a kind of both hard and tough structure, can provide excellent physical and mechanical properties for PUA, but polycarbonate structure Poor with the compatibility of other types resin or auxiliary agent, the polycaprolactone structure in polycaprolactone glycol structure is a kind of flexible chain Section, can be that PUA provides excellent pliability, and carry carboxyl can be PUA offer water solubility, and polycaprolactone structure and its The compatibility of his type of resin or auxiliary agent is fine.Therefore, when introducing PCDL not enough in PUA strand and polycaprolactone When glycol is excessive, the pliability of paint film is up to standard very well for PUA water-soluble, but the hardness of paint film, resistance to water, endurance and weather-proof Property is unqualified；When introducing PCDL excess in PUA strand and polycaprolactone glycol is not enough, the water solubility of PUA is relatively Difference, the hardness of paint film, resistance to water, endurance and weatherability are up to standard, and the pliability of paint film is unqualified.Only work as PCDL It is respectively 45.6g and 91.3g with the consumption of polycaprolactone glycol, when the consumption of dimethylethanolamine is 3.5g, three can produce Raw herbicide interactions, make paint film have excellent properties.

The consumption of table 15 PCDL, polycaprolactone glycol and dimethylethanolamine and water-based metal flash of light paint film The relation of energy

Embodiment 7

Table 16 change dihydromethyl propionic acid poly glycol monomethyl ether ester and IPDI consumption synthesis have the moon of IPN structure/ The basic recipe of nonionic PUA

Table 16 is embodiment 7 in the case of ensureing that other monomers consumption is constant, is stepped up the poly- second of dihydromethyl propionic acid The consumption of glycol monomethyl ether ester be 0,22.2g, 44.3g and 66.5g, be stepped up simultaneously IPDI consumption be 34.5g, 39.4g, Under conditions of 44.3g and 49.2g (keeping the constant rate of NCO and OH in formula) synthesis have IPN structure solvent-free cloudy/ The formula that feeds intake of nonionic PUA, its formula number is followed successively by 25,26,27 and 28, has 4 formulas.The synthesis of each formula Technical process is identical.

There is technical process synthesis table 16 institute of the solvent-free the moon/nonionic PUA of IPN structure by embodiment 1 synthesis Show 4 kinds of PUA that numbering is 25～28, prepare the formula of coating and the preparation of lacquer man's skill process containing having IPN structure by embodiment 1 Solvent-free the moon/nonionic PUA the single-component water-based metal flash paint of automobile, by metal flash paint in embodiment 1 Construction method prepares paint film.

Performance such as table 17 by formula 25, the automobile water-based property metal flash paint of formula 26, formula 27 and formula 28 preparation Shown.As seen from table, when the consumption that the consumption of dihydromethyl propionic acid poly glycol monomethyl ether ester in formula is 0, IPDI is 34.5g When, gained PUA is creamy white, metal flash paint surface blackening prepared therefrom, and aluminium powder arranges unqualified, the prepared paint of effect The impact strength of film, bending property are qualified, but the hardness of paint film, adhesive force, resistance to water, endurance and resistance to ag(e)ing are unqualified； When the consumption of dihydromethyl propionic acid poly glycol monomethyl ether ester and IPDI in formula is respectively 22.2g and 39.4g, PUA is micro- Transparent blueing light, metal flash paint outward appearance prepared therefrom blacks slightly, and aluminium powder arranges unqualified, the prepared paint film of effect Adhesive force, hardness, resistance to water, endurance and weatherability all unqualified；When dihydromethyl propionic acid polyethyleneglycol first in formula When the consumption of ether-ether and IPDI is all 44.3g, PUA is light blue translucent, and metal flash paint outward appearance prepared therefrom is good, Aluminium powder arrangement effect is qualified, the prepared hardness of paint film, adhesive force, impact strength, bending property, resistance to water, endurance and Weatherability all reaches and uses standard；When the consumption of dihydromethyl propionic acid poly glycol monomethyl ether ester and IPDI in formula is respectively During 66.5g and 49.2g, the transparent shape of PUA, metal flash paint outward appearance prepared therefrom is good, and aluminium powder arrangement effect is qualified, made The hardness of standby paint film, adhesive force are qualified, and impact strength, bending property, resistance to water, endurance and weatherability are all unqualified. This is because dihydromethyl propionic acid poly glycol monomethyl ether ester and segment on PUA molecular backbone for the IPDI belong to rigid chain segment, Introduce, in strand, the water solubility that dihydromethyl propionic acid poly glycol monomethyl ether ester not only can improve PUA, and can carry Macromolecule chain rigidity, therefore, when formula in without or add dihydromethyl propionic acid poly glycol monomethyl ether ester and IPDI When measuring less, the poorly water-soluble of one side PUA, PUA can not coat aluminium powder well, leads to the metal flash paint prepared by PUA Outward appearance blacks, and the hardness of the paint film on the other hand prepared by PUA is poor；When addition dihydromethyl propionic acid polyethyleneglycol in formula When methyl ether ester and IPDI are excessive, the pliability of the paint film prepared by PUA is poor, and resistance to water, endurance and resistance to ag(e)ing are all unqualified. Therefore, in formula, the consumption of dihydromethyl propionic acid poly glycol monomethyl ether ester and IPDI is all advisable with 44.3g.

The consumption of table 17 dihydromethyl propionic acid poly glycol monomethyl ether ester and IPDI and water-based metal flash of light paint film property Relation

Embodiment 8

The consumption synthesis of table 18 change trimethylolpropane has the base of the solvent-free the moon/nonionic PUA of IPN structure This formula

Table 18 is embodiment 8 in the case of ensureing that other monomers consumption is constant, is stepped up the use of trimethylolpropane Measure for 0,1.6g, 3.2g and 4.8g (because trimethylolpropane variable quantity very little, therefore fill a prescription in PU pre-polymerization monomer total hydroxyl Value is not changed in substantially, thus also just there is no need change IPDI consumption) under conditions of synthesis there is the solvent-free of IPN structure The moon/nonionic PUA the formula that feeds intake, its formula number is followed successively by 29,30,31 and 32, has 4 formulas.Each formula Synthesis process identical.

There is technical process synthesis table 18 institute of the solvent-free the moon/nonionic PUA of IPN structure by embodiment 1 synthesis Show 4 kinds of PUA that formula number is 29～32, prepare the formula of coating and the preparation of lacquer man's skill process containing having IPN by embodiment 1 The single-component water-based metal flash paint of automobile of the solvent-free the moon/nonionic PUA of structure, by flash metal luster in embodiment 1 The construction method of paint prepares paint film.

Performance such as table 19 by formula 29, the automobile water-based property metal flash paint of formula 30, formula 31 and formula 32 preparation Shown.As seen from table, when being added without trimethylolpropane in PUA formula or adding 1.6g trimethylolpropane, PUA is in pale blue Color is translucent, and metal flash paint outward appearance is qualified, and aluminium powder arrangement effect is qualified, and the adhesive force of paint film, impact strength, bending property are all Qualified, but the hardness of paint film, resistance to water, endurance and resistance to ag(e)ing are all unqualified；Amount when trimethylolpropane in PUA formula During for 3.2g, PUA is in light blue translucent, and metal flash paint outward appearance is qualified, and aluminium powder arrangement effect is qualified, the hardness of paint film, attached Put forth effort, impact strength, bending property, resistance to water, endurance and resistance to ag(e)ing all qualified；When trimethylolpropane in PUA formula When consumption is 4.8g, serious gel it is impossible to use in PUA.This is because trimethylolpropane carries three-functionality-degree, in PUA Certain cross-linked network can be formed, thus improve the physical and mechanical properties of PUA film, resistance to water, endurance and weather-proof in molecule Property, but when its consumption is excessive, the cross-linked network density being formed in PUA molecule is excessive, ultimately results in gel.Therefore, three in formula The consumption of hydroxymethyl-propane is advisable with 3.2g.

The consumption of table 19 trimethylolpropane and the relation of water-based metal flash of light paint film property

Embodiment 9

Table 20 changes the basic recipe that the synthesis of component j type has the solvent-free the moon/nonionic PUA of IPN structure

Table 20 is embodiment 9 in the case of ensureing that other monomers consumption is constant, respectively using having same molar IPDI, HMDI, HXDI and TDI synthesis of isocyanate groups has the throwing of the solvent-free the moon/nonionic PUA of IPN structure Material formula, its formula number is followed successively by 33,34,35 and 36, has 4 formulas.The synthesis process of each formula is identical.

Number as shown in the technical process synthesis table 20 that embodiment 1 synthesizes multiple interior cross-linked structure the moon/nonionic PUA and be 33～36 4 kinds of PUA, by embodiment 1 prepare the formula of coating and the preparation of lacquer man's skill process containing multiple interior cross-linked structure cloudy/non- The automobile of ionic PUA, with single-component water-based plain color paint, prepares plain color paint film by the construction method of plain color paint in embodiment 1.

Performance by formula 33, the automobile water-based property plain color paint of formula 34, formula 35 and formula 36 preparation is as shown in table 21. As seen from table, when introducing IPDI in PUA strand, paint film has excellent properties；As introducing HMDI in PUA strand When, the pliability of paint film is poor, and other performances are all qualified；When introducing HXDI in PUA strand, the hardness of paint film is poor, its His performance is all qualified；When introducing TDI in PUA strand, paint film has excellent physical and mechanical properties, resistance to water and resistance toization Property, but its weatherability is unqualified, the easy xanthochromia of paint film.This is because HMDI, IPDI and HXDI broadly fall into aliphatic or alicyclic two Isocyanates, does not contain benzene ring structure in molecule, and contains phenyl ring in TDI molecule, and the weatherability extreme difference of phenyl ring is exposed to the sun for a long time Paint film xanthochromia can be caused under ultraviolet, carry 2 saturation six-membered ring structures in HMDI molecule simultaneously, greatly strengthen PUA molecule Chain rigidity, the hardness ultimately resulting in paint film is very good and toughness is not enough, and only has a six-membered ring structure in HXDI strand, no Enough rigidity can be provided for PUA strand, the hardness ultimately resulting in paint film is not enough.Therefore, synthesis has the no molten of IPN structure During the moon of agent/nonionic PUA, the diisocyanate monomer without phenyl ring should be selected, be wherein advisable with IPDI.

Table 21 component j type and the impact of water-based metal flash of light paint film property

Claims

1. a kind of automobile containing the solvent-free the moon/nonionic PUA with IPN structure is with single-component water-based metal flash paint Preparation method is it is characterised in that comprise the following steps：

(1) prepare the solvent-free the moon/nonionic PUA with IPN structure：1. component a is added reactor, be warming up to 130- 140 DEG C, then dropping component b, component c, the mixture of component d, component e and initiator and chain-transferring agent toward in reactor, PA prepolymer is synthesized by bulk polymerization, was higher than 98% entrance next stage to monomer conversion；2. lower the temperature, then by group Divide f, component g, component h, component i, component j and catalyst to mix, add in PA prepolymer, treat that nco value reaches predetermined value Enter next stage afterwards；3. add amine neutralizer neutralization, add deionized water emulsification；

(2) prepare the single-component water-based metal flash paint of automobile containing the solvent-free the moon/nonionic PUA with IPN structure： Auxiliary agent, cosolvent, aluminum paste, deionized water and amine neutralization is added in the solvent-free the moon/nonionic PUA containing IPN structure Agent, stirs, and standing obtains water-based metal metallic finishe after filtering；Wherein,

Component a is that viscosity is low, the reactive diluent with versatic acid ester group and epoxy radicals, and its consumption is the total matter of mix monomer a-j The 5%-20% of amount；

Component c is that its homopolymer glass transition temperature (Tg) is higher than 20 DEG C, can improve the methyl acrylic ester of hardness of paint film Monomer, its consumption is the 5%-20% of mix monomer a-j gross mass；

Component d is the acrylate monomer with nonionic hydrophilic side chain, and its consumption is the 5%- of mix monomer a-j gross mass 20%；

Component f is as PU soft component, the PCDL for 1000-2000 for the number-average molecular weight, and its consumption is that mixing is single The 0%-40% of body a-j gross mass；

Component g be as PU soft component, number-average molecular weight be 1000-2000, the polycaprolactone with hydrophilic radical on strand Dihydroxylic alcohols, its consumption is the 10%-50% of mix monomer a-j gross mass；

Component h is component hard as PU, is dihydric hydrophilic monomer with nonionic water-wet side segment, main chain terminal, its use Measure the 10%-30% for mix monomer a-j gross mass；

Component i is the cross-linking monomer at least provided with three hydroxyls or amido, and its consumption is the 0.1%- of mix monomer a-j gross mass 3%；

J is as the aliphatic diisocyanate monomer without phenyl ring, good weatherability in the hard component of PU, molecular structure, its use Measure the 10%-30% for mix monomer a-j gross mass.

2. preparation method according to claim 1 is it is characterised in that described viscosity is low, carry versatic acid ester group and epoxy radicals Reactive diluent be tertiary carbonic acid glycidyl ester；And/or

The described acrylic ester monomer with carboxyl and big steric group is adjacent cyclohexane diacid -1- [1- methyl -2- [(1- oxygen Generation -2- acrylic) epoxide] ethyl] ester.

3. preparation method according to claim 1 is it is characterised in that described methacrylate-based monomer is metering system Sour methyl esters (MMA)；And/or

The described acrylate monomer with nonionic hydrophilic side chain is 2- acrylic acid -2- methoxy acrylate, ethoxy ethoxy Ethyl propylene acid esters, triethylene glycol monomethyl ether acrylate, methoxy poly (ethylene glycol) 400 acrylate, methoxy poly (ethylene glycol) The mixture of one or more of 550 acrylate.

4. preparation method according to claim 1 is it is characterised in that the described propylene at least provided with three unsaturated double-bonds Acid ester monomer is trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythrite 3 third The mixture of one or more of olefin(e) acid ester and tripentaerythritol eight acrylate；And/or

The described cross-linking monomer at least provided with three hydroxyls is trimethylolpropane.

5. preparation method according to claim 1 is it is characterised in that initiation used in described synthesis PA pre-polymer route Agent is azo-initiator or peroxide type initiators, and its consumption is the 0.1%-2% of mix monomer a-j gross mass；And/or

In described synthesis PA pre-polymer route, chain-transferring agent used is mercaptan type chain transfer agent, and its consumption is mix monomer a-j The 0.1%-2% of gross mass.

6. preparation method according to claim 5 is it is characterised in that peroxide used in described synthesis PA pre-polymer route Compound class initiator is di t-amyl peroxide；And/or

Described mercaptan type chain transfer agent is lauryl mercaptan.

7. preparation method according to claim 1 is it is characterised in that the hydrophilic radical that carried of described polycaprolactone diols It is one of carboxyl, sulphonate-base or hydrophilic ether chain；And/or

Described with nonionic water-wet side segment, main chain terminal be dihydric hydrophilic monomer be number-average molecular weight is 1000 two Hydroxymethyl propionic acid poly glycol monomethyl ether ester.

8. preparation method according to claim 1 is it is characterised in that described aliphatic diisocyanate monomer is different Fo Er One or more of ketone diisocyanate, dicyclohexyl methyl hydride diisocyanate, cyclohexanedimethyleterephthalate diisocyanate Mixture；And/or

Described catalyst be tertiary amine catalyst, bridged piperazine derivatives catalyst, morpholine class catalyst, imidazole derivatives species catalyst and One of organo-metallic catalyst.

9. preparation method according to claim 8 is it is characterised in that described organo-metallic catalyst is organic bismuth catalyst.

10. preparation method according to claim 1 is it is characterised in that amine neutralizer used in the process of described synthesis PUA It is one of ammoniacal liquor, triethylamine and dimethylethanolamine, its consumption is the 0.1%-3% of mix monomer a-j gross mass.

11. preparation methods according to any one in claim 1-10 it is characterised in that in step (2) aluminum paste, Cosolvent and part of auxiliary mix standby, add PUA, add remaining auxiliary agent under at the uniform velocity stirring action in stirred tank And portions of de-ionized water, stir 5min, be subsequently adding aluminum paste solution, stir 10min, then adjusted with remaining deionized water Viscosity, flies viscosimeter using rich Le, at 25 DEG C, No. 3 rotors, and the viscosity number under 5 turns is 1000-2000cps, is finally neutralized with amine It is 8-9 that agent adjusts pH value, and standing, filtering and discharging obtain final product water-based metal metallic finishe.