CN102317389B - Primer composition - Google Patents
Primer composition Download PDFInfo
- Publication number
- CN102317389B CN102317389B CN2010800079206A CN201080007920A CN102317389B CN 102317389 B CN102317389 B CN 102317389B CN 2010800079206 A CN2010800079206 A CN 2010800079206A CN 201080007920 A CN201080007920 A CN 201080007920A CN 102317389 B CN102317389 B CN 102317389B
- Authority
- CN
- China
- Prior art keywords
- base composition
- paint base
- urea resin
- resin
- multifunctional urethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
Abstract
Disclosed is a primer composition comprising (A) a polyfunctional urethane-urea resin that is obtained by reacting (A1) an organic polyisocyanate, (A2) a polymer polyol, and (A3) a chain extender made of a hydroxyl group-containing diamine, and that has hydroxyl groups derived from the aforementioned chain extender on molecule side chains, 5-20 functional groups and a number average molecular weight of 10,000-50,000, and (B) an organic solvent. The primer composition exhibits sufficient adhesion to an adherend made of a plastic, such as nylon, and a coating film with excellent solvent resistance can be formed even when the curing time is short.
Description
Technical field
The present invention relates to contain the paint base composition of polyurethane-urea resin.
Background technology
As the priming paint of using such as the products formed that is made of plastics etc., known to have by organic diisocyanate, macromolecule diol, amine be chain extension agent reaction and priming paint (for example with reference to patent documentation 1) that the solution of the polyurethane-urea resin that obtains consists of.
Compare with the priming paint that solution by urethane resin consists of, in patent documentation 1, water tolerance and the thermotolerance of the priming paint of record are good, simultaneously, and owing to the similar urea key of amido linkage, the products formed (adherend) that is made of nylon being had good cementability.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 62-129361 communique
Summary of the invention
The problem of solution is wanted in invention
For example, be applied to being contacted with solvent, gasoline etc. sometimes by filming of forming of priming paint of automobile associated components, therefore, requiring films has solvent resistance.
Yet, filming of forming of priming paint by record in patent documentation 1 do not have sufficient solvent resistance (for example for the erosion resistance of gasoline with the mixture of alcohol), or until needs (for example curing time about 120 hours) for a long time till showing sufficient solvent resistance.
In addition, for be applied to automobile associated components etc. by filming that priming paint forms, also require it to have good humidity resistance.
The present invention is based on above situation and makes.
The object of the present invention is to provide a kind of paint base composition, it can be to the sufficient cementability of the adherend that is made of plastics such as nylon performance, even the curing time shortly also can form filming of solvent resistance excellence.
Another object of the present invention is to provide a kind of paint base composition, and it can form filming of humidity resistance excellence.
For the scheme of dealing with problems
Paint base composition of the present invention contains multifunctional urethane-urea resin (A) and organic solvent (B), described multifunctional urethane-urea resin (A) be by make (A 1) organic multiple isocyanate and (A2) number-average molecular weight be that 500～5000 macromolecule polyol and the chain extension agent reaction that (A3) is made of the hydroxyl diamines obtain, it has the hydroxyl that derives from described chain extension agent on molecular side chain, functionality is 5～20, and number-average molecular weight is 10000～50000.
For paint base composition of the present invention, following embodiment is preferred.
(1) functionality of described multifunctional urethane-urea resin (A) is 8.5～18.5, is especially 8.5～17.
(2) described macromolecule polyol is the amorphism polyvalent alcohol.
(3) described macromolecule polyol is to make two or more low molecular polylol with side chain and the reaction of straight chain aliphatics polycarboxylic acid and the amorphism polyvalent alcohol that obtains.
(4) the end-capping reagent sealing that consisted of by the hydroxyl monoamine of the molecular end of described multifunctional urethane-urea resin (A).
(5) following the obtaining of described multifunctional urethane-urea resin (A): make described organic multiple isocyanate and described macromolecule polyol react to prepare isocyanate group end polyurethane prepolymer, make the reaction of gained isocyanate group end polyurethane prepolymer and described hydroxyl diamines and described hydroxyl monoamine.
(6) concentration of described multifunctional urethane-urea resin (A) is 5～15 quality %, described organic solvent (B) is made of lower than the aliphatics series solvent (B2) that the organic solvent (B1) of 130 ℃ and boiling point are 130～180 ℃ boiling point, do not contain the organic solvent that boiling point surpasses 180 ℃, (B1): (B2)=95～50: 5～50 (mass ratioes).
(7) it is the paint base composition of single component solidified nature, and described primer layer composition is used to form the prime coat that is coated with the resin combination take polyisocyanates as solidifying agent thereon.
(8) it is the paint base composition of the two-pack solidified nature take polyisocyanates as curing agent component.
(9) it is for being coated on the paint base composition on adherend by spraying.
The effect of invention
According to paint base composition of the present invention, can form film (prime coat) to the sufficient cementability of the adherend that consisted of by plastics such as nylon performance, simultaneously, though the curing time shortly also can form filming of solvent resistance excellence.
In addition, according to the paint base composition of the present invention of the embodiment of above-mentioned (6), can form film (prime coat) of humidity resistance excellence.
Embodiment
By making (A 1) organic multiple isocyanate and (A2) macromolecule polyol and the chain extension agent reaction that (A3) is made of the hydroxyl diamines obtain as the polyurethane-urea resin of the resinous principle of paint base composition of the present invention.
＜(A1) organic multiple isocyanate 〉
To being not particularly limited for the organic multiple isocyanate that obtains the polyurethane-urea resin, from forming the good viewpoint of filming of weathering resistance, aliphatic diisocyanate and alicyclic diisocyanate are preferred, consider the cementability of filming, and alicyclic diisocyanate is preferred.
Particularly, can list hexamethylene diisocyanate, lysinediisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, norbornene alkyl diisocyanate, these can be used singly or in combination of two or more.In the middle of these, isophorone diisocyanate is particularly preferred.
in addition, as the organic diisocyanate that can be used in combination with above-mentioned aliphatic diisocyanate and/or alicyclic diisocyanate, for example can list 1, the 5-naphthalene diisocyanate, 4, 4 '-diphenylmethanediisocyanate, 2, 4 '-diphenylmethanediisocyanate, 4, 4 '-phenylbenzene dimethylmethane vulcabond, 4, 4 '-dibenzyl vulcabond, PPDI, Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the aromatic diisocyanates such as 6-vulcabond, the O-phthalic group diisocyanate, between the xylylene vulcabond, terephthaldehyde's group diisocyanate etc. is difficult for the organic diisocyanate of xanthochromia, these can be used singly or in combination of two or more.
＜(A2) macromolecule polyol 〉
As the macromolecule polyol that is used for obtaining the polyurethane-urea resin, can to list number-average molecular weight be 500～5000, be preferably 1000～3000, average functionality is 1.9～3 polyester polyol, polyether glycol, polycarbonate polyol, polyolefin polyhydric alcohol.
here, as " polyester polyol ", can list by phthalic acid, m-phthalic acid, terephthalic acid, naphthalic acid, succsinic acid, tartrate, oxalic acid, propanedioic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, propene dicarboxylic acid, nonane diacid, sebacic acid, succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethyl succsinic acid, toxilic acid, more than one of the dicarboxylic acid such as fumaric acid or their acid anhydrides etc. and ethylene glycol, 1,2-PD, 1,3-PD, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 3,3-dihydroxymethyl heptane, Diethylene Glycol, dipropylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, hexanaphthene-Isosorbide-5-Nitrae-glycol, hexanaphthene-Isosorbide-5-Nitrae-dimethanol, the dimeracid glycol, the oxyethane of dihydroxyphenyl propane, propylene oxide adduct, two (beta-hydroxyethyl) benzene, xylyl alcohol, glycerine, TriMethylolPropane(TMP), more than one of the low molecular polylol classes such as tetramethylolmethane carry out polycondensation and the material that obtains.In addition, can list that the cyclic esters such as δ-valerolactone (so-called lactone) monomer that the 6-caprolactone, δ-valerolactone, the alkyl that are replaced by 6-caprolactone, alkyl replace carries out ring-opening polymerization and the lactone that obtains is polyester polyol etc.Can also use the polyester-amides polyvalent alcohol that a part of low molecular polylol is replaced to the low molecule polyamines such as hexanediamine, isophorone diamine, monoethanolamine, low molecule amino alcohol and obtain.
As " polyether glycol ", can list take the low molecule polyamines such as low molecular polylol class or quadrol, propylene diamine, tolylene diamine, mphenylenediamine, diphenylmethane diamine, benzene dimethylamine class etc. as the aforementioned have like this more than 2, the compound that preferably has 2～3 active hydrogen bases is as initiator, the polyvalent alcohol that the following substances addition polymerization is obtained: the cyclic ether monomers such as arylolycidyl ethers class, tetrahydrofuran (THF) such as alkyl glycidyl ether class, phenyl glycidyl ether such as the alkylene oxides such as oxyethane, propylene oxide, butylene oxide ring, methyl glycidyl ether.
As " polycarbonate polyol ", can list by more than one aforementioned low molecular polylols and ethylene carbonate, diethyl carbonate, diphenyl carbonate and carry out dealcoholization, take off the polyvalent alcohol that phenol reactant obtains.In addition, can also use the ester exchange offspring of aforementioned polycarbonate polyol and polyester polyol.
As " polyolefin polyhydric alcohol ", can list polyhutadiene with 2 above hydroxyls, hydrogenated butadiene polymer, polyisoprene, hydrogenated polyisoprene etc.
Be preferably the amorphism polyvalent alcohol for the macromolecule polyol that obtains the polyurethane-urea resin.Here, " amorphism polyvalent alcohol " refers to be at normal temperatures unbodied polyvalent alcohol.
By using the amorphism polyvalent alcohol, can give gained polyurethane-urea resin with binding property, can further improve by filming to the cementability of adherend that paint base composition of the present invention forms.
In addition, because the force of cohesion of amorphism polyvalent alcohol is low, therefore can improve the low temperature storage stability of paint base composition of the present invention.
In addition, the solvability of amorphism polyvalent alcohol in diluting solvent is also good.
for the amorphism polyvalent alcohol that is suitable as macromolecule polyol, can list the polyester polyol that is obtained by the low molecular polylol with side chain and straight chain aliphatics polycarboxylic acid, the polyester polyol that is obtained by two or more low molecular polylol (no matter unprotected side chain is arranged) and straight chain aliphatics polycarboxylic acid, the polyester polyol that is obtained by low molecular polylol and aromatic polycarboxylic acid and straight chain aliphatics polycarboxylic acid, has the polyester polyol that the cyclic ester monomer open loop addition of side chain obtains take low molecular polylol as initiator makes, has the polyether glycol that the cyclic ether monomer open loop addition of side chain obtains take low molecular polylol as initiator makes, the polycarbonate polyol that is obtained by the low molecular polylol with side chain and low molecular carbon ester compound.
In the middle of these, the polyester polyol that is obtained by the two or more low molecular polylol that does not have side chain and straight chain aliphatics polycarboxylic acid is preferred.Especially, the two or more low molecular polylols carbon number separately that does not have a side chain is preferably below 6.
The side chain that consists of the low molecular polylol of amorphism polyvalent alcohol has and hinders by the tendency of filming of forming of gained paint base composition to the cementability of nylon, therefore, by adopting the polyvalent alcohol do not have side chain as low molecular polylol, the cementability of filming in the time of can further improving take nylon as adherend.
＜the chain extension agent that (A3) consisted of by the hydroxyl diamines 〉
The compound that a part has 2 amino (but being limited to primary amino or secondary amino group) and 1 above hydroxyl for the hydroxyl diamines (chain extension agent) that obtains the polyurethane-urea resin.
Particularly, can 2-hydroxyethylethylene diamine (beta-aminoethyl thanomin), 2-hydroxyethyl propylene diamine (beta-amino propyl group thanomin), N be shown example, N '-two-2-hydroxyethylethylene diamine, N, N '-two-2-hydroxyethyl propylene diamine, 2-hydroxypropyl quadrol (beta-aminoethyl Propanolamine), N, N '-two-2-hydroxypropyl quadrol, 2-hydroxyl propylene diamine.
By using the hydroxyl diamines as chain extension agent, hydroxyl can be imported to the molecular side chain of gained polyurethane-urea resin.
In addition, by containing the diamines of primary hydroxyl, make the reactivity of the multifunctional urethane-urea resin of gained and isocyanic ester (solidifying agent) become excellent.
The chain extension agent that is used for obtaining the polyurethane-urea resin preferably only is made of the hydroxyl diamines, also the diamines of hydroxyl not can be used in combination together with the hydroxyl diamines.
＜the end-capping reagent that (A4) consisted of by the hydroxyl monoamine 〉
Consist of the end-capping reagent sealing that the molecular end of the polyurethane-urea resin of paint base composition of the present invention preferably is made of the hydroxyl monoamine.
The hydroxyl monoamine that can be used for obtaining the polyurethane-urea resin here, is the compound that has an amino (but being limited to primary amine groups or secondary amino group) and an above hydroxyl in a part.
Particularly, can list monoethanolamine, diethanolamine, N-Mono Methyl Ethanol Amine, N-ehtylethanolamine, N-normal-butyl thanomin, N-tertiary butyl thanomin, hydroxyethyl piperazine, N-(3-aminopropyl) diethanolamine, N-cyclohexyl ethyl alcohol amine etc.
By using the hydroxyl monoamine as end-capping reagent, can seal with hydroxyl group the molecular end of gained polyurethane-urea resin.
＜multifunctional urethane-urea resin (A) 〉
Multifunctional urethane-the urea resin that consists of paint base composition of the present invention has the hydroxyl that derives from hydroxyl diamines (chain extension agent) at molecular side chain.
In addition, preferably, has the hydroxyl that derives from hydroxyl monoamine (end-capping reagent) in molecular end.
Import to hydroxyl and isocyanic ester radical reaction in multifunctional urethane-urea resin, thus, be formed with crosslinking structure in film (prime coat) that is formed by paint base composition of the present invention.As a result, this is filmed and has excellent solvent resistance.
Here, with the isocyanate group of hydroxyl reaction in multifunctional urethane-urea resin by contain formed by paint base composition of the present invention film in the solidifying agent of resin combination (for example being used to form the resin combination of the two-pack solidified nature of stratum basale, finishing coat) of coating, perhaps, when being the composition of two-pack solidified nature, paint base composition of the present invention contained in the solidifying agent of this paint base composition.
Namely, in order to form crosslinking structure in film (prime coat) that is formed by paint base composition of the present invention, need paint base composition and thereon the coating resin combination at least one party contain isocyanate group (solidifying agent that contains isocyanate compound).
Here, the representative stacked mode as using paint base composition of the present invention to carry out can list following mode:
(1) by the paint base composition of the present invention that does not contain isocyanate group form prime coat, on this prime coat by the resin combination that does not contain isocyanate group form stratum basale, the resin combination of two-pack solidified nature by containing isocyanate group on this stratum basale forms the mode of finishing coat;
(2) form prime coat, forming stratum basale, form the mode of finishing coat by the resin combination that does not contain isocyanate group on this stratum basale by the resin combination that does not contain isocyanate group on this prime coat by the paint base composition of the present invention (resin combination of two-pack solidified nature) that contains isocyanate group;
(3) by the paint base composition of the present invention (resin combination of two-pack solidified nature) that contains isocyanate group form prime coat, on this prime coat by the resin combination that does not contain isocyanate group form stratum basale, the resin combination of two-pack solidified nature by containing isocyanate group on this stratum basale forms the mode of finishing coat.
The functionality of multifunctional urethane-urea resin (f) is 5～20, is preferably 8.5～18.5, more preferably 8.5～17.
In the present invention, " functionality " refers to the hydroxyl value in the multifunctional urethane-urea resin of a part, is import to the hydroxyl of molecular side chain and import to the sum of the hydroxyl of molecular end by hydroxyl monoamine (end-capping reagent) by hydroxyl diamines (chain extension agent).
(unit: mmol/g) pass through following formula: f=Mnc/1000 calculates the functionality of multifunctional urethane-urea resin (f) by the measured value (c) of the hydroxy radical content of the measured value (Mn) of the number-average molecular weight of this resin and this resin.
This functionality is 0 o'clock (not importing hydroxyl in the polyurethane-urea resin), is more than 100 hours even make the formed curing time of filming, and also can't show sufficient solvent resistance (with reference to comparative example 1).
In addition, this functionality was less than 5 o'clock, and needing for a long time, (for example more than 48 hours) just can make the formed performance solvent resistance (with reference to comparative example 2 and comparative example 3) of filming.
On the other hand, this functionality surpasses at 20 o'clock, formed filming to the cementability meeting variation of adherend, and in addition, formed solvent resistance of filming (required curing time) can produce fluctuation (with reference to comparative example 4).
The number-average molecular weight of multifunctional urethane-urea resin (Mn) is 10000～50000, is preferably 15000～41000.
Number-average molecular weight is less than 10000 o'clock, do not have sufficient mechanical characteristics by filming of forming of gained paint base composition.
On the other hand, number-average molecular weight surpasses at 50000 o'clock, and the coating of gained paint base composition is impaired, causes crawling even etc., and solvent resistance (required curing time) might produce fluctuation.
Functional group's equivalent (Mn/f) of multifunctional urethane-urea resin is preferably below 5000, more preferably below 2500, is particularly preferably 1500～2500.Functional group's equivalent surpasses at 5000 o'clock, and the distance between cross-linking set is elongated, so coating strength, solvent resistance reduce.
Method as synthetic multifunctional urethane-urea resin, adopt so-called prepolymer method, that is: make organic multiple isocyanate and macromolecule polyol react to obtain isocyanate group end polyurethane prepolymer, and make this prepolymer and hydroxyl diamines (chain extension agent) and hydroxyl monoamine (end-capping reagent) reaction.
If according to so-called single stage method, the reaction by organic multiple isocyanate and amine compound (hydroxyl diamines and hydroxyl monoamine) can produce the urea aggregation, and is therefore not preferred.
An example of method as the solution of the multifunctional urethane-urea resin of preparation, at first, organic diisocyanate is added in the solution of the macromolecule polyol that is formed by the solvent that does not have active hydrogen (such as ketone, ester, aromatic hydrocarbons etc.), under the existence of polyurethane-reinforcement catalyzer, hour come synthesizing isocyanate base end polyurethane prepolymer in 30～100 ℃ of stoichiometric numbers.
At this moment, as the usage rate of organic diisocyanate and macromolecule polyol, be preferably the mol ratio that makes NCO base/OH base and be 1.1～2.5, be especially 1.5～2.0 ratio.The mol ratio of NCO base/OH base is less than 1.1 o'clock, sometimes do not have sufficient solvent resistance by filming of forming of gained paint base composition.On the other hand, the mol ratio of NCO base/OH base surpasses at 2.5 o'clock, and the solvability of gained resin reduces sometimes, does not have sufficient cementability by filming of forming of gained paint base composition.
Then, add hydroxyl diamines (chain extension agent) and hydroxyl monoamine (end-capping reagent) in the solution of isocyanate group end polyurethane prepolymer, reaction under 30～50 ℃ is until isocyanate group disappears.
Here, the solvent (finally consisting of the solvent of the solution of multifunctional urethane-urea resin) that uses during as synthetic multifunctional urethane-urea resin, can list the aromatic series series solvents such as toluene, dimethylbenzene, the ester such as vinyl acetic monomer, N-BUTYL ACETATE series solvent, the ketone such as acetone, methylethylketone series solvent, the pure series solvents such as methyl alcohol, ethanol, Virahol etc., these can be used singly or in combination of two or more.
Especially, the preferred use to the toluene of the favorable solubility of polyol skeleton, polyurethane skeleton and methylethylketone and to this mixed solvent of three kinds of Virahol of the favorable solubility of urea groups.
As the resin concentration in the solution of the multifunctional urethane-urea resin that so obtains (solids component), be preferably 10～60 quality %, more preferably 15～55 quality %.
Then, as required, further dilute the solution of this multifunctional urethane-urea resin by solvent, can prepare paint base composition of the present invention thus.
Here, the concentration of the multifunctional urethane-urea resin in paint base composition of the present invention is preferably 5～15 quality %.
When the concentration of multifunctional urethane-urea resin is too low, need to increase glue spread, coating sagging etc. can be produced and film (prime coat) of homogeneous can't be formed.On the other hand, during this excessive concentration, spray-coating is impaired, and the smoothness of formed prime coat reduces, and solvent resistance might produce fluctuation.
＜organic solvent (B) 〉
The solvent that the solvent (consisting of the solvent of the solution of aforementioned multifunctional urethane-urea resin) that the organic solvent (B) that consists of paint base composition of the present invention uses during usually by synthetic multifunctional urethane-urea resin and being used for dilutes the solution of aforementioned multifunctional urethane-urea resin consists of.
As the preferred organic solvent (B) that consists of paint base composition of the present invention, can list following organic solvent: consisted of lower than the aliphatics series solvent (B2) that the organic solvent (B1) of 130 ℃ and boiling point are 130～180 ℃ by boiling point, do not contain the organic solvent that boiling point surpasses 180 ℃, (B1): (B2)=95～50: 5～50 (mass ratioes).
As the organic solvent (B 1) of boiling point lower than 130 ℃, can list the aromatic series series solvents such as toluene, dimethylbenzene, the ester series solvents such as vinyl acetic monomer, N-BUTYL ACETATE, the ketone series solvents such as acetone, methylethylketone, the pure series solvents such as methyl alcohol, ethanol, Virahol.
As the organic solvent (B1) that is fit to, can list the mixed solvent of toluene, methylethylketone, Virahol.
Be the aliphatics series solvent (B2) of 130～180 ℃ as boiling point, can list propylene glycol methyl ether acetate (boiling point: 146 ℃), pimelinketone (boiling point: 156 ℃), Pyranton (boiling point: 168 ℃) etc.
According to the paint base composition that is consisted of by the organic solvent (B) that contains aliphatics series solvent (B2) with the ratio more than 5 quality %, when it is sprayed, the sharply evaporation of the organic solvent in filming is suppressed, result, the smoothing of filming under the existence of organic solvent can form film (prime coat) of levelling property excellence.And, even following problem can be avoided in the space that the air that is involved in when not existing by spraying in the filming of the levelling property excellence that is formed by this paint base composition forms or exist also seldom therefore: solvent, moisture from external penetration to this space and make it to cementability reduction of adherend.In addition, levelling property high film in do not exist and can the stress concentration when consisting of the resin swelling of prime coat etc. produce float, peel off large concavo-convex.As a result, compare with the prime coat that paint base composition by not fatty family solvent (B2) forms, the solvent resistance of the prime coat that is formed by this paint base composition further improves, and humidity resistance is also more excellent.
In addition, the ratio of aliphatics series solvent (B2) is that 50 quality % are when following, according to the paint base composition that contains the organic solvent (B) that does not contain the organic solvent of boiling point over 180 ℃, the drying that can effectively film (removing of organic solvent).
In addition, when the use boiling point is the aromatic series series solvent replacement aliphatics series solvent (B2) of 130～180 ℃, according to the solvent that is used in combination, might cause the gathering of multifunctional urethane-urea resin.
In paint base composition of the present invention, in the scope of not damaging effect of the present invention, can contain various optional members.
As described optional member, can list the common additive for coatings such as curing agent component, pigment (pigment dyestuff, mineral dye), antioxidant, UV light absorber, weighting agent, softening agent, static inhibitor, dispersion agent, catalyzer such as resin except multifunctional urethane-urea resin, blocked isocyanate.
The composition that paint base composition of the present invention can be used as the single component solidified nature that does not contain curing agent component (compound that contains isocyanate group) uses.
In this case, need to formed by paint base composition of the present invention film at least a curing agent component (compound that contains isocyanate group) that contains of resin combination of coating.Filming that paint base composition by the single component solidified nature forms, by the isocyanic ester radical reaction that the curing agent component that consists of in this multifunctional urethane-urea resin of the filming hydroxyl that has and the resin combination that is coated with on this is filmed has, can be in this middle importing crosslinking structure (amino-formate bond) of filming.
In addition, paint base composition of the present invention can also use as the composition of the two-pack solidified nature that contains curing agent component (compound that contains isocyanate group).
Paint base composition of the present invention can be compatibly be used for the plastic molded article take (exterior) parts of automobile as representative, also can show sufficient bonding force for the adherend that is made of the nylon that is considered to difficult cementability.
Paint base composition of the present invention is coated on adherend by spraying, brushing, impregnating method.
Carry out drying treatment for desolventizing by filming of forming of paint base composition of the present invention.As the drying conditions of filming, it is for example under 10～50 ℃ 1～30 minute.
Usually carry out heat treated by filming of forming of paint base composition of the present invention, solidify thus.As heating condition, it is for example under 60～100 ℃ 10～60 minutes.Heat treated can be carried out after this dried coating film is processed, also can be on this be filmed coating resin composition and stratification upper strata (for example stratum basale and finishing coat) carry out afterwards.Yet, when not containing curing agent component (compound that contains isocyanate group) in paint base composition, carry out come the stratification upper strata by the resin combination that contains curing agent component after.
To formed by paint base composition of the present invention film on the coating resin combination also be not particularly limited, can be thermoplastic resin, can be also thermosetting resin (single component curing or two-pack curing).Particularly, can example acrylic resin, Synolac, urethane resin, epoxy resin, melamine-alcohol acid resin, acrylic acid-polyurethane be shown is the common coating such as resin.
In order to form film (prime coat) and the upper strata (for example stratum basale and finishing coat) that is formed by paint base composition of the present invention and to guarantee (after the heat treated prime coat) required bonding strength and sufficient solvent resistance, carry out the slaking of certain hour.Here, the slaking environment as being fit to is 10～30 ℃ of temperature, relative humidity 50～70%.
When using existing known paint base composition (for example paint base composition of record in patent documentation 1), need to surpass the curing time of 120 hours.
On the other hand, the paint base composition of the application of the invention even the curing time is in 12 hours, also can form film (prime coat) of solvent resistance excellence.
Consider this be because, completed at short notice by the curing reaction that the hydroxyl in prime coat and isocyanate group are carried out, imported highdensity crosslinking structure in prime coat.
Embodiment
Embodiments of the invention below are described, but the present invention is not limited to these embodiment.
＜embodiment 1 〉
(1) preparation of isocyanate group end polyurethane prepolymer solution:
Add 419g by ethylene glycol and 1 in the reaction unit of the capacity 2000mL that stirrer, thermometer, Allihn condenser (Allihn condenser), nitrogen ingress pipe are housed, the reaction of 4-butyleneglycol and hexanodioic acid and polyester glycol (hereinafter referred to as " polyester (1) ") and the 217g toluene of the number-average molecular weight 2047 that obtains stir to prepare the solution of macromolecule polyol under 45 ℃.
Add 91g isophorone diisocyanate (IPDI) and 0.05g two lauric acid dioctyl tins (DOTDL) in this macromolecular multi-component alcoholic solution, under stream of nitrogen gas, in 75 ℃ of reactions 3 hours, thereby obtain isocyanate group end polyurethane prepolymer solution.The NCO content of this prepolymer is 2.30%.
(2) preparation of multifunctional urethane-urea resin solution:
Add 152g toluene and 491g methylethylketone (MEK) in this pre-polymer solution, stir, then liquid temperature is cooled to 30 ℃, 369g Virahol (IPA), 16.9g isophorone diamine (IPDA), 6.8g are belonged to the beta-aminoethyl thanomin (A-EA) of hydroxyl diamines in interpolation and diethanolamine (DEA) that 7.0g belongs to the hydroxyl monoamine is pre-mixed the amine aqueous solution that forms, carry out the transfer reaction of 4 hours under 40 ℃, thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The resin concentration of this resin solution (solids component) is 30%, and viscosity (25 ℃) is 90mPas.
Measure the number-average molecular weight (Mn) of the multifunctional urethane-urea resin of gained by GPC (gel permeation chromatography), result is 15000.Condition determination herein is as follows.
Determining instrument: " HLC-8120 " (TOSOH CORPORATION manufacturing)
Post: " Styragel HR2 DMF " (Nihon Waters K.K. manufacturing)
Particle diameter=5 μ m, size=7.8mmID * 30cm * 4 piece
Carrier: the DMF (DMF) that contains 0.1%LiBr
Detector: differential refractometer
Sample: 0.1%LiBr/DMF solution
Working curve: polyoxyethylene glycol
In addition, by measure the hydroxy radical content (c) of this multifunctional urethane-urea resin according to the method for JIS K 1557, result is 0.375mmol/g.
The functionality (f) that obtains thus this multifunctional urethane-urea resin is 5.6.
(3) preparation of paint base composition:
The multifunctional urethane that obtains in 100 mass parts above-mentioned (2)-urea resin solution, 30 mass parts propylene glycol methyl ether acetates (PMA), 128 mass parts toluene and 128 mass parts isopropylcarbinols are mixed to mixing, thereby the preparation resin concentration is the paint base composition of the present invention of 7.8 quality %.
＜embodiment 2 〉
Add 147g toluene and 485g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 364gIPA, 16.9g beta-aminoethyl thanomin and 7.0g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 90mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 15000, and hydroxy radical content (c) is 0.567mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 8.5.
Then, except using the multifunctional urethane of gained-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition of the present invention that resin concentration is 7.8 quality %.
＜embodiment 3 〉
Add 146g toluene and 484g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 363gIPA, 17.8g beta-aminoethyl thanomin and 5.2g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 350mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 20000, and hydroxy radical content (c) is 0.519mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 10.4.
Then, except using the multifunctional urethane of gained-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition of the present invention that resin concentration is 7.8 quality %.
＜embodiment 4 〉
Add 146g toluene and 484g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 363gIPA, 18.3g beta-aminoethyl thanomin and 4.2g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 350mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 25000, and hydroxy radical content (c) is 0.490mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 12.3.
Then, except using the multifunctional urethane of gained-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition of the present invention that resin concentration is 7.8 quality %.
＜embodiment 5 〉
Add 146g toluene and 483g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 363gIPA, 18.6g beta-aminoethyl thanomin and 3.5g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 400mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 30000, and hydroxy radical content (c) is 0.471mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 14.1.
Then, except using the multifunctional urethane of gained-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition of the present invention that resin concentration is 7.8 quality %.
＜embodiment 6 〉
Add 145g toluene and 483g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 362gIPA, 18.9g beta-aminoethyl thanomin and 3.0g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 800mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 37000, and hydroxy radical content (c) is 0.458mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 16.9.
Then, except using the multifunctional urethane of gained-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition of the present invention that resin concentration is 7.8 quality %.
＜buy and execute example 7
Add 145g toluene and 483g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 362gIPA, 19.0g beta-aminoethyl thanomin and 2.6g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 1200mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 41000, and hydroxy radical content (c) is 0.447mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 18.3.
Then, except using the multifunctional urethane of gained-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition of the present invention that resin concentration is 7.8 quality %.
＜embodiment 8 〉
Except using 419g by the 3-methyl isophthalic acid, the polyester glycol (hereinafter referred to as " polyester (2) ") of the number-average molecular weight 2045 that 5-pentanediol (low molecular polylol with side chain) obtains with the hexanodioic acid reaction replaces polyester (1) in addition, similarly obtains isocyanate group end polyurethane prepolymer solution with embodiment 1 (1).The NCO content of this prepolymer is 2.30%.
Add 146g toluene and 484g MEK in the isocyanate group end polyurethane prepolymer solution that so obtains, stir, interpolation is pre-mixed with 363g IPA, 17.8g beta-aminoethyl thanomin and 5.2g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 350mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 20000, and hydroxy radical content (c) is 0.519mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 10.4.
Then, except using the multifunctional urethane of gained-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition of the present invention that resin concentration is 7.8 quality %.
＜comparative example 1 〉
Add 153g toluene and 494g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 373gIPA, 28.2g IPDA and 4.8g diethylamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thus synthesis of polyurethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 90mPas.
The number-average molecular weight (Mn) of gained polyurethane-urea resin is 15000, and hydroxy radical content (c) is 0mmol/g, and the functionality (f) that obtains thus this polyurethane-urea resin is 0.
Then, except using gained polyurethane-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition that resin concentration is the relatively use of 7.8 quality %.
＜comparative example 2 〉
Add 153g toluene and 493g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 370gIPA, 28.2g IPDA and 4.0g monoethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thus synthesis of polyurethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 90mPas.
The number-average molecular weight (Mn) of gained polyurethane-urea resin is 15000, and hydroxy radical content (c) is 0.122mmol/g, and the functionality (f) that obtains thus this polyurethane-urea resin is 1.8.
Then, except using gained polyurethane-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition that resin concentration is the relatively use of 7.8 quality %.
＜comparative example 3 〉
Add 155g toluene and 496g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 372g IPA, 28.2g IPDA and 7.0g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thus synthesis of polyurethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 90mPas.
The number-average molecular weight (Mn) of gained polyurethane-urea resin is 15000, and hydroxy radical content (c) is 0.251mmol/g, and the functionality (f) that obtains thus this polyurethane-urea resin is 3.8.
Then, except using gained polyurethane-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition that resin concentration is the relatively use of 7.8 quality %.
＜comparative example 4 〉
Add 145g toluene and 483g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 1 (1), stir, interpolation is pre-mixed with 362g IPA, 19.3g beta-aminoethyl thanomin and 2.1g diethanolamine the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 1 (2), thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 30%, and viscosity (25 ℃) is 2500mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 53000, and hydroxy radical content (c) is 0.433mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 22.9.
Then, except using the multifunctional urethane of gained-urea resin solution, similarly prepare with embodiment 1 (3) paint base composition that resin concentration is the relatively use of 7.8 quality %.
Resin concentration in the number-average molecular weight of the viscosity of the solids component (resin concentration) of the formula (unit is " g ") of embodiment 1～8 and comparative example 1～4, resin solution, resin solution, polyurethane-urea resin, hydroxy radical content, functionality, paint base composition is summed up be shown in following table 1.
[table 1]
(1) cementability (normality adaptation):
Use each paint base composition that obtains in embodiment 1～8 and comparative example 1～4, following evaluation cementability (normality adaptation).
Here, the stratum basale of coating forms with resin combination by interpolation 20 mass parts titanium oxide and 230 mass parts toluene in 100 mass parts acrylic resins " ACRYDIC A-801-P " (DIC (strain) manufacturing), prepared in mixing 10 minutes in dispersion machine on the filming of paint base composition.
In addition, finishing coat forms with resin combination by interpolation 18 mass parts polyisocyanate curing agents " CORONATE HX " in 100 mass parts acrylic resins " ACRYDIC A-801-P " (DIC (strain) manufacturings) (Japanese polyurethane industrial (strain) manufacturing) (NCO/OH=1) He 110 mass parts toluene, uniform stirring prepares at normal temperatures.
With methyl alcohol, sufficient skimming treatment is carried out on the surface of the adherend that is made of 6-nylon " Nylon 1022B " (the emerging product of space section (strain) manufacturing), dry at normal temperatures.
By aerial spraying primer coating composition, drying is 10 minutes under normal temperature (25 ℃) on the surface of this adherend, thereby forms the dry coating of thickness 8 μ m.
Then, use resin combination upper the formation by aerial spraying coated base bottom of the dry coating that is formed by paint base composition (prime coat), dry 10 minutes at normal temperatures, thus the dry coating of stratification thickness 10 μ m.
Then, formed the upper aerial spraying coated face coating formation resin combination that passes through of the dry coating (stratum basale) that forms with resin combination by stratum basale, dry 10 minutes at normal temperatures, thus the dry coating (finishing coat) of stratification thickness 30 μ m.
Then, carry out the heat treated of 30 minutes in the drying machine of 80 ℃, after this, carry out the slaking of 48 hours under the environment of 20 ℃ of temperature, relative humidity 65%.
For each test film that so obtains (stratification has the adherend of prime coat, stratum basale and finishing coat), form the cut of the square chessboard grid (10 * 10) of 1mm on the formation face of filming, carry out the stripping test based on adhesive tape, measure residual grid number.
In addition, for embodiment 1～8 and comparative example 1～4, make respectively 3 test films, obtain the mean value of the residual grid number of 3 test films.The results are shown in following table 2.
(2) the required curing time:
Use each paint base composition that obtains in embodiment 1～8 and comparative example 1～4, following mensuration is until the curing time till the performance solvent resistance.
Here, adherend, stratum basale form and form formation, paint base composition, stratum basale with resin combination with resin combination and finishing coat and form and form with the evaluation of the cementability of coating process, drying conditions, heat treated condition and the slaking environment of resin combination and above-mentioned (1) same with resin combination and finishing coat.
Coating and drying, the stratum basale formation of similarly carrying out paint base composition with the evaluation of above-mentioned (1) cementability form coating and drying with resin combination with coating and drying, the finishing coat of resin combination, implement heat treated, then make different test film of curing time (stratification has the adherend of prime coat, stratum basale and finishing coat).
In addition, for embodiment 1～8 and comparative example 1～4, respectively at lower 3 test films (embodiment: 8 * 7 * 3=168, comparative example: 4 * 7 * 3=84) of making of each curing time (3 hours, 6 hours, 12 hours, 24 hours, 48 hours, 72 hours, 120 hours).
At first, for embodiment 1～8 and comparative example 1～4, each test film that will obtain by the slaking of 3 hours respectively (12 * 3=36) is immersed in gasoline: in the mixed solvent (20 ℃) of ethanol=9: 1, mensuration arrives the time (dipping time) till inboard more than 2mm from the floating of filming of producing of the edge of test film (peeling off) from the edge, estimate solvent resistance according to following judgement criteria.
(judgement criteria)
More than 30 minutes: qualified (evaluation: ◎)
More than 20 minutes～and less than 30 minutes: qualified (evaluation: zero)
Less than 20 minutes: defective (estimate: *)
Then, for embodiment 1～8 and comparative example 1～4, the solvent resistance of each test film (12 * 3=36) that obtains with the above-mentioned slaking of similarly estimating by 6 hours respectively.As a result, in embodiment 2～8,3 test films are qualified (evaluation: ◎) (curing time shows sufficient solvent resistance when being 6 hours), thereby finish test to embodiment 2～8 all.
Then, for embodiment 1 and comparative example 1～4, the solvent resistance of each test film (5 * 3=15) that obtains with the above-mentioned slaking of similarly estimating by 12 hours respectively.As a result, in embodiment 1,3 test films are qualified (evaluation: ◎), thereby finish test to embodiment 1 all.
Then, for comparative example 1～4, respectively with the above-mentioned solvent resistance of similarly estimating each test film that obtains by the slaking more than 24 hours.
More than the results are shown in following table 2.
[table 2]
As shown in Table 2 above, according to the paint base composition of embodiment 1～8, the especially paint base composition of embodiment 1～6, can form the prime coat for the sufficient cementability of adherend performance that is consisted of by the nylon that is considered to difficult cementability.
In addition, according to the paint base composition of embodiment 1～8, the especially paint base composition of embodiment 2～8, even the short excellent prime coat of solvent resistance (for the erosion resistance of gasoline with the mixed solvent of alcohol) that also can form of curing time.
On the other hand, even the slaking that the paint base composition that the functionality of resinous principle is 0 comparative example 1 carried out 120 hours also can't form the prime coat with solvent resistance.
In addition, the functionality of resinous principle needs the very long curing time form the prime coat with solvent resistance less than the paint base composition of 5 comparative example 2～3.
In addition, it is inferior to the cementability of adherend that the functionality of resinous principle surpasses the paint base composition of 20 comparative example 4, in addition, finds that there is fluctuation in the required curing time of performance solvent resistance.
＜embodiment 9 〉
(1) preparation of isocyanate group end polyurethane prepolymer solution:
According to the formula shown in following table 3, add 708.0g polyester (1) and 216.0g as the MEK of organic solvent (B1) in the reaction unit of the capacity 2000mL that stirrer, thermometer, Allihn condenser, nitrogen ingress pipe are housed, stir to prepare the solution of macromolecule polyol under 45 ℃.
Add 153.8g IPDI and 0.08gDOTDL in this macromolecular multi-component alcoholic solution, under nitrogen gas stream, in 75 ℃ of reactions 3 hours, thereby obtain isocyanate group end polyurethane prepolymer solution.The NCO content of this prepolymer is 2.70%.
(2) preparation of multifunctional urethane-urea resin solution:
According to the formula shown in following table 3, add 356.0gMEK in this pre-polymer solution, stir, then liquid temperature is cooled to 30 ℃, interpolation is pre-mixed with 28.5g IPDA, 11.5g A-EA (hydroxyl diamines), 11.9g DEA (hydroxyl monoamine) and 342.0gMEK the amine aqueous solution that forms, carry out the transfer reaction of 4 hours under 40 ℃, thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 50%, and viscosity (25 ℃) is 3800mPas.
Measure the number-average molecular weight (Mn) of the multifunctional urethane-urea resin of gained by GPC (gel permeation chromatography), result is 15000.
In addition, by measure the hydroxy radical content (c) of this multifunctional urethane-urea resin according to the method for JIS K1557, result is 0.375mmol/g.
The functionality (f) that obtains thus this multifunctional urethane-urea resin is 5.6.
(3) preparation of paint base composition:
According to the formula shown in following table 3, the multifunctional urethane that obtains in 100.0 mass parts above-mentioned (2)-urea resin solution, 30.0 mass parts are mixed to mixing as the mixed solvent of toluene/MEK/IPA=3/4/3 (mass ratio) of organic solvent (B1) as the PMA of aliphatics series solvent (B2), 513.0 mass parts, thereby the preparation resin concentration is the paint base composition of the present invention of 7.8 quality %.The ratio that consists of the aliphatics series solvent (B2) in the organic solvent (B) of this paint base composition is 5.1 quality %.
＜embodiment 10～18 〉
According to the formula shown in following table 3, add 356.0g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 9 (1), stir, interpolation is pre-mixed with A-EA, DEA and MEK each amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 9 (2), thus synthetic multifunctional urethane-urea resin and prepare the resin solution of solids component 50%.Number-average molecular weight (Mn), hydroxy radical content (c) and the functionality (f) of the viscosity (25 ℃) of each resin solution of gained, multifunctional urethane-urea resin are summed up be shown in following table 3.
Then, according to the formula shown in following table 3, with 100.0 each resin solutions of mass parts gained, mix to mixing as the mixed solvent of the PMA of aliphatics series solvent (B2) or Pyranton (DAA) and toluene/MEK/IPA, thereby the preparation resin concentration is the paint base composition of the present invention of 7.8 quality %.
The ratio of the aliphatics series solvent (B2) in the organic solvent (B) of each paint base composition of formation gained is summed up be shown in following table 3.
＜embodiment 19 〉
According to the formula shown in following table 3, add 356.0g MEK in the isocyanate group end polyurethane prepolymer solution that similarly obtains with embodiment 9 (1), stir, interpolation is pre-mixed with 32.1g A-EA, 4.4g DEA and 327.0g MEK each amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 9 (2), thus synthetic multifunctional urethane-urea resin and prepare the resin solution of solids component 50%.The viscosity of this resin solution (25 ℃) is 23000mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 41000, and hydroxy radical content (c) is 0.447mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 18.3.
Then, according to the formula shown in following table 3, with 100.0 mass parts gained resin solutions, 59.3 mass parts aromatic hydrocarbon solvents " Solvesso 100 " (Exxon Chemical Co., Ltd. make) and the mixed solvent of 483.7 mass parts toluene/MEK/IPA mix to mixing, be the paint base composition of the present invention of 7.8 quality % thereby prepare resin concentration.
＜embodiment 20 〉
According to the formula shown in following table 3, use 708.0g polyester (2) to replace polyester (1), in addition, similarly obtain isocyanate group end polyurethane prepolymer solution with embodiment 9 (1); Add 356.0g MEK in gained isocyanate group end polyurethane prepolymer solution, stir, interpolation is pre-mixed with 30.1g A-EA, 8.8g DEA and 329.0g MEK the amine aqueous solution that forms, in addition, similarly carry out transfer reaction with embodiment 9 (2), thus synthetic multifunctional urethane-urea resin and prepare the resin solution of solids component 50%.The viscosity of this resin solution (25 ℃) is 3900mPas.
The number-average molecular weight of the multifunctional urethane-urea resin of gained (Mn) is 20000, and hydroxy radical content (c) is 0.519mmol/g, and the functionality (f) that obtains thus this multifunctional urethane-urea resin is 10.4.
Then, according to the formula shown in following table 3, the mixed solvent of 100.0 mass parts gained resin solutions, 59.3 mass parts N-Methyl pyrrolidone and 483.7 mass parts toluene/MEK/IPA is mixed to mixing, and is the paint base composition of the present invention of 7.8 quality % thereby prepare resin concentration.
[table 3]
(※ 1) IPDI: isophorone diisocyanate
(※ 2) DOTDL: two lauric acid dioctyl tins
(※ 3) IPDA: isophorone diamine
(※ 4) A-EA: beta-aminoethyl thanomin (hydroxyl diamines)
(※ 5) DEA: diethanolamine (hydroxyl monoamine)
(※ 6) PMA: propylene glycol methyl ether acetate (boiling point=146 ℃)
(※ 7) DAA: Pyranton (boiling point=168 ℃)
(※ 8) Solvesso 100: aromatic hydrocarbon solvents " Solvesso 100 " (Ltd. makes for boiling point=154～181 ℃, Exxon Chemical Co.)
(※ 9) N-Methyl pyrrolidone: boiling point=202 ℃
The mixed solvent of (※ 10) mixed solvent: toluene/MEK/IPA=3/4/3 (mass ratio)
Each paint base composition that obtains in embodiment 9～20 is estimated following project.Evaluation result is shown in following table 4.
(1) Air drying of primer coating film:
With methyl alcohol, sufficient skimming treatment is carried out on the surface of the adherend that is made of 6-nylon " Nylon 1022B " (the emerging product of space section (strain) manufacturing), dry at normal temperatures.
By aerial spraying primer coating composition, form filming of thickness 7 μ m on the surface of this adherend, this is filmed lower dry at normal temperature (25 ℃), measure until no longer can confirm time (sticking time) till the viscosity of film coated surface.
(2) glossiness of primer coating film:
Use turbidity-gloss reflexometer (Haze-gloss Reflectometer), the glossiness under 85 ° of filming of the thickness 7 μ m that measure by above-mentioned (1) in the formation of the surface of adherend according to JIS Z8741.This glossiness is higher, and the levelling property of filming is more excellent.
(3) cementability (normality adaptation):
With methyl alcohol, sufficient skimming treatment is carried out on the surface of the adherend that is made of 6-nylon " Nylon 1022B " (the emerging product of space section (strain) manufacturing), dry at normal temperatures.
By aerial spraying primer coating composition, drying is 10 minutes under normal temperature (25 ℃) on the surface of this adherend, thereby forms filming of thickness 7 μ m.
Then, use resin combination film (prime coat) that formed by paint base composition upper formation by aerial spraying coated base bottom, dry 10 minutes at normal temperatures, thus the dry coating of stratification thickness 10 μ m.
Then, formed the upper aerial spraying coated face coating formation resin combination that passes through of the dry coating (stratum basale) that forms with resin combination by stratum basale, dry 10 minutes at normal temperatures, thus the dry coating (finishing coat) of stratification thickness 30 μ m.
Then, carry out the heat treated of 30 minutes in the drying machine of 80 ℃, after this, carry out the slaking of 48 hours under the environment of 20 ℃ of temperature, relative humidity 65%.
For the test film that so obtains (stratification has the adherend of prime coat, stratum basale and finishing coat), form the cut of the square chessboard grid (10 * 10) of 1mm on the formation face of filming, carry out the stripping test based on adhesive tape, measure residual grid number.
In addition, for embodiment 9～20, make respectively 3 test films, obtain the mean value of the residual grid number of 3 test films.
(4) solvent resistance:
To be immersed in gasoline with the test film (stratification has the adherend of prime coat, stratum basale and finishing coat) that above-mentioned (3) similarly make: in the mixed solvent (20 ℃) of ethanol=9: 1, measure the time (dipping time) till the inboard that arrives from the floating of filming of producing of the edge of test film (peeling off) from the edge more than 2mm.
In addition, in above-mentioned (1), for the sticking time be embodiment 16,18,20 more than 20 minutes, use time of drying with primer coating film to change to 30 minutes and the test film made is estimated.
(5) humidity resistance:
After placing 240 hours under the environment of temperature 50 C, relative humidity 90% with the test film (stratification has the adherend of prime coat, stratum basale and finishing coat) that above-mentioned (3) similarly obtain, form the cut of the square chessboard grid (10 * 10) of 1mm on the formation face of filming, carry out the stripping test based on adhesive tape, measure residual grid number.
In addition, in above-mentioned (1), for the sticking time be embodiment 16,18,20 more than 20 minutes, use time of drying with primer coating film to change to 30 minutes and the test film made is estimated.
In addition, for embodiment 9～20, make respectively 3 test films, obtain the mean value of the residual grid number in 3 test films.
[table 4]
As shown in Table 4 above, according to the paint base composition of embodiment 9～20, can form the prime coat to the abundant cementability of adherend performance that is consisted of by nylon.
In addition, according to the paint base composition of embodiment 9～20, can form the prime coat of solvent resistance excellence.
According to embodiment 9～14,16,18,20 paint base composition, can form good the filming of levelling property, can form that solvent resistance is excellent especially, also excellent prime coat of humidity resistance.
In addition, according to embodiment 9～14,15,17,19 paint base composition, can form the primer coating film of drying property excellence.
Claims (10)
1. a paint base composition, is characterized in that, it contains multifunctional urethane-urea resin (A) and organic solvent (B),
Described multifunctional urethane-urea resin (A) be by make (A1) organic multiple isocyanate and (A2) number-average molecular weight be that 500～5000 macromolecule polyol and the chain extension agent reaction that (A3) is made of the hydroxyl diamines obtain, it has the hydroxyl that derives from described chain extension agent on molecular side chain, functionality is 5～20, and number-average molecular weight is 10000～50000.
2. paint base composition according to claim 1, is characterized in that, the functionality of described multifunctional urethane-urea resin (A) is 8.5～18.5.
3. according to claim 1 or paint base composition claimed in claim 2, it is characterized in that, described macromolecule polyol is the amorphism polyvalent alcohol.
4. paint base composition according to claim 3, is characterized in that, described amorphism polyvalent alcohol obtains two or more low molecular polylols and the reaction of straight chain aliphatics polycarboxylic acid with side chain.
5. paint base composition according to claim 1, is characterized in that, the end-capping reagent sealing that the molecular end of described multifunctional urethane-urea resin (A) is made of the hydroxyl monoamine by (A4).
6. paint base composition according to claim 5, it is characterized in that, following the obtaining of described multifunctional urethane-urea resin (A): make described organic multiple isocyanate and described macromolecule polyol react to prepare isocyanate group end polyurethane prepolymer, make the reaction of gained isocyanate group end polyurethane prepolymer and described hydroxyl diamines and described hydroxyl monoamine.
7. paint base composition according to claim 1, is characterized in that, the concentration of described multifunctional urethane-urea resin (A) is 5～15 quality %,
Described organic solvent (B) is made of lower than the aliphatics series solvent (B2) that the organic solvent (B1) of 130 ℃ and boiling point are 130～180 ℃ boiling point, (B1): mass ratio (B2)=95～50: 5～50.
8. paint base composition according to claim 1, it is the paint base composition of single component solidified nature, described primer layer composition is used to form the prime coat that is coated with the resin combination take polyisocyanates as solidifying agent thereon.
9. paint base composition according to claim 1, it is the paint base composition of the two-pack solidified nature take polyisocyanates as curing agent component.
10. paint base composition according to claim 1, it is coated on adherend by spraying.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-043162 | 2009-02-25 | ||
| JP2009043162 | 2009-02-25 | ||
| PCT/JP2010/051941 WO2010098210A1 (en) | 2009-02-25 | 2010-02-10 | Primer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102317389A CN102317389A (en) | 2012-01-11 |
| CN102317389B true CN102317389B (en) | 2013-11-06 |
Family
ID=42665421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800079206A Active CN102317389B (en) | 2009-02-25 | 2010-02-10 | Primer composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5585849B2 (en) |
| CN (1) | CN102317389B (en) |
| WO (1) | WO2010098210A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130056537A1 (en) * | 2011-09-06 | 2013-03-07 | E. I. Du Pont De Nemours And Company | Barrier layer dielectric for rfid circuits |
| CN102617364B (en) * | 2012-03-15 | 2014-04-23 | 南京工业大学 | Hydroxymethyl diamine compound and preparation method and application thereof |
| WO2017023765A1 (en) * | 2015-07-31 | 2017-02-09 | Basf Se | Pigmented primer composition for forming an n-acyl urea coating |
| CN105606768B (en) * | 2015-12-28 | 2018-08-10 | 上海维凯光电新材料有限公司 | Detect the test fluid and test pen of aluminizing transfer paint solvent resistance |
| JP7099074B2 (en) * | 2018-06-20 | 2022-07-12 | Dic株式会社 | Method for manufacturing urethane resin composition |
| CN116622046B (en) * | 2023-07-19 | 2023-09-26 | 四川大学 | Post-crosslinkable high molecular weight polyurethane and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250252A (en) * | 2007-02-22 | 2008-08-27 | 日本聚氨酯工业株式会社 | Polyurefhane resin for primer of decorative sheet and primer of decorative using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62129361A (en) * | 1985-11-29 | 1987-06-11 | Sanyo Chem Ind Ltd | Primer for molded article |
| JPH11152322A (en) * | 1997-11-20 | 1999-06-08 | Toyobo Co Ltd | Production of polyurethaneurea resin |
| US7875355B2 (en) * | 2005-07-01 | 2011-01-25 | The Sherwin-Williams Company | Multi-layer coating system including a hydroxyl modified polyurethane dispersion binder |
-
2010
- 2010-02-10 CN CN2010800079206A patent/CN102317389B/en active Active
- 2010-02-10 JP JP2011501549A patent/JP5585849B2/en active Active
- 2010-02-10 WO PCT/JP2010/051941 patent/WO2010098210A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250252A (en) * | 2007-02-22 | 2008-08-27 | 日本聚氨酯工业株式会社 | Polyurefhane resin for primer of decorative sheet and primer of decorative using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2010098210A1 (en) | 2012-08-30 |
| JP5585849B2 (en) | 2014-09-10 |
| WO2010098210A1 (en) | 2010-09-02 |
| CN102317389A (en) | 2012-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103204983B (en) | aliphatic polyisocyanate prepolymer and polyurethane resin coating composition using the same | |
| US8758862B2 (en) | Coating compositions with an isocyanate-functional prepolymer derived from a tricyclodecane polyol, methods for their use, and related coated substrates | |
| CN102333805B (en) | Aqueous polyurethane resin dispersion and manufacturing method thereof | |
| CN102482530B (en) | Coating compositions for glass substrates | |
| CN102317389B (en) | Primer composition | |
| CN103562255A (en) | Aqueous polyurethane resin dispersion and coating composition comprising same | |
| CN104884493A (en) | Aqueous polyurethane resin dispersion and use of same | |
| KR20130132905A (en) | Mdi based linings and membranes from prepolymers with very low free monomeric isocyanates | |
| CA2539599A1 (en) | Two-component composition for the production of polyurethane gel coats for epoxy resin and vinyl ester resin composite materials | |
| JP3700166B2 (en) | Binder for polyurethane-based printing ink and printing ink composition using the same | |
| US11492440B2 (en) | Clearcoat compositions and methods of forming clearcoat compositions | |
| JP4061631B2 (en) | Non-aqueous primer composition | |
| JP4798532B2 (en) | Emulsion composition for water-based printing ink and water-based printing ink using the same | |
| JPH0241379A (en) | Resin composition for primer | |
| CN1104483C (en) | Polyurethane resin adhesive | |
| JP5459463B2 (en) | Primer composition | |
| KR101310786B1 (en) | The Resin Mixture and Synthetic method of the Resins for high build primer which is applicable on automotive pre-coated coatings | |
| JP5510891B2 (en) | Primer composition | |
| JP3598823B2 (en) | Polyurethane urea and method for producing the same | |
| JPH1161082A (en) | Polyurethane adhesive | |
| JP2010215866A (en) | Primer composition for spray coating | |
| JP4015359B2 (en) | Metal coating method | |
| JP2003026995A (en) | Metal coating method | |
| JP2011213778A (en) | Primer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |