CN102317389A - Paint base composition - Google Patents
Paint base composition Download PDFInfo
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- CN102317389A CN102317389A CN2010800079206A CN201080007920A CN102317389A CN 102317389 A CN102317389 A CN 102317389A CN 2010800079206 A CN2010800079206 A CN 2010800079206A CN 201080007920 A CN201080007920 A CN 201080007920A CN 102317389 A CN102317389 A CN 102317389A
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- Prior art keywords
- base composition
- paint base
- urea resin
- resin
- multifunctional urethane
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of paint base composition; It contains multifunctional urethane-urea resin (A) and organic solvent (B); Said multifunctional urethane-urea resin (A) is through making (A1) organic multiple isocyanate and (A2) macromolecule polyol and the chain extension agent reaction that (A3) is made up of the hydroxyl diamines obtain; It has the hydroxyl that derives from said chain extension agent on molecular side chain, functionality is 5～20, and number-average molecular weight is 10000～50000.According to this paint base composition, can bring into play sufficient cementability to the adherend that constitutes by plastics such as nylon, even the curing time weak point also can form excellent the filming of solvent resistance.
Description
Technical field
The present invention relates to contain the paint base composition of polyurethane-urea resin.
Background technology
As the priming paint of the moulding article usefulness that for example is made up 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 constitutes.
Compare with the priming paint that solution by urethane resin constitutes, water tolerance and the thermotolerance of the priming paint of record are good in the patent documentation 1, simultaneously, and owing to the moulding article (adherend) that are made up of nylon being had good cementability with the similar urea key of amido linkage.
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 the patent documentation 1 do not have sufficient solvent resistance (for example to the erosion resistance of gasoline with the mixture of alcohol), or till the performance sufficient solvent resistance, needs (the for example curing time about 120 hours) for a long time.
In addition, for being applied to filming of automobile associated components etc., also require it to have good humidity resistance by what priming paint formed.
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 bring into play sufficient cementability to the adherend that is made up of plastics such as nylon, even the curing time weak point also can form excellent the filming of solvent resistance.
Another object of the present invention is to provide a kind of paint base composition, and it can form excellent the filming of humidity resistance.
The scheme that is used to deal with problems
Paint base composition of the present invention contains multifunctional urethane-urea resin (A) and organic solvent (B); Said multifunctional urethane-urea resin (A) be through 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 up of the hydroxyl diamines obtain; It has the hydroxyl that derives from said 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 said multifunctional urethane-urea resin (A) is 8.5～18.5, especially is 8.5～17.
(2) said macromolecule polyol is the amorphism polyvalent alcohol.
(3) said 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) molecular end of said multifunctional urethane-urea resin (A) is sealed by the end-capping reagent that is made up of the hydroxyl monoamine.
(5) said multifunctional urethane-urea resin (A) obtains as follows: said organic multiple isocyanate and said macromolecule polyol are reacted prepare the terminal polyurethane prepolymer of NCO, make terminal polyurethane prepolymer of gained NCO and said hydroxyl diamines and the reaction of said hydroxyl monoamine.
(6) concentration of said multifunctional urethane-urea resin (A) is 5～15 quality %; Said organic solvent (B) is lower than the aliphatics series solvent (B2) that 130 ℃ organic solvent (B1) and boiling point be 130～180 ℃ by boiling point and constitutes; 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 said primer layer composition is used to form and is coated with above that with the POLYMETHYLENE POLYPHENYLISOCYANATE is the prime coat of the resin combination of solidifying agent.
(8) it is to be the paint base composition of the two-pack solidified nature of curing agent component with the POLYMETHYLENE POLYPHENYLISOCYANATE.
(9) it is for to be coated on the paint base composition on the adherend through spraying.
The effect of invention
According to paint base composition of the present invention, can form film (prime coat) of the adherend that is made up of plastics such as nylon being brought into play sufficient cementability, simultaneously, even the curing time weak point also can form excellent the filming of solvent resistance.
In addition, according to the paint base composition of the present invention of the embodiment of above-mentioned (6), can form humidity resistance excellent film (prime coat).
Embodiment
As the polyurethane-urea resin of the resinous principle of paint base composition of the present invention is through making (A 1) organic multiple isocyanate and (A2) macromolecule polyol and the chain extension agent reaction that (A3) is made up of the hydroxyl diamines obtain.
(A1) organic multiple isocyanate
To being used to obtain not special qualification of organic multiple isocyanate of 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 enumerate out hexamethylene diisocyanate, LDI, isophorone diisocyanate, cyclohexyl diisocyanate, 4; 4 '-dicyclohexyl methane diisocyanate, norbornene alkyl diisocyanate, these can use separately or two or more combinations are used.In the middle of these, isophorone diisocyanate is preferred especially.
In addition; As making up the organic diisocyanate that uses, for example can enumerate out 1,5-naphthalene diisocyanate, 4 with above-mentioned aliphatic diisocyanate and/or alicyclic diisocyanate; 4 '-diphenylmethanediisocyanate, 2; 4 '-diphenylmethanediisocyanate, 4,4 '-phenylbenzene dimethylmethane vulcabond, 4,4 '-dibenzyl vulcabond, PPDI, Toluene-2,4-diisocyanate; 4-vulcabond, Toluene-2,4-diisocyanate; Aromatic diisocyanates such as 6-vulcabond, O-phthalic group diisocyanate, an xylylene vulcabond, terephthaldehyde's group diisocyanate etc. are difficult for xanthochromic organic diisocyanate, and these can use separately or two or more combinations are used.
(A2) macromolecule polyol
As the macromolecule polyol that is used to obtain the polyurethane-urea resin, can to enumerate out 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 enumerate out 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, 1 4-cyclohexyl dicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-Yi Jiwuersuan, α; More than one of dicarboxylicacid such as β-diethylammonium succsinic acid, toxilic acid, fumaric acid or their acid anhydrides etc. and terepthaloyl moietie, 1; 2-Ucar 35,1, ammediol, 1,2-butyleneglycol, 1; 3-butyleneglycol, 1; 4-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, 1; 8-ethohexadiol, 1; 9-nonanediol, 3-methyl isophthalic acid, 5-pentanediol, 3,3-dihydroxymethyl heptane, Diethylene Glycol, dipropylene glycol, NSC 6366, Diethylene Glycol, dipropylene glycol, hexanaphthene-1; 4-glycol, hexanaphthene-1, more than one of low molecular polylol classes such as the oxyethane of 4-dimethanol, dimeracid glycol, dihydroxyphenyl propane, propylene oxide adduct, two (beta-hydroxyethyl) benzene, xylyl alcohol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane carry out polycondensation and the material that obtains.In addition, can enumerate out by cyclic ester (so-called lactone) monomers such as 6-caprolactone, the substituted 6-caprolactone of alkyl, δ-Wu Neizhi, the substituted δ-Wu Neizhis of alkyl and carry out ring-opening polymerization and the lactone that obtains is a polyester polyol etc.Can also use a part of low molecular polylol is replaced to low molecule polyamines such as hexanediamine, isophorone diamine, monoethanolamine, low molecule amino alcohol and the polyester-amides polyvalent alcohol that obtains.
As " polyether glycol "; Can enumerate out as low molecule polyamines classes such as aforesaid low molecular polylol class or quadrol, tn, tolylene diamine, mphenylenediamine, diphenylmethane diamine, benzene dimethylamine etc., to have the compound that more than 2, preferably has 2～3 active hydrogen bases is initiator, the polyvalent alcohol that the following substances addition polymerization is obtained: cyclic ether monomers such as arylolycidyl ethers class, THF such as alkyl glycidyl ether class, phenyl glycidyl ether such as alkylene oxides such as oxyethane, propylene oxide, butylene oxide ring, methyl glycidyl ether.
As " polycarbonate polyol ", can enumerate out 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 enumerate out polyhutadiene with 2 above hydroxyls, hydrogenated butadiene polymer, TR 301, hydrogenated polyisoprene etc.
The macromolecule polyol that is used to obtain the polyurethane-urea resin is preferably the amorphism polyvalent alcohol.Here, " amorphism polyvalent alcohol " is meant and is unbodied polyvalent alcohol at normal temperatures.
Through using the amorphism polyvalent alcohol, can give gained polyurethane-urea resin with binding property, can further improve by what paint base composition of the present invention formed and film the cementability of adherend.
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 also is good.
For the amorphism polyvalent alcohol that is suitable as macromolecule polyol; Can enumerate out the polyester polyol that obtains by low molecular polylol with side chain and straight chain aliphatics polycarboxylic acid; The polyester polyol that obtains by two or more low molecular polylol (no matter unprotected side chain is arranged) and straight chain aliphatics polycarboxylic acid; The polyester polyol that obtains by low molecular polylol and aromatic series polycarboxylic acid and straight chain aliphatics polycarboxylic acid; It with the low molecular polylol polyester polyol that initiator obtains cyclic ester monomer open loop addition with side chain; With the low molecular polylol polyether glycol that initiator obtains cyclic ether monomer open loop addition with side chain, the polycarbonate polyol that obtains by low molecular polylol with side chain and low molecular carbon ester compound.
In the middle of these, the polyester polyol that is obtained by 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 constitutes the low molecular polylol of amorphism polyvalent alcohol has obstruction by the tendency of filming of forming of gained paint base composition to the cementability of nylon; Therefore; Through adopting the polyvalent alcohol do not have side chain, can further improve the cementability of filming when being adherend with nylon as low molecular polylol.
< chain extension agent that (A3) constitutes>by the hydroxyl diamines
The hydroxyl diamines (chain extension agent) that is used for obtaining the polyurethane-urea resin is the compound that a part has 2 amino (but being limited to primary amino or secondary amino group) and 1 above hydroxyl.
Particularly; But illustration goes out 2-AEEA (beta-aminoethyl thanomin), 2-hydroxyethyl tn (beta-amino propyl group thanomin), N; N '-two-2-AEEA, N; N '-two-2-hydroxyethyl tn, 2-hydroxypropyl quadrol (beta-aminoethyl Propanolamine), N, N '-two-2-hydroxypropyl quadrol, 2-hydroxyl tn.
Through using the hydroxyl diamines, can hydroxyl be imported to the molecular side chain of gained polyurethane-urea resin as chain extension agent.
In addition, through containing the diamines of primary hydroxyl, make the reactivity of multifunctional urethane-urea resin of gained and isocyanic ester (solidifying agent) become excellent.
The chain extension agent that is used to obtain the polyurethane-urea resin preferably only is made up of the hydroxyl diamines, also can the diamines of hydroxyl not be made up use with the hydroxyl diamines.
< end-capping reagent that (A4) constitutes>by the hydroxyl monoamine
Constitute 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 up 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 enumerate out monoethanolamine, diethylolamine, N-Mono Methyl Ethanol Amine, N-ehtylethanolamine, N-normal-butyl thanomin, N-tertiary butyl thanomin, hydroxyethyl piperazine, N-(3-aminopropyl) diethylolamine, N-cyclohexyl ethyl alcohol amine etc.
Through using the hydroxyl monoamine, can seal the molecular end of gained polyurethane-urea resin with hydroxyl group as end-capping reagent.
< multifunctional urethane-urea resin (A) >
Multifunctional urethane-the urea resin that constitutes 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, in film (prime coat) that forms by paint base composition of the present invention, be formed with crosslinking structure.As a result, this is filmed and has excellent solvent resistance.
Here; With the NCO of hydroxyl reaction in multifunctional urethane-urea resin by contain form 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,, paint base composition of the present invention contained in the solidifying agent of this paint base composition when being the compsn of two-pack solidified nature.
That is, in order in film (prime coat) that forms by paint base composition of the present invention, to form crosslinking structure, need paint base composition and above that the coating resin combination at least one side contain NCO (solidifying agent that contains isocyanate compound).
As the representative range upon range of mode of using paint base composition of the present invention to carry out, can enumerate out following mode here:
(1) through the paint base composition of the present invention that does not contain NCO form prime coat, on this prime coat through the resin combination that does not contain NCO form stratum basale, the resin combination of two-pack solidified nature through containing NCO on this stratum basale forms the mode of finishing coat;
(2) form prime coat, forming stratum basale, on this stratum basale, forming the mode of finishing coat through the resin combination that does not contain NCO on this prime coat through the paint base composition of the present invention (resin combination of two-pack solidified nature) that contains NCO through the resin combination that does not contain NCO;
(3) through the paint base composition of the present invention (resin combination of two-pack solidified nature) that contains NCO form prime coat, on this prime coat through the resin combination that does not contain NCO form stratum basale, the resin combination of two-pack solidified nature through containing NCO 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 " is meant the hydroxyl value in the multifunctional urethane-urea resin of a part, is to import to the hydroxyl of molecular side chain and the sum that imports to the hydroxyl of molecular end through hydroxyl monoamine (end-capping reagent) through 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 that crawling is spared 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 preferably 1500～2500 especially.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: organic multiple isocyanate and macromolecule polyol are reacted and obtain the terminal polyurethane prepolymer of NCO, 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, then the reaction through organic multiple isocyanate and amine compound (hydroxyl diamines and hydroxyl monoamine) can produce the urea aggregation, and is therefore not preferred.
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 forms by the solvent that does not have active hydrogen (for example ketone, ester, aromatic hydrocarbons etc.); In the presence of the polyurethane-reinforcement catalyzer, hour come the terminal polyurethane prepolymer of synthesizing isocyanate base 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, especially be 1.5～2.0 ratio.The mol ratio of NCO base/OH base is less than 1.1 o'clock, do not have sufficient solvent resistance by filming of forming of gained paint base composition sometimes.On the other hand, the mol ratio of NCO base/OH base surpasses at 2.5 o'clock, and gained dissolving resin property reduction does not sometimes have sufficient cementability by filming of forming of gained paint base composition.
Then, in the solution of the terminal polyurethane prepolymer of NCO, add hydroxyl diamines (chain extension agent) and hydroxyl monoamine (end-capping reagent),, disappear until NCO 30～50 ℃ of reactions down.
Here; The solvent (finally constituting the solvent of the solution of multifunctional urethane-urea resin) that uses during as synthetic multifunctional urethane-urea resin; Can enumerate out aromatic series series solvents such as toluene, YLENE, ester series solvents such as vinyl acetic monomer, N-BUTYL ACETATE, ketone series solvents such as acetone, methylethylketone; Pure series solvents such as methyl alcohol, ethanol, Virahol etc., these can use separately or two or more combinations are used.
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 %, further be preferably 15～55 quality %.
Then, as required, further dilute the solution of this multifunctional urethane-urea resin, can prepare paint base composition of the present invention thus through solvent.
Here, the concentration of the multifunctional urethane-urea resin in the paint base composition of the present invention is preferably 5～15 quality %.
Cross when low in the concentration of multifunctional urethane-urea resin, needing increases glue spread, can produce coating sagging etc. and can't form film (prime coat) of homogeneous.On the other hand, during this excessive concentration, spray-coating property is impaired, and the smoothness of formed prime coat reduces, and solvent resistance might produce fluctuation.
< organic solvent (B) >
The solvent formation of solvent (constituting the solvent of the solution of aforementioned multifunctional urethane-urea resin) that the organic solvent (B) that constitutes paint base composition of the present invention uses during usually by synthetic multifunctional urethane-urea resin and the solution that is used to dilute aforementioned multifunctional urethane-urea resin.
As the preferred organic solvent (B) that constitutes paint base composition of the present invention; Can enumerate out following organic solvent: be lower than the aliphatics series solvent (B2) that 130 ℃ organic solvent (B1) and boiling point be 130～180 ℃ by boiling point and constitute; Do not contain the organic solvent that boiling point surpasses 180 ℃, (B1): (B2)=95～50: 5～50 (mass ratioes).
Be lower than 130 ℃ organic solvent (B 1) as boiling point, can enumerate out aromatic series series solvents such as toluene, YLENE, ester series solvents such as vinyl acetic monomer, N-BUTYL ACETATE, ketone series solvents such as acetone, methylethylketone, pure series solvents such as methyl alcohol, ethanol, Virahol.
As the organic solvent (B1) that is fit to, can enumerate out the mixed solvent of toluene, methylethylketone, Virahol.
As boiling point is 130～180 ℃ aliphatics series solvent (B2), can enumerate out propylene glycol methyl ether acetate (boiling point: 146 ℃), pimelinketone (boiling point: 156 ℃), Pyranton (boiling point: 168 ℃) etc.
According to the paint base composition that constitutes by the organic solvent (B) that contains aliphatics series solvent (B2) with the ratio more than the 5 quality %; When it is sprayed; The rapid evaporation of the organic solvent in filming is suppressed; As a result, the smoothing of in the presence of organic solvent, filming can form leveling characteristics excellent film (prime coat).And; Even the leveling characteristics that forms by this paint base composition excellent film in the space that forms of the air that is involved in when not existing by spraying, or exist also seldom, therefore can avoid following problem: solvent, moisture from external penetration to this space and make its cementability reduction to adherend.In addition, leveling characteristics high film in do not exist and can the stress concentration when constituting the resin swelling of prime coat etc. produce float, peel off big 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 50 quality % when following, does not contain the paint base composition of organic solvent (B) that boiling point surpasses 180 ℃ organic solvent, the drying that can film effectively (removing of organic solvent) according to containing.
In addition, when the use boiling point is 130～180 ℃ aromatic series series solvent replacement aliphatics series solvent (B2),, might cause the gathering of multifunctional urethane-urea resin according to the make up solvent that uses.
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 said optional member, can enumerate out common coating such as curing agent component, pigment (pigment dyestuff, mineral dye), inhibitor, UV light absorber, weighting agent, softening agent, static inhibitor, dispersion agent, catalyzer such as resin except that multifunctional urethane-urea resin, blocked isocyanate and use additive.
The compsn 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 NCO) uses.
In this case, need form by paint base composition of the present invention film at least a curing agent component (compound that contains NCO) that contains of resin combination of coating.Film what paint base composition by the single component solidified nature formed; The isocyanic ester radical reaction that curing agent component had through in the resin combination that constitutes this hydroxyl that multifunctional urethane-urea resin had of filming and on this is filmed, be coated with can import crosslinking structure (amino-formate bond) in this is filmed.
In addition, paint base composition of the present invention can also use as the compsn of the two-pack solidified nature that contains curing agent component (compound that contains NCO).
(outer dress) parts that paint base composition of the present invention can compatibly be used for automobile are the plastic molded article of representative, also can show sufficient bonding force for the adherend that is made up of the nylon that is considered to difficult cementability.
Paint base composition of the present invention is coated on the adherend through spraying, brushing, impregnating method.
Film in order to carry out drying treatment by what paint base composition of the present invention formed except that desolvating.As the drying conditions of filming, for example be to descend 1～30 minute at 10～50 ℃.
Usually carry out heat treated by filming of forming of paint base composition of the present invention, solidify thus.As heating condition, for example be to descend 10～60 minutes at 60～100 ℃.Heat treated can be carried out after this dried coating film is handled, also can be on this be filmed coating resin compsn and stratification upper strata (for example stratum basale and finishing coat) carry out afterwards.Yet, when in paint base composition, not containing curing agent component (compound that contains NCO), after coming the stratification upper strata, carry out through the resin combination that contains curing agent component.
To form paint base composition of the present invention film on the resin combination of coating also do not limit especially, can be thermoplastic resin, also can be thermosetting resin (single component curing or two-pack curing).Particularly, but illustration goes out acrylics, Synolac, urethane resin, epoxy resin, melamine-alcohol acid resin, acrylic acid-polyurethane is common coating such as resin.
In order to form film (prime coat) and the upper strata (for example stratum basale and finishing coat) that forms by paint base composition of the present invention and to guarantee bonding strength and the sufficient solvent resistance that (after the heat treated prime coat) is required, 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 (the for example paint base composition of record in the patent documentation 1), need to surpass 120 hours curing time.
Relative therewith, the paint base composition of the application of the invention even the curing time is in 12 hours, also can form solvent resistance excellent film (prime coat).
Consider this be because, accomplish at short notice by the curing reaction that hydroxyl in the prime coat and NCO carry out, imported highdensity crosslinking structure in the 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 the terminal polyurethane prepolymer solution of NCO:
In the reaction unit of the capacity 2000mL that stirrer, TM, Allihn condenser (Allihn condenser), nitrogen ingress pipe are housed, add 419g by terepthaloyl moietie and 1; Polyester glycol of the reaction of 4-butyleneglycol and hexanodioic acid and the number-average molecular weight 2047 that obtains (below be called " polyester (1) ") and 217g toluene, under 45 ℃, stirring prepares the solution of macromolecule polyol.
In this macromolecular multi-component alcoholic solution, add 91g isophorone diisocyanate (IPDI) and 0.05g two LAURIC ACID 99 MIN dioctyl tins (DOTDL), under stream of nitrogen gas,, thereby obtain the terminal polyurethane prepolymer solution of NCO in 75 ℃ of reactions 3 hours.The NCO content of this prepolymer is 2.30%.
(2) preparation of multifunctional urethane-urea resin solution:
In this pre-polymer solution, add 152g toluene and 491g methylethylketone (MEK); Stir; Then the 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 diethylolamine (DEA) that 7.0g belongs to the hydroxyl monoamine is pre-mixed the amine aqueous solution that forms, and under 40 ℃, carries out 4 hours transfer reaction, thus synthetic multifunctional urethane-urea resin and prepare resin solution.The resin concentration of this resin solution (solids component) is 30%, and viscosity (25 ℃) is 90mPas.
Through the number-average molecular weight (Mn) of the multifunctional urethane-urea resin of GPC (GPC) mensuration gained, the result is 15000.The condition determination here is following.
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: contain the N of 0.1%LiBr, dinethylformamide (DMF)
Detector: differential refractometer
Sample: 0.1%LiBr/DMF solution
Working curve: polyoxyethylene glycol
In addition, through measure the hydroxy radical content (c) of this multifunctional urethane-urea resin according to the method for JIS K 1557, the result is 0.375mmol/g.
The functionality (f) that obtains this multifunctional urethane-urea resin thus is 5.6.
(3) preparation of paint base composition:
Multifunctional urethane-urea resin the solution that obtains in 100 mass parts above-mentioned (2), 30 mass parts propylene glycol methyl ether acetates (PMA), 128 mass parts toluene and 128 mass parts isopropylcarbinols are mixed to mixing, and are the paint base composition of the present invention of 7.8 quality % thereby prepare resin concentration.
< embodiment 2 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 147g toluene and 485g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 364gIPA, 16.9g beta-aminoethyl thanomin and 7.0g diethylolamine; In addition, likewise carry out transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution with embodiment 1 (2).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 this multifunctional urethane-urea resin thus is 8.5.
Then, except using the multifunctional urethane of gained-the urea resin solution, likewise prepare the paint base composition of the present invention that resin concentration is 7.8 quality % with embodiment 1 (3).
< embodiment 3 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 146g toluene and 484g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 363gIPA, 17.8g beta-aminoethyl thanomin and 5.2g diethylolamine; In addition, likewise carry out transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution with embodiment 1 (2).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 this multifunctional urethane-urea resin thus is 10.4.
Then, except using the multifunctional urethane of gained-the urea resin solution, likewise prepare the paint base composition of the present invention that resin concentration is 7.8 quality % with embodiment 1 (3).
< embodiment 4 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 146g toluene and 484g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 363gIPA, 18.3g beta-aminoethyl thanomin and 4.2g diethylolamine; In addition, likewise carry out transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution with embodiment 1 (2).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 this multifunctional urethane-urea resin thus is 12.3.
Then, except using the multifunctional urethane of gained-the urea resin solution, likewise prepare the paint base composition of the present invention that resin concentration is 7.8 quality % with embodiment 1 (3).
< embodiment 5 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 146g toluene and 483g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 363gIPA, 18.6g beta-aminoethyl thanomin and 3.5g diethylolamine; In addition, likewise carry out transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution with embodiment 1 (2).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 this multifunctional urethane-urea resin thus is 14.1.
Then, except using the multifunctional urethane of gained-the urea resin solution, likewise prepare the paint base composition of the present invention that resin concentration is 7.8 quality % with embodiment 1 (3).
< embodiment 6 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 145g toluene and 483g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 362gIPA, 18.9g beta-aminoethyl thanomin and 3.0g diethylolamine; In addition, likewise carry out transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution with embodiment 1 (2).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 this multifunctional urethane-urea resin thus is 16.9.
Then, except using the multifunctional urethane of gained-the urea resin solution, likewise prepare the paint base composition of the present invention that resin concentration is 7.8 quality % with embodiment 1 (3).
<buy and execute example 7 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 145g toluene and 483g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 362gIPA, 19.0g beta-aminoethyl thanomin and 2.6g diethylolamine; In addition, likewise carry out transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution with embodiment 1 (2).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 this multifunctional urethane-urea resin thus is 18.3.
Then, except using the multifunctional urethane of gained-the urea resin solution, likewise prepare the paint base composition of the present invention that resin concentration is 7.8 quality % with embodiment 1 (3).
< embodiment 8 >
Except using 419g by the 3-methyl isophthalic acid; The polyester glycol of the reaction of 5-pentanediol (low molecular polylol with side chain) and hexanodioic acid and the number-average molecular weight 2045 that obtains (below be called " polyester (2) ") replaces polyester (1) in addition, likewise obtains the terminal polyurethane prepolymer solution of NCO with embodiment 1 (1).The NCO content of this prepolymer is 2.30%.
In the terminal polyurethane prepolymer solution of the NCO that so obtains, add 146g toluene and 484g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 363g IPA, 17.8g beta-aminoethyl thanomin and 5.2g diethylolamine; In addition, likewise carry out transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution with embodiment 1 (2).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 this multifunctional urethane-urea resin thus is 10.4.
Then, except using the multifunctional urethane of gained-the urea resin solution, likewise prepare the paint base composition of the present invention that resin concentration is 7.8 quality % with embodiment 1 (3).
< comparative example 1 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 153g toluene and 494g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 373gIPA, 28.2g IPDA and 4.8g diethylamine; In addition, likewise 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 this polyurethane-urea resin thus is 0.
Then, except using gained polyurethane-urea resin solution, likewise prepare the paint base composition that resin concentration is the relatively usefulness of 7.8 quality % with embodiment 1 (3).
< comparative example 2 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 153g toluene and 493g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 370gIPA, 28.2g IPDA and 4.0g monoethanolamine; In addition, likewise 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 this polyurethane-urea resin thus is 1.8.
Then, except using gained polyurethane-urea resin solution, likewise prepare the paint base composition that resin concentration is the relatively usefulness of 7.8 quality % with embodiment 1 (3).
< comparative example 3 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 155g toluene and 496g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 372g IPA, 28.2g IPDA and 7.0g diethylolamine; In addition, likewise 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 this polyurethane-urea resin thus is 3.8.
Then, except using gained polyurethane-urea resin solution, likewise prepare the paint base composition that resin concentration is the relatively usefulness of 7.8 quality % with embodiment 1 (3).
< comparative example 4 >
In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 1 (1), add 145g toluene and 483g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 362g IPA, 19.3g beta-aminoethyl thanomin and 2.1g diethylolamine; In addition, likewise carry out transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution with embodiment 1 (2).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 this multifunctional urethane-urea resin thus is 22.9.
Then, except using the multifunctional urethane of gained-the urea resin solution, likewise prepare the paint base composition that resin concentration is the relatively usefulness of 7.8 quality % with embodiment 1 (3).
Resin concentration summary in the number-average molecular weight of the viscosity of the solids component (resin concentration) of the prescription (unit be " g ") of embodiment 1～8 and comparative example 1～4, resin solution, resin solution, polyurethane-urea resin, hydroxy radical content, functionality, the paint base composition is shown in below table 1.
[table 1]
(1) cementability (normality adaptation):
Use each paint base composition that obtains in embodiment 1～8 and the comparative example 1～4, estimate cementability (normality adaptation) as follows.
Here, the stratum basale of coating forms with resin combination through interpolation 20 mass parts titanium oxide and 230 mass parts toluene in 100 mass parts acrylicss " ACRYDIC A-801-P " (DIC (strain) manufacturing), in dispersion machine, prepared in mixing 10 minutes on the filming of paint base composition.
In addition, finishing coat formation (NCO/OH=1) prepares with 110 mass parts toluene, even stirring at normal temperatures through interpolation 18 mass parts polyisocyanate curing agents " CORONATE HX " (Japanese polyurethane industry (strain) is made) in 100 mass parts acrylicss " ACRYDIC A-801-P " (DIC (strain) manufacturing) with resin combination.
With methyl alcohol sufficient skimming treatment is carried out on the surface of the adherend that is made up of 6-nylon " Nylon 1022B " (the emerging product of space portion (strain) manufacturing), dry at normal temperatures.
Through aerial spraying primer compsn, 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 last formation of the dry coating that forms by paint base composition (prime coat) through aerial spraying coated base bottom, dry 10 minutes at normal temperatures, thus the dry coating of stratification thickness 10 μ m.
Then, go up to form through aerial spraying coated face coating and use resin combination being formed the dry coating (stratum basale) that forms with resin combination by stratum basale, drying is 10 minutes at normal temperatures, thus the dry coating (finishing coat) of stratification thickness 30 μ m.
Then, in 80 ℃ drying machine, carry out 30 minutes heat treated, after this, under the environment of 20 ℃ of temperature, relative humidity 65%, carry out 48 hours slaking.
For each test film that so obtains (stratification has the adherend of prime coat, stratum basale and finishing coat), on the formation face of filming, form the cut of 1mm quadrate chessboard grid (10 * 10), carry out stripping test based on adhesive tape, measure residual grid number.
In addition,, make 3 test films respectively, obtain the MV of the residual grid number of 3 test films for embodiment 1～8 and comparative example 1～4.The result is shown in below table 2.
(2) the required curing time:
Use each paint base composition that obtains in embodiment 1～8 and the comparative example 1～4, the following curing time of measuring till the performance solvent resistance.
Here, adherend, stratum basale form that to form formation with resin combination, paint base composition, stratum basale formation with resin combination and finishing coat same 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) with resin combination and finishing coat formation.
The coating of likewise carrying out paint base composition with the evaluation of above-mentioned (1) cementability forms coating and drying with resin combination with dry, stratum basale formation with coating and drying, the finishing coat of resin combination; Implement heat treated, make different test film of curing time (stratification has the adherend of prime coat, stratum basale and finishing coat) then.
In addition; For embodiment 1～8 and comparative example 1～4; Make 3 test films (embodiment: 8 * 7 * 3=168, comparative example: 4 * 7 * 3=84) down in each curing time (3 hours, 6 hours, 12 hours, 24 hours, 48 hours, 72 hours, 120 hours) respectively.
At first; For embodiment 1～8 and comparative example 1～4; Each test film that will obtain through 3 hours slaking respectively (12 * 3=36) is immersed in gasoline: in the mixed solvent (20 ℃) of ethanol=9: 1; Mensuration arrives the time (time of immersion) till the inboard more than the 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 likewise estimating through 6 hours respectively.As a result, in embodiment 2～8,3 test films are all qualified (to be estimated: ◎) (curing time shows sufficient solvent resistance when being 6 hours), thereby finish the test to embodiment 2～8.
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 likewise estimating through 12 hours respectively.As a result, in embodiment 1,3 all qualified (evaluations: ◎), thereby finish test of test film to embodiment 1.
Then, for comparative example 1～4, respectively with the above-mentioned solvent resistance of likewise estimating each test film that obtains through the slaking more than 24 hours.
Above result is shown in below table 2.
[table 2]
Shown in above-mentioned table 2,, can form the sufficient cementability of prime coat bring into play to(for) the adherend that constitutes by the nylon that is considered to difficult cementability according to the paint base composition of embodiment 1～8, the especially paint base composition of embodiment 1～6.
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 (to the erosion resistance of gasoline) that also can form of curing time with the mixed solvent of alcohol.
Relative therewith, even the slaking that the functionality of resinous principle is the paint base composition of 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 the terminal polyurethane prepolymer solution of NCO:
According to the prescription shown in the below table 3; In the reaction unit of the capacity 2000mL that stirrer, TM, Allihn condenser, nitrogen ingress pipe are housed, add 708.0g polyester (1) and the 216.0g MEK as organic solvent (B1), under 45 ℃, stirring prepares the solution of macromolecule polyol.
In this macromolecular multi-component alcoholic solution, add 153.8g IPDI and 0.08gDOTDL, under nitrogen gas stream,, thereby obtain the terminal polyurethane prepolymer solution of NCO in 75 ℃ of reactions 3 hours.The NCO content of this prepolymer is 2.70%.
(2) preparation of multifunctional urethane-urea resin solution:
According to the prescription shown in the below table 3; In this pre-polymer solution, add 356.0gMEK; Stir, then the liquid temperature is cooled to 30 ℃, add that 28.5g IPDA, 11.5g A-EA (hydroxyl diamines), 11.9g DEA (hydroxyl monoamine) and 342.0gMEK are pre-mixed the amine aqueous solution that forms; Under 40 ℃, carry out 4 hours transfer reaction, thereby synthesize multifunctional urethane-urea resin and prepare resin solution.The solids component of this resin solution is 50%, and viscosity (25 ℃) is 3800mPas.
Through the number-average molecular weight (Mn) of the multifunctional urethane-urea resin of GPC (GPC) mensuration gained, the result is 15000.
In addition, through measure the hydroxy radical content (c) of this multifunctional urethane-urea resin according to the method for JIS K1557, the result is 0.375mmol/g.
The functionality (f) that obtains this multifunctional urethane-urea resin thus is 5.6.
(3) preparation of paint base composition:
According to the prescription shown in the below table 3; Multifunctional urethane-urea resin the solution that obtains in 100.0 mass parts above-mentioned (2), 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 PMA, 513.0 mass parts of aliphatics series solvent (B2), are the paint base composition of the present invention of 7.8 quality % thereby prepare resin concentration.The ratio that constitutes 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 prescription shown in the below table 3; In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 9 (1), add 356.0g MEK; Stir, add that A-EA, DEA and MEK are pre-mixed each amine aqueous solution that forms, in addition; Likewise 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 functionality (f) summary of the viscosity (25 ℃) of each resin solution of gained, multifunctional urethane-urea resin are shown in below table 3.
Then; According to the prescription shown in the below table 3; With 100.0 each resin solution 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 summary of the aliphatics series solvent (B2) in the organic solvent (B) that constitutes each paint base composition of gained is shown in below table 3.
< embodiment 19 >
According to the prescription shown in the below table 3; In the terminal polyurethane prepolymer solution of the NCO that likewise obtains with embodiment 9 (1), add 356.0g MEK; Stir, add that 32.1g A-EA, 4.4g DEA and 327.0g MEK are pre-mixed each amine aqueous solution that forms, in addition; Likewise 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 this multifunctional urethane-urea resin thus is 18.3.
Then; According to the prescription shown in the below table 3; With 100.0 mass parts gained resin solutions, 59.3 mass parts aromatic hydrocarbon solvents " Solvesso 100 " (Exxon Chemical Co.; Ltd. make) mix to mixing with the mixed solvent of 483.7 mass parts toluene/MEK/IPA, be the paint base composition of the present invention of 7.8 quality % thereby prepare resin concentration.
< embodiment 20 >
According to the prescription shown in the below table 3, use 708.0g polyester (2) to replace polyester (1), in addition, likewise obtain the terminal polyurethane prepolymer solution of NCO with embodiment 9 (1); In the terminal polyurethane prepolymer solution of gained NCO, add 356.0g MEK; Stir; Interpolation is pre-mixed the amine aqueous solution that forms with 30.1g A-EA, 8.8g DEA and 329.0g MEK; In addition, likewise 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 this multifunctional urethane-urea resin thus is 10.4.
Then; According to the prescription shown in the below 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 99 MIN dioctyl tins
(※ 3) IPDA: isophorone diamine
(※ 4) A-EA: beta-aminoethyl thanomin (hydroxyl diamines)
(※ 5) DEA: diethylolamine (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 to obtaining among the embodiment 9～20 is estimated following project.Evaluation result is shown in below table 4.
(1) the Air drying property of primer coating film:
With methyl alcohol sufficient skimming treatment is carried out on the surface of the adherend that is made up of 6-nylon " Nylon 1022B " (the emerging product of space portion (strain) manufacturing), dry at normal temperatures.
On the surface of this adherend, through aerial spraying primer compsn, form filming of thickness 7 μ m, it is dry down at normal temperature (25 ℃) that this is filmed, and measures the time (not sticking time) till the viscosity that no longer can confirm 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 through above-mentioned (1) in the formation of the surface of adherend according to JIS Z8741.This glossiness is high more, and the leveling characteristics 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 up of 6-nylon " Nylon 1022B " (the emerging product of space portion (strain) manufacturing), dry at normal temperatures.
Through aerial spraying primer compsn, 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 form by paint base composition last formation through aerial spraying coated base bottom, dry 10 minutes at normal temperatures, thus the dry coating of stratification thickness 10 μ m.
Then, go up to form through aerial spraying coated face coating and use resin combination being formed the dry coating (stratum basale) that forms with resin combination by stratum basale, drying is 10 minutes at normal temperatures, thus the dry coating (finishing coat) of stratification thickness 30 μ m.
Then, in 80 ℃ drying machine, carry out 30 minutes heat treated, after this, under the environment of 20 ℃ of temperature, relative humidity 65%, carry out 48 hours slaking.
For the test film that so obtains (stratification has the adherend of prime coat, stratum basale and finishing coat), on the formation face of filming, form the cut of 1mm quadrate chessboard grid (10 * 10), carry out stripping test based on adhesive tape, measure residual grid number.
In addition,, make 3 test films respectively, obtain the MV of the residual grid number of 3 test films for embodiment 9～20.
(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) likewise make: in the mixed solvent (20 ℃) of ethanol=9: 1, measure the time (time of immersion) that arrives from the floating of filming of producing of the edge of test film (peeling off) from the edge till the inboard more than the 2mm.
In addition, in above-mentioned (1), for the sticking time be the 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:
The test film (stratification has the adherend of prime coat, stratum basale and finishing coat) that will likewise obtain with above-mentioned (3) is after the environment held of 50 ℃ of temperature, relative humidity 90% 240 hours; On the formation face of filming, form the cut of 1mm quadrate chessboard grid (10 * 10); Carry out stripping test, measure residual grid number based on adhesive tape.
In addition, in above-mentioned (1), for the sticking time be the 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,, make 3 test films respectively, obtain the MV of the residual grid number in 3 test films for embodiment 9～20.
[table 4]
Shown in above-mentioned table 4,, can form the prime coat of the adherend that is made up of nylon being brought into play abundant cementability according to the paint base composition of embodiment 9～20.
In addition, according to the paint base composition of embodiment 9～20, can form the excellent prime coat of solvent resistance.
According to the paint base composition of embodiment 9～14,16,18,20, can form good the filming of leveling characteristics, can form the prime coat that solvent resistance is excellent especially, humidity resistance is also excellent.
In addition, according to the paint base composition of embodiment 9～14,15,17,19, can form the excellent primer coating film of drying property.
Claims (10)
1. a paint base composition is characterized in that, it contains multifunctional urethane-urea resin (A) and organic solvent (B),
Said multifunctional urethane-urea resin (A) be through 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 up of the hydroxyl diamines obtain; It has the hydroxyl that derives from said 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 said multifunctional urethane-urea resin (A) is 8.5～18.5.
3. according to claim 1 or the described paint base composition of claim 2, it is characterized in that said macromolecule polyol is the amorphism polyvalent alcohol.
4. paint base composition according to claim 3 is characterized in that, said 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 said multifunctional urethane-urea resin (A) is made up of the hydroxyl monoamine by (A4).
6. paint base composition according to claim 5; It is characterized in that; Said multifunctional urethane-urea resin (A) obtains as follows: said organic multiple isocyanate and said macromolecule polyol are reacted prepare the terminal polyurethane prepolymer of NCO, make terminal polyurethane prepolymer of gained NCO and said hydroxyl diamines and the reaction of said hydroxyl monoamine.
7. paint base composition according to claim 1 is characterized in that, the concentration of said multifunctional urethane-urea resin (A) is 5～15 quality %,
Said organic solvent (B) is lower than the aliphatics series solvent (B2) that 130 ℃ organic solvent (B1) and boiling point be 130～180 ℃ by boiling point and constitutes, (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, said primer layer composition is used to form and is coated with above that with the POLYMETHYLENE POLYPHENYLISOCYANATE is the prime coat of the resin combination of solidifying agent.
9. paint base composition according to claim 1, it is to be the paint base composition of the two-pack solidified nature of curing agent component with the POLYMETHYLENE POLYPHENYLISOCYANATE.
10. paint base composition according to claim 1, it is coated on the adherend through 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 |
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| CN102317389A true CN102317389A (en) | 2012-01-11 |
| CN102317389B CN102317389B (en) | 2013-11-06 |
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| CN2010800079206A Active CN102317389B (en) | 2009-02-25 | 2010-02-10 | Primer composition |
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| JP (1) | JP5585849B2 (en) |
| CN (1) | CN102317389B (en) |
| WO (1) | WO2010098210A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617364A (en) * | 2012-03-15 | 2012-08-01 | 南京工业大学 | Hydroxymethyl diamine compound and preparation method and application thereof |
| CN105606768A (en) * | 2015-12-28 | 2016-05-25 | 上海维凯光电新材料有限公司 | Test liquid and test pen for detecting solvent-resistant performance of aluminum plating transferring paint |
| CN108137951A (en) * | 2015-07-31 | 2018-06-08 | 巴斯夫欧洲公司 | It is used to form the paint base composition of the coloring of N- acylureas coatings |
| CN116622046A (en) * | 2023-07-19 | 2023-08-22 | 四川大学 | Post-crosslinkable high molecular weight polyurethane and preparation method thereof |
Families Citing this family (2)
| 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 |
| JP7099074B2 (en) * | 2018-06-20 | 2022-07-12 | Dic株式会社 | Method for manufacturing urethane resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11152322A (en) * | 1997-11-20 | 1999-06-08 | Toyobo Co Ltd | Production of polyurethaneurea resin |
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62129361A (en) * | 1985-11-29 | 1987-06-11 | Sanyo Chem Ind Ltd | Primer for molded article |
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11152322A (en) * | 1997-11-20 | 1999-06-08 | Toyobo Co Ltd | Production of polyurethaneurea resin |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617364A (en) * | 2012-03-15 | 2012-08-01 | 南京工业大学 | Hydroxymethyl diamine compound and preparation method and application thereof |
| CN102617364B (en) * | 2012-03-15 | 2014-04-23 | 南京工业大学 | Hydroxymethyl diamine compound and preparation method and application thereof |
| CN108137951A (en) * | 2015-07-31 | 2018-06-08 | 巴斯夫欧洲公司 | It is used to form the paint base composition of the coloring of N- acylureas coatings |
| CN108137951B (en) * | 2015-07-31 | 2020-10-20 | 巴斯夫欧洲公司 | Pigmented primer composition for forming N-acylurea coatings |
| CN105606768A (en) * | 2015-12-28 | 2016-05-25 | 上海维凯光电新材料有限公司 | Test liquid and test pen for detecting solvent-resistant performance of aluminum plating transferring paint |
| CN116622046A (en) * | 2023-07-19 | 2023-08-22 | 四川大学 | Post-crosslinkable high molecular weight polyurethane and preparation method thereof |
| CN116622046B (en) * | 2023-07-19 | 2023-09-26 | 四川大学 | Post-crosslinkable high molecular weight polyurethane and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| CN102317389B (en) | 2013-11-06 |
| JPWO2010098210A1 (en) | 2012-08-30 |
| WO2010098210A1 (en) | 2010-09-02 |
| JP5585849B2 (en) | 2014-09-10 |
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