CN104130686B - Polyisocyantates composition and coating composition - Google Patents
Polyisocyantates composition and coating composition Download PDFInfo
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- CN104130686B CN104130686B CN201410171282.1A CN201410171282A CN104130686B CN 104130686 B CN104130686 B CN 104130686B CN 201410171282 A CN201410171282 A CN 201410171282A CN 104130686 B CN104130686 B CN 104130686B
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- XEFDXVWNHLICRX-UHFFFAOYSA-N CN(C(N1C)=O)C1=O Chemical compound CN(C(N1C)=O)C1=O XEFDXVWNHLICRX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention, which is provided, can make the polyisocyantates composition and coating composition of adaptation, acutance, surface smoothness, gloss and the film having excellent weather resistance.A kind of polyisocyantates composition, it is at least to use 1, polyisocyantates composition obtained from 6 two isocyanato- hexanes, the polyisocyantates composition has isocyanurate structure, and it is being obtained using thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument, at 210 DEG C heat 5 hours after weight conservation rate be 90.0~99.0%, it is being obtained using thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument, at 240 DEG C heat 5 hours after weight conservation rate be 80.0~88.0%.
Description
Technical field
The present invention relates to polyisocyantates composition and coating composition.
Background technology
All the time, by the isocyanato- hexane (HDI of 1,6- bis-；Also referred to as hexamethylene diisocyanate) obtain,
Polyisocyantates composition with isocyanurate structure is used (such as patent document 1~3) as the material of coating etc..
Prior art literature
Patent document
Patent document 1：Japanese Patent Publication 45-027982 publications
Patent document 2：Japanese Unexamined Patent Application 55-038380 publications
Patent document 3：Japanese Unexamined Patent Application 57-150677 publications
The content of the invention
Problems to be solved by the invention
But, the existing polyisocyantates composition described in the grade of patent document 1~3 be difficult to make adaptation, acutance,
Surface smoothness, gloss and weatherability excellent film, still having sufficiently improves leeway.
The present invention makes in view of the foregoing, its object is to provide can make adaptation, acutance, surface put down
The polyisocyantates composition of slip, gloss and the film having excellent weather resistance.
The solution used to solve the problem
Present inventor has performed further investigation, as a result find, by using at least use the isocyanato- hexanes of 1,6- bis-
Obtained from, with isocyanurate structure and with specific weight conservation rate polyisocyantates composition, can reach
Above-mentioned problem, so as to complete the present invention.
That is, the present invention is as follows.
[1]
A kind of polyisocyantates composition, it is at least to use polyisocyanic acid obtained from the isocyanato- hexanes of 1,6- bis-
Ester composition,
The polyisocyantates composition has isocyanurate structure, also,
It is being obtained using thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument, at 210 DEG C heat 5 hours after weight keep
Rate be 90.0~99.0%, it is being obtained using thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument, at 240 DEG C heat 5 hours after
Weight conservation rate be 80.0~88.0%.
[2]
Polyisocyantates composition according to [1], it also has iminooxadiazinedionepolyisocyanates diketone structure.
[3]
Polyisocyantates composition according to [2], wherein, utilize13C-NMR is determined, iminooxadiazinedionepolyisocyanates diketone
The mol ratio of structure/isocyanurate structure is 6.0/100~25/100.
[4]
Polyisocyantates composition according to any one of [1]~[3], it also has urea diketone structure, utilizes13C-
Mol ratio that NMR is determined, urea diketone structure/isocyanurate structure is 0.1/100~5.0/100.
[5]
Polyisocyantates composition according to any one of [1]~[4], it also has allophanic acid ester structure, profit
With13Mol ratio that C-NMR is determined, allophanic acid ester structure/isocyanurate structure is 0.1/100~4.0/100.
[6]
A kind of coating composition, it contains：
(a) glycol composition, the glycol composition contains acrylic polyol or PEPA, and hydroxyl value is
50~250mgKOH/g, glass transition temperature Tg is 0~80 DEG C, and number-average molecular weight is 500~10000；And,
(b) polyisocyantates composition any one of [1]~[5],
NCO in foregoing (b) composition is that NCO/OH is relative to the mol ratio of the hydroxyl in foregoing (a) composition
0.6~1.5.
The effect of invention
According to the present invention it is possible to which adaptation, acutance, surface smoothness, gloss can be made and have excellent weather resistance by providing
Film polyisocyantates composition.
Embodiment
Hereinafter, to being described in detail for implementing embodiments of the present invention (hereinafter referred to as " present embodiment ").
Following present embodiment is the illustration for illustrating the present invention, is not meant to limit the invention to following content.This
Invention suitably can deform to implement in the range of its main idea.It should be noted that in the case of no special declaration,
" (methyl) acrylic acid " includes methacrylic acid and acrylic acid, and " (methyl) acrylate " includes methacrylate and acrylic acid
Ester.
The polyisocyantates composition of present embodiment is at least using many obtained from the isocyanato- hexanes of 1,6- bis-
Isocyanate composition, the polyisocyantates composition has isocyanurate structure, and uses thermogravimetric and differential scanning
It is that calorimetric Simultaneous Determination instrument is obtained, at 210 DEG C heat 5 hours after weight conservation rate be 90.0~99.0%, use thermogravimetric
And means of differential scanning calorimetry Simultaneous Determination instrument obtain, heated 5 hours at 240 DEG C after weight conservation rate for 80.0~
88.0%.By using the polyisocyantates composition, adaptation, acutance, surface smoothness, gloss and resistance to can be made
The excellent film of time property.
Polyisocyantates composition is made by least using the isocyanato- hexanes of 1,6- bis-, can make to be obtained by it
Film turn into low, the soft and tough film of viscosity.
The polyisocyantates composition of present embodiment contains isocyanurate structure.By containing isocyanuric acid ester knot
Structure, can obtain the polyisocyantates composition of excellent heat resistance.Isocyanurate structure is the structure shown in formula (1).
[chemical formula 1]
Present embodiment it is polyisocyantates composition, obtained using thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument
, at 210 DEG C heat 5 hours after weight conservation rate be 90.0~99.0%.The lower limit of the weight conservation rate is preferably
More than 92.0%, it is more preferably more than 94.0%.The higher limit of the weight conservation rate is preferably less than 97.0%, is more preferably
Less than 96.0%.When the weight conservation rate is more than above-mentioned lower limit, the gloss and weatherability of film are above-mentioned higher limit fully
When following, the surface smoothness of film is good.
Present embodiment it is polyisocyantates composition, obtained using thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument
, at 240 DEG C heat 5 hours after weight conservation rate be 80.0~88.0%.The lower limit of the weight conservation rate is preferably
More than 82.0%, it is more preferably more than 83.0%.The higher limit of the weight conservation rate is preferably less than 86.0%, is more preferably
Less than 85.0%.When the weight conservation rate is more than above-mentioned lower limit, the gloss and weatherability of film are above-mentioned higher limit fully
When following, film is good to the adaptation of base material.
It is above-mentioned at 210 DEG C heat 5 hours after weight conservation rate and at 240 DEG C heat 5 hours after weight keep
Rate can be obtained according to the method described in aftermentioned embodiment.The weight conservation rate after being heated 5 hours at 210 DEG C and
Weight conservation rate after being heated 5 hours at 240 DEG C for example can be by controlling the structure of polyisocyantates composition to control.Example
Such as, the polyisocyantates composition of present embodiment contains isocyanurate structure, but is also fitted in addition to isocyanurate structure
Locality is containing iminooxadiazinedionepolyisocyanates diketone structure, urea diketone structure, allophanic acid ester structure etc., by controlling containing for they
Rate, can also control it is above-mentioned at 210 DEG C heat 5 hours after weight conservation rate, at 240 DEG C heat 5 hours after weight
Conservation rate.And then, except isocyanurate structure, iminooxadiazinedionepolyisocyanates diketone structure, urea diketone structure, allophanic acid ester structure with
Outside, can also be suitably further sub- containing carbamate structures, biuret structure, urea structure, uretonimine structure, carbon two
Amine structure etc., by controlling their containing ratio together, after also can more efficiently controlling the above-mentioned heating at 210 DEG C 5 hours
Weight conservation rate, at 240 DEG C heat 5 hours after weight conservation rate (still, the effect of present embodiment is not limited to this
A bit).
For the polyisocyantates composition of present embodiment, from viewpoints such as viscosity adjustment, preferably also there is Asia
An Ji oxadiazine structures., can be by the viscosity of polyisocyantates composition by with iminooxadiazinedionepolyisocyanates diketone structure
Suppress low.Thus, the compatibility with polyalcohol is improved, as a result, the acutance, surface smoothness and gloss when film is made are excellent
It is different.And then, the adaptation with various base materials is also excellent.Iminooxadiazinedionepolyisocyanates diketone structure is the structure shown in formula (2).
[chemical formula 2]
For the polyisocyantates composition of present embodiment, from the viewpoint of viscosity adjustment, preferably also contain urea
Diketone structure.By the way that acutance and the excellent film of surface smoothness can be obtained with urea diketone structure, when film is made.Urea two
Ketone structure is the structure shown in formula (3).
[chemical formula 3]
In addition, for the polyisocyantates composition of present embodiment, from the viewpoint of viscosity adjustment, preferably having
Allophanic acid ester structure.It is smooth by with allophanic acid ester structure, can further improve acutance when film is made, surface
Property.Allophanic acid ester structure is the structure shown in formula (4).
[chemical formula 4]
On each structural ratio in the polyisocyantates composition of present embodiment, it is not particularly limited, for example, imido
The mol ratio of Ji oxadiazines structure/isocyanurate structure is preferably 6.0/100~25/100.In addition, urea diketone structure/
The mol ratio of isocyanurate structure is preferably 0.1/100~5.0/100.And then, allophanic acid ester structure/isocyanuric acid ester knot
The mol ratio of structure is preferably 0.1/100~4.0/100.Also it is preferred that (urea diketone structure+allophanic acid ester structure)/different
The mol ratio of cyanurate structure is 0.2/100~8.0/100 etc..
In addition, as combinations thereof, for example, it is preferable that, iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure
Mol ratio be that the mol ratio of 6.0/100~25/100, urea diketone structure/isocyanurate structure is 0.1/100~5.0/
100th, the mol ratio of allophanic acid ester structure/isocyanurate structure is 0.1/100~4.0/100.
As described above, the mol ratio of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure be preferably 6.0/100~
25/100.The lower limit of the mol ratio of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure be more preferably 7.0/100 with
Above, it is more preferably more than 8.5/100, is still more preferably more than 10/100.Iminooxadiazinedionepolyisocyanates diketone structure/isocyanide
The higher limit of the mol ratio of urea acrylate structure is more preferably less than 20/100, more preferably less than 17/100, further
Preferably less than 15/100.The mol ratio of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure is more than above-mentioned lower limit
When, improved with the compatibility of polyalcohol, as a result, acutance, surface smoothness and excellent gloss when film is made.And then,
Adaptation with various base materials is also excellent.The mol ratio of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure is on above-mentioned
When below limit value, gloss and weatherability, the excellent heat resistance of film.
As described above, the mol ratio of urea diketone structure/isocyanurate structure is preferably 0.1/100~5.0/100.Urea two
The lower limit of the mol ratio of ketone structure/isocyanurate structure is more preferably more than 0.2/100, more preferably 0.5/100
More than.The higher limit of the mol ratio of urea diketone structure/isocyanurate structure is more preferably less than 3.0/100, further preferably
For less than 2.0/100.When the mol ratio of urea diketone structure/isocyanurate structure is more than above-mentioned lower limit, it can suppress many
The high viscosity of isocyanate composition, the acutance, flatness when being made film is more excellent.Urea diketone structure/isocyanuric acid
When the mol ratio of ester structure is below above-mentioned higher limit, the heat resistance and weatherability of polyisocyantates composition are more excellent.
As described above, the mol ratio of allophanic acid ester structure/isocyanurate structure is preferably 0.1/100~4.0/100.
The lower limit of the mol ratio of allophanic acid ester structure/isocyanurate structure is more preferably more than 0.2/100, is more preferably
More than 0.5/100.The higher limit of the mol ratio of allophanic acid ester structure/isocyanurate structure is more preferably less than 3.0/100,
More preferably less than 2.0/100.The mol ratio of allophanic acid ester structure/isocyanurate structure is more than above-mentioned lower limit
When, the viscosity of polyisocyantates composition can be further reduced, acutance and flatness can be further improved.Allophanate
When the mol ratio of structure/isocyanurate structure is below above-mentioned higher limit, polyisocyantates composition can be further improved
Heat resistance and weatherability.
The mol ratio of (urea diketone structure+allophanic acid ester structure)/isocyanurate structure is preferably 0.2/100~8.0/
100.The lower limit of the mol ratio of (urea diketone structure+allophanic acid ester structure)/isocyanurate structure is more preferably 0.3/100
Above, more preferably more than 0.6/100.Mole of (urea diketone structure+allophanic acid ester structure)/isocyanurate structure
The higher limit of ratio is more preferably less than 6.0/100, more preferably less than 4.0/100.(urea diketone structure+allophanate
Structure)/isocyanurate structure mol ratio to be more than above-mentioned lower limit when, the viscous of polyisocyantates composition can be reduced
Degree, can further improve acutance and flatness.(urea diketone structure+allophanic acid ester structure)/isocyanurate structure rubs
When you are than for below above-mentioned higher limit, the heat resistance and weatherability of polyisocyantates composition are more excellent.
Polyisocyantates composition contains above-mentioned isocyanurate structure, iminooxadiazinedionepolyisocyanates diketone structure, urea diketone knot
The situation of structure, allophanic acid ester structure etc. can pass through13C-NMR determines to confirm.Specifically, it can remember according in embodiment
The method of load is determined.
The quality of 1,6- bis- isocyanato- hexane (HDI) monomer in the polyisocyantates composition of present embodiment is dense
Degree (HDI monomer concentrations) is preferably below 1 mass %, is more preferably below 0.7 mass %, more preferably 0.5 mass %
Below.By the way that HDI monomer concentrations are set to below above-mentioned higher limit, danger during processing, and energy can be further reduced
Enough curability further improved when coating composition is made.
The containing ratio (NCO containing ratios) of the NCO of the polyisocyantates composition of present embodiment it is non-volatile into
Divide preferably 19.0~24.0 mass % under conditions of more than 98 mass %.The lower limit of NCO containing ratios is more preferably 20.0 matter
Measure more than %, more preferably more than 21.0 mass %.The higher limit of NCO containing ratios is more preferably below 23.0 mass %,
More preferably below 22.5 mass %.When NCO containing ratios are more than above-mentioned lower limit, polyisocyanic acid can be further improved
The bridging property of ester composition.When NCO containing ratios are below above-mentioned higher limit, the HDI that can reduce polyisocyantates composition is mono-
Bulk concentration, can further reduce danger.It should be noted that NCO containing ratios can be by polyisocyantates composition
Obtained after the excessive 2N amine neutralization of NCO, by using the back titration of 1N hydrochloric acid.Nonvolatile component can be by inciting somebody to action
Surplus when polyisocyantates composition is heated 3 hours at 105 DEG C is obtained.
Nonvolatile component (quality %)=(quality of the polyisocyantates composition after being heated 3 hours at 105 DEG C)/
(quality of the polyisocyantates composition before heating) × 100
Viscosity at 25 DEG C of solid constituent in the polyisocyantates composition of present embodiment is in nonvolatile component 98
It is preferably 1000mPas~4000mPas under conditions of more than quality %.The lower limit of viscosity is more preferably 1500mPas
Above, more preferably more than 2000mPa.s.The higher limit of viscosity be more preferably below 3500mPas, further preferably
For below 3000mPas.By the way that polyisocyantates composition viscosity is set to more than above-mentioned lower limit, polyisocyanates combination
The yield of thing is further improved.By the way that the viscosity of polyisocyantates composition is set to below above-mentioned higher limit, obtained film
Gloss further improve.Viscosity can use E types viscosimeter (manufacture of TOKIMEC Co., Ltd.) to determine.
The number-average molecular weight of solid constituent in the polyisocyantates composition of present embodiment is in the matter of nonvolatile component 98
It is 550~800 under conditions of amount more than %.The lower limit of number-average molecular weight is more preferably more than 600, more preferably 630
More than.The higher limit of number-average molecular weight is more preferably less than 750, more preferably less than 700.By the way that number-average molecular weight is set
For more than 550, the yield of obtained polyisocyantates composition is further improved.When number-average molecular weight is less than 800, obtain
The gloss of film is further improved.Number-average molecular weight can be obtained by gel permeation chromatography (GPC).Specifically, can be with
Method according to described in embodiment is measured.
An example of the manufacture method of the polyisocyantates composition of present embodiment is illustrated below.
The raw material of the polyisocyantates composition of present embodiment at least uses the isocyanato- hexanes of 1,6- bis-.And then,
As auxiliary material, alcoholic compounds such as alkyl monocarbon alcohol, alkyl diol etc. can also be applied in combination, it is excellent during using alcoholic compound
Choosing be set to make the mol ratio of allophanic acid ester structure/isocyanurate structure in polyisocyantates composition for 0.1/100/~
4.0/100 scope amount.
Polymerization catalyst can be added in raw material 1, the isocyanato- hexanes of 6- bis-, above-mentioned auxiliary material, carry out reaction
Untill the degree of polymerization as defined in reaching, the unreacted isocyanato- hexanes of 1,6- bis- are then removed as needed, so as to obtain
Polyisocyantates composition.
As the specific example of polymerization catalyst, preferably 5/100~100/ is calculated as with the mass ratio of A compositions/B component
5 ratio includes following mixture of A compositions and B component etc..
A compositions：Any of following (1)~(5) composition.
(1) for example, the hydroxide or such as acetic acid, fourth of tetra-allkylammonium of the tetra-allkylammonium such as tetramethyl-ammonium, tetraethyl ammonium
The organic monoacid salt of acid, capric acid etc.；
(2) for example, tetramethyl hydroxypropyl ammonium, trimethyl hydroxyethylammonium ammonium, triethyl group hydroxypropyl ammonium, triethyl group hydroxyethyl ammonium etc.
The hydroxide of hydroxy alkyl ammonium or the organic monoacid salt such as acetic acid, butyric acid, capric acid of hydroxy alkyl ammonium；
(3) belong to acetic acid, capric acid, octanoic acid, myristic acid etc. it is alkyl carboxylate, such as with tin, zinc, lead, sodium, potassium
Metal salt；
(4) for example, the metal alcoholate of sodium, potassium etc.；
(5) for example, the compound containing amino silyl such as HMDS.
(B) composition：Any composition in following (6)~(7).
(6) formula M such as Methanaminium, N,N,N-trimethyl-, fluoride hydrate, tetraethyl ammonium fluoride [Fn] or formula M [Fn(HF)m] shown in
(in formula, m and n are to meet m/n to (poly-) hydrogen fluoride>The integer of 0 relation, M represents the cation (mixture) of n electric charges or amounts to n
More than 1 free radical of valency.)
(7) by the carboxylic acid fluorides of 3,3,3- tri-；The fluorine butyric acid of 4,4,4,3,3- five；The fluorine valeric acids of 5,5,5,4,4,3,3- seven；3,3- bis-
The general formula Rs such as fluorine propyl- 2- olefin(e) acids1-CR’2- C (O) O- or general formula R2=CR '-C (O) O- (in formula, R1As needed for branched,
The perfluoroalkyl of ring-type, and/or undersaturated carbon number 1~30, R2As needed for branched, ring-type, and/or undersaturated carbon
The perfluorinated alkylidene of number 1~30, R ' can be with group that is identical or different, being constituted from hydrogen atom, the alkyl of carbon number 1~20 and aryl
Middle selection, contains hetero atom as needed) and quaternary ammonium cation, the compound of Huo quaternary phosphines cation formation.
Among above-mentioned (A) composition, from the viewpoint of catalytic efficiency, preferably above-mentioned (1) and (2).Above-mentioned (B) composition is worked as
In, from the viewpoint of easiness is obtained, preferably above-mentioned (6) set out, preferably (7) from a security point.
On the consumption of the polymerization catalyst relative to the isocyanato- hexanes of 1,6- bis-, it is not particularly limited, preferably 5
~5000ppm.On the lower limit of the consumption of polymerization catalyst, from the viewpoint of reactivity, more preferably more than 10ppm,
More preferably more than 20ppm.It is suppression from coloring/discoloration of product, anti-on the higher limit of the consumption of polymerization catalyst
From the viewpoint of should controlling, more preferably below 2000ppm, more preferably below 500ppm.
Polymeric reaction temperature is not particularly limited, preferably 40~150 DEG C.On the lower limit of polymeric reaction temperature,
From the viewpoint of reaction speed, more preferably more than 50 DEG C, more preferably more than 60 DEG C.On polymeric reaction temperature
Higher limit, from the viewpoint of the suppression of coloring and the discoloration of product, more preferably less than 120 DEG C, more preferably 110 DEG C
Below.
Stop polymerisation at the time of polymerisation reaches the desired degree of polymerization.The stopping of polymerisation can be real as follows
It is existing：, will by adding the acid compound such as phosphoric acid, acid phosphoric acid ester, sulfuric acid, hydrochloric acid, sulfoacid compound into reaction solution
Polymerisation catalysts are neutralized；Or its deactivation is made by thermal decomposition, chemical breakdown etc..After reaction stops, if desired
It can be filtered.
Reaction solution after reaction just stops generally comprises unreacted HDI monomers, it is therefore preferable that it is steamed by film
Device, extraction etc. is sent out to remove.It is preferred that by carrying out this post processing by HDI monomer concentrations contained in polyisocyantates composition
Control is in below 1 mass %.The higher limit of HDI monomer concentrations is more preferably below 0.7 mass %, more preferably 0.5 matter
Measure below %, still more preferably for below 0.3 mass %, much further preferably from below 0.1 mass %.By making HDI mono-
Bulk concentration is that below above-mentioned higher limit, can further reduce the toxicity of polyisocyantates composition, it is possible to increase security.
The polyisocyantates composition of present embodiment can also suitably be used as curing agent of coating composition etc..That is,
The coating composition of the polyisocyantates composition containing present embodiment can be made.As the coating composition resin into
Point, preferably comprise compound of the intramolecular with more than 2 reactive hydrogens for possessing reactivity with NCO.It is used as intramolecular
Compound with more than 2 reactive hydrogens, for example, polyalcohol, polyamines, polythiol etc. can be enumerated.Wherein, preferred polyol.
As the specific example of polyalcohol, PEPA, PPG, acrylic polyol, polyolefin can be included polynary
Alcohol, fluorine-containing polyalcohol etc..
On the coating composition of the polyisocyantates composition using present embodiment, solvent substrate, water system substrate are equal
It can be used.
When the coating composition of solvent substrate is made, in the tree of the compound containing intramolecular with more than 2 reactive hydrogens
Other resins, catalyst, pigment, levelling agent, antioxidant, ultraviolet radiation absorption are added as needed in fat or its solvent dilution
The additives such as agent, light stabilizer, plasticizer, surfactant, obtain mixture, and present embodiment is added in the mixture
Polyisocyantates composition further adds solvent as needed as curing agent, adjusts viscosity, then stirred by using hand,
Or be stirred with mixing plants such as Mazelar, so as to obtain the coating composition of solvent substrate.
When the coating composition of water system substrate is made, in the tree of the compound containing intramolecular with more than 2 reactive hydrogens
Other resins are added as needed in the aqueous dispersion or the hydrotrope of fat, it is catalyst, pigment, levelling agent, antioxidant, ultraviolet
The additives such as light absorbers, light stabilizer, plasticizer, surfactant, obtain mixture, this implementation are added in the mixture
The polyisocyantates composition of mode further adds water, solvent, then set by using stirring as needed as curing agent
It is standby to carry out action of forced stirring, so as to obtain the coating composition of water system substrate.
PEPA for example can by make butanedioic acid, adipic acid, dimeric dibasic acid, maleic anhydride, phthalic anhydride,
The single substance or mixture and ethylene glycol of the binary acid such as the carboxylic acids such as phthalic acid, terephthalic acid (TPA), 1,4 cyclohexanedicarboxylic acid,
Propane diols, diethylene glycol, 1,4- butanediols, neopentyl glycol, 1,6-HD, TMPD, cyclohexanedimethanol, three hydroxyls
The single substance of the polyalcohols such as methylpropane, glycerine, pentaerythrite, 2- methylols propane diols, ethoxylated trimethylolpropane
Or mixture carries out condensation reaction and obtained.For example, mentioned component is mixed, then heated at about 160~220 DEG C,
Thus allow for condensation reaction.And then, for example, obtained from the lactones such as 6-caprolactone are carried out into ring-opening polymerisation with polyalcohol
Such poly caprolactone etc. is also used as PEPA.These PEPAs can use aromatic diisocyanates
Ester, aliphatic diisocyanate, alicyclic diisocyanate and the polyisocyanates that is obtained by them are modified.Now, especially
It is aliphatic diisocyanate, alicyclic diisocyanate and the polyisocyanates that is obtained by them is from weatherability and resistance to Huang
It is preferred from the viewpoint of denaturation etc..During as water system base coating, the part such as binary acid of part residual is carboxylic acid remained, leads to
Cross to be carried out neutralizing with alkali such as amine, ammonia and the resin of water-soluble or water dispersible can be made.
As PPG, for example, it can include：In the single substance or mixture of polyol, use example
Such as hydroxide (lithium, sodium, potassium), strong alkali catalyst (alcoholates, alkylamine etc.), composition metal cyanide complex (gold
Belong to porphyrin, hexacyanocobaltate acid zinc complex etc.) etc., make alkylene oxide (oxirane, expoxy propane, epoxy butane, 7-oxa-bicyclo[4.1.0,
Styryl oxide etc.) single substance or mixture and polyol carry out random addition or block addition, so as to obtain
Polyether polyols alcohols；Make polyamine compounds (ethylenediamines etc.) and alkylene oxide reacted obtained from polyether polyols alcohols；
And using these polyether polyols alcohols as medium by acrylamide etc. polymerize obtained from, so-called polymer polyol alcohols
Deng.
As above-mentioned polyol, it can include：(i) for example, two glycerine, two trimethylolpropanes, pentaerythrite,
Dipentaerythritol etc.；(ii) for example, antierythrite, D- threitols, L-arabinose alcohol, ribitol, xylitol, D-sorbite,
The sugar alcohol based compound such as mannitol, galactitol, rhamnitol；(iii) for example, arabinose, ribose, xylose, glucose, sweet
Reveal the monosaccharides such as sugar, galactolipin, fructose, sorbose, rhamnose, fucose, deoxyribose；(iv) for example, trehalose, sucrose,
The disaccharides such as maltose, cellobiose, gentiobiose, lactose, melibiose；(v) for example, melitriose, gentianose, melezitose etc.
Three carbohydrates；(vi) for example, the carbohydrate of stachyose etc. four；Deng.
Acrylic polyol for example can be by the polymerizable monomer that makes to have more than 1 reactive hydrogen in a molecule and can
Copolymerization is carried out with other monomers of the polymerizable monomer copolymerization and is obtained.
Acrylic polyol can for example be obtained following material copolymerization by conventional method：Selected from by with work
The esters of acrylic acid (acrylic acid -2- hydroxyl ethyl esters, 2-hydroxypropyl acrylate, acrylic acid -2- hydroxy butyl esters etc.) of property hydrogen or with work
Methyl acrylic ester (2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate, the methacrylic acid -2- hydroxyls of property hydrogen
Butyl ester, methacrylic acid -3- hydroxypropyl acrylates, methacrylic acid -4- hydroxy butyl esters etc.)；(the first of the triols such as glycerine, trimethylolpropane
Base) acrylic monoester etc. has (methyl) esters of acrylic acid of multicomponent reactive hydrogen；Polyether polyols alcohols (polyethylene glycol, poly- the third two
Alcohol, polytetramethylene glycol etc.) monoether with (methyl) esters of acrylic acid of above-mentioned active hydrogen；(methyl) glycidyl acrylate
With the addition product of the monoacid such as acetic acid, propionic acid, p-tert-butyl benzoic acid；By (methyl) acrylic acid for making above-mentioned active hydrogen
In the group that the reactive hydrogen of esters is constituted with lactone (epsilon-caprolactams, gamma-valerolactone etc.) addition product obtained from ring-opening polymerisation
More than a kind, it is and as needed selected from by (methyl) esters of acrylic acid, (methyl acrylate, ethyl acrylate, acrylic acid are different
Propyl ester, n-butyl acrylate, acrylic acid-2-ethyl caproite, methyl methacrylate, EMA, methacrylic acid
Isopropyl ester, n-BMA, Isobutyl methacrylate, the just own ester of methacrylic acid, cyclohexyl methacrylate, first
Base lauryl acrylate, GMA etc.), unsaturated carboxylic acid class (acrylic acid, methacrylic acid, maleic acid,
Itaconic acid etc.), unsaturated acyl amine (acrylamide, N hydroxymethyl acrylamide, DAAM etc.) or with hydrolysis
Vinyl monomer class (vinyltrimethoxy silane, vinyl methyl dimethoxysilane, γ-(methyl) of property silicyl
Acryloxypropyl trimethoxy silane etc.), other polymerizable monomer (styrene, vinyltoluene, vinyl acetate,
Acrylonitrile, dibutyl fumarate etc.) composition group in more than a kind.
For example, by by above-mentioned monomer component in radical polymerization initiators such as known peroxide, azo-compounds
In the presence of carry out polymerisation in solution, diluted as needed with organic solvent etc., so as to obtain acrylic polyol.Obtain
During water system base acrylic class polyalcohol, water layer can be transferred to by the way that alefinically unsaturated compounds are carried out into polymerisation in solution
The known methods such as method, emulsion polymerization are manufactured.Now, by the way that acrylic acid, methacrylic acid etc. are contained into carboxylic acid monomer, containing sulfonic acid
The acidic moiety such as monomer amine, ammonia are neutralized, and can assign water-soluble or water dispersible.
The intramolecular that fluorine-containing polyalcohol refers to contains the polyalcohol of fluorine, for example, can include Japanese Unexamined Patent Application 57-341075
Fluoroolefin, cyclic vinyl ether, hydroxyalkyl vinyl ether disclosed in publication, Japanese Unexamined Patent Application 61-215311 publications etc.,
Copolymer of monocarboxylic acid vinyl acetate etc. etc..
Hydroxyl value to above-mentioned polyalcohol is not particularly limited, usually 30~200mgKOH/g, and acid number is 0~30mgKOH/
g.Hydroxyl value can be determined according to JIS K1557.
Above-mentioned central, as polyalcohol, from the viewpoint of weatherability, chemical proofing and hardness, preferred propylene
Acrylic polyol, from the viewpoint of mechanical strength and oil resistivity, preferred PEPA.
The NCO of the polyisocyantates composition of present embodiment relative to above-mentioned intramolecular there are more than 2 to be lived
Property hydrogen compound hydroxyl equivalent proportion (NCO/OH ratios) be preferably 0.2~5.0, more preferably 0.4~3.0, it is further excellent
Elect 0.5~2.0 as.When the equivalent proportion is more than 0.2, more tough film can be obtained.When the equivalent proportion is less than 5.0,
The flatness of film can further be improved.
Complete alkyl type, methylol type alkyl, imino-type alkyl etc. can be added as needed in the coating composition
Melamine series curing agent.
Above-mentioned intramolecular has compound, the polyisocyantates composition of present embodiment and the painting of more than 2 reactive hydrogens
Feed composition can mix to use with organic solvent.As organic solvent, preferably without with hydroxyl or NCO
The functional group of reaction.Additionally, it is preferred that being mixed with polyisocyantates composition.As this organic solvent, usual use can be included
Make the ester compounds of paint solvent, it is ether compound, assimilation compound, aromatic compound, glycol dialkyl ether based compound, poly-
Glycol dicarboxylate based compound, hydrocarbon system solvent, fragrant family solvent etc..
Wherein, as suitable coating composition, following coating composition can be included, it contains：
(a) glycol composition, the glycol composition contains acrylic polyol or PEPA, and hydroxyl value is
50~250mgKOH/g, glass transition temperature (Tg) is 0~80 DEG C, and number-average molecular weight is 500~10000；And,
(b) polyisocyantates composition of present embodiment,
(b) NCO in composition is 0.6~1.5 relative to the mol ratio (NCO/OH) of the hydroxyl in (a) composition.
In the present embodiment, for example, (b) composition can be used as so-called curing agent composition.
(a) composition is the glycol composition containing acrylic polyol or PEPA, can also be as so-called
Host use.
As polyalcohol contained in glycol composition, from the viewpoint of weatherability, chemical proofing and hardness,
It is preferred that acrylic polyol, from the viewpoint of mechanical strength, oil resistivity and pigment-dispersing, preferred PEPA.It is special
When not being used as the finish paint of automotive varinishing enamel, due to paying attention to weatherability, chemical proofing, hardness etc., therefore preferably third
Alkene acrylic polyol.When on the other hand, as floating coating, base-material, priming paint, due to paying attention to mechanical strength, pigment-dispersing etc., because
This preferred PEPA.
, can be by aforesaid propylene acrylic polyol or polyester polyols in the glycol composition used in the present embodiment
Alcohol is used alone a kind, and two or more can also be applied in combination.And then, can also be in acrylic polyol, PEPA
Further mix other resins etc..
As the other resins that can be applied in combination, for example, it can include PPG, fluorine-containing polyalcohol, aliphatic hydrocarbon
Polyalcohol, polyalcohol containing silicon systems, polycarbonate polyol, epoxy resin, alkyd polyol class etc..
In glycol composition, it can use aforesaid propylene acrylic polyol, PEPA aliphatic two is different
The urethane-modified acrylic of cyanate, ester ring type diisocyanate or the modified polyisocyanate obtained by them
Class polyalcohol, urethane-modified PEPA etc..
The number-average molecular weight of the glycol composition used in the coating composition of present embodiment is preferably 500~
10000.The lower limit of number-average molecular weight is more preferably more than 800, more preferably more than 1200.The upper limit of number-average molecular weight
Value more preferably less than 6000, more preferably less than 4000.When number-average molecular weight is more than above-mentioned lower limit, film is made
When crosslink density become sufficiently high.When number-average molecular weight is below above-mentioned higher limit, the viscosity of coating composition can be pressed down
Being made becomes low.Number-average molecular weight can be determined according to the method described in aftermentioned embodiment.
The hydroxyl value of glycol composition is preferably 50~250mgKOH/g.The lower limit of hydroxyl value is more preferably 60mgKOH/g
Above, more preferably more than 70mgKOH/g.The higher limit of hydroxyl value be more preferably below 200mgKOH/g, further preferably
For below 150mgKOH/g.When hydroxyl value is more than above-mentioned lower limit, solvent resistance when film is made is abundant.Hydroxyl value is on above-mentioned
When below limit value, the flatness of film becomes good.Hydroxyl value can be determined according to the method described in aftermentioned embodiment.
The glass transition temperature (Tg) of glycol composition is preferably 0 DEG C~80 DEG C.Glass transition temperature (Tg)
Lower limit is more preferably more than 10 DEG C, more preferably more than 20 DEG C.The higher limit of glass transition temperature (Tg) is more preferably
For less than 60 DEG C, more preferably less than 50 DEG C.Glass transition temperature (Tg) be above-mentioned lower limit more than when, film it is hard
Degree is abundant.When glass transition temperature (Tg) is below above-mentioned higher limit, the obdurability of film is abundant.Glass transition temperature
(Tg) it can be determined according to the method described in aftermentioned embodiment.
In present embodiment, the hydroxyl value of (a) composition is preferably 50~250mgKOH/g, more preferably 60~200mgKOH/
g.(a) number-average molecular weight of composition is preferably 500~10000, more preferably 800~6000.And then, it is more suitable as (a) composition
It is 60~200mgKOH/g containing acrylic polyol, hydroxyl value that suitable (a) composition, which is, and number-average molecular weight is 800~6000
Glycol composition.By having these conditions concurrently, the viscosity of acrylic polyol can be suppressed, and being capable of fully phase
Tough film to be formed.Due to the use of coating composition obtained from this polyol component being also low viscosity, therefore make
Quantity of solvent needed for when being used for coating is a small amount of.Accordingly it is also possible to fully expect as the solid constituent in coating (no
Volatile ingredient) amount for height ratio, so-called high solids coatings etc. use.If in addition, for example can be by the consumption of solvent
Reduction is then especially significant even counting % or so with intensity reference in plant-scale use.
Compound of the above-mentioned intramolecular with more than 2 reactive hydrogens, glycol composition, the polyisocyanic acid of present embodiment
Ester composition and coating composition can be mixed according to purpose and purposes in the range of the effect of present embodiment is not damaged
The technology neck such as catalyst, pigment, levelling agent, antioxidant, ultra-violet absorber, light stabilizer, plasticizer, surfactant
The various additives that are used in domain are used.
As the specific example of the catalyst of solidification promotion, dibutyl tin laurate, 2 ethyl hexanoic acid can be included
The metal salts such as tin, 2 ethyl hexanoic acid zinc, cobalt salt；Triethylamine, pyridine, picoline, benzyl dimethylamine, N, N- dimethyleyelohexanes
Amine, N- methyl piperidines, pentamethyl-diethylenetriamine, N, N '-interior ethylidene piperazine, N, the tertiary amines such as N '-dimethyl piperazine etc..
Coating composition using polyisocyantates composition as the curing agent of present embodiment may be used as roller coat, curtain
The coating of formula flow coat, spraying, clock-type application, electrostatic spraying etc..For example, being used as metal (steel plate, surface treated steel plate etc.), modeling
Priming paint, upper floating coat paint on the raw material such as material, timber, film, inorganic material are useful.In addition, including antirust steel
As for assigning dicoration, weatherability, acid resistance, rust-preventing characteristic, chipping resistance etc. in pre-coated metal, painting dressing automobiles of plate etc.
Coating is also useful.And then, it is former as the carbamate of bonding agent, adhesive, elastomer, foam, surface conditioning agent etc.
Material is also useful.
Embodiment
Hereinafter, the present invention is described in detail according to embodiment and comparative example, but the present invention is not by any limit of following examples
It is fixed.
<Weight conservation rate after being heated 5 hours at 210 DEG C>
Use thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument " TG/DTA6200 " (Seiko Instruments Inc. systems
Make), 10mg is determined into the shuttle that sample is put into aluminum.Blank vessel also uses the container of aluminum.With 100mL/ minutes
Condition circulates nitrogen and when design temperature is set into 220 DEG C, and actual temperature is heated to 210 DEG C.Measure keeps 5 under this condition
Weight conservation rate after hour.It should be noted that the weight conservation rate is obtained according to following formula.
Weight conservation rate (%)=(quality of the measure sample before quality/heating of the measure sample after heating) × 100
<Weight conservation rate after being heated 5 hours at 240 DEG C>
Use thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument " TG/DTA6200 " (Seiko Instruments Inc. systems
Make), 10mg is determined into the shuttle that sample is put into aluminum.Blank vessel also uses the container of aluminum.With 100mL/ minutes
Condition circulates nitrogen and when design temperature is set into 250 DEG C, and actual temperature is heated to 240 DEG C.Measure keeps 5 under this condition
Weight conservation rate after hour.It should be noted that the weight conservation rate is obtained according to following formula.
Weight conservation rate (%)=(quality of the measure sample before quality/heating of the measure sample after heating) × 100
<Viscosity>
Viscosity is determined using E types viscosimeter (manufacture of TOKIMEC Co., Ltd.) at 25 DEG C.Standard rotor is used during measure
(1°34’×R24).Rotating speed is as follows.
100rpm (situation less than 128mPas)
50rpm (more than 128mPas and the situation less than 256mPas)
20rpm (more than 256mPas and the situation less than 640mPas)
10rpm (more than 640mPas and the situation less than 1280mPas)
5rpm (more than 1280mPas and the situation less than 2560mPas)
It should be noted that investigating the polyisocyanate made in aftermentioned each embodiment and each comparative example by the method for following record
The ratio of the nonvolatile component of cyanate compositions, the value directly determines viscous for more than 98 mass % polyisocyantates composition
Degree.In addition, for the polyisocyantates composition less than 98 mass %, using purification devices such as thin film evaporators, making non-volatile
Composition is more than 98 mass %, then determines viscosity.
<Nonvolatile component>
The surplus when ratio of nonvolatile component is by polyisocyantates composition is heated 3 hours at 105 DEG C is obtained.
Nonvolatile component (quality %)=(quality of the polyisocyantates composition after being heated 3 hours at 105 DEG C/add
The quality of polyisocyantates composition before heat) × 100
<NCO containing ratios (NCO%)>
NCO containing ratios (quality %) after the excessive 2N amine neutralization of the NCO that will be determined in sample by using
The back titration of 1N hydrochloric acid is obtained.Made it should be noted that being investigated by the above method in aftermentioned each embodiment and each comparative example
Polyisocyantates composition nonvolatile component, the value directly surveyed for more than 98 mass % polyisocyantates composition
It is fixed.In addition, for the polyisocyantates composition less than 98 mass %, using purification devices such as thin film evaporators, making non-volatile
Composition is more than 98 mass %, then determines NCO containing ratios.
<Number-average molecular weight>
The number-average molecular weight for determining sample is determined using gel permeation chromatography (GPC).GPC assay method is as follows.
Use instrument：HLC-8120 (TOSOH Co., Ltd's manufacture),
Use post：TSK GEL SuperH1000, TSK GEL SuperH2000, TSK GEL SuperH3000 (are
TOSOH Co., Ltd manufactures),
Sample solution concentration：5wt/vol% (tetrahydrofuran (THF) that 50mg samples are dissolved in 1mL),
Carrier：THF,
Detection method：Differential refractometer,
Discharge 0.6mL/ minutes, 30 DEG C of column temperature).
Standard curve making using molecular weight 1000~20000 polystyrene and the isocyanato- hexanes of 1,6- bis- it is different
Cyanurate body (3 aggressiveness, 5 aggressiveness, 7 aggressiveness).
It should be noted that investigating the polyisocyanates made in aftermentioned each embodiment and each comparative example by the above method
The nonvolatile component of composition, the value is directly measured for more than 98 mass % polyisocyantates composition.In addition, for
Less than 98 mass % polyisocyantates composition, using purification devices such as thin film evaporators, it is 98 matter to make nonvolatile component
More than % is measured, number-average molecular weight is then determined.
<Isocyanurate structure and iminooxadiazinedionepolyisocyanates diketone structure, urea diketone structure, mole of allophanic acid ester structure
Ratio>
Rubbed on isocyanurate structure, iminooxadiazinedionepolyisocyanates diketone structure, urea diketone structure, allophanic acid ester structure
That ratio, by being measured sample13C-NMR is determined and obtained.Specific condition determination is as follows.
13C-NMR devices：AVANCE600 (manufacture of Bruker companies)
Cryogenic probe (manufacture of Bruker companies)
Cryo Probe
CPDUL
600S3-C/H-D-05Z
Resonant frequency：150MHz
Concentration：60wt/vol%
Shift standards：CDCl3(77ppm)
Cumulative frequency：10000 times
Pulse protocol：Zgpg30 (proton decouples method, stand-by period 2sec completely)
By the carbon number of the integrated value of following signal divided by measure, each mol ratio is obtained by the value.
Isocyanurate structure：Integrated value ÷ 3 near 149ppm
Iminooxadiazinedionepolyisocyanates diketone structure：Integrated value ÷ 1 near 145ppm
Urea diketone structure：157.5ppm near：Integrated value ÷ 2
Allophanic acid ester structure：Near 154ppm：Integrated value ÷ 1
<The making of blank>
By two-component-type polyurethane coating (trade name " Mighty Rack (white) ", the NIPPON PAINT of solvent system
Co., Ltd. manufactures) aluminium sheet (150mm × 75mm × 1mm, model are sprayed in the way of 50 μm by dry film thickness：A1050P
(JIS H4000), the manufacture of Testpiece Co., Ltd.).Then, after standing 2 weeks under conditions of 23 DEG C, 50% humidity, use
The sand paper lapped face of No. 1000, so as to make blank.
<Weatherability>
Reveal the weather-proof instrument of plate (Dew Panel Weather Meter (DPW))
Use equipment：" FDP/DPWL-5W " (SUGA TEST INSTRUMENTS CO., LTD. manufacture)
Light source：Ultraviolet fluorescent lamp：" SUGA-FS40 " (wavelength 313nm)
Condition：Irradiate (4hr)
60 DEG C of Black panel temperature
Humidity is without setting
Radiance 30W/m2
：Dark+moistening (4hr)
40 DEG C of Black panel temperature
Humidity 100%
Radiance is without setting
Gloss/initial gloss × 100 during gloss retention (%)=measure
(synthesis example 1；The synthesis of catalyst)
In the 500mL eggplant type flasks through nitrogen displacement, TMAH (10 mass % methanol are added at room temperature
Solution) (Tokyo is melted into Co., Ltd.'s manufacture) 200g (0.116mol), capric acid is added dropwise with dropping funel, and (Tokyo is melted into Co., Ltd.
Manufacture) 12.1g (TMAH/capric acid=1/1.1 (mol ratio)), it is stirred at room temperature 30 minutes.Then, exist
10Torr, at 50 DEG C, distillation for removing methanol under conditions of 30 minutes.32g n-butanols are added wherein, make tetramethyl capric acid ammonium
The mass % solution of n-butanol 50.In addition, adding 40g just in the mass % solution 10g of n-butanol 50 of the tetramethyl capric acid ammonium
Butanol, makes the mass % solution of n-butanol 10 of tetramethyl capric acid ammonium.And then, in the matter of n-butanol 10 of the tetramethyl capric acid ammonium
Measure and 15g n-butanols are further added in % solution 10g, make the mass % solution of n-butanol 4 of tetramethyl capric acid ammonium.
(embodiment 1)
1000g HDI are heated to 80 DEG C, (Tokyo is melted into Co., Ltd.'s manufacture, CAS to addition tetraethyl ammonium fluoride hydrate
Number：The tetramethyl capric acid ammonium made in the mass % solution 1.5g (0.77mmol) of n-butanol 10 665-46-3) and synthesis example 1
The mass % solution 0.5g (equivalent to 0.20mmol) of n-butanol 10, when the NCO containing ratios in reaction solution reach 39.3 mass %,
Addition phosphoric acid di-n-butyl 0.73g (3.5mmol) stops reaction.Then, using thin film evaporator, in 160 DEG C, 0.2Torr
Under conditions of purify 2 times, obtain the mass % of nonvolatile component 99.3, viscosity 2700mPas (23 DEG C), the matter of NCO containing ratios 22.0
Measure %, the polyisocyantates composition P-1 of number-average molecular weight 656.Obtained polyisocyantates composition P-1 structure point
Analyse, as a result the mol ratio of isocyanurate structure/iminooxadiazinedionepolyisocyanates diketone structure/urea diketone structure/allophanic acid ester structure
For 100/14/1.0/2.8.That is, the mol ratio of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure is 14/100, urea two
The mol ratio of ketone structure/isocyanurate structure is 1.0/100, the mol ratio of allophanic acid ester structure/isocyanurate structure
For 2.8/100.Weight conservation rate after polyisocyantates composition P-1 is heated 5 hours at 210 DEG C is 93.7%, at 240 DEG C
It is lower heating 5 hours after weight conservation rate be 82.6%.
(embodiment 2)
1000g HDI are heated to 80 DEG C, addition tetraethyl ammonium fluoride hydrate (Tokyo is melted into Co., Ltd.'s manufacture)
The matter of n-butanol 50 of the tetramethyl capric acid ammonium made in the mass % solution 0.20g (0.51mmol) of n-butanol 50 and synthesis example 1
% solution 0.10g (equivalent to 0.20mmol) is measured, when the NCO containing ratios of reaction solution reach 39.3 mass %, di(2-ethylhexyl)phosphate is added
N-butyl 0.60g (2.9mmol) stops reaction.Then, it is pure under conditions of 160 DEG C, 0.2Torr using thin film evaporator
Change 2 times, obtain the mass % of nonvolatile component 99.4, viscosity 2700mPas (23 DEG C), the mass % of NCO containing ratios 22.0, number equal
The polyisocyantates composition P-2 of molecular weight 660.Obtained polyisocyantates composition P-2 structural analysis, it is as a result different
The mol ratio of cyanurate structure/iminooxadiazinedionepolyisocyanates diketone structure/urea diketone structure/allophanic acid ester structure is 100/11/
0.9/0.2.That is, the mol ratio of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure is 11/100, urea diketone structure/different
The mol ratio of cyanurate structure is 0.9/100, and the mol ratio of allophanic acid ester structure/isocyanurate structure is 0.2/100.
Weight conservation rate after polyisocyantates composition P-2 is heated 5 hours at 210 DEG C is 95.2%, 5 is heated at 240 DEG C small
When after weight conservation rate be 85.0%.
(embodiment 3)
1000g HDI are heated to 60 DEG C, addition tetraethyl ammonium fluoride hydrate (Tokyo is melted into Co., Ltd.'s manufacture)
The n-butanol of the tetramethyl capric acid ammonium made in the mass % solution 0.30g (equivalent to 0.77mmol) of n-butanol 50 and synthesis example 1
50 mass % solution (the mass % of catalyst concn 50) 0.15g (equivalent to 0.31mmol), reaches in the NCO containing ratios of reaction solution
During 39.2 mass %, addition phosphoric acid di-n-butyl 0.90g (4.3mmol) stops reaction.Then, using thin film evaporator,
160 DEG C, purify 2 times under conditions of 0.2Torr, obtain the mass % of nonvolatile component 99.4, viscosity 2800mPas (23 DEG C),
The mass % of NCO containing ratios 22.0, the polyisocyantates composition P-3 of number-average molecular weight 664.Obtained polyisocyanates group
Compound P-3 structural analysis, as a result isocyanurate structure/iminooxadiazinedionepolyisocyanates diketone structure/urea diketone structure/allophanic acid
The mol ratio of ester structure is 100/7.0/0.4/0.7.That is, mole of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure
It is 0.4/100, allophanic acid ester structure/isocyanide urea than the mol ratio for 7.0/100, urea diketone structure/isocyanurate structure
The mol ratio of acrylate structure is 0.7/100.Polyisocyantates composition P-3 heated 5 hours at 210 DEG C after weight conservation rate
For 96.0%, the weight conservation rate after being heated 5 hours at 240 DEG C is 87.8%.
(comparative example 1)
1000g HDI are heated to 80 DEG C.The mass % of n-butanol 10 of the tetramethyl capric acid ammonium made in synthesis example 1 is molten
Liquid n-butanol further dilutes, and the mass % solution of n-butanol 4.0 is made.2.0g (equivalent to 0.32mmol) is added,
When the NCO containing ratios of reaction solution reach 39.3 mass %, addition phosphoric acid di-n-butyl 0.73g (3.5mmol) stops reaction.Connect
, using thin film evaporator, purified 2 times under conditions of 160 DEG C, 0.2Torr, obtain the mass % of nonvolatile component 99.5, glue
Spend 2700mPas (23 DEG C), the mass % of NCO containing ratios 22.0, the polyisocyantates composition C-1 of number-average molecular weight 655.Enter
The polyisocyantates composition C-1 structural analysis that row is obtained, as a result isocyanurate structure/iminooxadiazinedionepolyisocyanates diketone knot
The mol ratio of structure/urea diketone structure/allophanic acid ester structure is 100/3.0/1.0/2.8.That is, iminooxadiazinedionepolyisocyanates diketone knot
The mol ratio of structure/isocyanurate structure is 3.0/100, and the mol ratio of urea diketone structure/isocyanurate structure is 1.0/
100, the mol ratio of allophanic acid ester structure/isocyanurate structure is 2.8/100.Polyisocyantates composition C-1 is at 210 DEG C
It is lower heating 5 hours after weight conservation rate be 96.8%, at 240 DEG C heat 5 hours after weight conservation rate be 88.7%.
(comparative example 2)
1000g HDI are heated to 80 DEG C, addition tetraethyl ammonium fluoride hydrate (Tokyo is melted into Co., Ltd.'s manufacture)
The mass % solution 1.9g (equivalent to 1.0mmol) of n-butanol 10, when the NCO containing ratios of reaction solution reach 39.2 mass %, adds
The sour di-n-butyl 0.73g (3.5mmol) that phosphorates stops reaction.Then, using thin film evaporator, in 160 DEG C, 0.2Torr
Under the conditions of purify 2 times, obtain the mass % of nonvolatile component 99.3, viscosity 2500mPas (23 DEG C), the matter of NCO containing ratios 22.0
Measure %, the polyisocyantates composition C-2 of number-average molecular weight 660.Obtained polyisocyantates composition C-2 structure point
Analyse, as a result the mol ratio of isocyanurate structure/iminooxadiazinedionepolyisocyanates diketone structure/urea diketone structure/allophanic acid ester structure
For 100/30/1.0/2.7.That is, the mol ratio of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure is 30/100, urea two
The mol ratio of ketone structure/isocyanurate structure is 1.0/100, the mol ratio of allophanic acid ester structure/isocyanurate structure
For 2.7/100.Weight conservation rate after polyisocyantates composition C-1 is heated 5 hours at 210 DEG C is 88.7%, at 240 DEG C
It is lower heating 5 hours after weight conservation rate be 64.2%.
(comparative example 3)
1000g HDI are heated to 80 DEG C, addition tetraethyl ammonium fluoride hydrate (Tokyo is melted into Co., Ltd.'s manufacture)
The mass % of n-butanol 10 of the tetramethyl capric acid ammonium made in the mass % solution 1.5g (0.77mmol) of n-butanol 10 and synthesis example 1
Solution 0.5g (equivalent to 0.20mmol), when the NCO containing ratios of reaction solution reach 39.3 mass %, adds phosphoric acid di-n-butyl
0.73g (3.5mmol) stops reaction.Then, heated 1 hour at 160 DEG C.Then, using thin film evaporator, 160 DEG C,
Purified 2 times under conditions of 0.2Torr, obtain the mass % of nonvolatile component 99.1, viscosity 2600mPas (23 DEG C), NCO and contain
The mass % of rate 22.2, the polyisocyantates composition C-3 of number-average molecular weight 653.Obtained polyisocyantates composition C-3
Structural analysis, as a result isocyanurate structure/iminooxadiazinedionepolyisocyanates diketone structure/urea diketone structure/allophanic acid ester structure
Mol ratio be 100/14/9.0/2.6.That is, the mol ratio of iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure is 14/
100, the mol ratio of urea diketone structure/isocyanurate structure is 9.0/100, allophanic acid ester structure/isocyanurate structure
Mol ratio be 2.6/100.Weight conservation rate after polyisocyantates composition C-1 is heated 5 hours at 210 DEG C is
84.9%, the weight conservation rate after being heated 5 hours at 240 DEG C is 74.1%.
(synthesis example 2；The synthesis of acrylic polyol)
" SOLVESSO#150 " (Exxon Chemical is put into the four-hole boiling flask for being provided with agitator, thermometer, cooling tube
The fragrant family solvent of company's manufacture) 120.0g, dimethylbenzene 60.0g, inside is carried out after nitrogen displacement, 120 DEG C are warming up to.So
Afterwards, (methyl) acrylic monomer and benzoyl peroxide 8.0g as described below was added dropwise with 2 hours, stirring reacts it.Drop
Plus after terminating, further continue to react 4 hours at 120 DEG C, obtain acrylic polyol Ac-1.
(methyl) acrylic monomer for raw material
Methyl methacrylate：128.8g
N-butyl acrylate：84.8g
Cyclohexyl methacrylate：80.0g
2-hydroxyethyl methacry-late：74.4g
Styrene：32.0g
Obtained acrylic polyol Ac-1 is：The mass % of nonvolatile component 70, hydroxyl value 80mgKOH/g are (relative to tree
Fat composition, the calculated value calculated by rate of charge, JIS K1557), 40 DEG C of glass transition temperature (Tg), number-average molecular weight 1700.
<Embodiment 4>
Glycol composition is made in the acrylic polyol Ac-1 made in synthesis example 1.Then, by the polyalcohol group
Curing agent composition is made in the polyisocyantates composition P-1 made in compound and embodiment 1, thus makes coating composition.
Specifically, added in acrylic polyol Ac-1 (40.0g) and polyisocyantates composition P-1 (7.6g)
" SOLVESSO#100 " (the fragrant family solvent of Exxon Corporation's manufacture) (17.1g), it is 55 mass % to make solid constituent.By its
110mL sample bottle (trade name " TS screwed pipes ", Maruemu Corporation manufactures) is put into, 30 points are mixed with oscillator
Zhong Hou, stands 20 minutes, coating composition is made.It should be noted that coating composition, polyisocyantates composition P-1
Hydroxyl of the NCO relative to acrylic polyol Ac-1 mol ratio (NCO/OH) be 1.0.
<Embodiment 5>
In addition to 7.6g polyisocyantates composition P-2 this point is used as curing agent composition, by with implementation
The same method of example 4 makes coating composition.It should be noted that coating composition, polyisocyantates composition P-2 different
Cyanic acid ester group is 1.0 relative to the mol ratio (NCO/OH) of acrylic polyol Ac-1 hydroxyl.
<Embodiment 6>
In addition to 7.6g polyisocyantates composition P-3 this point is used as curing agent composition, by with implementation
The same method of example 4 makes coating composition.It should be noted that coating composition, polyisocyantates composition P-3 different
Cyanic acid ester group is 1.0 relative to the mol ratio (NCO/OH) of acrylic polyol Ac-1 hydroxyl.
<Comparative example 4>
In addition to 7.6g polyisocyantates composition C-1 this point is used as curing agent composition, by with implementation
The same method of example 4 makes coating composition.It should be noted that coating composition, polyisocyantates composition C-1 different
Cyanic acid ester group is 1.0 relative to the mol ratio (NCO/OH) of acrylic polyol Ac-1 hydroxyl.
<Comparative example 5>
In addition to 7.6g polyisocyantates composition C-2 this point is used as curing agent composition, by with implementation
The same method of example 4 makes coating composition.It should be noted that coating composition, polyisocyantates composition C-2 different
Cyanic acid ester group is 1.0 relative to the mol ratio (NCO/OH) of acrylic polyol Ac-1 hydroxyl.
<Comparative example 6>
In addition to 7.6g polyisocyantates compositions C-3 is used as curing agent composition, by similarly to Example 4
Method make coating composition.It should be noted that coating composition, polyisocyantates composition C-3 isocyanates
Base is 1.0 relative to the mol ratio (NCO/OH) of acrylic polyol Ac-1 hydroxyl.
1. the heat-resistance test of film
By the coating composition obtained in embodiment 4~6 and comparative example 4~6 using spraying using dry film thickness as 50 μm
Mode is coated on polypropylene board (manufacture of 150mm × 150mm, Testpiece Co., Ltd.).By it in 60 DEG C, the bar of 30 minutes
After being calcined under part, 1 week further is stood under conditions of 23 DEG C, humidity 50%, so as to form film on polypropylene board.Will
To film be cut into 5mm square, be used as sample.Use thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument " TG/DTA6200 "
(Seiko Instruments Inc. manufactures), the film 10mg for being cut into 5mm square is put into the shuttle of aluminum.Blank
Container also uses the container of aluminum.It is actual when with the condition circulation nitrogen of 100mL/ minutes and design temperature being set into 220 DEG C
Temperature is heated to 210 DEG C.Determine the weight conservation rate after being kept for 5 hours under this condition.It should be noted that weight conservation rate
Obtained by following formula.
Weight conservation rate=(example weight before example weight/heating after heating) × 100 (%)
2. the adaptation evaluation of film
For the coating composition obtained in embodiment 4~6 and comparative example 4~6, using spraying by coating composition application
In aluminium sheet (150mm × 75mm × 1mm, model：A1050P (JIS H4000), the manufacture of Testpiece Co., Ltd.).It will pass through
After the aluminium sheet of coating is calcined under conditions of 180 DEG C, 30 minutes, 1 day is stood under conditions of 23 DEG C, humidity 55%, so that
Film is formed on aluminium sheet.
For obtained film, grid test is carried out, adaptation is evaluated.Grid test is according to old
JIS K5400 are carried out.That is, using NT cutter, film is cut into 100 pieces of 1mm × 1mm, strongly pressed on lattice part drawing
Connect adhesive tape.Then, the end of adhesive tape is peeled off quickly with 45 ° of angle, by remaining in the grid on aluminium sheet
The quantitative assessment adaptation of (film).The quantity remained on aluminium sheet is more, then judges that the adaptation of film is more excellent.
3. the outward appearance (acutance and surface smoothness) of film is evaluated
For the coating composition obtained in embodiment 4~6 and comparative example 4~6, using spraying, ABS plates (acrylonitrile-
Butadiene styrene resin；Black, 150mm × 75mm) on by dry film thickness in the way of 50 μm applied coating composition.Will
After it is calcined under conditions of 60 DEG C, 30 minutes, 1 week is stood under conditions of 23 DEG C, humidity 50%, so that the shape on ABS plates
Into film.
Long side direction of the outward appearance (acutance and surface smoothness) of film along ABS plates uses digital oscilloscope " Wave Scan
DOI " (BYK Gardner company systems) is determined." Wave Scan DOI " are configured as follows：From the spot light of laser with
From the angular illumination laser beam of 60 ° of the vertical line inclination relative to film surface, detector is received to be located at relative to foregoing vertical line
Opposite side and in equal angular reflected light.The device is by making the spot light of laser move and be swept on the membrane surface
Retouch, to determine that the interval pointwise of light and shade of reflected light is determined, the optical profile thus, it is possible to detect film surface.Detect
Optical profile carries out spectrum analysis by frequency filter, can analyze the structure on surface.Wherein, using the Wb regions (wavelength of film
0.3~1.0mm), the value of Wc regions (1.0~3.0mm of wavelength) evaluated.Measured value is the arithmetic mean of instantaneous value of 3 measured values.
Wb, Wc are the index of the outward appearance on film, and Wb is the index of the acutance of film, and Wc is the index of the flatness of film, all
Be numerical value it is smaller be judged as it is more excellent.
4. the Gloss Evaluation of film
For the coating composition obtained in embodiment 4~6 and comparative example 4~6, using spraying using dry film thickness as 50 μm
Mode coating composition is coated on above-mentioned blank.Blank by coating is calcined under conditions of 200 DEG C, 10 minutes
Afterwards, 2 weeks are stood under conditions of 23 DEG C, humidity 50%.20 ° of gloss of obtained film are determined according to JIS Z8741.
5. atmospheric exposure test
For the coating composition obtained in embodiment 4~6 and comparative example 4~6, using spraying using dry film thickness as 50 μm
Mode coating composition is coated on above-mentioned blank.Blank by coating is calcined under conditions of 200 DEG C, 10 minutes
Afterwards, 2 weeks are stood under conditions of 23 DEG C, humidity 50%.Then, " the dew weather-proof instrument of plate (Dew Panel Weather are used
Meter (DPW)) " (SUGA TEST INSTRUMENTS CO., LTD. manufacture) progress promotion atmospheric exposure test.Carry out 1750 small
When promote atmospheric exposure test after, according to following formula determine gloss retention.Glossiness is determined according to JIS Z8741.Gloss is kept
Rate is higher, then judges that the weatherability of film is more excellent.
Gloss retention (%)=(promoting the glossiness after atmospheric exposure test) ÷ (promotes the gloss before atmospheric exposure test
Degree) × 100
[table 1]
According to result above, the adaptation of the coating composition of embodiment 4~6, acutance, surface smoothness, light are confirmed
Pool and weatherability are excellent.
Industrial applicability
The polyisocyantates composition of the present invention can be utilized as coating composition etc. in various fields.For example can be with
Coating as roller coat, curtain flow coat, spraying, clock-type application, electrostatic spraying etc..In addition, can act as steel plate, surface treated steel
Priming paint, upper floating coat paint on the raw material such as the metals such as plate and plastics, timber, film, inorganic material.And then, including anti-
Imparting heat resistance, dicoration (surface smoothness, acutance, gloss etc.) etc. are used as in pre-coated metal, painting dressing automobiles of rust steel plate etc.
Coating be also useful.When being especially formed into film, used due to surface smoothness, excellent adhesion, therefore in painting dressing automobiles
It is particularly useful in coating, factory coating (PCM, coil coating etc.).Wherein, coating composition of the invention can obtain surface
Flatness, acutance be good and heat resistance, the film that has excellent weather resistance., can when therefore, particularly as automotive varinishing enamel
Various vehicles for high-end car or even popular car.
Claims (3)
1. a kind of polyisocyantates composition, it is at least to use polyisocyanates obtained from the isocyanato- hexanes of 1,6- bis-
Composition,
The polyisocyantates composition has isocyanurate structure and iminooxadiazinedionepolyisocyanates diketone structure, and utilizes13C-NMR
Mol ratio determine, iminooxadiazinedionepolyisocyanates diketone structure/isocyanurate structure is 6.0/100~14/100, the polyisocyanate
Cyanate compositions also have urea diketone structure, utilize13Mole that C-NMR is determined, urea diketone structure/isocyanurate structure
Than for 0.1/100~5.0/100,
It is being obtained using thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument, at 210 DEG C heat 5 hours after weight conservation rate be
90.0~99.0%, it is being obtained using thermogravimetric and means of differential scanning calorimetry Simultaneous Determination instrument, at 240 DEG C heat 5 hours after weight
It is 80.0~88.0% to measure conservation rate, also,
Viscosity at 25 DEG C of solid constituent in the polyisocyantates composition is in more than the mass % of nonvolatile component 98
Under the conditions of be 1500mPas~4000mPas.
2. polyisocyantates composition according to claim 1, it also has allophanic acid ester structure, utilizes13C-NMR is surveyed
The mol ratio of fixed, allophanic acid ester structure/isocyanurate structure is 0.1/100~4.0/100.
3. a kind of coating composition, it contains：
(a) glycol composition, the glycol composition contains acrylic polyol or PEPA, and hydroxyl value is 50~
250mgKOH/g, glass transition temperature Tg is 0~80 DEG C, and number-average molecular weight is 500~10000；And,
(b) polyisocyantates composition described in claim 1 or 2,
NCO in (b) composition relative to the mol ratio of the hydroxyl in (a) composition be NCO/OH for 0.6~
1.5。
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| KR101943242B1 (en) * | 2014-12-15 | 2019-01-28 | 미쓰이 가가쿠 가부시키가이샤 | Self-repairing polyurethane resin material, self-repairing polyurethane resin, self-repairing coating material, self-repairing elastomer material, method for producing self-repairing polyurethane resin material, and method for producing self-repairing polyurethane resin |
| JP6718226B2 (en) * | 2015-12-11 | 2020-07-08 | 旭化成株式会社 | Fluorine coating composition |
| JP6568996B2 (en) * | 2016-03-09 | 2019-08-28 | 旭化成株式会社 | Polyisocyanate composition, coating composition, water-based coating composition, and coating substrate |
| WO2018212334A1 (en) * | 2017-05-19 | 2018-11-22 | 旭化成株式会社 | Polyisocyanate composition |
| EP3444288A1 (en) | 2017-08-15 | 2019-02-20 | Covestro Deutschland AG | Method for the preparation of polyisocyanates containing iminooxadiazindione groups using mixtures of catalysts |
| CN107913730B (en) * | 2017-11-30 | 2020-04-10 | 万华化学集团股份有限公司 | Imine type quaternary ammonium salt catalyst, preparation method thereof and polyisocyanate composition |
| WO2019183307A1 (en) * | 2018-03-23 | 2019-09-26 | Covestro Llc | Polyuretdione-containing resin blend compositions |
| CN111253552B (en) * | 2018-11-30 | 2023-08-22 | 科思创德国股份有限公司 | Modified polyisocyanates |
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| JP5112570B1 (en) * | 2012-07-09 | 2013-01-09 | 住化バイエルウレタン株式会社 | Coating method and curing agent for polyurethane paint |
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| CN1555401A (en) * | 2001-07-31 | 2004-12-15 | 拜尔材料科学股份公司 | Coating composition for forming structured paint surfaces, method for the production thereof and use thereof |
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| CN104130686A (en) | 2014-11-05 |
| JP6297398B2 (en) | 2018-03-20 |
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