CN107513339B - A kind of cured high levelling powdery paints semi-crystalline polyester resin of polyisocyanates and preparation method thereof - Google Patents
A kind of cured high levelling powdery paints semi-crystalline polyester resin of polyisocyanates and preparation method thereof Download PDFInfo
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- CN107513339B CN107513339B CN201710689365.3A CN201710689365A CN107513339B CN 107513339 B CN107513339 B CN 107513339B CN 201710689365 A CN201710689365 A CN 201710689365A CN 107513339 B CN107513339 B CN 107513339B
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to cured high levelling powdery paints semi-crystalline polyester resins of a kind of polyisocyanates and preparation method thereof, and the semi-crystalline polyester resin includes: A) at least one crystalline polyester, hydroxyl value is 50-70mg KOH/g；And B) at least one amorphous polyester, hydroxyl value is 20-40mg KOH/g；Wherein A: B weight ratio is between 1: 9-1: 25.
Description
Technical field
The present invention relates to a kind of polyester resin for powder coating, and in particular to the cured high levelling powder of polyisocyanates applies
Material uses semi-crystalline polyester resin.The invention further relates to the powder paint compositions containing the semi-crystalline polyester resin.
Background technique
Powdery paints is widely used in providing decoration and/or protective coating on substrate.Powdery paints has to be applied with general
Expect entirely different form, it is existing for state with attritive powder.Due to not using solvent, so referred to as powdery paints.
Powdery paints has the characteristics that harmless, high efficiency, saves resource and environmental protection.By the development of many years, powdery paints achieves length
The progress of foot, application field expand year by year.
Traditional powder coating mainly uses amorphous polyester resin, and the distinguishing feature of amorphous polyester resin is its vitrifying
Transition temperature and being positively correlated property of melt viscosity, that is, glass transition temperature is higher, and viscosity is bigger.And to powdery paints people
It is expected that polyester resin glass transition temperature with higher guarantees its storage stability, and it is lower it is expected that polyester resin has
Melt viscosity, when such powder coating solidification, can obtain the coating with good flow leveling.Traditional amorphous polyester tree
Rouge can not meet the requirement of higher glass transition temperature and lower melt viscosity simultaneously.Therefore, people have used for reference half hitch
The physicochemical property of crystalline polymer, has synthesized semi-crystalline polyester resin, and efficiently solving amorphous polyester resin can not meet simultaneously
Higher glass transition temperature and the problem of compared with low viscosity.However, these synthesis semicrystalline polyesters usually exist manufacture at
The problems such as this is high.
Therefore, there is still a need for the semi-crystalline polyester resins that one kind can overcome disadvantages mentioned above in powder coating industry.
Summary of the invention
On the one hand, the present invention provides a kind of polyisocyanates cured powder paint semi-crystalline polyester resin, it includes:
A) at least one crystalline polyester, hydroxyl value are 50-70mg KOH/g；And B) at least one amorphous polyester, hydroxyl value 20-
40mg KOH/g；Wherein the weight ratio of A:B is between 1: 9-1: 25.Preferably, semi-crystalline polyester resin according to the present invention is logical
It crosses the physical mixed of at least one crystalline polyester and at least one amorphous polyester and obtains.
On the other hand, the present invention provides a kind of powder paint compositions, it includes: semicrystalline polyester according to the present invention
Resin, polyisocyanate crosslinker and optionally auxiliary agent or additive.
On the other hand, the present invention provides a kind of methods for being used to prepare powder paint compositions comprising the following steps:
A) by all semi-crystalline polyester resins according to the present invention for being used to manufacture powdery paints, multi isocyanate crosslinking
Agent, optionally auxiliary agent or additive are pre-mixed crushing in premixing machine；
B) raw material crushed by premixing is passed through into extruder melting extrusion；
C) by the cooling tabletting of the material of melting extrusion；
D) tablet is crushed and is sieved by pulverizer, the powder particle for obtaining appropriate particle size is powdery paints.
Will also on the other hand, invention further provides a kind of substrates, partly or entirely by powder according to the present invention
Last coating composition or the powder paint compositions that can be obtained by means of the present invention coating.
The present invention provides a kind of polyisocyanates cured powder paint semi-crystalline polyester resins, and it includes A) at least one
Kind crystalline polyester, hydroxyl value are 50-70mg KOH/g；And B) at least one amorphous polyester, hydroxyl value is 20-40mg KOH/
g；Wherein A: B weight ratio is between 1: 9-1: 25.The present inventor surprisingly it has been found that, semicrystalline polyester according to the present invention
Resin is the mixture of the high hydroxyl value crystalline polyester of the amorphous polyester and relatively small amount that have low hydroxyl value comprising relatively large amount, In
The polyisocyanates for solidifying Shi Huiyu relatively small amount is covalently attached, thus has excellent levelability by the powdery paints that it is prepared
Energy.The present inventor has further surprisingly found that, the hypocrystalline that crystalline polyester and amorphous polyester are obtained by physical mixed
Polyester has obvious compared with the amorphous polyester with similar hydroxyl value and the semicrystalline polyester covalently synthesized with similar hydroxyl value
More preferably flow leveling, this is beyond expectation.
The details of one or more embodiments of the invention illustrates in the following description.According to specification and right
It is required that other features, objects and advantages of the present invention will be apparent.
Definition
As used herein, unless otherwise indicated, "an", " this ", "at least one" and " one or more " with
And it is used interchangeably without using the situation of numeral-classifier compound.Thus, for example the coating composition comprising "an" additive can be solved
It is interpreted as indicating in the coating composition comprising " one or more " additive.In addition to being otherwise indicated herein, odd number shape herein
The use of formula is also intended to including plural form.
It is described as including in composition or in the case where comprising specific components, it is contemplated that this hair is not precluded in the composition
The bright optional component being not directed to, and it is expected that the composition can be constituted or be formed by related component, or retouched in method
State be include or comprising specific process step in the case where, it is contemplated that the optional technique that is not directed to of the present invention is not precluded in this method
Step, and it is expected that this method can be constituted or be formed by related processing step.
For simplicity, some numberical ranges are only expressly disclosed herein.However, any lower limit can be with any upper limit group
Close the range for being formed and being not known and recording；And any lower limit can form the range for being not known and recording with other lower values, together
Any upper limit of sample can combine the range to be formed and not yet explicitly be recorded with any other upper limit.In addition, recorded although being not known,
Each point or single number between endpoints of ranges are included within the scope of this.Thus, each point or single number can be used as certainly
The lower limit or the upper limit of body, which combine with any other point or single number or combine to be formed with other lower limits or the upper limit, not yet explicitly to be recorded
Range.
As used herein, term " binary acid " includes its corresponding ester, acid anhydrides or acyl chlorides.
Unless otherwise indicated, " acid value " (AV) and " hydroxyl value " (OHV) of polyester resin respectively refers to measurement AV and the survey of resin
Measure OHV.The acid value (AV) (mg KOH/g polyester) of polyester and the hydroxyl value (OHV) (mg KOH/g polyester) of polyester are respectively according to ISO
2114 and ISO 2554 is measured with titration.The acid value of polyester resin is the measurement to the amount of carboxylic acid group in polyester resin, and is gathered
The hydroxyl value of ester resin is the measurement to the amount of hydroxyl in polyester resin.
" viscosity " or equivalent " melt viscosity " indicates the melt viscosity at 160 DEG C herein (in terms of Pa.s).In
Viscosity measurement is carried out at 160 DEG C on Brookfield CAP 2000+H Viscometer.Applied shear rate is
21s-1And use the rotor (spindle) (cone rotor CAP-S-05 (19.05mm, 1.8 °)) of 19.05mm.
Term " unbodied " and " crystallization " for characterizing resin are this fields for indicating have in terms of crystallinity
Close the informal term of the main feature of resin." amorphous " polyester resin indicates no melting temperature (T hereinm) tree
Rouge, characterized by with glass transition temperature." crystallization " polyester resin is indicated herein characterized by melting temperature
Resin.If the resin wherein crystallized has glass transition temperature, glass transition temperature is lower than its melting temperature.
" composition " indicates herein: the combination of different chemical substance and/or component and/or mixture are formed
One is whole.
" physical mixed " indicates herein: as the technical staff in powder coating field understands, i.e., mixture is wanted
Element be caught and mix and there is no: i) be related to using can dissolve or any liquid medium (example of dispersion powders
Such as organic solvent, water) substantive physical transformations and/or process and/or ii) be related to for example chemically reacting the chemical conversion of generation
And/or process.For example, the physical blending (mechanical mixture/blending) of the element of the mixture carried out using mixer is considered as root
According to physical mixed of the invention, and the melting extrusion (being also referred to as coextruded) of the element of mixture is considered as non-physical mixing.
In the present invention, pass through all any numerical value that the numberical range that endpoint limits includes within the scope of this, such as 1 to 5
Range cover numerical value 1,1.5,2,2.75,3,3.80,4,5 etc..Moreover, disclosed numberical range is included in the wider range
Interior all subset ranges, such as 1 to 5 range includes subrange 1 to 4,1.5 to 4.5,1 to 2 etc..
Term " preferred " and " preferably " refer to the embodiment of the present invention that can provide certain benefits in some cases.
However, in the case that it is identical or other, other embodiments are also likely to be preferred.In addition, one or more preferred implementations
The narration of scheme does not mean that other embodiments are disabled, and is not intended to and excludes other embodiments in the present invention
Outside range.
Specific embodiment
According to the first aspect of the invention, the present invention provides a kind of cured powdery paints hypocrystallines of polyisocyanates
Polyester resin, it includes: A) at least one crystalline polyester, hydroxyl value are 50-70mg KOH/g；And B) at least one amorphous poly-
Ester, hydroxyl value are 20-40mg KOH/g；Wherein A: B weight ratio is between 1: 9-1: 25.
Crystalline polyester A) be at least one hypocrystalline or crystallization polyester, hydroxyl value be 50-70mg KOH/g, preferably
50-60mg KOH/g, more preferably 50-56mg KOH/g.The crystalline polyester A) it can have within the scope of 50-100 DEG C, preferably
Melting temperature within the scope of 50-80 DEG C.The melting temperature can pass through differential scanning calorimetry according to ISO 11357
(DSC) it is measured under the rate of heat addition of 5 DEG C/min.Dihydric alcohol of the polyester based on linear binary acid and aliphatic series.In principle here
All that, which can be used, can provide required crystalline polyester A) performance binary acid and dihydric alcohol.It is however preferred to use
Binary acid is succinic acid, adipic acid, decanedioic acid, dodecanedioic acid and its mixture.In the present invention, term " binary acid " also wraps
Include its ester, acid anhydrides or acyl chlorides.If necessary, other aliphatic, alicyclic or aromatic diacids also can be used.This kind of binary
The example of acid is glutaric acid, azelaic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 1,3- cyclohexane dicarboxylic acid, 1,2- cyclohexane dicarboxylic acid, right
Phthalic acid or M-phthalic acid.
As preparing crystalline polyester A) diol component, it is preferable to use ethylene glycol, 1,4-butanediol, 1,6- oneself two
Alcohol, neopentyl glycol and its mixture, based on the integral molar quantity of whole diol components, dosage is at least 80mol%.
In one embodiment, the crystalline polyester is made of following component, and relative to being used to prepare, the crystallization is poly-
The gross weight of the component used of ester:
(i) neopentyl glycol of 51 to 55 parts by weight；With
(ii) succinic anhydride of 45 to 49 parts by weight,
Wherein, the total amount of component (i)-(ii) is 100 parts by weight.
Amorphous polyester B) hydroxyl value be 20-40mg KOH/g, preferably 25-35mg KOH/g；Its acid value is less than 6mg
KOH/g.The amorphous polyester can have the glass transition temperature within the scope of 40-75 DEG C, preferably within the scope of 40-65 DEG C
Degree.The glass transition temperature can pass through differential scanning calorimetry (DSC) in the heating of 5 DEG C/min according to ISO 11357
It is measured under rate.Amorphous polyester is based on binary acid and is made with alkoxide component, and the alkoxide component includes dihydric alcohol, and the alcohol group
Divide also extraly comprising the first alcohol of one or more ternarys or more.In principle, it is possible to amorphous needed for being assigned using all energy
Polyester B) those of performance binary acid and polyalcohol.The example of suitable binary acid include M-phthalic acid, phthalic acid,
Adipic acid, azelaic acid, decanedioic acid, dodecanedioic acid, succinic acid or Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid.However, amorphous as preparing
Polyester B) alkoxide component, it is preferable to use linear aliphatic series or alicyclic diol, dosage is at least 90mol%, be based on alkoxide component
Integral molar quantity.The dihydric alcohol is selected from ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,4-butanediol, 1,
5- pentanediol, neopentyl glycol, 1,6- hexylene glycol, 1,9- nonanediol and its mixture.In addition, the alkoxide component also extraly includes
One or more ternarys or more member alcohol.The integral molar quantity of alkoxide component based on the amorphous polyester, the alkoxide component include
Ternary of 1-10mol%, preferably 2-9mol% or more member alcohol.The ternary or polyalcohol be selected from trimethylolpropane, glycerol,
Pentaerythrite and its mixture.
In one embodiment, the amorphous polyester is made of following component, fixed relative to the nothing is used to prepare
The gross weight of the component used of shape polyester:
(i) neopentyl glycol of 37 to 39 parts by weight；
(ii) trimethylolpropane of 0.01 to 1 parts by weight；
(iii) M-phthalic acid of 58 to 61 parts by weight,
Wherein, the total amount of component (i)-(iii) is 100 parts by weight.
Crystalline polyester A) and amorphous polyester B) can according to methods known in the art by alkoxide component and acid constituents (including
Acid, its ester, acid anhydrides or acyl chlorides) it is prepared by esterification in an inert atmosphere, optionally in common esterification catalyst (such as dibutyl
Tin oxide, butyl stannonic acid or butyl titanate) and antioxidant (such as pentaerythritol diphosphites) in the presence of into
Row.Preparation condition and-COOH/-OH ratio can be selected to obtain the polyester with the hydroxyl value in target range.It is excellent
Selection of land, ontology prepare polyester resin without the use of solvent.Polycondensation reaction can 100-350 DEG C, preferably 290 DEG C or lower, more
Occur at a temperature of preferably 150-270 DEG C.Reaction time can be 1-5 hours, preferably 1-2 hours.Polycondensation reaction is preferred
Ground carries out in reactor vessel.Polycondensation reaction carries out preferably in nitrogen atmosphere.Preferably, reacted in a vacuum with
Remove the water generated during polycondensation reaction.
According to the present invention, crystalline polyester A) and amorphous polyester B) synthesis process in, can also extraly add solidification
Promotor, such as triphenyl ethyl phosphonium bromide phosphorus, to adjust the gelation of gained polyester.
According to the present invention, crystalline polyester A) and amorphous polyester B) between weight ratio there is lower hydroxyl value for obtaining
Polyester resin is important.Semi-crystalline polyester resin according to the present invention is by the way that relatively large amount is had the amorphous of low hydroxyl value
The high hydroxyl value crystalline polyester of polyester and relatively small amount is mixed to get.Such semi-crystalline polyester resin is in solidification Shi Huiyu phase
A small amount of polyisocyanates is covalently attached, thus there is excellent flow leveling by the powdery paints that it is prepared.Thus, according to
The present invention, crystalline polyester A) and amorphous polyester B) between weight ratio between 1: 9-1: 25, be more preferably between 1: 15-1: 20,
Most preferably 1: 19.
In one embodiment, the semi-crystalline polyester resin can have within the scope of 1000 to 8000g/mol, be excellent
It is selected within the scope of 2000 to 7000g/mol, the number-average molecular weight more preferably within the scope of 3000 to 6000g/mol.The half hitch
Brilliant polyester resin can have within the scope of 6000 to 30000g/mol, preferably within the scope of 8000 to 25000g/mol, be more excellent
The weight average molecular weight being selected within the scope of 8000 to 20000g/mol.GPC can be used in the number-average molecular weight and weight average molecular weight
To measure.
In one embodiment, it is measured at 160 DEG C according to ISO 3219, the melting of the semi-crystalline polyester resin is viscous
Degree is 8-35Pa.s, preferably 10-30Pa.s.
In one embodiment, the crystallinity of the semi-crystalline polyester resin is 0-60%, preferably 0-50%.Crystallization
Degree is defined as: melting heat when the practical melting heat of polymer is crystallized than upper a hundred percent, as crystallinity.Art technology
Personnel can determine crystallinity by known method by DSC.
Semi-crystalline polyester resin according to the present invention is by least one crystalline polyester and at least one nothing
The physical mixed of amorphous polyester and obtain.So-called physical mixed refers to that mixed element is caught and mixes
And there is no: i) it is related to using can dissolve or the essence of any liquid medium of dispersion powders (such as organic solvent, water)
Physical transformations and/or process and/or ii) it is related to for example chemically reacting the chemical conversion and/or process of generation.
Inventors hereof have unexpectedly found that crystalline polyester and amorphous polyester are obtained by physical mixed
The semicrystalline polyester tool that covalently synthesizes of the semicrystalline polyester compared with the amorphous polyester with similar hydroxyl value and with similar hydroxyl value
There is significantly superior flow leveling.
Powder paint compositions
According to another aspect of the present invention, a kind of cured powder paint compositions of polyisocyanates are provided, it includes:
Semi-crystalline polyester resin according to the present invention and polyisocyanate crosslinker, and optionally auxiliary agent or additive.
The content of semi-crystalline polyester resin of the invention, relative to the polyisocyanates cured powder paint composition
Gross weight, in the range of 45 to 60wt%, preferably in the range of 50 to 55wt%.
Terms used herein " polyisocyanate crosslinker " refer to polyisocyanate compound, oligomeric isocyanates or its
Combination.The polyisocyanate crosslinker contains two or more isocyanate functional groups, can be with semicrystalline polyester tree
Chain extension and cross-linking reaction occur for rouge, to form three-dimensional net structure in the coating.
Polyisocyanate crosslinker appropriate includes aliphatic polyisocyanate, aromatic polyisocyanate or any combination thereof.
Terms used herein " aliphatic polyisocyanate " refer to the polyisocyanates that isocyanate group is directly connected on aliphatic chain or ring
Compound.Terms used herein " aromatic polyisocyanate " refer to that isocyanate group is directly connected to the polyisocyanic acid on aromatic ring
Ester compounds.
As the example of polyisocyanate compound appropriate, hexamethylene diisocyanate, 12 methylenes can be used
Group diisocyanate, hexamethylene-Isosorbide-5-Nitrae-diisocyanate, 4,4 '-two cyclohexyl methane diisocyanates, pentamethylene -1,3- bis-
Isocyanates, paraphenylene diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, naphthalene-Isosorbide-5-Nitrae-diisocyanate, biphenyl -4,4 '-two is different
Cyanate, benzene -1,2,4- triisocyanate, dimethylbenzene-Isosorbide-5-Nitrae-diisocyanate, dimethylbenzene -1,3- diisocyanate, diphenyl
Methane diisocyanate, butane -1,2,3- triisocyanate or poly methylene poly phenyl poly isocyanate.
As the example of oligomeric isocyanates appropriate, any polyisocyanate compound listed above can be used
Polyurethane-type prepolymer, any polyisocyanate compound listed above polyester based prepolymers or listed above any
The polyether based prepolymers and any combination thereof of polyisocyanate compound.Polyurethane-type prepolymer, polyester based prepolymers or polyethers
Type prepolymer can be made up of any proper method known to persons of ordinary skill in the art.For example, polyurethane-type prepolymer
Can could be made by: make one of monomeric polyol and polyisocyanate compound or it is a variety of under suitable condition into
Row reaction；Polyester based prepolymers or polyether based prepolymers can could be made by: make polyester polyol or polyether polyol with
One of polyisocyanate compound a variety of is reacted under suitable condition.Alternatively, as polyurethane-type prepolymer,
Any commodity appropriate can be used in polyester based prepolymers or polyether based prepolymers.
In embodiments of the present invention, as the example of polyisocyanate crosslinker, it can be used and appoint conjunction is appropriate can
Commercial products, the B1530 (caprolactam blocked polyisocyanates) of such as Ying Chuan Specialty Chemical (Shanghai) Co., Ltd..
According to the present invention, semi-crystalline polyester resin and the weight ratio of polyisocyanate crosslinker can 6: 1 to 8: 1 model
Enclose interior variation.
The example of additive suitable for powder paint compositions includes colorant, inorganic filler, surfactant, flowing
Controlling agent, heat stabilizer, preservative, antioxidant, adhesion promoter, light stabilizer, levelling agent, defoaming agent and combinations thereof.For example, powder
Last coating composition may include colorant, such as pigments or dyes.The example packet of colorant suitable for powder paint compositions
Titanium dioxide, barium sulphide, carbon black and iron oxide are included, and can further include organic dyestuff and pigment.Suitable colorant, for example, quotient
The titanium dioxide of chemical (Shanghai) Co., Ltd. is admired purchased from section and is commercially available from the barium sulfate of Sha Haliben chemistry (Shanghai) Co., Ltd..
Colorant may make up the about 50 weight % of about 1 weight %- of powder paint compositions, more preferably about the 10 of powder paint compositions
About 45 weight % of weight %-, the even more preferably about 40 weight % of about 35 weight %- of powder paint compositions.
Exemplary inorganic filler suitable for powder paint compositions of the present invention includes but is not limited to clay, cloud
Mother, alumina silicate, fumed silica, magnesia, zinc oxide, barium monoxide, calcium sulfate, calcium oxide, aluminium oxide, oxidation magnalium, oxidation
Zinc-aluminium, magnesium oxide titanium, oxidation ferrotitanium, calcium oxide titanium and its mixture.If it does, inorganic filler constitutes, such as powder applies
The about 20 weight % of about 0 weight %- of feed composition, the more preferably about 15 weight % of about 1 weight %- of powder paint compositions,
The even more preferably about 10 weight % of about 2 weight %- of powder paint compositions.
In addition, the present invention also provides the methods for being used to prepare powder paint compositions comprising the following steps:
A) by all semi-crystalline polyester resins according to the present invention for being used to manufacture powdery paints, multi isocyanate crosslinking
Agent, optionally additive are pre-mixed crushing in premixing machine；
B) raw material crushed by premixing is passed through into extruder melting extrusion；
C) by the cooling tabletting of the material of melting extrusion；
D) tablet is crushed and is sieved by pulverizer, the powder particle for obtaining appropriate particle size is powdery paints.
Obtained powder particle is sprayed on suitable ground using electrostatic gun, is placed in the baking oven of certain temperature
Solidification.Just powder coating is obtained after solidification.The powder coating can be priming paint, finishing coat or inter coat.
In heating powder coating composition so that in its cured situation, the heating of powder paint compositions can be in certain temperature
The degree lower time for carrying out and being persistently suitble to is to solidify powder paint compositions of the invention.
The heating of powder paint compositions can use conventional method progress, such as with convection oven and/or (N) IR lamp,
And/or it can be heated using infrared laser and/or microwave equipment.
Preferably, the curing time of polyisocyanates cured powder paint composition according to the present invention is at most 60 points
Clock, more preferably up to 45 minutes, even more preferably at most 30 minutes, most preferably at most 20 minutes, in particular up to 15
Minute, more particularly at most 12 minutes, even more particularly at most 10 minutes, most particularly at most 5 minutes.
Preferably, solidify powder paint compositions according to the present invention at a temperature in the range of 130-180 DEG C and continue 5-
Time within the scope of 30 minutes；It is highly preferred that cured powder paint composition continues 5- at a temperature in the range of 130-170 DEG C
Time within the scope of 30 minutes.
Thus, the present invention also provides a kind of products, and it includes partly or entirely applied by powder according to the present invention
Feed composition or the substrate that can be coated with by the powder paint compositions obtained according to the method for the present invention.Ordinary skill
Personnel can select and determine suitable material as substrate according to actual needs.
The substrate can be the substrate of such as glass, ceramics, fiber cement board or metal (such as aluminium, copper or steel).
Test method
Unless otherwise noted, following test methods are utilized in following embodiment.
Melt viscosity
It is measured according to ISO 3219.
Glossiness
The test is used to measure the glossiness of solidify coating.20 ° and 60 ° are assessed using vancometer according to ISO 2813
Under glossiness.
Levelability
The test is for measuring flow behavior of the powder paint compositions in melt-flow.It is assessed according to ISO 8130
Levelability.
Embodiment
In the following, present disclosure is more specifically described by embodiment.These being only intended to illustrate property of embodiment
Illustrate, and be not construed as limiting protection scope of the present invention, because being carried out in scope of the present disclosure various
Amendment and variation are apparent for a person skilled in the art.
Unless otherwise stated, all parts, percentage and the ratio reported in following embodiment are by weight meter, and
And all reagents are all commercially available used in embodiment and can be used directly without being further processed.
Material
Used material is listed in the table below in 1.
Table 1: used material and relevant information
| Material | Supplier |
| Neopentyl glycol | Sigma-Aldrich |
| M-phthalic acid | Sigma-Aldrich |
| B1530 (caprolactam blocked polyisocyanates) | Ying Chuan Specialty Chemical (Shanghai) Co., Ltd. |
| Triphenyl ethyl phosphonium bromide phosphorus | Sigma-Aldrich |
| Titanium dioxide | Chemical (Shanghai) Co., Ltd. is admired by section |
| Barium sulfate | Sha Haliben chemistry (Shanghai) Co., Ltd. |
| Levelling agent | Sigma-Aldrich |
| Styrax | Sigma-Aldrich |
| Butyl stannonic acid | Sigma-Aldrich |
| Pentaerythrite diphosphorous acid rouge | Sigma-Aldrich |
| Trimethylolpropane | Sigma-Aldrich |
The preparation of semi-crystalline polyester resin
Embodiment 1:(Resin A)
Step 1:
By 591.6 grams of neopentyl glycols, nitrogen is added in 0.5 gram of catalyst butyl stannonic acid and 0.8 gram of pentaerythrite diphosphorous acid rouge
In lower 6 liters of the reactor in compression ring border, heating is heated to 150 DEG C or so, and the neopentyl glycol monomer in observing response device melts completely
After add 511.6 grams of succinic anhydrides, stir evenly.250 DEG C are heated to, at this point in the reaction, dihydric alcohol and binary
Esterifying polycondensation reaction, heat preservation to reaction system clear occur for anhydride monomers.Stop heating, controls the temperature of reaction system extremely
230 DEG C, then vacuum polycondensation 1-2 hours.Sampling analysis acid value and hydroxyl value, acid value should be less than 3mg KOH/g, and hydroxyl value should be
50-56mg KOH/g.Stop heating, discharges after cooling, it is spare.
Step 2:
By 426.4 grams of neopentyl glycols, 16.1 grams of trimethylolpropanes, 0.5 gram of catalyst butyl stannonic acid and 0.8 gram of Ji Wusi
Alcohol diphosphorous acid rouge is added in lower 6 liters of the reactor of nitrogen environment, and heating is heated to 150 DEG C or so, new in observing response device
Pentanediol monomer adds 656.7 grams of M-phthalic acid monomers after melting completely, stir evenly.250 DEG C are heated to, herein
Under reaction condition, esterifying polycondensation reaction, heat preservation to reaction system clear occur for dihydric alcohol and binary acid.Stop heating, control
The temperature of reaction system processed is to 230 DEG C, and then vacuum polycondensation 1-2 hours.Sampling analysis acid value and hydroxyl value, acid value should be less than 6mg
KOH/g, hydroxyl value should be in 25-35mg KOH/g.Stop heating, the temperature of reaction system is down to 195 DEG C from 230 DEG C, is added
The resin and 2.5 grams of curing accelerators of 50g first step synthesis, mixing discharge after 30 minutes.
Comparative example 1:(resin B)
By 448.8 grams of neopentyl glycols, 17 grams of trimethylolpropanes, 0.5 gram of catalyst butyl stannonic acid and 0.8 gram of pentaerythrite
Diphosphorous acid rouge is added in lower 6 liters of the reactor of nitrogen environment, and heating is heated to 150 DEG C or so, and new penta in observing response device
Diol monomer adds 691.3 grams of M-phthalic acids after melting completely, stir evenly.250 DEG C are heated to, reacts item herein
Under part, esterifying polycondensation reaction, heat preservation to reaction system clear occur for dihydric alcohol and dicarboxylic acid monomer.Stop heating, control
The temperature of reaction system is to 230 DEG C, and then vacuum polycondensation 1-2 hours.Sampling analysis acid value and hydroxyl value, acid value should be less than 6mg
KOH/g, hydroxyl value should be in 25-35mg KOH/g.Stop heating, the temperature of reaction system is down to 195 DEG C from 230 DEG C, is added
2.5 grams of triphenyl ethyl phosphonium bromide phosphorus discharge after 30 minutes as curing accelerator, mixing.
Comparative example 2:(resin C)
By 426.2 grams of neopentyl glycols, 40.7 grams of trimethylolpropanes, 0.5 gram of catalyst butyl stannonic acid and 0.8 gram of Ji Wusi
Alcohol diphosphorous acid rouge is added in lower 6 liters of the reactor of nitrogen environment, and heating is heated to 150 DEG C or so, new in observing response device
Pentanediol monomer adds 23.8 grams of succinic anhydrides and 666.4 grams of M-phthalic acid monomers after melting completely, stir evenly.Heating
250 DEG C are warming up to, at this point in the reaction, esterifying polycondensation reaction, heat preservation to reaction system occur for dihydric alcohol and dicarboxylic acid monomer
Clear.Stop heating, controls the temperature of reaction system to 230 DEG C, then vacuum polycondensation 1-2 hours.Sampling analysis acid value
And hydroxyl value, acid value should be less than 3mg KOH/g, hydroxyl value should be in 25-35mg KOH/g.Stop heating, by the temperature of reaction system
195 DEG C are down to from 230 DEG C, 2.5 grams of curing accelerators are added, mixing discharges after 30 minutes.
The component proportion and its performance of powder paint compositions
Powder paint compositions are prepared according to the dosage of following table 2, and spray to degreasing, iron-phosphorus using electrostatic gun
In the steel plate strip for changing processing, then baking-curing in an oven.After solidification can test powders coating performance.
Table 2:
It can be seen that from the result of upper table 2 by with the crystalline polyester of the specific hydroxyl value of certain proportion physical mixed and without fixed
Semi-crystalline polyester resin obtained from shape polyester is used directly for preparing powder paint compositions.
The solidify coating formed by this powder paint compositions, to the amorphous polyester with similar hydroxyl value and with phase
It is compared like the solidify coating that the semicrystalline polyester of hydroxyl value covalently synthesized is formed, there is significantly superior flow leveling.
All patents referred to herein, patent application and publication and can electronics obtain material entire disclosure it is equal
It is incorporated herein by reference.Detailed description of the invention and embodiment above-mentioned are used for the purpose of being clearly understood that and providing.Cannot therefrom it understand
For unnecessary restriction.The present invention is not limited to shown and described fine details, for those skilled in the art significantly
Variation will be included in the present invention being defined by the claims.In some embodiments, property described herein it is public
The present invention opened not specifically disclosed any element can be implemented in the case where being not present herein.
Although the present invention is described referring to a large amount of embodiments and examples, those of ordinary skill in the art according to
Present disclosure, which is able to recognize that, can design other embodiment, this is without departing from protection scope of the present invention and essence
Mind.
Claims (14)
1. a kind of cured powdery paints semi-crystalline polyester resin of polyisocyanates, it includes:
A) at least one crystalline polyester, hydroxyl value are 50-70mg KOH/g；With
B) at least one amorphous polyester, hydroxyl value are 20-40mg KOH/g；
Wherein the weight ratio of A:B is between 1:9-1:25；And
Wherein the number-average molecular weight of the semi-crystalline polyester resin is 1000-8000g/mol.
2. semi-crystalline polyester resin according to claim 1, wherein the weight ratio of A:B is between 1:15-1:20.
3. semi-crystalline polyester resin according to claim 1, wherein the melting temperature of the crystalline polyester is 50-100
℃。
4. semi-crystalline polyester resin according to claim 1, wherein the glass transition temperature of the amorphous polyester is
40-75℃。
5. semi-crystalline polyester resin according to claim 1, wherein measured at 160 DEG C according to ISO 3219, described half
The melt viscosity of crystallized polyurethane resin is 8-35Pa.s.
6. semi-crystalline polyester resin according to claim 1, wherein pass through dsc measurement, the half hitch according to ISO11357
The crystallinity of brilliant polyester resin is 0-60%.
7. semi-crystalline polyester resin as claimed in any of claims 1 to 6, wherein the crystalline polyester is by least
Following component is made: binary acid, and it is corresponding that the binary acid is selected from succinic acid, adipic acid, decanedioic acid, dodecanedioic acid, these acid
Acid anhydrides, ester or acyl chlorides and its mixture；Dihydric alcohol, the dihydric alcohol be selected from ethylene glycol, 1,4-butanediol, 1,6- hexylene glycol,
Neopentyl glycol and its mixture.
8. semi-crystalline polyester resin as claimed in any of claims 1 to 6, wherein the amorphous polyester is by two
First acid is made with alkoxide component, and the alkoxide component includes dihydric alcohol, and the alkoxide component also extraly includes one or more three
Member or more member alcohol.
9. semi-crystalline polyester resin according to claim 8, wherein the alkoxide component based on the amorphous polyester always rubs
You measure, and the alkoxide component includes the first alcohol of ternary of 1-10mol% or more.
10. semi-crystalline polyester resin according to claim 8, wherein the dihydric alcohol be selected from ethylene glycol, diethylene glycol,
Neopentyl glycol, cyclohexanedimethanol, 1,4- butanediol, 1,5- pentanediol, neopentyl glycol, 1,6-HD, 1,9- nonanediol and
Its mixture；The ternary or polyalcohol are selected from trimethylolpropane, glycerol, pentaerythrite and its mixture.
11. semi-crystalline polyester resin as claimed in any of claims 1 to 6, wherein the crystalline polyester is by following
Component is made, the gross weight relative to the component used for being used to prepare the crystalline polyester:
(i) neopentyl glycol of 51 to 55 parts by weight；
(ii) succinic anhydride of 45 to 49 parts by weight.
Wherein, the total amount of component (i)-(ii) is 100 parts by weight.
12. semi-crystalline polyester resin as claimed in any of claims 1 to 6, wherein the amorphous polyester is under
Column component is made, the gross weight relative to the component used for being used to prepare the amorphous polyester:
(i) neopentyl glycol of 37 to 39 parts by weight；
(ii) trimethylolpropane of 0.01 to 1 parts by weight；
(iii) M-phthalic acid of 58 to 61 parts by weight.
Wherein, the total amount of component (i)-(iii) is 100 parts by weight.
13. semi-crystalline polyester resin as claimed in any of claims 1 to 6, wherein the semi-crystalline polyester resin
It is to be obtained by the physical mixed of at least one crystalline polyester and at least one amorphous polyester.
14. a kind of powder paint compositions, it includes semi-crystalline polyester resin described in claim 1-13 and polyisocyanic acid
Ester crosslinking agent, and optionally additive.
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| CN108752572A (en) * | 2018-05-22 | 2018-11-06 | 浙江光华科技股份有限公司 | A kind of preparation method of hypocrystalline high-melting-point hydroxyl telechelic polyester resin |
| CN112424286B (en) * | 2019-11-21 | 2023-01-31 | 擎天材料科技有限公司 | Polyester resin composition and preparation method and application thereof |
| CN112457474A (en) * | 2020-10-11 | 2021-03-09 | 芜湖市森沐知识产权科技服务有限公司 | Low-temperature cured hydroxyl polyester resin |
| CN114231135A (en) * | 2021-12-23 | 2022-03-25 | 安徽神剑新材料股份有限公司 | Outdoor mirror powder coating, preparation method thereof and coating formed by same |
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