CN103764774B - Coating composition, and preparation method thereof - Google Patents

Coating composition, and preparation method thereof Download PDF

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Publication number
CN103764774B
CN103764774B CN201180071494.7A CN201180071494A CN103764774B CN 103764774 B CN103764774 B CN 103764774B CN 201180071494 A CN201180071494 A CN 201180071494A CN 103764774 B CN103764774 B CN 103764774B
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weight
coating composition
dispersion
alkyd
acid
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CN103764774A (en
Inventor
C.坎
R.奥蒂兹
J.罗珀
J.维尔
T.扬
G.斯皮尔曼
R.德鲁姆赖特
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Dow Global Technologies LLC
Rohm and Haas Co
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Dow Global Technologies LLC
Rohm and Haas Co
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Priority claimed from PCT/US2011/031765 external-priority patent/WO2012138348A1/en
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Abstract

The present invention provides coating composition, the method preparing coating composition, is derived from one or more dope layers of this coating composition, and includes the goods of one or more such dope layer.Coating composition according to the present invention comprises: aqueous, high solids content, the solvent-free alkyd dispersion of (a) 10 to 90 weight %, this dispersion comprises: one or more alkyd resin of (i) 40 to 70 weight %, gross weight based on described dispersion, the wherein said respective acid number of one or more alkyd resin is less than 20 and molecular weight (Mn) it is more than 1000 dalton；(ii) less than one or more surfactants of 10 weight %, gross weight based on described dispersion；(iii) water of 30 to 55 weight %, gross weight based on described dispersion；Wherein said mean particle diameter aqueous, high solids content, solvent-free alkyd dispersion is 0.05 to 5 μm；One or more second dispersions of (b) 10 to 90 weight %, one or more the second emulsion or a combination thereofs；The solid content of wherein said coating composition is the solid content of 25 to 65 weight %, gross weight based on described coating composition, the pH of described coating composition is 7 to 11, and the volume average particle sizes of wherein said coating composition is 0.03 to 5 μm, and the viscosity of wherein said coating composition is 100 to 10,000cP.

Description

Coating composition, and preparation method thereof
Technical field
The present invention relates to coating composition, the method preparing coating composition, it is derived from of this coating composition or many Individual dope layer, and include the goods of such dope layer.
Background technology
Alkyd resin is the Major Members of Coating Market.The major part of this sales item is still based on solvent-based coating.Water base Coating becomes more and more important, because solution stands the strictest VOC (" VOC ") regulation.At present, Alkyd resin based on water be emulsion or can diminishing thing (water-reducibles) (can with in water-soluble mixed solvent) shape Formula.The alkyd resin being currently based on water uses low-molecular-weight resin to prepare, this low-molecular-weight resin or to have high acid value (the most right In neutralizing more than 50 with amine, thus improve water-dispersible by forming salt), or have the emulsifying agent of high-load or stabilizer or Particular functional effect is such as with as modified in monomer chemistries such as Polyethylene Glycol or the compounds containing sulphonic acid ester/salt.
However it is still necessary to coating composition based on alkyd dispersion, wherein alkyd dispersion has Gao Gu Body burden, ultralow VOC, and wherein it is derived from coating composition based on such alkyd dispersion One or more dope layers have improvement coating performance and with the suitable performance of those coatings of grade solvent alkyd resin, And without functionalized resins and/or non-blended form.Therefore, the present invention provides Coating material composition based on alkyd dispersion Thing, wherein said alkyd dispersion has VOC highly filled, ultralow, and wherein Coating material composition Thing have improvement coating performance and with the suitable performance of those coatings of grade solvent alkyd resin, and without functionalized resins And/or non-blended form.
Summary of the invention
The present invention provides coating composition, the method preparing coating composition, is derived from of this coating composition or many Individual dope layer, and include the goods of one or more such dope layer.
In one embodiment, the present invention provides coating composition, and it comprises:
A aqueous, high solids content, the solvent-free alkyd dispersion of () 10 to 90 weight %, this dispersion comprises: (i) One or more alkyd resin of 40 to 70 weight %, gross weight based on described dispersion, one or more alkyd wherein said The respective acid number of resin is less than 20 and molecular weight (Mn) it is more than 1000 dalton；(ii) less than one or more of 10 weight % Surfactant, gross weight based on described dispersion；(iii) water of 30 to 55 weight %, gross weight based on described dispersion Amount；Wherein said mean particle diameter aqueous, high solids content, solvent-free alkyd dispersion is 0.05 to 5 μm；(b) One or more second dispersions of 10 to 90 weight %, one or more the second emulsion or a combination thereofs；Wherein said Coating material composition The solid content of thing is the solid content of 25 to 65 weight %, gross weight based on described coating composition, the pH of described coating composition It is 7 to 11, and the volume average particle sizes of wherein said coating composition is 0.03 to 5 μm, and wherein said Coating material composition The viscosity of thing is 100 to 10,000cP.
In interchangeable embodiment, the present invention further provides the method preparing coating composition, including following step Rapid: (1) provides one or more melted or the alkyd resin of liquid, one or more melted or alkyd trees of liquid wherein said The respective acid number of fat is less than 20 and molecular weight (Mn) it is more than 1000 dalton；(2) one or more surfactants are provided； (3) water is provided；(4) one or more nertralizers optionally provided；(5) one or more melted or alkyd trees of liquid described are made Fat in water one or more surfactants described and optional described in the presence of one or more nertralizers continuously Emulsifying；(6) thus prepare High Internal Phase Emulsion；(7) other water is provided；(8) described High Internal Phase Emulsion and described other water are made Contact；(9) thus prepare described aqueous alkyd dispersion, wherein said alkyd dispersion comprises 40 to 70 weights One or more alkyd resin described of amount %, less than one or more surfactants described in 10 weight %, and wherein institute The mean particle diameter stating dispersion is 0.05 to 5 μm；(10) one or more second dispersions and/or the second emulsion are provided； (11) described alkyd dispersion and one or more second dispersions and/or the second emulsion contacts are made；(12) thus shape Become described coating composition.
In interchangeable embodiment, present invention offer is derived from coating composition of the present invention as here depicted One or more dope layers.
In interchangeable embodiment, the present invention provides the Coating material composition of the present invention including being derived from as here depicted The goods of one or more dope layers of thing.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the second dispersion is selected from polyolefin dispersion, poly- Urethane dispersion, epoxy resin dispersion, polyester dispersions, and combinations thereof.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the second emulsion is selected from following latex: propylene Acrylic latex, vinyl-acetic ester acrylic latex, styrene-acrylonitrile copolymer acids latex, vinylacetate ethylene latex, and A combination thereof.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that described dope layer include pendulum hardness be 50 to The film of 150 seconds, the thickness of wherein said film is at least 40 μm.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that described dope layer includes modulus hardness (modulus Hardness) it is (2*107) to (1*1011) dyne/cm2Film.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that described dope layer includes resistance to frontal impact (direct impact resistance) is the film of 65 to 160 inchpounds.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that described dope layer includes resistance to reverse impact (reverse impact resistance) is the film of 20 to 160 inchpounds.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that described dope layer includes film, this film 60 ° Little loss of gloss after QUV is less than 30；Such as, less than 20, less than 15, less than 10, less than 5, less than 2, or less than 1.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that described dope layer includes film, this film 20 ° Little loss of gloss after QUV is less than 50；Such as, less than 40, less than 30, less than 20, or less than 10.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that described dope layer includes film, this film is after QUV The change of Δ E color less than 8；Such as, less than 5, less than 4, or less than 3.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that one or more alkyd resin are neutralized by nertralizer At most 100%.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the viscosity of alkyd dispersion is 100 to 10, 000cP。
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that one or more alkyd resin are neutralized by nertralizer At most 200%.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the solid content of alkyd dispersion is more than 60wt%, weight based on alkyd dispersion.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the solid content of alkyd dispersion is more than 65wt%, weight based on alkyd dispersion.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the solid content of alkyd dispersion is more than 70wt%, weight based on alkyd dispersion.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the acid number of described alkyd resin is less than 20.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the acid number of described alkyd resin is less than 15.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that the acid number of described alkyd resin is less than 10.
In interchangeable embodiment, the present invention provide according to the coating composition any one of aforementioned embodiments, Method, the one or more dope layers being derived from coating composition of the present invention of preparing coating composition and include being derived from this The goods of one or more dope layers of bright coating composition, except that alkyd dispersion has the heat ageing of improvement Stability, i.e. initial average external volume particle size diameter and final average external volume particle size diameter (are i.e. being tested according to hot ageing stability After the accelerated ageing of method) difference less than 20%.
Accompanying drawing explanation
For the purpose of the present invention is described, shown in accompanying drawing is exemplary form；It should be understood, however, that this Bright it is not limited to shown accurate structure and instrument.
Fig. 1 is photo, illustrates the change of the color after QUV of the embodiment of the present invention 9 (being expressed as 3), and the present invention is real Execute the color change after the QUV of example 10 (being expressed as 4), and the color change after the QUV of comparative example's (being expressed as 73)； With
Fig. 2 is photo, illustrates resistance to after brine spray Kesternich test of the embodiment of the present invention 13 (being expressed as 9D) Corrosivity, and the corrosion resistance after brine spray Kesternich test of the embodiment of the present invention 14 (being expressed as 10D).
Detailed description of the invention
The present invention relates to coating composition, the method preparing coating composition, it is derived from of this coating composition or many Individual dope layer, and include the goods of one or more such dope layer.
Coating composition according to the present invention comprises: aqueous, high solids content, the solvent-free alkyd of (a) 10 to 90 weight % Resin dispersion, this dispersion comprises: one or more alkyd resin of (i) 40 to 70 weight %, based on described dispersion total Weight, the wherein said respective acid number of one or more alkyd resin is less than 20 and molecular weight (Mn) it is more than 1000 dalton； (ii) less than one or more surfactants of 10 weight %, gross weight based on described dispersion；(iii) 30 to 55 weight The water of amount %, gross weight based on described dispersion；Wherein said aqueous, high solids content, solvent-free alkyd dispersion Mean particle diameter is 0.05 to 5 μm；One or more second dispersions of (b) 10 to 90 weight %, one or more second breasts Liquid or a combination thereof；The solid content of wherein said coating composition is the solid content of 25 to 65 weight %, based on described coating composition Gross weight, the pH of described coating composition is 7 to 11, and the volume average particle sizes of wherein said coating composition is 0.03 To 5 μm, and the viscosity of wherein said coating composition is 100 to 10,000cP.
The method preparing coating composition of the present invention comprises the following steps: (1) provides one or more melted or liquid Alkyd resin, one or more melted or liquid respective acid numbers of alkyd resin wherein said are less than 20 and molecular weight (Mn) it is More than 1000 dalton；(2) one or more surfactants are provided；(3) water is provided；(4) optionally provided one or more Nertralizer；(5) make the alkyd resin of one or more melted or liquid described in one or more surface activitys described in water Emulsifying continuously in the presence of agent and optional one or more nertralizers described；(6) thus prepare High Internal Phase Emulsion；(7) carry For other water；(8) described High Internal Phase Emulsion is made to contact with described other water；(9) thus prepare described aqueous alkyd tree Fat dispersion, wherein said alkyd dispersion comprises one or more alkyd resin described in 40 to 70 weight %, less than 10 One or more surfactants described of weight %, and the mean particle diameter of wherein said dispersion is 0.05 to 5 μm； (10) one or more second dispersions and/or the second emulsion are provided；(11) described alkyd dispersion and one or many are made Plant the second dispersion and/or the second emulsion contacts；(12) thus form described coating composition.
In interchangeable embodiment, present invention offer is derived from coating composition of the present invention as here depicted One or more dope layers, and include the goods of one or more such dope layer.
Coating composition according to the present invention can comprise one or more optional solvents further；Optional one or Multiple cosolvent；One or more optional fillers；One or more optional additives；One or more optional pigment, Such as titanium dioxide, Muscovitum, calcium carbonate, silicon dioxide, zinc oxide, milled glass, aluminum trihydrate, Talcum, antimony trioxide, fly Ash and clay；One or more optional modified pigments, the pigment of such as polymeric encapsulate, such as the titanium dioxide of polymeric encapsulate Titanium, the zinc oxide of polymeric encapsulate, and the Griffith's zinc white. of polymeric encapsulate, comprise titanium dioxide and the one being connected with its surface or Multiple polymers or the optional pigment of emulsion, one or more optional hollow spheres, including containing one or more spaces Such hollow sphere；One or more optional dispersants, such as amino alcohol, and polycarboxylate or salt；Optional one or Kinds of surface activating agent；One or more optional defoamer；One or more optional preservative, such as biocides, Antifungus agent, antifungal, algaecide, and combinations thereof；One or more optional thickening agents, such as based on cellulose family increasing Thick dose, the alkali-soluble emulsion of such as hydroxy ethyl cellulose, hydrophobically modified and the ethoxylated urethane of hydrophobically modified increase Thick dose (HEUR)；One or more optional biocides；One or more optional defoamer；Optional one or more Flowable；One or more optional levelling agents；Or one or more optional other nertralizers, such as hydroxide, amine, Ammonia and carbonate.
Coating composition can comprise coloring agent further.Multiple coloring agent can be used.Example includes that pigment is the most yellow Color, magenta and green pigment.As black colorant, it is possible to use white carbon black and use yellow/magenta/cyan shown below The coloring agent of coloring agent furnishing black.Coloring agent used in this application includes dyestuff, pigment and predispersion etc..These colorings Agent can be used alone, uses as a mixture or use as solid solution.In various embodiments, pigment can carry For for following form: untreated pigment, the pigment of process, the pigment of pre-grinding, pigment powder, pigment press cake, pigment mother criticize Material, recovery pigment and solid or liquid pigment predispersion.As used in this application, untreated pigment is following pigment Grain, not to its surface applied wettability treatment, such as, makes various painting be deposited on its surface.Untreated pigment and the pigment of process Discuss in PCT Publication WO2005/095277 and U.S. Patent Application Publication 20060078485 further, the phase of these documents Pass part is incorporated by reference into the application.On the contrary, the pigment of process can have gone through wettability treatment, such as thus at granule Surface provides coating of metal oxides.The example of coating of metal oxides includes aluminium oxide, silicon dioxide and zirconium oxide.Reclaim Pigment is also used as starting pigment granule, and wherein reclaiming pigment is to be insufficient as at the moistening that coating pigment is sold in quality Pigment after reason.
Exemplary colorant particle includes but not limited to following pigment, such as, can use yellow colorants, representative Compound for condensation azo-compound (condensed azo compound), Isoindolone compounds, anthraquinone compounds, idol Nitrogen metal complex methylidyne compound and allyl amide compound.As magenta colorant, it is possible to use condensation azo compounds Thing, diketopyrrolo-pyrrole compound, anthraquinone, quinoline Azone compound, base dye lake (base dye lake) compound, naphthalene Phenolic compounds, benzimidazolone compound, thioindigo compound and perylene compound.As cyan colorant, it is possible to use Copper phthalocyanine compound and derivant, anthraquinone compounds, base dye lake compound etc..
Alkyd dispersion component
Coating composition comprises aqueous, high solids content, the solvent-free alkyd dispersion of 10 to 90 weight %；Such as, It is 20 to 90 weight %；Or in interchangeable embodiment, be 30 to 90 weight %；Or in interchangeable embodiment, for 40 to 85 weight %；Or in interchangeable embodiment, be 30 to 80 weight %.The application include and discloses 10 to 90 weights The all single numerical value of amount % and subrange；Such as, percentage by weight can be lower limit 10 weight %, 20 weight %, 30 weight %, 40 weight %, 50 weight %, 60 weight %, 70 weight %, 80 weight % or 85 weight % are to higher limit 20 weight %, 30 weight %, 40 weights Amount %, 50 weight %, 60 weight %, 70 weight %, 80 weight % or 90 weight %.Alkyd dispersion comprises 40 to 70 weight % One or more alkyd resin.The application include and discloses all single numerical value and the subrange of 40 to 70 weight %；Such as, Percentage by weight can be lower limit 40,45,50,55 or 60 to higher limit 60,65 or 70.One or more alkyd resin are each From acid number be 20 or less.The application include and discloses all single numerical value and the subrange of 20 or less acid numbers；Such as, Acid number can be lower limit 0.1,0.5,1,2,5,70 or 10 to higher limit 5,7,10,15 or 20.One or more alkyd resin Respective molecular weight (Mn) it is equal to or more than 1000 dalton；Such as, equal to or more than 2000 dalton, or interchangeable In embodiment, equal to or more than 4000 dalton.
The alkyd resin being applicable to the present invention is 100 to 1,500 in the viscosity of 80 DEG C He the shear rate of 0.10/sec, 000 centipoise (mPa s).It is 100 to 1,500,000 that the application include and discloses the shear rate at 80 DEG C He 0.10/sec The all single numerical value of centipoise (mPa s) and subrange；Such as, the viscosity at 80 DEG C He the shear rate of 0.10/sec is permissible For lower limit 100 centipoise (mPa s), 1000mPa s, 5000mPa s, 15000mPa s or 25000mPa s to the upper limit It is worth 100,000 centipoises (mPa s), 250,000mPa s, 500,00mPa s, 750,000mPa s, 1,000,000mPa S or 1,500,000mPa s.
Alkyd resin is that polyhydric alcohol and polycarboxylic acid pass through chemical bond in varing proportions with various drying oil and semi-drying oil Polyester.Polyhydric alcohol can include but not limited to, example component described as follows: ethylene glycol, diethylene glycol, neopentyl glycol, Isosorbide-5-Nitrae-fourth two Alcohol, 1,6-HD, glycerol, tetramethylolmethane, Sorbitol and mannitol.
Therefore suitable glycol includes, ethylene glycol, propylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), five glycol, hexaethylene glycol, Seven glycol, eight glycol, nine glycol, ten glycol, neopentyl glycol, glycerol (glycerol), 1,3-propylene glycol, 2,4-dimethyl-2- Ethyl-hexan-1,3-glycol, 2,2-dimethyl-1,2-propylene glycol, 2-ethyl-2-butyl-1,3-propylene glycol, 2-ethyl-2-are different Butyl-1,3-propylene glycol, 1,3 butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-HD, 2,2,4-trimethyl-1,6- Hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2,4-tri- Methyl isophthalic acid, 3-pentanediol, 2,2,4-tetramethyl-1,3-cyclobutanediol, xylol glycol, hydroxyl neopentyl hydroxy new pentane acid Ester, 1,10-decanediol, hydrogenated bisphenol A, trimethylolpropane, trimethylolethane, tetramethylolmethane, erythritol, threitol, Dipentaerythritol, Sorbitol, mannitol, glycerol (glycerine), trimellitic anhydride, pyromellitic acid dianhydride, dihydroxymethyl third Acid etc..
Polycarboxylic acid can include but not limited to phthalic acid, maleic acid, fumaric acid, M-phthalic acid, succinic acid, oneself two Acid, Azelaic Acid and decanedioic acid, p-phthalic acid, tetrachlorophthalic tetrachlorophthalic anhydrid, tetrabydrophthalic anhydride, dodecanedioic acid, the last of the ten Heavenly stems Diacid, Azelaic Acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 2,6 naphthalene dicarboxylic acid, 1,3-propanedicarboxylic acid, trimellitic acid Acid anhydride, citric acid, pyromellitic acid anhydride, trimesic acid, sulfoisophthalic acid sodium and the anhydride of such acid and ester thereof (when present).Monocarboxylic acid, monocarboxylic acid can be optionally used to include but not limited to benzoic acid.
Drying oil can include but not limited to Oleum Cocois, fish oil, Semen Lini oil, Oleum Verniciae fordii, Oleum Ricini, cottonseed oil, Flos Carthami Oil, Oleum helianthi, soybean oil and tall oil.
Except with the polyhydric alcohol amount of fatty acid, fatty acid ester or naturally-produced partly-hydrolysed oil reaction in addition to, can make Polyhydric alcohol or other branching agent (such as polycarboxylic acid) by additional amount make the molecular weight of alkyd resin and branched increase, and described The polyhydric alcohol of additional amount or other branching agent can be selected from trimethylolethane, tetramethylolmethane, erythritol, threitol, two seasons Penta tetrol, Sorbitol, glycerol, trimellitic anhydride, pyromellitic acid dianhydride, dihydromethyl propionic acid and trimethylolpropane.
Alkyd resin can pass through, and such as, prepared by directly melting of glycerol, phthalic anhydride and drying oil.Permissible Add solvent and reduce viscosity.Use the polycarboxylic acid of various ratio, polyhydric alcohol and oil to obtain the alkyd tree with various character Fat, as known in the art.
Alkyd resin may further include any one or more of modification, and such as, alkyd resin can be that polyurethane changes Property, acrylic modified, phenylethene modified, that vinyl esters is modified, vinyl ethers is modified, organic-silicon-modified, Epoxy resin modification, and combinations thereof etc..
One or more alkyd resin are permissible, such as, are one or more urethane alkyd resins (uralkyds), The most urethane-modified alkyd resin.Urethane alkyd resins can be by making have isocyanate-reactive group Alkyd resin prepare with polyisocyanates and optional other component reaction with isocyanate-reactive group.Carbimide. Ester reactive group is defined as the group that will react with isocyanate groups (-NCO), and example includes-OH ,-NH2,-NH-and- SH.Preferably isocyanate-reactive group is-OH.Other component includes but not limited to polyamines and polyhydric alcohol, and such as having can In water, the polyhydric alcohol of scattered group, as described below.
The example of suitable polyisocyanates (usually diisocyanate) includes aliphatic series and alicyclic polyisocyanates, example As ethylidene diisocyanate, 1,6-hexamethylene diisocyanate HDI, isophorone diisocyanate (IPDI), hexamethylene- 1,4-diisocyanate, 4,4'-dicyclohexyl methyl hydride diisocyanate, cyclopentadiene diisocyanate, p-four-methyl dimethoxy Phenylene diisocyanate (p-TMXDI) and meta-isomer (m-TMXDI), hydrogenation 2,4 toluene diisocyanate and hydrogenation 2, 6-toluene di-isocyanate(TDI).It is used as araliphatic and aromatic polyisocyanate, such as p-xylene diisocyanate, Isosorbide-5-Nitrae- Phenylene vulcabond, 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), 4,4'-diphenyl methane two isocyanide Acid esters, 2,4'-methyl diphenylene diisocyanate and 1,5-naphthalene diisocyanate.Particularly preferably 2,4-toluene diisocynate Ester (TDI), optionally with its 2, in the mixture of 6-isomer.
Two functional alcohol, trifunctional alcohol is included for preparing the example of the suitable polyhydric alcohol of urethane alkyd resins (such as, glycerol, trimethylolpropane, trimethylolethane, tri hydroxy methyl butane, trihydroxy ethyl isocyanurate etc.), four Unit alcohol or the alcohol (such as, tetramethylolmethane, diglycerol etc.) of higher level, and combinations thereof.Trifunctional alcohol is preferred, is because them The degree of branching allowed.If used, two functional alcohol (or glycol) are preferably to make with the combination of the alcohol of trifunctional alcohol or higher level With.The example of suitable glycol includes neopentyl glycol (NPG), ethylene glycol, propylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), five sweet Alcohol, hexaethylene glycol, seven glycol, eight glycol, nine glycol, ten glycol, 1,3-propylene glycol, 2,4-dimethyl-2-ethyl-hexan-1,3- Glycol, 2,2-dimethyl-1,2-propylene glycol, 2-ethyl-2-butyl-1,3-propylene glycol, 2-ethyl-2-isobutyl group-1,3-the third two Alcohol, 1,3 butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-HD, 2,2,4-trimethyl-1,6-HD, sulfur generation two Ethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2,4-trimethyl-1,3-penta 2 Alcohol, 2,2,4-trimethyl-1,3-cyclobutanediol, xylol glycol, hydroxyl neopentyl hydroxy new pentane acid ester, 1,10-last of the ten Heavenly stems two Alcohol and hydrogenated bisphenol A.
The reactant mixture preparing alkyd resin includes that the polymerization of one or more aliphatic series or aromatic multi-carboxy acid, its esterification is produced Thing, and combinations thereof.As used in this application, term " polycarboxylic acid " includes polycarboxylic acid and acid anhydride thereof simultaneously.It is suitable for the present invention many The example of carboxylic acid includes phthalic acid, M-phthalic acid, p-phthalic acid, tetrahydrophthalic acid, naphthalenedicarboxylic acid and acid anhydride thereof And combinations thereof.
Can also use polyisocyanates mixture and by introduce carbamate, allophanate, urea, Many isocyanides that biuret, carbodiimides, uretonimine (uretonimine) or isocyanurate residues (residues) are modified Acid esters.
Alkyd resin can be included in scattered group in water, such as, ionic group such as anionic carboxylic acid group, and/or Non-ionic scattered group such as poly(ethylene oxide) (PEO) chain group in water.
The suitable polyhydric alcohol with hydroxy-acid group is, such as, low-molecular-weight (< 500 dalton) polyhydric alcohol, particularly two Alcohol, thus can be provided carboxylate anion group by hydroxy-acid group after neutralizing with suitable alkali.Suitable glycol include but It is not limited to dihydroxy alkanol acid resin and 2,2-dihydromethyl propionic acid (DMPA).
One or more alkyd resin partially or completely can neutralize with nertralizer.In some embodiments, Yi Zhonghuo The neutralization on a molar basis of multiple alkyd resin can be 5 to 200%；Or in interchangeable embodiment, it is at a mole base Neutralization on plinth can be 25 to 100%.Nertralizer can be alkali, such as ammonium hydroxide or potassium hydroxide.Other nertralizer such as may be used To include Lithium hydrate or sodium hydroxide.In another kind of interchangeable embodiment, nertralizer is permissible, such as, is carbonate. In another kind of interchangeable embodiment, nertralizer is permissible, such as, is any amine, such as monoethanolamine or 2-amino-2-first Base-1-propanol (AMP).Amine for embodiment disclosed in the present application can include monoethanolamine, diethanolamine, three ethanol Amine and TRIS AMINO (respectively purchased from Angus), NEUTROL TE (purchased from BASF) and triisopropanolamine, diisopropanolamine (DIPA), And N, N-dimethylethanolamine (respectively purchased from The Dow Chemical Company, Midland, MI).Other useful amine can To include ammonia, MMA, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single n-propylamine, dimethyl n propylamine, N-first Hydramine, N-amino ethyl ethanolamine, N methyldiethanol amine, monoisopropanolamine, N, N-dimethyl propanol amine, 2-amino-2-first Base-1-propanol, three (hydroxymethyl)-aminomethanes, N, N, N'N'-tetra-(2-hydroxypropyl) ethylenediamine, 1.2-diaminopropanes. In some embodiments, it is possible to use the mixture of amine or amine and the mixture of alkali.Will be apparent to those skilled in the art that Prepared particular composition is depended in selection to suitable nertralizer, and knows that such selection is common in this area Within technical staff's ken.
Aqueous alkyd dispersion also comprises one or more stabilizers less than 10 weight %, based on dispersion total Weight.The application include and discloses all single numerical value less than 10 weight % and subrange；Such as, percentage by weight is permissible For lower limit 1,2,3,4,5,6 or 7 weight % to higher limit 2,3,4,6,8,9 or 10.Stabilizer is permissible, such as, is outside steady Determine agent or internal stability agent.In the embodiment selected, stabilizer can be surfactant, polymer or its mixture. In some embodiments, stabilizer can be polar polymer, and it comprises the polar group as comonomer or grafted monomers Group.In exemplary embodiment, stabilizer includes one or more polar polyolefins, and it comprises as comonomer or grafting The polar group of monomer.Exemplary polymer stabilizer includes but not limited to, ethylene-acrylic acid (EAA) copolymer and ethylene- Methacrylic acid copolymer, as with trade mark PRIMACORTMIt is purchased from Dow Chemical Company commercially, with trade mark NUCRELTMCommercially purchased from E.I.DuPont de Nemours with trade mark ESCORTMIt is purchased from commercially Those of ExxonMobil Chemical Company, and it is described in United States Patent (USP) 4,599,392,4,988,781 and 5,938,437, aforementioned each piece document is the most all incorporated by reference into the application.Other exemplary polymer stabilizer include but It is not limited to, ethylene-ethylacrylate (EEA) copolymer, ethylene methyl methacrylate (EMMA) copolymer and ethylene-propylene Acid butyl ester (EBA) copolymer.Other ethylene-carboxylic acid's copolymer can also be used.Will be apparent to those skilled in the art that and also may be used To use other useful polymer a lot.
Other stabilizer spendable includes but not limited to, comprises the long-chain fatty acid of 12 to 60 carbon atoms, fatty acid Salt or fatty acid alkyl esters.In other embodiments, can to comprise 12 to 40 carbon former for long-chain fatty acid or soap Son.
Stabilizer partially or completely can neutralize with nertralizer.In some embodiments, stabilizer is (such as long-chain fatty acid Or EAA) neutralization on a molar basis can be 25 to 200%；Or in interchangeable embodiment, it is on a molar basis Neutralization can be 50 to 110%.Such as, for EAA, nertralizer can be alkali, such as ammonium hydroxide or potassium hydroxide.In other Mediating recipe can include such as Lithium hydrate or sodium hydroxide.In another kind of interchangeable embodiment, nertralizer is permissible, example As, it is carbonate.In another kind of interchangeable embodiment, nertralizer is permissible, such as, is amine, such as monoethanolamine or 2- Amino-2-methyl-1-propanol (AMP).Amine for embodiment disclosed in the present application can include monoethanolamine, diethanol Amine, triethanolamine and TRIS AMINO (respectively purchased from Angus), NEUTROL TE (purchased from BASF) and triisopropanolamine, two Isopropanolamine and N, N-dimethylethanolamine (respectively purchased from The Dow Chemical Company, Midland, MI).Other has Amine can include ammonia, MMA, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single n-propylamine, dimethyl n Propylamine, N-carbinolamine, N-amino ethyl ethanolamine, N methyldiethanol amine, monoisopropanolamine, N, N-dimethyl propanol amine, 2- Amino-2-methyl-1-propanol, three (hydroxymethyl)-aminomethanes, N, N, N'N'-tetra-(2-hydroxypropyl) ethylenediamine, 1.2-bis- Aminopropane.In some embodiments, it is possible to use the mixture of amine or amine and the mixture of surfactant.This area is general Leading to and skilled artisans will appreciate that, prepared particular composition is depended in the selection to suitable nertralizer, and knows such Selection is within those of ordinary skill in the art's ken.
The other stabilizer that can be used for present invention practice includes but not limited to cationic surfactant, anionic surface Activating agent or nonionic surfactant.The example of anion surfactant include but not limited to sulfonate, carboxylate and Phosphate.The example of cationic surfactant includes but not limited to quaternary amine.The example of nonionic surfactant include but not It is limited to block copolymer and the organic silicon surfactant comprising oxirane.Outside the stabilizer of present invention practice can be Portion's surfactant or Internal surfactants.External surfactants is not occur chemical reaction to combine in prepared by dispersion Enter the surfactant in alkyd resin.Example for the external surfactants of the application includes but not limited to dodecyl Benzene sulfonate and dodecane sulfonate.Internal surfactants is chemical reaction to be occurred to be incorporated into alcohol in prepared by dispersion Surfactant in acid resin.Example for the Internal surfactants of the application include 2,2-dihydromethyl propionic acid and Salt.Other surfactant of the practice that can be used for the present invention includes cationic surfactant, anion surfactant, non- Ionic surface active agent or a combination thereof.Various commercially available surfactants may be used for embodiment disclosed in the present application, this Including: OP-100 (sodium stearate), OPK-1000 (potassium stearate), and OPK-181 (potassium oleate), respectively purchased from RTD Hallstar；UNICID350, purchased from Baker Petrolite；DISPONIL FES77-IS、DISPONIL FES-32-IS、 DISPONIL FES-993 and DISPONIL TA-430, respectively purchased from Cognis；RHODAPEX CO-436, SOPROPHOR4D384,3D-33, and 796/P, RHODACAL BX-78 and LDS-22, RHODAFAC RE-610, and RM-710, With SUPRAGIL MNS/90, respectively it is purchased from Rhodia；E-sperse100, E-sperse700, and E-sperse701, be purchased from Ethox Chemical；With TRITON QS-15, TRITON W-30, DOWFAX2A1, DOWFAX3B2, DOWFAX8390, DOWFAX C6L, TRITON X-200, TRITON XN-45S, TRITON H-55, TRITON GR-5M, TRITON BG-10, With TRITON CG-110, respectively purchased from The Dow Chemical Company, Midland, Michigan.
Alkyd dispersion also comprises fluid media (medium).Fluid media (medium) can be any medium；Such as, fluid media (medium) is permissible It is water.The alkyd dispersion of the present invention comprises the fluid media (medium) of 35 to 75 weight %, gross weight based on dispersion.Spy In fixed embodiment, water content can be 35 to 65 weight %, or is 35 to 55 weight % in interchangeable embodiment, or Interchangeable embodiment is 45 to 55 weight %, gross weight based on dispersion.Alkyd resin can be preferably controlled divide The water content of a prose style free from parallelism so that solids content is about 1 weight % to about 90 weight %, gross weight based on dispersion.Specifically In embodiment, solids content can be about 10 weight % to about 70 weight %.In other particular implementation, solids content is About 40 weight % are to about 70 weight %.In some other embodiment, solids content is about 25 weight % to about 55 weight %.
The mean particle diameter of the solids content of alkyd dispersion is 0.05 to 5 μm.The application includes and discloses The all single numerical value of 0.05 to 5 μm and subrange；Such as, mean particle diameter can be lower limit 0.05,0.1,0.2, 0.5 or 1 μm is to higher limit 1,2,3,4 or 5 μm.
Alkyd dispersion according to the present invention can be blended with following components further: one or more binding agent groups Point, such as acrylic latex, vinyl acrylic latex, styrene-acrylonitrile copolymer acids latex, vinylacetate ethylene glue Breast, and combinations thereof；One or more optional solvents；One or more optional cosolvents；One or more optional fillers； One or more optional additives；One or more optional pigment, such as titanium dioxide, Muscovitum, calcium carbonate, titanium dioxide Silicon, zinc oxide, milled glass, aluminum trihydrate, Talcum, antimony trioxide, flying dust and clay；One or more optional dispersants, Such as amino alcohol and polycarboxylate or salt；One or more optional surfactants；One or more optional defoamer； One or more optional preservative, such as biocides, antifungus agent, antifungal, algaecide, and combinations thereof；Optionally One or more thickening agents, such as based on cellulose family thickening agent, the such as alkali of hydroxy ethyl cellulose, hydrophobically modified are molten Property emulsion and the ethoxylated urethane thickening agent (HEUR) of hydrophobically modified；One or more optional biocides； One or more optional defoamer；One or more optional flowables；One or more optional levelling agents；Or it is optional One or more other nertralizers, such as hydroxide, amine, ammonia and carbonate.
Alkyd dispersion can comprise a coloring agent part as alkyd dispersion further.Can use Multiple coloring agent.Example includes pigment such as yellow, magenta and green pigment.As black colorant, it is possible to use white carbon black, With the coloring agent using yellow/magenta/cyan colorant furnishing black shown below.Coloring agent used in this application includes dye Material, pigment and predispersion etc..These coloring agent can be used alone, use as a mixture or make as solid solution With.In various embodiments, pigment can be provided as following form: untreated pigment, the pigment of process, the face of pre-grinding Material, pigment powder, pigment press cake, pigment mother's batch of material, recovery pigment and solid or liquid pigment predispersion.Such as this Shen Please be used, untreated pigment is following granules of pigments, not to its surface applied wettability treatment, such as, makes various painting be deposited to On its surface.The pigment of untreated pigment and process is further in PCT Publication WO2005/095277 and U.S. Patent Application Publication Discussing in 20060078485, the relevant portion of these documents is incorporated by reference into the application.On the contrary, the pigment of process can be Through experienced by wettability treatment, such as thus provide coating of metal oxides at particle surface.The example bag of coating of metal oxides Include aluminium oxide, silicon dioxide and zirconium oxide.Reclaiming pigment and be also used as starting pigment granule, wherein reclaiming pigment is at product Matter is insufficient as the pigment after the wettability treatment that coating pigment is sold.
Exemplary colorant particle includes but not limited to following pigment, such as, can use yellow colorants, representative Compound for condensation azo-compound, Isoindolone compounds, anthraquinone compounds, azo metal complexation methylidyne compound, With allyl amide compound.As magenta colorant, it is possible to use condensation azo-compound, diketopyrrolo-pyrrole chemical combination Thing, anthraquinone, quinoline Azone compound, base dye lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, With perylene compound.As cyan colorant, it is possible to use copper phthalocyanine compound and derivant, anthraquinone compounds, alkali Dye lake compound etc..
In one embodiment, by one or more alkyd resin, one or more stabilizers in an extruder with water With nertralizer such as ammonia, potassium hydroxide or the combination melt kneading of the rwo thus form alkyd dispersion.At another kind In embodiment, by one or more liquid alcohol acid resins, one or more stabilizers in an extruder with water and nertralizer example Such as ammonia, potassium hydroxide or the combination melt kneading of the rwo thus form alkyd dispersion.In some embodiments, First dispersion is diluted to comprise the water of about 1 to about 20 weight %, is diluted to the most further comprise greater than about 25 weight % Water.
Any melt kneading method known in the art can be used.In some embodiments, use kneader,Mixer, single screw extrusion machine or multi-screw extruder such as double screw extruder.Preparation is according to this Method the non-specifically of bright dispersion are limited.Such as, extruder, is such as double screw extruder in some embodiments, It is combined with back-pressure regulator, Melt Pump or gear pump.Exemplary embodiment also provides for alkali container and initial condition container, It is described that both each include pump.The desired amount of alkali and initial condition are provided by alkali container and initial condition container respectively.Can use and appoint What the most suitable pump, but example is about the pump of 150cc/min as used in the pressure flow of 240 bars in some embodiments, from And alkali and initial water are provided to extruder.In other embodiments, liquid infusion pump provides 300cc/min's at 200 bars Flow or 133 bars provide 600cc/min flow.In some embodiments, pre-add thermokalite and initial water in preheater.
One or more are that the alkyd resin of liquid, pellet, powder or sheet-form is fed to extruder from feeder Entrance, wherein resin melted or mixture in this extruder.Can be by one or more optional fillers and one or more alcohol Acid resin is simultaneously in feeder is fed to extruder；Or in interchangeable embodiment, can first one or more be filled out Material mixture is entered in one or more alkyd resin, then by this mixed thing in feeder is fed to extruder.Interchangeable In embodiment, can further one or more other fillers entrance before emulsion band be metered into comprise one or In the melted mixed thing of multiple alkyd resin and one or more optional fillers.In some embodiments, stabilizer passes through And add to together with one or more alkyd resin in one or more alkyd resin, and in other embodiments, will Stabilizer is individually fed in double screw extruder.Then it is delivered to squeeze from mixing and the transit area of extruder by resin melt Go out the emulsion area of machine, added from water and the water of the primary quantity of alkali container and alkali by entrance in emulsion area.Real at some Execute in mode, stabilizer can be added in these current extraly or exclusively.In some embodiments, can be in extrusion The dilution of machine and cooled region add the other dilution water from water container through water inlet.Generally, will in cooled region Dispersion is diluted to the water of at least 30 weight %.Furthermore, it is possible to by any secondary for the mixture dilution of dilution, until it reaches required Dilution level.In some embodiments, at melt after extruder leaves, do not add water to double screw extruder In, and be added in the logistics comprising resin melt.In this way, eliminate the vapour pressure of accumulation in extruder, and Dispersion is formed in two grades of mixing arrangement such as roto-stator mixers.
In interchangeable embodiment, by liquid or one or more alkyd resin of melted form are fed to first In mixing arrangement such as roto-stator mixers, and make itself and water and optional nertralizer depositing at one or more stabilizers In lower contact, thus form High Internal Phase Emulsion.Then, make High Internal Phase Emulsion contact with other water, thus prepare the present invention's Alkyd dispersion.One or more alkyd resin can melt through such as Melt Pump.Such Melt Pump is typically ability Known to field technique personnel.
Aqueous alkyd dispersion is substantially free of any VOC；Such as, aqueous alcohol acid resin divides A prose style free from parallelism does not contains any VOC.It is substantially free of any VOC such as some solvent and refers to this The alkyd dispersion of invention comprises any VOC less than 0.5 weight %, gross weight based on dispersion Amount；Such as, less than 0.05 weight %, or less than 0.01 weight %.The viscosity of aqueous alkyd dispersion is 100 to 10, 000cP；Such as, it is 100 to 1,000cP.The pH of the aqueous alkyd dispersion of the present invention is less than 12；Such as, less than 11 or little In 10, or less than 9, and more than 5, or more than 6, or more than 7.
Prepare aqueous, high solids content, the continuation method of solvent-free alkyd dispersion to comprise the following steps: (1) carries Melted or the liquid alcohol acid resin for one or more, one or more melted or respective acid numbers of liquid alcohol acid resin wherein said Less than 20 with molecular weight (Mn) more than 1000 dalton；(2) one or more stabilizers are provided；(3) water is provided；(4) optionally One or more nertralizers are provided；(5) in one or more surfactants described and optional described one or many in water Plant one or more melted or liquid alcohol acid resins described in continuous emulsification in the presence of nertralizer；(6) thus prepare high internal phase breast Liquid；(7) other water is provided；(8) described High Internal Phase Emulsion is made to contact with described other water；(9) thus prepare described aqueous Alkyd dispersion, wherein said alkyd dispersion comprise one or more alkyd resin described in 45 to 70 weight %, Less than one or more stabilizers described in 10 weight %, and the mean particle diameter of wherein said dispersion is 0.05 to 5 μ m。
The desiccant of the alkyd dispersion component being applicable to the present invention includes but not limited to, comprises the chemical combination of metal Thing；Such as, the compound of cobalt, zirconium, manganese, calcium, zinc, copper, barium, vanadium, cerium, ferrum, potassium, strontium, aluminum, bismuth and lithium is comprised.Nonmetal dry The example of agent accelerator includes 8-hydroxyquinoline, quinoline, salicyl aldoxime, pyridine-2-formaldehyde oxime, enamine acetylacetonate Thing, 2-2 '-bipyridyl, ethylenediamine, propane diamine, pyridine, o-vinylpyridine, o-aminopyridine, aniline, ortho-phenylene diamine, O-toluidines, alpha-naphthylamine, o-phenanthroline, dipropylamine, diamyl amine, acrylonitrile, ethylene dicyanide, o-toluic nitrile, o-first Benzamide, pyrroles, benzimidazole, benzotriazole, benzophenone, benzophenonemethyl acrylate etc..Desiccant and desiccant The amount of accelerator can be 0.0002 weight % to 1.0 weight %, gross weight based on alkyd resin, such as, is 0.0002 Weight % is to 0.5 weight %, weight based on alkyd resin；Or in interchangeable embodiment, be that 0.0005 weight % is to 0.5 Weight %.Oxi-coating (OMG Fe backbone drying prescription) and Co Hydro-Cure II, Dri-RX HF and Zr Hydro-CEM's Combination may be used for obtaining having the coating improving performance profile.
Second dispersion/the second emulsion components
Coating composition comprise one or more second dispersions of 10 to 90 weight %, one or more second emulsions or A combination thereof；Such as, it is 20 to 90 weight %；Or in interchangeable embodiment, be 30 to 90 weight %；Or in interchangeable reality Execute in mode, be 40 to 85 weight %；Or in interchangeable embodiment, be 30 to 80 weight %.The application includes and discloses The all single numerical value of 10 to 90 weight % and subrange；Such as, percentage by weight can be lower limit 10,20,30,40, 50,60,70,80 or 85 to higher limit 20,30,40,50,60,70,80 or 90.
Second dispersion can be selected from dispersions of polyurethanes, polyolefin dispersion, epoxy resin dispersion, and polyester dispersion Body.
Second emulsion can be emulsion polymer latexes, selected from acrylic latex, vinyl-acetic ester acrylic compounds glue Breast, styrene-acrylonitrile copolymer acids latex, vinylacetate ethylene latex, and combinations thereof.
Dispersions of polyurethanes
Second dispersion can be dispersions of polyurethanes, such as, and based on natural oil (NOP) dispersions of polyurethanes.
Dispersions of polyurethanes based on natural oil can include being derived from dredging of one or more polyhydric alcohol based on natural oil Water dispersions of polyurethanes.In interchangeable embodiment, dispersions of polyurethanes includes being derived from one or more based on natural oil The hydrophobic polyurethane prepolymer of polyhydric alcohol.
Hydrophobic polyurethane dispersion components can be prepared as follows: forms isocyanate-terminated prepolymer, makes this prepolymer It is dispersed in aqueous phase, then by making this prepolymer chain form polyurethane and/or urea polymers.This prepolymer is itself by making The polyisocyanates of excess is prepared with the polyol reaction being derived from one or more polyhydric alcohol based on natural oil.
The polyurethane prepolymer being derived from one or more polyhydric alcohol based on natural oil for the present invention can be by appointing What conventional known method produces, such as, solwution method, hot melt method or polyurethane prepolymer mixing method, such as, in interval or Continuity method produces.And, the polyurethane prepolymer being derived from one or more polyhydric alcohol based on natural oil is permissible, such as, and warp Make the side that polyisocyanate compound reacts with the compound (i.e. one or more polyhydric alcohol based on natural oil) containing reactive hydrogen Method and produce, and the example of the method includes: 1) make polyisocyanate compound and one or more many based on natural oil Unit's method of react in the case of not using organic solvent of alcohol, and 2) make polyisocyanate compound and one or more based on The method that the polyhydric alcohol of natural oil reacts in organic solvent, described organic solvent such as, N-Methyl pyrrolidone (NMP) or Acetone or methyl ethyl ketone (MEK), PROGLYDE DMM (dipropylene glycol, CAS No.111109-77-4), so After optionally remove solvent.In one embodiment, polyurethane prepolymer optionally originates from polyisocyanate compound and Kind or multiple polyhydric alcohol based on natural oil for example originating from the reaction of the polyhydric alcohol of seed oil.
Such as, polyisocyanate compound can be the most anti-with one or more polyhydric alcohol based on natural oil Should: the temperature of 20 DEG C to 150 DEG C；Or in interchangeable embodiment, the temperature of 30 DEG C to 130 DEG C, with isocyanates Group is such as 1.1:1 to 3:1 with the equivalent proportion of active hydrogen group, or in interchangeable embodiment, for 1.2:1 to 2:1. In interchangeable embodiment, prepolymer can use excess one or more polyhydric alcohol based on natural oil preparation thus Promote that preparing end group is the polymer of hydroxyl.
Polyhydric alcohol based on natural oil based on or be derived from renewable raw materials resource (such as natural and/or transgenic plant Plant seed oil and/or animal sources fat) polyhydric alcohol.Such oil and/or fat generally include triglyceride, i.e. fat Acid is connected with glycerol.Example includes but not limited to, has the vegetable oil of at least 70% unsaturated fatty acid in triglyceride.My god So product can comprise the unsaturated fatty acid of at least about 85 weight %.Exemplary vegetable oil includes but not limited to, such as, comes From Semen Ricini, Semen sojae atricolor, Fructus Canarii albi, Semen arachidis hypogaeae, Semen Brassicae campestris, Semen Maydis, Semen Sesami, Cotton Gossypii, Semen Brassicae Campestris (canola), Flos Carthami (safflower), Caulis et Folium Lini Son, Petiolus Trachycarpi, Semen Vitis viniferae, black Herba Coriandri (black caraway), Fructus Cucurbitae moschatae core, borage seed, timber fungus, Semen Armeniacae Amarum (apricot Kernel), pistachio, Semen Armeniacae Amarum (almond), macadamia, American Avocado Tree, ocean Fructus rhamni (Rhamnus davurica Pall.) plant (sea buckthorn), Fructus Cannabis, hazelnut, Radix Oenotherae erythrosepalae, wild rose, Ji, Semen Juglandis, Helianthi, leprosy seed oil (jatropha seed oils) or a combination thereof Those.In addition it is also possible to use the oil deriving from organism such as algae.Exemplary animal product include but not limited to Adeps Sus domestica, Adeps Bovis seu Bubali, fish oil and any mixture thereof or combination.The combination of oil/grease fat based on plant and animal can also be used.
Several chemical methodes can be used to modified seed oil and seed grease, thus prepares polyhydric alcohol based on natural oil. This modification of Renewable resource includes but not limited to, such as, epoxidation, hydroxylation, ozone decomposed, esterification are made With, hydrocarbonylation, dimerization or alkoxylation.Such modification is well known in the art.
After preparing such polyhydric alcohol (by modified natural oil), modified product can be carried out further alkane Epoxide.Use oxirane (EO) or EO and other hopcalite, hydrophilic group is incorporated in polyhydric alcohol.One Plant in embodiment, make the product experience of modification comprise 10 to 60 weight % (examples with the alkoxylation of enough EO with preparation Such as, 20 to 40 weight %) polyhydric alcohol based on natural oil of EO.
In another embodiment, polyhydric alcohol based on natural oil is obtained by multistep processes, wherein makes animal or plant Oil/grease fat stands ester exchange reaction and reclaims fatty acid ester component.After this step, to the carbon-to-carbon in fatty acid ester component Double bond carries out hydroformylation to form hydroxymethyl group, and then by the fatty acid of HM and suitable initiation The reaction of immunomodulator compounds forms polyester or polyether/polyester.Such multistep processes is to it is known in the art that and be described in, such as, PCT Publication WO2004/096882 and 2004/096883.Described multistep processes makes the polyhydric alcohol produced comprise hydrophobic group simultaneously And hydrophilic group, this can strengthen polyhydric alcohol and water and the miscibility of polyhydric alcohol based on oil with routine simultaneously.
Preparation routine is could be for based on oil for preparing the initiator of the multistep processes of polyhydric alcohol based on natural oil Any initiator of polyhydric alcohol.Initiator is permissible, such as, selected from neopentyl glycol；1,2-propylene glycol；Trimethylolpropane；Season Penta tetrol；Sorbitol；Sucrose；Glycerol；Diethanolamine；Alkane diol, such as 1,6-hexanediol, BDO；1,4-hexamethylene Glycol；2,5-HD；Ethylene glycol；Diethylene glycol, 2,2'-ethylenedioxybis(ethanol).；Double-3-aminopropyl methylamine；Ethylenediamine；Diethylenetriamines；9 The double hydroxymethyl hexamethylene of (l)-hydroxymethyl octadecanol, 1,4-；Double (hydroxymethyl) three ring [5,2,1,0 of 8,8-2,6] last of the ten Heavenly stems Alkene；Dimerol alcohol (derives from the 36 carbon glycol of Henkel Corporation)；A Hydrogenated Bisphenol A；9,9 (10,10)-bis-hydroxymethyls Octadecanol；1,2,6-hexanetriol and combinations thereof.In interchangeable embodiment, initiator can be selected from glycerol；Ethylene glycol； 1,2-propylene glycol；Trimethylolpropane；Ethylenediamine；Tetramethylolmethane；Diethylenetriamines；Sorbitol；Sucrose；Or it is any aforementioned Material, wherein present in material at least one in alcohol or amine groups with oxirane, expoxy propane or its mix Thing reacts；And combinations thereof.In another kind of interchangeable embodiment, initiator is glycerol, trimethylolpropane, season penta Tetrol, sucrose, Sorbitol and/or a combination thereof.
In one embodiment, will with the mixture of oxirane or oxirane and at least one other epoxyalkane Initiator alkoxylate is to obtain the initiation that molecular weight is about the alkoxylate of 200 to about 6000 (such as, for 500 to 5000) Agent.
The degree of functionality greater than about 1.5 of at least one polyhydric alcohol based on natural oil and normally no higher than about 6.Real in one Executing in mode, this degree of functionality is below about 4.In one embodiment, this degree of functionality is 1.5 to 3.In one embodiment, This degree of functionality is 1.5 to 2.2, such as, is 2.The hydroxyl value of at least one polyhydric alcohol based on natural oil is less than 300mg KOH/g； Such as, it is 50 to 300；Or in interchangeable embodiment, be 60 to 200；Or in interchangeable embodiment, for being less than 100。
Renewable raw materials content in polyhydric alcohol based on natural oil can be 10 to 100%；Such as, it is 10 to 90%.
Polyhydric alcohol based on natural oil can account at most 90 weight % of polyol blends.But, at a kind of embodiment In, polyhydric alcohol based on natural oil can account at least 5 weight % of polyol blends gross weight, at least 10 weight %, at least 25 Weight %, at least 35 weight %, at least 40 weight %, at least 50 weight % or at least 55 weight %.Polyhydric alcohol based on natural oil can To account for 40 weight % of polyols blend gross weight or more, 50 weight % or more, 60 weight % or more, 75 weight % or more Many, 85 weight % or more, 90 weight % or more or 95 weight % or more.The base of two or more type can also be used Combination in the polyhydric alcohol of natural oil.
Polyhydric alcohol based on natural oil be typically smaller than 6,000mPa.s 25 DEG C of viscosity recorded；Such as, based on natural The polyhydric alcohol of oil 25 DEG C of viscosity recorded less than 5,000mPa.s.
Polyhydric alcohol based on natural oil can also be blended with one or more polyhydric alcohol, and described polyhydric alcohol includes but not limited to Aliphatic series and/or aromatic polyester polyols, including PEPA based on caprolactone, any polyester and polyether polyols blend, base Polyether polyol in PTMEG；Polyether polyol based on oxirane, expoxy propane, epoxy butane and mixture thereof；Poly-carbon Acid esters polyhydric alcohol；Polyacetal polyols, polyacrylate polyol；Polyester amide polyol；Polythioether polyols；Polyolefin is many Unit's alcohol, the most saturated or undersaturated polybutadiene polyol.Polyhydric alcohol based on natural oil can also be short with one or more Chain diol, one or more molecule such as dihydromethyl propionic acids, dimethylolpropionic acid with ion center are blended.
The example of polyisocyanate compound includes 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), isophthalic Diisocyanate, PPDI, 4,4'-methyl diphenylene diisocyanate, 2,4'-diphenylmethane diisocyanate Ester, 2,2'-methyl diphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethoxy-4 ', 4'-biphenyl diisocyanate, 3,3'-bis-chloro-4,4'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene Diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, ten dimethylene diisocyanates, three Double (isocyanatometyl) hexamethylene of methyl hexamethylene diisocyanate, 1,3-and double (isocyanatometyl) hexamethylene of 1,4- Alkane, XDI, tetramethylxylene diisocyanate, hydrogenated xylene diisocyanate, lysine two isocyanide Acid esters, isophorone diisocyanate, 4,4'-dicyclohexyl methyl hydride diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexyl Methane diisocyanate, its isomer and/or a combination thereof.
The polyurethane prepolymer being derived from polyhydric alcohol based on natural oil can be in one or more reactivity or chemical inertness Ethylenically unsaturated monomers in the presence of prepare.Such monomer can be polymerized further.
The polyurethane prepolymer being derived from polyhydric alcohol based on natural oil can also include hydrophilic group.Art used in this application Language " hydrophilic group " refers to anionic group (such as, carboxyl, sulfonic group or phosphate), or cation group (such as, tertiary ammonia Base or season amino), or non-ionic hydrophilic group (such as, the group being made up of the repetitive of oxirane, or by epoxy second The group of the repetitive composition of the repetitive of alkane and another kind of epoxyalkane).
In hydrophilic group, it is possible to use, such as, comprise the non-ionic hydrophilic group of the repetitive of oxirane.Draw Enter carboxyl and/or sulfonic group can make granular size thinner effectively.
When ionic group is anionic group, include for the nertralizer neutralized, the most non-volatile alkali such as hydrogen-oxygen Change sodium and potassium hydroxide；With can use volatile base such as tertiary amine (such as, trimethylamine, triethylamine, dimethylethanolamine, first Base diethanolamine and triethanolamine) and ammonia.
When ionic group is cation group, available nertralizer includes, such as, mineral acid such as hydrochloric acid, sulphuric acid and Nitric acid；With organic acids such as formic acid and acetic acid.
Neutralization can occur polymerization at the polyurethane prepolymer of the polyhydric alcohol based on natural oil being derived from containing ionic group Before, during or after carry out.Neutralization can be by being directly appended to be derived from the poly-of polyhydric alcohol based on natural oil by nertralizer Complete in urethane prepolymer or by nertralizer is added in aqueous phase during preparing dispersions of polyurethanes.
Polyurethane prepolymer is generally through cahin extension agent chain.Known to the those of ordinary skill in the field preparing polyurethane any Cahin extension agent may be used for the present invention.The molecular weight of such cahin extension agent usually 18 to 500 and comprise at least two containing activity The group of hydrogen.Polyamines is an exemplary class cahin extension agent.Other material particularly water can be used to increase chain length and therefore It it is the cahin extension agent for the object of the invention.It is particularly preferred that cahin extension agent is the mixture of water or water and amine, described amine such as amine Change polypropylene glycol such as derive from the JEFFAMINE D-400 of Huntsman Chemical Company, aminoethylpiperazine, 2-methyl piperazine, 1,5-diaminourea-3-methyl-pentane, isophorone diamine, ethylenediamine, diethylenetriamines, triethylene four Amine, triethylene five amine, ethanolamine, lysine in its any stereoisomeric forms in any ratio and salt, hexamethylene diamine, hydrazine and piperazine.? In the practice of the present invention, cahin extension agent can use as cahin extension agent solution in water.
Dispersions of polyurethanes can produce through batch process or continuity method.The polyurethane of polyhydric alcohol based on natural oil will be derived from Prepolymer, optional surfactant, He Shui are fed in mixer such as OAKS mixer or IKA mixer, so that source It is distributed in water from the polyurethane prepolymer of polyhydric alcohol based on natural oil.Then, scattered be derived from based on natural oil polynary The polyurethane prepolymer of alcohol is with one or more primary amine or secondary amine chain thus forms dispersions of polyurethanes.
In one embodiment, polyurethane aqueous dispersion body is prepared by following steps: many by being derived from based on natural oil Prepolymer and the water of unit's alcohol is optionally at surfactant or other additive and/or phase modifier (phase modifier) And/or at the temperature mixing of 25 to 90 DEG C in the presence of cahin extension agent, thus obtain required dispersions of polyurethanes.React with prepolymer Water and the amount of optional cahin extension agent and the isocyanate functionality phase in the prepolymer being derived from polyhydric alcohol based on natural oil Deng.The water of excess can also be used.
In addition to cahin extension agent, one or more surfactants may be embodied in aqueous phase.Surfactant can be Anion surfactant, ionic surface active agent, cationic surfactant or zwitterionic surfactant or nonionic Surfactant and cationic surfactant, anion surfactant or the mixture of zwitterionic surfactant.Excellent Select nonionic and anion surfactant.The surfactant not being incorporated in main polymer chain is selected from metal or the sulfonic acid of ammonia Salt, phosphate and carboxylate.Suitable surfactant includes the alkali metal salt of fatty acid, such as sodium stearate, sodium palmitate, oil Acid potassium, the alkali metal salt (such as sodium lauryl sulphate) of fat-based sulphuric acid (fatty acid sulfates), alkyl benzene sulphonate and The alkali metal salt (such as dodecylbenzene sodium sulfonate, Negel) of alkyl naphthalene sulfonic acid；The alkali gold of dialkyl sulfosuccinate succinic acid Belong to salt；The alkali metal salt (such as Octylphenoxypolyethoxy sodium ethyl sulfate) of Sulfated alkyl phenol ethoxylate compound； The alkali metal salt of polyethoxy alcohol sulphuric acid and the alkali metal salt of polyethoxy alkylphenol sulphuric acid.It is highly preferred that anionic surface Activating agent is dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, positive decyl diphenyloxide two Sodium sulfonate, 2-aminopropane. dodecyl benzene sulfonate or hexyl diphenyl sodium disulfonate, and most preferably, anionic surface is lived Property agent is dodecylbenzene sodium sulfonate.Preferably nonionic surfactant is the ethylene oxide adduct of phenol, such as nonyl Phenol.When it is present, surfactant generally accounts for 0.1 to 6 weight % of dispersions of polyurethanes, most preferably 0.5 to 4 weight Amount %.General it is desired that adding enough surfactants thus obtaining particle mean size is 50 to 1000nm and polydispersity is The dispersion of 1.0 to 2.0.And, if prepolymer is by by making non-ionic group, cation group or anionic group Emulsifying introducing and self emulsifying, then can need maybe can need not external surfactants.
Epoxy resin dispersion
Second dispersion can comprise epoxy resin dispersion.Epoxy resin represents that per molecule has one or more vicinal The component of epoxide group, i.e. per molecule have at least one 1, the component of 2-epoxide group.Generally, such compound is full With or undersaturated aliphatic series, alicyclic, aromatics or heterocyclic compound, this compound have at least one 1,2-epoxide group.As Fruit expectation, such compound can by one or more non-interfering substituent (as halogen atom, oh group, ether group, Low alkyl group etc.) replace.
Illustrative epoxy resin is described in being existed by McGraw-Hill, New York of H.E.Lee and K.Neville The Handbook of Epoxy Resins published for 1967 and United States Patent (USP) 4, in 066,628, it is incorporated by reference into this Application.
The useful especially compound that may be used for present invention practice is the epoxy resin with following formula:
Wherein the meansigma methods of n is 0 or more.
Epoxy resin for the present invention can include, such as, and polyhydric phenols and the glycidyl polyether of polyhydric alcohol.As saying Bright, the example of the known epoxy resin that may be used for the present invention includes, such as, and the diglycidyl ether of following material: isophthalic two Phenol, catechol, hydroquinone, '-biphenyl diphenol, bisphenol-A, bisphenol-ap (1,1-double (4-hydroxy phenyl)-1-diphenylphosphino ethane), double Phenol F, bis-phenol K, tetrabromobisphenol A, phenol-formaldehyde novolaRs resin, the substituted phenol-formaldehyde resin of alkyl, phenol-hydroxy benzenes Formaldehyde resin, cresol-hydroxybenzaldehyde resin, Dicycldpentadiene-phenol resin, bicyclopentadiene-substituted phenolic resin, four Methyl biphenyl diphenol, tetramethyl-tetrabromo '-biphenyl diphenol, tetramethyl tribromo '-biphenyl diphenol, tetrachlorobisphenol A and any combination thereof.
The example of the diepoxide being used in particular for the present invention includes that double (4-hydroxy phenyl) propane of 2,2-is (the most double Phenol A) diglycidyl ether and two contractings of double (the 3,5-bis-bromo-4-hydroxy phenyl) propane (commonly referred to tetrabromobisphenol A) of 2,2- Water glycerin ether.The mixture of any two or more kinds of polyepoxide can be used for the practice of the present invention.
Other diepoxide that can be used for present invention practice includes the diglycidyl ether of dihydric phenol, as being described in the U.S. Patent 5,246,751；5,115,075；5,089,588；4,480,082 and 4, those of 438,254, all of aforementioned documents is led to Cross with reference to being incorporated herein, or the 2-glycidyl ester of dicarboxylic acids, as being described in United States Patent (USP) 5, those of 171,820.Other Suitable diepoxide includes such as, and epoxy resin based on α ω-diglycidyl epoxide isopropylidene-bis-phenol is (commercial It is referred to asThe epoxy resin of 300 and 600 series, for Dow Chemical Company, Midland, Michigan's Product).
The epoxy resin that may be used for present invention practice also includes by the diglycidyl ether of dihydric phenol and dihydric phenol Reaction or the epoxy resin (also referred to as " too prince wife (taffy) resin ") by dihydric phenol with the reaction preparation of chloropropylene oxide.
Exemplary epoxy resin includes, such as, and the diglycidyl ether of following material: bisphenol-A；4,4'-sulphonyl biphenyl Diphenol；4,4-oxydiphenyl phenol；4,4'-dihydroxy benaophenonel；Resorcinol；Hydroquinone；9,9'-is double (4-hydroxy phenyl) Fluorenes；4,4' dihydroxy diphenyl or 4,4'-dihydroxy-Alpha-Methyl and the 2-glycidyl ester of dicarboxylic acids.
Other the useful epoxide compound that may be used for present invention practice is cycloaliphatic epoxides.Alicyclic ring Oxide is made up of saturated carbon ring, and this saturated carbon ring comprises and is bonded in the oxygen atom of the epoxy of two vicinal atoms, example in carbocyclic ring As by illustrated by below general formula:
Wherein R is alkyl, its optionally include one or more hetero atom (e.g., being Cl, Br and S without restriction) or With atom or the group (e.g., be Si, P and B without restriction) of atom that carbon atom forms stable keys, wherein n is more than or equal to 1。
Cycloaliphatic epoxides can be monoepoxide, diepoxide, polyepoxide or their mixture. Such as, being described in United States Patent (USP) 3, any cycloaliphatic epoxides of 686,359 may be used for the present invention, and it is incorporated by reference into The application.As explanation, the cycloaliphatic epoxides that may be used for the present invention includes, such as, and (3,4-epoxycyclohexyls-first Base)-3,4-epoxy-cyclohexane carboxylate, adipic acid be double-(3,4-epoxycyclohexyl) ester, vinylcyclohexene monoxide and Its mixture.
Dispersion based on polymer
Second dispersion can include dispersion based on polymer, such as polyolefin dispersion.Polymeric dispersions can To comprise (a) at least one or multiple base polymer, one or more surfactants that (b) is optional, and (c) liquid be situated between Matter.
(a) base polymer
Dispersion based on polymer comprises one or more base polymers of 5 to 99 weight %, is based on polymer The gross weight of solids content of dispersion.The application include and discloses all single numerical value of 5 to 99 weight % and sub-model Enclose；Such as, percentage by weight can be lower limit 5 weight %, 8 weight %, 10 weight %, 15 weight %, 20 weight % or 25 weight % To higher limit 40 weight %, 50 weight %, 60 weight %, 70 weight %, 80 weight %, 90 weight %, 95 weight % or 99 weight %.Example As, dispersion based on polymer can comprise one or more base polymers of 15 to 99 weight %；Or in interchangeable reality Execute one or more base polymers comprising 15 to 90 weight % in mode；Or comprise in interchangeable embodiment 15 to One or more base polymers of 80 weight %, are based on the gross weight of the solids content of the dispersion of polymer.Based on The dispersion of polymer comprises at least one or multiple base polymer.Base polymer is permissible, such as, selected from thermoplasticity material Material and thermosets.One or more base polymers described can include one or more polymer based on alkene, one Kind or multiple polymer based on acrylic compounds, one or more polymer based on polyester, one or more solids epoxies gather Compound, one or more thermoplastic polyurethane polymers, the polymer of one or more styrene-based classes or a combination thereof.
The example of thermoplastic includes but not limited to homopolymer and the copolymer (including elastomer) of alpha-olefin, described α- Alkene such as ethylene, propylene, 1-butylene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-heptene, 1- Hexene, 1-octene, 1-decene and 1-dodecylene, the wherein homopolymer of typical alpha-olefin and copolymer (including elastomer) Example include polyethylene, polypropylene, poly-1-butylene, poly-3-methyl-1-butene, poly-3-Methyl-1-pentene, poly-4-first Base-1-amylene, ethylene-propylene copolymer, ethylene-l-butylene copolymer and propene-1-butene copolymer；Alpha-olefin and conjugation Or the copolymer (including elastomer) of non-conjugated diene, the example of the most typical described copolymer (including elastomer) includes second Alkene-butadiene copolymer and ethylene-ethylidene norbornene copolymer；With polyolefin (including elastomer), the most two or more Planting alpha-olefin and conjugation or the copolymer of non-conjugated diene, the example of the most typical described copolymer (including elastomer) includes Ethylene-propylene-diene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,5-hexadiene copolymer, And ethylene-propylene-ethyiidenenorbomene copolymer；Ethylene-vinyl compound copolymer, such as vinyl-vinyl-acetic ester Copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, ethylene acrylic acid co polymer or ethylene-(methyl) propylene Acid copolymer and ethylene-(methyl) acrylate copolymer；Styrene copolymer (includes elastomer), such as polystyrene, ABS, acrylonitritrile-styrene resin, α-methyl styrene-styrol copolymer, styrene ethylene alcohol copolymer, styrene third Olefin(e) acid ester copolymer is (such as styrene methylacrylate copolymer, styrene-butyl acrylate copolymer, styrene methacrylic acid Acrylate copolymer) and styrene-butadiene-copolymer and the styrene polymer of crosslinking；(include with styrene block copolymer Elastomer), such as SB and hydrate thereof and styrene-isoprene-phenylethene triblock copolymer Thing；Polyvinyl compound, such as polrvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polyacrylic acid Methyl ester and polymethyl methacrylate；Polyamide, such as nylon 6, nylon 6,6 and nylon 12；Thermoplastic polyester, it is right such as to gather PET and polybutylene terephthalate (PBT)；Merlon, polyphenylene oxide etc.；With vitreous tree based on hydrocarbon Fat, including poly-bicyclopentadiene polymer and relevant polymer (copolymer, terpolymer) thereof；Saturated monoolefine, such as Vinyl-acetic ester, vinyl propionate base ester, versatic acid vinyl esters (vinyl versatate) and butanoic acid vinyl esters etc.；Second Alkenyl esters, the most monocarboxylic ester, including acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, 2-ethylhexyl acrylate, dodecylacrylate, n-octyl, phenyl acrylate, methyl methacrylate, Ethyl methacrylate and butyl methacrylate etc.；Acrylonitrile, methacrylonitrile, acrylamide, its mixture；By opening The resin that ring double decomposition and cross metathesis polyreaction etc. prepare.These resins can be used alone or with two or more Be applied in combination.
Based on the example of suitable (methyl) acrylate of polymer include acrylic acid methyl ester., ethyl acrylate, Butyl acrylate, Hexyl 2-propenoate, 2-ethylhexyl acrylate, 1-Octyl acrylate and Isooctyl acrylate monomer, acrylic acid positive last of the ten Heavenly stems Ester, isodecyl acrylate, tert-butyl acrylate, methyl methacrylate, butyl methacrylate, N-Hexyl methacrylate, first Base Isobutyl 2-propenoate, isopropyl methacrylate and acrylic acid 2-hydroxy methacrylate and acrylamide.Preferably (methyl) third Olefin(e) acid ester is acrylic acid methyl ester., ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 1-Octyl acrylate, acrylic acid Different monooctyl ester, methyl methacrylate and butyl methacrylate.What other was suitable can be polymerized, by monomer, (methyl) propylene formed Acid esters includes lower alkyl acrylate and methacrylic acid lower Arrcostab, including acrylate monomer and methacrylate Monomer: acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, propylene Acid ester in the last of the ten Heavenly stems, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, n propyl methacrylate, metering system The secondary butyl ester of isopropyl propionate, n-BMA, isobutyl methacrylate, methacrylic acid, methacrylic acid cyclohexyl Ester, isodecyl methacrylate, isobornyl methacrylate, t-butyl aminoethyl ethyl ester, methacrylic acid Stearyl, glycidyl methacrylate, methacrylic acid dicyclopentenyl ester, phenyl methacrylate.
In the embodiment selected, base polymer is permissible, it may for example comprise selected from ethene-alpha-olefin copolymer and third The polyolefin of alkene-alpha olefin copolymer.Particularly, in the embodiment selected, base polymer can include one or many Plant non-polar polyolefinic.
In certain embodiments, it is possible to use polyolefin such as polypropylene, polyethylene, its copolymer, and blend, And ethylene-propylene-diene terpolymer.In some embodiments, it is preferred olefin polymer include homogeneous polymerization Thing, as being presented to the United States Patent (USP) 3 of Elston, described in 645,992；High density polyethylene (HDPE) (HDPE), as being presented to Described in the United States Patent (USP) 4,076,698 of Anderson；Non-homogeneous branched linear low density polyethylene (LLDPE) (LLDPE)；Non-all Even branched extremely-low density Hi-fax (ULDPE)；The uniform branched linear copolymer of ethylene/alpha-olefin；Ethylene/alpha-olefin The most branched essentially linear polymer, it can pass through, and such as, United States Patent (USP) 5,272,236 and 5, disclosed in 278,272 Method prepare, the disclosure of which is incorporated by reference into the application；The ethene polymers being polymerized with high-pressure free radical and copolymer, Such as Low Density Polyethylene (LDPE) or ethylene vinyl acetate polymer (EVA).
In other specific embodiment, base polymer is permissible, such as, is based on ethylene vinyl acetate copolymerization The polymer of thing (EVA).In other embodiments, base polymer is permissible, such as, is based on ethylene-methyl acrylate altogether The polymer of polymers (EMA).In other specific embodiment, ethene-alpha-olefin copolymer is permissible, such as, is ethylene-fourth Alkene copolymer or interpretation, ethylene-hexene co-polymers or interpretation or ethylene-octene copolymer or interpretation.Specific at other Embodiment in, propylene-alpha-olefin copolymers is permissible, such as, be propylene-ethylene copolymers or interpretation or propylene-ethylene- Butylene copolymer or interpretation.
In some other embodiment, base polymer is permissible, such as, be semi-crystalline polymer and its fusing point permissible Less than 110 DEG C.In a preferred embodiment, fusing point can be 25 to 100 DEG C.In preferred embodiment, fusing point can Think 40 to 85 DEG C.
In the specific embodiment of one, base polymer is propylene/α-olefin copolymer, it is characterised in that have base Isotactic propylene sequences in basis.It is single that " the most isotactic propylene sequences " represents that this sequence has isotactic three Tuple (triad) (mm), this triad passes through13C NMR is measured as greater than about 0.85；In interchangeable embodiment, greatly In about 0.90；In another kind of interchangeable embodiment, greater than about 0.92；And at another kind of interchangeable embodiment In, greater than about 0.93.Isotactic triad be well known in the art and, such as, United States Patent (USP) 5,504,172 Hes Being described in International Publication WO00/01745, it refers to pass through13Unit three in copolymer molecule chain determined by C H NMR spectroscopy The isotactic sequence of group unit meter.
The melt flow rate (MFR) of propylene/α-olefin copolymer can be 0.1 to 15g/10 minute, according to ASTM D-1238 (at 230 DEG C/2.16Kg) is measured.The application include and discloses all single numerical value of 0.1 to 15g/10 minute and sub-model Enclose；Such as, melt flow rate (MFR) can be that the lower limit of 0.1g/10 minute, 0.2g/10 minute or 0.5g/10 minute is to 15g/ The higher limit of 10 minutes, 10g/10 minute, 8g/10 minute or 5g/10 minute.Such as, the melt of propylene/α-olefin copolymer Flow rate can be 0.1 to 10g/10 minute；Or in interchangeable embodiment, the melt of propylene/α-olefin copolymer Flow rate can be 0.2 to 10g/10 minute.
The degree of crystallinity of propylene/α-olefin copolymer is that at least 1 weight % (heat of fusion is at least 2 joule/gram) is to 30 weight % (heat of fusion is less than 50 joule/gram).Application include and discloses 1 weight % (heat of fusion is at least 2 joule/gram) to 30 weight % The all single numerical value of (heat of fusion is less than 50 joule/gram) and subrange；Such as, degree of crystallinity can be that (heat of fusion is 1 weight % At least 2 joule/gram), 2.5 weight % (heat of fusion is at least 4 joule/gram) or 3 weight % (heat of fusion is at least 5 joule/gram) Lower limit (melts to 30 weight % (heat of fusion is less than 50 joule/gram), 24 weight % (heat of fusion is less than 40 joule/gram), 15 weight % Antipyretic it is less than 24.8 joule/gram) or the higher limit of 7 weight % (heat of fusion is less than 11 joule/gram).Such as, propylene/alpha-olefins is common The degree of crystallinity of polymers can be at least 1 weight % (heat of fusion is at least 2 joule/gram) to 24 weight % (heat of fusion less than 40 joules/ Gram)；Or in interchangeable embodiment, the degree of crystallinity of propylene/α-olefin copolymer can be that (heat of fusion is at least 1 weight % At least 2 joule/gram) to 15 weight % (heat of fusion be less than 24.8 joule/gram)；Or in interchangeable embodiment, propylene/α- The degree of crystallinity of olefin copolymer can be that to 7 weight %, (heat of fusion is less than 11 at least 1 weight % (heat of fusion is at least 2 joule/gram) Joule/gram)；Or in interchangeable embodiment, the degree of crystallinity of propylene/α-olefin copolymer can be that at least 1 weight % is (molten Antipyretic is at least 2 joule/gram) to 5 weight % (heat of fusion be less than 8.3 joule/gram).Degree of crystallinity is surveyed through DSC method as above Amount.Propylene/α-olefin copolymer comprises the unit being derived from propylene and the polymer being derived from one or more alpha-olefin comonomer Unit.It is C for preparing the exemplary comonomer of propylene/α-olefin copolymer2Alpha-olefin and C4To C10Alpha-olefin；Example As, C2、C4、C6And C8Alpha-olefin.
Propylene/α-olefin copolymer comprises one or more alpha-olefin comonomer of 1 to 40 weight %.Application includes also Disclose all single numerical value and the subrange of 1 to 40 weight %；Such as, co-monomer content can be 1 weight %, 3 weight %, 4 The lower limit of weight %, 5 weight %, 7 weight % or 9 weight % is to 40 weight %, 35 weight %, 30 weight %, 27 weight %, 20 weights Amount %, 15 weight %, 12 weight % or the higher limit of 9 weight %.Such as, propylene/α-olefin copolymer comprises the one of 1 to 35 weight % Plant or multiple alpha-olefin comonomer；Or in interchangeable embodiment, propylene/α-olefin copolymer comprises 1 to 30 weight % One or more alpha-olefin comonomer；Or in interchangeable embodiment, propylene/α-olefin copolymer comprises 3 to 27 One or more alpha-olefin comonomer of weight %；Or in interchangeable embodiment, propylene/α-olefin copolymer comprises 3 One or more alpha-olefin comonomer to 20 weight %；Or in interchangeable embodiment, propylene/α-olefin copolymer Comprise one or more alpha-olefin comonomer of 3 to 15 weight %.
The molecular weight distribution (MWD) of propylene/α-olefin copolymer (is defined as weight average molecular weight divided by number-average molecular weight (Mw/ Mn)) it is 3.5 or less；In interchangeable embodiment 3.0 or less；Or in another kind of interchangeable embodiment be 1.8 to 3.0.
Such propylene/α-olefin copolymer describes in further detail in United States Patent (USP) 6,960,635 and 6, and 525,157, It is incorporated by reference into the application.Such propylene/α-olefin copolymer can be with trade name VERSIFYTMCommercially available from The Dow Chemical Company or with trade name VISTAMAXXTMCommercially available from ExxonMobil Chemical Company.
In one embodiment, propylene/α-olefin copolymer be further characterized by comprise (A) 60 to being less than 100wt%, be preferably 80 to 99wt% and the unit being derived from propylene of more preferably 85 to 99wt%, and (B) more than 0 to 40wt%, be preferably 1 to 20wt%, more preferably 4 to 16wt% and even more preferably 4 to 15wt% be derived from ethylene and/or C4-10The unit of at least one in alpha-olefin；And every 1000 carbon atoms averagely comprise at least 0.001, are preferably the most extremely Few 0.005 and average at least 0.01 long chain branches.The maximum number of the long chain branches in propylene terpolymers Definition for the present invention is not critical, but it is typically not greater than 3 long chain branches/1000 entire carbon atom.The application makes Term long chain branches represent the chain length of at least one (1) carbon atom more than short chain branch, and short chain used in this application The chain length of branching representation two (2) carbon atoms fewer than carbon atom number in comonomer.Such as, propylene/1-octene interpretation Main chain have in length for the long chain branches of at least seven (7) carbon atom, but these main chains also have and are only in length The short chain branch of six (6) carbon atoms.Such propylene/α-olefin copolymer describes in further detail in US provisional patent Shen Please 60/988,999 and International Patent Application PCT/US08/082599, every document is incorporated by reference into the application.
In some other embodiment, base polymer such as propylene/α-olefin copolymer is permissible, such as, is half hitch Crystalline polymer and its fusing point can be less than 110 DEG C.In a preferred embodiment, fusing point can be 25 to 100 DEG C.More excellent In the embodiment of choosing, fusing point can be 40 to 85 DEG C.
In other embodiment selected, olefin block copolymers such as ethylene multi-block copolymer, such as it is described in Those of International Publication WO2005/090427 and U.S. Patent application 11/376,835 can serve as base polymer.Such Olefin block copolymers can be the ethylene/alpha-olefin interpolymers having the following properties that:
(a)Mw/MnIt is 1.7 to 3.5, at least one fusing point Tm, in degrees celsius, and density d, by gram/cc in terms of, Wherein said TmWith the numerical value of d corresponding to following relation:
Tm>-2002.9+4538.5(d)–2422.2(d)2；Or
(b)Mw/MnIt is 1.7 to 3.5, it is characterised in that heat of fusion Δ H, in terms of J/g, and Δ amount in degrees celsius, Δ T, Being defined as the temperature difference between the highest DSC peak and the highest CRYSTAF peak, the numerical value of wherein said Δ T and Δ H has with ShiShimonoseki System:
For Δ H more than 0 and at most 130J/g, Δ T >-0.1299 (Δ H)+62.81,
For Δ H more than 130J/g, Δ T >=48 DEG C,
Wherein said CRYSTAF peak uses the accumulation polymer of at least 5% to determine, and the polymer if less than 5% has Have discernible CRYSTAF peak, then CRYSTAF temperature is 30 DEG C；Or
C () is characterised by the bullet when 300% strain and 1 circulation measured with the compression moulding film of ethylene/alpha-olefin interpolymers Property response rate Re, with percentage, and there is density d, by gram/cc in terms of, wherein interpolymerized when described ethylene/alpha-olefin Thing is substantially free of described R during cross-linked phaseeFollowing relation is met with the numerical value of d:
Re>1481-1629(d)；Or
(d) have when use TREF classification time between 40 DEG C and 130 DEG C the molecule fraction of eluting, it is characterised in that described The molar comonomer content of fraction is than the most suitable random ethylene interpretation being total to of the fraction of eluting between mutually synthermal Poly-monomer molar content height at least 5%, the most suitable wherein said random ethylene interpretation has identical comonomer, and And its melt index (MI), density and molar comonomer content (based on whole polymer) and described ethylene/alpha-olefin interpolymers Within these character difference ± 10%；Or
E () is storage modulus G of 25 DEG C ' (25 DEG C), and storage modulus G at 100 DEG C ' (100 DEG C), wherein said G ' The ratio of (25 DEG C) and G ' (100 DEG C) is about 1:1 to about 9:1.
Ethylene/alpha-olefin interpolymers can also have:
(a) when using TREF classification at the molecule fraction of 40 DEG C～130 DEG C eluting, it is characterised in that described molecule fraction Blockiness index be at least 0.5 and at most about 1, and molecular weight distribution Mw/MnGreater than about 1.3；Or
B () average block index is more than 0 and at most about 1.0, and molecular weight distribution Mw/MnGreater than about 1.3.
In some embodiments, base polymer is permissible, such as, comprises and has as comonomer or grafted monomers The polar polymer of polar group.In an exemplary embodiment, base polymer is permissible, such as, comprises one or more Have as comonomer or the polar polyolefin of the polar group of grafted monomers.Exemplary polar polyolefin includes but does not limits In ethylene-acrylic acid (EAA) copolymer and ethylene-methacrylic acid copolymer, such as with trade mark PRIMACORTMAvailable commercially from Those of The Dow Chemical Company, with NUCRELTMAvailable commercially from those of E.I.DuPont de Nemours, With with ESCORTMAvailable commercially from those of ExxonMobil Chemical Company, described polar polyolefin is described in the U.S. Patent 4,599,392,4,988,781 and 5,938,437, described document is the most all incorporated by reference into the application.Other shows The base polymer of example includes but not limited to ethylene ethyl acrylate (EEA) copolymer, ethylenemethylmethacrylate (EMMA) copolymer and ethylene butyl acrylate (EBA) copolymer.
In one embodiment, base polymer is permissible, it may for example comprise polar polyolefin, selected from ethylene-acrylic acid (EAA) copolymer, ethylene-methacrylic acid copolymer, and combinations thereof；And stabilizer is permissible, it may for example comprise Polar polyolefin Hydrocarbon, selected from ethylene-acrylic acid (EAA) copolymer, ethylene-methacrylic acid copolymer, and combinations thereof；But, condition is basis The acid number that polymer is measured according to D-974 is permissible, such as, low than the acid number of stabilizer.
In some embodiments, base polymer is permissible, such as, comprises polyester resin.Polyester resin refers to wrap Include the thermoplastic resin of polymer containing at least one ester bond.Such as, PEPA can use relatively through conventional esterification process Prepared by aliphatic diol or glycol in chain docosandioic acid molar excess.Can be used for preparing the exemplary diols of polyester be ethylene glycol, two Glycol, propylene glycol, dipropylene glycol, 1,3-propylene glycol, 1,4-butanediol and other butanediol, 1,5-pentanediol and other penta Glycol, hexanediol, decanediol and dodecanediol.In some embodiments, can to comprise 2 to about 8 carbon former for aliphatic diol Son.The exemplary diacid that can be used for preparing polyester is maleic acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 2-methyl isophthalic acid, 6- Adipic acid, Azelaic Acid, decanedioic acid and dodecanedioic acid.In some embodiments, chain docosandioic acid can comprise 4 to 12 carbon Atom.Exemplary PEPA is poly-(adipic acid hexanediol ester), poly-(tetramethylene adipate), poly-(adipic acid second two Alcohol ester), poly-(diethylene glycol adipate), poly-(oxalic acid hexanediol ester) and poly-(decanedioic acid glycol ester).Other of the present invention is real The mode of executing uses the polyester resin containing aliphatic diol, described aliphatic diol such as UNOXOL (cis and trans 1,3-hexamethylene two Methanol and the mixture of 1,4-CHDM), it is purchased from The Dow Chemical Company (Midland, MI).
In some embodiments, base polymer is permissible, it may for example comprise comprise the thermosetting of epoxy resin as above Property material.
In some embodiments, base polymer includes thermoplastic polyurethane polymer.Such thermoplastic polyurethane Polymer is known, and is further described in, such as, International Publication 2008/057878, thermoplastic polyurethane described in it The part of polymer is incorporated by reference into the application.
Those of ordinary skill in the art recognize, list above is merely illustrative the non-comprehensive list of base polymer. Will be appreciated that and be limited only by the claims that follow.
(b) stabilizer
Dispersion based on polymer can comprise at least one or plurality of stable agent further, is also referred to as in this application Dispersant, thus promote to form stable dispersion based on polymer.Stabilizer can be preferably external stabilization agent.The present invention Dispersion based on polymer comprise one or more stabilizers of 1 to 50 weight %, solids content based on dispersion Gross weight.The application include and discloses all single numerical value and the subrange of 1 to 45 weight %；Such as, percentage by weight is permissible Be 1 weight %, 3 weight %, 5 weight %, 10 weight % lower limit to 15 weight %, 25 weight %, 35 weight %, 45 weight % or 50 The higher limit of weight %.Such as, dispersion can comprise one or more stabilizers of 1 to 25 weight %, or in interchangeable reality Execute one or more stabilizers comprising 1 to 35 weight % in mode, or in interchangeable embodiment, comprise 1 to 40 weight % One or more stabilizers, or in interchangeable embodiment, comprise one or more stabilizers of 1 to 45 weight %, base Gross weight in the solids content of dispersion.In the embodiment selected, stabilizer can be surfactant, polymerization Thing or its mixture.In some embodiments, stabilizer can be to have the polar group as comonomer or grafted monomers The polar polymer of group.In an exemplary embodiment, stabilizer includes that one or more have as comonomer or connect The polar polyolefin of the polar group of branch monomer.Exemplary polymer stabilizer includes but not limited to ethylene-acrylic acid (EAA) Copolymer and ethylene-methacrylic acid copolymer, such as with trade mark PRIMACORTMAvailable commercially from The Dow Chemical Those of Company, with trade mark NUCRELTMAvailable commercially from those of E.I.DuPont de Nemours, with trade mark ESCORTMAvailable commercially from those of ExxonMobil Chemical Company, it is special that described polymer stabilizer is described in the U.S. Profit 4,599,392,4,988,781 and 5,938,437, described document is each via with reference to being fully incorporated the application.Other example The polymer stabilizer of property includes but not limited to ethylene ethyl acrylate (EEA) copolymer, ethylenemethylmethacrylate (EMMA) copolymer and ethylene butyl acrylate (EBA) copolymer.Other ethylene-carboxylic acid's copolymer can also be used.This area Those of ordinary skill will be appreciated by, it is possible to use other useful polymer multiple.
Other stabilizer spendable includes but not limited to, comprises the long-chain fatty acid of 12 to 60 carbon atoms, fatty acid Salt or fatty acid alkyl esters.In other embodiments, can to comprise 12 to 40 carbon former for long-chain fatty acid or soap Son.
Stabilizer can use nertralizer partly or entirely to neutralize.In some embodiments, stabilizer is (such as long-chain fat Acid or EAA) neutralization on a molar basis can be 25 to 200%；Or in interchangeable embodiment, it is at mole foundation On neutralization can be 50 to 110%.Such as, for EAA, nertralizer can be alkali, such as ammonium hydroxide or potassium hydroxide.Such as, Other nertralizer can include Lithium hydrate or sodium hydroxide.In another kind of interchangeable embodiment, nertralizer is permissible, example As, it is carbonate.In another kind of interchangeable embodiment, nertralizer is permissible, such as, is any amine, such as monoethanolamine or 2-amino-2-methyl-1-propanol (AMP).The amine used in disclosure embodiment can include monoethanolamine, diethanol Amine, triethanolamine and TRIS AMINO (respectively purchased from Angus), NEUTROL TE (purchased from BASF) and triisopropanolamine, two Isopropanolamine and N, N-dimethylethanolamine (respectively purchased from The Dow Chemical Company, Midland, MI).Other has Amine can include ammonia, MMA, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single n-propylamine, dimethyl n Propylamine, N-carbinolamine, N-amino ethyl ethanolamine, N methyldiethanol amine, monoisopropanolamine, N, N-dimethyl propanol amine, 2- Amino-2-methyl-1-propanol, three (hydroxymethyl)-aminomethanes, N, N, N'N'-tetra-(2-hydroxypropyl) ethylenediamine, 1,2-bis- Aminopropane.In some embodiments, it is possible to use the mixture of amine or amine and the mixture of surfactant.This area is general Leading to and skilled artisans will appreciate that, prepared particular composition is depended in the selection to suitable nertralizer, and knows such Selection is within those of ordinary skill in the art's ken.
The other stabilizer that can be used for present invention practice includes but not limited to cationic surfactant, anionic surface Activating agent or nonionic surfactant.The example of anion surfactant include but not limited to sulfonate, carboxylate and Phosphate.The example of cationic surfactant includes but not limited to quaternary amine.The example of nonionic surfactant include but not It is limited to block copolymer and the organic silicon surfactant comprising oxirane.Outside the stabilizer of present invention practice can be Portion's surfactant or Internal surfactants.External surfactants is not occur chemical reaction to combine in prepared by dispersion Enter the surfactant in base polymer.Example for the external surfactants of the application includes but not limited to dodecane Base benzene sulfonate and dodecane sulfonate.Internal surfactants is chemical reaction to be occurred to be incorporated in prepared by dispersion Surfactant in base polymer.Example for the Internal surfactants of the application includes 2,2-dihydromethyl propionic acid And salt.Other surfactant of the practice that can be used for the present invention includes cationic surfactant, anion surface active Agent, nonionic surfactant or a combination thereof.Various commercially available surfactants may be used for embodiment party disclosed in the present application Formula, this includes: OP-100 (sodium stearate), OPK-1000 (potassium stearate), and OPK-181 (potassium oleate), respectively purchased from RTD Hallstar；UNICID350, purchased from Baker Petrolite；DISPONIL FES77-IS and DISPONIL TA-430, respectively Purchased from Cognis；RHODAPEX CO-436, SOPROPHOR4D384,3D-33, and 796/P, RHODACAL BX-78 and LDS- 22, RHODAFAC RE-610, and RM-710, and SUPRAGIL MNS/90, respectively purchased from Rhodia；With TRITON QS-15, TRITON W-30, DOWFAX2A1, DOWFAX3B2, DOWFAX8390, DOWFAX C6L, TRITON X-200, TRITON XN- 45S, TRITON H-55, TRITON GR-5M, TRITON BG-10, and TRITON CG-110, respectively purchased from The Dow Chemical Company, Midland, Michigan.
(c) fluid media (medium)
Dispersion based on polymer also comprises fluid media (medium).Fluid media (medium) can be any medium；Such as, fluid media (medium) Can be water.The dispersion based on polymer of the present invention comprises the fluid media (medium) of 25 to 90 weight %, gross weight based on dispersion Amount.In specific embodiment, water content can be 35 to 75 weight %, or is 35 to 70 in interchangeable embodiment Weight %, or be 45 to 60 weight % in interchangeable embodiment, gross weight based on dispersion.Dispersion based on polymer The water content of body the most controlled can make solids content (base polymer is together with stabilizer) be that 1 weight % is to 74 weight %. In specific embodiment, solids content can be that 10 weight % are to 70 weight %.In other specific embodiment, solid Content is that 20 weight % are to 65 weight %.In some other embodiment, solids content is that 25 weight % are to 55 weight %.
D component that () is other
Dispersion based on polymer can comprise one or more adhesive components, such as acrylic compounds glue further Breast, vinyl acrylic latex, styrene-acrylonitrile copolymer acids latex, vinylacetate ethylene latex, and combinations thereof；Optional One or more fillers；One or more optional additives；One or more optional pigment, such as titanium dioxide, Muscovitum, Calcium carbonate, silicon dioxide, zinc oxide, milled glass, aluminum trihydrate, Talcum, antimony trioxide, flying dust and clay；Optional one Or multiple cosolvent, such as glycol, glycol ethers, 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate, alcohol, mineral spirits and Benzoate；One or more optional dispersants, such as amino alcohol and polycarboxylate or salt；One or more optional tables Face activating agent；One or more optional defoamer；One or more optional preservative, such as biocides, antifungus agent, Antifungal, algicide, and combinations thereof；One or more optional thickening agents, such as based on cellulose family thickening agent, such as Hydroxy ethyl cellulose, the alkali-soluble emulsion (HASE thickening agent, such as UCAR POLYPHOBE TR-116) of hydrophobically modified and dredge The ethoxylated urethane thickening agent (HEUR) that water is modified；Or one or more optional other nertralizers, such as hydrogen Oxide, amine, ammonia and carbonate.
E coloring agent component that () is other
Dispersion based on polymer can comprise a coloring agent part as polyolefin dispersion further.Can make Use multiple coloring agent.Example includes pigment such as yellow, magenta and green pigment.As black colorant, it is possible to use charcoal Black and use the coloring agent of yellow/magenta/cyan colorant furnishing black shown below.Coloring agent bag used in this application Include dyestuff, pigment and predispersion etc..These coloring agent can be used alone, use as a mixture or as solid solution Use.In various embodiments, pigment can be provided as following form: untreated pigment, the pigment of process, the face of pre-grinding Material, pigment powder, pigment press cake, pigment mother's batch of material, recovery pigment and solid or liquid pigment predispersion.Such as this Shen Please be used, untreated pigment is following granules of pigments, not to its surface applied wettability treatment, such as, makes various coating deposit to On its surface.The pigment of untreated pigment and process is further in PCT Publication WO2005/095277 and U.S. Patent Application Publication Discussing in 20060078485, the relevant portion of these documents is incorporated by reference into the application.On the contrary, the pigment of process can be Through experienced by wettability treatment, such as thus provide metal oxide coating at particle surface.The example bag of metal oxide coating Include aluminium oxide, silicon dioxide and zirconium oxide.Reclaiming pigment and be also used as starting pigment granule, wherein reclaiming pigment is at product Matter is insufficient as the pigment after the wettability treatment that coating pigment is sold.
Exemplary colorant particle includes but not limited to following pigment, such as yellow colorants, representational compound For condensing azo-compound, Isoindolone compounds, anthraquinone compounds, azo metal complexation methylidyne compound and can make With allyl amide compound as pigment.As magenta colorant, it is possible to use condense azo-compound, diketone pyrrolo-pyrrole Cough up compound, anthraquinone, quinoline Azone compound, base dye lake compound, naphthol compound, benzimidazolone compound, thioindigo Compound and perylene compound.As cyan colorant, it is possible to use copper phthalocyanine compound and derivant, anthraquinone Compound, base dye lake compound etc..
F () forms dispersion based on polymer
Dispersion based on polymer can be formed by any number of method known to those skilled in the art.One In kind of embodiment, one or more base polymers, one or more stabilizers are in an extruder with water and nertralizer such as Ammonia, potassium hydroxide or the combination melt kneading of the rwo thus formed dispersion based on polymer.In another embodiment In, by one or more base polymers and one or more optional filler mixtures, then base polymer/filler mixed thing Melt kneading in the presence of optional stabilizer, water and one or more nertralizers in an extruder, thus formed based on poly- The dispersion of compound.In some embodiments, first dispersion is diluted to the water comprising 1 to 3 weight %, the most further It is diluted to comprise the water of greater than about 25 weight %.
Any melt kneading device known in the art can be used.In some embodiments, use kneader,Mixer, single screw extrusion machine or multi-screw extruder such as double screw extruder.Preparation is according to this Method the non-specifically of bright dispersion are limited.Such as, extruder, is such as double screw extruder in some embodiments, It is combined with back-pressure regulator, Melt Pump or gear pump.Exemplary embodiment also provides for alkali storage tank and initial water storage tank, It is described that both each include pump.The desired amount of alkali and initial water are provided by alkali storage tank and initial water storage tank respectively.Can use and appoint What the most suitable pump, but example is about the pump of 150cc/min as used in the pressure flow of 240 bars in some embodiments, from And alkali and initial water are provided to extruder.In other embodiments, liquid infusion pump provides 300cc/min's at 200 bars Flow or 133 bars provide 600cc/min flow.In some embodiments, pre-add thermokalite and initial water in preheater.
The base polymer that one or more are pellet, powder or sheet-form is fed to extruder from feeder Entrance, wherein resin melted or mixture in this extruder.Optionally can be by one or more fillers and one or more bases Plinth polymer is simultaneously in feeder is fed to extruder；Or in interchangeable embodiment, can be first by one or more Filler mixture is entered in one or more base polymers, then by this mixed thing in feeder is fed to extruder.Can replace In the embodiment changed, further one or more other fillers entrance before emulsion band can be metered into and comprise one Plant or in the melted mixed thing of multiple base polymer and one or more optional fillers.In some embodiments, dispersion Agent is passed through and adds to together with resin in one or more base polymers, and in other embodiments, by dispersant Individually it is fed in double screw extruder.Then resin melt is delivered to extruder from mixing and the transit area of extruder Emulsion area, is added from water and the water of the primary quantity of alkali storage tank and alkali by entrance in emulsion area.At some embodiments In, dispersant can be added in these current extraly or exclusively.In some embodiments, extruder dilution and Cooled region can add through water inlet and use the other dilution water from water storage tank.Generally, by dispersion in cooling zone Territory is diluted to the water of at least 30 weight %.Furthermore, it is possible to by any secondary for the mixture dilution of dilution, until it reaches required is dilute Release level.In some embodiments, do not add water in double screw extruder, but leave from extruder at melt Afterwards, add in the stream comprising resin melt.In this way, eliminate the vapour pressure of accumulation in extruder, and disperse Body is formed in two grades of mixing arrangement such as roto-stator mixers.
Emulsion polymer latexes
Second emulsion can be selected from following emulsion polymer latexes: acrylic latex, vinyl-acetic ester propylene Acrylic latex, styrene-acrylonitrile copolymer acids latex, vinylacetate ethylene latex, and combinations thereof.Such emulsion polymer glue Breast can comprise at least one synthetic latex.It has been generally acknowledged that synthetic latex is the emulsion polymerization by one or more monomers The aqueous dispersion of the polymer particle of preparation.This latex can have unimodal or that multimodal is the most bimodal particle size distribution.Can make With mixture or the blend of latex.
In one embodiment of the invention, the polymer of latex is copolymer, i.e. formed by least 2 kinds of monomers Polymer.Latex can comprise single copolymer or more than one copolymer.Advantageously, the vitrification of the polymer of latex turns Temperature (Tg) is-50 DEG C to 100 DEG C.
In the practice of the invention, it is different from the copolymer being only used for blend, the Tg expectation of the copolymer being used alone Be not less than about-10 DEG C, preferably at least about 0 DEG C.Desirably, the Tg of copolymer no more than about 50 DEG C, the most about 40 ℃.Generally preferably in the range of 0 DEG C to 40 DEG C.The Tg of the copolymer of the present composition passes through differential scanning calorimetry (DSC) Determine.
Although various of monomer compositions can be used for the latex component of key component of the present invention, but at special embodiment In, it is preferred that due in the group of the ethylenically unsaturated monomers in being present in the polymerization reaction mixture being prepared There is not cross-linking monomer, and make copolymer not cross-link.That is, it is desirable in this embodiment, copolymer passes through There is not the polyreaction in the case of cross-linking monomer or some other cross-linking agent to prepare.
In interchangeable embodiment, it is desirable to copolymer is slightly cross-linked.This can be by polymerization reaction mixture (altogether Polymers is prepared by this mixture) middle introducing polyfunctional monomer (its known effectiveness is cross-linking agent) such as divinylbenzene or (first Base) allyl acrylate completes.In this specific embodiment, cross-linking monomer content in the copolymer is the most not More than about 2 weight %, preferably 0.001 to 2 weight %, more preferably 0.01 to 1.5 weight %, still more preferably from 0.1 to 1 weight Amount %, the gross weight of each monomer during wherein percentage by weight is based on polymerization reaction mixture.
Various of monomer can be used to prepare the copolymer being applicable to key component of the present invention.Mainly comprise (methyl) acrylic acid (methyl) acrylate copolymer of ester monomer is the copolymer of a kind of desirable type.
For the purpose of the emulsion polymer latexes of the present invention, term " (methyl) " represents, methyl substituted compound bag It is contained in this compounds modified by this term.Such as, term (methyl) acrylic acid represents acrylic acid and methacrylic acid.
About the emulsion polymer latexes of the present invention, term " (methyl) acrylate copolymer " table used in this application Show (methyl) acrylate monomer of at least 80 weight % comprised in polymerized form and the copolymer of (methyl) acrylic monomers. In a preferred embodiment, copolymer comprises (methyl) acrylate monomer and the (first of at least 90 weight % in polymerized form Base) acrylic monomers, and it is even furthermore preferable that implementation below, wherein copolymer comprises at least 95 in polymerized form (methyl) acrylate monomer of weight % and (methyl) acrylic monomers.
In highly preferred embodiment, copolymer is pure (methyl) acrylate, or except the non-wherein comprised Pure (methyl) acrylate beyond (methyl) acrylate seed.These copolymers are the most substantially by (methyl) acrylic acid Ester monomer forms, or is substantially made up of (methyl) acrylate monomer and (methyl) acrylic monomers.
About emulsion polymer latexes, term " (methyl) acrylate monomer " used in this application be intended to include for Preparation is applicable to those monomers of (methyl) acrylate copolymer of the compositions of the present invention.Wherein comprise is conventionally known Acrylate, such as, by formula CH2Acrylic acid Arrcostab that=CHCOOR represents and by formula CH2=CCH3The first that COOR represents The acrylic acid Arrcostab of base, wherein R is the alkyl comprising 1 to 16 carbon atom or substituted alkyl.Term " (methyl) acrylic acid Monomer " it is intended to include acrylic acid, methacrylic acid and substituted derivant thereof.
About emulsion polymer latexes, term " (methyl) acrylate monomer " used in this application is also intended to include third Olefin(e) acid mono-vinyl monomer and methacrylic acid mono-vinyl monomer.(methyl) acrylate can include ester, amide and take The derivant in generation.Generally, it is preferred to (methyl) acrylate be acrylic acid C1-C8Arrcostab and methacrylic acid C1-C8Alkyl Ester.
The example of suitable (methyl) acrylate includes acrylic acid methyl ester., ethyl acrylate, butyl acrylate, acrylic acid Own ester, 2-ethylhexyl acrylate, 1-Octyl acrylate and Isooctyl acrylate monomer, acrylic acid ester in the positive last of the ten Heavenly stems, isodecyl acrylate, third Enoic acid ter-butyl ester, methyl methacrylate, butyl methacrylate, N-Hexyl methacrylate, isobutyl methacrylate, methyl Isopropyl acrylate and acrylic acid 2-hydroxy methacrylate and acrylamide.Preferably (methyl) acrylate be acrylic acid methyl ester., Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 1-Octyl acrylate, Isooctyl acrylate monomer, methyl methacrylate Ester and butyl methacrylate.Other suitable monomer includes lower alkyl acrylate and methacrylic acid lower Arrcostab, Including acrylate monomer and methacrylate monomer: acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, acrylic acid The tert-butyl ester, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, methyl methacrylate, methacrylic acid Ethyl ester, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, methyl Sec-butyl acrylate, cyclohexyl methacrylate, isodecyl methacrylate, isobornyl methacrylate, metering system Acid t-butylamino ethyl ester, octadecyl methacrylate, glycidyl methacrylate, methacrylic acid bicyclo-penta Alkenyl esters, phenyl methacrylate.
In one embodiment, key component comprises one or more and enters (methyl) acrylic acid as comonomer incorporation The branched vinyl esters of ester polymer.Such (methyl) acrylate polymer can be purchased with trade name NEOCAR820 From The Dow Chemical Company.
It is suitable for use as in polymer the monomer of component generally according to the glass transition temperature of the homopolymer prepared by this monomer Spend (Tg) and be referred to as " firmly " or " soft " monomer.As used in this application, hard monomer is characterised by that the Tg of its homopolymer is more than 40 DEG C, and soft monomer is characterised by that the Tg of its homopolymer is less than or equal to 40 DEG C.The hardest (methyl) acrylate monomer is Methyl methacrylate.
(methyl) acrylate monomer of soft nonfunctionalized has a following formula:
Wherein R1Selected from hydrogen and methyl, and R2For alkyl, preferably comprise at most about 15 carbon atoms.Used in this application Term " alkyl " refers to ring-type and acyclic saturated hydrocarbyl, and this alkyl can be branched or non-branching.Exemplary is soft The acrylic monomer of nonfunctionalized include but not limited to butyl acrylate, Isobutyl 2-propenoate, ethylhexylacrylate, Isodecyl methacrylate, lauryl methacrylate, Tridecyl methacrylate base ester.Butyl acrylate is the softest The monomer of nonfunctionalized.
Sometimes the suitable non-ester monomer with the classification of (methyl) acrylate is nitrile.Preferably nitrile monomer is acrylonitrile.
Although the more highly preferred embodiment of (methyl) acrylate copolymer of the present invention can comprise at most Other comonomer of not (methyl) acrylate monomer of about 5 weight %, but the not (first that other embodiment comprises Base) other comonomer of acrylate monomer can up to 10 weight % or the most up to 20 weight %.For the present invention these Other monomer of copolymer includes vi-ny l aromatic monomers, aliphatic conjugated dienes monomer, Mono-olefinic unsaturated carboxylic acid monomer, second Acid vinyl ester monomers, vinylidene halide monomer and vinyl halide monomer.What at some, other was required is applicable to this In the copolymer of invention, the monomer of polymerization reaction mixture includes one or more (methyl) acrylate lists of 1 to 40 weight % Body.
" vi-ny l aromatic monomers " used in specification and claims be defined as comprising at least one aromatic ring and At least one has any organic compound containing aliphatic group of vinyl degree of unsaturation.Illustrative vi-ny l aromatic monomers Include but not limited to styrene, p-methylstyrene, methyl styrene, neighbour, p-dimethyl styrene, neighbour, p-diethylbenzene Ethylene, p-chlorostyrene, isopropyl styrene, t-butyl styrene, ortho-methyl-p-isopropyl styrene, neighbour, p-dichloro Styrene and mixture thereof.Preferably vi-ny l aromatic monomers is styrene and vinyltoluene；And due to its commercial availability And low cost, styrene is more preferred vi-ny l aromatic monomers.
Term used in this application " conjugate diene monomer " includes following compound, such as 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene and 4-methyl-1,3-pentylene, 2-methyl isophthalic acid, 3-butadiene, pentadiene Other hydrocarbon analog of (1,3-pentadiene) and 1,3-butadiene.Preferably alkadiene monomer is 1,3-butadiene.Aliphatic series is altogether Other monomer that yoke diene includes is the compound of halogenation, such as, chlorbutadiene.
There is the monomer of vinyl, such as, " vinylidene halide " and " vinyl halide ", be suitably included in this In bright copolymer, and it includes, such as, vinylidene chloride and vinyl chloride, both is highly preferred.Can also use Sym-dibromoethane and bromine ethylene partially.Other vinyl monomer in the range of vinyl is vinyl-acetic ester.
Suitable α, β-ethylenic unsaturated aliphatic carboxylic acid monomer is Mono-olefinic unsaturated monocarboxylic, dicarboxylic acids and tricarboxylic Acid (it has ethylene linkage degree of unsaturation in the alpha-beta position of at least one carboxylic group) and the carboxylic group that comprises higher number Similar monomer.It should be understood that carboxylic group can in acid or salt form (-COOM, wherein M represents cation, as ammonium, Hydrogen or metal (such as, sodium or potassium)) exist, and by known to simple program can easy mutual inversion of phases.
The instantiation of α, β-ethylenic unsaturated aliphatic carboxylic acid be acrylic acid, methacrylic acid, fumaric acid, itaconic acid, Maleic acid, aconic acid, the acrylic acid (such as α-ethylacrylate, α-propylacrylate and α-butylacrylic acid) of various alpha-substituted. Highly preferred acid monomers is acrylic acid and methacrylic acid.
About required in copolymer as discussed above or preferably acid monomers amount, by the pKa indication in aqueous solution Seem between the amount that the acid strength of the monomer shown and expectation comprise acid monomers in the copolymer to there is balance.Although for relatively Weak acid monomers can bear and expect higher acid content, but for those acid monomers for the strongest acid monomers, Still expect that the acid content of copolymer is less.
In a preferred embodiment, α, β-ethylenic unsaturated aliphatic carboxylic acid monomer content in the copolymer is desirably Being 0 to 4 weight %, more preferably 0.2 to 3 weight %, still more preferably from 0.3 to 2 weight %.
It is within the scope of the invention that other embodiment, the copolymer wherein used will not be classified as (methyl) propylene Acid ester copolymer.Other copolymer type that can use includes, such as, and vi-ny l aromatic monomers and (methyl) acrylate list Combination (the example of the combination (such as, styrene-acrylic copolymer) of body and vi-ny l aromatic monomers and conjugate diene monomer Such as, styrene-butadiene-copolymer) and the combination (such as, (methyl) of vinyl ester compound and (methyl) acrylate monomer Vinyl esters that acrylate is branched and the branched vinyl ester copolymer of vinyl-acetic ester).Other copolymerization that can use Species type includes such as vinyl acetate ethylene copolymers.These copolymers can with right and wrong Carboxylation or Carboxylation.
Copolymer is desirably prepared by procedure below, such as, by monomer component, water and surfactant (when deployed) It is filled in reaction vessel, by noble gas (such as nitrogen) purge reaction vessel to remove the most complete from reactor vessel The oxygen in portion, and reactor vessel is heated to reaction temperature (usually 80 DEG C to 100 DEG C).When reactor vessel reaches required Reaction temperature time, then initiator and remaining monomer component are joined in reaction vessel, make this reaction proceed 2 to 4 Hour.After the reaction was completed, reactor vessel is made to cool down.This synthesis obtains comprising the aqueous copolymerization group of copolymer in water Compound.In some cases, said composition has the appearance of emulsion liquid, although in other cases its look like clarification molten Liquid.
The method preparing copolymer can include using seed, and described seed can be (methyl) acrylate, polyphenyl second Alkene or for control prepared copolymer Limit Grain Size or be otherwise used for this polymer production any other Seed.As known in the art, the regulation of initial seed can be used to control the limit model of the granularity of prepared copolymer Enclose.The granularity of available copolymer is 700 to 10,000 angstroms.
Anion, nonionic and amophoteric surface active compound, i.e. surfactant, may be used for copolymer synthesis side In method.But in some cases, it is not necessary to surfactant.Exemplary anion, nonionic and amphoteric surfactant It is respectively the surfactant that trade mark is SIPONATE A246L purchased from Rhone-Poulenc, polyoxyethylene alkylphenols table Face activating agent, and N, N-pair-carboxy ethyl lauryl amine (lauramine).Other useful surfactant is DOWFAX2EP, The sodium salt of the phenyl ether of the most myristalated sulfonation, it is purchased from The Dow Chemical Company, Midland, Mich.48640, U.S.A.
Form the coating composition of the present invention
The method preparing coating composition of the present invention comprises the following steps: (1) provides one or more melted or liquid Alkyd resin, one or more melted or liquid respective acid numbers of alkyd resin wherein said are less than 20 and molecular weight (Mn) it is More than 1000 dalton；(2) one or more surfactants are provided；(3) water is provided；(4) optionally provided one or more Nertralizer；(5) make the alkyd resin of one or more melted or liquid described in one or more surface activitys described in water Emulsifying continuously in the presence of agent and optional one or more nertralizers described；(6) thus prepare High Internal Phase Emulsion；(7) carry For other water；(8) described High Internal Phase Emulsion is made to contact with described other water；(9) thus prepare described aqueous alkyd tree Fat dispersion, wherein said alkyd dispersion comprises one or more alkyd resin described in 40 to 70 weight %, less than 10 One or more surfactants described of weight %, and the mean particle diameter of wherein said dispersion is 0.05 to 5 μm； (10) one or more second dispersions and/or the second emulsion are provided；(11) described alkyd dispersion and one or many are made Plant the second dispersion and/or the second emulsion contacts；(12) thus form described coating composition.
Alkyd dispersion and the second dispersion and/or emulsion can be mixed through continuity method or batch process thus be formed The coating composition of the present invention.Such mixing can be through, and such as, stirring, Oaks mixer, IKEA mixer etc. complete.
The final use application of coating composition of the present invention
The coating composition of the present invention may be used for, such as, different coating application, such as industrial coating application, building Coating application, car paint application, outdoor utensil coating application.
The goods of the coating according to the present invention or structure include being connected with one or more surfaces of goods or structure Dope layer, wherein said dope layer is derived from the coating composition according to the present invention.
Coating composition according to the present invention is the compositions forming film.The film being derived from coating composition can have any Thickness；Such as, the thickness of such film can be 0.01 μm to 1mm；Or in interchangeable embodiment, be 1 μm to 500 μ m；Or in interchangeable embodiment, be that 1 μm is to 100 μm；Or in interchangeable embodiment, be 1 to 50 μm；Or can In the embodiment replaced, it is that 1 μm is to 25 μm；Or in interchangeable embodiment, be 1 to 10 μm.
Coated article or the method for structure according to the present invention comprise the following steps: (1) selects Coating material composition of the present invention Thing；(2) this coating composition is applied over one or more surfaces of goods or structure；(3) from these goods or structure One or more surfaces be connected coating composition remove a part of water；(4) thus be coated with described goods or structure.
Coating composition can be applied over one or more surfaces of goods or structure through any method.Such method Include but not limited to spraying, dipping, roller coat and other routine techniques any generally known to those skilled in the art.Coating group Compound can be applied over one or more surfaces of goods or structure the temperature of greater than about 5 DEG C.Such structure includes But it is not limited to commercial establishment, residential building and warehouse.Coating composition can serve as internal applications, applications or its The coating of combination.The surface needing to be coated with this structure of coating composition can include concrete, timber, metal, mould Material, glass, drywall etc..
In one embodiment, the film that pendulum hardness is 50 to 150 seconds, Qi Zhongsuo are included according to the dope layer of the present invention The thickness stating film is at least 40 μm.
In interchangeable embodiment, include that modulus hardness is for (2*10 according to the dope layer of the present invention7) to (1*1011) Dyne/cm2Film.
In interchangeable embodiment, include that resistance to frontal impact is 65 to 160 inches according to the dope layer of the present invention The film of pound.
In interchangeable embodiment, include that resistance to reverse impact is 20 to 160 inches according to the dope layer of the present invention The film of pound.
In interchangeable embodiment, including film according to the dope layer of the present invention, this film is at 60 ° of light after QUV Pool degree loss is less than 30；Such as, less than 20, less than 15, less than 10, less than 5, less than 2, or less than 1.
In interchangeable embodiment, including film according to the dope layer of the present invention, this film is at 20 ° of light after QUV Pool degree loss is less than 50；Such as, less than 40, less than 30, less than 20, or less than 10.
In interchangeable embodiment, include film according to the dope layer of the present invention, this film Δ E color after QUV Change is less than 8；Such as, less than 5, less than 4, or less than 3.
Embodiment
Following example illustrate the present invention but are not intended to limit the scope of the invention.
Alkyd resin synthesizes
It is two stage alcoholysis-polyesterification method for preparing the synthetic schemes of alkyd resin.
(a) first stage
In the first stage, carry out the alcoholysis of typical high-volume, wherein product is divided into quarter and is used for next step.To 5L Three neck RB flasks add Oleum helianthi.Glass puddler and impeller are placed at the inter-engagement of flask.Flask is connected to With the bracing frame of unsettled stirring, by the oil bath lifting of room temperature with submergence flask.Oil bath is set as 220 DEG C, begin to warm up and Stirring.Trimethylolpropane (TMP), season is added in the Oleum helianthi (alkyd resin 1) or Oleum Cocois (alkyd resin 2) of stirring Penta tetrol (PE) and Dibutyltin oxide (1200ppm amount of fill), as table 1 is reported.Once with the addition of all of reactant, will Set point is that the condenser of filling of 95 DEG C attaches to covering in the lump at side engagement and is connected to the hose cock joint of bubbler (hosebarb adaptor).The hose cock joint being connected with nitrogen inlet is attached to opposite side joint.Introduce to system Nitrogen purges and observes bubbler slowly.Reactant mixture is heated and to mix 16 hours (the most overnight) sweet to guarantee to be formed Oil one acid esters, this is verified by the dissolubility in 4 parts of methanol.Turn sky, flask is taken out from oil bath, 900g equal portions are shifted To single 2L tri-neck RB flask.Make flask at N2Protection under cool down, until prepare use.
Table 1
Oil type Oil TMP PE PIA PAN Benzoic acid
Alkyd resin 1 Oleum helianthi 46.298 0 23.785 11.967 17.951 0
Alkyd resin 2 Oleum Cocois 32.552 28.646 0 0 32.552 6.250
(b) second stage
The 2L round-bottomed flask (RBF) comprising alcoholysis mixture is equipped with glass puddler and impeller.Flask is attached to band There is the bracing frame of unsettled stirring.By the oil bath lifting of room temperature with submergence flask.Oil bath is set as 220 DEG C, begins to warm up and stir Mix.The component that interpolation table 1 is listed in flask, for alkyd resin 1 and alkyd resin 2 be i.e., the isophthalic diformazan of such as purification Acid (PIA), isophthalic anhydride (PAN), benzoic acid and dimethylbenzene (2% total amount of fill).Then, by Dean-Stark trap It is connected to covering in the lump at side engagement and is connected to the Friedrichs condenser of bubbler.The flexible pipe being connected with nitrogen inlet Hook joint attaches to opposite side joint.Nitrogen purging is introduced to system.System is heated (～220 DEG C), the water formed is made Steam for the azeotropic mixture with dimethylbenzene.After 3 hours, collect 1～2g reactant mixture, and titrate to determine acid to it Value (AV).Making reaction proceed, until reaching required AV, in the case of this, AV is 8-10, then by reaction content Pour in glass jar, and make it be cooled to room temperature under nitrogen protection.
Alkyd dispersion 1
The acid number of medium oil alkyd resin (alkyd resin 1) is 7.5mg KOH/g resin, is heated to 95 DEG C of (heating about 3 To 4 hours to form molten condition) and be fed in rotor-stator mixer with 50g/min.By 28% (w/w) hydrogen-oxygen Change the ammonium salt solution other water with 0.365g/min charging and with the speed pumping with 22.0g/min to be blended, simultaneously by other Surfactant E-sperse100 (60% active component) (commercially available from Ethox Chemical) is with the speed pump of 3.33mL/min Send and be expelled in mixer produce High Internal Phase Emulsion.Mixer speed is set in about 700rpm.The solids content of emulsion The mean particle diameter of thing is 0.17 micron.The solid content of High Internal Phase Emulsion is 69wt%.Add with 23g/min later by by water It is added in initial High Internal Phase Emulsion dilute High Internal Phase Emulsion；Thus form alkyd dispersion 1, its solid content is 52wt%, Viscosity is about 900cP (by Brookfield viscometer, mandrel #2,20rpm, 21 DEG C of measurements).The heat of alkyd dispersion Ageing stability was at least 8 weeks, and its final size is 0.18 micron, and solid content is not changed in.
Alkyd dispersion 2
The acid number of Cortex cocois radicis short oil alkyd resin (alkyd resin 2) is 9.4mg KOH/g resin, is heated to 75 DEG C and (adds Heat about 3 to 4 hours is to form molten condition) and be fed in rotor-stator mixer with 15g/min.By 28% (weight/weight Amount) Ammonia is blended with 0.137g/min charging and with the other water pumped with the speed of 5.0g/min, will simultaneously Other surfactant E-sperse100 (60% active component) (commercially available from Ethox Chemical) is with the speed of 10mL/min Rate pumps and is expelled in mixer to produce High Internal Phase Emulsion.Mixer speed is set in about 1300rpm.The solid of emulsion The mean particle diameter of content is 0.26 micron.The solid content of High Internal Phase Emulsion is 74wt%.Later by by water with 8g/min Add in initial High Internal Phase Emulsion and High Internal Phase Emulsion is diluted；Thus forming alkyd dispersion 2, its solid content is 53wt%, viscosity is about 500cP (by Brookfield viscometer, mandrel #1,20rpm, 21 DEG C of measurements).The heat of dispersion is old Changing stability was at least 8 weeks, and its final size is 0.30 micron, and solid content is not changed in.
Epoxy resin dispersion 1
Epoxy resin dispersion 1 is modified based on bisphenol-A " 1 " type solid epoxy dispersion, its epoxide equivalent It is about 500g/eq, pH > 6, it is 3000-9000mPa.s (mandrel #4,10rpm) the Brookfield viscosity of 23 DEG C, solid content Being 47%, it derives from The Dow Chemical Company with trade name XZ92533.0.
Epoxy resin dispersion 2
Epoxy resin dispersion 2 is modified semi-solid epoxy novolac dispersion, and its epoxide equivalent is about 200g/eq, pH > 6, it is 5000-10000mPa.s (mandrel #4,10rpm) the Brookfield viscosity of 23 DEG C, solid content is 58%, it derives from The Dow Chemical Company with trade name XZ92546.00.
Prepare polyolefin dispersion 1
Polyolefin dispersion 1 is prepared according to procedure below.
The Engage of polymer based on byTM8200 (CAS No.26221-73-8) and as stabilizer PRIMACORTMThe 5980i (CAS No.9010-77-9) ratio by 70/30 is fed to 25mm by means of rate controlled feeder They are wherein transported forward at feeder and melt, wherein Engage by diameter twin screw extruderTM8200(CAS No.26221-73-8) being ethylene-octene copolymer, its density is 0.87gm/cm3It is about 5g/10min (ASTM with melt index (MI) D1238,190 DEG C/2.16Kg), purchased from The Dow Chemical Company, and PRIMACORTM5980i(CAS No.9010-77-9) being ethylene-acrylic acid copolymer, its acrylic acid content is about 19.5 to 21.5wt% and melt index (MI) is about 300g/10 minute (ASTM D1238,190 DEG C/2.16Kg), purchased from The Dow Chemical Company.Original adding Water and extruder temperature distribution is ramped to about 160 DEG C as before the KOH of nertralizer, then adding after dilution water, will It cooled down to the temperature less than 100 DEG C before leaving extruder.Extruder speed is about 450rpm.KOH and water are mixed Together and introduce point at initial condition and be fed to extruder.Dilution water is fed through the second pump, and is introduced into extruder Dilution zone.Initial condition and dilution water flow are optionally preheated to extruder temperature.At outlet of extruder, back-pressure regulator is used In the pressure in extruder barrel being regulated to suitable pressure to reduce at operation temperature formation steam.By dispersions obtained cooling And it is filtered through 200 micron filters.The dispersion of preparation contains the solid of 46.8%, and its pH is 10.2, and granularity is 0.58 μm.
Prepare polyolefin dispersion 2
Polyolefin dispersion 2 is prepared according to procedure below.The Engage of polymer based on byTM8407(CAS No.26221-73-8) with as the PRIMACOR of stabilizerTM5980i (CAS No.9010-77-9) by 85/15 ratio by It is fed to 25mm diameter twin screw extruder in rate controlled feeder, wherein at feeder they is transported forward and melt Melt, wherein EngageTM8407 (CAS No.26221-73-8) are ethylene-octene copolymer, and its density is 0.87gm/cm3With molten Body index is about 30g/10min (ASTM D1238,190 DEG C/2.16Kg), purchased from The Dow Chemical Company, and PRIMACORTM5980i (CAS No.9010-77-9) is ethylene-acrylic acid copolymer, its acrylic acid content be about 19.5 to 21.5wt% and melt index (MI) are about 300g/10 minute (ASTM D1238,190 DEG C/2.16Kg), purchased from The Dow Chemical Company.Add initial condition and as the KOH of nertralizer before by extruder temperature distribution ramp to about 160 DEG C, then after adding dilution water, it was cooled down to before leaving extruder the temperature less than 100 DEG C.Extrusion machine speed Degree is about 450rpm.KOH and water are mixed and introduces point at initial condition and be fed to extruder.By dilution water through the second pump Charging, and it is introduced into the dilution zone of extruder.Initial condition and dilution water flow are optionally preheated to extruder temperature.? Outlet of extruder, back-pressure regulator is for regulating the pressure in extruder barrel to suitable pressure to reduce in operation temperature Form steam.By dispersions obtained cooling and be filtered through 200 micron filters.The dispersion of preparation contains the solid of 47.4%, Its pH is 10.7, and granularity is 0.39 μm.
Polyester dispersions 1
Polyester dispersions 1 is prepared according to procedure below.By Dynapol L952, (saturated linear, aromatic polyesters, its Tg is About 70 DEG C, molecular weight is 18000g/mol, and acid number is 2mg KOH/g, and hydroxyl value is 6mg KOH/g, purchased from Evonik Industries) and Crylcoat1510 (aromatic polyester, its Tg is about 58 DEG C, is 8500 pools the melt viscosities of 200 DEG C, acid Value for 71mg KOH/g, and hydroxyl value be < 2mg KOH/g, purchased from Cytec) weight ratio with 80/20 passes through the most rate controlled Feeder is fed to 25mm diameter twin screw extruder.In an extruder, by polymer melt, mixing and transport forward.Adding Before adding initial condition and nertralizer, extruder temperature distribution is initially set 150 DEG C.Add initial condition and nertralizer it After, the temperature in whole machine barrel is down to 120 DEG C.DMAE (120% neutralizes) (CAS No.108-01-0) is used Make nertralizer.Extruder speed is about 450rpm.Amine base and initial condition are mixed and introduces point at initial condition and be fed to Extruder.Dilution water is fed through the second pump, and is introduced into the dilution zone of extruder.By optional to initial condition and dilution water flow Be preheated to extruder temperature.At outlet of extruder, back-pressure regulator is for regulating the pressure in extruder barrel extremely Suitably pressure forms steam to reduce in operation temperature.By dispersions obtained cooling and be filtered through 200 micron filters.Polyester The solid content of dispersion 1 is 52wt%, and viscosity is that 86cP is (by Brookfield viscometer, mandrel #1,20rpm, 21 DEG C of surveys Amount), pH is 7.9, and granularity is 1 μm.
Polyester dispersions 2
By polyester resin Fine-Tone T-382-ES, i.e. (Reichhold, acid number is 21mg to bisphenol-A fumarate KOH/g resin, Tg56 DEG C, Mw13900) 150 DEG C (heating about 2 to 3 hours to form molten condition) it are heated to and with 50g/min It is fed to rotor-stator mixer.The dimethylethanolaminesolution solution of 25% (w/w) is fed with 3.67g/min, by it It is blended and is injected into mixer to produce High Internal Phase Emulsion with the other water pumped with the speed of 25.0g/min.By mixer Speed sets and is about 750rpm.The mean particle diameter of the solids content of emulsion is 0.16 micron.Consolidating of High Internal Phase Emulsion contains Amount is 65wt%.Later by adding water to initial High Internal Phase Emulsion with 50g/min, High Internal Phase Emulsion is diluted；Thus formed Polyester dispersions 2, its solid content is 39wt%, viscosity be about 100cP (by Brookfield viscometer, mandrel #1,20rpm, 21 DEG C of measurements).
Dispersions of polyurethanes 1
By polyurethane pre-polymer resin, (based on 45 parts of isophorone diisocyanate, 43 parts derive from The Dow The MW850 natural oil polyols of Chemical Company, 5 parts of dihydromethyl propionic acids and 7 parts derive from The Dow Chemical The UNOXOL DIOL of Company) heat 1 hour at 70 DEG C, it is then transferred to the feed well of 2 inches of Oakes dispersion systems In.Feed well temperature is set as 70 DEG C.Nitrogen pressure head is placed on feed well.Then gear pump is used polymer pump to be sent into System.The feed rate of pump is set as 15g/min.By heat tracing, polymer production line and gear pump are heated to 70 DEG C.To add The polymer of heat introduces an Oakes rotor-stator mixer.By initial condition (IA), i.e. deionized water, coaxially add with polymer Add.Syringe pump is used also coaxially to be pumped to before Oakes head by triethylamine (nertralizer).The speed of Oakes is set as 1500rpm.Oakes head is 20 DEG C.
With～the Oil:IA charge ratio of 1:2 start to feed IA.The most slowly reduce IA to increase High Internal Phase Emulsion (HIPE) Solid.When solid content increases, granularity diminishes, because Oil:IA ratio is close to reversal point, in this reversal point system from O/W emulsion Be converted to W/O emulsion.This being gradually reduced of IA allows us to systematically granularity is down to required size.Then by HIPE It is pumped to the 2nd Oakes for carrying out chain extension (with 100% reaction of residual NCO) with ethylenediamine and being diluted to required with DI water 35% solid.
Dispersions of polyurethanes 2
Dispersions of polyurethanes 2 is based on isophorone diisocyanate and natural oil polyols MW850, QRXP1820, poly-ammonia Ester dispersion 2 is purchased from The Dow Chemical Company.
The coating composition of the present invention
The coating composition of the present invention is prepared according to following general process for preparation.By alkyd dispersion 1 and 2 with as above Described epoxy resin dispersion, dispersions of polyurethanes, polyolefin dispersion and polyester dispersions is blended, and forms the present invention's Coating composition.
General process for preparation is listed below.
1. coating composition blend includes 70 weight portions solid from the first dispersion, based on coating composition total Solids content.
2. coating composition blend includes 30 weight portions solid from the second dispersion, based on coating composition total Solids content.
3. coating composition blend includes 1 weight portion butyl cellosolve, and it is commercially available from The Dow Chemical Company, solids content based on 100 parts of coating compositions (solids content=component 1+ component 2).
4. coating composition blend includes 0.2 part of Surfynol104 deriving from Air Products, based on 100 parts of paintings The solids content (solids content=component 1+ component 2) of feed composition.
5. coating composition blend includes 0.1 part of Halox Flash-X deriving from Halox, based on 100 parts of Coating material compositions The solids content (solids content=component 1+ component 2) of thing.
6. coating composition blend includes 0.1 part of Acrysol deriving from The Dow Chemical Company RM825, solids content based on 100 parts of coating compositions (solids content=component 1+ component 2).
Other component
Desiccant formula for alkyd dispersion 1 preparation is the 1% Co Hydrocure II deriving from OMG, 2.2% Deriving from the Zr HydroCEM of OMG, 0.26% derives from the Dri-RX HF of OMG, based on total score prose style free from parallelism solid.
Cymel303 is purchased from Cytec, and it is used for alkyd dispersion 2 preparation.By 80 parts of alkyd dispersion 2 (bases In solids content) prepare with 20 parts of Cymel303 (based on solids content).
Anquamine401 is purchased from Air Products, and it is used for making epoxy resin dispersion preparation 1 and 2 cross-link.Amine: ring Epoxy resins ratio is 1.2:1.
Embodiment of the present invention 1-15 and comparative example 1-5
Preparation embodiment of the present invention 1-15 also tests its following character: (A) modulus and hardness, (B) resistance to impact, (C) is resistance to Solvent borne, (D) is at the glossiness being exposed to after QUV and color retention rate, and the improvement of (E) corrosion resistance.
A.Modulus and hardness
Embodiment of the present invention 1-4 is prepared according to following preparation:
The embodiment of the present invention 1 is 70/30 blend of alkyd dispersion 1 and dispersions of polyurethanes 1.The present invention implements Example 2 is 70/30 blend of alkyd dispersion 1 and dispersions of polyurethanes 2.The embodiment of the present invention 3 is alkyd resin dispersion Body 1 and 70/30 blend of polyester dispersions 1.
The embodiment of the present invention 4 is 70/30 blend of alkyd dispersion 1 and polyester dispersions 2.
Comparative example 1 is alkyd dispersion 1.
Testing embodiment of the present invention 1-4 and the modulus of comparative example 1 and hardness, result is reported in table 2 below.
Table 2
Sample MFFT Average pendulum hardness (sec) Average thickness (um)
The embodiment of the present invention 1 <-5 74 44
The embodiment of the present invention 2 <-5 60 46
The embodiment of the present invention 3 <-5 52 51
The embodiment of the present invention 4 <-5 67 52
Comparative example 1 <-5 46 49
The embodiment of the present invention 1 and 2 is respectively 4x10 in the modulus of room temperature8Dyne/sq cm and 3x108Dyne/sq cm.This Inventive embodiments 3 and 4 is respectively 4.2x10 in the modulus of room temperature8Dyne/sq cm and 5.6x108Dyne/sq cm.Contrast is implemented Example 1 is 1.8x10 in the modulus of room temperature7Dyne/sq cm.
B.Resistance to impact
Embodiment of the present invention 5-6 is prepared according to following preparation:
The embodiment of the present invention 5 is 70/30 blend of alkyd dispersion 1 and polyolefin dispersion 1.The present invention implements Example 6 is 70/30 blend of alkyd dispersion 1 and polyolefin dispersion 2.
Comparative example 1 is alkyd dispersion 1.
Table 3
C.Chemical resistance
The embodiment of the present invention 7 is prepared according to following preparation:
The embodiment of the present invention 7 is 70/30 blend of dispersions of polyurethanes 1 and alkyd dispersion 1.
Comparative example 1 is alkyd dispersion 1.
Comparative example 2 is dispersions of polyurethanes 1.
The test embodiment of the present invention 7 and the chemical resistance of comparative example 1 and 2, result is reported in table 4.
Table 4
Sample ID Water Bleach Ammonia 50%EtOH 409 Machine oil
The embodiment of the present invention 7 5 5 5 5 3 5
Comparative example 1 3 5 3 2 3 5
Comparative example 2 5 5 5 1 1 5
D. at the glossiness being exposed to after QUV and color retention rate
The embodiment of the present invention 8 is prepared according to following preparation:
The embodiment of the present invention 8 is 70/30 blend of epoxy resin dispersion 1 and alkyd dispersion 2.
Comparative example 3 is epoxy resin dispersion 1.
The test embodiment of the present invention 8 and comparative example 3 are at the glossiness being exposed to after QUV and color retention rate, knot Fruit is reported in table 5.
Table 5
Sample Glossiness 20 loses % Glossiness 60 loses %
The embodiment of the present invention 8 8.21 0.93
Comparative example 3 61.36 30.37
The embodiment of the present invention 9 and 10 is prepared according to following preparation:
The embodiment of the present invention 9 is 70/30 blend of alkyd dispersion 1 and dispersions of polyurethanes 1.
The embodiment of the present invention 10 is 70/30 blend of alkyd dispersion 1 and dispersions of polyurethanes 2.
Comparative example 1 is alkyd dispersion 1.
The test embodiment of the present invention 9 and 10 and the color retention rate of comparative example 1, result is reported in table 6 and Fig. 1. With reference to Fig. 1, the embodiment of the present invention 9 is expressed as 3, and the embodiment of the present invention 10 is expressed as 4, and comparative example 1 is expressed as 73.
Table 6
Sample Aberration E
The embodiment of the present invention 9 7.67
The embodiment of the present invention 10 7.30
Comparative example 1 9.72
E. the improvement of corrosion resistance
The embodiment of the present invention 11 is prepared according to following preparation:
The embodiment of the present invention 11 is 70/30 blend of dispersions of polyurethanes 2 and alkyd dispersion 1.Contrast is implemented Example 1 is alkyd dispersion 1.
Comparative example 4 is dispersions of polyurethanes 2.
The test embodiment of the present invention 11 and the corrosion resistance of comparative example 1 and 4, result is reported in table 7.
About table 7, deciding grade and level of bubbling is for vF (considerably less), F (lacking), and M (medium), MD (medium dense), numeral represents bubbles Size.Deciding grade and level of getting rusty is sl (slightly), med (medium), hvy (seriously), and numeral represents the area got rusty, end eclipse (undercut) refer to that rusty stain penetrates the distance under cut.
Table 7
20 hours brine sprays
Bubble Get rusty End eclipse (mm)
The embodiment of the present invention 11 7-9F sl6% 2
Comparative example 1 9MD sl4% 1
Comparative example 4 6F med15% 5
The embodiment of the present invention 12 is prepared according to following preparation:
The embodiment of the present invention 12 is 70/30 blend of polyolefin dispersion 2 and alkyd dispersion 1.
Comparative example 1 is alkyd dispersion 1.
Comparative example 5 is polyolefin dispersion 2.
Testing the embodiment of the present invention 12 and the foaming of comparative example 1 and 5, get rusty and end eclipse, result is reported in table 8.
Table 8
20 hours brine sprays
Bubble Get rusty End eclipse (mm)
The embodiment of the present invention 12 9F med20% 1
Comparative example 1 9MD Sl4% 1
Comparative example 5 6F hvy60% 1
The embodiment of the present invention 13 and 14 is prepared according to following preparation:
The embodiment of the present invention 13 is 70/30 blend of alkyd dispersion 2 and epoxy resin dispersion 1.
The embodiment of the present invention 14 is 70/30 blend of alkyd dispersion 2 and epoxy resin dispersion 2.
Comparative example 1A is alkyd dispersion 2.
The test embodiment of the present invention 13 and 14 and the foaming of comparative example 1A, get rusty and end eclipse, result is reported in table 9.Comparative example 1A does not forms film, does not therefore test its character.With reference to Fig. 2, the embodiment of the present invention 13 is expressed as 9D, the present invention Embodiment 14 is expressed as 10D.
Table 9
The embodiment of the present invention 15 is prepared according to following preparation:
The embodiment of the present invention 15 is 70/30 blend of epoxy resin dispersion 1 and alkyd dispersion 1.
Comparative example 1 is alkyd dispersion 1.
Comparative example 3 is epoxy resin dispersion 1.
Testing the embodiment of the present invention 15 and the foaming of comparative example 1 and 3, get rusty and end eclipse, result is reported in table 10.
Table 10
Method of testing
Method of testing includes following:
Minimum film-forming temperature
Minimum film-forming temperature is measured according to ASTM-D2354-91.
Pendulum hardness
Pendulum hardness uses and is equipped withThe pendulum hardness tester deriving from BYK Gardner of pendulum is measured.Survey Examination instrument runs according to ISO1522, and sets it to the hardness tested in seconds.The following evaluation hardness of the method: measure when shaking The amplitude of the pendulum swung is the damping time of vibration pendulum in seconds in time being down to 3 ° for 6 °.Pendulum is 2 stainless steel balls, a diameter of 5mm, is on coating surface.When making pendulum setting in motion, ball rolls from the teeth outwards and coating is applied pressure.Damp is strong The weak elasticity depending on coating.Without elastic force, the damping of pendulum is stronger.High resiliency will obtain more weak damping.In other words, In the case of softer coating, the oscillation amplitude of pendulum reduces ground comparatively fast, obtains shorter damping time.
Film thickness
Film thickness is through Gardner micro TRI-glarimeter measurement.
Resistance to impact
Impact test instrument ftractures for the formation testing coating, fractures, bonds and elastic.Use derives from BYK-Gardner Heavy impact test instrument PF-1120 or equivalent.Place the sample of metal coated so that coating side is aspect under instrument platform Upward.Peak that four pounds of stamping machines are raised in guide pipe is also decontroled, and this stamping machine is equivalent to 160 inchpounds.Punching Press simulation platform also forms indenture in the panel, and this is concave surface deformation.Remove panel, and see whether to there is coating damage. Good luminaire and magnifier can aid in the damage checked around indenture external diameter.Ring is modal visual defects； Sometimes coating and metal decking are layered and ftracture or peel off.Think that these are defective, therefore use relatively low landing level again Repeat test, until not showing underproof sign to the three of set a distance continuous landing.On guide pipe, the distance of labelling is Inchpounds of equal value based on four pound weight.When impacting front face coating surface, direction and numerical value are reported as with English The resistance to frontal impact of very little pound meter.
Reversely or indirect stroke
Also reverse or indirect stroke is tested.Impact panel down with coating, on panel, thus produce projection.So After panel is removed, observe coating side damage.Modal defective be star burst cracking (starburst cracking) or Layering and peeling.If there is defective, the most again repeat test with relatively low landing level, until to the three of set a distance companies Continuous landing does not shows underproof sign.Numerical report is the resistance to reverse or indirect stroke in terms of inchpound.
Chemical resistance
Coating material solidified chemical resistance and stain resistance according to ASTM-D1308 by making coating be exposed to various chemicals Test.The inventory of the chemicals that can comprise is: deionized water, 50% ethanol water, bleach, common ammonia, 409 and olive Olive oil.Several chemicals are each placed on coating, and cover 24 hours with watch crystal, be then evaluated.1 inch diameter Filter paper for preventing the initial capillarity of liquid in some samples.At 24 hours later, wash chemicals with water, use napkin It is dried panel.After 1 hour, visual inspection coating is by chemical erosion or any sign of pollution, and fixed extremely 1-5 grade, From 5 (not impacts) to 1 (coating is defective).
QUV
Standard practices ASTM-D4587 that QUV exposes according to the light/water of paint vehicle is measured.
Corrosion resistance
Corrosion resistance is measured according to the ASTM-B117-09 standard practices of operation brine spray (smog) equipment.
Acid value measuring
Take out 1～2g alkyd resin sample with glass pipet from reactor, and weighed and put into 250mL Erlenmeyer flask.With Glass rod, 50/50 mixture of 25mL isopropanol/dimethylbenzene is added in flask.Flask is put On agitator/drying-plate, it is made to mix until material dissolution under mild heat.Then, several phenolphthalein indicator solution are added It is added in flask, and uses 0.1N potassium hydroxide methanol solution that content is titrated to phenolphthalein terminal point.Then calculate according to following formula AV:
Average external volume particle size diameter can be by using the light scattering method of Particle Size Analyzer or by using transmitted electron to show The electron microscope method of micro mirror method (TEM) or scanning electron microscopy (SEM) is measured.
Particle Size Analyzer
Beckman Coulter LS230 Particle Size Analyzer with make together with the small volume module of sample delivery system With.The software version used is version 3 .29.Hardware and software derives from Beckman Coulter Inc., Miami, Florida.
The analysis condition of all measurements uses the fluid refractive index of 1.332, the Sample Real Refractive of 1.5, and the sample of 0.0 Product imaginary refractive index.Do not use the optical model of extension.Polarization intensity differential scanning (PIDS) option is activated and is used for producing Granular information.Measure mean particle diameter and be reported as μm.
Electron microscope method
(1)TEM
First with distilled water diluting sample (in the D.I. water of 1 latex entrance 10mL), then incite somebody to action～5 μ L drops are placed in On the TEM grid that Formvar (polyvinylformal) is coated with and make its air be dried.It is used in the accelerating potential operation of 120kV JEOL JEM-1230TEM utilizes master sample frame or uses the low temperature-stage at-120 DEG C to check sample.Digital picture is with dividing Resolution is that the Gatan Multiscan794CCD camera of 1024x1024 pixel obtains and uses Adobe Photoshop5.0 process. Graphical analysis uses ImageJ software to carry out.Grey scale image is used threshold value, uses watershed function separation agglomerate, measure Particle area.Through equation diameter=2*sqrt (area/π), particle area is converted into equivalent diameter.A diameter of～3nm to 3 μm Particle can pass through TEM commercial measurement.
(2)SEM
Sample deionized water is diluted, then they is dropped on the part of clean silicon wafer and in drying at room temperature. After by them with the sputtering coating of 10nm osmium, they are in FEI Nova NanoSEM field emission rifle scanning electron microscope In 3 to 5keV imaging.Graphical analysis uses ImageJ software to carry out.Grey scale image is used threshold value, uses watershed merit Agglomerate can be separated, measure particle area.Through equation diameter=2*sqrt (area/π), area is converted into diameter.Can measure～ The diameter of 50nm to 50 μm.
Viscosity can be through Brookfield viscometer, in 20rpm and 21 DEG C of measurements.
The viscosity of alkyd resin in melt
The viscosity measurement of alkyd polymer uses TA Instruments AR2000 flow graph to carry out.Alkyd resin The sample of polymer is analyzed by using parallel plate geometry body to carry out flowing rheometry at assigned temperature.Viscosity is by recording Torque arithmetic and based on be specific to test solid the factor that rectifies an instrument, the shear rate recorded is 0.10/sec.
Hot ageing stability is identified below: remeasure the granularity of (after the temperature and time circulation specified) dispersion With solid content to determine whether to change.Dispersion samples is put in the glass jar with vinyl cover.Glass jar is put into In temperature is set in the baking oven of 50 DEG C and placed at most 12 weeks.At the end of this time period, without macroscopic The sedimentation/separation of dispersion, then before using, the identical process of general introduction remeasures the granularity of sample.
The present invention can implement with other form without departing from its spirit or essential characteristics, therefore, when indicating the present invention's During scope, it should with reference to claims rather than with reference to aforementioned specification.

Claims (12)

1. coating composition, it comprises:
Aqueous, high solids content, the solvent-free alkyd dispersion of (a) 10 to 90 weight %, this dispersion comprises:
One or more alkyd resin of 40 to 70 weight %, gross weight based on described dispersion, wherein said one or many Plant the respective acid number of alkyd resin less than 15 and molecular weight MnFor more than 1000 dalton；
Less than one or more surfactants of 10 weight %, gross weight based on described dispersion；With
The water of 30 to 55 weight %, gross weight based on described dispersion；
Wherein said mean particle diameter aqueous, high solids content, solvent-free alkyd dispersion is 1 to 5 μm；
(i) of (b) 10 to 90 weight % one or more second dispersions, its be selected from polyolefin dispersion, dispersions of polyurethanes, Epoxy resin dispersion, and polyester dispersions, (ii) one or more second emulsions, it is selected from acrylic latex, acetic acid second Alkenyl esters acrylic latex, styrene-acrylonitrile copolymer acids latex, and vinylacetate ethylene latex, or (iii) a combination thereof；
The solid content of wherein said coating composition is the solid content of 25 to 65 weight %, gross weight based on described coating composition Amount, the pH of described coating composition is 7 to 11, and the volume average particle sizes of wherein said coating composition is 0.03 to 5 μm, And the viscosity of wherein said coating composition is 100 to 10,000cP, through Brookfield viscometer, 20rpm and 21 DEG C Measure.
2. the coating composition of claim 1, one or more alkyd resin wherein said are neutralized to many 100% by nertralizer.
3. the coating composition of claim 1, the viscosity of wherein said alkyd dispersion is 100 to 10,000cP, warp Brookfield viscometer, in 20rpm and 21 DEG C of measurements.
4. the coating composition of claim 1, the solid content of wherein said alkyd dispersion is more than 60wt%, based on described The weight of alkyd dispersion.
5. the coating composition of claim 1, the solid content of wherein said alkyd dispersion is more than 65wt%, based on described The weight of dispersion.
6. the coating composition of claim 1, the solid content of wherein said alkyd dispersion is more than 70wt%, based on described The weight of dispersion.
7. the coating composition of claim 1, the acid number of wherein said alkyd resin is less than 10.
8. it is derived from one or more dope layers of the coating composition of claim 1.
9. include the goods being derived from one or more dope layers of the coating composition of claim 1.
10. the method preparing coating composition, comprises the following steps:
There is provided one or more melted or the alkyd resin of liquid, one or more melted or alkyd resin of liquid wherein said Respective acid number is less than 15 and molecular weight MnFor more than 1000 dalton；
One or more surfactants are provided；
Water is provided；
One or more nertralizers optionally provided；
Make the alkyd resin of one or more melted or liquid described at one or more surfactants described with appoint in water Emulsifying continuously in the presence of one or more nertralizers described of choosing；
Thus prepare High Internal Phase Emulsion；
Other water is provided；
Described High Internal Phase Emulsion is made to contact with described other water；
Thus prepare described aqueous alkyd dispersion, wherein said alkyd dispersion comprises 40 to 70 weight % One or more alkyd resin described, less than one or more surfactants described in 10 weight %, and wherein said point The mean particle diameter of a prose style free from parallelism is 1 to 5 μm；
Thering is provided (i) one or more second dispersions, it is selected from polyolefin dispersion, dispersions of polyurethanes, and epoxy resin disperses Body, and polyester dispersions, (ii) one or more second emulsions, it is selected from acrylic latex, vinyl-acetic ester acrylic acid Class latex, styrene-acrylonitrile copolymer acids latex, and vinylacetate ethylene latex, or (iii) a combination thereof；
Make (i) described one or more second point of the described alkyd dispersion of 10 to 90 weight % and 10 to 90 weight % A prose style free from parallelism, it is selected from polyolefin dispersion, dispersions of polyurethanes, epoxy resin dispersion, and polyester dispersions, (ii) described one Or multiple second emulsion, it is selected from acrylic latex, vinyl-acetic ester acrylic latex, styrene-acrylonitrile copolymer acids glue Breast, and vinylacetate ethylene latex, or the contact of (iii) a combination thereof；With
Thus form described coating composition；
The solid content of wherein said coating composition is the solid content of 25 to 65 weight %, gross weight based on described coating composition Amount, the pH of described coating composition is 7 to 11, and the volume average particle sizes of wherein said coating composition is 0.03 to 5 μm, And the viscosity of wherein said coating composition is 100 to 10,000cP, through Brookfield viscometer, 20rpm and 21 DEG C Measure.
The method of the coating composition of 11. preparation claim 3, one or more alkyd resin wherein said are neutralized by nertralizer At most 100%.
The method of the coating composition of 12. preparation claim 3, the viscosity of wherein said alkyd dispersion is 100 to 10, 000cP, through Brookfield viscometer, in 20rpm and 21 DEG C of measurements.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1745140A (en) * 2003-01-31 2006-03-08 克雷·瓦利有限公司 Aqueous dispersion of alkyde resin which is treated with an oxidizing agent and which has improved drying properties

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1745140A (en) * 2003-01-31 2006-03-08 克雷·瓦利有限公司 Aqueous dispersion of alkyde resin which is treated with an oxidizing agent and which has improved drying properties

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