CN101595158A

CN101595158A - Resin, low temperature formulations and by the coating of its acquisition

Info

Publication number: CN101595158A
Application number: CNA2006800144389A
Authority: CN
Inventors: 比马·R·维贾因德兰; 杰里·L·金; 凯瑟琳·P·米切尔; 迈克尔·C·克林哲曼; 杰弗里·T·卡夫梅尔
Original assignee: Battelle Memorial Institute Inc
Current assignee: Battelle Memorial Institute Inc
Priority date: 2005-03-18
Filing date: 2006-03-20
Publication date: 2009-12-02
Also published as: CN101189276B; CN101189276A

Abstract

Use is synthesized the molecular structure of a series of resins with control resin of the present invention based on the material of biology widely, and controls the performance of resin of the present invention thus.The effectiveness of these resins has obtained displaying in powder paint compositions, such as the beta-hydroxy acid amides crosslinked with the hydridization type.As a rule, during heating, get faster based on the resin of biology than the resin flows based on petroleum chemicals of routine, permission is adopted in curing oven and is lower than usually possible and has more in the active catalyst system, particularly the temperature that is adopted in the hybridization coating composition of carboxylic acid-epoxy cross-linking.

Description

Resin, low temperature formulations and by the coating of its acquisition

The application requires to enjoy the provisional application NO.60/663 that submitted on March 18th, 2005, the provisional application No.60/758 that on January 13rd, 422 and 2006 submitted to, 757 rights and interests.

Be incorporated herein by reference at this full content these two pieces of provisional application.

Invention field

The present invention is used to produce powder coating, and this powder coating is used for substrate, particularly thermally sensitive substrate.Typical thermally sensitive substrate comprises organic substrates (including, but are not limited to polymkeric substance, as plastics) and matrix material (including, but are not limited to the matrix material of timber and plastics).

Background of invention

There are a kind of serious deficiency in present powder coating resin and composition: promptly described powder coating resin and the composition furnace temperature (generally being higher than 177 ℃) that needs are quite high usually is so that obtain the required good fluidity of acceptable performance and crosslinked.Great majority have substrate to be coated (such as plastics, timber and Biocomposite material) quite responsive and can not stand the high temperature that adopted in the present powder paint compositions to temperature.The use that shows this type of substrate recent years significantly increases and is expected in following sharp increase.Referring to the Muthiah reference about an example in the work recently of low temperature cured powder coating field.

Need a kind of temperature sensitive substrate, durable, cost-efficient low temperature thermosetting powder coating that is used for, described low temperature thermosetting powder coating also can be gone up at pyritous substrate (as metal) and use.In this case, lower temperature can make the energy waste of this process reduce.Cheap cost will significantly improve the degree of recognition to new technology.

The focus that receives much concern is some petroleum chemicals raw materials are replaced with raw material based on biology so that use in far-ranging Application Areas.The sign of this concern can be reflected by a large amount of summary papers of having published in the last few years.U.S. Pat 6,063,464 for example understand with people's such as Guo paper (vide infra) and to attempt to utilize the raw material based on biology to come the synthesizing polyester resin, wherein the Isosorbide with the cereal biomass derived is used for the synthetic of polyester material.

Also need to produce can be in being lower than industry currently used temperature current downflow and solidified powder coating.This powder coating has multiple environmental advantage, because they in use produce VOCs discharge seldom.Unfortunately, since in the cure cycle high energy requirement and the coarse finished product (rough finishes) that obtains because of the powder coating of low temperature current downflow difference usually lost some advantage.

Patent and journal of writings that other are relevant comprise:

Low-temperature curing: US 6,703,070 03/2004 Muthiah

Synthesize and processing: EP1491593 12/2004 Mons

Summary based on the material of biology: Applied Microbiology and Biotechnology (2001), 55 (4), 387-394.Huttermann, A.; Mai, C.; Kharazipour, A. " Modification of lignin for the production of new compounded materials "; Biopolymers from Renewable Resources (1998), 1-29.Kaplan, David L. " Introduction to biopolymers from renewable resources "; BioresourceTechnology (1994), 49 (1), 1-6.Sharma, D.K.; Tiwari, M.; Behera, B.K. " Review of integrated processes to get value-added chemicals and fuels frompetrocrops "; And Applied Biochemistry and Biotechnology (1988), 177-22.Narayan, Ramani. " Preparation of bio-based polymers for materialsapplications ".

Synthetic based on the resin of biology: the abstract of a thesis, the 224th ACS meeting, Boston, MA, the U.S., August 18-22,2002 (2002) .Guo, Yinzhong; Mannari, Vijaykumar M.; Massingill, John L., Jr. " Hyperbranched bio-based polyols ".

Powder coating: " Powder Coatings Volume 1:The Technology; Formulation; and Application of Powder Coatings " .Howell, David M.John Wiley and Sons, London, 2000.Polymer Preprints 2003,44 (1) .Gedan-Smolka, Michaela; Lehmann, Dieter; Lehmann, Frank. " Catalysis in Uretdione Powder CoatingsEnables Innovative Processing Lines ".

Except needs flow at low temperatures and the solidified powder coating, do not considering to apply under the situation of type, also need be in paint matrix finely disseminated pigment.For reaching this purpose, the polymkeric substance that design has different compatible components.Usually in most applications, the polymeric dispersion agent makes pigment and other compositions in colored paint, coating and the ink set reach stable via steric stabilization.The polymeric dispersion agent has two component structures of being made up of anchoring group and polymeric chain.Usually in most applications, described anchoring group is a polar material, and itself and particle surface and the polymeric chain compatible with the external phase of coating interact.In fact, polymer-based group forms coating around particle, thereby prevents that described particle from contacting, being condensed into bigger inconsistent polymer.

Has the multiple anchoring group/polymkeric substance configuration that obtains effective polymeric dispersant of can expecting.Resin of the present invention has polar carboxyl combining site and nonpolar vegetables oil chain and can play dispersion agent and tackiness agent thus.The cure adhesive that also can play the dispersion agent effect can be eliminated the demand for the independent additive that is used to disperse multiple pigment.Relevant technology comprises US 5,959,066, US 6,025,061, US 6,063,464 and US 6,107,447.

The invention summary

In brief, need a kind of be used for the temperature sensitive substrate, durable, cost-efficient low temperature thermosetting powder coating, described low temperature thermosetting powder coating also can be gone up at pyritous substrate (as metal) and use.Also need to find the material that substitutes the petroleum chemistry raw material, this is especially true when alternative when competent raw material based on biology can be used for.Powder coating technology based on biology disclosed herein satisfies this demand by combining with proprietary compounding process (particularly low-temperature curing technology) from the new type resin in recyclable organism source.In the later case, lower temperature makes the energy waste of this process reduce and will improve significantly the degree of recognition based on the new technology of biology.

One embodiment of the invention provide the synthetic of vibrin, described vibrin have the Tg that is higher than 50 ℃, at least 5% based on the content of biology and be at least 50% and low relatively viscosity in another embodiment.

In wide in range embodiment, resin is applied to coating composition, particularly powder paint compositions.

In yet another embodiment, resin comprises the carboxyl-functional polyester from diacid and glycol reaction.

In yet another embodiment, be based on biological or as required in order to the acid that forms vibrin and glycol, so that make the performance of resulting coating reach best and make in the resin amount reach maximum based on the material of biology based on the acid and the glycol of oil.

In another embodiment of the present invention, resin and cross-linked resin mixed to solidify have excellent fluidity under the relative low temperature and flexible protectiveness is filmed.

In another embodiment of the present invention, resin and PRIMID mixed with resin are gone into to have excellent fluidity and flexible protectiveness is filmed to solidify.

In another embodiment of the present invention, resin and acrylic acid or the like Resins, epoxy mixed to solidify have excellent fluidity under the relative low temperature and flexible hydridization (hybrid) powder is filmed.

In yet another embodiment, composition comprises catalyzer, flow control agent, cured modified additive etc. so that control appearance character, solidification rate and other performances.

In yet another embodiment, composition comprises the catalyzer of being made up of the imidazoles of imidazoles and replacement.

In yet another embodiment, composition comprises the activity of cured modified additive (as acid additives) with the imidazoles of change imidazoles and replacement.

In yet another embodiment, composition can comprise additive known in the art and vehicle, and described additive and vehicle comprise pigment, is used for painted, outward appearance, corrosion control, covering or other functions.

The accompanying drawing summary

Fig. 1 has shown to adopt hard crystalloid Isosorbide to mix to come the indicative flowchart in the path of synthesizing polyester material with unbodied dimer diol, aromatic diesters and other compositions.

Fig. 2 has shown to adopt hard crystalloid Isosorbide to mix to come the indicative flowchart in the path of synthesizing polyester acid with unbodied dimerization diacid and other compositions.These materials can be specifically designed to the hydridization powder paint compositions with cross-linked epoxy functionalized position.

Fig. 3 has shown to adopt hard crystalloid Isosorbide to mix to come the indicative flowchart in the path of synthesis of polyurethane with dimer diol, unbodied dimerization diacid, polymeric polyisocyanate (as vulcabond) and other compositions.

Fig. 3 A illustrates typical isomer-1a, 1b and the 1c to the useful Isosorbide of the present invention.

Fig. 4 shows the resin (embodiment 2) based on biology and typically is purchased resin (FINE-CLAD

) the figure of rheological curves.

Fig. 5 is the composition (embodiment 4A) and the figure that is purchased the viscosity profile of composition under about 121 ℃ of control group that shows based on biology.

Fig. 6 is the synoptic diagram of the different elements of the instrument that shows the resin be used to prepare embodiment 1 to 3F.

Fig. 7 is for showing the viscosity histogram of composition A to G under 90 ℃ and 100 ℃ of embodiment 8.

Detailed Description Of The Invention and preferred forms

Say that generally the present invention will combine with demand to the lower temperature powdery paints based on the intended use of the raw material of biology. Can use cereal and soybean material and prepare the resin with the equalization performance that is suitable for powdery paints enforcement. These resins can be mixed with the various powders coating composition subsequently.

Usually, prepare according to powder paint compositions of the present invention via following process: pulverize primary resin (principal resin), itself and the additive of the curing agent of pulverizing with the pulverizing of selecting are dry mixed, make that to be dry mixed thing melt-blended, push melt-blended mixture, cool off fast subsequently. Mixture with cooling is ground into the particle diameter of expectation afterwards, and makes at last the powder of gained be categorized into final particle diameter.

As used herein, for embodiments more of the present invention, based on the fingers such as the raw material of biology, composition, product, material, resin at least part of via routine chemical modification and/or process raw material, composition, material, resin and the product etc. that produce based on the conversion of the renewable resource of agricultural and forest via bioprocess (such as fermentation). Carbon source is from reproducible crops/tree resources, and they are different from the carbon source that conventional fossil limited and that can exhaust is derived.

As used herein, hybrid resin refers to that this resin is resin blend thing more than a type, for example mixture of polyester and epoxy resin.

Can be the well balanced following two kinds of obvious performances of opposition of useful especially resin according to the present invention:

(1) have lower viscosity under the molten condition in order to can flow well when using, it is the characteristic of amorphous resin, but also must have,

(2) have relatively high glass transition temperature (Tg) in order to obtain good bin stability, it is the characteristic of crystalloid resin. If Tg is excessively low, powder particle can be " softness " and particularly in the situation that storage temperature raises, be condensed into disabled at lay up period. Usually, by crystalloid resin and amorphous resin are mixed into the merocrystalline resin compound and balanced these performances effectively. The general resin that obtains according to the present invention provides the performance of these expectations.

Note: except as otherwise noted, otherwise when % referred to the quantity of composition, it referred to percentage by weight (wt%).

Four kinds of approach commonly used for the synthesis of resin disclosed herein:

1. the polyester of the glycol of deriving based on dimer diol, isobide and/or the hydroxyl-functional of dimeric dibasic acid. Usually, recently determine carboxyl or the hydroxy functionality of polyester via diacid or the excessive mole of glycol group. Usually, the net content based on biology that polyester has is at least about 5wt%, but in most cases is generally about 20 to about 50wt%.

2. the polyester of the glycol of deriving based on dimer diol, isobide and/or the carboxyl-functional of dimeric dibasic acid. Usually, recently determine carboxyl or the hydroxy functionality of polyester via diacid or the excessive mole of glycol group. Usually, the net content based on biology that polyester has is at least about 5wt%, but in most cases is generally about 50 to about 70wt%.

3. based on the polyurethane of hydroxyl, carboxyl or the isocyanate-functional of dimeric dibasic acid and/or dimer diol. Usually, excessive isobide and/or dimer diol generate hydroxy functionality and excessive dimeric dibasic acid generation carboxyl functionality, and excessive PIC generates isocyanate functionality. Usually, the net content based on biology that polyurethane has is at least about 5wt%, but in most cases is generally about 20 to about 50wt%.

4. amido-amine functional resins is as the disclosed amido-amine functional resins that is used for easy deinking ink powder among the WO2004/077169 of the submission on February 2nd, 2004 and the appointment U.S..Described in this patent application, amido-polyimide resin is the reaction product of dimeracid and diamines, and the content of this patent is hereby incorporated by.In some embodiments of the present invention, typical amide amine functional resins has and is lower than about 80 ℃ Tg.In other embodiments of the present invention, amido-amine has and is lower than about 70 ℃ Tg.Net content based on biology is generally 5wt% at least, but in most cases is generally about 40 to about 60wt%

Can be according to resin of the present invention by the coreaction component that trends towards producing sclerization, as Isosorbide (from cereal materials) and the component that produces ramollescence (flexiblizing effects), (from the vegetables oil raw material) constitutes as dimeracid or dimer diol.Thereby can generate resin control resin flow and package stability by these components being carried out coreaction.Generally speaking, the sclerosis component comprises the chemical functional group who links to each other with the ring texture that limits its mobility, as alcohol, ester, carboxylic acid or chloride of acid; And softening component comprises the chemical functional group who links to each other with aliphatic carbon chain.The glycol that Isosorbide is made up of condensed ring-type ether ring and be the member based on the sugar derivatives extended familys of biology, it generally is called two dewatering hexitols.Dimeracid and dimer diol are respectively from natural main aliphatics---based on the dicarboxylic acid and the glycol of the lipid acid of biology.Similarly, these sclerosis and ramollescence can also be applied to the urethane described as Fig. 3.

Usually, by utilizing the crosslinked of catalyzer and/or heating to make resin solidification.Typical solidification value is up to 125 ℃.

Polyester polyol resin disclosed herein can be used from coating, tackiness agent, sealing agent and other application with isocyanic ester, epoxy resin, melamino-formaldehyde, urea formaldehyde and other compositions one in reactive composition.

Poly-carboxy resin disclosed herein can be used from coating, tackiness agent, sealing agent and other application with beta-hydroxy acid amides, epoxy resin and other compositions one in reactive composition.

Amido-amine functional resins can be used from coating, tackiness agent, sealing agent and other application with isocyanic ester, epoxy resin, melamino-formaldehyde, urea formaldehyde and other compositions one in reactive composition.

The specific practicality of disclosed biologically-derived resin is the application in powder paint compositions.Embodiment 4 has described biologically-derived carboxyl-functional resin, and its mode and beta-hydroxy acid amides with transesterify in powder paint compositions solidify to form bright coating.Embodiment 4A describes the resin that is similar to embodiment 4, but the resin of embodiment 4A has carried out scale operation.The resin of gained has slightly high Tg.Embodiment 5 has described biologically-derived carboxyl-functional resin, and it solidify to form the coating of light with acrylic acid epoxy resin in powder paint compositions.Embodiment 6 has described biologically-derived carboxyl-functional resin, and it forms the coating of black with the epoxy cross-linking resin solidification that is purchased in coloured powder paint compositions.When embodiment 6A has described the pigment dispersion of being made up of biologically-derived carboxylic-acid functional resin and carbon black and has been added in the white powder coating composition, with the carboxyl-functional resin that is purchased and carbon black and they contrast to the effect of color.Embodiment 6B describes the carboxylic-acid functional resin based on biology that uses isocyanuric acid three-glycidyl ester (TGIC) linking agent to be cured.

Embodiment 7 describes biologically-derived amido-amine functional resins, and it forms the coating of light with the epoxy cross-linking resin solidification that is purchased in powder paint compositions.

Embodiment 8 illustrates use and prepares powder coating based on the polyester of biology as flow improver additive.Vibrin is described among the embodiment 3B.

Last embodiment 9 illustrates the colo(u)rant dispersion performance according to the resin of embodiment 3F preparation.

One embodiment of the invention relate to a kind of method of being produced the resin that uses in the powder coating application by minimum to the material based on biology of maximum.In another embodiment of the invention, this resin comprises at least a saturated or unsaturated polyester based on biology.

The invention still further relates to these based on one or more purposes in multinomial application in the material of biology, described application includes, but are not limited to coating, powder coating, tackiness agent, ink powder, printing ink, sealing agent, polymeric additive and other application.Utilizing suitable melt rheology is to have to be lower than about 80 ℃ glass transition temp (Tg) with the resin design of an embodiment, with other the resin design of embodiment is to have to be lower than about 70 ℃ glass transition temp, is to have to be lower than about 60 ℃ glass transition temp with the resin design in the another embodiment.Use suitable melt rheology, the resin of a total embodiment of generalized has minimum glass transition temp that is at least about 20 ℃ and the maximum glass transition temp that is about 80 ℃ according to the present invention.Can be used for controlling the low side (Tg as embodiment 3B is about 28.4 ℃) that mobile resin is in the glass transition temp scope usually, but its scope can be by about 20 ℃ to about 80 ℃, and can be about 25 ℃ to about 60 ℃ usually in some embodiments.

The hydridization powder coating resin of forming greater than 50% the resin based on the carboxyl functional group of biology that contains of the present invention is mixed with powder coating.Resin of the present invention described herein by trend towards hardening and the coreaction component of highly functional with trend towards softening and the flexible component constitutes, wherein saidly trend towards hardening and the example of the coreaction component of highly functional is Isosorbide (generally from a cereal materials), the described example that trends towards softening and flexible component is dimeracid (generally from a soy material).Thereby can generate resin control resin flow and package stability by these components being carried out suitable coreaction.

The invention still further relates to powder paint compositions by one or more resins of the present invention.The distinguishing characteristics of this powder coating is that this coating is being lower than the ability that is commonly used to carry out the temperature current downflow of powder coating operation and is solidified into continuous film.Above-mentioned low-temperature curing ability stems from the low viscosity character based on the resin of biology, and described resin based on biology is applied in the composition and composition of flow performance of the dominance that has made full use of resin Composition of the present invention.The advantage that obtains by resin of the present invention be when its during with being purchased resin and comparing of about equivalent, to having lower viscosity under the fixed temperature.

The key characteristic of employed resin is glass transition temp (Tg) in the powder paint compositions, and in order to obtain the package stability of final powder coating powder, it is at least about 50 ℃ usually and also preferably is at least about 60 ℃.Table 1 shows the catalogue of several resins based on soybean, and functionality and Tg.The explanation of this table is difficult to by comprising that the material preparation based on the low viscosity monomer of soybean has the resin that can accept Tg.

Have only resin 1-1 to meet the standard of Tg.In order in based on the situation of the material of soybean, to obtain higher Tgs and to keep the high amount of filler of material in resin based on biology, utilized another kind of based on biology but have material---the Isosorbide that higher intrinsic Tg distributes.

The material based on biology (from the Isosorbide of cereal materials) with higher Tg is differentiated described material based on biology can obtain high content and the resin that is used for enough high Tg of powder paint compositions based on biology with the material coreaction based on soybean.Subsequently synthetic seeking balance soybean, Isosorbide and other components are so that in resin, and the suitable equilibrium that obtains multiple performance in final powder coating.

Synthetic (referring to the embodiment 1 and 2) of resin:

The purposes of material in preparation coating based on biology can be described below:

Prepare polyester polymers via following step: (1) in reactor with Isosorbide (from cereal materials), fatty dimer diol and/or dimerization diacid (from soy material), diacid, diester or diacyl chlorine, optional common glycol and optional common diacid, altogether diester or altogether diacyl chlorine be suitable for aromatic diacid and mix with glycol polymeric condensation catalyst; Reach (2) heating monomer and catalyzer so that described monomer generation polymerization obtains polyester.(referring to Fig. 1)

The vibrin for preparing carboxyl-functional via following step: mix Isosorbide, fatty dimerization diacid, optional common diacid, common diester or common diacyl chlorine and optional common glycol in reactor (1) with condensation catalyst; And (2) heating monomer and catalyzer are so that described monomer generation polymerization obtains the vibrin of carboxyl-functional.(referring to Fig. 2)

The urethane for preparing hydroxyl, carboxyl or isocyanate-functional via following step: (1) in reactor with Isosorbide, fatty dimerization diacid and/or dimer diol, polymeric polyisocyanate, optional common glycol and optional common diacid, diester or diacyl chlorine and be suitable for that two pure and mild diacid are mixed with polymeric polyisocyanate polymeric catalyst mix or under catalyst-free altogether altogether; The catalyzer that reaches (2) heating monomer and choose wantonly is so that described monomer generation polymerization obtains urethane.(referring to Fig. 3)

With reference now to Fig. 1,2 and 3,, it discloses and has been used for the different reactant of embodiment herein.Except that disclosed dimer diol and dimeracid, the present invention includes according to wide in range embodiment and to have about 4 aliphatic chains usually to about 20 carbon atoms.More preferably, described aliphatic chain has about 6 to about 16 carbon atoms.

Disclosed in addition dimer diol and dimeracid comprise six-ring, and wherein two side chains are about 4 aliphatic lateral chains to about 20 carbon atoms, and other two side chains are about 8 to 12 carbon atoms with alcohol or carboxyl functional group.

In addition, diester, diacid, common diacid and common diester can have formula R ₂-CO-R ₁-CO-R ₂, R wherein ₂=-OH ,-OR ₃Or-Cl, wherein R ₃=have an aliphatic chain of 1 to 4 carbon atom.R ₁Be aryl or aliphatic group with 2-12 carbon atom.

Although do not wish to be bound by theory, think that at present aliphatic lateral chain in dimeracid and the dimer diol provides the low viscosity performance of resin.Described aliphatic lateral chain trends towards softening under lower temperature, thereby makes it have lower viscosity and better mobile.Also can soften quickly during the long more just easy more softening and heating of this chain.

Think that also described side chain provides pigment-dispersing 9 shown as embodiment, that improve in certain embodiments.A flowability result preferably is that pigment wetting is good, thereby can improve dispersing of pigments.

In addition and more in a broad sense, the present invention can use two dewatering hexitols (dihanhydrohexitols).Therefore, can contain the dicyclo that can be used for other cyclic diols of the present invention by introducing makes other two dewatering hexitols substitute D-Isosorbide or its isomer for preparing in the rigid structure.The glycol of introducing cyclohexyl, isophorone and other ring texturees can strengthen and is similar to the sclerization that Isosorbide rises.

The dimerization diacid is generally and passes through C ₁₈The dimerisation of unsaturated fatty acids and the viscous liquid that generates.C ₁₈Unsaturated fatty acids has three kinds of biogenetic derivations---plant, tallol and animal.C ₁₈The unit can several modes link together.Known main ingredient C ₃₆Four kinds of main structure types of diacid are acyclic, monocycle, dicyclo and aromatics.Each of these structure types all has multiple constitutional isomer.The processing condition that ratio and dimerisation adopted of the monounsaturated fatty acids/polyunsaturated fatty acid in the starting fat acid starting material are depended in the distribution of these structure types and isomer.The dimerization diacid of the minimum of Shi Yonging C normally in certain embodiments ₁₈Diacid.

Below four types the common commercially available acquisition of dimerization diacid: (1) standard substance (undistilled), it contains 80% the C of having an appointment ₃₆Diprotic acid, (2) distillation product, wherein said C ₃₆The content of diprotic acid has been increased to 92-98%, and (3) distillation and partial hydrogenation to be improving the product of color, and (4) distillation and fully hydrogenation to obtain the product of maximum stable.

The typical dimeracid that is used to prepare based on the vibrin of biology is Empol

(embodiment 3,3C and 3E) and Pripol (embodiment 2,3A and 3D), both are the dimeracid based on plant.Empol

The Pripol by the preparation of Cognis company

Prepare by Uniqema company.Cognis company has paid close attention to the dimeracid based on tallol more since stopping its dimeracid based on plant.Table 3 has contrasted Pripol

With Empol

Physicals and composition.Pripol

Color is more shallow and have higher diprotic acid content.Use these two kinds different dimeracid synthetic carboxyl-functional resins to have similar physicals.

Table 1A. dimeracid is formed and performance

Dimer diol is prepared by the high-pressure hydrogenation of dimerization diacid methyl ester usually.The dimer diol that is used to prepare the vibrin (embodiment 1,1A and 3B) based on biology is SPEZIOL C36/2

Dimer diol.This be a kind of by Cognis company produce, based on the dimer diol of plant.

Resin disclosed herein promptly has with respect to the lower viscosity for the resin that is purchased based on petroleum chemicals once fusing (referring to embodiment).In the toner coating composition that is purchased at present, must add runny material (flow control additive) so that after cure cycle, make resulting film obtain good flowability and levelling property (leveling).Resin based on biology needs to need examples of such additives just to obtain good film levelling property and outward appearance on a small quantity or not.Successfully will be incorporated into containing in the composition based on the resin of conventional oil chemical products wherein based on the resin of biology, described resin based on biology itself also can play flowing additive.Usually, with about 0.1wt% to about 5wt%, be used for the purpose that the utilization of resin flow control performance of the present invention combines with the use of other main powdexes that are used for coating composition based on the content of the resin of biology.

Polyester polymers of the present invention prepares by the fusing polymerization of following material: Isosorbide, dimer diol and/or dimeracid, diacid, diester or diacyl chlorine, optional common glycol and the common diacid of choosing wantonly, common diester or common diacyl chlorine (method of Fig. 1).

Embodiment 1 has described a kind of exemplary steps that is used to prepare polyester of the present invention.Aliphatic polyester is soft, flexible elastomeric material.Most aromatic polyester is a crystalline.Soft dimer diol mixed with the Isosorbide of highly functional and with the crystalloid aromatic diacid obtain balanced good performance.Yet, can help this proportionality action by in reaction, comprising other materials (that is, as " glycol " among Fig. 1 and Fig. 2) as ethylene glycol.

Prepare the research (table 2A and 2B) that polyester carries out various monomer effects by use range from 61 ℃ to 165 ℃ glass transition temp (Tgs).Table 2A shows that place like this is described and the typical performance of synthetic resin and have the various monomeric effect of scope by 61 ℃ to 165 ℃ glass transition temp (Tgs).Table 2B demonstration is described and the typical performance of synthetic carboxyl-functional resin as embodiment 2-3A.

Data presentation utilize these monomers can obtain large-scale Tgs.Not use the test polyester of Isosorbide preparation be not unbodied, the similar Isosorbide that contains, but belong to crystal in nature.

D-Isosorbide (1,4:3,6-two dehydration-D-glucose) (1a) or the mixture of its isomer and/or all isomer (comprising the D-Isosorbide) can substitute the D-Isosorbide and use.1,4:3,6-two dehydration-D-N.F,USP MANNITOL (1b) and 1,4:3,6-two dehydration-D-iditols (1c) are two kinds of isomer of Isosorbide.The present invention has used the D-Isosorbide, but also can expect the isomer that uses the D-Isosorbide.Fig. 3 A illustrates the spendable Isosorbide isomer of the present invention.

The example that is used to form the suitable polyvalent alcohol of acid functional polyester comprises: 1,2-ethylene glycol (1, the 2-ethylidene glycol), 1, ammediol, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, decamethylene-glycol, 1, the 12-dodecanediol, 1, the 4-cyclohexanedimethanol, glycol ether, triglycol, neopentyl glycol, TriMethylolPropane(TMP), hydrogenant dihydroxyphenyl propane (2,2-(dicyclo hexanol) propane), 2,2,4-trimethylammonium-1, the 3-pentanediol, the 2-methyl isophthalic acid, ammediol, 2-methyl-2-methylol-1, ammediol, 2-ethyl-2-methylol-1, ammediol etc., and the combination that comprises at least a aforementioned polyvalent alcohol.Because current target is to make the content based on biology reach maximization, so preferred polyhydric alcohols is Isosorbide (from cereal materials) and dimeracid glycol (from soy material), ethylene glycol and other polyvalent alcohols that can be used to as required strengthen the property.

Suitable poly carboxylic acid, acid ester and chloride of acid comprises and derives from following those: Succinic Acid, hexanodioic acid, nonane diacid, sebacic acid, 1; 12-dodecanedioic acid, terephthalic acid, m-phthalic acid, 1; 3; 5-benzenetricarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1; 4-cyclohexane dicarboxylic acid, trimellitic acid, naphthalene dicarboxylic acids, dimeracid etc., and the combination that comprises at least a aforementioned poly carboxylic acid.Preferred diester is the dimethyl esters of terephthalic acid (terephthallic acid).Dodecanedioic acid (DDA) uses as properties-correcting agent in several compositions.At present preferred diacid is 1,4-cyclohexane dicarboxylic acid, Empol

Pripol

Deng.

In order to obtain the carboxyl-functional polyester of desired molecular weight, have suitable excessive carboxyl functionality for hydroxy functionality usually in order to the monomer mixture that forms polyester, wherein the ratio of equivalent hydroxyl and angelic acid is generally 0.85-0.95.The polyester scope can be by amorphous to crystal.

Beta-hydroxy acid amides reaction in carboxyl by making the carboxyl functionality and the autocatalysis transesterification reaction (being commonly referred to PRIMID reaction (table 3)) or realize crosslinked with the poly-epoxide functional polymers reaction that is purchased with the trade(brand)name name of acid amides.Preferred polyepoxides, polyepoxides especially for the low-temperature curing composition is epoxy functionalized acrylic or methacrylic acid resin, as glycidyl acrylate or glycidyl methacrylate copolymer (being generically and collectively referred to as " GMA ") resin.The GMA resin is usually by about glycidyl acrylate of 5 to about 30wt% or glycidyl methacrylate and the acquisition of about methyl methacrylate of 80 to about 95wt%, wherein the methyl methacrylate up to about 50wt% can substitute with another kind of α, β unsaturated monomer, such as vinylbenzene, vinyl cyanide etc.Suitable GMA resin has about 200 to about 1000, preferred about 200 weight to about 600 epoxy equivalent (weight)s, and have 200 Mn to about 2000 atomic mass units (AMU) via gel permeation chromatography.Described GMA resin at room temperature is a solid, and it has and surpasses about 40 ℃ fusing point, preferred about 50 ℃ to about 75 ℃ softening temperature, and about 40 ℃ to about 60 ℃ Tg (table 3).

Suppose that use can realize that based on the resin Composition of biology low temperature flows, use so be selected from multiple commercially available, to cause the solidified catalyzer at about 115 ℃ to about 140 ℃ temperature be favourable.Usually, catalyzer can each hundred parts of resin about 0.1 to about 5 parts concentration (phr), preferably the concentration of about 0.2-2phr is used, so that quicken curing reaction with low temperature curing agent.Being used for preferred catalyst of the present invention is imidazoles and adducts thereof, and this imidazoles has the general formula that formula 1 shows:

R wherein ₁, R ₂, R ₃And R ₄Be hydrogen, methyl, phenyl or benzyl independently.

Broadly, substituting group can be any substituting group that does not react with Resins, epoxy.Tertiary amine and polyamine materials also can be the spendable catalyzer that is used for this reaction.

In order to keep good flowability, must block the reactivity that the reactive adducts of imidazole catalyst changes described imidazole catalyst by forming part.Sometimes this can realize by the adducts of preparation imidazoles and epoxide (referring to, as USP 6,703,070).In one embodiment of the invention, the catalyzer of selection is imidazoles parent (parent imidazole) and acid material is added in the said composition to reduce the reactivity of imidazoles.

Be applicable to that reducing the reactive acid material of imidazoles comprises aromatic sulphonate, as the variant of benzene or naphthene sulfonic acid and replacement thereof; The aromatics carboxylate, as or the variant of naphthoic acid and replacement thereof; Can also adopt the solid acid material, as inorganics or super acid.In the later case, a part of imidazole catalyst can be adsorbed to the surface of solid acidic materials, and therefore can not utilize most tackiness agent before heating.An example of such solid material is the blocked super acid that obtains from Jin Shi industrial (King Industries)

7231 (ammonium antimonates).

Coating powder can also contain flow control agent, and its scope is by about 0 to about 5wt%, wherein most preferably from about 0.1wt% to the scope of about 2wt%.The example of described flow control agent comprises

Poly-(alkyl acrylate) (that is MODAFLOW,

) product and other flow control agents, such as

Alkyne diol (that is, ), it contains hydroxyl, carboxyl or other functional group.In the situation that powder coating need be polished or repair, functionalized flowing additive also helps ply adhesion.Described flowing additive can be used singly or in combination.Can also working concentration by about oxidation inhibitor of 0.5 to about 2.0phr to prevent described coating even to decolour being applicable under the low relatively solidification value of the object of the invention.Mentioned as this paper other places, resin of the present invention self can play the effect of the flow control agent of giving an example as the resin of the embodiment 3B in the composition of embodiment 8.

The example of pigment such as titanium dioxide and/or carbon black; The example of filler such as lime carbonate; The example of texturizing agent such as crumb rubber, wilkinite; The example of powdery polytetrafluoroethylene teflon (PTFE) that contains or do not contain polyethylene powders is as with trade(brand)name

Those that sell; And can there be other conventional additives that improve outward appearance and reduce cost.

St-yrax uses (referring to Weir reference (Howellreference)) as anti-pitting additives usually.

Table 3 shows the catalogue that is purchased powder coating resin, and it has described the functionality and the Tg thereof of described powder coating resin.In these resins some are used for the preparation of embodiment herein.Other resin is used for other composition and can be used for the different embodiment of the present invention.

As described below applicable to preparation according to the general process of powder paint compositions of the present invention:

Process: powder coating hybrid plan: use usually Mixing tank, but this process also can adopt the mixing tank of other types.

● the groove size based on 120ml is calculated powder paint compositions, makes it equal about 70 to 80g.Typical small-sized Sigma blade groove (blade bowl) can hold the coating composition to low resin-pigment ratio (P/B) that 70g does not add pigment, perhaps holds the colored paint (paint) of the higher P/B ratio of 80g.

● incite somebody to action by starting oil heater

Mixing tank or similar mixing tank are preheated to 99 ℃.Allow preheating 30 minutes.

● when preheating is finished, start the security of the groove of rotor and testing tool.

● open torque sensor.It will play guiding and mix the effect how to carry out.

● about 30g unmodified resin is added in the groove lentamente.

● allow this mixed with resin and fusing to show stable value (about 5 minutes), add remaining any unmodified resin in the tempering tank lentamente then and allow its mixing and fusing up to described torque sensor.

● any/whole additives are added to the central authorities of the mixing zone between the rotor.

● allow to be mixed to torque value stable (about 10 minutes usually).

● all cross-linked resins are added in the groove lentamente.Allow to mix at least 3 minutes, under the situation of crosslinked beginning, keep stable (torque readings will begin to raise fast) so that guarantee torque readings.

● add catalyzer (if requirement) at last, the close observation torque readings.Torque should increase and should stop this batch turnout after viscosity (torque) rising 10%.

● by taking out dense thick melting material product in the tempering tank apace and being cooled to desired temperatures (being generally room temperature) until its hardening (it typically is crisp hard, glossiness material).

● after being cooled to desired temperatures, this product is ground into small shreds.

● use ball mill that described fragment is ground then or otherwise carry out micronization (for example in the presence of 10mm-15mm stainless steel medium with ball mill grinding coating fragment 16 hours) to obtain meticulous powder.

● described powder is sieved to remove any bigger piece by suitable screen cloth, be generally greater than about 105 microns piece.

Adopt the method for describing to prepare the powder paint compositions of several types.

It is as follows to be used to the general process produced according to final powder coating of the present invention.

● the solvent that is applicable to substrate by use prepares its wiped clean the substrate (as water, methyl ethyl ketone, Virahol) that is used to apply

● give substrate priming (grounded).

● in the sample reservoir with powder coating impouring dust gun, the example of described spray gun is as the Versa-by the supply of Nordson company limited

● the voltage controller of regulating on the gun controls unit is applied to this powder to guarantee suitable electric charge.

● this powder is used so that obtain the film thickness of the expectation of about 50.8-76.2 micron (2-3 mil) build via the powder coating technology of standard.

● then described substrate is inserted in the baking box with appropriate time and temperature.

Typically, it is crosslinked to be based on the transesterify of carboxyl-functional and two-N-beta-hydroxy acid amides linking agent based on the powder coating of beta-hydroxy acid amides.Such powder is by being purchased

The type powder is illustrated.Embodiment 4 has shown the details of composition and based on the curing of the resin of biology and curing based on the resin of conventional oil chemical products.Such chemical action is insensitive to catalyzer, so the significant difference of solidification rate in not occurring expecting, and in fact, does not also find the advantage of any resin solidification speed in this kind situation.

These two kinds of coating were solidified 30 minutes down in two kinds of different temperature (121 ℃ and 147 ℃).Its maximum differential is the gloss under the comparatively high temps, promptly based on the gloss of the resin combination of biology than bright about 50 units of the gloss of control group.But, based on the solvent resistance of the composition of biology slightly a little less than.Significantly, when comparing, all has competitiveness based on the resin of the biology over-all properties in the crosslinked composition of beta-hydroxy acid amides with the control group that is purchased.

Hydridization powder coating: carboxylic acid-epoxy cross-linking

The powder coating of carboxylic acid-epoxy cross-linking is modal hybridization coating.Usually, these hybridization coatings comprise can with the polyester acid that prepare, petroleum derivation of acrylic acid epoxy linking agent.Synthetic carboxyl-functional of the present invention based on the resin of biology and in typical composition, comparing test with the polyester acid that is purchased based on petroleum chemicals.

When Fig. 4 A has shown 121 ℃, from this research based on the resin of biology and the analogous viscosity that typically is purchased resin (FINE-CLAD 8400) (with the pool expression) to 121 ℃ shearing rates.Noticeable biological resin (data point of the low group) viscosity that is based on is lower than its comparison (counterpart).

Given this viscosity differences possiblely is---under lower temperature, can provide better based on the material of biology and flow, thereby make the outward appearance of cold curing paint overall the improvement occur.The roughness average measurement value that described improvement can use various industrial processes to obtain is represented approx.

In embodiment 4A, with Clear coating surfaceness (R based on biology _a) definite value 1.3 compares, and will be decided to be 4.2 based on the surfaceness of the Clear coating of the control group of petroleum chemicals.The roughness of the plate of petroleum derivation and common sawing operation quite, and is and suitable based on the plate of biology and typical electronic bundle or laser operations.Composition based on biology more approaches " A level " surface smoothness than control group.

The powder coating and low temperature cured powder coating (the Forrest Powder Low Temperature that is purchased obtainable petroleum derivation that have prepared embodiment 4A based on biology

) plate of usefulness relatively.Spray two plates of the film thickness of about 2.5 mils, then in 121 ℃ of thermofixations 30 minutes.Show with contrasting based on the powdered material of biology and to compare still less tangerine peel (or surfaceness) with powder coating.In addition, the plate based on the powder coated of biology shows higher glossiness (72 minutes to 50 minutes) under 60 ℃.Detailed content referring to the composition of embodiment 4A.

The melt flow of the improvement of the composition that service stress control type rheometer measurement is biologically-derived.Powdered sample is placed between the platen that is heated to 100 ℃ and with it is compressed to the thickness (about 2 mils) of typical powder coating film.This temperature is risen to 121 ℃ and measure viscosity change (with pool expression) until this sample solidifies.Viscosity data is shown in Fig. 5.

The curve data point of top is represented correlated control group powdered sample, and the curve data point of below is represented the powdered sample based on biology.Be starkly lower than the sample (3694 pools are than 11980 pools) of control group based on the initial viscosity of the composition of biology.Along with time lapse, owing to sample solidifies makes the viscosity of two kinds of samples increase.Because the viscosity based on the composition of biology remains on lower level in remaining set time, thus such powder at film crosslinked and solidify before have higher fusing and mobile probability.

Snappiness (tolerance of roughness) is the coating attribute of a key, the use that it can withstand last finished product to follow coated object and the bump that takes place every day and fiercely attack.When bump took place, relatively poor snappiness caused coating cracking and makes coating be peeled off by substrate sometimes.When substrate out of doors, when using under chemical substance (as the acid rain) condition in the water, in uv irradiation, oxidation and the atmosphere, may performance degradation and film is become fragile.Multiple in these factors also can cause corrosion, and corrosion can cause gets rusty and make outward appearance and snappiness variation.

In the flexibility test that is called bending shaft (Mandrel Bend) (ASTM D522), and then the sample of control group discussed above and composition based on biology are compared.For this test, the substrate that applies sandwiched in the anchor clamps and around the cone axis surface rotate.Adhesive tape binding power test on this zone has been determined the final performance of coating.Tear to determine whether described coating still is attached to this plate with the bending area of described tape applications on coating and with this adhesive tape.

Cone axis has different width along its length, and is the narrowest for 3.18mm (1/8 inch)---and this is the minimum size that can be used for testing and is flexible size, peeling off or ftractureing of coating just can not occur after withstanding this size.

Coating based on biology has good snappiness, and it only has small crack and does not have and significantly peel off sign.The coating of the control group of petroleum derivation is about 40% of bending length along whole plate length cracking and the coating peeled off.Detailed content referring to the composition of embodiment 5.

If can remedy more low viscous words under the certain temperature by the surface of pigments excellent wetting capacity, then painted powder coating also can obtain some advantages based on the resin combination of biology.In embodiment 6, the composition of two kinds of black has been described, a kind of is control group and a kind of biology that is based on.

Under 60 ℃, compare with petroleum chemicals deutero-coating based on the powder coating of biology, have higher glossiness (85 proportions by subtraction 44 minutes).This may be once more owing to the good melt flow of composition during the thermofixation.

Use improves the colour developing/blackness of black pigment based on the composition of biology.Can determine described blackness by L and the b color component measured in the coating.(be used to explain Hunter color meter (Huntercolor Scale), referring to " Organic Coatings:Science and Technology ", second edition, Wicks, Z.W. etc., particularly 351-355 page or leaf, Wiley Interscience, NY, NY.ISBN0-471-24507-01999).

The total Delta E or the aberration of two black plates are 0.52, and wherein the composition based on biology is easier to colour developing (black).Because the black pigment of the plate of control group (left side) does not resemble based on the black pigment of the composition of biology and is dispensed in the vanish system fully, so the plate of control group (left side) demonstrates than based on the more grey color of the composition of biology.This may be owing to described based on the lower viscosity of the resin of biology.

With reference now to Fig. 6,, this figure is the synoptic diagram of the different elements of display unit 100, and described device 100 is used for preparation according to resin of the present invention.Heating mantles 102 to small part around reactor 101 and be used to control the temperature of the reactor 101 that contains reaction mixture 104.Reactor 101 is made up of reactive tank 106 and top 108.Top 108 has a plurality of necks 110,112,114,116, and it is used to connect various utensils.Be positioned at the terminal oar 120 of stir shaft 122 (as stainless steel) provide stirring (as, be generally the blade of 45).Stir shaft 122 passes neck 116.The thermopair controller 130 that links to each other with thermopair 132 via web member 131 passes neck 110 with the distributing style of sealing at gas inlet web member 111 places and enters in the reaction mixture 104.Vigreux column 140 (Vigreauxcolumn) is fixed on the neck 114 in mode hermetically.Thermometer 141 or other temperature measurement equipment are fixed on the top (still head) of Vigreux column 140.Use web member 146 condenser 150 to be fixed in Vigreux column 140 at neck 144 places via condenser inlet 152.Vigreux column 140 can by sheath around independent unit or described sheath and described post be one.Condensator outlet 154 is connected in the neck inlet 162 of neck 160, and described neck 160 has exhaust outlet 164 and neck outlet 166.Receiving bottle 170 has and neck outlet 166 inlets that link to each other 172.Cooling fluid 155 enters condenser 150 by inlet 156 and is flowed out by outlet 158.

In operation, argon gas 111-1 is entered to cover reaction mixture 104 and to be flowed out by pneumatic outlet 164 by gas inlet web member 111.Various compositions can add or pass through neck 112 places before this device sealing seal connector 118 adds.It should be noted that in Fig. 6 neck 112 is set directly at the rear of neck 116.Neck 112 is arranged on the axis 190 of reactor 101.Overhead product 178 is collected in receiving bottle 170.

Each side of the present invention is set forth in following examples expections, but does not expect and limit the scope of the invention by any way.

Preparation resin (embodiment 1 to embodiment 3F)

Embodiment 1

Present embodiment for example understand hydroxyl-functional, based on the preparation of the vibrin of biology.

Instrument (referring to Fig. 6)

1 liter 4 neck cylindrical wall round bottom glass flask add Vigreux column, still head, gas inlet and outlet web member, stainless steel stir shaft and four blades (45) oar, condenser and the receiving bottle of sheath.

Process

With dimethyl terephthalate (DMT) (228.30g, 1.1757 moles), SpeziolC36/2

Dimer diol (lot number #415252) (77.61g, 0.1411 D-Isosorbide (123.90g mole),, 0.84785 mole) and ethylene glycol (EG) (102.81g, 1.6563 the mole) reactor of packing into, pack into subsequently four hydration manganous acetates (II) (0.0917g), four hydration cobaltous acetates (II) (0.0618g) and weisspiessglanz (III) (0.103g).Use argon to cover reactor.Then, in argon gas downhill reaction mixture, add 1,2,3,4-tetralin (2ml).(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 30 minutes time, reaction mixture slowly is heated to 250 ℃ (1.6 ℃/min).Drop to 30 ℃ or lower with this temperature maintenance 30 minutes or up to the head temperature of Vigreux column.When reaction is heated to about methyl alcohol of constantly collecting more than 150 ℃ the time.When the head temperature of Vigreux column descended, this explanation methyl alcohol was removed.Distill out about 95ml methyl alcohol.Subsequently the polyphosphate solution (0.0634g) among the EG (1g) is joined in the reaction mixture.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 2 hours time, reaction mixture is heated to 280 ℃ (0.25 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill ethylene glycol (91g), and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 3 hours 10 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

The intrinsic viscosity of solution: 0.29 (solvent is an orthomonochlorphenol, only dissolves 92%)

Tg＝61℃

Hydroxyl value=24.3

Acid number=8.0

Molecular weight (MW)=3470 (calculating) by acid number and hydroxyl value

Polymer features:

Color: brown

Tackiness: non-adhesiveness

Transparency: translucent slightly

Snappiness: frangible

Solid

Embodiment 1A

Present embodiment is for example understood the preparation based on the vibrin of biology.

Instrument (referring to Fig. 6)

Process

With dimethyl terephthalate (DMT) (197.74g, 1.0183 moles), D-Isosorbide (119.05g, 0.81463 mole) and Speziol C36/2

Dimer diol (lot number #415252) (112.06g, the 0.20371 mole) reactor of packing into is packed 1,2,3,4-tetralin (2ml) and weisspiessglanz (III) into (0.089g) subsequently.Use argon to cover reactor.(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 12 minutes.In 20 minutes time, reaction mixture slowly is heated to 250 ℃ (2.5 ℃/min).With this temperature maintenance 8 minutes.When reaction is heated to about methyl alcohol of constantly collecting more than 150 ℃ the time.When the head temperature of Vigreux column descended, this explanation methyl alcohol was removed.Distill out about 83ml methyl alcohol.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distillate Isosorbide.In 13 minutes time, reaction mixture slowly is heated to 280 ℃ (2.3 ℃/min).Allow reaction mixture to be cooled to 260 ℃ then.Pack D-Isosorbide (14.87g, 0.1018 mole) into other to reaction mixture.Reaction mixture is heated to 280 ℃.This temperature was kept 30 minutes.Use evacuated receiver to replace the overhead product receptor also to use vacuum (≤9 holder) gradually.During this period of time, form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 2 hours 40 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following character:

The intrinsic viscosity of solution: 0.10 (solvent is an orthomonochlorphenol)

Tg＝165℃

Hydroxyl value=45.0

Acid number=2.3

Molecular weight (MW)=2372 (calculating) by acid number and hydroxyl value

Polymer features:

Color: light brown

Tackiness: be clamminess

Transparency: translucent

Snappiness: somewhat frangible

Solid

Embodiment 2

Present embodiment for example understand carboxyl-functional, based on the preparation of the vibrin of biology.

Instrument (referring to Fig. 6)

The top has 5 liters of round bottom glass reaction containers of 4 necks, adds Vigreux column, still head, gas inlet and outlet web member, stainless steel stir shaft and four blades (45) oar, condenser and the receiving bottle of sheath.

Process

With D-Isosorbide (1337.0g, 9.1490 moles) (by received), Pripol

Dimeracid (lot number #091687) (699.1g, 1.215 moles) and 1, (1,4-CHDA) (1563.8g, the 9.0826 moles) reactor of packing into is packed weisspiessglanz (III) into (1.231g) to the 4-cyclohexane dicarboxylic acid subsequently.Use argon to cover reactor.Under argon gas, 1,2,3,4-tetralin (2ml) is joined in the reaction mixture then.(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 47 minutes time, reaction mixture slowly is heated to 250 ℃ (1.1 ℃/min).Drop to 30 ℃ or lower with this temperature maintenance 3.1 hours or up to the head temperature of Vigreux column.When reaction is heated to about water of constantly collecting more than 180 ℃ the time.When the head temperature of Vigreux column descended, this illustrated that most of water is removed.Distill out about 329ml water.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 2 hours time, reaction mixture slowly is heated to 280 ℃ (0.25 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill remaining water, and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 3 hours 10 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

Tg＝64.2℃

Acid number=34.8

Molecular weight (MW)

GPC (polystyrene standard) M _n=1689

GPC (polystyrene standard) M _w=11681

Polymolecularity (M _w/ M _n)=6.91

Polymer features:

Color: light amber

Tackiness: non-adhesiveness

Transparency: translucent

Snappiness: frangible

Solid

Embodiment 3

Instrument (referring to Fig. 6)

Process

With 1, and the 4-cyclohexane dicarboxylic acid (1,4-CHDA) (204.66g, 1.1886 moles), Empol

Dimeracid (lot number #U42G151910) (72.54g, 0.1251 mole) and D-Isosorbide (172.80g, the 1.1824 moles) reactor of packing into are packed weisspiessglanz (III) into (0.1594g) subsequently.Use argon to cover reactor.Under argon gas, 1,2,3,4-tetralin (2ml) is joined in the reaction mixture then.(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 30 fens clock times, reaction mixture slowly is heated to 250 ℃ (1.6 ℃/min).Drop to 30 ℃ or lower with this temperature maintenance 30 minutes or up to the head temperature of Vigreux column.When reaction is heated to about water of constantly collecting more than 180 ℃ the time.When the head temperature of Vigreux column descended, this illustrated that most of water is removed.Distill out about 47ml water.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 2 hours time, reaction mixture slowly is heated to 280 ℃ (0.25 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill remaining water, and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 3 hours 10 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

The intrinsic viscosity of solution: 0.25dl/g (solvent is an orthomonochlorphenol)

T _g＝66.9℃

Hydroxyl value=13.0

Acid number=36.3

Molecular weight (MW)

GPC (polystyrene standard) M _n=2995

GPC (polystyrene standard) M _w=9560

Polymolecularity (M _w/ M _n)=3.19

Polymer features:

Color: light brown

Tackiness: non-adhesiveness

Transparency: the overwhelming majority is translucent

Snappiness: frangible but hard

Solid

Embodiment 3A

Instrument (referring to Fig. 6)

Process

With 1, and the 4-cyclohexane dicarboxylic acid (1,4-CHDA) (1570.3g, 9.1202 moles), Pripol

Dimeracid (lot number #091687) (675.7g, 1.174 moles) and D-Isosorbide (by received) (1354.0g, 9.2648 moles) reactor of packing into is packed weisspiessglanz (III) into (1.247g) subsequently.Use argon gas to cover reactor.Under argon gas, 1,2,3,4-tetralin (2ml) is joined in the reaction mixture then.(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 51 minutes time, reaction mixture slowly is heated to 250 ℃ (1.0 ℃/min).Drop to 30 ℃ or lower with this temperature maintenance 3.1 hours or up to the head temperature of Vigreux column.When reaction is heated to about water of constantly collecting more than 180 ℃ the time.When the head temperature of Vigreux column descended, this illustrated that most of water is removed.Distill out about 334ml water.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 2 hours time, reaction mixture is heated to lentamente 280 ℃ (0.25 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill remaining water, and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 3 hours 10 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

Tg=65.3 ℃ of acid number=29.0

Molecular weight (MW)

GPC (polystyrene standard) M _n=2162

GPC (polystyrene standard) M _w=11872

Polymolecularity (M _w/ M _n)=5.49

Polymer features:

Color: yellow/light amber

Tackiness: non-adhesiveness

Transparency: translucent

Snappiness: frangible

Solid

Embodiment 3B

Instrument (referring to Fig. 6)

1 liter 4 neck cylindrical wall round bottom glass flask add Vigreux column, still head, gas inlet and outlet web member, stainless steel stir shaft and four blades (45) oar, condenser and the reception flask of sheath.

Process

With dimethyl terephthalate (DMT) (228.30g, 1.1757 moles), SpeziolC36/2

Dimer diol (lot number #415252) (129.40g, 0.23523 D-Isosorbide (123.90g mole),, 0.84785 mole) and ethylene glycol (EG) (89.66g, 1.444 the mole) reactor of packing into, pack into subsequently four hydration manganous acetates (II) (0.0917g), four hydration cobaltous acetates (II) (0.0618g) and weisspiessglanz (III) (0.103g).Use argon gas to cover reactor.Then, in argon gas downhill reaction mixture, add 1,2,3,4-tetralin (2ml).(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 30 minutes time, reaction mixture slowly is heated to 250 ℃ (1.6 ℃/min).Drop to 30 ℃ or lower with this temperature maintenance 30 minutes or up to the head temperature of Vigreux column.When reaction is heated to about methyl alcohol of constantly collecting more than 150 ℃ the time.When the head temperature of Vigreux column descended, this explanation methyl alcohol was removed.Distill out about 95ml methyl alcohol.Subsequently the polyphosphate solution (0.0634g) among the EG (1g) is joined in the reaction mixture.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 30 fens clock times, reaction mixture slowly is heated to 280 ℃ (1 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill ethylene glycol (84g), and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 3 hours 10 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

The intrinsic viscosity of solution: 0.19 (solvent is an orthomonochlorphenol)

Tg＝28.4℃

Hydroxyl value=35.4

Acid number=6.1

Molecular weight (MW)=2700 (calculating) by acid number and hydroxyl value

Polymer features:

Color: brown

Tackiness: non-adhesiveness

Transparency: the overwhelming majority is translucent

Snappiness: frangible

Solid

Embodiment 3C

Instrument (referring to Fig. 6)

Process

With dimethyl terephthalate (DMT) (213.96g, 1.1018 moles), Empol

Dimeracid (lot number #U42G151910) (71.02g, 0.1225 D-Isosorbide (128.79g mole),, 0.88128 mole) and ethylene glycol (EG) (116.28g, 1.8734 the mole) reactor of packing into, pack into subsequently four hydration manganous acetates (II) (0.0859g), four hydration cobaltous acetates (II) (0.0579g) and weisspiessglanz (III) (0.0965g).Use argon gas to cover reactor.Then, in argon gas downhill reaction mixture, add 1,2,3,4-tetralin (2ml).(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 30 fens clock times, reaction mixture slowly is heated to 250 ℃ (1.6 ℃/min).Drop to 30 ℃ or lower with this temperature maintenance 30 minutes or up to the head temperature of Vigreux column.When reaction is heated to about methyl alcohol of constantly collecting more than 150 ℃ the time.When the head temperature of Vigreux column descended, this explanation methanol/water mixture was removed.Distill out about 93ml methanol/water mixture.Subsequently the polyphosphate solution (0.0594g) among the EG (1g) is joined in the reaction mixture.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 2 hours time, reaction mixture slowly is heated to 280 ℃ (0.25 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill ethylene glycol (95g), and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 3 hours 10 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

The intrinsic viscosity of solution: 0.23 (solvent is an orthomonochlorphenol)

Tg＝58.8℃

Hydroxyl value=23.7

Acid number=1.4

Molecular weight (MW)=4470 (calculating) by acid number and hydroxyl value

Polymer features:

Color: light brown

Tackiness: non-adhesiveness

Transparency: some is translucent, and is muddy a little

Snappiness: frangible

Solid

Embodiment 3D

Instrument (referring to Fig. 6)

2 liters 4 neck cylindrical wall round bottom glass reaction containers add Vigreux column, still head, gas inlet and outlet web member, stainless steel stir shaft and four blades (45) oar, condenser and the receiving bottle of sheath.

Process

With 1, and the 4-cyclohexane dicarboxylic acid (1,4-CHDA) (610.68g, 3.5468 moles), Pripol

Dimeracid (lot number #091687) (262.78g, 0.45670 mole) and D-Isosorbide (use acetone recrystallization) (526.54g, the 3.6030 moles) reactor of packing into are packed weisspiessglanz (III) into (0.4849g) subsequently.Use argon gas to cover reactor.In argon gas downhill reaction mixture, add 1,2,3,4-tetralin (2ml) then.(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 30 fens clock times, reaction mixture slowly is heated to 250 ℃ (1.6 ℃/min).With this temperature maintenance 2.1 hours.When reaction is heated to about water of constantly collecting more than 180 ℃ the time.When the head temperature of Vigreux column descended, this illustrated that most of water is removed.Distill out about 129ml water.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 2 hours time, reaction mixture slowly is heated to 280 ℃ (0.25 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill remaining water, and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 3 hours 10 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

Tg＝62.3℃

Acid number=34.7

Molecular weight (MW)

GPC (polystyrene standard) M _n=3517

GPC (polystyrene standard) M _w=12753

Polymolecularity (M _w/ M _n)=3.63

Polymer features:

Color: amber/orange

Tackiness: non-adhesiveness

Transparency: translucent

Snappiness: frangible

Solid

Embodiment 3E

Instrument (referring to Fig. 6)

Process

With 1, and the 4-cyclohexane dicarboxylic acid (1,4-CHDA) (318.36g, 1.8490 moles), Empol

Dimeracid (lot number #U42G151910) (112.84g, 0.1946 mole) and D-Isosorbide (268.80g, the 1.8393 moles) reactor of packing into are packed weisspiessglanz (III) into (0.2479g) subsequently.Use argon gas to cover reactor.In argon gas downhill reaction mixture, add 1,2,3,4-tetralin (2ml) then.(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 30 fens clock times, reaction mixture slowly is heated to 250 ℃ (1.6 ℃/min).With this temperature maintenance 2.3 hours.When reaction is heated to about water of constantly collecting more than 180 ℃ the time.When the head temperature of Vigreux column descended, this illustrated that most of water is removed.Distill out about 74ml water.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 2 hours time, reaction mixture slowly is heated to 280 ℃ (0.25 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill remaining water, and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 3 hours 10 minutes again at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

Intrinsic viscosity=the 0.24dl/g of solution (solvent is an orthomonochlorphenol)

Tg＝72.3℃

Hydroxyl value=0.0

Acid number=32.8

Molecular weight (MW)

GPC (polystyrene standard) M _n=4027

GPC (polystyrene standard) M _w=15756

Polymolecularity (M _w/ M _n)=3.91

Polymer features:

Color: yellow-brown

Tackiness: non-adhesiveness

Transparency: the overwhelming majority is translucent

Snappiness: frangible

Solid

Following examples 4 to 8 are for example understood according to several typical powder compositions of the present invention and the coating of finishing.

Embodiment 3F (pigment dispersing agent)

Present embodiment for example understand carboxyl-functional, based on the preparation of the vibrin of biology, it has the dispersing property of improvement when using in the presence of pigment.

Instrument (referring to Fig. 6)

The top has 2 liters of round bottom glass reaction containers of 4 necks, adds Vigreux column, still head, gas inlet and outlet web member, stainless steel stir shaft and four blades (45) oar, condenser and the receiving bottle of sheath.

Process

With D-Isosorbide (545.35g, 3.7317 moles) (by received), Pripol Dimeracid (lot number #091687) (272.17g, 0.47302 mole) and 1, (1,4-CHDA) (632.49g, the 3.6734 moles) reactor of packing into is packed weisspiessglanz (III) into (0.498g) to the 4-cyclohexane dicarboxylic acid subsequently.Use argon gas to cover reactor.In argon gas downhill reaction mixture, add 1,2,3,4-tetralin (2ml) then.(solid fusing back) rises to 200 ℃ with the temperature of reactor contents when stirring under argon gas.With this temperature maintenance 30 minutes.In 30 minutes time, reaction mixture slowly is heated to 250 ℃ (1.6 ℃/min).With this temperature maintenance 2.1 hours.When reaction is heated to about water of constantly collecting more than 180 ℃ the time.When the head temperature of Vigreux column descended, this illustrated that most of water is removed.Distill out about 134ml water.Check that the argon gas flow velocity of reaction mixture top and the flow velocity that ought slow down in case of necessity are to prevent to distill out Isosorbide.In 2 hours time, reaction mixture slowly is heated to 280 ℃ (0.25 ℃/min).Use evacuated receiver to replace the overhead product receptor also to use vacuum (＜1 holder) gradually.During this period of time, distill remaining water, and form low-molecular-weight polymkeric substance.The temperature of reaction mixture was kept 30 minutes at 280 ℃.Come termination reaction by cover reaction mixture with argon gas to obtain normal atmosphere.Then reaction mixture is cooled to≤250 ℃ and pour on fluorizated fiberglass sheet.

The resin that preparation has following performance:

Tg＝52.9℃

Acid number=47.7

In 120 ℃ viscosity=7772 pools

In 160 ℃ viscosity=247 pools

Polymer features:

Color: yellow/light amber

Tackiness: non-adhesiveness

Transparency: translucent

Snappiness: frangible

Solid

Embodiment 4

Present embodiment is for example understood the vibrin and the crosslinked powder paint compositions for preparing of beta-hydroxy acid amide type of the carboxyl-functional resin that uses embodiment 3.Then this powder composition is applied on the substrate.

In the typical powder paint compositions that mixes in a manner described and be crosslinked, carboxyl-functional polyester (product of embodiment 3) and the polyester that is purchased are walked abreast relatively by the exchange of beta-hydroxy carboxylic acid amide esters.Following table 4 has shown the weight percentage of these compositions.

FINE-CLAD

It is an example that is used for the polyester acid of comparison purpose.

Program: the powder coating hybrid plan (

Mix in 99 ℃ in the mixing tank):

At first calculate total composition weight according to the groove size of 120ml; Perhaps adopt the total composition weight of about 70 grams.Will

Mixing tank is heated to 99 ℃ (groove is warming up to about 99 ℃) in advance.Allow about 30 minutes of preheating.When preheating is finished, start and mix oar and open torque sensor.It plays guiding and mixes the effect how to carry out, and adds 30g unmodified resin and mixing then lentamente up to fusing in groove; Add remaining 35.2g unmodified resin then.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor.The center of the mixing region between rotor adds 1.3g additive (0.9g st-yrax and 0.4g Modaflow then

);

Continue to mix 10 minutes (the monitoring torque value is to determine stability); In previous mixture, add 3.4g cross-linked resin (Primid XL-then

); Continue to mix at least 3 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.Torque increases and stop this batch turnout after viscosity increases by 10% (torque).

This product is taken out from tempering tank, and it is smooth, hard, glossiness material, and allows it to be cooled to room temperature.With hammer this material is ground into fragment.At last in the presence of 10mm-15mm stainless steel medium with the micronization 16 hours in ball mill of this product.Obtain final powder and sieve and what is no longer held the post greater than 150 microns particle.

The Versa-that use is provided by Nordson company

Manual spray gun is ejected into this powder static electricity on 4 inches * 6 inches the naked stainless steel plate.This plate solidifies 30 minutes (referring to the test result of table 6) 121 ℃ of curing 30 minutes or at 147 ℃.

Repeat above process to obtain the material of control group.

Under different temperature, better in effect aspect the gloss based on the coating of biology, described coating based on biology has identical gloss when lesser temps, but its gloss far wins and raises when comparatively high temps.

The result of dsc (DSC) shows that the resin of testing usefulness all can not influence forward or the negative sense demonstration of the final Tg of solidification value, curing amount or coating.This solidification rate with the beta-hydroxy acid amides is insensitive to external influence to be consistent (referring to the Howell reference).

Coating based on biology also has the final performance similar to being purchased control group under two kinds of solidification values:

Two kinds of coating of the data presentation of table 5 and table 6 are basic identical on overall performance.The gloss of coating under higher solidification value based on biology has superiority slightly, and be purchased control group a little advantage is arranged on solvent resistance.As previously noted, the gloss under the comparatively high temps has significant advantage in the composition of demanding durability temperature (robustness).

Therefore, this type, can be used for carrying out the transesterify crosslinking reaction based on the resin of biology with beta-hydroxyalkylamides.

Embodiment 4A

Present embodiment is for example understood use carboxyl-functional resin and the crosslinked powder paint compositions for preparing of beta-hydroxy acid amide type.

In the typical powder paint compositions that mixes in a manner described and be crosslinked, carboxyl-functional polyester (embodiment 3E) and the polyester that is purchased are walked abreast relatively by the exchange of beta-hydroxy carboxylic acid amide esters.Following table 4A has shown the weight percentage of these compositions.

At first calculate total composition weight, perhaps adopt total composition weight of about 85g according to the groove size of 120ml.Will

Mixing tank is preheating to 99 ℃ (groove is warming up to about 99 ℃).About 30 minutes of warm up time.When preheating is finished, start and mix oar and open torque sensor.It plays guiding and mixes the effect how to carry out; In groove, add 30g unmodified resin and mixing then lentamente up to fusing; Add remaining 37.8g unmodified resin then.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; The center of the mixing region between rotor adds 3.6g additive (1.1g st-yrax and 2.5g Fine Clad then

); Continue to mix 10 minutes (the monitoring torque value is to determine stability); In previous mixture, add 4.1g cross-linked resin (Primid XL-then

); Continue to mix at least 3 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.Torque increases and stop this batch turnout after viscosity raises 10% (torque).This product is taken out from tempering tank, and it is smooth, hard, glossiness material, and allows it to be cooled to room temperature.With hammer this material is ground into fragment.At last in the presence of 10mm-15mm stainless steel medium with the micronization 16 hours in ball mill of this product.Obtain final powder and sieve and what is no longer held the post greater than 150 microns particle.

The Versa-that use is provided by Nordson company

Manual spray gun is ejected into this powder static electricity on the naked stainless steel plate of 10.16cm * 15.24cm (4 inches * 6 inches).This plate solidifies 30 minutes (referring to the test result of table 6) 121 ℃ of curing 30 minutes or at 147 ℃.The process that repeats above embodiment 4A is to obtain the material of control group.

The result of dsc (DSC) shows that the coating of testing usefulness all can not influence forward or the negative sense demonstration of the final Tg of solidification value, curing amount or coating.This solidification rate with the beta-hydroxy acid amides is insensitive to external influence to be consistent (referring to the Howell reference).

Coating based on biology also has the final performance similar to being purchased control group under two kinds of solidification values, referring to following table 6A:

Two kinds of coating of data presentation of table 5A and table 6A are basic identical on overall performance.The advantage that has harder film based on the coating of biology under lower solidification value---the #H pencil is to the #HB pencil.The gloss of coating under higher solidification value based on biology has superiority slightly, and be purchased control group a little advantage is arranged on solvent resistance.As previously noted, the gloss under the comparatively high temps has significant advantage in the composition of demanding durability temperature.

Embodiment 5

Present embodiment is for example understood the hybridization coating preparation of compositions of using carboxyl-functional polyester resin (product of embodiment 2) and acrylic acid epoxy linking agent to prepare.

Process: be used for based on the hydridization powder coating of biology the powder coating hybrid plan (

Mix in 99 ℃ in the mixing tank):

At first calculate total composition weight, perhaps adopt the total composition weight of about 70g according to the groove size of 120ml.Will

Mixing tank is preheating to 99 ℃ (groove is warming up to about 99 ℃).Allow about 30 minutes of preheating.When preheating is finished, start and mix oar and open torque sensor.It plays guiding and mixes the effect how to carry out.In groove, add 30g unmodified resin (resin of describing among the embodiment 2) and mixing then lentamente up to fusing; Add remaining 21.5g unmodified resin.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; Continue to mix 10 minutes (the monitoring torque value is to determine stability); In previous mixture, add 16.9g cross-linked resin (Fine Clad A229-

); Continue to mix at least 3 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.Catalyzer is ground to form fine powder and last add (0.4g imidazoles and 1.1g dodecanedioic acid).Torque increases and stop this batch turnout after viscosity raises 10% (torque).

This product is taken out from tempering tank, and it is for smooth, hard, glossiness material and allow it to be cooled to room temperature.With hammer this material being pulverized is fragment.At last in the presence of 10mm-15mm stainless steel medium with the micronization 16 hours in ball mill of this product.Obtain final powder and sieve and what is no longer held the post greater than 150 microns particle.

The Versa-that use is provided by Nordson company

Manual spray gun is ejected into this powder static electricity on the naked stainless steel plate of 10.16cm * 15.24cm (4 inches * 6 inches), so that build is 2.5 mils.This plate was solidified 30 minutes at 121 ℃.

Process: be used for the polyester hydridization powder coating of control group the powder coating hybrid plan (

Mix in 99 ℃ in the mixing tank):

At first calculate total composition weight, perhaps adopt total composition weight of about 70g according to the groove size of 120ml.Will

Mixing tank is preheating to 99 ℃ (groove is warming up to about 99 ℃).Allow preheating 30 minutes.

When preheating is finished, start and mix oar and open torque sensor.It plays guiding and mixes the effect how to carry out; Slowly in groove, add about 30g unmodified resin (Fine Clad then ) and mix up to fusing; Add remaining 25.8g unmodified resin.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; Continue to mix 10 minutes (the monitoring torque value is to determine stability); In previous mixture, add 12.7g cross-linked resin (Fine CladA229- ); Continue to mix at least 3 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.Add catalyzer (0.4g imidazoles and 1.1g dodecanedioic acid) at last, tightly observe torque readings.Torque increases and stop this batch turnout after viscosity raises 10% (torque).

The Versa-that use is provided by Nordson company

Manual spray gun is sprayed to this powder static electricity on the naked stainless steel plate of 10.16cm * 15.24cm (4 inches * 6 inches), so that build is 2.5 mils.This plate was solidified 30 minutes at 121 ℃.

Two kinds of vibrin of Miao Shuing have the viscosity described in Fig. 4 in the present embodiment, can be mixed with Clear paint and demonstration in following table 7 according to these processes.Table 7 has shown the weight percent quantity of each composition.

The influence of solidifying based on the outward appearance of the material of biology and control group system is compared.Select the powder coating of low solidification value to organize in contrast.Test product called after 1PC-306-0040 (F-0040) S-9 Clear

Be 145 ℃ of 15 minutes or 162 ℃ 10 minutes set time.

Quantize by the surfaceness of surfagauge coating.Fine needle passes coating surface and writes down this surperficial Feng Hegu simultaneously in this test process.Paddy is recorded as R _v(nm) and the peak be recorded as R _p(nm).According to these two numerical evaluation mean roughness (R _a).Lower R value shows more level or smooth of surface.Referring to the R value of table 8 about coated plate.

Can compare with the value of table 8 by the formed typical surfaceness R value of general method for making (as listed among the ASME B46.1-1995).Based on the surfaceness of the plate of biology to produced by grinding, honing and electropolishing surperficial similar.The surfaceness of the plate of control group to produce by corase grind, planing and shaping operation surperficial similar.

Embodiment 6

Present embodiment for example understand to use embodiment 3A, prepare coloured hydridization powder coating based on the carboxyl-functional polyester and the epoxy crosslinking agent of biology.

If have good dispersive ability and demonstrate the color of pigment based on the resin of biology, then coloured powder coating also is useful.With the example (following) of black powder coating composition be purchased control group and compare, referring to table 9.Composition exhibiting in the table 9 respectively become dosis refracta based on weight percent.

At first calculate total composition weight, perhaps adopt total composition weight of about 70g according to the groove size of 120ml.Will Mixing tank is preheating to 99 ℃ (groove is warming up to about 99 ℃).Allow preheating 30 minutes.

When preheating is finished, start and mix oar and open torque sensor.It plays guiding and mixes the effect how to carry out; In groove, add about 30g unmodified resin (described) then lentamente as embodiment 3A; Permission mixes up to fusing and adds remaining 23.1g resin.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; The center of the mixing region between rotor adds 1.7g additive (0.8g black pigment and 0.9g st-yrax); Continue to mix 10 minutes (the monitoring torque value is to determine stability); In previous mixture, add the 11.3g cross-linked resin, have the vinylformic acid (FineClad of epoxy-functional

); Continue to mix at least 3 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.Catalyzer is ground to form fine powder and last (0.5g imidazoles, 1.7g dodecanedioic acid and the 1.7g Nacure XC-of adding

).Torque increases and stop this batch turnout after viscosity increases by 10% (torque).

This product is taken out from tempering tank, and it is for smooth, hard, the glossiness material of black and allow it to be cooled to room temperature.With hammer this material being pulverized is fragment.At last in the presence of 10mm-15mm stainless steel medium with the micronization 16 hours in ball mill of this product.Obtain final powder and sieve and what is no longer held the post greater than 150 microns particle.

The Versa-that use is provided by Nordson company Manual spray gun is ejected into this powder static electricity on the naked stainless steel plate of 10.16cm * 15.24cm (4 inches * 6 inches), so that build is 76.2 microns (about 3 mils).This plate was solidified 30 minutes in 121 ℃ convection oven.

For the coloured coating powder of the polyester of control group, calculate total composition weight according to the groove size of 120ml, perhaps adopt total composition weight of about 70g.Will

Mixing tank is preheating to 99 ℃ (groove is warming up to about 99 ℃).Allow about 30 minutes of preheating.

When preheating is finished, start and mix oar and open torque sensor.It plays guiding and mixes the effect how to carry out; Slowly in groove, add about 30g unmodified resin (Fine-Clad then

); Mixing is up to fusing and add remaining 21.9g resin.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; The center of the mixing region between rotor adds 1.7g additive (0.8g black pigment and 0.9g st-yrax) then.Continue to mix 10 minutes (the monitoring torque value is to determine stability); In previous mixture, add the 12.5g cross-linked resin; Continue to mix at least 3 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.Add catalyzer (0.5g imidazoles, 1.7g dodecanedioic acid and 1.7g Nacure XC-at last

), tightly observe torque readings.Torque increases and stop this batch turnout after viscosity increases by 10% (torque).

The Versa-that use is provided by Nordson company

Manual spray gun is ejected into this powder static electricity on the naked stainless steel plate of 10.16cm * 15.24cm (4 inches * 6 inches), so that build is 76.2 microns (3 mils).This plate was solidified 30 minutes in 121 ℃ convection oven.

Powder coating based on biology has 60 ° of very high glossiness (85 minutes to 44 minutes) than petrochemicals deutero-coating.This may be the cause that has better melt flow owing to said composition during thermofixation.

Use can improve the colour developing and the blackness of black pigment based on the composition of biology.Can assign to determine blackness by L and the b color-set of measuring coating.(referring to the Wicks that above quotes, people such as Z.W. are for the explanation of Hunter color meter).

Determine ater and determine dark blue background color by low-L value by low b value.L and b value are low more, and the blackness of coating is high more.Improve blackness with better colo(u)rant dispersion and colour developing.Following table 10 has shown the color measurenent value of coated board:

The total δ E or the aberration of two kinds of black plates are 0.52.Because the black pigment of the plate of petroleum derivation does not resemble based on the black pigment in the composition of biology and is dispensed into vanish system fully, so the plate of petroleum derivation looks more grey than the composition based on biology.

Embodiment 6A

Powder coating flows except that needs low temperature and solidifies, also need be under the situation of not considering coating type, the pigment in the paint matrix has good dispersiveness.For realizing this purpose, designed polymkeric substance with different compatible components.The polymeric dispersant great majority are used for making pigment and other stable components in colored paint, coating and the ink set via steric stabilization.Polymeric dispersant has diadactic structure, and it comprises anchoring group and polymeric chain.In most cases, anchoring group is the polar material with particle surface compatible with coating external phase and polymer chain effect.In fact, polymer-based group forms coating around particle, to prevent their contacts and to agglomerate into bigger, inconsistent condensation product.

There are many anchoring group/polymkeric substance configurations that are supposed to provide effective polymeric dispersant.Resin of the present invention has polar carboxyl combining site and nonpolar vegetables oil chain, thereby can play dispersion agent and tackiness agent.When the cure adhesive that also can play the dispersion agent effect can reduce multiple colo(u)rant dispersion for the demand of independent additive.

In the composition exhibiting of table among the 10-6A-1 based on the amount of the various compositions of weight percent.

Mixing tank is preheating to 110 ℃ (groove is warming up to about 110 ℃).Allow preheating 30 minutes.

When preheating is finished, start and mix oar and open torque sensor.It plays guiding and mixes the effect how to carry out; In groove, add 30.0g unmodified resin (as described in Example 3) then lentamente; Mixing is up to fusing and add remaining 33.0g resin.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; With the speed setting that mixes oar is that per minute 40 changes; The center of the mixing region between rotor adds the 7.0g black pigment; Continue to mix 15 minutes.This product is taken out from tempering tank, and it is for smooth, hard, the glossiness material of black and allow it to be cooled to room temperature.With hammer this material being pulverized is fragment.

For the polyester black point prose style free from parallelism of control group, calculate total composition weight according to the groove size of 120ml, or adopt total composition weight of about 70g.Will

When preheating is finished, start and mix oar and open torque sensor.It plays guiding and mixes the effect how to carry out; The polyester (FineCladM8400) that in groove, adds about 30.0g control group then lentamente; Permission mixes up to fusing and adds remaining 33.0g resin.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; With the speed setting that mixes oar is that per minute 40 changes; The center of the mixing region between rotor adds the 7.0g black pigment; Continue to mix 15 minutes.This product is taken out from tempering tank, and it is for smooth, hard, the glossiness material of black and allow it to be cooled to room temperature.With hammer this material being pulverized is fragment.

In composition subsequently, use these materials to determine the degree of scatter of carbon black pigment.Carbon black pigment is overstepping the bounds of propriety to loose the color of final composition dark more (black more).

In the composition exhibiting of table among the 10-6A-2 based on the amount of the various compositions of weight percent.

At first calculate total composition weight, or adopt total composition weight of about 70g according to the groove size of 120ml.Will

When preheating is finished, start and mix oar and open torque sensor.It can play guiding and mix the effect how to carry out; In groove, add 34.9g unmodified resin (FINE-CLAD then lentamente

); Mixing is up to fusing.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; The center of the mixing region between rotor adds 22.1g additive (21.0g white pigment (Kronos 2310) and 1.1g st-yrax); With the speed setting of rotor is that per minute 60 changes and continue mixing 15 minutes; Adding 3.5g before had been dispersed in the black pigment in the vibrin (the example A of table 10-6A-2) based on biology and the speed of rotor is reduced to per minute 40 change; Continue to mix 5 minutes.In previous mixture, add 7.2g cross-linked resin (FineClad

); Continue to mix at least 2 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.Catalyzer is ground to form fine powder and last add (0.5g imidazoles and 1.9g dodecanedioic acid).Continue to mix 2 minutes.

This product is taken out from tempering tank, and it is for smooth, hard, the glossiness material of grey and allow it to be cooled to room temperature.With hammer this material being pulverized is fragment.At last in the presence of 10mm-15mm stainless steel medium with the micronization 16 hours in ball mill of this product.Obtain final powder and sieve and what is no longer held the post greater than 150 microns particle.

The Versa-that use is provided by Nordson company

Calculate total composition weight of the polyester powder coating of control group according to the groove size of 120ml, or adopt total composition weight of about 70g.Will

When preheating is finished, start and mix oar and open torque sensor.It can play guiding and mix the effect how to carry out; In groove, add about 34.9g unmodified resin (FineCladM8400) then lentamente; Mixing is up to fusing.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; The center of the mixing region between rotor adds 22.1g additive (21.0g white pigment (Kronos 2310) and 1.1g st-yrax) then; With the speed setting of rotor is that per minute 60 changes and continue mixing 15 minutes; Adding 3.5g before had been dispersed in the black pigment in the vibrin (the example B of table 10-6a-2) based on biology and the speed of rotor is reduced to per minute 40 change; Continue to mix 5 minutes.In previous mixture, add 7.2g cross-linked resin (FineClad ); Continue to mix at least 2 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.Catalyzer is ground to form fine powder and last add (0.5g imidazoles and 1.9g dodecanedioic acid).Continue to mix 2 minutes.

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Use can improve the colour developing and the tinctorial strength of black pigment based on the composition of biology.Tinctorial strength is that carbon black comes blackening/the influence ability of other pigment (as titanium dioxide) that exist in the composition.Can assign to determine tinctorial strength by L and the b color-set of measuring coating.(referring to the Wicks that above quotes, people such as Z.W. are for the explanation of Hunter color meter).

Determine higher tinctorial strength by low-L value.The L value is low more, and carbon black is overstepping the bounds of propriety to loose, and color shows in coating more better.Can disperse and manifest more fully the color of carbon black better based on the polyester of biology, thereby produce higher tinctorial strength.Following table 10-6A-3 has shown the color measurenent value of coated board:

The total δ E or the aberration of two kinds of black plates are 2.53.Because the black pigment of petroleum derivation plate does not resemble based on the black pigment in the composition of biology and is dispensed into vanish system well, so the color of petroleum derivation plate looks lighter than the composition based on biology.

Embodiment 6B

Present embodiment for example understand by embodiment 3A, prepare coloured hydridization powder coating based on the carboxyl-functional polyester and triglycidyl isocyanurate (TGIC) linking agent of biology.

Flow and make the uniform ability of coating dyeing if having good promotion based on the resin of biology, and do not have white point or film defective in appearance, then powder coating also is useful.With the example (following) of white powder coating composition be purchased control group and compare, referring to table 10-6B-1.The composition exhibiting of table among the 10-6B-1 based on the amount of each composition of weight percent.

At first calculate total composition weight, or adopt the total composition weight of about 70g according to the groove size of 120ml.Will

When preheating is finished, start and mix oar and open torque sensor.It can play guiding and how mix the effect of carrying out; In groove, add about 30g unmodified resin (as described in embodiment 3) then lentamente; Mixing is up to fusing and add remaining 27.2g resin.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; The center of the mixing region between rotor adds 42.8g additive (4.4g TGIC, 37.9g titanium dioxide (Kronos CR2310) and 0.5g st-yrax);

Continue to mix 10 minutes (monitoring torque value to guarantee stablize);

This product is taken out from tempering tank, and it is for smooth, hard, the glossiness material of white and allow it to be cooled to room temperature.With hammer this material being pulverized is fragment.At last in the presence of 10mm-15mm stainless steel medium with the micronization 16 hours in ball mill of this product.Obtain final powder and sieve and what is no longer held the post greater than 150 microns particle.

The Versa-that use is provided by Nordson company Manual spray gun is ejected into this powder static electricity on the naked stainless steel plate of 10.16cm * 15.24cm (4 inches * 6 inches), so that build is 76.2 microns (3 mils).This plate was solidified 30 minutes in 121 ℃ convection oven.

For the coloured polyester powder coating of control group, calculate total composition weight according to the groove size of 120ml, or adopt total composition weight of about 70g.Will

Mixing tank is preheating to 110 ℃ (groove is warming up to about 110 ℃).Allow about 30 minutes of preheating.

When preheating is finished, start and mix oar and open torque sensor.It can play guiding and mix the effect how to carry out; In groove, add 30g unmodified resin (Albester 5140) then lentamente; Mixing is up to fusing and add remaining 27.2g resin.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; The center of the mixing region between rotor adds 42.8g additive (4.4g TGIC, 37.9g titanium dioxide (Kronos CR2310) and 0.5g st-yrax) then; Continue to mix 10 minutes (monitoring torque value to guarantee stablize).

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Have better solvent resistance, higher glossiness and the pencil hardness of Geng Gao based on the composition of biology than the composition of control group.Overall appearance based on the composition of biology is better than the composition of control group, and the composition of control group has the film defective that is called " white point ".The white point that exists in the coating is not only problem of appearance, and makes that because substrate is exposed to environment these zones are easy to get rusty and corrode.

Can be used as additive pigments with dispersed color more effectively according to the resin of another embodiment of the invention.For example, can add this pigment so that help colour developing.

Embodiment 7

Present embodiment is for example understood the preparation of the hydridization powder coating that uses amido-amine functional polyester and epoxy crosslinking agent preparation.

Amido-amine functional polyester powder coating also can be prepared with the resin based on biology.Shown an example of powder paint compositions in following table 11, wherein the amount of composition shows with weight percent.Owing to do not obtain to be purchased obtainable amido-amine functional polyester resins, therefore do not use control group.

* amido-amine the functional resins that is used for easy deinking ink powder is open at the WO 2004/077169 of the submission on February 2nd, 2004 and the appointment U.S., and its whole disclosures are incorporated herein by reference.The resin sample that is numbered 36-24 has 72.5 ℃ Tg and is about 1.6 * 10 ²The viscosity of pool.

Mixing tank is preheating to 99 ℃ (groove is warming up to about 99 ℃).Allow about 30 minutes of preheating.When preheating is finished, start and mix oar and open torque sensor.It can play guiding and mix the effect how to carry out; In groove, add 30g unmodified resin (49251-23-22) then lentamente.Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; Add remaining 3.7g unmodified resin then and mixed about 5 minutes.The center of the mixing region between rotor adds 0.7g additive (Modaflow then

).Continue to mix 10 minutes (the monitoring torque value is to determine stability).In previous mixture, add 30.6g cross-linked resin (FineClad then

); Continue to mix at least 3 minutes (the monitoring torque readings keeps stable to guarantee it under the situation of crosslinked beginning) (torque readings will begin to raise fast); Tight monitoring torque readings.Add catalyzer (0.7g imidazoles, 2.1g dodecanedioic acid and 2.1gNacure XC-at last

), tightly observe torque readings.Torque increases and stop this batch turnout after viscosity raises 10% (torque).

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Manual spray gun is ejected into this powder static electricity on the naked stainless steel plate of 10.16cm * 15.24cm (4 inches * 6 inches), so that build is about 76.2 microns (3 mils).This plate was solidified 30 minutes or in 121 ℃ convection oven, solidifies 30 minutes (referring to the test result of table 13) in 95 ℃, 107 ℃ convection oven.

Use DSC that the sample of embodiment 7 is analyzed, the results are shown in following table 12.

Although described plate does not have very bright gloss, the film properties under 107 ℃ of solidification values is reasonable, referring to table 13.Hardness and solvent resistance are significantly improved (MEK is two to be wiped).The result of bending shaft also demonstrates the bounding force and the snappiness of improvement.

Embodiment 8

Present embodiment for example understand to use based on the preparation as the powder coating of flow improver additive of the polyester of biology.In embodiment 3B, polyester polymers is described.

At first the composition of control group is prepared as follows:

Mixing tank is preheating to 99 ℃ (groove is warming up to about 99 ℃).Allow about 30 minutes of preheating.When preheating is finished, start and mix oar and open torque sensor.It can play guiding and mix the effect how to carry out.In groove, add about 30g unmodified resin (Fine-Clad then lentamente

); Hybrid resin and fusing show stable value (about 5 minutes) up to torque sensor; Add remaining 31.8g unmodified resin then and allow and mix, mixed about 5 minutes.The center of the mixing region between rotor adds 0.44g additive (st-yrax) then.Continue to mix 10 minutes (the monitoring torque value is to determine stability); In previous mixture, add 17.7g cross-linked resin (FineClad

); Continue to mix at least 3 minutes, the monitoring torque readings keeps stable (torque readings will begin to raise fast) to guarantee it under the situation of crosslinked beginning; Tight monitoring torque readings.

This product is taken out from tempering tank, and it is for smooth, hard, glossiness material and allow it to be cooled to room temperature.With hammer this material being pulverized is fragment.

Above process is repeated more than six times to mix three kinds of flow improver additives of 1% (weight) or 3% (weight) respectively.When adding is benzoic, add flow improver additive.Use is based on flow improver additive (embodiment 3B) and two kinds of commercially available flow improver additive (Fine-Clad of biology

With Additol VXL

), referring to following table 14 with preparation composition B to G.

*-composition of the present invention

The viscosity of composition reduces the effect of powder coating viscosity to determine flow improver additive in the test chart 14 under low solidification value.Lower viscosity will mean to have better mobile and more slick finished film during toasting.Table 15 has shown 90 ℃ to 140 ℃ viscosity (pool).

* composition of the present invention

Adding the 1% polyester flow improver additive based on biology (sample B) down and add other test flow improver additives in lower temperature (90 ℃ with 100 ℃) and compare, is being the most effective reducing aspect the powder coating viscosity.Still the material than commercially available is low to add 3% (sample C) down at 90 ℃.In Fig. 7 by the illustrated exemplary explanation.

Can reduce melt viscosity even this serial DSC result shows 90 ℃ and 100 ℃ of addings based on the flow improver additive of biology, but the Tg of whole powder paint compositions minimizing and power stability do not suffer damage yet.The reaction enthalpy of cure peak temperature and powder coating (δ H) is not subjected to the negative impact of flow improver additive.Table 16 has shown the result of composition A to G.

*-present composition

Embodiment 9

Adopt color enriched material (color concentrates) that the colo(u)rant dispersion performance of the resin of embodiment 3F is estimated.

Material:

Selected the composition of two kinds of color enriched materials.A kind of is the PB 15:3 (phthalocyanine blue) of 10% amount of filler in the polystyrene support resin, and another kind is based on the green of specially joining in acrylonitrile butadient styrene (ABS) vector resin.The green of specially joining is made up of and amount of filler about 18% organic and blend mineral dye.Control sample is tested (run) with typical dispersion agent, the combination of the example of described dispersion agent such as Zinic stearas and Zinic stearas and ethylene bis stearamide dispersion agent (ethylene bistearamide).Sample is tested with the dispersing auxiliary of embodiment 3F.

Mix:

In the Leistritz twin screw extruder of the 18mm diameter that corotation changes, mix.

Test:

Use to filter that distributed test is carried out in test and with accumulative pressure Israel and Palestine/every gram pigment record.This is that quantitative dispersion test and lower value explanation disperse well more.

Table 17 has shown composition and the result who is used to test.

Table 17

Composition no	Pigment	Vector resin	Dispersing auxiliary	Filter test value Bar/gm pigment
Composition no	Pigment	Vector resin	Dispersing auxiliary	Filter test value Bar/gm pigment	6C-303295-05	10％PB 15:3	Polystyrene	Zinic stearas	8.5
6C-303296-05	10％PB 15:3	Polystyrene	Embodiment 3F	4.5	6C-303295-05	10％PB 15:3	Polystyrene	Zinic stearas	8.5
6C-303296-05	10％PB 15:3	Polystyrene	Embodiment 3F	4.5	9C-602331-05	18% mixes	ABS	EBS and Zinic stearas	0.82
9C-602332-05	18% mixes	ABS	Embodiment 3F	0.55	9C-602331-05	18% mixes	ABS	EBS and Zinic stearas	0.82

The PB=phthalocyanine blue

The ABS=acrylonitrile butadient styrene

The EBS=ethylene bis stearamide

What use was purchased dispersion agent Zinic stearas and EBS and Zinic stearas mixture has relatively shown good result.This result shows all to demonstrate in two kinds of different polymer systems and continues good colour developing.

Although various forms of the present invention disclosed herein has constituted present embodiment preferred, other multiple scheme also is possible.This paper does not expect and mentions all possible equivalent form of value of the present invention or derivative.It should be understood that term used herein only is descriptive, rather than restrictive, and can carry out various variations and do not break away from essential scope of the present invention.

Claims

1. powder coating, it comprises following reaction product:

A. use hydroxyl, carboxyl or isocyanate group functionalized resin, described resin has and is lower than about 80 ℃ Tg;

B. be at least the resin of 5wt% based on the content of biology; And

C. linking agent.

2. powder coating according to claim 1, wherein said resin are vibrin, polyamide resin or urethane resin.

3. powder coating according to claim 1 and 2, wherein said powder coating is at about 125 ℃ or more be cured under the low temperature.

4. carboxyl or hydroxyl-functional vibrin, it comprises following reaction product:

A. two dewatering hexitols;

B. dimer diol and/or dimerization diacid;

C. diacid, diester or diacyl chlorine; And

D. catalyzer.

5. vibrin according to claim 4, it also comprises non-ethylene glycol, optional glycol.

6. resin according to claim 4, it comprises the second optional diacid, second diester or the second diacyl chlorine.

7. resin according to claim 4, wherein said two dewatering hexitols comprise Isosorbide.

8. urethane resin with hydroxyl, carboxyl or isocyanate functionality, it comprises following reaction product:

A. two dewatering hexitols;

B. dimer diol and/or dimerization diacid;

C. polymeric polyisocyanate; And

D. catalyzer.

9. resin according to claim 4, wherein said two dewatering hexitols are Isosorbide.

10. powder composition, it comprises following reaction product:

A. resin, it is selected from the group of being made up of claim 4 or the described resin of claim 8, amido-polyimide resin and composition thereof; And

B. linking agent.

11. powder composition according to claim 10, wherein said linking agent has epoxy functionalities.

12. powder composition according to claim 10, wherein said linking agent has the beta-hydroxy amide functionality.

13. a powder coating, it comprises:

A. substrate;

B. the curing powder on the described substrate, wherein said curing powder are following reaction product:

B. linking agent.

14. powder coating according to claim 13, wherein said linking agent has epoxy functionalities.

15. powder coating according to claim 13, wherein said linking agent has the beta-hydroxy amide functionality.

16. powder coating according to claim 13, wherein said powder coating provide A level surface smoothness.

17. powder coating according to claim 13, wherein said substrate is temperature sensitive.

18. powder coating according to claim 13, wherein said powder coating provide A level surface smoothness.

19. powder coating according to claim 13, the Tg of wherein said resin is between about 40 ℃ and 80 ℃.

20. a method, it comprises:

A. select a kind of tough and tensile, based on the aligned crystalline monomers of two dewatering hexitols of biology;

B. react with unbodied, runny resin one and comprise following resin with formation based on biology:

A. be higher than about 40 ℃ and be lower than about 80 ℃ Tg;

B. by weight, at least 5% biomass in the described resin combination; And

C. at 125 ℃ or more solidify under the low-temperature bake condition of low temperature, softening and flow out it is continued 30 minutes.

21. method according to claim 20, wherein said resin carries out functionalized with hydroxyl, carboxyl and/or the nitrogen that contains group (amine, isocyanic ester or acid amides).

22. method according to claim 20, wherein said resin have the excessive degree of unsaturation that can be used for regelate mechanism.

23. method according to claim 20 wherein adopts the exchange of beta-hydroxy carboxylic acid amide esters to solidify the described resin of claim 2 is mixed with coating composition; Described beta-hydroxy carboxylic acid amide esters exchange is cured as the curing reaction of the carboxyl of beta-hydroxy acid amides and polyester acid resin.

24. method according to claim 21, wherein said resin and result for example form the composition of the hydridization powder coating of epoxy acrylate and prepare.

25. method according to claim 20, wherein said hybridization coating composition and catalyst reaction with following general formula:

R wherein ₁, R ₂, R ₃And R ₄Be hydrogen or any substituting group of not reacting with Resins, epoxy independently.

26. a composition of matter is wherein tough and tensile, reacting with unbodied, runny resin one based on biology based on the aligned crystalline monomers (as Isosorbide) of biology can be used for producing the resin of coating, tackiness agent, printing ink, sealing agent, polymer application and other industrial materials with formation.

27. a composition of matter is wherein tough and tensile, react to form new type resin based on the aligned crystalline monomers (as Isosorbide) and unbodied, the runny resin one based on biology of biology, described new type resin has:

A. about 40 ℃ to about 80 ℃ Tg;

B. in the resin combination at least about the biomass of 5wt%; And

C. continue 30 minutes 125 ℃ solidification value.

28. composition according to claim 27, wherein said resin carries out functionalized with carboxyl, hydroxyl and/or the nitrogen that contains group (amine, isocyanic ester and/or acid amides).

29. composition according to claim 27, wherein said resin has excessive degree of unsaturation.

30. composition according to claim 27, wherein said resin carries out functionalized with carboxyl.

31. composition according to claim 27, wherein said resin carries out functionalized with hydroxyl.

32. composition according to claim 27, wherein said resin carries out functionalized with the nitrogen that contains group (amine, isocyanic ester, acid amides etc.).

33. composition according to claim 27 wherein adopts the exchange of beta-hydroxy carboxylic acid amide esters to solidify the described resin of claim 30 is mixed with coating composition; Described beta-hydroxy carboxylic acid amide esters exchange is cured as the curing reaction of the carboxyl of beta-hydroxy acid amides and described resin.

34. composition according to claim 27, wherein said resin have 〉=40 ℃ Tg and 〉=20% content based on biology, and it can be mixed into powder coating, these powder coating can use for example following cross-linked resin to be cured:

A. beta-hydroxy acid amides

B. the resin that contains epoxy, it includes, but are not limited to the glycidyl methacrylate acrylic copolymer resin.

35. a powder coating, it comprises:

A. resin, described resin comprises following reaction product:

A. two dewatering hexitols;

B. dimeracid and/or dimer diol;

C. diacid, diester or diacyl chlorine;

B. linking agent; And

C. Ren Xuan pigment.

36. powder coating according to claim 35, it comprises and is used for described catalyst for reaction.

37. powder coating according to claim 35, it comprises pigment dispersion aids.

38. powder coating according to claim 35, it comprises: when described resin has carboxyl, make the carboxyl functionality carboxyl or with the autocatalysis transesterification reaction in beta-hydroxy acid amides reaction, perhaps with poly-epoxide functional polymers reaction.

39. powder coating according to claim 35, it comprises: when described resin has hydroxy functional group, make the hydroxyl and the epoxy functional acrylic reaction of hydroxy functionality.

40. powder coating according to claim 35, it comprises optional vehicle.

41. all novel and non-obvious composition, method and purposes disclosed herein.