CN101321838A - Emulsifiers for use in water-based tackifier dispersions - Google Patents
Emulsifiers for use in water-based tackifier dispersions Download PDFInfo
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- CN101321838A CN101321838A CNA200680045573XA CN200680045573A CN101321838A CN 101321838 A CN101321838 A CN 101321838A CN A200680045573X A CNA200680045573X A CN A200680045573XA CN 200680045573 A CN200680045573 A CN 200680045573A CN 101321838 A CN101321838 A CN 101321838A
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- tackifier
- emulsifying agent
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- rosin
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Abstract
Anionic emulsifiers based on rosin acid or derivatives thereof, and to methods of preparing said emulsifiers. The emulsifiers are useful for preparing tackifier dispersions having improved properties with respect to foam stability. As such, said tackifier dispersions are advantageously used in water-based adhesives providing improved adhesive and cohesive properties. The adhesives may be used for labels on any kind of surface, packaging applications, flooring adhesives, road markings or for any type of water-based tapes, barrier coatings or sealants.
Description
Invention field
Relate generally to emulsifying agent of the present invention field, and relate to the preparation of its stable dispersions.
Background of invention
Emulsifying agent (for the present invention's purpose, this term to manage for " tensio-active agent " this term be synonym) stability is provided and prevents condensing of the particulate that generates during the emulsifying effect.Emulsifying agent further prevents condensing or agglomeration of particulate in the final dispersion liquid.Because its amphoteric character, the emulsifying agent molecule all has avidity to oil phase and water.As a result, between the molecule that the emulsifying agent molecule that exists on the oil-water interface and oil phase and aqueous phase exist, exist a kind of balance.In category of the present invention, the functionality of emulsifying agent of the present invention is mainly discussed in the tackifier dispersions scope.Yet, it being understood that emulsifying agent of the present invention can easily be used for reducing viscosity and/or improve the emulsification of any other conceivable dispersion liquid.
The description of relevant prior art
US 2,194,429 relate to be adapted in paint industry and other industry as auxiliary agent, based on the production method of the condensation product of resinol and resin amine.It is disconnected that the product that obtains according to US ' 429 comprises a kind of abietin substrate that is connected with (gathering) oxyalkyl or oxyalkyl ether segment.The abietin substrate disconnected with this chain between be connected and be limited to ehter bond.Thereby the length of this ether chain improves total availability that this compound is used to form this dispersion liquid and sees along with improving hydrophile.US ' 429 has described the free-end hydroxyl and has used the functionalized of sulphonating agent.Tenderizer provides in US ' the 429 main concern lacquers.
US 5137572 has described a kind of emulsifying agent molecule of partly being made up of tallol sylvic acid segment, phosphoric acid functionalities and hydrocarbon oxide.Total weight range according to oxide unit in the emulsifying agent of US ' 572 is 50～100.The sum of oxide unit is greatly because this emulsifying agent is used for producing the cause of the purposes of mixed class bitumen emulsion.The open document of US ' 572 is limited to the preparation of described bitumen emulsion.
US 6274657 relates to a kind of tensio-active agent that is used to form with the stable dispersions of the rosin ester of elastomer latices compatibility.This tensio-active agent has chemical formula R
1-R
2-R
3R
1And R
3Each all is rosin (being the mixture of rosin, rosin dimerization body or rosin and rosin dimerization body).R
2Be selected from one group that polyoxyethylene glycol (PEG) and modified PE G chain are formed.This tensio-active agent is by making this rosin material esterification preparation with polyoxyethylene glycol.These compounds are used for stablizing the rosin ester in the tackifier dispersions.
All surface promoting agent described in the US ' 657 all is a non-ionic type, and water-solublely reaches by importing long especially PEG chain (promptly having a large amount of ethylene oxide units).A similar invention is described among the US 5552519, and this patent also relates to a kind of based on the pulsating nonionic surface active agent of sylvic acid, and wherein the hydrophilic functional degree is provided by the high molecular weight polyethylene glycol chain.
Main concern in the water-based tackifier dispersions production is that foamy forms and stability." foam " can be considered as the stable air filled cavity of emulsifying agent molecule by this aqueous phase existence.Stable foam can cause the formation of thick particulate in this dispersion liquid.Thick particulate is the exsiccant result often, and may cause filter stoppage.The dehydration of film when thick particulate also may bring out the finished product that comprise this dispersion liquid and is administered on the base material, thus the hole in the final coating on this base material caused.It also is undesirable that the foam that recirculation flow is brought out in the coating process forms, because air filled cavity may cause the hole in the final coating.The recirculation that is administered to the coating on the base material labelling/be common in the packaging industry, even and must make this product touch air one this tackiness agent and/or tackifier dispersions air not in the presence of preparation.
Foam forms and need avoid, limits or destroy, so that these and other latent defect drops to bottom line.Except that other factors, lather collapse is subjected to the stability of air/liquid interface and the speed influence that air filled cavity moves to the surface of this dispersion liquid owing to prevail density difference.The latter can control by total viscosity of adjusting this dispersion liquid.In general, along with this dispersion liquid viscosity reduces, the foaming behavior improves, and promptly produces less foam.
As what learn from prior art, water-based tackifier dispersions typically comprises alkylphenol or alkyl alcohol ethoxylation anionic emulsifier.With the dispersion liquid of these emulsifying agent preparations, with regard to its foaming behavior and/or its total solids level and/or its granularity, all be limited.In general, following at least a problem is to use these emulsifying agents to take place: or observe foaming, either solids content is not high enough, or particulate is too big.The use of these emulsifying agents of learning from prior art typically causes increasing foam when the solids content of this dispersion liquid improves and forms.
The feature of emulsifying agent also can produce remarkably influenced to the cohesiveness and the binding property of tackiness agent.Especially true for aqueous-based adhesive.The anionic emulsifier of learning from prior art, especially alkylphenol or alkyl alcohol ethoxylation anionic emulsifier knownly can play the softening agent effect, thereby reduce the cohesive strength of tackiness agent.Other tensio-active agent of learning from prior art tend to be non-ionic type thereby be suitable for that not too the aqueous-based dispersions that improves the foaming feature is arranged.
And then, contain the emulsifying agent of alkyl phenol ethoxylate because the toxicity of this compounds is withdrawing from tackiness agent and other application gradually with causing the female hormone activity.Therefore, still need to provide the emulsifying agent that does not contain alkyl phenol ethoxylate in the industry.
Also still need to provide the emulsifying agent that can be used to prepare tackifier dispersions in the industry, this dispersion liquid beforely has the dispersion liquid of the technical emulsifying agent of learning unlike using, especially comprises the dispersion liquid of alkylphenol commonly used or alkyl alcohol ethoxylation anionic emulsifier on the total solids level and/or restricted on the granularity.Ideally, should be able to reach the solids content of raising and/or the viscosity of reduction, the behavior of reasonably being bubbled again simultaneously.
At last, still need in the industry to provide and to be used for tackiness agent, can to avoid the shortcoming of prior art, the tackifier dispersions that improves bounding force on cohesive strength and/or the base material of improving of this tackiness agent can be provided again.
Brief summary of the invention
The present invention relates to novel emulsifier and relate to its preparation.The invention further relates to the application that described emulsifying agent is used for preparing novel water-based tackifier dispersions.
One aspect of the present invention relates to the emulsifying agent that is used for tackifier dispersions.This emulsifying agent comprises at least a sylvic acid segment or at least a rosin acid derivative segment, polar chain that is connected with described sylvic acid or rosin acid derivative and a kind of anionic headgroup that is connected with this polar chain, wherein this polar chain comprises at least 2 repeating units, and the latter comprises the carbon-oxygen bond at least at least one repeating unit.
Another aspect of the present invention relates to water-based tackifier dispersions.According to described water-based tackifier dispersions of the present invention comprise with water and following emulsifying agent at least a combination, according at least a emulsifying agent of the present invention: (i) at least a rosin ester, (ii) at least a hydrocarbon resin is C for example
5-C
9Hydrocarbon resin, (iii) at least a low molecular weight propylene acid esters, or (iv) at least a terpine resin.Can suitably use in these tackifier any mixture of two or more, or any mixture of one of these tackifier and another kind of tackifier.
A further aspect of the present invention relates to the purposes of these water-based tackifier dispersions and elastomer latices combination.For example, can make up with acrylate copolymer or styrene butadiene rubbers (SBR), be used for preparing aqueous-based adhesive according to water-based tackifier dispersions of the present invention.Can be used for following field according to tackiness agent of the present invention: any lip-deep label, packaging application, ground tackiness agent, road sign, or the water base band of any kind.
The accompanying drawing summary
Fig. 1 illustrates the balance that has the emulsifying agent molecule in the tackifier dispersions.
Detailed description of the Invention
By reaching wherein included embodiment with reference to following detailed description the in detail of the present invention, can more hold Change places and understand the present invention.
This theme composition and method open with describe before, it being understood that the present invention does not limit Due to concrete synthetic method or concrete prescription, unless point out in addition, and therefore, can be different from this Open document. Also it being understood that employed term just for describe specific embodiments it Purpose, and be not intended to limit scope of the present invention.
" one ", " one " and " being somebody's turn to do " these singulatives comprise a plurality of referred things, Unless context spells out in addition.
In this specification, in the situation of mentioning patent or publication, these lists of references Disclosure all be intended to classify as in full with it list of references of present patent application, in the hope of more fully Classification involved in the present invention is described.
The invention provides and to improve dispersion liquid, the emulsifying agent of the foaming behavior of tackifier dispersions especially.Be not subjected to any theory constraint, the reason that the foaming behavior of this improvement how can realize is attributable to dispersion liquid viscosity and reduces.This aqueous viscosity is illustrated among Fig. 1 with reducing diagram.A kind of tackifier particulate is represented in the left side of Fig. 1.As shown in the figure, there is a kind of balance between the emulsifying agent molecule that emulsifying agent molecule that exists on the emulsifying agent molecule that exists (with individual molecular or based on micella), the tackifier oil-water interface and aqueous phase exist in the tackifier oil phase.
Emulsifying agent of the present invention also can be functionalized, to have the water-oil interface avidity of increase.This emulsifying agent molecule that causes aqueous phase to exist reduces.As a result, produce a kind of different balance shown in the right side of Fig. 1.Because less emulsifying agent molecule is present in aqueous phase, thereby the viscosity of this water reduced, thereby causes the overall viscosity of this dispersion liquid to reduce.And then because less emulsifying agent molecule is present in this aqueous phase, thereby less molecule can be used for stable air-water termination.Stable air-water interface can be considered as increasing a reason of foam generation and froth stability.Therefore, be not subjected to any theory constraint, emulsifying agent of the present invention can be by providing because the hydrophobic pulsating anionic emulsifier with tendency that minimizing exists at aqueous phase that comprises improves the foaming behavior with the dispersion liquid of its preparation.
Emulsifying agent of the present invention can comprise hydrophobic sylvic acid segment or derivatives thereof.The emulsifying agent that connects thereon comprises a polar chain of being made up of at least 2 repeating units that comprise at least one carbon-oxygen bond.The Sauerstoffatom of this polar chain contributes to the hydrophilic functional degree of (totally) amphoteric emulsifier.The emulsifying agent that is connected in the other end of this polar chain further comprises a negatively charged ion head group, thereby gives this overall emulsifying agent with anionic.This anionic headgroup also contributes to the hydrophilic feature of this amphoteric emulsifier.
Another aspect of the present invention relates to the adhesive character with the adhesive formula of tackifier dispersions preparation of the present invention.Bonding is a kind of surface phenomena, thereby may be subjected to the selection influence of the emulsifying agent that exists in this tackiness agent.Generally, the tendency of the interfacial migration between oriented air of emulsifying agent and the tackiness agent.Therefore, emulsifying agent can change the surface property and the energy of adhesion of this tackiness agent.The present invention relates to such effect, according to this effect, the bond properties that comprises the tackiness agent of a kind of (comprising anionic emulsifier) (water base) tackifier dispersions can be subjected to employed emulsifier type remarkably influenced.The existence that can change the emulsifying agent of viscosity also may exert an influence to the adhesive property of this tackiness agent.
Some relevant technical terms of using in the category of the present invention mean and be appreciated that following (unless specifically noting in addition) in this descriptions in full.
" bonding " (or bond properties) in the implication of the present invention relates to the interaction of the base material of this adhesive formula and it using.On feature, bounding force relates generally to the interface between tackiness agent and the base material.Be applicable to that the test that bounding force is measured is, for example, " ring is sticking " test and " stripping strength " test.These tests are described in FINAT Technical Handbook, 6
ThEd., 2001.Ring is sticking to be measured according to FINAT Test Method (FTM) 9 (should " the 22nd page of handbook and after).Stripping strength is measured according to FTM 1 (should " the 6th page of handbook and after).
" bonding " (or adhesive property) in the implication of the present invention relates to the interaction/power of this tackiness agent inside.Typically, cohesive force (force of cohesion) relates generally to the body phase of this tackiness agent.Be applicable to that the test that cohesive force is measured is " shear bond " test.Shear bond is measured according to FTM 8 (should " the 20th page of handbook and after).
Relate to a kind of entity that following molecular backbone chain is arranged according to " sylvic acid " of the present invention:
In one embodiment, R
1-R
4Each can be any alkyl, for example ethyl or methyl.In another embodiment, this structure comprises 2 conjugated double bonds.In a kind of further embodiment, this sylvic acid molecule comprises 20 carbon atoms.The constitutional isomer of this main chain also is suitable for.
At least one can be aromatic in these three rings.Be appreciated that to also comprising the mixture of various sylvic acid molecules according to " sylvic acid " of the present invention.Obtain easily and the mixture of naturally occurring this kind includes but not limited to (wood pulp) starex, (natural gum) rosin or wood (steaming) rosin.These natural mixtures can comprise the sylvic acid of abietic acid type and/or Korean pine acid type, for example abietic acid, palustric acid, neoabietic acid, levopimaric acid, pimaric acid, isopimaric acid or dehydroabietic acid, and its content is different.It is sylvic acid that any such mixture all is considered as, as long as at least a in the molecule of this mixture have the above sylvic acid main chain or its constitutional isomer.
Except that the sylvic acid that a carboxylic functionality is arranged, there is the sylvic acid of 2 or more a plurality of carboxylic functionality also to be considered as sylvic acid in the implication of the present invention.
According to " rosin acid derivative " of the present invention is anyly molecule sylvic acid main chain as mentioned above to be arranged but with the molecule of following at least a mode modification.In one embodiment, at least one two key is hydrogenation (hydrogenation).In another embodiment, at least one is dehydrogenation in the ring of this rosin and main chain, thereby produces an aromatic ring (dehydrogenation).In a kind of further embodiment, carboxyl functionality's modification of sylvic acid becomes such as carbinol-functional degree (for example, methylated and (natural gum) rosin dehydrogenation changes into hydroabietyl alcohol by means of hydrogenolysis).In another embodiment, carboxyl functionality's modification is become the amide functionality.In another embodiment again, comprise the adducts on the conjugated double bond of sylvic acid main chain, the especially addition of maleic anhydride in the reaction of Diels Alder type.Resulting adducts is considered as a type according to rosin acid derivative of the present invention.
According to " rosin ester " of the present invention is any molecule of connecting by means of at least one ester bond of at least 2 sylvic acids or rosin acid derivative unit wherein.There is any molecule of at least 2 hydroxyls can be used to provide at least 2 ester bonds between the sylvic acid unit.Common example includes but not limited to glyceryl ester, pentaerythritol ester and triethyleneglycol ester.
" solids content " of tackifier dispersions is that the gross weight with this dispersion liquid is (unless pointing out in addition) that the wt% of benchmark provides.Illustrate that testing program how to measure solids content provides in " embodiment " joint.
According to " water base " of the present invention tackifier dispersions is that wherein solvent usually is the dispersion liquid water or the aqueous solution, the tackifier entity.Yet water and non-aqueous solvent, especially the mixture of organic solvent also can be to be suitable for, as long as lathering property or other dispersion liquid performance are not subjected to negative impact.Also can make the mixture of water and other water-soluble solvent.
According to emulsifying agent of the present invention
In one embodiment of the present invention, this emulsifying agent molecule comprises following sense entity (segment) at least:
At least a sylvic acid segment or at least a rosin acid derivative segment,
, a polar chain that is connected with described sylvic acid or rosin acid derivative,
An anionic headgroup that is connected with this polar chain.
The mixture of two or more types of the emulsifying agent molecule of this structure also is according to emulsifying agent of the present invention.
This sylvic acid (derivative) segment is considered as giving of hydrophobic (oleophylic) feature on this emulsifying agent molecule.This polar chain and this anionic headgroup all are considered as giving of hydrophilic (oleophobic) feature on this emulsifying agent molecule.
In one embodiment of the present invention, hydrophobic segment is a kind of sylvic acid.When using sylvic acid, can obtain the low viscosity value together with good foaming behavior and the granularity below the 250nm as hydrophobic segment.If use sylvic acid to comprise oxygen, then a kind of typically ester bond of formed key between this hydrophobic segment and this polar chain as hydrophobic segment and this polar chain.
In another embodiment, this sylvic acid derives from a kind of natural source for example (wood pulp) starex, (natural gum) rosin or wood (steaming) rosin of existing.The fraction in these sources or mixture also can use.This mixture can be two or more combinations each other in these natural product, and perhaps these natural product also can be mixed with the sylvic acid that purified or synthesis method are produced.There is not any restriction in degree about any one hydrogenation, dehydrogenation or variation in " R " group of this sylvic acid, if in this molecule at least some this carboxyl functionality still constant.
In another embodiment, the carboxyl functionality of this sylvic acid changes into hydroxy functionality such as the hydrogenolysis by the sylvic acid that methylates.
In another embodiment, this polar chain comprises at least 2 and contains the unitary repetition that at least one carbon atom is connected with at least one Sauerstoffatom, i.e. at least 1 carbon-oxygen bond/repeating unit.For example, the unit of forming by oxyethane (EO), promptly-C
2H
4-O-is fit to, thereby causes polyethylene oxide chain.This polar chain need not stopped by a kind of oxy radical, does not need only to comprise C, O and H atom yet.The polar chain that the amine end is arranged also can be to be fit to.(" Pluronics ") also is considered as according to polar chain of the present invention such as the segmented copolymer that comprises polypropylene block and polyethylene block.
In a kind of further embodiment, this polar chain comprises 2～50 (repetition) unit.For example, can use 3～20 unit or Unit 4～20.Equally, according to the present invention, 4～15 unit or 4～11 unit or even 5～9 unit all can be to be suitable for.
The unit number that constitutes the polar chain of this emulsifying agent may exert an influence to the granularity of tackifier particulate in the dispersion liquid that produces with this emulsifying agent.Small grain size generally is favourable, and it be the reasons are as follows.The first, the tackifier particulate is more little, thereby this particulate gravity settling makes the possibility of this dispersion liquid unstability just more little.Tackifier dispersions with the emulsifying agent preparation of the present invention that suitable polar chain length is arranged can be stablized the several years.Secondly, little tackifier granularity can cause the total surface area that increases, thereby makes more emulsifying agent molecule be attached in the oil phase and reduce the emulsifier content of aqueous phase.The viscosity that this should cause total dispersion liquid to reduce.At last, the tackifier that have been found that volume particle size may cause worse foaming behavior.For polyethylene oxide chain, have been found that when using the emulsifying agent of the polar chain that the EO unit number in 4～15 scopes is arranged, can reach the minimum particle size of tackifier in this dispersion liquid.For example, 4～11 unit or 5～9 unit can be to be suitable for.
About the anionic headgroup, the end group that can give this polar chain all is suitable for any group of (part) negative charge.For example, the end group of this polar chain can for example (gather) phosphoric acid or sulfuric acid with mineral acid and carries out functionalized.For phosphorylated, can adopt oxide compound or halogenide, for example Vanadium Pentoxide in FLAKES (P
2O
5), phosphorus trichloride (PCl
3) or inferior phosphinylidyne trichlorine (POCl
3).For sulfation, can use corresponding oxysulfide or sulfur halide.In another embodiment, this polar chain can be carried out modification, to cause a kind of carboxylic functionality (for example esterification).According to the present invention, any method all can be acceptable, as long as this headgroup can be given a kind of anionic emulsifier.
The use of anionic headgroup obviously can provide electrostatic repulsion in category of the present invention, thereby prevents particulate agglomeration/aggegation.Use the anionic headgroup, also make to allow shorter polar chain in the present invention when comparing, because this hydrophilic feature is not all need be from (length) polar chain with known emulsifying agent on the prior art.
According to hydrophobic segment of the present invention, sylvic acid (derivative) segment for example, can cause a kind of with comprise prior art on known hydrophobic part for example rosin ester, hydrocarbon resin or its mixture have the emulsifying agent that increases avidity to hydrophobic tackifier when for example the emulsifying agent of alkylphenol or alkyl alcohol is compared.
Therefore, provide the pulsating emulsifying agent of sylvic acid (derivative) and can be considered as improving the selectivity of this emulsifying agent, thereby cause the emulsifying agent molecule of the aqueous phase existence of this water-based tackifier dispersions to reduce water-oil interface in the tackifier dispersions.As a result, can reduce the viscosity of this water.Therefore, also can reduce the viscosity of total dispersion liquid.
According to tackifier dispersions of the present invention
Comprise in water, at least a emulsifying agent as mentioned above and the following tackifier at least a according to tackifier dispersions of the present invention: at least a rosin ester, or at least a hydrocarbon resin, or from vinyl aromatic monomers for example vinylbenzene, indenes, alpha-methyl styrene, Vinylstyrene, at least a resin that has the Vinylstyrene of one or more alkyl to produce, at least a terpine resin, or any mixture of at least 2 kinds in these tackifier.
For example, at least a in these tackifier can be a kind of rosin ester.In the present embodiment, the structural similarity between the sylvic acid segment of using in this rosin ester and this emulsifying agent can reduce the migration of this emulsifying agent to the surface.Migration may be harmful in the binder performance of the tackiness agent that comprises described emulsifying agent potentially.Suitably, in using the embodiment of hydrocarbon resin, can use C individually or with rosin ester as tackifier with mixing
5-C
9Hydrocarbon resin.
In one embodiment of the present invention, this rosin ester can have＜25 acid number (promptly with in and the value that provides of the mg number of should the acid required KOH of 1g).In another embodiment, the weight-average molecular weight of this hydrocarbon resin is 200～20, and 000g/mol, for example 4,000～7 is in the 000g/mol scope.
In another embodiment, the softening temperature of at least a tackifier of this tackifier dispersions can be in-30 ℃～160 ℃ scopes, in for example 20 ℃～120 ℃ scopes [measure according to " global " method of ASTM E28-99 (2004) Standard Test Method, promptly with global device mensuration, from the softening temperature of naval stores product deutero-resin].
The mean particle size of tackifier μ m suitably＜2 in the tackifier dispersions discussed above.For example, the mean particle size of these tackifier＜1 μ m or even＜500nm.In another embodiment, the mean particle size＜250nm of these tackifier.Usually, granularity and size-grade distribution are with (laser) light scattering method measuring.
In a kind of further embodiment, the Brookfield viscosity＜300mPa.s of this tackifier dispersions or＜250mPa.s.Usually, viscosity is with Brookfield LVT viscometer determining.The higher emulsifying agent of viscosity is contained in the present invention, if the foam behavior be acceptable and this solids content within the limits prescribed.
According to the solids content of tackifier dispersions of the present invention suitably in 50wt%～70wt%, for example 55wt%～65wt% scope.
According to adhesive formula of the present invention
Being applied to emulsifying agent of the present invention according to tackifier dispersions of the present invention causes improving adhesive property and bond properties with the aqueous-based adhesive of described tackifier dispersions preparation.For example, such tackiness agent can be advantageously used in label industry and packing business, be used for water base adhesive tape, road sign and floor applications.In above-mentioned application, this tackiness agent is pressure-sensitive.Comprise that also wherein tackiness agent is not other pressure-sensitive application.Such application includes but not limited to gas barrier coating or sealing agent.
In another embodiment of the invention, use the tackifier dispersions of emulsifying agent of the present invention can be used for preparing a kind of adhesive formula.This adhesive formula comprises at least a tackifier dispersions as mentioned above and at least a component of polymer.Generally speaking, this component of polymer is a kind of elastomerics composition, comprises elastomer latices, for example polyacrylate(s) or styrene butadiene rubbers.Be suitable for including but not limited to other polymkeric substance that uses according to tackifier dispersions of the present invention:
-natural rubber suspension,
-from 2-EHA, butyl acrylate, methyl methacrylate, methacrylic acid and vinylformic acid or its mixture deutero-acrylic polymers,
-polystyrene,
-styrene-butadiene copolymer,
-from vinyl-acetic ester ethane-acetic acid ethyenyl ester derived polymers for example,
-sovprene, or
-propylene-butadienecopolymer.
Also can suitably use in these polymkeric substance any mixture of two or more.
In order to prepare wet binder of the present invention prescription (being water-based formulation), can fusion a kind of according to tackifier dispersions of the present invention and latex.In general, this adhesive formula is by 15%～50% tackifier, for example 20%～40% (is benchmark with the dry weight) formed.
Exemplary preparation method according to emulsifying agent of the present invention
Based on polyethylene oxide chain as polar chain, as follows by means of case description according to the schematic preparation synthetic route of non-ionic type intermediate of the present invention and anionic emulsifier:
(I) possible synthetic route:
The esterification route
(a) make the sylvic acid esterification with excessive polyoxyethylene glycol (PEG);
(b) midbody product (A) of step (a) is separated with unreacted PEG;
(c) make product and a kind of mineral acid or the carboxylic acid reaction of step (b), obtain anionic emulsifier; Used herein is (many) phosphoric acid.
Comprise one based on the main molecules structural representation of the anionic emulsifier of the part of hydrophobic sylvic acid show below:
This product mixtures also can contain a small amount of bisphosphate and free phosphoric acid (20～60mol%) etc.Purification step in case of necessity can be carried out according to the standard method of learning from prior art.
(II) substitute synthetic route:
The ethoxylation route
(a) by the conversion of carboxyl, prepare a kind of rosin acid derivative to hydroxyl;
(b) hydroxy functionality obtains a polyethylene oxide chain with oxyethane (EO) ethoxylation;
(c) crude product carries out vacuum desorption, to remove unreacted EO;
(d) intermediate product (B) of step (c) and a kind of mineral acid or carboxylic acid reaction;
Used herein is Tripyrophosphoric acid.
Though described rosin acid derivative and ethoxylation here, also can use sylvic acid.The basic molecular structure that comprises the pulsating anionic emulsifier of hydrophobic hydroxyl modification sylvic acid schematically shows below:
This product mixtures also can contain a small amount of (20～60mol%) bisphosphates and free phosphoric acid etc.Purification step in case of necessity can have the technical standard method of learning to carry out according to before.
Are a kind of semisolids, at high temperature become liquid and moderate solubility is arranged in water according to the typical product of these two lines.Typically, the product that is its salt form has good water-solubility.
In a kind of preparation method according to the non-ionic type intermediate (A) of esterification route, sylvic acid (or mixture) is with the polyoxyethylene glycol reaction of molar excess in the presence of at least a metal oxide catalyst.Typically, this temperature of reaction is 270 ℃～290 ℃.This reaction is carried out under the inert nitrogen condition more fortunately.Usually, the number-average molecular weight scope of the polyoxyethylene glycol that uses in present method is 100～1000g/mol, 200～500g/mol for example.
The typical reaction times is 30 hours, reaches 90～99% transformation efficiency.In one embodiment, the unreacted polyoxyethylene glycol is by water repeatedly-diethyl ether extraction and remove from middle reaction product.In another embodiment, general＜2wt%NaCl adds in this water, in the hope of well being separated in extraction step.Typically, need 5 extraction step just can reach in this intermediate non-ionic type product＜the polyoxyethylene glycol level of 2wt%.If make this PEG chain longer, then find undesirable non-ionic type intermediate solubleness than 7EO unit; On the other hand, if make this PEG chain shorter, find that then PEG significant institute in ether does not wish solubleness than 5EO unit.
In another embodiment, the molar ratio range of sylvic acid and polyoxyethylene glycol is 1: 2～1: 10, for example 1: 3～1: 7.As further example, 1: 5 ratio also is suitable for.
A kind of alternative preparation method of this non-ionic type intermediate comprises sylvic acid or the rosin acid derivative and the oxyethane of at least one hydroxy functionality is arranged or the reaction (ethoxylation) of the molecule of similar functionality is arranged.This reaction is carried out in the presence of the KOH of catalytic amount typically.In addition, this reaction is 160 ℃～190 ℃ temperature, carries out under the inert nitrogen condition more fortunately.And then, generally apply the pressure of 4～5bar.The advantage that this method is compared with the above esterification route is, extraction step is unnecessary, thus the unitary number of unqualified EO.
Can be by non-ionic type intermediate (A) as mentioned above or (B) or the prepared in reaction of its mixture and a kind of mineral acid, a kind of carboxylic acid or its any mixture according to anionic emulsifier of the present invention.
In another embodiment, can use (many) phosphoric acid.The equivalent of Tripyrophosphoric acid is typically expressed with % phosphoric acid.This can be converted into P
4O
10Equivalent quality.This equivalent quality can with the hydroxyl reaction of equivalent quality.In this case, hydroxyl and P
4O
10Molar ratio range suitably be 5: 1～1: 5, for example 3: 1 (this is excessive corresponding to hydroxyl).
If the employing phosphorylated, then the phosphorylated step better is included under the temperature in 60 ℃～70 ℃ scopes Tripyrophosphoric acid to non-ionic type intermediate (A) or (B) or the slow interpolation in its mixture.Tripyrophosphoric acid is with 1～90min, for example the timed interval in 10～70min scope adds.In one embodiment, this temperature of reaction can be brought up to 100 ℃ in 3～4 hours after Tripyrophosphoric acid adds.
According to the present invention, about the manufacturing of this emulsifying agent, because the omission of the extraction step that can save money, thereby can use ethoxylation to replace esterification.What also be suitable for is to make sylvic acid rather than rosin acid derivative ethoxylation, so that ester bond rather than ehter bond to be provided.Generally speaking, the suitable manufacture method according to emulsifying agent of the present invention comprises in the following step at least one: (a) at least a sylvic acid ethoxylation of oxyethane; (b) reaction of the intermediate product of step (a) and mineral acid or carboxylic acid.
Use prepares the exemplary methods of tackifier dispersions according to emulsifying agent of the present invention
In causing based on a kind of embodiment according to the tackifier dispersions of emulsifying agent of the present invention, described tackifier dispersions can be according to a kind of conversion method preparation at intermittence.
In another embodiment, these tackifier or tackifier mixture can be heated to above about 10～30 ℃ of the softening temperature of this tackifier/tackifier mixture.Then, can will add in described tackifier/tackifier mixture according to emulsifying agent of the present invention.In further embodiment, this emulsifying agent can add with a kind of neutralizing agent.The neutralizing agent that is suitable for comprises NaOH, KOH or trolamine.
In a further step, can under agitation water be added in this tackifier mixture slowly until reaching commutation.In one embodiment, resulting milk sap further is diluted to desirable total solid concentration.Then, resulting dispersion liquid cooling slowly under mild stirring.
The reasonable quantity ground that adds the emulsifying agent in the tackifier to 4～9 parts, for example between 5～8 parts, be benchmark with per 100 parts of tackifier (weight part) respectively.The addition of neutralizing agent is adjusted in such a way: make the pH value of final dispersion liquid in 4～10 or 6～8 scopes.
The present invention can further specify with the following example of its potential embodiment, although should be understood that what just these embodiment just comprised for the purpose that illustrates, and be not intended to limit the scope of the invention, unless specifically note in addition.
Embodiment
The preparation (esterification) of embodiment 1 intermediate product A
Be equipped with agitator, thermopair, nitrogen inlet and have in 2 liters of glass reactors of an electrically heated of Dean Rodney Stark couch water trap of water cooler and add resin (Yisiman Chemical Company, the Middelburg, NL) and polyoxyethylene glycol (PEG 300, Aldrich chemical company, Milwaukee, the state of Wisconsin), its number-average molecular weight is 300, and molar equivalent is than COOH: OH=1: 10.This mixture is heated to 180 ℃ under the inert nitrogen condition, and adds 0.01%ZnO (weight with resin is benchmark) as esterifying catalyst.This mixture further is heated to 290 ℃ and water steamed continuously.
Allow reaction mixture react, until the transformation efficiency that reaches at least 90%.The typical reaction times is between 25～30 hours.Thick intermediate is cooled to normal temperature and is dissolved in the diethyl ether.100 parts of crude products are dissolved in 80 parts of diethyl ether.In this solution, add 67 parts of NaCl aqueous solution (2wt%).This mixture acutely sways in separating funnel, leaves standstill, until obtaining 2 or 3 layerings.The water layer that will contain PEG 300 and NaCl is removed.This program repeats 4 times with former diethyl ether solution, until remove at least 98% of residual PEG 300 from this adducts.Under reduced pressure (100～200mbar) remove diethyl ether with rotary film evaporator, until not detecting the diethyl ether steam 70～80 ℃ temperature.
The preparation (esterification) of embodiment 2 intermediate product B
By being that 200 polyoxyethylene glycol (PEG 200, Aldrich chemical company, Milwaukee, the state of Wisconsin) replaces PEG 300 with number-average molecular weight, repeat the program of embodiment 1.
The preparation (ethoxylation) of embodiment 3 intermediate product C
To be equipped with agitator, thermopair, nitrogen inlet and manometric 1 liter of autoclave and be heated to about 85 ℃, and (Yisiman Chemical Company, the Middelburg is NL) with 0.3g KOH powder to add 300g Abitol E.Stirring begins with 500rpm.Nitrogen purging 3 times of this reactor.With mixture heating up to 180 ℃.Use a material container that adds that is pressurized to 5bar,, in this reactor, add continuously oxyethane (be generally 5,7,9 or 11mol) with about 16 hours time.Pressure in this reactor is 4.7bar.Allow this mixture reaction spend the night.This reactor with nitrogen purging 3 times, be cooled to normal temperature, discharging.Mol ratio Abilol E: EO=1 preferably: 7.
The preparation of embodiment 4 anionic emulsifier
Be equipped with in three mouthfuls of glass flask of an electrically heated 250mL of agitator, thermopair, nitrogen inlet, dropping funnel and water cooler, add the intermediate product of embodiment 1,2 and 3 respectively with independent batch, and be heated to 120～140 ℃.The decompression (200～400mbar) and nitrogen purging under remove trace water, until the water-content＜500ppm of this adducts.This adducts is cooled to 80 ℃, with equivalence ratio OH: P
4O
10Slowly add Tripyrophosphoric acid (115%H at=3: 1
3PO
4Aldrich chemical company, Milwaukee, the state of Wisconsin).Observe about 10 ℃ heat release.After Tripyrophosphoric acid adds, temperature of reaction is brought up to 100 ℃, made its reaction 3～4 hours.By measuring the progress that this titration curve monitors this reaction.
The preparation of embodiment 5 tackifier dispersions-200g scale
Add in the stainless steel beaker 100 parts of Precursor 105 resins (Yisiman Chemical Company, the Middelburg, NL) and be heated to about 100 ℃.6～8 parts of tensio-active agents (deriving from embodiment 4) and 20% sodium hydroxide are added in this molten bat resin.The weight ratio of tensio-active agent and sodium hydroxide is so that the pH of final dispersion liquid is that 6～9 a kind of like this modes are selected.This mixture reheated 90～100 ℃ temperature.Stirring velocity is brought up to 1800rpm, hot water is added in this viscous mixt slowly, convert the water-in-oil-type dispersion liquid to until this system.This dispersion liquid further is diluted to desirable solids content.Then, this dispersion liquid is cooled to normal temperature.Resulting dispersion liquid has 6～9 pH and the mean particle size of 200～300nm.
The performance of different dispersion liquids is summarized in the table 1.Dispersion liquid A and B are from embodiment 1 (non-ionic type intermediate), embodiment 4 (aniorfic surfactant) and embodiment 5 (dispersion liquid) preparation.Dispersion liquid C is with dispersion liquid A and B, and different is that this dispersion liquid obtains according to the following stated embodiment 6.Dispersion liquid D is from embodiment 3, embodiment 4, embodiment 5 preparations.Dispersion liquid E is from embodiment 3, embodiment 4, embodiment 6 preparations, and dispersion liquid F is from embodiment 2, embodiment 4, embodiment 5 preparations.
The preparation of embodiment 6 tackifier dispersions-3.5kg scale
In 4 liters of electrically heated stainless steel reactors of a scraper plate that is equipped with the rack type agitator and moves in the opposite direction, (Yisiman Chemical Company, Middelburg NL) are heated to about 100 ℃ with 100 parts of Precursor 105 resins.7 parts of tensio-active agents (deriving from embodiment 4) and 20% sodium hydroxide are added in this molten resin.The weight ratio of tensio-active agent and sodium hydroxide is so that the pH of final dispersion liquid can a kind of like this mode select between 6～7.This mixture is with the stirring velocity homogenizing 1min of 150rpm.This stirring velocity is brought up to 250rpm.Speed with 50g/min is added hot water slowly.Temperature is reduced to about 90 ℃, converts the water-in-oil-type dispersion liquid to until this system.Generally, conversion just takes place when adding 10～20% water (weight with resin is benchmark).This dispersion liquid further is diluted to desirable solids content with the speed of 100g/min.Then, this dispersion liquid is cooled to normal temperature, discharging from this reactor.Resulting dispersion liquid has 6～7 pH and the mean particle size of 200～300nm.
The performance of different dispersion liquids is summarized in the table 1 (sees embodiment 5).
The preparation of embodiment 7 pressure sensitive adhesives
(Acronal V215, available from BASF AG, Ludwigshafen is D) with from tackifier dispersions fusion, the standing over night of embodiment 5 and 6 with acrylic latex.The resin content level of resulting wet binder prescription is 25% (is benchmark with the dry weight).This wet binder prescription is applied on the silicon release paper (90gsm), is in 110 ℃ the preheating oven dry 60 seconds in temperature.Then, this adhesive coating is transferred to a kind of paper gasket material (78gsm; Grown van Gelder) goes up and stores a night (23 ℃ and 50%RH).Measured binder performance, for example the ring is sticking, stripping strength and shear bond.These measurements are carried out according to FINAT Standard Methods.
Binder performance is summarized in the table 1.
Table 1
0) about the details of the manufacturing of each dispersion liquid, sees embodiment 5.
1) chemical bond between hydrophobic segment and the hydrophilic fragments.
2) measure with laser scattering method (Horiba LA-900).
3) measure with method (Labwave 9000) described in " embodiment joint ".
4) Brookfield LVT viscosity: all measurements are all carried out with 60rpm and axle 2.
5) +=medium foaming behavior (not having air in 24 hours),
The behavior (not having air in 16 hours) of bubbling of ++=well,
The excellent foaming behavior of ++ +=(not having air in 8 hours).
6) FINAT Test Method 9; PE=polyethylene base material.
7) FINAT Test Method 1; The CB=mill bristol.
8)FINAT?Test?Method?8。
9) dispersion liquid demonstrates excellent foaming behavior when being diluted to when solids content is 55%.
10) the prior art emulsifying agent of preparation dispersion liquid is the phosphoric acid ester of nonyl phenol ethoxylate.
Tackifier solid content measuring test method in the tackifier dispersions
The measuring method of the total solids level of the resin dispersion liquid that uses in this specification sheets category utilizes a kind of Lab Wave 9000Microwave.According to this testing method, this sample is to use the constant weight methods analyst.Make this sample drying, until reaching constant weight.Ridity is can accept weightless regulation by the maximum that defines in a certain specific time interval.In this specific time interim, when this weightlessness was equal to or less than defined weightless, this analysis just stopped and calculation result.This constant weight program makes and need not to know in advance and just can carry out sample analysis needed time of drying.
The constant weight parameter
Microwave power: 75% (487.5 watts; 100% equals 650 watts of maximum outputs)
The timed interval: 10 seconds
Weightless poor: 0.1mg
Maximum test period: 10min.
The balance setting point
Minimum weight: 1g
Maximum weight: 2g
In drawing and description, the typical better embodiment of the present invention is disclosed, although adopted specific term, they just use on general and descriptive meaning rather than the purpose in order to limit, and scope of the present invention proposes in following claims.The present invention specifically describes in detail with reference to its better embodiment, but it being understood that within the spirit and scope of the present invention and can make a variation and modify.
Claims (21)
1. an emulsifying agent that is used for tackifier dispersions comprises
(i) at least a sylvic acid segment or at least a rosin acid derivative segment,
(ii) polar chain that is connected with this sylvic acid or rosin acid derivative and
(iii) anionic headgroup that is connected with this polar chain,
Wherein this polar chain comprises at least 2 repeating units, and comprises at least one carbon-oxygen bond at least one repeating unit.
2. according to the emulsifying agent of claim 1, wherein the number of repeating units scope is 3～20 in this polar chain.
3. according to the emulsifying agent of claim 1, wherein the number of repeating units scope is 5～9 in this polar chain.
4. according to the emulsifying agent of claim 1, wherein this repeating unit is an ethylene oxide unit.
5. according to the emulsifying agent of claim 1, wherein this polar chain is connected on this sylvic acid or the rosin acid derivative segment via ester bond.
6. according to the emulsifying agent of claim 1, wherein this sylvic acid or rosin acid derivative obtain from tall oil rosin, resin or wood rosin or from its mixture or fraction.
7. according to the emulsifying agent of claim 1, wherein this anionic headgroup imports in this emulsifying agent with following at least a method: phosphorylated, sulfation or carboxylated.
8. tackifier dispersions that is used for adhesive formula comprises:
(i) water,
(ii) according in the claim 1～7 any one at least a emulsifying agent and
At least a in the (iii) following tackifier: (a) at least a rosin ester or (b) at least a hydrocarbon resin or (c) at least a from vinyl aromatic monomers for example vinylbenzene, indenes, alpha-methyl styrene, Vinylstyrene, resin that the Vinylstyrene of one or more alkyl produces or (d) at least a terpine resin or (e) mixture of one of at least two kinds or these tackifier and at least a other tackifier these tackifier are arranged.
9. according to the tackifier dispersions of claim 8, wherein these tackifier comprise the rosin ester of a kind of acid number＜25.
10. according to the tackifier dispersions of claim 8, wherein to comprise a kind of chain length scope be C to these tackifier
5～C
9Hydrocarbon resin.
11. according to the tackifier dispersions of claim 8, the mean particle size of tackifier in this tackifier dispersions＜2 μ m wherein.
12. according to the tackifier dispersions of claim 8, the mean particle size of tackifier in this tackifier dispersions＜1 μ m wherein.
13. according to the tackifier dispersions of claim 8, the mean particle size＜500nm of tackifier in this tackifier dispersions wherein.
14. according to the tackifier dispersions of claim 8, the mean particle size＜250nm of tackifier in this tackifier dispersions wherein.
15. according to the tackifier dispersions of claim 8, wherein the solids content scope of this tackifier dispersions is 55wt%～65wt%.
16. an adhesive formula comprises at least a tackifier dispersions and at least a component of polymer according to claim 8.
17. according to the adhesive formula of claim 16, wherein this component of polymer is a kind of elastomer latices.
18. adhesive formula according to claim 17, wherein this elastomer latices is selected from a group of following composition: acrylic polymers, styrene-butadiene copolymer, natural rubber suspension, or from the vinyl-acetic ester derived polymers, sovprene or acrylonitrile butadiene copolymer.
19. according to the adhesive formula of claim 16, wherein this adhesive formula is made up of 20～40% tackifier that with the dry weight are benchmark.
20. the manufacture method of the emulsifying agent of claim 1 comprises
(a) make at least a sylvic acid ethoxylation with oxyethane;
(b) make intermediate product and at least a mineral acid and/or at least a carboxylic acid reaction of step (a).
21. be used for making label to be attached to any surface, be used for packaging application, be used for floor applications, be used for road sign or be used for water base band, gas barrier coating or any tackiness agent of sealing agent, comprise the adhesive formula of claim 16.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74866905P | 2005-12-08 | 2005-12-08 | |
| US60/748,669 | 2005-12-08 | ||
| US11/604,497 | 2006-11-27 |
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| CN101321838A true CN101321838A (en) | 2008-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614806A (en) * | 2012-02-17 | 2012-08-01 | 茂名职业技术学院 | Rosin polyoxyethylene ether nonionic surfactant |
| CN102660249A (en) * | 2012-04-06 | 2012-09-12 | 西南石油大学 | Oil-in-water type crude oil emulsification viscosity reducer and preparation method thereof |
-
2006
- 2006-11-29 CN CNA200680045573XA patent/CN101321838A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614806A (en) * | 2012-02-17 | 2012-08-01 | 茂名职业技术学院 | Rosin polyoxyethylene ether nonionic surfactant |
| CN102660249A (en) * | 2012-04-06 | 2012-09-12 | 西南石油大学 | Oil-in-water type crude oil emulsification viscosity reducer and preparation method thereof |
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